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"::-..... It)I_ ;:> 0},7 T r_l_,'_r_m'r'r;_ '
]_]_.t](O,)0 Ol:'.()Irr' ATTI) 1!,o IOit,.,ix.I0_k,
J. t.t. Boye7 _
I
l2
li
lTei.r,e)l_._ui-_ ]Tes_;arch Ftmd, Ar_ze_:_:{can Che.,_].ca] Soc.i.ety,
Uctsb_r_LTbon , Z). C. and C}.,ios.cgo CiT, o!o (i',_._r_pt,.s, Un$\,oz_sit;)ro.C I].]_:__noi_, 0]lio<<t_(o, Illinois
A. Introduction
B. Preparative Methods
1. Nitric oxide and radicals
2. Irradiation of nit.]_osyl halide with a].kanes
3. Pyrolysis and photolysis of ilitrite esters
4. Oxidative nitrosation (Baudj. sch reaction)
5. Nit_:.osation of i-e]:tiary aromatic _7 _lJ.es
6. NJ.trosation of secondary aromatic am:ir_es
a. FJ.scher--IIepp reaction
b. Base cata]_ysed migratiorl of the nitroso group
from nitrogen to carbon
Nitrosation of primary aromatic amines
Nitrosation of phenols
Nitrosation of aromatic ethers
Nitrosative decarboxylation
Nitrosation of o!efins
a. Nitrous acid, nitrites, nitrogen oxides and
nitrosamines
b. Nitrosyl halides and nitrosyl sulfuric acid
c. Dehydrohalogenation of olefin nitrosohalides
Nitrosation of phenols and heterocycles with nitrite
•
8.
9.
i0.
i]..
12.
esters and a].koxides
(THRU!
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4
5
8
9
14
]_4
]. 5
18
].8
19
20
20
24
26
29
29
-2-
13.
14.
15.
16.
17.
18.
]9.
20.
21.
22_
23.
24.
25.
26.
2'7.
28.
C.
i.
2.
3.
4.
5.
6.
7.
8.
Organornetallic compounds and nitrosyl chloride
Geminal nitrosohalides from oximes
Esters of geminal nitrosoalcohols from oximes
Oxidation of dioximes
Oxidation of hydroxylamines
Oxidatlon of primary amines
Oxidation of secondary amines
Oxidation of tertiary amines
Oxidatlon of nitrones and Schiff bases
Reduct].on and deoxyge.nation of nitro corrLpounds
Nef reaction
Pyrolysis of heterocycles
}']].ectrolysis of oxime salts
Condensation reactions
Nitroso compounds from diazo compounds
Natural occurrence
Structure and Reactions
Dimerization
Isomerization to oximes
Nitrosoaromatic amine zwitterions
Activation of other substituents
Reduction
Deoxygenation
Oxidation
Free radicals
32
33
38
40
42
44
46
47
48
49
57
59
6-I
6}3
63
83
6)_t.
73
71_
76
79
83
8.6
8_
9. Monoolefins 90
i0. Acetylenes and arynes 93
ii. Thioketones, phosphorous ylids, azomethine derivatives 9)I
12. DJ .<<zoalkanes 05
].3. Conjugated dienes 96
14. Compounds with active hydrogen 9<$
].5. Complexes with metal salts and Lewis acids and
meta], chelates I0i
].6. Methylene and methynyl groups in olefins, Schiff
bases, carbonyl com]?ou1_dls I0_
17. Grignard ._ieagen ts I0[]
].8. Ehrlich-Sachs reaction :109
].9. Amines, hydroxylaminesj, hydrazines i].2
20. Substitution reactions in aromatic nJtroso compounds ]_0
"_ ..... c ' j_ %. .., .21. C±eavuge O.t C-nl_.o:_o bond .]2]
22. Pyrolytic and photolytic disproportionation 127
23. Miscellaneous reactions of nitroso compounds
a. Conjugate addJ.tion ]2_8
b. Fragmentation ]P_8
c. Reactions promoted by the presence of nitroso-.benzene ]29
The assistance from a NASA grant No. NGR-14-012-004 is
gratefully acknowledged.
4
A. Introduction
Appreciation of the ch.emfstry of the C-nitroso group has
developed slow].y notwit]Istanding its extensive literature.
Undoubtedly a contributing factor has been its absence, except
for a few examp].es, in naturally occurring materia].s.
In the past decade there have been several important
deve]_opments including the n.m.r, ar)alysis of the structural
re].ationship between benzfuroxan and o-dinitrosobenzene, the
e.s.r, determination of nitroso radic, al-ar)ions, photochemical.
nitrosations, deoxygenat:ion to a nit):ene and a.ddition to dienes
Organic synthesis has beer._ substantially he].ped by the
chem:i.stry of the C-nitroso function Lut it would appear that it
will be even more richly rewarded in the future. Two examples
may serve to illustrate. In the first t addition of the nitroso
group to a C-H bond adjacent to an o]e:Einic, azomethine or other
unsaturated linkage offers a promising method to be developed
2for introducing a functional group at an sp carbon atom. The
second example consists in the emerging chemistry of the nitroso
group conjugated with one or more unsaturated linkages and is
demonstrated in conjugate addition and valence isomerization
reactions of nitroso olefins and in the recently discovered
ethynyl nitroso compounds.
A comprehensive presentation(1)of the chemistry of the
C-nitroso compounds appeared recently. The present work is
intended to be complementary and to include new information in
the rapidly growing field.
5
B. Preparative Methods
i. Nitric oxide and radicals
In an early recognition of the affinity between nitric oxide
and organic rad:Lcals, i't was assumed that the appearance of a
blue color on mixing triphenylmethyl with nitric oxide in ether
in the absence of air denoted the presence of triphenylnitroso...
methane (equation i). Reversibility of the reaction was
suggested by the disappearance of the. blue color and recovery of
starting materials on evaporation of the solvent (2).
(C6115)3C. + NO ,<............... (C6H5)3CNO(1)
Many reactions which lead to the fc)rmation of nitroso
c.ompounds are best understood on the basis of a combJ.nation of
nitric oxide with. an appropriate free radical. It is such a
combination, for example, which permits r-J..trJ.c oxide to inhibit
free radical chain reactions (3). The formation of the lower
molecular-weight nitrosoalkanes has been observed in gas-phase
reactions between nitric oxide and the corresponding a!kyl group
generated in. situ by the photolysis of an azoa].kane (4), pyrolysis
of a dia]_kyl mercury compound (5), photolysis of an alkyl ha].ide
(6, 7), the addition of a radical such as nitrogen dJ.oxide to an
olefin (8) (equation 2), and by other means. It is reported that
_!-irradiation of a mixture of carbon tetrachloride and nitric
oxide leads to the formation of trJchloronitrosomethane (9).
NO2 \
CF2==CF 2 ................ 7 02NCF2CF 2'
NO
O2NCF2CF2NO (2)
Nitric oxide readily combines with the cyclohexyl radical which
may have been generated by the action of a chlorine atom on
cyclohexane (10) (equation 3) and with the reactive diradical
form of _p-xylylene (ii) (equation 4).
</_ _ .__NO_ <)NO
:NOH(3)
CI{2_ CH2NO CH:NOH
(4)
2Nitroso olefins in which the substituent is attached to sp
carbon a c:_ less '_Tell-k_iown; nevertheless perfluoronitrosoethylene
has been obtained from the reaction between trifluoroiodoethylene
and nitric o:_ide (12) (equation 5)° in contrast trifluoronitroso-
ethylene has not been detected in the reaction mixture obtained
from trifluorochloroethylene and nitric oxide (13) and a reaction
presumably initiated by nitrogen dioxide gives satu_.ated products
3instead. Nitroso olefins with the substituent attached to sp
carbon have been prepared in a similar way (14) (equation 6)
through irradiation of an allylic iodide in the presence of nitric
oxide.
NOCF2=CFI "_ CF2=CFNO (5)
h_
NOCF2=CIICII2I 2 C_2=:CHCH21_O (6)
h_
+ other products
Apparently pure nitric oxide does not react with monoolefins
Under ordinary conditic_ns (15) ; however, a trace of nJ..trogerl
dioxide which is usuallv present will ini[.tiate a reaction leading
to a mixture of products in which nitro compounds predominate.
From isobut.ylene up to 45% tri._(nitro-t.-butyl)hydro>;.ylamJ.ne has
been reported (].6) (equation 7). The transformation of o].efirls
NO 2 __.). NO(CH 3) 2C=CI-12 O2NC4}-I 8" -.................) ONC4H8N02
......v (C4HsNO 2) NOC II NO202NC4H8 _ + ONC4HsNO 2 "_ 2 4 8 2('7)
into nitriics by nitric oxide at high tempe_:atures is not comp.]_etely
Understood (17) (equation 8) and the intermediacy of nitroso
derivatives has not been established.
NO
CH2=CHCH 3 _ CI-]2:CHCN (8)450 °
arg on
Carhonyl derivatives with the nitroso group attached to the
carbony], carbon are unknown; however, CH3CONO has been a Suggested
intermediate in the photochemical oxidation of nitric oxide to
nitrogen dioxide in acetone (18). The formation of nitroso
aromatic compounds by the combination of aryl rad.icals and
nitric oxide apparently has not been reported.
Only a few nitrosoacetylenes in which the substituent is
attached to an sp carbon are known, none of which have been
obtaihed in reactions employing nitric oxide. Experiments with
bromoacetylene and nitric oxide led to the conclusion that the
ethynyl radical (HC_C- Z---_.HC=C:) is unreactive to_Jard nit,:ic
oxide (19). Primary products formed arc carbon mono_{ide and
Cyanogen bromide_ An indication that radicals at sp carbon
Will .rea, t with 10itric oxide is found in the form_tion of nitrosyl
Cya_ide on f],_s}:_ photo!ysis of e.ither. cyanogen or cyanogen bromJ_.]e
:i.n the p:_;esence of nitric oxide (20) (equation 9) and in the
Pyroi[ysis of mei_icuric cyanide iI_ the prese1._ce of nitric oxide (21),,
h-,- NO
BrCN ...........n2 ,,CN ...... _, ONCN (9)
2. Irradiation of nitrosyl halides and alkanes
Irradiation of mixtures of saturated aliphatic hydrocarbons
and nitrosyl halides will also lead to the formation of corres-
ponding nitrQsoparaffins. A mixture Of products may be obtained
from a hydrocarbon in which hydrogen atoms are not equivalent.
The dimer of nitrosocyclohexane has been obtained from cyclohexane
and nitrosyl chloride upon irradiation by ultra-violet light (22).
When the reaction, assumed to proceed by the formation and
recolabination of radicals, is carried out in the presence of
strong acid, such as hydrochlo._fic or sulfuric acid or phosphorous
oxychloride, the product underg<_es isomerization, first to the
Oxime and then by a Beckman rearrangement into the cyclic amide,
caprolactam (23) (equation i0). There is a report that irradia-.
tion of a mixture of cyclohexane, benzophenone, concentrated
hydrochloric acid and nitric oxide in which oxygen is also
present leads to the formation of an unidentified dJnitroso-
cyclohexane (24).
=NO]i(! 0)
Irradiation with Co 60 of cyc!ohexane solutions containing
nitrosy] chloride has also brought about the formation of nitroso-
cyclohexane (isolated as the isomeric oxime of cyclohexanone)
along with cyclohexyl chloride and cyclohexanone (25).
3. Pyrolysis and photolysis of nitrite esters
Pyrolysis or photolysis of a nitrite ester may reault in an
intramolecular rearrangeraent by a concerted mechanism or may
require a dissociat_o_ followed by a recombination. _%0
formation of nitrosomothane and acetone from tort-butyl nitrite
by e ithc.r pyrolysis (26) or pLotolysis (27)
i0
is satisfactorily accounted for on. the has:is of initial cleavage
into nitric oxide and the trimethylme'[:hoxy radical. The ]atLer
then further dissociates into acetone and the methyl radical
which combines with nitric oxide (equation ]].). Ethane -is a].so
approxima.i:e Im H
(kcal/mo] s )
(d)
(e.)
' "- ) 3C0 _ + NO 35(a) (CH3) 3COl,_O .........._,.(Cl! 3
(c) (C}I3) 3C0_.{0 + CI{ 3 ............. _]>(CH3) 3C0,. + C_-I3NO -30
C}I 3. + NO ;,, CII3NO
(CH3)3C0, + NO ........ } (CH 3)3CO]_.I0
-65
_5-.,_ (].].)
produced and its formation supports the..intermediacy of methyl
• w._th nitrites, step (c),radicals That alkyl radicals may react "_
is demonstrated in the formation of nitrosomethanc from either
butyl, or amyl nitrite and acetyl. "" _'_peroxlct_ in which the latter must
serve as the precursor of the l_ethyl group (28). One of the
many preparations for ni[trosocyclohexane is based on a similar
reaction and demonstrat:_ the expected tendency for the largest
of the three 'alkyl groups which may migrate to become attached
to niCrogen (29) (equation 12).
R 1
-CONO NO+ RIcoR 2 (12)
ii
The pyrolytic ring-opening of perfluorocyclobutyl nitrite
has been explained on %be basis of ini-tJal dissocia.tion into
radicals but with the recognition that the reaction could proceed
with ionic in.termediates or could requ.J.re an intramolecula.r
eonce):ted mechan:[,_}i,;:_(30) (equation 13), In general cycloa]kyl
nJ.trites (ri__g size of 4 to 7 atoms) photolyse into _>.nitroso
a]dehydes (31.), A similar rearrangement of a s_)ggest.ed in-ter _-
medJ.ate vinyl nitrite has been post:ulatcd to account for the
p]]ot.olyt.ic isomerization of ].-]?he:i-lyl--2-_itro])._;ol)enc_ (32)
(eq_.:4a[-j..on].4), A photo]ytic i.so1.rLe_-i_:ation of certain _.)it:robuta,-
di.enes .a.n(! arom,:-_tic c()ml?On_ds may requi];e a 1,5-.m:i..g_::atJ.onof the
n-_lt):'oso 9:_rou]? (32) (eqt_.atJon:-_ 15, 16) <Erom oxygen t:o ca:r])on,
}...................... ONO
' lj F!
.....,22,O]:qCF2C]?2(]I 2CO]J ( 13 )
C h .C.**-,CCh6 .5 i 3
NO 2
/ - ]. • ...........:>A,.-cH-.coc i3 .........................-..>ON-O NO
ArCC _,_JI.li 3NOH (].4)
O0|
NO 2
h.v-
HON:
II0
(15)
12
lqO 2
#..)Io>j ..................->-_,v / " .....</", ..../
0
->[ lo!IiNO}I
/
O
II
, " .() ..ol } ..I......"_/"if "_" .....
0
(16)
A !,5..migr_.at:_.or_of tbc: nitroso g_<-oup from o);:ygo_:_-[-ocarbon
is a c]Ja:_;,£,cLc'zi;i;tic f<;._...'.:.uz,_,, of the Barton .t:e.a(.;tJo.n., J.)_ wh:[(;h
a.1],.}_], nit:<ite:: ( ",.,,:].-!:_h a car].)o:__, chain of at least four ate)ms) may
be t.ra_l:_fo:):me.d into 4--nit?,:":>so alcohols (33, 34)° Ev:i.derltly a
rear:_:angement of an intermediate alko>:y radical J.s r_-'quired
(33, 35) (eqdation 1.7). It has provJded a dramatic synthesis for
H ONO tI 0 OH NO OltI I hv" I I I NO I I
......... 7; -C-I z I -NO I I z I
(17)
a number of organic molecules otherwise available only with
difficulty. Cycloheptyl nitrite undergoes photolytic isomerization
into Loth 7-nitrosoh.eptanal and 4-nitrosocycloheptanol (31) but
cyclo:)ctyl nitrite gives only the Barton product, 4-nitrosocyclo-
octanol (3!).
].3
A perfluoro acyl nitrite is avaJ.).nble from eithe:L" the
corresponding acid anhyd]:ide or sJ..ive]: salt of the ca]:boxylJ.c
acid. TrJ.fluoronitrosomethar)e can be obtained in yields betteJ::
than fifty percent from Lhe pyrolysis or the photoly_Js of
trifluoroacetyl nitrite (36) (equation ]_8).. It has also been
prepared from silver trifluoroacetat<. _ _.u_d nitrosyl chloride
(37) (equation ].9). Each reactJ.on has been extended to perfluoro
homo]ogs (38, 39) and to cyclic anhydrid.es (39) (equation 20).
N203 l).'_....
3 c¢- 2 "(CF3CO)20 ................... ,., CF "% YO C3-:'3NOol:
(is)
NOC 1
C tv CO Ag ........................ :::.... CF.$:qO"3 2": c) e .)
< -].0
(19)
OII
y N203 >; l) h,,_F2C _" 0 l z z
................ CF. CO..]:qO ....................... >2
/
CF2_ 2) I-I20CF2CO2NO
0
-_ _(C]e2 C 3211ICF2NO
(20)
With or without irradiation nitrosyl chloride reacted
explosively with silver trichloroacetate and no product could be
identified (ll.0). A successful z_eactio_-1 led to the fo:pmabion of
trichloronitrosomethane from the treatment of the sodium salt of
trichlorosulfinate with nitrosyl chloride in a sealed tube at O °
(40) (equation 21).
].4
NOC1
" C13CSO2N 0 ............:> C]3CNONa02SCCi 3 ........................... i (21)
J" ' _ ' (", -r x ' - -" •4. Oxidative l:itrosat..x.,n (]',aL_d:L._:;cl_ _..... _c. tzon.)
' '_' o>_:ida.t[ve nitrosa"-" " of e_."cm_g_t:i.cAccording to ]_3aud_L..,c]_, L_.._.o::
,..].m.?.lLane:o: .....].n_..zo.]uct3.oz: of -t]-:ccompounds procec.ds by the _" :- .... , ?," " _ ": .... " '-
nitroso and hydroxyl g:coup int:o adjac:e:nt positior:s on the
nuc:]eus when 1:_-eatecl wJ..th nitros],], hydride.' an:Y. oxygen, Paztici-
T'_FI+-_ ,-'_,'_ _'f:: r-n_,_-,rr, y" <"_'1 "l'-e ;_",',',r-_;:,:',:", r,¢_C'P_:I<t;1T"_7 t(b ,q l: ,'q ]') 7 ] JZe t}]C_
nitzc)sy], radical and go prc.,vc,rlL th.c' fo.rma, tion of Ee__:a: nJ_Lroso ....
pher:o].s (41) (equaLion 22).
"I'"" /_' C u'l 2._ ]:qOH ..... "'<>'_ " ' :=NO]I
..........................;"" N............. _ ..................................../
. "-.-/.a 0 2 .... 0 .,,.,',_" . Oi-t
0
cu/2
0
(22)
5. Nitrosation of tertiary aromatic amines
Probably the first knov,m method for nitr'osation at carbon
consisted in the treatment of certain aromatic _ _-'ter _lary amines
w-kth nitrous acid (42). In this way p.--nitroso-N,N-dimethylatnilin:e
"i n • c, a_ . ' ,is easil. 7 prepa:'c:c_ (43) A ,_t.er3_c hindrance to the reaction may
be introJuccd when larger groups are atzac]]c.o_ e=c.hex at nlcz(._gcn
1511£ DI. C,:] toor at the ]?,osition ort]lo to the amino function (44). "....r "
achieve dir_itrosation ]lave not been successful. Nitrosation of
N,N.-.dip]_,:-:r_y]mt-,thy]_ amine gave only the mononii:roso derivative,
....P-'nil-roso--N-phoyl_']-N-.IrLeth.y ..... ._..,]ani].i:rla (45) . Again only one be_nzcne
l I
•,,-" I -..dipheny] -ril_g wi;ts nitrosated :i.n ex]?e::":Lments with N,N ....d4_etny].-b,N
..............so group Js :.qc.-L2...])1.:_i:en(_-..l,4...d:ka,m:i.ne(46) (equation 23).. 'l!>e _,:.......
............. .:,O:fu<._<j.Z'teS 0..]'!OKI: ]:tO....inva_::i;_d:,],f -introduced into the para.-p()sition and ........ __................
" I ipom:i.t:_on is selcct.cd (41) (<-'.qu<,,tion 24), In c_.;,t:Lu,:i_n e:,,d.__q:.,c:_ so.c]l
"2H5 _-"2H 5 HONO, (, ,. ]-_. • ,-_( _-J ...............................X
C6t15t_ .[t2(. L.-....C,_....... 2I,!C6H 5 H+ /
2t[5 C2II 5I
C 611.5NCII 2 C] !:=:C HCIt 2FiC 6It 4 I<!O-.])(2 3)
f", ......','I" "( ('-h'] - oNo.| k.../ I ! ,,...j _ .........7 ................/
CH2CH2 r"n T.' ,,, - v'"_'2" ' ( _' ;I-J 3 ) 2
R NO
(24)
._ . ....... L'J *-3. .as ]]!---ben:,_']:]---],_,N-din-ethylaniline where the ]?a:<a--]?o ''-'on is alread.y
occupied, nitrosation presumably occurs ortho to the amine
function (48) .
6. Nitrosation of secondary aromatic amines
. Fz=,cher-Hepp reaction Nitrosation of secondazy aromatica .' t-,
amJn< s generally occurs initially at nitrogen and is reversib].e.
In hydroch].o:_ic or hydrobromic acid the N-nitroso comloound
rearranges to the para-nitroso isomer. The isomerization, known
16
as the Fischer-Nepp reaction, proceeds intermolecular]_y with the
intermedial.e formation of nJtrosyl chloride follo',_ed by nitro-
sation generally at the para-position (49) (equation 25).
Denitrosation of an aromatic N-nitrosamine appears to be more
rapid in hydrochloric acid than it is in sulfuric acid (50),
in agreement with low yields for the isomerization step when
carried out in sulfuric acid (49). This suggests that nuclear
NO
+ HONO ,t._,-._'--" [_!__ NCIll3 + I]OH
NO
+ HC! m_._-'-_-_" !<_'l NNCH3 + NOCI'
__ NHCH3 ............NOCI i ON__ NNcH3 (25)
nitrosation occurs directly wheh certain secondary aromatic amines
are appropriately treated in concentric.ted sulfuric acid. The
reaction does not occur in nitric acid (51).
The intermediate formation of nitrosyl chloride in the
Fischcr-l]e]pp reaction was demonstrated in the formation of the
].7
n.itrosy_], cll]oride adduct of arl(r[-llo](-_ when the latt.er was prc::_'en-[.
during, the txea-_e.nt of N--.n]troso-N..-.m,,th:fl_.... ,... . a_-i_lJ_ne with alco]_o]/l.c
hydrogen ch].oride in ether (49),
Nitrosation in t]]c: ring may bo hindered when t_he B__!.}_._{-.
position is occupied by a)_c)tl_mr subr:Jtitt:ient. (_9) or by ].a_"ge[- .
substituents on the amine "- .... , . ' -r]lL]:.Oj-C_]](5]_) fOOl- yl.c::].<tSO;[f _.).--nJ.tl?o_:o
N"-n-]2exy].a.ni.lil]e were obtair_ed _i "_. . ]:.:om the N--nit:roso ]_somer and-t:be
corrospond]ng N-octyl analog was n.ot t:_ansformed into its p&_:a.-
ni.tzoso isbmer (5][) ,
A particu].arly...... interestin[ ] o:.:ar,/]_/It:,...... of the lT':i_sche):--l]ieL, p
! I
<ca.cl:ion is found .i.r >, the isom(_rizatic;n of the _. ,N -dinit_:oso-N,N_ -
djmet.byl derivative of m-.pl,.{:_.y].e_.:.c...J.amine (52) (equation 26)°
NO
ONNCH 3 NHCH 3
(26)
The reaction proceeds smoothly to transform secondary N-.nitroso-
_,-naphthylamines into the expected 4-nitroso isomers (49) ;
but N-nitroso'-l-bromo..-.2-methy]ari1ino-naphtha].ene does not undergo
t-he Fischer-llepp reaction.
A few secondary amines have been nitrosated by nitric acid
in the presence of hyd_och]_oric acid. The addition of sodium
nitrate to fum.J_ng hydrochloric acid cont:aining N-e-thy]_ant]n_anilic
18
acid transforrFLs the latter into ;]..ts }_--,nitrc)so derivative (53)
(equation 27). From its reaction with nil:tic acJ.d in al,:._oholic"
h.ydro_]en <"11].oride, __P-acehami@3dJ'(p]-lony]a_rl].. ....ne gi.....vo:: -.P'nitr°s°-i £'-.
aco-tarLi@od:..phc;nylam:i.n<-_ (54) .
............J:,_.J<.:.h _ HC1
[,, ........ /; CO.,H ]IN0 3 [!<:!1ON , fi CO2}._
(_7)
k)_..........}i}.D:'.?..,£_q_.]kfi.b,>?__-£(] .]]g: <.[:-![_-t-kg£}..:.. A 1,3...migrat.ion of th.e .nit-xo::;o
group from nit].:ogc.n to c'.a:,:].>onappc<:,._:s to be requJ.:_red fen: an
t<aN.':._rSt_..];,,:.]].ng of the ].)ase..-,cak£_].yzed iso_i_erJ.zatJ<H_ of certaJ _l
N..n:].t:,<o;-.cg<_f_razon<:::,qinto corrospondir).g ,.)rimes (55) (equation 28) ,
6h
C_L., ....--,_-.._ ......... }i,. ".................. ]
r (-N__
C.N,-N:::N'"CHC..t({.. -...................."'_ C..H,.N-":N.-.CC6tt 5
NO NOH
(2s)
A base-.-cata].y:-:ied 1,2--migration of the nit:r.oso group from
nit:Cc,gc_.n z:<:,carbon was recently discovered (56) (C:'.qU,:.._,..LOn29).
base
R-N-- (',H2CN ............._ RNI-ICCN
NO NOH
(29)
7. Nitrosation of primary aromatic amines
Under appropriate conditions a variety of primary aromatic
aminc, s will undergo nuclear ni-trosation rather than diazotization.
Nitrosy! sulfuric acid in concc:_rtrated sulfuric acid transforms
19
_-naphthylamine into its 4-nitro._-{o derivative (57) and nitrous
acid nitrosated a pyrimidine ring carbon in the presonce of
both a primary and secondary amine function (5<1) (equation 30).
In a similar reaction nitrosation occurs at the 3.-position in
2-hydroxy- 4- amino-pyridin e (59).
t%"O)
8. Nitrosation of phenols
Phenols arr'c readily nitrosated at _o-and ]_.positions; tbjmo]
(60) and _.-naphthol (60), undergo mononitrosation. Both 2,6-
dibromophenol and 2,6-dibromophenol-4-D react with soditurL nitrite
in aqueous alcohol by general base catalysis (61) (equation 3])
with nitrosodeprotonation occurring faster than ni[-rosodedeuteration
(kH/kD=3.6). _/{ith nitrous acid, resorcinol is dinitrosated to
2,4-dinitrosoresorcinol (62) and phlorogucinol to trinitroso-
phlor0glucinol (62).
tt NO
Br__Br + NOX K----b_Br<)Br
O O
tI NO NO
Br<_Br + B _/_" Br_Br
O 0
+ BH +
(31)
2O
9. Nitrosation of ,,r_I ' ctl-_er <"a]-C :.,l.c.....L C ,.:,
H 0 ~j ]Nitrosation of aromatic ethe:_:-s is vz]. A.._.]ly un]_1_;.<.)wn In
mine;tal ac:id containing an al]t.y], nitrite, reso:ccinol d__eunyl
J ..... •
eLhe.< Is partial].y %r_ansEo;r_iT<_d ].n-to a nitroso derivative of the
diether (63) (equat.ion 32). With the a.<:sumption. [hat th,e
unassigned nitloso g::oulD is at the 4-position.0 in nitroso dietbh_l--
resorcino]. (2), the o ......{:::rv_:dproduc'ts att:e so,_>_.:<t':)r;[].y
..........."',,...........;,{-,-,,:!,...........{:r,-rl'p,._,th(, _o_r',=:'c_e_].. ..........5nfi.er.q_c_diates (,,c_-i--_;,'_,_...._,..,..._..33) .
) ,£..22 ]'{q O tt O C ._H t
I k.../ J, r)r-,2t.15•.. ....",..,"_0 ..'-2115 H + /" ............. . : 2<..,/" ., .:...." NO "
I'_()
.].,
( 32)
-I..o/C2H 5
II +
...................
._. .._ OC2Ii 5"......_// - .
}I/"_NO
0
II
<// "-...,
") (" 2 t._ 5
tt NO
.........._" ]. (33 )
I0. Nitrosevtive decarboxyla.tion
Nitrosa-tion by displacement of subst:J.l:uents is rarely found.
An interesting e::am_,le has come to be kno\,,.n as nj._-_-t.._ O :.'2.O
2]_
decarboxylation (64). On adding sodium niiL._tJ_te to an aqueous
alcoholic so]_ut:[on of 3,5-d.: b:!:omo--4--hydl:o>:y].)':;nzoJ.c aci_.] t1!.er(-
is an immediavte evolution of carbon dio:_J.do, Fzom tile reac-tion,
3,5-dibromo--4-hyd:_;o;<ynii::dos<J_e.nzcrlo. J.s isoloL-o.,d qnaT.',tii:.akivc].y
(64) (equation 34) °
CO2H NO
._r_N,N.I// Br .,_..--",......]{r'/()It OII
..If<::.kJnct-lcs of the reactJ.on and ............- - (_OIhL.)c_]LJ.,%Oi-] wJ -CII ])ICC)]_'[C_d(:]'--
carbo,',<.y]at Jc)n and ]:)zomodesu]_:i-onat ion a:_:G in a,:]:l__oc;:me.t;t_'J.[-.]_-[:he
fol]_owJ.!:Hi T,!oc]:r_vn.Jsm. (61) (equat:i.orl 35). .-It is sJgnificani: [-.o
no-he that:. _.).--t).yd:i:o)q?]:_enzoic. acid rl:[t:t:osodocarbo><y!ai:es _!,L:. ].easl-
300 tJ.mes more rapi_].y than does ]i>--meth.o:<y]:>er_zoic ocid (61[) o
- d_.l.lvat.tv_,= undergo.'.....LcylJ_c &_cid and J.%s 3-,4 and 5--..rrc:tbyl
this reac, tion but 3- a:nd 5-nitro and 3,5.-dinit-<osalicy].ic acid
do not (64).
Br - . Br
O
o\
() -x+ NOX \:_-Br Br
ItO
ON ('O 2
z Br
0
NO
>' _i_ + CO2}_.,- ;_r
i
O
(35)
22
Following the observation that an attache_ methyl group
decreased, whereas an attached carboxyl group incJ;eased, the
reactivity Of a tertiary carbon in a cyelohexane ring toward
nitrosation by nitrosyl sulfuric acid in concentrated sulfuric
acid (65) (equations 36, 37) it was found that cyeloa!ky! (ring-
size 5 through 7) carboxylic acids and the _-branched carboxvlic
acids generally decarbo;<ylated on similar treatment (66). q_he
assumntion that c_-nitrosocarbo-:ylic acids a_;e intermediates (67)
has been eh_).llenged and it is claimed that c_-nLtrohocyc!ohe_;ane-
car])oxylic acid [s not an intermediate in the nitrosative
decarbo_/ylation of cyclohe}_:anecarboxylic acid with the formation
of Capro\actam (68).
(36)
<i<IH2SO 4
=NOII
(37)
The carboxyl group may be replaced by other carbonyl groups,
e.g., ci<clododecanone oxime is obtained from formylcyclododecane
(69) and cyclohexanone oxime is obtained from benzoylcyclohe_,_ane
(70). These latter reactions are reminiscent of the base catalyzed
nitrosation and cleavage of certain cyclic ketones (71) (equation 38).
23
"_%_ '_ f j
C}{ ..
C=NOil
-, T .
CH2 Cit. 2 (02 t.2h5
(3 _{)
. .].C._h,.Anot]_._cu: rc]_ated "__'"-" -). ].L.c,....L..t(n OCCU:r's \.;,he]u r_it:co:.:y]_ (]-)]<)r."Lda t.:cat_ ':-, ....._"
n, , -° r, . ,,,_,-b:c_,,_nc:'.]_ed ]?e:uo:,:ycarboxy].ic _c:td,:, into riit:.:_:oso comDo_:!nd _-_ (22)
(Oqb &ti.O.'.], a..,"°) .
R2C-ICO3J
_Ou]_
_"2 ......... -1-CO 2 02(3-_)
({,_t.._ J o.__ l;.]_e ]_c,.octioyl of i]rOi.llE_{;ii.(:t ]<C!ZO_ir:':b %,11/I'
acid. :h_' s._Ifuric acid is satisfied ]:5' a m,':r];am:.,_;,"_ u_hi.cI_ _ __'<_o]. \, <'.,s
the ..... .r a-tc_-dc,.te:l:m_-] r_J ng ste]? o.L (z(:.prot-or_. a :.:i ,:-, f:_:-om -[.]ue p.t()[:, o_ :-[. (_d
' " a_ ,.._ _i,o]_voly'-.;is (/._)ketc;ne, fol]ov,,cC] by a raplcz n:Lt:iL(.',:_;at:ic_n " "_ ....
(equaL-ion _0) (cf, eqJation 62). '])l_J.s may be fo].].owc:;d by t:_-__::to.--
nleri',..:ation to an. o>[]rae and a Sec]_-mam_ xear:ce.nge._.;._t-. When the
teatt ion J.s carried out with p_-toly]cyc_].o]'_,<:::y]. ]:c-ton,c and
nitro,,_y], chloride in po!yphosphorio _ acid, c,a]2.ro].acLam _._._d
p-met:hylbenzoic acid are fozn,u<:d along v,d.th ].)_-to]_y].--._--niLrosocyclo-
hexyl ketone (74) .
I + H + _::b --.At <__:_. Ar
i<0
/-""-.._.j ....... C+._OH H 20 "_--_..:;[
Ar _A:cCO2.1I .
./ ._1t4
0.',i
/(_0)
ii. Nitrosa.tion of olefins
a NJtrov_ c. acid l-_ibrii-es, n41]-.oc_c_u o-,]<]c,s _:_-_d_-,--b-_c<_,o::u,ine o....."_..........::_.__2......i ";'__..".'._-].'I.T._f_.....-":...:_---.L._.....< .. ': " . :.__1"..... :2,. .':t- . _ "::....". .....::f.2L: t:_ ....L_L_t
Other o].ofins r__ay ut_oGz_o nJt.l.o,=,e.tio:_ by it ]:_.latcd m.<:c]lani,t:;>_,of,
oqua-tion. 40. In -c.rlcn_' ' ].oroacet-]_c acid, cc..>f:a:Ln ]::i;_g.--s_bsv±_.t.._.c<__" " ....... '
derivatives of prope.n;_7].b_:.nz=n,:. -............ ...... c-_ _, bzc'<__t,t d with, j..j-;.c:i'--but--y] nit rite a.<e
trans:[;c)rmcd into [D-nitroso trichlc<i:oace.t;:.dm<s ('/]_) (cqui:vt:ion 41),
Ill CO_] t.l.b.,;t,...... <_ the t:.:<eatemnt o:?: _:n_-o]::>e,uy]]:)enzc_ne with nil.s:ous ac:i.d ].ed
to -t]).o form_ct:i.oiu of the c.or.:espondin 9 n:l.i:),e:>s:it(.., ].--phc_..,.7)],]..-..].-riit_:c)so--
2-nitro];)rol;.>u_ne (76) (equa-tion 42) and simiTI..a:i: restllt:::_ l-_,\_('-. ].,ee_
Ol:)L_il_c(] \?:i t.]_ ni-tro<]<::ll triox:i_c]e (77) . A p- Y_:l_[rC)so n:{.'_.......J.... u,,.." ]).O.s
OCOc .... I.
-; ..........71.........;.......""C13CC02tI , ,
Olt OR
(<ll)
ttNO 2
C'-]-lrt.,.:)CH=CHCH3 ........... ::"_" C6HrCItC]:I"-) i (]t02) C}I3
NO
(42)
been prepared from cyc].ohexene in concentrated nitric acid and
nitrogen dioxj.de (equation 43) and a similar reaction has bc'en
reported for the initial product from isobutylc'ne and dinit_:ogen
tetrox].de (equation 44) in the absence of weakly basic solvents
such as ethe_:;s and esters which promote the formation of nitro
co,,c_pou>ds by a free radical process (78). A mar]..',c:dly different
re,::ction t._.:ansformed propylene into 2-nit__:o-'3--methylfuro:<_;n when
treated with dinitrogen tetroxide (79) (equation 45).
25
N O 2O _ .
• O , 1 hou:r."
(43)
(CH 3) 2C=CH2 f
_:,t-l,r', 'i- .--, l (I Oo
(C] 1%
ONO 2i
2CC_]2N() (44)
CII3CI]=C]) 2
}_204..... : .............................:I.... Ct]
e th <'_'..]: 7,] ]:q. ;. O•-60 to ....20 ° "0 ....
(4!_,)
Nitrosites (_{---n.itro:r_:[i:.:r_osoc:or!:,.pounds, cf. , equation 42) are
g(!_nera]_].y p:coduced from o]efins treated with di]_itrogen trioxide
(KI20,{.".........NO + NO2) (80). The react:i.on prob_]:,,ly p]:oceeds ]:.',1,a
free rad:Jcal mechanism initiated by an a.ti:ac]<: on an olefinic
Carbon by nitrogen dioxide, cf., equation 2. Terpen_e nitro':_ites
are often solid derivatives helpful in cbazacterization.
Photochemically produced adducL,., of nitrosamines and olef_<!'.s
have been repo:cted. The adduct from N.-n:i..tr¢::;opiper:i.dine and
Cyc]ohexene has been isolated in its tautomer-ic oxime form (81)
(equation 4.6) .
(46)
26
of nit;cosyl halides w-Lth a g._;e.at variety of hydzoc_<_rbon anti
fluo.roca-_:]:.:on o]_ofins ]_;:,,s._:ecc:r)1:.]yal:)pc,a:¢ed. Tbc, c-zpected adduc;t
(cquat;[on 47) is not only o:Et.c_::rlformod along with other }?-<oduct::,
but also it may occur as an .]_nto._mc,diat<.'. ;.t:oqu,j.:l._odfo:c the
forru_ttion of a product isolated (82). _,_ono-- and dJ.--olefi.ns
]<l¢_C' 1
P'2 C:-::C}I 2 ................ >_i It 217C1I 2 NO ( 4 '/)
C1
(co;r_jt,g:' <el a]-_d t_ric;cw,,jt:l,{]_c-t-cc_d) _ ]<r_# _.,<_ <-t(..,:.c......t.q ltr_s,::tttl;l..7;_tc_] a].c->]_ol<:,
"V ;[ ])._; ]. ([-_L]i([<if[--]# C,L.'.LC']DOll],''I - r - " ... ,, ....... Cl)si_j:)O].;'r!C.J'.i>. ]lit.Y_(J()[!C__"'ill_.; iftJ.J(:[O t; ]/ <._;;- ]<)'O.,..OC_t:>])C)]'i.
o;I. ,!!:JT:;..r) .Cs.c_:ivativ,:.:;_; wJ]l react wi!::!,_ n_it..J;c,;:_y.t c]_lo);J.d,, fei_c,.z,-_l].y
]t;I.)}C_(_')'/ l[Ij " <' ..... ":' i ..... ' ......... , cc.,_ .s,.i::i C)?_P-; . ]_71 Cc-:..i. t ct_._]l Jl],rJ'[[.;"S')(']_[.'_ -', _ l;;]').t) -_] ;]_[; ]" O S C) ]_a!ic]e
11";::_, It;C, "_<; " ,/11].-" :,_[ _;r] F'{-t-_, i0];Ol!t O_.,'.t _:}]. ]-'i Tf ]_ ll:{i-l'j [2(:; _illd })y<i,'(<']ll OF] '-" O;I;"'- .... >; ........ . .......... £i.2._7. :L/ ......................
hydt'c.)]b;voTcj.c acid. Te:irt?er_,<- - nit;(;c;soc.']_].c.:_]:idc>s ].) .;-tv c'. (;_;[;.c,.yi }.)cc_]_. ]lt6J.dc:,
fC)]'.' (--;]]_.t.t?_iC_;.(2;C;[21 Ci12 i.r.)]] _D_t]."i)O[_t)[_ ,
}7']to,;oe._rl-;on otefins' also 9-ivo adduct<_ \.:;i.t:h r_:Lt::cosy] h_t].ides
({73) (ecluati.ons 48, 49, 50).
NOF
C_:"2=C (C]_'3) 2 .............. )' (C:_ 3) 3C,-'70 (48)K]7'
N 00 !
1 -, Crn{-C: 3CF=CbOCtI3 .........................), CF3i:" ,._.! (C1) OCII 3 (49)
NO
CF2=CCOF
CF3
NO],"
\ (CF 3 ................. i ) 2c t co}? ( 50)
27
Both cJ.}:_ .." and trans-.-riitrosc)]t,:tl:i({c <-dducts of olefJ_n,<:{ mi_y.........................
......... "_" " ' O(;_]O-,:'t_.<"-R'J. _...... ]............
U±].L; )"_,O.O'0.']..Ol't. ,)'_ ' )O<',]._ C],_;;t,._!S _,.I;_' C,O(._ _.7) %,.JO [{'C" ..... [:'_ OY 09 • .....
.'] "_ " _':c, • " 1 , . ...... _.c,i,.q--yAd(]lJeL o] (,.} c.[O]lc ..... ::]]f£ ]]1 (!]c ].:.!]2 (-]1] oio_:o]t_] _ }_e[ ]ly]o.])o
ch].o,]:'.].dc_ or t:l:icl)]_oJ_oe _.t_.7.1_c:_J:: an.d t.t_e -tr_ns_,-adduct .].n ].:i.q-_.:Ld
su].:f:.uz .... " -- , r..(tt.O_J,(]O ({>o), A c,@].)c_n(-[t:;)_c-:(7, o!1 o].c.'._!i]] st.]__tJ.o];u;_3 ]lRs b,,{.!e]J
o]:)socv_,d in the fo:r_mat.:i.o]_ o:[- c.]..:,-.-_..d,. <cLs ::re,:< n:,:.trosy].. (:t]_or_t_(_s
ctll t.l"- i'". . _ . • (+__ .... )_ • ._or bromide and __o:Nf),:)ri).cnr_ :i_]l c,n]<, <,-'>:el) and hoch.......... " ...... _ 4 " . ...........
liH-]c.._loKyi]o:c.;jor]le]]@ dN(1-" _ N.o]LbcJr])'dO"' <.'Y)C'.fl............... i]] L,] CCq'tc_)]_.iC <:;<........... _"",..,_.<.'_ CIC'._ i
"- _ , ....L(also con. tain:i.ng h\jri.__o,_.,._.l.o:r:.£o at" t (84) + ]<_._c:]_ xe ::.ci -i_on oc_(?.t];J;icdy(]
_tYj.];;]'i 1-_O r!lO]C_Ott].a.r _C_.£t]f]Yar}__.jC:hYTi(;J-t];;, ]:)oI:I-_ a f(:,ll]---..oer_tc,77(-_d cyc'].ic
tra))r',][-...(on s-LaL:e ]<-,ad:[r)c.j oxc].u,_i-;Jcy,].y to R (;::[_'--__ ".-i ..... ;>_lrl........ c_ (,(.t __.. c....... _!1
h.]n.:ee-meml:.,ered n:Lti:mc, sonit!m Jr,'.term,.K]iate \.sh-c]) m_4_,.j)rt clive r-; <;,"
]_].tc) eit]]or (or boo:)) cis'- add %:c_'_)'iS-..ad(:[tkC.r.,<D ]i_tze b£;@l-i cc.',Yts:].c_]@::cc.c]............................
_? ,4, __ ... " -(_._.). An interconversion of init:[a].]v :{o-;:<':{S c;t.s-ad(]uci:s bo.-[\.,'mer_
.... <.... ,_,I_ ty!: a£.1:.!-ni-L:rosy], ch].o:cide and sev(;ral C} .]_. (l f :i. ]] ;{] {11:') rt t.]-) ,:_ ]lio!'e ..:,cc.._
.... _'......J.]. ]_eadd tlc:-t (86) su.qqe st_s that t iI(. _ 7] ci£] J_ t.lo_ J ]re ........... ]_p] ]:'(_\7 c,
ao<'..1 tIn a kinetic study of the .... " ion of nitrosy], chloric]e to
ti]irt, y different o].efins in chloroform it was found that the
reacL.ion rate was influenced ])y both electronic and steric effecLs.
Low activation enthalpies of 8.1 and 9.3 kcal/mol and activation
-i -].entropies of -43,0 and -36.9 ca]_/mol, deg. were obtaii.ned for"
Styrene and'cyclohexene respcctive],y, Ra-tes for the addition to
Styrene and to cyc]ohcxene increased in the solvent sequence:
-' .... ' ..... " H4C] 2Ct_3('h '< C2H5C';_ "< C'c-'14' C6H5CII3- < --n-C7![16 "" C6H'-C]-a < C6" -
5NO2 < c:c_-L..O_t of L sC6Ii5CN < CN_2C] 2 < C6H , < C}]CI 3 _'"Id ' _-'-' " ewis acid did
28
not a.cce]erate the roact:i.on (87 Eq_.ile t]_e evider_ce seems
to be ac,cor_,mod,:._t.odby a c'ycl:i.c onJ.um J.n1:.c.z1_-c,diaLe (8/:)
(equakion 51) (of., equation 40) a f._:ee..-:1<adJ,cal mecl_a__:]__.ni1has
not been e].inli_-_a.t(_.d(88); ]xo_,,'.evc.,.r_:i.t_ou]d have to) be: J.n:Lt:iatod
by a ch]_o._:-i.ne atom since, it is wo]_! esLa]:)].ishc'd tha-[: s_.:Jcb a.
reac.tion could I_c)t be ir_:]-LiaLed by nitrJ_c o:4ide (see sect:ic:_b. ]],.]..),
0 0 0It
-I .,.{i N-I-NO + / \ k ./
>c=c.. ,... ........- >c . c,.' ..............:",.................... _',_, >c- -c ._" " " ........t<" _............7 >c ........ ,,
]]n:(::,ducts 5])
An t_nsatt-J:_ta-tc.d nitroso derJ_ati.ve of a bisu].fa.te c,s-l:.erJs
fo]:med on t.rcatment of 2,3--dimet.]_y] ]:)uLad:i.e:r_<.'.\,,7j.-t]_,nitrosy].sl_] ft"]::ic
acid. Aoparent].y t.]).ereaction J.s one of c(>_jugat.e add:i.tio_l since
the ester readily cyc].izes with t:he e].:imJ,naIzJo_) of su!ft]:ric, acid
and the formation of an oxazJ.r,,<._ (89) (equation 52), It seems
probable that the loss of sulfuric acid occuzs p]tJ.or to ring-
closure which then may occur by valence isomerization of a
presumed nitrosobutadici, ne intermediate.
....._" OttrSO4H ....._" No -}_2so4
---_%/OSO 31I
...... / "<%N
(52)
29
c. Dehyd:,:ohu.!og<:nation of o]cfin ni_-i.ro;::oc]:_]o_-ido.<, Zn t])o
. _ _: %n " _ ], L.]. 0,.;]. 1 (]]'i] O:C: (].(] _'.(II(_).OL c; tO OJ (:): ...L]],_ 1._]]d[C_:f.'(i'Opli(_so_]Or] O.L ]_._:._:. the D. ".... o , - ,.. " .. <--" _-. _
c]ehydroch].orination -to :F_o]m _,_-unsa[-ura-Led nitros() co.,:_]£ounds.
Styreno. nitrosochlo:r.4.de with %:ci.ethy]a:.',_iro :in oLh<:]: lo::_cs
llydrogcn chloride t.o fc_rm nit_:osc)st..y:re_)o (90) (equa-Lic_n 53). It_,
similar rc, acL.].o.ns nit :r:o;:;oo]_ofins bcivo boon fo]r_.:.od :ffrol;_ t.l._uj,er_.c
nitrosoc]:_.]o:tr[de (9]..) and mct.hyl o].c:al-e nJt):osoch].oridi(_ (92),
Et 3N ..(. 'r...-C_ _'-}"_
C6 l_:5_:t](q".... 2 r,rr_.... ........................ / C:6t15 .,k.." .... ,,,, (53).' e th P r
Cl
Del_')Tdrobrom:i.]]at:i. on of t] _ oY..i.mo, of 3-d.):<o:'.:::,-..3---m(-'.t_ .hy]..--
bu1::.a._ol._c.-.2 by alha]:l giv.inHj a po!y:,:nc.::r: of 2....n:i.t:!:o_;o-3--m,::_Lhylb_:!-[.:'._<:--
2 ]_{:_:!_ bec::_] claim(:(] (93) ((2quatJ..on 5_) ]>!_.L probab].y s]]oL_ld b::::
c(:,,rJ:[[j..rm,ad no1: only to c]_a.rif.y the st]:uct.u:,:('_ c.:F i::]]c po]],i:i;c..r ]>u[:.
also to) elucidate 1:-.]_(: elimination mec])anJsm :kY'.sofa.r as :initial
iSONOZ".:[2;L:t;:'.,_.o::, %0 _::_iK].[;i:CSO (_C'! p(:R:;_C] ::_S J.:.]_:<;o'b'.'.]_].:_, [[%.<_ ).:'c_7,c.[,.io:_J
a(_d:tl;io.',-_ I:o a:._ ;.(', (_.wr__s._vbu:,:r..'.%,:_:C. ;.S.b:_,o:;o (;o::<:o::.._:: (of. C. 2. ).
NOIt NOII KOH I
............... A/ (CH3) 2c=cCH 3 '...........-_:. po]_ymo.<(C t{ 3 ) 2(:- C.- C H 3/
Br
(54)
]_2. N:i.trosation with nitrite esters and a].koxidcs
p_c.no]_, e.g. :_:esorcino]_ (94), and aromatic heLero-
cycles may b : nitrosa-Led by an a_!ki,1 nitr-L-Le J_n the presence of
3O
a metal a]_ko:-;:Jde. From 2,5-'diT:,.ot]_y].pyr]:()]r:, treated :i.n t]:.i:i:
mo.n]_.c.r a sodJ..u]n sa.]_-tmoy bo obtaJ_]-)(:<] fro,"_.\,.,]].:]c]l3.-Nitroso ....
2,5-drimoLhy].py:,.:ro]e may be ].J bc>:_atcd on mi.].d -[;reai::,-ua_}.t: _.J..t-]_.
acid (5:5) (.<:97oatJ.on 55) , Zn a ,s:i.m.]_]ar man:get 3..nj_i:Lros_:,::._,,:]o]c::s
t.................... ! D J] '....... ,t J2 _ ;
.... I ..................... /......................................... /
]I.}C CH] C2N,_(tN.:: ]I._C, _....... } Cii._ ..... _<" ,..: _,..:'r ]] ._C C]I: i.:.......... 1 j' . - =.. ..... ,-j,! .-]_ ..... . _._ ...
( TtI ]i
(._ ..')
<.l.E. O])_..,?:l!d;:.,:._ f]"OhL L.]i<:: CO'r'_:'F'")O,_)(_]_.]_N l'tOt:L::f:O£'yC].."._ O.:Gd a;_'_.y! l] :[ [:.]:":i.%.(t........ JL - ,,
("6)., . A]::,t).:lyc-,n.k-ly... L]):.zso a:r_{:: nit:ror;:::.tio!_s of ]):.:cc:rocvcle__ anions
((_qoa.t.ic, n g6) Wl}.ci-.t t:])c' hc:l:.erocy<::l.;< _,_; ....... , ........ ':-,i ......ies a su]:)sti_"""l r-
0 tt
!i ii " "l!...........,i:b_ ""N "
H
._<.......... ;,
]R0 N 0
/
1{ ,$ R - ()R
II
[....NO NaOR • =:NONa +O ......... NO
/ R R
!H
(56)
in place of the acidic hydrogen, nit:rosp-tion may be achieved with
nitrous ac:;d (97, 98) (equations 5"7, 58).
3]_
C C)C .[C........ 3
.._q j..i:, ............ C113C021[ cO _............... ]<:0
( s 7 )
1<)! !i ................:--:i/' "F_.
""".'" "']t_"" "",*" i'_I
I I,
1
I .J! ....... =:o....... I : : _.) ] I :l" 0 ?:: [_ ) '
_,)£-- %'1! ¢< _ .. I TZ/'_'I r
• , JJ ..... ::,
(.'_-;9)
]]ONO
CH3CH2NO 2 ................... )% C}13C (=-'_,7OI!) I:,:0 2 (60)
C 2 I] 50NO r:::::: :: \I "
2.-5
: ?:',O)_ (6!)
32
C d]!90NO
ATC.OCIH2CI..... .................... \/ AI:C()CC, i ( @2 )]ICI ti
NO]I
!
R OHO
RCIJ
(c°21J)"2 ".........................) (G!;)NOII
]?:Lesumably th,:_ :ccac:i_ion, whu.t:]:d_:cacid o:i: ]:_,-_:_._ca-[alysocI,
[.)ZOcc_cds hi, o_I.(:-cLz<,/.)].,:].]j c _[.LCL£:]: O)_ atJ) _- (:C,JT],O'J. L=[.L>i.:tJ__l _',S.,_(_:<.'i,_.:t_[
VTJ.[/]I Oii:]lC.']2 col]de]3sa-[.i£._)] :L-C_aC::i:].<.,:'3S: 0:[ L'. C [: i V ', -' met.J0::/]., __<-h])y.]c_c ,-'ndi
ITI_" [ 1,. 1-:*' i'_:-ly .,_. g i:o'ctI2:7;.
]3. O]?g_uIo]P,<'L/;]}I..:[.c co;tl])ot_T:ds a:n(l n'L{:.Z'OSy]_ c]:]..o:_:'J.<':,:_
All._y]_)._il:ros,..,]<.[d:,:ox_]ai_d.r_c.s (_t_O].) ,':<,-:::, (,[i::c:;,. i):J:od_..ci::--; Y:<o>,
:_:c'.ac. Lio.ns ]:,::_tw,:_e.n a]].<y]meta!s a:)d n:_.!:::,i'o,<yl ch:!oz:;.dc (egui:_.t.ior_, 64) ..
l'_it:::_:o,so]_yd.<o×yl_.m_>¢_::; m_y :l_ose. nit:cor.,-,,,].hy,:.?._::i.(]e v,ith i:.]._(:: :[:o:cmv.l..:;_c:,n
of -LLe (:;or._:(_sl)ondi_-,_.g ni[:]:'oso compound (t0]),. N.i.i.:,:<):.:;<.,]:).::,_:."::r_,,:: hL_,<;
N (_qO) (. :_ ....N 0 ]t -." "-.
-[i............................. /"
NO
(64)
been preT;a._:ed by passing n_itrosyl chloride :i.nto a solution of
p]_eny]_m_gne,_};ium bromide (i02) and penta.methy]ni.trosobc:).)zc:ne f>,<,m
the corr(-spondiT:.g arylme_:curiacetate and eth].,l nitrite in hydro-
ch].or.ic ac.:i_d (]03).
Rc:cently a nit:co,t:oca:cbo:,:ane ]_.:_s ]_"ebtl.[llc_d f:coI_t t]qO t:rfo&t]itol-:,-h
of 1--caz]:<):_:vn.yl-li-thiu'._:: v;ith n:;i-.:cosyl chto:i:J_de (104) (c:{.iuati<,T] 65)
and r.,.:i.t:<os,:.,:.t]]::ane d:Lme:vs resu]_-,,, from i-].,._: s:i.rg.J ].or treahm<:nt o:.F a>.
33
..'.i< 5 .aluminum tria].kyl wi[:]i nitrosy], ch]or]o.,. (10 ) Trj. cyc].ohe>::y].--
boron and nitrosy], sulfuzJ.c acid reacted with the apparent
initial formation of nJ_trosocyclo]le>:ane; howeve]:, product:{
isolated represcqlted fu.l:ther chan[]es (106).
./
n-BuLl NOC]
- -> Hc "5- eli -............. -> I C:-6-CNO
-'].0 IU ±v _-_,
The long unknown l-nitrosoacetylenes were first produced
in a reaction in which nitrosyl chloride attacked an organo-
mercux'y bond (110.7) [equation 66).
(65)
(CH 3 (CIi2) 3C-=C)2Hg
NOCl
CH 3 (CH 2) 3C_CNO (66)
14. Geminal nitrosohalides from oxJmes
Oximes are transformed into gem-halonitroso derivatives on
treatment with hypohalous acid. Development of the blue color
of the product is the basis for Piioty's qualitative determina-
tion of the presence of an oxime (].08). With only occasional
bursts of interest, Piloty's reaction lay dormant until gem-
chloronitroso derivatives of hydrocarbons attracted attention
as products in the reaction between irradiated nitrosyl chloride
and hydrocarbons or irradiated mixtures of chlorine, nitric oxide
34
and hydrocerb.o_s (109). The p:_:incipal product is an oxJme
as is demonstrated in this im]?o.rtant method for the synthesis
of cyclohexanone oxime, an intermc_diate in a preparation of
caprolactam.
Oxidation of the product to the corresponding halonitro
derivative by halogens in a.n alkal:i.ne medium may be elimJ.nated
by treating the oxime with chlorine in ether (ii0) or by treat-
ment with chloroamides, e.g. N-chloroacetamide, N-chlorocaprolactam,
N-chlorourea and N,N-dichlorosulfonamides (lll). N-Bromosuccinimide
in aqueous sodium carbonate has also been used (112). A lesser
known reaction discovered by Rheinboldt (_113) occurs between
nitrosyl chloride and an oxime (equation 67) and is especially
interesting in its application to aldoximes.
NOClR2C=NOH _ R2C(NO)CI (67)
-NO-HCI
Explanations for the transformation of ketoximes into gem-
halonitrosoalkanes on treatment with halogen have been based upon
Conceivable tautomers for an oxime. Hal0genation of a tautomeric
monofunctional primary or secondary nitrosoalkane appears to be
1_nlikely since their prototropic rearrangement in the gas phase,
melt or in solution into oximes _.s not detectably reversible (114)
(equation 68). In addition, it is reported that nitrosoparaffins
35
are not halggenalied under tile conditions which transform oximes
into gem-.halonitrosoa].]tanes (115). Addition of chlo_:ine to the
}{2cHN° ............_' _{2c=_°n (6@)
oxime double bond followed by an elimination of h.ydrogen chloride
(equation 69) has been accepted as more probable (l].0) but
has been chal].enged (.].].5) on the basis of an apparent require-
ment fo:¢ hydrogen to be attached to at least one (_,-carbon
Cl Cl
C12 I I -HCl
R2C=:NO H ..] R2C--N-.OH .......-) R2C (C].) NO (69)
in the oxime. Of twelve monoximes which lacked hydrogen at an
_-Carbor, only Michler's ketone oxime reacted, as predicted, in
the presence of acid, with chlorine with the formation of a
nitroso compound. Although the proposed requirement for hydrogen
attached to at least one _-carbon was fulfilled in 75 examples
of oximes which were transformed by chlorine into nJ.troso
derivatives, it is difficult to understand why o- and m-nitro-
acetopl-_enone o_:.Jmes each failed to _eact v,hereas aoeto]-)l:,cnone
and p-nitro_.cetop]_enone oximes did. Other reaction. _, bet_:,een
chlorine an_ c,):imes which also eonta._.n additional, r'esctive
funcl.:]_onal SrouT, s ma_, occur B._._._,o ime, ._ _ ......... , _._• _....I" ilz OX "['CCI' C..._ :j. ]__,, _ l'I _
not t;ra_forned i_nto a nii.r, oso derivative and t_:-_.,'-_ e.7_ps.renbly
c,)tidize;i to benzi!.
36
monoxime. Nitroso compounds were not obtained from c_--dioximes
but these a:ce known to be transformed into furoxans under .the
Conditions employed (1].6).
To account for the possibility of participation by
hydrogen at an _-carbon, Kosinski has proposed (.]_15) a r_echanism
which invokes Raikova's fiautomerization of an oxime (].].7)
(e<Tuation 70). Followinq chlorination at nitrogen Jn a vinyl
NOH NHOH }tON
(70)
hydroxylamine, this mechanism requires elimination of, followed
by recombination with, hydrogen chloride [1].5) (equation 71);
however, the final step in equation 71 must be questioned insofar
as conjugate addition of hydrogen chloride to an _,B-unsaturated
nitrosoalkene would be expected (equation 72), cf. C.22.
Cl Cl
l 1RCII=CR 1 2 _ RCI-I:CRI _-') RCH:CR 1 .... -_ RCH_CR
I -HCI I I ZlNHOII NCI HCI -NO NO
lOH
(71)
HCl
RCH=CNO -_ RCH-C:NOH
IR1 / I IiCl R
(72)
37
After t])e report that hexafluo:L:oacetc)xime reacts wit]_
chlorine at -78 ° and is transfoi_.,=d_l_ into the correspond_i_r_q. _g°m..........
nitrosoc:hloride (118) (equation 73), the proi?osed requi_-emer:t
for participation by hydrogen attached to an a,-car].)on must be
reevaluated. Benzophenone oxime in the presence of chlorine
underwent a Beckmann rearrangement into benzanilide (1].5),
(.CF3 ) 2C=NOH-78 °
-> (CF3)2C (NO)Cl (73)
An example of an aliphatic ketoxime which does not. contain
19_ydrogen on an _-carbon is found in fenchone oxime, which is
unreactive toward chlorine bubbling through alkaline or neutral
solutions of the oxime (.].].5) (equation 74). In contrast nor.ca.raphor
C] 2
,h9 NO reaction (74)
oxime is transformed into the gem-haloni :rosoc_er-,vatlve (ll9)
(equation 75) .
_ :NOtt Cl 2 _C1
NOdry ether
b°
(75) '
The .....'re_c,..J.on between nitrosyl chloride and oximes may also
give gem-nJi:<osochloridcs. Addition of nitrosyl chlorid-<_ to the
38
OXintO " "" " " ' '_iJnk{_.ge fo].lowed by eliminat:i_on of nit.rosyl hy_rz_e has
].)_,:.cn,s_Jggesked (120) (equatioD. 76) . In support, of the final
Step i.t is known-that N-nitrosohyd.ro)-ylamincs reve.rsibly
Ci Cl.-NOtt /
].•."......................... )RCH2_P 1 NOC1 RC}12!RI RCH2/ - I
NOH NO}I NOINO
(;,6)
dissociate into C--nitroso derivatives and nitrosyl hydride (i01,
121)o Oximes which are ordinarily unreactive to nitrosyl chloride
include the oximes of benzopbenone, fluorenone, phenanthrene-
quinone an.d other ketones some of which contain hydr09en at an
a-carbon (ill.3) .
15. Estcts of geminal r,,.itrosoalcohols from oximes
Two methods for oxidation at the a-carbon of nitroso compounds
are reminiscent of the reactJ.ons leading to the formation of
gem-nitrosoha].oalkanes discussed in the last section.
The intermediacy of a. gem-nitrosofluoro derivative was
assumed in the formation of dimethyl fluoronJ, tromalonate from
the reaction between potassium dimethyl oximinomalonate and
perchloryl fluoride in dimethylformamide (].22) (equation 77) and
in the sarae reaction mixture the formation of a perchlorate ester
of a 9em-hydroxynitroso derivative is considered in an explanation
for the formation of another product, a ketomalonic ester.
]?CIO 3 ................... ".............. C) ('=NOCIO .......
(CH30 C)2C=NO / ICl!3) 2 2 .... 3 /
NO
(CH302C)2COC102 (CH.30z....)2 C.7 -I-.,,O3 -I-
X
(CIt302C) 2C=NOC].O3 ........................................ [}(Cl or 17 )
' c (s0× @] >(C]]302 ..) 2 C . -................ .
• _ , (No2) x(CH3C 2C) 2C
39
(7 7 )
In the other oxidation, ge.m n3_tlc,.,o_ceta{,eo are produced
from ketoximes and lead tetraacetate (123) (equation 78) and
OXime O-methyl ethers are reported as by-products (125). Nitro-..
sobenzoates are similarly prepared with lead tetra.]enzoace (124)
The suggestion (123, 125) that the reaction proceeds with the
m., __ ....intermediate formation of free raoica.] ....has been confirmr_d by
an e.s.r, study of comparatively stable iminoxy radicals
Obtained from ketoximes by oxidation with lead tetraacetate.
It was concluded that the unpaired spin density resided on oxygen
and nitrogen and that the structure was best described as a
resonance hybrid: R2C:N-O-_:_--_, R2C:N-O: (]_26). This result
is consistent with initial acetoxylation at nitrogen from which
either a _em-.nitrosoacetate or an oxime O-methyl ether could be
formed (equations 78 and 79). Further interaction between the
-_em n__trosoc,cut_te and acetoxy radicals may occur (126)
4O
B
R.,C ---2:.-N-O .......... _ R2('2KIO/
",.C /
ICtt
3
(78)
+ .7
R2c=:".C/ 3
IIO
......-7 R2C=:NOCH 3 + CO 2 (79)
For a discussion of _-hydroxynitroso compounds in the Nef
reaction see B.23.
16. Oxidation of dioximes
Oxidation of dioximes of e.-diketones may lead to the forma-
tion of .furoxans (].16). Benzil dioxime when treated with alkaline
ferricyanide, chlorine in ethanol or benzene, alkaline ]-_ypochlorite,
or dinitr0gen trioxide is transformed into diphenylfurcn<an
(equation 80).
I(C6H5C=NOH) 2 .....
b :)tl I1+N N NO NO
II
C _Hr.C-CC6115 .... _' C6H5/_-- CC6H5b :)I}li / XX
+N N N N ....-_oI1 I "O /0 0--
(80)
4.].
The :J.ntcrmcdiacy.. of ],2-d:i.ph.eny]---],2--d-injt-rosoeth,y]one Js
assu_ne(]; howevGiT, it .... _ _dpj: :.a] ..... lJ]<.O.]_y t]).,-_t.: the zwittc:_.rJ.on;[c
for:ta of the int.crr_.ediai:e is the im]?orLant species ].ec.._ding _:o
ring-closure. Both furo>:ans arc, generally obtained from
glyo×imes in which the two s=ub_,t.i_tucnt,._'<,..... _....c, at carbon are differerJ.t.
The dio:.;imes of both o- and p- benzoquinone underc3o sJmJ. iar
oxidations (116) (equation 81). An interesting analog,, for
O
+
", <_..........."_<.<<_1 ..... % " \0
2 StrUCtU];es
0
NOH +_. NO
" @...... -_ < ...............'>
NOH N NOI0
(81)
2 structures
the latter reaction is found in the oxidation of an o>:ime
hydrazone derivative of p_-benzoquinone (].27) (equation 82).
42
NOH NO
l, <[\
NNHCOC 6 tI 5 N:=N COO 6 H 5
(82)
Oxidation of hydroxylamines is a preferred method for the
preparation of corresponding nitroso d<::rivatives but limited in
al?plication by the accessibility of the starting materials which
generally are reduc.tion products from nitro compounds or oxid.gtion
products from primary amines. In such a two-step process nitro--
benzene is reduced by zinc and ammonium chlol-ide to phenyl-
hydroxylamine which is oxidized by sodium dichromate in sulfuric
acid to nitrosobenzene in ove:call yie].d of near].y 55% (128).
Other reagents which have been used[ to oxidize hydroxylamine.s
include mercuric oxic]e(129)_ potassium ferricyanide (130) perio-
dates in alkaline medium (].31) periodic acid (132) chlorine (133),
air (134) and chromium trioxide (135, 136) (equations 83, 84, 85,
86) .
tlOt]N _ NHOH02N NO 2 cro 3 . ON_/'_'>-.[O_jNO...... ;., (s3)
O2N NO 2
43
(84)
i<lO.
HC (=NOH) NIK)H ..............:_"--_]_]C(=NO}<)NOalkali
(85)
IIF
(F3C)2_:NOh ...................7 (F3C)2 C(F)NO
CrO 3
r(__)
A]t]Joug]! N,...n:it):o;_o]:iydl:oxylamines tend to d:Jssoc.iate into
]ij ['.tO<SO " ,. _---' \,- .... " _7_c- v• c].:.-._.J..a_..! ...... and r::itrosyl hydride (].01) chc. T..-...... enc.(.
of sodium hypochlo:rit.e is adwmtageous (137) (eqv_at:ion 87).
NOI
NOH NONa NO
0 NaOCJ ,/"["--.No _/ 7
- NaOCtt 3IINOH NONa NO
INO
(87)
Hydro)<ylamines have a tendency to disproportionate into the
o ol"!_e s],c..:.......,.",r"P-"._ nitro::_o cc<:il:,o'_t::K] and c,r:_Jne. A.['t._:P [.},:r _ .......... _..<ec..'.s', J.n a
"' ' _ 1,-, d _ " " ' 1,C ] 0 S ,"' (.] -o ,7 :£:S ," _'] _ ]:,l!::' ,_: Y:.O ;.::,]. i: ",;].]_ ',: ('.}? O:Y.V .,. 8k':J ]! <:: C '_ _ _, .... _ :i ]] T: 0 _' 6
44
tzimethylnitrosobenzer_e and mesidine, along with 2,4,6-trimethyl-
nitrobenzene and azomesitylene (138).
18. Oxidation of primary amines
Oxidation of primary amines to hydroxylamines requires a
reagent which attaches oxygen to nitrogen. Reagents which have
been successful include Ca_?o's acid (monopero-_ysulfuric acid),
anhydrides, hydrogen peroxide in acetic acid, permanganate
(often with formaldehyde) and hypochlorous acid. Generally the
subsequent ozidation occurs readily thereby providing an impor-
tant route for the preparation of nitroso compounds. The
elimination or suppression of further oxidation, e.g., oxidation
at nitrogen to the corresponding nitro compound or oxidation
at c_rbon, is often a limiting factor to consider.
Nitrosobenzene is one of at least seven o'<idation products
obtained when aniline is treated with hypochlo;_:ous acid (139).
On the other hand, the o;<idation of o-nit:_:oanili_)e ])y a
hypochlorite solution is a preferred method for the preparation
of benzfuroxan (].16) (equation 88). An impl-oved yield of
OCI
0
(88)
45
nitrosobenzene is reported for the oxidation of aniline by
permanganate with formaldehyde in sulfuric acid (].40), a
method which transforms cyc]ohe__ylamine into nitrosocyclo---
hexane in yields over 80% (141). The latter oxidation is
also effected by hydrogen peroxide in the presence of sodium
tungstate (142) .
Bamberger found Cafe's acid to be a general reagent for
oxidizing aliphatic primary amines in which the amino group
is attached to a tertiary carbon atom and re): primary aromatic
amines (]43, 144). Quantitative amounts of nitroso compounds
were obtained from the isomeric nitroanJlJnes (145). Apparently,
the oxidation j:< facilitated by elects:on releasing groups;
P_-phenylenediamine is transformed into p-nitroaniline, but
p-nitrosoan].line may also be isolated when the reaction is carried
out in ether (146) (equation 88a). Acylation of one amino g:coup
H2SO5 _.
]_-C6}14 (NIl2) 2 .......... fetherp_-H2NC6H4NO + _p-.H2NC6114N02
(88a)
controls the oxidation which proceeds to the formation of a
nitroso derivative without substantial further oxidation (147).
After three mi:¢utes Caro's acid in ether can oxidize terh-
butylamine to 2-methyl-2-nitrosoprop&_ne (144). Better yields
are obtained in the similar oxidation of 4--amino-4-methylpentanone-2
(144) (equation 89). The inte)m-_ediate formation of nitroso
46
compounds in the c)-.:iclation of tertiary alky], p: imary amines to
COrresponding nitroparc!ffins is d(_:morJstz-atEd by the formatioyl
of a characteristic b].ue color which persists if oxidation is
incomplete (]48).
H2NC (CH 3) 2CH2COCII 3
H .),_,O v..........-:i........."]...%.
/ ONC (CI13) ' ' C2CH2 cO -t{ 3 (89)
r_,_,_ _, ,.4 ,_l ,q_ 1_-_-_,,_ 1 ......... -_.,,-,_-4.,..,_ -C, _-- .1-1-._, ,._," P,-,4- " ,.-.., _._: ....... ' ...........
aromatic aminEs to correspondi!._g n._.trcn;o derivatives by a peroxy-
disu]_fate in _ _ ' " . . " _ . ...... " .....conc(:.n_racee su].fuYic acid (]., o) (eqU,'.t..LO_ 90) but
20C]{ 3 cocil 3
</<'x "K_o, 0.,Z Z b %
........................"C1 NtI 2 conc. C1 ,, .... . NO"X/ " H. qO. "..... /
2" _-J *"'"
(9O)
perpbosphoric acids failed to tra ns:[oxm certain primary aromatic
amines into nitroso compounds (2_50).
Nitrosobenzene along with phenol, diphenylamine, a_uonia and
nitrobenzene was a detected product following x-ray irradiation of
an aqueous solution of aniline (151).
19. Oxidation of secondary amines,
There are a few reports of the formation of nitroso compounds
from the oxidation of secondary amines. By Caro's acid,
N-benzylan.ilinE is transformed ilrto nitrosobenzene, nitrobenzene,
47
azoxybenzene and benzoic acid (149). N:Ltrosobenzcme :Ls one of
at ].east eight products obtained from N-met]:_ylaniline on
treatment with Caro's acid (152) . Cold dilute permanganate
so].utions transfo):m 2-,phcnyl-3-hyd._:o>:yindole into O-,]]i-[I]7OZO])d%D.zoJ.c
acid (153) (equation 91).
• . ./3 C6tI 5
H
KMnO _-,/ "" ' '
...............L',. i (_I"" [...<--' /[ _o
(9].)
20,_ Oxidatior! of tertiary amines
o-Nitrosocinnam]c acid is a proposed intermediate in the.
oxidation of quJ.noline by hydrogen peroxide in. acetic acid to
O-nitrocinna:inic acid (154) (equation 92).
• . C1t3C02tt
-4-0
OH
(92)
48
W
It is relpOr.ted t:hat oxida-tion of 3-met:hylanthra,:_:i 1 occu:_:s with
Opening of tho isoxazole ring and the forma.tion of o-nitzo_:o-
" _'IT f .... J ' . •aceto]:?henone (.t.o.,) (eclu__czon 93)
t:H 3
1 ' t<I/ If') S0,1
40-50 °
(93)
2]. Oxido.tion of nitrone.c:; and Schiff b:_ses
O;_,or_J.zai.ion of n_i-_'o]_t_........ h.as I°rodtJced......... rlJtzoso compou]_ds_ (]_56)
(equat:;_on. 94), SJ_:!r'd.] ar i..J--(,....._lt:.cGnl:.-m_ of Schiff ba::¢:_:..... diJ.d not gJ.ve
nit-ro-o p_::odu.ct.'._ (1%6); hr,,7_v_,-r the presence '_ blue co0 ±. ,.:1 ]. 0 r
,-,_.> OZOi-tj.,_- _...during. ." ...... ,.__on. __.J__the SchJ.f:[ base de.riv(:d from tert-.but:f].,....,. .......
amj.ne and "Lsobutyraldehyde. has been r.....0J feted as evJdence for the
fo]:mal-.j<)n of 2-.nitroso-2-me.t:hylp:l<o}Tano (].57) (equation 95). It
Was <._.i.e-_fu].iyestablished t,ha_-" _- the o_,_.c_ani.""_- - was ozone rat.he_-_ than
oxygen s,ome_,,Q_at in contrast- with the catalytic o;:._.o.a"' " tion of
cert.a.in perfluoro Scbiff bases (158) (equation 96) in which-
trifluoronitrosomethane was a considered intc:,:modiate.
0
,]- 03
C6H5CH=NR ...............t,. C6h5C.::O P,NO
R=:C6H 5 ,t-C4H 9 (94)
O
(cH3) 3 oN:cHert (c]]3) 2 ....... !!-[__-%' (c_3) 3 cN-/'\t_cN (CH3) 2
49
} (CH 3) 3CNO (95)
R.bF
CF3N=CF 2 + 02 ----_0;'o]_ 2COF 2 + NOF
CF3N=CF 2 + NOF ...."j, (CF3)2N-NO (96)
22. Reduction and deoxygenatio1_ of nitro compounds
Reduction of a nitro compound leads first to the formation
of a nii roso compound_ In an acid medium the latter is rapid]y
reduced to an amine with the coy_responding hydroxylamJne as an
intem_ediate_ Reduction in an a]kaiine medium gives rise to an
azo,-<v com_:ound resuiting from a condensation betwe<'n the nitroso
eompk}und and the corresponding hydroxylamineo Best yields of
nitzoso compounds are generally obtained from reductions in
neutral media. The exceptional reduction of primary and
secondary nitroparaffins by stannous chloride does not proceed
beyond the initial stage presumably because rapid isomerization
to an oxime takes place.
5O
An electrolytic reduction of nitro])enzene with a ncutra].
electrolyte gave a good yield of nitz-osobenzcne (159). Poor
yields have been reported for deo>:y(3c_lation with bar:lure o>:ide
(160) and reduction _,;ith hydzoxy].amine in methanol (]_61) or
meta]_lic salts such as mercuric ch].oride, zinc c;h!orJ.de (162
or sodium bisulfite (163). In the latte:i: example nit_:oso
compounds are intermediates .i.n the rcductive su].fonation of
azo_It_tic nitro com]?ounds to _]ll]iY!ostl]_!o]]ic:,-._C_-l.C[s{]:'J_]?J_aro_iE:L:l.oll
With an intramolecular condensation the reduction of 3---nitro-
4-dimethylami_]oto].uene was stopped at the nJ.troso st.age wJLh
the formation of 1,5-dimethylbenz:kmidazole (]_(53) (e,']uation 97).
N (CH 3) 2
NaSO 3
H3c ['_-_"'()Il,I0• <._j .........-:.% , N(c._._3) 2 '
,.., N
nBC -.,/ %
_//I ell
t
Ct! 3
(97)
n__--Trifluoromethylnitrobenzene is reduced to the corrdsponding
nitroso compound by ethyl mercaptan (]_65), Aromatic o- and
p-nitronitroso derivatives are produced by tre;_Ling the cortes-
ponding dinitro compounds with eit.]_er hydroxylamine or stannous
5i
o>:ide in methyl_ alcoho!Jc a].k,-l]i (!6(]). The be]n_v.io:r of
0:-nit-_:onaphthale.ne- to,,,_a:_tdsalcoholic alkali is es])ecfial].y
in_ezc,_tJ.n.," _-_, ....' a. _.1_._t'"-_- on< _ and e_jct_t.ually two metbo.',.:y g:-coui_s become
a.ttac]led to the C4 posJ. tJ.o_ (].67) (eguat:[on 98). I?resuma])].y a
related pro)tess is required in the formation of ]_..-]0:i..t.ro,:_odiphcr_y].-
amine from aniline and n.it):ob,_r_n:_,er_e Jn alkali (].68) (eqt,,ut-:].on 99).
NO 2
]',Olt
p,
C}I301i
%Tfh] 7
No 11
, /\
OC]] 3 C]I30 OCiI 3
alkali
C6H5NII2 -I- C6H5NO 2 ].25<)_-..-C ,. H _.NtIC r. ti _ NO
_-., L) ,9 O
(99)
A deoxygenation mechan:i_sm proba])ly best accounts for the formation
of nit.rosobenzene from nitrobcnzcne treated with irc)n powder in
the presen<_e of carbon dioxide at 220 ° (169). Similar dcoxy-
genations have been carr'_.<,,d out in dry organic solvents with
sodium, potassium, calcium, strontium, barium, magnesium, zinc
and aluminum amalgam (170). Deoxygenation of aromatic nitro
deri-'atives by fre,<, radicals also ].e_.ds to the formatior_ of
corresponding nitroso compounds (171) .. Dimeric nitrosobenzene
52
iron trica:rbonyl J.s produced on J:crad:[aLJon of Jrcu: ]:.,'.n,_tacarcbo!_yl
in n:_[Arobe._zon,_ (172) (oquatior._ i00).
h -< r.... I
-I- C 1] _,r) .............]ICI : iC6]Is]"IOL"("(CO)3 1/ _ I 2 (100)
l"e (C:O) 5 6"5 ..... 2
Ring..- closure of an intermediate o_--ni-[::._:osoazo]_cnzene presumably
accounts for _,+]]m.... [l_-),(]¢_-]-iC@ of .....LU, thc_]_ _ rt]Q]t[(][]i<]_] Of O-]]J__]]_.Oi;l__(_]l{._.]]}_(._]]e
by sodium _'"l _-' -_ -o_..i_.lue (173) (equation 10:l). A s:[m:i].ar reason.
........,,,, -.............................-'7/ _-_ NO
/"'.,. / N
O
NC6H 5 (!o].)
_l.._dto (but is not necessari].y required for) themay b(_ appl'o
deoxygenation of a n_i.tro g]_-oup in the transformaL.ion of picryl
ch].oride into 4,6-dinitrobenzfu]:oxan by hydroxy].a:r__ine in [l_e
p.e,_e.__ct_ of so(]ium _{-_-,.... c]_ (]_7/_.) ((:.duation i0 ",)
O
O N, NI!20H f._1"_-'N_
2 _ <'% z / "_"Ni
NO 2
(102)
53
In view of the ])auc:ity of info]:mat:ion on az:omatJ_c, m-din.:i_l:}o ....
SOC/C_.:C].V{IL.].VtJS iJA@ - s .... :' - . _.re[cruc:o. fo:Lmation of N-]_,3,5--L}/J.nJ.it:cosol.J_cn},]..--
I
N -pho.nyl]-lydz-az.ine f_zom pj.cry].azobonze:r_e., --,_-,-'-_t:..r_._, u<_d wJ t]: ......[.,0 L, _ o ;3 il!Tfi
iod-lde J.n acot.ic acid takes on adcqod :i_nL.ct_-o _:- (175) ( ........ _- " '3c;c,,t,._, ____on .t..( )
N--=I,]C_!Ir NI!N]iC 6 ]!5b" .)
1 t[.O._N/L-. "x,._NO,) t(_[ ON .... "" a,_ ,_, ............................. ?. t ,"'"\ "I ]:40
I .. , l<..al
NO 2 i_0
k_L_, .J !
13y ._i_,...zam(_.].cculac transfej: of oxygen cortain nitro qroul:,s
are zeaC]ily d.eoxyc;cncuted. . A classic e,-;a]n-ll: --c-' ]."s four_d in the
photoc]] oll:.c _.1 J. sc)m.e ]:i z ation of __-'o;q :'.":)_ r c,;k)r',_n _.,a.]_c[:_".,b_._"ao,c_ into __°-nit]:°-
sObenzoic acz_' d' (].76) which takes p].ace }::ot:n_' :i.n solution and in
the so].id st, eLe. ][J!- and '" ...........r_)--]_.L_.cob,_:l_._d.dchydes do not: gJ.ve
nJtroso compoundls, but cer-hain oh];or o-nitro derivatives undc.'r9o
s.im:i_].aT_rea]::.va]-:gements (cquat:ious ].04, ].05, ]06) .
./., _qo2
/H
"3cO.3clL.2c ..-[/") COcti32cI 3N
H
h-< _!NO........_-, (104)
"N
tt
54
(105)
.lc-)r [<. . .... "'- .... . C(;' .,i.C l] _
-_ t u g "--.. ,.'* tJ _}
(].Or7,
]in the isomoriz.at:;_on of o--n:Ltrobc2n>ald<-!:.yd..}, Lhe transfer
of oxygen from an acLiwvted nitro gxo_d])Lo t]-_<::c';J;:N:)op..y.],ca_i>o.n
pzobab!y occurs by a redistrj..])vl-tion o£ electror)s when the
nitro and aldehyde, groups at,2 cop]_:,:r)ar wi-L]] [2],.earomatic ring
(180). A kinetic study by e.s,.r, of free :,:_:dJca]_s produced
du:r.:j_ng the reaction did noi: ]cad to a def:i_-}:itive explanation
(181.). Nhen the reaction is run .i..n ruel...]Jano] , it i.s cT, aimed
that irradiation first brings al)ouL t]!c-} fo:cm.>.tion of the
dimotl-_ylacetal of o-nitrobenzaldehydc, from an intermediatte
methoxy-c!-nitroben;_:yl radical (182) (equation 107). The acetal
is [:hen transformed in1:o methyl o-.]2J-lTz-osob,£n>::oal.
l/_'_O_ NO2 CH3OH \ ___INO2 . . _"i_] NO2' / CH..(OCY. 3 } 2 /CliO h% ...CItOCti 3
--' '"-- NO
.- 'x i<'---) co2c%(107
55
_..__c_Inolecula_:t.r(..n._)fer of oxv(pt-_'nfrom the nitro
group to n.:ur0gcn at tacnect a-L the o_t__]:!o.- })osit:i_cn: is requ:_red
in both the py:,rolytic and the photofyhic transfo:_:mation of
O-nitrophenyl_<<.:d:B into benzfuro}:an (116) (equat.io:,: i08),
mr_c_. B. 16.
O
hh" or/_ NO_ be:_t /_"',A N.
[ j" ..............:I l -:o (los)
A derivative of. o.-nitrosobenzamide is a p:robable Jnte_:.--
mediat.e in t]-_e von Richter reaction whereby an aromatic nit:<o
compound is transformed by aqueous alcohol containing an alkali
Cyanide into an ai:omatic acid in which the car]?oxyl group
OCcupies a positJ..on ortho to ;.he position from which the. nitro
group was ejectod (].83) (equation ].09). o--N:!.t:roso]_)enza:_ide,.
R R R R
%--0<%<CN _""_, \ N.
.............. /" t! ...... ? ....... / CONH 2
. C N _'=N I-] '
NO 2 NO 2 __/.N ........ 0 NOO'
R R R
i<" t<?. "-H20 \ -N2 ,. _ ]t20
......................" ._'-.[-'/ ......c=o,i.......oI-}..............;" ":" ."tc°2_: -o:_ . co_N : : ,:-:'.::: N
(!0_:)
56
indcj?c)_dcuLt]_y prepe.rc'd, unde_-_,;.ont the :ceq[uired __<ac:tjo:r__.with
both aqueous hydro-<id<_ and cyani4]o ions with the. :Eosm_.<tJ_c,n of
benzoic acid (!84).
An. e>.,'planation, for t]_o t]-ansfo]._matj_or) of o-mandc]onitri]_e
by tro.a.tment wit.h am]:_onia into o-nitrosobcnzoic acid, first
report.ed in 1906 (185) and of o-nitrobenza!dehydc: by t.reatme:r_t
with ])otassium cyanido into the same product (!.86) may now be
given an explanation simi].a:c to Rosenb]..um's mechanism for the
yon Rj.cht(:,.r reaction (eqt_ation I.I0). A simJ.]a)_- r(->actJ_or_ was
(].10
found in the forma-tio_ of o-nitroso]:_e.nzophenor_.c on t:_:c, at:ing
2-nitrobenzhy,:]:_:o]. with K)-tolueriesulfony]_ ch].or:ide in pyridine
for which the fo].]owi[_g exp].anat:ion wa.s offe):e.d (]87) (equat.ion ]].1).
0
" CO"" -C
_11OSO2C6114C]13 x.// N I
C6115 C6!:5-' ' l{ C6H 5
(i11)
57
The step .in whicl] a ni1:_:oso group is 9enerated :]_n equat:i.o:.-;s
93, 109, ii0 and 111 and p:cob,a.b].y in equations ]04, ].06 and ].07
requires opening of an i_soxazoline ring , cf. B.24. When this
derivative is a].so a cyclic hydro:(am_t-Le anion (109 ai_d ].!0)
there is an analogy with the dissocJ..a.tion of linear hlTd:L-oxamate
anions (]_8}) (equations ].12, 1].3). ..
• ]:1_0 2.." ,../--..., ._ _ /i..
...................... / ......................... 7
., NaC) R
NO
O [.I -- O
! 0t3. ', It-1 _'"' "_r':,_.,_ C _ SO ]<'Ct:{R
C:6 5":;""2 ........ 2 ...............Y 6L5 2 '- " 2 ................l-,: C )::_,{C} (113)/ 2 " "
2 3 . " _f:N<__ reaction
Hyd:cc,].ysis o£ a_l([i_-.-nit.roalkanes , the N:,f react_:[o]}, is often
Utilized as a prepara.t.ive method for carbonyl compounds. A
persf stent b]ue color in t]_e reaction mixture durin.g the, time
that acj:-nitroa]_kane is being destroyed -':.ndJcates t,he presence
of a nitz:oso group, A reasonable mec:hanisrf_ for the k<,f reactiLon
i]] _'/]]J..C]] _-]l].'C_lOXy nit]Lo:L;(._a]_};aio::s a:c_-, J.,:.t: meG_Ld __. ha_' ]:)e<'l]
]--.c)_,...,_cI (.7 o_'_.,:,, 190) (ec]Ll&hiOl2 ]_]_/=) .
58
O
,? H+ +
R2f>0:,_On "<......... R2C=N (OSi)_it -t
OlI _H20I£,.O I..... _ ...... \ ' . .............. b
, R2C'-N "')'<_
---tI -t - x i120
Of{ ONI tl + ,., I +
R2CNO <............. R2 C---N=.,OI!
-- H +N
........................;_* R2CO + NOI]. (]_ia)
soiatJorl of an o:.-]ly(],_,;,.yJ_.LL,.,J:._,_,l,..,;_ .... ,,_,. _u/i:- ........... t-'-i .......
b "-,c_"....._i realized; howove:c t]_e reaction carried out in co].d hydroch].oric
acid has led to [.-.hef:c);c;,laLion of 0:..-chJo:con:Ltrosoalkanes (].91)
(equation.s ].]5 I].6)l .... •
4_....................................... -/.
%_. <e,l"/' ". ,_,/ _......
(i].5)
Na0R hClC .....................P'- "-
(_.-}.3) 2CNTqO 2 ., .......................... >. (CI!%)2C'.(NO)Ctt7.Oit
(I] 6)
The second ,ttep Jn the formation of 2--nit.roso--.3-.nifi:_<)-
___ (.lnzcr(_ co:,Npc>v,P,c_ by reductionp-xy].©N.@ from t].]@, co-cresporJdin(j ]" "_ "
folJowcd by tre_rLment with aqueous acid appears to fol]_ow -[:lleNef
rcac. o_on up to the stage of an alte_namive dshyc._rac._on with
aromatization (192) (eq_{ation ]_]7).
59
C}1
"-.h/N°2CH 3
H2NOII
/KOCIi
CH30]]
J.T3_-. ::lqO I<
Ctt 3
<]ilute
/
HC__O o
ClI 3 CH 3I I
.J . ]'q U... p
h j...-o._I-h/-. No _;:,,_o
Cll 3 C]i 3
(117)
24. Pyro].ysis of heterocycles
A few re[:_orts begJ.n to j.ndj.cate that sagura.ted and certain
partia.l]y sai:urate.d rings contaJ.ning a :<J_ng o;_ygo.n adjacent to a
ring nit:cogen bc'<_rJng an exoc.yclic su.bstii:ue.".,t will undergo
pyrolysis wJ..th the relea::;e of the correspo_dJ.ng nit.roso compound.
Both 3,6--.dihydro- and tetrahydroo-.::azines will liberate nJtroso
Compovtnds on hea-Ling (]_93) (equations 1].8, ].]_9) and a s:j.mJ_!a:,.-
reaction is known for a 4,4-diphenylo>:azetidinone (194)
(equation ].20).
f] 0 h e a t -'_
I%[ /NC6115 .N. <-.+ C6HsNO (118)
k. ' ...............:,i I..... />'_c6H5 ........................
-I-C6}IsEO (119)
6O
C]?31,_0C61.. 5 "_(, _i )2C=C=O ................ /
(c6][_-) .............. :O:) 2;t IO ............i._CF 3
300 °
/
C}!'3]:iCO + C]:'3I,iO (!20)
A prediction that certain five--:.n,:>mb,<:ced ]_._::Lerocyc].ic ]'V-oxides
Would undergo py:co].ytic or photo].ytic ri!ig.--cle_)v, tie with the
fozJ._:{atJon of a n.it_roso co_.:lpound is based on-[:he formati.on of
nitrosobenzene from azox)]_)e_}iene by py:k'olyr_;jS (].95) and from
N-.ph<;n],].ben::;a_!nitro!0e by p])oto]..ys:[.s (196) (equation .].2].) and the
ring,--o])c_!:i.ng of benzfu:to>:an, cf. B.].6. A._ e>:am]:_,le may have ]:)o<_n
O
i' h.,-
C 6 l] ..5C.I_=-_qC 6 }_5 .............../ C61{51,_,0 + other ]?z"oducbs(12])
found in the py:_olytic transformation of 2,3,5- triphcnyl--2--
methoxi.:})yrrolc-N--oxide into the corros]?ond]ng ]_,2,6-o-:azjne (]_97) .
An al_c]/act3_vc,, c_,l._._nat]_on based on the pz-inci]]les c)f valence
isome.t-ization ze<(uires ring-o?ening to [: nJ..trosodiene ft..]_].o\.,Ted]:_
a new ring-closure (,eCuatJon 122) _ cf. B.l]..b. The facile
C ..Hb :)
. ::_[N.,,,,, /OCH 3
,>,,,C b"H _r .::,<, ./ C 6 H 5
K.I
O
heat
/
C6H 5
IO_I] 3
......... C6H 5,O
C6H5 "_._.N .{.,,
/
6lJs
• TT I _7<_'<;';''_'/!<C6,-, 5
OC}ID
C (]])"5' (122)
6-!..
c;onvo:L_sion of an imidaR;o]_c-N-.-oxi(_c_ inho an oxadia:_iP,(_ (198)
eqg.au_io.',:]].23) may a.tsc, }::rocct ,(l by v,:_]cr_ce jsoutecizat:ion iNE.o
a nii:.:,:oso compo,ar_d fo]_].o',._cx] by ;, r_o.w ring--c:].oso::e.
O 0 O
II liN , ./ .... N"
R' Iq" "....... ' / "q 0
_' ._.3.4 .......... 7O= . , _ '* O-=._ . ,., /(:J-( R
"_"N / "_: _i ...... j. N ""-)
IR I-P
0
IJ tN
, //_-.. 4>i _'_ 0
R _._ V In--! t.... .-,R3},,_
" N ' " NIo
(__.23)
• f.2u }_]].e(" - _- .... ' _ :F O:::kK',e ..... lh_"
. . . j. , z-} , ....A zepcr_c tha£ elec'tt:coly,q:l.s of a ] :]. m-_;.uuze of the oxj.me o.L
..... V,."J. t ]-_ j_l]£ e zif_O ]. e ctl 1 arIP-@SO>fa]j.C e'. hot o.Jl(_ i_CS SOC].-i.L]i;] SE;.]_Iz OCCU]?E,
coupling between l:]_e two e.--carbon atoms and the foN:t_ation o2 a
].,2-.dinitN:oso clerivagive of an ethane (19S) (equation ].23) shou]c]_
-= c ]_o..l.m,=c t.h a%be reinvestica%ed. -3.: ..... In anot:he_: rc:Ro_.t-it is _-' _-':1
zU.!_ ]. ac J_c]keto:-:-]mes undergo e]__CLZo]_yhic oxidalion in di]_vuhe sut .... "c
: _,.. ( ] c" oto cjj..vc_ q .,__ trc,nJ.tro_so co_apo_u-,."_. ..... ).
(52
2G ( .'::t,.(¢> ,,<.,_..'_" L")r.l iCl' _ C L i Oil,_!;
t_, -v_ziet.).,. of 1-_i[t_:c)_,o dc ?:Lv_t4vc.:_..._ oJ! b.(zLe:_:ocyc3_:].c ,2,_LCm,c_L._.C'.... '
CO._:@.}?OI:H1.(]SI;,'.__.VC'.boo.l]. O]DLC,_I.._I(.:C] }.)y YO.CLC[L_iOIM_; JAI vJl_i.c,]l t::].!e hcLc'-2:o ....
cyc.l.:Lc _:.i.ng is 12zo_!uccc] ]:,y an in-tr_-:,,,_o]_ecul_-:_: condcLs_.-kion, T]-i<.'
fo]].ow:i_> 9 e::om]2:Je8 m._:e i:!_].>sLro£j_vc: (oq{u,-:_,L-:;.c]_>s ff i,: , :L25, ] 2(;) ,
! I! e i.L ,-: r
C (; tJ ,_(.:OC::J'_Oi] -l- (_16t-J5{.:!._.,ti 2 _ ]iC ]_ -....................... _'_c]z _1.t., I....
1'.7_:_Oi [
.i7.:2:7 • /. 0 0
O },7 .............
ii l,C6II 5 ... C i}_,
N
tt
( ]_ 24 )
I F'" -,
t*
I:':!0}:}
4 (.i; 3 C CC.X..C!] B/
I
CII3
zof. 20]_
(1.25)
(11215]) (..... ,2 "--? " ONCE[ (C_q) 2
lq]g 2/
..... 7.................. "", /
/ < _It)! "-._" Ikj.,_D,'.'iI? t9 F "
2 "_']':t"" 2
(126)
z;_f, 20 2
63
2"7. Nihros<_ cor,-t_ounds f:co;u d:i_"._-:oand dJt'_,ionium com]'otnuds
]]erivatJ.v(:'s of dis.zoacettc;i_)llenon,<-' in the ]:)_:esence of nitYosyl
c]_]_o_:Jd© release nJ_t_:ogcn and fo:_:m [;<:lu:i.>._,.li)it_:o,_:.o(::l,_]o:,:::;d<:
addocLs (203) (cq_,)<vl:io,).127); h.o,,,",<t,e:c,iL :i.s not c::',ti-:]_;)is]-_<:d
that a carbene is an int-,e_ri,,_cdiatc. N:i.t.:l:icc)>:id<-_,z:ea.cL:, with
NOC _
.............. AzC__ Cn (el)F_O ......_ ArCOC (C].) :_,_O]I;ArCOCIIN 2 •,-_', " h .... " (12'/)
. .t_ } l "d'i._])..,-O_,:"y.].diazome_.].at_e...... Lo fo-,:m a nit_:Jmine (20 _')._, (eql:ac>on.. . 128)
Pz"e_._tlmak)lv_. ., by way of an Jmino:.:y_ zadica]., (C61t5)2C=N0,, which ]_as
]:._e c 1i • ' " _ ]'.q3_tzo_.,O.. _I.,.t.IIG ]I[IS ].:).2,.:_11 p:C<}?,.-_.rc. 4t f:.]."o_n t:]c:t{:_(._Ct_tCtO. d (205) . i-' - c, l-),-_ "_v:, _ . _
O'oyil-_kl_:t:. ....... ion of pl_cr ytd-;azonium....... ch]_o_:ide g_nd ar_ a].k_-_t "_),-:,..... ._. so].ut:i.oYJ
of potas,s_u_m f(>r.ricyani<_e at 0° foz 80 hours (206).
NO
(.C6H5) 2CN2 ....................> (C'6tI5) 2C=NN02 (].2S)
28. Natural oc(-urrer_cc
Azom_,],c nitroso compou>ds have been iso]at:c-d as animal.
• . a ...... " " ,_ .J.. .¢2 ...._eta}:)o],ic in_.er_L<,,dm_.<e, zzo-,{ co];respondir_g aromat't.c p]Ti:_a_z]_ amines
-no. from corz_esDondzng _ro_,a._zc nitro compot)nds (207, 208, 209).
-_(] " , . ....Bact<__rial degr__,atlo_) of p.-_o,itrobenzoic acid to p_-aminobenzo_c
acid .........- *- , ,_(.jp_n_en_l] requizes -the in-termedJ:,Py of p-r_itroso]g)enzoic
acid (210). The g_-een pi_]me_.t fe:l;:coverdin is obtaJ.ned from a
.t,pecics of 8-t:_reptomyce_; (23_1).
_d
..........
,,....../(%,,p_"-CII2::--ClIC6}I4'-OC \ .., / O
\ ................./
"NO
]_0 T]T(3VQ "Z C. _!]
C,. St]-t!otuve and I]e_: < L.J.ons
].. Dimorizatio_i
- . c ,.The d.L_n_._gJ,:_.__m i(_z C-l_itroso • ]. ....._ CO;h, ,_t].J._ L; \'/_]S f;[]_-,% c. (]_C]_..O]l--
,. m] .... [.(2c_ .[L!'I il ]'LI(_ (). .< :!rd3n(-Ji]{; of the m,<,.gnet:ic ,:u,sc. u>tib:] !ii.:y- of
]_ J-t.Iz'C, SOIo(.-T) Z el] o i_.I-_(] " = '" - '.-..LL-,_> ],_]'-ClJi,_:_[]]y]ariL]no__ .. .., .... d<;c:.va-L] \._(.,. (2]_o;....
I(._c:],t]_y i::he --_' ..... t , ' '.,_._J_.t>h ex_ -r,_-_]e of t)ail-_a],:A_.q]'._etJ.c ]:oso]_,-.-ac(.. _ cL.),L]O]_]I)U3.(/]"_,........... lY " " . . - " .
fC,_. a C-]Jj.ir];o,".:;o '- ........ct,-_}.<)hoO_. W_:.'] i(_])ori:(?d fro]." ]."....._C ..........." _ r _....._ ,..--h!f:'t]_'_.... ],]--.
2-.-n:i. :r(-) < ,.;, <( <;L, : r(,:, (colorless sol:Ld) J..,_. a O. ]M soI.t:,i:.:i.on (bI.ue.)
.i.]] i] () ] \] () ]i ) ,'-" , _'"'i_.}.::c" ;-,r.],,_...._._.___4r_-; (.'O]]I/{'].].I]Q.(.."' " " :' tl])O',.i[l] .......c_._ ]_)(''I'I'C('-]I_L ()f[ a
])iradic{:_] ]).<-(._._;a.<-;,:2:_].y dez'J.v,:.:/ from a. d_m,e_-,. An e.s.:r, s:}_g_al
was _).__:,__o}.;t.u,.:] ;]:/.d Jn _" "i " " ".... ,.... 1.... ]_aY JI_LVC-'S-LL[CIaL]c:,nsOn _:)-n.J.l:)[(i)_ioto].uc:T_c,
2'--c])!oro-.2-.n:itrosopz-opane and ],.-.ch]_c).uo--]..-]_._.L.,_o'._._.,(.:yc._.o,_.c:.,.xa_.e (2]3
( " . _A tci:..f, cncy i:ov;,a_rd c]J_mcz-izat:ion J.s a .]._:;_i]_c_L.JY<_ p:<oz_)a]tLy o:.C
the ])itroso grou]? when at.i:a.ched to c<_zd:,on. It is .inhJ_mafie].7,
assoc;J.ated with, and usv_a!].y det©chcO by, the dJ_sa.Tqpea_:a_nco_ of
the blue o:c gre_u__ color which originates from an n ........"} "_- trans-
J-tJ_o_] wJ_th _-- _-v,e_t,, absoz-ption in the 6300--8300 A ° range (<=.l to 60)
and is characL::-r',.su_.c-'-' of the rnonome:c. ])ia:_.y, but by no m':_'-..........._ a].]_,
CO_.O_,_ ].eo'-" ()_ cexamp]_c.s _,._--,,-,,_" ] ,- _',, l.)u'.!e yo.l]o,:¢ di,:_c;z J_ [b.':; so]id __-_-,-_
6 5
]3ecc)2t]-i.n_ lao.no_m23::i_c oil me)A:in_, :Jn -th(:_ q_:s ]ph:Lno r o]7 in so]_.]L:]_on,
!
'])wo types of c-limc..-£s aze }.:no_¢n; o_ge is an .I>_,N --axod:i.o>:_Jc]e, %h_J
J.s no ]:.r:owr_ c-.':_¢amplc_o-F._a _-.,r_,,o_.o_,.-,..,_......_,.,h._cl._-:_giv,:,:_..,._ bo-L-.l_(]-[',.no'._:_.
NiLtrc>som ;,tt]3un._,...... (ti 1-tt:-':z h&s t]],P.. ...._....fl].\]" ............l...tl.._t., o_.£ c::i ,7,-- d_;d-' " l:._Ta):-_S---
I
N, ]'q _ '¢...... , - - _ .--c,_l..>.>,o_,..ome.tha:,..,.e(214) (c(iuoLion 12°). Each c:o:_::igu2"_t:_:_._
I_OV 1-)¢:, ]:{::%)Lcc:2:5<;Y_[:(-_d _,/:i-[:]1 "__ =_. ........... c,o¢3i-tion<,..] rcsonan<:c stru,_c-L.u]:es c.,o s;Jo.,/_"" }.
H-_C.-! .... '_ 0-- t l- Cii
2 C).I 3 i<IO "_'......:' ":'O5]?_::::]'_*'C'_3' "O '1- tt ""IN:::: N.,/O 3....... 3C ......
0 -" 0!i + I
]:_.--!_-.-.i'.! - F. R-- iT-. I',_-. :[?.t + il0" 0
(].2 9 )
},v*-,-.n i:hr:-y w:[]:, dime3:.i..zc, n:i.troso devivaivc_{_ of a]]:<;nes all:ones'_ I..: ..................... I !
}:].c_:m2]_2. t, _].;.,]] .... _:,, &lid _]]'o];!_:i:lC: coTr,._;ol.li2c]s_._ f:c]_]_oT,; £]_,:' _'_P;'+r_'_'n-_'-'-'-_-'",%oi2
by ]lit]:'osc)_P,E_[:]}&1].r':al]<_ yic!]¢]. t]3<T,expect:.c.:d {:.Iio>::]Seo£ an azo
co::_pound. This dJ_mer s-t:_ruct.u-ce J.s v:,::'!]_ c:st&b!:i.,_::,hed by 1)oth
chemical and 1: i(sical evic]c,.nce (,¢]_5) ]:P0.-t pzimari].y l) Z >:--:r:ay
Czystal!ocjrapby (2].6), Ilc, ductio_n of the dimor of 0-ni!:roso--.
I
toluene to N._ --dibonzyl]]yd_-ca._..-'.,.ne .)b-' a!u.min_:,.n_ _'.ma].qam. (2]7), 5ks
acid h:_'d_:olys:[s in'c,., ben>..:n_' c_:_-( :::ido (2].8) a;:([-,1;_,.... fo):m.:_.t:Lon of
te_._..¢_z_ b __LOI/,,Z'_ _:_:,:j.:r:,CS f:,:O_:_ ni[::,:o::_o d, ;:,a:cs _:.;:.< d:i.c:..:.._,!:s (c. 23, )
_6c
clear]), d.':mons-Lr_:t,e the, dir,_,<::c N--I_ bond. Ir_. oe_-,'-,ral=,.__ .. , m_.x<_o c_<me_....
8.yO U]_]£Nd.)?;q]; h©...;,,._]\_o.k' C).] i]']CO;'F_)]-C''[L@)-y C:]jC_]FUCt:CTT'LVO(] ],<i. XOd (}_j.iiO. ffT
f]::o],l a 1].j_-t.]:O_:,C.,.']o_)u_t.LJ'_ ct]_c] 4"-n.iL._-'o;.._o"]"oo ka-Y]ol ]]&s ].)_cn k_,:_.,..).,.L.eCl_
• . _.... • .... ,- -' .... .... i]}Lio'-'_(2].9) There co_)L.niuc::s to be att.emi_.ts _.o ]:eJ-j)_e- t.hc c_.... c..__
of the boil, dine] e]ld recently bc, nd oz(!e_:s of _/2 _.z<.,rc consj.d:-:xocl
for the dimer C)Nf_O syst.e_,'_ (220).
A g:<eal:.c?.: t]iezir<)dyr!ar_,,Jc sta];ilit:y by a.'.oovt 25 ]_c_a]_/mo.]. fo]:
..... ].c .,zJ .c.. to oo;l_-]fo_7]}_c)]]<.t.t]_ ]fi.,.b]).(.))!'L<_);f:_ J '•],n.£t:,cosc_-,L._a.:c_._C:C:<nd]_?_'_ \.dt.h -_-"e 'i-
e c' L - o n--\'. _1 tth(_ zaw ._._,gcl:i_minJ,_!:c..d and mono:,_u::,zs are st:_.,.;:i_].:].z-'"
. _ . ,-.u (_- p o s ..............c,_z-oups c'ze at-tachcct -,'- the -, t:.ion (20]) _ _;o (_ t_]]C, ])] \]] ]t'<)Y_C)i'/I<:-'I<
2--bro:-no-.-2...-nJtrosof:,]:o];,ane, gJ..v<_q __o :_..]__:.(:at::_on of Cl.:.],_or v_ation (222)
•La£__,. ]_ized _-G]"_OY._Oi[!C_.l::f_Of _.)i.Lt]--o,_os.:t?ol"atttJ c (_]@)::[Ll_t.ttzJ.xzc _ _t_;}_)f ]';)e S _ ¢ ' "
]:esontan(T'.e. Pi:e_;tm_a])].y this accotr_ts :[oy thc_ dis:-;c..,cia.tion of
l'lJ.t," ]"'r_)C'.,rl2:({:l'l<}"(]'].H.':."-''--_-i.ri ber_zerle ooot-_:c:_ip.cji.oo ]ftt[oJ.([]..]ft.o ].)c,._.C SO._-
z2_. . . - "..... "moasured (" _,). Copjucv_tJ_on ].)etween an e!ec.t:<or,. _re]-_'a,_::',:Lng s_dJ--
si:itueiyt J.rl the ...... ""-' .[)a._:.,._.-.,po._ _.___on and the. n:]_t_vo'.:,o c]roup fu:ct.hc:r
enhances the stal)J].Jty of the morton:eric: i-ozm of nj.-Lxosobe_:tT.on(:'.
\:i-hh _ ; ..... ' _- ,_ 224) . • rj'tlj.s c-_cCt :i.S n!o.)ur(.::%),.,c..uto its o..]_m<.t (223,
p_konounc:c;.c_ in p.-d:irr_ct:hy]amir ,_o-- and 2-iodoni-trosobcnzenc: wbJq'h are
blue sol id monom.::_:cs (223) and i.n ]_--nitrosoanisole (225) ar-d
p-bromonihzoso})c'.nzcna (223) which are b]_ue so.lid r__onomers under
some conditions.
Sitabi.!:i.zatJon of the dJ.merJ.c form relativ.o to monomc:¢:i.c
-i......of _ " _ _ ,--,,..... b:::ouq]yt abo_.t by ortho-_ " ' l]._.{_._0.=O.Del .......... isQ 0 ]-?L'%,_it\2._\ ,.:.,:...............
SU})L, hj.t_ut:].On -'" "_ ..........L_,.., i,S )-_OSL _:'OYiOl._.:0C.CC_ "_.... ]_ob]_ O:Ct.]]..o- pOS{ itJ C>):_n
G7
).1l@tz_i C ;3 bL_]_2 C.):[: t:]_.O 100_-,'OFL;O;C---(_]__: .'_t r or, _, '1 [I -1 ])",*- \ ;,, J _] }1.)C_]37,C'.1J.O: :_O_ ^
a so:cj_c,_ of (_erixT,::tj_vc_.: of 9,(i.-cT_kcl._].o_-oz_.i_k::ro ..................... ;., O.tl)O.' ! Z (1)]] (} (9 ',__i_k_) _] -"
" C-,"c"'] "( _ ._., .. h. ,..s t-.ra.t:c,.(]-t-hal-....... ar,, e]_c__(:;-h__:on _-c: _l_.::._.........]_ ::;u}:_h._ c,._,.._._____ at. t.ho 4--_._oqJ.tz:Lc:,_:,..
.l_kvofc_: d:J._:_,t;oc:J.ut:.ion tto £h,e rnc_:_c::,,. :_: '_" _,- ' ' ..... " ' "........... 04 :_.L C]J].__;fSOCtj_'IG_'L(.:] J ,%
e.]..O( t ±:oJc--.czC;r_..-.::':_ , ;,. :_ _,_,_............:; _i_)q _ _::-[.:.dl ]:.._..... ,.'.: p \_ _1. t_c.' c)._ --"_.1.,5 _ O]_;t _.-:].:',_q_(';
Jr:, t.}.'.¢; Ut-U_;1 " .... ' .... I ° -*-._--_
In(_;;:-_::,d.,::e c:£ i:]_,:" "._("_(_.,:_':_,:-:c. c':.[.., :-._. ,. o:;: t:]±:: t--,_:,ttbs-[ ih]]e]__! __--.
((:O,,C _-:' H C'_:_3 ...."z 2....a', , _, , C1..., 13_-c and! O__.!J3) _.._]_,J.c}-;. .,,q_,_..... fovtn,fl t.o l.:(_ Jd_'.:mfi:._..o._t]_
.t _ r-
J.]T())[, 7, tlhr-I ..................."["f,V ">.-- I:; 4 ])1 t-, fO"r'_l_t_'..iO] _'- O:': C7._2i:':; \7[ktL.._._O/:; O'F .__( n:.:,-.-_.q(:eu_._,__" _ o
(._;._-,._ • .. :, .. ..
7_. 1:.::':_ , ._.,,l_:o o:U_!,!_:t:':i_z .... on ])y an io._JJ.c _:(-a,.:L.-i. on. (22a)
(t::(l_,::_-..].,,L,r-:._ .i .'_()) -; .,.:. :__:,'" .-.'_g_]._C:o1:'.o;r_L W.]_[.]] i:]]o ]7fD%c.):];,.]-.(3c. _ S_ JT_]c.;[:.k.]]i"o:-z
....__,.) j _. ,_.,h-; ("h c]_ :.' n:)_h:_7.o_:_o c]z:ou]:_ Ls e.].:..;c;{:.:_:o_-._ _,,.'J_-l:bd:_:_:tv:d_ng.
';i'],r c:>]rt;_c,--' c >' .[":-,_'c'.h n)_G, h,a at.-hz_:;_}::,u b_od _o s___.c...... __.r)n'' _."]>''-'v,..__,._n o£
z:e,_'c:,.',._;x_,:.o J..u the: r,'.onon:e_ (226) o_? Lo a. s!:__t})5.;I..:;_:._:.{:__i_(:,_._,o£ t..l,_e c]j.r__<_':z
t:h:_:ough _t:e:,LrLc; j.; ' '" "' .... o£ ]:es o. .... _-;u, N--.tq_].]u_l. cl O:lz O_l_t).lOC; ZOh;Vi ].[. _. _',tCj ;]..)_ D ,__u:t. C :r)_ _.3;"
bol_c] (;_:o:t::c; nea]t]G_ a c] o u l :,.] <; ].)ond) (215, 22'7). Zn cor_l:._:ast: wil:h
t{-tq.-,--o..,+ R-_,_.....,, : ..........)- (]_!:_0) 2 (]30)
/ -. ' , .0
X ., ........... ./
(13.]_)
i
C'
' ' ' '_/ is _,_ ] yc.].tc;,.:; ,.:o7 iC, d::i_!<:_.;l)--lJJ.'t)"i)]33.[2C{')::_(?]-_C ]IV,<<)iC: \,.,: i C]I (l _" ._ (_. r ,- __
....]D-"CLL_.].].'c-r(;"(',I_ :]l::;".}!]3C_ T::])C':]I .[:.s......... '_ I_', -2_' f31_t_] _]_"f" J "-'_' L] c_rCO],_,............... c:c)i -1¢:_ ..............
Zi:-ra]p:__c;.ly c,_ ,..:::_, Lo ¢' ]78].o y_lt.o_ p'.:_].v_,..:_:c (2)o) ('.:L_a_ ...... ,.,: 2I.:;')
(132)
DJJLI@:C ........ : - ' " _ . '..Zc',.L..LO;_ !O_._}z ]>'.:" (:_].:iy!Zi!l[_LC'd ]:[: :]n#::Eg_h-!O]..C:CVl_La:O .iT_[.©]L'aC[:-LCt:l
]:_et.w<_cn th.e rzitxc)r:;o 9-_:ouL:, a_.;d 8:o o-su].)_, i:.[h_ c,,_t, in an axo.me.t:ic
C!Ol{]_C>1711<_. ]{l O,y QCCL]:L", O-]Jilli[ XO:- r>]):_l_z....... 27'"' 1-_Ct:-, _;....."' .....;] _ t" _O S [:l!]- _ '-" :_,Z_. <.t .CL
ir_t,_::mc:f]j..ai:e (229) :[._:_ t]lc; e£{u',].:.]), aL:[(_q of u:_;r-:':,_.rv-.,<:L:_:ica.]].y.
Si]])_:_Lt CI:IL.G'{[ ]:;O]-1 'u _ ...... ,. _. 22 o' ' _ ,,. u,:.) .... _;_r:', (930) (c:::.{v ......" " '"_ ¢_c. i(,'.. 7 .. ) _'\ c7_.;ii_-_:," Of
N1 _...o_,c . .._i _{:_.,_72 _U_]:.:f:'.Ov,P.._. _:::. '.'q]:y SJT_!-L]_ P.:_d equ]_lJ_]:)rium,
0
,j,
! /"
O
(]_33)
(1ini-hro_-oo].:2 _4v,_'.............................. a}_-e as;;__:_:',q i_r.'.-tc_ :: OC;:L¢_, ,::S""-"" in t:he p_y:colytic
iso;;:o:cizal::i on Of mp_sl,]Y,.mct:i,.i.c a]_]_y subs _- " ......L..:Li:.I.L.OC_ ILIOIqOC][C]_:[C _tl_]:'O>_2d}c3
(230) (ec!us.,.-t.io]-l_. .f13,_).... .... n o'.::.ch c'.:': ......... <:_" ("c_.u.,:.,.,"_r'l -:, ]33, ]_34) the
--,- C]- C:--C,'C. j! ..... ' .......-_/,, '.,.. 6 ) X:x C;-"5
N ",7. " 0 0 ' 2,; N
"- () _ ON i'i0 "" 0/"
(]9A
69
•""-:- "'. " " 0
[,/" "} "'" -" ....
£--.. _ =N--.0
-'q .... -...... i9,. ()
......... ( ::--N:=O(]_35
R--C ...... C. ].:t ,,-'" c--..C--!¢..P, ii t: :i
-I-N N /._ "_, N N-b
I ! .... " I0 O 0 0
( 136 )
II1 cJeliC>]YC_]. :'" .......... .......• Ct) JtlC']. b O_ ]]_i t:)"O -_¢ 7 ] 1Lal"(:S _tl'(-' }>O:L"( :a ,'_,12ab_].o J.)71 %h{::
t.:ra_,:::- c".o.n:_i_.i>:,:,:vt:ion (214), Ce::taLn. cy,::;].ic a_;o--N,N'-._T:i..o:_:ide.s _,.r,::
a].].ow<,(i on]G; :in t]-c cJ.a;-- c<>nfiqu>a, tio_-_, c,9. , tl__e a;;odio>:idos
( 3 , _4 , .[_ ) z IJI:( J _ _.-i..]_(]I.-C_]..c):i:_].J.[l.7(_: O.L ]. ! _. .., ................" n . _ :.-d:].c!._]_ozo---t ,.I.-..(! i _-i t-]-osoc'ycl o-
!
hc:.:ane (]..3_6) , 2,2 --dic,.JL:r_o_obJ ]:)l-_elty]_ (1].6) an,:] 4-met.i]'s]_ci>lto] i,.](::--
]-,2-.dic,:.:j.(!.e. (23]_). D£s::;ociat5. o_ o: the., ':inte:cna]. nJtroso d-j_c,::::_:s"
\.,'hj.c.']_ a].?e a.].so ciN]qo].Jp, c ('lio',:_ .......... O.c.:-: has 1"10"[2 bco./] c_£_!:....... t(_:: ,._L",::,"kO_..%. ]_N'r
con£rasIz wit]: -{:}:© ]"i",g-O];:'r_ nq of fcxo:':a:a_L,, _.(:- supra.
c, iO I Cti3
/.]. o o . • 0
C l .... _0
3 4 5
V 0
"4 _- _. L_2@.... __...j ......
its ]_.-b._:o:,io d<2_.::i\Ta.t-;¢_-: :L,s _.',.........t:r:a_s---(_k.ru.::..:.-'' _- 7',S,]_::_:o::1y:........... _:n exa);:_i)].r'-
OF_- & di)::L,_3:i:O.f a I);:_h:UOX3 ........ ""- (. Ct. C)LL[C L..L. CJ C(_):i!:_.)C.)::]](_] .:.]] }D- r) [:.-)')_ (_i]-,c-_ .-" _.:l'i(.] tJ'J.':t:':S ....
(:OJ_f_:].qVL:C_::',t_C",::S 1-_:;_; ii,'_i bC:(.-']] :-,'_ .... ,] (:,:'_ ' .............. ) ,O_i_- t-.L, ._-I ) , C()Yi'jC' _,% 1 C).I} r-, .C ;_
-[-r_!):f;--]:i::C:i?Of:,OLt] ] {>]_.... *'' " "....... 0_)',2.:" I:O 'CI:(:_ :?-;:,%:_ f:,?:?..?: 1;_<:.-L_,, ];C) ]:;'ui?ej:,-{:.
&]Dot,i:.b).; u].-h:r_avJ.o].(_tJ_z:,s:::c]J.a.[:lon;t:}_(.:_:e\ze._:._T(- })):occ;_;.<:;(>O(;t:LZ'::
< -] - .j_: ) o:i: (::a c] .......:L:L:_ J.y: :: o :c:p o ] a.:L" ,:;U._ ', :-;SJL ._; '_'::LL }-JOt _-h :i. :l.t]: .... / -:,::::.{::J_o r: ( ") /'
Si.::,:i.:l.:_::i::i.-t..i.c:s :Ln ,<o:!.v(::_L (:: :[ i: ,mc" L l:_ :ox boO]J LI,:. c:(>::vc,:s:Lon o:F
CiS .... h:O ].:l............."]<"--- C-{_ :?,@:F_I:; aN.d {:.]1C-'. _ ' ..... " 'ct.t.s:>oc._:at::,oT.]o:;: dl:i),c-_]:s:-, <,--_,<':--<'.............................. - - - ,-> '--' .l ':_J'---""_ u.,,
"LI]r:: 1]_ .......... " - ():F L:h".:: o(;:s5"2-o, _:. ............. :; ............1 _t-(-' L._,tL.,-t.i_ct'_. 3' e: ,_,-,-.:7 • r, y_<........... .: ..... :i.n c; -; _r', <--,): 4 S(')?t':(:7]- 3.
2:7_t :i o.r_.
.I.]._(:::" ' ""/" _ -'" ......_ ' - "(..L.L (:)]:"]:.1:C)\'711):C._,_.¢._:C) . ¢!_ I_L::':#.:] /7:__'.I"5,,_S:__-'<:1:: 1):±() (D,.:I:L t_:.(.J{:J.
):C:t?(:,', :_ "11)-I r_ ....... ' -{;;. ...L.:::-(_. Wj 4.:1"_ 7:'j.:_P] t:O:::o:_iJ_Lro................... .Lc::<tt: t.].C)lq_ a.11(] ]:Y{:l.y ]1)@ _].] ].I._;L]:'Q .... :l
:;Ol:tc:_L]:l&:;_O (_ " ") L:c:.S:O.C_:IC.]_ -[:(_C., ) (<qt]::l:]o;: ] 37) Tl]e]:o is no _'" '
Cl_(me:?:.tze. i::Lo:r) -L.o oc'(uz i]_ tl._e On_):, oven a_t:c:._: <_->,zr....... " .... _.....
.b:.o:"- on m:',:_._>o::::;.:oto .L._UziL:' _ (:?a_:c{:J.ou].a.::]_y t:]L._r:Y",-,:L©:IeL].:LS}.tL) l::.};c])].uo
(Ja.,<; ...... _ ................... _ .i._]ac a ]):t:ot,_s]---:re({ cja,<:; <"!_0v71-) tOc:)(:]_.<:]c:L: :_]..[::c):s_:c,17:_: t] L_4-4v ,_] _ " " '- ,.,
. 0
bo t]](_ ({ :i ]it::: _? 'i'i:(_ z'c2a.cL_ (',11 _::,].,_..-_ ,-_] _.-.,-j :::::::::::::::::::::::::: \,TJ {:h t::](_; fO:l'iLt::" " " "
2 CF,,_,:.Oj ...........- (P:?.... 3 ) 2t':°'_°._ ::'h '"
(337)
oZ -Lh:_ :<:<.7 ceT__,m, .i-:j_._7:_t,.:::rc.:;_(_-Lb-S2:::_c...... n,].L:cJc o::::.Clo_:'::ic:]:t-_l::m:-:.
a.(]¢] I.:(:> 12)-:r:1_; 1o'-._ ].... :-"_:_<:_, c_,C <q 7D. c-l_,:'-:,:- ():r l':',---c})]o:r-:ot:c::t:L::.--
_!] t]C;:U0!_ _:.]:C?:" ":__:..l)$__YsO h-::,G ]DO(_l] O];:)L:c!t:]_Y_;; 'q _ ..... _ -' . ........... J_TO:: h._:<:: C'Oht::b:j_:::EL].::.C':: (_:_
"7_.
(C] L:]72C]!'2)_. 2!,:IONO :.::x::..., :: ('r'IP_'2 Ct_'2 ) 2 NO : !70C138)
2o :[soKte]:izahio]] to o-.:J_K',es
'i'he nJt:cos.::_1::io:,._ oi a].i.phaLic caxbon _rho;c:s is an :i.n-..,por%a_rk
Pr,ui}tirati-g._; meL].zod f:o.t oximcs (isol_iL.to,so c:c)_;;po!tnds in hho oldc-,:
].il:.era-t:l.:tro.) in whic:h the i_rtermed:] ate nJt:roso d_r:ivativo m_.y or
nLg_y ]lo_ be _i.solahed. Iso_:_ :rizat:ion -Lo the oximt_, :i_.n £he gas
p]lase, w:i_th melting oz in a. sol.u_-ion, may oc:cu:t: more rapidly -hha.',:_
dir,_::,r:i.z:t_,-l, iion, e:nd is cat:.a:!yzcd by' polar sotvc::r[:s, s-l::,:ol_g acids
a]::,d bas,-s ,N.Jd 17:i tric o>:i("ie (231). It is app:_rer_t:.].y fi.rzeversible
(,.!:qna!:J.on :!39), V.,.'R:eY3 the ni1:..'.:osakJRg agent 5. s ni£rous .fJu,p::s
(F;203) c_n_[ itbc zo.aci-i.,'_,n is caK]:ic;d out:. 5n e1:!)c_.r, -1:],<- j]_ticr]:_ctdtia1:.(,
P,2CHNO ............>'- > C---r.{,>;- (139)
n:i t _,",",so.. co:".pound m,:'y t:,o :i.so ].at-co.. " (23",:) . '.[1;.'- e_. S_t.;.._-"" _ '<.--.o.,.... {..<:r:'- v e_'p,a.t
phase J_somerJ.zat:i.on of nitroso:-0.othenc, compl:icahc.d, b-* a contr:i.bu--
tion f.l:om a surface reaction, appezent]y proceeds by an ir_.tramo].ccular
hydrogen transfer in e.greemer_t wAth a high negative ent:ropy o_
activation (235} .
As the molecular weig]rt inc_reas,'_-s, the. rute of isomerJzahion
:U.r'.y (',>C:)i £,:" .._C:' aS J_S c_'.C:l_ ir:.. 'J]!<lt N._:.crc,: :_'Si]!%; _'- .:: .:; ;r.i '. J ) :q:," [:L"_. tt:cd
72
i°'_m_"l '_ ...... ' -).... Ct] 3 (']_ C]i { C]:] 3................. ,_L].._.n. :.o J_ PJ<O J__; the se:cio:{; R ::: " ' .... 2 " :_' CII( )2'
C(CH3) 3 (236). A p.<t:t:ic.ulg_z- :i>.t<:::,_:;t me.y be fou>'.d :].n
_, --rl_ h-"c)sO¢:O ] uc:T_c .... " "_....... _'' ] .... C ] ] po.rLi<_l.]y :i.some.:_:]:..:c:s i_]ho ]:)enz,::_ldo::,::i.mc
_7 "] :'- _ " ; f ' "_on foYmahic, by the o>_i<l;_i:jc> of 1-o_;,4.'. .]...................... _yC__r:O".y.[c._:_.] 0 \]..1.'.i
dic]._:,:omate but is p ..... t].y t.r,: ]_,:.,J.c).L_:,. d ' '-"J-'k}(._.)} :LJJ. t*[J-_l - c r_ ..... ..t.] tO _1] C): [: "_0--"
ordJnar:i, ly scab].e_".... r_.i_t.r<)so <]i;m::;.r (218). When t.]_(:._(__r.::_[-- - -..' c w:i_th
h.ydo,jcq] C]I].OYiLC].C J.Yl C]I]OY()[OIX'][I i-t J '.' C(:)]].Ve3_'tC!<] h(] _z ]nJ t " -.>__ 1117{:
r_ . t}o J_ b< nz]_.yc :c_zido _:nd :i [. _,,.,]:)enzy] id(.:r.,c.. ( { <!::F i_\r _::_[i jVC,._ ]DOhi1 O._. V;_l:LC'h
h_'lV6,' _'- -' ' : t.J, {._,,;OY].re_...:,].ned .]_inked hi ........ 7 atoms (2].8). Bc-,..:c:c._: on this xnz(""_:,: ....
matj_oi_., it would ap]:,ea:i: p]:c, bab]_<_ -that. t_J_,e......... c................" ...... ,_.i.on of certain
}:,.J t:r'osOP 1 kay O. (]i]0<:::< '_ J.]_tc' co]::<'c'_t.:,ol)(-I-; "_ o._.,_; _,-_::;.,. :r'c"(,ni r-(-- c t]:l<(_
'r ' l_Zz<:: ZG_}].:]:_C,?.I'.."I(] "Ir:]<'ilC]-]II.C LI"_:L::L.k._.L<,y Of t:.]lC': L v.)I,C)I,3C.Y. _ J 1] P<J:FC C1]!:0ii[: \';i [.]D _- _'
0 .f ......seccn{ary.... n<troso d:Jmezs :i.r)the -_c,_e-ocP of hydz-ogc._ ch]o rJ.]'_(_.<:._2 .....
_,.C_t .]._ ct(:_.)@r_..t_ .P,t: C.',1].].v011 (]{lifOr CO] <'O]_;:.]?&t:LOii <_( CT(_<ti13_ _, £]_C:I:
t]-ic __.......,_.e_--o,._._.r_,._._.,z_.v=_'_- .... _""-,-_ st:el_:) is ]ik(:.,].y t.o be d:i.ssoc:i_at:i cr__ to
mci--!o,_er (237: .
t._q,:. ]>_:_,<;<1 C:__[:_._.yzcd J. SC)i%!@]:'ii.k,O[:lOY1It may be assu]c.o@ that -]-,
of a nitroso n,c,nomex to the coz:res,,-)o__:]:J_ng:.., c,>:ime proc,ccds by the
ini-t::i_al a])strac-tJ.on of a p]:ot:o_ from ltho e:-carbon a-tom. ,[t v;,ot_]_cl
then dz.L:,=ax->*_-.........t].,-_:_, the _::e_:ultin,q., carbanior_ e.-,:_sto_....... in rc'_onaz_c.'e \,:..;,_n
t,-.,_.-,-,._.q ,,.., bow{::-,>ex' " ] able c]]emice_]_an o::imino an:;_on _,.q .... __...,.,_. 140): , av_-,z
ev±G<:,_ce mndgi.catrc:,_¢_._ t",,,-t_ -'-t_hzs' _,nion react.s \,zJ.th cat.i.on._ o.t_]_y ak
Oil tl _
,2( .-'_ _2C-._- _ R2 C
"-1_ /i
, (u-', t}2 ....
',1
(:_0)
"73
OX:_gO.i_ a:@(1/o,_ ]_£hrogor_ ° A]] ena].;,.._._,)t]s ........-r-,.:,,',,-_._<<,..,.._.:"-_"_',_"s[-]uc-[.l_]- : for• • . - ...... :j ..........
the i_irdr,.o:<y :r:ac].i (.:,::_]_ (!:, ]_5 ) 4 _ -_ " _..... "_ \,'i:..C-,__ t._}lC- t_J",i_Da]rc.'d _-,,-j- Y. (]C,_s:i_-[.y
xes:.cles o]1 O"".,._7"goT.,_. ,_ al_c]. TJ:L£)_-ocje)]. a] ct Y_oh (,_..... c".-_..:.s..:(pz_ ttas boen
- r[',l ] . , 1") " % -,1 _ -'
exl_c;;._F!c.d l:.o hhe in hc-:,:-c<-:h:i_r_(_ r.,J I-re)so]<-, L(.-" a.u:Lo.-_s / ......... ,.,,_. .tNO
Ava:L:lat)l ,-_ intf:ozs_.'.Pt..:.u,_ c o' ........... (:__.L.]...... th<::_ qtT.ostio_3s o_)the............. 3
quesLic)n r.,f a]_ky]_ation al: ..... _...... . _ O<.:t.L_.)o.u A}bpa):cl]l:].y _ -,,, 7 • -• _. . ? j£!i,:" o a ] J:]-t :co r-',c_'
c:ompot_y_Ss of tl-e tyi",_, lt2C(,_,,_,) \,_!_+a]:(:_ R ' ]I" :"" 2 ),- ar(-_ liOt: ">_" .... A
,:,_-t.]..[' },..'L._r''",; (:X amp ].e os.<: c)>: :] r,'<e _ntabl' ].i ty wJ.th rcsp,ac I.: Lo .1'....._.....:> l, .LL'" ]+....(.,,:.<C.J
.., ' -_ " ¢ ' , I J.(.j..,": I _ l:l.,qO7]!"_:C .i.S J (_I)7).(]. ; 7] k:,7.L .]_l]O(.).]...)l]_::O>:].77R':) :[t._; :ffC.LtC: ' - _ " (3, (l
])e:c_ :,]_o;.:.....r.._.-_-<_...... o_'>I.-id{_L:Lc)n -Lo the- (:or]::c-_sr_r"."d-:,.._;,_, ....r, 9 3--nii::rc,inc:Jc;]_ .....o _ do T_ot:
, , , <.- _-,-,(.._. . .... \T-{P.e.]t]:[::C: t:;}(_ .] F}-L(_]_R_c!:_C:[].E,'.(" Z (D:_: a I]].[:.]:c)F_O 3.,.)o ...... _ (oc{%:ILt{:Ao)._ ] z]:l _,
7[n d G_,-:_.:] 3- :_':i ........... : .......... L£<.;,-,,,) _ J,C]_)] (:'.<_ 2.T6-'- "di_].:JzO\7:::). c.xccTp-L i:o '< .... '........ (..;.!_ L ;.JJ l') C'.,"[_t)i][)_(]__
• _- ]1- "k'" ......... , []--_l LT"( %r)>')\']'"'O] (:,cW}](']:C t]lo- :tL'].;'-qq l:.j.L:LrOgC;l] C ;.:'t.r:"]: i (; S a ,-_t ...... :.... }.LLI_.I')L ........ L.Z ......
• _. .
i.:.i c- i. ]: £.lL! t.(,_:J.-V(ff _]. .]_-] t:'ci ....']i hcf. g]L'C!(:'.]l C;O].C) C C)l].... ] J.b(:!k.'-:!_tJ.orl :[:X:C;L:L _ " ' " ,t:-',__[.lL,q _ ....
.......... " -- " S:i._.:{:.," :i ,,',: o " :,_ 4 SO'::tcP.LJ.C:_:ajS({]_y (::}'_,1__,,_:; : ,.._ .ye] lo..:, p:..'.c:.°.u:_:_.,.!.y _ _, ...... ...
ox:lmino-py:,-:_:o]. ::m:. _._,:" s hru(:', _!..:-' (238) (e.:iu;::tion 2.,': 2) .
/" --- /3_;7"-....................r'-_°2l j ...............;,_o::.... 1(__.] ,,i -P,0 -- ....! I
IN
(]4;i)
=:NO _::0 St- ................_c_Ii............../! -. li "
..... =NC>H..... ': f'" I
• f (:La2)
_//'L.
An c-,r1_-i]ib::it_:_:_ ] , :,i: ';,_o.(::.t_ .(iL _2".,_CI}i,..n:i_L:_:o_;c]2!-:c_no]. ._-'--'-,................ " _.,j._.i. []_C'.
l_eSi .r!_C Lj_V,::" _1.1 il]Oi] r-:,....... ):,OI_C)[j l[:ii_ j c \._(._l -L ( _'I_.. ;_]_].__ ........._ c,1-_ -:, -l<. .[i1 S()] _....,. c. J" O.]_ .._'_,
J:_--r._ii::ro,,.::opb:_:_.Jo! (abortt:: ].5%) u__.,c] ).£...]:Jc._:,oc_.c_:k._cu:,o _L:<)_t(;>:i;r_c_, (_d__c:,ut:
85%) e:L_e dct:oc,..c..._ by _:_:e]_y:.;:;..,_ o£ r] e(:t_:or:-_c_,j: ic .....c:.:: t. _:" ( 2 .;:'_ )
(equation ]_,t3), The J_soi:?_c:cs a._:,:_ :i.,_;o]._'cLed :i_n two c'.:vy_L_:_ll:[.r..o
fo_:_m_;, cm,_ i._- p:?._lo <-_-_:.-:,_-_ the c_t]_L_]: j_- co] o):]_o_s A] _,:_] j_r_e
soluh.ions gJ.vc,. _:,,. ]:c_r. ..... ._:;]_,.--"gkt'._.!_c().].o.r. A _;.:L].?,?,].___.:brigITL zc.c:.
allji(i)_] \',"[L,[: C)])(/u_J _IQC': r:r'," ' " Ill() r [11":,'1 "] ._ 2 .............. .__..c.L:_-c_.__ O:: (.',,: L._])........... o ar;h_'(_r]c]o (')AO)
(e._tla_[:J.o_ ].4 4 ) .
NOIt NC_) NO NO
'- II+ "/_' """ -'" "" -"'" " "
3,. =-, z.!l " ' ..'.-J l ' ..........;i ii ....io o o 0!i
( ]. 4.3 )
NOi{ -"-
./c' _ t... /c ...:. ,/.c.N0
ifiO _ O_,
(l a)
3. Nit].-osoa]to_;_athj_(; amine z\,,_Jthc_]TJ,ons
A co:] h?ziL_ut:J on f :co:t_. a ]:c,_:o:]_m (::e >:a,:'_L [-o -,-:Lo"] .tc:_ .>_'_._u--r- • _:'_t,-"__-e.
'_-'::"L;!.Cj-.t_fL'C[ t.o ].]):C ;; T: . -'['J: '--;("CO'_-3(];,i"'_ O.T!(]. ......... ' .........':> L L . _ ]i [L)TV iD'-o!:l] ')0!I' ] (} >('1,:.]Yl:{;OI]d]' .......... u :--
_.O2_"_].V,:ic , VC:2 ._.: , .: ......', q_-=.......l /'.h) i F: ]_"C:?/i ;,_ :::(" ,_11. r,:[-, __i _SJ._i!J_]_i?)? ():.L.I)>,Z:!:;:;]_C)I%
-g-O'_" ][!(!J.?.): [L" :.'. ,] :?-,:T.q'i]q:_ C:[ C ]. ][ , ;:_' ; ]::," ]:, ]_"c) v :[ (] (" .% _.:t ]?.:!_: :c .r:........... . r.,]]
.,./).,,,. i i
-, f.{it_R 2 .fN R 2
......c.... ctJ(.L a_L]'.:j.].o.'-].o__<_ (o,'._rtT;:_. s0.):_)_!._:-:]__ i pc'r l':C;&C[t;t C)YI:; :,,.;_ ,.:n._, _ -.<c.>, c_;]"! ])=7<-, -,c-,
].46, 147, 14o) artc:! ..... ' ...... . .....<_ <(.._c.?...l,.<:> fo:_: -L]..t.:,. h:Lcjh d:l_:,:3].:._ _:to:r_-,.<:_-:!_,,.o:[-
p--l:iitl:o::od:i.r_t©tlk.y.].<:n_.iJ.J.]i<._ ({_] f , }?. 22(.)) ,
NO NO}!
I/ 1t"1- ,i ....
!\!" ..................::' t,,%
" f,i" i,,, ]
ti it
+fTR 2 .INR 2
(I,7- ::i)
---. .._.
NO NO[I li
0 J!
i"
+NR. 2 0
-I- :-> ]'7'J\2 .k ]
(147)
1']O NOR
II + II
............>.!i ,) "i':.....
b ],, :.. >'+ )( -I-
(1_0)
76
Alky];-'c.i.on (o.q_a.[Jon ].48) oc_curs at o;.:yge_, r_:d:k,o?: hhu_! cut a,<,,:i.nc
nitrogo_l (see eq_]at;;o>. 145) as i.s seen from th(:. prodoct which
o.; ]].ydro]_sJs giT<:s a dial]-_y]_, r,Rt]]er t]_a'] a -[-):ia]_]cy]_,amine (24])°
It ha.s been r(::q?o:ct(i:d t]2u.[: acylaLi.oJ), also occurs all o:.:ycjen (2/.2)
(equat:io)). 149). In contrast nitvosop]',.ono]s.may a].]:y]__:4-,.--_ at tzhe
NOI_ NOCOCIi 6}J5.
"" "- C - ._-I_-COC J_ /"'" ....
II ti {' ,, i!
Ii It-I- N (,'N.,...3) 2 4. _.,'(CI]:j)_ 2 C1
(14 9 )
p]zcr_o]..i_ (.*';ygo. p. RC:. J.S S£CT_ ;i_n ,--1 - . - '• " " _._)c:f,or_:::rl_iof of 2,4,5.-.[-:r:tmethox_ .......
]lJ.t-r'O <-:_],_']!2.('}.._O :[rOB] 2 ': " "-- ".......... , !,,---Chtu. 15tho>:y-" _.'-b.,pd;r;c)xy?_ .-;.Lxosob(r._1}.x(!::}:e and
"......... ( 2 ', , .._,=...............d:b',l,::tj.y.L ::.;t_].J ....... _ /!.. ) t,-_"-_,:_:-:i_on ] r:,l'_)
OH OC ]t3I
" ,.. OCIt 3 ) c'O /" ""- ()'_}_2 '-_'_ " '" ' 3/ "_
c:H..o. / I ci_3o3 --...i/.-' ......i/- -_
NO NO
(150)
4. Activa-t:ion of other su]Dstituen-l-s
A subst.ituep..C other than hydrogen may be ].abilc at: the
o.-position. In mild acid troatme;rrt, 2-.accty]_--.2--_.-].trosopro})ane
].one,<, tb,'!,,acety! gro>p (244) (eq'o,atSon .I_5]}. A sJ_-i.]ar reaction
in base b.u.s bee._ ]:cpo-£Lcd for the b<:.r_<o];l _.,;_a].og (245) (c:quo_t-Lon ]52),
77
+
(c}_ B) 2c (No) coc}_: 3 . Ii__>
H20
(CH3) 2C=IqO}I + Ctt3CO2tt(151)
OCH3 >C6H5CO# (CH3) 2
No C_3oi{
C6HsCO2CII 3 + (CH 3 )20=_10H (152)
The :cing-ex;}{_,nsion of 2-alk;]!-2-rt-tros'o-!-:,.nd.a:_..oncs to isocarbostyril
IIO
acid
i
ok-
base
/O '''_'_' /<"''" l"
( /-... NOH
An. incompletely understood acid hydrolysis converts 2-chloro ....
2-nitrosobutane int.o a mixture of the oxime of butanone-.2 and the
Y[IO]]OX j.xle _-'-c,_ butanedione-2,3 (246) (equation !54). It has been
C1 NOII NOH1 acid I! II
CH3CCH2CH 3 -)_ CH3CCH2CH 3 + Ctt3COCCH 3NO H20
(154)
. /- 24- •suggested that these two oximes are first formed in the pho__ol_L..zc
tra.ns ...... _-"., forma_lo.,.l of the geminal nitrosochloride into an imidazole-
di-N-oxide (246) (equation 155).
78
C!I
CH3_/CH2CH3NO
!
CH 30H
(CH3CH 2 )20
C8H14 O2 N2,,!IC!C2H 5) 3N
i
O
I I\
CIt3k'Z<. - / \CH2CII"N 3
I
0
(is!s)
A].iphatic carboxylic ac.ids in oleum a_:e nitre)sated a-t the
_"'po_li%ion and decarboxylated on trea L-.mont with nitrosyl .<-:'.:LG.:EU:r.:iC
acid, cf.I_.].0, h:'hen _-hydrogen is present decarboxylation :[T:_:oman
OXime wou].d account for the product, an aldoxime (247) ; but in
the nitrosative decarboxylation of an a:comatic acid dec.:.irboz<ylat]on
from a tertiary nitroso compound is proposed, cf.B.].0.
There is at ].east one exmi_.ip].c:of o,--halogen dJsi:'!ace_.:_ent (248)
(equation 156)o The electron..w;',.th@._ravling pow<_-.rof t1<e >itroso
(CH 3) 2CINO AgNO2 7\ (CH 3) 2cINO
"_ Br "_ NO 2
(-l.s6)
grou<)_ has been demonst_-ateo." with __p-br°m°nitr°s°]_enz- e_>._,_-_ which
reac-ts more rapidly with silver nitrate solution than
p--l)ro.__:-:,{t;co}_c-mzene does (2:]9).
5. i:lc,duc t.-j 0-_
...... .. ., < c:,.J_,.,:_ ( ,'.!' " ) ai_dOver pI<LL.:.n_,:. (25£) , _Jic::?.:__]. (251!.) , p..--_]" .... ._,_.
O[i},r::F C.tt[._t L,.:';i [..:/ t P'-]-.;i.""!"&"C3-r' _i_:] _'.::£):.i.tLL;LL: r;] [r" _<;_ ,-.t ........ -t . c2
(iOT)r_fL"C__.- .[ 1)/ XRt_'(!t_.C,Od '[:O ]j,}7.i_12C}Ty L" ;; rJ.:L',"£, . )% ]7(-;:]1;O1i"[ O.(] __i_' :£r' ,:-)]..,.. (. [;(':
redt:tc-h_ on with +_-.,r:_...,.........J.o:c:m,/t-L:Lo_ o-i! cyc o] Lc":y. ....1 ll),.,,S_,:o:,:y]_a,_uiip.(: :_tro)_',
n.]%r(_socyc_l_o}.io}:al,o (I_IR£}: OVO]i' a coF_-Iv_-[7. :is £",c'_'")1 " c, na]_ (?r:/-,-,............. .z ....... J.......... ) ) "
_,].(_t._ ] _Nd pc, (_, CO.YS)-] !?.[\£2C):t_5 il]].r.i (] }). [:-£t-] r) ]_c&'/'q:r \ra ].¢:_._ c _r,:,-l _ ]
'-' ' ' _ .... -''J:ig LNi!.LI}Oo C()FLtl_tt,;.:,t '.°D.ILS D_D(.) _i.V(" ]I'OC]C_.:L]_,_)_, %0 [.]i,.; C()r.LCSL..unL'.!.
('.:X[-t.'_.pIC,.; iNc].U.d@ hJ_ri ff.l_ h},d:,::oc}'.,]c,._::lc _-:c-.S o:c :-::L._nnoc.,s (."]-J I c) ;i; i. c] o
(2a,., 2 .... ) or zinc "_ ' . Co.,...L, .,...:I.,:,<..,<,_!;ycb:(.u::_. "L_ a_-,___ ( ....:,6) oc:l_.1o:r]("
_: c..:L(,< ])O[:]i -'r" ,_- ,o..... L. /.._.O.:, _1!](] ]]._C].O_(;]]C'._L-O_; 1'] ] -L}/O_'.c)bcI.t:::(}:I£: t1.C) __:OZ1[l C}]] 0]-'(}--
sz()x'y'b£:li>:( _](:t [.ziLc}t] ():iT;()[ ]_]i].iIl@ _ ( '_,-I orc ,".b .... _yll._,,-t.i..o..tzl '. ............. J ..... _. .... _._ .......... _z ..;11K[LN(! <'-ii1d
o LI.',c:z.......... -......... < o1>, _,. .,.. _... (257) SodLum b:Lsu].fit:c_ rc_k_cc.,._;' .._Pn ............rc,sol:c:,_,t,,"r<>
[O p--.l-o]_ii/:J.r),::_ _:'_-_cq, a'<-_, su.7. f01Ja/:c-:] ..... • ........._.. ._......... t._._, .... ring (258) I-tyd-,oJ(d±,
c_c _ c] -_.ra.}-l,.<_ _- .... ................ .,_o; ]:_,.d p-..riitrosodil:_,'_L!-._}*] ai-/i].5 :_)e i ni o p--CTL 4 nC_; c:[.]_yl--
anil -lP,-_..... by _.;:irm,!tai:eous re.duc":_ _Lon...........cJ_n<,..(. c._k::thy] ;ti.ion (;_':5_s.,) .
OK:L(]<:,joi_ .......... o.L vali].]_]_y], c,_tt...) .... I l-o \,art].l] ;_] lii;Fv'_. ];,.9 .],ly_..... ....t.:_._l-_, c_bc;-.!l-
W J. t h p... -, -: ......... ' ........ . .... ., . ..,.... . i ..... L-LC.,_ 'L,L.!_ r,'.c: .!.t I J__HI :L .I_i l] e (250) (o(lr,_ i:].c._l .Gr)'7) _:']ic'.>l'/]t:}z;xuv."._c
O]t N (cN B ) Ot{ N (CIi B)
./.j... 2 ! . 2
1()i I£ I(>iOOIt 3 ¢ "'k -- "_ _ OC]} //*"''" .....
q-- .,/) ............ ,' ,_1 j -F
I | I ]C1}2(}}! NO C}_O NI! 2
(!57)
J
ac;.1.o (2Gi) L'n(l ]'7--}_Lu_r,:i_].-1 ,/ ._. , .......... - u:i_,.:,.7{rr>,_, ,':_o;.:; _'._: :__ '-_e- (2C_2) _c] r.-_o
............. ...... "..... ' ....... _: tJ :i]( (r:,]u _t Li c>n]:_"c]_,,'r, ).,__j.t].o<.c;rl.i_;;,t:]j.7/_le.r-_;i.l iY_> Lo cJ. i.d.s__,,,:_.,._ ..........
]..r:_'3.) }:,c::.::. ]_/_.::,::-t_._..].o (tc:i. r:l... Y,-: cj.lb.t:,L,.. [}_r: s_]: i.:!7C.',r:O OC'I__,r)_I .tC]. L-O [-_]t)c:_
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7. Oxidc, t j.on
Nitric acid (297) , hydrogen })e:_/oxicT.e (2o8) , po._:mang&-tn-:,-te• -" . ,.{ , ,
(299) chromic o.',<ide (300), _r .................ac "_,.....' -_r_,'_"t_7 st_l--_ ,-, i.d. (300) , (_.a_,,an.Ll ....
t.,ersu.lfate (301) , l-_ypoeh.lo_:ito (300) , 1::e:co.;.:y_:,x:et.ic _,cid (302)
....... ] r7 ]-, f:_]?e._:o×:ytriF]uoroace_ic (303), c,_o.,,__ (304) and ot:hc_: reage.nt:s
oxidize nitroso compounds to nitxo comL<_un<]so _..... _-. i_l:: react..]ol_t
_J _-- I J '.:..< <.*..L..L.y .].]'[L ].. "k _.;'. _ t..k.; t. _.: ]. t. t (,! J_ ]' C-*]...l.]J.. ]. _:_ _ _t k_ (1 [)* _. ,t:.'..t <._] l l f I. _, .. J.t.. J / ..I.. _..h _.._ ;__ <.J
derivat:ives, o_._en 1 -'_ec_c,.<_ to sevexal p]"oducts In s[_onc[ ]__].Lz] .....
acid, n] t:]:(-)_: obc:n.zene is t:t'O.]lSfOltl-l(-_d J.l]to _.:i_t_:o]:,.e___zc_z)c._ .].:_.---dJ.n.it.:to ......
") _; I .... )-_c" ,'-1 2 4.-d_ nil:::co,-t.J-_:.:,:_<)] . p-i cx:ic ac':l<!l andso]i-c}:nze:rle, I: --.i ...... ( ,:......::_.,........., , __. : ....
o>:_].ic acid. (305).
Wj. th f zst:-.o'"?lc]- de]_eqde]__ce on each react_.nt, nJ..tn::o:::o-..
_-'Cbenze.nes are o;;:J.c].i'_(w_ by pe:coxyaee_.a_..: acid in ,,<_n,,n,,9 eth;_no.]_ t:o
co:l:_-eg_w x_<l.q];_:, _,_._.<( b,_nz,,_.n,:s (302) The rcact:io_o, is acc'.e].({:_:_-_::t.ed
by c_].ect}:on---rc_]_easing }:.-_--s.._'1;_tztu=nt._,-"_-,-_ and by......c'hangJn.g.t.]_e sol•vent
.I .... 7 I " - " " 7 ........from oth,:::-;o]. _o water, a]_c- J.t J.s (]eCole_< u_(_ by r,]_.<..... t.._o_--_; "_'_lc]lc_za.,,,,±ng"
]_i_-sub;til;uenL_ ' , Al:.',t,a.x'ently a gzeater acidity in i:t_e', p<:.:ro:,,';y acid
ra " 7 " -C" _ ":_ _ a_ "i . . _enbanc(-:s the .reaction; p..rox_c],].o__c,,:_ce___.c and Ca_-o's aci(l each
oxidiz,a nit]:oso benzene more rapidly tha.n does _,--)_- _ _-'p...zt ..y....e_.zc acid,,
A mechanis:; consistent with these ":acts ca].is for a reaction
Jr_JJ-J_-.it_d by a nuclecpnilic attack of the nit.).:oso nitrogen on the
outer o.',.:ygen of the e)-o_-,,ac_d with a t_-an,_ition state composed
of the pe)7o;-:yacid, the nitroso com]?ou_._d and a ;:',olven' molecule°
ii m
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of L]:_.._ ,<:;ul_.-t:_ _-,-,,,-n '- e:f..l--c,.:"...._ (p - 1 5 o ) r ".,............... {:]1{_ acEivatj.oll ]: ................ S
, ..,].)for :c_it:":c><_c)bc':r_::':c:ae- (1!:a J_6 . 1 ]:ca,]_ mc;Je -:1 , tD."-"o---z2" cai :mole -].. (<c:g_ ,
and i:.I:)<::_ abscn:.,ce of acDj.(, cat:aJ),sLs.
The resisI:ance of !_.-l::riflc[o]::omc_t]%,]nit ..... _ '-, ......L-£) _o-r) 6!]9._:,t_I] (1" L 0 _Td.i.Ct
ox:id,::.hio:rl by .'[:>(-!:NMaN.cral'l,::t%C, ,,. o.]:""(-"r)ro;.t;<::_{ c, or ].t,,7d.,_:oqen pe.i:o:>:ic;.(-.::' jlJ
....... <"' ......;1"4 ""C" . ......acetic acid (306) is noh typical a;,(l give;, <._ a ....Lz.,_..,._,..._,_:.jconira:t
wit-h .....the fa,"i].e oxid].-_Lion o_,.: the ] _.].t:.:t::o :- c) group Jn 2-- _,,F_-_--_I___..... c ,, t, -- :,"--
n:ii.re,_-o-4-.am.l.nopyr].d:l..N.o+" " " ]:.,y hyd.ro,]c:_h ]-_exo:4:i_de. J.._1 su].ft_.rJ.c <.,o..cd:_-'-'• (307)
(equ,;:i.t_J.on ].70) ,
i 2 ,t?
.i"..... NO H20 _ .. ....I f''", '_ , - -- ' /, ........ ,_qO 2
>[ I_%./] it }i"-,. .......,,,ON H 2 SOl., ,- ' " '0_i
"N 70 o N
( i. 7 0 )
An in.t.]ra!uo!ocu!ar transfer of oxygen b:::t:-w<:(::nnitroso and.
nitro groups ortho to each o-Lher i]_ aroma-[:it compour:.ds or on
adjacent parafinic ca:cbon atoms is -t]_erma].!y produced in one
instance and base-catalyzed j_n the o-Lher (equa[:ions 171, 172).
The intermediacy of a furoxan oxJ.de and a dihydro furoxa.n oxLde
respc:ctively may be required (308, 309).
C]_
-/_ NO heat .... _ Ro 2 pi " <•NO2 C]..{ .......J No(171)
_J
t,
-a
O Oo b
Oil
..... " t(21: ......... C]<R2_2 CI_R ............ 7'
NO NO 2 NO 2 NO"
(i72)
8 o Free " " ".if 6t<tl C_! ] '_-
]?Fe(:_ l:adJ.c_,].,s l: <_J:),,:.[ to attack t!Ic y_it.:t:oso gJ_'ollp j.:ri r-:_-t-_,- in
a ]:e,::_.ction ] cad; ng to the formation o.7_ aD. O,N-.-disubst-Ltu-ted
1- "1 • .
o .., ,, ..............._.L, ,<, ,' C.'{: # Y-,,,"n "1-c'{ -F ] 1](_-cO]q ] S ]'OS D. [, t.._lc..,],_, cq.l'!C_ LLV..'O
1T'OI.:i'<:-U.lt_S Of nj..[-r]C..... o:<ide ho.s beei_ isolat:.cc._ (3]0) ; ]:.o_,;<.'\,¢-*r, Lhe
react::5.o:. _a.lly p,c,c,_.,,x]s at !:,i(3]_<:-:r te,a-.',eYatu,"c:,- w:i. th L_._ rc_ .:;,.
me;_i... -'-<c.) _., ,'}.5:_z.o>:.U_.m. nit]:>.i-c: a>,g ,.sbL,:.ccja<_::-L-'" " ........ decc':u,,;?c,r;_:i..t___o.r:-' (.)]_.L)"-
(,;_,u,;:_ l:i (.n, ]..7%),. C :- .Lc &i >c"' a.] J.]p]-,,::vL:]_c :_l.i.L:i'_,.)sO" co>_:.,,.,'unds., coY!l)[n::e. ._ .
2 i,! 0
CF.BI"X) .................. :) CVJi_"'h;:_O"... _ ............_ C]?_N=I:_O;vO._ 2 ..............':). C[, 3 -t- N 2 + NO 3
b]O
NO.. 4- ]:<!C: ........ >. ?r<Z- (.]_7B)
w:[-Lh niLric oxid,:" ho form co:<r.:--spc, nSing ni-Lro c.:o:.rtpou-:,.ds and
nitrate esLe.n:s a.!onq. _ W'Lt.h t_r.aC.,:_ ,...mounl_-' .....-_"of nitrite_ es_cz._,F_ -_ (312)
(equa.tio:,:_ ].74). P:<esumably, a c_._nmtroso].,._,o..ro>'.:l;lam:!.n<_ and a
c].J.az ,'-_o._zL._.,_.t:.._-c_ are 5.ntermediates
89
I IL_O
l
25_50 °
!--6 arm.
"'"_ .... "_0
I i .....!..i" ""'-.. (-]bX). (" 2
+
"_,] 0_0(],7_)
,8-.-L]C[;1)t..]_.0]. is [..Lc_.,l_::,_[O.__,,.___d il_tlt.O"...... _! (_.J_-]ZOO.::J_C]t'. C)]_ ;_.r,r_q...........-i r)n _.-0
ILlh-:.. ]Z'(.! O.C'.. 7i.C)),] ri'li}[]'[.l_l]__" <{: in _,\'1]'! ......."]r',]] ] .. t]-i_'h ]-'02;().? _!].[ Z._r. (:]]....].] ( \ 1 JIF:_ "[.JL.......(.{rZi _.............'.__(] "_ "P-i "I" 1'1
njL:<:i c c3.:_.:__...;{" ..... .J'n qy:t3]l',," _:_',_, cb'l or-j d..:::: c:,-'- low '_{:-T,,)c_c_: L uv{_ (:,.L °)"
(egaai::ic, n 175) ,, On s:i.............i] _._......,....,.._,_._,.4-,-c,-v-,,<_._.,_-.=_,,_._("i_::,ae1:Iw];:_ni].:in(:..... :is i.;:cuns-.
:I:o:tr,. d -{a-r_ i: < T" _:'i-t,'o ....,:_a._.'J}:)...dI.]_o.:.;(.;:_]:[_>._;os_.tl._{/'.... " ......'
_'70 ,:/C _ H O,q..._ .,." , __.(I"7 ....-,
o._,!c'<:<:c_.u_._ /£_:;-7 "..................................;-- Id
li 2
"{ ]_C::C(" 4] c (175)
Many,. but not al!,. radicals readily :react w_4..Lh Lh,:" nJi:zoso
group. Nit.rosobe.nzene has an e'<ceptio_:_a].ly _hi_,_h "methyl. affinity"
(ca 105 ) (.:,.L">'_) bt:vt has less tendency to re.act "_--. v:._.__h trip]l c'.r_.y].me tliy ].
(315). ]:i: has been zeport:.ed that nit].-osobc_nzen, :-'. reacts v:ith.
tr:l:phc:r_.y].met-:hyl :i.n benzene to prod_ce tz:;..L:J::c.n:flcvr]:,:Lr_o], and
P_Ip. -'Ctlt....._].i).lv_sly].ilb0]t.]]]?l._t?O]'[y]D(,yi:<C;"_O (3] 6) . r.[_hq' .kO-] li!,l£]O]% of
tri.raethy].)ll"d-_coi.:l'].a._:Lne f:,:om n:Lt:coso..!\eLhL, nc a><7. _.;ethb,]... ):ad.ica].s at
room tcmi,<,_:at>r,:_ has bo.c.:t demo__s,:re:Led (3]_7). i_ c<:nt_:_st-,
9O
ap})._:_r(u._.t..].3:>9it].,<,.)?an O,_:_-di_:[t_:o_:<)],;/4{,;o>'_l_]_s<,._ineno J: a t:r::.[],-ar....
fluo:_oalkL_].!<_.C].,:o>:.y!_miiJ<-: has been dct(-.cto.d dt:tS:i_, 3 [:.]_e
d:J..merization of a l)eicf]_uo:k-on_ t:L-osoa].];an.c: wL:].c]_ r_re<'_.,:_:a]:>].y
procec:ds w].th the i_u:i.t.ia],fo)n0at.j.o_)of a r)Jt:cJ.c o}cide and a
t','..t'.rf].u<,.oa].]';.yl with su})'.-_cque_'t ad,:[J.tJ_o.r_ of e0.ch to _:d:_ u:n<:l)angod
perf].uozor_it:l:osoa.!.]<anc, of, C. ]., A radica] mechan..f..,<'m ,.,,.-as
]proposed to e}:Dia.in, the. :[."o:_:mat:i.,..)r.L of N..-t:l.:i:fluo_tom<::thy].-]._" ....
fluo:codiimide o><J_de f:c(.'.m e i_-t ]"_c: ]: L!-:e phohochemic.a] or the t}:e.zm;:_t
Y(_,fio[-.[o]_ o._ _Cl-i)'.:_lti(TpZ'(;q-l] t:rosometh_;:;nc:: and tc-',:rc.f ].u')rol!yd...r.a:t :[.ne
(-;]8) (c:guat.ic,_: ]./oj'c'
0 0
f'f2 ,, I I]ZNO ................R-,]:_--I_F.........}:.r..,..,-.L,,.:
-I- -I-
R := a] .;G']-, , "....-c,..: _ ._. ]__C'ii.?f ] <7.(',17C)<!.!t. _7 ]
( ]. 7 d )
_<- _:
The high .........efJ.._cJ_ency oF ])_..-iq;:)'O _cC_r',--[!',-_,],::I]":]iloc,...... aS _:_.
s,cav(:_r_<re_: _or the hyc_roxyl rad._c-al (3_<_ -_,_-t"_,-.:._ ...... J..:) d CP.bO]"_r;"[:_i<_ _._t_L-.;
the affinity the nih:,:oso g_:ou.,) t._::o fo; _ ?:adica]_s
9 _:onoo ]_e ,_3_n.:,
Both. o)_a:,'v.__].( ......._ u,":,,<_ _.:nd co]:)o).wm,:,_",-:._ ................ c,"" r_.:....f:-) -m_:d. in reac[-] on;-:_
between pez-f]_uo_:o<.!efins and pe_rf!uo:co ni-tro:>c, derivat.ive.s (320)
(equation 177) At lowe__-: tempe._.atu.,.e._, po].vme:c F , "- -': - " _-"_'_ _ :_;O]TZi]E,.'CILC)Y ]t_!y
P):,C._(]:_.CtiTLLtte . t)}/]:O]-_S.]_f; ()_. "L,f}'-_ c_........... ":'" ;2 "''-" f- l,..............'_" 1-'C "v'r_ "<.)$('11 di::)]](.F:_,7_]i('.:g,":n'-),
3 t_._. "-_ i ' 2 - 11 ......_ "_'';CI).3C- _.. -,"<: CI' . 2_. _ _ _ .. _.')
"" CTi'2- C:J.:'., ',-' :" r".:,_. "'-?i' 3
9].
and tx"ifluozcw}.itro.<;or>>thane gives both triflt3orc_meth]l
isocyanate a_nd trif]uo)ronit]_<)somet:ha:,_e (32].) (ec.{uation ]_78).
Appa:cen±:]y two o>:,.---z.c-_tidinone:_ resulted from the c'.o>-,b-lna-tion
'-C::O(C6H5) 2(I ` I
0 - N C t"
30 0 °
. _';'-h (IF3NOCP3_, <.0 4(178)
of' d:iphr.:v<l,'lketene and nitrosobr.._nzt'nc_. Pyrolysis of one geve
benzopbenone and phenyl isoc_;,an_:te; %he. o%her v-,.s less stable
and readily dissociated into carbon dioxide and benzophonone
an_i.l (322) (equaOions ].79, 180);
(C6H5) _ C-C=Ozl I
O-NC6H 5
,,.__(C6H 5) 2 CO + C6H5NCO (179)
(C6H 5)2]C-{ :=:O ....... _ (C6I{ 5)2C=NC6115 + CO 2
C6H5_._-O
(is0)
'frifl.u,aronit.rosc_)',,,cL._<,-'_,-""_-_.g.l_ves a i:i adduct v,-:t]-,c:,_].kfl
" (_c_.... ct. ",,75_-hb_d ........azoc]ic_]:boxy]ate and ._v_., a. ]:]. anct a 2:]_ :,'_,_ ' "
._('.Lt.t-'.E C(]l.li]{lO]__lr addY{ct undergoesst:yrono. (32].). '].'he1 ......._-" • -
pyro]_ys._"_ ......w_t.h the fo]:mation of t:cif].uoro: i.t:Yosou_.e.t]lo_o-,_.
._ 1L]IU h}]v] au"._ r](!'.iorma]c'c,nyc= and thc-: Schiff L_.qc o _ tr '_- oxow..c_ =
; ' " "-,el £rO1"c ......... (.::<itaLic,',.] ] {:71) A 2 - 1 e_:2<].uc .. _'_'<,-".7 r_,............and 1:,:::1- 5,1.:: .-< ,::z::z,_.v,:: . - - '-
92
(CF3NO)2 _ C6H5CIb:CH2 ..........._;C61]"CH=7'TCi_"b_4 + C}I20 -I.-C]:'31,]0 (]al)
tr/_fluoronitros,_,h,,,tl_<.,n=.[''_-", c-_and t_z.L].uo_:oshyrerle--'_ (329) also
releases trif]uo.ronJ.i-:cosometharJe on bcatJ!).9. From n,rn.):.
data the first of the 2:]. adducts has been assigned the
.:tructureq.... of a tetrahyd:co (1,2,3) oxadJ_azol<- (6) and the
lat.ter the structure of a 1,2-diazacyclobutane (7) (323),
]!'3 76H5 ]7' ]?I |O<--N CH C H C-C-F" 651 I
3C-N--N-CF 3r3c --.o/ell2 $ .b
O O
6 7
These adducts are, struc%u_a!ly different from the adduct which
ha,'-3 been obta'Lned fro;.:_ nitrosobenzene and styrene and has been
sho,,..,n to be an unstable tet:rahydrofu:Poxan which dissociates
into nitz'o::;es (32!i) (equation ].($/<).
2C6H5NO + C6HsCH:C.g_- ....
C6H_q_O//NC6115O
O
b b( 'I=:;_C6H5
0 O"]" I_
+ C<,.2--,,C6t.<5_-;_ _ _ ( ..... :':. ..... :::_J,..6II 5) (is2)
93
m
10. Acetylenes and arynes
Certain acetylenes com]6Jn).o with two moles of a nitroso
compound to gJ.ve vicinal bis-nit)r:o_c_s (325) (_:_<]I:_ation 183).
A bis-nitrone, 1,2,3,4-tetrahydrophenazJ_nc-N,N'-dioxide is
also obtained from l-morpho].inocyclohexene and o-.-dJ.NJ_troso--
benzene (benzfuroxan) (326) (equation ].84). Other enea.minos
gave similar reactions. Nitrosobc, nzene adds to benzyne in a
more complicated reaction whJ.ch leads to the formation of
N-phenylcarbazole (327) (equatJ.on ]85). '
C6HsC_CC6H 5
C6H5 NO I
-_ (CBH5N (0)=C06H5) 2 (].83)
N (CH2CH 2) 20 ___ NO+ NO
0
t
0
(184)
(185)
94
ii. Thiok_:_iones, phosphorous y]ids, azomethirle derivatives
Nitrosobenzene combines wit-b a variety of doubly unsatu_a.l:ed
bo]_ds connecting carbon t.o a hefieroat(-)m (equat.J.o_).s !.86, 187, 188,
].(]9) ,. bub it .i.s no-t; k}._o_,q"_ _,,_7_-<t-,}_o_:, or not t}.}.os_ r(-;ac;tions p.>ococ:d
with the initial fo2°mation of four-membered.ri_ngs (328, 329),
The cleavage of nitrones by nitrosob.cBnzene (equation 189) is
apparent].y slow since nitrone.s are often prepared by reactior__t
of n;Ltb-oso compounds,
C 6 H 5}_0
Ar 2 c: S -) Ar z_C=NC o"I-Ior (].86 )
+ C6H5NO-- . _-rgr-_
T ) -> Ar2C-..._.6}I 5 (187)Ar2C-P (_61-5 3
(C6b< 5 )3 _?:=N-N=c (C 6_-"5 ) 2
C6H5 NO....................._. (C6D: 5) 2C=NC6115
+ _:2 + (C6t]5).;!-"O
(].88)
0 0
................ \ _, _--:,,1 CRC]_=NC6]T 5 . RCHO + C6,,5,'_--_,..6115
(189)
As a nucleo]phi]e, nitrosobenzene combines wit:h b.enzon:i.t.rile
oxide to produc.'e a nit-rosonit>-ona (330) (<,quation 190), On mild
__j_ •
he_-_.l,.__T the ].att:c_r cyc.'lizc:s.
C-Hr_NO6 :)C6H5CHO
0 oII+ £-, ..
C6HsC=NC6}I5| k/.........."/ C61]<C"N'.'_ H,:. ..............7_") II __oNO N- O
O
I
N ",._/- NIOH
95
(190)
].2. Diazoalkanes
Many combinations of nitroso compounds and diazoalkanes
lead to nitrones (331) (equations 19]_, 192, 193, 194). In the
reaction wi.th diazomethane oxidation may occur and the product:
is a bis-nitrone (equation ].91). The same nitrone is obtained
from the reaction between formaldehyde and phenylhydroxylamine
and from the reaction between diazomethane and nitrosobenzene
(332) (equation 195). It has been suggested that the reaction
proceeds by e].ectrophilic attack by ni12roso nitrogen upon
diazoalkane carbon (333). This is in agreement with the formation
of an adduct between trifluoronitrosomethane and diazomethane
which subsequently loses nitrogen (321). On treatment with
di_2zomethane, the reduction of nitrosomesitylene to the corres-
ponding hydroxylamine (334) may have proceeded with the initial
formation of a nitrone followed by the KrBhnke reaction, cf.C.18.,
in which the nitro-_._e is c]_ec_ved 12o an _:]_dc]2yde and a der_ivative
of hydro>:},] am_;_>.,-?.
96
" (c6F! (o)--::<'H)C6F5NO ........... :--: ..... > " 2 (191)
(C6115) 2CN2,c6F5_° ......................:...... =-_ Cr>.'r_ (O)==C (Crn__)
• O D O D 2(192)
CF., CHN.,
C6H5NO ............................. 7 C6H5N(O)=CI-ICF 3 (193)
CF 3CHN 2 -')(CIl3) 3 CNO (CH 3) 3CN (O) =CIICF_ (].94)- 3
CH20 .)C 6t{5N}]OH .................... CH 2 (lq (C 6tt5 )OH) 2
CH2N 2
(-CI_=N (O) C6115) 2 < C6H5NO (195)
13. Conjuqated dienes
Dihydro-l,2--oxaz:knes are read.ily obtained from aromatic
nitroso compounds and conjugated dienes. The addition of an
aroma tic nitroso compound to 2,3-dimethyl-l,3-butadiene fo].lows
first order kinetics in each reactant with low actJ.vation
energies (14.23 kcal/mole for nitrosobenzen,n) (335) (equation 196).
97
ArNO +............. / II
(196)
dlcn=o wJ_th the formation ofNitroso dJ_mers may combirle with '", _<'
tetrah.ydropyridazin.c_N,N,_dj oxides (336) (eq_Jation 197).
O
..__NAr +0
(197)
An unsymmetrically substituted diene raay combine with a
nitroso monomer to give a mixture of the two expected structural
isorr,,ers (337). Apparently the monosubstituted ].--aryl-butadienes
give exclusively the dJhydrooxazJnes in which oxygen is attached
to the benzylic carbon; the disubstituted 1-phenyl--.4-carbomethoxy-
butadiene gives the J.somer in which nitrogen is attached to the
benzy].ic carbon (338). Nitrosobenzene failed to react with
ant ]i:_:acene (335).
Aliphatic nitroso compounds arc: more resistant to dienes;
2-mei.hyl-2-nitrosopropane failed to react with 2,3-dimethyl-
butadiene (339), however its perfluoroanalog combined wit:]/
butadiene over a three day period in a sealed tube (340)
(equation ]_98).
c 3)(C]73) 3CNO -k ..... i%/ @ - a (].98)
"< t<.. />.
98
Both t_-halo- and g.--cyanonitrosoa].kanes a].so combine with
dienes to give the expected dihydrooxazine (339). The resis-,
tance of both l-chloro-l-nitrosocyclohexane and nitrosobenzene
to react with 2,3-diphenyl-, l,].-diphenyl-, and 1,2,3,4-tetra-
pheny]butadier_e -1,3 (34].) may be attributed to a combination
of steric and electronic effects but a steric hJmdrance does
not prevent the addition of aromatic nitroso compounds to 1,3-
alphenylisobenzofuran (342) (equation ].99) or to tetraphenyl-
cyclopentadienone (343).
76"5 ,c6"5
o :> I L..) i o i• --c /
I I
C6H 5 C6H 5
].4. Compounds with active hydrogen
A compound which contains an active hydrogen may add in
the expected manner to a nitroso group; di.ethyl acid phosphite
adding to trifluoronitrosomethane gives an example (344)
(equation 200). The nitroso group may also combine with
CF3N 0 + (C2H50)2PHO .... "9" CF31NP(O) (OC2ii 5)2
OH
(].99)
(200)
hydrogen azide. From aromatic nitroso compounds the corresponding
aryl azides are often obtained in good yield As expected,
99
electron withdr_:wing ring substituents facilitate the reaction.
In support of both a linear and a cyclic pentazene intermediate
(_345), it has been shown by isotopic labeling that the two outer
nitrogens in the product azide are derived from the outer nitro--
gens in hydrogen azide (equation 201). The_ reaction has been
extended to the preparation of _-nitroazidoalkanes (346).
0Ott
ArNO -} ArN-N ArN=NII
-N 2 O:P
ArN=N01-1
+ +
ArN2N3--> ArN=N-N:N:N
/N= i -N 2 [H] N].5).....-_ ir-N ...........i@ ArN3 ......._ ArNH 2 (._o (20:1.)m
_" N=N -N 2
Nitrosobenzene is feebly basic (pEa "-_-" 0 at 25 ° in absolute
methanol) (347) ; neverthele.ss, aliphatic and aroraatic nitroso
comFounds arc; sufficiently nucleophilic to form adducts with
P_-to]uene sulfinic acid (328) hydrogen chloride (348, 349, 350)
and hydrogen bromide (349). Presumably the adduets are hydroxyl-
amines (.equation 202). In one instance a nitrosotoluene was
transformed into a cresol by mineral acid conceivably by cleavage
to a nitrosyl halide followed by diazotization of unchanged
nitrosoto].uene and hydro].ysis (348) (equation 203). This agrees
with the demonstration of the reversibility of nitrosation at
carbon J n whJ.ch p_-nitrosodimethylaniline _,:as produced in an
alcoholic hydrogen chlorJ.de solution of D-nitro<od[_ben',lamine
and dimet]]y]aniline (351) . Concentrated s_"_]............fiur_,- (352)
• 3-00
HX
ArNO _--_ ArN(X)OII (202)
HX
ArNO ...... --_ ArH + NOX
NOX HOH
ArNO ---_-_ ArN2X _ ArOH (203)
hydrofluoric (.353) or peroxytrifluoroacetic (303) acid may cata-
acid
2C6H5N 0 -_ p__ONC6H4N(C6H5)OH (204)
condensations occur with o- and m-substituted derivatives of
nitrosobenzene (352), but more complicated reactions occur when
a Substituent is para to the nitroso group. From p_-nitrosotoluene
in Concentrated suifuric acid in acetic acid, dimethy].phenazine
oxide, dimethylphenazine, p-azoxytoluene, _.-azotoluene and
unidentified compounds are obtained (354).
Phenols combine with nitroso compounds with the generation
of a new carbon-nitr0gen rather than a new oxygen-nitrogen bond
(355) (equations 205, 206)• Ring-closure to phenoxazine derivatives
may follow.
COC6H5 _ H5
--h/OH O!i
C0C6H5 _'i..... .,_Noi
ttO !0/_ 0II
OH
\
(2o5)
].01
N (cH. 3) 2
NO
,,,IICI +
Oil
..)ON
OH
4Y '<'7 _1 f2_6 _,
There are at least two condensations with phenols which have
been developed in qualitative detection of i.he nitroso group.
On treatment of a nitroso compound with a one percent solution of
resorcinol in concentrated hydrochloric acid, a blue-violet color
develops which after dilution with water, and extraction with
el:her, gives a red color (355a). In the other test, C-nitros0
COmpounds, from which nitrous acid is eliminated upon treat-
ment with concentrated sulfuric acid, give Liebermann's test
with alkaline phenol. The nitrous _:
to give p-nitrosopheno]., which cond{
give indophenol; when the product i:
blue color of the anion appears (35[i
' reacts with the phenol
with more phenol to
_red into alkali, the
(equation 206a) .
OH
NO
ON,
..-
OH
o:-: k£)........./--o (206_.,)
8
102
15. Complexes with metal salts and Lewis acids and metalchelates
Certain nitroso bases give colored precipitates of the
Corresponding ferro- and ferricyanide complexes. For example,
P_-nitroso-N,N-dimethylaniline ferrocyanide precipitates in
red-brown needles which appear blue by reflected light (356).
Sunlight irradiation of a potassium ferrocyanide solution with
the formation of a complex salt with RNO of the type K 3
_e(CN) 5 . RNO I (357). A similar exchange reaction between.--.A
i
_e(CN)5NH_3 ] and RNO is brought about by sunligh, t and isNa 3
accompanied by a color change from bright yellow to violet or
green and has been used for the detection of aromatic nitroso
compounds (358).
Complex salts from nitroso compounds and certain metallic
halides have been noted in several instances. The green solution
of nitrosobenzene, when mixed with an alcoholic solution of
cadmium iodide, slowly deposits very small colorless crystals of
tl_e salt, (C6H5NO)5.CdI 2 (359). With bismuth trichloride and
P_-nitroso-N,N-dimethylaniline, a similar complex,
2 ._P-NOC6114N(CH3)2_, 3BiCl3, is formed (360). Yellow amorphous
COmplexes have been reported for 2C6H5NO.SnC14 and 2C6H5NO_TiCl 4
(361). By the direct addition of one mole of p_-nitroso-N,N-
dimethylaniline with one mole each of various uranyl salts in
t
103
suitable sol_vents, amorphous colored addition compounds are
formed. For example, p-nitroso-N,N-dimethylaniline uranyl
nitrate is amorphous, dark yellow and explosive; bis (p-nitroso-
N,N-dimethyl-aniline) uranyl nitrate is orange-red and also
explosive (362). Attempts to prepare similar salts from
unsubstituted dimethylaniline failed.
A i:i adduct from nitrosobenzene and boron trichloride
has been detected but not isolated (363) and a 2:1:]_ adduct from
trifluoronitrosomethane, perfluoroethylene and phosphorous
trichloride has been isolated (364) (equation 207).
2CF3NO 4- C2F 4
F F
c13__>c 3i icF3o_p/o,
C13
H20
H3PO 4 + 3HCf + CF3_CF2CF2_CF3 (207)
OH OH
A nitroso compound may be completely decomposed on shaking
with mercury for a day (365) but nitrosoacetylenes and their
mercury derivatives can be prepared from the corresponding mercury
acetylides (1366) (equation 208).
NOCI
(C4}]9C--C)2Hg _ C4H9CqCNO + (C6HgNO_]g) n (208)
i04
Chelates of nitrosophenols and metal ions have been adapted
to analytical procedures and are of wide importance in bonding
metal dyes to fibers (367). 'i'he cobalt chelate of Gambine y
(]--nitroso-2-nap]ithol) is a representative example (equation 209).
NOHII
Co +3
.-)
/o
N Co/3
|f ! -(209)
The sam.o nitrosonaphthol combines with dia].kyltin chlorides
without chelating the nitroso group (368) (equation 210).
NO
(CH 3 ) 2 Snci o0
(210)
In the prese.nce of acid, copper combines with the rLr)g-opened
isomer, ()-dinitrosobenzene, of benzfuroxan (281) (equation 211).
-7.0:3
+
C tl
.>H +
(2 structures)
O-- O] + ll+
N,_
-(211)
16. Terminal methylene groups
Certain olefins which do not combine with the nitroso
group to give oxazetidines, cf.C.9, and have hydrogen attached
to olefinic carbon may add to the nitroso double bond with the
formation of an N,N-disubstituted hydroxylamine (323)
(equation 212, 213). The reaction in which three molecules of
CH2=CHCO2CH 3
CF 3NO/ CF3_C]I=CHCO2CH 3
OH
(212)
CH 2=CHOCOCH 3
CF 3NO
CF3_CH:CHOCOCH 3
OH
(213)
106
nitrosobenzene combine with a C5H8 unit in rubber may require
an initial addition of this kind with subsequent oxidation
to a nitrone and azoxybenzene (369) (equation 2].4). The bis-
nitrone obtained from nitrosobenzene and _p-benzquinone (370)
(equation 215) may also require initially t_{e formation of a
bis-hydroxylamine since azoxybenzene is also produced.
CH3 CIi3 N (C6H5)O14
-CH::C ----C--CHe-f II z
C H 3 N,--:>O
C6H 5
+ C6H5NHOH
O
C6H5 NO
C6H5NHOH _ C,- tlr N=NC,-H_-D D D D
(214)
O O
il iJ
> N (Oil) C6H 5
IIO O
C6H5NO
•-C6 H5N}tOtt-_
O
l!
=N (O) C61I 5=N (O) C6H 5
(2]I5)
]..07
A similar attack by nitroso nitrogen on a terminal
methylene group in an azomethine linkage has been described
(371) (equation 216). Probab]_y the base catalyzed addition of
an aldehyde to the nitroso group is a related reaction (372)
(equation 21"7). Safrole reacts with nitrosobenzene to give a
C6H5NO N
_2 -_- / v6...s,i..........OH
I-;_ P
ArNO
RCHO "_ ArNCORI
AI (OR) 3 OH
(217)
nitrone and azoxybenzene; presumably the expected hydroxylamine
is an intermediate (373) (equation 218).
C6H5 NO [0]
> ArCH 2CH:CH_qC6 H5 _i_
OH
0 O
ArCII:CI]CH:NC6H 5 + C6H5N:NC6H 5 (218)
108
r_
17. Grignard reagents
The early work of Wieland demonstrated the initial formation
of an N,N-disubstituted hydroxylamine salt which subsequently
may be reduced by an excess of the Grignard reagent to a
secondary amine (374, 375) (equation 219). Hydroxylamines were
Ar'MgBr H20
Ar'MgBr _H20 -_Arir'NOMgBr " > irir'NMgBr ...... irhr'mH (219)
not is.olated from nitrosobenzenes in which powerful electron-
donating groups such as methoxy and dimethylamino occupied the
para-position and further reaction leading to the expected sec-
ondary amine was detected (375) as well as reduction to corresponding
aZobenzenes (376). The formation of intermediate nitroso radical
anions (1377) appears probable but would not be required for the
formation of £-tolylphenylnitric oxide from either p_-nitroso-
toluene with phenylmagnesium bromide or nitrosobenzene wil-h
P_-to].ylmagnesium bromide (378) (equation 220). Both dialkylzinc
p-CH3C6H4NO
+
C_}I_M Brb u [_
C6H5
--> p_-CH3C 4No <---
p-CH3C6H4ML_Br
+
C6H5NO
and alkyl Grignard reagents transform 2-halo-2-nitrosopropane into
products of dehydrohalogenation , reduction and condensation (379).
109
r _
18. Ehrlich-Sachs reaction
A base catalysed condensation between an active methylene
group and the nitroso group attached to an aromatic ring is
known as the Ehrlich-Sachs reaction (380). It is presumably
initiated by a nucleophilic attack by the corresponding carbanion
on nitroso nitrogen. Dehydration of an assumed intermediate
hydroxylamine gives tile expected product, an anil, in competition
with oxidation to a nitrone (equation 221). Unreacted nitroso
compound may serve as the oxidizing agent and is thereby reduced
to an azoxy compound or an amine. The catalyst is usually
provided by an aqueous alcoholic soda solution but sodium alkoxides
(381, 382) , alkali (383), piperidine (384) potassium cyanide,
trisodium phosphate and other bases have been effective. In
general the reaction leads to a mixture and there is limited
Success in predicting a pr<_dominance of dehydration or of oxidation
P_.O_mct. Typical examples of comDounds containing an active
hrOH-- ArNO 1 H20
> c_2 .... -) > ci_- -> > c_N-0- _-'_-OH
CHN (At) OH
[0]
> C:N (0)Ar
- H 2°> C=NAr (.221)
ii0
t_
methylene group which participates in the Ehrlich-Sachs
reaction include benzyl cyanide, 2,4-dinitrotoluene (384),
certain cyclopentadienes (385), benzy].diphenylphosphine
oxide (382), indole (386) and certain other heterocycles
(38"7) .
For an example of a postulated intramolecular condensation
of an o-nitroso-N,N-dimethy].aniline leading to the formation of
the corresponding N-methylimidazole see B.22. In the condensation
with indo].e the required anion is one expression of the resonance
anion of indole [equation 222). An unidentified product,
C6H5NO
H20 __ /_ :NC6H5(222)
N
C9H703N , formed in the absence of base from paraldehyde and
o-nitrosobenzoic acid exposed to sunlight may be the expected
ani]. (388) (equation 223).
paral dehyde _ N:CHCHOsunlight > CO2H
? (223)
Benzyl and certain other halides also condense with aromatic
nitroso compounds to give nitrones (383) (equation 224) by a
reaction sequence in which initial attack by either a carbanion
].ii
Ar INO -Br--._ }, ArcHm: % _.rC_{ (22_)ArC:t-J2sr I _ II
0t-I Az I N-O Ar I N--:_ 0
or a carbene seems plausible. Additional base is not requi:
for the condensation between p-nitrosodimethylaniline and
& " 7 "edl_].ene dJbromide. The product, identical with the bis-J
nit_,one ob5_.ined from [-rlitrosodimeth_,lani]ine, and diazo_ethane
(389) (equation 225), cf.C.i2., is transfon_ed i_]to bi___sso-di_r:ethyl-
a_fi.noazoxybenzene on being heated with _-nitrosodi_let, h_qaniline
in ethar_o]. A ])reparsl, ion of aldehydes fro_ nitrones by hydroly-
P---ONC6H4 N (Ci{3) 2
(CH2Br) 2
C2H5OH
((c%)2Nc6'_N(0)::cH)2 (225)
sis (19:'Uhnke reaction) calls for a v_riation fi.n the; }_.fitrone
sy_tl-_,sis J.n _.;hich the halide is first t,r's_sfor'r'_._d J.r,,to its
pyrJ.dJ.rliur_ s_It (390).
+ -
Sulfonimn (R2S-CR 2) and phosphonium ylides readily combine
with nJtrosobenzene to give a nitrone and a sulfide in the former
examples (391) (equation 226) and an anil and a phosphine oxide
in the latter (328) , cf.C.ll.
!
_ + C6H5NO
Ar2C"S(CH3) 2 _ Ar2C=N(O)C6}i5 + (CH3) 2S (226)
i12
19. Amines, hydroxylamines, hydrazines
Amines.{ hydrazines and hydroxylamines are additional
reagents which may attack the nitroso nitrogen. Azo compounds
are formed in the condensation of primary aromatic amines with
aromatic nitroso compounds generally carried out under mild
Conditions in acetic acid (.392) (equation 227). Unsymmetrically
Substituted azo compounds are readily obtained; p.-toluidine and
nitrosobenzene or aniline and p-nitrosotoluene give near].y the
theoretical amount of benzene-azo-p_-toluene (393).
Ar'NH 2
ArNO _ ArN:NAr' (227)
CH3CO2H
From a kinetic study a rate determining step in which
protonated or acid-activated nitrosobenzene attacks nitrogen of
free aniline in acetic acid has been postulated (394) with the
recognition that a protonated N-anilinohydroxylamine may be an inter-
mediate. Oxidation of the interraediate accounts for the formation
of corresponding azoxy compounds as by-products (395).
In reaction with m- and p-nitroani]ine, nitrosobenzene gives
the expected azo compound; but o-nitroaniline combines with
nitrosobenzene to give o-nitro-E'-nitrosodiphenylamine (392)
(equation 228). It is reported that o-nitroaniline does not react
with either o- or m- nitronitrosobenzene.
_t
113
.O-02NC6H4NH2
C 6115NO
- > o_02NcGH4 I (22 )p-ONC6H 4
The condensation may lead to interesting variations
as the following three reactions will illustrate. (i) An
unidentified product, C26HIdON2, was obtained from nitroso-
benzene and _-naphthylamine (396). (2) Aniline condenses
with each nitroso group in derivatives of p-dinitrosobenzene
to give both the expected bis___-azo- as well as the azoazoxy-
products (397). (3) Azophenine is obtained on treating p-
nitrosodiphen_lamine with aniline in the pl_e_(:,r_ces_of its hydro-
chloride (398) (equation 229 ) .
_C6H 5
H5 _NHC6H 5C6H5NH2
He1 _ _ NHC6H5
11NO NC6H 5
(229)
There is a lack of information on possible reactions
between primary aliphatic amines and nitroso compounds.
Dilute aqueous ethyl amine reacts with l-nitroso-2-naphthol
to give l-nitroso-2-N-ethylaminonaphthalene (399, 400) and
no produc[ was reported which would indicate a reaction at
114
the nitroso group. In genera] aromatic nitroso amines are
produced by digesting nitrosophenols with hot solid alr_onium
chloride and ammonium acetate (401). Secondary amines may
react in a complicated way with nitros0benzene to give
azobenzene, nitrobenzene, aniline and azoxybenzene. A small
portion of the a_aine is changed into an N,N-dialkylhydroxyl-
amine which also appears to be formed when nitrosobenzene is
heated for a long time with a tertiary amine (402). It would
appear that secondary amines are not highly reactive toward
the nitroso group since piperidine is sometimes employed as
a catalyst for other reactions. In concentrated sulfuric
acid certain nitroso compounds and diphenylamine condense
through the a_-position to form highly colored blue
quinonimines, sometimes used to detect the presence of a
nitroso group [403).
Safranine, one of the earliest synthetic dyes, is a
derivative of phenazine. A safranine dye may easily be
Obtained by heating p_-nitroso-N,N-dimethylaniline with a
primary aromatic amine in the presence of its hydrochloride
(404).
Hydroxylamine will transform an aromatic nitroso compound
into a diazonium hydroxide (400, 405). The reaction is probably
catalysed by base and is limited to those nitroso derivatives
which may not isomerize into oximes. As expected, many
115
nitrosopyrroles and nitrosophenols do not react in this way
with hydroxylamine (406). On the other hand primary and
Secondary amino derivatives of aromatic nitroso compounds are
more resistant to isomerization and are often diazotized by
hydroxylamine. The transformation of p_-anilinonitrosobenzene
into _-anilinophenyl azide also demonstrates that an initially
fomned diazonium hydroxide may react further with hydroxylamine
to form an azide (.407) (equation 230).
_-C6H5NHC6H4NO H2NOH__ C6H5NHC6H4N20[[ H2NOH
OH
C6H5NHC6H4N3 (.230)
In the presence of hydroxylamine, 8-nitroperfluoronitro-
soethane is transformed into nitrodifluoroacetic acid (408)
(equation 231), apparentiy by way of an intermediate diazonium
Compound.
OH
H2NOH I -H20
o2NcF2c 2No ->O2NCF2Cr2NNI OHH20
<5 °
O2NCF2CF2N:NOH
-N 2 -IlF
) o2NcF2cF2oH
02NCF2COF
H20
O2NCF2CO2 H (231)
116
A condensation between an aromatic hydroxylamine and an
aromatic nitroso compound leads to (an) azoxy compound(s) and
may occur in acidic, neutral or basic solutions. From either
p_-chlorophenylh_droxylamine and nitrosobenzene or _-chloro-
nitrosobenzene and pheny]hydroxylamine, a mixture of all
possible (Tour) symmetrically and unsymmetrically substituted
azoxybenzenes are formed (.409) (equations 232, 233). Apparently
an equilibrium between each nitroso and hydroxylamino compound
is present. In the condensation between nitrosobenzene and phenyl-
R-XC6H4NO + C6H5NHOH x-'_--p-XC6H4NHOH + C6tt5NO (232)
O
_-XC6H4NO _-XC6H4NHOH+ ---_ArN=NAr'
C6H5NO C6H5NHOH i4 products)(233)
hydroxylamine in acid or neutral media, the rate is proportional
to the concentration of each reactant and shows a variation with
acid concentration. Two mechanisms proposed to fit the data
(409) require (i) a reaction between free hydroxylamine and free
nitrosobenzene in neutral media (equation 234) and (2) a
Condensation between phenylhydroxylamine and protonated nitroso-
benzene in acidic media (equation 235). Either intermediate
117
C6}{5_HOH
OH OC6H5NO _ 4"
CrH5NII- NCrH= ------ > C6H5N:NC6H5 (234)o .+ I o a
0
+ OH O
C6H5NOH I 9"• _ C6H5N:NC6H5C 6H 5NHOH ._ C 6H 5NH- _C 6H5 ....--_
4- OH
(235)
accounts for the rapid equilibration between substituted and
unsubstituted nitroso and hydroxylaraino compounds (equation 232)
and for the loss of one-half of the isotope when one reactant
is labeled with 018 (410). Each is consistent with the require-
ment for an intermediate with equivalent nitrogen atoms as
demonstrated with the coidensation between phenylhydroxylamine
and nitrosobenzene containing N 15 (411). In the latter example,
azoxybenzene was monobrominated and reductively cleaved with
the result that half of the isotope was found in aniline and half
in p-bromoaniline.
Activation energies for corresponding condensations in
acid or neutral media of nitrosobenzene with aniline (Ea 5.83
kcal/mole) ahd phenylhydroxylamine (E 10.8 kcal/mole) anda
activation entropies (_$½-55.6 cal deg -I mole -I for aniline
and L_S_-32.5 cal deg -I mole -I (estimated) for phenylhydroxyl-
amine) reveal a higher order of reactivity for the aniline-
nitrosobenzene reaction in agreement with a greater basicity of
aniline over phenylhydroxylamine (pKa 5.804 for protonated
_A
118
aniline and 3.462 for protonated phenylhydroxylamine in
methanol at 29 ° (394)).
In the presence of certain bases nitrosobenzene and phenyl-
hydroxylamine rapidly produce quantitatively nitrosobenzene
anion radicals detected by e.s.r. Second-order kinetics for
the decay of the radical anions is consistent with the following
rapid equilibrium for the condensation in basic solution (412)
(equation 236]. It is particularly interesting that the nitro-
sobenzene radical anion is slowly formed in a solution of
azoxybenzene in dimethyl sulfoxide 50% saturated with potassium
hydroxide (1412).
0
2c6HSNo--+_e C6HsN-NC6H50
0I -oH
C6H5_-NC6H5 -
OH
C6H5N:N (0) C6H5(236)
Apparently an expected adduct is readily formed on mixing
a monosubstituted or an unsymmetrically di'substituted hydrazine
with an aromatic nitroso compound. Dehydration to a triazene
either does not occur or is insignificant and the predominant
reaction for the intermediate is an oxidation to a triazene-N-
oxide (413, 414_ (equations 237, 238). A diarylamine is also
119
C6H5NHNH2
0 OHC6nsNO I
) C6H5NH-N:NC6H 5 _ C6H5N:N-NC6H 5 (237)
_H 3 C6H5NO CH 3 0+
C6H5NNH 2 -_ .C6H5N-N=NC6H 5 (238)
produced in certain condensations between an arylhydrazine and
an aromatic nitroso compound. From isotope labeling it has
been shown that the amine nitrogen is generated from the nitroso
group [415). A possible explanation would require dehydrogenation
to phenyldiimide and its decomposition to phenyl radicals. A
diaryl nitroxide, produced by the combination of nitrosobenzene
and phenyl, would then be reduced to a corresponding diaryl
amine [equation 239).
ArNO
C6H5N2H3 -ArNHOH
In support of the step requiring
C6H5N=NH ---_ C6H 5 + N 2 + H
ArNOC6H 5 H
"> Ar-NO ------} ArNHI i
C6H 5 C6H 5
(239)
dehydrogenation, it is known that nitrosobenzene combines with
hydrazobenzene to give azobenzene and phenylhydroxylamine (416)
(equation 240).
120
C6H5NO+ (C6H5NH)2 ----> C6H5N:NC6H5 + C6H5NHOH (240)
Semicarbazide colmbines with p-nitrosodimethylaniline to
give the expected triazene-N-oxide (417) (equation 241) which
is transformed into p-dir0ethylaminophenol on hydrolysis.
p-ONC6H4N (CH3) 2H2NCONHNH2
O
(CH 3) 2NC6H4N=N-NHCONH2
H2SO 4. .>
H_O
(CH3)2NC6H4OH + NH 3 + N 2 + CO 2
On mild heating in pyridine, chloramine-T reacts with
nitrosobenzene to form an azoxysulfone (4].8) (equation 242)
and may proceed either w_th the formation of an intermediate
nitrene or by an addition and elimination sequence (419).
C6H5NO + p-CH3C6H4S02 N(Na)CI --_---> C6H5N=NSO2C6H4CH 3
O
(241)
(242)
20. Substitution reactions in aromatic nitroso compounds
Substitution reactions of nitrosobenzene are unknown.
Bromination '(349) and nitration (420), which give p-bromo- and
p-nitronitrosobenzene respectively, do not require ring-activation
121
through electron release from the nitroso group since they
may proceed with the formation of intel_ediate hydroxylamine
derivatives. An explanation for the catalysis of the
bromination reaction by hydrogen bromide requires the initial
formation of N-bromophenylhydroxylamine (.349) (equation 243).
In the absence of more definitive information a similar
explanation based on the intermediacy of a phenylhydroxylamine
derivative in the nitration reaction should be questioned.
The reaction is carried out in carbon tetrachloride containing
phosphorous pentoxide with dinitrogen pentoxide as the
nitrating agent.
C6H5NOHBr
_-_-_ C6H5N(OH)Br -----_BrC6H4NHOH --_>
pBr-C6H4N (OH) Br
-HBr
-----_ p_Br--C 6H 4 NO (243 )
As an activator in nucleophilic displacement reactions of
certain aromatic compounds, the nitroso group is more effective
than the nitro group. In boiling sodium hydroxide solution
2,4-dinitrodimethylaniline is barely attacked whereas p-nitroso-
dimethylaniline is hydrolyzed to give nearly quantitative
yields of dimethylamine and quinone monoxime (421). Extension
of this reaction to other p-nitroso-N,N-dialkylanilines provides
122
an important preparative method for pure secondary amines.
Displacement of the alkoxy group in an alkyl ether of p-nitroso-
phenol may occur in a similar manner on treating the ether
with a primary aromatic amine in the presence of acid (421a)
(equation 243a) but £-nitrosophenol undergoes more complex
changes. In the presence of aniline, it is transformed into
ArNH3+
_-ONC6H4OR + ) £-ONC6H4NHAr (243a)
-ROH 2
p-hydroxyazobenzene in acetic acid medium, into azophenine
(cf. equation 229) in hydrochloric acid and into an indoaniline
in strong sulfuric acid. A greater reactivity of p-bromonitro-
sobenzene in comparison with _-bromonitrobenzene toward silver
nitrate has been described also as an illustration of the
electron withdrawing power of the nitroso group (421).
Dipole moments and base-strengths provide additional
evidence of the electron-withdrawing capacity of the nitroso
group. The dipole moment of 3.2D for nitrosobenzene is reduced
to 0.84D for _-nitronitrosobenzene (422). The large value of
6.9D for £-nitrosodimethylaniline which exceeds the vector sum,
4.8D, of the moments of dimethylaniline and nitrosobenzene has
been ascribed to a contribution from a zwitterionic structure,
cf.c.3., where the zwitterion itself would be expected to have
a dipole moment in the order of 30D (423).
123
The zwitterionic structure for _-nitrosodimethylaniline
may accoun£ for its otherwise unpredictably high base strength
(pKa 4.0) (424) which is about one pK unit lower than that of
N,N-dimethylaniline (pKa 5.15) (425). In marked contrast
p--nitroaniline (pKa i.ii) (426) is a weaker base than aniline
(pKa 4.62) (425) by over three pK units.
Resonance between the nitroso group and an attached aromatic
ring would be reflected in a shortening of the C-nitroso bond.
In p-iodonitrosobenzene this has been demonstrated in a C-nitroso
o o
bond of 1.28 A, appreciably shorter than the C-N bond of 1.49 A
in aliphatic amines (427).
21. Cleavage of the C-nitroso bond
It has been suggested that initial nitrosation at carbon
is reversible in nitrosative decarboxylation (equation 35) and
that mineral acid may replace the nitroso group in a nitroso-
toluene with hydrogen (.equation 203). There are several other
reactions in which cleavage of the C-nitroso bond occurs
readily. Geminal dihalides may be prepared from corresponding
nitrosochlorides and chlorine (428) (.equation 244). At room
temperature dimethylaniline in ether replaces the nitroso
group in perfluoro 2-nitroso-2-methylpropane with hydrogen
(.428) _quation 245).
(CF3) 2C (NO) C1
C1
2 _ (CF3)2CCI 2 (244)
124
(CF3) 3CNOC6H5N(CH3) 2
> (CF3) 3CH +3)2
NO2
(245)
Pyrolysis of trifluoronitrosomethane and of pentafluoro-
nitrosoethane has been assumed to proceed with initial
cleavage of the C-nitroso bond (429) (equations 246, 247).
CF3NO
300°
NO + CF3
(Products isolated: (CF3)2NOCF3, CF3NO2, CF2=NF, (CF2NF) and COF2)
(246)
CF3CF2NO150°
NO + CF3CF2
(.Products isolated: CF3NO2, CF3N=NCF3, (CF3)2NF, CF4,
C0F2 and nitrogen oxides) (247)
_8
125
It should be noted that a molecular rearrangement is apparently
required for the formation of the product, hexafluorodimethyl-
amine, in the latter reaction. A similar cleavage in the mass
spectrometer leads to the forraation of the nitrosyl cation
(NO + ) (429). Pyrolysis of geminal nitrosocyanides also proceeds
with initial cleavage of the C-nitroso bond (430) (equation 248).
R2C(NO)CN
C6H5CH3 k CN]2 CN
The reversible photochemical dimerization of perfluoro-
nitrosoalkanes cf°C.l., provides a classical example of the
photolytic cleavage of the C-nitroso bond. In another example
it is presumed that perfluoronitrosoethylene is initially
formed in the irradiated mixture of perfluoroiodoethylene and
nitric oxide which gives decomposition products (431) (equa£ion
249). Irradiation of nitrosyl cyanide brings about dissociation
into nitric oxide and cyanogen radicals (432).
(248)
CF2=CFI
NO
hY--_ CF2=CFNO--- _ F2CO + FCN + N 2 + NO 2 (249)
Following cleavage of the C-nitroso bond by irradiation,
radical recombinations may bring about the formation of nitric
126
oxides which may be detected by e.s.r, and their subsequent
transformation into trisubstituted derivatives of hydroxylamine
(433) (equation 250).
h_C6H5NO _ (C6H5)2 NO
F2C(NO)CF2CO2CH_----_ (CH302CCF2CF2) 2NO (250)
A photolytic elimination of nitrosyl hydride from certain
nitrosoalkanes has been observed (434) (equation 251). It
h_( cH3)2 cR2c 2c (oH3)2
NO -NOH
(CH3) 2C=CHCH2 CH (CH3) 2 (251)
would appear that a similar elimination of nitrosyl bromide
Occurs as exposure to sunlight converts 2-nitroso-3-bromo-2,3-
dimethylbutane into 2,3-dimethyl-2,3-dibromobutane (435)
(equation 252). Elimination of the elements of nitrosyl bromide
as both nitrous and hydrobromic acids occurs in boiling water
(equation 252).
127
(CH3) 2C=c (CH3) 2 <
CH_CHsteam ! _l 3 sun
CH_-C-- _--CH 3-HBr 5 i light
-HONO NO Br
. 2CBr)2_CH 3 ) l "
->
(252)
22. Pyrolytic and photolytic disproportionation
ALL_
portionate with the simultaneous formation of a hydroxylamine
and a nitro compound. On this basis he explained the formation
of azoxybenzene, nitrobenzene, aniline, o-hydroxyazobenzene,
O-hydroxyazoxybenzene, hydroquinone, _-hydroxyazoxybenzene and
Other products on exposing nitrosobenzene in benzene to sunlight.
The same reaction(s) occur(s) more slowly in the dark or on
heating nitrosobenzene in petroleum ether (436).
Disproportionation may lead directly to the formation of
an azoxy and a nitro compound, the products obtained from both
pyrolysis and photolysis of 8-nitroperfluoronitrosoethane (437)
(equation 253). Photolysis tran_form_ methyl o-nitrosobenzoate
O2NCF2CF2NO
125 °., 8 hr.
no 02
or h_, 17 hr.
"> (O2NCF2) 2 + (O2NCF2CF2)2N20 (253)
into the corresponding azoxy compound through an intermediate
claimed to be the three-membered ring isomer of the azoxy
COmpound (182) (equation 254). Methyl nitrobenzoate was not
reported.
. 128
NOC02CH3
h_
C02CH3
dark
(254)
23- Miscellaneous reactions of nitroso compounds
a. Conjugate addition. Piperidine adds in the 1,4-manner
to _,_-unsaturated nitrosoalkenes (438) (equation 255).
ArCH=CHNO(CH 2 )5 NH
ArCHCH=NOHI
N (CH 2 ) 5
(255)
b. Fragmentation. On formation trihydroxymethylnitroso-
methane dissociates into the oxime of dihydroxyacetone and
formaldehyde (129). An appealing explanation calls for a
redistribution of electrons in a cyclic transition state
(equation 256) from which formaldehyde is eliminated. The
reaction is reminiscent of decarboxylation of e-nitroso-
carboxylic acids, cf.A.10.
. 129
Z_H2C " O
%?
-CH20
(HOCH 2 )2C=NOH (256)
c. Reactions promoted by the presence of nitrosobenzene.
Trimerization of phenyl isocyanide in the presence of nitroso-
benzene gives the dianil of 4-aza-l,2 naphthoquinone (439)
(equation 257).
3 C6H5NC
NC _11_
II
__.____H_:NO _=NC6H 5
(257)
In the presence of nitrosobenzene, ethyl _-nitrophenyl-
propiolate undergoes isomerization with ring-closure (440)
(equation 258).
CECCO2C2H 5NO 2
C6H5 NO
.
C
N//CCO2C2H5
0
(25s)
130
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