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~ -~-fl1(il A111Jfl rrsan
ft11'tif1 i 111
I • I ,.1 I .. ~ :'1 I*~ .. ~ ~ n~11911lil:noun\I\\Jfl111JEin'"JJaLlJU\I\ijn~n-uu fl1111~1111ntto~n11LLtlnfl1 wn1~
if ~..r-1 _, ~ ~~ .. I ~ n1tlLLft: 't't EJYlLnU'ltl El~ Rli1Jtln1 U111~ fl111JR1JY4U11'1:\I\11~Rli1Jtlfl1~n1 EJ111~ LLa:
lt11~ri1~· RlltJ~Lflii LLa:l11:lu1Ju n11L;vn~on1f1fl1fuon·ln n11Lntnnao n11Lfi;EJll
n1fl fl1f1J El n tfi n 1.1 ~ fl~ EJ1tl a~ n 1ft fl1f1J El n•fi n~\ ~ R11EI"t ~ uf 1.1 ~ n; EJ11 tl EJ orr 1 l 1.1 fl L~U1iD~n1Jm1LLYlUa:fiDll~iiR111~l~fhatJR~tl1UU1flR1ol~tf
~
.,.!'!!! ... ~.,~~ Llla LflflnH11JYlL 1UU1JYlULLft1UnflnH1fl11't:911111ll
1. -;l1LLUn\I\11Yf~niutto~n1tlfl1fuantlnLLa:au ..,uMflth~ 'l lti ~ .
2. aiu1UR111~n1tltta~n1flfl1fuantln iJ'tiu~i1ft'qJ LLa:n.AuuL fiuufl1111911111n \u ~ ar.!! ... ~ • 11 _,
n11LLtlnfl1 LLii:LJJ1U1JLYlU1Jn1J91-1aU Ltl
3. 1Lfl11:~ft'l1Uiin1~n1u.n1v. tta~n1flfl1fuantln iJ'tiu~Lftu1ia~LLa:LtnEJtJLfivult1 4. L;un~oLLa:L;ivuwtl11fl1~m~n1f1tnfuantlnlt1
~ .
5. L ;ivuli~MU1n11Lfi;Ulln1flfl1ftJantfin li~MU1~ LLRfi~Rli1Jil Lflii LLRfi~911U1:n au~ . \,Y R1111:11~MU1 J.JftU~MtJ1~Lntl(u f11U1UJ.JfttlJ.Ja~Lntllt1.
6. \l1li~MU1 11.11. iLfl;Uli911U1:L11Yl~U ') lti
CM225 371
• 1Jt1141
,¥ ..1 " .., • I _,..,. • I' !If " .., .., ..1 . ll •• 1.'!1 . unuL n t.l1, a~n u ft11111:n au nuvuJ fi1'UJ a ~a Ln1~ ~ uli:n u a: tt e111 n w 1l1 v. ~-,.,,au '1.1
~~ tiam~nu-.,~ ~oH fl1fuau,a~-.,~•nfua\tau~m~~uD":nu,u1tt1fl1fuau ft11luun i{~~ii'MlhBfB (acyl group) m-3~'UD':nu 'MJ.i 0H tJ1~SJin~nL:,t1,1JLiJU . '1.1 . • '1.1 .
• 0. • II • .,....C,••
R Z
acyl group
L~El z = OH rrnJ1:nn1J flEl n1ttfl1funniin
mflmfua~inLiiWl1flBU't1;tf il'M~f11f.~~of@ (carboxyl group;- COOH -.,1a-C02H)
Lilu"MliYt~niu n1ttrnfuan~inLLu~tt111-.rJilfl,eJ~f11fuau~ri1~~ucnu"Mlifl1fllDnis LiJu '1.1 ~ '1.1
n1fi,.UfiUDiuwiin (aliphatic acids; RCOOH) LLa:n1~,-\i.ttuDf1LUJin (aromatic acids;
ArCOOH) ttl'Mi''Un1fi,,JJ'U (fatty acid) Lilun1fl,-itf'ILLelftLL~iln 11JitJ11
tf1UiJ1:neJ'U,el~'MJ.ifl1f1JDnf~ ij-.,Jj tllfl1DnfRLn1:LteJ1Jrl'Ufl1f1JDUR R11Utl't11\l . ·--·--~············ ..
LflilLLa:n1tJ1l1~th~~1n"MliLilll,f\IReJ\I ifiLilu"MliM\Iniul"Mli • '1.1 . '1.1
,.... ..carbonyl ,·.·- .. '. ~··
(:' 0'f. ..·hydrOxYl ii II :'--·~·:-:.··· a: : ,· "':'.
R~C.H:011: } \::::·'''·.:.~-,:.·-·"·
amonyl + hydrgg! ~----.. ca~oxyl group
'Mllfl1fllDnfR iJW1JUflLU'U01flfl111\i.tJ1111JJel~L1J7u&JLflfl-R171 011Wa1U~U1J': 0-H '1.1
LiiULL'U'U,J.iW1Jll1fl1 \-.,1tJ1fiDULLft:fJ~fllDni&Rfl tBDDU (carboxylate io~) fl1111ft11111tl,el\l
n11LLflni1 W1l1~n1tlLLa:iJ~ir.JLrlu1io~~='t1nth1lui1io 9.4
~ ~ ·R-C-0-H + H20 ~ R-e-o- + H30+
carboxylic acid carboxylate lon
fnfueJu,o~'Mlifl1fuontal'Jl'oofihia,-\i.tl sp2 ti1~il1iJ't11~LLU'U trigonal planar nn .. . .. ~
o:fiD11'U1L1n&.d'odi1111:U1'UnU iJJJli~UD':~fl1ftJo14lnaLtlU.a .120° fl1111tJ11~U1J': C=O 'IJ I 1
Lfun11 C-0 L~U n1flWBfDn (bmlc aCid)
372 CM225
a- , sp2 :o: ,' II ,' c' H/a~o;~
120 pm lllltiuc H-C=O 124° • 134 pm O=C-0 125°
fl11llt111tium: C=O
C-0 H-C-0 111°
o on~L ~'" i" RD-311 D-3'VI a.ifnfu onttufluL 1JRfl111ibnlJ11 o-3i'J 6 B tt1utnfu a utA" ij .. R1l1?4l~fhRu'ltauni1DDn~L~U ~:£iRil1wf11J1nLLR:£iRlJ1J~LU'UDLRn1fl1lvhfLiULtlU1rl1J luLLaRfilrrtiLLR:fil'nu Li1o-3~1n'VIlifl1fuonttnfiflL1l'JJLLUu41.ti 1hl~fl1fuou11D-3fl1fuoi1R-,. .
Lilus,R'nT,,-twl..tauni1luLLaRillrrtiLLft:fllnu ,,.LUW
iLinltt,\Mi .• 0a-
1 ,,,
' ... , . ...... ,11 '
...,.......c~ ;,H•-----~"'" R a+ -.o~ ..
I a. Ill II ~ fl111J'VIU1LLU\LOLRnfl10UUOU'Y1Rfl •
........ ,u.
..e :o: I
.....-. ..,.......c~,H H ep_.
9.2 fl11'L1unn1'ttA14uunian (Nomenclature of Carboxylic Acids)
9.2.1 i1oa1UIJI
4oR11i'ty'VI1a4oLQV.1~111~1nLL'VIa-3n11lJ,,~~-?4tJn1fl,fU'J L~u n1flfl1fuan'Ban
,uflti1" 'l LLR:n1fll111iu \ut1111"~ 9.1 LLR: 9.2 n11rl1'VIUfl.,iLL'VI""'"'4otnlitytio'nl!t1 n1n a, p, y, a,... Lill11nf11fuou~~flrl1J'VIlifl1fuonlDRLflu~1LL'VI14-3usRW1 1ul1Jil" .. -
tl1LL'VI14-3UR1URflflD 1suJn1 (co) • ~
c- --- -c-c-c-c-c-c-oH m E 8 Y p a
CM225 373
I
p 0 p 0 p 0 y a' II H2N~OH rOH CH3-CH:...CH-C-OH
I.· I . Y a . CH30H NH2
a-hydroxy-J3-methylbutyrlc acid y-aminobutyric acid a-aminopropionic acid (GABA) (alanine)
.& t ... ..J ~ -- -et111"f1 9.1 ocrUJqJu.a:YJll1-nEh'ln1flfl1n.JEln'lfanu1-3~Ufl
w1nlnn EJll faruicy .J ff -n12!11rl1111l 1Lfl11 fi71VM1/1lJ
HCOOH Formic acid a:ilu; formica . llfl
CH3COOH Acetic acid a::ilu; acetum J1fll, LtRt11
CH3CH2COOH Propionic acid ... . n1n; protus pnon 'Ll1\W
CH3(CH2)2COOH Butyric ~d a:ilu; ,butyruni LUtl
CH3(CH2)3COOH Valerie acid a:ilu; valeriana ~1n11nm.Ju\,..,
" ana Valeriana
CH3(CH2) 4COOH Caproic acid a:ilu; caper U.Vi:
CH3(CH2) 10COOH Lauric acid a:il'"; taurus tiu bay laurel
HOOC(CH2)2COOH Succinic acid a:ilu; succinum i51..iU
HOOC(CH2)4COOH Adipic acid a:ilu; adip l-nJu
HOOC(CH2)5COOH Pimelic acid n;n; pimelle l,.JuLt.Ja1
C6H5COOH· Benzoic acid D1'V\'nJ; luban jawi = benzoin I .
rht11U (gum benzoin)
COOH
Q--oH Salicylic. acid ;l~ana Salix . "
o-yHCOOH . Mandelic acid Lt101Ju; mandel ~ U.DiliDUtl
OH
!JJ!JJ~.;!."! LiJu.n1tlfl1fuani.Bin l'liu11. lfltl,t1ltJLiJu.l'lifl1-3LLR::~1'U1'Ufnfuau.LiJ\L LR,~ 'nn 4 n-3 30 ElttlElJJ iJtf-3ttr~tl~JJtl1LLR::la.i~JJtl1 n1flttfUtllli6JJtl"l~WltlqJs:i~\Llr::~ 1
n-3 6 ~'Ulrt LLR:nn~'U1ftLU'ULL1J1J Z -.,1a itr (c/s) n1l1'l,JJLRnR,.,~n"a LLfttitltl1L\L1tl~an • ' • 'U
lliLL U\L ni~u.n-:fiuuuim. vh.t4'U';lfl1'lRElJJL 'V\R1';l::ii~~1R-3 (fl.fl111~~ 3.4) 'U • . .. :
n11L1unn1t1l,tTu.iJ 4 1i fia ialfltJ'lJ ia1:uu IUPAC LLa::ia1::uua1-3o-3tA._,£j 2
LLUU tiae1-3D-31'llifnfuani.Ba (COOH-reference) ua::01-3D-3ti1u-.,\L-3 fEJu.Jn1 (ro-reference) 'U . .
.. A ~- --..I ~ t~ ..I .: ~ I ~ ~ ... .. I ..I . L\L,1\L1'U'UJJ 3 11r'Yl1J8n'Yl-3fl11lltl11 ·DLLR:::•t1LL'V\-..-3..,.\L1Jtt) ,Ul81lJqJ Lfl';l1nLL1'lR-3'Yl'VUJJJ1n
..,;a.,uflf-3LL1n iae1-3o-3lf~wa-31::uul,Yti1LR,LLRfl-3fl11llt111l'li n11e1-3D-31'la.ifl1fullni.Ba , 'U
374 CM225
LLRth1'41'U1Ufl1fUEl\4 '41U1ULLft::f11LL~1l-3~Ulf::fi 1fltJL~~Hl1n~1ifl1fuan~ftLi'UL.,tJ1flU .. .. IUPAC LLtlfl1-3flU~Li9l1Lft'!IUElOfl11lltJ1111Ji
i1~i'u1::uu ei1-3e-3f11 LL ~1l-3 fBu1n1 LLRfl-3'41U1Ufl1.fuau ~1u 1u~utr::fi LLft:: .. tl1LL~1.L-3~lniti1LL~1l" TBuJn1ll1n~wfl L~ll~fl1fuaua::flallt1ft1tJ l'Ji fl'l-3-D'1ll~litnfuan~ft
~ ' .. (f11LL~1l-3fBuJn1) Luutl1u~1l-3LL'ln Liu tl1LL~.\L" c.o-3 ~li1Un-3tl1LL~li"~ 3 'll'u·;nnt1ft1u
"" n'lfll'!la7u ro-3 ~-3Lilun'lfll~Ju~ihiur::fi~fl1fuaua::flall~ 3 'll'u~1nUft1tJRfl ~ .. ~
(t) y a
. ~ .~ .. ... " ... ... ~ ...... fl111"fl 9.2 L1J"U.Jt.JLfltJt.Jn11L1tJnn1tl L~l1Ut.J1-3,-Uflfl-3 4 1tr
I --------------------~
_!fJtnVqJ -· IUPAC ____ _j ... _qamo~:.!_~~~~_j ··-·~:.~~!~!!9.!J Palmitic add Hexadecanoic acid I 16:0 I 16:0 I Stearic acid Octadecanoic acid I 18:0 I 18:0 I Oleic acid J 9-0ctadecenoic acid j_ 18:~~-·--J __ 18_:_!_{~_:~L ... ...J
I ! I j ···-~in~~!~~--!~!~·--···-..J --~' 1 ~~~-~-~~.!~.~~--~~ ................ .! .... -~.~.~.?. .. ~~.: ... ~.=··········-·························· •...... !~.~.?. .. ..(~~) ............ . I l I y-linolenic acid I 6,9,12-0ctadecatrienoic acid I 18:3 A6
•9•
12 18:3 (ro-6)
a-linolenic acid I 9,12,15-0ctadecatrienoic acid I 18:3 A9'
12•
15 j 18:3 (ro-3)
oxalic acid (n=O)
glutaric acid (n=3)
malonic acid (n=1) succinic acid (n=2)
·cM22S
adipic acid (n=4) LLft: pimelic acid (n=5)
~ a' J3' y' ~ H-c-c-c-c-c-c-c-c-oH
y J3 a
HO~OH 0 Br
a-bromo-a' -methyladipic acid
375
~LU14fl1flUDf1UViffl4~iitl1f1JElfl~R 2 \'\li~1~L1J141JU L-DU uninuDifl (phthalic acid), .. ta T'lfuninuaifl (isophthalic ·acid) LLR:&n&muninuai~ (terephthalic acid)-
COOH
&COOH phthalic acid
(0-phthalic acid)
9.2.2 ioo'tw"d'
&:OOH lsophthalic acid (m-phthalic acid)
QH COOH
terephthalic acid (p-phthalic acid)
L1tlnLUUEIU~una~n1flUB9nn LUU alkyl "';El arylacetic acid fl1llfl11LL'Y1UltJLfl1L~U • · 11EJ~"li -CH3 lu n1flua9nn L-Du . ..
H'O I II
H-C-C-OH I H
H+ acetic acid trlrnethylacetic acid
9.2.3 is1tU,).i IUPAC
9.2.3.1 DJ~#.flft"r!.~D. (Aliphatic acids)
La en 11Ji"9n 4~LiJullfifl1fue'l4tienuo11~RflLLa:ii"IJ -eooH . - . .. fl1f1JEIU'IIEI~ -COOH B!hJa1u Llfi ii.,1LL\1\\W 1 l1JtiEJ~1:1JLU~El .. . £hU~EJLIJi\'\Rntl1ll'lfilfl11El~lDLfl1tl1f1JEIU Lt.Jiuufin~1 -e' n1ufeLiJU -oic .acid
0 II
H-C-OH
rnethanoic acid
yH3 ~ CH3-C-CH2-CH-C-OH
I 1 I CH3 CH2CH3 .
0 Q-cH2-8-oH ·phenylethanoic acid
Q~ CH3-qH-C-OH
propanoic acid
2-ethyl-4,4-dimethylpentanoic acid 2-cyclohexylpropanoic acid 2-pentenoic acid
F 0 I II
F-C-C-OH I r
F 2,2,2-trlfluoroethanoic acid
376
~ ~-CH3-yH--<(H-C-OH
CH3 OH 2-hydroxy-3-methylbutanolc acid 4-amlnobutanoic acid
CM225
QOOH cyclohexanecarboxylic acid 5-methyl-3-cyclohexene
CH(CH3)2
3-isopropylcyclopentane carboxylic acid carboxylic acid
9.2.3.2 !l1.~M~J1.~~~Q. (Aromatic carboxylic acids)
LUUtn'1flii,_,1i -COOH ·m~~uD:ntJ1~U.£ll1U.lltln LiU n1tlLtJUliJfan (benzoic acid) • • ,.,1a benzene carboxylic acid ~~Lilun1tlUtll1u.uiin~J1ti~Rfl n11L1un~an1lti1:t1u •
COOH
6- ~OH benzene carboxylic acid ma benzoic acid
0 3-formylbenzoic acid 2-methyl-5-nitrobenzoic acid
3-methylbenzoic acid (m-toluic acid)
2-hydroxybenzoiC acid (salicylic acid)
9.2.3.3 n1t1 ~,,,fvsniin ..... , ......................... . ..liiT~iJ .. .,. t~., ...... I 'YlL \h-nL fl L,.,LRan -n,.,Rn 'Ylll -COOH 2 ,.,ll •
COOH.
~COOH
v benzene-1,2- .
dicarboxylic acid (phthalic acid)
~COOH
~S03H
o-sulfobenzoic acid
¢~ COOH
benzene-1 ,4-dicarboxyllc acid
(terephthalic acid)
L1tlflfl1~ltrlfl.1fl1ftJ£lU~iifl1ftJ£lUL Yhnu U.R::tian1Utl1tl dioic acid fl1ftJ£lU 11a~ -eooH ti1u~lnft',.,liu.'Ylu~111nni1 Lilu.,,u.,.,u~fl 1 . ..
0 0 II II
HO-C-CH2-CH2·CH2-C-OH
pentanedioic acid
OtOH4
~ 2~oH
Br 3-bromohexanedioic acid
CM225 377
tl1LUU cyclic dicarboxylic acids llfiifrl1l-U.i -COOH ff'lft'El'ILUU,.UlLL'YIU~lu1'1 ~ ~
LL1'\1U L~U
QOOH &:OOH COOH
1,3-cyclopentanedicarboxylic acid 1,3-benzenedicarboxylic acid
.. ... .. ~--9.2.4 n11'L1'tJnLnaD!ID"n,.tttt11'Uiln'llan
Lnaa11a'ln1tlfnfuen'Bin LU'ULnaa,.a" la'V\: ,Lnaaua11 lJJ\ilr.Ju ua:Lna·aa~iiu n11
L1~n~Elfi1ltittlr.JL1r.JnUflfltDDDULLL'l::fl1lltl1r.JUDUtaaau
Uflfl taaau ltiLLrl laaau1JEl'l la'V\::, LLElll l~L ilt~11leaau ua::a:-iiulaaau
uau taaau 111~1n~an;t1 LtJ5r.~uan~1 ic acid ,;,r.J~an1tlLUu ate
~Lflfllaaau I + ,, uaulaaau (ic acid·-+ ate~
0 ·~aQl
. ONH4
common name: ammonium butyrate IUPAC: ammonium butanoate
~- ~ ~-9.3 ftJJtJtln1lii11Yt!Uh1n1tttl1'11JBn'llan
common name : sodium propionate IUPAC: sodium propanoate
C=O LLR:: 0-H LUU~UtJ::ii~1 fl1llfn1tlfl1fuan'BinLnflU1'11::1'\i1'1ltll~altiil LLR::
Lnfl~'UD":lu lfl1L~U1:1'\11'1 l11L&naii111n LL1'11:1'\i1'1 l11Lanal un1tlfl1fuan'Bin lflr.JLQ~1: ' . . ... ' , 1 fit I .. ..1 al l ... ... V.UC lJ tl1L~ULL1J-3LL1'1n111110'U') 'Yl~JJ'YI1'1·LLfl:ll1& liLRf1Rflt'l1r.JnU
n1flfl1fuan'Binff'IRCl1U::1Ja-3.L1'\R"HLR:,.a'ILL;i-3 Lnt~~un-:lt~lfl1L~u1:1'\i1'1nu 2
lliLRnR lt~r.Jiunu\u-,tJtflUJDf (dirner) tfiL~flfl ~tl1'\RflliL'KR1 LLR:n11R:R1r.Jtl1~'1R'Ini1 . ~ . . . ' . ~
111BU'Y11U~U~li1R lliLRnaL fi1 ')nU . . '
378 CM225
~ --Jl OH 0
~ ~OH alkene ketone alcohol carboxylic acid
,fiL~Bfl 31°C 80°C ggoc 141°C
.. ~.¥ 1 ~ 1!111 .... I ,¥ ... ... ~fiLtHlflL YUJ1J'Ufl1li1.1'U.1fl 2JLSfllU~'U.Ltl tl1fl1Jft'11£l~ LLfl,fll·U~ £llJL 'V\ 611J'Ufl1Jfl1·1~fl
tl11.1Eh1 l2.1Lant=t lou 1tl~9nti1 u n1t1~1..,1n 11ifl1"~iif1Tfu EJ'U.LU'U.Lt=t1Jtiii~fl'V\t=t EllJL 'V\t=t1w"ni1 "'U ...... 'U
..1 iJ ..1 ~ ... .. 1 .. ,., 1 ~ _, A . t -! ..,,nnL 'U.LR1.1fi'JJ"llfi11U£l'U.2J1nn11'V\1B""'Btln11 1 EJ:flEJll -n"w:'YlB'U.fl"fl11liLLflnfl1" L'U.
L1El"fl11-i'fl1liLRnaL'U1U~ftn &tl'V\~1Jfl1fll-nJ'U.lli~iJtl1 :j"'"'"lr:flLU'U.LLUU Z 'Vl'iElift' rhL~ " 'U 'U
1liLRnt=tifltl1L'U1U~ftnltl\liLL\L'U ~tl'V\RB2JL'V\R1SfiR"L~B'"'U.CflLLU1Jift'L~ll;f'U. (fl111" 3.4) " 'U " . 11
t.,,.un1.:~ '41'Ut 1'Uttl1'fu El'Ut mp bp n11a:a1 ml1
"' {oCl tel {S n1fl/U1100 mq
HC02H 1 8.4 101 ...
a:a1tJflaJ1n
CH3C02H 2 16.6 118 ...
a:a1tJflaJ1n
CH3CH2C02H 3 -20.8 141 ...
a:a1tJflaJ1n
CH3(CH2)2C02H 4 -5.5 164 ...
a:a1tJflaJ1n
CH3(CH2)3C02H 5 -34 186 4.97
CH3(CH2)4C02H 6 '-4.0 205 1.08
CH3(CH~)5C02H 7 -7.5 223 0.24
CH3(CH2)8C02H 8 16.3 239 0.07
CH3(CH2)rC02H 9 12.5 254
~COOH (aromatic acid) 122 250 0.34 ~
o5 . (aromatic acid) 160 300 'bia:a1t1
~
n11'ata1s
CM225 379
. ~ ~" 9.4 A111JLL1\1!JD"n1'tlfl11'UUn'DiU'I
n1flfl1fuan'BiinLiJUn1fiEien.t. (PI<,. > 0) iith PKa ~ 4 - 5 LLfiLiJUn1fiLLrin11~'U.ElL'l
(PI<a ~10) LLL'l:LLaL'lnauatf (PI<a -16) fl113Jft'11111nlun11LLflnt11l'V\Lthflau 4unuumv1n1~ ., -....... . - •. ~1 t ..
~El-3UDU 'DDDU A '.D'-311n11n1:~11tJElL·anfi~El:'U. 'tH fltl inductive effect LLL'l:l1,'11UUU'11
.. .. . H20 .. -e H3o+ R....,O,H + • R-0: + ••
alcohol alkoxicle ion
cr~H •• e
+ H20 .. o-2= + H3o+ .. )< y.:
G G .
phenol phenoxicle ion
-----------·--------------------------------------------------------------------------------.I
tP' R-C +
bH carboxylic acid
~-'1/ R-C"~ ~ . b9
~-~e -l R-C · + ,, 0
carboxylate anion ·
I ....... ~ I .
9.4.1 NR!I£h1M~LLfi\U1fiNfU1.n1ftn1fl
9.4.1.1 !;l.~-;rJ.n.!nf!YQt!¥!!.f!.ftf!.f!!. · - tl 1 ,.,.. -11 •••• ~ " .. - fit Lnfl11nn11n1:-;t1tJ 1:1au tltJEl.:fiEl11flllft1l1·~ ~nn111Jft-3 tl1ttn11fi-3ElLL'lnfi1El'U. . ~
N1u~un-:'Bn111 .Yh\~unu tnnnuihmtt11l1~111n4~ fl1.}11LiJUn1fl~~ll;fu (fh pKa afla-3)
inductive effect 4unu1:tt:.:'J:'V\~1-3'V\~tl-3DLinfi1El'U.n1J'V\~fnfuan'Bati1tt Wl'V\i'u'V\~LLaaila 1:ii~atiaftll1~n1fl,~ll1n"n
"~-~iLinttTBU
¢::::::3 0 ¢::::1 0 II . . II e
z~c-C-OH :.ii•i=::=:l.,!:' z-c--:-C-0 + H+ c:::::) r::::::::>
"IJ\~LinttTD'Il .
380 CM225
110 H-C
o· HcJ
H 0 ·~- 1.~+ II
CI ........ C-C
~-
~· 0 ~- . T ~+ II \ 0-H
3 \ 0-H
I \ H 0-H
Cl ........ £~c,
Cl 0-H ~-
P.~a 3.75 4.74 2.86 0.64
0 H2 H~+ ·/;
H c-c -!-c 3 \
. I ~- 0-H
P.~a 4.52 4.06 2.84
-•"" -~ ... I ..a 40io ..1 ... I I ... ..1 'Sufi 9.2 L1J'UJ1JL'YlU1J~&11£h1~2JLL'Yl\lflWfl inductive f.llJflOfl1LLflnfl1f\~'Yl1JO~n,-tl • v .
' ~· _. • ' •• I 9.4.1.2 fli111Ln~n:-DB"V11JB~fiB1JflfJ11JJDUfi1UVIU"UDAn1 ........................... .., ................................................... .
lfl1~.rn~~t.\m~.Y\nJJ~. Acetic acid
'V\a.iLLDl&LiiU.ytthLL 'V\U~UDRW1'th \~Ril1l'm1fiL ~ll;f\4 ................................................. ~····················· Iodoacetic acid
Bromoacetic acid
Chloroacetic acid
Fluoroacetic acid
Trichloroacetic acid
Trifluoroacetic acid
1 .. - - .. t ..I..J \-~ ..:. ~ 'V\llfl~manfl,-ouou flU inductive effect 'Ylll1 l'\Ril1l'4n,.tlL l'4lJ11\l ........................................................................................... Methoxyacetic acid
· Cyanoacetic acid
Nitroacetic acid
·cM225
r,,,m,
CH3COO!:!
ICH2COO!:!
BrCH2COOf:!
CICH2C00t!,
FCH2COOf:!
CI3CCOO.tl
F3CCOO.tl
CH30CH2COP.t!
NECCH2COO!:!
0 2NCH2COO.tl
pKa
4.74
3.10
2.90
2.85
2.59
0.9
0.23
3.6
2.5
1.7
381
9.4.2 n1'tUtlntl1!1D"n1flUDf1'LLIIin
U';JitJ~L~tJ1-lfl~ ltiLLri'
9.4.2.1 !i.ft?!ll~!J.?!JJ!Y1lfli (Hybridization effect)
.. ... ..... .. ..... .t!t 2 .... fit . ... ...... • .. 3 .. ... fl11tJfl~,fl~1~LtJ~'111h'lfflfl1tJ'Y1a'Jfl4t1 sp tl~flLanfl1fl~ Ltltl011'Jf~t1 sp L ~a~;,1n3J
in~m::,f.i~aafih1a s lnnn11 L-rl~ n1tutn4f'lfenLiJ~n,.fiLLrin11n1tluD9nn Ltia~';J1nl'lli - ..
fl1fuanlgaLn1:nutnfua~'Jfitfl sp2 lflEJtl1-J ~~LLflnfi'1iln11l'l~fl1fuanlga~Ln1:nufl1fua~
.. 3 'Jf'Utl sp
PKa
sp'l \ 0
' II
·etC,~ benzoic acid
4.2
• .J . .J ~ 9.4.2.2 #JR'JJD.JM1/U'YIU'YI'Yii.JUJU"DU ··············v····························
COOH COOH COOH
sp3 \
\~ 1!0 H3c~c,
0-H - acetic acid
4.74
¢ 6 ' 0 · N02
9H OCH3 . N02
p-methoxy benzoic acid m.nltro p.nitro-
P.~ 4.46 4.19 3.47 3.41
OH N02 '
~
a-nitro
2.16
'nJfl9.3 J.II,.S-3'MlJLL 'n\L~~~fien1nLftni1,.8-3n1fiU8 f 1UUfin .. . .
382 CM225
., .. ~- ... I t • a ~ ... -., ..;... I ..
n1fl 'flf1111JEJn·D6n1Jfl1 pK8 2 fl1 L1JEIL1J'UJ1.JL flti1Jn1J pK8 ~El-3n1fi'YUJ'V\11fi111JEln 'U
'Ba 1 'V\3.i~iifl1fua14L Yhn'\4 fh pK1 ,El-3n1fl ~,,,.funn'iinii~11l'aun11 'V\Jjf11fuantaaLLfi 'U 'U
a :'V\ 3.i L il '"'V\ 1i ~"aLi~ n fl1 El '", El-3 ii n 'V\ li'V\ it" W1 'V\ ~1J n1fl LL 1J1.J H02C-(CH2)n-C02H fl1111 'U 'U 'U
I t • .! ,¥ LLflnfi1-31:'V\11-3 pK1 LLa: pK2 afla-3UJO n LYUJ'il'\4
.a • ... ""' If .. ~.. .. fi1Tl"fl 9.5 fl1LLtlOtl1fl~'t101fllf.l£l~ 'fJn1flfl11lJDn"DBnU1~'UUfl
rfl,.,m.,
HOOC-COOH
HOOC-CH2-COOH
HOOC-(CH2)2-COOH
HOOC-(CH2~-COOH
HOOC-(CH2)4-COOH
():COOH COOH
qCOOH ~
COOH
.. ~ ~~ 9.5 fl11Lt11UaJfl1tlfl11tJDfl'Ditfl
fan1fl
Oxalic acid
Malonic acid
Succinic acid
Glutaric acid
Adipic acid
Phthalic acid
lsophthalic acid
Rh3+
HI 30-60 atrn 150-200 °C
9~5.2 Lfl;tJuTtatJUDMtJ1ooniLtti\6
pK1 pK2
1.2 4.2
2.9 5.7
4.2 5.6
4.3 5.4
4.4 5.6
2.9 5.4
3.5 4.6
9.5.2.1 ffltJn11DEJn'i~fiBUD6nEJliEJtfl.ltvnii U6~UD6~~ll~ .............................................. _ .. ..,. ....................... . (~11ia 6.6.1.5 ua: 8.6.3.1)
CM225 383
~ •'1 .. 0 .. ~" .. ~· ~ a'l .. ...~ I 'YI:3LUlf4fl Lllfl LLC'4: 1 LL£lf40£ltUlft .vnaan-n Lflftfl1[Jfl1£l£lO'lf Ltlft'YILL1:3 L'Jf'U KMn04,
K2Cr201, H2Cr04 llfn1flfnfuan'iin i1~i'uLL£lfttlLtrfinnaan'ilflRlflvi1aan'ilfltfarh:3 ~ .
Eiau L~u Ag20 ua: Ag(NH3}/ OH- llfn1tlfl1fuan~anl.i
'~ 0 oxidize ~ II
R,....C,H R,....C,OH
aldehyde carboxylic acid
OH 0 0 I oxidize II oxidize II
R-C-H R-C-H R-C-OH I H
1° alcohol ald•hyde carboxylic acid
e 1) KMn04 • OH, A
2) H3c9l
9.5.2.2 IftP111!~fl!J.'P.!ftl.ijf!_,_~HM.,EM.'J.'!J!l.tf (~1-ia 3.7.9.4 LLft: 3.8.2.7)
LL£lftflU1J1:3'Jf;lfl LLa:uaa ltnf f111Jimv1n1Jltl1a:a~ vi'au, a:3 KMn04 Lnfl n11 LLtlnin~uctiua:~uctnJJllfn1flfl1fuan41n
384
~
R • R . \ I I
,c::;::q + KMn04 H H
I I I I
R-C!C:C-R + KMn04 I I I I
H3C, : ,CH2CH3 ,c::;::q
H H
R H~o .. C=O ..
Hd carboxylic acid
H30$ NaOH, H20 .. A
+
R +
I O=C
bH carboxylic acid
R R I
C=O + O=C Hcf
- \
C~CH3 o=c OH
propionic acid
OH
CM225
I I I
CH3-C$C-CH2CH3 KMn04
NaOH~~ 4
H30ED H3C\ __..;;...-~~ C=O
Hc:f acetic acid
~ ... ~ ., ... IBu ... ., 9.5.2.3 .. ~J!OJ!~Ul!J.! .. !!~~R.~.~UUY.H ..... (Y\1,0 4.10.~) I
propionic acid
LLoaileuu"U~'U~ii,u1fl1L~"Uti1LL\IlU-3LtJ"Uta nnoon,,flR~1tJ KMn04 L~\llaj -COOH ~ ~
R Q-C-R· - H R, R' = alkyl, aryl, H .
propylbenzene
e KMno ... oH ..
A
benzoic acid
~ I .,tl .. _ ... L w ., ... ., 9.5.2.4 .. ~JL~ .. D.n~J!J.rrr!.~nfl.'!V..§ ... tl!N. (\1\1-no. a.7.4)
LU'UU~mtJ1-n0-3,1/naffTnu ntJLLD1tU~'U (CI2 \1\10 Br2) L'U R11l'4:~1tJ NaOH l~n1fl
fnfu on,~n
carboxylate anion haloform
Br2 (excess) .. H o• 3 .. '
' ... ... f': - ... ~ 9.5.3 LCA1'UIJ~1nft1'Su1::notJ nn1::D\6rl'SU
.• 1 ... .. .. ~ ... ... ., .. 1 ... .. ..t ···- ... tn1lJ1:nou a'V\:OWY11tJ Lll'U n1tlJ111£EJUJUfl ua:oo1LLn 'Ul'IL'YitJ11 Tl1lJ~n1t.nnu
·,r,u;j"u~" (C02) LLa:,D1fl1,aRL"URil11:n1tl ~:l~n1flfnfuon,in~"ii1-rlfnfuo"Ulnnn11 tn1U1:nouuulat1Lii11 1 o:t1o11
CM225 385
a- a+ a+~ •• r •• a-R-MgBr + O=C=O __.....
·o: • .. ee R-C-0 MgBr
H·o· 3 •
:o: II
. R-C-OH . ..
Li pentane
Mg .... dry ether
·~· 9$ R-C-0 Li
VCH2U
organolithium
H o• 3 •
:oz II
R-C-OH
\/ 1. C02 \/ ~MgCI 2. H30~ -. ~COOH
:Z,2-c:timethylpropanoic acid
9.5.4 Lt~1sa.a\l1flft11"tl1tnou luln1l
n11lultt1latflutn1lf (nitriles) LUW11a:a1vn1tt ~:lti'n1ttfnfuen'iin LLa:LnsoLLell LlJL iltJll n1LUUU~MtJ1' UL1Jn: ltl'LnR O'lle-3n1tttl1fuen-iin LLli:LLell LliL ilu
H3o• R-COOH M1o Ar-COOH
+ NH/ R-C:N M1B Ar-C:N
H20 R-eo& M1B Ar-C009
OH
+ NH3
LLeRLL~~n Jutn,.,( Ltt1ulllti~ntJ~mrme-3 UBftflftUliJsl nu NaCN .IJ1-3LUUU~MU1 ... "' - ... 1 ........ m1LLfiUfltt1tJU1flli e Lnli
KCN. I ~CN
386
2-bromobutane
Br~B; 1,3-c:tibromopropane
2-methylbutanenitrile
Hao• J M1e .. COOH
1. N.OH 2-methylbutanoic acid 2. H3o•.
H·o• 3 • HOOC~COOH
glutaric acid · (dlcarboxylic acid)
CM225
ttwriuuD T1uvin ~u ~r11l ltl'·;nnn1.,...R81Jfl1tu,D1s'lfs Tvliln (arylsulfonic acid) ... • ... • " r ... ... ~ ..r " r :-~ .. " .., ,. .. nu NaCN ~1ElLtt1tiiJ';J1nLnaa LflD!''~'uvvntJ CuCN 'lh1LIJEl Ll1Lfl1 LftR';J: Lfi01flLLEl L1LLIJfln
~S03H
~CH3 arylsufonic acid
NaOH ~
diazonium salt
CJ:sEO,Nf -~-~-: ...... o:c=N , CH3 CH3,
aromatic nitrile
aromatic nitrile
9~6 tJfin'!l1!1ih1n"ttlA1411onian (Carboxylic Acid Reactions)
t.l --- ..a rJ 9.6.1 !Jn"I!J1fiLLftfh1fl111JL '14n1'fl
9.6.1.1 yj_ljj_fi.J.ff.1J.f~U,.; l ~Lna £) UR:LLfi RlD 1fl1L ';1\l
Lnaa11a~ 1a~:LLaatnlaa:a1uli'1lfl' Ltl~'iuLnaa11a~ 1a~:~un L~u Ag, Hg. Pb i.i ... 1 .. .~ ·' 1 • iJ • ""... .. ROMnL: flL 1Lft\lfiiJ1fl11\l n11R:R1ti"K1ftflft~ fltiL~~1:LIJElL ULnREl11El~01fi'YliJfl111JEl\l
~. .~,._, fi~Ufl 4 O:fl£11111\l LlJ
CM225
0 0 II II
2 R-C-OH + Zn ~ (R-C-0)2Zn + H2
0 II
2 CH3-C-OH + Zn ~
0 II
R-C-OH + NaOH ~
lJJa:I1UU1
i1~u11~JJnm~n 0
o-8-0H + NaOH --
lala:111u11'1
0 II
R-e-o- Na• + H20
1:11u1f1
387
0 II ~·
R-C-OH + NaHC03 --... R-c-o-.Na+ + C02 + H20
i.1~u!:l~J.J!imP.:t . 0
Q'-8-oH
"
0 I
+ NaHC~ - Q'-8-o-Na• + C02 + H:z()
.. 1•- ., T ., • ., t" • 1 ,.. • • ,.. 9.6.1.4 J:I.D.TJ.1.(l!J1Y.U.J.~Hfli!J!l.Ul.'='..Yl.1f.l.EJ.;.~Y, -v\LntUlLLElll liL lUJll -v\1BLnaea:li'U
f11ll~1i1J
0 0 II - II~$ R-C-OH + NH3
__.... R-C- NH4
\ala::11u1l'1 mi~LLBII laJL ilua~
0 ~ $ II •• R-C-~ N(CH3h R-C-OH + N(CH3h __.... . I
H \ala::11u1l'1 3°amlne 'nlae::llu
a::11u1l'1
-·-~ ........ 9.6.2 ul)n1'!11'tflntf16
n1flfl1fuan'Bin~n;t;,Lfti1u LIAIH4 (~11ia 6.5.4.2) -.,;a 11D,1U (BH3) t~
LLBftnBDElftUJllllii. (lliLfifiU~MU1L~at,Y NaBH4 LiJ'Uft1ntl1R) ~ .
388
0 II LIAIH..
R-C-OH --et~he~r~..,~
carboxylic acid
0
R-g-OH _B_H.;;..3 -• THF
LIAIH4 ether
H o• 3 ...
H o• 3 ..
' H I
R-C-OH I H
1° alcohol
H I
R-C-OH I H
CM225
9.6.3 tlfimu1t~itiA1fuoM1ttoun lwtf (Decarboxylation reaction)
iJ -·-- .., .. ., 1,1 ... ~ f' ... ... f' I .. L -ulJnnnnn L-ufl11111EI\Uf~ LViE:rnflfl111JEI'U LflElEin L'lfflVln'V\11 -COOH 'V\1EI COONs ~ . .
lttu'V\aEl11Lnial'lfLfiu11t~a~n1tt n1J f'l1fJ1tau (soda lime) ~~LiJUft'11~Rllt~EI~ l'lfLtlullltrfl1an
l'lfti' ua::ufla L'lu11a an l'lftf
0 0 II II
R-C-OH Mo R-C-ONa IOdallrile .., R-H + Na2C03 (decarboxylation)
0 Q-8-oH soc:taUme .., 0'
(decarboxylation) ~ b +
9.6.4 tlfimu1 Heii-Volhard-Zellnaky'
LiJUn11LL nufilu lfl1L~Uti1LL'V\U~UBIW1 (a-H) 1.1EI~'V\lifl1f1Jonlia tl1 ULLlJ laL~'U .. (Br2 ,.,;o C~) Jj~omorw ,.,;o PX3 (X= Cl, Br) LfJ\li1Li~ ltl' a-haloacids
,r1R~J~.1JnmP.:t CH30 I II
CH3·CH-C-OH + Br2
isobutyric acid
p ...
p ..
0
R00H + HBr
Br
CH30 I II
CH3·C-C-OH I Br
2-bromo-2-methyl propanoic acid
C1 H3011 1) N OH 2) H 0E& CH301 3 I I CH3·C-C-OH aq. a .. -..:......:::.......-...; ... ~ CH3·C-C-OH I I ~ OH
r
2-hydroxy-2-methylpropanolc acid
1 tJ-- .r ... ~ ~ ... ...t I iJ ~ • 1Jn1UlUli'IStnliUnLflll 3 Tt1U llN?l1ULL1nL UL!JQ1lJU flO Call Magnus \G'J Hel (flfl. 1849-1926) LLR:
Jacob VolhsrrJ (flfl. 1834-1910) anu'ti1Uflrtll Nicolay Zeinsky (flfl. 1861-1953) LiJuunLfliifm.fu
CM225 389
•
s.a.4.2 ~.!!l~NJ:~~mtiJ9..1!q!g
CH3 0 I II
CH3·C-C-OH . I Br
CH o " I 3 ii
CH -C-C-OH 3 I
Br
CH3 0 I II
H2C-C-C-OH I I H Br
NaCN,_
ale. KOH
CH3 0 I II 1) aq. NH3
2) H,tf • CH3·C-C-OH I NH2
2-amino-2-methylpropanoic acid
CH3 0 I II
CH -C-C-OH 3 I
c=N
e CH3 0 H 0 I II ~ CH3-C-C-OH
I
COOH 2,2-dimethylmalonic acid
CH3 0 I II
H2C=C-C-OH
. methacrylic acid
9.6.5 tJfiins1n11'LLfiHrflllf"1'L\JHif1\1LtJHiHtiD\1n1'fUUJf1'LLIIin
'VIli -COOH LiJ'U'VIliti~~Lftnfl1EI'U LL~:LiJ'U meta director DLRn Lfl1lvhf~~Li1LL'Y1'U .. .. lDLfi1L~ou\utl1LL'VI"-3'1/f11~El~'VI~fl1f1JEin'i~ (i1iEl 4.7.2)
0 II C-OH
6~ . cone. H2S04 ,.., + cone. HN03 ---~~
0 II ;(oH ~NO . 2
m-nltrobenzoic acid
acyl group', ____ ---· ',i o:
• II : : R-CiOH ·-------
Ntf3
Carboxylic acids
390 CM225
0 II
R-C-CI Acid chlorides
0 0 II II
R-C-0-C-R Acid anhydrides
0 b
. II
II R-C-OR Esters
R-C-OH Carboxylic acids 0
II R-C-NH2
0 II
R-C-NHR Amides
0 II
R-C-NR2
11·- .. IB ~ .. 9.6.6.1 .. !l1.1J.1.1:1.!.11111Qfl.LJ..(J. •• !J1~'-•• ~.!!
n1tlf'l1fuen~anrhtl~ffit11 nu~nfDUSflSD~1~ (thionyl chloride; SOC~) ,_,7£1 SOBr2 . . .... ~ ., .. . .. ., .. ~~ ,_,1£1 PCI3 ,_,1£1 oxalyl chloride L,_, UD'"llfiLLll 'Sfl ,.,1£1 'D'lfSLLll 'Sfl (acyl harldes) tl-\1'\.l
0 II
R~C-OH soc~
0 II
R-C-OH + CIHO 0 Cl
oxalyl chloride
,r1.~.tt1~.Y!lmP.1 0
Q-g-OH N02
CM225
soc~ ...
... 0 II
R-C-CI + HCI + S02
acid chloride
ft R-C-CI + HCI + CO + C02
acid chlorid~
0
Q-g-CI + HCI + S02
N02
2-nitrobenzoyl c~loride
0 II
,/'y. · C. 'Br L_j + H3P03
cyclopentanecarbonyl bromide
391
' . .. n11Lfl1ttll acetic anhydride l14~flR1\'\n11lll,Yn1'nliflu1~1nn1flLUl'Anntl'1uf111ll .
i'EI'\4~~ lflttii trtethyl ·phosphate LU'\4tl1Li~ lti ketene ~~n1tl~ffitt1tlEill1nun1flLLEl'Annl~ acetic anhydride tl~ffiu1it'~EI ketene process
0 II
CH3-C-OH 750°C
0 II
CH2=C=O + CH3-C-O-H
ketene
ketene
n11Lfl1ttlll14\fa~tl~uf1n11li'ti~Mt11111111ifiJ1fl~m\'\1Jli"~ n-:tl~n1flf11fuEin4 fin 2111Lanan1Jn'\4LLa::iin1'T21ifiJ1EIEin 11aJLana • •
0 0 II r-.--------~ II
R-c:~~ ___ ~ __ 110-C-R .acid anhydride
trifluoroacetlc acid
t'llflinusu t,.tfJ7lflii,141fl1~ 5 ..,;EI 6 o::t1E11J Ltl1EJ11,1nn1nJitlJ,·;nnn1fl tfJ~f usniin
392
9.6.6.3 y!i_fi1.~.1.U11.\0fl.'.~ft'~11~f. (Esterification) (~11To 6.6.1.2) I
n1flrnfuon'iinLuiuwihuomfloiV 2 ii ;~d' (1) Fischer esterification tl~mr.n1:wli~n1flrnfuEin'iinnuLLoanorJEia l,Yf111a.Ji'EI14
ua::lin1fl L'Jt'\4 ~4 ..,;o H3P04 Lilt.~.t11Li.;
CM225
ho R-c1
~------------, ~ 9.:::1:1 __ +_ _ -~::-o-:-R1
carboxylic acid \
ho R-c1
\ O-R1 + H20
carboxylate ester
(2) tJ~ffitnn11LL n~~ LL1.J1.J ~2 ltuJLtJa v~n1flfl1ftJon~snLiJ~fl1fvaniLsf1uau ~DDDU :A~LiJ~it1flaLol~a L~1LL'Yim:tLLOt'lflt'lLLlJlatftJ13J11ii ~1DL3JnaLLDlatf
~.o R-c
1 \ 0-H
carboxylic acid
+ NaOH
~!.~.tb~J:J!imP-1 0 II
CH3-C-OH
acetic acid
0 Q-C-oH + NaOH ------~ .. -..
...
u·- .... ~ ~ 9.6.6.4 .JJJ.TJ.1ltJ.TJ.11.VJflll.; .. ~.fJ.
' 0 h /; r\-C
'oe carboxylate anion
... "'
ethyl acetate
~.o R-c1
\ O~CH2R1 ester
butyl benzoate
., ~ !'I ~ .. ~ ... ll !1" .. .. .. I ~ .. ... •
a~ '1/fl Lu~a~~~tr'YILfl1li1J Lfl Lflllfl1~·;nnn1flfl11lJEln'lfan v1nn11 au~utr-nufl au ~ ~
...1 1 .,. .., !'I ...1 .1 tJ • •• ~ .- • • ll .., • L 'U.El~';J1n LLEl3J 1J L ~ll LLt'l:D~1/UL u'U.LlJ W LlJ El 111 !Jn1ll1 n1.Jn1fl fl111.J Eln'lfa n-;J: Lfl L n tHl
tJ~ffiv,d\fLfl1li3JD:wt1u1~-nitfllu~flft'1~nnlllti LLtilliL~ll1:ntJn11Lfl1li1JLu,.;o~tJ~u~n11 (~1-ia 10.4.3.3)
tJ1iffiv11:~1,~n1flfl1fuan~snnuLLall lllL itv, a~i7ut11llnii~1onilvnii LnfiLnaa w ... "' ~ "'
1 ... .. .. .., ,.._ • .. ... ... ... .r ll ... ., ~ ~ ~ LLEllJ lJL ~llll ~1ElLnaOD~1/U 'JJ~LlJEl L~fl111J1El~';J:La'lll\1LLa: LfiD~ '1/fl fl-3~
0 0 0 II II fl11lli'ou II
R-C-OH + NH3 .. R-c-o-NH"+ R-C-NH2. + H20
ammonium salt amide
0 0 9@
0 II II fl11lli'ou II
R-C-OH + R1NH2 R-C-0 NH3R1 R-C-NHR1 + H20
1° amine amine salt amide
CM225 393
394
i.1RP.1~.lli\mP.:1 0 H-8-oH · + o-{H3
N-methylbenzenamlne ~amine
toluene
1100C
N-methyi-N..;phenylformamlde
CM225
Fumimycin
3. ft111fl~:~1tltl1fl~Rfl • (1) CH3CH2CH2COOH
(2) CH3CH2CH2COO-~
CH3CH2CHCOOH I
(3t CH3
O COOH (4)
CM225
1'!11 II; .cl LLVtiRD\llfl 'Vflfl 9
Cefaclor (antibiotic)
395
4. n11L'1th1~1iuwn1~n1fi11El-3W11t.h::naufialt.Jdialfltu1 . .
N02 0 .·dOH UOH (YloH UOH ~
A B c D
(1) C > B > D >A (2) B > C >A> D
. (3) A > C > B > D (4) D > B > C >A
5. 1 .. ' iJ ·-' fl1-3RTl-3 fiL 14n1fiLLn't1Rfl • o-CH2·COOH 0-9-cooH
(1) .(2) Cl
Cl Q-CH2·COOH 0-¢-cooH
(3) Cl (4) Cl
6. ' ... I -' n1fl flllfl1 pKa R-3'YIRfl • • COOH COOH
¢ qN02 ~
(1) N02 (2) N02
COOH COOH
H3C*CH3 ~ I~ N02 .
(3) CH3 (4) N02
1. R11'L11:nau A, B, c ua: o £ifi1 pKa -na-31'L11f1El14 J:i_lu1fl1-3n1-3LiJu 25,.23, 8.8
ua: 4.2 f11lJa1iu iafl11lllfllajtn'ltia-3
396
.... .., ......... . 0
~~H Utt
A, pKa = 25 8, pKa = 23
(1) B LiJ14Ti1fiUfin11 A
(2) B Lilun1fiDEl14n11 c (3) o Lilun1fl~urln11 c
(4) A, B LLI: C LU14n1f1Ufin11 0
C, pKa = 8.8
~9 Utt D, pKa =4.2
CM225
(1) 2-methylbutanal
(3) 3,3-dimethylbutanoic acid
s. tn1ti£JltJdti£Jtn1Lfl 0 II
· CH3-CH2-CH2-CH2-CH-C-OH . I CH3-CH2
(1) 2-ethylpentanoic acid
(2) 3-methylpentan-2-one
(4) 3-ethylpentanoic acid
(2) 2-butylbutanoic acid
(3) 2-ethylhexanoic acid (4) 1-ethylhexanoic acid
10. CH3CH2C(CH3)2CH2CH2COOH flDft11Lfl
( 1) 4-methylhexanoic acid
(2) 3,3-dimethylhexanoic acid
(3) 4,4-dimethylpentanoic acid
(4) 4,4-dimethylhexanoic acid
11 .. tn1dti £l tn1Lfl
(1) 4,4-dimethyl-3-hexanoic acid
(2) 2-ethyl-3,3-dimethylpentanoic acid
(3) 3,3-dimethyl-2-ethylpentanoic acid
(4) 4,4-dimethyl-3-carboxylhexane
CM225 397
13. 1f11~rn~1flfi~ 2-hexen-4-ynoic acid 0 '
~ JoH ~OH ~ «OH (/ {H
(1) (2) (3)
14. ft11~1:nau1flnnaan,,flal~n1flfl1fuan'ftn .. (1) methanol (2) propan-2-ol
(3) H-C:CCH2CH2CH3 ~
(5) 'YI~ a, b, c LLS: d
16. ~~m[J11fl~1~n1flf11fuan,ftni1Lil[J1ri'" 0
A o-CH~-H
8 o-CH2CH2Br Mg C02 • .. ether
o-CH2CH3 KMn04 H o+
3 .. Ho-c
o-CH20H K2Cr20 7 .. H2S04
D
0 .. ~
(1) 1. BriAIBr3 ; 2. Mg/ether ; 3. 002 ; 4. H30
(2) 1. CH3CHCICHJAICI3 ; 2. KMn04, H30 +
+ (3) 1. (CH3)3CCI/AICI3 ; 2. KMn04, H30
(4) ,jg 1 LLS: 2
398
H o+ 3 ..
+
(4)
CM225
~0 (2) OH
0
+ H)l_OH
~0 (3) OH
~0 (4) OH
0
~OH Br
~0 0
0
~OH OH
(1) (2) (3)
<4> lliLnt1t.l~ffiv1 20. i1LaBnlfliifl11aJL1tiBn11Li1fht.l~ffiv1~B-3it1flalBl~&fann~~.,
(1) (2)
... ~ -(4)' ?4B ')n'Ut'Yl-3 3 -uutl
21 .. LBRL nBf'Y11-3ti1U~11111';'11nn1flLtl 0
CM225
(1) HO~ ('YCOOH'
<a>v
~ OH
d'OH
(3)
0
(2) HO~ ~COOH
<4>v
,.cj' ........ _ ...... o .. :~J i :
t ............................................ .J
399
400
22. LLtift::iatia,tJd'LiJoutl1tt13JLL1.J1.Jttn-Nfl ia~~"l~annu~1aLLrf'L~l~nnti'Eh1 .. ' .. ( 1) R1tl1.Jfl112J LiJoun1fl~ a"n1flfnfu an 'Bin
0 0 Cl .o 0
~OH > ~OH > A)l_OH .> CI~OH Cl
............................................................................... ·~ .......... .
0 0
~o~>~H ' · > /".../'oH > /"o...-.....,.
....... -......................................................................... • ......... .
(3) ~EJ~EJ"r11d' fia 2,2-dibromopropanedioic acid
0 0
HoVoH Br Br -
' ................. •·• ...................................................................... .
CM225
'\