Journal of Scientifi c & Industri al Research Vol. 59, May 2000, pp 339-349

New Dimensions on Value Added Aldol Chemicals of Acetone

K V Ramanamurty and G S Salvapati * Coal Division , Indian Institute of Chemical Technology, Hyderabad 500007, India

Aldol condensati on of acetone provides a class of value added chemicals: O'. , ~-unsaturated ketones and phenols. O'.,~­

Unsaturated ketones are formcd by va ri ous cross condensation and Mi chael reactions of aldol products with acetonc or betwccn themselves and phenol s are formed by either condensation of acetone with methanol or ~-ket o-a l coho l or isopropanaldehyde or by dienone-phenol rcarrangement of O'. , ~-unsaturated ketone such as isophorone or by alkylati on of iso phorone wi th mcthano l. These proccsses are hi ghl y eco-friendly and economica ll y viab le and are also very selecti ve. All the products can be separated and recovered by di still ati on and opti onall y, a more valuable ketone iso phorone can be obtained frec of other products by selecti ve ly converting them bac k to the starting materi al acctone, thus abso lutely requiring no diluent treatment. All thesc processes highlight many new dimensions in the production and emergin g trends in the unconventi onal utility in wide range of industries ex tending to pharmaceutical , food and vegetable and aillied industries.

Introduction

Acetone serves as an important industrial intenne­diate leading to numerous chemicals, thus making it a frontline raw material in many industries. There are many reviews on acetone-based chemicals; it is not the inten­tion of this paper to add to this line. In recent years, ac­etone is gaining signifi cance as the starting material for making selectively a,~-unsaturated ketones , wherein the aldol products formed from acetone (Chart I) undergo various cross condensation and Michae l reactions with acetone or between themselves, leading to a variety of products and the production line extends to dimethyl­and trimethyl phenol s by ecofriendly processes (water is the only byproduct) (Chart 2) . These chemicals find many industrial applications and, in fact , the primary

condensation product, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol, DAA) exhibits some wondeIi'u I prop­et1ies and it may be tenned as "viagra" to elephants. Thus, the aim of this paper is to reveal new dimensions of these aldol products of acetone in many areas in term s of the versati I ity of the process , se lectivity, ecofri endl i ness, abso lutely requiring no efflu ent treatment and also wide range of industrial applications ex tending their utility in pharmaceutical , food , vegetable and allied industri es in

recent years .

The basic raw material is acetone and under mild process conditions, the process is very viable for the pro­duction of two classes of compounds, a,~-unsaturated

. Author for correspondence

ketones and phenols. Acetone is a cheaper raw mate ri al and the processes for producing these compounds are highly selective compared to the establi shed industri al processes and it is abundantly available in India . HOCL produces 24,000 MT while Herdilli a has a capac ity of 18,000 MT mostly by oxidation of cumene, NOCIL makes 14,000 MT from isopropyl alcohol I. Regarding the conventional end use pattern , 60% of the total de­mand is accounted by DAA, MIBK and methyl meth­acrylate. In thi s direction, the future production and end use potential of aldol products of acetone have been high­

lighted.

a.,~-Unsaturated Ketones from Acetone

Auto-condensation of acetone proceeds by aldol condensation which can be catalysed by acids as we ll as bases . A large number of products (Chart I) are formed through either competitive paths at the addition-dehy­dration stage of diacetone alcohol itse lf or with the un­used reactant, acetone. The major products in the reac­tion are: diacetone alcohol , mesityl oxide, phorone, mes i­tylene, triacetone dialcohol , isophorone and isoxy litones which have significant market potentiaj2 - I ~ (Table I). A detailed di scuss ion on the reaction pathways of forma­tion of these products has been reported earl ier"()ll. Though multiplicity of products arise in the product, re­action can be optimi sed for the des ired product through proper choice of process conditions (temperature, pres­

sure and catalyst) .

340 J SCI IND RES VOL S9 MAY 2000

Chart 1

Reaction pathways of formation of aldol products from acetone

1 Fonnation of Diacetone alcohol by aldol condensation of Acetone

000

" "" 2CH3- C - CH3 -- (CH3}2C - CH2- C- CH3

2 Formation of Mesityl oxide by dehydration of Diacetone alcohol OH 0 0 I " - H20 "

(CH3}2C - CH2- C - CH3 --- (CH3}2C = CH - C - CH 3

3 Formation of Triacetone dialcoho! by aldo! condensation of Diacetone alcohol with Acetone

o OH 0 " OH 0 OH I II + CH3 - C - CH3 I " I

(CH3}2C - CH2- C - CH3 .. (CH3)2C - CH2- C - CH2

- C(CH3

}2

4 Fonnation of Phorone by dehydration of Triacetone Dislcohol

5 Fonnation of Phorone by aldol condensation of Mesltyl oxide with Acetone

6 Fonnation of Isophorone by 1,S-Michael cydization of Phorone

o

(CH3l,C=CH-tCH=C(CH3)2 - H3cD H3C CH3

7 Fonnation of Mesitylene from Mesityl oxide and Acetone by aldol condensation and 1,S-internal cydization reaction

Contd .....

RAMANAMURTY & SALVAPATI : VALUE ADDED ALDOL CHEM ICALS OF ACETONE

Chart 1-Contd

8 Formation of Semiphorone by dehydration of triacetone dialcohol

OH 0 OH OH 0 I II I I II

(CH3)2C - CH 2 - C - CH2- C(CH3) - (CH3)2C - CH 2 - C - CH = C(CH3)2

9 Formation of Semiphorone by hydration of Phorone

0000 II I II

(CH3)2C = CH - C - CH = C(CH3)2 + H20 - (H3C}2C -CH2- C - CH = C(CH3)2

10 Formation of t. .ifetralone by reaction of Isophorone with Mesityl oxide

o

HC A I ~ 3 ~ + (CH3 )2C =CH-C-CH3 _

H3C CH3

o 11 Formation of lsoxylitones by aldol condensation of lsophorone with Acetone

12 Formation of Isoxylitones by self,condensation of MesItyt oxide

13 Formation of 2,2,6,6,-Tetramethyl pyron-4-one by cydization of Semiphorone

o

(C~3)2r CH,- g. CH = C (CH3l:. - . H3cDCH,

H3C 0 CH3

14 Formation of 3,3,6,8-Tetramethyl tetralone by reaction of lsophorone with Mesityl oxide

o C~ 0

H C A + (CH3)2C=CH.tCH, 3~ H3C CH3 H3C

34 1

342 J SCI INO RES VOL S9 MAY 2000

Chart 2

Reaction paths of formation of phenols from acetone

Formation of m-Cresol by condensation of Methanol with Acetone

CH30H --- CH20 + H20

CH3·CO.CH3+ CH20 - CH3·CO.CH2·CHzOH

CH3·CO.CHz·CH20H --- CH3·CO.CH2·CHO + H2 OH

CH3·CO.CH2·CHO + CH3·CO.CH 3 --- ~ + 2H2

0

CH3 2 Fonnation of 3,5-Xylenol by condensation of ethanol with Acetone

CH3·CH20H - CH3·CHO + H2

CH3·CHO + CH3·CO.CH3 - CH3·CO.CH2·CHOH.CH3

CH3·CO.CH2 ·CHOH.CH3 - CH3·CO.CH2·CO.CH3 + H2

OH

3

CH,.CO.CH2CO.CH, + CH,COCH, -~ + 2 H20

H3C CH3 Fonnation of 3,5-Xylenol by die none-phenol rearrangement of lsophorone (fanned from Acetone) 0

H,cD + 2H20 H3C CH3

o 0

H,cD n H3C CH3 H3C CH3

4 Fonnatlon of 2,3,5-Trimethyl phenol and m~resol by disproportionation of 3,5-Xylenol

OH OH OH

H~C~CH' ~CH' + H,che::: 5 Fonnation of 2,3,5-Trimethyl phenol by alkylation of lsophorone with Methanol

H,C ~ + CH,OH -.. - k CH, + CH, + H20

H3C~CH3 H3C CH3 6 Fonnation of 2,3- and 2,5-xyIenols by decomposition of 2,3,5-Trimethyl phenol

2 ~CH' ~(H' + iirCH, + C

2H,

H3C~CH3 CH3 H3C

RAMANAMURTY & SALVAPATI : VALUE ADDED ALDOL CHEMI CA LS OF ACETO E 343

Tab le I - Industri al app li ca ti ons of aldol chemicals from acetone

SI No. Product

Diacetone alcohol

Indus tri al Applications

Bacteri cidal to S t aphylococc i ~

In brakc fluid s 1

In polyvinylacetate. styrene-butadiene latex compositions·

In printing inks without envi ronment al hazard s'

2 Mesit yl ox ide

In corrosion in hibiting paints, leuco vat dyes compositions"

As solvent and plasticiser in PVC formul ati ons7

In paint remover formulations and in remov ing resins or chl orinated rubber coatin ti ngs'

Perfume il nd fragrance compositionsY

As solvent of' polymer in phenoli c resi ns, polys tryrenes, epoxy resins

and pol yisoeyanates" l

3 Isophorone In phenol-formaldehyde and phenol furural resin s"

In PVC compositions, swelling agents'l

Industrial solvent for epoxy and phenolic resins"

Chl ori nated isophorone as fungicide'·

4 Mesitylene

In making 3,5-xylenol and 2,3,5-trimethyl phenol';

In offset press for cleanin g rubber bl anket'"

In di sinfecting and clean ing pastes' 7

5 Phorone As stimul ant for stem and leaf growths in beans "

For decreasing the storage breakdown of apples'"

The formation of di acetone alcohol is equilibrium controlled so that reverse reacti on to ace tone or dehy­dration to mes ityl ox ide can occur. Tri acetone di alcoho l is formed by the condensati on of acetone with diacetone a lcohol, but it gets e ither reverted to acetone rapidl y or dehydrated to phorone over the catalyst. The condensa­ti on reaction of acetone with mes ityl ox ide anion gives phorone which can undergo I ,6-intemal Michael cyc li za­li on to isophorone. Isoph orone can a lso be obtained through condensation of acetone ani on with mesityl ox­ide and subsequent 1,6-aldol reacti on . Mes ilyle ne is fo rmed by e ither condensati on of acetone with mes ityl ox ide anion or acetone anion with mes ityl ox ide fo ll owed by 1,6-aldol reaction2 1

•

As menti oned above, it is essentia l to exercise con­tTol over process conditi ons; otherwise the reacti ons lead to hi gher condensat ion products. For example, se lf-con­densation of mesity l oxide on anion-exchange res in yie lds 4-isopropy I idene-3,5 ,5-tri methy 1-2-cyc lo hexeno ne22

,

mes ityl ox ide can a lso dimerize over lithium 10 give 6-acety l- I ,3,5,5-tetramethyl-2-cycl ohaxanoF' . Formation of2-acety l- 1 ,],3,4,4-pentaethylcyc lo- pentene and 5-(2-methy I-I-propeny 1-) 2,4,4,5- tet ramethyl di hydrofuran

has also been reported24.

D e hydr ati o n of triace to ne dialcoh o l y ie ld s semiphorone. 2 ,2 ,6 ,6-Tetramethyl-pyron-4-one is the cyc li zat io n product of he miph o ro ne 2'1 . Tetral o ne is

formed by the reaction of mes ityl ox iode with isophorone with the loss of methane. Isoxy litones are formed by e i­ther the condensation of acetone with isophorone or by auto-condensation of mesity l oxide26

.

The processes in volving the formation o f a ld ol products of acetone are governed by ac id-base cata lys is. The steps aimed at achieving the selectivity of des ired product and process conditions have been reported in detail earii e r2o.21

• Now stage is set for the ne xt step, sepa­ration of products. Aldolization o f acetone constitutes such a versatile process whereby the process conditi ons can be very sat isfac toril y achieved for obtaining the de­s ired prod uct. Though a, ~-un saturated keto nes and phenols synthes ized from acetone differ significantly in their boiling points and can be separated by di still at ion, the separat ion of ketones forms a separate entity by it­self. Isophorone can be separated from other ke tones by distillation27

• If the sampl e is coloured, decolouri sation may be effected by heating it to 90- ISO°C wi th ac id­full e rs earth of pH 4.02X . In case mesity l ox ide and diacetone alcoho l are to be removed, they can be freed

.144

51 No.

2

3

4

5

Product

III-Cresol

3.5-Xylenol

J SCI I D RES VOL 59 MAY 2000

Table 2 - Industria l applications of phenols made from aeetone.lO.70

Industrial App li ca ti ons

For the production of thymol, methanol and III-toluidinc")

Starting material for pcrfume fixat ive musk ambrcttc'O

Antioxidant for polycthylcnc and pol ypropy lene-'o

Ch loroderi vat i vcs nrc disi nfectant s and preservati vcs'o

Fica repe llcnt ' )

Laminating paper adhesivcs'!

Antimicrobial powders, salves, deodourant sprays"

Disinfectan t and cleaning pastes and antiseptic shampoos'"

Antioxidan t for butadienc-styrenc, butadiene-acrylonit ri lc po lymcrs' .

In copolymers with urca, furans and formaldehydc'';

2,J ,5-Trimcthyl phenol In thc synthcs is of vit am in P "

2,5-Xylcnol

2,J-Xylcnol

In making leuo dyc thcrmo-rccording IlHllCrial ,7

In thc manufacture of cpoxy rcsins"

In rad iati on sensiti vc res in co mpositions''!

In fungicidal compos iti onsW

As a stabili zcr to polyolerins agai nst heat and light")

In injecti on mouldablc phenoplast composi ti ons"!

In di sinfcctant compositions for use in poultry and animal husbandry',J

In hair dye compositi ons·'

As antiviral agcn t against herpes-meas les-influenza-and sancari os virus'"

As stabili scr to vi nyl chloridc resin s""

As antioxidan t and li ght stabi lizer for polyoxadiazonc fibrcs, sheets and mou ldings"7

In mak ing cpoxy hased and po lyurethane elect ricall y insula ti on coatings6X

In fungicidal composi ti ons"'!

In pcrfume composit ions70

by treatment at 130-200DC with suffic ient amount of 0 . 1 N NaOH so lution so that they are converted back to ac­etone without affecting isophorone2') . If the product is to be c leansed of mesityl ox ide and phorone, treatment with 3% aqueous FeCI

1 or NH

4C1 so luti on at 100DC reverts

them to acetone, whil e isophorone remains unchanged in the so lutionJ().

etone . Further, if by chance, hig her condensation prod­ucts - isoxy litones - are formed in the process, they can be hydrolysed with 2.6 % alkali so lution at 175DC under a pressure of 10 atm to g ive isophoroneJ2

. Thus, produc­tion of a,p-unsaturated ketones from acetone is economi­cally viable and a very eco-friendl y process s ince all the byproducts can be converted back to acetone and the e ffluents contain onl y water and do not necess iate any treatment.

Another interesting fact is that the product can be freed of mesi ty lene by azeotropic di still at ion with ace­ti c acidJ I . Thus, a more va luable ke tone, isophorone, can be recovered opti onally from the product while other ketones are reverted back to the starting compound , ac-

Phenols from Acetone Phenol s are va lu ab le industri a l intermed iates

(Tab le 2) for obtaining various bacteri c idals, polymers,

RAMANAMURTY & SALVAPATI : VALUE ADDED ALDOL CHEM ICALS OF ACETONE 345

resins, dyestuffs, etc. A number of processes such as alkl ylation of phenol" , sulphonation of benzene homo­logues34

, hydrodealkylati on of polyalkylated phenols" , ox idation of aromatic hydrocarbons' (', pyrol ys is of Mannich bases of 2-methyl cyclohexanones 17

, cal'ulytic conversion of aromatic carboxy lic ac ids}X, etc. are avail­able for making phenol s. Phenol s can also be sourced from tars of low temperature carbonization of Indian coa ls·w . Phenol contents can vary fr om 30 % in Kothagudem coa ls (S ingareni Collieries) to 40% in l ambad-Bowla or upper Kajora coals. About 62 indi­vidual phenols such as cresols, dimethyl- , trimeth yl- , ethyl-phenols, 4,5-indanols , methyl dih ydri c phenols have been characterized and separated by Rao et 01. 40

(Indian Institute of Chemical Technology, Hyderabad). However, it is not viable to produce any individual phe­nol from coal tars. In thi s context, it is mentioned that processes have been developed and patented for the se­lective preparation of alkyl phenols, in particular, 0-

cresol, 2,6-xylenoI41, 2,3,6-trimethyl phenol and 3,5-

xylenol42.

Phenol, m-cresol, 2,5 xy lenol and 3,5-xy lenol can be obtained by the condensati on of methanol with ac­etone (Table 3) by passing their mi xture over an alu­mina catalyst containing 10% Fe at 400-41 ODC with a flow rate 8-8.5 mLihour over 100 mL of the catalyst4

} .

Formation of phenols is believed to have originated with the initi al formation of formaldehyde which condenses with acetone to give CH}.CO.CH 1.CH10H. This com­pound yields read il y CH}CO.CH1CHO, which in turn , condenses with acetone to yield phenol and water in the product (Table 3). Similarly, catalytic condensation of ethanol with acetone gives 3,5-xylenoI44

.

m-Cresol ca n a lso be prepared by cyclocondensation of acetone with a ~-ketoalcohol over FeoO - AI?O catalyst at 400DC. The required ~-

- } -}

ketoalcohol, 2-butanone-4-01 can be obtained by the re-action of acetone and fo rmaldehyde in 60-62 % yield . 7.6% yield of phenol is reported at 24.5% conversion4

'i .

Phenols can also be prepared by dehydrogenation­condensat ion of acetone with isopropanaldehyde over chromi a supported on magnesia. Phenol, l11-cresol, 3,5-xy lenol and m-ethyl phenol can be prepared in 12-34% yield4} •

Phenols, in general 3,5-xy lenol, can be prepared selectively from acetone in hi gh yields (Table 3). Sev­eral improved processes have been developed and pat­ented with various catalysts such as magnesia, nickel­chromium-iron , chromia-alumina, etc.42. 1n principle, the reaction takes place in two steps, dehydrocyclization of

acetone to isophorone and dienone-phenol rearrangement of isophorone to 3,5-xy lenol. These processes gave 80% yield of3 ,5-xylenol at 95% selectivity4('. The aromatiza­ti on ac ti vity of these meta l ox ides is asc ri bed to coordinatively unsaturated cation sites (e.g. Cr}+), ac­companied by the formation of carbanion which rear­ranges to the dienone leading finall y to 3,5-xy lenol. Jt is also found that the aromatization reaction is a fun cti on of the extent of c..}+ spec ies present on the surface of the catalys t47

. I11-Creso I and 2,3 ,5-tri meth y I phen ol are formed in the reacti on by di sproportionati on of 3,5-xylenol. Alternatively, 2,3,5-trimethyl phenol can also be prepared by methylation of 3,5-xylenol with metha­nol (Table 3). A sin gle step process by alkylati on of isophorone with methanol has also been reported to give 2,3,5-trimethylphenoI4x . The mechani stic pathway fo r thi s reaction is not yet established. It is possible that 2,3 ,5-trimethyl phenol formation can be routed in wh ich isophorone is aromatized to 3,5-xylenol which in turn gets methylated to 2,3,5-trimethylphenol, or isophorone itself can get methylated foll owed by dienone-phenol rearrangement leading to 2,3,5-trimethyl phenoI 4

<J. In fac t, available literature on the alkylation of isophorone to 2,3,5-trimethyl phenol is very limited. All these phenols find many industrial applicati ons'il)· 711 (Table 2) and it is economically more viable to make them from acetone. A bird's eye view of the proven processes71

.X6 of aldol

chemicals of acetone is given in Table 3.

Patterns in the End-use of Aldol Chemicals The final scenario regarding the aldol chemic.als

centres round the new dimensions in the end-use pattern of two classes of compounds - phenols and a, ~-un sat­

urated ketones. The end-use pattern of phenol is: about 60% in the manufacture of phenolic res ins, 10% in alky l phenols, 7% in epoxy resins and 4% in tanning agents. The utility is now increasingly being extended to per­sonal and health care market which is gaining @ 10% annually. Phenols are increas ingly finding applications in such areas as eye make-up, hair tonics and dyes, mouth wash , germicides in soap, deodourants, shampoos , bio­cides and insect repellantsx7. However, the aldol prod­ucts besides possessing industrial applications are up­holding their utility in nascent areas. Diacetone alcohol is reported to affect chemical communications among As ian ElelphantsXX eliciting Flehman response and erec­tion in elephants with amazing effect, indicating its po­tenti al use in pharmaceutical industry. White crystallil e reaction products of urea, acetone and mes ityl oxide in the proportion 1-10% are used either directly or dispersed

346 J SC I I D RES VOL 59 MAY 2000

Tab le 3 - Proven processes and selec tivities of aldol chemicals of acetone

SI No. Aldol Cata lys t React ioll Reactor, reacti on Yield Select ivi ty Ref.

chemical tcmp.oC pcriod (h) (%) (%)

Diacetone a metal n Batch 26.7 92.1 7 1

(3gr l of feed 5

Ca(OHh:Ba(OHh,8H1O 20 Flow 12- 13 100 72

( I : 1- 15) (NA)*

BaO 0 batch 22.9 100 7.'

1.5

2 Mesityl SiCIjZn powder Room tcmp. Lab. Batch 25.9 60.n 7-1

ox ide ZnO - Zr01 (82 : I ~%) 450 0.8

Adiabatic 17.9 77.2 75

Oxides / hydroxides of Ce, ISO (LHSV 0 .7#h· l)

K, Zr, Hf, Ta, C r I h batch 15.9 87.4 76

Z110-Cr10.1 300 (NA)

Fixed bed 14.2 ~7.7 77

Activated wilh Fe10.1 (LHSV 0.3#h' l)

:I Isophorol1e Alka li hydroxide 240 Fi xed bed Flow 13.8 54 .9 7'11.

(93 Ig/h)

(0.36 h)

Fixed bed 2 1.8 64 .5 79

LHSV 2.0#h' l

Fixed bed 13.7 36.0 !lO

LHSV )

4 Phorone AIC I, . 10% Roomlemp. Lab. balch 22 24 8 1

5 Mesilylene HCI 200 Balch 39 3 1 X2

(NA)

AI 10 .1+ IO%Mo0.1 253 Fixed bed 38 74 83

(28 atm) (LHSV 0.99#h' l)

6 3,5-Xyleno l Lithium phosphale 530 Fixed ved 75.4 80.7 84

(NA)

MgO 580 Fixed bed 74.2 82.S 42

(L HS V 1.0)

Fixed bed 79 .6 83.2 42

(LHSV 0.5#h' l)

7 2.3.5- Magnesium 400-600 Fixed bed 8.6 A 85

Trimelhyl carbonalc / Mg (O H)2 (LHSV 0.1-3 )

phenol Cr10-Alp, / Cr10.r CuO :iOO-600 Fixed bed 100 ~6

8 III-Cresol Fe20.rAI10.1 400 Fixed bed 7 .6 3 1 45

NA = Dala no t availahle

RAMANAMURTY & SALVAPATI : VALUE ADDED ALDOL CHEMICALS OF ACETONE 347

in edible feeds for cattle, sheep, foxes , minks, skumps and poultry animalsx9.

India is the second largest (next to China) producer of vegetables (33 million tonnes) with a share of 13.38% in total global output. It is also a large producer of fruits (47 million tonnes), accounting for 10% of the world production. India occupies top position with regard to mangoes, bananas, grapes and chikku . But, our country is a very poor global player and its global market share is a meagre I %. It is worth noting that only 1.3% of the total fruits are processed against 40% in the developed countries. Though many reasons are given for these short falls, it needs attention for remedy regarding the use of obsolete technology, traditional methods of processing, lack of awareness with respect to scientific methods, etc. Aldol products of acetone show promising trends in this area also. To brief a few, phorone is reported to stimu­late greatly the stem and leaf growth in beansl x. It also showed marked reduction in the disorders regarding core flush , superficial scald and bitter pit in apples. It also decreased storage breakdown in apples l9 too. Aldol chemicals are also found useful as perfume and fragrance compounds . They are reported to impart roasted chicken like odour to certain food preparations911 .

Diacetone a1coholls bactericidal to staphylococei, and it considerably increases the bactericidal action of phenol'JI. The condensation product of diacetone alco­hol with urea, diacetone monourea, is reported to im­prove the egg laying capacity of hens92. Chlorionated isophorones are fungicides l4 . Isophorone is a selective insecticide against Ceratitis capitata, Daens olenc, Rhagoletis cerasi and Anastopha ludens but has limited affect on Musca domesfica (housefly)93 .

Hence, it may bp. concluded that acetone provides a potential source of a class of aldol chemicals a,~- un·, saturated ketones and phenols which be"ides being very important indmtrial intemediates show f!eW dimensions in their uti! i::y i.!1 pharmaceutical, foC'd ,'/eget~ble and allied indust{~e~ . The Jrocesses are ver; ' ecofriendly leav­ing p'~. s~d(, ;]!"Iyjuct except water necess iating nc efflu­e 1.t treat,!,F;n ~ . 'Che processp.s <>fP. als0 so versatile that by proper Gi'.oice ::Jf process :;orlli itlon ~ the reaction can be o~timized for the desired produc~ .

Acknowledgement The authors thank Dr K.V Raghavan, Director,

Indian Institute 'J~ Chemlcal Technology, Hyderabad for

providing facilities to carry out this work and giving permission to publish this paper.

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15 Salvapati G S , Ramanamurty K V, Janardanarao M & Vaidyeswaran R, Ind Pat, 167,840 (10 CSIR) , Yoshida Y, Japan

Pat , 08,245,486 (to Daicell Chem Japan) , 24 Sept 1996; Chel/l Ab.l'tr, 126 ( 1997) 7740 ; N etll Pal , 6 ,713 ,25 3 (Shell Intemationale Research Maat schappij NV) 0 I April 1968; Chem Abstr, 69 ( 1968) 96221.

16 Helmond V & Johannel PC M, Neth Pat, 7,113,138; 27 March 1973; Chel/l Abstr, 79 (1973) 67649.

17 Vinarski i M S, Mikitenko L N, Kochergin V A, Bibll L M & Kuznetsova T I, USSR Pat, 467 ,927 (From Otkryti ya lzobrct prom Obraztsy Tovarnye Znaki, 52 ( 15) ( 1975) 46) 25 April 1975; Chell! Abstr, 83 ( 1975) 117634.

18 Worley J F & Drowne M E, Nature, 223 ( 1969) 1386.

19 Wills R B H & Scott K J, J Hort Sci, 49 (2) ( 1974) 11 9: Chem

Abstr, 81 ( 1974) 146785.

348 J SCI IND RES VOL 59 MAY 2000

20 Salvapati G S & Janardanarao M, 1 Sci Ind Res, 42 (1983) 261. (1984) 19156; Ehsan M, Salvapati G S, Janardanamo M &

21 Salvapat i G S, Ramanamurty K V & Janardanarao M, 1 Mol Cawl, Vaidyeswaran R, Indian Pat, 151 ,656 (to CSIR), 18 June 19!D;

54(1989)9. Chem Abslr, 102 (1985) 78550.

22 Hauser M, Chem Rev, 63 (1963) 311. 42 Salvapati G S , Ramanamurty K V, Janaru anarao M &

23 Brande E A, Goffton B F, Lowe G & Waight E S, .I Chelll Soc, Vaidyeswaran R, Indian Pal, 167,840 (to CSIR ), 29 Decemher 1990, Chem Abslr, ll8 (1993) 61910; Illd Pal, 173,630 (to

(1956) 4054. CSIR), 1989; Chem Abslr, 125 (1996) 65699. 24 Bacon N, Brewis S, Usher G E & Waight E S , .I Chelll Soc, (1961) 43 Dolgov B N & Samsonova, Zlll/r Obshehei Khim, 22 (1952) 632;

2255 . Chelll Abslr, 47 (1953) 2691 . 25 Kirk R E & Othmer D F, Encyclopedia o/Chelllical Technology. 44 Nizovkina T V, Kataliz V Vyssbei Shkole Nin , VI'S shego I

Vol 13, (Wieley-Interseience, New York ), 1981 , p. 9 18. Sridnego Soecls Gbrazov SSSR Tr I-go (Pervogo) Mah - Vi z.So

26 Bailey W A (Jr) & Peterson W H, US Pal , 2,344,226 (to Sheila Veshch po Katalizu, Pt 2( I) (1958) 275 (Pub 1962); Chelll Abslr.

Development Co), 14 March 1944; Chelll Abslr, 38 (1944) 3300. 59 (1963) 8632.

27 Craven E C, 1 Appl Chem Lond, 12 (1962) 120 Fewlass M W, Br 45 Pardee Wm A & Weinrich W, hul Eng Chem , 36 (1944) 595 ;

Pal , 833,099 (to Distillers Co Ltd), 21 April 1960; Chem Ahslr, Chem Abslr, 38 ( 1944) 4170.

55 (1961) 1480. 46 Sa lvapati G S , Ramanamurty K V, Janardanarao M and

28 Craven E C & Fewlass M W, Br Pal, 832,124 (to Distillers Co Vaidyeswaran R, Appl Cawl, 48 (1989) 223.

Ltd), 6 April 1960; Cllem Ahslr, 54 ( 1960) 13 358. 47 Sai Prasad P S, David Raju B, RamaraQ K S, Salvapnti G Sand

29 Me Allister S H & Bailew W A Jr, Br Pal, 655.305 (to NV de Kantarao P. 1 Mol Calal, 78 (1993) L 19.

Bataafsehe Petroleum Maatsehappij) , 18 July 1951 , Cllelll Abslr, 48 Fritzheim M, Lang K F, Rappan L, SchweYIll E and Turowski J,

46 (1952) 2562; US Pal, 2,35 1,352 (to shell Development Co) , Gel' Pal, 1,254,155 , (to Reutgerswerke and Teeverwertung AG).

13 June 1944; Chem Abslr, 38 (1944) 5225. 16 November 1967; Cllelll Abslr, 68 ( 1968) 104725; Fr Pal, 1,538,224 (to Shell International Research Maatschappij, NV)

30 Pincs H & Ipatief V N, US Pal , 2,465,475 (to Universal Oil 30 August 1968; Chem Abslr, 72 (1970) 2 148 1. Products Co), 29 March 1949; Chem Abslr, 43 (1949) 5039. 49 Salvapati G S, Ph .D. Thesis (Osmania University, India) 1988 ,

3 1 Carbon C S, US Pal , 2,530,325 (to Standard Oil Development 12-14.

Co), 14 November 1950; Cllelll Abslr, 45 (1951 ) 2976. 50 Ullmanll:v Encyclopedia of fI/{IIISlrial Chelllislrl', Vol. AS. cd-'1

32 Ballard S A & Haury V E, US Pal, 2,419,05 1 (to Shell Develop- ited by Wgerhart z (VCH Verlags gesellschaft mBH Weinheim,

ment Co) , 15 April 1947; Chelll Abslr, 41 (1947) 4802. Germany) 1987, p.46.

33 Chem Ellg, 75 (27) 16 December 1968,56; Chem Ind, (23 May 51 Linduska J P, Cochrens J H & Morton F A, .I Econ Enlomol, 39

1970) 689. (1946) 767; Chelll Abslr, 41 (1947) 3580.

52 Golick A J & Stephan J T, US Pal, 3,336,246 (to West ri x Corp), 34 Payne R K, Clarke F K & Kenneth F, Fr Pal , 1,580,963, 02 6 October 1959; Chelll Abslr, 67 (1967) 82780.

Septmber 1969; Chelll Abslr, 73 (1970) 3654, Grat' K, Turowski , 53 Noesler H G, Schnege lberger H & Bell inger H, Gn Pal.

Collin G & Ruch K, Gel' Pell , 1,956,804, 19 May 1971 ; Cllem

Abslr, 73 (1971) 35389. 1,284,040 (to Henkel and Ge GmbH) , 28 November 1968; Chelll Abslr, 72 ( 1970) 6252.

35 Dedina J, Henco & Offutt W C, US Pal, 3,284,5 14 (to Gulf Re- 54 Kitchen L J, Albert HE & K Smith G E P, Ind Eng Cllelll , 42 y

scarch and Development Co), 08 November 1966; Chelll AinU', (1950) 675 . 66 (1967) 28515.

55 Jucnger H & Weissent'els F, Gel' Pal , 1,8 15 ,897 (to Dynamit 36 Bajer F J & Carr R L K, US Pal, 3,394, 399 (to Hooker Chemical Nobel AG), 02 July 1970; Chelll Abslr, 73 (1970) 56767.

Corp) , 23 July 1968; Chelll Alwr, 69 (1968) 106230. 56 Burke W J, Warburton J A, Bishop J L & Bi lls J L, .I Olg Chelll .

37 Nellr Pal, 6,613,970 (to Imperial Chemical Industries Ltd) , 5 April 26 (1961) 4669; Sato K & Abe S,.I Olg Chem , 28 (1963) 1928;

1967; Chem Abslr, 68 (1968) 12689. Caldwell W T & Thompson T R , .I Am chem Soc, 61 ( 1939)

Toland Wm G Jr, US Pal, 2,762,838 (to California Research 765. 38

57 Furuya H & Tani guchi K, lap Pal , 62, 242,58 1, 23 October 1987; Corp), II September 1956; Cirelli Abslr, 51 (1957) 5831, Barnard R D & Meyer R H, US Pal, 2,852,567 (to Dow Chemical Co) , Chell! Abslr, 109 (1988) 148744.

16 September 1958; Cirelli AIJs/r, 53 ( 1959) 10128. 58 Nakamura S, Ehara T & Sakata H, .lap Pa!, 3,221 ,51 () (To Dai

39 Raj P, Akmal M A K, Subbarao Y V, Ahmed S M & Vaidyeswaran nippon Inc and Chemicals Inc), 30 September 1991: Cirelli Ahs/r, .. Il6 (1992) 42561.

R, 1 Appl Clrem, ( 1970) 352. 59 Kajita T, Okuda C. Miura T & Shimokawa T. lap Pat, 3. 128.959

40 Subba Rao Y V, Pridvi Raj , Vijaysarathi A, Maliikarjunan M M. (Japan Synthetic Rubber Co Ltd), 3 1 May 1991 ; Cirelli Ahs/I', Sarma P P Sand Vaidyeswaran R, .I Mines Melells & Fuels, Il6 (1992) 48927. (1969) 75 .

60 Copes G V, Mart in J T & Byrde R J W, AI/n Rep! Agr HoI'/ Re-4 1 Janardanarao M, Salvapati G S. Ehsan M & Vaidyeswaran R, search S/a, Long Ashton Bristol (1956), 101 ; Cllelll Ah.l'/r, 52

Indian Pal, 151 ,690 (to CSIR ), 02 July 1983; Cirelli Abs/r, 100 (1958) 14064.

RAMANAMURTY & SALVAPATI : VALUE ADDED ALDOL CHEMICALS OF ACETONE 349

61 Tocker S, US Pal, 3,288,880 (EI de pont de Nemours & Co), 29 76 Maki T, Yokoyama T & Sumino Y, lap Pal , 63 ,225 .329 (to November 1966; Gem Abslr, 66 ( 1967) 2960 I. Mitisubishi Kasci Corpn), 20 September 1988; Cho ll Ah.l'lr, llO

62 Schoenthalcr W, Sauer H, Hans G, Lohmann & Ni emann , Ger ( 1989) 38619.

Pal, 1,694,853. (Ruetgerswere A-G), 13 February 1975 ; Chelll 77 Macho V, Polievka M & Gregor F, Czech Pal, 122,761, 15 Apri l

Abslr, 83 ( 1975) 80473. 1967; G em Abslr, 68 ( 1968) 29258.

63 Tevis M, Kai tz C & Maier G D, US Pal, 4,022,911 , (to Damon 78 Yoshida Y, l ap Pal, 8,245,485 (to Daicel Chem, Japan), 24 Sep-

Corp) , 28 August 1967; Chem Abstr, 87 ( 1977) 29035 tember 1996; Chem Abslr, 126 ( 1997) 7739.

79 R a manamurty K V, S a lvapat i G S , J anardan a rao M & 64 Leon N H & Ricketts GAG, US Pal, 4,212,645 , 15 July 1980;

Vaidyeswaran R, Proc. 81h Nalional Symposilllll on Calal.l'.I'is, . Chell! Abslr, 94 ( 198 1) 20235.

Sindri,India, 12- 14 February 1987, 649. 65 Leach B E, US Pat , 4,084,006, II Jul y 1973; Chelll Ahslr, 89 80 Ramanamurty K V & Salvapati G S, Indian.l Chem, 38B ( 1999)

( 1978) 5356 1. 24.

66 Szczepanek A & Koenen G, US Pal , 3,297,584 (to Chemische 81 Koniezny M & Sosnovsky G , Natur Forsch B, Anonl Chelll OIR Fabrik Hoesch K-G), 10 January 1967 ; Chem Ahslr, 66 ( 1967) Chem , 33B ( 1978) 454; Chem Absu',-89 ( 1978) 237 16. 56201. 82 Ipatiev V, Doglov B & Volnov I, Ber, 63B ( 1930) 3072.

67 Kranse H, Mi cek K P, Taeger R, Seyforth H E, St rauss K H & 83 Hwang Y, Kraver W A & Sandner W A, UK Pal , 92 1,510 (to Wiesener E, Ger Pal, 270,549 (to VEB Chemic Laserkombinat Shawinigan Chemicals Ltd), 1963; Chem Abslr, S9 ( 1963) 9802. Schwarza a:Wi lhelm Pi eckiE), 02 August 1989; Chelll Ahslr, 84 Brarinock K C & Hargis C W, US Pal , 3,833,673 (to Eastman 112 ( 1990) 58 196 Kodak Co) , 3 September 1974; Chem Abslr, 81 ( 1974) 169290.

68 Hagiwara Y, Bril Pat, 2,206,35 I (to Minnesota Mining and Mfg 85 Weghofer H J M, Nelh Pal , 6,713 ,253 (to She ll International

Co), 05 Janu ary 1989; Yokota H, Tanabe F, Kit amura A & Research), 0 I Apri I 1968; Chem Abslr, 69 ( 1968) 9622 1.

Asoshina H, lap Pal, 01,182,372 (to Nitto Denko Corp), 20 86 Talley J J, US Pal , 4,55 1,563 (to General Electric Co) , 05 No-Jul y 1989; Chelll Abslr, 112 ( 1990) 58385. vember 1985; Chelll Abslr, 104 ( 1986) 109204.

69 Wei nhaus 0 , Fischer K, Beer V, Fieseler C, Kemter P & Hirsch 87 Noes ler H G , Schnegelberger H & Bellinger H, Ger Pal,

B, Ger Pal, 279,389 (to Techni sche Univeritaet, Dresden), 06 1,284,040 (to Henkel and Cie GmbH) , 28 November 1968; Gelll

June 1990; Chem Abslr, 114 ( 199 1) 11690 I. Abslr, 72 ( 1970) 6252.

70 Mookherjee B D & Trenkle R W, Bril Pal , 2,1 65, I 50 (to Inter-88 Rasmussen L E, Schmidt M J & Daves G D, Chell! Sigllals Ver/ehr

national Flavours and Fragrances Inc), 09 Apri l 1986; Chem (Proc Int ConI' 4th 1985) 627; Chem Abslr, 107 ( 1987) 94305.

Abslr, 106 ( 1987) 55675. 89 Harvey M T, US Pal, 2,592,565 (to Harvel Research Corp) 15

71 Belg Pal, 613 ,490 (to Nippon Sekiyu Kabushik i Kais ha), 28 April 1952; Chelll Abslr, 47 (1953) 601.

February 1962; Chen! Abslr, S7 ( 19.62) 136 18. 90 Noleau I & Tou lemonde B, LebenslIlwiss Technol, 20 ( I) ( 1987)

72 Yamada S, Noguchi S & Tago S, .lap Pal , 456 (58) (to Nippon 37 ; Chem Abslr, 107 ( 1987) 174659.

Oil Co), 30 January 1958; Chem Abslr, S3 ( 1959) 615. 91 Cooper E A, 1 Soc Chem IlId, 64 ( 1945) 5 I ; Chelll Ah.l'lr, 39

73 Bourdio l C & Ducasse, Bull.Soc Chim Fr, 8 ( 194 1) 375. ( 1945) 3566

~ 74 Galun A, Israeli Pal , 25 ,589 , 21 May 1970; Chelll Abslr, 73 92 Harvey M T, US Pal, 2,782, 197 (to Harvel Research Corp) 19

( 1970) 34804. February 1957; Chell! Abslr, SI ( 1957) 12157.

75 UK Pal , 909 ,941 (to Esso Research and Engi ncering Co), 7 No- 93 Rohr 0 , S Afr Pal, 69 ,06,439 (to C IB A Ltd), 18 March 1970;

vember 1962; Chem AinU', S9 ( 1963) 2652. Chell! Abslr, 74 ( 197 1) 5249 1.