Vinyl ketostearates. Preparation, properties, infrared spectra, and analysis of 4- and 12-ketostearates

1 3 2 T m ~ : , I O U R N A L OP T H E A M E R I C A N O I L C I - I E M I S T S ' SOCIETY VOL. 37

The l i terature gives pollnd-cal~e volume values of around 250 as being the best obtainable. The cake baked with palladimn catalyst shortening had a finer texture. This shm'tening was tested by official Fed- eral Stalnlards for iodine nulnber, acidity, stability, moisture, and smoke point (10). It was satisfactory in all tests.

Summary Shortening stocks obtained in the pihit plant dif-

fer slightly f rom those obtained in the laboratory under nominally the same (~onditioi,s. Pi lot-plant processing is easily controlled to give a ei)lnmercially at t ract ive shortening at a ,.o,~t i'olnpetitive witb nickel. By repeated re-use I g. of 5% palladium on carbon catalyst wi|l hyflrogeim.te about 718 kg. of oil to a satisfactory product, and I g. of 2% palla- dinni on earbon catalyst about 11 kg. of oil.

Acknowledgment The members of the research laboratories of Engel-

hard Industries Inc. are indebted to Edward Hand- sehumaker of Spencer Kellogg and Sons inc. for helpful discussions and confirmatory analytical data, also for deodorizing samples of our product.

]~EFERENCES 1. Za~cew, Mykola, J. Am. Oil Chemists' Soe., 87, 11-14 (1960). 2. Zajcew, Mykola, J. Am. Oil Chemists' Soc., 35, 475-477 (1958). 3. Za.i('ew, Mykola, Fettc, Seifen, Anstriehmittel, 60, 1051-1052 (1958) . 4. Cohn, G., Anal. Chem., 19, 832-835 (1947). 5. American ()il Chenlists' Society Os and Tentative Methods,

edited by M(qllenbachcr, V. C., and Hopper, T. It., 2nd ed., l~ev. 1958, Chicae'o, Ill.

6. Sworn, Daniel, Knight, H. B., Shreve, O. D., and I-Ieether, M. R., J. Am. Oil Chemists' So('., 27, 17-21 (1950).

7. O'Connor, :R. T , et at., J. Am. Oil Chemists' So('., 34, 600-603 (t957).

8. Bailey, A. E , "Industr ia l Oil and Fat Products, 1951," 2nd ed., lnters(.ience [)ublishcrs ]n('., New York, p. 691.

9. Steffen, A. H., and ~ n d e r Wal, :R. J., J. Am. Oil Clwmists' So('., 34, 159-161 (1957).

10. Federal Standards Stock Catalog EE-S-321.

[.Re<'cived A u g u s t 31, 1959]

Vinyl Ketostearates. Preparation, Properties, Infrared Spectra, and Analysis of 4- and 12-Ketostearates l ROBERTO CALDERON,'-' H. P. DUPUY, E. R. McCALL, R. T. O'CONNOR, and L. A. GOLDBLATT, 3 Southern Regional Research Laboratory, 4 New Orleans, Louisiana

T IlE PREPARATION of vinyl 4 - a n d 12-ketostearates was under taken to provi(le monomers ff)r polymerization and copolynmrization investigations,

to determine the potential ut i l i ty of vinyl keto esters as internal plasticizers, and to s tudy the effect of the position of the keto group. P(ilymerization studies will be reported elsewhere.

Vinyl esters of hmg-ehain fa t ty acids have gener- ally been prepared either by reacting all excess of vinyl acetate with the fa t ty acid in the presence of a mercuric sulfate catalyst or by vinylation of the f a t ty acid with acetylene in the presence of zinc salts (5, 10). 12-Ketostearic and 4-ketostearic acids, which have previously been reported (2), were vinylated with vinyl acetate according to the general procedure of Adehnan (1).

The i n f r a r e d s p e c t r a of me thy l 4 -ke tos t ea ra t e , methyl 12-ketostearate, 4-ketostearie acid, 12-ketostearie acid, vinyl 4-ketostearate, vinyl 12-ketostearate, and the ~/-laetone of 4-hydroxy-2-oetadecenoie acid were detelmained in carbon tetrachloride solutions. The absorption bands in the 5.6 micron region (characteristic of the laetone-carbonyl), 5.7 micron region (char- aeteristic of the ester-earbonyl), 5.8 micron region (eharaeteris*ie of ketone-earbonyl), and 6.1 micron region (characteristic of the vinyl group) were stud- ied and used as a basis for quanti tat ive determination of these groups.

* Presented at the nard fall meeting. American Oil Chemis~,s' Society, Los Angeles, Calif., September 28-30, 1959.

2Fellow of the Banco de M@xico. (Present address: Institnto :M'exi- cano de Investigaciones Tecn616gieas, Lcgaria No. 694, Mexico 10, D. :F., :NIexico.)

a Present address: Western Utilization :Research and Development Division, Agricultural Research Service, U. S. Department of Agricul- ture, Albany, Calif.

4 One of the laboratories of the Southern Utilization tCesearch a n d Development Division, &grienltural R~esearch Service, U. S. Depar tment of Agriculture.

Experimental Materials. Commercial methyl ]2-hydroxystear'ato.

obtained from hydrogenated castor oil, Brazilian oiti- ciea oil (ca. 56% conjugated triene, calculated as eleostearic acid), Eas tman 's p-dioxane and practical grade vinyl acetate (freshly distilled), Merck's reagent grade mercuric acetate, Girdler 's supported- t y p e ( e l ee t ro ly t i ca l ly p r e c i p i t a t e d , d r y - r e d u c e d ) uick~-q catalyst, Baker ' s reagent grade sodium acetate, chromium trioxide, sulfuric acid, potassium carbonate, glacial acetic acid, methanol, petroleum ether (b.p. 30-60~ and acetone, and Johns-Manville 's analytical filter-aid (Celite) were used.

Methyl 12-Ketostearate. Commercial methyl 12-hydroxystearate was fract ionally distilled under high vacuum. DistiIlate fractions (b.p. 191~ mm., :Rl.p. 54.5-55.4~ were oxidized with chromic acid by the general procedure of Rockett (1.7). To a 5-liter flask, equipped with a mechanical stirrer, a thermometer, and a dropping funnel, were added with s t i rr ing 660 ml. of glacial acetic acid and 314 g . (1 mole) of me thy l 12 -hyd roxys t ea r a t e . The t e m p e r a t u r e was maintained between 30. and 32~ while adding drop- wise, with stirring, a solution of chromic acid (92 g. of chromic acid, 67 ml. of water, and 1320 ml. of glacial acetic acid) in about 2 hrs. The tempera ture was maintained between 35 and 40~ for 90 rain. The mixture was poured into 5 liters of water contained in a separatory fmlnel. Af ter shaking the mixture gently and allowing it to stand for a few hrs., the aqueous layer was drained off. The ester layer was heated to boiling in 3 liters of 6 N hydrochloric acid for 10 rain. After siphoning out the aqueous layer, the ester was again heated in 1 liter of 6 N hydro- ehh)ric acid for 10 rain. The ester was washed twice

MARCH, 1960 CALDERON ET AL.: VINYL KETOSTEARATES 133

with 3 liters of boiling water. Methyl 12-ketostearate was crystallized f rom 10 volumes of methanol at 5~ yield 220 g. I t s earbonyl oxygen content (11) indicated it was reasonably pure kcto ester.

Anal. Caled. for C19HaaO3: C, 73.03; H, 11.61; carbonyl O, 5.12; sap. equiv., 312.5. Found: C, 73.01; H, 11.36; carbonyl O, 5.10; sap. equiv., 311.6; m.p. 45.3-46~ n ~~ 1.4391.

12-Ketostearic Acid. Methyl 12-ketostearate (220 g.) was refluxed with an alcoholic potassium hydroxide solution (700 ml. of 1.5 N potassium hydroxide in 80% ethanol) for 1 hr. The warm soap solution was poured slowly, with vigorous stirring, into 1 liter of 1.5 N hydrochloric acid: The 12-ketostearic acid was filtered off, washed with boiling water, then crystallized fronl 3 volumes of acetone at 25~ yield 159 g.

Anal. Calcd. for Clsl134Oa: C, 72.43; H, 11.48; carbonyl O, 5.36. Found : C, 72.44; It , 11.57; car- bonyI O, 5.35; m.p. 82.0-82.5~

Vinyl 12-Ketostearatc. 12-Ketostearic acid was vinylated, employing a 5-molar excess of vinyl acetate in the presence of a mercuric acetate-sulfuric acid catalyst, according to Ade lman ' s (1) vinyl inter- change reaction. To a l - l i ter flask, equipped with a thermometer , were added 298 g. (1 mole) of 12-ketostearic acid and 516 g. (6 moles) of vinyl acetate. This mixture was heated to 70~ while being swirled gently. Thcn 0.1 g. of copper resinate and 6.0 g. of mercuric acetate were added. When all these materials were in solution, 0.83 ml. of concentrated sulfuric acid was added while the mixture was swirled gently. The reaction mix ture was mainta ined between 38 and 42~ for 48 hrs. Maximmn conversion obtained was 65%. The reaction was stopI)ed by adding 3 g. of sodium acetate and s t i r r ing the mix ture for 15 rain. The reaction mixture was dissolved in 2 liters of diethyl ether and washed twice with l - l i ter portions of water. The ethereal solution was then extracted with a slight excess of dilute potassium carbonate (800 ml. of 10% potassium carbonate) to remove the free f a t ty acids. Af te r distilling the ether and excess vinyl acetate under reduced pressure, the crude vinyl ester was distilled rap id ly under high vacuum to rcmow'~ traccs of mercury. Distil late fract ions (b.p. 175-200~ ram.) were dissolved iu 10 volmnes of ether and re-extracted with dilute potassium carbonate. Af t e r distill ing the ether under reduced pressure, v iny l 12 -ke tos t ea ra t e wets success ive ly c rys t a l l i zed front 3 volunms of acetone at 5~ in the presence of 0.02% hydroquinone, and from 15 volumes of petro- leunt ether at - 5 ~ yield 150 g. I ts I[ . l .V. (hydro- gen iodine value) (15) indicated that it was reasonably pure vinyl ester.

A,~al. Caled. for C,)0[-Ia~Oa: C, 74.02; 1I, 11.18; carbonyl O, 4.93; H.I .V., 78.2. Fouud: C, 73.90; H, 11.16; earbonyl O, 4.95; l t . I .V. , 78.0; m.p. 48.2- 48.8~ ; n 5~ 1.4457.

Methyl 4-Ketostearatc. One kg. of Brazi l ian oiticica oil, having a H.I .V. of 185, was hydrogenated in a P a r r pressure reaction appara tus at 30 p.s.i, in the presence of 40 g. of supported-nickel catalyst (20% nickel and 80% coconut oil and (liatomaceous earth) at about 150~ dur ing a 24-hr. period, to an H.I .V. of about 5. The hot hydrogenated oil (ca. 100~ was filtered by suction through a thin layer of hot filter-aid to remove the catalyst. The hydrogenated oil was interesterified with methanol (650 ml., 5-molar excess) in the presence of a 1% sodium methoxide catalyst , at about 70~ dur ing a 2-hr. period. The

warm methy l esters were poured into 500 ml. of N hydrochloric acid contained in a separa to ry funnel, then the mixture was shaken gently. Af t e r the aqueous layer was removed, the esters were washed with a 500-ml. port ion of wa rm distilled water. The crude esters were f ract ional ly distilled under high u Disti l late fract ions (b.p. 170-180~ ram.) were crystall ized f rom 12 volumes of acetone at 5~ to precipi tate most of the nonketo esters. Af t e r the acetone was evaporated under reduced pressure, methyl 4-ketostearate was successively c rys ta l l ized f rom 15 volumes of petroleum ether at 5~ f rom 15 volumes of methanol at 5 ~

Anal. Calcd. for C19Hae~()a: C, 73.03; H, 11.61 ; carbonyl O, 5.12; sap. equi-J., 312.5. Found : C, 72.91; H, 11.67; carbonyl O, 5.09; sap. equiv., 312.4; m.p. 47.3-48.0~ n "~~ 1.4391.

4-Ketostearic Acid. Methyl 4-ketostearate was sa- ponified, the soap solution was acidified, and the f a t ty acid was crystallized as described for 12&etostearic acid.

Anal. Calcd. for ClsHa4()a: C, 72.43; H, 11.48; carbonyl O, 5.36. Found: C, 72.45; H, 11.57; carbonyl O, 5.26; m.p. 96.5-97.1~

Vinyl 4-Ketostearate. 4-Ketostearic acid was vinylated, and the vinyl 4-ketostcaratc was purified as described for 12-ketostearie acid and vinyl 12-kcto- stearate, respectively.

Anal. Calcd. for C~oll:,;()a: C, 74.t)2; II , 11.18; H.I.V., 78.2. Found : C, 73.(i3; Ii , 11.23; I[ .I .V., 78.0; m.p. 53.6 54.2~ n ~m/D 1.4411.

-/-Lactonc of 4-Hydroxy-2-Octadecc~to,ic Acid. 4-Ke- t(~stearic acid was reih~xcd, in the l)rescnce of a sulfuric acid catalyst, for 4 hr. in a (tioxanc solution (20 g. of 4-kctostearic acid, 60 ml. of dioxane, and 0.5 ml. of sulfnric acid). Thc mixture was t)oured into 4 volumes of diethyl ether and extracted three times with 100-mI. portions of 10% aqueous potassium carbonate. Af te r the ethereal solution was evaporated under reduced pressure, the residual nmter ia l was crystallized fronl 10 vohtmes ()f acetone at - 5 ~ In f r a r ed and ultraviolet analyses indicated that the -/-lactone of 4-hydroxy-2-o~t*adeccnoic acid ra ther than the wlactone of 4-hy(Iroxy-3-o(:tadeeenoic acid was formed.

Anal. Calcd. for (),.slla.,():: C, 77.08; H, 11.50; sap. equiv., 200.08. Found: C, 76.56; 11, 12.24; sap. equiv., 195.35; m.p. 48.5-4!1.3~ ; n r'''/l' 1.4487.

Spectrophotometric Detcr'mi~atio'~s. Complete in- f ra red absorption curves from 2 to 12 microns of all compounds investigated were. obtained with a Perkin- Elmer Model 21 infrared spcetrophotometer . Sett ings used were resolution, !)27; SUl)l)rcssion, 3; gain, 6; response, 1; and speed, 0.5 micron/rain. The spectra of the esters, acids, and lactone were obtained in carbon tetrachloride solutions at about 10, 6, and 5 g . / liter, respectively, with a 0.48-ram. absorpt ion cell. The absorption of the lactone-carbonyl, ester-carbonyl, ketone-carbonyl, and vinyl group at about 5.6, 5.7, 5.8, and 6.1 microns, resl)ectively, were determined at various concentrat ions in carbon tetrachloride solutions.

Results and Discussion

l'rcparalion of Compow~d.~. 12-Ketostearic acid was readily p repared by fract ional ly distilling commercial methyl 12-hydroxystearate, followed by oxidation of the hydroxy ester with a chromic acid solution, saponification of the keto ester, acidification of the

134 THE JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY VoL. 37

soap of the keto ester, and crystallization of the keto acid from methanol. About 65% conversion of the keto acid to the vinyl keto ester was obtained when the keto acid was reacted in the presence of a mercuric sulfate catalyst and an excess of vinyl acetate at 40~ for 48 hrs. Attempts to pur i fy the reaction mixture by distillation under high vacuum resulted i~l excessive polymerization. However, af ter the reaction mixture was dissolved in diethyl ether and the fa t ty acids and the inorganic materials were extracted with a dilute, aqueous solution of potassium carbonate, distillation was successful. Vinyl 12-ketostearate was readily obtained from suitable distillate fractions by dissolving in diethyl ether and re-extracting with dilute potassium carbonate, to remove traces of keto acid, followed by successive crystallizations from acetone and i)etroleum ether.

Methyl 4-ketostearatc was prepared from Brazilian oiticica oil with somc diffi(~ulty. A considerable amount of polymerized nlaterial was present in the processed oil, thus decreasing the amount of available licanic acid (4-keto-9,1],13-octad(~catrienoic acid, the princi- pal component of oiticica oil). Lactonization of the 4-keto acid (which produced two ~/-laetones) occurred during hydrogenation, and only a small amount of the ~,-laetones was hydrolyzed dur ing the interesterifica- tion of the hydrogenated oil with methanol. Attempts to pur i fy the crude methyl esters by prolonged ~rac- tional distillation, through a packed column under high vacuum, resulted in excessive decomposition. lh)wever suitable fractions of methyl 4-ketostcarate were obtained by rapid distillatio,l u~lder high vacuum. This concentrated the nonkcto esters in the early fractions, gave a heart cut of keto ester, and left the more highly mlsaturatc(l and polymerized materials ill the pot residue. The suitable fractions were crystallized from acetone to precipitate the re- maining nouketo esters. Af ter the acetone was evaporated u~lder reduced pressure, methyl 4-ketostearate was obtained by successive crystallizations from petroleum cther and methanol.

A considerable amount of ]actonizatiou occurred dur ing the x, inylation of the 4-ketostearic acid. How- ever relatively pure vinyl 4-ketostearate could be obtained by dissolving the vinylated mixture in diethyl ether and extract ing the fa t ty acids with a dilute aqueous solution of potassium carbonate, followed by rapid distillation under high vacuum to remove traces of mercury. Suitable fractions were successively crystallized from acetone and petroleum ether.

Since it was impossible to duplicate the saponification equivalents of the vinyl esters, they are not reported. In saponification acetaldehyde, the tautomer of vinyl alcohol, apparent ly reacts with some of the alkali, thus indicating abnormally high saponification equivalents. Vinyl 4-ketostearate was slowly hydrolyzed in an aqueous-alcoholic solution of hydroxylamine hydrochloride. Therefore its carbonyl oxygen value is not reported since the acetaldehyde formed dur ing the hydrolysis also reacted with the hydroxylamine.

I n f r a r e d Spec t ra . Fischmeister (7) in a note dis- cussed briefly the inf rared absorption of the methyl esters of monoketostearic acids. Progression bands (9, 12) were found in K B r disc spectra between 7.4 and 8.4 microns, which permit ted complete identifica- tion of the different positional isomers. These bands ~ere determined mainly by the distance between the

lOC 9 C 8O 70 60 50 40 30 20 I0 0

90 80 70

6C f 4C

~ 3c ~ 2O

z C ~ 9r

. c 7C

~ 6 C - ~ 5c

4G 3G 2O IO 0

9a 80 7O 60 5O 4O 30 2O I0 0

i ~ l , i i i i I I I

! 5.75 :5.45

B

,.44 5.75

k 4 4 5.70 6.66

5 . 4 3 5 . 6 9 8 . 7 ~ I I I I I I I ] I 3 4 5 6 7 8 9 I0 II 12 13

WAVELENGTH (MICRONS) FIG. 1. Infrared spectra of methyl and vinyl ketostea~ates in

carbon tetrachloride solution. A, methyl 4-ketostearate; B, methyl 12-ketostearate; C, vinyl 4-ketostearate; D, vinyl 12- ketostearate.

carbomethoxy and keto groups. No solution-spectra data were reported.

Carbon tetrachloride solution spectra of methyl 4-ketostearate, methyl 12-ketostearate, vinyl 4-ketostearate, and vinyl 12-ketostearate are given in F igure 1. The spectra of 4-ketostearic acid, 12-ketostearic acid, and the 7-1aetone of 4-hydroxy-2-octadecenoie acid are given in F igure 2. F rom previously reported investigations of long-chain compounds (14) correlations of the bands which appear in these spec- t ra with vibrational groups giving rise to them can be made with considerable degree of certainty. Table I lists the wavelength positions of absorption maxima for all bands with absorptivities of ca. 0.05 or more, with their most probable assignments for the seven compounds.

The different classes of compounds can readi ly be identified by their in f ra red absorption spectra. Methyl esters are characterized by the C - H deformation (COOCH3) band at 6.97 microns; the vinyl esters are characterized by the C--H deformation ( C H e = C H ) bands at 6.07, 10.53, and 11.49 microns; the keto acids are characterized by the O--H deformation (COOI-I) band at 10.74 microns (13) ; and the ,/-lactone is characterized by the vibrat ion (lactone r ing) band at 10.99 microns and the C=O stretching at 5.6 microns.

The stretching of the ]actone-carbonyl, ketone-carbonyl, ester-carbonyl, and vinyl group were easily resolved in carbon tetrachloride solution. Their ab-

MARCH, 1 9 6 0 C A L D E R O N E T A L . : V I N Y L K E T O S T E A R A T E S 1 3 5

I00 9 0 80 70 60 5 0 4 0 3 0 2 0

~ . I 0

0

8o 7o 6 0

z 5 0 4 0

_. 3 o 20 3.43

z IC r C

9(] t 8G 7G 6(] 50 40 30 2.0 3.43 IO

i.44 5 .84

6 .85

5.85

8.53

5.6(

I I I I I 1 I I 5 6 7 8 9 I0 II 12

WAVELENGTH (MICRONS) 13

:Fro. 2. Inf rared spectra of ketostearie acids and the laetone of 4-ketostearic acid. A, 4-ketostearie acid; B, 12-ketostearic acid; C, ~/-lactone of 4-hydroxy-2-octadecenoic acid.

sorpt ion bands were used for quant i ta t ive determi- nat ion of 7-1actone (Aa,~-butenolide), methy l keto ester and vinyl keto ester. As shown in F igure 3, the absorpt ions of these various carbonyl groups and vinyl group obey the Lamber t -Beer law over a wide range of concentrations. Lactonizat ion of 4-ketostearic acid dur ing hydrogenat ion of the oiticica oil and during vinylat ion of the 4-ketostearic acid, and purifica- t ion of the methyl keto esters and vinyl keto acids were conveniently followed by in f ra red analyses. In addition, in f ra red analyses help to establish the struc- ture of the two 7-1aetones formed dur ing the lactonization of 4-ketostearic acid.

Previous invest igators (4, 6, 8, 16, and 18) have found tha t Aa,~-butenolides absorb in the inf rared region at about 1750 cm. -1 (ca. 5.7 microns) and in the ul t raviolet region between 200 and 220 millimicrons and tha t A~,~-butenolides absorb in the infrared region at about 1800 cm. -~ (ca. 5.55 microns) . Therefore the lactone which absorbed at 5.6 microns was assigned the s t ruc ture of the 7-1actone of 4-hydroxy-2-octadecenoic acid (],-tetradeeyl-A~,~-butenolide) and the lactone which absorbed at 5.53 microns was assigned the s t ruc ture of the ~,-lactone of 4-hydroxy-3-octadecenoic acid (7-tetradeeyl-A~,~-butenolide). This was confirmed by ul t raviolet analyses as the A~,~-butenolide absorbed at 214 millimicrons and the A~.~-butenolide did not have any absorption peak in that region. When a mixture of the two laetones was heated, the A~,~-butenolidc isomcrized to the A~,~-buten(/lide, as indicated by a del'xease in absorption at 5.5'1 mi(;rons and an increase ill absorption at 5.6 microns. This is consistent with the find-

u~ 1.2 z 0 n,- o I.C

~E

O.e I,-

' . ' O.E 0 Z

0.4 O o3 IIB < 0 2

z 0 I.( nr

:E 0.8 r

0.6

0 Z 0.4 III 0g O u~ 0.2 m .<

- 1.2

I . 1.0

t / ~ 0.8

0.6

0.4

0.2

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.</ ~>"

I o .5 0.2

0.1

2.5 5D 7.5 I0.0 12.5 15.0 17.5

CONCENTRATION IN G R A M S / L I T E R

-- / /r

[ I I I l I i 2.5 5.0 7.5 I0.0 12.5 15.0 17.5

'm'.

2.5 5.0 7.5 I0.0 12.5 15.0 17.5

CONCENTRATION IN G R A M S / L I T E R

0D U~ 0

Z 0 m

"4

O Z U}

O -n O3

Z O m

m

O

O Z ID

I I I . O, methy l 4 -ke tos tea ra te A, methy l 12-ke tos tea ra te D , v iny l 4 -ke tos t ea ra t e 0, v iny l 12-ke tos tea ra te

I V . O , v iny l 4 -ke tos tea ra te A, v iny l 12-ke tos teara te

some of their derivatives. I . O, 5,-laetone of 4-hydroxy-2-

octadecenoic acid I I . O , methy l 4 -ke tos tea ra te

~ , me thy l 12-ke tos tea ra te El, v iny l 4 -ke tos tea ra te <>, v iny l 12 -ke tos t ea ra t e

:FIG. 3. Relationship between the absorbance of various earbonyls and vinyl groups of ketostearic acids and

1 3 6 T H E J O U R N A L O F T H E A M E R I C A N O I L C H E M I S T S ' S O C I E T Y V O L . 3 7

ings of Cocker et al. (3) that the Au,~-butenolides are more stable than the ~r The ~,-lactone of 4-hydroxy-2-oetadecenoic acid was isolated in rela- t ively pure form, but the 7-1actone of 4-hydroxy-3- octadecenoic acid was merely concentrated.

S u m m a r y

Vinyl 12-ketostearate and vinyl 4-ketostearate were p repared by v inyla t ing 12-ketostearie and 4-ketostearic acids, respectively, with vinyl acetate in the presence of a mercur ic sulfate catalyst. The crude vinyl esters were purified by extract ing the free f a t t y acids with dilute potassium carbonate, removing the mercury by distillation, and crystall izing successively f rom acetone and pet roleum ether.

In f ra red analyses revealed that laetonization occurred with the 4-ketostearic acid dur ing the hydrogenation of the oiticica oil and dur ing the "r (If the keto acid. Two y-laetones were produced. The 7-1el;tone of 4-hydroxy-2-octadecenoic acid was isolated

T A B L F I

Absorp t ion B a n d s in the I n f r a r e d Spec t ra of 4- and 12-Ketos tear ic Acids and Some of T h e i r D e r i v a t i v e s

Fun( . t ional g r o u p

C - - H s t r e t c h i n g C - - H s t r e t c h i n g C = O s t r e t c h i n g

(Aa,~-butenol ide) C----O s t r e t c h i n g

(a( . id)

C ~ O s t r e t c h i n g (i~stcr)

C- -O s t r e t c h i n g (ke tone )

C H ~ = C H s t r e t c h i n g C - - I I d e f o r m a t i o n c - - n d e f o r m a t i o n

(COOCH~) C - - I t d e f o r m a t i o n ( ) - -H de fo rma t ion C--O s t r e t c h i n g

C - - O - - C s t r e t c h i n g U n a s s i g n e d CH~----CH d e f o r m a t i o n

O - - H d e f o r m a t i o n ( C O O H )

Lac tone r i n g

W a v e h m g t h posi t ion of m a x i m a ( m i c r o n s ) a

A l~ C D E F G

3.45 3.44 3.44 "1.43 3.44 3.43 3.43 3.52 3.51 3.5,'1 3.51 3.52 3.51 3.51

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.60

. . . . . . . . . . . . . . . . . . . . . . . . 5 .70 5.70 ...... 5.84 5.85

5.75 5.75 5.70 5.6!} . . . . . . . . . . . . . . . . . .

5.82 5.83 5.82 5.82 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.08 6.07 . . . . . . . . . . . . . . . . . .

6.85 6.85 6.84 6.84 6.85 6.85 6.85

6.97 6.97 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.10 7.10 7.11 7.09 7.08 7.97 7.04 7.37 7.35 7.37 7.34 7.32 7.31 7.42 8.35 8.37 8.66 8.75 7.80 7.81 7.83 8 .54 8 .58 8.53 9.16 9.04 9.17 9.04 . . . . . . . . . . . . 8.89 9.84 9,80 . . . . . . . . . . . . . . . . . . . . . . . . 9.81 . . . . . . . . . . . . 10.56 10.54 . . . . . . . . . . . . . . . . . .

11.49 11.49

. . . . . . . . . . . . . . . . . . . . . . . . 10.74 10.74 ......

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10,99

aA, methy l 4 -ke tos t ea ra t e ; B, me thy l 12 -ke tos t ea ra t e ; C, v inyl 4-keto- s t e a r a t e ; D, v iny l 12 -ke tos t ea ra t e ; ]g, 4 -ke tos tear ic ac id ; F, 12-keto- s t e a r i e ac id ; G, q/-!aetone of 4-hydroxy-2-octadeeenoic a d d .

in relat ively pure form, and evidence was obtained for the concurrent format ion of the less stable T-lee- tone of 4-hydroxy-3-octadecenoie acid. The inf rared spectra Gf the methyl keto esters, keto acids, vinyl keto esters, and the ~,-laetone of 4-hydroxy-2-octadecenoic acid were determined in carbon tetraehloride solutions. I t was fomld that the characterist ic absorb- antes for the lactone-earbonyl, ester-earbonyl, ketone- carbonyl, and the vinyl group at about 5.6, 5.7, 5.8, and 6.1 microns, respectively, obey the Lamber t -Beer law over a wide range of concentrations.

Acknowledgments

The authors express their appreciat ion to Lawrence E. Brown and Alva F. Cucullu for the elemental analyses and to Novis Smith and Edwill R. Cousins for hydrogenat ion of some of the oiticica oil. We are also grateful to W. fL Bickford for his many helpful suggestions. Generous samples of methyl 12-hydroxystearate were kindly supplied by The Baker Castor Oil Company, amt generous samples of Brazil ian oiticica oil were kindly supplied by Brazilian hldustr ia l Oils Inc.

:m~,~"t~ RE ~CE S 1. Adehnan , R. L., J . O r s Chem., 14, 1 0 5 7 - 1 0 7 7 11949) . 2. B e r g s t r 6 m , S., A u l i n - E r d t m a n , O., Rolander , B., Stenhatzcn, E.,

and i~stling, S., Aeta. Chem. Scan&, 6, 1 1 5 1 - 1 1 7 4 11952) . 3. Cocker, W., and Hornsby , S., J . Chem. Soc. ( L o n d o n ) , 1947,

1 1 5 7 - 1 1 6 6 . 4. Cocker, W. , Cross, B. E., and I I ayes , D. H., Chem. and Ind .

( L o n d o n ) , 1952, 3]4 . 5. Cra ig , L. E., K le inschmid t , R. F., Miller, E. S., Wi lk inson , J . 1~t

J r . , Dav i s , R. W., Montross , C. P., and :Port, W. S., I n d . Eng . C'hcm., 47, 1 7 0 2 - 1 7 0 6 11955) .

6. D a u b e n , W. G., and 1lance, P. D., J . Am. Chem. See., 75, ;1352- 3356 ( 1 9 5 3 ) .

7. F i schme i s t e r , I . , Acta. Chem. Scand. , 10, 159 11956) . 8. Grove, J . F., and Will is , H. A., J . Chem. Sol'. ( I m m l o n ) , 1951,

877-883 . 9. Jones , R. N., McKay, A. :F., and SinclMr, 1~. G., J . Am. Chem.

See., 74, 2 5 7 5 - 2 5 7 8 11952) . 10. K a i n e r , F., Kolloid g. , 129, 4 0 - 5 l 11951) . 11. K ing , G., J . Chem. See. ( L o n d o n ) , 1954, 2 1 1 4 - 2 1 2 2 , 12. Meikle.iohrL, R . A., ~ieyer , R. 5., Aronovic , S. M., Sehuet te , H. A,.

and Meloch, V. W., Anal . Chem., 29, 3 2 9 - 3 3 4 11957) . 13. O 'Connor , R. T., Field, E. T., and Singleton, W. S., .T. Am. Oil

Chemis t s ' Soc., 28, 1 5 4 - 1 6 0 11951) . 14. O 'Connor , R. T., J . Am. 0i l Chemis t s ' Sot., 33, 1 - 1 5 ( 1 9 5 6 ) . 15. Pack , F. C., P l anck , R. W., and Dollear , F. G., J . Am. Oil

Chemis t s ' Soe., 29, 2 2 7 - 2 2 8 ( 1 9 5 2 ) . 16. Pa i s t , W. D., Blout , E. R., Uhle, F. G., and Elderfield, R. C.,

J . Org. Chem., 6, 2 7 3 - 2 8 8 11941) . 17. Rocket t , J . , 5. Am. Chem. Sot., 78, 3 1 9 1 - 3 1 9 3 11956) . 18. Shaw, E., J . Am. Chem. Sec., 68, 2 5 1 0 - 2 5 1 3 ( 1 9 4 6 ) .

[ R e c e i v e d S e p t e m b e r 14 , 1 9 5 9 ]

The Fatty Acid Composition of Clothes Soil W. C. P O W E and W. L. MARPLE, Whirlpool Corporation, Research Laboratories, St. Joseph, Michigan

C I,OTI1ES SOIL is a complex mixture of inorganic and organic materials. The nature of soil on clothes varies with the occupation and environ-

ment of the wearer. To a t t empt an analysis of all the components that occur as soil on clothing would be an impractical, if not impossible, task. The analysis can be simplified however if only the problem soils are considered. These are materials that are not removed by normal laundering procedures. Accumu- lated soil causes the yellowish-grey cast associated with the gradual deterioration in appearance of white garments (Figure 1). Previous work in oar laboratories has shown that a major inorganic component of soil retained on clothing are clay particles that aver-

age about 0.1/~ in diameter (7) . Concurrently there is an accumulation of organic material on the surface of the cotton fibers (Figure 2).

Information on the composition of this organic material is limited. Brown (1) and Oldenroth (5) extracted and analyzed freshly-adsorbed organic ma- ter ia l f rom soi led garments . B r o w n (1) reported about 60% of the extracted soil to be free and com- bined fatty acids. In addition to fatty acids, he found about 15% cholesterol and fatty alcohols and 21% hydrocarbons. Oldenroth (5) reported 60-70'% sa- ponifiable material and about 8% cholesterol.

Yel lowing of garments in areas that are in contact with the skin has been reported (5, 8, 10). These

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Vinyl ketostearates. Preparation, properties, infrared spectra, and analysis of 4- and 12-ketostearates