INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY
1638
ACKNOWLEDGMENT
Vol. 43, No. 7
(4) Lewis. W. K.. J . IND.ENG.CHEW..13. 427 (1921). ( 5 ) Marks, L. S.,“hlechanical Engineers Handbook,” 4th ed., p. 1695, New York, McGraw-Hill Book Co., 1941. (6) Rosin, P., and Rammler, E., J . Inst. Fuel, 7, 29 (1933). (7) Scott, G. S.,U. S. Bur. Mines, Rept. Invest. 3732 (1943). (8) Smith, R. C., Jr., and Howard, H. C., IND.ENG.CHEM.,34, 438 ~I
The authors wish to thank Thomas L. Kemp, general manager of the Citizens Gas and Coke Utility, for permitting pu181i cation of this report. LITERATURE CITED (1) Bennett, J. G., J . Inst. FueE, 10, 22 (1936). (2) Ceaglske, N. H., and Hougan, 0. A., Trans. A m . Inst. Cherrr Enors.. 33. 283 (1937). (3) Fisher, E. -‘.’, J . Soc. Chem. I n d . , 54, 343 (1935).
(1942). (9) Van Arsdel, W. B., Chem. Eng. Progress, 43, 13 (1947). RECEIT-ED June 15, 1950.
Sulfur Co pounds as Antioxidants BETA-ALKY LMERCAPTOKETONES R. B. THOMPSON Universal Oil Products Co., Riverside, Ill. This study was made for the purpose of finding new antioxidants. I t was discovered that certain types of sulfur-containing compounds are antioxidants. These compounds may be classified as p-alkylmercaptolcetones and have the follow-
0 I I I/ ing general formula: R-S-k-C-k-R’.
I
They may be
I
prepared readily by the addition of mercaptans to a#unsaturated ketones in the presence of acidic or basic catalysts. The most effective inhibitors were synthesized from di-a,@-unsaturated ketones with primary alkylmercaptans. A new type of inhibitor to retard autoxidation of organic materials has been developed, These compounds are very different from the usual aromatic amino or hydroxy compounds.
I
N T H E study of oxidation inhibitors for use in fats and oils a new class of compounds which are effective antioxidants has been found (9). These materials constitute a radical departure from the usual inhibitors t h a t comprise hydroxy and/or amino aromatics. These new inhibitors are p-alkylmercaptoketones all containing R‘R“‘0
\\ I/
the group RSCCC-R””,
I\
where the It’s represent hydrogen or
R“H organic radicals of the type of alkyl, aryl, or heterocycle. Representative compouiids of this class are listed in Tables I t o 111. I n general, all these compounds are antioxidants in lard, but they are not all of equivalent effectiveness. This paper reports the results of work intended to investigate the features of @-alkylmercaptoketones t h a t lead to high potency as antioxidants. p-Alkylmercaptoketones are readily prepared by the addition of mercaptans t o a,p-unsaturated ketones using either acid or basic catalysts.
P’ Y’’R’Itf ! I
C=C-k=O
R”
p’ft”’
+ RSH --3
1
1
,R,lu
/
RSC CI-IC=O
R“
(1)
Posner (6) carried out a large number of additions of mercaptans to a,p-urisaturated ketones. However, usually he did not isolate the primary addition product but preferred to oxidize it to the
corresponding sulfone, ordinarily a crystalline substance which can easily be isolated. Posner’s reactions were carried out using anhydrous hydrogen chloride as a catalyst; this acid type catalyst promotes addition, at the p-carbon atom, of a mercapto residue as well as reaction a t the carbonyl group to form dithioacetals. R’ Rll/ R f / / I R! R!// E”// I / .kcid I 1 /’ C=CC=O 3RSH +RSC-CHC (SR)z HzO (2) I I
+
kf,
+
kf,
However, in some instances, dithioacetals are not formed, and the only reaction product is the one that results from addition of the mercaptan across the double bond according to Equation 1. Ruheman (8) repeated much of Posner’s work using basic catalysts which do not cause the formation of the dithioacetals but give reactions only of the type of Equation 1. Later Nicolet ( 5 ) was able t o carry out some of the reactions of Equation 1 without any catalyst by heating the mixture of reactants to the temperature of a steam bath for short intervals of time. The addition of mercaptans to a,P-unsaturated ketones does not proceed with equal facility in all cases but depends on the nature of the ketone and the mercaptan. Thus ketones with two hydrogen atoms on the p-carbon atom add mercaptans most readily, those with only one hydrogen atom with more difficulty, and those with no hydrogen atoms least readily. Of the mercaptans those with long chains (10 or more carbons) are relatively sluggish and do not react readily. The primary mercaptans add much more easily than the tertiary. Mercaptans t h a t have polar groups-for example, thiocresol, mercaptoethanol, thioglycolic acid, and thioglycerol-add most readily. Various ketones and mercaptans were employed as reactants to prepare p-alkylmercaptoketones. The potency of the products as antioxidants was determined using the Swift active oxygen method (A.O.M.) ( 3 ) . In these tests lard was used as the substrate for testing purposes. Preliminary tests on a compound of this type indicate a low order of toxicity. Potency as antioxidant was found to depend on the nature both of the mercaptan and of the ketone. Table I, wherein products obtained from the reaction of mercaptans with mono-a,p-unsaturated ketones are shown, demonstrates the effect of varying the nature of the mercaptan on potency. Thus the products obtained by adding thiocresol or tert-butyl mercaptan to benzalacetophenone (compounds 3 and 4) are less effective as compared t o the one prepared with chiefly primary mercaptans (compound 9). The same result is
I N D U S T R I A L A N D E N G I N E E R I N G CHE.MISTRY
July 1951
TABLEI.
MOKO-CY,~-UNSATURATED KETONESPLUSMERCAPTANS
Compound 1. 7,8-Dihydroxy-5-thia-2-octanone 2.
Formula CHzCHCHzSCHeCHzCOCHr
bH bH 4-Phenyl-4-ethylmereapto-2-butanone CeHsCHCHzCOCHs L H S w-Phenyl-w-teri-butylmeroaptopropio- CeHaCHCHzCOCeHs phenone I SC(CHs)a w-Phenyl-w-(4-methy1phenylmercapto) CeHsCHCHeCOCeHs propiophenone $CeNICHs-P 4-Phenyl-4-p-methylphenylmercapto-2- p-CHaCaH4SCHCHzCOCHa butanone &He 4-Methyl-4-p-methylphenylmereaptop-CHsCsHaSCCHzCOCHs 2-pentanone (&Ha)* 4-Alkylmereapto-‘2-butanone R’SCHeCHzCOCHad 4-h~ethyl-4-ethylmercapto-2-pentanone CzHaSCCHzCOCHa
Melting Point, O
c.
Boiling Point, O
c.
a
a
10
962.6mm.
A.O:M. Strtblllty Time, Hours 50-66 b
48-66b
1639 ketotetrahydrothiophene aa well as from cyclopentanone and cyclohexanone are shown. 2,4 - Dibenzal 3 ketotetrabydrothiophene adds only one molecule of ethyl mercaptan under the same conditions t h a t
- -
2,6-dibenzalcyclohexanoneadds
two; likewise addition of two molecules of ethyl mercaptan to 2,5-dibenzalcyclopentanone 4. 113-114 ..... 4benzal-3-ketotetrahydrounsaturated ketones. For example, phorone reacts with ethyl thiophene. However, in 2,6-bis(~-ethylmercaptobenzyI)cyclomercaptan in t h e presence of piperidine as a catalyst t o give hexanone these two groups can attain a close approximation chiefly addition of 1 mole of mercaptan, whereas with hydrogen because of the flexibility of the six-membered ring. It appears chloride as a catalyst the chief product contains 2 moles of that some type of specific steric arrangement, possibly quasiring formation, involving close approach of the sulfur and the mercaptan. oxygen of the keto groups, is necessary in order to have a more effective inhibitor. There does not appear t o be any other explanation for all of the facts of (1)lower potency of some cyclic HCI Piaeridine ketones and (2) lower potency of compounds derived from terfalkyl and aromatic mercaptans. Thus the bulky tert-butyl group may also offer steric hindrance t o the proper spacial arrangement of the molecule necessary in a more effective inhibitor. In materials made with aromatic mercaptans steric Z’erl-butyl mercaptan, which is more sluggish than ethyl merhindrance does not appear t o be a valid explanation for lower captan, requires more drastic conditions t o effect reaction with potency; it is conceivable t h a t the free electrons on sulfur are phorone than does the primary mercaptan. Only one molecule too much involved in resonance with the nucleus t o participate of the terb-alkyl mercaptan adds to dibenzalacetone; in this in any sort, of ring formation t h a t may be necessary. respect it is similar t o s u l h i c acids only one molecule of which I n order t o learn more about the importance of steric relaadds to dibenzalacetone (4). tionships a n attempt was made to prepare the diphenyltetraAs a whole the compounds prepared from the di- unsaturated hydrothiopyrone ( I ) by the reaction of 1 mole of hydrogen sulfide ketones are more potent than those from the mono- unsaturated. with 1 mole of dibenzalacetone t o yield I Again the same less effective inhibitors result in those products prepared from tert-alkyl or aromatic mercaptans (compounds 10 0 and 14). // C One other group of compounds has been prepared which A belongs t o this class (Table 111). This group, discussed sepaHzC CHz rately because the results show the effect of varying the nature of the ketone and are not in accord with those already reported, C ~ H ~ C~ HH C , H , includes 3-ketotetrahydrothiophene and the products obtained by adding mercaptans t o a,a’-dibenzal cyclic ketones. 3-Ketotetrahydrothiophene (10) should be a n inhibitor, since it contains which‘ would have sulfur p t o the carbonyl on both sides, una sulfur @ t o the keto group. Condensation of 2,4dibenzalketo-, like 3-ketotetrahydrothiophene; but because of the ring, tetrahydrothiophene with two molecules of mercaptan should close approximation of the keto and sulfur is prevented. On give an inhibitor. I n Table I11 the products prepared from
3.
80-81
.....
