,. 3,404,176 United States Patent 0 ICC . Patented Oct. 1, 1968

1 (II) 3,404,176 0 PROCESS FOR DIRECT PREPARATION OF HzSOz g I ALPHA-KETO ESTERS CHQONO + CHQCOOH (:2 CH3 0—NO + CHaOH Paul E. Burton, West?eld, and Herbert K. Wiese, Cran methyl acetic acid acetyl nitrite methanol ford, N.J., assignors to Esso Research and Engineering nitrlte Company, a corporation of Delaware (III) No Drawing. Filed Jan. 27, 1965, Ser. No. 428,534 0 CH3 CH: 26 Claims. (Cl. 260-497) CH3—- '6 -—0-—NO + CH3—- J7 =CH—CH3 -———)H2504 CHr- A: -—C—-CH3 10 acetyl nitrite 2-methyl-2-butene O NOH ABSTRACT OF THE DISCLOSURE 0:5 A one-step process for the preparation of alpha-keto Ha alkyl esters comprising reacting a Type II or IV ole?n 3-acetoxy-3 with a nitrosating agent and a carboxylic acid reactant methyl-2 consisting of either carboxylic acids, carboxylic acid an butanone hydrides, or mixtures thereof in the presence of a strong oxime acid catalyst. The process is conducted most e?‘iciently at (IV) pressures ranging from 1 to 75 atmospheres and at tem peratures in the range of from about —10 to 100°. Pref CH3 IO erably, monocarboxylic acids and monoole?ns are used. CH3- —C-——OH3 + CH30NO(or CH3—~(JJ—ONO) ———> 0 NOH 0: This invention relates to a process for the preparation of alpha-keto alkyl esters from ole?nic hydrocarbons. Ha More speci?cally, it relates to the direct preparation of CH3 alpha-keto alkyl esters by reacting a Type II, or IV ole CHa-éf-C-CHa —|- N20 + CH3OH (or CHsCOOH) ?n with a nitrosating agent and a normal aliphatic mono carboxylic acid or its anhydride in the presence of a cata lytic amount of a strong acid. 0:3 Keto alkyl esters ?nd utility as solvents, especially as 3O 41H. solvents for epoxy and vinyl resins. Thus while such com 3-acetoxy-3-methyl positions are highly desirable, present methods for pro Z-butanone ducing keto alkyl esters have certain disadvantages, for example, the methods either involve a multiple of steps (V) (I) or use expensive reagents. For example ethyl oxaloacetate CHsOH + CHzCOOH -—> CH3~JIOCH3 + 1120 is prepared by a crossed Claisen type condensation using An alternative way of producing an acid nitrite as illus ‘ethyl oxalate, ethyl acetate, and sodium ethylate. Another trated in the above Equation 11 by the formation of acetyl method involves using expensive acetylenic carbinols as nitrite from acetic acid and methyl nitrite is by the reac starting materials. These acetylenic carbinols are con tion of a nitrosating agent with a carboxylic acid anhy vertecl to keto alkyl esters by a reaction also involving dride. For example, with acetic anhydride and methyl a multiple of steps. In the ?rst step the acetylenic car nitrate the reaction is as follows: binols are hydrated to hydroxy kctones which are subse (VI) quently esteri?ed in a second step with a carboxylic acid 0 or acid anhydride. Still another expensive method in volves the reaction of ketones, particularly cyclic ketones, 45 CHs-PJ o with mercuric acetate. 0 + CHgONO --> CHg-il-ONO + CH3Ct|)OH3 It has now :been found that alpha-keto alkyl esters can CH3-C be advantageously prepared in one step by the reaction of Type II or IV ole?ns, as de?ned herein, with a nitro il) setting agent and a carboxylic acid reactant and/or its 50 acetic anhydride methyl nitrite acetyl nitrite anhydride in the presence of an acid catalyst. The fol Thus, it is possible to obtain the same end-product, i.e., lowing chemical equation is representative of the reaction alpha-keto esters, as claimed in this invention, by using of the present invention and describes the reaction of 2 either a carboxylic acid, a carboxylic acid anhydride or a methyl-Z-butene with methyl nitrite in acetic acid with combination of the two. Utilization of a mixture of car 55 sulfuric acid as catalyst: boxylic acid and carboxylic acid anhydride in the reac tion is generally preferred, however because it advan (I) tageously improves the yield of alpha-keto esters. This CH3 é ' H2504 may be attributable to the fact that when an alkyl nitrite CH3CH= CH3 + 2CH3ON0 + CH3CO0H ——-> is used as the nitrosating agent, the carboxylic acid an 2-methyl-2- methyl acetic acid 60 hydride reacts with the alcohol to produce an ester and butane nitrite thus shift the equilibrium of the reaction shown by Equa CH3 tion II to the acid nitrite side. Appreciable quantities of CH3—C——C-CH3 + N20 + 2CH3OH alkyl nitrite present in the reaction are undesirable inas much as a side reaction may occur which results in a loss CHSCOO 0 65 3~acetoxy-3-methyl of nitrosating agent. Such side reaction involves an oxida butanone-2 tive double bond cleavage of the ole?n to carbonyl com While the above equation represents the overall reac pounds wherein the nitrosating agent, particularly an tion contemplated in this invention, there are actually sev alkyl nitrite, acts as the oxidizing agent. The presence of a carboxylic acid anhydride can also be important from eral reactions involved. These are illustrated below with 70 2-methyl-2-butene, methyl nitrite, and acetic acid as re a standpoint of reacting with any water present or pro actants and sulfuric acid as the catalyst. duced during the reaction. The removal of water by reac 3,404,176 4‘ , . tion with a carboxylic acid anhydride prevents the loss of cyclohexene; ole?n fractions containing any one or more acid nitrite according to the following equations: of these ole?ns; polymers containing Type II or IV double (VII) 0 O bonds, such as natural rubber, butyl rubber, etc. Also ole ?n derivatives may ‘be employed which form Type II or IV ole?ns under the acidic reaction conditions employed herein, and thus the ole?n may be formed in situ. For The alpha-oximino alkyl ester shown by Equation example, tertiary ethers, carboxylic esters, or alcohols de III, e.g., 3-acetoxy-3-methyl-2-butanone oxime, is an in rived from Type IV ole?ns are converted under acidic termediate in the reaction and may be isolated in varying conditions to unsaturated hydrocarbons, e.g.' according to amounts depending on the ratio of ole?n and nitrosating the following equation: ‘ _ agent employed and upon the reaction conditions. The 10 alpha-oximino alkyl ester may be converted to the corre sponding alpha-keto alkyl ester by reaction with a nitro sating agent, as shown in Equation IV or by suitable hy drolysis. The terms Type H and IV ole?ns as employed herein refer to aliphatic ole?ns, as well as monocyclic and poly The nitrosating agents found suitable for use in accord cyclic ole?ns. The position and number of substituents of ance with the method of this invention are well known in the aliphatic Type II and IV ole?ns contemplated herein the art and, for example, include those oxides of nitrogen capable of forming nitrosyl sulfuric acid. Non-limiting are the same as indicated by C. E. Boord, The Science of 20 Petroleum, volume 2, page 1349 et seq., Oxford Univer examples of such oxides include nitrosyl sulfuric acid, sity Press, New York (1938). The de?nition of the ali N203, NO+air, and organic nitrates of the formula phatic, monocyclic and polycyclic Type II and IV ole?ns, A—ONO, wherein A is an alkyl, alkenyl, cycloalkyl, cy is presented below. cloalkenyl, aralkyl or aralkenyl radical. In addition to containing carbon and hydrogen, the A radical may also 25 Aliphatic Monocyclic and contain oxygen, halogen and sulfur as inert substituents. polycyclic When A is alkyl or aralkyl, the alkyl moiety may either be straight chain or branched chain. When A is cyclo H H /C- alkyl or cycloalkenyl, the cycloalkyl or cycloalkenyl Type II ...... R—é=nitrites may contain from It’ H C-Z 1 to 20 carbon atoms and preferably contain from 1 to l l / l 16 carbon atoms. Type IV...... _- R—C=C-—R” Y\ \ Non-limiting examples of organic nitrites include the (Jr-Ii following: rbenzyl nitrite; methyl nitrite; isoamyl nitrite; ethyl nitrite; n-amyl nitrite; isopropyl nitrite; tert-butyl With regard to the aliphatic ole?ns suitably employed, nitrite; cyclohexyl nitrite; 2-methyl-2-ethyl butyl nitrite; each of R, R’ and R” may be an alkyl, alkenyl, cyclo ethylene glycol mono- and dinitrites; 2-ethoxy ethyl nitrite; alkyl, aralkyl, aralkenyl, aryl, or alkaryl and each may allyl nitrite; etc. be unsubstituted or inertly substituted, i.e., possess sub The nitrosating agent may also be prepared in situ by stituents which are inert to the reactions contemplated reaction of a nitrite salt, for example, sodium nitrite, with by this invention. Thus, when R, R’ or R" represents an acid such as sulfuric acid. alkyl, the alkyl group may be a straight or branched chain It has been found that 2 moles of the said nitrosating alkyl group. Moreover, said alkyl group may contain a agent are required per mole of ethylenic unsaturation in cycloalkyl moiety in addition to its straight or branched said ole?nic material converted to alpha-keto alkyl ester. chain moiety. In the case of the Type II and, IV mono 45 About 0.1 to 2 moles of said nitrosating agent per mole of ole?ns, each R, R’ and R" group may contain from 1 to ethylenic unsaturation in said ole?nic material are suitably 18 carbon atoms,- and preferably from 1 to 10 carbon employed, with about from 0.5 to 1.0 mole of said agent atoms. In cases where one or more of the R, R’ and R” being preferably employed. groups is aralkyl, the alkyl moiety thereof is usually un In accordance with the invention, the acid reactant suit substituted and contains from 1 to 12 carbon atoms. 50 ably used herein may be de?ned as a monocarboxylic acid With regard to the monocyclic and polycyclic Type II or corresponding anhydride of the formula R—COOH or and IV ole?ns, the Y group represents the remaining part O 0 of the mono- or polycyclic ring system. For example, in the instance of l-methyl-l-cyclopentene, the Y group is Hints. (CH2)3. The Y group may contain from 1 to 16 carbon wherein R is an alkyl, cycloalkyl, aryl or aralkyl radical. atoms for a monocyclic ring system and from 3 to 20 car In addition to containing carbon and hydrogen, the R radi bon atoms for a polycyclic ring system. The Z substituent cal may also contain oxygen, one or more halogen and/ or of the monocyclic and polycyclic Type IV ole?ns is the sulfur as inert substituents. When R is cycloalkyl, the cy same as de?ned hereinabove for the R, R’ and R" sub cloalkyl moiety may be unsubstituted or may contain alkyl stituents of the aliphatic Type II and IV ole?ns. It is also 60 or aryl substituents. The organic acid or anhydride contains contemplated herein that the same R, R’ and R" sub from 1 to 20 carbon atoms and preferably contains from stituents listed for the aliphatic ole?ns may also be sub 1 to 6 carbon atoms. stituents on the Y group of the mono- and polycyclic ole The carboxylic acids and anhydrides suitably employed ?ns. include, but are not limited to, formic acid; acetic acid; The ole?ns suitably employed herein may be mono 65 acetic anhydride; propionic acid; propionic anhydride, ole?nically unsaturated or polyole?nically unsaturated, butyric acid; butyric anhydride; isobutyric acid; isobutyric cyclic or acyclic. anhydride; benzoic acid; benzoic anhydride; tri?uoroace The following Type II and IV ole?ns are exemplary of tic acid; tri?uoroacetic anhydride; etc. those which may be employed in accordance with this in Accordingly, from about 1 to 25 moles of said acid re vention. These ole?ns include, but are not limited to the 70 actant per mole of ethylenic unsaturation in said ole?ns following: ‘ are suitably employed, with from 1 to 10 moles of acid Cyclohexene; cyclohexadiene; dicyclopentadiene; dimer reactant per mole of ethylenic unsaturation being pre of methylcyclopentadiene, dicyclohexadiene; butene-Z; ferred. pentene-2; Z-methyl-Z-butene; Z-methyl-Z-pentene; 3 In accordance with the process of this invention, any acid methyl-Z-pentene; l-methyl-l-cyclopentene; l-methyl-l catalyst may be employed including acids classi?ed as 3,404,176 5 Lewis acids or LoWry-Bronsted acids. Suitable acid cata The nitrosating agent may be added after the acid cata lysts which may be employed in accordance with this in lyst has been admixed 'with the reactants or it can be added vention include, but are not limited to, the following: sul simultaneously with the acid catalyst. The reaction on furic acid; alkyl acid sulfates, e.g., methyl hydrogen sul which the instant invention is predicated then takes place fate; potassium bisulfate; HF; alkyl acid sulfates plus HI, and it is found that suitable reaction time periods range e.g. methyl hydrogen sulfate plus HI; sulfonated resins, from about 1 up to about ‘600 minutes and preferably range e.g. sulfonated polystyrene resin; benzene mono-, di—, and from 1 up toyabout 120 minutes. As heretofore mentioned, tri-sulfonic acids; alkylated-, lhalogenated, or nitrated however, such period is a function of the operating condi benzene sulfonic acids, zinc chloride; zinc bromide; zinc tions employed, i.e., the speci?c ole?n used, the acid-ole?n iodide; hydrochloric acid; hydrobromic acid; phosphoric ratio, temperature, pressure and the like and the required acid; polyphosphoric acid; alkyl acid sulfates plus alkyl contact time period will, accordingly, vary with the condi alkali metal sulfates, e.g. methyl hydrogen sulfate plus tions applied. methyl sodium sulfate; AlCl3; BF3; BCl3; BF3- (C2H5)2O; The chemical compounds formed in accordance with the invention are predictable from the ole?n hydrocarbon and 15 monocarboxylic acid employed as starting reactants. In order to illustrate this, the following Table I sets out the FeCl3; acidic mixtures containing any two or more of the alphaketo alkyl esters produced in this way and the ole?n above mentioned acids; etc. hydrocarbons and monocarboxylic acids from which they In this regard, it has been found that from about 0.01 were derived. to 1.0 mole of catalyst per mole of nitrosating agent em 20 ployed suitably catalyzes this reaction. Preferably about TABLE I 0.01 to 0.1 mole of catalyst per mole of nitrosating agent Starting ole?n Starting acid Keto alkyl ester is used. When nitrosyl sulfuric acid is employed as the product nitrosating agent it serves as its own catalyst. (1) H3C—C=OCH3 011300 011 CHgClH-C-CH; In addition to the carboxylic acid or carboxylic acid an 25 III CHsC O 0 0 hydride, which may also function as a solvent in addition to its primary function, an additional solvent may be em H ployed as the reaction medium. Thus, any volatilizable (2) o2H5o=o-(olH5) CHzC 00H o¢H5cl:—o—(ClH5) solvent which is liquid under the reaction conditions and 1:1]: HI: H3 (321150 0 O 0 which is resistant to the catalyst and the nitrosating agent 30 (8) employed, may be utilized herein. Non-limiting examples OHzC 0 OH —0 of solvents suitable for use herein include: para?inic hy drocarbons, lhalogenated hydrocarbons, e.g., dichloroarneth O 0 CH3 ane, hydrocarbon ethers, e.g., diethyl ether, halogenated acetic acid, liquid 50;, nitrohydrocarbons, dimethyl sulf ll) oxide, and the like. (4) CH3 CH3 The reaction of the present invention may be carried out at less than atmospheric, atmospheric or at su-peratmos pheric pressure, depending upon the other conditions of tit 0 H30 0 0 o operation. Thus, the operating pressure will depend on the 40 (5) CHsH CH3 particular ole?n feed, as well as the other reactants em ployed. The preferred pressure utilized, however, ranges from about 1 up to about 75 atmospheres. 0 H30 0 0 o It is found that optimum results are obtained at reaction temperatures of from about —50° to about 200° C. Prefer (6) 01130 0 OH —0 ably, temperatures of from about —l-0° to about 100° C. 45 0 H3 0-0 —0 H, are employed. The proportions of the reactants employed are prefer CH3 ably chosen such that at least 1 mole of monocarboxylic acid or anhydride or preferably a mixture of both is pres In order to recover the product resulting from the' ent for each mole of ethylenic unsaturation present in the 50 process of this invention, the acid catalyst is neutralized ole?n hydrocarbon. When the monocarboxylic acid is also with a base, the solvent is removed by distillation, and employed as the solvent, it follows that said acid is em the product, after separation byv ?ltration from the salt ployed in much greater excess. When an inert solvent, in of the catalyst acid, is puri?ed by distillation or other addition to the carboxylic acid is employed, the propor suitable means. tion of the solvent can be such as to constitute less than 1 55 Example I.—-Preparation of to about 100 parts or more by volume for each part by 3-methyl-3~acetoxybutanone-2 weight of monocarboxylic acid, one part by volume being Methyl nitrite (65 ml.) was ‘added ‘during 1.5 hours equivalent to the volume of one part by weight of water at 15-30° C. to a stirred solution of 70 g. 2-methyl-2 at the ‘same temperature. It should be noted that although butene, 100 ml. acetic acid, 102 g. acetic anhydride and use of a solvent is preferred, the reaction may be carried 60 38 g. methyl hydrogen sulfate. Upon completion of the out without employing a solvent. The duration of the reaction depends upon the tempera addition, the methyl hydrogen sulfate was neutralized ture, pressure, concentration of the reagents and varies with sodium acetate, and the acetic acid and methyl over a wide range, hence the reaction period is not critical acetate were separated from the product by distillation. The residue was ?ltered to remove sodium methyl sulfate to the process of this invention. 65 In carrying out the process, the ole?nic starting reactant and distilled yielding 31 g. of 3-methyl-3-acetoxybu and the monocarboxylic acid or anhydride or mixture of. tanone-Z (B.P. 88—100° C./50 mm., nd2° 1.4238). both are mixed together, preferably by slowly adding the Example II.—~Preparation of 3-acetoxybutanone-2 acid to the ole?n with proper stirring. Suitably, the acid catalyst is then addedto the thus-mixed reactants with 70 Butene-2 (90 ml.) and methyl nitrite (70 ml.) were additional stirring so as to insure optimum absorption of added simultaneously during 3 hours at 25-36° C. to a the acid throughout the reaction mixture. Alternately, the stirred solution of 200 ‘ml. acetic acid, 102 g. acetic an ole?n and the nitrosating agent are added simultaneously hydride, and 20 g. of sulfuric acid. Upon completion of to they mixture of carboxylic acid and/or anhydride. with the adidtion, one liter of pentane was added to the re the catalyst. 75 action mixture and a second phase appeared. A-fter separa 3,404,176 7 8 tion of the phases, the upper one was distilled yielding keto alkyl esters which comprises contacting an ole?nic 20 g. of 3-acetoxybutanone-2 (B.P. 86-95“ C./5O mm., hydrocarbon material selected from the group consisting ndzo 1.4126). Neutralization of the lower phase, fol of Type II and Type IV monoole?ns having the ‘for lowed by distillation gave an additional 4.1 g. of S-ace mulas toxybutanone-2. 5 Examples III-VII H H 041 C—~Z R’ H . . R—tJ.‘/=é}—R' Y/ Y/ or R-o=d-R" In a manner similar to that of Examples I and II, a ' \ ’ \ series of experiments was effected in order to illustrate 041 ‘3-3 further the process of this invention. The reactants, re action conditions and product data are set forth below 10 wherein each R, R’, R", Y and Z is a hydrocarbon radical in tabular form in Table II. with from 0.1 to 2 moles of a nitrosating agent, se It is to be understood that this invention is not limited lected from the group consisting of oxides of nitrogen and to the speci?c examples which have been offered merely organic nitrites based on said ole?nic material and from as illustrations and that modi?cations may be made with- 1 to 25 moles of a carboxylic acid reactant selected out departing from the spirit of the invention, 15 from the group consisting of aliphatic monocarboxylic

TABLE II Nitrosating Ole?n Acetic Acetic agent (moles) Catalyst Example acid anhydride methyl Name Moles Type (grns.) (gms.) nitrite 1 Name Moles III ______-. Cyelohexene ...... __ 1.0 II 210 102 1.0 H2804 0.25 IV-.._. .-- 2-methyl-2-butene...-. 2.1 IV 525 None 2.0 H1804 0.20 V-.. - ____do ...... _. 2.1 IV None 540 2.0 H2804 0.20 VL. .-._d0. -_ 1. 0 IV 105 102 1. 1 CH3SO4H 0. 34 VII . . . _ . -. Butene~2 ...... _. 1.0 II 210 102 1.15 H2804 20

Temp. of Time of Alpha-keto Alpha oximino Example Name Reaction Reaction alkyl ester Alkyl ester FootnQte (°C) (hrs.) (moles) (moles)

III ______._ Cyclohexene ______20-33 2.4 0.024 30-42 1.0 0. 028 21-34 3. 1 0. 040 13-30 1.5 0. 215 25-30 3.0 0.189 1 Two moles of nitrosating agent are required for each mole of alphaketo alkyl ester produced. 1 0.58 mole of the ole?n was converted to cleavage products (acetone and acetaldehyde). 3 0.11 mole of the ole?n was converted to cleavage products (acetone and acetaldehyde). What is claimed is: acids, aliphatic monocarboxylic acid anhydrides, and 1. A process for the preparation of alpha-keto alkyl mixtures thereof having the formula RCOOH and esters which comprises contacting an ole?nic hydrocarbon material selected from the group consisting of Type II 40 and Type IV ole?ns having the formulas Billet. / (3-2 B’ H wherein R is an alkyl or cycloalkyl radical of l-20 car bons per mole of ethylenic unsaturation of said ole?nic Y\Ll , 3((1 or R—(lJ=(g-—R" material in the presence of from 0.01 to 1 mole of acid —H -H 45 catalyst per mole of said nitrosating agent, said process wherein each R, R’, R”, Y and Z is a hydrocarbon radi being effected in the liquid phase at a temperature in the cal with a nitrosating agent selected from the group range of from -50° to 200° C. for a reaction period consisting of oxides of nitrogen and organic nitrites and from 1 minute up to about 600 minutes. an acid-reactant selected from the group consisting of 8. The process of claim 7 in which from 0.5 to 1 mole carboxylic acids, carboxylic acid anhydrides, and mix 50 of said nitrosating agent is employed per mole of eth tures thereof having the formula R—COOH and ylenic unsaturation in said ole?nic material. 9. The process of claim 8 in which from about 1 to 10 moles of carboxylic acid reactant are employed per mole of ethylenic unsaturation in said ole?nic material. wherein R is an alkyl, cycloalkyl, aryl or arylalkyl radi 55 10. The process of claim 9 in which from about 0.01 cal of 1 to 20 carbon atoms in the presence of an acid to 0.1 mole of acid catalyst per mole of nitrosating agent catalyst at a temperature ranging from about —50 to is employed. about 200° C. 11. The process of claim 10 in which from about 1 2. The process of claim 1 in which from about 0.1 to about 100 parts by volume of an inert solvent are em to 2 moles of nitrosating agent are employed per mole 60 ployed for each part by weight of carboxylic acid re of ethylenic unsaturation in said ole?nic material. actant utilized. 3. The process of claim 1 in which from 1 to 25 12. The process of claim 11 in which said process is moles of said acid-reactant are employed per mole of effected in the liquid phase at a pressure from 1 up to ethylenic unsaturation present in said ole?nic material. about 75 atmospheres, at a reaction temperature of from 4. The process of claim 1 in which from about 0.01 65 about —-10° to about 100° C. and for reaction periods to 1.10 mole of said acid-catalyst is employed per mole of from 1 to about 120 minutes. of said nitrosating agent. 13. A process for the preparation of alpha-keto alkyl 5. The process of claim 1 in which an inert volatile esters which comprises adding to an ole?nic hydrocarbon solvent is employed. material selected from the group consisting of Type II 6. The process of claim 1 in which said process is 70 and Type IV monoole?ns having the formulas carried out in the liquid phase at reaction temperatures of from about —50° to about 200° C. and for a reaction time period of from about 1 minute up to about 600 minutes. 7. A one step process for the preparation of alpha 75 3,404,176 10 with an acid-reactant selected from the group consisting 21. The process of claim 20 wherein said nitrosating of aliphatic monocarboxylic acids, aliphatic monocar agent is an organic nitrite having from 1 to 20 carbon boxylic acid anhydrides, and mixtures thereof having atoms. the formula RCOOH and 22. The process of claim 7 wherein said monole?ns are compounds having the general formula selected from the group consisting of: wherein R is an alkyl or cycloalkyl radical of 1-20 car bons while agitating the resulting mixture, adding an acid catalyst to the thus-mixed reactants with additional stir 10 and ring and adding a nitrosating agent selected from the group consisting of oxides of nitrogen and organic nitrites to mixture of reactants. 14. The process of claim 13 in which from 0.1 to 2 wherein R, R’, and R" represent alkyl radicals having moles of said nitrosating agent are employed per mole of 15 from 1 to 18 carbon atoms. ethylenic unsaturation in said ole?nic material. 23. The process of claim 22 wherein R, R’ and R" 15. The process of claim 13 in which from about 1 are alkyl radicals having from 1 to 10 carbon atoms. to 25 moles of acid-reactant are employed per mole of 24. The process of claim 23 wherein said carboxylic ethylenic ‘unsaturation in said ole?nic material. acid has from 1 to 6 carbon atoms. 16. The process of claim 13 in which from about 20 25. The process of claim 22 wherein said nitrosating 0.01 to 0.1 mole of mineral acid-catalyst per mole of agent is an alkyl nitrite having from 1 to 16‘ carbon atoms. nitrosating agent is employed. 26. The process of claim 22 wherein said acid catalyst 17. The process of claim 13 in which from about 1 to about 100 parts by volume of an inert volatilizable is a mineral acid. solvent are employed for each part by weight of acid 25 References Cited reactant utilized. 18. The process of claim 13 in which said process is UNITED STATES PATENTS effected in a liquid phase at a pressure vfrom 1 up to 3,055,934 9/ 1962 Heisler et al. ______2‘60—-497 about 75 atmospheres, at a reaction temperature of from about —50° to about 200° C. and for reaction periods 30 OTHER REFERENCES of from 1 to about 120 minutes. Adams et 211., Organic Reactions, vol. ‘7, 1953, p. 328. 19. The process of claim 1 wherein said ole?nic ma terial is a monoole?n. LORRAINE A. WEINBERGER, Primary Examiner. 20. The process of claim 19 wherein said acid-reactant is one in which R is alkyl or cycloallkyl. V. GARNER, Assistant Examiner.