CA1275111A

CA1275111A - 1-acyloxy-3-hydrocarbylthiopropene componds and processes for their production

Info

Publication number: CA1275111A
Application number: CA000559288A
Authority: CA
Inventors: Mark C. Cesa; James D. Burrington
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1983-08-03
Filing date: 1988-02-18
Publication date: 1990-10-09
Anticipated expiration: 2007-10-09

Abstract

ABSTRACT

Discloses (1) reacting a 3-(hydrocarbylthio) propionaldehyde with a compound <IMT> to make , (2) reacting latter compound with CO and R"YH
where y is O or S to make

Description

~_ ~ . . ,. ?, (5711) ~ 3 SYNTHESIS OF METHIO~NINE HYDROXY ANALOG
OR DERlVATIVE, AND ESTERS THEREOF; SYNTHESIS
OF 1-ACYLOXY-4 HYDROCARBYLTHIOPROPENE, AND PRODUCTS
____________.______________ ________________ In one aspect this invention relates to making methionine hydroxy analog or derivative, and esters thereof.
Specifically, the methionine hydroxy analog or derivative has OH
the formula, RSCH2CH2CHC-OH. In this formula where R is methyl, O

the compound is known as methionine hydroxy ana10g, also known as 4-methylthio-2-hydroxybutanoic acid. In this application, the "derivative" means a compound of the foregoing formula where R is other than methyl. ln one aspect there is disclosed and claimed a ~ethod of making such compound in a three step process which starts with a 3-(hydrocarbylth;o)propionaldehyde.
In another aspect of the invention there is disclosed and claimed a method of making esters of methionine hydroxy analog or its derivative beginning with a l-acyloxy-3-hydrocarbylthiopropene.
In a still further aspect of the inventiùn a new method of making a 1-acyloxy-3-hydrocarbylthiopropene from a 3-(hydrocarbylthio)propionaldehyde is disclosed and claimed, as are certain new l-acyloxy-3-hydrocarbylthiopropenes ~er se.
The now most important product of the present invention is the hydroxy analog of methionine. It is a well known and important feed supplement for various animal feeds.

--1-- .~ ., ~ (5711) It is generally commercially made by a 4-step process in which acrolein is reacted with methane thiol to produce 3-(methylthio)propionaldehyde; thereafter the 3-(methylthio)propionaldehyde is reacted with HCN to produce

2-hydroxy 4-methylthiobutyronitrile. This compound is then reacted with water to produce 2-hydroxy-4-methylthiobutyramide, which in turn is reacted with water and sulfuric acid to produce the methionine hydroxy analog.
This prior art process is disadvantageous because of the use of HCN which requires costly handling because of possible safety hazards. In addition, production of unwanted by-product ammonium sulfate is also a problem. Stoichiometric amounts of sulfuric acid are also required, an added cost and a corrosion problem.
--- It is one object of the present invention to provide a new process for making methionine hydroxy analog without using HCN as a reactant and without producing by-product ammonium sulfate. It is a further object to provide a process for OH
making compounds of the formula RSCH2CH2CH,C,-OH (including methionine hydroxy analog) wherein R is 3 hydrocarbyl group --~ containing 1-30 carbon atoms but not containing any ethylenic or acetylenic unsaturation.
It is a still further object to provide a useful intermediate for preparing said compound of the formula OH
RSCH2CH2CHC-OH by reacting a 3-(hydrocarbylthio)propionaldehyde with a suitable reagent to produce a compound RSCH2CH=CHOCR', 1-acyloxy-3-hydrocarbylthiopropene.

~7~ (5711) Other objects, as well as aspects, advantages and features, of the present invention will become apparent from a study of the specification and the appended claims. The foregoing and other objects are fulfilled in accordance with the present invention described more fully hereafter.
According to one aspect of the present invention there is provided a process for producing a compound which is hydrolyzable to produce methionine hydroxy analog or a derivative thereof which comprises (a) reacting a 3 (hydrocarbylthio)propionaldehyde o RSCH2CH2CHO, with a reactant of the formula R'CX to produce a compound RSCH2CH=CHOCR', 1-acyloxy-3-hydrocarbylthiopropene, -~ (b) intimately contacting and reacting said compound, RSCH2CH=CHOCR'? with CO and a reactant of the formula R"YH to OCR' produce a co~pound, RSCH2CH2CHCYR", which is hydrolyzable to o produce said methionine hydroxy analog or derivative, `~ OH
RSCH2CH2CHC-OH, where Y is O or S; R is Cl to C30; X is O-~R', F, Cl, Br, 1, 0-2-propenyl, O-l-propenyl or O-vinyl;
R is C to C30 ~75~1 (5711) hydrocarbyl, R' is H or C1 to O O
C30 hydrocarbyl and each R' in R'C-0-C R' may be the same or different, but only one R' can be H; R" is H or C1 to C30 hydrocarbyl when Y is 0 and is C1 to C30 hydrocarbyl when Y is S;
and wherein R, R'and R" contain no ethylenic or acetylenic unsaturation, and wherein R' is not H when X is haloyen or 0-CR'. Usually in such a process R, R' and R" are limit~d to a maximum of 10 carbon atoms, all of which are members of an open chain alkyl group.
In another aspect of the invention there is provided a process for making an enol ester having the o formula RSCH2CH=CHO~R' comprising reacting a

3-(hydrocarbylthio)propionaldehyde with a reactant of the O O
~1 "
formula R'CX, wherein X is 0-CR', F, C1, Br, I, 0-2-propenyl, 0-1-propenyl, or 0-vinyl; R is C1 to C30 hydrocarbyl; R' is O O
. H or C1 to C30 hydrocarbyl, and each ~' in R'C-0-C R' may be the same or different; and wherein R and R' contain no ethylenic or acetylenic unsaturation~ and wherein R' is not H

o when X is halogen or 0 CR'. Usually in such process each of R
and R' are limited to a maximum of 10 carbon atoms, all of which are members of an open chain alkyl group.

~2~5~ (5711) In still another aspect of the invention there is provided a process which comprises making a compound, QCR
RSCH2CH2CH&YR , by intimately contacting and reacting an enol ester of the formula RSCH2CH=CHOCR with C0 and a reactant of the formula R YH
wherein Y is 0 or S; R is C1 to C30 hydrocarbyl;
R is H or C1 to C30 hydrocarbyl when Y is 0 and is C1 to C30 hydrocarbyl when Y is S; and wherein R, R , and R
contain no ethylenic or acetylenic unsaturation. Usually ~in such process each of R and R are limited to a maximum of 10 carbon atoms, all of which are members of an open chain alkyl group.
In a further aspect of the invention, we have provided a new compound, 2-acetoxy-4-(methylthio)thiobutanoic acid, methyl ester.
In yet another aspect of the present invention we have provided certain new compounds, 1-acyloxy-3~methylthiopropenes.
The objects of the present invention are realized in accordance with our invention wherein methionine hydroxy analog or a derivative thereof is made through the hy~rocarboxylation of the enol acylate of a 3-(hydrocarbylthio) propionaldehyde rather than by the route of hydrocyanation of such an aldehyde, in accordance with the following principal reactions:
Reaction ~
_________ _ _ 0, Cat 0, RSCH2CH2CH0 + R CX ~ RSCH2CH=CHOCR + XH

`~

~ ~ 75 ~ ~ ~ (5711) Reactln_(2~
O
O Cat OCR' Il ~
RSCH2CH=CHOCR' + CO ~ R"YH ~ RSCH2CH2CH&YR"

Reaction (31:
__ ______ _ _ O acid, OCR' base OH O
~1 O RSCH2CH2CHC OH + HOCR' + HYR"

In the foregoing reactions the various R groups and are as before stated. p It is advantageous that the starting material in Reaction (1), the 3-(hydrocarbylthio)propionaldehyde is easily obtained from the relatively inexpensive and widely available acrolein, by reaction of acrolein with a h~ycrocarbyl mercaptan having the formula RSH. Such reactions are shown, for instance, in U.S. Patents 2,676,190; 29584,496; 2,564,105;
2,557,913; 2,512,677; 2,485,236; 2,776,996 and 2,626,282.
Reaction ~1) is carried out catalytically, and a variety of catalysts can be used. For example, the catalysts can be any Lewis acid or base or Bronsted acid or base, or combinations of these, including:
a) HhXX, where X = F, C1, Br, I, CN, SCN, NCS, O, S04, N03, P04, RS03, OCR, Cl04, Cl03, ClO, HC03, C03, S, Se, BF4, BC1 (C6H5)4~ PF6- PC16; h = 1-3, x = 1-3;
b) a heteropolyacid or acidic or basic organic resin, or any metal oxide;
c~ BX3 (X as above), PX~, SnX2, CuX2, ZnX2;
d) NR3, PR3, AsR3, BiR3;

~7'~ ( 5711) e) Mm(OH)nOx, where M = Li, Na, K, Rb, Cs, Be, Mg, Ca, Fe, Co, Rh, Ir, Ni, Pd, Pt, Ru, Mn, Re, Cr, Mo, ~I, or combination of the above; m = 1 4, n = 1-8; x = 0-4, wherein ntx 7 1;
f) MmXX with M, m, X and x as defined above;
wherein R is H or any hydrocarbyl, usually with 1-30 C
atoms, more often 1-10 C atoms, and wherein the R's in any particular compound can be the same or different.
The catalysts may be used in a homogeneous mode or may be supported on or incorporated into a heterogeneous-mode support or polymer.
A by-product of Reaction (1) can be the 1,1 diacyloxy compound, RSCH2CH2CH(02CR')2, and acid catalysts favor its formation. Therefore, even though the diester can be recycled in a continuous process by hydrolysis to the aldehyde and the R' acid R'C02H, this involves an extra step. We therefore now prefer to use basic catalysts. Of the basic catalysts we now prefer KOAc, NaOAc or other alkali metal acetates, alkali metal hydroxides, and amines.
The reaction can be carried out in batch operation or continuously in the homogeneous or heterogeneous modes. If in the liquid phase, the catalyst can be dissolved in the reactants or can be present as a liquid or a solid. If the reactants are gaseous, the catalyst can be in the form of a liquid or a solid.
The concentrations of reactants and catalysts can vary widely. The ratio o~ the acylating agent R'~X to the aldehyde can be 0.1 to 100, usually 0.5 to 10, more usually 1.0 to 5, but most often is 1.0 to 1.5 on a molar basis. The amount of catalyst in the reaction system in batch operation can also vary widely. For convenience, the amount of catalyst can be between 0.01 to 100 mole-percent, usually Ool to 10 mole-percent based on the aldehyde reactant.

~ J

~ 2 ~ (5711) The reaction system can include a solvent, although this is not necessary. Examples of suitable solvents, which should be inert in the reaction mixtures, are carbon tetrachloride, dimethyl formamide, and toluene. Any amount of solvent can be used, although for convenience the reactant should be present in amounts of at least 0.01 weight percent in the solvent. An especially useful solvent i5 diethylene glycol dimethyl ether, or 2,2'-dimethoxydiethyl ether since use of this solvent minimizes or eliminates formation of the 1,1-diester, especially when using a basic catalyst. This and any other inert solvent that dissolves all reactants have this effect.
The reaction time can vary widely. Suitable reaction times are 0.1 to 50 hours, preferably 0.1 to 3 hours. The reaction temperature can also vary widely. Usual reaction temperatures are 80 to 130C, more usually 90 to 110C.
After the reaction has terminated, the gross reaction product is separated and recovered in a conventional manner.
For example, 1-acetoxy-3-methylthiopropene can be recovered from a liquid reaction system by vacuum distillation.
Hydrocarboxylation of vinyl acetate with H20 is known. See U.S. Patent 4,377,708. In the inventive process carboxylation is carried out on a sulfur-containing enol ester _, using water, alcohols, or hydrocarbyl sul~ides, etc. In accordance with this aspect oF the invention, it has been found ~s~
( --that the sulfur in the sulfur-containing enol ester does not poison the ef~ective metal compound catalyst as discussed below, even though sulfur is a known poison in other types of systems using such catalysts.
Hydrocarboxylation Reaction (2) is carried out catalytically, discussed in more detail hereafter. Reaction (2) can also be carried out continuously or in batch operation in the liquid or vapor phases. Usually the reaction is carried out in batch operation in a solvent under pressure.
The reactant concentrations can vary widely and are not critical. For convenience, the ratio of the hydrocarboxylation reactant (R'YH) to the enol ester should be no greater than 10/1 on a molar basis. The amount of carbon monoxide can vary widely, but it is preferred to carry out the reaction under a carbon monoxide pressure of 15 to 3500 psig, preferably 500 to 2500 psig. The amount of catalyst can also vary widely. Most conveniently, the amount of catalyst is between 0.01 and 100 mole-percent based on the enol ester, more usually 0.1 to 10 mole-percent.
Usually, the reaction is carried out with a solvent.
The solvent should be inert under the reaction conditions and preferably dissolves the active catalyst species. Suitable solvents found to date are tetrahydrofuran, benzene, CH3CN
.
and CH2C12 and CH3Cl. The now preferred soivent is tetrahydrofuran, particularly when using (~3P)2PdC12 catalyst, or other palladuim compounds. Usually~ the amount of solvent in the system will be such that the enol ester concentration is at least about 0.01 weight percent in the solution, but not over 70 weight percent.

S~
(5711`

The reaction is normally carried out at a temperature of O to 250 C, preferably 20 to 150 C. However, the reaction temperature can be below or above this if desired. Reaction times on the order of 0.1 to 250 hours can be employed, with reaction times on the order of 2 to 100 hours being more convenient.
While a wide variety of complexes of transition metals are known as catalysts for the hydrocarboxylation of alkenes (See, for instance, 1) Pino, P., Piacenti, F., in Or~anic Synthesis via Metal Carbonyls, Yolume 2, Wender, I., Pino, P., eds., Wiley, New York, 1977, pp. 233-296; 2) Falbe, J., New S~ntheses with Carbon Monoxide, New York, Springer Verlag, ____________________._______ Chapter 3 and 5; 3) Forster, D.; Hershman, A.; Morris, D. E., Catal. Rev. - Sci. En~. 23, 89-lOS (1981); 4) Parshall, G. W., C~tal. Rev. Sci. - En~., 23, 107-124 (1981); 5) Bittler, J, v.
_____________________ _ ___ Kutepow, N., Neubauer, D., Reis, H.p Angew. Chem. Intl. Ed.
En~., 7, 329-335 (1968),) many such catalysts are poisoned by sulfur compounds. Indeed, we have found that most such catalysts tried are not effective in reaction (2) herein, as will be seen from the specific examples. We have discovered that palladium coordination complexes are remarkably effective when considered in the light of experience with other known transition metal catalyst complexes for hydrocarboxylation of alkenes, or for hydroformylation for enol ethers or enol acetates (U.S. Patent 3,888,880; B. Fell, M. Barl, J. Mol.
Catal., 1977, 2, 301-6; Tinker, Harold 8. (Monsanto) Ger.
Offen. 2,623,673; U.S. 4,072,709). Especially useful Pd complexes are (~3P)2PdCI~ and (~3P)4Pd with HCl as a co-catalyst. When (~3P)2PdCl2 is the catalyst, the now preferred reaction solvent is tetrahydrofuran.

~L'~

Once a reaction is completed, the 2-acyloxy-4-(hydrocarbylthio)butanoic acid (or thioacid) or ester product can be recovered from the reaction system in a conventional manner, such as for example, by vacuum distillation.
The third step in the inventive process i5 the hydrolysis of the 2-acyloxy-4-(hydrocarbylthio)butanoic acid or thioacid or ester.
Reaction (3) is a conventional hydrolysis reaction.
It is catalyzed by any dilute aqueous acid or base. Suitable acids or bases are HCl, H2S04, HN03, H3P04)acetic acid, KOH, NaOH and NH40H. The reaction is conveniently carried out at temperatures at above O C to 120 C, more usually about 20 to 100 C. If desired, non~interfering hydrophilic solvents other than water can be employed. Examples of such solvents are tetrahydrofuran, CH3CN, and the like. Reaction times on the order of 0.1 to 24 hours, usually 0.5 to 4 hours, can be employed.
The methionine hydroxy analog or derivative product of the Reaction (3) can be recovered from the reaction medium in a conventional manner. For example, the reaction product can be recovered by crystallization of the MHA.
The above reaction scheme comprising reactions (1) to (3) provides a simple and straightforward system for producing methionine hydroxy analog or derivative using acrolein as the starting material. As can be seen, it totally avoids the use of deleterious HCN and the production of unwanted by-product ammonium sulfate.

The following examples are merely illustrative and are not to be considered dS limiting.

~75~ ( 5711) __ _____ Potassium acetate (12 g., 0.12 mol) was added to a solution of CH3SCH2CH2CH0 (108.2 9, 1.04 mol) in acetic anhydride (153.4 g, 1.50 mol). The solution was heated to 145 C for 3 hours. The amber-colored reaction mixture was cooled to room temperature, dissolved in 200 mL of pentane, washed with three 300 mL portions of H20, and stirred for 1 hour over 300 mL of saturated aqueous NaHC03 solution. After drying (MgS04), the product mixture was distilled at reduced pressure. The enol acetate, 1-acetoxy-3-methylthiopropene, was collected as a clear, colorless oil, bp 84-90 /10 mm (105 g,), a 43:57 mixture of Z and E isomers, as determined by gas chromatographic analysis. The remainder of the product was 1, 1-diacetoxy-3-methylthiopropane (22g). The isolated yield of the mixture of the Z and E isomers was 72 percent. Small samples of the Z and E mixture were collected by preparative gas chromatography for the analysis, which was by gas chromatography, nmr, and infra-red spectroscopy.

__________ 47.9 mmoles of 3-(methylthio)propionaldehyde and 81.8 mmole of acetic anhydride, together with 6 mmoles of a catalyst comprising KOAc, and 5 mmoles of m-xylene internal standard were charged into a reaction vessel and heated to a temperature of 137 C for 3.5 hours. The reaction was monitored quantitatively by gas chromatography. It was found that the conversion of the aldehyde was ~0.9 percent, with a selectivity of 80,1 percent of the mixed Z and E isomers of 1-acetoxy-3-methylthiopropene and a selectivity of 17.3 percent for the diacetoxy compound mentioned in Example 1, with a Z/E
isomer ratio of 41/59.

~ S ~ ~ ~ (5711) 49.5 mmoles of 3-(methylthio)propionaldehyde and 76.~
mmole of acetic anhydride together with 6 mmoles of a catalyst comprising KOH, and 5 mmol of the m-xylene internal standard ~ere charged into a reaction vessel and heated to a temperature of 140 C for 3.5 hours. The reaction was monitored quantitatively by gas chromatography. It was found the the conversion of the aldehyde was 78.3 percent, with a selectivity of 75.2 percent of the mixed Z and E isomers of 1-acetoxy-3-methylthiopropene and a selectivity of 18.6 percent for the diacetoxy compound mentioned in the Example 1, with a Z/E isomer ration of 41/59.

43.7 mmoles of 3-(methylthio)propionaldehyde and 48.3 mmole of acetic anhydride together with 6 mmoles of a catalyst comprising pyridine, and 5 mmol of m-xylene internal standard were charged into a reaction vessel and heated to a temperature of 134 C for 4 hours. The reaction was monitored quantitatively by gas chromatography. It was found that the conversion of the aldehyde was 75.6 percent, with a selectivity of 74.4 percent of the mixed Z and E isomers of i 1-acetoxy-3-methylthiopropene and a selectivity of 24.2 percent for the diacetoxy compound mentioned in Example 1, with a Z/E
isomer ratio of 38/62.

~ S ~ ~ ~ (5711) 48.2 mmoles of 3-(methylthio)propionaldehyde and 53 mmole of acetic anhydride together with 2.5 mmoles of a catalyst comprising sodium ben~oate, and 5 mmol of m-xylene internal standard were charged into a reaction vesse1 and heated to a temperature of 133 C for 4 hours. The reaction was monitored quantitatively by gas chromatography. It was found that the conversion of the aldehyde was 87.2 mol percent, with d selectivity of 58.0 percent of the mixed Z and E isomers of 1-acetoxy-3-methylthiopropene and a selectivity of 21.1 percent for the diacetoxy compound mentioned in Example 1, with a Z/E
isomer ratio of 39/61.

~0 mmoles of 3-(methylthio)propionaldehyde and 75 mmole of acetic anhydride together with 6 mmoles of a catalyst comprising triethylamine, and 5 mmol of m-xylene internal standard were charged into a reaction vessel and heated to a temperature of 138 C for 4 hours. The reaction was monitored quanti-tatively by gas chromatography. It was found that the conversion of the aldehyde was 88.2 percent, with a selectivity of 65.8 percent of the mixed Z and E isomers of 1-acetoxy-3-methylthiopropene and a selectivity of 9.1 percent for the diacetoxy compound mentioned in Example 1, with a Z/E
isomer ratio of 38/62.

50 mmoles of 3-(methylthio)propionaldehyde and 50 mmole of acetic anhydride together wi~h 6 mmoles of a catalyst comprising triphenyl phosphine, and 5 mmol of m-xylene internal standard were charged into a reaction vessel and heated to a ~ ~7 S ~ ~ ~ (5711) temperature of 130 C for 3 hours. After 70 minutes of the 3 hours 26.4 more mmoles of triphenyl phosphine were added. The reaction was monitored quantitatively by gas chromatography.
It was found that the yield of the mixed Z and E isomers of 1-acetoxy-3-methylthiopropene was 14.1 mmoles and the yield of the diacetoxy compound mentioned in Example 1 was 2.3 mmoles with a Z/E isomer ratio of 41/59.

45.6 mrnoles of 3-(methylthio)propionaldehyde and 51~5 mmole of acetic anhydride together with 6 mmoles of a catalyst comprising RbOAc, and 5 mmol of m-xylene internal standard were charged into a reaction vessel and heated to a temperature of 131 C for 4.5 hours. The reaction was monitored quantitatively by gas chrorrlatography. It was found that the conversion of the aldehyde was 87.6 percent, with a selectivity of 6507 percent of the mixed Z and E isomers of 1-acetoxy- 3-methylthiopropene and a selectivity of 13.9 percent for the diacetoxy compound mentioned in Example 1, with a ZIE isomer ratio of ~2/58.

45.4 mmoles of 3-(methylthio)propionaldehyde and 51.7 mmole of acetic anhydride together with 10.6 mmoles of a catalyst comprising HOAc, and 5 mmol of m-xylene internal standard were charged into a reaction vessel and heated to a temperature of 135 C for 8 hours. The reaction was monitored quantitatively by gas chromatography. It was found that the conversion of the aldehyde was 56.4 percent, with a selectivity of 55.7 percent of the mixed Z and E isomers of 1-acetoxy-3-rnethylthiopropene and a selectivity of 38.9 percent for the diacetoxy compound mentioned in Example 1, with a Z/E
isomer ratio of 63/37.

~7 5 1 ~ ~
EXAMPEE 10_ 40.5 mmoles of 3-(methylthio)propionaldehyde and 47.4 mmole of acetic anhydride together with 0.5 mmoles of a catalyst comprising [Pd(OAc)2]3, and 5 mmol of m-xylene internal standard were charged into a reaction vessel and heated to a temperature of 135 C for 5 hours. The catalyst was insoluble. The reaction was monitored quantitatively by gas chromatography. It was found that the conversion of the aldehyde was 35.3 mol percent, with a selectivity of 24.5 percent of the mixed Z and E isomers of 1-acetoxy-3-methylthiopropene and a selectivity of 25.9 percent for the diacetoxy co~pound mentioned in Example 1, with a Z/E isomer ratio of 51/49.

48.2 mmoles of 3 (methylthio)propionaldehyde and 39.7 mmole of propionic anhydride together with 6 mmoles of a catalyst comprising KOAc~ and 5 mmol of m-xylene internal standard were charged into a reaction vessel and heated to a temperature of 135 C for 4 hours. The catalyst was insoluble.
~he reaction was monitored quantitatively by gas chromatography. It was found that the conversion of the aldehyde ras 86.4 mol percent. Substantially, the only products'~formed were l-propionyloxy-3-methylthiopropene, as the mixed Z and E isomers, plus 1,1'-dipropionyloxy-3-methylthiopropane, with the majority being the former. The products were identified by gas chromatography and mass spectroscopy.

11.6 mmoles of 3-(methylthio)propionaldehyde and 8.3 mmole of acetic anhydride together with llmmole ~f a catalyst comprising KOAc, and 5 mmol of m-xylene internal standard were 7S~
(57 dissolved in 2.5 ml of diethylene alycol dimethyl ether and charged into a reaction vessel and heated to a temperature of 100 C ~or 6 hours. The reaction was monitored quantitatively by gas chromatography. lt was found that the conversion of the aldehyde was 57.8 mol percent, with a selectivity of 100 percent of the mixed Z and E isomers of l-acetoxy-3-methyl~hiopropene and with no diacetoxy compound being formed.

___________ A mixture of 0.1 moles of 3-(methylthio)propionaldehyde and 0.15 moles of isopropenyl acetate together with 200 mg. of p-toluenesulfonic acid as catalyst was heated to reflux (90 C) with stirring ~or 24 hours. Gas chromatographic analysis at the end of this time showed four components in addition to unreacted isopropenyl acetate and acetone. Treatment of Et20 solution of the crude product mixture with aqueous NaHC03 solution and drying over an MgS04-activated charcoal mixture removed the allylidene diacetate. The products were distilled at reduced pressure.

Component Peak_Area(U/~of total) 1) CH2=CHCH(02CCH3)2 46.4%
2) Z-CH3SCH2CH=CH02CCH3 18.6U/, 3) ~CH3SCH2CH=CH02CCH~ 11.7%

4) ~H3SCH2CH2CH(02CcH3~2 23.3%

Treatment of a solution of CH3SCH2CH2CH0 (0.10 mol) in 45 ml of dry pyridine with acetyl chloride (0.20 mol) at 90 C, follûwed by aqueous wash and Et20 extraction, gave approximately 1 9 of oil whose GC showed presence of the enol acetate and the l,l-diacetate.

~ _ ~, Z~5~
(5711) 0.5 mmoles 1-acetoxy-3-methylthiopropene (Z:E ratio 43:57) and 2.5 mmoles methanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a reflon coated stir bar. Ten mole percent, based on 1-acetoxy-3-methylthiopropene, of a catalyst comprising bis(triphenylphosphine)dichloropalladium, (~3P)2PdC12, was added. Toluene was included as an internal standard. five milliliters of tetrahydrofuran as a solvent were also included in the reaction system. The reaction mixture was charged under argon. The bomb was sealed and carbon monoxide at a pressure of 1000 psi (at room temperature) was charged to the bomb, and the bomb was heated to 100 C and allowed to react for 92.5 . `t hours with stirring. At the termination of the reaction, the reaction products were analyzed by gas chromatography and it was found that 2-acetoxy-4-(methylthio)butanoic acid, methyl ester was produced in a yield of 28.6 percent and that 2-acetoxy-4-~methylthio)thiobutanoic acid, me~hyl ester was produced in a yield of 19.5 percent, based on the 1-acetoxy-3-methylthiopropene reactant charged. Note that each of the products is hydrolyzable to methionine hydroxy analog.

O.S mmoles 1-acetoxy-3-methylthiopropene (Z:E ratio 43:57) and 2.5 mmoles 2-propanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. No catalyst was added. Toluene was included as an internal standard. Five milliliters of tetrahydrofuran as a solvent were also included in the reaction system. The reaction mixture was charged under argon. The bomb was sealed and ~L~75i~
(5711) carbon monoxide at a pressure of lO00 psi (at room temperature) was charged to the bomb, and the bomb was heated to 100 C and allowed to react for 44 hours with stirring. At the termination of the reaction, the reaction products were analyzed by gas chromatography and it was found that no 2-acetoxy-4-(methylthio)butanoic acid, 2-propyl ester was produced and that no 2-acetoxy-4-(methylthio)thiobutanoic acid, methyl ester was produced. 0.0515 mmoles of ,acrolein and 0.0456 mmoles of methyl acetate were the only products detectable.

-~ 0.5 mmoles 1-acetoxy-3-methylthiopropene, pure E
isomer, and 2.5 mmoles methanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. No catalyst was added. Toluene was included as an internal standard. Five milliliters of tetrahydrofuran as a solvent were also included in the reaction system. The reaction mixture was charged under argon. The bomb was sealed and carbon monoxide at a pressure of 1000 psi (at room temperature) was charged to the bomb, and the bomb was heated to lO0 C and allowed to react for 44 hours with stirring. At the termination of the reaction, the reaction products were analyzed by gas chromatography and it was found that no 2-acetoxy-4-(methylthio)butanoic acid, methyl ester was produced and that no 2-acetoxy-4 (methylthio)thiobutanoic acid, methyl ester was produced. 0.16 mmoles of acrolein and 0.0294 mmoles of CH3SCH2CH2CH0 were the only detectable products.

1;~'7S~ ( 5 7 1 1 ) 0.5 mmoles l-acetoxy-3-methylthiopropene, pure Z
isomer, and 2.5 mmoles methanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. No catalyst was added. Toluene was included as an internal standard. Five milliliters of tetrahydrofuran as a solvent were also included in the reaction system. The reaction mixture was charged under argon. The bomb was sealed and carbon monoxide at a pressure of 1000 psi (at room temperature) was charged to the bomb, and the bomb was heated to 100 C and allowed to react for 44 hours with stirring. At the termination of the reaction, the reaction products were analyzed by gas chromatography and it was found that no 2-acetoxy-4-(methylthio)butanoic acid, methyl ester was produced and that no 2-acetoxy-4-(methylthio)thiobutanoic acid, methyl ester was produced. 0.15 mmoles of acrolein and 0.11 mmoles oF methyl acetate, and 0.04 mmoles of CH3SCh2CH2CHO were the only detectable products.

0.5 mmoles 1-acetoxy-3-methylthiopropene (Z:E ratio 43:57) and 0.5 mmoles methanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. One mole percent, based on 1-acetoxy-3-methylthiopropene, of a catalyst comprising Mn2(CO)10 was added. Toluene was included as an internal standard. Five milliliters of tetrahydrofuran as a solvent were also included in the reaction system. The reaction mixture was charged under argon. The bomb was sealed and carbon monoxide at a pressure of 1000 psi (at room temperature) --~0---~2'7~ ( 5711) was charged to the bomb, and the bomb was heated to 120 C and allowed to react for 44 hours with stirring. At the termination of the reaction, the reaction products were analyzed by gas chromatography and it was Found that no 2-acetoxy-4-(methylthio)butanoic acid, methyl ester was produced and that no 2-acetoxy-4-(methylthio)thiobutanoic acid, methyl ester was produced.

Examples 20-31 ~, Example 19 was repeated several times except that the following catalysts were used in separate experiments:

20) RUcl2(p~3)3 21) RU3(C)12 22) RhCl3 * ~100 psi H2 23) [Rh(C~)~Cl]2 24) PtC12(1 /) + SnCl2(1~/O) ~ ~3As (2~/o) 25) NiCl2 * ~100 psi H2 2~ Ni(co)2(p~3)2 27) Ni(~Ac)2 + HI(2%) 28) ClIr(CO)(P~3)2 Results were the same as reported for Example 19, l.e., no desired product was formed.
*10 percent instead of 1 percent.
When Fe(C0)5(29); Co2(C0)8(30); or PtCl2(31) were used to repeat Example 19 in place of Mn2(C0)10 catalyst, no 2-acetoxy-4-(methylthio)butanoic acid, methyl ester, was formed, but a small amount of the corresponding _Y~ thiobutano~ic acid ester formed. I!
All of the catalysts of Examples 20-31 are known catalysts for the hydrocarboxylation of alkenes, but are not effective in the present Reaction (2).

;J ~ /~' , ~

~2~7~ 711) 0.5 mmoles 1-acetoxy-3-methylthiopropene, (Z: E ratio 43:57)~ and 2.5 mmoles methanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. No catalyst was added. Toluene was included as an internal standard. Five mil1iliters of tetrahydrofuran as a solvent were also included in the reaction system. The reaction mixture was charged under argon. The bomb was sealed and carbon monoxide at a pressure of 1000 psi (at room temperature) was charged to the bomb, and the bomb was heated to 100 C and allowed to react for 44 hours with stirring. At the termination of the reaction, the reaction products were analyzed by gas chromatography and it was fsund that no 2-acetoxy-4-(methylthio~butanoic acid, methyl ester was produced, and that no 2-acetoxy-4-(methylthio)thiobutanoic acid, methyl ester was produced.

0.5 m~oles 1-acetoxy-3-methylthiopropene, (Z: E ratio 43:57), and 2.5 mmoles methanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. A catalyst comprising ~Pd(CH3CN)4J CBF4~2 plus P~3 was added. Toluene was included as an internal standard. Five mllliliters of tetrahydrofuran as a solvent were also included in ~he reaction system. The reaction mixture was charged under argon. The bùmb was sealed and carbon monoxide at a pressure of 1000 psi (at room temperature) was charged to the bomb, and ~'7S~11 (5711) the bomb was heated to 100 C and allowed to react for 44 hours with stirring. At the termination of the reaction, the reaction products were analyzed by gas chromatography and it was found that 2-acetoxy-4-(me~hylthlo)butanoic acid, methyl ester was produced in a yield o~ 8.5 percent, and that 2-acetoxy-4-(methylthio)thiobutanoic acid, methyl ester was produced in a yield of 24.6 percent, based on the 1-acetoxy-3-methylthiopropene react~nt charged. Note that each of the products is hydrolyzable to methionine hydroxy analog.

______ __ _ 0~5 mmoles 1-acetoxy-3-methylthiopropene, (Z: E ratio 43:57), and 2.5 mmoles methanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. Ten mole percent, based on l-acetoxy-3-methylthiopropene, of a catalyst comprising Pd(P~3~4 plus lO mole percent HCl co-catalyst was added. Toluene was included as an internal standard. Five milliliters of tetrahydrofuran as a solvent were also included in the reaction system. The reaction mixture was charged under argon. The bomb was sealed and carbon monoxide at a pressure of 1000 psi (at room temperature) was charged to the bomb, and the bomb was heated to lOO C and allowed to react for 45.25 hours with stirring. At the termination of the reaction, the reaction products were analyzed by gas chromatography and it was found that 2-acetoxy-4-(methylthio)butanoic acid, methyl ester was produced in a yield of 21.7 percent, and that 2-acetoxy-4-(methylthio)thiobutanoic acid, methyl ester was produced in a yield of 17.8 percent, based on the 7S ~ ~ i 1 acetoxy-3-methylthiopropene reactant charged. Note that each of the products ls hydroly~able to methion~ne hydroxy analog, When th~s run was repeated without the HCl co-catalyst (run length 44 hours), the y~elds of the above ester and th~oester w~re 3.93 percent and 4.48 percent, respectively.

¦ 0.5 mmoles 1-acetoxy-3-methylthiopr^opene~ (Z: E ratio 43 5?)~ and 10 mmoles methanol were charged lnto a 71 cc stainless steel bomb equ~pped w~th a glass liner and a ~eflon coated;st~r bar. ~en mole percent, based on 1-acetoxy-~-methylthiopropene, of a catalyst comprising b~s(tr~phenylphosph~ne)dichloropalladium, (d3P)2PdC12, was added. Toluene was ~ncluded as an internal standard. Five mill¦liters of tetrahydrofuran as a solvent were also included in the reaction system. The react~on mixture was charged under argon. The bomb was sealed and c~rbon monoxide at a pressure of lOjOO psi ~at room temperature) was charged t-o the bomb, and the b;omb was heated to 100 C and alluwed to react for 44 hours with Istirring. At the termination of the reaction, the reaction products were analyzed by gas chromatography and it was found that 2-acetoxy-4-(~ethylthio)butanoic acid, methyl ester was produced in a yield of 28~6 percent, and that 2-acetoxy-4-(methy1thio)thiobutanoic ac~d, methyl ester was produced in a yield of 16.8 percent, based on the l-acetoxy-3-methylth~opropene reactant charged. Note that each of the prùducts is hydrolyzable to meth~on~ne hydroxy analog.

~ ~ S ~ ~ ~ (5711) 0.5 mmoles 1-acetoxy-3-methylthiopropene, (Z: E ratio 43:57), and 2.5 mmoles ethanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. Ten mole percent, based on 1-acetoxy-3-methylthiopropene, of a catalyst comprising bis(triphenylphosphine)dichloropalladium, (~3P)~PdC12, was added. Toluene was included as an internal standard. Five milliliters of tetrahydrofuran as a solvent were also included in the reaction system. The reaction mixture was charged under argon. The bomb was sealed and carbon monoxide at a pressure of 1000 psi (at room temperature) was charged to the bomb, and the bomb was heated to 100 C and allowed to react for 44 hours with stirring. At the termination of the reaction, the reaction products were analyzed by gas chromatography and it was found that 2-acetoxy-4-(methylthio)butanoic acid, ethyl ester was produced in a yield of 1005 percent, and that 2-acetoxy-4-(methylthio)thiobutanoic acid, methyl ester, was produced in a yield of 10.8 percent, based on the 1-acetoxy-3-methylthiopropene reactant charged~ Note that each of the products is hydrolyzable to methionine hydroxy analog.

O.S mmoles 1-acetoxy-3-methylthiopropene, (Z: E ratio 43:57), and 2.5 mmoles 2-propanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. Ten mole percent, based on l-acetoxy-3-methylthiopropene~ of a catalys~ comprising ;

.~'7S~
(5711) bis(triphenylphosphine)dichloropalladium, (~3P)2PdCl2, was added. Toluene was included as an internal standard. Five milliliters of tetrahydrofuran as a solvent were also included in the reaction system. The reaction mixture was charged under argon. The bomb was sealed and carbon monoxide at a pressure of 1000 psi (at room temperature) was charged to the bomb, and the bomb was heated to 100 C and allowed to r~act for 44 hours with stirring. At the termination of the react~on, the reaction products were analyzed by gas chromatography and it was found that 2-acetoxy-4-(methylthio)butanoic acid, 2-propyl ester was produced in a yield of 4.7 percent, and that 2-acetoxy-4-(methylthio)thiobutanoic acid, methyl ester was produced in a yield of 10.1 percent, based on the acetoxy-3-methylthiopropene reactant charged. Note that each of the produ~ts is hydrolyzable to methionine hydroxy analog.

0.5 mmoles 1-acetoxy-3-methylthiopropene, (I: E ratio 43:57), and 2.5 mmoles methyl mercaptan were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. Ten mole percent, based on 1-acetoxy-3-methylthiopropene, of a catalyst comprising bis(triphenylphosphine)dichloropalladium, (~3P)2PdCl2, was added. Toluene was included as an internal standard. Five milliliters of tetrahydrofuran as a solvent were also included in the reaction system. The reaction mixture was Charged under argon. The bomb was sealed and carbon monoxide at a pressure of 1000 psi (at room temperature) was charged to the bomb, and the bomb was heated to 100 C and allowed to react for 44 hours with stirring. At the termination of the reaction, the 7 S ~ ~

(~711) reaction products were analyzed by gas chromatography and it was found that a small amount of 2-acetoxy-4-(methylthio) thiobutanoic acid, methyl ester was produced. Previously, this new thio compound frorn a number of runs similar to Example 15 were isolated by preparative gas chromatography and identified by mass spectroscopy and gas chromatography, as well as by infrared spectroscopy.

~ 410 mg (2.0) mmoles~ 2-acetoxy-4-(methylthio)butanoic acid~ methyl ester in 10 cc 2N aqueous HCl was maintained at a temperature of about 50 C for 4 hours with stirring. The reaction system was cooled to room temperature and extracted twice with 25 ml aliquots of ethyl ether. The ethyl ether layer was then dried with magnesium sulfate which was filtered off. Then the ether was evaporated from the dried ether solution, leaving a yellow oil product which was analyzed by proton nmr and determined to be composed of 300 mg (representing a 92 percent yield) methionine hydroxy analog.
This analysis was confirmed by gas chromatography.

__________ 0.5 mmoles 1-acetoxy-3-methylthiopropene, (Z: E ratio 43:57), and 0.5 mmoles methanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. Ten mole percent, based on 1-acetoxy-3-methylthiopropene, of a catalyst comprising t(allyl)PdCl]2 plus P~3 co-catalyst (200 mole percent) was added. Toluene was inGluded as an internal standard. Five milliliters of `` ' ~ ~2'~

tetrapydrofuran as a solvent were also included in the reaction system. The reaction mtxture was charged under argon. The bomb ~as sealed and carbon monoxide at a pressure of 500 psi (at rbom temperature) was charged to the bomb, and the bomb was heate¦ to 100 C and allowed to react for 44 hourslwith stirr~ng. At the termination of the reaction, the reaction products were analyzed by gas chromatography and it was found that 2-acetoxy-4-(methylthio)butanoic acid, methyl ester was produced in a yleld of 1.5 percent, and that 2-acetoxy-4-(methylthio)thiobutano c acid, methyl ester was produced in a yiPld of 3 percent, based on the 1-acetoxy-3-methylthiopropene reactant charged. Each of the products is hydrolyzable to methionine hydroxy analog.

;~ EXAMPLE 41 ~ 0.5 mmoles 1-acetoxy-3-methylthiopropene, (Z:E ratio 43:57~, and 2.5 mmoles methanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. Ten mole percent7 based on 1-acetoxy-3-methy~thlopropene, of a catalyst comprising bis(triphenylphosphine)dichloropalladium, (~3P)2PdCl2, was added. Toluene was 1ncluded as an internal standard. Five `~ milli~iters of benzene as a solvent were also included in the react~on system. The reaction mixture was charged under argon¦ The bomb was sealed and carbon monoxide at a pressure o~ lO~O psi (at room temperature) was charged/to the bomb, and the b mb was heated to 100 C and allowe~ to react for 44 hours with tlrring. At the terminat~on of the reaction, the reaction products were analy2ed by gas chromatography and it was f~und that 2-acetoxy 4-~methylthio)butanoic acid, methyl -2~-`' ~,r~75i9,~1il, ester was produced in a yield of 22 percent, and that 2-acetoxy-4~(methylthio)thiobutanoic acid, methyl ester was produced in a yield of 10 percent, based on the l-aceiltoxy-3-methylthiopropene reactant charged. Each of the products is hydrolyzable to methionine hydroxy analog.
i ______ ___ 0.5 mmoles 1-acetoxy~3-methylthiopropene, (Z:E ratio 43:57), and 2~5 mmoles methanol were charged ;nto a 71 cc stainless steel bomb equipped with a g1ass liner and a Teflon coated stir bar. Ten mole percent, based on 1-acetoxy-3-methylthiopropene, of a catalyst comprising b~s(triphenylphosphlne)d~chloropalladium, (~3P)2PdC12, was added~ Toluene was included a~s an ~n~ernal standard. Five milliliters of CH3CN as a solvent were also included in the reaction system. The reaction mixture was charged under argon. The bomb was sealed and carbon monoxide at a pressure of 500 ps; (at room temperature) was charged to the bomb, and ~he bomb was heated to 120 C and allowed to react for 44 hours with stirring. At the termination of the reaction, the reaction products were analyzed by gas chromatography and it was found that 2-acetoxy-4-(methylthio)butanoic acid, methyl ester was produced in a yield of 3 percent, and that 2-ace~oxy-4-(methylthiojthiobutanoic acid, methyl ester was produced in a yield of 10 percent, based on the l-acetoxy-3 methylthiopropene reactant charged. Each of the products is hydrolyzable to methionine hydroxy analog.

! - 29-`~ LZ~7~
(5711) 0.5 mmoles 1-acetoxy-3-methylthiopropene, (Z:E ratio 43:57), and 2.5 mmoles methanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. Ten mole percent, based on 1-acetoxy-3-methylthiopropene, of a catalyst comprising bis(triphenylphosphine)dichloropalladium, (d3P)2PdC12, was added. To~uene was included as an internal standard. Five milliliters of tetrahydrofuran as a solvent were also included in the reaction system. The reaction mixture was charged~under argon. The bomb was sealed and carbon monoxide at a pressure of 500 psi (at room temperature) was charged to the bomb, and the bomb was heated to 100 C and atlowed to react for 44 hours with stirring. At the termination of the reaction, the`
reaction products were analy7ed by gas chromatography and it was found that 2-acetoxy-4-(methylthio)butanoic acid, methyl ester was produced in a yield of 12.4 percent based on the l-acetoxy-3-methylthiopropene reactant charged. 2-acetoxy -4-(methylthio)thiobutanoic acid, methyl ester was recovered in a yiPld of 8.7 percent.

--~0-O,S mmoles 1-acetoxy-3-methylthiopropene, (Z:E ratio 43:57), and 2.5 mmoles methanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. One mole percent, based on 1-acetoxy-3-methylthiopropene, of a catalyst comprising bis(triphenylphosphine)dichloropalladium, (~3P)2PdCl2, was added. ~oluene was included as an internal standard. Five milliliters of tetrahydrofuran as a solvent were also included in the reaction system~ The reaction mixture was charged under argon. The bomb was sealed and carbon monoxide at a pressure of lOOO psi (at room temperature) was charged to the bomb, and the bomb was heated to 120 C and allowed to react for 44 hours with stirring. At the termination of the reaction, the reaction products were analyzed by gas chromatography and it ~ .
was found tha~ 2-acetoxy-4-(methylthio)butanoic acid, methyl ester was produced in a yield of 17 percent and that 2-acetoxy-4-(methylthio)thiobutanoic acid, methyl ester was produced in a yield of 12.3 percent, based on the 1-acetoxy-3-methylthioprnpene reactant charged. Each of the products is hydrolyzable to methionine hydroxy analog.

~ 27 ~ (5711) In each run about 0.5 mmoles 1-acetoxy-3-methylthiopropene and 2.5 mmoles methanol were charged into a 71 cc stainless steel bomb equipped with a glass liner and a Teflon coated stir bar. One mole percent, based on 1-acetoxy-3-methylthiopropene, of a catalyst comprising bis~triphenylphosphine) dichloropalladium, (03P)2PdCl2, was added. Toluene was included as an internal standard. Five milliliters of the indicated solvent were also included in the reaction system. The reaction mixture was charged under argon. The bomb was sealed and carbon monoxide at a pressure of 1000 psi (at room temperature) was charged to the bomb, and the bomb was heated to 100 G and allowed to react for 44 hours.
Various ratios of the enol acetate isomers were used as starting material, as shown. At the termination of the reaction, the reaction products were analyzed by gas chromatography and the yields of 2-ace~oxy-4-(methylthio)butanoic acid~ methyl ester t1) and 2-acetoxy-4-(methylthio)thiobutanoic acid, methyl ester (2), based ~n the 1-acetoxy-3-methylthiopropene reactant charged, were as shown in ~he table below. Shown also are the conversion of Z and E isomers and their percent conversions.
Starting Mat. Conversion Run No Solvent mmoles mmo~es Percent Ylelds THF 0.213 0.2430.163 0.217 76.5 89.3 29.213.2 46 T~F 0.53 0.0220.441 0 83.2 0 26.88.0 47 THF 0.01 0.542 * 0.444 * 82.0 31.28.2 48 benzene 0.212 0.2600.165 0.244 78.1 86.1 23.310.6 49 benzene 0.01 0.542 * 0.397 * 73.2 20.54.6 * not measured As will be evident to those skilled in the art, various modifications of this invention can be made or followed in the light of the foregoing disclosure and discussion without departing from the spirit and scope of the disclosure or from the scope of ~he claims.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for making a carboxylic acid ester having the formula comprising catalytically reacting a 3-(hydrocarbylthio)propionaldehyde with a reactant of the formula wherein X is , F, Cl, Br, I, 0-2-propenyl, 0-1-propenyl or 0-vinyl; R is C1 to C30 hydrocarbyl; R' is H or C1 to C30 hydrocarbyl, and wherein R and R' contain no ethylenic or acetylenic unsaturation; wherein R' is not H when X is halogen or , and wherein R' is not methyl when R is methyl.

2. A process according to claim 1 wherein each of R and R' are limited to a maximum of 10 carbon atoms, all of which are members of an open chain alkyl group.

3. A process according to claim 1 wherein a suitable solvent is utilized which is diethylene glycol dimethyl ether.

4. A process according to claim 1 wherein the reaction temperature is 80 to 130'C.

5. The compound, 1-propionyloxy-3-methylthiopropene.