US3194822A - Preparation of carboxylic acid esters - Google Patents

Preparation of carboxylic acid esters Download PDF

Info

Publication number
US3194822A
US3194822A US182658A US18265862A US3194822A US 3194822 A US3194822 A US 3194822A US 182658 A US182658 A US 182658A US 18265862 A US18265862 A US 18265862A US 3194822 A US3194822 A US 3194822A
Authority
US
United States
Prior art keywords
borate
methyl
ethyl
ester
acid esters
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US182658A
Inventor
Jr David D Neiswender
Robert D Offenhauser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
Original Assignee
ExxonMobil Oil Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ExxonMobil Oil Corp filed Critical ExxonMobil Oil Corp
Priority to US182658A priority Critical patent/US3194822A/en
Application granted granted Critical
Publication of US3194822A publication Critical patent/US3194822A/en
Anticipated expiration legal-status Critical
Application status is Expired - Lifetime legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11CFATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils

Description

United States Patent ()fiice g 3,194,82 Patented any is, was

3,194,822 PREPARATKON F CARBOXYLIC ACID ESTERS David D. Neiswender, Jan, Haddonfield, and Robert D. Ofi'enhauser, Seweil, N.J., assignors t0 Socony Mobil Oil Company, Inc., a corporation of New York No Drawing. Filed Mar. 26, 1962, Ser. No. 182,658 8 Claims. (Cl. 260410.9)

' rium. If one component is readily removed from the reaction, this equilibrium can be displaced. When one of the interchange products is the component readily removed, the reaction can proceed to good yields of desired ester.

It is the discovery of this invention that methyl or ethyl esters of fatty acids can be converted into higher alkyl esters by ester interchange with the corresponding higher alkyl borates. The methyl or ethyl borate product of the equilibrium can be readily removed from the reaction, thereby effecting food conversion into the higher alkyl fatty acid ester.

Accordingly, it is a broad object of this invention to provide a method of effecting ester interchange. Another object is to provide a method for converting ethyl or methyl fatty acid esters into higher alkyl fatty acid esters. A specific object is to provide a method for effecting esterester interchange between ethyl or methyl fatty acid esters and higher alkyl borates. Other objects and advantages of this invention will become apparent to those skilled in the art, from the following detailed description.

The present invention provides a method for converting methyl or ethyl fatty acid esters into higher alkyl fatty acid esters that comprises reacting a methyl or ethyl ester of a fatty acid having between about 8 and about 30 carbon atoms and a trialkyl borate having between about 4 and about 18 carbon atoms per alkyl group, with or without an acid catalyst, at a temperature of between about 175 C. and about 300 C., under a pressure of between about 0.1 atmosphere and about one atmosphere, and continuously removing trimethyl or triethyl borate.

The fatty acid ester reactant contemplated herein is a methyl or ethyl ester of a fatty acid having between about 8 and about 30 carbon atoms per molecule and, preferably, between about 10 and about 18 carbon atoms. These methyl or ethyl esters are readily prepared by many methods well known in the art. Non-limiting examples of the fatty acid ester reactant are methyl octanoate, ethyl octanoate, methyl Z-ethylhexanoate, methyl valerate, ethyl decanoate, ethyl isodecanoate, methyl dodecanoate (methyl laurate), ethyl dodecanoate, ethyl tetradecanoate, ethyl tetradecanoate, methyl pentadecanoate, ethyl hexadecanoate, methyl octadecanoate, ethyl octadecanoate, methyl eicosanoate, ethyl docosanoate, methyl pentacosanate, ethyl octacosanate, and methyl triacontanate.

The alkyl borate reactant is a trialkyl borate having between about 4 and about 18 carbon atoms per alkyl radical. The borate esters are readily prepared by heating boron oxide (B 0 with the desired alcohol at temperatures of the order of about 100 C. and higher. Non-limiting examples of the alkyl borate reactant are tributyl bo rate, triisoamyl borate, triamyl borate, trihexyl borate, triisohexyl borate, tri-(Z-ethylhexyl) borate, trioctyl borate, trinonyl borate, tridecyl borate, tri-dodecyl borate, tritetradecyl borate, tri-hexadecyl borate, and tri-oct-a'decyl borate.

The molar ratio of the methyl (or ethyl) ester of fatty acid reactant to alkyl borate reactant will be at least 3, i.e., at least the stoichiorhetric amount. It can be advantageous to use an excess.

The temperature at which the ester interchange is effected is dependent to a large extent upon the pressure. When operating at about atmospheric pressure, temperatures between about 240 C. and about 300 C., preferably between about 25 0 C. and about 300 C., are most effective. However, operation under reduced pressures will permit the use of lower temperatures. Superatmospheric pressures do not appear to be advantageous in this process. Thus, at pressures approaching 0.1 atmosphere,

temperatures as low as about C. can be employed.

In general, therefore, the process of this invention can be carried out at temperatures between about 175 C. and about 300 C. and at pressures between about 0.1 atmosphere and about one atmosphere.

Although it is not necessary to the process, the use of an acid catalyst can be advantageous. Typical catalysts are hydrochloric acid, phosphoric acid, and sulfuric acid. Sulfuric acid is particularly preferred. The amount of catalyst used is very small, in the order of about 0.1 to 0.5 percent, by weight of the reactants.

As has been mentioned hereinbefore, the ester interchange reaction is driven toward completion by removing trimethyl or triethyl borate from the reaction zone. Thus, any apparatus can be employed that will permit the removal of the more volatile borate ester product while rctaining the remaining materials in the reaction zone. Thus, for example, there can be used a jacketed autoclave provided with a reflux column having a condenser takeoff. The time of reaction will depend upon the efliciency of removal of the volatile borate ester, and upon the temperature and pressure conditions employed. In general, the time of reaction can vary between about 0.5 hour and about 48 hours, preferably between about 2 hours and about 24 hours.

EXAMPLE 1 Reaction time, hrs

2 Yield butyl lanrate, percent l0 EXAMPLE 2 Using the same reactants and amounts thereof and the apparatus of Example 1, another run was made at a temperature of C. and under a reduced pressure of 150 mm. mercury (about 0.2 atmosphere). The progress of this run, as shown by vapor phase chromatographic analysis, is set forth in Table II.

Table II Reaction time, hrs 1 Yield butyl laurate, percent 71 EXAMPLE 3 Another run was carried out as described in Example 1, except that 2 drops of concentrated sulfuric acid were added to the reaction mixture as a catalyst. The progress Table III Reaction time, hrs Yield butyl laurate, percent r- Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope thereof as those skilled in the art may readily understand. Such variations and modifications are considered to be within the purview and scope of the appended claims.

What is claimed is:

1. A method for converting fatty acid esters into higher alkyl fatty acid esters that comprises reacting an ester selected from the group consisting of methyl and ethyl esters of fatty acids having between about 8 and about 30 carbon atoms and a trialkyl borate having between about 4 and about 18 carbon atoms per alkyl group, at a temperature of between about 175 C. and about 300 C., under a pressure of between about 0.1 atmosphere and about one atmosphere, and continuously removing an ester of the group consisting of trimethyl borate and triethylborate.

2. The method defined in claim it wherein said method is carried out in the presence of a mineral acid catalyst.

3. A method that comprises reacting a methyl ester of a fatty acid having between about 10 and about 18 carbon atoms and a trialkyl borate having between about 4 and about 18 carbons atoms per alkyl group, at a temperature of between about 240 C. and about 300 C., at about atmospheric pressure, and continuously removing trimethyl borate.

4. The method defined in 3 wherein said method is carried out in the presence of a mineral acid catalyst.

5. A method that comprises reacting methyl. laurate with tributyl borate, at a temperature of between about 240 C. and about 300 C., at about atmospheric pressure, and continuously removing trimethyl borate.

d. The method defined in claim 5, wherein said method is carried out in the presence of sulfuric acid.

'7. A method which comprises reacting a methyl ester of a fatty acid having between about 10 and about 18 carbon atoms and a trialkyl borate having between about 4 and about 18 carbon atoms peralkyl group, at a temperature of between about C. and about 240 C., under reduced pressure, and continuously removing trimethyl borate.

8. The method defined in claim '7 wherein said methyl ester is methyl laurate, and said trialkyl borate is tributyl borate.

Owen et al., Journal otthe Science of Food and Agriculture, 7, 88- 2 (1956).

Iublishers Inc,

CHARLES B. PARKER, Primary Examiner.

TOBIAS E. LEVOW, DANIEL D. HGRWITZ,

Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,194,822 July 13, 1965 David D. Neiswender, Jr. et a1 I It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 29, for "food" read good line 59, for "ethyl tetradecanoate read methyl tetradecanoate Signed and sealed this 5th day of April 1966',

(SEAL) Attest:

ERNEST W. SWIDER Attesting Officer EDWARD J. BRENNER Commissioner of Patents

Claims (1)

1. A METHOD FOR CONVERTING FATTY ACID ESTERS INTO HIGHER ALKYL FATTY ACID ESTERS THAT COMPRISES REACTING AN ESTER SELECTED FROM THE GROUP CONSISTING OF METHYL AND ETHYL ESTERS OF FATTY ACIS HAVING BETWEEN ABOUT 8 AND ABOUT 30 CARBON ATOMS AND A TRIALKYL BORATE HAVING BETWEEN ABOUT 4 AND BOUT 18 CARBON ATOMS PER ALKYL GROUP, AT A TEMPERATURE OF BETWEEN ABOUT 185*C. AND ABOUT 300*C., UNDER A PRESSURE OF BETWEEN ABOUT 0.1 ATMOSPHERE AND ABOUT ONE ATMOSPHERE, AND CONTINUOUSLY REMOVING AN ESTER OF THE GROUP CONSISTING OF TRIMETHYL BORATE AND TRIETHYLBORATE.
US182658A 1962-03-26 1962-03-26 Preparation of carboxylic acid esters Expired - Lifetime US3194822A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US182658A US3194822A (en) 1962-03-26 1962-03-26 Preparation of carboxylic acid esters

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US182658A US3194822A (en) 1962-03-26 1962-03-26 Preparation of carboxylic acid esters

Publications (1)

Publication Number Publication Date
US3194822A true US3194822A (en) 1965-07-13

Family

ID=22669473

Family Applications (1)

Application Number Title Priority Date Filing Date
US182658A Expired - Lifetime US3194822A (en) 1962-03-26 1962-03-26 Preparation of carboxylic acid esters

Country Status (1)

Country Link
US (1) US3194822A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3523955A (en) * 1966-01-25 1970-08-11 Ugine Kuhlmann Process for the preparation of epsilon-caprolactone
US4049824A (en) * 1976-05-03 1977-09-20 Harry Weldon Diehl Cetyl myristoleate
US4552702A (en) * 1981-07-20 1985-11-12 Henkel Kommanditgesellschaft Auf Aktien Process for the preparation of fatty acid alkyl esters having improved processing properties
WO1996039259A1 (en) 1995-06-06 1996-12-12 Kasmark James W Jr Machine and method of making a filter
US5596099A (en) * 1992-11-21 1997-01-21 Hoechst Aktiengesellschaft Process for the preparation of N-(2-sulfatoethyl)-piperazine in high purity
US6559213B2 (en) * 1995-03-16 2003-05-06 Henkel-Teroson Gmbh Plastisol composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2587753A (en) * 1949-04-26 1952-03-04 Stanolind Oil & Gas Co Method for purifying alcohols
US2842586A (en) * 1955-06-02 1958-07-08 Armour & Co Process for obtaining alcoholysis of aminoacid esters

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2587753A (en) * 1949-04-26 1952-03-04 Stanolind Oil & Gas Co Method for purifying alcohols
US2842586A (en) * 1955-06-02 1958-07-08 Armour & Co Process for obtaining alcoholysis of aminoacid esters

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3523955A (en) * 1966-01-25 1970-08-11 Ugine Kuhlmann Process for the preparation of epsilon-caprolactone
US4049824A (en) * 1976-05-03 1977-09-20 Harry Weldon Diehl Cetyl myristoleate
US4552702A (en) * 1981-07-20 1985-11-12 Henkel Kommanditgesellschaft Auf Aktien Process for the preparation of fatty acid alkyl esters having improved processing properties
US5596099A (en) * 1992-11-21 1997-01-21 Hoechst Aktiengesellschaft Process for the preparation of N-(2-sulfatoethyl)-piperazine in high purity
US6559213B2 (en) * 1995-03-16 2003-05-06 Henkel-Teroson Gmbh Plastisol composition
WO1996039259A1 (en) 1995-06-06 1996-12-12 Kasmark James W Jr Machine and method of making a filter

Similar Documents

Publication Publication Date Title
US2870099A (en) Production of polymers of epoxide compounds
US2053474A (en) Higher alkyl borates and silicates and process for preparing same
CA1092144A (en) Process for the production of esters
US2563506A (en) Quaternary ammonium salts of
US3753968A (en) Selective reaction of fatty acids and their separation
US2558520A (en) Production of acrolein from glycerol
US2021698A (en) Vinyl ester
US3558597A (en) Process for the production of sugar esters
CA1049443A (en) Distillation process for purification of triaryl phosphate esters
US2621193A (en) Polymeric titanium compounds
US3328443A (en) New tetrakis(organophosphorus) nickel, tetrakis(organoarsenic) nickel, and tetrakis(organoantimony) nickel complexes and methods of preparing the same
US2802856A (en) Methods of preparing tri-esters of thiophosphoric acids
US2731481A (en) Dimeric fatty acids
US3458552A (en) Process for the preparation of condensed mixed metal alcoholates
US3253040A (en) Process for the production of primary 3-hydrocarbyloxypropylamines
US1996115A (en) Alkyl halide synthesis
US2282469A (en) Production of ethers from alcohols
US2066075A (en) Vinyl esters of carboxylic acids and their production
US1968601A (en) Preparation of olefine derivatives
US3028417A (en) Process of making hydroxy ester compounds
US2212895A (en) Process for the preparation of acyl sulphides and products resulting therefrom
US2164188A (en) Esterification of allyl type alcohols and products resulting therefrom
US2394829A (en) Allyl-type phosphates and their preparation
US3091632A (en) Process for the production of glycol monoesters from aldehydes
US3075999A (en) Glycidyl esteks