US1999976A - Process for the preparation of higher alkyl esters of the carboxylic acids - Google Patents
Process for the preparation of higher alkyl esters of the carboxylic acids Download PDFInfo
- Publication number
- US1999976A US1999976A US672810A US67281033A US1999976A US 1999976 A US1999976 A US 1999976A US 672810 A US672810 A US 672810A US 67281033 A US67281033 A US 67281033A US 1999976 A US1999976 A US 1999976A
- Authority
- US
- United States
- Prior art keywords
- preparation
- alkyl esters
- esters
- higher alkyl
- carboxylic acids
- 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
Links
- 125000005907 alkyl ester group Chemical group 0.000 title description 23
- 238000000034 method Methods 0.000 title description 17
- 238000002360 preparation method Methods 0.000 title description 10
- 150000001735 carboxylic acids Chemical class 0.000 title description 3
- 150000002148 esters Chemical class 0.000 description 15
- 239000002253 acid Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- -1 for X Chemical compound 0.000 description 3
- 230000002140 halogenating effect Effects 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- PYLDCZJUHYVOAF-UHFFFAOYSA-N 4-chlorobutyl acetate Chemical compound CC(=O)OCCCCCl PYLDCZJUHYVOAF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- SMJYMSAPPGLBAR-UHFFFAOYSA-N chloromethyl acetate Chemical compound CC(=O)OCCl SMJYMSAPPGLBAR-UHFFFAOYSA-N 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/297—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
Description
. boxylic acids and Patented Apr. 30, 1935 THE PREPARATION 0F.
Es'rEiss PRGQESS roe arenas Atari. Boxymo ACIDS Donald J. Loder,
E. R. du Pont OF THE CAR-' Wilmington, Del assignor to de'Nemours & Company,
Wil-
mington, Del.,a corporation of Delaware I N0 Drawing."
Serial This'invention relates to'a process for the prep 'aration of the higher alkyl esters of the carmore particularly to the preparation of the higher alkyl esters of the aliphatic carboxylic acids from the lower alkyl esters thereof.
Esters are ordinarily prepared by direct esterificatiomthat is by direct action oi the acid on the alcohol. It is well known cation by the direct esterification process is extremely slow and particularly so when'the higher acids are reacted with the higher alcohols. Furthermore, the higher alcohols to preparation of the higher alkyl esters are generally expensive which results in a product too costly for general use.
An object of the present invention is to provide a simple and economical process for the preparationof higher alkyl esters. Another object of the present'invention is to provide a. process for the preparation of the higher alkyl esters of the carboxylic' acids from .thelower alkyl esters of those acids. A further object of the invention is to provide a process for the preparation of the higher alkyl esters ofthe carboxylic acids by the steps of halogenating a lower alkyl ester of the acid, condensing the halogenated ester with an olefinic hydrocarbon, and finally dehalogenating the resulting higher alkyl ester. A still further object of the invention is to provide optimum conditions and highly efiicient cat alysts for use in carrying out such processesi Other objects and advantages of the invention will hereinafter appear. I
I have found that the higher alkyl esters can 1 be preparedreadily and economically by halogenating the lower alkyl ester, condensing it with an olefinic hydrocarbon, and finally dehalogenating the resulting higher alkyl ester. A still further object of the invention is to provide optimum conditions and highly efficient catalysts for use in carrying out such 'processes, Other objects and advantages of the invention will hereinafter appear.
I have found that the higher alkyl esters can be prepared readily and economically by halogenating the lower alkylester, condensing it with an olefinic hydrocarbon, and finally dehalogenating the resulting'higher .alkyl ester. The esterforming reaction apparently proceeds in accord with the following equations in which halogens other than chlorine may, of course, be used:
nooonlxo1+nz=acooaixn+ncr (s) that esterifibe used in the.
higher aliphatic .acidssuch,
alkyl ester. and react it Application wit-a925, 193s,"
t e Claims. (01. 260-106) The compounddesignated as RCOORrl-lin the halogenation reaction designated as Reaction (1) may have substituted for R any alkyl, aryl, or aralkylgroupi.ng' and R1 any alkylene, arylene, or aralkylene grouping, while the X of Equation (2)v designates any olefinic hydrocarbon. Thus, by the substitution of a methyl group for ,R and R1, and the olefine, ethylene, for X, propyl acetate is produced from methyl acetate; i
' CHsCOOCl-ls+Cl2=CH3COOCH2Cl+HC1 CHSCOOCH2C1+CH2ZCH2=CH3COOC3H6C1 I Cl-IsCOOCsHsCl+H2=CH3COOC3Hv+HC1 Propylene and butylene similarly yield the butyl ester and amyl ester of aceticacid respectively.
Esters suitable for use in my process are read ily available from a number of sources. They may be prepared from the primary, secondary, or tertiaryalcohols by simple esterification, by ester interchange, or by any suitable process and include,I for example, the alkyl esters of the aliphatic carboxylic acids generallly, i. e. such esters asrnethyl, ethyl, propyl, butyl, and higher alkyl esters jof'acetic, propionic, butyric, and even the for example, as oleic,
palmitic, stearic,,and the like. It is tobeunderstood that my process is primarily directed to the preparation of the higher alkyl'esters, from the lower alkyl estersyand in lieu of condensing a high allayl esterofacetic acid, 1 such as ethyl acetate, withethylene, in order to obtain a butyl ester, for example, I usually prefer to use a lower with a higher olefine, for example the'methyl ester with utylene to get the 'amyl ester. .Nor do I limit'myseli to the condensation of the olefine with the saturated esters, of the..monocarboxylicacid for the unsaturated esters and polycarboxylic acid 4 esters, for example methyl acrylataethyl acrylate, -methyl citrate, ethyl tartratefand' equivalent estersmay likewise be used, in acccrd'with my invention,for the preparation of their corresponding higher esters. It is not essential that a condensed with an higherester, for a mixture or esters maybe used such as are obtained by esterification of the oxygenated organic compounds, principally alcohols, which areobtained by the catalytic hydrogena tion of carbon oxides under pressure according t o the process described by E; F; lzard. in U. S; appli-' cation Ser. No. 6565166. 'Theproduct obtained; by condensation of these esters inv accordwith, my process will-give higher alkyl esters offthis mixture of {oxygenated Y organic-compounds;
Furthermore, aromatic esters, such, 'for example,
singleester be olefine to obtain a single it is desired to convert be employed in a 'rela tively high degree of purity.
The halogenation of the lower alkyl ester may,
be carried out by any suitable halogenation process, for example by passing chlorine into the liquid ester at a suitable temperature and pressure, such, for example, as from 0 to the boiling of approximately C. and a pressure of approximately 50 atmospheres have been found suitable for many condensations of this type.
c Any suitable dehalogenation process may be Ewample.Methyl acetate (into which 0.5%
pressure at a temperature'of C. product is fractionated to remove chloromethyl acetate.
unchanged 7 e chlorobutyl acetate may be distilled to purify it. In case it is desired 7 carbon,- thus condensed halogenated 5. A process for ogenated' and condensed ester.
6. A process for the ester with an olefinic hydrocarbon.
8. In a process for the preparation of the higher alkyl esters of the organic carboxylic acids from the lower halogenated alkyl an: olefinic hydrocarbon.
DONALD}. LODER.
preparation of propyl
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US672810A US1999976A (en) | 1933-05-25 | 1933-05-25 | Process for the preparation of higher alkyl esters of the carboxylic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US672810A US1999976A (en) | 1933-05-25 | 1933-05-25 | Process for the preparation of higher alkyl esters of the carboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1999976A true US1999976A (en) | 1935-04-30 |
Family
ID=24700092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US672810A Expired - Lifetime US1999976A (en) | 1933-05-25 | 1933-05-25 | Process for the preparation of higher alkyl esters of the carboxylic acids |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1999976A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1057858A2 (en) * | 1999-05-31 | 2000-12-06 | Daicel Chemical Industries, Ltd. | A citrate compound, a plasticizer, and a thermoplastic resin composition |
-
1933
- 1933-05-25 US US672810A patent/US1999976A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1057858A2 (en) * | 1999-05-31 | 2000-12-06 | Daicel Chemical Industries, Ltd. | A citrate compound, a plasticizer, and a thermoplastic resin composition |
| EP1057858A3 (en) * | 1999-05-31 | 2002-01-02 | Daicel Chemical Industries, Ltd. | A citrate compound, a plasticizer, and a thermoplastic resin composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4092368A (en) | Vapor phase transesterification | |
| GB467433A (en) | Improvements in or relating to the manufacture of esters of methacrylic acid | |
| US3057909A (en) | Esterification of terephthalic acid with aqueous glycol | |
| US2697729A (en) | Preparation of ketones from carboxylic acids and esters thereof | |
| US1433308A (en) | Process of obtaining complete alcoholysis | |
| US2416756A (en) | Continuous production of esters of methacrylic acid | |
| US2479066A (en) | Preparation of mono-alkyl esters of terephthalic acid | |
| US2491660A (en) | Preparation of esters of terephthalic acid | |
| US2010154A (en) | Ether acid ester of polyhydric alcohols | |
| US1999976A (en) | Process for the preparation of higher alkyl esters of the carboxylic acids | |
| US2072806A (en) | Process for the separation of primary from secondary alcohols | |
| US2578647A (en) | Method of preparing esters of 1, 2, 4-butanetriol | |
| US1882808A (en) | Ester interchange with organic acids | |
| US2257021A (en) | Esters of di halo propionic acid | |
| US2177407A (en) | Alcoholysis of glycerides | |
| US2373583A (en) | Conversion of methyl formate to formic acid | |
| US2399595A (en) | Process for manufacturing acyloxy carboxylic acids | |
| US3293283A (en) | Process for transesterifying lower alkyl acrylates | |
| US2028012A (en) | Process for the preparation of esters of unsaturated acids | |
| US2111509A (en) | Production of esters of methacrylic acid | |
| US2460603A (en) | Preparation of alpha-cyano esters | |
| US2336223A (en) | Ester of isobutane-1,3-di-ol and method of making same | |
| US3321509A (en) | Preparation of alkyl esters of parahydroxybenzoic acid | |
| US1160595A (en) | Process for the manufacture of esters of oxy fatty acids. | |
| US2020685A (en) | Process for the preparation of the esters of unsaturated acids |