US2612516A - Condensation chloromethyl benzoates - Google Patents

Description

Patented Sept. 30, 1952 T UNITED STATES, PATENT.

. CON-DENSATION CHLOROMETHYL BENZOATES Robert A. Heimsch and William S. Emersom: I Dayton, Ohio, assignors to -Monsanto Chemical V Company, St. Louis, Mo., a corporationof-Dela Ware NoDrawings ;Application March 25 19 50,

, Serial No. 151,992

The present invention relates to esters of diaryl dicarboxylicacids and deals more particularly with the production of certain esters of 1,2-bis- (carboxyphenyl) ethane. The invention provides roams; (Cl. zen-r15 an improvedmethod for-the preparation of suchf 5 esters."-

"Esters" of 1,2 highly valuable 'asplasticizers and as intermedibis (carboxyphenyl) ethane are ates for th'e-production-of surface-active agents, 1

Water repellants, lubricants, etc. While a'number of these esters have been known for some time, their usefulness hasbeen limited because the known methods'of preparation either gave very poor yields or werebased on the use of difiicultly available starting materials.

,Now wehave found that esterslof l,2-'bis(car boxyph'e'nyl) ethane withaliphatic, saturated a1- cohols of from 1 to 8 carbon atomsare readily obtainable by heating an. alkyl-(halomethyl) benzoate in aqueous-suspensions of nickel-aluminum alloys, the reaction. proceedingsubstantiallyV according to the scheme:...

y is contacted with'the.--.a1loy; Optimumrryieldszof';

the ester are obtained by conducting:- the-;hejat ing for a time-oi say,--;one-hour to twentysfourhours. i c

It has been found that during a the: reaction; some of the" alkyl (halomethyl)benzoater-is ia1so:- converted ruby-products; i. e.;, toluic:acid-?andtoluates. Separationof "thef desired dicarboxyla-tes from the-by-productsds readilyeffected-a because of the wide differences in-therespective boilingpoint-andsolubility:characteristicsw 360G a t i In some instances, particularly when'iworking; c I H coon with the higher'alky1(halomethylibenzoate it:

,2- D G: maybe advantageous; to employan-inertjdiluentc I v r or a polar "solvent-with the aqueous suspension: R000" 3 of the nickel-aluminum alloy. As examples-of:

inlwhich. Ri-is an" alkylcgroup of1from :1 to 8 carbon atoms and X is'halogen. AlkylKp-halomethyl) :benzoates us'efullfor the present pur-' pose include methyl 4- '(c'h1oromethy1) benzoate, butyl 2- (chloromethyl) benzoate; ethyl 3- (bromo methylibenzoate, isoamyl '4 --(iodomethyl)benzoate; 2 ethylhexyl 4- (chlo'romethyl) benzoate,

etc.? As illustrative of esters of 1,2-bis(carboXy-- phenyl) ethane obtainable by the present process aqueoussuspensionof the nickel aluminum alloy,

at below the decomposition point of the halide, at. say, temperatures of from 140? C. .to 150 0., depending upon the nature of the individual reactants employed. Conveniently, the heating is conducted by refluxing the mixture of halide, water and the nickel alloy. Inasmuch as the ploy'ed maybe-mentionedl'clioxane benzene; etlrano1,ether, etc.; 1. l

The -.-nickel,aluminum alloy :fcundsuitablefior,- the present process may containvaryingfamounts 5 of nickel alloyed witlr'a-luminum: Good results" are obtainable by using the-alloys-describedz-in? the Raney patent, U. S. 1,628,190, and ,zconsisting of from 10% to 85% nickel and'from-90.%uto 15% aluminum, and particularly thealloys disclosed therein which---consist of approximately equal quantities of nickeland'alumin'um. Silicon may be present.- The alloy generally disclosed intll. S.

Patent 1,628,190 will be hereinafter referred to briefly as .Raney alloiyl" The invention is further illustrated, butjnot;

limited by the following exampl es:

Emampiri,

Twelve grams of Raney alloy..(from Gilman %Paint and Varnish Co.) and 100 cc. of water The resulting mixture was then refluxed for a washings were then combined and the benzene was removed by distillation under reduced pressure. The material which remained after separating the benzene was allowed to cool, and the crystals which formed in the cooled material were filtered off, washed with hexane and then recrystallized from methanol. The crystals thus obtained com rised substantially pure 1,2-

bis(4',4" carbomethoxyphenyl) ethane, M. P. 118.5 C.'119.0 C.

Example 2 This example shows the use of an inert solvent with water in the pre aration of 1,2-bis(4',4"- carbomethoxyphenyl) ethane.

Forty grams of Raney alloy, 150 cc. of dioxane and 150 cc. of water were charged to a 1-liter flask and the mixture was heated to a temperature of 80 C. To the mixture there was then added 1' 8 g. (0.965 mol) of methyl para(chloromethyDbenzoate during a time of 45 minutes and at temperatures of from 80 C. to 90 C. The resulting reaction mixture was then maintained at a temperature of from 87 C. to 91 C. for a time of 4 hours. At the end of that time 75.0 cc. of benzene was added to the reaction mixture and the whole was then cooled, with rapid stirring. The product was then filtered to remove the Raney alloy, and the filtrate was allowed to separate into an aqueous phase and an organic layer. The aqueous layer was washed with benzene. and the washings thus obtained as well as washings obtained by washing the filtered alloy with benzene were combined with the separated organic layer. Distillation of the combined organic layer and benzene washings to remove benzene and dioxane gave as residue a material from which the crude 1,2-bis(4',4"-carbomethoxyphenyl)ethane, M. P. 115-1l8 C., crystallized out upon cooling. Recrystallization of'the crude material, employing methanol, gave the substan-' tially pure 1,2-bis(4',4"-carbomethoxyphenyl) ethane.

Operating as in the above examples, but using ethyl, n-butyl or 2-ethylhexyl 4-(chloromethyl) benzoates instead of the methyl ester, there may be similarly obtained 1,2-bis(4',4"-carboethoxyphenyl) ethane, 1,2-bis(4',4"-carbo n butoxyphenyDethane or 1,2-bis[4',4"-carbo-(2-ethylhexyl) oxyphenyllethane.

We claim:

1. A process for producing a dicarboxylate having the general structure:

ROOC COOR wherein R is an alkyl group of-from 1 to 8 carbon atoms, which includes refluxing a mixture comprising Raney .alloy, water and anlester having the general structure:

4 2. A process for producing a dicarboxylate having the general structure R000 coca wherein R is an alkyl radical of from 1 to 8 carbon atoms, which includes heating a mixture comprising an aqueous suspension of an alloy, containing from 10% to nickel and from to 15% aluminum, and an ester having the general formula ROOC in which R is an alkyl radicalof from 1 to 8 carbon atoms, and recovering said dicarboxylate from the reaction product.

3. A process for producing a dicarboxylate having the general structure ROOC in which R is an alkyl radical of from 1 to 8 car-- bon atoms, which includes heating at a temper:

ature of from 40 C. to C. a mixture comprising an aqueous suspension of an alloy, containing from 10% to 85% nickel and from 90% to 15% aluminum, and an ester having the general structure in which R is an alkyl radical of from 1 to 8 carbon atoms, and recovering said dicarboxylatev from the reaction product.

4. A process for producing a condensation product which includes refluxing a mixture com-' prising Raney alloy, water and methyl 4-(chloromethyDbenzoate and recovering 1,2-bis(4',4"

carbomethoxyphenyDethane from the reaction product. 7

5. The process of producing a condensation product which includes refluxing a mixture com- 6. The process of producing a condensation product which includes refluxing a mixture com prising Raney alloy, water, butyl 4-(chloromethyDbenzoate and recovering l,2-bis(4,4"-carbobutoxyphenyhethane from the reaction product.

7. The process of producing a condensation product which includes refluxing a mixture comprising Raney alloy, water and Z-ethylhexyl ROBERT A. HEIMSCH.

WILLIAM S. EMERSON.

REFERENCES CITED The following references are of record in the fileof this patent:

.Sabatier, Catalysis in Organic Chemistry ,(sec- 0nd printing), page 148, paragraph 402 (1923 edition).

Adkins, Reactions of Hydrogen, edition).

pp. 19-20. (19ml

Claims (1)

1. A PROCESS FOR PRODUCING A DICARBOXYLATE HAVING THE GENERAL STRUCTURE: