US3476797A

US3476797A - Process for producing esters

Info

Publication number: US3476797A
Application number: US573799A
Authority: US
Inventors: Joseph B Mettalia Jr; Edward H Specht
Original assignee: Rohm and Haas Co
Current assignee: Rohm and Haas Co
Priority date: 1966-08-22
Filing date: 1966-08-22
Publication date: 1969-11-04
Anticipated expiration: 1986-11-04

Description

United States Patent M 3,476,797 PROCESS FOR PRODUCING ESTERS Joseph B. Mettalia, Jr., Southampton, and Edward H. Specht, Huntingdon Valley, Pa., assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Filed Aug. 22, 1966, Ser. No. 573,799 Int. Cl. C07c 69/66, 69/52 US. Cl. 260-484 7 Claims ABSTRACT OF THE DISCLOSURE This invention relates to a method for the preparation of alkyl 7-hydroxy-2,S-heptadienoates and dialkyl 2,5,8- decatriene-1,10-dioates by the reaction of 2-butene-1,4- diol, acetylene, nickel carbonyl, carbon monoxide, an alkanol of one to eight carbon atoms, an acid, and a halide, where the acid is an organic acid of one to eight carbon atoms, phosphoric acid, phosphorous acid, or

boric acid, and the halide is a bromide or iodide of the alkali metals, lithium chloride, or the iodide of the alkaline earth metals.

present invention are the alkyl 7 -hydroxy- 2,5 -heptadienoates, the alkyl portion depending directly on the alkanol employed in the reaction. These esters have known utilities, for instance, to form polyesters and polyamides, whichare useful as films or fibers. They may also be hydrogenated to form the corresponding saturated ester or further reacted under the circumstances of the present invention to form dialkyl 2,5,8-decatriene-1,10-dioates which have known utilities, particularly in the fiber field, such as for garments, tires and others.

Many attempts have been made in the prior art to produce the alkyl 7-hydroxy-2,5-heptadienoates and dialkyl 2,5,8-decatriene-1,10-dioates. Various degrees of success have been reported but all previous attempts have been plagued by substantial competing reactions which inevitably lead to large amounts of undesired side products or no reaction at all. By rigidly adhering to the teachings of the present invention, one consistently achieves good yields of desired product.

The alkanols used in the present process are those containing from one to eight carbon atoms and may be straight or branched chain in any of the known spatial configurations. It is preferred to use the lower alkanols, such as from one to four carbon atoms and especially methanol. Typically, there may be employed methanol, ethanol, isopropanol, butanol, hexanol, Z-ethylhexanol, octanol and the like. It is preferred to employ methanol or ethanol.

In addition to 2-butene-1,4-diol, which is the preferred reactant, there may be employed 2,3-dialkyl substituted 2-butene-l,4-diols. These alkyl substituents should contain no more than four carbon atoms each, preferably one to two carbon atoms. It is possible to havejust 'one alkyl substituent. These alkyl embodiments include methyl, ethyl, propyl or butyl. With the propyl or butyl em- Patented Nov. 4, 1969 bodiments, it is preferred to employ the straight chain configurations.

The acid employedincludes organic acids of one to eight carbon atoms, such as formic, acetic, butanoic, octanoic, benzoic and the like. There also may be employed phosphoric acid, phosphorous acid and bo'ric acid. The preferred acid is phosphoric. In this respect, it is emphasized that strong acids, such as hydrochloric and sulfuric acids, do not react according to the teachings of the present process.

To conduct the reaction of the present invention, one adds, as desired, the various defined reactants, preferably substantially simultaneously. In some instances, it is preferable to react the 2-butene-1,4-dio1 with the defined acid to form a diester and then continue the reaction with the remainder of the defined reactants. Such a modification is within the gamut of this invention.

The halide employed comprises the bromides and iodides of the alkali metals, lithium chloride and the iodides of the alkaline earth metals. Typically, these include sodium iodide, sodium bromide, potassium iodide, potassium bromide, lithium chloride, lithium iodide, lithium bromide, calcium iodide, barium iodide and strontium iodide. The preferred embodiments are calcium iodide, lithium chloride, lithiumbromide and sodium bromide...

The present reaction is conducted at a temperature of 25 to 75 C., preferably 40 to C. Atmospheric pressure is perfectly satisfactory although increased pressures may be employed, if desired.

The halide is employed in the range of 0.01 mole per mole of the diol to 1.0 mole per mole of the diol, preferably 0.05 to 0.20 mole per mole of the diol.

The acetylene is employed in the range of 0.3 mole per mole of diol to 3.5 moles per mole of the diol,,preferably 1.0 to 2.0 moles per mole of the diol.

The acid is employed'in the range .of 0.2 mole per mole of diol to 2.0 moles per mole of the diol, preferably 0.3 to 0.7 mole per mole of the diol.

The nickel carbonyl is employed in the range of 0.25 mole per mole of the diol to 1.0 mole per mole of th diol.

Carbon monoxide is supplied to the reaction system entirely or principally, as desired,- through the agency of nickel carbonyl.

In many instances, carbon monoxide gas, in addition to the carbon monoxide supplied-by the nickel carbonyl, is advantageouslyadded to the reaction system. lnqsuch instances, there may be, employed amountsup to about 0.8, preferably 0.5 to 0,,75, moleofcarbonmonoxide per mole of the diol.

During the course of the present reaction, both alkyl 7- hydroxy 2,5 heptadienoate and dialkyl 2,5,8 decatriene 1,10 dioate are formed. The formation of the monoester is favored by shorter reaction times and the use of the lower molar ranges of acid, acetylene and is, reduced. Theuse of longerreaction.times and higher molar amount of acid, acetylene and halide favors a higher yield of the diester and a higher total yield of products.

- At the conclusion of the reaction, the product (both monoester and diester) is isolated by stripping unused, volatile reactantsand extracting the remainder with a suitable ex'tractant, such as diethyl etherand, water. The product is found in the ether layer, which-may then be isolated by standard distillation -ftechniqu es,-. preferably under reduced pressure. f if.

The present process may be merc fully understood from the following examples, which are offered by, way of illustration and not by way of limitation. r f f A solution of 44 g. (0.5 mole) 2-butene-1,4-diol and 29.4 g. phosphoric acid (aqueous 86%, 0.3 mole) made up to 240 cc. with methanol was charged to a 1-liter 4 EXAMPLE 3 A solution of 0.12 mole LiBr in 250 cc. anhydrous ethanol was charged to l-liter reactor. The temperature was held at 55 C, while a total of 0.6 mole of 1,4 di- I Trifluoroacatic acid.

continuous flow stirred tank reactor. The reactor was 5 flushed with nitrogen and maintained at 45 C. A solua-ceqaxy-gbut-ene (prepared .prehmmanly by ieactmg tion of NKCO) in methanol was fed 'at a mm of 31 acet1c ac1d w1th 2-butene-l,4-d1ol), 0.4 mole of N1(CO) 4 mole/hour of Ni(CO) and a solution of NaBr in metha- 56 2 2 g gfi i g ii z E: 512 3; grxg f ig i 1101 was fed at -a rate of 0.27 mole/ hour of NaBr. Initially, S f acetylene and carbon monoxide were fed at 0 56 mole/ and Nl(co).'4 were stripped under reduced pres' hour and 0.14 mole/hour, respectively. After the reaction sure and the resldile extfacted with ether fi Water The had initiated (as evidenced b an exotherm and the ether layer was dried w1th Na SO and stripped of ether. a earance of a red color) theiilarious feeds were main The residue could not be distilled without decomposition. gg at the following rats Ni(co) at 0 31 m mom Pure product was isolated, however, from a preparative i gas-liquid chromatograph. Diethyl 2,5-8- decatriene-1,10- Eiifhfiifii. Z3;151322;.ffiffilfisiifi'dfi1332 53.3 35 gfi g g g g g- H 0 (66 hour, Phosphoric acid at 0.31 m./hour and methanol at th (7 3 & f 957 m./hour. The reaction was maintained for eight hours g t 1 a e ry a at which time a sufiicient number of reactor volume turn- 1 is c almef 18 v E 1k 1 7 h d overs had occurred to ensure obtaining an equilibrium 20 procfass or t e Preparanon o a y foxy sample for workup. The material in the reactor was haiptadlnoate and decamen? I filtered, stripped of Ni(CO) and methanol under reduced dloate 1n whlch h alkyl i from one to elght pressure, and the residue extracted with ether and water. ig g g fifi g? i 2535 5? g i g Analysis of the aqueous layer showed 0.15 mole of 0 Ni++/O 5 mole butenediol reacted. The ether layer was 25 moles of acetylene per mole of said d1ol, about 0.25 to dried with Na SO filtered and distilled under reduced 1110,16 of mckel carbonyl Per {nole of sald dlo carbon pressure to give two major products. The first was methyl g g g a 1 122 3? :5 2:5 gsg ggig z?zgg gi 7 hydroxy 2,5 heptadienoate, B.P. 90 C. 21 1.4870, O a identical in infrared and NMR spectra with an authentic {mole of F Z mole of f sample prepared by a different route and which gave the wherem said ac1d is an orgamc ac1d of one to eight carfollowing elemental analysis: calculated for C H O C hon P F P P ,bonc aclds (61 4 theory 52% H (757% theory 7 75%) wherem sald halide 1s a bromlde or iodide of the alkali metals, lithium chloride or the iodide of the alkaline and O (31.25%, theory 30.73%). The second product th t ls was dimeth 1 2,5,8 decatn'ene 1,10 dioate, B.P. 0.1 ear me a vmm o 20 1.4396, i f d Spectrum (liquid 2. The process according to cla1m 1 wherein the resmear): strong bands at 1715 to 1730 cmr 1435 cmraction is conducted w1th1n the range of about to 60 1400 emf- 968 cm." and 815 cmr' C. and there are employed:

Analysis.-Calculated for C I-1 0 C (64.35%, about 0.05 to 0.20 mole of said hahde per mole of theory 64.27%), H (7.32%, theory 7.19%) and O 40 the diol,

( theory 28.54%). about 1.0 to 2.0 moles of said acetylene per mole of A sample was hydrogenated to give, after purification, the di l,

a compound identicahwith dimethyl sebacate. The first about 03 to 7 mole f Said i per mole f the product was obtamed 1n 29% converslon and the second diol, and

m 34% converslon both basgd on the 'butenedlol' about 0.25 to 1.0 mole of said nickel carbonyl per mole EXAMPLE 2 of the diol.

A series of experiments was performed in which a 3. The process according to claim 1 wherein there 1s solution of 0.95 mole 2-butene-1,4-diol in 300 cc. of emPloyed up to flbout mole of carbon ,monoxlde gas methanol was charged to a one-liter reactor. Separate P mole of the d101- f d f halide i Ni(c()) acetylene carbon 4. The process accord ng to cla1m 1 wherem said alimoxide and additional methanol were then maintained for r101 18 methanol, s'ald ac1d -p p n and said halide a period of 1 to 2 hours. The results are given in the is lithium bromide. table. 5. The process according to claim 1 wherein said alka- TABLE Runs Halide Cal: LiCl LiBr NaI NaBr Halide (moles fed) 0. 2a 0.62 0.10 0. 23 0. 23 Acid HaP04 Acid (moles red).-." 0. 00 1.08 1.50 1.80 1. so -Ni(CO) (m oles fed) 0.56 0. 40 0. 42 0.43 0.40 Acetylene (moles fed) 2. 75 2. 70 2. 70 1. 46 2. 70 Carbon monoxide (moles fed) 0. 63 0.20 0. 65 0. 60 Methanol (cc. led) 300 300 300 300 300 Temperature C.) 45 45 35 Percent Conversion (on butenediol) Methyl 7-hydr0xy-2,5heptadienoate 0. 50 5. 00 1.00 0. 02 4. 00 Di methyl 2,5,8-decatrieue-L10-dioate..-. 56.00 1.00 50. 00' 51.00 53.00

' Formic acid;

I Benzoic acid.

nol is ethanol, said acid is phosphoric and said halide is 2,882,298 4/1959 Luberoif 260-486 sodium bromide. 3,110,725 11/ 1963 Chiusoli 260-486 XR 6. The process according to claim 1 wherein said 3,146,256 8/1964 Chiusoli 260485 XR alkanol is methanol, said acid is benzoic and said halide 3,236,879 2/1966 Chiusoli 260-484 is sodium iodide. 5 3,238,246 3/1966 Chiusoli et al 260-486 7. The process according to claim 1 wherein said 3,312,731 4/1967 Chiusoli et al 260-485 alkanol is methanol, said acid is phosphoric and said halide is calcium iodide. JAMES A. PATTEN, Primary Examiner References Cited 10 ALBERT P. HALLUIN, Assistant Examiner UNITED STATES PATENTS U.S. C1. X.R.

2,599,424 6/1952 Albrecht et a1. 260-486 XR 269-485 2,613,222 10/1952 Specht et a1 260L-486XR