Патент USA US2403686код для вставки
2,403,686 Patented July 9, ‘1946 ] UNITED STATES PATENT OFFICE MONO-GLYCOL ' ETHERS AND - UINS’A'ITU1 RATED NITRILES‘ ‘ _ i h I p I :‘ f;- I‘: - . Edward John S’chwoegler, Wya'ndotte,’Mich., as > -' slgnor‘ to Wyandotte Chemicals Corporation,‘ Wyandotte, Mich., a corporation of Michigan " ' '7 No Drawing. ‘ "31:1 . v " .7. I v V 7 Application November 22, 1944, Serial No. 564,716 . .14 Claims. ' v _ (01. 260——34;5) ' carbon atom of the nitrile becomes linked to" the “The present invention relates to chemical com-' pounds of the following indicated general for mula, and. their method of preparation: oxygen of such hydroxyl group, substantially as illustrated by the following equation: , a. v. , Suzanne CHz=GHCH1O CHICHIOH + CHFCHCEN -—-> h R=wlunsaturated hydrocarbon vradical R1=a hydrogen or alkyl group . ' '~ “ v _ catalyst OHFOHCHQO omomoomCmoN I V'I'he products of myrpresentiinventien amuse: iul intermediates in organic synthesis. ‘ ~ The alkaline condensinjgrorr catalytical agents used in the present reaction. are of I agstrongly 7 ._, 1A1; example of such product isv the following; ’ alkaline nature, such as alkali oxides. hydroxides, .. g . . amines, alcoholates or plienates; alkali or alkaline earth. metals, alkaline earth hydroxides, alkali wwlweemmeme, hydrides, strongly alkaline quaternary ammonia “Brie?y outlined, my invention involves the re ' action of a "monoglycol etherjof; anrunsaturated alcohol, with‘ an cz? unsaturated open chain nitrile, inthepresence of an alkaline condensing agent. V'Such' open chain (nltrile possesses the annular . ‘ capo-GEN " 1; ~ : hydroxides and the like; In general, the amount of such condensing agent or catalyst to be used is. from 1/2. to 5% by weight of the unsaturated mono-glycol ether employed in the‘ reaction. 20 . ‘The following unsaturated mono-‘glycol ethers a’ - may be employed inthe performance of my pres entinventioni ethylene, propylene and butylene where 1i’.v "glycol ethers of the following listed unsaturated ‘hydrogen or a methyl group, vizzé acrylonitrile‘or a methyl aorylonitrilet I alcoholsf ‘ #:The mono-‘glycol ethers of an unsaturatedalco hol are suitably’prepared by the reaction of ole?n trated by the following chemical equatiom-j 30 om=onomoomomon _ reaction of the alkali metal salt of the unsatu rated alcohol and an ole?n chlorhydrin, thusly: ' A Furfuryl alcohol Crotyl alcohol Oleyl alcohol Propargyl alcohol Cinnamyl alcohol Geraniol Methylvinylcarbinol Allylcarbinol Pentene-1-ol-5 Linalool Citronellol Alpha terpineol Methylallyl alcohol oxides and the unsaturated. alcohol, such as illus Such ethers may alternatively be prepared by ' Anyl alcohol . In' the case of the propylene and butylene ethers of the unsaturated alcohols, it isto be understood that two or more isomers may be formed by in teraction of the ole?n oxide and the unsaturated alcohol; The inclusion of such isomeric forms of ethers is within the purview and scope of my _ present invention. Mixtures ; of ole?n chlorhydrins, such . ‘as ethylene .and propylene chlorhydrin may also be employed in the abovereaction to produce mixed . - . The process is carried out in general by slowly adding acrylo- or metha‘crylonitrile to the ether containing the catalyst; the rate of addition being 7 regulated so that‘ the temperature of the reaction open chain nitrile, as subsequently" described. mixture-remains below 70‘? C. External cooling When such'a mono-glycol ether of the unsatu; 45 may be employe'd'if desired. The reactants may ratedv alcohol is reacted with the open‘ chain . beemployed in 'equimolar proportions although it is sometimes advantageous to use a small ex nltrile', and-in the presence of ‘an ‘alkaline cata alcohols which are in turn condensed with an, lyst, the _‘hydrogen of thehydroxy group in the cess of ‘unsaturated ether. ether-attaches itself to the double bonded carbon ‘By way of further'explanation and illustration in the‘beta position of the nitrile, and the‘ alpha of my invention, in order that it may readilybe 2,403,686 3 4 understood and practiced by those skilled in the dissolved sodium. The oily reaction mass was separated from the aqueous layer, washed with water, dried and distilled. Fifty-four grams of art, the following examples are given: Example 1 Mfurfuroxy ethoxy) propionitrile boiling at 152° Mono allyl ether of ethylene glycol in the Ca to 154° C. at 1 mm. Hg pressure were obtained. amount of 671 grams was placed in a reaction Nitrogen analysis showed this compound to be vessel ?tted with an agitator and surrounded by practically pure. a jacket suitable for heating or cooling. Methyl I claim: alcohol (10 grams) were added to the ether fol 1. As anew composition of matter, thereaction lowed by the addition of 5 grams ofv sodium in 10 product of an ether of a saturated glycol and an small chips. The mixture was agitated until all unsaturated alcohol, and an an unsaturated open sodium had dissolved. Acrylonitrile (265 grams) chain nitrile, were added to the agitated mixture over a period 2. As a new composition of matter, the reac of 2 hours while the reactants mixture was main tion product of an ether of a saturated glycol and tained at a temperature of 18-20" C. The reac 15 an unsaturated alcohol, and acrylonitrile. tion mixture was agitated for 1 hour at the above 3. As a new composition of matter, ,8- (allyloxy temperature on completion of acrylonitrile addi ethoxy) propionitrile-. tion and then poured into 200 cc. of water and 4. As a new composition of matter, a mixture neutralized with dilute sulfuric acid. The oily of [i cyano ethyl ethers of mono allyl propylene layer was separated from the aqueous layer, 20 glycol ethers. washed two times with sodium chloride solution, 5. As a new composition of matter, l-allyloxy dried and distilled. A water white product boil -2 [i cyanoethoxy propane. ‘ ing at 110° C. at 2 mm. Hg pressure (and weighing 6. As a new composition of matter, 18(furfuroxy 620 grams) was obtained. Its analysis agreed ' ethoxy) propionitrile, ‘ with the formula: '7. The method of making chemical compounds 25 of the formula CI~Iz='CH—CH2—O—-CI-lz——" . CH2,——OCH2—CH2—-CEN B(allyloxy ethoxy) propionitrile Example 2 Mixed mono allyl ether of propylene glycol where R is an unsaturated hydrocarbon radical, 30 and Y is an alkylene» group, consisting in react (232 grams) were placed in a reaction vessel ?t ted with an agitator, dropping device and a re?ux condenser. — Two grams of sodium were added to the ether in small chips and the mixture warmed 35 to~80° C. to effect solution. The solution was cooledv to 15° C. by means of an ice bath. Acrylo--v nitri'le (98' grams) was added to the agitated gly ing an ether of asaturated glycol and an un saturated alcohol with an unsaturated open chain nitrile in the presence of. an alkaline condensing agent. . ' n 8. The method of making chemical compounds of the formula . ' - . .. col ethers containing the dissolved sodium over , where R is an unsaturated hydrocarbon radical, a'period of 3 hours. The temperature of the re 40 and Y is an alkylene group, consisting in react action mass was maintained between 15 and 25° ing an ole?n oxide and an unsaturated alcohol, C; during ‘theaddition period. After all acrylo to form an unsaturated mono-glycol ether-and nitrile had been added, the reaction mass was agi then reacting the latter with an open chain nitrile tated for 30 minutes at 20° C., poured into water in the presence of an alkaline condensing agent. and neutralized with hydrochloric acid. The 45 9. The method of making chemical compounds aqueous, layer was separated from the oily con densation product. The crude condensation product was then distilled under vacuum. Two of the formula W " ' hundred and forty-?ve grams of the desired‘ con where R is an unsaturated hydrocarbon radical, densation products boiling at 138° to 142° C. at 50 and 'Y is an alkylene. group, consisting in react 12 mm. Hg pressure were obtained. Analysis ing the sodium salt of an. unsaturated alcohol showed they products. to be ,B-cyano ethyl ethers with an ole?n chlorhydrin to form an unsatu of mono allyl propylene glycol ethers. rated mono-glycol. ether jandthen. reacting the latter with an open chain nitrile, in the presence Example 3 of an alkaline condensing agent. One hundred and sixteen grams“ of 1,-allyloxy 10. The method of making chemical compounds propanol-2, prepared by the interaction of sodium _ of the formula allylate and l-chloro-propanol-Z, were condensed with 49 grams of acrylonitrile, 1 gram of sodium being used‘ as a catalyst, by the same procedure 60 Where R is an unsaturated hydrocarbonradical, as set out in Example 2. One hundred and twenty and Y is an alkylene group consisting in reacting grams of l-allyloxy 2(B-cyanoethoxy) propane the sodium salt of an unsaturated alcohol with boiling at 140° to 142°C. at 12 mm. Hg pressure a mixture of ethylene and ‘propylene chlorhy were obtained. drins to form mixed unsaturated mono-glycol ' ' Escample 4 65 ethers and then reacting the. latter with an open chain nitrile. in. the presence ofv analkaline con Metallic-sodium (1 gram) in the form of thin chips was dissolved in 108 grams of the furfuryl ether of ethylene glycol by vigorously agitating 11. The method oimaking aichemical.v com pound ofclaim 3 consisting vin reacting, mono allyl the vmixturevat 25° to 28° C.v Acrylonitrile (38 grams) Was added to the agitated ether over a 70 ether of ethylene glycol with acrylonitrile in. the period of 2 hours while the temperature was presence of dissolved metallic sodium. at a tem maintained below 25° C. by meansof an external perature of 18° to 20° C., neutralizing, thereaction mixture and then‘ separating and distilling the cooling bath. The reaction mixture was then stirred for ‘,5 hour at 25° C. and poured into water desired product therefrom.v 1 . containing just sufficient H2804 to neutralize the 75 12. The method of making a chemical com densing agent, . , ~ , . . 2,403,686 5 6. pound of claim 4 consisting of reacting a mix ture of mono allyl ethers of mono propylene glycol with acrylonitrile in the presence of dissolved metallic sodium at a temperature of 15° to 25“ C., temperature of 15° to 25° 0., neutralizing the re neutralizing the reaction mixture, separating and distilling the desired product. ' r 13. The method of making a product of ‘claim 5 consisting in reacting sodium allylate and 1 chloro-propanol-Z to form l-allyloxy propionol-2, condensing the product thereof with acrylonitrile 10 in the presence of dissolved metallic sodium at a sultant mixture andthen separating and distilling the desired product. 14. The method of making the product or claim 6 consisting in reacting furfuryl ether of ethylene glycol with acrylonitrile in“ the presence or dis solved metallic sodium at a temperature below 25° 0., neutralizing the resultant mixture and then separating and distilling the desired product. EDWARD JOHN SCHWOEGLER.