2,410,294 Patented Oct. 29,’ 1946 ' UNITED PATENT “OFFICE ‘ ': helm,‘ , Germany; vested in the iAlienuiPi-operty _ 1: Custodian‘: ‘ No‘nr'awiiig; App, cation-February 6;"1941, Serial No. 377,711. ' In‘G'ermanTFebruary 8,1940- H: g: ' " ' V 1'3 Claims. ‘. ’ vi1‘ i; = ‘r’ i“ ‘F’ xi wd-i > .J. i The present invention ‘relates to valuable ‘ “ passes over at 1.5 mms. pressure at 180 tov 8,5?l assay colorless and todourless; oil." iwhichcissndt softening agents more particularly to those of miscible withuiivatertv H the general formula: H2C———-CH1 I -~Corresp_ondin_g products are obtained whenlire H2C———CH1 5, placing the acetic acid; by other aliphaticjacids " such] as. caproic; caprylic or capric acid to . v a ‘ A mixture of 228fzpartsrof the alcohol | -, Mai m V. wherein R stands for a member of the group con sisting of a methine ‘radical and the methine used ‘10 in‘ Example, _1 and 250a parts of benzoic acid an hydride; the esteri'?cation is usiowiyjiifeated has ‘, beenmfihished. atj2oofito 220°,‘ the‘? eact n radical forming a part, of-‘ai-‘cjyclohexane ringz‘and product is digested with afdilute ‘sodium carbi R1 stands for a ‘radical ‘selected frp'rntheialiphatic . . solution-in order to 'r'emoveathe formed‘ 10qii'zl'oi'c and benzene series ~ the essential; characteristic 15 acid._. ,Then the residue is distilled invacuoq ‘ The of the‘ methine radical being ‘the existenceoi three esterfthus obtained ofthfe formula; ' ‘ " " linkages. each'iof whichis satisfied by‘ other sep ‘Him-Leon, arate alkylene or arylene‘sub'stituentsr ' ’ _ V The'new softeningiagents, are obtained by con densing two molecular" proportionsofyiuriural cycloaliphatic ketone?containi'ng reactive alkyl 29 . > ' 1- o 'v _ ‘ , wind-5cm (‘:0 with one molecularf proportion of an aliphatic or I groups, entirely hydrogenating the formed con densation products and esterifying the secondary I alcoholsrthus obtainedrbny means of jcarboxylic acids of the aliphatic and ‘benzene series or-their reactive derivatives._ ‘ ‘ , boils at 1 mm.;15iessjii'reatf2oo_ to 721p“ asayiscquvs, ' The present new ester compounds exhibit an excellent softening effect on the various thermo plastic compounds of a highamolecularl weight and the arti?cial masses-obtained therewith, such as highly polymerised vinyl compounds, polyacrylic acid esters and mixed polymerisation products therefrom, moreover cellulosicderiva tives. 30 *C““rrespo'ndin‘g‘ estersare obtained'wh'eri‘ steifif fying with derivatives of benzoic acid‘bei'ngfs v‘b-l iiiilltei by’ methyl girl“ 191: Helped: >, or - if; mamas» 4 50 partsjoithealcohol asji‘is‘d i by oxidising the higher aicohb‘isiwhich are ‘wen parts being by weight 1 and all temperatures in 7 known lay-products“ of thelimethanol synthesis. I ‘Example! ( _ vLe‘gfcregoin'it; ex" mp1es__ ‘re'lmiie'd with 310 "parts‘gof alfmixliulfe er'éai-boiiyiic‘ acids ‘of'ac'id mining; 324-, oh?aih'able presentuin- ‘ In order to furtherillustrate vention the following examples are given, the degrees centigrade. a? ‘i a) 11153113111‘? isslqvlv-hcaied 15? 209 to 250° While introducing? nitrogen into the reaction 'yvve'ssel. , . ith the nitrogen" which passes- through also furyl-3-_hydroxypentane" and 6.6 parts oiFa'cetic' ‘acid anhydride isfheated vfor about ~2v hours ‘in’ an apparatus provided‘ with ‘a? 'r‘e?u ‘ ' ‘ condenser. Then the formediacetic acidis'i re'i'no whac tional distillation. Subsequently1Iitlie'““reaction product of'theformulaz 111. 15:; '1 wateris-jrernovédnw 7' , ;, ,, The same estefisobtain .‘accordingi-‘toqthe 45 . following method: A mixture‘ of equal quantities of the alcohol and the aforesaid mixturerofv car boxylic acids-_-is">subiected'lin ‘the-1 presence of toluene as assistant liquor and a small amount of benzene sulfonic acid to the aceotropic dis tillation. ,When the splitting off of water has been ?nished the reaction product is isolated'as described in'iExa'mple 2. ifiieicrmeadmixtiire pfesiarsyboils. ‘pressure ammo 5?? less 011. 240?.v-asa1c0lqr1e ‘am 0d s ' l - 2,410,294 3 Example 4 4 A similar ester is obtained when using the phenoxy Propionic acid as esterifying agent. Example 7 By condensing the alkali metal compound of glycolmonobutylether with the sodium salt of monochloroacetic acid there is obtained the di When esterifying by means of adipic acid the formed diester of the formula: .10. etheracetic’ acid of the formula: CHr-O-CHz-COOH ‘ v'boiling'at 15 mm. pressure at 163 to 165°. 176 parts of thisacid are mixed with 246 parts of 1:5-ditetrahydrofuryl-3-hydroxypentane and the mixture is heated at reduced pressure. With .an almost theoretical yield the ester of the for is an odourless oil boiling above swat 151mm.’ pressure. . .7 Instead of adipic acid other dicarboxylic acids such as succinic acid may be used as esterifying 20 agent. I , V ,. , ‘ , . In the manner as described in the Zforegoing I a, examples other entirely hydrogenated condensa (5H: l tion products of furfural with suitable lketones such as methylethylketone, ' diethyl-ketone, cyclo _ hexanone and its alkylated derivatives such‘as is obtained as a colorless and odourless oil, which is not miscible with water and boils at 0.5 mm. pressure at 215 to 220°. isooctylcyclohexanone yield valuable products by esteri?cation. ‘ O-CHrCHr-O-CHn-CHFCHz-CH: 25 ‘ The ethercarboxylic acid derived from glycol monophenylether yields an ester of similar prop Avmixture of 246.parts of 1.5-ditetrahydrofur— yl-3-hydroxypentane and 116 parts of isohept oxyacetic acid is heated for about 6 hours at erties. _ , I ' ‘ Example 8 ' ' 300 parts of 2.6-di-trahydr0furfurylmethyl-cy about 140° ‘in,a vacuo of 20 to 25 mm. pressure, clohexanol obtainable by hydrogenating the yel the-formed‘ water distilling 011“. Then the tem perature is increased during about Ghours to 180° 35 low condensation product of two molecular pro portions of furfural and one molecular propor-v and the reaction mixture is held at this tempera tion of cyclohexanone are mixed with 400 parts of ture for 12 hours. The formed ester is isolated by fractionating ‘distillation. acetic acid anhydride and the mixture is heated The ‘yield is nearly theoretical. The ester thus obtained of the for mula: under ‘re?ux for about 3 hours. By a fractionat 40 \ I 0 Y \ / I o 45 ' ‘HaC--—.-CH1 ' ‘Ha’ \ CH:—Q—-C 1111: - _ - g n-cm-nc 0 is a colorless and odourless .oil, which is not mis cible with‘water and boils at 1 mm. pressure at H10 ~ , Y H2C——-CH2 CH—ICHz—HC\_ /onl 011, 0 pressure at 190 to 200°. ' I claim: ' hols of a lower or higher number of carbon atoms, 1. Asoftening agent of the formula: such as from a-ethylcyclohexanole or from. the .mc-om higher alcohols, which are well known :as by _ g , . Example 6 _ H, ‘ with water, and exhibits an excellent softening o ‘i' . o e?ect on thermoplastic compounds of high mo _' iHlO--'_'CH2 ' cn-cmom-on-omonrnc \'/.r; . 65 on, -\_/ ‘ 0 - 70 is obtained as a colorless and odourlesso'il, which ‘boils at‘223 to 226° at 0.7 mm. pressure and-is not miscible with water. Hz being a colorless and odourless oil, which boils at 223 to 226° at 0.7 mm. pressure and is not miscible an almost theoretical yield by fractional distil lation the formed ester ofathe formula: v o Ame-Q yl-3-hydroxypentane and 152 parts of p‘henoxy acetic acid is heated-at reduced pressure. With ? M HaC-—CH: ' A mixture of 246 parts of 'LS-ditetrahydrofur mc-----_cn, ' HIzQ\ 0 /CH—-CH2CH2—(|3H~—CH2CH2—H 0 productsof the methanol synthesis, very similar ' ‘ OH: is obtained as a colorless oil boiling at 0.6 mm. I When replacing the isoheptoxyacetic acid by other ether-carboxylic acids derived from alco estersarelobtained. " 000125 I ' (‘a 0 210to 215?. ing distillation with an almost theoretical yield the formed ‘ester ‘of ‘the formula; HaC-CH: H2C-——CHI H20 n-cmom-cH-cmom-no H: ‘ ' ' ' ’ 75 lecular weight and cellulose derivatives. 2.- A softening agent of the formula: 2,410,294 5 6 being a colorless and odourless oil, which boils at 3. Softening agents or the general formula 210 to 215° at 1 mm. pressure and is not miscible H,Q.__CH, with water, and exhibits an excellent softening effect on thermoplastic compounds of high molecular weight and cellulose derivatives. . H,Q___QH, __ _ H’(B\ / H CHPCHPCH CHPCHPH \ / H’ 5 0 to ° H: 10 iv wherein, R’ is selected from the group consisting of alkyl and aryl. ERNST KORTEN.