BE534731A - - Google Patents

Description

       

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   The present invention relates to novel tricyclohexyl borates.



   Organic borates have been used in various industrial and laboratory processes, and have been incorporated into cosmetic and pharmaceutical preparations, paint compositions, synthetic resins, and frosting agents. However, due to the extreme sensitivity to hydrolysis of boric acid esters known today, their practical applications have been limited to processes in which moisture can be excluded.



   The Applicant has found that tricyclohexyl borates, the cyclohexyl rings of which bear certain substituents exhibiting remarkable stability and resistance to decomposition in the presence of water.



   The compounds of the present invention have the general formula:
 EMI1.1
 wherein R represents an aryl or cyclohexyl group (substituted or unsubstituted), is an integer equal to at most 4, and X represents hydrogen, a halogen, or an alkyl, aryl or alkoxyl group, each X being the same or different.



   The resistance that these borates show to hydrolysis is quite surprising, since the corresponding phenyl esters, such as tri- (2-cyclohexyl-phenyl) borate,
 EMI1.2
 are known to hydrolyze easily on contact with water (ef. United States Patent No. 2,260,339 of October 28, 1941).



   The present compounds can be prepared by directly reacting the corresponding alcohols with a suitable boron compound, for example boric acid, borax and sulfuric acid, boric anhydride, boric acetate or a boric ester such as. than trimethyl borate. The water which forms during the reaction can be removed by stripping in an inert solvent, such as xylene, benzene or toluene, which with water forms a binary azeotrope.

   Among the alcohols suitable for the purpose of their transformation into borates according to the invention, the following may be mentioned: 2 -cyclohexylcyclohexanol, 2 - phenylcyclohexanol, 2 - (2'.4'-

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 EMI2.1
 dichlorophenyl) cyclohexanol, 2- (2t-ethoxyphenyl) -cyclohexanol, 2- (4'-tert-butyphenyl) cyclohexanol, 2- (2'-chlorocyclohexyl) cyclohexanol, 2- (2'.4'- 6'-trichlorocyclohexyl) cyclohexanol, 2- (beta-naphthyl) cyclohexanol, 2- (2'.4 '
 EMI2.2
 -dichlorocyclohexyl) -4-ohlorooyclohexanol, and 2-cyclohexyl- ° phenylcyclohea- nolo
The invention is illustrated, but not limited, by the following example., Example
110 g (1.75 mol) of boric acid, 1000 gb (5.52 mol) are loaded into a 5 liter round-bottomed flask fitted with a 60 cmo reflux condenser lined with glass helices.

   of 2-cyclohexyloyolohexanol and 2 liters of xylene. The mixture is heated so as to maintain a regular distillation of the azeotropic mixture of xylene and water through the condenser at a rate capable of removing the theoretical quantity of water (95 g.) In four hours. About 1 liter of xylene is then distilled off, then the cooled residue is poured, before crystallization begins, into 2 liters of acetone.

   The ester separates immediately as a white powdery crystalline solid, which is filtered off with suction and washed with fresh acetone. The crude product is purified by dissolving it in hot benzene (1 g in 6 cc. ) and pouring it into three times its volume of acetoneo
A final washing and drying gives 806 g. of white crystalline ester, which corresponds to a yield of 83%.



   A small sample is recrystallized from benzeneacetone for analysis. It melts at 198-199 C and gives the analysis C: 78.04-H:: 11.50 - B: 1.96 percent, which agrees with the calculated numbers (C: 77.95 - H: 11, 45 - B: 1.95) for C36H63O3B. The neutralization equivalent is 184 (theoretical: 185).



   The product is very soluble in benzene, toluene, xylene, carbon tetrachloride, chloroform and petroleum ether. It is slightly soluble in diethyl ether and substantially insoluble in acetone.



   Unlike the boric esters known to date, which are almost completely hydrolyzed after a few minutes of contact with water, the new ester showed only less than 3% hydrolysis after 70 hours of contact. with water at room temperature.


    

Claims (1)

ABSTRACT I - As new compounds, tricyclohexyl borates characterized by the following points, separately or in combinations: 1 Their formula is: EMI2.3 <Desc / Clms Page number 3> wherein R represents an aryl or cyclohexyl group (substituted or unsubstituted), is an integer equal to at most 4, and X represents hydrogen, a halogen, or an alkyl, aryl or alkoxyl group, each X being the same or different. 2 X represents hydrogen or a halogen, for example chlorine. R 3 is cyclohexyl and X is hydrogen or halogen, for example chlorine. 4 A particular compound is tri (2'-cyclohexyl-cyclohexyl) borate. II - Process for the manufacture of the compounds according to paragraph I, characterized in that it consists in esterifying using a suitable boron compound, for example boric anhydride, boric acid, borax and l 'sulfuric acid, boric acetone or an alkyl borate, a substituted cyclohexanol of the formula: EMI3.1 where R, n and X have the same meaning as above.