3,527,816 United States Patent Office Patented Sept. 8, 1970 1. 2 1,2-bis(2-methyl-3-cyclohexen-1-yl)ethylene 3,527,816 1,2-bis(3-ethyl-3-cyclohexen-1-yl)ethylene OLEFNC ALCOHOLS 1,2-bis(4-methyl-3-cyclohexen-1-yl-)ethylene John R. Norell, Bartlesville, Okla., assignor to Phillips 1,2-bis(5-ethyl-3-cyclohexen-1-yl)ethylene Petroleum Company, a corporation of Delaware No Drawing. Original application Oct. 22, 1965, Ser. No. 1,2-bis(6,6-dimethyl-3-cyclohexen-1-yl)ethylene 502,332, now Patent No. 3,433,928, dated Mar. 18, 3,4-bis(3-cyclohexen-1-yl)-3-hexene 1969. Divided and this application July 29, 1968, Ser. 1,2-bis(2,6-dimethyl-3-cyclohexen-1-yl)ethylene No. 748,162 2,3-bis(3-methyl-3-cyclohexen-1-yl)-2-butene Int. C. C07c35/00, C08g 17/00 1,2-bis(1,3-dimethyl-3-cyclohexen-1-yl)ethylene U.S. C. 260-617 6 Claims 2,3-bis(4-methyl-3-cyclohexen-1-yl)-2-butene O 1,2bis(1,4-dimethyl-3-cyclohexen-1-yl)ethylene 1,2-bis(5,6-dimethyl-3-cyclohexen-1-yl)ethylene ABSTRACT OF THE DESCLOSUIRE 2,3-bis(1,3,4-trimethyl-3-cyclohexen-1-yl)-2-butene Novel esters such as 1-(3-cyclohexen-1-yl)-2-(acetoxy 1,2-bis(2,5,6-trimethyl-3-cyclohexen-1-yl)ethylene cyclohexyl)ethylene and alcohols such as 1,2-bis(4-hy 5 1,2-bis(2,6-diethyl-3-cyclohexen-1-yl)ethylene droxycyclohexyl)ethylene are formed from 1,2-bis(3-cy 3,4-bis(4-ethyl-3-cyclohexen-1-yl)-3-hexene clohexen-1-yl)ethylene and derivatives thereof. The esters 1-(3-methyl-3-cyclohexen-1-yl)-2-(2-methyl-6-ethyl-3- are useful as plasticizers and the alcohols are useful as cyclohexen-1-yl)-ethylene intermediates in the formation of polyesters and poly 1-(3-cyclohexen-1-yl)-2-(2-methyl-3-cyclohexen urethanes. 1-yl)ethylene. The acids which can be employed as one of the re This is a division of application Ser. No. 502,332, actants in the practice of this invention are represented filed Oct. 22, 1965, now U.S. Pat. 3,433,928, issued by the formula Mar. 18, 1969. This invention relates to a process for the esterification 25 O of novel triolefins and also to the esters formed in Said R'lot: process. In another aspect this invention relates to the wherein R is selected from the group consisting of hy formation of alcohols by the saponification of said novel drogen and alkyl, aryl, and cycloalkyl radicals and com esters. In another aspect this invention relates to the 30 binations thereof such as alkaryl and aralkyl radicals, hydrogenation of those alcohols possessing olefinic un and alpha-haloalkyl radicals, each of said radicals con saturation. In another aspect this invention relates to a taining from 1 to 10 carbon atoms inclusive. process for the esterification of 1,2-bis(3-cyclohexen-1-yl)- Specific examples of acids which can be employed are ethylene. formic acid, acetic acid, propionic acid, isobutyric acid, According to the invention, novel compounds are pre 35 n-octanoic acid, n-decanoic acid, n-undecanoic acid, ben pared by esterifying triolefins characterized by the follow zoic acid, 4-n-butylbenzoic acid, cyclohexanecarboxylic ing formula: acid, 5-phenylvaleric acid, chloroacetic acid, trichloro R R. R. R. R. R acetic acid, dibromoacetic acid, trifluoroacetic acid, and l/ R R the like. R N7 -R 40 Catalysts that can be used for this purpose are the R / acid-type, for example, sulfuric acid, boron trifluoride, R. R. R. R. R. R. R. R. borontrifluoride-ether complex, stannic chloride and ferric chloride. where R is at least one member selected from the group Diluents that can be employed if desired include chloro consisting of hydrogen, methyl and ethyl, the total number 45 form, carbon tetrachloride, and 1,1,2-trichloroethane. The of carbon atoms in all of said R's preferably being not choice of diluent will depend upon the particular organic greater than 8. acid chosen, but whatever diluent is used, both the The preparation of these triolefins is described in a triene reactant and the organic acid reactant should be copending application of D. L. Crain, Ser. No. 502,544, soluble in the diluent. The amount of diluent employed filed Oct. 22, 1965, now abandoned and its continuation 50 can vary over a wide range, but will generally range in-part application Ser. No. 665,239, filed Sept. 5, 1967, from 100-1500 m. per mol of triene being reacted. If now U.S. Pat. 3,463,828, issued Aug. 26, 1969, assigned desired, the acid reactant can serve as a diluent. to a common assignee, Phillips Petroleum Company of In forming the mono-, di-, and/or triesters, the re Bartlesville, Okla. action temperature will generally range from 20-120' C. These triolefins can be prepared by contacting an 55 with the preferred range being from about 50-70 C., alkenyl-substituted cycloalkene with an alumina-Supported when a catalyst is employed. In those situations wherein molybdenum or tungsten catalyst at a temperature rang the reaction is carried out in the absence of a catalyst, ing from 25-300° C. and under a pressure ranging from the preferred temperature range is from about 70-100° C. 0 to 1500 p.si.g. Above-identified U.S. Pat. 3,463,828 The amount of catalyst employed can vary widely, but contains a disclosure of preparing these triolefins in greater 60 will generally range from about 1-10 weight percent detail. 8 based on the 1,2-bis(3-cyclohexen-1-yl)ethylene. The re It is also within the scope of the present invention action time for formation of the mono-, di-, and/or tri that these novel esters can then be saponified to form esters can range from a few minutes up to several days, the mono-ols, diols, and/or triols. Furthermore, it is within but generally will range from about 10-30 hours. the scope of this invention that the mono-ols and/or 65 Although the monoesters predominate at low acid:triene diols can be hydrogenated to form Saturated mono-ols mol ratios such as 1:1 or less, higher acid:triene mol and/or diols. ratios such as 2:1 give diesters as the principal products; Specific examples of those materials which can be substantial amounts of the triesters are produced with used as the starting material in the esterification afe as further increase of the acid:triene ratio. Less reactive acids follows: 70 often yield the monoesters as the major product even 1,2-bis(3-cyclohexen-1-yl) ethylene though an excess of acid is used. As the cycloolefinic 1,2-bis(1-methyl-3-cyclohexen-1-yl)ethylene double bonds tend to be more reactive than the ethylenic 3,527,816 3 4. double bond in this process, the major annount of the other acids according to the process of this invention gives monoesters and diesters will generally be those in which the following compounds: the ethylenic double bond remains intact. Saponification 1-formyloxy-1,2-bis(3-cyclohexen-1-yl)ethane of these esters by the process of this invention results in 1-(3-cyclohexen-1-yl)-2-(3-formyloxycyclohexyl)ethylene the formation of the corresponding mono-ols, diols, and 1.(3-cyclohexen-1-yl)-2-(4-formyloxycyclohexyl)ethylene triols. In the process of this invention, formic acid is the 1-formyloxy-1-(3-cyclohexen-1-yl)-2-(3-formyloxycyclo preferred reacting acid if one is to prepare alcohols in a hexyl)ethane subsequent saponification step. If the esters themselves 1-formyloxy-1-(3-cyclohexen-1-yl)-2-(4-formyloxycyclo are the desired products, the chosen acid will depend hexyl)ethane upon the desired properties such as boiling point, etc., O 1-formyloxy-1-(3-formyloxycyclohexyl)-2-(3-cyclohexen of the esters. 1-yl)ethane Examples of esters produced according to the above 1-formyloxy-1-(4-formyloxycyclohexyl)-2-(3-cyclohexen described process consist of compounds characterized by 1-yl)ethane the following formulas: 1,2-bis(3-formyloxycyclohexyl)ethylene monoesters having the formulas 5 1,2-bis(4-formyloxycyclohexyl)ethylene R. R. R. R. R. R. 1-(3-formyloxycyclohexyl)-2-(4-formyloxycyclohexyl) N ethylene R s = 7 -R 1-formyloxy-1,2-bis(3-formyloxycyclohexyl)ethane R. x X R. 1-formyloxy-1,2-bis(4-formyloxycyclohexyl)ethane R. R. R. R. R. R. R. R. 20 1-formyloxy-1-(3-formyloxycyclohexyl)-2-(4-formyloxy and cyclohexyl)ethane R. R. R. R. R. R. X. 1-formyloxy-1-(4-formyloxycyclohexyl)-2-(3-formyloxy R. R. N. X cyclohexyl)ethane R st-c- { 25 1-acetoxy-1,2-bis(3-cyclohexen-1-yl)ethane R. R. R 1-(3-cyclohexen-1-yl)-2-(3-acetoxycyclohexyl)ethylene R. R. R. R. R. R. R. R. 1-(3-cyclohexen-1-yl)-2-(4-acetoxycyclohexyl)ethylene diesters having the formulas 1,2-bis(3-acetoxycyclohexyl)ethylene R. R. R. R. R. R. X. 1,2-bis(4-acetoxycyclohexyl)ethylene 30 1-(3-acetoxycyclohexyl)-2-(4-acetoxycyclohexyl)ethylene Yl- k X 1-acetoxy-1,2-bis(3-acetoxycyclohexyl)ethane R r - r^ R 1-(chloroacetoxy)-1,2-bis(3-cyclohexen-1-yl)ethane X X N 1-(3-cyclohexen-1-yl)-2-3-(chloroacetoxy) cyclohexyl) R. R. R. R. R. R. R. R. ethylene and 35 1-(3-cyclohexen-1-yl)-2-4-(chloroacetoxy) cyclohexyl) X R.