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United States Patent Office Patented Apr 3,657,317 United States Patent Office Patented Apr. 18, 1972 2 3,657,317 EI 1,3-FUNCTIONALLY DISUBSTITUTED BECYCLOBUTANES rx'A/N - Charles Eugene Coffey, Brandywood, Wilmington, Del, assignor to E. I. du Pont de Nemours and Company, LX. Wilmington, Dei. wherein R, R2, R3, R4, and Rs are as defined above. The No Drawing. Filed June 5, 1967, Ser. No. 643,339 term "lower,' when used in the definitions, denotes a car Int. C. CO7c 61/12, 69/74 bon length of 1-6 carbon atoms. U.S. C. 260-468 B 13 Claims This invention also provides certain novel intermediate 10 compounds of the above process having the general for ABSTRACT OF THE DESCLOSURE mula This invention relates to 1.3-functionally disubstituted R. H. bicyclobutanes, to a process for their manufacture, and to CHNO homopolymers obtainable therefrom. 15 CN ^ 4 OE R. R. BACKGROUND OF THE INVENTION wherein R3, R4, and Rs are defined as above. Recent interest in substituted bicyclobutanes has been DESCRIPTION OF THE PREFERRED stimulated by the discovery of their utility as intermedi 20 EMBODIMENTS ates and additives in the manufacture of various polyesters The starting material for the process of the instant and polyamides. Research in this field has disclosed vari invention is selected from compounds of the general ous substituted bicyclic compounds including some having formula: functional substituent groups. While functionally disubsti tuted bicyclobutane compounds have also been disclosed, 25 R. H. the particular 1,3-functionally disubstituted compounds wherein functional groups are attached at both bridge head carbon atoms have been heretofore unknown. R. Rg SUMMARY OF THE INVENTION 30 wherein Ra, Ra, and R5 can be hydrogen or hydrocarbyl groups of from 1 to 18 carbon atoms which are free of The instant invention provides compounds of the gen aliphatic carbon-to-carbon unsaturation. These compounds eral formula: can be prepared by reaction of an allene with a 1-cyano 1H-olefin. 35 Illustrative hydrocarbyl groups included within the pres R R ent invention are alkyl groups such as methyl, ethyl, ter tiary butyl, hexyl, isooctyl, dodecyl and octadecyl; cyclo R5 RA alkyl groups such as cyclopropyl, cyclobutyl, cyclopenty, cyclohexyl, cyclooctyl, methylcyclohexyl, 3,5-dicyclohex wherein R and R2 each are selected from carboxy, lower 40 ylcyclohexyl and cyclooctadecyl; aryl groups such as alkyl carboxylates including cycloalkyl carboxylates, hy phenyl, naphthyl, anthryl, p-biphenylyl, p,p'-triphenylyl, droxymethyl, aminomethyl, carbamoyl, chloroformyl, and naphthacenyl, benzathryl and chrysenyl; alkaryl groups cyano, and wherein R3, Ra, and R5 are selected from hy such as p-tolyl, p-cumenyl, 2,4,6-tributylphenyl, 9,10-di drogen and hydrocarbyl groups of from 1 to 18 carbon ethyl-1-anthryl and 6-methyl-2-naphthyl; and aralkyl atoms which are free of aliphatic carbon-to-carbon unsatu 45 groups such as benzyl, phenylethyl, diphenylmethyl, ox ration. naphthylethyl, 2-(2-anthryl)ethyl and 4-(2-anthryl) butyl. This invention further provides a process for the prep This starting material is first contacted with dinitrogen aration of these compounds. This process comprises con tetroxide preferably in the presence of a solvent. Suitable tacting a compound of the general formula: solvents can include, for example, halogenated hydrocar 50 Rs bons such as methylene chloride; per-halohydrocarbons such as hexafluoroethane, trichlorotrifluoroethane, and carbon tetrachloride; acids such as acetic acid; ethers such as ethylene glycol dimethyl ether and ethyl ether. The ni C i-xx- H tration is preferably carried out at a temperature of above R R4 55 25 C. and generally proceeds most satisfactorily when (wherein R3 RA, and Rs are defined as above) with NO4 the reaction mixture is maintained at reflux at atmospheric and contacting the product with water; hydrolyzing the re pressure, but preferably not at temperatures greater than sulting 1-cyano-3-hydroxy-3-nitromethylcyclobutane with 150 C. The time necessary for completion of the reaction water and a strong mineral acid; esterifying the resulting is generally about from 1 to 3 hours, and varies accord 1,3-dicarboxy-3-hydroxycyclobutane with a lower alkanol 60 ing to the particular solvent selected, amount of reactants, in the presence of an acid catalyst; halogenating the re temperature, and other reaction conditions. The product is sulting product to form a 1,3-bis(lower alkoxy carbonyl)- then contacted with water to yield a 1-cyano-3-hydroxy 3-halocyclobutane and dehydrohalogenating to form the 3-nitromethylcyclobutane. bicyclo[1.1.0 butane 1,3-dicarboxylate. This carboxylate This product is then contacted with water and a strong can then be treated according to methods such as those 65 mineral acid such as hydrochloric or sulfuric acid. The shown in copending, coassigned application S.N. 622,937, amount of acid used is not critical to the process of this now abandoned e.g., amidation with ammonium hydrox invention; however, quantities of about 5-50 times the ide, dehydration, nitration, and reduction, to yield bicyclo weight of the nitrated compound are preferred in this butane compounds with different functional substituent process. The reaction temperatures can vary between groups. This invention further relates to homopolymers 70 0-200° C., a temperature within the range of 50-150° C. having the recurring structural unit being particularly preferred. The reaction time for the 3,657,317 3. 4. completion of the reaction is generally between 1 and tion is generally completed within about from 1 to 10 48 hours, 16 hours being sufficient in most cases. The hours. The resulting product can then be purified by resulting product is a 1,3-dicarboxy-3-hydroxycyclobu methods well known to those skilled in the art, for exam tane. ple, removal of the excess solvent by distillation and a This diacid is then contacted with an alkanol of from further purification distillation of the remaining product. 1-6 carbon atoms to produce the corresponding ester. Alternatively, reduction to the diamine can be effected The alcohol is generally supplied in quantities of about through the use of LiAlH4. from 2-100 parts by weight of the alcohol per part of The ester substituent can be changed by contacting the the diacid. To facilitate the esterification, small quantities 1,3-bis-(alkoxy carbonyl) bicyclo1.1.0 butane with an al of a strong mineral acid are added to the reaction mix O cohol such as a lower alkanol, e.g., ethanol, butanol, pro ture. The esterification is usually complete within a period panol, or a cycloalkanol such as cyclohexanol, in the pres of from about 6 to 48 hours. The reaction temperature ence of a catalyst. can vary between 0-200 C., a temperature within the The difunctionally substituted bicyclobutane products range of 50-150° C. being particularly preferred. The of this invention can be polymerized by the standard ester reaction product can then be halogenated to the methods of polymerization known to those skilled in the corresponding 1,3-bis(alkoxy-carbonyl-3-halocyclobutane. art. For example, the compounds can be polymerized in This may be facilitated by contacting the previous prod bulk by the simple addition of a suitable catalyst such as duct with a halogen containing compound such as thionyl di-tertiarybutylperoxide or azo-bis-isobutyronitrile or can chloride, phosphorous trichloride, phosphorous tribromide, be treated by dispersion, emulsion, or solution methods or hydrobromic acid. This halo compound is then de 20 through free-radical polymerization. Suitable solvents for hydrohalogenated to form the bridge-bond between the the latter three types of polymerization include water, hy 1- and 3-carbon atoms. This can be effected, for example, drocarbons such as benzene or hexane, chlorinated aro by contacting the halogenated product with bases such as matic hydrocarbons such as chlorobenzene, nitriles such Sodium methoxide, Sodium hydroxide, sodium hydride, as acetonitriles, amides such as dimethylformamide and and sodium tertibutoxide. 25 N-methyl-pyrrollidone, and sulfoxides such as tetramethyl The bridge-head substituted diesters can be converted enesulfoxide. to the corresponding dicarbamoyl compound by contact The free radical-generating initiators which can be ing them with an ammonia solution. An aqueous solution used in each of these polymerizations can be selected of ammonium hydroxide having a concentration of about from a wide variety of compounds representative of this from 10 to 30% (saturated) of ammonium hydroxide is 30 type of initiator, including, for example, azo initiators preferred. This amidation can be effected at room tem Such as, c,c'-azodiisobutyronitrile, 1,1-azodicyclohexane perature or at moderately elevated temperatures, and the carbonitrile, dimethyl ox,c'-azodiisobutyrate and ox,c'-azo reaction is generally completed in a period of from 1-20 disobutyramide, and organic peroxides and hydroperox hours. The pressure during the course of the reaction is ides such as dibenzoyl peroxide, di-t-butyl peroxide, and preferably maintained at about from 1 to 3 atmospheres. 35 t-butyl hydroperoxide. These initiators may be used in The diamide product is generally present as a precipitate concentrations ranging from about 0.01 to 10 percent by in the reaction vessel and can be readily isolated by a re weight of the bicyclobutane monomer to be polymerized. moval of the solvent, e.g., by filtration or decantation. Other free radical sources for polymerization initiation If desired, the crude product can then be further purified can be also used, such as electron bombardment and ultra by recrystallization from water. 40 violet light in the presence of a sensitizer. This diamide can be dehydrated to the corresponding Reaction times for preparing the homopolymers from dinitrile with a dehydrating reagent, for example, thionyl the bicyclobutane monomers described above may vary halides such as thionyl chloride or thionyl bromide, phos from approximately a few seconds (e.g., 5 sec.) to several phorous oxychloride, and acetyl chloride, of which thionyl days, for example, two or three days depending on the chloride is preferred.
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