Patented May 16, 1944 2,349,232 UNITED STATES PATENT OFFICE 2,349,232 MANUFACTURE OF ALICYCLC COMPOUNDS Lloydi M. Joshe, Hyattsville, Md., assignor to the United States of America as represented by Claude R. Wickard, Secretary of Agricult2 re, and his successors in office No Drawing. Applieation October 16, 194A, Seria No. 4:5,263 4. Caians. (CA. 260-666) (Granted under the act of March 3, 1883, as amended April 30, 1928; 3 (0. (G. 57) This application is made under the act of and that greater yields may be obtained with March 3, 1883, as amended by the act of April other compounds at higher temperatures. The 30, 1928, and the invention herein described, if temperature used, however, in any case should patented, may be manufactured and used by or not be so high as to have a destructive effect upon for the Government of the United States of the final product being formed. The pressures America, for governmental purposes Without the used also depend a great deal upon the character payment to me of any royalty thereon. of the diene being used, as well as the vessel in This invention relates to a news process for which the reaction is carried out. Generally, manufacturing organic compounds of the ali there is not a critical upper limit with respect to cyclic class. 0 pressure and, ordinarily, pressures above about In general, the process comprises reacting 1,000 pounds per Square inch at room tempera ethylene with a conjugated diene, also known as ture can be used to obtain satisfactory results. 1,3-diene, under the action of heat. The reac The following examples will further illustrate tion proceeds by the 14-addition of the ethylene the invention: to the diene, whereby the alicyclic compound 5 EKAPLE I produced has, in each case, one additional six membered ring than the starting diene. Forty grams of 1,3-butadiene and about 200 By means of this process a large number of ali cubic centimeters of ethylene were sealed in a cyclic compounds can be synthesized which are rocking-type autoclave at room temperature under a pressure of about 900 pounds per square - not otherwise readily available, such as cyclo 20 hexene and derivatives thereof, including the inch. The autoclave was then heated to about alkyl, aryl, alkyloxy, carboalkoxy, and halogeno 200 C., whereupon the pressure rose to about derivatives. In addition to these monocyclic 4,500 pounds per square inch. After shaking at compounds, various polycyclic compounds can this temperature for 15 hours the pressure also be formed. dropped to about 28.75 pounds per square inch. More specifically, this invention comprises 25 The system was then cooled to room tempera heating the ethylene and a 1,3-diene at an ele ture, and the cyclohexene formed was recovered vated pressure until an allicyclic compound is by fractional distillation of the Contents of the formed having one more six-membered ring than autoclave. The reaction is indicated as follows: the original diene. In general, the reaction is 30 indicated as follows: CE C &B, H as-H) R. R.2 R. C N/ R c1 YR R - CH, R-C CH 35 EXAMPLE I R-C -- annum) About 200 cubic centimeters of ethylene and 39 S CH R- H grams of 2,3-dimethyl-1,3-butadiene were sealed g-R. c^ in a rocking-type autoclave at room temperature Rs.5 R? Y, under a pressure of 1,175 pounds per Square inch where one or more of the pairs consisting of R1. 40 and heated to about 200° C. The pressure rose to 6,200 pounds per square inch. The autoclave was and Re, R2 and R3,R4 and R5, and R3 and R4 may shaken for 21 hours at 190° to 200° C., during be connecting bridge linkages consisting of which the pressure gradually dropped until it be came constant at 3,550 pounds per Square inch. The system was then cooled to room temperature and the 1,2-dimethylcyclohexene formed was iso n being an integer, and where substituents Ri lated by fractional distillation. The reaction is and Rs and substituents R1, R2, R3, R4, R5, and indicated as follows: P Re, not already included in a bridge linkage, are 50 CH, CE chosen from the group consisting of alkyl, aryl, CH C-C alkyloxy, carboalkoxy, halogen, and hydrogen. sh, and CH-5 bH, The particular temperature and pressure at OH,- n N/ which the reaction is most favorably carried out CH CE depends in each case upon the characteristics of 55 EXAMPLE III ... the conjugated diene used. In most cases, a Thirty-three grams of freshly distilled cyclo temperature in the range of 175 to 300° C. is ap pentadiene were sealed in a rocking-type auto plicable, although it is possible that certain con clave with about 200 cubic centimeters of ethylene jugated dienes will react at lower temperatures under a pressure of about 1,270 pounds per square 2 3,849,282 inch at room temperature. On heating to about ExAMPLE VI-IIalogen derivatives of cycloherene 200 C., the pressure rose to about 5,800 pounds CE CE per square inch. The mixture was shaker & 2 this temperature for about 23 hours, although the C-C o-o/ Yoh, reaction appeared to have been cornpieted much is S bH,Fis am sooner, as indicated when the pressure dropped to 4,600 pounds per square inch and remained. Con Sc stant. The content of the autoclave was then 2-chloro-1,3-butadiene 1-chlorocyclohexene found to consist almost entirely of bicyclo(2.2.) as EXAEPLE VI-I-Polycyclic compounds 2-heptene. This alicyclic compound was distilled 0. and the fraction boiling at about 95 to 96° C. Was B CB collected. This product immediately solidified in cá, Yos, CB You, the form of pure white crystals. The reaction is indicated as follows: d C th CE d C (r C s -- le, am be, -- a ch, - \"\n O 5 off, Yob. of, Yo?, H bH, SSo ? ". / C É, cá, In some cases, in carrying Out the process of 20 1,1'-bicyclohexenyl A-perhydro this invention, compounds are produced other phenanthrene than the desired alicyclic compound, thereby .EXAMPLE VII.--Carboalkoacy derivatives of causing a decrease in the yield Of the desired COm cycloheacene pound. The formation of these undesired con CGOCH pounds may be suppressed by the addition of 25 agents to prevent dimerization and polymeriza &H tion, such as acetylene-dicarboxylic acid, hydro quinone, and others. The above examples illustrate the method of 30 this invention as applied to specific compounds. Other Specific compounds which may be mans factured in accordance with this invention are as Ethyl-sorbate 3-carboethoxy-6-methylcyclohexene follows: ExAMPLE IX-Alkyloay derivatives of ExAMPLE IV-Alkyl derivatives of cycloheacene - 85 Cycloheaceae CE (1) CE CBs 2 CH, bH H CO-C CB Yoh, + - CO ofs + C - of(s Ych,bH, 40 cho C cá, 2,3-diethoxy-1,3-butadiene 1,2-diethoxycyclohexene 1-methyl-1,3- 3-methyl Having thus described my invention, I claim: butadiene cyclohexene 1. The process comprising heating ethylene and (2) C CB 45 a 1,3-diene at a temperature below about 300° C. 2 - / N and at a pressure above 1000 pounds per square C-C C C-C C. inch until an alicyclic compound is formed hav R. * u, in bh, ing One more six-membered ring than the original N N dene, and thence recovering said alicyclic com Ca cá, pound. 2-methyl-1,3-butadiene 1-methylcyclohexene 50 2. The process of manufacturing bicyclo (3) CH, CE (2.2.1)-2-heptene, comprising heating ethylene and cyclopentadiene at a temperature below about bH bH 300 C. and at a pressure above 1000 pounds per cf. CB of Ych, 55 square inch until the heptene compound is g -- bu, arm- (s bh, formed, and thence recovering said heptene com pound. CE C 3. The process comprising heating while agi bH, bH, tating ethylene and a 1,3-diene at a temperature below about 300° C. and at a pressure above 1000 pounds per square inch until an alicyclic come ExAMPLE V-Aryl derivatives of cyclohe-cene pound is formed having one more six-membered ring than the Original diene, and thence recov Ces Cas ering said alicyclic compound. h d 85 4. The process Comprising heating ethylene and CE C of Yoh, a 13-diene in the absence of a catalyst at a ten perature below about 300° C. and at a pressure s + L- (s de, above 1000 pounds per square inch until an H. C. alicyclic compound is formed having one more bit, &H, 70 six-membered ring than the original diene, and 1,4-diphenyl-1,3- 3,6-diphenyl thence recovering the alicyclic compound. butadiene cyclo LLOYD M. JOSE