[1]Un'i'ted States Patent Office 324392057 3,439,057 PREPARATION OF MACROCYCLIC COMPOUNDS Nissim Calderon, AkriDn, Ohio, assignor to The Goodyear Tire & Rubber Company, Akron, Ohio, a corporation of Ohio 5 No Drawing. Filed Sept. 1, 1967, Ser. No. 664,947 Int. Cl. C07c 3100; C08f 3102 U.S. Cl. 260-666 6 Claims 10 ABSTRACT OF THE DISCLOSURE The invention described is one of preparation of unsattirated large rin- -a] I icyclic compounds by subjecting, acyclic unsaturated compounds containing at least two 15 non-conjugated double bonds and containing at least 16 carbon atoms, to a catalyst which is a mixture of (a) at least one organo metallic compound wherein the metal is from Groups la, @ Jla, IIb and Illa of the Periodic Table of Elements, (b) at least one metal salt wherein the metal is selected from the .-roup of molybdenum and 20 tun@sten and (e) at least one compound of the -eneral formula RYH wherein Y is from the group of oxygen and stilfur and R is a radical selected from the group of hydrogen, alkyl, aryl, aralkyl, alkaryl and alkenyl and when Y is S, R may be a thioalkyl, thioaralkyl and a 25 thioalkaryl and when Y is 0, R is an alkoxy, alkaryloxy or an aralkoxy and radicals of alkyl, aryl, aralkyl -alkaryl, and alkenyl which a hydrogen is substituted @y a thiol or a hydroxyl .-roup. These unsaturated lar.@e rin.- 30 alicyclic compounds are useful as intermediates to produce such things as large ring ketones which in turn are useful as perfume bast@s. This invention Telates to a novel method of prepara- 35 tion of unsaturated large ring alicyclic compounds and the products obtained thence. More particularly, it concerns with the conv@rsion of various organic unsaturated materials, which will be classified extensively later, into compounds possessin- large alicyclic rings containin-at 40 least one carbon to carbon double bond by exposure of said unsaturated materials to catalysts whose compositions are described elsewhere in this specification. The term "unsaturated large rin.- alicyclic compounds," 45 used throu.ahout t@e present invention, relates to the .-roup of materials characterized by the presence of at least one alicyclic ring containin.- at least twelve carbon atoms in said rin.- skeleton and -at least two carbon atoms of the said ring are connected by a double bond. Prior to the present invention, a common method of 50 synthesis of large ring alicyclic compounds from acyclic precursors involved the intramolecular reaction of a linear alpha, ome.-a-disubstituted compounds, for instance, the acyloin condensation: 55 0 oc2HS (C H2).-2 0 + 2Na - (C H2) @-2 1 @o + 2NaOC2Hs 60 c I 002Hs Accordin.a to the present invention at least one acyclic unsaturated bydrocarbon correspondin.- to the general G5 formula: R@-CH,-CH=CH-Z-CH,--CH=CH-CH,-R" wherein: 70 (1) R' and R" may be at least one member of a group consisting of alkyl, aryl, alkenyll aralkyl, alkaryl, cyP a'Lented Apr. 15, 1969 2 cloalkyl, cycloalkenyl, bicycloalkyl, bicycloalkenyl radicals -and hydroaen; (2) Z is a hydrocarb'on fra-ment containing at least 9 carbon atoms situated in linear succession between the methylidene a.roup, =CH, and the methylene -roup, - CH2, and may contain both carbon-carbon single bonds and carbon-carbon double bonds; (3) any of said carbon atoms in the linear succession of Z may be substituted by at least one member of the grotip consisting of alkyl, aryl, -alkenyl, aralkyl, alkaryl, cycloalkyl, cycloalkenyl, bicycloalkyl and bicycloalkenyl radicals; (4) any of the said carbon atoms in the linear succession of Z may be constituents of aromatic rin.-s and alicyclic rings; and (5) the said acyclic unsaturated hydrocarbon contains no conju-ated double bonds is converted into at least one macrocyclic compound pos@essing alicyclic unsaturated rin@.s, said rings comprisin.@ at least 12 carbon atoms and said rings containin.at least one carbon to carbon double bond. For example, the intramolecular metathesis reaction of the two dotible bonds in the followin- acyclic diolefin leads to the formation of butene-2 and an unsaturated alicyclic compound denoted by "I" CH-CHI H (C H2). 1- CH3-CH=CH-CI-13 cii Cl-i-CH3 LCH The example in the previous para.-raph is not meant to imply that butene-2 is always formed in the preparation of the macrocyclic compounds possessing alicyclic rings from the acyclic unsaturated hydrocarbons which are the starting materials. The second compound that is formed, in addition to the macrocyclic compound possessing the alicyclic unsaturated ring, will depend upon what R' and R" are in the formula R'-CH,--CH=CH-Z-CH,-CH=CH-CH,-R" In the example above, R' and R" were hydro,@ens. If they had been methyl groups, the second compound formed would have been hexene-3. The occurrence of an intermolecular olefin metathesis side reaction, which may occur in addition to the intramolecular reaction such as that desired as illustrated in the formula above, will lead to acyclic rather than alicyclic unsaturated molecules. This intermolecular metathesis can be exempified as follows, where the new acyclic compound is denoted by "II,,: (CH2)@ CH3--CH=CH ClT=CH-CH3 C113-CH=Cil C-11=cn-CIT3 (CH2). (CH2)@ CI-I3-CH=C@ \CH 11 + CH3-cli=CH-CH3 CH CH3-CH=CH-(C /2). The acyclic compound II may further undergo either an intramolecular metathesis to yield a large rin- unsaturated alicyclic compound or anintermolecular olefin metathesis reaction to yield another acyclic unsaturated molecule. One may adjust the reaction conditions by employing sufficient amounts of diluent leading to an enhancement of the intramolecular mode of reaction, thus
[2]32439,057 3 obtaining high proportions of large ring unsaturated alicyclic compounds. A drution of about 10% or lower of the acyclic unsaturated molecule in an inert diluent will usually cause, the mode of reaction to be intramolecular and form hi.-h proportions of large ring unsaturated ali5 cyclic compounds. However, a dilution to about 5% or lowe,r of the acyclic unsaturated molecule in the inert diluent is more preferable. Stiitable diluents for this purpose are liquids @which do not adversely effect the catalyst activity or the olefin methathesis reaction. Representative 10 of such diluents are saturated hydrocarbons such as butane, heptane, hexane, pentane and the like or aromatic hydrocarbons such as benzene, toluene and the like. Hy@ drocarbons which contain other substituents may also be used provided they are inert. 15 The precursors employed in the formation of the alicyclic unsaturated compounds of this invention can be any acyclic unsaturated hydrocarbon corresponding to the general formula: W-CH,CH=CH-7--CH,CH=CH _CH,R,, 20 wherein the limitations are previously set forth in paragraph numbers (1), (2), (3), (4) and (5). These precursors can be long chain hi.-h molecular weight polymers containing carbon-to-carbon unsaturation along the POIY- 25 mer chains. For example, polybutadiene 1,4 may be used to form the alicyclic ring according to the following: /\@/\CH2-CH=CIEI 1 CH=CH 30 CH2 CH2 @OH2---CH@CH-CH2). //'\//'\CH2-CH=CH-CHz//'\//'\ <-@@ 35 + CH2-CH@CH I @H2 @CHZ--CH=CH-@H2). 40 tt=2,3,4 . . . The assortment of ring sizes obtanable from a given unsaturated polymer, an example of which is 1,4-polybutadiene, depends on the structure of the repeat unit. It can be shown that the intramolecular olefin metathesis of 45 1,4 polybutadiene may lead to rings containing 312, 161 20, 24 and so for-th carbon atoms while a polypentameter may lead to rings of 15, 20, 25, 30 and so forth carbon atoms while a polyoctanometer wiU lead to rings of 16, 24, 32, 4 be understood that the fohowing formulas are set forth for illustrative purposes only and are not limiting of the scope of the present invention. In the following formulas M is intended to represent any substituent member of the group: alkvl, aryl, alkenyl, aralkyl, alkaryl, cycloalkyl, bicycloaliyl, cycloalkenyl and bicycloalkenyl radicals. Z Group Large Ring Obtainable Linear Unsiibstituted -CH2) ivhere n is equal to or greater tliaii 9 IC I )I-i (CII@). CH2 I - (C H2) @ C II= C H- (C H2) Cif-(CH2). 11 wliere x+y is equal to or greater thail 7 CH c a I 11 CH2 Cil L-(C/ H2)@ Linear Substittited --(C)H2).-CH-(CH2)Y C@CH2) m CH-ill 11 I wherp x+y is equal to or greater than 8 CH (UU2)@ c@2 -(CH2)!-C]I=CH-Cll-(CH2),- CH2). m CH CH 11 11 where x+y is equal to or greater than 6 CEL CH I I L;ti2 L;.U-illl (CH2)y Alicyclic -(CH2) (CH2)y- CH-(CH2). -C--> - S wliere x+y is equal to 5 or more H 40, and so forth, carbon atoms and polydodecenamer will 50 -(CH2)!lead to rings of 12, 24, 36, 48, and so forth carbon atoms. The following formula, designated by "IW' further ex- (CH2)@- plains the precursors which may be employed in this inwhere x+y is equal to 6 or more vention: R'-CH,--CH=CH-Z-CH,-CH=CH-CHZ--R!' 55 (,][II) Bicycl ic wherein R' and R" can be similar or dissiinilar and may represent an alkyl, aryl, alkenyl, aralkyl, alkaryl, cyc-loCH2-(CH2). alkyl, bicycloalkyl, cycloalkenyl or hydrogen, and Z rep- 6o -(CH2).:- <f!@>- (CH2)@- CH2--( H2), CH-(CH2). resents the fragment of Ill which is - characterized by the possession of at least 9 carbon atoms in a backbone sequence. Any of the carbon atoms in Z may be interconnected by either single or double bonds provided that no two double bonds in III are conjugated. Any of the carbon 65 atoms in Z may be substitutde by one or more substituents which are members of theg roup of alkyl, aryl, alkenyl, aralkyl, alkaryl, cycloalkyl, bicycloalkyl, cycloalkenyl and bicycloalkenyl. Any of the carbons in Z may be constituents of aromatic or alicyclic rings. 70 The selected skeletal formulas set forth below will illustrate the nature of certain Z groups and the resulting large ring unsaturated compounds obtainable by the intramolecular olefin rnetathesis reaction. It is believed that this will further explain this invention. However, it should 75 where x+y is equal to 5 or more Cli H L-(i CH2), Aromatic CH2--(CH2). -(CH2)r-<7D- (OH2)y I cii vvhcre x+y is equals to 5 or inoro 11 Cli H2)@
[3]3,439,057 5 It is understood that the above definition includes the polymeric precursors that may contain the group: -CH,-CH-CH-Z-CH,-CIE--CHas a se-,ment of the main or side chain of the polymeric molecule. The intramolecular olefin metathesis process of this invention can be carried out over a wide temperature range from about -100' C. and lower to about 200' C. and higher, but generally, temperatures in the -70' C to 70' C. ran.ae are suitable for this reaction. The pressure is not important and may be varied widely. The reaction proceeds rapidly at room temperature and atmospheric pressure. In several cases exemplified above, the formation of a low molecular weight olefin as the second product of the macrocyclization process in addition to the large ring unsaturated alicyclic compound has been described. Therefore, if one desires to remove the low boiling species produced during the cyclization reaction, employment ofsub-atmospheric pressures and elevated temperatures can be employed conveniently, since the large rin.- compounds possess low volatilities and the separation is thi-is easily achieved. A class of catalysts employed in the macrocyclization reaction of this invention is a combination comprisin-. (A) at least one organo-m,-tallic compound wherein the metal is selected from the group consisting of la, Ila, Ilb and Illa groups of the Periodic Table of Elements, (B) at least one metal salt wherein the metal is selected ftom the aroup consistin- ofmolybdenum and tun-sten, and (C) at least one compound of the general formula R-Y-H wherein Y is selected from the group of oxygen and sulfur and wherein R is a radical selected from the group consistin@ of (1) hydrogen, (2) alkyl, (3) aryl, (4) arylalkyl, (5) alkaryl, (6) alkenyl, (7) when Y is S, R is thioalkyl, tioarylalkyl, and thioalkaryl, (8) when Y is 0, R is alkoxy, arylalkoxy, and alkaryloxy, and radicals of (2) through (6) wherein at least one hydrogen is substituted by a material selected ftom hydroxyl (OH) and thiol (SH) groups. The Periodic Table of El.-ments referred to may b(- found in the Handbook of Chemistry and Physics, 44th ed., April 1962 reprint, published by the Chemical Rubber Publication Company, Cleveland, Ohio, U.S.A., p. 448. Representative examples of metals from which the Organometallic compound, the first or (A) component of the c,atalyst system of this invention, can be derived are lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, aluminum, gallium, indium and thallium. The preferred organo-metallic compounds are compounds of lithium, sodium, magnesium,!aluminum, zinc, and cadmium with aluminum bein.- most preferred. Representative examples of organo-metallic compounds useful as the first or (A) catalyst component of this invention are aluminum compounds having at least one aluminum-to-carbon bond. Representative of such com-pounds jare trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-npropylaluminum, tri-nbutyaluminum, triisopropylaluminum, triisobutylaluminumtrihexylaluminum, trioetylaluminum and the like; triarylaluminums such astritolylaluminum, tribenzylaluminum, triphenylaluminum:and the like; dialkylaluminum halides such as diethylaluminum chloride, di-n-propylaluminum chloride,- diisobutylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide and diethylaluminum fluoride and the like; mixtures of dialkylaluminum halides and alkylaluminum dihalides such as ethylaluminum sesquichloride and bromides may also be employed; alkylaluminum dihalides such as ethylaluminum dichloride, ethylaluminum dibromide, propylaluminum dichloride, isobutylaluminum dichloride, ethylaluminum diiodide and the like; dialkylaluminum hydrides such as diethylaluminum hydride, di-n@propylaluminum hydride, diisobutylaluminum hydride and the like; arylalliminum hydrides and di6 hydrides such as diphenyliluminum hydride and phenylaluminum dihydride; the arylaluminum halides such as phenylaluminum dibromide, tolylaluminum dibromide, benzylaluminum dibromide, phenylaluminum diiodide, tolylaluminum diiodide, benzylaluminum diiodide, diphenylalumipum chloride, ditolylaluminum chloride, dibenzylatuminum bromide and the like. Other organometallic compounds are also useful in the practice <)f this invention. Representative of such organo-metallic com10 pounds are organoalkali metal compounds such as alkyllithium compounds as ethyllithium, n-butyuithium, tbutyllithium, iand the like; lithium-aluminum-tetraalkyls such as lithium-aluminum-tetrabutyl, lithium-aluminumtetraethyl and the like; alkali metal alkyls and aryls such 15 as amylsodium, butyl@potassium, phenylpotassium, pheriylsodium, phenyllithium, butyllithium;and the like; ma.-nesium alkyls and aryls such as diphenylmagnesium, diethylmagnesium, etbylmagnesium chloride phenylmagnesium chloride, butylmagnesium bromide an@ the like; calcium, 20 strontium and barium organo compounds such as barium ialky-Is and aryls; alkyls and aryls of Group Ilb metals such as diethylzinc, diphenylzine, ethylzinc chloride, diethylcadmium, dibutylcadmiun-1 and the like; Grignard a,-ents stich as phenylmagnesium bromide may also be employed. 25 Mixtures of these compounds -may be employed as the first or (A) catalyst component in the catalyst of this invention: It is usually preferred to employ aluminum compounds such as trialkylaluminums, dialkylaluminum halides, alkylaluminum dihalides and aluminum sesqui30 halides. The metal salts employed in the catalyst of this invention @as the second or (B) catalyst com-ponent are selected from the salts or molybdenuin and tungsten. Representatives of such salts include halides such as chlorides, bro35 mides, iodides, and fluorides, which include compounds such as molybdenum pentachloride, tun.asten hexachloride, molybdenum pentabromide, tungsten hexabromide, molybdenum pentaiodide, tungsten hexaiodide, molybdenum pentafluoride, molybdenum hexafluoride,,and tung40 sten hexafILloride. Other representative salts are those of acetylacetonates, sulphates, phosphates, nitrates @and the like which include compounds such as molybdenum phosphate, tungsten phosphate, molybdenum nitrate, tungsten nitrate, molybdenum acetylacetonate, tun.-sten acetyl45 acetonate, molybdenum sul-phate, and tun.-sten sulphate. Mixtures of these salts may also be employed. Of these, it is usually preferred to employ -tungsten halides and molybdenum halides representative of which are tungsten hexachloride and molybdenum pentachloride. 50 The third or (C) component of the catalyst system of this invention are compounds which respond to the formula R-Y-H wherein Y is selected from the group consisting of oxy@en and sulfur and R is a radical selected from the group consisting of (1) hydrogen, (2) ;alkyl, (3) 55 arvl (4) arylalkyl, (5) alkaryl, (6) alkenyl, (7) when Y is S, R is thioalkyl, thioarylalkyl, and trioalkaryl, (8) when Y is 0, R is alkoxy, arylalkoxy, and alkaryloxy, and (9) radicals of (2) through (6) wherein at least one hydrogen of R is substituted by at least one hydroxyl (OH) 6o or thiol (SH) group. Thus, the formula above defines a number of types of compounds. It defines water (HOH), hydrogen sulfide (HSH), both saturated andunsaturated alcohols (ROH), mercaptans (RSH), hydroperoxides (ROOR), hydrodi65 sulfides (RSSH), polyalcohols (HOROH), polymercaptans (HSRSH), and hydroxy mercaptans (HSROH) or thioalcobols (HO@RSH). Representative examples of the materials responding to the formula above are alcohols representative of which are methanol, ethanol, isopropa7o nol tertiarybutyl alcohol, arnyl alcohol, benzyl alcohol, allyl alcohol, 1, 1 -dimethyl benzyl alcohol, phenol, tertiarybutyl catechol, alpha and beta naphthyl alcohol; mercaptans such as methyl, ethyl, propyl, isopropyl, butyl, amyl, and similar mercaptans, allyl mercaptan, thiophenol, 4- 75 methylthiophenol, 4-mercaptophenol; the bydroperoxides
[4]3,439,057 7 such as cumyl hydroperoxide, tertiarybutyl hydroperoxide; the hydrodisulfides such as cumyl hydrodisulfide, t-butyl hydrodisulfide; the polyalcohols such as ethylene glycol, glycerol, and similar polyglycols; catechol, resorcinol, hydroquinone, pyrogallol; the polymercaptans such as 1,3- 5 propane dithiol, 1,4-dithiobenzene; the hydroxymercaptans or thioalcohols such as ethane-2-ol-l-thiol, 1-hydroxy-4-thiobenzene. One of the unusual and distinguishing features of the catalyst system of this invention is that the compounds of 10 the formula R-Y-H, wherein R and Y have been previously defined, depending on the particular diolefin employed, the particular organo-metallic compound and the particular Group Vlb metal salt chosen and on the particular R-Y-H compound chosen, when employed in 15 fairly substantial amounts are known to reduce drastically the activity of the olefin-metathesis reaction by which the macrocyclization of this invention occurs. An - unexpected high activity of the catalyst of the present invention was found when compounds of the R-Y-H type were em- 20 ployed in relatively small amounts and added according to the teachings set forth in the present specification and examples. Since the instant invention contemplates the use of organo-metallic compounds in combination with transition metal salts and various oxygen and sulfur-con- 25 taining compounds, and since various factors or - considerations will influence the optimum ran,-e of the three catalyst components in relation to each other, the molar ratios of the three components which optimize the reaction conditions cannot be readily set forth. However, by following 30 the teachings found in this application, those skilled in the art can readily determine the optimum molar ratio of the three catalyst components to each other. Obviously, if one employs the oxygen or sulfur-containing compound, or as is desi.-nated above, component C in relatively large 3.5 amounts, the activity of the catalyst will be reduced considerably or even destroyed. It has been found that good results are obtained in the practice of this invention when the molar relationship between the three catalyst components, A, B, and C as pre- 40 viously defined, are within a molar ratio of BIC ranging from about 0.3/1 to at least about 20/1 and the molar ratio of 41B is within the range of about 0.511 to at least 1511. More preferred ratios are BIC of 0.511 to 511 and 41B of 0.511 to 8/1. Still more preferred ratios are 45 BC of 1/1 to 2/1 and AIB of 0.75/1 to 511. The catalysts employed in this invention are prepared by mixing the components by known techniques. Thus, the catalysts may be prepared by "preformed" or "in situ" techniques. By the "preformed" method the catalyst com- 50 ponents are mixed together prior to exposure of any of the catalyst components to the unsaturated compound to be used in the macrocyclization reaction. In the "in situ" method the catalyst components are added separately to the unsaturated cofnpound to be used in the macrocycliza- 55 011 -CIH2 tion reaction. The catalyst coniponents may be mixed either as pure compounds or as suspensions or solutions in liquids which do not adversely affect catalyst activity or the olefin-metathesis reaction. Representative of such liquids are saturated hydrocarbons such as hexane, pentane 65 and the like or aromatics such as benzene, toluene and the like. While the presence of the unsaturated precursor is not essential during the formation of active catalyst by a mixing of components A, B, and C and this fact facilitates 70 the use of "preformed" catalysts, it has been found that freshly preformed catalysts are ge-nerally more active than catalysts which have been allowed to age before use. The order of addition of the three catalyst components to each other is of interest in the practice of this - invention. 75 8 There are various niethods in which the three catalyst components can be brought into contact with the -unsaturated precursor or unsaturated precursor/solvent mixture. The following is a numerical listing of these various methods in which A, B, and C stand for the catalyst components as previously defined: (1) Simultaneous addition of A, B and C. (2) C followed by A and B which were previously preformed. (3) A and B preformed followed by C. (4) A fohowed by B and C which were preformed. (5) B and C preformed followed by A. (6) B followed by A and C which were preformed. (7) A and C preformed followed by B. (8) A followed by B followed by C. (9) B followed by A followed by C. (10) CfollowedbyBfollowedbyA. (11) CfollowedbyAfollowedbyB. (12) B followed by C followed by A. (13) A followed by C followed by B. (14) Preformed A, B, and C which was prepared by adding A to B and C preformed. (15) Preformed A, B, and C which was prepared by adding B to A and C preformed. ( 1 6) Preformed A, B, and C which was prepared by adding C to A and B preformed. Of these various procedures, procedures (6), (7), (I 1), (13), and (15) listed above are methods of preparations which reduce somewhat the catalyst activity. The remaining of the listed procedures (1), (2), (3), (4), (5), (8), (9), (10), (12), (14), and (16) lead to the most active catalyst systems. The amount of catalyst employed in the macrocyclization reaction of this invention may be varied over wide concentrations and has not been found to be critical. Of course, a catalytic amount of the catalyst inust be employed. The optimum amount of catalyst depends upon a number of factors such as temperature, unsaturated precursors used, purity of precursors, reaction times desired and the like. Those skilled in the art will readily determine the optimum catalytic ranges. The macrocyclization can be conducted wherein the amount of catalyst employed is about 0.01 part by weight of B per 100 parts by weight of unsaturated precursor employed, with components A and C adjusted to yield a desirable atomic ratio of 41BIC. The practice of this invention is further illustrated by z--ference to the following examples which are intended to be representative rather than restrictive of the scope of the invention. EXAMPLE I A 3.0 gram sample of purified polyoctenamer prepared by the chain opening polymerization of cyclooctene and having the structuralformula: CH2 [CHz-CH=CHOlf2(CHt)]. CH C]12 CH (C Ir2)4 C II2 C (C H2)4- was dissolved in 50 ml. of dried benzene under a nitrogen atmosphere. The viscous cement was trea;ted with 1.0 ml. of a 0.05 molar solution of tungsten hexacbloride (WC16) in benzene, which was prereacted with ethanol (C2H50H) so that the molar ratio of WC]6/C2H50H equaled 1: 1, followed by 1.5 mole of a 0.20 molar solution of ethylaluminum dichloride (EADC) in benzene and thus maintaining an Al/W/0 molar ratio of 61111. The mixture was allowed to react for 15 minutes before terminated by introduction of 2.0 ml. benzene solution containing 0.03 gram of tetraethylene pentamine (TEPA) and 0.02 gram of di-ter-butyl-p-cresol and evaporated to dryness. The reaction mixture was extracted three times with 50 ml. portions of 1: I volurne ratio of an isopropanol/hexane solvent system and a low, moleculat
[5]weight extractable portion thus isolated. Parent mass spectroscopic analysis by low voltage mass spectroscopy was carried out and it was found that the extractable mixture was compris@-d of components possessing molecular weights accordin.,@ to the series: 220+nX 1 10 (n=O, 1, 2, 3 . . . ). This corresponds to a dimer (when iz=O), a trimer (when n=1), a tetramer (when n=2), and so forth, of the repeating monomer unit of the ori, inal polyoctenamer, that is -CH,-CH==CH-CH,-(CH,)4- The Nuclear Ma.-netic Resonance spectroscopic analysis (NMR) of the low molecular weight extractable portion indicates the presence of one vinylene dolble bond for every ei.-ht carbons, similar to cyclooetene and POIYoctenamer, and possessing three types of hydrogens (A) vinylic: (CH=CH); (B) allylic: (CHz--CH--CH); and (C) methylenic: (CH2). The relative ratio of vinylic/- allylie/methylenic types of hydrogens was found to be essentially 1/2/4. Methyl hydrogens: (CH3) or terminal unsaturation type of hydrogens: (CH=CH2) were not detected in the NMR spectrum. Hence, the mass spectroscopy and NMR spectroscopy results reveal that the low molecular weight extractable portion consists of a mixttire of macrocyclics of the gen@ eral formula: CIT2 CH -,e \ (CH 4 CH cil 2 CH (CH2)4 CH n x where x= 1, 2, 3 . . . For x=l, the rin.- is of 16 carbons, 2 double bonds and has a molecular wei.-ht of 220. For x@2, the ring is of 24 carbons, 3 double bonds and has a molecular weight of 330. For x@3, the ring is of 32 carbons, 4 double bonds and has a molecular weight of 440. This series of molecular weights is consistent with the experimentally determined low voltage mass spectroscopy and the structure presented above is consistent with the NMR spectrum analysis. EXAMPLE 2 A 20 gram sample of macrocyclic mixture, wbich was prepared by a procedure similar to the one described in Example 1, was fractionated by molecular distillation and four fractions isolated as follows: Fractionation Composition Conditions (Percent)' Fraction No. Temp. PreSSUre CIB C24 C32 C4o+higher (' (-./Hg) 1 --------------- 85 1.5 85 15 --------------- ----- 2 --------------- 120 1.0 32 66 2 --------- ----- 3 --------------- 175 0.5 ------ 82 18 -------- ------ 4 --------------- 210 0.3 ------ 4 96 ------- ------- Pot Rpsidue ---------------------------------------- 10 90 *Composition was determined by gas chromatography. The NMR analyses of the fractions indicated that all had essentially the same spectra Nvhich was also identical to the spectrum of mixture before fractionation. Only vinylic, allylic and methylenic hydro.-ens were found and in a ratio of 1/2/4. Fraction No. 4 contained almost ptire cyclic tetramer of cyclooctene (4% cyclic trimer). This fraction -,vas catalytically hydro,-enated, using H. C. Brown's HydroAnalyzer procedure, and the hydrogenated product was analyzed by NMR, low voltage mass spectroscopy and X-ray diffraction. The NMR indicated one and only one type of hydrogens, namely, methylenic: (CH2). The molecular weight obtained by low voltage mass spec32439)057 10 troscopy was 448 which is in perfect agreement with (CH2)32. The crystallographic d-spacings of the solid C32H64 macrocyclic found to be 3.75 A. and 4.53 A. EXAMPLE 3 A 3.0 gram sample of purified polybutadiene, which Nvas prepared by the ringopening polymerization of 1,5 cyclooctadiene, and had the structural formula: CH CH2 CH2 CH 10 / \ \ -CII2 C ff (CH2-CH=CH=0112). CH CHZ-- was dissolved in 50 ml. benzene under -nitrogen and treated with the @EADC/WC16/C2H,90H catalyst system 15 as in Example 1. After termination and extraction of the low molecular vveight product as described in Example 1, parent mass determination by low voltage mass spectroscopy and NMR analysis were carried out. Th.e molecular weights found in the extractable portion by mass 20 spectroscopy comprised of the series: 162+nX54 (n=O, 1, 2, 3 . . . ), which are consistent with the molecular wei.-hts of butadiene oligomers, wi'@h the trimer as the lowest rnember of the series (n=O). The NMR spectrum of the mixture of components in the extractable portion 25 indicates the presence of one vinylene double bond for every four carbons, similar to polybutadiene, and two types of hydrogens: (A) vinylic: (CH@CH); and (B) allylic: (CH2-CH@CH). The relative ratio of vinylic/allylic was found to be 1/2. The presence of methyl 3o hydrogens: (CH3), methylene hydrogens (CH2), or terminal unsaturation: (CH=CH2) were not detected in the NMR spectrum. Hence, the mass spectroscopy and NMR results reveal that the low molecular weight extractable portion consists of a mixture of macrocyclics of 35 the general formula: CH z 2 CH CH 11 CH?-CH Cli=CH CH CH2 \ C H = CH C H4 3 I 11 n C H 2 C H \LCH2 50 where n=O, 1, 2, 3 . . . For n=O, the rin.a is of 12 carbons, three double bonds, nd has a molecular weight of 162, i.e. 1,5,9-cyclododecatriene. For n=l, the ring is of 16 carbons, four 55 double bonds and has a molecular weight of 216. This series of molecular weights is consistent with the experimentally determined low voltage mass spectroscopy and the structure consistent with the NMR spectrtim. Thus, it can readily be seen that the formation of macrocyclic 60 compounds or mixtures of macrocyclic compounds possessinalicyclic unsaturated rings with a ring size of at least 12 carbon atoms and containing at least one carbonto-carbon double bond can be prepared from at least one unsaturated compound corresponding to the general 65 formula: R'-CHz-CH=CH-Z-CH2--CH=CH-CH2-R" 70 While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from th-. spirit or scope of the - 5 invention.
