Re. 26,875 United States Patent Of?ce Reissued May 12, 1970 1 2 26,875 wherein: PREPARATION OF MACROCYCLIC COMPOUNDS Nissim Calderon, Akron, Ohio, assignor to The Goodyear (l) R’ and R" may be at least one member of a group Tire & Rubber Company, Akron, Ohio, a corporation consisting of alkyl, aryl, alkenyl, aralkyl, alkaryl, cy of Ohio cloalkyl, cycloalkenyl, bicycloalkyl, bicycloalkenyl radi No Drawing. Original No. 3,439,057, dated Apr. 15, 1969, cals and hydrogen; Ser. No. 664,947, Sept. 1, 1967. Application for reissue (2) Z is a hydrocarbon fragment containing at least 9 Aug. 7, 1969, Ser. No. 853,563 carbon atoms situated in linear succession between the Int. Cl. C07c 3/10 methylidene group, =CH, and the methylene group, US. Cl. 260—666 6 Claims —CH2, and may contain both carbon-carbon single Matter enclosed in heavy brackets II] appears in the 10 original patent but forms no part of this reissue speci? bonds and carbon-carbon double bonds; cation; matter printed in italics indicates the additions (3) any of said carbon atoms in the linear succession of made by reissue. Z may be substituted by at least one member of the group consisting of alkyl, aryl, alkenyl, aralkyl, alkaryl, 15 cycloalkyl, cycloalkenyl, bicyeloalkyl and bicyclo ABSTRACT OF THE DISCLOSURE alkenyl radicals; (4) any of the said carbon atoms in the linear succes The invention described is one of preparation of un sion of Z may be constituents of aromatic rings and saturated large ring alicyclic compounds by subjecting, alicyclic rings; and acyclic unsaturated compounds containing at least two (5) the said acyclic unsaturated hydrocarbon contains non-conjugated double bonds and containing at least 16 20 no conjugated double bonds carbon atoms, to a catalyst which is a mixture of (a) at least one organo metallic compound wherein the metal is is converted into at least one macrocyclic compound from Groups la, 11a, 11b and IIIa of the Periodic Table possessing alicyclic unsaturated rings, said rings compris of Elements, (b) at least one metal salt wherein the metal ing at least 12 carbon atoms and said rings containing at is selected from the group of molybdenum and tungsten 25 least one carbon to carbon double bond. and (c) at least one compound of the general formula For example, the intramolecular metathesis reaction of RYH wherein Y is from the group of oxygen and sulfur the two double bonds in the following acyclic diole?n and R is a radical selected from the group of hydrogen, leads to the formation of butene-2 and an unsaturated alkyl, aryl, aralkyl, alkaryl and alkenyl and when Y is alicyclic compound denoted by “I” S, R may be a thioalkyl, thioaralkyl and a thiolkaryl and 30 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 by a thiol or a hydroxyl L OH-CHI group. These unsaturated large ring alicyclic compounds are useful as intermediates to produce such things as large The example in the previous paragraph is not meant to ring ketones which in turn are useful as perfume bases. imply that butene-Z is always formed in the preparation of the maerocyclic compounds possessing alicyclic rings from the acyclic unsaturated hydrocarbons which are the This invention relates to a novel method of preparation 40 starting materials. The second compound that is formed, of unsaturated large ring alicyclic compounds and the in addition to the macrocyclic compound possessing the products obtained thence. More particularly, it concerns alicyclic unsaturated ring, will depend upon what R’ and with the conversion of various organic unsaturated ma R" are in the formula terials, which will be classi?ed extensively later, into com pounds possessing large alicyclic rings containing at least one cabon to carbon double bond by exposure of said 45 In the example above, R’ and R" were hydrogens. If they unsaturated materials to catalysts whose compositions are had been methyl groups, the second compound formed described elsewhere in this speci?cation. would have been hexene-3. The term “unsaturated large ring alicyclic compounds," The occurrence of an intermolecular ole?n metathesis used throughout the present invention, relates to the group 50 side reaction, which may occur in addition to the intra~ of materials characterized by the presence of at least one molecular reaction such as that desired as illustrated in alicyclic ring containing at least twelve carbon atoms in the formula above, will lead to acyclic rather than ali said ring skeleton and at least two carbon atoms of the cyclic unsaturated molecules. This intermolecular meta said ring are connected by a double bond. thesis can be exempli?ed as follows, where the new acyclic Prior to the present invention, a common method of compound is denoted by “II”: synthesis of large ring alicyclic compounds from acyclic 55 precursors involved in the intramolecular reaction of a ( CH2), linear alpha, omega-disubstituted compounds, for in CHa~CH=CH CH=C H~CH3 stance, the Acyloin condensation: C HreGH=CH CH=OH—C H; (CH2): (CH2). CH3—CH=C CH A % 9-0 Call; The acyclic compound II may further undergo either According to the present invention at least one acyclic an intramolecular methathesis to yield a large unsaturated unsaturated hydrocarbon corresponding to the general alicyclic compound or an intermolecular ole?n metathesis formula: 70 reaction to yield another acyclic unsaturated molecule. molecule. One may adjust the reaction conditions by em ploying sufficient amounts of diluent leading to an en 26,875 4 trate the nature of certain Z groups and the resulting large hancement of the intramolecular mode of reaction, thus ring unsaturated compounds obtainable by the intramole obtaining high proportions of large ring unsaturated ali cular ole?n metathesois reaction. It is believed that this cyclic compounds. A dilution of about 10% or lower of will further explain this invention. However, it should ‘be the acyclic unsaturated molecule in an inert diluent will understood that the following formulas are set forth for usually cause the mode of reaction to be intramolecular illustrative purposes only and are not limiting of the scope and form high proportions of large ring unsaturated ali of the present invention. In the following formulas M is cyclic compounds. However, a dilution to about 5% or intended to represent any substituent member of the lower of the acyclic unsaturated molecule in the inert group: alkyl, aryl, alkenyl, aralkyl, alkaryl, cycloalkyl, bi diluent is more preferable. Suitable diluents for this pur cycloalkyl, cycloalkenyl and bicycloalkenyl radicals. pose are liquids which do not adversely effect the catalyst activity or the ole?n metathesis reaction. Representative of such diluents are saturated hydrocarbons such as bu Large Ring tane, heptane, hexane, pentane and the like or aromatic Z Group Obtainable hydrocarbons such as benzene, toluene and the like. Hy drocarbons which contain other substituents may also be Linear Unsubstituted used provided they are inert. The precursors employed in the formation of the ali 611 cyclic unsaturated compounds of this invention can be —'(CH2JD— P: H (6112)“ where n is equal to or greater than 9 l any acyclic unsaturated hydrocarbon corresponding to the C H: general formula: 20 1. ([JH—( CH2) 1 wherein the limitations are previously set forth in para —(CH2) :—CH=CH—(CH¢) ,-—- #H (%H graph numbers (1), (2), (3), (4) and (5). These pre where x+y is equal to or greater than 7 CH, ilH 25 cursors can be long chain high molecular weight polymers (CH2), containing carbon-to-carbon unsaturation along the poly mer chains. For example, polybutadiene 1.4 may be used Linear Substituted to form the alicyclic ring according to the following: (0 H2) y
—-(CH2J x—’CH_(CH2)v_l C /II CII-M M H i C H (C H2) ,, where x+y is equal to or greater than 8 \ CH2 35 —'(C1'Iz) ,—CH=CH—(|JH—(CHz)y— ?lH2 (IT‘H M (EH C H 40 where x-l-y is equal to or greater than 6 / CH2 C?g] y (cH,-CH=CH—\(JHnn Alieyrltc (CH2) 1 n-2,3,4The assortment. . . of ring sizes obtainable from a given // \ unsaturated polymer, an example of which is 1,4-poly 45 butadiene, depends on the structure of the repeat unit. It can be shown that the intromolecular ole?n metathesis ..(C1h),-®——(CH¢,—_ C 4 Q of 1,4 polybutadiene may lead to rings containing 12, 16, l H / 20, 24 and so forth carbon atoms while a polypentameter 60 where x+y is equal to 5 or more (alkali-fang) y may lead to rings of 15, 20, 25, 30 and so forth carbon 2 1 atoms while a polyoctanometer will lead to rings of 16, 24, 32, 40, and so forth, carbon atoms and polydodecenamer —(0 H2) ‘—< ) Cg \ will lead to rings of 12, 24, 36, 48, and so forth carbon ( H2) y_ ‘1111 atoms. 55 The following formula, designated by “HP‘ further ex where x+y is equal to 6 or more i plains the precursors which may be employed in this in H'1-—-—(CH2)y vention: Bycyclle 60 0 Hz--- ( CHQ)\, C H wherein R’ and R" can be similar or dissimilar and may represent an alkyl, aryl, alkenyl, aralkyl, alkaryl, cyclo "(0112) :—©-(C}Iz)w alkyl, bicycloalkyl, cycloalkeuyl or hydrogen, and Z rep where x+y is equal to 5 or more TH @ resents the fragment of III which is characterized by the 65 L- t on!) ,/ possession of at least 9 carbon atoms in a backbone se quence. Any of the carbon atoms in Z may be intercon Aromatic nected by either single or double bonds provided that no 0 Hz-— (C Hi) ‘ two double bonds in III are conjugated. Any of the car bon atoms in Z may be substituted by one or more sub 70 stituents which are members of the group of alkyl, aryl, ‘_OI'IZ)l—)©_(CH2)y (‘EH alkenyl, aralkyl, alkaryl, cycloalkyl, bicycloalkyl, cyclo where x+y is equal to 5 or more HIE alkenyl and bicycloalkenyl. Any of the carbons in Z may \ / be constituents of aromatic or alicyclic rings. Ltcn?y The selected skeletal formulas set forth below will illus 75 5 26,875 It is understood that the above de?nition includes the 6 polymeric precursors that may contain the group: dihydrides such as diphenylaluminum hydride and phenyl aluminum dihydride; the arylaluminum halides such as phenylaluminum dibromide, tolylaluminum dibromide, as a segment of the main or side chain of the polymeric benzylaluminum dibromide, phenylaluminum diiodide, molecule. tolylaluminum diiodide, benzylaluminum diiodide, diphen~ The intramolecular ole?n metathesis process of this ylaluminum chloride, ditolylaluminum chloride, dibenzyl invention can be carried out over a wide temperature aluminum bromide and the like. Other organo-metallic range from about —100° C. and lower to about 200° C. compounds are also useful in the practice of this invention. and higher, but generally, temperatures in the —70° C. Representative of such organo-metallic compounds are to 70° C. range are suitable for this reaction. The pres o'rganoalkali metal compounds such as alkyllithium com sure is not important and may be varied widely. The re pounds as ethyllithium, n-butyllithium, t-butyllithium, and action proceeds rapidly at room temperature and atmos the like; lithium-aluminum-tetraalkyls such as lithium— pheric pressure. In several cases exempli?ed above, the aluminum-tetrabutyl, lithium-aluminum-tetraethyl and the formation of a low molecular weight ole?n as the second like; alkali metal alkyls and aryls such as amylsodium, product of the macrocyclization process in addition to 15 butylpotassium, phenylpotassium, phenylsodium, phenyl~ the large ring unsaturated alicyclic compound has been lithium, butyllithium and the like; magnesium alkyls and described. Therefore, if one desires to remove the low aryls such as diphenylmagnesium, diethylmagnesium, boiling species produced during the cyclization reaction, ethylmagnesium chloride, phenylmagnesium chloride, employment of sub-atmospheric pressures and elevated butylmagnesium bromide and the like; calcium, strontium temperatures can be employed conveniently, since the 20 and barium organo compounds such as barium alkyls and large ring compounds possess low volatilities and the sepa aryls; alkyls and aryls of Group Ilb metals such as diethyl ration is thus easily achieved. zinc, diphenylzinc, ethylzinc chloride, diethylcadmium, A class of catalysts employed in the macrocyclization dibutylcadmium and the like; Grignard agents such as phenylmagnesium bromide may also be employed. Mix reaction of this invention is a combination comprising 25 (A) at least one organo-metallic compound wherein the tures of these compounds may be employed as the ?rst metal is selected from the group consisting of la, Ila, IIb or (A) catalyst component in the catalyst of this in and Illa groups of the Periodic Table of Elements, (B) vention. It is usually preferred to employ aluminum com at least one metal salt wherein the metal is selected from pounds such as trialkylaluminums, dialkylaluminum ha the group consisting of molybdenum and tungsten, and 30 lides, alkylaluminum dihalides and aluminumsesquiha (C) at least one compound of the general formula lides. R—Y-—H wherein Y is selected from the group of oxygen The metal salts employed in the catalyst of this in and sulfur and wherein R is a radical selected from the vention as the second or (B) catalyst component are group consisting of (1) hydrogen, (2) alkyl, (3) aryl, selected from the salts of molybdenum and tungsten. Representatives of such salts include halides such as (4) arylalkyl, (5) alkaryl, (6) alkenyl, (7) when Y is 35 S, R is thioalkyl, thioarylalkyl, and thioalkaryl, (8) when chlorides, bromides, iodides, and ?uorides, which include Y is O, R is alkoxy, arylalkoxy, and alkaryloxy, and radi compounds such as molybdenum pentachloride, tungsten cals of (2) through (6) wherein at least one hydrogen hexachloride, molybdenum pentabromide, tungsten hexa is substituted by a material selected from hydroxyl (OH) bromide, molybdenum pentaio-dide, tungsten hexaiodide, and thiol (SH) groups. The Periodic Table of Elements 40 molybdenum penta?uoride, molybdenum hexa?uoride, referred to may be found in the Handbook of Chemistry and tungsten hexa?uoride. Other representative salts are and Physics, 44th Edition, April 1962 reprint, published those of acetylacetonates, sulphates, phosphates, nitrates by the Chemical Rubber Publication Company, Cleveland, and the like which include compounds such as molyb Ohio, U.S.A., page 448. denum phosphate, tungsten phosphate, molybdenum, ni Representative examples of metals from which the trate, tungsten nitrate, molybdenum acetylacetonate, tung~ organo-metallic compound, the ?rst or (A) component 45 sten acetylacetonate, molybdenum sulphate, and tungsten of the catalyst system of this invention, can be derived sulphate. Mixtures of these salts may also be employed. are lithium, sodium, potassium, rubidium, cesium, beryl~ Of these, it is usually preferred to employ tungsten ha lium, magnesium, calcium, strontium, barium, zinc, cad lides and molybdenum halides representative of which are mium, aluminum gallium, indium and thallium. The pre tungsten hexachloride and molybdenum pentachloride. ferred organo-metallic compounds are compounds of The third or (C) component of the catalyst system of lithium, sodium, magnesium, aluminum, zinc, and cad~ this invention are compounds which respond to the for mium with aluminum being most preferred. mula R—Y-—H wherein Y is selected from the group Representative examples of organo-metallic compounds consisting of oxygen and sulfur and R is a radical selected useful as the ?rst or (A) catalyst component of this in from the group consisting of (1) hydrogen, (2) alkyl, vention are aluminum compounds having at least one 55 (3) aryl, (4) arylalkyl, (5) alkaryl, (6) alkenyl, (7) aluminum-to-carbon bond. Representative of such com when Y is S, R is thioalkyl, thioarylalkyl, and thioalkaryl, pounds are trialkylaluminums such as trimethylalurninum, (8) when Y is O, R is alkoxy, arylalkoxy, and alkaryloxy, triethylaluminum, tri-n-propylalurninum, tri~n-butylalumi and (9) radicals of (2) through (6) wherein at least one num, triisopropylaluminum, triisobutylaluminum, trihexyl hydrogen of R is substituted by at least one hydroxyl aluminum, trioctylaluminum and the like; triarylalumi 60 (OH) or thiol (SH) group. nums such as tritolylaluminum, tribenzylalurninum, tri Thus, the formula above de?nes a number of types of phenylaluminum and the like; dialkylaluminum halides compounds. It de?nes water (HOH), hydrogen sul?de such as diethylaluminum chloride, di-n-plropylaluminum (HSH), both saturated and unsaturated alcohols (ROH), chloride, diisobutylaluminum chloride, diethylaluminum mercaptans (RSH), hydroperoxides (ROOH), hydrodi bromide, diethylaluminum iodide and diethylalurninum 65 sul?des (RSSH), polyalcohols (HOROH), polymercap ?uoride and the like; mixtures of dialkylaluminum halides tans (HSRSH), and hydroxy mercaptans (HSROI-l) or and alkylaluminum dihalides such as ethylaluminum thioalcohols (HORSH). Representative examples of the sesquichloride and bromides may also be employed; alkyl materials responding to the formula above are alcohols aluminum dihalides such as ethylaluminum dichloride, representative of which are methanol, ethanol, isopro ethylaluminum dibromide, propylaluminum dichloride, 70 panol, tertiarylbutyl alcohol, amyl alcohol, benzyl alcohol, isobutylaluminum dichloride, ethylaluminum diiodide and allyl alcohol, 1,1-dimethyl benzyl alcohol, phenol, terti the like; dialkylaluminum hydrides such as diethylalumi arybutyl catechol, alpha and beta naphthyl alcohol; mer num hydride, di-n-propylaluminum hydride, diisobutylalu captans such as methyl, ethyl, propyl, isopropyl, butyl, minum hydride and the like; arylaluminum hydrides and amyl, and similar mercaptans, ally] mercaptan, thiophenol, 75 4-methylthiophenol, 4-mercaptophenol; the hydroper 26,875 8 components can be ‘brought into contact with the unsatu oxides such as cumyl hydroperoxide, tertiarybutyl hydro rated precursor or unsaturated precursor/ solvent mixture. peroxide; the hydrodisul?des such as cumyl hydrodisul The following is a numerical listing of these various ?de, t-butyl hydrodisul?de', the polyalcohols such as ethyl methods in which A, B, and C stand for the catalyst com ene glycol, glycerol, and similar polyglycols; catechol, resorcinol, hydroquinone, pyrogallol; the polymercaptans ponents as previously de?ned: . . . . , s Zuchr9xymercap as 1512mm“ ans or. t‘tillthlfl’10a c0 h1’14'd“h1‘1°bmif’0 S Suc as e am," ‘h; '0 ' ' (2)(1) SimultaneousC followed by addition A and ofB A,Bwhich and were c. previously pre ll‘llOl, l-hydroxy-4-th1obenzene. formed to? if the “11:53:: land ilstmgutllslhinti features of, 1h‘; (3) A and B preformed followed by C. ca 3 Y5 System 0 S “wen 1?" 15 a e compo“ S 0. l0 (4) A followed by B and C which were preformed. the formula R-Y—H, wherein R and Y have been prevr- (5) B and C reformed followed b A ous ly de?ned ’ depending. on the particular. diole?n em- (6) B followedp by A and C WhlCl’l- werey ' preformed. ployed,. the particular organo-metalhc compound and the (7) A and C preformed followed by B. particular. Group Vlb metal salt chosen and on the par. (8) A followed by B followed by C. trcular. R--Y—H. compound chosen, when employed. 1n 15 (9) B followed by A followed by C. fairly substantial. . amounts are known. to reduce. drastically. (10) C followed b y B f o1 lowed ,by A. the activity. of. the ole?n-metathesis. . . reaction by wh1ch¢the (11) C followed by A followed by B. macrocyelrzation. . . of fins invention occurs. An. unexpected. (12) B followed by C followed by A. high act1v1ty of the catalyst of the present invention was (13) Afouowedb Cfonowed b B found when. compounds. of the R—Y--H type were. em- 20 (14) Preformed A,y B, and C whichy -' was prepared by ployed in relatively small amounts and added according to addin A to B and C reformed the teachings. set forth. in the. present. speci?cation and ex- (1S) Preformedg A, B,p and C which' - was prepared by amples. Since the. instant invention. contemplates. . . the use. addin g B to A and C preformed. of organo-metalhc compounds in comblnauon with transr- (16) Preformed A B and C which was Prepared by tion metal salts and various oxygen and sulfur-containing 25 adding C to A an‘; B informed, compounds, and since various factors or considerations will influence the optimum range of the three catalyst of these various procedures, procedures 6, 7, 11, 13, components in Elation *0 Ba?h other, the molar fatiOS 0f and 15 listed above are methods of preparations which the three components which optimize the reaction condi- reduce somewhat the catalytic activity. The remaining trons cannot be readily set forth. However, by following 30 of the listed procedures 1, 2, 3, 4, 5, 8, 9, 10, 12, 14, and the teachings found in this application, those skilled in 16lead to the most active catalyst systems. the art can readily determine the optimum molar ratio The amount of catalyst employed in the macrocycliza of the three catalyst components to each other. Obviously, tion reaction of this invention may be varied over wide if one employs the oxygen or sulfur-containing compound, concentrations and has not been found to be critical. Of or as is designated above, component C in relatively large 35 course, a catalytic amount of the catalyst must be em amounts, the activity of the catalyst will be reduced con- polyed. The optimum amount of catalyst depends upon siderably or even destroyed. a number of factors such as temperature, unsaturated It has been found that good results are obtained in the Pfecursofs use?’ Purity of PIQCIIFSOYS, reaction times (16 practice of this invention when the molar relationship 40 sired and the like. Those skilled in the art Wlll read1ly_de between the three catalyst components, A, B, and c as termlne the optimum catalyticranges. The macrocychza previously de?ned, are within a molar ratio of 13/0 rang- no“ can be conducted Whel'em the {lmolmt °f catalyst ing from about 0.3/1 to at least about 20/1 and the erglog’ed 1s_ label? 0-01 Patl'etd by Welght of ‘3 PS1’ 1%: molar ratio of A/B is within the range of about 0.5/1 to P 8 Y W618 1'- ° lmsalul'a PTBFUYSOI' 611}? 0Y6 , W1. at least 15/1. More preferred ratios are B/C of 0.5/1 4, ‘309130116113 A and C adlllsled 10 Yield a de?nable 91011116 to 5/1 and A/B of 0.5/1 to 8/1. Still more preferred "’ Tat") OfA/‘B/Q . _ . . _ ratios are B/C of 1/1 to 2/1 and A/B of 0.75/1 to 5/1. The Prac?ce of the mventlon 15 further Illustrated by The catalysts employed in this invention are prepared reference to the following examples which are intended by mixing the components by known techniques. Thus, to be representative rather than restrictive of the scope the catalysts may be prepared by "preformed" or “in situ” 50 of the invention- EXAMPLE 1 techniques. By the “preforme " method the catalyst com- Q pollenls are mixed together Prior 1° exposure of any of A 3.0 gram sample of puri?ed polyoctenamer prepared the catalyst components 10 the unsaturated compound 10 by the chain opening polymerization of cyclooctene and be used in the macrocyclization reaction. In the “in situ” having the structural formula: on our lom—ou=orr—orn(cnolm on CH2 ~01; \\ch’ \(cHm/ \chg \\c? \cnm method the catalyst components are added separately to was dissolved in 50 ml. of dried benzene under a nitrogen the unsaturated compound to be used in the macrocycliza‘ atmosphere. The viscous cement was treated with 1.0 ml. tion reaction. The catalyst components may be mixed 60 of a 0.05 molar solution of tungsten hexachloride (WClB) either as pure compounds or as suspensions or solutions in benzene, which was prereacted with ethanol (Cal-{50H} in liquids which do not adversely a?ect catalyst activity so that the molar ratio of WCl6/C2H5OH equaled l;l, or the ole?n-metathesis reaction. Representative of such followed by a 1.5 mole of a 0.20 molar solution of ethyl liquids are saturated hydrocarbons such as hexane, pen- aluminum dichloride (EADC) in benzene and thus main tane and the like or aromatics such as benzene, toluene 65 taining an Al/W/O molar ratio of 6/1/ 1. The mixture andthe like, was allowed to react for 15 minutes before terminated While the presence of the unsaturated precursor is not by introduction of 2.0 ml. benzene solution containing essential during the formation of active catalyst by a mix- 0.03 gram of tetraethylene pentamine (TEPA) and 0.02 ing of components A, B, and C and this fact facilitates the gram of di-ter-butyl-p-cresol and evaporated to dryness. use of “preformed” catalysts, it has been found that fresh- 70 The reaction mixture was extracted three times with 50 ly preformed catalysts are generally more active than cata~ ml. portions of 1:1 volume ratio of an isopropanol/ ly'sts which have been allowed to age before use. hexane solvent system and a low, molecular weight ex— The order of addition of the three catalyst components tractable portion thus isolated. Parent mass spectroscopic to each other is of interest in the practice of this invention. analysis by low voltage mass spectroscopy was carried out There are various methods in which the three catalyst 75 and it was found that the extractable mixture was com 26,875 prised of components possessing molecular weights ac 10 cording to the series: 220+n>
12085 1. 05 3285 6615 ______175 0. 5 ...... -. 82 210 0. 3 ______- 4
‘ Composition was determined by gas chromatography. The NMR anaylses of the fractions indicated that all had essentially the same spectra which was also identical to readily be seen that the formation of macrocyclic com the spectrum of mixture before fractionation. Only vinylic, pounds or mixtures of macrocyclic compounds possessing allylic and methylenic hydrogens were found and in a 55 alicyclic unsaturated rings with a ring size of at least ratio of l/2/4. 12 carbon atoms and containing at least one carbon-to Fraction No. 4, contained almost pure cyclic tetramer carbon double bond can be prepared from at least one of cyclooctene (4% cyclic trimer). This fraction was unsaturated compound corresponding to the general for catalytically hydrogenated, using H. C. Brown’s Hydro mula: Analyzer procedure, and the hydrogenated product was 60 analyzed by NMR, low voltage mass spectroscopy and X-ray diffraction. The NMR indicated one and only one While certain representative embodiments and details type of hydrogens, namely, mcthylenic: (CH2). The mo have been shown for the purpose of illustrating the in lecular weight obtained by low voltage mass spectroscopy vention, it will be apparent to those skilled in this art was 448 which is in perfect agreement with (CH3)32. The 65 that various changes and modi?cations may be made crystallographic d-spacings of the solid CHHM macrocylic therein without departing from the spirit or scope of the found to be 3.75 A. and 4.53 A. invention. What is claimed is: EXAMPLE 3 1. A macrocyclization process which comprises sub A 3.0 gram sample of puri?ed polybutadiene, which jecting at least one alicyclic unsaturated hydrocarbon was prepared by the ring-opening polymerization of 1,5 70 corresponding to the formula cyclooctadiene, and had the structural formula:
75 (1) R’ and R" may be at least one member of a group 26,875 12 where x:1,2, 3 . .] consisting of alkyl, aryl, alkenyl, aralltyl, alkaryl, cyclo 6. A composition of matter comprising a cyclic poly alkyl, cycloalkenyl, bicycloalkyl, bicycloalkenyl radi mer corresponding to the formula cals and hydrogen; (2) Z is a hydrocarbon fragment containing at least 9 carbon atoms situated in linear succession between the methylidene group, :CH, and the methylene group, ——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 10 group consisting of alkyl, aryl, alkenyl, aralltyl, alkaryl, cycloalkyl, cycloalkenyl, bicycloalkyl and bicycloal kenyl radicals; (4) any of the said carbon atoms in the linear succession of Z may be constituents of aromatic rings and ali cyclic rings; and
(5) the said acyclic unsaturated hydrocarbon contains wheren-—-1,2,3 . . . no conjugated double bonds 7. A composition of matter comprising a cyclic poly while said hydrocarbon is diluted to about 10% in an 20 mer corresponding to the formula inert diluent to a catalyst which is a mixture of (a) at least one organo metallic compound wherein the metal is from groups Ia, Ila, IIb and Illa of the Periodic Table of Elements, (b) at least one metal salt wherein the metal (0 f5’Hut 0 c H, is selected from the group of molybdenum and tungsten H2 CH and (c) at least one compound of the general formula RYH wherein Y is from the group of oxygen and sulfur CH CH: --~ 2 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 thioalkaryl and where x=2,3 . . . when Y is O, R is an alkoxy, alkaryloxy or an aralkoxy and radicals of alkyl, aryl. aralkyl, alkaryl and alkenyl References Cited which is hydrogen is substituted by a thiol or a hydroxyl The following references, cited by the Examiner, are group to form at least one macrocyclic compound pos of record in the patented ?le of this patent or the original sessing alicyclic unsaturated rings comprising at least 12 patent. carbon atoms and containing at least one carbon-to UNITED STATES PATENTS carbon double bond. 2. A method according to claim 1 in which the organo 3,257,332 6/1966 Ziegler ______252-429 3,259,616 6/1966 Grammer et al. _____ 260-855 metallic compound of (a) is an organoaluminum com 40 pound, the transition metal salt of (b) is a tungsten FOREIGN PATENTS halide and in the compound de?ned in (c), Y is oxygen. 3. A method according to claim 2 wherein the com 6,601,466 8/ 1966 Netherlands. pound de?ned in (c) is an alcohol. 6,605,105 10/ 1966 Netherlands. 667,392 11/1956 Belgium. 4. The macrocyclization process of claim 2 in which 4 the compound de?ned by the formula is a polyalkenamer. 1,425,601 1/1966 France. [5. A composition of matter comprising a cyclic poly OTHER REFERENCES mer corresponding to the formula A. J. Hubert, J. Chem. Soc., 1963, pp. 4088 and 4090. ‘ 50 DELBERT E. GANTZ, Primary Examiner V. O’KEEFE, Assistant Examiner mu'mb s'm'ms .ATEN'I‘ OFFL'CE (5/09) CERTIFICATE CF?‘ CCQIFS’LEUIE‘WN
Patent No. Reissue 26,875 Dates! my 12, 1970
Invonto?s) Nissim Calderon Page 1
It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line 14.6, "cabonu should read -- carbon H.
line 57, H in" should be deleted. Column 2, line 66, between lax-go and uns uturatod" --ring--. Column 3, line 10, "effect" should read -— affect . line 14.7, "intromoleoular" should read -~intramolecular~~~ Column 1;, the first formula under the title "Alicyclio" shown
Column 7, line 9, "On" should read »- One --. Column 8, under- "Example 1.", the formula (shown in column 7) should be moved to the right to be directly under "Example 1" .
Column 9, first formula ( after first paragraph) shown as :
('u. (‘H CH, CH’ / ' \ should be: . / “\ i, Reissue 26,875 (2)
Column 11, line 33,. "is" (first occurrence) should read —-a--.
Column 11 (Claim 5) , the formula shown as :
(‘Hg ( |I / \ A \ (rpm or fan IL—~\UJ/l(‘n (‘H\cn» (bun 1* shoulo1 ‘no., 1
Column 12 (Claim 6}, the formula shown as:
on 2 /CH?‘\ (.41 I ‘1:’ "II: (‘Ii (In-r1! CH2~c2r cn=cn ,4: I (hm , should. be: m/ CH CHw t; : H gr!“' $.11"!9;!‘ \cn -= on (Iii-CH2]-_ 2 (1:11: ru CH| c‘!H -n P“ (911' - 2 / CH2
Column 12 (Claim 7), the formula shown as:
‘J
cm on (‘In won / 2 \ (p?m‘r’n(Jul/cu \LUM(61ml ShOUld be: lffizjh02s,, ‘Ci! CH (CHDL u \ (“1/ (.‘ll » 1 > l u \mf/. \m _ L’u X
(SEAL)
Emu-M01311‘, llu?ngof?oer mm x’ W ' J Ora-1:51am of Patem