United States Patent 1191 [11] Patent Number: 4,940,831 Drake et a1. [45] Date of Patent: Jul. 10, 1990

[54] PURIFICATION OF CIS OLEFINS OTHER PUBLICATIONS [75] Inventors: gharlfs A‘ Drake’ Nowafa; Jlm D‘ “Chemistry and Biochemistry of Plant Pigments”, yerls’ silelven D‘ Bndges’ both of Goodwin, Academic Press, New York, 1965, p. 496. I - Bart esvl 6’ all of Okla‘ “Comprehensive Organic Chemistry”, Pergamon Press, [731 Asslgnee: Phillips Petroleum Company, New York, V01. 3, pp. 320-322. Bartlesvlne, Ok1a~ “Sul?nic Acid Catalyzed lsomerization of Ole?ns”, J_ Org. Chem. 41: p. 791 (1976). [21] Appl, 1510,; 312,103 “The Reaction Between Sulfochlorides and Or , ganomagnesium Halides”, Gilman et al, pp. 3501-3508, [22] Filed- Feb 15 1989 NW‘ 1929' ' ' ’ “The Constitution of Some Bacterial Casotenoids and their Bearing on Biosynthetic Problems”, Jensen, 1962, [51] Int. Cl.5 ...... C07C 7/17 p. 106. [52] US. Cl...... 585/836, 558855386668, Primary ExaminerwGlenn C 31 darola [58] Field of Search ...... 585/833, 836, 856, 866, Ammey’ Agent’ 0’ F’""_Ha1 Brant w°°dr°w 585/868, 324 [57] ABSTRACT A method for purifying a cis-ole?n formed by alkylat [56] References Cited ing a sulfonate ester comprising mixing the reaction U_S_ PATENT DOCUMENTS formed by alkylatinga sulfonate ‘ester with an acid

3 ’ 444261’ 5/1969 Caprioli et al ‘ ------" 585/809 S°I“§1°“;S°P?,““§gresu an pun 1ca ion sad to :0“:no W1$915103’ a 1- 33‘‘ 4a 3min? co 0 an‘hf; (13/1970 Ga?“ et a1‘ "" " 585/811 X optionally a base follpowed by separation and distilla , , /1982 Szantay et a1...... 424/84 tion or assin .d t. . t th h .1. 4,609,498 9/1986 Banaslak e161. 260/4109 R ’ P 5 Sa‘ “8° 1°“ m“ ‘"9 "mg a 811” 4,673,672 6/1987 Houlihan et a1...... 514/95 gel and collectmg the “$916511 fractm 4,740,627 4/1988 Byers et al. . 568/4699 4,749,818 6/1988 Byers et al...... 585/324 22 Claims, N0 Drawings 4,940,831 1 2 (b) separating said acid solution from said ?rst puri? PURIFICATION OF CIS-OLEFINS cation mixture to.form a ?rst puri?cation product, (0) mixing said ?rst puri?cation product with a FIELD OF THE INVENTION C1-C4 alcohol to form a second puri?cation mix This invention relates generally to the puri?cation of ture, cis-ole?ns. (d) separating said C1-C4 alcohol from said second puri?cation mixture to form a second puri?cation BACKGROUND OF THE INVENTION product, and (e) distilling said second puri?cation product to yield Cis-ole?ns are an important source of pharmacologi cal and biological compounds such as pheromones. a third puri?cation product containing said cis-ole ?n. Unfortunately, the synthesis of cis-ole?ns is a very dif? cult and expensive process because of the tendency of In accordance with another embodiment of the pres ent invention, we have also discovered a process the reaction products to isomerize into inactive or inhib for the puri?cation of a cis-ole?n formed by alkyl itory trans-isomers. An example of a simple cis-ole?n ating a sulfonate ester wherein said cis-ole?n is which has proven dif?cult to produce economically is puri?ed from a reaction mixture formed by the cis-9-tricosene, a house?y pheromone. alkylation of said sulfonate ester, which process Many of the more classical syntheses require the use comprises of alkynes or Wittig reagents to obtain the desired cis (a) passing said reaction mixture through a suitable stereochemistry. Although these reagents produce cis chromatographic gel packed in an organic solvent ole?ns in high purity, their use in large scale production and of pure cis-ole?ns is prohibitively expensive. Many (b) recovering the organic fraction containing said cis-ole?ns, however, could be economically produced cis-ole?n. in high yields via a synthesis process which uses sulfo nate esters, if a method could be developed to avoid DETAILED DESCRIPTION isomerization from cis- to trans-isomers during the puri In accordance with one embodiment of this invention ?cation of the cis-olefm product. For instance, we have a process is provided for the puri?cation of a cis-ole?n discovered that cis-9-tricosene (and many other cis-ole formed by alkylating a sulfonate ester, wherein said ?ns) can be synthesized by a simple three step process cis-ole?n is puri?ed from a reaction mixture formed by beginning with readily available cis-alcohols. The ?rst the alkylation of said sulfonate ester, which process step of this process is to deprotonate the cis-ole?nic comprises alcohol to form a lithium or sodium alkoxide salt fol (a) mixing said reaction mixture with an acid solution lowed by reacting the ole?nic alkoxide salt to form a to form a ?rst puri?cation mixture, sulfonate ester, then alkylating the sulfonate ester with (b) separating said acid solution from said ?rst puri? an appropriate alkylmagnesium compound and a eu 35 cation mixture to form a ?rst puri?cation product, prous salt. After alkylation it is usually desirable to (0) mixing said ?rst puri?cation product with a recover the cis-ole?n in a highly puri?ed form. Most C1-C4 alcohol to form a second puri?cation mix schemes for puri?cation of the cis-ole?n rely on a distil ture, lation process. Unfortunately the cis-ole?n is substan (d) separating said C1-C4 alcohol from said second tially converted to a trans-ole?n during distillation from puri?cation mixture to form a second puri?cation the alkylating reaction mixture containing the sulfonate product, and ester. (e) distilling said second puri?cation product to yield It would also be advantageous if a process for the a third puri?cation product containing said cis-ole puri?cation of cis-ole?ns formed by alkylating a sulfo ?n. nate ester could be developed which is economical, 45 One suitable method of forming a cis-ole?n utilizing a simple, and easy to scale-up. sulfonate ester synthesis consists of It is an object of this invention to provide an econom (a) the deprotonation of a cis-ole?nic alcohol to form ical process for the puri?cation of cis-ole?ns produced a lithium or sodium salt followed by by alkylating a sulfonate ester. (b) the formation of a sulfonate ester and It is also an object of this invention to provide a sim 50 (c) the alkylation of the sulfonate ester with an alkyl ple, easy to scale-up process for the puri?cation of cis magnesium compound and a cuprous salt. ole?ns formed by alkylating a sulfonate ester. To produce a cis-ole?n, one need only begin with a It is a further object of this invention to provide a cis-ole?nic alcohol having a hydroxyl-group at the process for the puri?cation of cis-9-tricosene, which is desired site or sites of alkylation and choose an appro produced by alkylating a sulfonate ester. 55 priate alkylmagnesium compound having the desired Other aspects, objects, and several advantages of this alkyl group. invention will be apparent from the speci?cation, in Appropriate cis-ole?nic alcohols for use in the three cluding the examples and accompanying claims. step synthesis set forth above are non-conjugated, non cumulated, non-enolic (without a double bond adjacent SUMMARY OF THE INVENTION to a hydroxyl group) cis-ole?nic alcohols. The cis-ole In accordance with the present invention, we have ?nic alcohols can also contain more than one double discovered a process for the puri?cation of a cis-ole?n bond. A cis-ole?nic alcohol with more than one double formed by alkylating a sulfonate ester, wherein said bond can be employed with a double bond allylic to the cis-ole?n is puri?ed from a reaction mixture formed by hydroxyl group if the allylic double bond position is the alkylation of said sulfonate ester, which process inconsequential in the ?nal cis-ole?n, because said al comprises lylic double bond may shift position. Although cis-ole (a) mixing said reaction mixture with an acid solution ?nic allylic alcohols may be suitable for this process, to form a ?rst puri?cation mixture, they are not recommended because of the tendency for 4,940,831 3 4 allylic bonds to shift with the resultant isomerization to sulfonyl halide and alkoxide, but will generally be that trans-ole?nic alcohols. The cis-ole?nic alcohols can time period needed for the reaction to reach substantial also include glycols and polyols, however, each hy completion before the next step is begun, which time droxyl may serve as a site of alkylation. period has been found to be about 1 hour. Preferably the The ?rst step in this three step synthesis of a cis-ole?n reaction time is in the range of fromabout 1 hour to is a deprotonation reaction of a cis-ole?nic alcohol with about 24 hours. a source of an alkali metal ion selected from the group The third step in the three step synthesis of a cis-ole consisting of lithium and sodium ions. The ?rst reaction ?n is the reaction of the second reaction product with product comprises an alkoxide which can be formed an alkylmagnesium compound and a cuprous salt to utilizing reagents and techniques well known to those of 10 form a third reaction product comprising a cis-ole?n. skill in the art. Suitable sources of alkali metal ions The alkylmagnesium compound may be selected from include, but are not limited to, alkali metal ion sources the group consisting of dialkylmagnesium and alkyl selected from the group consisting of sodium metal, magnesium halide wherein the halide of said alkylmag lithium metal, alkyllithium, alkylsodium, aryllithium, nesium halide is selected from the group consisting of and arylsodium. A preferred source of alkali metal ions iodide, bromide, and chloride. Preferred for the three is an alkyllithium compound selected from the group step synthesis of cis-ole?ns are alkylmagnesium halides consisting of phenyllithium, butyllithium, and methylli selected from the group consisting of alkylmagnesium thium. It is preferred that the temperature at which bromide and alkylmagnesium chloride. The alkylmag deprotonation is performed should be maintained in the nesium compounds suitable for the practice of this in range from about —70‘ C. to about 50' C., more prefer 20 vention can be synthesized by those skilled in the art ably from about - 10° C. to about 50' C. The ratio of using any appropriate synthesis technique. cis-ole?nic alcohol hydroxyl groups to the alkali metal The alkylmagnesium compound used must be se ions may range from about 1:0.25 to about 1:1.5. Prefer lected to result in the appropriate alkyl group being ably, this ratio will range from about 1:1 to about 1:1.1. transferred to the sulfonate ester. For example, if cis Time is not a critical factor for reacting the cis-ole?nic oleyl alcohol were to be reacted by the present inven alcohol to form a lithium or sodium alkoxide, and may tion to cis-9-tricosene, an n-pentylmagnesium halide vary depending upon the temperature and concentra would be employed as the alkylmagnesium halide to tion of reactants. Generally the reaction should be al alkylate the sulfonate ester of oleyl alcohol. The pre lowed to reach substantial completion before the next ferred alkylmagnesium halide for the alkylation of oleyl step is begun. However, the reaction will go to comple alcohol to cis-9-tricosene is n-pentylmagnesium chlo tion almost as quickly as the source of alkali metal ions ride. is mixed with the cis-ole?nic alcohol. A wide variety of alkylation catalysts are capable of The second step in this three step synthesis of a cis promoting the alkylation of the sulfonate ester with the olefm is the reaction of the ?rst reaction product, com alkylmagnesium compound. The present invention is prising an alkoxide, with a sulfonyl halide compound to 35 not limited to the use of a speci?c alkylation catalyst. form a sulfonate ester. Sulfonyl halide compounds suit Any alkylation catalyst which will promote the alkyla able for this three step synthesis process can be selected tion of the sulfonate ester with an alkylmagnesium com from the group consisting of alkylsulfonyl halides and pound so as to produce a cis-ole?n can be used. Suitable arylsulfonyl halides wherein the sulfonyl halide will not alkylation catalysts include, but are not limited to: cu interfere with the alkylation in the third step. For the prous salts selected from the group consisting of cu purpose of this speci?cation and the accompanying prous bromide, cuprous chloride, cuprous iodide, and claims, alkylsulfonyl halides shall also include triflates, dilithium cuprous tetrachloride. The preferred cuprous including but not limited to, trifluoromethanesulfonyl salt is cuprous bromide. halides. Preferred sulfonyl halide compounds include, The alkylation catalyst can be employed in any suit but are not limited to, those selected from the group 45 able amount which will facilitate the alkylation of the consisting of p-toluenesulfonyl halides, p-and o sulfonate ester with the alkylmagnesium compound so toluenesulfonyl halides, tri?uromethanesulfonyl ha as to produce a cis-ole?n. Generally the ratio of the lides, methanesulfonyl halides, and benzenesulfonyl moles of sulfonate ester to the moles of alkylation cata halides. The halides which can be used in sulfonyl hal lyst is in the range of from about 1:1 to about 1:0.005. ide compounds are selected from the group consisting Preferably the ratio is in the range of from about 120.01 of chloride and bromide. The most preferred sulfonyl to about 1:0.05. halide compounds are p-toluenesulfonyl chloride and Although the second reaction product, said sulfonate benzenesulfonyl chloride. ester and the alkylmagnesium compound, can be re The reaction of the ?rst reaction product with the acted together in about any ratio of sulfonate ester to sulfonyl halide compound to form the sulfonate ester, alkylmagnesium compound, the ratio will generally be can take place under a wide variety of reaction condi in the range of from about 10:1 to about 1:10, and pref tions. Generally the reaction temperature will be in the erably the ratio is in the range of from about 1:1 to about range of about 0‘ C. to about 70‘ C. Preferably the 1:2. reaction temperature is in the range of from about 30' The alkylation of sulfonate ester with alkylmag C. to about 60' C. In this step of the three step synthesis 60 nesium halide and cuprous salt alkylating catalyst can of a cis-ole?n, pressure is generally not critical, but will take place under a variety of reaction conditions. Gen generally be in the range of from about 0 psig to about erally the temperature of the alkylation will be in the 2,000 psig. Preferably the pressure is in the range of range of from about —70' C. to about 10' C. Preferably from about 1 psig to about 25 psig. the temperature is in the range of from about — 30‘ C. to The time of reaction for reacting a sulfonyl halide 65 about 10° C., and most preferably in the range of from compound with a ?rst reaction product to form a sulfo about -l0° C. to about 5' C. In this alkylation step, nate ester will depend upon the desired degree of con pressure is not critical, but will generally be in the range version, the reaction temperature, and concentration of of from about 0 psig to about 2,000 psig. Preferably the 4,940,831 5 6 pressure is in the range of from about 0.1 psig to about After the acid solution and reaction mixture have 250 psig, and most preferably in the range of from about been mixed to form a ?rst puri?cation mixture, the 1 psig to about 25 psig. puri?cation mixture will separate into two phases. One The time of the alkylation of sulfonate ester with phase will be an aqueous phase containing the acid and alkylmagnesium compound will depend upon the de other soluble contaminates. The second phase will be an sired degree of conversion, the reaction temperature, organic phase containing the cis-ole?n. These two pha ratio of sulfonate ester to alkylmagnesium compound, ses may be separated by conventional techniques known and the alkylation catalyst utilized, but will generally to those skilled in the art to form a ?rst puri?cation depend on the speed at which the three reaction compo product. One suitable separation technique would be to nents of this step can be mixed while still keeping the 0 decant the aqueous phase. The ?rst puri?cation product reaction mixture within the recommended temperature is then mixed with a C1-C4 alcohol. The amount of ranges. Preferably the time is in the range of from about C1-C4 alcohol mixed with the ?rst puri?cation product 1 minute to about 360 minutes, most preferably in the should range from a volumetric ratio of from about range of from about 5 minutes to about 120 minutes. 0.01:1 to about 100:1 preferably of from about 0.5:1 to The preceeding three step processes will take place in 5 about 2:1. a wide variety of organic solvents. Generally any or The C1-C4 alcohol should be contacted with the ganic solvent in which the reactants are soluble will be puri?cation product containing the cis-ole?n synthe suitable. Preferably ethers such as tetrahydrofuran and sized utilizing a sulfonate ester in a manner which facili diethyl ether are used as solvents. Currently preferred tates thorough mixing of the C1-C4 alcohol with the are organic solvents which include, but are not limited aforesaid ?rst purification product. In most syntheses of to, organic solvents selected from the group consisting cis-ole?ns this will require the mixing of a C1-C4 alco of diethyl ether, methylpropyl ether, ethylpropyl ether, hol with an organic phase containing the puri?cation 2-methoxylethyl ether, and tetrahydrofuran. product. Mixing may be effectuated by mechanical The three step synthesis of cis-ole?ns may also be agitation, stirring, or any other suitable means known to performed sequentially in one vessel. Those skilled in 25 those skilled in the art. the art will recognize that the reactants should be uti The time in which the C1-C4 alcohol is mixed with lized in ratios at each step which will be close to the the puri?cation product need only be suf?cient to allow stoichiometric ratios, thereby avoiding the possibility of thorough mixing of the aforesaid C1-C4 alcohol and side reactions which could interfere with the succeed puri?cation product. The temperature at which the ing step in the process of the present invention. The mixing of the C1-C4 alcohol and the puri?cation prod process of this invention should be practiced in the uct is conducted should range of from about 0‘ C. to substantial absence of 02, CO2, and H20 to avoid inacti about 40° C. and preferably of from about 0° C. to about vation of the alkylmagnesium compound of the third 30° C. step. The third reaction product will be predominately After the C1-C4 alcohol and the puri?cation product a cis-ole?n. Those skilled in the art will recognize that have been mixed, another puri?cation mixture will be other synthesis processes could be used to produce formed. This puri?cation mixture will also separate to cis-ole?ns utilizing sulfonate esters. form two phases. One phase will be the methanol solu To recover the desired cis-ole?n synthesized utilizing tion and other soluble contaminates. The second phase a sulfonate ester it is necessary to contact the reaction will be an organic phase containing the cis-ole?n. The ‘mixture resulting from the alkylation of said sulfonate 40 two phases may be separated by conventional tech ester to form said cis-ole?n with an acid solution, then a niques known to those skilled in the art to form a second short chain alcohol solution and optionally a base solu puri?cation product. Again, one suitable separation tion. technique would be to decant the aqueous phase from The acid solution should consist of an aqueous acid of the second puri?cation mixture. about 1 molar to 6 molar selected from the group con 45 Optionally, a base may be added to the C1-C4 alcohol sisting of hydrochloric acid, sulfuric acid, phosphoric or provided as a separate aqueous solution before or acid, and acetic acid. The volumetric ratio of acid solu after the C1-C4 alcohol is mixed with the ?rst puri?ca~ tion to be mixed with the reaction mixture should be tion product. The base may consist of an base selected from about 0.01:1 to about 100:1. Preferably the volu from the group consisting of potassium hydroxide and metric ratio of acid solution to the reaction mixture will sodium hydroxide. The preferred base is potassium be in the range of from about 0.5:1 to about 2:1. hydroxide. The concentration of the base may range The acid solution should be mixed with the reaction from about 0.5 molar to about 4 molar with a preferred mixture containing the cis-ole?n synthesized utilizing a . range of from about 1 molar to about 2 molar. sulfonate ester in a manner which facilitates thorough The quantity of base in solution, mixed with the puri mixing of the acid solution and the reaction mixture. In ?cation product or puri?cation mixture should range most syntheses of cis-ole?ns this will require the mixing from a volumetric ratio of about 0.1:1 to about 10:1 with of the aqueous acid and an organic phase containing the a preferred range of from about 0.5:] to about 2:1. reaction mixture. Mixing may be effectuated by me The base in solution should be mixed with the puri? chanical agitation, stirring, or any other suitable means cation product or puri?cation mixture containing the known to those skilled in the art. cis-ole?n in a manner which facilitates thorough mixing The time in which the acid solution is in contact with of the base in solution with the aforesaid puri?cation the reaction mixture need only be suf?cient to allow for product. Mixing may be effectuated by mechanical thorough mixing of the aforesaid acid solution and reac agitation, stirring, or any other suitable means known to tion mixture. those skilled in the art. The temperature at which the mixing of the acid 65 The time for which the base in solution is mixed or in solution and the reaction mixture should range of from contact with a puri?cation product or puri?cation mix about 0° C. to about 40° C. and preferably will range of ture need only be suf?cient to allow thorough mixing from about 0° C. to about 30° C. with the puri?cation product or mixture. The tempera 4,940,831 7 8 ture at which the puri?cation product and the base in Utah. The film thickness of the column was 0.15 mi solution should be mixed should range from about 0' C. crons. The GC was programmed from 80° C. to 160° C. to about 40' C. and preferably will range from about 0' at 4‘ C. per minute ramping rate. The retention time for C. to about 30' C. After the puri?cation product and the base in solution cis-9-tricosene, trans-9-tricosene, and tricosane was are mixed, the mixture will separate into two phases. 16.89, 17.31, and 17.66 minutes, respectively. One phase will contain the base in solution and other EXAMPLE I soluble contaminates. The second phase will be an or ganic phase containing the cis-ole?n. These two phases Synthesis of cis-9-tricosene should be separated by conventional techniques known A 12 l flask equipped with a re?ux condenser, Fire to those skilled in the art. One suitable separation tech stone valve, mechanical stirrer, and addition funnel was nique would be to decant the phase containing the base flushed with N2. 500 g of oleyl alcohol and 1500 ml of in solution and other soluble contaminates. The ?nal puri?cation product may be further puri?ed tetrahydrofuran were added to the ?ask and the reac by distillation. Distillation may be accomplished by tion mixture was cooled to 0' C. 1330 ml of nv-butylli conventional techniques known to those skilled in the thium (1.6M in hexane) was added dropwise while art. Currently, preferred for the practice of this inven maintaining the temperature below 5‘ C. The addition tion is distillation under reduced pressure, approxi of butyllithium was completed in approximately 45 min. mately one-tenth of a millimeter of mercury, wherein 420.6 g of p-toluenesulfonyl chloride was then added the distillation head temperature ranges from about 160' 20 and the temperature was increased to 35’-40° C. using a C. to about 175' C. Preferably the distillation will be heating mantle. The temperature was held at 40° C. for performed using a column packed with an inert packing 3 hr. The reaction mixture was then cooled to 0° C. material including, but not limited to, stainless steel and using a dry ice/isopropanol bath. 10 g of cuprous bro the distillation head temperature will be maintained in mide was added followed by the dropwise addition of the range of from about 165' C. to about 170' C. 25 In another embodiment of the present invention, an 1120 ml of n-pentylmagnesium bromide (2.5M in diethyl other process is provided for the puri?cation of a cis ether). This addition was completed in 48 min and the ole?n formed by alkylating a sulfonate ester wherein temperature was maintained near 0' C. during this time. the cis-ole?n is puri?ed from the reaction mixture The reaction mixture was stirred for 1 hr following the formed by the alkylation of said sulfonate ester which 30 addition of n-pentylrnagnesium bromide, then warmed comprises passing said reaction mixture through a suit to room temperature and held overnight under N2. able silica gel packed in a nonpolar organic solvent and recovering the cis-ole?n from the fraction generated EXAMPLE II therefrom. The silica gel used may be any chromoto Puri?cation of cis-9-tricosene graphic grade silica gel. Currently preferred are 70-230 35 mesh silica gels such as Kiesel gel 60 TM . The gel Crude tricosene made by the process described in should be packed in a nonpolar organic solvent such as Example I was treated two different ways and distilled nonpolar organic solvents selected from the group con under vacuum in order to determine whether isomeriza sisting of hexane, pentane, and petroleum ethers. Col tion had occurred. The ?rst treatment involved wash umn sizing will depend on the amount of material de ing with equal volumes of water, and then drying over sired to be processed and the degree of separation de MgSO4 prior to distillation. This resulted in 30.7% cis sired as may be determined by one skilled in the art. and 43.4% trans. In the second treatment, 6.5 l of 4M Generally the amount of reaction mixture to be loaded will range from about 3 to about 4 times the weight of HCl was added followed by phase separation. The or the silica gel. 45 ganic phase was then washed with 3 l of saturated so The temperature at which the column of silica gel dium bicarbonate solution prior to distillation. This should be used may generally range from 0' C. to 40‘ treatment resulted in 39.0% cis and 35.2% trans deter C., wherein the temperature is selected below the boil mined by GC as described above. ing point of the nonpolar organic solvent used. The pressure at which the separation is performed is not 50 EXAMPLE III believed to be critical to the present invention. Puri?cation of cis-9-tricosene Using Silica Gel Additionally, the gel used in the present invention may be reused by washing contaminated gels with suit~ Crude tricosene made by the process described from able polar solvents including, but not limited to, ethyl Example I was immediately chromatographed using acetate. 55 Kiesel gel TM60 (70-230 mesh) silica gel (from EM The fraction to be saved containing the cis-ole?n may Science). The column was packed in hexane, and hex be determined by monitoring the fraction yielded by ane was used as the developing solvent. Analysis with methods including, but not limited to, GC, HPLC, or GC as described above showed 69% cis-9-tricosene, paper chromotography. 11% trans-9-tricosene, and 4% tricosane. The following non-limiting examples are provided to Another sample that had been chromatographed further illustrate the practice of the present invention. using silica gel as described above was heated to 217‘ C. EXAMPLES in a distillation pot and refluxed up through metal To separate and identify cis-9-tricosene, trans-9-trico Goodloe TM packing for 6-7 hours followed by GC sene, and tricosane, a mixture of these pure samples was 65 analysis. The results showed 70.9% cis-isomer, 7.5% injected into an HP 5880A gas chromatograph (GC). trans-isomer, and 4.5% tricosane, determined by GC as The column was a Smetic column (200 microns><25 described above, indicating little or no isomerization meters) purchased from Lee Scienti?c, Salt Lake City, after removal of impurities. 4,940, 83 1 9 10 8. The process of claim 6 wherein the C1-C4 alcohol EXAMPLE IV is added to said puri?cation product before the addition Puri?cation of cis-9-tricosene Using a KOH/MeOH of the base in solution in step (c). Wash 9. The process of claim 6 wherein the C1-C4 alcohol 5 is added to said ?rst puri?cation product after the addi A sample of crude tricosene was prepared as set forth tion of the base in solution in step (c). in Example I and was treated with 6.5 l of 4M HCl, 10. The process of claim 6 wherein the cis-ole?n is followed by phase separation. The organic phase was formed utilizing a sulfonate ester synthesis consisting washed with 3 l of saturated sodium bicarbonate solu essentially of the following steps: tion, followed by 2 volumes of a 1M KOH/MeOH 10 (a) reacting a cis-ole?nic alcohol with a source of solution (an aqueous KOH/MeOH solution was pre alkali metal ion selected from the group consisting pared by mixing one part of methanol and one part of of lithium and sodium ions to form a ?rst reaction water, with a ?nal KOH concentration of 1M). The product, aqueous phase was then decanted. The organic solvent (b) then contacting said thus formed ?rst reaction was removed by rotor evaporation and the residue dis product with a sulfonyl halide compound wherein tilled at 0.1 mm Hg vacuum. The distilled yield based on the sulfonyl halide compound is selected from the pure oleyl alcohol was 92.3%, with the ?nal product group consisting of an alkyl sulfonyl halide and an containing 75% cis-isomer as determined by GC analy aryl sulfonyl halide wherein the halide of said sul sis. fonyl halide compound is selected from the group That which is claimed is: 20 consisting of chloride and bromide to form a sec 1. A process for the puri?cation of a cis-ole?n formed ond reaction product, by alkylating a sulfonate ester, wherein said cis-ole?n is (c) then contacting said thus formed second reaction puri?ed from a reaction mixture formed by the alkyla product with a cuprous salt and alkylmagnesium tion of said sulfonate ester, which process comprises the compound selected from the group consisting of steps of: 25 dialkylmagnesium and alkylmagnesium halide (a) mixing said reaction mixture with an acid solution wherein the halide of said alkylmagnesium halide is selected from the group consisting of hydrochloric selected from the group consisting of iodide, bro acid, sulfuric acid, phosphoric acid, and acetic acid mide, and chloride to form a third reaction product to form a ?rst puri?cation mixture, comprising a cis-ole?n wherein the steps are car (b) separating said acid solution from said ?rst puri? 30 ried out in a suitable organic solvent. cation mixture to form a ?rst puri?cation product, 11. The process of claim 9 wherein the C1-C4 alcohol (c) mixing said ?rst puri?cation product with a and the base in solution are simultaneously added to said C1-C4 alcohol to form a second puri?cation mix ?rst puri?cation product in step (c). ture, 12. The process of claim 9 wherein the acid solution (d) separating said C1-C4 alcohol from said second 35 concentration is in the range of from about 1 molar to 6 puri?cation mixture to form a ?nal puri?cation molar wherein the volume ratio of said acid solution to product, and said reaction mixture is from about 0.01:1 to about (e) distilling said ?nal puri?cation product to yield 100:2. said puri?ed cis-ole?n. 13. The process of claim 11 wherein the temperature range at which said acid solution is mixed with said 2. The process of claim 1 wherein the acid solution is reaction mixture ranges from about 0° C. to about 40° C. hydrochloric acid. ' 14. The process of claim 9 wherein the volume ratio 3. The process of claim 1 wherein the C1-C4 alcohol of C1-C4 alcohol mixed with said ?rst puri?cation prod is methanol. uct ranges from a volume ratio of about 0.01:1 to about 4. The process of claim 1 wherein the C1-C4 alcohol 45 100:1 C1-C4 alcohol to ?rst puri?cation product. is isopropanol. 15. The process of claim 13 wherein said C1-C4 alco 5. The process of claim 1 wherein the cis-ole?n is hol is mixed with said ?rst puri?cation product at a Z-9-tricosene. temperature range from about 0° C. to about 40° C. 6. A process for the puri?cation of a cis-ole?n formed 16. The process of claim 9 wherein said base in solu by alkylating a sulfonate ester, wherein said cis-ole?n is tion is provided at a concentration range from about 0.5 puri?ed from a reaction mixture formed by the alkyla molar to about 4 molar wherein the volume ratio of said tion of said sulfonate ester, which process comprises the aqueous base solution to said puri?cation product is steps of: about 0.1:1 to about 10:1. (a) mixing said reaction mixture with an acid solution 17. The process of claim 15 wherein the temperature selected from the group consisting of hydrochloric range at which said base in solution is mixed with said acid, sulfuric acid, phosphoric acid, and acetic acid puri?cation product ranges from about 0° C. to about to form a ?rst puri?cation mixture, 40° C. (b) separating said acid solution from said ?rst puri? 18. The process of claim 9 wherein the cis-ole?n is cation mixture to form a ?rst puri?cation product, cis-9-tricosene. (0) mixing said ?rst puri?cation product with a 19. A process for the puri?cation of a cis-ole?n C1-C4 alcohol and an base in solution, formed by alkylating a sulfonate ester, wherein said (d) separating from said C1-C4 alcohol and said base cis-ole?n is puri?ed from a reaction mixture formed by in solution to form a ?nal puri?cation product and the alkylation of said sulfonate ester which process (e) distilling said ?nal puri?cation product to yield comprises the steps of: said cis-ole?n. (a) passing said reaction mixture through a suitable 7. The process of claim 6 wherein the C1-C4 alcohol silica chromatographic gel packed in an organic and the base in solution are simultaneously added to said solvent to fractionate said reaction mixture, and ?rst puri?cation product in step (c). (b) recovering the fraction containing said cis-ole?n. 4,940,831 11 12 20. The process of claim 18 wherein the cis-ole?n is (c) then contacting said thus formed second reaction formed utilizing a sulfonate ester synthesis consisting product with a cuprous salt and alkylmagnesium essentially of the following steps: compound selected from the group consisting of (a) reacting a cis-ole?nic alcohol with a source of dialkylmagnesium and alkylmagnesium halide alkali metal ion selected from the group consisting 5 wherein the halide of said alkylmagnesium halide is of lithium and sodium ions to form a ?rst reaction selected from the group consisting of iodide, bro product, mide, and chloride to form a third reaction product (b) then contacting said thus formed ?rst reaction comprising a cis-ole?n wherein the steps are car product with a sulfonyl halide compound, wherein ried out in a suitable organic solvent. the sulfonyl halide compound is selected from the 10 21. The process of claim 19 wherein the silica chro group consisting of an alkylsulfonyl halide and an matographic gel is a 70-230 mesh silica gel. arylsulfonyl halide wherein the halide of said sulfo- 22. The process of claim 20 wherein the organic sol nyl halide compound is selected from the group vent is selected from the group consisting of hexane, consisting of chloride and bromide to form a sec- pentane, and petroleum ethers. 0nd reaction product, 15 ‘ ' ' ‘ ‘

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