GB2085881A - A process for the preparation of 11-dodecen-1-ol and derivatives - Google Patents
A process for the preparation of 11-dodecen-1-ol and derivatives Download PDFInfo
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- GB2085881A GB2085881A GB8132023A GB8132023A GB2085881A GB 2085881 A GB2085881 A GB 2085881A GB 8132023 A GB8132023 A GB 8132023A GB 8132023 A GB8132023 A GB 8132023A GB 2085881 A GB2085881 A GB 2085881A
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- formula
- compound
- dodecen
- general formula
- ester
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- 238000000034 method Methods 0.000 title claims abstract description 30
- QNXYZQSFDTZEBK-UHFFFAOYSA-N dodec-11-en-1-ol Chemical compound OCCCCCCCCCCC=C QNXYZQSFDTZEBK-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 15
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 230000000397 acetylating effect Effects 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 16
- -1 1-dodecen-1-yl Chemical group 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- CQKHFONAFZDDKV-UHFFFAOYSA-N dodec-1-en-1-ol Chemical compound CCCCCCCCCCC=CO CQKHFONAFZDDKV-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052987 metal hydride Inorganic materials 0.000 claims description 2
- 150000004681 metal hydrides Chemical class 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims 1
- 230000032050 esterification Effects 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 150000002168 ethanoic acid esters Chemical class 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000003016 pheromone Substances 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 244000309464 bull Species 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KNRCBASNXNXUQQ-UHFFFAOYSA-N 11-hydroxyundecanoic acid Chemical compound OCCCCCCCCCCC(O)=O KNRCBASNXNXUQQ-UHFFFAOYSA-N 0.000 description 2
- FRYAHUIXVSJEBC-UHFFFAOYSA-N 11-hydroxyundecyl acetate Chemical compound CC(=O)OCCCCCCCCCCCO FRYAHUIXVSJEBC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TXHIDIHEXDFONW-UHFFFAOYSA-N benzene;propan-2-one Chemical compound CC(C)=O.C1=CC=CC=C1 TXHIDIHEXDFONW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- ZIPHBQHTAWKZCG-UHFFFAOYSA-N methyl dodec-11-enoate Chemical compound COC(=O)CCCCCCCCCC=C ZIPHBQHTAWKZCG-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000001198 (Z)-tetradec-7-enoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ANBOMSJGDBBKMR-UHFFFAOYSA-N 11-Dodecenyl acetate Chemical compound CC(=O)OCCCCCCCCCCC=C ANBOMSJGDBBKMR-UHFFFAOYSA-N 0.000 description 1
- IUDGNRWYNOEIKF-UHFFFAOYSA-N 11-bromo-undecanoic acid Chemical compound OC(=O)CCCCCCCCCCBr IUDGNRWYNOEIKF-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241001350371 Capua Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000060469 Eupoecilia ambiguella Species 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000000877 Sex Attractant Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000091 aluminium hydride Inorganic materials 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002418 insect attractant Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- VASIFKMMXNGAGN-UHFFFAOYSA-N methyl 11-hydroxyundecanoate Chemical compound COC(=O)CCCCCCCCCCO VASIFKMMXNGAGN-UHFFFAOYSA-N 0.000 description 1
- RHGDHBUHYHTCSH-UHFFFAOYSA-N methyl 11-oxoundecanoate Chemical compound COC(=O)CCCCCCCCCC=O RHGDHBUHYHTCSH-UHFFFAOYSA-N 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
11-dodecen-1-ol and its acetic acid ester are prepared by reducing an alkyl dodec-12-enoate (V) and, optionally acetylating. The compounds (V) may be prepared from compounds of formula (IV> OCH-(CH2)9-COOR<1> (IV> by a method suitable for the formation of a vinyl group, and the compounds of formula (IV) may be prepared by the oxidation of an ester of the general formula (III> HO-CH2-(CH2)9-COOR<1> (III> wherein R<1> has the same meaning as above. Esters of formula (III) may be prepared in a variety of ways, such as the treatment of a corresponding haloester with a base, or the esterification of the corresponding acid. <IMAGE>
Description
SPECIFICATION
A process for the preparation of 11-dodecen-1-ol and derivatives
The process relates to a process for the preparation of 1 1-dodecen-l-oI and derivatives.
It is known that 1 1-dodecen-l-yl derivatives of the general formula (I),
CH2=CH-(CH2)9-CH2-R (I) wherein
R represents a hydroxyl group or an acetoxy group, can be found in the natural sex lure or sex pheromones of several insect species, and can be used to advantage in integrated plant protection. The compounds of general formula (I) have been extracted e.g. from the pheromones of the following pests: red bellworm (Diparopsis castanea) [B.F. Nesbitt, P.S. Beevor, R.A. Cole, R. Lester and R.G. Poppi: Nature, New
Biol. 1973, 244(137)208; B.F. Nesbitt, F. Cole, R.A. Beevor, R. Lester and R.G. Poppi: J. Insect Physiol. 1975, 1907; R. J. Marks: Bull. Entomol.Res. 1976, 219; R. J. Marks: Bull. Entomol. Res. 1976, 427; R. J. Marks: Bull.
Entomol.Res. 1976, 243] and Eupoecilia ambiguella [P. Saglio, C. Descoins, M. Galloix, D. Jaouen and J.
Mercier: C. R. Reun. Pheromones Sex Lepid. 1976,119; P. Saglio, C. Descoins, M. Galiois, M. Lettere, D.
Jaouen and J. Mercier: Ann.Zool.Ecol.Anim. 1977, 5531. The compounds of the general formula (I) can serve as insect attractants for the above insects.
When used with other pheromone components, the compounds of the general formula (I) exert a stimulating effect on springworm (Spargonothis pilleriana): P. Saglio, E. Priesner, C. Descoins and M.
Gallois: C. R. Reun. Pheromones Sex.Lepid. 1976, 109; and show a pheromone-inhibiting effect on summer-fruittortrix (Adoxophyies orana): S. Voerman and A.K. Minks: Environm.Entom. 1973,751; S.
Voerman, A.K. Minks and N.W.H. Houx: Environmn.Entom. 1974, 701.
For the preparation of the derivative of the general formula (I), wherein R is an acexoty group, Bestmann et al. have elaborated a synthesis which was laid open with reference to their unpublished results [Chem.Phys.Lipids 24. 335(1979)]. The starting substance of their synthesis is the 11 -octadecenyl-1 -ol acetate, which is a scarcely available derivative of a natural substance. This compound is ozonolyzed into 11 -acetoxy-undecanol. Ozonolysis requires expensive equipment and can be applied only as a laboratory semi-micro method. The Wittig reaction of the 11 -acetoxy-undecanol with the corresponding alkylidenephoshorane results in the desired product with a low yield.
For the preparation of the compound of the general formula (I), in which R stands for a hydroxyl group, no synthetic method has been published in the technical literature.
According to the invention we provide a process for the preparation of the compounds of the general formula (I), in which R has the same meanings as defined above, which comprises reducing an ester of the general formula (V) CH2=CH-(Ch2)9-COOR7 (V) wherein R1 is a CiA alkyl group, followed, where a compound of formula (I) in which R represents an acetoxy group is desired, by acetylation of the compound of formula (I) in which R represents a hydroxyl group thus obtained.
The compound of general formula (V) may be prepared by a variety of methods. Such methods include the step of forming a compound of formula (V) from a compound of formula (IV) OCH-(CH2)9-COOR1 (IV) wherein R1 is as defined above, by a method enabling the formation of a vinyl group.
The compounds of general formula (IV) may be prepared by a variety of methods. Such methods include the step of oxidising a compound of formula (III) HO-CH2-(CH2)9-COOR1 (III) wherein R' is as defined above. Such oxidation may be achieved by methods known per se.
The ester of formula (ill) may be prepared by a variety of methods. Such methods include a1) reacting an 1 1-halogen-undecanic acid of the general formula (II), Hal-CH2-(CH2)9-COOH (II) wherein
Hal represent a halogen atom, with a base, and reacting the 1 1-hydroxy-undecanic acid thus obtained with an aliphatic alcohol containing 1 to 4 carbon atom(s) preferably in the presence ofthe catalytic amount of an acid; or a2) reacting 1 1-hydroxy-undecanic acid with a CiA aliphatic alcohol preferably in the presence of the catalytic amount of an acid.
The halogen-undecanic acid of the general formula /II/ used as starting substance is a commercial product.
The conversion of the compounds of the general formula /II/ into the corresponding 11 -hydroxy-derivatives is carried out with the aid of an alkali or alkaline-earth hydroxide. Preferred representative of the alkali hydroxides is the sodium hydroxide. The reaction is preferably carried out in aqueous medium. One proceeds preferably under heating, particularly at the boiling points of the reaction mixture. As starting substance, preferably the 11 -bromoundecanic acid /II: Hal=Br/ is used. The 11 -hydroxy-undecanic acid thus-obtained can be isolated by acidifying the reaction mixture with a strong acid /e.g. hydrochloric, sulfuric acid, etc./ and filtering off the separated product.
The 1 1-hydroxy-undecanic acid thus-obtained is esterified into the ester of the general formula /II/. The reaction is preferably carried out with the aid of the corresponding alkanols. The excess of the alkanol can serve as reaction medium. The reaction is preferably carried out in the presence of the catalytic amount of an acid /e.g. hydrochloric, sulfuric, phosphoric, p-toluenesulfonic acid/. The reaction is performed under heating - preferably at the boiling point of the reaction mixture. The compounds of the general formula /III/ thus-obtained can be used for the next reaction steps after or without isolation.
The ester of the general formula /III/ is oxidized preferably with pyridinium-chlorochromate, pyridiniumbichromate or active manganese dioxide. As reaction medium aprotic soivents can be used. When oxidizing with pyridinium chlorochromate, the oxidation is preferably carried out in a halogenated aliphatic hydrocarbon /e.g. dichloromethane, chloroform, carbon tetrachlorid/. When oxidizing with manganese dioxide, aromatic hydrocarbons/e.g. benzene, toluene, xylene, etc./ are used as reaction medium. The reaction temperature varies between about 0 C and 60 "C. One proceeds preferably at room temperature.
The compound of the general formula /IV/ thus-obtained is converted into an ester of the general formula
Nl. This reaction can be carried out with a method suitable to build a vinyl group. The compound of the general formula /lav/ is preferably treated with a mixture of methylene iodide, zinc and triethyl-aluminium. As reaction medium different ethers /e.g. diethyl ether, tetrahydrofurane, dioxane, etc./ can be used. The reaction temperature varies between 0 C and 60"C. One proceeds preferably at room temperature.
The compound of the general formula N/thus-obtained is reduced into 1 -dodecon-1 -ol /I; R=OH/. The reduction can be carried out with a complex metal hydride /e.g. lithium-aluminium hydride orsodium-bis-/ 2-methoxy-ethoxy/-aluminium-hydride/ in an ether-type solvent/e.g. diethyl ether, tetrahydrofurane, dioxane, etc./ or in an aromatic hydrocarbon /e.g. benzene, toluene, xylene/. It is also preferable to carry out the reaction with sodium in the presence of an alcohol. The reaction temperature varies between about 0 C and 60"C, one proceeds preferably at room temperature.
The 11 -dodecen-1 -ol thus-obtained is optionally converted into the 1 1-dodecen-1 -yl-acetate after or without isolation. The acetylation is carried out with acetic acid or a reactive derivative thereof. As acylating agent preferably acetyl chloride or acetic anhydride are used. When acetylating with acetyl chloride the reaction can be performed in an ethereous solvent/e.g. diethyl ether, dioxane, tetrahydrofurane/. When acetic an hydride is used as acyiating agent, the excess thereof can serve as reaction medium. The reaction is preferably carried out in the presence of an acid binding agent. For this purpose alkali carbonate /e.g. sodium or potassium carbonate/, alkali bicarbonates /e.g. sodium or potassium bicarbonate/ or organic bases /e.g.
pyridine, triethylamine, etc./ can be used. The reaction temperature varies between about 0 C and 80 "C, one proceeds preferably at about 20 C to 40 OC.
The advantage of the method according to the invention is that the desired compounds can be produced with a good yield also on industrial scale.
The process is illustrated by the following Examples of non-limiting character:
EXAMPLE 1
Preparation of 1 1-hydroxy-undecanic acid/I, R=CH3COO-/
13.2 g /0.05 moles/ of 1 1-bromoundecanic acid /II; Hal=Br/ are dissolved in 100 ml of 2N sodium hydroxide solution and the mixture is boiled for 5 hours. Then it is cooled and poured into 25 ml of concentrated hydrochloric acid, the separated crystalline product is filtered off and washed with water.
Yield: 9.1 g/90%/
M.p.: 69-70 C
IR /KBr/: 3350, 1700cm1 1H-NMR /CDCl3/: 6.7 [s /wide/, 2H, OH];
3.65 It, J=10 Hz, 2H, CH2-O/; 2.35
It, J=11 Hz, 2H, CH2-COO/; 1.1-1.9
/m, 16H, -CH2-/.
Analysis: C11H22O3/202.30/
calculated: C=65.31 % H=10.96 % found: C=65.10% H=11.10%
EXAMPLE 2
Preparation ofmethyl- 1 1-hydroxy-undecanoate /III, R1 =CH3/ To a solution of 10.1 g /0.05 moles/ 11 11-hydroxy-undecanic acid in 50 mi of anhydrous methanol 0.3 ml of sulfuric acid are added, then the mixture is boiled for 6 hours. The hot solution is neutralized with 1.2 g of barium carbonate, cooled, filtered and the filtrate is evaporated in vacuo.
Yield: 9.7 g/90%/
IR /film/: 3400, 1735 cm 1 aH-NMR /CDCI3/: 3.70/s+t, 5H, COOCH3 + CH2O/;
2.33 /t, J=11 Hz, 2H, CH2-COO/;
1.1-1.9/m, 17H, -CH2- +OH/.
Analysis: C12H24O3/216.325/
calculated: C= 66.63% H=11.18%
found: C= 66.42% H=11.06%
EXAMPLE 3
Preparation of methyl- 10-formyl-decanoate /IV R1 = CH3/ 6.46 g /0.03 ml/ of pyridinium chlorochromate and 0.32 g /0.004 moles/of anhydrous sodium acetate are admixed with 50 ml of anhydrous dichloromethane, then a solution of 4.32 g /0.02 moles/ of methyl-11-hydroxy-undecanoate in 10 ml of anhydrous dichloromethane is added. The reaction mixture is stirred under inert gas/nitrogen or argon/at room temperature for 2.5 hours, then it is treated with 300 ml of anhydrous ether and the ethereous solution is decanted. This operation is repeated several times with a few anhydrous ether. The ethereous solutions are combined and filtered on Bentonitfilter, evaporated in vacuo, and the residue is distilled in vacuo.
Yield: 3.6 g /85 %/
B.p.: 111-113 C/0.3mm nD23=1,6695
IR/film/:2720, 1735 cm-1 1H-NMR /CDCI3/: 9.83 It, J=3Hz, 1 H, CHO/;
3.68/s, 3H, COOCH3/; 2.32/t, J=11Hz,
4H, CH2-COO+CH2-CHO/; 1.1-1.9/m 14H, -CH-/.
Analysis: C12H22O3/214.30/
calculated: C= 67.25% H=10.35%
found: C= 67.10% H=10.28%
EXAMPLE 4
Preparation of methyl-11-dodecenoate IV: R1 = CH3/ To a mixture of 8.39 g /0.03 moles, 2.93 ml/ of diiodomethane, 5.88 g /0.09 moles/of zinc dust and 50 ml of anhydrous tetrahydrofurane 0.69 g /0.006 moles, 0.83 ml/ of triethyl-aluminium are added under inert gas and under vigorous stirring, and stirring is continued for 20 minutes.Then the reaction mixture is cooled to room temperature, and a solution of 2.14 g/0.01 mole/of methyl-10-formyl-dodecanoate in 10 ml of anhydrous tetrahydrofurane are dropped under 15 to 20 minutes. The mixture is stirred at room temperature for an hour, then it is diluted with 100 ml of ether, water is added and the solution is acidified with 1 N hydrochloric acid.The aqueous phase is separated by decantation and extracted twice with a total amount of 60 ml of ether. The organic phases are combined and washed with 1 N hydrochloric acid, 5 % sodium hydrogen carbonate, 5 % sodium bisulfite, water and concentrated sodium chloride solution; dried over magnesium sulfate, the ether is removed and the residue is distilled in vacuo.
Yield: 1.85 g/87%/
B.p.: 110-112 C/0.3 mm nD23=1.4395
IR/film/: 1745, 1640 cm-1 H-NMR/CDCl3/: 5.5-6.3/n, 1H,/; 4.7-5.3/m, 2H, 12-H/;
3.65/s, 3H, COOCH3/; 2.32 It, J=11 Hz, 2H,
CH2COO/; 2.2/t, J=15Hz, 2H, 10-H/; 1.1-1.9
/m, 14H, -CH2-/.
Analysis: C13H24O3/212.37/
calculated: C=73.54% H=11.39%
found: C=73.58 % H=11.21 %
EXAMPLE 5
Preparation of 1 1-dodecen-1-ol/l, R=OH/
To a suspension of 0.23 g /0.006 moles/of lithium-aluminium hydride in 20 ml of anhydrous ether a solution of 2.12 9 /0.01 moles/of methyl-1 1 -dodecenoate in 5 mi of anhydrous ether is added dropwise under inert gas, and the mixture is stirred at room temperature for an hour. Then it is decomposed with water under cooling, acidified with 1 N hydrochloric acid, and the upper ethereous phase is separated. The aqueous phase is shaken with ether, the ethereous phases are combined, washed with 1 N hydrochloric acid, water, concentrated sodium chloride solution and dried over magnesium sulfate.The ether is removed by distillation in vacuo and the residue is purified by column chromatography. /Kieselgel 60, benzene-acetone 10:2/
Yield: 1.6 g/88%/
Rf=0.28 /benzene-acetone 10:1/
IR/film/: 3350, 1640 cm-1 H-NMR/CDCl3/: 5.5-6.3/m, 1H, 11-H/; 4.7-5.3/m, 2H, 12-H/;
3.65 It, J=10 Hz, 2H, -CH2-O/; 2.10 Im, 2H, 10-H/; 1.1-1.9/m, 17H, -CHr +OH/.
Analysis: C12H240 184.33 calculated: C=78.19% H=13.12% found: C=78.06 % H=13.17% EXAMPLE 6
Preparation of 11-dodecen-1-yl-acetate/I, R=CH3COO/
To a solution of 1.84 g /0.01 mole/of 1 1-dodeccen-1-ol and 1.19 g /0.015 moles, 1.2 ml/ of anhydrous pyridine in 25 ml of anhydrous ether 0.86 g /0.011 moles, 0.71 ml/ of acetyl chloride are added and the mixture is stirred at room temperature for 10 hours. Then it is diluted with 50 ml of ether, washed with water, 1N hydrochloric acid, 5% sodium hydrogen carbonate, water again, concentrated sodium chloride and dried over magnesium sulfate. The solvent is removed and the residue is distilled in vacuo.
Yield: 1.7 g/75%/
B.p.: 96-98 C/0.3 mm nD23=1.4398
GC; Rt=20 min./SE 30; 3% Ch-AWSr 80-100; 150 C/
IR/film/: 1740, 1635, 120 cm-1 H-NMR/CDCl3/: 5.5-6.3/m, 1H, 11-H/; 4.7-5.3 /m, 2H, 12-H/; 4.18/t, J=10 Hz, 2H, CH2-O/; 2.05/s+m, 5H, COCH3+10-CH2/;
1.1-1.9/m, 16H, -CH2-/.
Analysis: C14H26O2/226.36
calculated: C=74.29% H=11.58%
found: C=74.11% H=11.40 %
Claims (1)
1. A process for the preparation of 1 -dodecen-1 -ol and derivatives of the general formula (I) CHP=CH - (CH2)9- CH2- R (I) wherein
R represents a hydroxyl group or an acetoxy group which comprises reducing an 1 1-dodecen-1-yl ester of the general formula (V) CH2=CH-(CH2)9-COOR1 (V) wherein
R1 is a CiA alkyl group, and, where a compound of formula (I) in which R represents an acetoxy group is desired, acetylating the 11-dodecen-1-ol thus obtained.
2. A process as claimed in claim 1 wherein the compound of formula (V) as defined in claim 1 is prepared by the reaction of a compound of formula (IV) OCH-(CH2)s-COOR1 (IV) wherein R1 is as defined in claim 1 with a compound enabling the formation of a vinyl group.
3. A process as claimed in claim 2 wherein the compound of formula (IV) as defined in claim 2 is prepared by the oxidation of a compound of formula (III) HOCH2-(CH2)9-COOR1 (Ill) wherein R1 is as defined in claim 1.
4. A process as claimed in claim 3 wherein the compound of formula (III) as defined in claim 3 is prepared by reacting a 11 -halogen-undecanic acid of the general formula (II), HaI-CH2(CH2)-COOH (II) wherein hal represents a halogen atom with an alkali metal or alkaline-earth metal hydroxide.
5. A process as claimed in claim 3 wherein the compound of formula (III) as defined in claim 3 is prepared by the reaction of 1 1-hydroxy-undecanic acid with an aliphatic alcohol in the presence of a catalytic amount of sulfuric, hydrochloric phosphoric, or p-toluenesulfonic acid.
6. A process as claimed in any of claims 3 to 5 wherein the oxidation of the 11 -hydroxy-undecanic ester of the general formula (III), wherein R1 has the same meaning as defined in claim 1, is carried out using pyridinium chlorochromate, pyridinium bichromate or active manganese dioxide.
7. A process as claimed in any of claims 2 to 6 wherein the 11 -hydroxy-undecanic formly ester of formula (IV) is converted into the 1 1-dodecen-1-yI ester of the general formula (V) using a mixture of methylene iodide, zinc and triethyl-aluminium.
8. A process as claimed in any of claims 1 to 7 wherein the 11 -dodecen-1 -yl ester of the general formula (V) is reduced with complex metal hydride, or with sodium metal in the presence of an alcohol.
9. A process as claimed in claim 1 wherein acetyiation is carried out with acetic acid or a reactive derivative thereof.
10. A process as claimed in claim 1 substantially as hereinbefore described.
11. A process as claimed in claim 1 substantially as hereinbefore described with reference to the accompanying Examples.
New claims or amendments to claims filed on 4th Feb 1982
Superseded claims 1,2
New or amended claims:
1. A process for the preparation of 11 -dodecen-1 -ol and derivatives of the general formula (I)
CH2=CH-(CH2)9-CH2-R (I) wherein
R represents a hydroxyl group oran acetoxy group which comprises reacting a compound of formula (IV)
OCH-(CH2)9-COOR (II) wherein R1 is a CiA alkyl group, with a compound enabling the formation of a vinyl group, followed by reduction of the 11-dodecen-1-yl esterformed of the general formula (V) CH2=CH-(CH2)s-COOR1 (V) wherein
R1 is as defined above, and, where a compound of formula (I) in which R represents an acetoxy group is desired, acetylating the 11-dodecen-1-ol thus obtained.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
HU80802575A HU180386B (en) | 1980-10-24 | 1980-10-24 | Process for producing 11-dodecen-1-ol and 11-dodecen-1-yl-acetate of insect-feromone activity |
Publications (1)
Publication Number | Publication Date |
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GB2085881A true GB2085881A (en) | 1982-05-06 |
Family
ID=10960083
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Application Number | Title | Priority Date | Filing Date |
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GB8132023A Withdrawn GB2085881A (en) | 1980-10-24 | 1981-10-23 | A process for the preparation of 11-dodecen-1-ol and derivatives |
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BE (1) | BE890748A (en) |
DE (1) | DE3142114A1 (en) |
ES (1) | ES506524A0 (en) |
FR (1) | FR2492816A1 (en) |
GB (1) | GB2085881A (en) |
GR (1) | GR74694B (en) |
HU (1) | HU180386B (en) |
IT (1) | IT1139272B (en) |
PT (1) | PT73870B (en) |
RO (1) | RO82277A (en) |
YU (1) | YU252981A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4560792A (en) * | 1982-07-20 | 1985-12-24 | Phillips Petroleum Company | Disproportionation of functional olefins |
EP0341538A1 (en) * | 1988-05-04 | 1989-11-15 | BASF Aktiengesellschaft | 1-Tert.-butoxy-omega-alkenes and their use in aroma compositions |
WO2017087710A2 (en) | 2015-11-18 | 2017-05-26 | Provivi, Inc. | Production of fatty olefin derivatives via olefin metathesis |
US9695385B2 (en) | 2013-03-13 | 2017-07-04 | Stepan Company | Surfactants based on monounsaturated fatty alcohol derivatives |
US11155505B2 (en) | 2017-02-17 | 2021-10-26 | Provivi, Inc. | Synthesis of pheromones and related materials via olefin metathesis |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1096345B (en) * | 1959-02-28 | 1961-01-05 | Bayer Ag | Process for the preparation of hexadecadiene- (10, 12) -ol- (1) |
CA961862A (en) * | 1971-04-23 | 1975-01-28 | Andre Comeau | Trans-8-trans-10-dodecadien-1-o1 |
-
1980
- 1980-10-24 HU HU80802575A patent/HU180386B/en unknown
-
1981
- 1981-10-16 BE BE1/10334A patent/BE890748A/en not_active IP Right Cessation
- 1981-10-22 IT IT24627/81A patent/IT1139272B/en active
- 1981-10-23 YU YU02529/81A patent/YU252981A/en unknown
- 1981-10-23 FR FR8119930A patent/FR2492816A1/en active Pending
- 1981-10-23 ES ES506524A patent/ES506524A0/en active Granted
- 1981-10-23 GB GB8132023A patent/GB2085881A/en not_active Withdrawn
- 1981-10-23 PT PT73870A patent/PT73870B/en unknown
- 1981-10-23 DE DE19813142114 patent/DE3142114A1/en not_active Withdrawn
- 1981-10-23 GR GR66339A patent/GR74694B/el unknown
- 1981-11-19 RO RO81105823A patent/RO82277A/en unknown
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4560792A (en) * | 1982-07-20 | 1985-12-24 | Phillips Petroleum Company | Disproportionation of functional olefins |
EP0341538A1 (en) * | 1988-05-04 | 1989-11-15 | BASF Aktiengesellschaft | 1-Tert.-butoxy-omega-alkenes and their use in aroma compositions |
US10287530B2 (en) | 2013-03-13 | 2019-05-14 | Stepan Company | Surfactants based on monounsaturated fatty alcohol derivatives |
US11560530B2 (en) | 2013-03-13 | 2023-01-24 | Stepan Company | Surfactants based on monounsaturated fatty alcohol derivatives |
US9695385B2 (en) | 2013-03-13 | 2017-07-04 | Stepan Company | Surfactants based on monounsaturated fatty alcohol derivatives |
US20200261898A1 (en) * | 2015-11-18 | 2020-08-20 | Provivi, Inc. | Production of fatty olefin derivatives via olefin metathesis |
EP3377465A4 (en) * | 2015-11-18 | 2019-10-09 | Provivi, Inc. | Production of fatty olefin derivatives via olefin metathesis |
US10596562B2 (en) | 2015-11-18 | 2020-03-24 | Provivi, Inc. | Production of fatty olefin derivatives via olefin metathesis |
CN108473390A (en) * | 2015-11-18 | 2018-08-31 | 普罗维维公司 | Fatty alkene derivatives are produced by olefin metathesis |
US11077433B2 (en) * | 2015-11-18 | 2021-08-03 | Provivi, Inc. | Production of fatty olefin derivatives via olefin metathesis |
IL259459B (en) * | 2015-11-18 | 2022-07-01 | Provivi Inc | Production of fatty olefin derivatives via olefin metathesis |
CN108473390B (en) * | 2015-11-18 | 2022-08-09 | 普罗维维公司 | Production of aliphatic olefin derivatives by olefin metathesis |
WO2017087710A2 (en) | 2015-11-18 | 2017-05-26 | Provivi, Inc. | Production of fatty olefin derivatives via olefin metathesis |
US11779911B2 (en) | 2015-11-18 | 2023-10-10 | Provivi, Inc. | Production of fatty olefin derivatives via olefin metathesis |
EP4234522A3 (en) * | 2015-11-18 | 2023-10-25 | Provivi, Inc. | Production of fatty olefin derivatives via olefin metathesis |
US11155505B2 (en) | 2017-02-17 | 2021-10-26 | Provivi, Inc. | Synthesis of pheromones and related materials via olefin metathesis |
Also Published As
Publication number | Publication date |
---|---|
PT73870A (en) | 1981-11-01 |
ES8206411A1 (en) | 1982-08-16 |
IT1139272B (en) | 1986-09-24 |
DE3142114A1 (en) | 1982-06-16 |
RO82277B (en) | 1983-08-30 |
PT73870B (en) | 1983-01-25 |
YU252981A (en) | 1983-10-31 |
FR2492816A1 (en) | 1982-04-30 |
BE890748A (en) | 1982-04-16 |
IT8124627A0 (en) | 1981-10-22 |
RO82277A (en) | 1983-09-26 |
GR74694B (en) | 1984-07-04 |
ES506524A0 (en) | 1982-08-16 |
HU180386B (en) | 1983-02-28 |
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