CN1169416A - Method for synthesizing sex information hormone of bollworm - Google Patents
Method for synthesizing sex information hormone of bollworm Download PDFInfo
- Publication number
- CN1169416A CN1169416A CN 96106728 CN96106728A CN1169416A CN 1169416 A CN1169416 A CN 1169416A CN 96106728 CN96106728 CN 96106728 CN 96106728 A CN96106728 A CN 96106728A CN 1169416 A CN1169416 A CN 1169416A
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- CN
- China
- Prior art keywords
- hexadec
- enol
- hexadeca
- acid
- acetoxy
- Prior art date
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- Granted
Links
- 241000255967 Helicoverpa zea Species 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title claims 2
- 229940088597 hormone Drugs 0.000 title abstract 3
- 239000005556 hormone Substances 0.000 title abstract 3
- YJCJVMMDTBEITC-UHFFFAOYSA-N 10-hydroxycapric acid Chemical compound OCCCCCCCCCC(O)=O YJCJVMMDTBEITC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 3
- 238000004227 thermal cracking Methods 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims abstract 2
- 238000007254 oxidation reaction Methods 0.000 claims abstract 2
- -1 1-acetoxy-hexadeca-9-enol Chemical compound 0.000 claims description 18
- 150000001299 aldehydes Chemical class 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- LBIYNOAMNIKVKF-UHFFFAOYSA-N hexadec-9-en-1-ol Chemical compound CCCCCCC=CCCCCCCCCO LBIYNOAMNIKVKF-UHFFFAOYSA-N 0.000 claims description 15
- KHKUUQIMOYQNHB-UHFFFAOYSA-N 10-acetyloxydecanoic acid Chemical compound CC(=O)OCCCCCCCCCC(O)=O KHKUUQIMOYQNHB-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000877 Sex Attractant Substances 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- RHVMNRHQWXIJIS-UHFFFAOYSA-N hexadec-11-en-1-ol Chemical compound CCCCC=CCCCCCCCCCCO RHVMNRHQWXIJIS-UHFFFAOYSA-N 0.000 claims description 11
- PMOWTIHVNWZYFI-WAYWQWQTSA-N cis-2-coumaric acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1O PMOWTIHVNWZYFI-WAYWQWQTSA-N 0.000 claims description 10
- XBLFUMKMXKPZCT-UHFFFAOYSA-N methyl hexadec-11-enoate Chemical compound CCCCC=CCCCCCCCCCC(=O)OC XBLFUMKMXKPZCT-UHFFFAOYSA-N 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004359 castor oil Substances 0.000 claims description 8
- 235000019438 castor oil Nutrition 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 8
- AMTITFMUKRZZEE-UHFFFAOYSA-N hexadec-11-enal Chemical compound CCCCC=CCCCCCCCCCC=O AMTITFMUKRZZEE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- IUDGNRWYNOEIKF-UHFFFAOYSA-N 11-bromo-undecanoic acid Chemical compound OC(=O)CCCCCCCCCCBr IUDGNRWYNOEIKF-UHFFFAOYSA-N 0.000 claims description 5
- QFPVVMKZTVQDTL-UHFFFAOYSA-N hexadec-9-enal Chemical compound CCCCCCC=CCCCCCCCC=O QFPVVMKZTVQDTL-UHFFFAOYSA-N 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 150000004714 phosphonium salts Chemical group 0.000 claims description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 4
- ZLUALHMNABZRAJ-UHFFFAOYSA-N 9-bromononyl acetate Chemical compound CC(=O)OCCCCCCCCCBr ZLUALHMNABZRAJ-UHFFFAOYSA-N 0.000 claims description 3
- QFPVVMKZTVQDTL-FPLPWBNLSA-N 9Z-Hexadecenal Chemical compound CCCCCC\C=C/CCCCCCCC=O QFPVVMKZTVQDTL-FPLPWBNLSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229940101209 mercuric oxide Drugs 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 3
- JGMYDQCXGIMHLL-WAYWQWQTSA-N (Z)-hexadec-11-enoic acid Chemical compound CCCC\C=C/CCCCCCCCCC(O)=O JGMYDQCXGIMHLL-WAYWQWQTSA-N 0.000 claims description 2
- JGMYDQCXGIMHLL-AATRIKPKSA-N (e)-11-hexadecenoic acid Chemical compound CCCC\C=C\CCCCCCCCCC(O)=O JGMYDQCXGIMHLL-AATRIKPKSA-N 0.000 claims description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims description 2
- RHVMNRHQWXIJIS-AATRIKPKSA-N 11E-Hexadecen-1-ol Chemical compound CCCC\C=C\CCCCCCCCCCO RHVMNRHQWXIJIS-AATRIKPKSA-N 0.000 claims description 2
- 238000006584 Barton reaction Methods 0.000 claims description 2
- 229910010084 LiAlH4 Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910000085 borane Inorganic materials 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- AYFDQIWGOQIGOF-UHFFFAOYSA-N methyl 2-bromoundecanoate Chemical compound CCCCCCCCCC(Br)C(=O)OC AYFDQIWGOQIGOF-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910001923 silver oxide Inorganic materials 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- RHVMNRHQWXIJIS-WAYWQWQTSA-N 11Z-hexadecen-1-ol Chemical compound CCCC\C=C/CCCCCCCCCCO RHVMNRHQWXIJIS-WAYWQWQTSA-N 0.000 claims 1
- 241001147381 Helicoverpa armigera Species 0.000 claims 1
- QYZBCWXZSYTIOY-UHFFFAOYSA-N Mercuric oxide Chemical compound [O-2].[Hg+2] QYZBCWXZSYTIOY-UHFFFAOYSA-N 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 238000007239 Wittig reaction Methods 0.000 claims 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims 1
- NOXYEXFQXDRHTA-UHFFFAOYSA-N [O-2].[O-2].[O-2].[Cr+3].[Cr+3].C1=CC=NC=C1 Chemical compound [O-2].[O-2].[O-2].[Cr+3].[Cr+3].C1=CC=NC=C1 NOXYEXFQXDRHTA-UHFFFAOYSA-N 0.000 claims 1
- XKGDWZQXVZSXAO-ADYSOMBNSA-N Ricinoleic Acid methyl ester Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC XKGDWZQXVZSXAO-ADYSOMBNSA-N 0.000 abstract description 4
- XKGDWZQXVZSXAO-SFHVURJKSA-N Ricinolsaeure-methylester Natural products CCCCCC[C@H](O)CC=CCCCCCCCC(=O)OC XKGDWZQXVZSXAO-SFHVURJKSA-N 0.000 abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 4
- XKGDWZQXVZSXAO-UHFFFAOYSA-N ricinoleic acid methyl ester Natural products CCCCCCC(O)CC=CCCCCCCCC(=O)OC XKGDWZQXVZSXAO-UHFFFAOYSA-N 0.000 abstract description 4
- 229940114074 10-hydroxycapric acid Drugs 0.000 abstract description 2
- 235000003846 Ricinus Nutrition 0.000 abstract 1
- 241000322381 Ricinus <louse> Species 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 31
- 239000000243 solution Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- HFNPVFKUZYCDIB-UHFFFAOYSA-N methyl 11-bromoundecanoate Chemical compound COC(=O)CCCCCCCCCCBr HFNPVFKUZYCDIB-UHFFFAOYSA-N 0.000 description 6
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LBIYNOAMNIKVKF-FPLPWBNLSA-N palmitoleyl alcohol Chemical compound CCCCCC\C=C/CCCCCCCCO LBIYNOAMNIKVKF-FPLPWBNLSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 229960002703 undecylenic acid Drugs 0.000 description 3
- AMTITFMUKRZZEE-WAYWQWQTSA-N (Z)-hexadec-11-enal Chemical compound CCCC\C=C/CCCCCCCCCC=O AMTITFMUKRZZEE-WAYWQWQTSA-N 0.000 description 2
- USJDOLXCPFASNV-UHFFFAOYSA-N 9-bromononan-1-ol Chemical compound OCCCCCCCCCBr USJDOLXCPFASNV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- LBIYNOAMNIKVKF-BQYQJAHWSA-N 9-Hexadecen-1-ol Chemical compound CCCCCC\C=C\CCCCCCCCO LBIYNOAMNIKVKF-BQYQJAHWSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- SYRKSQMQOSOIGG-UHFFFAOYSA-N chloro(2,3-dimethylbutan-2-yl)borane Chemical compound CC(C)C(C)(C)BCl SYRKSQMQOSOIGG-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VAKBQCYSUVICLV-UHFFFAOYSA-N hexadec-9-enyl acetate Chemical compound CCCCCCC=CCCCCCCCCOC(C)=O VAKBQCYSUVICLV-UHFFFAOYSA-N 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 description 1
- 229940066675 ricinoleate Drugs 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a synthesis method fo sex-information hormone of cotton bollworm, which is characterized by that it uses ricinus oil as initiation raw material or mares methyl ricinoleate respectively pass through thermal cracking treatment and base catalytic cracking treatment to obtain undeca-10-olefine acid and 10-hydroxycapric acid, then uses the former as raw material and adopts direct reduction or oxidation process to synthesize (Z) -hexadeca-11-olefine aldehyde, and uses the latter as raw material and adopts five steps to synthesize (Z)-hexadeca-9-oleine aldehyde, then the obtained two products are mixed so as to obtain the invented sex-information hormone of cotton bollworm. It possesses the advantages of easily available raw material, mild operation condition and safety process, etc..
Description
A synthetic method of sex pheromone of cotton bollworm belongs to the technical field of the synthesis of sex pheromone of insects.
The cotton bollworm is the main pest of cotton in cotton areas in China, and after three or forty generations of propagation, the cotton bollworm can generate complete resistance to the existing pesticide, and the most reliable prevention and treatment measure at present is to utilize sex pheromone, namely sex attractant secreted by female cotton bollworm moth to kill male cotton bollworm moth or generate mating block to realize prevention and treatment. The sex pheromone secreted by female bollworm moth is composed of the mixture of (Z) -hexadeca-11-enal and (Z) -hexadeca-9 enal, and its structure is as follows:(Z) -hexadec-11-enalThe (Z) -hexadeca-9-enal is prepared by the existing internationally-available synthetic method, or raw materials are difficult to obtain, or the method is not easy to operate and is unsafe in process.
The invention aims to provide a synthetic method of cotton bollworm sex pheromone, which takes castor oil as a starting material, has mild operation conditions and higher yield in each step.
The invention is characterized in that: it uses castor oil as raw material, and adopts the known technology to make it pass through or pass through respectivelyMethyl ricinoleate is subjected to thermal cracking and alkali catalytic cracking respectively to prepare undecyl-10-olefine acid and 10-hydroxydecanoic acid, then (Z) -hexadec-11-olefine aldehyde is synthesized by taking the undecyl-10-olefine acid as a raw material, and (Z) -hexadec-9-olefine aldehyde is synthesized by taking the 10-hydroxydecanoic acid as a raw material, and then the raw materials and the raw material are mixed to obtain the compound, wherein the synthesis steps of the hexadec-11-olefine aldehyde and the hexadec-9-olefine aldehyde are as follows (1) (Z) -hexadec-11-olefine aldehyde synthesis step, ① the undecyl-10-olefine acid reacts with hydrogen bromide under the action of illumination or peroxide to generate 11-bromoundecanoic acid: ② 11, esterifying 11-bromo-undecanoic acidwith methanol to generate 11-bromo-methyl undecanoate; ③ 11 methyl bromoundecanoate reacts with triphenylphosphine to form a quaternary phosphonium salt, which reacts with valeraldehyde to form methyl hexadec-11-enoate, which is a mixture of (Z) -hexadec-11-enoate as the main component but a small amount of (E) -hexadec-11-enoate:④ reducing hexadec-11-olefine acid methyl ester with lithium aluminum tetrahydride to obtain hexadec-11-enol, wherein the ratio of (Z) -hexadec-11-olefine alcohol and (E) -hexadec-11-enol is the same as that of hexadec-11-olefine acid methyl ester, and oxidizing the hexadec-11-enol with chromic oxide-pyridine reagent to obtain hexadec-11-olefine aldehyde: or ⑤ methyl hexadeca-11-enoate with borane sulfideSelective reduction of the complex leads directly to hexadec-11-enal, which, since all reactions are free from isomer conversion, has a constant ratio between the (Z)/(E) formulae: (2) the synthesis step of (Z) -hexadec-9-enal comprises the reaction of ① 10-hydroxydecanoic acid and acetic anhydride to obtain 10-acetoxydecanoic acid: ② 10-acetoxy decanoic acid reacts with silver oxide or mercuric oxide to form salt through Hunsdiecker-Kochi-Barton reaction, and then reacts with bromine under illumination to obtain 1-bromine-9-acetoxy nonane: ③ 1 the quaternary phosphonium salt is formed by 1-bromo-9-acetoxynonane and triphenylphosphine, then it reacts with heptanal to form 1-acetoxy-hexadeca-9-enol, which is a mixture mainly comprising (Z) -1-acetoxy-hexadeca-9-enol and containing a small amount of (E) -1-acetoxy-hexadeca-9-enol, and the mixture is treated with LiAlH4Reduction gives hexadec-9-enol with unchanged isomer composition: ④ 1 Deethoxylation of 1-acetoxy-hexadec-9-enol with aluminum tetrachloride to give hexadec-9-enol wherein the ratio between (Z) -and (E) -is the same as in 1-acetoxy-hexadec-9-enol;⑤ oxidizing the hexadec-9-enol with a chromia-pyridine reagent to obtain another target product, hexadec-9-enol, having the same ratio between (Z) -formula and (E) -formula as in 1-acetoxy-hexadec-9-enol: wherein the purification of the respective (Z) -isomer and the removal of the (E) -isomer in the hexadeca-11-enol, the hexadeca-11-enal and the 1-acetoxy-hexadeca-9-enol, the hexadeca-9-enol and the hexadeca-9-enal are carried out by means of column chromatography separation using silica gel treated with copper salt to form silver salt or active aluminum as packing material, so that the (E) -form is eluted first to obtain the completely pure (Z) -form and a small amount of impure (E) -form containing the (Z) -form, and then in the presence of a sensitizer acetophenone, irradiating the impure (E) -form with ultraviolet light to convert it into (Z) -form containing a small amount of (E) -form, the impure product of formula (Z) is then fed to the process cycle of the separation process described above.
Experiments prove that: the cotton bollworm sex pheromone prepared by mixing (Z) -hexadecane-11-olefine aldehyde and (Z) -hexadecane-9-olefine aldehyde which are prepared by using castor oil as an initial raw material has the same structure with two natural effective components secreted by female cotton bollworm moths.
Example (b): 1. the preparation of undec-10-enoic acid and 10-hydroxydecanoic acid from castor oil was slightly modified using well known techniques:
100 g of castor oil, 20 g of methanol and 0.5 g of phosphoric acid are added, heated under reflux for 4 hours, and the glycerol and excess methanol are washed off with water to give 102 g of crude methyl ricinoleate for further preparation.
50 g of castor oil or 50 g of crude methyl ricinoleate are thermally cracked by heating to 400 ℃ and are first distilled off at 153 ℃ to give heptanal, the former giving 1.1 g of heptanal and the latter 5.1 g of heptanal. The reactor was cooled slightly, the pressure was reduced to 15 mm Hg, and undecylenic acid was distilled off at 165 ℃ to give 1.8 g in the former and 8.3 g in the latter. The refined heptanal is colorless liquid with b.p.152.8 ℃,D4 150.8216,nD 201.4257. refined undecylenic acid 10-m.p.24.5 deg.C, b.p.137 deg.C (2 mm Hg), D24 40.9072,n25 D1.4486。
20 ml of 40 percent caustic soda concentrated solution is added with 20 ml of 2-octanol, the solution is heated to 150 ℃ under stirring, 50 g of castor oil or the mixed solution of 50 g of methyl ricinoleate and 20 ml of 2-octanol is dripped into the solution, the solution is stirred and refluxed for 10 hours, cooled, added with water and acidified by hydrochloric acid, the solid is washed by water and added with petroleum ether to separate out 10-hydroxydecanoic acid, the 10-hydroxydecanoic acid is recrystallized by benzene, the former obtains 3 g of the benzene and the latter obtains 12 g of pure 10-hydroxydecanoic acid m.p.75.5-76.5 ℃, in addition, if the former 2-octanol is recovered, the 2 g can be increased, and the latter adds 8 g of 2.hexadeca-11-olefine aldehyde for synthesis, wherein the synthesis can be directly reduced or oxidized, and the direct reduction synthesis is (1) ① for preparing 11-bromoundecanoic acid by using undecenoic acid:
26.72 g of undecylenic acid and 1.75 g of benzoyl peroxide are dissolved in n-hexane, HBr gas is introduced,the reaction is carried out for half an hour (or the illumination is carried out for 4 hours without peroxide), after the solvent is removed by evaporation, the solid is recrystallized by acetone to obtain 30 g of white crystals, the melting point is 52-52.5 ℃, and the yield is 78%. IR (cm)-1Neat) 3200(OH), 3010(C ═ C-H), 1680(C ═ O), 690(C ═ C), elemental analysis: theoretical C49.64%, H7.90%, experimental C49.78%, H7.77%, ② preparation of methyl 11-bromoundecanoate from 11-bromoundecanoic acid:
50 ml of methanol, 0.5 ml of sulfuric acid and 10 ml of chloroform are added into 26.6 g of the undecyl bromoundecanoic acid, reflux reaction is carried out under a water separator, and after the reaction is finished, neutralization, water washing and reduced pressure distillation are carried out. The boiling point is 158-159 ℃/6 mm Hg. The colorless liquid collected was 26.5 g, yield 95%. Elemental analysis: theoretical value C51.45%, H8.22%; experimental values C51.50%, H8.31%. IR (cm)-1Neat) 1730(C ═ O), 1230, 1045, ③ preparation of methyl hexadec-11-enoate from methyl 11-bromoundecanoate:
2.8 g of methyl 11-bromoundecanoate and 2.62 g of triphenylphosphine are refluxed in toluene overnight, and the solid obtained after evaporation of toluene is dissolved in 20 ml of DMF and then 0.1 g of dicyclohexyl- [18]dicyclohexyl]Crown Ether and 1 g K2CO3In the presence of the solvent, 0.9 g of valeraldehyde was added dropwise, the reaction was carried out for 3 hours, filtration was carried out, the solvent was distilled off, and the resulting product was treated with a silica gel column to obtain 2.30 g of an oily liquid, which was 93: 7 in terms of (2)/(E) and 86% in terms of yield, elemental analysis showed that theoretical values ofC76.12% and H11.94% and experimental values of C76.27% and H12.01% and ④ were carried out for direct reduction synthesis of hexadec-11-enal from methyl 11-bromoundecanoate:
2.7 g of methyl 11-bromoundecanoate are dissolved in 10 ml of THF and, with stirring at room temperature, 10 ml of 2, 3-dimethyl-2-butylchloroborane disulfide (prepared by the method of Brown et al, see Fieser, supra) are added&Fieser, vol 12, page 485) in THF solution and reacted for half an hour. Adding water, acidifying, extracting with diethyl ether, drying the extractive solution, and evaporating. Separating and purifying by column chromatography. The oily product was 2.15 g, yield 90%. Elemental analysis: theoretical value C48.42%, H8.40%; the experimental values are C48.29% and H8.31%. IR (cm)-1Neat) 3010(═ C-H), 2710(HC ═ O), 1730(HC ═ O), 730(C ═ C); ` H-NMR (. delta.ppm) 0.9 (3H),t,CH3),0.3(18H,br.-(CH2)n-),2.0(4H,m,CH2C=CCH2),2.3(2H,m,-CH2CHO), 5.35(2H, t, CH ═ CH), 8.9(1H, br. CHO), MS (M/Z, O/O)238(2.21), 220(4.8), 55(71.57), 41(100), (2) oxidative synthesis ① hexadec-11-enoic acid methyl ester from undec-10-enoic acid, procedure as above, ② hexadec-11-enol from hexadec-11-enoic acid methyl ester:
2.7 g of hexadeca-11-enoic acid methyl ester are dissolved in 20 ml of anhydrous ether and 0.7 g of LiAlH are gradually added dropwise with stirring4Dissolving in 100 ml of diethyl ether, refluxing for 4 hr, decomposing with ice water, dissolving the precipitated alumina with 50% sulfuric acid, washing the ether layer with water, and MgSO4Drying gave a pale yellow liquid which was purified by column chromatography to give 2.1 g of product in 88% yield. Elemental analysis: theoretical values C80.00%, H13.33%; experimental values C79.91%, H13.16%;③ Hexadecyl-11-enal is obtained from hexadec-11-enol:
7.8 g of pyridine in 100 ml of CH2Cl2In the reaction solution, 4.8 g of CrO are added3Stirred for 15 minutes under ice water, to which CH containing 1.2 g of hexadec-11-enol was added dropwise2Cl2Stirring the solution to react for half an hour, pouring out the supernatant, and adding CH2Cl2Washing the brownish black solid, and washing the organic layer with dilute hydrochloric acid, NaHCO3Liquid and water washing, MgSO4Drying, evaporation of the solvent and purification by column chromatography gave 1.17 g of product in 90% yield. Elemental analysis: theoretical value C80.67%, H12.61%; the experimental values are C80.75% and H12.55%. The IR, NMR and MS were in agreement with those obtained in the direct reduction synthesis example. 3. Synthesis of hexadeca-9-enal: (1) preparation of 10-acetoxydecanoic acid from 10-hydroxydecanoic acid:
1.9 g 10-hydroxy capric acid, 1.6 g pyridine, adding 1.5 g acetic anhydride, reacting in 10 ml ether, evaporating to remove ether, adding water for decomposition, washing with hydrochloric acid and sodium bicarbonate solution, recrystallizing with alcohol to obtain 2.03 g product with 95% yield. m.p.34-35 ℃, b.p.175-176 ℃/3 mm Hg. IR (cm)-1Clean) 1740, 1710(C ═ O), 1240, 1075 (CH)3COO);′H-NMR(δppm)0.89(16H,Br,-(CH2)8-),2.04(3H,s,COCH3),2.34(2H,t,-CH2COO),4.05(2H,-OCH2-), 11.6(1H, s, -COOH); (2) preparation of acetate of 9-bromononanol from 10-acetoxydecanoic acid:
2.14 g of 10-acetoxydecanoic acid in 40 ml of CH2Cl2Adding anhydrous magnesium sulfate 1.4 g and mercuric oxide 3.02 g, stirring, refluxing, and dripping bromine 0.7 ml in CH 20 ml under illumination2Cl2Refluxing the solution for 2 hr to colorless, cooling and filtering, and using NaHCOas organic layer3Liquid and water washing, MgSO4After drying and evaporation of the solvent, the oily product obtained after column chromatography was 2.18 g, 82% yield. IR (cm)-1Net) 1740(CO), 1240, 1035 (CH)3COO);′H-NMR(δppm)1.32(14H,Br,-(CH2)7-),2.04(3H,s,COCH3),3.33(2H,-CH2-Br),4.05(2H,t,-CH2O-), MS (M/Z%) 264 (0.5); (3) preparation of the acetate of hexadec-9-enol from the acetate of 9-bromononanol:
2.66 g of 9-bromononanol acetate, i.e.acetic acid-9-nonanol ester, 2.62 g of triphenylphosphine and 1.0 g of heptanal, 2.45 g of an oily liquid are obtained by refining on silica gel in the procedure described above for the preparation of hexadeca-11-enoic acid carboxylic acid from methyl 11-bromoundecanoate, yield 87%. The (Z)/(E) -form is 91: 9. Elemental analysis: theoretical value C76.60%, H12.06%; the experimental values are C76.48% and H11.99%. (4) Preparation of hexadec-9-enol from hexadec-9-nonanol ester:
2 g of hexadec-9-enol acetate 50 ml ether solution, 0.5 g of lithium aluminum hydride in 50 ml ice-cooled ether solution was added dropwise and refluxed for 4 hours, after decomposition in cold water, alumina was dissolved in dilute sulfuric acid, the ether layer was washed with water and dried, and the ether was evaporated to obtain 1.5 g of oily substance with a yield of 88%. Elemental analysis: theoretical values C80.00%, H13.33%; experimental values C80.15%, H13.16%; IR (cm)-1Neat) 3320(OH), 3000(C ═ CH)710(C ═ C); ' H-NMR (delta ppm) 5.16-5.35 (2H, m, -CH ═ CH), 3.35-3.66 (2H, m, OCH)2-),2.85(1H,s,OH),1.7~2.15(4H,m,CH2c=CCH2),1.2~1.3(24H,m,-(CH2)n-),0.9(3H,t,-CH3) (ii) a (5) Preparation of hex-9-enal from hex-9-enol:
1.56 g of pyridine, 9.6 g of chromium oxide and 2.4 g of hexadec-9-enol, in the same manner as in the preparation of hexadec-11-enal from hexadec-11-enol, 2.15 g of the product are obtained after purification by column chromatography, the yield being 90%. Wherein, IR (cm)-1Neat) 3000(C ═ CH), 2700, (H — CO), 1680(C ═ O); ' H-NMR (. delta.ppm) 9.55(1H, s, CHO), 5.2 to 5.3(2H, m, CH ═ CH), 1.6 to 2.5(6H, m, CH)2C=CCH2,-CH2CO),1.2~1.3(24H,m,-(CH2)n-),0.9(3H,t,-CH3). 4. The hexa-11-enal and hexa-9-enal are mixed to obtain the sex pheromone of bollworm.
In addition, in the purification of (Z) -isomer and the removal of (E) -isomer, since no isomerization occurs in the reaction, this purification and removal process is carried out in the preparation of methyl hexadec-11-enoate, hexadec-11-enol, hexadec-11-enal or hexadec-9-enol, hexadec-9-enal, and we can obtain pure (Z) -formula target product. The packing material for column chromatography is silica gel or activated aluminum treated with copper salt or silver salt, eluted with chloroform/petroleum ether, and the (E) -form is first separated from the column, and the (Z) -form is prepared as a completely pure substance, and the (E) -form contains a small amount of the (Z) -form. The impure (E) -form is then fed to the next conversion cycle.
Purification of (Z) -hexadec-9-enol: 100 g of 80-100 mesh silica gel, 200 ml of 2% CuSO4And (4) treating the solution and performing suction filtration. Drying and activating at 110 ℃.1 g of hexadec-9-enol was dissolved in petroleum ether (Z/E. apprxeq. 91/9) in a 1 m column packed with the stationary phase as above, eluted with chloroform/petroleum ether (1: 3) and detected by gas chromatography. (E) The form (I) first eluted and 0.8 g of (Z) -hexadec-9-enol was finally obtained. 0.10 g of an impure (E) -form was recovered, containing 80% of the(E) -form and 20% of the (Z) -form. Purification of the other (Z) -forms was similar.
(E) When the isomer is converted into the (Z) -isomer, the impure (E) -isomer can be converted into the corresponding (Z) -form body at a conversion rate of 80-100% in the presence of ultraviolet light and a sensitizer such as acetophenone, and then put into the above separation cycle.
(E) -isomerization of hexadec-9-enol: 0.1 g of impure (E) -hexadec-9-enol (containing 20% of (Z) -form) is dissolved in 5 ml of petroleum ether, 0.01 g of acetophenone is added, after ultraviolet light irradiation for half an hour, the solvent is evaporated off to obtain 0.1 g of (Z) -hexadec-9-enol (gas chromatography analysis, wherein the content of (E) -form is 0-5%). The above separate cycles can be put into use, if necessary.
The transformation of the other (E) -forms is similar.
The above tests demonstrate that: the sex pheromone of cotton bollworm prepared by the method of the invention shows strong sexual attraction effect to male cotton bollworm moth.
Claims (2)
1. A synthetic method of bollworm sex pheromone is prepared by mixing (Z) -hexadeca-11-olefine aldehyde and (Z) -hexadeca-9-olefine aldehyde, and is characterized in that castor oil is used as a starting material, and is respectively subjected to thermal cracking and alkali catalytic cracking to prepare undec-10-olefine acid and 10-hydroxydecanoic acid, then the undec-10-olefine acid is used as a raw material to synthesize (Z) -hexadeca-11-dilute aldehyde, the 10-hydroxydecanoic acid is used as a raw material to synthesize (Z) -hexadeca-9-olefine aldehyde, and then the (Z) -hexadeca-11-olefine aldehyde and the-hexadeca-9-olefine aldehyde are mixed, wherein the following synthetic steps of the hexadeca-11-olefinealdehyde and the-the hexadeca-11-olefine aldehyde are respectively as follows (1), namely, the synthetic step of ①, the undec-10-olefine acid is reacted with hydrogen bromide under the action of light or peroxide to generate the 11-bromoundecanoic acid: ② 11, esterifying 11-bromo-undecanoic acid with methanol to generate 11-bromo-methyl undecanoate; ③ 11 methyl bromoundecanoate reacts with triphenylphosphine to form a quaternary phosphonium salt, which reacts with valeraldehyde to form methyl hexadec-11-enoate, which is a mixture of (Z) -hexadec-11-enoate as the main component but a small amount of (E) -hexadec-11-enoate:④ Hexahex-11-enoic acid methyl ester is reduced with lithium aluminum tetrahydrideThe hexadec-11-enol is obtained in the same ratio of (Z) -hexadec-11-enol to (E) -hexadec-11-enol as the methyl hexadec-11-enoate; then oxidizing the hexadecane-11-enol by using a chromium oxide-pyridine reagent to obtain hexadecane-11-enal: alternatively, ⑤ methyl hexadec-11-enoate can be reduced selectively with borane sulfide complex to directly produce hexadec-11-enal, with the ratio between (Z)/(E) being unchanged since all reactions are without isomer conversion: (2) the synthesis step of (Z) -hexadec-9-enal comprises the reaction of ① 10-hydroxydecanoic acid and acetic anhydride to obtain 10-acetoxydecanoic acid: ② 10-acetoxy decanoic acid reacts with silver oxide or mercuric oxide to form salt through Hunsdiecker-Kochi-Barton reaction, and then reacts with bromine under illumination to obtain 1-bromine-9-acetoxy nonane: ③ 1 the quaternary phosphonium salt is generated by reacting 1-bromo-9-acetoxynonane with triphenylphosphine and then Wittig reaction with heptanal to generate 1-acetoxy-hexadeca-9-enol, which is a mixture mainly comprising (Z) -1-acetoxy-hexadeca-9-enol and containing a small amount of (E) -1-acetoxy-hexadeca-9-enol, and using LiAlH4Reduction gives hexadec-9-enol with unchanged isomer composition: ④ 1 Deethoxylation of 1-acetoxy-hexadec-9-enol with aluminum tetrachloride to give hexadec-9-enol wherein the ratio between (Z) -and (E) -is the same as in 1-acetoxy-hexadec-9-enol, ⑤ further oxidation of the hexadec-9-enol with chromic oxide-pyridine reagent gives another desired product hexadec-9-enal wherein the ratio between (Z) -and (E) -is the same as in 1-acetoxy-hexadec-9-enol:
2. the method for synthesizing sex pheromone of Heliothis armigera according to claim 1, which comprises the following steps: wherein the purification of the respective (Z) -isomer and the removal of the (E) -isomer in the hexadeca-11-enol, the hexadeca-11-enal and the 1-acetoxy-hexadeca-9-enol, the hexadeca-9-enol and the hexadeca-9-enal are carried out by means of column chromatography separation using silica gel treated with copper salt to form silver salt or active aluminum as packing material, so that the (E) -form is eluted first to obtain the completely pure (2) -form and a small amount of impure (E) -form containing the (Z) -form, and then in the presence of a sensitizer acetophenone, irradiating the impure (E) -form with ultraviolet light to convert it into (Z) -form containing a small amount of (F) -form, the impure product of formula (Z) is then fed to the process cycle of the separation process described above.
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JPS5951232A (en) * | 1982-09-14 | 1984-03-24 | Shin Etsu Chem Co Ltd | Stabilization of higher aliphatic aldehyde compound |
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