JPH04330032A - Production of e,z-2,13-octadecadiene compound - Google Patents
Production of e,z-2,13-octadecadiene compoundInfo
- Publication number
- JPH04330032A JPH04330032A JP4621791A JP4621791A JPH04330032A JP H04330032 A JPH04330032 A JP H04330032A JP 4621791 A JP4621791 A JP 4621791A JP 4621791 A JP4621791 A JP 4621791A JP H04330032 A JPH04330032 A JP H04330032A
- Authority
- JP
- Japan
- Prior art keywords
- octadecadiene
- reaction
- compound
- octadecadienal
- diethyl acetal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- -1 orthoformic acid ester Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- NCFULMZVHNTQOK-RAPDCGKPSA-N 2E,13Z-Octadecadienal Chemical compound CCCC\C=C/CCCCCCCCC\C=C\C=O NCFULMZVHNTQOK-RAPDCGKPSA-N 0.000 claims description 13
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052987 metal hydride Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000004681 metal hydrides Chemical class 0.000 claims description 3
- NCFULMZVHNTQOK-JNHUCFJMSA-N (2e,13e)-octadeca-2,13-dienal Chemical group CCCC\C=C\CCCCCCCCC\C=C\C=O NCFULMZVHNTQOK-JNHUCFJMSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- NXRVLIATOKLQBL-JLXBFWJWSA-N (2E,4E)-octadeca-2,4-dienal Chemical compound CCCCCCCCCCCCC\C=C\C=C\C=O NXRVLIATOKLQBL-JLXBFWJWSA-N 0.000 claims 1
- NWRSOYAGXTXEMK-QRNOYXLNSA-N [(2e,13e)-octadeca-2,13-dienyl] acetate Chemical compound CCCC\C=C\CCCCCCCCC\C=C\COC(C)=O NWRSOYAGXTXEMK-QRNOYXLNSA-N 0.000 abstract description 8
- NWRSOYAGXTXEMK-UHFFFAOYSA-N (2E,13Z)-2,13-octadecadien-1-yl acetate Natural products CCCCC=CCCCCCCCCCC=CCOC(C)=O NWRSOYAGXTXEMK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003016 pheromone Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- GSNYYUGUPSMGOF-HBRQTTMKSA-N (2Z)-octadeca-2,13-diene Chemical class C\C=C/CCCCCCCCCC=CCCCC GSNYYUGUPSMGOF-HBRQTTMKSA-N 0.000 abstract 1
- DZACDSIUBROTPM-KTKRTIGZSA-N (z)-1,1-diethoxyoctadec-13-en-2-yne Chemical compound CCCC\C=C/CCCCCCCCCC#CC(OCC)OCC DZACDSIUBROTPM-KTKRTIGZSA-N 0.000 abstract 1
- OLUFPBTWIYZNJD-UHFFFAOYSA-N 1,1-diethoxyoctadeca-2,13-diyne Chemical compound CCCCC#CCCCCCCCCCC#CC(OCC)OCC OLUFPBTWIYZNJD-UHFFFAOYSA-N 0.000 abstract 1
- 150000004678 hydrides Chemical class 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 241000238631 Hexapoda Species 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- SGQJDSWMXBPVNF-BENRWUELSA-N (z)-heptadec-12-en-1-yne Chemical compound CCCC\C=C/CCCCCCCCCC#C SGQJDSWMXBPVNF-BENRWUELSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000007818 Grignard reagent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000004795 grignard reagents Chemical class 0.000 description 4
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000000877 Sex Attractant Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 3
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000255777 Lepidoptera Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- SFDZETWZUCDYMD-UHFFFAOYSA-N monosodium acetylide Chemical compound [Na+].[C-]#C SFDZETWZUCDYMD-UHFFFAOYSA-N 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- YCOMGIOWVNOOBC-RAPDCGKPSA-N (2e,13z)-octadeca-2,13-dien-1-ol Chemical compound CCCC\C=C/CCCCCCCCC\C=C\CO YCOMGIOWVNOOBC-RAPDCGKPSA-N 0.000 description 1
- AZIRITIZCLFDGA-WAYWQWQTSA-N (z)-15-bromopentadec-5-ene Chemical compound CCCC\C=C/CCCCCCCCCBr AZIRITIZCLFDGA-WAYWQWQTSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- BYFGZMCJNACEKR-UHFFFAOYSA-N Al2O Inorganic materials [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- AJPFSPZWXISACO-UHFFFAOYSA-N CCCCC=CCCCCCCCCCC=CC(OCC)OCC Chemical compound CCCCC=CCCCCCCCCCC=CC(OCC)OCC AJPFSPZWXISACO-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- NCFULMZVHNTQOK-UHFFFAOYSA-N Koiganal II Natural products CCCCC=CCCCCCCCCCC=CC=O NCFULMZVHNTQOK-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 241001306288 Ophrys fuciflora Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 241000885728 Synanthedon tipuliformis Species 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 1
- 239000012345 acetylating agent Substances 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000011981 lindlar catalyst Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- CDRWAQLPLNODEE-UHFFFAOYSA-N octadeca-1,3-dien-3-yl acetate Chemical compound CCCCCCCCCCCCCCC=C(C=C)OC(C)=O CDRWAQLPLNODEE-UHFFFAOYSA-N 0.000 description 1
- VKTFDHJQXBRZJP-UHFFFAOYSA-N octadeca-1,4-dien-3-one Chemical compound C=CC(C=CCCCCCCCCCCCCC)=O VKTFDHJQXBRZJP-UHFFFAOYSA-N 0.000 description 1
- DGVWPKNUMBHOTH-UHFFFAOYSA-N octadeca-15,17-dien-6-one Chemical compound C=CC=CCCCCCCCCC(CCCCC)=O DGVWPKNUMBHOTH-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、鱗翅目昆虫性フェロモ
ンの1つとして重要なE,Z−2,13−オクタデカジ
エン化合物の有用な製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a useful method for producing an E,Z-2,13-octadecadiene compound, which is important as one of the insect pheromones of the order Lepidoptera.
【0002】0002
【従来の技術】近年害虫防除の方法として性フェロモン
を応用することが注目を集めており、モニタリング、大
量誘殺、交信撹乱防除などが広く研究されている。中で
も交信撹乱法に性フェロモンを利用する場合、高純度で
低コストでフェロモン原体を供給することが産業上、不
可欠の条件になっている。鱗翅目昆虫性フェロモンの中
で、E,Z−2,13−オクタデカジエン構造を有する
ものは、具体的には以下のようなものがあげられる。
昆虫名(学名)
性フェロモン Synanth
edon tipuliformis :E,Z−2
,13−オクタデカジエニルアセテート Z
enzera pyrina
: 〃 Tineo
la bisselliea(Hummel):E,Z
−2,13−オクタデカジエナール
(Ko
iganal II )E,Z−2,13−オクタデカ
ジエニルアセテートの合成に関しては、Ramiand
rasoaらは13位のZ体をPd°触媒下アセチレン
のCarbocuprationにつづく有機亜鉛試薬
とのカップリングにより、2位のE体をプロパルギル型
アルコールのsodium (2−methoxy e
thoxy)aluminium hydrideの還
元によって、E,Z−2,13−オクタデカジエン骨格
を構築している。(Synthetic commun
ication, 19(15), 2703〜271
2(1989))また、Sorochinskaya
らは13位のZ体をWittig反応で2位のE体をプ
ロパルギルアルコールとpentadec−Z−10−
enyl bromideとのアルキル化ののちに得ら
れたプロパルギル型アルコールを水素化リチウムアルミ
ニウムで還元することによって合成している。(Khi
m Prir Soedin, 2, 264 〜26
6(1989))さらに、E,Z−2,13−オクタデ
カジエナール(Koiganal II) に関して山
岡らはSorochinskaya らと同様にして合
成したプロパルギル型アルコールを水素化リチウムアル
ミニウムで還元したのち PCC酸化して、アルデヒド
を合成している。(質量分析.33(3)189.(1
985))BACKGROUND OF THE INVENTION In recent years, the application of sex pheromones as a method of pest control has attracted attention, and methods such as monitoring, mass attraction, and control of communication disruption are being widely studied. In particular, when sex pheromones are used in communication disruption methods, it is industrially essential to supply pheromone raw materials with high purity and at low cost. Among lepidopteran insect pheromones, those having an E,Z-2,13-octadecadiene structure include the following. Insect name (scientific name)
Sex pheromone Synanth
edon tipuliformis :E, Z-2
,13-octadecadienyl acetate Z
enzera pyrina
: 〃 Tineo
la bisselliea (Hummel): E, Z
-2,13-octadecadienal
(Ko
iganal II) For the synthesis of E,Z-2,13-octadecadienyl acetate, Ramiand
By coupling the Z-isomer at position 13 with an organozinc reagent following carbocupration of acetylene under a Pd catalyst, the E-isomer at position 2 was converted into propargyl-type alcohol sodium (2-methoxy e
The E,Z-2,13-octadecadiene skeleton is constructed by reduction of aluminum hydride. (Synthetic community
cation, 19(15), 2703-271
2 (1989)) and Sorochinskaya
et al. used the Wittig reaction of the Z-form at position 13 and the E-form at position 2 with propargyl alcohol and pentadec-Z-10-
It is synthesized by reducing the propargyl alcohol obtained after alkylation with enyl bromide with lithium aluminum hydride. (Khi
m Prir Soedin, 2, 264 ~26
6 (1989)) Furthermore, regarding E,Z-2,13-octadecadienal (Koiganal II), Yamaoka et al. and synthesizes aldehydes. (Mass spectrometry.33(3)189.(1
985))
【0003】0003
【発明が解決しようとする課題】上記3者の合成方法は
、いずれも2位のE体を得るのにプロパルギル型アルコ
ールの三重結合をアルミニウム水素化金属で還元する際
、立体選択的にE体の立体異性で二重結合ができる性質
を利用したものである。しかしながら、使用するアルミ
ニウム水素化金属は非常に高価で空気中で発火する恐れ
があるなど非常に取扱いにくく工業的規模で使用するに
はふさわしいものではない。またアルデヒド体E,Z−
2,13−オクタデカジエナールについても相当するア
ルコール体を酸化する場合のクロム酸の後処理方法が煩
雑であり問題点も多い。従って大規模合成にふさわしい
工業的なE,Z−2,13−オクタデカジエン化合物の
製造方法が求められていた。[Problems to be Solved by the Invention] All of the three synthetic methods described above stereoselectively reduce the triple bond of propargyl type alcohol with metal aluminum hydride to obtain the E form at the 2-position. This takes advantage of the stereoisomerism of , which allows double bonds to form. However, the aluminum metal hydride used is very expensive and difficult to handle due to the risk of ignition in the air, making it unsuitable for use on an industrial scale. Also, aldehyde E, Z-
Regarding 2,13-octadecadienal, the post-treatment method of chromic acid when oxidizing the corresponding alcohol is complicated and has many problems. Therefore, there has been a need for an industrial method for producing E,Z-2,13-octadecadiene compounds suitable for large-scale synthesis.
【0004】0004
【課題を解決するための手段】本発明者らはこれらの課
題を解決すべく鋭意検討の結果、一般式 CH3(
CH2)3HC=CH(CH2)9C≡C−MgX (
式中Xはハロゲン原子を示す)…(1−1)で示される
グリニャール試薬と、一般式 CH(OR)3 (式
中Rはメチル基またはエチル基を示す)で示されるオル
ソギ酸アルキルエステルとを反応させて、一般式
CH3(CH2)3HC=CH(CH2)9C≡CCH
(OR)2…(2−1)で示されるZ−13−オクタデ
セン−2−インナールジエチルアセタールとするか、一
般式 CH3(CH2)3C≡C(CH2)9C≡C
MgX(式中Xはハロゲン原子を示す)…(1−2)で
示されるグリニャール試薬と、前記と同様のオルソギ酸
エステルとを反応させて、一般式 CH3(CH2
)3C ≡C(CH2)9C≡CCH(OR)2…(2
−2)で示される2,13−オクタデカジイナールジエ
チルアセタールとし、 ついで、それぞれを水素添加
したのち加水分解を行なって、CH3(CH2)3HC
=CH(CH2)9HC=CHCHO …(3)で示
されるE,Z−2,13−オクタデカジエナールとすれ
ば、2位の二重結合が官能基のホルミル基と共役してい
るため自動的に、E体が保証されることが明らかとなっ
た。さらに、これを水素化金属で還元すると、CH3(
CH2)3HC=CH(CH2)9HC=HCCH2O
H …(4)で示されるE,Z−2,13−オクタデ
カジエン−1−オールとなり、これをアセチル化すれば
CH3(CH2)3HC=CH(CH2)9CH=HC
CH2OCOCH3…(5)で示されるE,Z−2,1
3−オクタデカジエニルアセテートが立体選択的に合成
できることを見出した。この工程を利用すれば、鱗翅目
昆虫性フェロモンの1つとして重要な、E,Z−2,1
3−オクタデカジエナールおよびE,Z−2,13−オ
クタデカジエニルアセテートを高純度で、しかも低コス
トで製造できる。[Means for Solving the Problems] As a result of intensive studies to solve these problems, the present inventors found that the general formula CH3 (
CH2)3HC=CH(CH2)9C≡C-MgX (
A Grignard reagent represented by the formula (1-1) (wherein X represents a halogen atom) and an orthoformic acid alkyl ester represented by the general formula CH(OR)3 (wherein R represents a methyl group or an ethyl group). By reacting, the general formula
CH3(CH2)3HC=CH(CH2)9C≡CCH
(OR)2...Z-13-octadecene-2-innal diethyl acetal shown by (2-1) or the general formula CH3(CH2)3C≡C(CH2)9C≡C
MgX (wherein X represents a halogen atom)...The Grignard reagent represented by (1-2) and the same orthoformic acid ester as described above are reacted to obtain the general formula CH3(CH2
)3C ≡C(CH2)9C≡CCH(OR)2...(2
2,13-octadecadiinal diethyl acetal represented by -2), and then hydrogenated and hydrolyzed to produce CH3(CH2)3HC.
=CH(CH2)9HC=CHCHO...If we use E,Z-2,13-octadecadienal shown in (3), the double bond at position 2 is conjugated with the formyl group of the functional group, so it is automatically Therefore, it has become clear that the E-body is guaranteed. Furthermore, when this is reduced with metal hydride, CH3 (
CH2)3HC=CH(CH2)9HC=HCCH2O
H...(4) becomes E,Z-2,13-octadecadien-1-ol, and when this is acetylated, CH3(CH2)3HC=CH(CH2)9CH=HC
CH2OCOCH3...E, Z-2,1 shown by (5)
We have found that 3-octadecadienyl acetate can be synthesized stereoselectively. By using this process, E, Z-2, 1, which is important as one of the insect pheromones of Lepidoptera, can be produced.
3-Octadecadienal and E,Z-2,13-octadecadienyl acetate can be produced with high purity and at low cost.
【0005】本発明の出発物質であるグリニャール試薬
(1−1または1−2)は、メチルマグネシウムクロリ
ド、エチルマグネシウムブロミドなどにZ−12−ヘプ
タデセン−1−インまたは1,12−ヘプタデカジイン
を反応させることにより、容易に得ることができる。
CH3MgCl( またはCH3CH2MgBr
) + CH3(CH2)3HC=CH(CH2)9C
≡CH → CH3(CH2)3HC=
CH(CH2)9C≡C−MgX (X=ハロゲン原子
)…(1−1) CH3MgCl( またはCH3
CH2MgBr) + CH3(CH2)3C≡C(
CH2)9C≡CH → CH3(C
H2)3C≡C(CH2)9C≡C−MgX (同前)
…(1−2)本反応に用いら
れる溶媒はテトラヒドロフラン、エチルエーテル、n−
ブチルエーテルなどのエーテル類、トルエン、ベンゼン
、キシレンなどの炭化水素類を単独もしくは組み合わせ
て用いられる。The Grignard reagent (1-1 or 1-2), which is the starting material of the present invention, is prepared by reacting methylmagnesium chloride, ethylmagnesium bromide, etc. with Z-12-heptadecen-1-yne or 1,12-heptadecadiyne. It can be easily obtained by CH3MgCl (or CH3CH2MgBr
) + CH3(CH2)3HC=CH(CH2)9C
≡CH → CH3(CH2)3HC=
CH(CH2)9C≡C-MgX (X=halogen atom)...(1-1) CH3MgCl( or CH3
CH2MgBr) + CH3(CH2)3C≡C(
CH2)9C≡CH → CH3(C
H2) 3C≡C(CH2)9C≡C-MgX (same as before)
...(1-2) The solvents used in this reaction are tetrahydrofuran, ethyl ether, n-
Ethers such as butyl ether and hydrocarbons such as toluene, benzene, and xylene are used alone or in combination.
【0006】このグリニャール試薬とオルソギ酸アルキ
ルエステルとは少なくとも等モル量もしくはオルトギ酸
アルキルエステルを1〜 1.5倍モル量使用し、反応
温度60〜140℃、望ましくは80〜 100℃で反
応すれば4〜10時間で反応が完結する。ここで使用さ
れるオルソギ酸アルキルエステルにはオルソギ酸エチル
、オルソギ酸メチルなどが挙げられる。The Grignard reagent and the orthoformic acid alkyl ester are used in at least equimolar amounts, or the orthoformic acid alkyl ester is used in 1 to 1.5 times the molar amount, and the reaction is carried out at a reaction temperature of 60 to 140°C, preferably 80 to 100°C. The reaction is completed in 4 to 10 hours. Examples of the orthoformic acid alkyl esters used here include ethyl orthoformate and methyl orthoformate.
【0007】ここで得られたアセタール(2−1または
2−2)は次に水素添加反応されるが、ここで用いられ
る触媒にはP−2ニッケル、ラネーニッケル、リンドラ
ー触媒、Pd−C、Pd−BaSO4、Pd−Al2O
3、Pd−ケイソウ土、Pd−BaCO3、Pd−Ca
CO3、Rh−C、Ru−Cなどが挙げられる。これら
のうちではP−2ニッケルが優れている。使用する触媒
の量は反応基質に対し 0.001〜 0.2当量であ
り、水素圧は常圧から10kg/cm2Gの範囲、好ま
しくは1〜5kg/cm2G である。反応温度は0〜
80℃であるが反応速度に大きく影響するので20〜5
0℃がよい。反応後通常の分離操作で触媒を除去する。
加水分解反応は水素添加後の化合物を有機溶媒に溶解し
、塩酸水、酢酸などと共に撹拌すれば容易にアルデヒド
基に変換される。有機溶媒にはトルエン、ベンゼン、ヘ
キサンなどの炭化水素類や、テトラヒドロフラン、エチ
ルエーテル、塩化メチレンなどを挙げることができる。
これらの量割合は反応生成物、20%塩酸水、有機溶媒
がほぼ等容量であることが望ましい。
反応時間は5〜 120分とくには5〜60分がよい。
反応温度は0〜60℃であるが高温では重合したり、三
量体を形成したりすることがあるので0〜40℃が望ま
しい。反応終了後有機層を中性になるように、洗浄して
溶媒を除去するだけで自動的に高純度の2位のE体(3
)が生成する。このものは通常の単離操作すなわち蒸留
やカラムクロマトグラフィーなどの操作により精製され
ることができるし、更にアセテート体(5)に進む場合
には、濃縮操作で次工程へ進むことができる。The acetal (2-1 or 2-2) obtained here is then subjected to a hydrogenation reaction, and the catalysts used here include P-2 nickel, Raney nickel, Lindlar catalyst, Pd-C, and Pd-C. -BaSO4, Pd-Al2O
3. Pd-diatomaceous earth, Pd-BaCO3, Pd-Ca
Examples include CO3, Rh-C, Ru-C, and the like. Among these, P-2 nickel is superior. The amount of catalyst used is 0.001 to 0.2 equivalent relative to the reaction substrate, and the hydrogen pressure is in the range of normal pressure to 10 kg/cm2G, preferably 1 to 5 kg/cm2G. The reaction temperature is 0~
Although the temperature is 80℃, it greatly affects the reaction rate, so the temperature is 20~5℃.
0℃ is better. After the reaction, the catalyst is removed by conventional separation operations. In the hydrolysis reaction, the compound after hydrogenation is easily converted into an aldehyde group by dissolving it in an organic solvent and stirring it with aqueous hydrochloric acid, acetic acid, etc. Examples of organic solvents include hydrocarbons such as toluene, benzene, and hexane, as well as tetrahydrofuran, ethyl ether, and methylene chloride. It is desirable that the amounts of the reaction product, 20% hydrochloric acid water, and organic solvent are approximately equal in volume. The reaction time is preferably 5 to 120 minutes, particularly 5 to 60 minutes. The reaction temperature is 0 to 60°C, but it is preferably 0 to 40°C since polymerization or trimer formation may occur at high temperatures. After the reaction is complete, simply wash the organic layer to remove the solvent so that it becomes neutral, and the highly pure 2-position E isomer (3
) is generated. This product can be purified by ordinary isolation operations, such as distillation and column chromatography, and if the acetate (5) is to be obtained, it can be carried out to the next step by concentration.
【0008】アルデヒド体(3)の還元反応は一般に水
素化金属類を用いればよく、具体的には水素化リチウム
アルミニウム、水素化ホウ素ナトリウム、水素化ホウ素
リチウム、水素化ナトリウム、ジイソブチル水素化アル
ミニウム(DIBAL −H)などを各種溶媒中で反応
させればよいが、価格面、使いやすさの点で水素化ホウ
素ナトリウムのNaOH水溶液をアルデヒド体に対して
0.5〜 2.0倍モル、テトラヒドロフラン、エタノ
ールまたはメタノールをアルデヒド体1モルにつき 1
00〜 600g使用して−30〜40℃で還元する。
特に反応温度が高い場合、1、4−還元がおこり不純物
生成の原因となるので−30〜10℃が望ましい。The reduction reaction of the aldehyde (3) can generally be carried out using metal hydrides, specifically lithium aluminum hydride, sodium borohydride, lithium borohydride, sodium hydride, diisobutyl aluminum hydride ( DIBAL-H) etc. may be reacted in various solvents, but from the viewpoint of cost and ease of use, it is preferable to use a NaOH aqueous solution of sodium borohydride, 0.5 to 2.0 times the mole of the aldehyde, and tetrahydrofuran. , ethanol or methanol per mole of aldehyde
Using 00 to 600 g, reduce at -30 to 40°C. In particular, when the reaction temperature is high, 1,4-reduction occurs and causes the formation of impurities, so a temperature of -30 to 10°C is desirable.
【0009】アルコール体(4)のアセチル化は無溶媒
または不活性溶媒中、アセチル化剤として無水酢酸、ア
セチルブロミド、アセチルクロリドなどを用い通常アル
コール体に対して等モル〜3倍モル量用いて0〜 13
0℃の範囲で反応させる。溶媒としてはヘキサン、石油
エーテル、ベンゼン、トルエン、酢酸などが例示できる
が脱酸剤としてピリジン、トリエチルアミンなどの塩基
性化合物存在下に反応を行なってもよい。反応後は通常
の単離手段、例えば蒸留、カラムクロマトグラフィー、
溶媒抽出などにより容易に単離精製される。Acetylation of alcohol (4) is carried out without a solvent or in an inert solvent using acetic anhydride, acetyl bromide, acetyl chloride, etc. as an acetylating agent, usually in an equimolar to 3-fold molar amount relative to the alcohol. 0~13
The reaction is carried out in the range of 0°C. Examples of the solvent include hexane, petroleum ether, benzene, toluene, and acetic acid, but the reaction may be carried out in the presence of a basic compound such as pyridine and triethylamine as a deoxidizing agent. After the reaction, conventional isolation methods such as distillation, column chromatography,
Easily isolated and purified by solvent extraction etc.
【0010】0010
【実施例】以下に実施例を示す。
参考例1.Z−12−ヘプタデセン−1−インの製造:
反応器中に 250gのキシレンと 100μm以下に
分散された金属ナトリウム23gとを加えて 100〜
110℃に加熱し、ここにアセチレンガスを1L/分
の流速で1時間吹き込んだところ、ナトリウムアセチリ
ドがほぼ定量的に得られた。次いでこのナトリウムアセ
チリドのキシレン分散溶液を内容積2Lのオートクレー
ブに仕込み、液体アンモニア 600gを加えたのち温
度−10〜−5℃、圧力 3.5〜4kg/cm2Gに
保持し、ここに1−ブロモ−Z−10−ペンタデセン
289gを1時間かけて滴下し、終了後有機層のキシレ
ンを除去して、この濃縮物を減圧蒸留したところ沸点1
48〜 151℃/2mmHgのZ−12−ヘプタデセ
ン−1−イン 182.5g(収率78%)が得られた
。[Example] Examples are shown below. Reference example 1. Production of Z-12-heptadecen-1-yne:
Add 250 g of xylene and 23 g of metallic sodium dispersed to a particle size of 100 μm or less into a reactor.
When the mixture was heated to 110° C. and acetylene gas was blown therein at a flow rate of 1 L/min for 1 hour, sodium acetylide was obtained almost quantitatively. Next, this xylene dispersion solution of sodium acetylide was charged into an autoclave with an internal volume of 2 L, and after adding 600 g of liquid ammonia, the temperature was maintained at -10 to -5°C and the pressure was maintained at 3.5 to 4 kg/cm2G, and 1-bromo- Z-10-pentadecene
289 g was added dropwise over 1 hour, and after the completion of the addition, the xylene in the organic layer was removed, and this concentrate was distilled under reduced pressure, and the boiling point was 1.
182.5 g (yield 78%) of Z-12-heptadecen-1-yne was obtained at 48-151°C/2 mmHg.
【0011】参考例2.1,12−ヘプタデカジインの
製造:反応器を−40℃に冷却して液体アンモニア 6
00mlを入れ、−40℃から1,12−トリデカジイ
ン88gを加えた。
つぎに−40℃で金属ナトリウムの小片を少しづつ合計
12gを加えた。−34℃で1時間攪拌した後、ヨウ化
n−ブチル 100gをエチルエーテル 150mlに
溶かしたものを−34℃で滴下し、−34〜−32℃で
12時間攪拌した。反応後−40℃で塩化アンモニウム
30gを投入し、アンモニアを回収した。残渣に純水
300gを加えエチルエーテルで抽出し、濃縮後蒸留し
たところ、1,12−ヘプタデカジイン61gが得られ
た(沸点 150〜 153℃/2mmHg)収率52
.6%。Reference Example 2. Production of 1,12-heptadecadiine: The reactor was cooled to -40°C and liquid ammonia 6
00 ml, and 88 g of 1,12-tridecadiine was added from -40°C. Next, small pieces of metallic sodium were added little by little at -40°C, totaling 12 g. After stirring at -34°C for 1 hour, a solution of 100 g of n-butyl iodide dissolved in 150 ml of ethyl ether was added dropwise at -34°C, and the mixture was stirred at -34 to -32°C for 12 hours. After the reaction, 30 g of ammonium chloride was added at -40°C to recover ammonia. Pure water to the residue
300g was added, extracted with ethyl ether, concentrated and distilled to obtain 61g of 1,12-heptadecadiine (boiling point 150-153°C/2mmHg) yield 52
.. 6%.
【0012】実施例1−1.Z−13−オクタデセン−
2−インナールジエチルアセタール(2)の製造:反応
器に1モル相当のエチルマグネシウムブロミドのテトラ
ヒドロフラン溶液(テトラヒドロフラン 300g)を
仕込み、50〜60℃で 234gのZ−12−ヘプタ
デセン−1−インを滴下した。次に、60℃で1時間撹
拌したのちにオルソギ酸エチル150gを30分で滴下
し、90℃で7時間撹拌した。
反応後、NH4Cl 70g、純水 400gを加えて
分液し、その有機層のテトラヒトロフランを減圧下除去
したのち蒸留したところ、Z−13−オクタデセン−2
−インナールジエチルアセタール 269gが得られた
(収率80%、沸点 165〜 170℃/0.1mm
Hg)。Example 1-1. Z-13-octadecene-
Production of 2-innal diethyl acetal (2): A reactor was charged with a tetrahydrofuran solution (tetrahydrofuran 300 g) of ethylmagnesium bromide equivalent to 1 mole, and 234 g of Z-12-heptadecen-1-yne was added dropwise at 50 to 60°C. did. Next, after stirring at 60°C for 1 hour, 150 g of ethyl orthoformate was added dropwise over 30 minutes, followed by stirring at 90°C for 7 hours. After the reaction, 70 g of NH4Cl and 400 g of pure water were added to separate the layers, and the organic layer was distilled after removing tetrahydrofuran under reduced pressure. Z-13-octadecene-2
269 g of -innal diethyl acetal was obtained (yield 80%, boiling point 165-170°C/0.1 mm)
Hg).
【0013】実施例1−2.E,Z−2,13−オクタ
デカジエナール(3)の製造:オートクレーブ反応器に
Z−13−オクタデセン−2−インナールジエチルアセ
タール( 336g)と、エタノール 200g中で、
酢酸ニッケル15gを水素化ホウ素ナトリウム 2.8
gで還元して得られたP−2ニッケルを加え、エチレン
ジアミン4gを加えて、水素圧5kg/cm2G で水
素を導入した。水素が減少しなくなった時点で反応をや
め、n−ヘキサン 300g、純水 300gを加えて
分液して、その有機層を取り、n−ヘキサンを減圧によ
り除去した。次に反応器に濃縮液とテトラヒドロフラン
300ml、10% HCl水 300mlを加え、
20〜25℃で1時間撹拌した。反応後10%NaOH
水でpH7に調整後分液して、その有機層を取り濃縮後
蒸留したところ、E,Z−2,13−オクタデカジエナ
ール 215gが得られた。純度93%、沸点 170
〜 174℃/1mmHg、収率82%。Example 1-2. Production of E,Z-2,13-octadecadienal (3): In an autoclave reactor, Z-13-octadecene-2-innal diethyl acetal (336 g) and 200 g of ethanol were added.
15g of nickel acetate to 2.8g of sodium borohydride
P-2 nickel obtained by reduction with 5 kg/cm2G was added, 4 g of ethylenediamine was added, and hydrogen was introduced at a hydrogen pressure of 5 kg/cm2G. The reaction was stopped when hydrogen no longer decreased, 300 g of n-hexane and 300 g of pure water were added to separate the layers, the organic layer was taken, and the n-hexane was removed under reduced pressure. Next, add the concentrate, 300 ml of tetrahydrofuran, and 300 ml of 10% HCl water to the reactor.
Stirred at 20-25°C for 1 hour. 10% NaOH after reaction
After adjusting the pH to 7 with water, the organic layer was separated, concentrated, and distilled to obtain 215 g of E,Z-2,13-octadecadienal. Purity 93%, boiling point 170
~174°C/1mmHg, yield 82%.
【0014】実施例2−1.2−13−オクタデカジイ
ナ−ルジエチルアセタール(2−2)の製造:反応器に
0.27モル相当のエチルマグネシウムブロミドのテト
ラヒドロフラン溶液(テトラヒドロフラン78g)を仕
込み、50〜60℃で60gの1,12−ヘプタデカジ
インを滴下した。次に、60℃で1時間撹拌したのちに
オルソギ酸エチル40gを30分で滴下し、90℃で7
時間撹拌した。反応後、NH4Cl20g、純水 10
0gを加えて分液し、その有機層のテトラヒトロフラン
を減圧下除去したのち蒸留したところ、2,13−オク
タデカジイナールジエチルアセタール70gが得られた
(収率81%、沸点 178〜 186℃/0.4mm
Hg)。Example 2-1. Production of 2-13-octadecadiinal diethyl acetal (2-2): A solution of ethylmagnesium bromide in tetrahydrofuran (78 g of tetrahydrofuran) equivalent to 0.27 mol was charged in a reactor, 60 g of 1,12-heptadecadiine was added dropwise at 60°C. Next, after stirring at 60°C for 1 hour, 40g of ethyl orthoformate was added dropwise over 30 minutes, and the mixture was heated to 90°C for 7 hours.
Stir for hours. After reaction, NH4Cl20g, pure water 10
0 g was added and the liquid was separated, and the tetrahydrofuran in the organic layer was removed under reduced pressure and then distilled to obtain 70 g of 2,13-octadecadiinal diethyl acetal (yield 81%, boiling point 178-186 °C/0.4mm
Hg).
【0015】実施例2−2.E,Z−2,13−オクタ
デカジエナール(3)の製造:オートクレーブ反応器に
2,13−オクタデカジイナールジエチルアセタール(
70g)と、エタノール50g中で、酢酸ニッケル 3
.9gを水素化ホウ素ナトリウム 0.8gで還元して
得られたP−2ニッケルを加え、エチレンジアミン1g
を加えて、水素圧5kg/cm2G で水素を導入した
。水素が減少しなくなった時点で反応をやめ、n−ヘキ
サン 100g、純水 100gを加えて分液して、そ
の有機層を取り、n−ヘキサンを減圧により除去した。
次に反応器に上記濃縮液とテトラヒドロフラン 100
ml、10% HCl水 100gを加え、20〜25
℃で1時間撹拌した。反応後10%NaOH水でpH7
に調整後分液して、その有機層を取り濃縮後蒸留したと
ころ、E,Z−2,13−オクタデカジエナール53g
が得られた。純度93%、沸点 175〜 179℃/
1.2mmHg、収率80%。Example 2-2. Production of E,Z-2,13-octadecadienal (3): 2,13-octadecadienal diethyl acetal (
70g) and 3 nickel acetate in 50g of ethanol.
.. Add P-2 nickel obtained by reducing 9g with 0.8g of sodium borohydride, and add 1g of ethylenediamine.
was added, and hydrogen was introduced at a hydrogen pressure of 5 kg/cm2G. The reaction was stopped when hydrogen no longer decreased, 100 g of n-hexane and 100 g of pure water were added to separate the layers, the organic layer was taken, and the n-hexane was removed under reduced pressure. Next, the above concentrate and tetrahydrofuran were added to the reactor.
ml, add 100g of 10% HCl water, 20-25
Stirred at ℃ for 1 hour. After reaction, adjust the pH to 7 with 10% NaOH water.
When the organic layer was taken, concentrated and distilled, 53g of E,Z-2,13-octadecadienal was obtained.
was gotten. Purity 93%, boiling point 175-179℃/
1.2 mmHg, yield 80%.
【0016】実施例3.E,Z−2,13−オクタデカ
ジエニルアセテート(5)の製造:反応器にE,Z−2
,13−オクタデカジエナール 262gとテトラヒド
ロフラン 100gを仕込み、0℃に冷却した中へ、水
素化ホウ素ナトリウム18gを1%NaOH液 150
gにとかした溶液を5℃を超えないように滴下した。滴
下後5℃で1時間撹拌した。次に50%酢酸水60gを
ゆっくり滴下して、未反応の水素化ホウ素ナトリウムを
消費させた。分液して有機層を取り減圧下濃縮してアル
コール体(4)を得た。次いで、濃縮したアルコール体
(4)とn−ヘキサン 500ml、トリエチルアミン
110gを仕込み、40℃を超えないようにして塩化ア
セチル78.5gを滴下した。滴下終了後40℃で3時
間撹拌して、純水 400gを加えて分液し、5%Na
HCO3水400gで洗浄後、n−ヘキサンを濃縮後蒸
留したところ、E,Z−2,13−オクタデカジエニル
アセテート 234gが得られた。(収率76%)沸点
179〜 183℃/1mmHg、純度 E,Z:9
2.5%、 E,E: 3.3%、 Z,E:1.2%
、Z,Z: 1.8%であった。Example 3. Production of E,Z-2,13-octadecadienyl acetate (5): E,Z-2 in the reactor
, 262 g of 13-octadecadienal and 100 g of tetrahydrofuran were cooled to 0°C, and 18 g of sodium borohydride was added to 150 g of 1% NaOH solution.
A solution dissolved in g was added dropwise so that the temperature did not exceed 5°C. After the dropwise addition, the mixture was stirred at 5°C for 1 hour. Next, 60 g of 50% aqueous acetic acid was slowly added dropwise to consume unreacted sodium borohydride. The organic layer was separated and concentrated under reduced pressure to obtain alcohol (4). Next, the concentrated alcohol (4), 500 ml of n-hexane, and 110 g of triethylamine were charged, and 78.5 g of acetyl chloride was added dropwise without exceeding 40°C. After dropping, stir at 40°C for 3 hours, add 400g of pure water to separate the liquids, and add 5% Na.
After washing with 400 g of HCO3 water, n-hexane was concentrated and distilled to obtain 234 g of E,Z-2,13-octadecadienyl acetate. (Yield 76%) Boiling point 179-183℃/1mmHg, Purity E, Z: 9
2.5%, E,E: 3.3%, Z,E: 1.2%
, Z, Z: 1.8%.
【0017】[0017]
【発明の効果】このように本発明によれば昆虫性フェロ
モン成分の1つであるE,Z−2,13−オクタデカジ
エナールおよびE,Z−2,13−オクタデカジエニル
アセテートのようなE,Z−2,13−オクタデカジエ
ン化合物を立体特異的に容易に製造することができる。As described above, according to the present invention, insect pheromone components such as E,Z-2,13-octadecadienal and E,Z-2,13-octadecadienyl acetate, E,Z-2,13-octadecadiene compounds can be easily produced stereospecifically.
Claims (3)
)9C≡CMgX(式中Xはハロゲンを示す)とCH(
OR)3 (式中Rはメチル基またはエチル基を示す)
で示されるオルソギ酸エステルとを反応させてZ−13
−オクタデセン−2−インナールジエチルアセタールと
し、水素添加した後、加水分解してE,Z−2,13−
オクタデカジエナールとすることを特徴とするE,Z−
2,13−オクタデカジエン化合物の製造方法。[Claim 1] CH3(CH2)3HC=CH(CH2
)9C≡CMgX (in the formula, X represents a halogen) and CH(
OR)3 (in the formula, R represents a methyl group or an ethyl group)
Z-13 is obtained by reacting with the orthoformic acid ester shown by
-octadecene-2-innal diethyl acetal, hydrogenated and then hydrolyzed to form E,Z-2,13-
E, Z- characterized by being octadecadienal
A method for producing a 2,13-octadecadiene compound.
≡CMgX(式中Xはハロゲンを示す)とCH(OR)
3 (式中Rはメチル基またはエチル基を示す)で示さ
れるオルソギ酸エステルとを反応させて2,13−オク
タデカジイナールジエチルアセタールとし、水素添加し
た後、加水分解してE,Z−2,13−オクタデカジエ
ナールとすることを特徴とするE,Z−2,13−オク
タデカジエン化合物の製造方法。[Claim 2] CH3(CH2)3C≡C(CH2)9C
≡CMgX (in the formula, X represents halogen) and CH(OR)
3 (wherein R represents a methyl group or an ethyl group) is reacted with orthoformic acid ester to form 2,13-octadecadiinal diethyl acetal, which is hydrogenated and then hydrolyzed to form E,Z- A method for producing an E,Z-2,13-octadecadiene compound, characterized in that it is 2,13-octadecadienal.
E,Z−2,13−オクタデカジエナールを水素化金属
で還元した後、アセチル化してE,Z−2,13−オク
タデカジエニルアセテートとすることを特徴とするE,
Z−2,13−オクタデカジエン化合物の製造方法。3. E,Z-2,13-octadecadienal obtained by the method according to claim 1 or 2 is reduced with a metal hydride and then acetylated to obtain E,Z-2,13- E, characterized in that it is octadecadienyl acetate,
A method for producing Z-2,13-octadecadiene compound.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4621791A JP2868161B2 (en) | 1991-02-19 | 1991-02-19 | Method for producing E, Z-2,13-octadecadiene compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4621791A JP2868161B2 (en) | 1991-02-19 | 1991-02-19 | Method for producing E, Z-2,13-octadecadiene compound |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04330032A true JPH04330032A (en) | 1992-11-18 |
JP2868161B2 JP2868161B2 (en) | 1999-03-10 |
Family
ID=12740942
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4621791A Expired - Fee Related JP2868161B2 (en) | 1991-02-19 | 1991-02-19 | Method for producing E, Z-2,13-octadecadiene compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2868161B2 (en) |
-
1991
- 1991-02-19 JP JP4621791A patent/JP2868161B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2868161B2 (en) | 1999-03-10 |
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