WO2024040754A1 - Procédé de synthèse de cis-2-méthyl-7-octadécène et de cis-7,8-époxy-2-méthyloctadécane - Google Patents
Procédé de synthèse de cis-2-méthyl-7-octadécène et de cis-7,8-époxy-2-méthyloctadécane Download PDFInfo
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- WO2024040754A1 WO2024040754A1 PCT/CN2022/131263 CN2022131263W WO2024040754A1 WO 2024040754 A1 WO2024040754 A1 WO 2024040754A1 CN 2022131263 W CN2022131263 W CN 2022131263W WO 2024040754 A1 WO2024040754 A1 WO 2024040754A1
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- WIPO (PCT)
- Prior art keywords
- cis
- methyl
- octadecene
- synthesis method
- reaction
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- XDBKLFODBADBED-YPKPFQOOSA-N (z)-2-methyloctadec-7-ene Chemical compound CCCCCCCCCC\C=C/CCCCC(C)C XDBKLFODBADBED-YPKPFQOOSA-N 0.000 title claims abstract description 42
- HFOFYNMWYRXIBP-MOPGFXCFSA-N 2-methyl-7S,8R-Epoxy-octadecane Chemical compound CCCCCCCCCC[C@H]1O[C@H]1CCCCC(C)C HFOFYNMWYRXIBP-MOPGFXCFSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 150000007530 organic bases Chemical class 0.000 claims abstract description 13
- 230000009471 action Effects 0.000 claims abstract description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 60
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 36
- -1 phosphonium salt compound Chemical class 0.000 claims description 29
- 239000003208 petroleum Substances 0.000 claims description 28
- 238000001308 synthesis method Methods 0.000 claims description 26
- 238000004440 column chromatography Methods 0.000 claims description 19
- 239000012141 concentrate Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 16
- 238000007363 ring formation reaction Methods 0.000 claims description 16
- 239000000741 silica gel Substances 0.000 claims description 16
- 229910002027 silica gel Inorganic materials 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 238000006467 substitution reaction Methods 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 150000004965 peroxy acids Chemical class 0.000 claims description 11
- 229940038384 octadecane Drugs 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- 238000012805 post-processing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 4
- 230000005526 G1 to G0 transition Effects 0.000 claims description 4
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 3
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 3
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 3
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 claims description 3
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 claims description 3
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 claims description 3
- LVKCSZQWLOVUGB-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].C[CH-]C LVKCSZQWLOVUGB-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000001209 o-nitrophenyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])[N+]([O-])=O 0.000 claims description 3
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 6
- 238000010189 synthetic method Methods 0.000 claims 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 2
- NRUBUZBAZRTHHX-UHFFFAOYSA-N lithium;propan-2-ylazanide Chemical compound [Li+].CC(C)[NH-] NRUBUZBAZRTHHX-UHFFFAOYSA-N 0.000 claims 1
- 150000003003 phosphines Chemical class 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- XDBKLFODBADBED-BUHFOSPRSA-N (e)-2-methyloctadec-7-ene Chemical compound CCCCCCCCCC\C=C\CCCCC(C)C XDBKLFODBADBED-BUHFOSPRSA-N 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 description 14
- 235000011152 sodium sulphate Nutrition 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 241000721703 Lymantria dispar Species 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 150000003839 salts Chemical group 0.000 description 5
- 239000002274 desiccant Substances 0.000 description 4
- 239000000877 Sex Attractant Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012267 brine Substances 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- JKVYAKJCVCKKGL-UHFFFAOYSA-N 2-hexadecyl-2-methyloxirane Chemical compound CCCCCCCCCCCCCCCCC1(C)CO1 JKVYAKJCVCKKGL-UHFFFAOYSA-N 0.000 description 1
- HFOFYNMWYRXIBP-RBUKOAKNSA-N 2-methyl-7R,8S-Epoxy-octadecane Chemical compound CCCCCCCCCC[C@@H]1O[C@@H]1CCCCC(C)C HFOFYNMWYRXIBP-RBUKOAKNSA-N 0.000 description 1
- WQMKDHREUPHQQE-UHFFFAOYSA-N 2-methyloctadec-7-yne Chemical compound CCCCCCCCCCC#CCCCCC(C)C WQMKDHREUPHQQE-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- BYRPTKZOXNFFDB-UHFFFAOYSA-N lithium;bis(trimethylsilyl)azanide;oxolane Chemical compound [Li+].C1CCOC1.C[Si](C)(C)[N-][Si](C)(C)C BYRPTKZOXNFFDB-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical compound CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/34—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen reacting phosphines with aldehydes or ketones, e.g. Wittig reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
Definitions
- the invention relates to the technical field of organic synthesis, and in particular to a synthesis method of cis-2-methyl-7-octadecane and cis-7,8-epoxy-2-methyloctadecane.
- the racemic gypsy moth sex pheromone, cis-7,8-epoxy-2-methyloctadecane is often used. Therefore, the key intermediate cis- 2-Methyl-7-octadecene is used as raw material, and the target product cis-7,8-epoxy-2-methyloctadecane is synthesized through epoxidation reaction.
- the key intermediate cis-2-methyl-7-octadecene is usually made of 2-methyl-7-octadecyne as the raw material, and is hydrogenated in the cis form under the action of Lindler catalyst, or using a highly hindered boron reagent. Reduction is obtained (Chemistry of Natural Compounds 1983,19,593; J.Chem.Ecolo.1983,9(2),211.).
- the object of the present invention is to provide a synthesis method of cis-2-methyl-7-octadecane and cis-7,8-epoxy-2-methyloctadecane.
- the synthesis method of cis-2-methyl-7-octadecene provided by the invention can avoid the generation of trans-2-methyl-7-octadecene, thereby improving the synthesis of cis-7,8-epoxy-2 -Yield and purity of methyloctadecane.
- the invention provides a synthesis method of cis-2-methyl-7-octadecene, which includes the following steps:
- the N-sulfonylhydrazone compound with the structure shown in formula a and the phosphonium salt compound with the structure shown in formula b undergo a substitution reaction to obtain cis-2-methyl-7-octadecene;
- Ar is an aromatic group
- the Ar is phenyl, p-methylphenyl, p-cumylphenyl, p-tert-butylphenyl, o-methylphenyl, o-cumylphenyl, o-tert-butylphenyl, 1-naphthyl, 2-naphthyl, o-chlorophenyl, o-nitrophenyl, p-methoxyphenyl, o-methoxyphenyl or 2,4,6-trimethylphenyl.
- the organic base is sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, n-butyllithium, tert-butyllithium, phenyllithium, lithium diisopropylamide, and hexamethyldisilamine
- the molar ratio of the N-sulfonylhydrazone compound having the structure represented by formula a and the phosphonium salt compound having the structure represented by formula b is 1:1 to 1.2.
- the molar ratio of the N-sulfonylhydrazone compound having the structure represented by formula a to the organic base is 1:1 to 1.2.
- the temperature of the substitution reaction is -80 ⁇ -30°C and the time is 4 ⁇ 6 hours.
- the invention provides a synthesis method of cis-7,8-epoxy-2-methyloctadecane, which includes the following steps:
- cis-2-methyl-7-octadecane undergoes a cyclization reaction to obtain cis-7,8-epoxy-2-methyloctadecane.
- the peroxyacid is one or more selected from the group consisting of peroxyformic acid, peracetic acid, perbenzoic acid and m-chloroperoxybenzoic acid.
- the molar ratio of cis-2-methyl-7-octadecene and peroxyacid is 1:1.2-1.8.
- the temperature of the cyclization reaction is -10 to 30°C, and the time is 1 to 5 hours.
- the invention provides a synthesis method of cis-2-methyl-7-octadecene, which includes the following steps: under the action of an organic base, an N-sulfonylhydrazone compound with a structure shown in formula a and a compound with formula b
- the phosphine salt compound with the structure shown undergoes a substitution reaction to obtain cis-2-methyl-7-octadecene.
- the invention uses N-sulfonyl hydrazone and phosphonium salt as raw materials, and under the action of organic base, can obtain cis-2-methyl-7-octadecene in one step, and can avoid trans-2-methyl-7 -Generation of octadecene.
- the yield and purity of cis-2-methyl-7-octadecene obtained by the present invention are both relatively high. Among them, the yield of cis-2-methyl-7-octadecene is 68 to 96%, and the purity is higher than 98.8%. At the same time, the raw materials used in the synthesis method of the present invention are easily available and the cost is low. It has the advantages of short synthesis route, simple operation, convenient product separation and purification, wide applicability of reaction substrates, etc., and is suitable for industrial mass production.
- the invention provides a synthesis method of cis-7,8-epoxy-2-methyloctadecane.
- cis-2-methyl-7-octadecane is synthesized according to the above method, and then the peroxyacid Under the action of , cis-2-methyl-7-octadecane undergoes a cyclization reaction to obtain cis-7,8-epoxy-2-methyloctadecane.
- cis-2-methyl-7-octadecane has higher purity
- the yield and purity of cis-7,8-epoxy-2-methyloctadecane obtained in the present invention are relatively high, among which cis-7,8-epoxy-2-methyloctadecane has higher purity.
- the yield of formula-7,8-epoxy-2-methyloctadecane is higher than 90%, and the purity is higher than 99%.
- the synthesis method provided by the invention is simple to operate, low in cost, and suitable for industrial mass production.
- Figure 1 shows the synthetic route of cis-7,8-epoxy-2-methyloctadecane
- Figure 2 is the carbon spectrum NMR spectrum of cis-7,8-epoxy-2-methyloctadecane obtained in Example 1.
- the invention provides a synthesis method of cis-2-methyl-7-octadecene, which includes the following steps:
- the N-sulfonylhydrazone compound with the structure shown in formula a and the phosphonium salt compound with the structure shown in formula b undergo a substitution reaction to obtain cis-2-methyl-7-octadecene;
- Ar is an aromatic group
- the Ar is preferably phenyl, p-methylphenyl, p-isopropylphenyl, p-tert-butylphenyl, o-methylphenyl, o-isopropylphenyl, o-tert-butyl Phenyl, 1-naphthyl, 2-naphthyl, o-chlorophenyl, o-nitrophenyl, p-methoxyphenyl, o-methoxyphenyl or 2,4,6-trimethylphenyl.
- the organic base is sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, n-butyllithium, tert-butyllithium, phenyllithium, lithium diisopropylamide, hexamethyldimethyl Lithium silamide, sodium hexamethyldisilamide, potassium hexamethyldisilamide, benzyllithium, methylmagnesium bromide, ethylmagnesium bromide, isopropylmagnesium bromide and phenyl bromide
- magnesium magnesium
- the molar ratio of the N-sulfonylhydrazone compound having the structure represented by formula a and the phosphonium salt compound having the structure represented by formula b is preferably 1:1 to 1.2, more preferably 1:1.1.
- the molar ratio of the N-sulfonylhydrazone compound having the structure represented by formula a to the organic base is preferably 1:1 to 1.2, more preferably 1:1.1.
- the organic solvent used in the substitution reaction is preferably one of toluene, trifluoromethylbenzene, fluorobenzene, tetrahydrofuran, methyltetrahydrofuran, methyl tert-butyl ether and ethylene glycol dimethyl ether, or Several kinds.
- the substitution reaction is preferably carried out under a protective atmosphere, and the protective atmosphere is preferably argon.
- the preferred mixing method is: first mix the phosphonium salt compound having the structure represented by formula b with an organic base and an organic solvent, and then add the N-sulfonylhydrazone compound having the structure represented by formula a.
- the temperature of the substitution reaction is preferably -80 to -30°C, more preferably -80 to -60°C; the time is preferably 4 to 6 hours, more preferably 5 hours.
- the present invention after the substitution reaction, the present invention preferably performs post-treatment on the obtained substitution reaction liquid, and the post-treatment preferably includes the following steps:
- the organic solvent of the quenched reaction solution is removed, the remaining liquid is mixed with petroleum ether, and solid-liquid separation, washing, drying and concentration are performed in sequence.
- the obtained concentrate is purified by column chromatography to obtain cis-2-methyl-7- Pure octadecene.
- the solid-liquid separation method is preferably suction filtration; the washing detergent is preferably salt water; the drying is preferably desiccant drying, and the desiccant is preferably sodium sulfate.
- the present invention has no special requirements for the concentration method, and any concentration method well known to those skilled in the art can be used.
- the stationary phase used for column chromatography purification is preferably silver nitrate-loaded 400 mesh silica gel;
- the mobile phase is preferably petroleum ether and ethyl acetate, and the volume ratio of petroleum ether and ethyl acetate is preferably 150: 1.
- the invention provides a synthesis method of cis-7,8-epoxy-2-methyloctadecane, which includes the following steps:
- cis-2-methyl-7-octadecane undergoes a cyclization reaction to obtain cis-7,8-epoxy-2-methyloctadecane.
- cis-2-methyl-7-octadecane undergoes a cyclization reaction to obtain cis-7,8-epoxy-2-methyloctadecane.
- the peroxyacid is preferably one or more of peroxyformic acid, peracetic acid, perbenzoic acid and m-chloroperoxybenzoic acid.
- the molar ratio of cis-2-methyl-7-octadecene and peroxyacid is preferably 1:1.2-1.8, more preferably 1:1.4-1.6.
- the organic solvent used in the cyclization reaction is preferably toluene, trifluoromethylbenzene, fluorobenzene, tetrahydrofuran, methyltetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, 1,2 -One or more of dichloroethane, chloroform and methylene chloride.
- the temperature of the cyclization reaction is preferably -10 ⁇ 30°C, more preferably 0 ⁇ 10°C; the time is preferably 1 ⁇ 5h, more preferably 2 ⁇ 4h.
- the present invention preferably performs post-processing on the obtained cyclization reaction liquid, and the post-processing preferably includes the following steps:
- the detergent used for washing is preferably a sodium carbonate aqueous solution, and the number of washings is preferably 2 times.
- the drying is preferably drying with a desiccant, and the desiccant is preferably sodium sulfate.
- the present invention has no special requirements for the concentration method, and any concentration method well known to those skilled in the art can be used.
- the stationary phase for column chromatography purification is preferably 200 mesh silica gel
- the mobile phase is preferably petroleum ether and ethyl acetate
- the volume ratio of petroleum ether and ethyl acetate is preferably 20:1.
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Abstract
La présente invention relève du domaine technique de la synthèse organique, et concerne un procédé de synthèse de cis-2-méthyl-7-octadécène et de cis-7,8-époxy-2-méthyloctadécane. La présente invention utilise des sels de N-sulfonylhydrazone et de phosphine comme matières premières, ce qui permet d'obtenir du cis-2-méthyl-7-octadécène par un procédé en une étape sous l'action d'une base organique sans générer de trans-2-méthyl-7-octadécène. Le rendement et la pureté du cis-2-méthyl-7-octadécène obtenu selon la présente invention sont tous deux élevés, le rendement du cis-2-méthyl-7-octadécène est de 68 à 96 %, et la pureté du cis-2-méthyl-7-octadécène est supérieure à 98,8 %. Le cis-2-méthyl-7-octadécène a une pureté élevée, le rendement et la pureté du cis-7,8-époxy-2-méthyloctadécane obtenus selon la présente invention sont tous deux élevés, le rendement du cis-7,8-époxy-2-méthyloctadécane est supérieur à 90 %, et la pureté du cis-7,8-époxy-2-méthyloctadécane est supérieure à 99 %.
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US5463149A (en) * | 1993-07-20 | 1995-10-31 | Shin-Etsu Chemical Co., Ltd. | 1-halo-cis-3-tetradecenes and processes for the preparation of cis-olefin compounds by using same |
US20130231499A1 (en) * | 2012-03-05 | 2013-09-05 | California Institute Of Technology | Synthesis of z-olefin-containing lepidopteran insect pheromones |
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BE788547A (fr) * | 1971-09-10 | 1973-03-08 | Bayer Ag | Procede de preparation de cis-7,8-epoxy-2-methyloctadecane |
DE2758882A1 (de) * | 1977-12-30 | 1979-07-05 | Basf Ag | Verfahren zur herstellung von cis-7,8-epoxy-2-methyloctadecan |
CN1258294A (zh) * | 1997-05-30 | 2000-06-28 | 万有制药株式会社 | 2-氧代咪唑衍生物 |
ITMI20031975A1 (it) * | 2003-10-14 | 2005-04-15 | Ind Chimica Srl | Processo per la preparazione del d-cloprostenolo |
KR101109375B1 (ko) * | 2009-06-17 | 2012-01-30 | 경기대학교 산학협력단 | (+)-디스파루어 및 이의 거울상 이성질체와 트랜스-이성질체의 제조 방법 |
CN102321050B (zh) * | 2011-06-02 | 2014-08-13 | 厦门大学 | 一种舞毒蛾性信息素的合成方法 |
CN110724042A (zh) * | 2019-12-09 | 2020-01-24 | 中国林业科学研究院森林生态环境与保护研究所 | 一种杨小舟蛾性信息素活性成分的合成方法 |
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US5463149A (en) * | 1993-07-20 | 1995-10-31 | Shin-Etsu Chemical Co., Ltd. | 1-halo-cis-3-tetradecenes and processes for the preparation of cis-olefin compounds by using same |
US20130231499A1 (en) * | 2012-03-05 | 2013-09-05 | California Institute Of Technology | Synthesis of z-olefin-containing lepidopteran insect pheromones |
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I. UJVARY, E. VOIGT, K. LESKO: "ChemInform Abstract: Synthesis of a Possible Degradation Product of (.+-.)-Disparlure, the Sex Pheromone of the Gypsy Moth, Lymantria dispar.", CHEMINFORM, ELECTROCHEMICAL SOCIETY, vol. 19, no. 41, 11 October 1988 (1988-10-11), pages 152, XP009553001, ISSN: 0931-7597, DOI: 10.1002/chin.198841318 * |
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