CN1019975C - 环戊烷衍生物的制备方法 - Google Patents
环戊烷衍生物的制备方法 Download PDFInfo
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- CN1019975C CN1019975C CN89107874A CN89107874A CN1019975C CN 1019975 C CN1019975 C CN 1019975C CN 89107874 A CN89107874 A CN 89107874A CN 89107874 A CN89107874 A CN 89107874A CN 1019975 C CN1019975 C CN 1019975C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 14
- 125000001511 cyclopentyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 26
- -1 cyano, hydroxy Chemical group 0.000 abstract description 16
- 125000000217 alkyl group Chemical group 0.000 abstract description 10
- 230000000855 fungicidal effect Effects 0.000 abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 7
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 125000003282 alkyl amino group Chemical group 0.000 abstract description 3
- 125000004644 alkyl sulfinyl group Chemical group 0.000 abstract description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 abstract description 3
- 125000004414 alkyl thio group Chemical group 0.000 abstract description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 abstract 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 abstract 2
- 125000001589 carboacyl group Chemical group 0.000 abstract 2
- 125000004663 dialkyl amino group Chemical group 0.000 abstract 2
- 125000004438 haloalkoxy group Chemical group 0.000 abstract 2
- 125000001188 haloalkyl group Chemical group 0.000 abstract 2
- 239000000417 fungicide Substances 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 20
- 229940073608 benzyl chloride Drugs 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000004480 active ingredient Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000005201 scrubbing Methods 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- 239000000654 additive Substances 0.000 description 4
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- 238000007701 flash-distillation Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004563 wettable powder Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 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 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical group 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
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- 150000002148 esters Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000004436 sodium atom Chemical group 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
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- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
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- 241000233866 Fungi Species 0.000 description 1
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- 241001136616 Methone Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
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- SATQNYRZLIROHO-UHFFFAOYSA-N [NH4+].[Na].OS([O-])=O Chemical class [NH4+].[Na].OS([O-])=O SATQNYRZLIROHO-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical class [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000002521 alkyl halide group Chemical group 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/14—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by free hydroxyl radicals
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- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/20—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom three- or four-membered rings
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- 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
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
本发明提供一种通式为(其中n表示0-5的整数，每个R表示卤原子硝基、氰基、羟基、烷基、卤烷基、烷氧基、卤烷氧基、氨基、烷基氨基、二烷基氨基、烷氧基羰基、羧基、烷酰基、烷基硫代，烷基亚磺酰、烷基磺酰基、氨基甲酰基、烷基酰胺基、环烷基或苯基，R1和R2分别表示氢原子或烷基，和R5表示氢原子或烷基或环烷基)的新环戊烷衍生物的制备方法；含上述化合物的组合物和用它们作杀菌剂、式I的化合物也可用作制备某些具有杀菌活性的环戊烷衍生物的中间体。
Description
本发明涉及某些环戊烷衍生物、它们的制备方法、含上述化合物的组合物和用它们作杀菌剂。
本发明提供通式为：
（其中n表示0～5的整数;每个R表示卤原子、硝基、氰基、羟基、烷基、卤烷基、烷氧基、卤烷氧基、氨基、烷基氨基、二烷基氨基、烷氧基碳基、羧基、烷酰基、烷基硫代、烷基亚磺酰基、烷基磺酰基、氨基甲酰基、烷基酰胺基、环烷基或苯基团;R1和R2分别表示氢原子或烷基;和R5表示氢原子或烷基或环烷基团）的化合物。
当上述任何一个取代基表示或含烷基取代基时，该取代基是直链或支链，并可含高达12，优选的为6，且特别优选的达4个碳原子。环烷基取代基可含3-8，优选的为3～6个碳原子。
R1和R2分别表示氢原子或C1-4烷基，最好是甲基。
R表示卤素，最好表示氯原子。
优选的R5表示氢原子或C1-6烷基。
特别优选的式Ⅰ化合物的辅助基团是其中的n是1，R表示氯原子优选是在苯环4-位置取代的氯原子，R1和R2两者都表示氢原子或两者都表示甲基;和R5表示甲基。
本发明还提供了一种上面定义的式Ⅰ化合物的制备方法，该方法包括将通式：
（其中n、R、R1、R2和R5的定义如上）的化合物与过酸反应。
可使用多达3，优选的为1～3当量的过酸。优选的过酸是过乙酸、过苯甲酸或过苯二甲酸。就过乙酸来说，如果需要，通过过氧化氢与乙酸反应可就地产生过乙酸。
本发明的方法可在溶剂存在下完成。适合的溶剂包括氯化的溶剂，诸如二氯甲烷和三氯甲烷、酯和芳香烃。
如果在室温至溶剂回流温度的条件下，可方便地进行该反应，优选的温度是30～70℃。
在有极性溶剂的情况下，将通式
（其中n、R、R1、R2和R5的定义加上，并且X和Y分别表示卤素，优选的是氯或溴原子）的化合物与通式：
（其中R5的定义如上，M表示碱金属，优选的是钠原子）的化合物进行加热，可方便地制得式Ⅱ的化合物。优选的极性溶剂是通式：
（其中R5的定义如上）的化合物。R5在式Ⅴ或式Ⅵ中的含义最好相同。例如，如果式Ⅴ化合物是甲醇钠，优选的式Ⅵ溶剂是甲醇。式Ⅱ化合物及其制备方法涉及待审查专利申请T616。
在有如上定义的溶剂Ⅵ的情况下，在优选的温度范围0～20℃下，将如上定义的式Ⅳ的化合物与如上定义的式Ⅴ的化合物反应。可方便地制得式Ⅲ的化合物、式Ⅲ化合物及其制备方法涉及待审查专利申请T616。
将通式：
（其中n、R、R1和R2的定义如上）的化合物与化合物XY（其中X和Y的定义如上）反应，可方便地制得式Ⅳ的化合物。此外，式Ⅳ化合物可以就地产生。然后，采用一釜合成法，在有上述式Ⅵ溶剂的情况下，将该化合物与式Ⅴ化合物一起加热，可生成式Ⅱ的化合物。式Ⅳ化合物及其制备方法涉及待审查专利申请T616。
将通式
（其中n、R、R1和R2的定义如上，且R4表示烷基，优选的是C1-4烷基）的化合物与适合的还原剂（例如，复合的金属氢化物，诸如氢化铝锂或氢化铝钠，或与催化剂相结合的氢）进行反应，可方便地制得式Ⅶ的化合物，然后水解该反应混合物。式Ⅶ化合物及其制备方法及待审查专利申请T616。
在有酸（诸如硫酸、P-甲苯磺酸）或离子交换树脂的情况下，将通式
（其中n、R、R1和R2的定义如上）的化合物与通式
（其中R4的定义如上）的化合物反应，可方便地制得式Ⅷ的化合物。式Ⅷ的化合物及其制备方法涉及待审查的专利申请T616。
在有适当碱（诸如氢氧化钾）的情况下，将通式
（其中R1和R2的定义如上）的化合物与通式
（其中R和n的定义如上，且L表示适当的离去基团）的化合物反应，可方便地制得式Ⅸ的化合物。
式Ⅴ、Ⅵ、Ⅹ、Ⅺ、ⅩⅢ的化合物和化合物XY是已知化合物，或能用与已知方法类似的方法制备。
本发明的某些化合物在特殊的晶格内呈现出有用的杀菌活性，因而，本发明另一方面提供一种杀菌组合物，这种组合物包括载体和上述作活性组分的式Ⅰ化合物。本发明还提供一种将Ⅰ化合物引入，并与至少一种载体相结合来制备上述组合物的
方法。上述组合物可包括本发明的一种化合物或几种化合物的混合物。
本发明优选含0.5～95%（重量）活性组分的组合物。
本发明组合物中的载体是任何一种可使配制成的活性组分容易作用于要处理的所在地（例如，可以是植物、种子或土壤），或便于贮藏、运输或加工的物质。载体可以是固体或液体，包括通常是气体但已经压缩成液体的物质。通常用来配制杀菌组合物的任何载体都可使用。
适合的固体载体包括天然和合成粘土和硅酸盐，例如天然硅石，诸如硅藻土;硅酸镁，例如滑石;硅酸铝镁，例如美国活性白土和蛭石;硅酸铝，例如高岭石、蒙脱石和云母;碳酸钙;硫酸钙;硫酸铵;合成水合氧化硅和合成硅酸钙或硅酸铝;元素，例如碳和硫;天然和合成树脂，例如苯并呋喃脂脂，聚氯乙烯，和苯乙烯聚合物和共聚物;固体多氯酚;沥青;蜡，例如蜂蜡，石蜡，和氯化地蜡;和固体肥料，例如过磷酸钙。
适合的液体载体包括水;醇，例如异丙醇和乙二醇;酮，例如，丙酮，甲基乙基酮，甲基异丁基酮和环己酮;醚;芳香或脂肪烃，例如，苯、甲苯和二甲苯;石油馏份，例如，煤油和轻质矿物油;氯化烃，例如，四氢化碳，全氯乙烯和三氯乙烷，不同液体的混合物通常是适合的。
通常，用浓缩形式配制和输送杀菌组合物，然后，在应用前，由使用者加以稀释。载体中存在少量表面活性剂有助于稀释过程，因此，本发明组合物中最好至少一种载体是表面活性剂，例如，该组合物至少可含二种载体，其中至少一种载体是表面活性剂。
表面活性剂可以是乳化剂，分散剂或湿润剂;可以是非离子或离子型的。适合的表面活性剂的例子包括聚丙烯酸和木素磺酸的钠盐或钙盐;脂肪酸或脂肪胺或分子中至少含12个碳原子的酰胺与氧化乙烯和/或氧化丙烯的缩合物;丙三醇、山梨醇、蔗糖或季戊四醇的脂肪酸酯，上述这些与氧化乙烯和/或氧化丙烯的缩合物，脂肪醇或烷基酚，例如，P-辛基苯酚或P-辛基甲酚与氧化乙烯和/或氧化丙烯的缩合物;这些缩合物的硫酸盐或磺酸盐;碱金属盐或碱土金属盐，优选钠盐，分子中含至少10个碳原子的硫酸酯或磺酸酯，例如，十二烷基硫酸钠，仲烷基硫酸钠，磺化蓖麻油的钠盐，和烷基芳基磺酸钠，例如十二烷基苯磺酸盐;和氧化乙烯的聚合物，和氧化乙烯和氧化丙烯的共聚物。
例如，本发明的组合物可配制成可湿粉剂，粉剂、粒剂、溶液、可乳化的浓缩物，乳化液，悬浮浓缩物和气溶胶。可湿粉剂通常含25、50或75%W活性组分，除含固体惰性载体外，通常含3-10%W分散剂，必要时，可含0-10%W稳定剂和/或其他添加剂，例如，渗透剂或粘着剂。通常，将粉剂配制成与可湿粉剂有类似组成，但没有分散剂的粉状浓缩物。在使用时，可再用固体载体稀释，得到通常含1/2-10%W活性组分的组合物。通常将粒剂配制成大小在10和100BS筛目之间（1.676-0.152mm）的颗粒。并可用团聚或浸渍技术制备。通常，粒剂含1/2-75%W的活性组分和0-10%W的添加剂，诸如，稳定剂，表面活性剂，慢释放调节剂和粘结剂。所谓“可流动的干粉”是由含相对高浓度活性组分的相对小的颗粒组成。可乳化的浓缩物除了含溶剂外，必要时，通常还含有助溶剂，1-50%W/V活性组分，2-20%W/V乳化剂和0-20%W/V其他添加剂，诸如稳定剂，渗透剂和腐蚀抑制剂。通常，将悬浮浓缩物调配成稳定的，无沉淀的，可流动的产物，并通常含10-75%W活性组分，0.5～15%W分散剂，0.1-10%悬浮剂，诸如，保护胶体，和触变剂，0-10%W其他添加剂，诸如消泡剂，腐蚀抑制剂，稳定剂，渗透剂和粘着剂，和水或有机液体（其中活性组分基本上不溶）;将某些有机固体或无机盐溶入制剂有助于防止沉淀或作为水的抗凝固剂。
液体分散剂和乳化剂，例如，用水稀释本发明的可湿粉或浓缩物得到的组合物也属于本发明范围。所说的乳化剂可以是“水在油中”或“油在水中”型的，可具有稠“蛋白酱（mayonnaise）”似的稠度。
本发明的组合物也可含其他组分，例如，含具有除草，杀虫或杀菌性质的其他化合物。
特别令人感兴趣的是利用载体将慢释放杀菌化合物引入到要保护的植物的周围，可提高本发明化合物保护活性的延续性。例如，可将上述慢释放制剂嵌入土壤，与植物根部相邻，或可含胶粘组分，
使其能直接应用于植物茎部。
本发明还提供上述通式Ⅰ化合物或上述组合物作杀菌剂的应用，和在所在地（包括处理的场所，例如，经受或易受霉菌侵袭的植物，植物的种子，或供植物生长的培养基）用上述化合物或组合物消灭霉菌的方法。
式Ⅰ化合物也可用作制备通式为：
（其中n、R、R1和R2的定义如上，且A表示氮原子或CH基团）的具有杀菌活性的环戊烷衍生物的中间体，某些式ⅩⅡ化合物涉及待审查的专利申请GB-A1-2180236和EP-A2-0-267778。
EP-A2-0-267778和GB-A1-2180236公开的化合物存在着具有下面结构的两种立体异构物：
下文中，字母A和B可用来表示与上述异构体A和B具有相同立体化学结构的化合物。
例如，异构体A和B可用色谱法分离，并呈现出不同的杀菌活性。通常，式ⅩⅢA的异构体比式ⅩⅢB的异构体呈现出更大的杀菌活性。式Ⅰ化合物存在着具有下面结构的单个立体异构体：
用下面的反应图解可说明用式Ⅰ化合物合成式ⅩⅢ化合物的工艺方法。（见文后）
在上述反应图解中，n、R、R1、R2、R5、X和A的定义如上，R3表示任意取代的烷基或芳基，优选的是C1-C4烷基或苯基（各自被一个或多个选自卤原子，硝基、氰基、羟基，C1-4烷基、C1-4卤烷基，C1-4烷氧基，C1-4卤烷氧基，氨基，C1-4烷基氨基，＝-C1-4烷基氨基，C1-4烷氧基羰基、羧基、C1-4烷酰基、C1-4烷基硫代、C1-4烷基亚磺酰基、C1-4烷基磺酰基，氨基甲酰基、C1-4烷基酰胺基、C3-8环烷基和苯基的取代基任意取代），和Q表示氢或碱金属，优选的是钠原子。上述反应图解中的中间化合物和方法步骤涉及待审查专利申请T623和T626。
用下面实施例进一步说明本发明。
实施例1
制备1-（4-氯苄基）-1，2-环氧-3，3-二甲基-2-甲氧基羰基环戊烷
（n＝1，R＝4-cl，R1＝R2＝CH3，R5＝CH3）（a）制备2-（4-氯苄基）-5，5-二甲基-环己烷-1，3-二酮。
将449克（3.21摩尔）双甲酮（5，5-二甲基环己烷-1，3-二酮）加到在700毫升水中含166克85%氢氧化钾（2.52摩尔）的氢氧化钾水溶液中。然后，将该混合物升温，在47℃，得到纯净的棕色溶液。然后将该溶液加热到59℃。在1小时内，加入544克（3.21摩尔）熔化的4-氯化苄基氯，同时，进一步加热到85℃。再继续加热2.5-3小时直到温度达到100℃。然后，冷却该混合物，过滤出固体产物，用水洗涤，在50℃下用真空炉干燥。然后在回流下将该粗制固体（815克）溶于2400毫升甲醇，并加入200毫升水，产生永久浊度。然后，让该混合物冷却到室温，并搅拌一
夜。将这样得到的固体过滤，用约400毫升冷甲醇洗涤并用真空炉干燥，得到340克的白色固体状的2-（4-氯苄基）-5，5-二甲基环己烷-1，3-二酮，熔点：188-190℃，产率为42%。
（b）制备2-（4-氯苄基）-3-（2-甲基-丙氧基）-5，5-二甲基环己-2-烯-1-酮
在迪安-斯达克装置中，在回流下，将由（a）得到的325克（1.23摩尔）2-（4-氯苄基）-5，5-二甲基环己烷-1，3-二酮，1.6升甲苯，182克（2.5摩尔）异丁醇和5克P-甲苯磺酸一起搅拌。该反应混合物的温度约为90℃。随着水被蒸馏出，该反应混合物由稀浆变成黄色溶液。回流14小时后，冷却该反应混合物，用500毫升10%氢氧化钠水溶液的等分试样搅动二次。然后闪蒸甲苯层，得到389克的黄色/棕色油，静置后结晶。用60/80石油重结晶该固体，得到331克2-（4-氯苄基）-3-（2-甲基丙氧基）-5，5-二甲基环己-2-烯-1-酮的白色晶状固体，熔点60-61℃，产率为84%。
（C）制备2-（4-氯苄基）-3-甲氧基-5，5-二甲基环己-2-烯-1-酮。
将154克由实施例1得到的2-（4-氯苄基）-3-（2-甲基丙氧基）-5，5-二甲基环己-2-烯-1-酮在1200毫升甲醇（含3克P-甲苯磺酸）中的溶液回流2小时。然后，用3升水和1升二乙醚萃取该反应混合物，另用1升二乙醚再行萃取。然后将该有机相先用200毫升10%水状氢氧化钠回洗，然后用100毫升饱和的氯化钠回洗，用无水硫酸镁干燥，并闪蒸。然后将剩余物用60/80石油结晶，过滤并用空气干燥，得到98克2-（4-氯苄基）-3-甲氧基-5，5-二甲基环己-2-烯-1-酮白色固体，熔点为62-63℃，产率：73%。
（d）制备2-（4-氯苄基）-5，5-二甲基-环己-2-烯-1-酮
在足以维持回流的速度下，将由（c）得到的98克（0.35摩尔）2-（4-氯苄基）-3-甲氧基-5，5-二甲基环己-2-烯-1-酮添加到6.65克（0.175摩尔）氢化铝锂在490摩尔二乙醚的浆液中，将得到的反应混合物再回流30分钟。然后，加入5毫升水，接着，加入5毫升15%氢氧化钠水溶液，再加15毫升水，将生成的沉淀过滤出。然后，将滤液在200毫升5M盐酸中搅动5分钟，然后分离有机层。用100毫升饱和碳酸氢钠溶液等分试样洗涤二次，用无水硫酸镁干燥并汽提。然后，将生成的油溶于430毫升二氯甲烷，加入18克（0.085摩尔）氯铬酸吡啶嗡，并将该反应混合物搅拌3小时。加入600毫升二乙醚，然后，过滤出固体。用10%氢氧化钠水溶液将该滤液洗涤三次。用2.5M盐酸洗涤一次，用碳酸氢钠饱和溶液洗涤一次。然后，用无水硫酸镁干燥，汽提，得到82克粗制产物，在减压（0.15mm汞柱）下，蒸馏该粗制产物，得到79克2-（4氯苄基）-5，5-二甲基环己-2-烯-1-酮，在0.15mm汞柱下，沸点为130℃，产率91%。
（e）制备2-（4-氯苄基）-2，3-二溴基-5，5-二甲基环己烷-1-酮。
在0℃，将10克（40.2毫摩尔）由（d）得到的2-（4-氯苄基）-5，5-二甲基环己-2-烯-1-酮溶于50毫升30/40石油。然后，将6.72克（40.2毫摩尔）溴加到该溶液中。5-10分钟后，溶液脱色，生成沉淀物。然后，将该溶液进一步冷却，过滤沉淀物，得到12.4克2-（4-氯苄基）-2，3-二溴-5.5-二甲基环己烷-1-酮固体，熔点为82-84℃，产率：75%。
（f）制备1-（4-氯苄基）-3，3-二甲基-2-甲氧基羰基环戊-1-烯。
将2.8克（121毫摩尔）钠加到50毫升甲醇中制备甲醇钠溶液，然后，将由（e）制得的2-（4-氯苄基）-2，3-二溴-5，5-二甲基环己烷-1-酮在甲醇中配制成浆液，并在回流下，加到甲醇钠溶液中，继续回流整流夜。然后，用200毫升水骤冷该反应混合物，用100毫升二乙醚等分试样洗涤两次，用水回洗，用无水硫酸镁干燥，闪蒸，得到8克黄色油。用气体色谱法分析，对产生的6.6克1-（4-氯苄基）-3，3-二甲基-2-甲氧基羰基-环戊-1-烯油状物进行测定，用n.m.r光谱测定该产物结构，产率：78%。
（g）制备1（4-氯苄基）-1，2-环氧-3，3-二甲基-2-甲氧基羰基环戊烷。
将23.5克（3当量）“PROXLTANE4002”（商标：乙酸中36-40%W/W过乙酸）加到9.8克（35.1毫摩尔）由（f）制得的1-（4-氯苄基）-3，3-二甲基-2-甲氧基羰基环戊-1-烯在90毫升三氯甲烷的溶液中。将生成的混合物回流3小
时，用水稀释，然后，用50毫升三氯甲烷等分试样将水相重复萃取两次，用50毫升碳酸氯钠稀溶液将混合的萃取物回洗一次，用50毫升饱和的亚硫酸氨钠等分试样回洗两次，用氯化钠饱和溶液洗涤用无水硫酸镁干燥，闪蒸，得到12克的一冷却就结晶的浅黄色油。在30/40石油中研制产生出5.8克1-（4-氯-苄基）-1，2-环氧-3，3-二甲基-2-甲氧基羰基环戊烷白色晶状固体，熔点86-87℃，产率：56%。
Claims (6)
1、一种制备具有如下通式的化合物的方法
其中n表示0-5的整数；R表示卤原子；R1和R2分别表示C1-4烷基；R5表示C1-4烷基，该方法包括将通式为
(其中n、R、R1、R2、R5的定义同上)的化合物与过酸反应。
2、根据权利要求1所述的方法，其中n为1，R表示氯原子，R1和R2都表示甲基，R5表示甲基。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8820603.2 | 1988-08-31 | ||
| GB888820603A GB8820603D0 (en) | 1988-08-31 | 1988-08-31 | Cyclopentane derivatives |
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| Publication Number | Publication Date |
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| CN1042353A CN1042353A (zh) | 1990-05-23 |
| CN1019975C true CN1019975C (zh) | 1993-03-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN89107874A Expired - Fee Related CN1019975C (zh) | 1988-08-31 | 1989-08-29 | 环戊烷衍生物的制备方法 |
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| Country | Link |
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| US (1) | US5006552A (zh) |
| EP (1) | EP0361560B1 (zh) |
| JP (1) | JP2952493B2 (zh) |
| KR (1) | KR0135418B1 (zh) |
| CN (1) | CN1019975C (zh) |
| BR (1) | BR8904340A (zh) |
| CA (1) | CA1339676C (zh) |
| DE (1) | DE68914376T2 (zh) |
| GB (1) | GB8820603D0 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5262543A (en) * | 1988-08-31 | 1993-11-16 | Kureha Kagaku Kogyu Kabushiki Kaisha | Process for the preparation of cyclopentane derivatives |
| GB2225006B (en) * | 1988-08-31 | 1992-02-12 | Shell Int Research | Process for the preparation of cyclopentane derivatives |
| AU6522498A (en) * | 1997-04-07 | 1998-10-30 | Nissan Chemical Industries Ltd. | Cycloalkyl benzyl ether compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4174344A (en) * | 1977-11-14 | 1979-11-13 | Hoffmann-La Roche Inc. | Process for the preparation of methyl 3,4-anhydro-2,6-dideoxy-L-ribo-hexopyranoside |
| US4863505A (en) * | 1985-09-12 | 1989-09-05 | Kureha Kagaku Kogyo Kabushiki Kaisha | Novel derivative of azole, and agricultural and horticultural composition containing the same as an active incredient |
| JPH0625140B2 (ja) * | 1986-11-10 | 1994-04-06 | 呉羽化学工業株式会社 | 新規アゾール誘導体、その製造方法及び該誘導体の農園芸用薬剤 |
-
1988
- 1988-08-31 GB GB888820603A patent/GB8820603D0/en active Pending
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1989
- 1989-08-21 CA CA000608905A patent/CA1339676C/en not_active Expired - Fee Related
- 1989-08-23 US US07/397,288 patent/US5006552A/en not_active Expired - Lifetime
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- 1989-08-25 EP EP89202160A patent/EP0361560B1/en not_active Expired - Lifetime
- 1989-08-29 JP JP1220516A patent/JP2952493B2/ja not_active Expired - Fee Related
- 1989-08-29 BR BR898904340A patent/BR8904340A/pt not_active IP Right Cessation
- 1989-08-29 CN CN89107874A patent/CN1019975C/zh not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1042353A (zh) | 1990-05-23 |
| EP0361560B1 (en) | 1994-04-06 |
| CA1339676C (en) | 1998-02-17 |
| DE68914376T2 (de) | 1994-07-28 |
| KR0135418B1 (ko) | 1998-04-23 |
| BR8904340A (pt) | 1990-04-17 |
| JP2952493B2 (ja) | 1999-09-27 |
| DE68914376D1 (de) | 1994-05-11 |
| US5006552A (en) | 1991-04-09 |
| GB8820603D0 (en) | 1988-09-28 |
| EP0361560A1 (en) | 1990-04-04 |
| KR900003143A (ko) | 1990-03-23 |
| JPH02108681A (ja) | 1990-04-20 |
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