CN1262670A - 1－芳基－3－环丙基－1,3－丙二酮的制备方法 - Google Patents
1－芳基－3－环丙基－1,3－丙二酮的制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 21
- 150000002367 halogens Chemical class 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 18
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims abstract description 15
- -1 CH2SR5 Chemical group 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 239000005864 Sulphur Substances 0.000 claims abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 23
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000000177 1,2,3-triazoles Chemical class 0.000 claims description 4
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical group N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 4
- 150000003217 pyrazoles Chemical class 0.000 claims description 4
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical class 0.000 claims description 3
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 229910052987 metal hydride Inorganic materials 0.000 claims description 2
- 150000004681 metal hydrides Chemical class 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 6
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 abstract 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 4
- 125000004737 (C1-C6) haloalkoxy group Chemical group 0.000 abstract 4
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 abstract 2
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 abstract 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 abstract 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 2
- 125000005842 heteroatom Chemical group 0.000 abstract 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 abstract 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 abstract 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 abstract 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 229910052717 sulfur Chemical group 0.000 abstract 1
- 239000011593 sulfur Chemical group 0.000 abstract 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- HVCFCNAITDHQFX-UHFFFAOYSA-N 1-cyclopropylethanone Chemical compound CC(=O)C1CC1 HVCFCNAITDHQFX-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000003880 polar aprotic solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- WNVZOHNNPDZYFN-UHFFFAOYSA-N 1,2-oxazole-3-carbaldehyde Chemical compound O=CC=1C=CON=1 WNVZOHNNPDZYFN-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- FIGXUYQWSMOGBU-UHFFFAOYSA-N 5-cyclopropyl-1,2-oxazole Chemical compound C1CC1C1=CC=NO1 FIGXUYQWSMOGBU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QJZUPDUXEBVQHR-UHFFFAOYSA-N methyl 2-chloro-4-(trifluoromethyl)benzoate Chemical compound COC(=O)C1=CC=C(C(F)(F)F)C=C1Cl QJZUPDUXEBVQHR-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Cephalosporin Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Saccharide Compounds (AREA)
Abstract
本发明涉及制备式(Ⅰ)化合物的方法,其中:R2是C1－6直链或支链烷硫基、C1－6烷基、C1－6卤代烷基、CH2SR5、C1－6烷氧基、C1－6卤代烷氧基或卤素;或是N－连接的咪唑、吡唑、1,2,3,4－四唑、1,2,3－三唑或1,2,4－三唑环,环系统任选地被一个或多个选自卤素、C1－6烷基、C1－6卤代烷基或C1－6直链或支链烷硫基的取代基所取代;R3是C1－6直链或支链卤代烷基、C1－6直链或支链烷基、C1－6烷氧基、C1－6卤代烷氧基、卤素、C1－6直链或支链烷硫基或硝基;或是N－连接的咪唑、吡唑、1,2,3,4－四唑、1,2,3－三唑或1,2,4－三唑环,环系统任选地被一个或多个选自卤素、C1－6烷基、C1－6卤代烷基或C1－6直链或支链烷硫基的取代基所取代;R4是氢、C1－6直链或支链卤代烷基、C1－6直链或支链烷基、C1－6烷氧基、C1－6卤代烷氧基、卤素、C1－6直链或支链烷硫基;或为含1－3个选自氧、氮和硫的杂原子的5或6元杂环(可为不饱和或部分饱和),所述杂环可任选地被卤素、C1－6卤代烷基、C1－6烷基、C1－6卤代烷氧基、C1－6烷氧基、SOnR5、硝基或氰基所取代;或者R3和R4与和它们相连的碳原子一起形成5到7元饱和或不饱和、含最多三个选自氮、氧和硫的杂原子的杂环,该环任选地被一个或多个选自卤素、硝基、C1－6直链或支链烷硫基、C1－4烷基、C1－4烷氧基、C1－4卤代烷基、C1－4卤代烷氧基、=O和=NO－R5的取代基所取代;R5代表C1－6直链或支链烷基;和n代表0,1或2;该方法包括使式(Ⅱ)化合物:其中R1;是C1－6直链或支链烷基,R2,R3和R4的定义同上,与式(Ⅲ)化合物在非质子传递溶剂中及在碱存在下反应。
Description
本发明涉及制备1，3-二酮化合物的方法和由该方法制得的产物。更具体的是，本发明涉及制造杀虫剂时使用的中间化合物的制备。
杀虫剂4-苯甲酰异噁唑，特别是5-环丙基异噁唑杀虫剂和它们合成中的中间化合物已记载在文献中，例如欧洲专利0418175、0527036、0560482、0609798和0682659。制备这些化合物的各个方法是已知的。本发明意在提供一种制备它们合成中的中间化合物的改进的方法。
本发明提供了制备式(I)化合物的方法：其中：
R2是C1-6直链或支链烷硫基、C1-6烷基、C1-6卤代烷基、CH2SR5、C1-6烷氧基、C1-6卤代烷氧基或卤素；或是N-连接的咪唑、吡唑、1，2，3，4-四唑、1，2，3-三唑或1，2，4-三唑环，环系统任选地被一个或多个选自卤素、C1-6烷基、C1-6卤代烷基或C1-6直链或支链烷硫基的取代基所取代；
R3是C1-6直链或支链卤代烷基、C1-6直链或支链烷基、C1-6烷氧基、C1-6卤代烷氧基、卤素、C1-6直链或支链烷硫基或硝基；或是N-连接的咪唑、吡唑、1，2，3，4-四唑、1，2，3-三唑或1，2，4-三唑环，环系统任选地被一个或多个选自卤素、C1-6烷基、C1-6卤代烷基或C1-6直链或支链烷硫基的取代基所取代；
R4是氢、C1-6直链或支链卤代烷基、C1-6直链或支链烷基、C1-6烷氧基、C1-6卤代烷氧基、卤素、C1-6直链或支链烷硫基；或为含1-3个选自氧、氮和硫的杂原子的5或6元杂环(可为不饱和或部分饱和)，所述杂环可任选地被卤素、C1-6卤代烷基、C1-6烷基、C1-6卤代烷氧基、C1-6烷氧基、SOnR5、硝基或氰基所取代；
或者R3和R4与和它们相连的碳原子一起形成5到7元饱和或不饱和、含最多三个选自氮、氧和硫的杂原子的杂环，该环任选地被一个或多个选自卤素、硝基、C1-6直链或支链烷硫基、C1-4烷基、C1-4烷氧基、C1-4卤代烷基、C1-4卤代烷氧基、＝O和＝NO-R5的取代基所取代；
R5代表C1-6直链或支链烷基；和
N代表0，1或2；
该方法包括使式(II)化合物：
其中R1是C1-6直链或支链烷基，R2，R3和R4的定义同上，与式(III)化合物在非质子传递溶剂中及在碱存在下反应：
当R4代表杂环时，优选的环包括3-异噁唑基、5-异噁唑基、2-噻唑基、5-噁唑基、2-呋喃基、3-呋喃基、2-噻吩基和3-噻吩基，
R1优选地是甲基，
R2优选地是甲硫基或甲硫基甲基，
R3优选地是三氟甲基或溴，
R4优选地是氢。
在本发明特别优选的技术方案里，R1代表C1-6烷基(最佳的是甲基)；
R2代表甲硫基甲基；
R3代表溴；R4代表氢。
在本发明最优选的技术方案里，R1代表C1-6烷基(最佳的是甲基)；
R2代表C1-6烷硫基(最佳的是甲硫基)；
R3代表C1-6卤代烷基(最佳的是三氟甲基)；R4代表氢。
用这些反应条件业已发现，该反应能高得率地得到所需的最终产物。
上述的欧洲专利申请揭示了某些式(I)化合物和它们的制备方法。式(II)化合物是已知的或可通过已知方法制备。式(III)化合物和其制备方法是已知的。
可使用的非质子传递溶剂是非极性或极性的。合适的非极性非质子传递溶剂包括芳烃或脂族烃，特别是甲苯和二甲苯(优选的是甲苯)；芳族卤代烃(优选的是氯苯)或诸如叔丁基甲基醚、二噁烷或四氢呋喃的醚类。合适的极性非质子传递溶剂的例子包括二甲亚砜、N-甲基吡咯烷酮、N，N-二甲基甲酰胺或N，N-二甲基乙酰胺(优选的是二甲亚砜和N-甲基吡咯烷酮)。氯苯和甲苯最好，因为这类溶剂在大规模制备时能得到良好的结果，成本低，和其适合性好。
一般来说，用于上述方法的反应温度通常为约0℃到溶剂的沸点，优选的是约0℃到约100℃；对于诸如甲苯或氯苯的非极性溶剂，特别优选的是约40℃到约90℃的温度；而对于诸如二甲亚砜和N-甲基吡咯烷酮、氯苯的极性非质子溶剂的温度优选的是约20℃到约40℃。
一般来说，反应在强碱的存在下进行，所述的强碱优选地选自碱金属或碱土金属的烷醇盐，特别是乙醇钠、甲醇钠、叔丁醇钠或叔丁醇钾；和金属氢化物(特别是氢化钠)。甲醇钠是能有效进行反应的特别优选的碱。
根据本发明的方法优选的变体是，进行反应的同时，在大气压下或减压下(优选的是150-250毫巴)连续蒸去在反应进程中形成的醇R1-OH。或者，所形成的醇R1-OH可通过使用合适的分子筛，如4埃分子筛来除去。
可这样制备式(II)中R2代表C1-6烷硫基；R3代表C1-6卤代烷基；和R4代表氢的化合物：使式(IV)化合物
其中R1和R3的定义同上，R6代表选自氟、氯和溴(优选的是氟或氯)的卤原子，与式R2-X的烷基硫醇(或其金属盐)反应，其中R2的定义同上(优选的是甲硫基)，X代表氢或碱金属(优选的是钠、钾或锂)。
优选的是，上述制备式(II)中间体的反应在基本无水条件下，用极性非质子传递溶剂，优选的是N-甲基吡咯烷酮，乙腈或二甲亚砜，在约-20℃到约150℃温度下，优选的是在0℃到约50℃温度下进行。
下列非限定性实施例阐述了本发明。
实施例1
1-环丙基-3-(2-甲硫基-4-三氟甲基苯基)-1，3-丙二酮的制备(小规模)。
将甲醇钠(3.51克，0.065M)加到2-甲硫基-4-三氟甲基苯甲酸甲酯(12.5g，0.050M)和环丙基甲基酮(7毫升，0.070M)在甲苯里的混合物中。使混合物在55-57℃下加热1小时。减压蒸馏甲醇。冷却到20℃后，酸化混合，洗涤有机相(碳酸氢钠和水)，蒸发得到1-环丙基-3-(2-甲硫基-4-三氟甲基苯基)-1，3-丙二酮的黄色晶体(14.03克)，熔点64℃。得率92.9％。产品的纯度是95％。
实施例2
1-环丙基-3-(2-甲硫基-4-三氟甲基苯基)丙-1，3-二酮的制备(大规模)
将甲醇钠(64克，1.15M)加到2-甲硫基-4-三氟甲基苯甲酸甲酯(200克，0.8M)在氯苯(380克)里的混合物。使混合物加热到75℃，在2小时期间加入环丙基甲基酮(75克，0.88M)，同时在75℃下搅拌。4小时后减压蒸馏甲醇，让混合物冷却到50℃，加入水，然后加入硫酸(53克，36N)。减压蒸馏有机相得到1-环丙基-3-(2-甲硫基-4-三氟甲基苯基)-1，3-丙二酮的黄色晶体(240克)，熔点58-60℃。得率88％。产品的纯度未90％。
实施例3
1-环丙基-3-(2-甲硫基-4-三氟甲基苯基)-1，3-丙二酮的制备(小规模)。
将甲醇钠(0.54g，0.01M)加到2-甲硫基-4-三氟甲基苯甲酸甲酯(1.25g，0.005M)和环丙基甲基酮(0.5g，0.006M)在无水N-甲基吡咯烷酮中的混合物，在30℃下加热3小时。冷却的混合物酸化，萃取(醚)，洗涤(水)，蒸发得到1-环丙基-3-(2-甲硫基-4-三氟甲基苯基)-1，3-丙二酮(1.43克)，熔点68℃，得率94％。产物纯度大于95％。
重复上述实验，但用二甲亚砜代替N-甲基吡咯烷酮，得到所需产物，其得率为97％。产物的纯度大于95％。
实施例4
根据实施例1所述的方法，但使用甲醇钠(1.5当量)和环丙基甲基酮(1.5当量)，用叔丁基甲基醚代替甲苯，在55℃下保持3小时(蒸馏甲醇)后得到1-环丙基-3-(2-甲硫基-4-三氟甲基苯基)-1，3-丙二酮，得率92％(纯度95％)。
实施例5
根据实施例1所述的方法，但用环丙基甲基酮(1.5当量)，用四氢呋喃代替甲苯，在40℃下保持5小时(不蒸馏甲醇)得到所需产物，得率75％。
参比实施例1
在5℃下将无水甲硫醇钠(0.385g，0.0055M)加到2-氯-4-三氟甲基苯甲酸甲酯(1.19g，0.005M)在无水N-甲基吡咯烷酮(10毫升)中的溶液。3小时后酸化混合物，萃取(醚)，洗涤(水)，蒸发得到2-甲硫基-4-三氟甲基苯甲酸甲酯(1.18g，94％得率)。1H NMR 2.44(s，3H)，3.89(s，3H)，7.33(1H)，7.41(1H)，8.02(1H)。
Claims (9)
1.一种制备式(I)化合物的方法：其中：
R2是C1-6直链或支链烷硫基、C1-6烷基、C1-6卤代烷基、CH2SR5、C1-6烷氧基、C1-6卤代烷氧基或卤素；或是N-连接的咪唑、吡唑、1，2，3，4-四唑、1，2，3-三唑或1，2，4-三唑环，环系统任选地被一个或多个选自卤素、C1-6烷基、C1-6卤代烷基或C1-6直链或支链烷硫基的取代基所取代；
R3是C1-6直链或支链卤代烷基、C1-6直链或支链烷基、C1-6烷氧基、C1-6卤代烷氧基、卤素、C1-6直链或支链烷硫基或硝基；或是N-连接的咪唑、吡唑、1，2，3，4-四唑、1，2，3-三唑或1，2，4-三唑环，环系统任选地被一个或多个选自卤素、C1-6烷基、C1-6卤代烷基或C1-6直链或支链烷硫基的取代基所取代；
R4是氢、C1-6直链或支链卤代烷基、C1-6直链或支链烷基、C1-6烷氧基、C1-6卤代烷氧基、卤素、C1-6直链或支链烷硫基；或为含1-3个选自氧、氮和硫的杂原子的5或6元杂环(可为不饱和或部分饱和)，所述杂环可任选地被卤素、C1-6卤代烷基、C1-6烷基、C1-6卤代烷氧基、C1-6烷氧基、SOnR5、硝基或氰基所取代；
或者R3和R4与和它们相连的碳原子一起形成5到7元饱和或不饱和、含最多三个选自氮、氧和硫的杂原子的杂环，该环任选地被一个或多个选自卤素、硝基、C1-6直链或支链烷硫基、C1-4烷基、C1-4烷氧基、C1-4卤代烷基、C1-4卤代烷氧基、＝O和＝NO-R5的取代基所取代；
R5代表C1-6直链或支链烷基；和
n代表0，1或2；
该方法包括使式(II)化合物：
其中R1是C1-6直链或支链烷基，R2，R3和R4的定义同上，与式(III)化合物在非质子传递溶剂中及在碱存在下反应：
2.根据权利要求1所述的方法，其中溶剂是甲苯，氯苯，二甲亚砜或N-甲基吡咯烷酮。
3.根据权利要求1或2所述的方法，其中碱选自碱金属和碱土金属烷醇化物和金属氢化物。
4.根据权利要求1-3任一所述的方法，它在蒸馏所形成的醇R1-OH，或用分子筛除去醇R1-OH的条件下进行。
5.根据权利要求1-4任一所述的方法，其中R1代表C1-6烷基；R2代表C1-6烷硫基；R3代表C1-6卤代烷基；R4代表氢。
6.根据权利要求1-5任一所述的方法，其中R1代表甲基；R2代表甲硫基；R3代表三氟甲基；R4代表氢。
7.根据权利要求1-4任一所述的方法，其中R1代表C1-6烷基；R2代表甲硫基甲基；R3代表溴；R4代表氢。
8.根据权利要求1所述的方法，它基本上与实施例1-5任一所述的方法相同。
9.根据权利要求1所述的式(I)化合物，它用前述任一权利要求所述的方法制备。
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| PT994840E (pt) | 2003-08-29 |
| BR9810685A (pt) | 2000-08-22 |
| EP0994840A1 (en) | 2000-04-26 |
| IL133814A0 (en) | 2001-04-30 |
| HUP0003452A3 (en) | 2002-12-28 |
| HU225020B1 (en) | 2006-05-29 |
| US6486356B2 (en) | 2002-11-26 |
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| IL133814A (en) | 2005-07-25 |
| HUP0003452A2 (hu) | 2001-02-28 |
| US20020002309A1 (en) | 2002-01-03 |
| CN1135210C (zh) | 2004-01-21 |
| ZA985769B (en) | 2000-01-13 |
| CA2295913C (en) | 2008-03-18 |
| TWI244476B (en) | 2005-12-01 |
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| ATE240286T1 (de) | 2003-05-15 |
| ES2199453T3 (es) | 2004-02-16 |
| GB9714305D0 (en) | 1997-09-10 |
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| DE69814637D1 (de) | 2003-06-18 |
| PL337894A1 (en) | 2000-09-11 |
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| KR20010021554A (ko) | 2001-03-15 |
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