JP6181168B2 - ある種の2−(ピリジン−3−イル)チアゾール類の製造方法 - Google Patents
ある種の2−(ピリジン−3−イル)チアゾール類の製造方法 Download PDFInfo
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- JP6181168B2 JP6181168B2 JP2015516070A JP2015516070A JP6181168B2 JP 6181168 B2 JP6181168 B2 JP 6181168B2 JP 2015516070 A JP2015516070 A JP 2015516070A JP 2015516070 A JP2015516070 A JP 2015516070A JP 6181168 B2 JP6181168 B2 JP 6181168B2
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- substituted
- unsubstituted
- alkyl
- aryl
- cycloalkyl
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- 238000000034 method Methods 0.000 title claims description 28
- 238000002360 preparation method Methods 0.000 title description 9
- WPCSNGBKVXKBPU-UHFFFAOYSA-N 2-pyridin-3-yl-1,3-thiazole Chemical class C1=CSC(C=2C=NC=CC=2)=N1 WPCSNGBKVXKBPU-UHFFFAOYSA-N 0.000 title description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000006717 (C3-C10) cycloalkenyl group Chemical group 0.000 claims description 4
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 4
- 125000004445 cyclohaloalkyl Chemical group 0.000 claims description 4
- 125000005347 halocycloalkyl group Chemical group 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 239000012024 dehydrating agents Substances 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 2
- 125000006643 (C2-C6) haloalkenyl group Chemical group 0.000 claims description 2
- 125000006765 (C2-C6) haloalkenyloxy group Chemical group 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 2
- 230000002140 halogenating effect Effects 0.000 claims description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 230000026030 halogenation Effects 0.000 claims 1
- 238000005658 halogenation reaction Methods 0.000 claims 1
- -1 thiazole amides Chemical class 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000575 pesticide Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 241000607479 Yersinia pestis Species 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- YMKPPZRXLDTHJS-UHFFFAOYSA-N 4-chloro-n-methyl-2-pyridin-3-yl-1,3-thiazol-5-amine Chemical compound ClC1=C(NC)SC(C=2C=NC=CC=2)=N1 YMKPPZRXLDTHJS-UHFFFAOYSA-N 0.000 description 3
- 125000002015 acyclic group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- TZIAPQZWKNKJOP-UHFFFAOYSA-N n-(4-chloro-2-pyridin-3-yl-1,3-thiazol-5-yl)-n,2-dimethyl-3-methylsulfanylpropanamide Chemical compound ClC1=C(N(C)C(=O)C(C)CSC)SC(C=2C=NC=CC=2)=N1 TZIAPQZWKNKJOP-UHFFFAOYSA-N 0.000 description 3
- VSOQIINZFNRMKF-UHFFFAOYSA-N n-methyl-2-pyridin-3-yl-1,3-thiazol-5-amine Chemical compound S1C(NC)=CN=C1C1=CC=CN=C1 VSOQIINZFNRMKF-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000004529 1,2,3-triazinyl group Chemical group N1=NN=C(C=C1)* 0.000 description 1
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 description 1
- 125000004530 1,2,4-triazinyl group Chemical group N1=NC(=NC=C1)* 0.000 description 1
- 125000001781 1,3,4-oxadiazolyl group Chemical group 0.000 description 1
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 description 1
- 125000006426 1-chlorocyclopropyl group Chemical group [H]C1([H])C([H])([H])C1(Cl)* 0.000 description 1
- 125000004776 1-fluoroethyl group Chemical group [H]C([H])([H])C([H])(F)* 0.000 description 1
- ABEXEQSGABRUHS-UHFFFAOYSA-N 16-methylheptadecyl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC(C)C ABEXEQSGABRUHS-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- YLOQOKWBOKKTMX-UHFFFAOYSA-N 2-methyl-3-methylsulfanylpropanoyl chloride Chemical compound CSCC(C)C(Cl)=O YLOQOKWBOKKTMX-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DNRZNHBJCHIFKJ-UHFFFAOYSA-N C1(=CCC1)OC1(C2(C(=C(C(C1)(C2)OC2=CCCCCCCCC2)OC2=CCCCCCC2)OC2=CCCCCC2)OC2=CCCCC2)OC2=CCCC2 Chemical compound C1(=CCC1)OC1(C2(C(=C(C(C1)(C2)OC2=CCCCCCCCC2)OC2=CCCCCCC2)OC2=CCCCCC2)OC2=CCCCC2)OC2=CCCC2 DNRZNHBJCHIFKJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- 241000256602 Isoptera Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000005133 alkynyloxy group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004604 benzisothiazolyl group Chemical group S1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000004465 cycloalkenyloxy group Chemical group 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JHAYEQICABJSTP-UHFFFAOYSA-N decoquinate Chemical group N1C=C(C(=O)OCC)C(=O)C2=C1C=C(OCC)C(OCCCCCCCCCC)=C2 JHAYEQICABJSTP-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005070 decynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- 238000005417 image-selected in vivo spectroscopy Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000012739 integrated shape imaging system Methods 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ADDHFAKARYDTKQ-UHFFFAOYSA-N methyl 2-(pyridine-3-carbothioylamino)acetate Chemical compound COC(=O)CNC(=S)C1=CC=CN=C1 ADDHFAKARYDTKQ-UHFFFAOYSA-N 0.000 description 1
- KQSSATDQUYCRGS-UHFFFAOYSA-N methyl glycinate Chemical compound COC(=O)CN KQSSATDQUYCRGS-UHFFFAOYSA-N 0.000 description 1
- SKFLZKSHPQZTCO-UHFFFAOYSA-N methyl pyridine-3-carbodithioate Chemical compound CSC(=S)C1=CC=CN=C1 SKFLZKSHPQZTCO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- VNRTZUHHIPFKQC-UHFFFAOYSA-N n-methyl-2-(pyridine-3-carbothioylamino)acetamide Chemical compound CNC(=O)CNC(=S)C1=CC=CN=C1 VNRTZUHHIPFKQC-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005069 octynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000005968 oxazolinyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012363 selectfluor Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
Description
本出願は、2012年6月4日に出願された米国仮出願第61/655,089号からの優先権およびその利益を主張する。この仮出願の全部の内容は本明細書に引用することによりここに組み込まれる。
本文書に開示される本発明は、殺虫性チアゾールアミドの合成のための中間体としてのある種の2−(ピリジン−3−イル)チアゾール類の製造方法の分野に関する。
病害虫集団を防除することは現代の農業、食品貯蔵および衛生に不可欠である。農業における損害を引き起こす1万種以上の病害虫が存在する。世界の農業の損害は毎年合計数十億米ドルに達する。シロアリ類のような病害虫は、全部の種類の民間および公的建造物に対する被害を引き起こして毎年数十億米ドルの損害をもたらすこともまた知られている。病害虫はまた貯蔵食品も食べかつ質を落として、毎年数十億米ドルの損害ならびに人々に必要とされる食物の剥奪をもたらす。
定義に示される例は、全般に網羅的でなく、そして本文書に開示される本発明を制限すると解釈されてはならない。置換基は、それが結合されている特定の分子に関する化学結合則および立体適合性の制約に従うはずであることが理解される。
t−ブトキシ、ペントキシ、2−メチルブトキシ、1,1−ジメチルプロポキシ、ヘキソキシ、ヘプトキシ、オクトキシ、ノノキシおよびデコキシを意味している。
トリクロロメチルおよび1,1,2,2−テトラフルオロエチルを意味している。
本発明の一態様はスキーム1
ここで
(A)各R1は、H、F、Cl、Br、I、CN、NO2、および置換若しくは未置換(C1−C6)アルキルから独立に選択され、ここで各置換されているR1は、F、Cl、Br、I、CN、NO2、(C1−C6)アルキル、および(C1−C6)ハロアルキルから独立に選択される1個若しくはそれ以上の置換基を有し;
(B)R2は、置換若しくは未置換(C1−C6)アルキル、置換若しくは未置換(C2−C6)アルケニル、置換若しくは未置換(C1−C6)アルコキシ、置換若しくは未置換(C2−C6)アルケニルオキシ、置換若しくは未置換(C3−C10)シクロアルキル、置換若しくは未置換(C3−C10)シクロアルケニル、置換若しくは未置換(C6−C20)アリール、置換若しくは未置換(C1−C6)アルキル)(C6−C20)アリール、および置換若しくは未置換(C1−C20)ヘテロシクリルから選択され、ここで、各置換されているR2は、F、Cl、Br、I、CN、NO2、(C1−C6)アルキル、(C2−C6)アルケニル、(C1−C6)ハロアルキル、(C2−C6)ハロアルケニル、(C1−C6)ハロアルキルオキシ、(C2−C6)ハロアルケニルオキシ、(C3−C10)シクロアルキル、(C3−C10)シクロアルケニル、(C3−C10)ハロシクロアルキル、(C3−C10)ハロシクロアルケニル、(C6−C20)アリール、および(C1−C20)ヘテロシクリルから独立に選択される1個若しくはそれ以上の置換基を有し;
(C)R3は、H、置換若しくは未置換(C1−C6)アルキル、置換若しくは未置換(C3−C10)シクロアルキル、置換若しくは未置換(C1−C6)アルキル(C3−C10)シクロアルキル、置換若しくは未置換(C6−C20)アリール、および置換若しくは未置換(C1−C6)アルキル(C6−C20)アリールから選択され、ここで各置換されているR3は、F、Cl、Br、およびIから独立に選択される1個若しくはそれ以上の置換基を有し;ならびに
(D)R4は、H、置換若しくは未置換(C1−C6)アルキル、置換若しくは未置換(C3−C10)シクロアルキル、置換若しくは未置換(C1−C6)アルキル(C3−C10)シクロアルキル、置換若しくは未置換(C6−C20)アリール、置換若しくは未置換(C1−C6)アルキル(C6−C20)アリール、置換若しくは未置換(C1−C6)アルキル(C2−C6)アルケニル、および置換若しくは未置換(C1−C6)アルキル(C2−C6)アルキニルから選択され、ここで置換されている各前記R4は、F、Cl、Br、I、CN、NO2、(C1−C6)アルキル、(C1−C6)ハロアルキル、(C1−C6)アルキルオキシ、(C1−C6)ハロアルキルオキシ、(C3−C10)シクロアルキル、(C3−C10)ハロシクロアルキル、(C6−C20)アリール、および(C1−C20)ヘテロシクリルから選択される1個若しくはそれ以上の置換基を有する。
ルが好ましい。
45mlのParr反応装置中の20ml中の2−(ピリジン−3−カルボチオアミド)酢酸メチル(2.5g、11.89mmol)の冷却された(−40℃)溶液にエチルアミン(6.6g、146.00mmol)を添加した。Parr反応装置を封止しかつ60℃に5時間加熱した。この溶液に5gのシリカゲルを添加しそして該混合物を乾固まで蒸発させた。サンプルを、酢酸エチルおよびジクロロメタン、次いで100%酢酸エチルの勾配を使用してISCOでクロマトグラフィー分離した。溶媒を真空中で除去して表題化合物を黄色固形物(1.8g;68%);mp 136−138℃;1H NMR(400MHz、d6−DMSO)δ 10.62(s、1H)、8.94(dd、J=2.4、0.7Hz、1H)、8.68(ddd、J=13.4、4.8、1.7Hz、1H)、8.15−7.94(m、2H)、7.49(tdd、J=8.0、4.8、0.8Hz、1H)、4.34(s、2H)、3.21−3.03(m、2H)、1.03(
t、J=7.2Hz、3H);13C NMR(101MHz、DMSO−d6)δ 195.74(s)、166.34(s)、151.87(s)、151.29(s)、148.66(s)、147.70(s)、136.20(s)、135.02(d、J=18.7Hz)、123.37(s)、123.00(s)、48.79(s)、40.13(s)、39.93(s)、39.72(s)、39.51(s)、39.30(s)、39.09(s)、38.88(s)、33.51(s)、14.71(s)として提供した。
8.98(dd、J=2.3、0.7Hz、1H)、8.53(dd、J=4.8、1.6Hz、1H)、8.07(ddd、J=8.0、2.2、1.7Hz、1H)、7.40−7.21(m、1H)、6.96(s、1H)、4.18(s、1H)、2.96(s、3H);13C NMR(101MHz、CDCl3)δ 153.23、149.
15、146.54、132.23、130.47、123.65、121.20、34.48;分析 C9H9N3Sの計算値:C、56.52;H、4.74;N、21.97;S、16.77。実測値:C、56.31:H、4.74;N、21.81;S、16.96として生じた。
磁気攪拌子、温度計および窒素入口を装備された乾燥500ml丸底フラスコに4−クロロ−N−メチル−2−(ピリジン−3−イル)チアゾル−5−アミン(22g、97mmol)およびジクロロメタン(250ml)を添加した。該懸濁液を、ピリジン(8.48g、107mmol)およびDMAP(1.20g、9.75mmol)を添加しながら周囲温度で攪拌した。この懸濁液に塩化2−メチル−3−(メチルチオ)プロパノイル(17.8g、117mmol)を5分にわたり添加した。添加の間に全部の固形物が
溶液の状態になり、そして該反応は20℃から30℃まで発熱性であった。該反応を周囲温度で16h攪拌した。該混合物をHPLC(YMC AQカラム 1.0ml/minで20Minにわたり5%ACN 95%水−0.05%TFAないし95%ACN 0.05%TFAを含む5%水)により確認し、それは全部の出発原料の完全な転化を示した。該反応混合物をジクロロメタンで希釈しかつ水をその後添加した。該混合物をジクロロメタンおよび水を含む分液ロート中に注ぎかつ層を分離した。有機層を塩水で洗浄し、無水硫酸マグネシウムで乾燥し、濾過しかつロータリー蒸発させて33.6gの黒ずんだ油状物を提供した。該油状物をISCO Combiflash Rf(330gシリカゲルカートリッジ、移動相A=ヘキサン、B=酢酸エチル、勾配 20分にわたり0%Bないし100%B)で精製した。画分を25ml試験管に収集した。所望の生成物を含有するチューブを合わせ、そして溶媒をロータリー蒸発により除去した。これが22.8gの粘稠な黄色液体を68.4%の単離された収率で提供した。サンプル全体が結晶化し、そしてヘキサン(200mL)を添加してスラリーを生じた。該スラリーを真空濾過しかつ固形物を風乾させた。これが、N−(4−クロロ−2−(ピリジン−3−イル)チアゾル−5−イル)−N,2−ジメチル−3−(メチルチオ)プロパンアミドを灰白色固形物;mp 75−80℃;1H NMR(400MHz、CDCl3)δ 9.12(d、J=1.4Hz、1H)、8.73(d、J=3.8Hz、1H)、8.34−8.09(m、1H)、7.43(dd、J=7.9、4.9Hz、1H)、3.30(s、3H)、3.06−2.70(m、2H)、2.49(d、J=7.4Hz、1H)、2.04(s、3H)、1.21(d、J=6.4Hz、3H);13C NMR(101MHz、DMSO−d6)δ 175.22、162.37、151.91、146.53、136.46、134.64、133.35、127.98、124.27、37.47、36.71、36.47、17.56、15.44;分析 C14H16ClN3OS2の計算値:C、49.18;H、4.72;N、12.29;S、18.76。実測値:C、49.04:H、4.68;N、12.29;S、18.68として生じた。
Claims (19)
-
(ii)化合物(IIb)を化合物(IIc)と反応させて化合物(III)を製造すること;次いで
(iii)脱水剤を使用して化合物(III)を環化して化合物(IV)を製造することであって、
ここで
(A)各R1は、H、F、Cl、Br、I、CN、NO2、および置換若しくは未置換(C1−C6)アルキルから独立に選択され、ここで各置換されているR1は、F、Cl、Br、I、CN、NO2、(C1−C6)アルキル、および(C1−C6)ハロアルキルから独立に選択される1個若しくはそれ以上の置換基を有し;
(B)R2は、置換若しくは未置換(C1−C6)アルキル、置換若しくは未置換(C2−C6)アルケニル、置換若しくは未置換(C1−C6)アルコキシ、置換若しくは未置換(C2−C6)アルケニルオキシ、置換若しくは未置換(C3−C10)シクロアルキル、置換若しくは未置換(C3−C10)シクロアルケニル、置換若しくは未置換(C6−C20)アリール、置換若しくは未置換(C1−C6)アルキル)(C6−C20)アリール、および置換若しくは未置換(C1−C20)ヘテロシクリルから選択され、ここで、各置換されているR2は、F、Cl、Br、I、CN、NO2、(C1−C6)アルキル、(C2−C6)アルケニル、(C1−C6)ハロアルキル、(C2−C6)ハロアルケニル、(C1−C6)ハロアルキルオキシ、(C2−C6)ハロアルケニルオキシ、(C3−C10)シクロアルキル、(C3−C10)シクロアルケニル、(C3−C10)ハロシクロアルキル、(C3−C10)ハロシクロアルケニル、(C6−C20)アリール、および(C1−C20)ヘテロシクリルから独立に選択される1個若しくはそれ以上の置換基を有し;
(C)R3は、H、置換若しくは未置換(C1−C6)アルキル、置換若しくは未置換(C3−C10)シクロアルキル、置換若しくは未置換(C1−C6)アルキル(C3−C10)シクロアルキル、置換若しくは未置換(C6−C20)アリール、および置換若しくは未置換(C1−C6)アルキル(C6−C20)アリールから選択され、ここで各置換されているR3は、F、Cl、Br、およびIから独立に選択される1個若しくはそれ以上の置換基を有し;ならびに
(D)R4は、H、置換若しくは未置換(C1−C6)アルキル、置換若しくは未置換(C3−C10)シクロアルキル、置換若しくは未置換(C1−C6)アルキル(C3−C10)シクロアルキル、置換若しくは未置換(C6−C20)アリール、置換若しくは未置換(C1−C6)アルキル(C6−C20)アリール、置換若しくは未置換(C1−C6)アルキル(C2−C6)アルケニル、および置換若しくは未置換(C1−C6)アルキル(C2−C6)アルキニルから選択され、ここで置換されている各前記R4は、F、Cl、Br、I、CN、NO2、(C1−C6)アルキル、(C1−C6)ハロアルキル、(C1−C6)アルキルオキシ、(C1−C6)ハロアルキルオキシ、(C3−C10)シクロアルキル、(C3−C10)ハロシクロアルキル、(C6−C20)アリール、および(C1−C20)ヘテロシクリルから選択される1個若しくはそれ以上の置換基を有する、
を含んでなる方法。 - 各R1がH、FおよびClから独立に選択される、請求項1に記載の方法。
- 各R1がHである、請求項1に記載の方法。
- R3が、H、(C1−C6)アルキル、(C1−C6)ハロアルキルおよび(C6−C20)アリールから選択される、請求項1に記載の方法。
- R3がH、CF3、CH2F、CHF2、CH3、CH2CH3、CH(CH3)2およびフェニルから選択される、請求項1に記載の方法。
- R3がHおよびCH3から選択される、請求項1に記載の方法。
- R4が(C1−C6)アルキル(C3−C10)シクロハロアルキルである、請求項1に記載の方法。
- R4が、H、(C1−C6)アルキル、(C1−C6)アルキル(C6−C20)アリール、(C1−C6)ハロアルキル、(C1−C6)アルキル(C3−C10)シクロアルキル、(C3−C10)シクロアルキル−O−(C1−C6)アルキル、および(C3−C10)シクロハロアルキルから選択される、請求項1に記載の方法。
- R4が、H、CH3、CH2CH3、CH(CH3)2、CH2CH(CH3)2、シクロプロピル、(C6−C20)アリール、CH2−フェニル、CH2−フェニル−OCH3、CH2OCH2−フェニル、CH2CH2CH3、CH2CH2F、CH2CH2OCH3、CH2シクロプロピル、およびシクロプロピル−O−CH2CH3から選択される、請求項1に記載の方法。
- R4が、H、CH3、CH2CH3、CH(CH3)2、CH2CH(CH3)2、CH2CH2CH3、シクロプロピル、CH2シクロプロピル、およびCH2CH=CH2、CH2C≡CHから選択される、請求項1に記載の方法。
- 段階aが、ギ酸、n−ブタノール、イソプロパノール、n−プロパノール、エタノール、メタノール、酢酸、水若しくはそれらの混合物中で実施される、請求項1に記載の方法。
- 段階aがメタノール中で実施される、請求項1に記載の方法。
- 段階b化合物(III)が、POCl3、H2SO4、SOCl2、P2O5、ポリリン酸、p−トルエンスルホン酸、無水トリフルオロ酢酸およびそれらの混合物から選択される脱水剤を使用して環化される、請求項1に記載の方法。
- 段階bが60℃から120℃までの温度で実施される、請求項1に記載の方法。
- 段階bがアセトニトリル中で実施される、請求項1に記載の方法。
- 化合物(IV)のR3がHであり、前記方法が前記R3をF、Cl、Br若しくはIにハロゲン化することをさらに含んでなる、請求項1に記載の方法。
- 前記ハロゲン化することが、ジクロロメタン、テトラヒドロフラン、酢酸エチル、アセトン、ジメチルホルムアミド、アセトニトリルおよびジメチルスルホキシドから選択される溶媒中で実施される、請求項16に記載の方法。
- 前記溶媒がジクロロメタンである、請求項17に記載の方法。
- R3がClである、請求項16、17および18のいずれか1つに記載の方法。
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