CN1091423A - 含有二烯酰胺衍生物的农药组合物 - Google Patents
含有二烯酰胺衍生物的农药组合物 Download PDFInfo
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- CN1091423A CN1091423A CN93117309A CN93117309A CN1091423A CN 1091423 A CN1091423 A CN 1091423A CN 93117309 A CN93117309 A CN 93117309A CN 93117309 A CN93117309 A CN 93117309A CN 1091423 A CN1091423 A CN 1091423A
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- Prior art keywords
- methyl
- cyclopropyl
- penta
- diene amide
- compound
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 122
- -1 diene amide Chemical class 0.000 title claims description 136
- 239000000575 pesticide Substances 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 179
- 238000002360 preparation method Methods 0.000 claims abstract description 48
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 241000238631 Hexapoda Species 0.000 claims abstract description 17
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 164
- 238000000034 method Methods 0.000 claims description 128
- 239000001257 hydrogen Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000011737 fluorine Substances 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
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- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 230000009545 invasion Effects 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Chemical group 0.000 claims description 5
- 125000005879 dioxolanyl group Chemical group 0.000 claims description 5
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 125000004076 pyridyl group Chemical group 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
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- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 claims description 3
- 125000006583 (C1-C3) haloalkyl group Chemical group 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 2
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- 230000002508 compound effect Effects 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- JVGPVVUTUMQJKL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl thiocyanate Chemical compound CCCCOCCOCCSC#N JVGPVVUTUMQJKL-UHFFFAOYSA-N 0.000 claims 1
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- 230000000694 effects Effects 0.000 abstract description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 71
- 239000000243 solution Substances 0.000 description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 59
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- 150000002148 esters Chemical class 0.000 description 57
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 54
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 44
- 239000002253 acid Substances 0.000 description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 36
- 229910052757 nitrogen Inorganic materials 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 28
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 26
- 239000000377 silicon dioxide Substances 0.000 description 26
- 239000002904 solvent Substances 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 150000001299 aldehydes Chemical class 0.000 description 22
- 238000013375 chromatographic separation Methods 0.000 description 21
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 19
- 150000001412 amines Chemical class 0.000 description 18
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 18
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- 125000003118 aryl group Chemical group 0.000 description 13
- 239000002585 base Substances 0.000 description 13
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 238000003763 carbonization Methods 0.000 description 12
- 238000009472 formulation Methods 0.000 description 12
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 10
- 125000001246 bromo group Chemical class Br* 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
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- 241000244206 Nematoda Species 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical compound CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 8
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- UHBXGHADNVDXMM-UHFFFAOYSA-N C(C)(C)N(C(C)C)CC[Li] Chemical compound C(C)(C)N(C(C)C)CC[Li] UHBXGHADNVDXMM-UHFFFAOYSA-N 0.000 description 7
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- 125000000217 alkyl group Chemical group 0.000 description 7
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- XYDYWTJEGDZLTH-UHFFFAOYSA-N methylenetriphenylphosphorane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=C)C1=CC=CC=C1 XYDYWTJEGDZLTH-UHFFFAOYSA-N 0.000 description 7
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- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 5
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- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- NTNUDYROPUKXNA-UHFFFAOYSA-N methyl 2-(triphenyl-$l^{5}-phosphanylidene)acetate Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=CC(=O)OC)C1=CC=CC=C1 NTNUDYROPUKXNA-UHFFFAOYSA-N 0.000 description 1
- BDGDWWGTAFXEEW-UHFFFAOYSA-N methylsulfinylmethane;oxalyl dichloride Chemical compound CS(C)=O.ClC(=O)C(Cl)=O BDGDWWGTAFXEEW-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000008164 mustard oil Substances 0.000 description 1
- UYYCVBASZNFFRX-UHFFFAOYSA-N n-propan-2-ylcyclohexanamine Chemical compound CC(C)NC1CCCCC1 UYYCVBASZNFFRX-UHFFFAOYSA-N 0.000 description 1
- IOMMMLWIABWRKL-WUTDNEBXSA-N nazartinib Chemical compound C1N(C(=O)/C=C/CN(C)C)CCCC[C@H]1N1C2=C(Cl)C=CC=C2N=C1NC(=O)C1=CC=NC(C)=C1 IOMMMLWIABWRKL-WUTDNEBXSA-N 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012053 oil suspension Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- KHPXUQMNIQBQEV-UHFFFAOYSA-N oxaloacetic acid Chemical compound OC(=O)CC(=O)C(O)=O KHPXUQMNIQBQEV-UHFFFAOYSA-N 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- WLJNZVDCPSBLRP-UHFFFAOYSA-N pamoic acid Chemical compound C1=CC=C2C(CC=3C4=CC=CC=C4C=C(C=3O)C(=O)O)=C(O)C(C(O)=O)=CC2=C1 WLJNZVDCPSBLRP-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000004540 pour-on Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000384 rearing effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- FDBYIYFVSAHJLY-UHFFFAOYSA-N resmetirom Chemical compound N1C(=O)C(C(C)C)=CC(OC=2C(=CC(=CC=2Cl)N2C(NC(=O)C(C#N)=N2)=O)Cl)=N1 FDBYIYFVSAHJLY-UHFFFAOYSA-N 0.000 description 1
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- 208000005687 scabies Diseases 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical class CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000004546 suspension concentrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N trimethyl-ethylene Natural products CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IIHPVYJPDKJYOU-UHFFFAOYSA-N triphenylcarbethoxymethylenephosphorane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=CC(=O)OCC)C1=CC=CC=C1 IIHPVYJPDKJYOU-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/247—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aromatic amines (N-C aromatic linkage)
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- A—HUMAN NECESSITIES
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- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
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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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- 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
- A01N49/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds containing the group, wherein m+n>=1, both X together may also mean —Y— or a direct carbon-to-carbon bond, and the carbon atoms marked with an asterisk are not part of any ring system other than that which may be formed by the atoms X, the carbon atoms in square brackets being part of any acyclic or cyclic structure, or the group, wherein A means a carbon atom or Y, n>=0, and not more than one of these carbon atoms being a member of the same ring system, e.g. juvenile insect hormones or mimics thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/09—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an acyclic unsaturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/10—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an unsaturated carbon skeleton containing rings other than six-membered aromatic rings
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- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/11—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
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- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/17—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/22—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to an acyclic carbon atom of a carbon skeleton containing six-membered aromatic rings
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- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
- C07C235/34—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
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- C07C327/00—Thiocarboxylic acids
- C07C327/38—Amides of thiocarboxylic acids
- C07C327/40—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C327/44—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/292—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with chromium derivatives
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
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- C07C47/00—Compounds having —CHO groups
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- C07C47/24—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing halogen
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- C07C47/457—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings containing halogen
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- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/227—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
- C07C49/237—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings and other rings
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- C07C57/58—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings
- C07C57/60—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings having unsaturation outside the rings
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Abstract
本发明公开了以下所示的式(I)化合物或它们的
盐作为其活性成分的组合物
QQ1CR2=CR3CR4=CR5C(=X)NHR1[其中Q,Q1,
R1,R2,R3,R4,R5和X的定义如说明书中所述]以及式
(I)化合物和该组合的制备方法。式(I)化合物或它们
的盐以及含这些化合物的组合物具有杀虫、杀螨的活
性,可用于治理害虫。
Description
本发明是关于农药化合物,它们的制备方法,含有该农药化合物的组合物和它们用于治理害虫的用途。
具有任意包含至少一个氧原子或附加亚甲基的1至至少10个碳原子的亚甲基链的不饱和酰胺被认为是具有各种不同端部基团的农药或杀虫剂,这些端部基团包括任意取代的苯基(欧洲申请号228222,194764,225011,日本申请号57-212150,Meisters和Wailes:Aust,J,Chem,1966,19,1215,Vig等人的:J,Ind,Chem,Soc,1974,51(9),817)或吡啶基(欧洲申请269457)或稠合二环系(欧洲申请号、143593,228853),二卤代乙烯基或任意取代的乙炔基(欧洲申请228222)。
但目前尚未公开由任何环烷基填隙基团,(其中二烯单元与端部基团相联)组成的不饱和酰胺农药化合物。
H.O.Huisman等人的Rev,trav.Chim,97-102(1958)公开了一组5-(2,6,6-三甲基环己烯基)2,4-戊二烯酰胺的杀虫剂。
现在我们惊奇地发现了新的不饱和酰胺,它们具有与二烯单元相邻的1,2-环丙基环,二烯单元与端部基团相联,所说的端部基团选自任意取代的单芳香环或稠合双环系,二卤代乙烯基或任意取代的具有有利的杀虫特性的乙炔基。
因此,本发明提供了一种结构式(Ⅰ)的化合物或它们的盐:
其中Q是单芳香环或稠合的双环系(其中至少有一个环是含有9或10个原子的芳香环,在该9或10个原子中有一个可以是氮原子而其它的为碳原子),每个环系都可以被任意取代,或Q是二卤代乙烯基或R6-C≡C-基团(其中R6是C1-4烷基,三C1-4烷基甲硅烷基,卤素或氢:'Q1是任意被一个或多个选自C1-3烷基,卤素,C1-3卤代烷基,链炔基或氰基的取代基所取代的1,2-环丙基环:R2,R3,R4和R5可以相同或不同,其中至少有一个为氢而其它的为分别选自氢,卤素,C1-4烷基或C1-4卤代烷基的基团:X是氧或硫;和R1是选自氢和任意被二氧戊环基,卤素,氰基,三氟甲基,三氟甲硫基或C1-6烷氧基取代的C1-8烃基。
当Q是单芳香环时,适合的可以是苯基,吡啶基或噻吩基,优选的是苯基。当Q为双环系时,优选的可以是萘基。
当Q含有芳香环时,合适的取代基包括1至4个选自C1-6烃基,C1-6烷氧基或亚甲二氧基的基团,每个取代基被1至3个卤素任意取代,或选自卤素,氰基或硝基或取代基是S(O)nR7基团其中n为0,1或2和R7是选一个或多个卤素任意取代的C1-6烷基或R7是任意被1至2个C1-6烷基取代的氨基或取代基为NR8R9基团,其中R8和R9分别选自氢,C1-6烷基或COR10基团(其中R10是C1-6烷基)。
Q环系通常最多含有3个取代基并未被取代或被1个,2个或3个取代基如卤素或C1-4卤代烷基如三氟甲基所取代。Q环系的取代是根据该环系的性质而定的,但是当Q是6元环时优选的是在3,4或5位上进行取代。
适合的R2,R3,R4和R5选自氢,甲基或氟。适合的双键立体化学是(E)。当R3或R5为氟时,适合的与R3或R5相连的双键的立体化学是(Z)。
优选的R2是氢,R3是氢或氟R5是氢或氟和R4为氢或C1-4烷基,最优选的为甲基。
在链中的Q1的立体构型优选的是在取代基连到环上后能给出反式几何构型。环丙基环的3位最好是未被取代。在环丙基环的1和2位上适合的取代基包括氟,氯,甲基或三氟甲基。优选的是1位上不取代,2位上不取代或被氟或氯取代。
适合的R1是任意被环烷基,二氧戊环基取代的烷基或R1是C2-5链烯基。最适合的R1是支链的C4-6烷基,如异丁基,1,2-二甲基丙基,1,1,2-三甲基丙基,2,2-二甲基丙基或R1是2-甲基丙-2烯基或(2-甲基-1,3-二氧戊环-2-基)甲基。优选的R1是异丁基或2-甲基-丙-2-烯基,其中R2和R3为氢,R4为甲基,R5为氢或甲基。
结构式(Ⅰ)中的一组适合的化合物是结构式(Ⅱ)的化合物或它们的盐:
(Ⅱ)
其中Qa是任意取代的苯基或吡啶基或稠合双环系(其中至少有一个环是含9或10个原子的芳香环,在该9或10个原子中有一个原子可以是氮,其它的为碳)或Qa是二卤代乙烯基或R6a-C≡C-基团,其中R6a是C1-4烷基,三烷基甲硅烷基或氢:Q1a是任意被一个或多个选自C1-3烷基,卤素,或C1-3卤代烷基的基团取代的1,2-环丙基环;R2a,R3a,R4a和R5a可以相同或不同,其中至少有一个为氢而其它的分别选自氢,卤素,C1-4烷基或C1-4卤代烷基;Xa是氧或硫:R1a选自氢和被二氧戊环基,卤素,氰基,三氟甲基,三氟甲硫基或C1-6烷氧基任意取代的C1-6烃基。
当Qa含有芳香环时,适合的取代基包括一个或多个选自卤素,氰基,硝基,C1-6烷基,C1-6烷氧基和亚甲基二氧基的基团,这些取代基各自被1~5个卤素任意取代,或该取代基为S(O)nR7a基团,其中n为0,1或2,R7a是被卤素任意取代的C1-6烷基或R7a是氨基。
优选的Qa是取代的苯基或萘基。
适合的R2a,R3a,R4a和R5a选自氢,甲基或氟。
适合的R1a是被二氧戊环基任意取代的C1-6烷基或R1a是C2-5链烯基。最适合的R1a是支链的C4-6烷基如异丁基,1,2-二甲基丙基,1,1,2-三甲基丙基,2,2-二甲基丙基或R1a是2-甲基-丙-2-烯基或(2-甲基-1,3-二氧戊环-2-基)。优选的R1a是异丁基或2-甲基丙-2-烯基,而R2a和R3a为氢,R4为甲基。
结构式(Ⅱ)的一组优选化合物包括结构式为(Ⅲ)的化合物:
其中Qa,Q1a,R4a和R1a如上述定义。
本发明的一组优选化合物包括结构式为(Ⅳ)的化合物:
其中Q,Q1和R1~R5如上述定义。
结构式(Ⅳ)的优选化合物包括其中的Q为取代的苯基,Q1为反1,2-环丙基环,在该环丙基环的2位上未取代或被氟或氯取代,R4为甲基或氢,R2为氢,R3和R5为氢或氟,R1是异丁基或1,2-二甲基丙基或2-甲基丙-2-烯基,X为氧或硫的化合物。
因此,优选的结构式(Ⅰ)的化合物包括:
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(4-溴代苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E/Z,4E)N-异丁基-3-甲基-5-(反-2-(3,5-双三氟甲基苯基)环丙基)-2,4-二烯酰胺。
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-(反-2-(3,5-双三氟甲基苯基)环丙基)-2,4-二烯酰胺。
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-(反-2-(3,4-二氯苯基)环丙基)-2,4-二烯酰胺。
(±)-(2E,4E)N-异丁基-3-甲基-5-(反-2-(3,4-二氯苯基环丙基)-2,4-二烯酰胺。
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-(反-2-(4-氯代苯基)环丙基)-2,4-二烯酰胺。
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-异丁基-3-甲基-5-甲基-5-〔反-2-(4-氯代苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔反-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3-三氟甲基-4-氯代苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3,5-二氯-4-溴代苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3,4,5-三氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4Z)N-异丁基-3-甲基-4-氟-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3-氯-4-溴代苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3-氯-4-溴代苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3-溴-4-氯代苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-(1,2-二甲基丙基-5-〔r-1-氟-C-2-(3,4,5-三氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-异丁基-3-甲基-5-〔r-1-氟-C-2-(3,4,5-三氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2Z,4E)N-异丁基-2-氟-3-甲基-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2Z,4E)N-(2-甲基丙-2-烯基)-2-烯基)-2-氟-3-甲基-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-(仲-丁基)-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔r-1-氟-C-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔r-1-氟-C-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔r-1-氟-C-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔r-1-氟-C-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔r-1-氟-C-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔r-1-氟-C-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4Z)N-(2-甲基丙-2-烯基)-3-甲基-4-氟-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-异丁基-3-甲基-5-〔r-1-氯-2-C-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔r-1-氟-2-C-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔r-1-氟-2-C-(3,4,5-三氯苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔反-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺。
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔C-2-(3,4-二氯苯基)-r-1-氟-环丙基〕戊-2,4-二烯硫代酰胺。
术语“卤素”是指氟、氯、溴和碘。术语“烃基”是指烷基,链烯基,链炔基,芳烷基(包括环烷基或被烷基、链烯基或链炔基任意取代的链烯基);被环烷基和链烯基和苯基任意取代的烷基或链烯基。
本发明化合物的盐是通常的酸加成盐。这种盐可以由无机或有机或环烷基酸来形成。优选的盐是由下列这些酸加成而生成的:盐酸,氢溴酸,硫酸,柠檬酸,硝酸,酒石酸,磷酸,乳酸,苯甲酸,谷氨酸,天冬氨酸,丙酮酸,乙酸,琥珀酸,富马酸,马来酸,草酰乙酸,羟基萘酸,羟乙磺酸,硬脂酸,甲磺酸,乙磺酸,苯磺酸,对甲苯磺酸,乳糖酸,葡糖醛酸;硫氰酸,丙酸,(3-羟基-2-萘酸)(embonic acid),环烷酸,高氯酸。
结构式(Ⅰ)的化合物存在有多种立体异构体,本发明包括各个几何异构体和立体异构体以及它们的混合物。本发明还包括含有放射性同位素的结构式(Ⅰ)的化合物,特别是那些有1至3个氢原子变为氚或1个或多个碳原子变为14C的化合物。
另外,本发明还提供了制备上述定义的结构式(Ⅰ)化合物的方法,它包括(比较方案1):
a)当X为氧时,通过相应的酸或酸衍生物QQ1CR2=CR3CR4=CR5C(=X)Z1与胺H2NR1的反应来制备,其中Q,Q1,R2,R3,R4,R5和R1如上述定义,X为氧,Z1为羟基,C1-6烷氧基,卤素或亚氨膦酸酯(-P(O)(O-芳基)NH-芳基,芳基为C6-10芳基)。
b)通过维悌希反应生成CR2=CR3CR4=CR5C(=X)NHR1部分,并可用本领域的普通技术人员熟知的方法任意地将一种结构式(Ⅰ)的化合物转化成另一种结构式(Ⅰ)的化合物。
方法(a)通常是在常规的温度下进行,例如在-25℃-150℃的温度下,在无水的非质子传递溶剂如醚、二氯甲烷、甲苯或苯中进行。实际的准确条件将取决于基团Z1的性质,例如当Z为烷氧基时,反应是在高温下即50℃-125℃下方便地进行和在回流温度下方便地进行。优选的是在三烷基铝化合物如三甲基铝(它与胺H2NR1将生成络合物)存在下进行。当Z1为卤素或亚氨膦酸酯时,反应是在0°-30℃下,适宜的是在室温下进行,优选的是在叔胺如三乙胺存在下进行。
如果酸衍生物为酰基卤,例如酰基氯。则它可以由相应的酸通过与合适的试剂如草酰氯或亚硫酰氯反应而制得。当Z1为亚氨膦酸酯基时则它可由(PhO)P(→O)NHPhCl(其中Ph为苯基)制得。酸或在化合物QQ1CR2=CR3CR4=CR5COZ1中的酸官能团可通过相应酯的水解来制得。
酯可以用各种不同的方法来制得,例如,(比较方案2):
(ⅰ)常用的Wittig或Wadsworth-Emmons反应,使用如醛和乙氧基羰基亚甲基三苯基正膦或来自三乙基膦酰基丁烯酸酯或3-甲基三乙基膦酰基丁烯酸酯阴离子来制备。后一种反应可产生异构体混合物,例如(Z)和(E)取代的二烯酸酯的混合物,这种混合物可以进行如上所述的反应,结果得到的酰胺混合物可通过色谱法或其它便利的技术进行分离。Wittig试剂可按下列的制备途径或其他类似的途径制得:
其中Z2是(芳基)3P,(芳基)2P(O)或(C1-4烷氧基)2P(O),优选的芳基为苯基,优选的烷氧基为乙氧基。
(1)N-溴代琥珀酰亚胺
(2)例如(EtO)3P或(Ph)3P
(3)该反应通常是在碱,如二异丙基氨基化锂,丁基锂,醇钠,氢化钠。
(ⅱ)通过结构式:
的化合物的HS(→O)Z3的重排和消除反应来制得,上述结构式中Q,Q1,R2,R3和R4如前述定义,Z3是任何合适的基团如苯基,取代苯基如4-氯苯基,或C1-4烷基如甲基,Z4为C1-4烷基如甲基或乙基。
上述化合物可由化合物QQ1CHR2CHR3CR4O与化合物
Z3S(O)CH2CO2Z4反应来制得。
(ⅲ)通过在化合物QQ1CHR2CR3(OZ5)CR4=CR5CO2Z4(其中Q,Q1,R2,R3,R4,R5和Z4如前述定义,Z5为氢或C1-4酰基如乙酰基)上进行消除反应来制得。该消除反应最好是在芳香性溶剂中在钼催化剂和碱如双-三甲基甲硅烷基乙酰胺存在下进行。上述化合物可通过合适的醛与合适的硫基化合物反应,接受进行酰化反应来制得。
(ⅳ)结构式QQ1CR2=CR3C(=O)R4的化合物与结构式Me3SiCHR5CO2Z4(其中Q,R2-R5,Q1和Z4如前述定义)中的一种化合物进行反应。该反应可以在无水溶剂如四氢呋喃中,并在无氧气情况下和有碱如环己基异丙基氨基化锂的存在下进行。
(ⅴ)通过结构式QQ1CR2=CR3C(OZ6)=CR5CO2Z4的化合物与结构式R4M1化合物的反应来制得。其中Q,Q1,R2,R3,R4,R5和Z4如前述定义,Z6是适合的基团如二烷基磷酸酯或三氟甲磺酸酯基,M1为金属如铜(Ⅰ)或与锂或镁结合的铜(Ⅰ)。该反应可在低温下在无水醚溶剂(如二乙醚,甲硫醚)或四氢呋喃中,并在无氧气存在下进行。
(ⅵ)通过结构式QQ1CR2=CR3M2的化合物与结构YCR4=CR5CO2Z4的一种化合物的反应来制得,其中Q,Q1,R2,R3,R4,R5和Z4如前述定义,Y为卤素或锡,M2是甲硅烷基或含基团如三甲基甲硅烷基的金属或含锆,锡,铝或锌的基团如双(环戊二烯基)锆氯化物。该反应通常是在常规的温度下即0℃和100℃下进行,和在室温下,在无水的醚溶剂如四氢呋喃中,在钯(O)催化剂(如双(三苯基膦)钯)和惰性气体氮气或氩气存在下进行。
(ⅶ)通过结构式
(其中Q,Q1,R2,R3,R4,R5,Z3和Z4如前述定义)化合物中的Z3S(→O)H的消除反应来制得。上述化合物可由化合物QQ1CHR2CR3=CHR4与Z3S(O)CH2COZ4反应制得。
方法(b)可以通过先得到连接在结构式(Ⅰ)中的酰胺/硫代酰胺端部上或QQ1片段上的醛基或酮基,然后再使其与合适的亚磷内鎓盐反应来进行。
例如,QQ1(CR2=CR3)COR4+Z2CHR5.C(=X)NHR1
或 QQ1COR2+Z2CHR3.CR4=CR5.C(=X)NHR1或
QQ1(CR2=CR3)CHR5Z2+R5CO.C(=X)NH.R1
其中Q,Q1,R2,R3,R4,R5,R1,X和Z2如前述定义。
方法(b)是在无水惰性溶剂(醚,如四氢呋喃)中,在碱,如从亚磷内鎓盐的制备过程中得到的胺即异丙胺存在下进行,优选的是在无氧气存在下即在氮气氛下,在低温下(-60°-20℃)进行。亚磷内鎓盐如上所述是通过与碱如二异丙基氨基化锂,丁基锂,醇钠或氢化钠反应,从它的母体制得的。结构式(Ⅰ)中X为硫的化合物当Z2为(C1-4烷氧基)2P=0时最好由方法(b)来制备。醛中间体QQ1CR2=O可通过在溶剂如丙酮-水中的缩酮,烯醇型醚或缩醛的酸解来制得或通过使用氯铬酸盐吡啶鎓,重铬酸盐吡啶鎓或草酰氯-二甲基亚砜氧化在溶剂如二氯甲烷中的合适的醇来制得。该醛也可以通过合适的腈与试剂如在己烷中的二异丁基氢化铝进行还原反应来制得。
醇(方案3)可由下列方法制得:
(a)QCH=CX2OH与(Z7)2M2和CH2X32在惰性溶剂如己烷或二氯甲烷中在适中的温度下(-20°-+20℃)进行反应,其中CH2和CH=CX2结合形成Q1,上述结构式中X2为氢、氟、氯或甲基,X3为卤素如碘,Z7为C1-4烷基如乙基,M2为金属如锌。
(b)QCH=CX2CH2OH与CX42X5CO2M3(其中X4和X5为卤素如氟和氯,M3为碱金属如钠)在惰性溶剂如二甘醇二甲醚,在适中/高温度下(150°-200℃)进行反应,CX42和CH=CX2结合形成了Q1。
中间产物醇可以通过酯QCH=CX2CO2Z4与例如二异丁基氢化铝在惰性溶剂如二氯甲烷或四氢呋喃中,在适中的温度下(-20-25℃)进行还原反应来制备。
(c)酯QQ1CO2Z4或合适的羧酸与例如二异丁基氢化铝或乙硼烷在惰性溶剂如二氯甲烷或四氢呋喃中,在适中的温度下(-20°-25℃)进行反应,上述这些酯可以通过重氮基乙酸酯N2CHCO2Z4与化合物QCH=CH2在含铜催化剂如硫酸铜存在下进行反应来制备,反应中CH和CH=CH2结合形成了Q1。这些酯还可以通过QCH=CHCO2Z4与MeZS(O)mC(Z7)2(其中Z7为氢或C1-6烷基,m为1或2)得到的阴离子进行反应来制备。
附加的反应方案有助于说明中间产物和它们转化成结构式(Ⅰ)化合物的制备方法。本发明的中间产物构成了本发明的另一个方面。它们可以用本发明描述的方法以外的其它合适的标准方法来制得。
结构式(Ⅰ)的化合物可用于防治虫害如节肢动物类虫害,例如可以防治昆虫,蜱螨和蠕虫即线虫类病虫害。因此本发明提供了一种防治节肢动物和/或线虫病虫害的方法,它包括将有效量的结构式(Ⅰ)的化合物施用于节肢动物和/或线虫或它们的生存环境中。本发明还提供了一种防治和/或根除节肢动物和/或线虫在动物(包括人)和/或植物(包括树)和/或储藏产品上的侵袭,它包括将有效量的结构式(Ⅰ)的化合物施用于动物或现场。本发明还提供了可用于人和兽用的药物以保护人类健康和在农业上防治节肢动物和/或线虫病虫害的结构式(Ⅰ)的化合物。
结构式(Ⅰ)的化合物对于农田,饲料,植物园,暖房,果园,葡萄园作物的保护,观赏植物和人造林以及森林树木的保护具有特殊的价值。例如可用于保护谷类(如玉米,小麦,水稻,高粱),棉花,烟叶,蔬菜和生菜(如豆,油菜作物,葫芦,莴苣,洋葱,西红柿和胡椒),田间作物(如土豆,甜菜,落花生,大豆,油菜),甘蔗,草地和饲料(如玉米,高粱,苜蓿),人造林(如茶叶,咖啡,可可,香蕉,油棕,椰子,橡胶,香料),果园和园林(如核果和仁果类果实,柑桔类,猕猴桃,油梨,芒果,榄橄和胡桃)葡萄,观赏植物,花,在绿草下面和花园及公园内的灌木,森林树木(落叶的和长青的),植物和苗圃。
它们对保护木材(直立的,伐倒的,加工的,储藏的或用于建材的)免遭锯锋(例如Urocerus)或甲虫(例如棘胫小蠹,长小蠹,粉蠹,长蠹,天牛,窃蠹)的侵袭也具有价值。
它们还可用于保护储藏产品如种子,水果,坚果,香料,烟叶(无论是原产物还是加工过的或化合到产品中的)免遭蛀虫、甲虫,蜱螨的侵袭。同样也可用于保护储藏的动物制品如皮,毛,羊毛和天然皮草或加工后的成品(例如地毯或纺织品)免遭蛀虫和甲虫的侵袭;还可用于保护储存的肉和鱼免遭甲虫,蜱螨和苍蝇的侵袭。
结构式(Ⅰ)的化合物对于防治节肢动物或线虫病虫害使用注射或喷洒的方法作用于人和家禽的传病媒介最为有效,例如,如上面所述的那样具体的是防治蜱,螨,虱,跳蚤,蚋,刺螫,nuisance和蝇蛆。
对于上述这些用途,结构式(Ⅰ)的化合物可直接应用或以稀释的形式应用,如常用的浸渍剂,喷雾剂,雾剂,涂抹剂,泡沫剂,粉剂,粉末剂,含水悬浮剂,膏剂,凝胶,乳膏,洗发剂,脂膏,可燃性固体,汽雾垫,蚊香,诱饵,毒饵,可湿性粉剂,颗粒剂,气溶胶浓缩乳剂,油悬浮液,油溶液,压力填充剂(Pressure-Pack),浸渍物品,浇注制剂(Pour-on formation)或其它本领域内的普通技术人员公知的标准制剂。浸渍剂浓缩液不单独使用而是用水稀释后将动物浸泡在含有浸渍溶液的浸渍浴中。喷雾剂可用手喷洒或旋转喷洒或拱形喷洒。要被处理的动物,土壤,植物或表面可通过大量的喷雾使其饱和或通过少量或极少量的喷雾使其表面层覆盖上一层喷雾剂。含水悬浮液同样可以用喷雾或浸渍的方法来使用。粉剂可用粉末撒粉机来分散,或在用于动物的情况下,可将它们放入多孔的袋中,然后将这些袋挂在树上或耐磨的杆上。膏剂,洗发剂,脂膏可用手使用或涂在惰性物质上,然后将这些涂有药物的惰性物质与动物表皮摩擦并使药物传送到它们的皮肤上。浇注制剂可将其以一少量的液体单位分洒在动物的背部以使全部或大部分的液体停留在动物身上。
结构式(Ⅰ)的化合物可以先制成制剂以备用于动物,植物或表面,也可以制成在使用前需要稀释的制剂,但是这两种制剂都紧密混合有一种或多种载体或稀释剂。载体可以是液体,固体或气体或它们的混合物。根据制剂是否需要进一步稀释,结构式(Ⅰ)的化合物可以0.025-99%W/V的浓度存在,这取决于制剂是否要进一步稀释。
粉剂,粉末剂和颗粒剂和其他固体制剂都由结构式(Ⅰ)化合物和与其紧密混合的粉末状固体惰性载体所组成,所说的惰性固体载体可以是粘土,高岭土,膨润土,美国活性白土,吸附性碳黑,滑石,云母,白垩,石膏,磷酸三钙,木屑,硅酸镁,植物载体,淀粉和硅藻土。这些固体制剂通常是通过将固体稀释剂浸渍在挥发性溶剂中的结构式(Ⅰ)化合物的溶液中,然后再蒸出溶剂来制备的,如果需要可将所得产物研磨成所需的粉末,如果需要还可将其颗粒化,压制或包封。
结构式(Ⅰ)化合物的喷雾剂由在有机溶剂(例如以下所列的溶剂)中的溶液或在水中的乳化液(浸渍液或喷雾液)所组成,它们可在田间由可用于浸渍目的的可乳化的浓缩物(或称为水可溶性油)来制备。该浓缩物最好是由活性组分,有机溶剂(或不含有机溶剂)和一种或多种乳化剂所组成。溶剂可以一个较宽范围的量存在,但优选的量为组合物的0-90%W/V。它们可选自煤油,酮,醇,二甲苯,芳香族石脑油和其它制剂领域内已知的溶剂。乳化剂的浓度可以在一个较宽范围内变化,优选的为5-25%W/V,乳化剂通常为非离子表面活性剂,它们包括烷基苯酚的聚亚氧烷基酯和己糖醇酐的聚氧乙烯衍生物,和阴离子表面活性剂,包括十二烷基硫酸钠,脂肪族醇醚硫酸盐,烷基芳基磺酸钠,烷基芳基磺酸钙,烷基磺基琥珀酸钠,烷基磺基琥珀酸钙。阳离子乳化剂包括benzalkonium chloride和乙硫酸季铵盐。
两性乳化剂包括羧甲基化油酸咪唑啉和烷基二甲基三甲铵乙内酯。
气雾垫通常是由棉花和纤维混合压制成尺寸约为35×22×3mm的块,然后用最多0.3ml含有在有机溶剂中的活性组分的浓缩物,任意的防老化剂,染料,香料处理而制得的。通过热源如电加热垫的加热器使杀虫剂蒸发。
可燃性固体通常是由木屑和粘结剂与活性组分相混合,然后制成条状(通常为螺线形的)而制得。其中也可加入染料和杀真菌剂。
可湿性粉末是由惰性载体,一种或多种表面活性剂和任何稳定剂和/或抗氧化剂所组成。
浓缩乳剂是由乳化剂和有机溶剂如煤油,酮,醇,二甲苯,芳香族石脑油和其他本领域内已知的溶剂所组成。
可湿性粉剂和浓缩乳剂通常含有5-95%(重量)的活性组分,并在使用前可用水稀释。
涂抹剂由在有机溶剂中的活性组分的溶液,树脂,和任何的增塑剂所组成。
浸渍液不但可以由浓缩乳剂制得,而且也可由可湿性粉剂,皂基浸渍剂。含水悬浮液是在含有分散剂和一种或多种表面活性剂的紧密混合物中含有结构式(Ⅰ)化合物。
结构式(Ⅰ)化合物的含水悬浮液可能包括与悬浮剂、稳定剂或其它试剂一起悬浮在水中的悬浮液,该悬浮液或溶液可以直接使用或以已知的稀释形式使用。
油脂可以从蔬菜油、脂肪酸合成酯或羊毛脂与惰性基质,如软石蜡一起来制备。结构式(Ⅰ)的化合物最好通过混合物混匀分布在溶液或悬浮液中,油脂也可以通过用油脂基质稀释可乳化的浓缩物的方法,由可乳化的浓缩物制备。
软膏和洗发剂也是半固制备物,其中结构式(Ⅰ)的化合物可均匀分散在合适的基质中,例如软石蜡或液态烃,或与甘油、胶水或合适的皂一起在非油脂基上形成。作为油脂,洗发剂和软膏通常不需要进一步稀释就能使用,它们包含适当百分比的结构式(Ⅰ)化合物供处理。
气溶胶喷涂物可以在气溶胶促进剂和共溶剂(例如,前面分别所述的卤代烷和溶剂)中的活性组份的简单溶液形式来制备。浇注制剂可制成结构式(Ⅰ)化合物在溶液介质中的溶液或悬浮液,通过使鸟类或哺乳动物宿主携带用结构式(Ⅰ)化合物浸渍后的合适的成型塑料物品,来预防其免遭acarine ectoparasites的感染,这些物品包括与身体合适部位接触的浸渍后的衣领、标签、带、片和条,合适的塑料物质是聚氯乙烯(PVC)。
施用于动物、房屋或户外的结构式(Ⅰ)化合物的浓度根据选择的化合物、处理间隔、配制物的性质和易于感染的情况而改变,一般为0.001至20.0% W/V,最好为0.01至10%(在所用的组合物中)。沉积在动物上的化合物的量根据使用方法、动物的大小,所用配制物中化合物的浓度、配制物的稀释程度和配制物的性质而改变,但通常为0.0001%至0.5% W/W,除了未稀释的配制物,例如喷涂配制物,它的沉积浓度通常为0.1至20.0%,最好为0.1至10%。使用于贮存产物的化合物用量通常是0.1至20ppm。可以应用空间喷雾使平均初始浓度为每立方米被处理的空间为0.001至1mg的结构式(Ⅰ)化合物。
结构式(Ⅰ)化合物也用于保护和处理植物品种,在这种情况下使用有效量的活性组份可使其有效地杀昆虫、杀螨、或杀线虫。使用量可根据选择的化合物、配制物的性质、使用方式、植物种类、种植密度和易感染程度和其它类似的因素而变化,但通常对于农作物来说,合适的使用量为0.001至3Kg/Ha,最好0.01和1Kg/Ha。农用配制物一般含有0.0001%和50%的结构式(Ⅰ)化合物,最好0.1至15%的结构式(Ⅰ)化合物。
粉剂、油脂、软膏和气溶胶配制物如上所述通常以自由方法使用,使用浓度为使用配制物中0.001至20% W/V的结构式(Ⅰ)化合物。
已经发现结构式(Ⅰ)的化合物具有抗普通家蝇(Musca domestica)的活性,此外结构式(Ⅰ)的某些化合物还具有抗其它节肢动物的活性,这些节肢动物有:Myzus Persicae,Tetranychus Urticae Plutella Xylostella,Culex SPP.Tribolium Castaneum,Sitophilusgranarius,Periplaneta ameircana和Blattellagermanica。因此,结构式(Ⅰ)化合物有效地在存在害虫的任何环境中控制节肢动物,如昆虫和螨,其中所说的存在害虫的环境例如农田中,动物饲养地,公共健康治疗地和家庭环境。
昆虫害虫包括鞘翅目(例如,Anobium,Ceutorhynchus,Rhynchophorus,Cosmopolites,Lissorhoptrus,Meligethes,Hypothenemus,Hylesinus,Acalymma,Lema,Psylli odes,Leptinotarsa,Gonocephalum,Agriotes,Dermolepida,Heteronychus,Phaedon,Tribolium,Sitophilus,Diabrotica,Anthonomus或Anthrenus SPP.),鳞翅目(例如,Ephestia,Mamestra,Earias,Pectinophora,Ostrinia,Trichoplusia,Pieris,Laphygma,Agrotis,Amathes,Wiseana,Tryporysa,Diatraea,Sporganothis,Cydia,Archips,Plutella,Chilo,Heliothis,Spodoptera或Tineola SSP.),双翅目(例如,Musca,Aedes,Anopheles,Culex,Glossina,Simulium,Stomoxys,Haematobia,Tabanus,Hydrotaea,Lucilia,Chrysomia,Callitroga,Dermatobia,Gasterophilus,Hypoderma,Hylemyia,Atherigona,Chlorops,Phytomyza,Ceratitis,Liriomyza和Melophagus SPP.),虱目(Malophaga例如,Damalina,SPP.和Anoplura,例如Linognathus和Haematopinus SPP.)半翅目(例如,Aphis,Bemisia,Phorodon,Aeneolamia,Empoasca,Parkinsiella,Pyrilla,Aonidiella,Coccus,Pseudococus,Helopeltis,Lygus,Dysdercus,Oxycarenus,Nezara,Aleurodes,Triatoma,Psylla,Mysus,Megoura,Phylloxera,Adelyes,Niloparvata,Nephrotetix,或Cimex SPP.),直翅目(例如,Locusta,Gryllus,Schistocerca或Acheta SPP.),网翅目(例如Blattella,Periplaneta或Blatta SPP.),膜翅目(例如,Athalia,Cephus,Atta,Solenopsis或Monomorium SPP.),等翅目(例如,Odontotermes和Reticulitermes SPP.),蚤目(例如,Ctenocephalides或Pulex SPP.),缨尾目(例如,Lepisma SPP.),革翅目(例如,Forficula SPP.),Pscoptera(例如,Peripsocus SPP.)和缨翅目(例如Thrips tabaci)的昆虫。
螨虫害包括蜱,例如Boophilus,Ornithodorus,Rhipicephalus Amblyomma,Hyalomma,Ixodes,Haemaphysalis,Dermacentor和Anocentor属的成员,以及螨和疥,例如Acarus,Tetranychus,Psoroptes,Notoednes,Sarcoptes,Psor'ergates,Chorioptes,Eutrombicula,Demodex,Panonychus,Bryobia,Eriophyes,Blaniulus,Polyphagotarsonemus,Scutigerella,和Oniscus SPP.
通过传播细菌、病毒、支原体或植物真菌疾病或直接进攻对农业、林业、园艺重要的植物和树的线虫包括根瘤线虫,例如
Meloidogyne SPP.(例如M.incognita);囊线虫,例如Globodera,SPP.(例如G.rostochiensis);
Heterodera SPP.(例如hydrogen,avenae);
Radopholus SPP.(例如R.Similis);致病线虫,例如Pratylenchus SPP.(如,P.Pratensis);
Belonolaimus SPP.(例如B.gracilis);
Tylenchulus SPP.(例如T.Semipenetrans);
Rotylenchulus SPP.(如R.reniformis);
Rotylenchus SPP.(如R.robustus);
Helicotylenchus SPP.(如 hydrogen,
multicinctus);
Hemicycliophora SPP.(如hydrogen,gracilis);
Criconemoides SPP.(例如C.Similis);
Trichodorus SPP.(如T.Primitivus);剑形线虫,例如Xiphinema SPP.(如X.diversicaudatum),Longidorus SPP.(如L.elongatus);Hoplolaimus SPP.(如hydrogen Coronatus);Aphelenchoides SPP.(如A.ritzema-bosi,A.besseyi);茎和鳞茎鳗蛔虫,例如Ditylenchus SPP.(如D.dipsaci)。
本发明的化合物可与一种或多种其它农药活性组分(例如除虫菊类、氨基甲酸酯和有机磷酸盐)和/或引诱剂、驱散剂、杀菌剂、杀真菌剂、杀线虫剂、治蠕虫剂等等结合,此外,已经发现本发明化合物的活性可以通过添加增效剂或促进剂得到提高,所说的增效剂或促进剂例如一种增效剂的氧化酶抑制剂类,如胡椒基丁氧金属化物或2-丙炔基苯基磷酸丙酯;本发明的第二化合物;或除虫菊类杀虫化合物。当本发明制剂中存在氧化酶抑制剂增效剂时,增效剂与结构式(Ⅰ)化合物之比为25∶1-1∶25,例如大约10∶1。
防止本发明化合物发生化学降解的稳定剂包括抗氧剂(例如抗生育酚、丁基羟基苯甲醚和丁基羟基甲苯)和清除剂(例如表氯醇)和有机或无机碱,如三烷基胺,例如三乙胺,它起碱性稳定剂和清除剂的作用。
工业实用性
本发明的化合物作为杀虫剂显示了活性。
下列实施例以非限定方式说明了本发明的优选方面。
配制物
1.可乳化的浓缩物
结构式(Ⅰ)的化合物 10.00
烷基酚乙氧基化物*7.50
烷基芳基磺酸酯*2.50
C8-13芳香溶剂 80.00
100.00
2.可乳化的浓缩物'
结构式(Ⅰ)的化合物 10.00
烷基酚乙氧基化物*2.50
烷基芳基磺酸酯*2.50
酮溶剂 64.00
C8-13芳香溶剂 18.00
抗氧化剂 3.00
100.00
3.可湿性粉末
结构式(Ⅰ)的化合物 5.00
C8-13芳香溶剂 7.00
C18芳香溶剂 28.00
陶土 10.00
烷基芳基磺酸酯*1.00
萘磺酸 3.00
硅藻土 46.00
100.00
4.粉剂
结构式(Ⅰ)的化合物 0.50
滑石 99.50
100.00
5.毒饵
结构式(Ⅰ)的化合物 0.50
糖 79.50
石蜡 20.00
100.00
6.乳化浓缩物
结构式(Ⅰ)的化合物 5.00
C8-13芳香溶剂 32.00
十六烷醇 3.00
聚氧乙烯甘油单油酸盐*0.75
聚氧乙烯脱水山梨醇酯*0.25
硅氧烷溶液 0.10
水 58.90
100.00
7.悬浮液浓缩物
结构式(Ⅰ)的化合物 10.00
烷基芳基乙氧基化物*3.00
硅氧烷溶液 0.10
烷烃二醇 5.00
发烟硅石 0.50
汉生胶(xanthan gum) 0.20
水 80.00
缓冲剂 1.20
100.00
8.微乳化液
结构式(Ⅰ)的化合物 10.00
聚氧乙烯甘油单油酸酯*10.00
烷烃二醇 4.00
水 76.00
100.00
9.水分散颗粒剂
结构式(Ⅰ)的化合物 70.00
聚乙烯吡咯烷 2.50
烷基芳基乙氧基化物 1.25
烷基芳基磺酸酯 1.25
陶土 25.00
100.00
10.颗粒剂
结构式(Ⅰ)的化合物 2.00
烷基酚乙氧基化合物*5.00
烷基芳基磺酸酯*3.00
C8-13芳香溶剂 20.00
硅藻土颗粒 70.00
100.00
11.气溶胶(压力填充)
结构式(Ⅰ)的化合物 0.3
胡椒基丁氧金属 1.5
C8-13饱和烃溶剂 58.2
丁烷 40.0
100.00
12.气溶胶(压力填充)
结构式(Ⅰ)'的化合物 0.3
C8-13饱和烃溶剂 10.0
脱水山梨醇单油酸酯*1.0
水 40.0
丁烷 48.7
100.00
13.气溶胶(压力填充)
结构式(Ⅰ)的化合物 1.00
CO23.00
聚氧乙烯甘油单油酸酯*1.40
丙酮 38.00
水 56.60
100.00
14.涂抹剂
结构式(Ⅰ)的化合物 2.50
树脂 5.00
抗氧化剂 0.50
高度芳香化的石油溶剂 92.00
100.00
15.喷雾剂(备用)
结构式(Ⅰ)的化合物 0.10
抗氧化剂 0.10
无味煤油 99.80
100.00
16.增效喷雾剂(备用)
结构式(Ⅰ)的化合物 0.10
胡椒基丁氧金属 0.50
抗氧化剂 0.10
无味煤油 99.30
100.00
17.微囊化的制剂
结构式(Ⅰ)的化合物 10.0
C8-13芳香溶剂 10.0
芳香二-异氰酸酯#4.5
烷基酚乙氧化物*6.0
烷基二胺#1.0
二亚乙基三胺 1.0
浓盐酸 2.2
Xanthan gum 0.2
发烟二氧化硅 0.5
水 64.6
100.00
*=表面活性剂
#=反应形成微囊的聚尿壁
抗氧化剂可以是下列物质或它们的混合:
丁化羟基甲苯
丁化羟基甲氧基苯
维生素C(抗坏血酸)
下列实施例以非限定方式说明本发明的优选方面:
实验
一般的合成方法和步骤:
按照下列实验步骤合成多种化合物并鉴定之。
在氘代氯仿溶液中,用四甲基硅烷作内标,在Bruker AM-250色谱仪上得到1H.N.m.r.光谱,并用TMS的PPm、质子数、峰数、偶合常数JHz来表示。
反应进程用预先涂有0.25mm带莹光指示剂的硅胶层的铝片(40×80mm)来控制,并且在合适的溶剂或溶剂混合物中显层,整个过程的温度均用摄氏温度。
常规方法是如下进行的:
将反应混合物分布在有机溶剂和水之间,进行相分离,用至少等体积的稀释碱溶液洗涤有机相,然后用饱和盐水洗涤,有机相再用干燥剂(适用的为硫酸镁)干燥,并过滤,除去挥发性溶剂,将生成的产物进行提纯,在下步作为最终产品合成或分析使用。
从Aldrich,BDH,Fluorochem,Fluka或Lancaster合成得到醛、肉桂酸和胺起始物料,但以下描述的制备方法除外。
a).用浓硫酸(1ml)处理乙醇(100ml)中的4-三氟甲氧基苯甲酸酯(5g)。(例如Fluorochem),回流几小时后,真空浓缩混合物,按常规方法处理残余物,得到乙基4-三氟甲氧基苯甲酸酯(5g)。NMR′H:S.90(2H,d),7.22(2H,d),4.37(2H,q),1.40(3H,t)。
上述-20℃氮气氛中在二氯甲烷(40ml)中的酯(5g)用二异丁基氢化铝(43ml)处理,在25℃处理18小时后,加入稀盐酸,用常规方法处理该混合物。得到4-三氟甲氧基苄基醇(4.1g),NMR′H:7.24(2H,d),7.15(2H,d),4.52(2H,S),3.37(3H,S)。
上述醇用二氯甲烷中的Swern(草酰氯2.05ml,二甲基亚砜3.33ml和三乙胺14.8ml)氧化,得到4-三氟甲氧基苯甲醛(4g)。NMR′H:10.04(2H,S),7.98(2H,d),7.35(2H,d)。
b).将在冰乙酸(88ml)和乙酐(89.7g)中的4-溴-2-氟甲苯(例如Fluorochem)冷却至-10℃,逐滴加入硫酸(11.7g),保持反应温度低于-5℃,在0℃分批添加三氧化铬(14.7g),将该混合物倒入冰(300g)中,按常规方法处理,得到二乙酸基甲基-2-氟-4-溴苯。
上述在乙醇(30ml)和水(30ml)中的二乙酸酯用浓硫酸(3ml)处理,回流几小时后,浓缩该溶液,用常规方法处理残余物,得到2-氟-4-溴苯甲醛(4.89g)。NMR′H:10.3(1H,S),7.5(3H,m)。
c).按类似方法制备4-溴-3-氟苯甲醛。
d).向4-氟-3-三氟甲基苯胺(ex Fluorochem)(15.9g)在水(16ml)中的悬浮液加入浓盐酸(18ml),加入冰(30g),将混合物冷却至0℃,用水(8ml)中的硝酸钠(5.6g)处理,15分钟后使用水(10ml)中的乙酸钠(8g)使该混合物对刚果红呈中性。由甲醛肟氢氯化物(ex Lancaster)(9.9g)和水(57ml)中的乙酸钠(12g)(ex BDH)制备的甲醛肟溶液,在10℃时用硫酸铜(2g)(ex BDH)和亚硫酸钠(0.34g)处理,然后用水(60ml)中的乙酸钠(55g)再处理。在10-15℃逐滴加入前面制备的混合物(从苯胺制备),1小时后,在15℃加入盐酸(77ml),按常规方法处理该混合物,蒸馏提纯(80℃,0.5mmHg),得到4-氯-3-三氟甲基苯甲醛(1.5g)。
e).在回流时,向冰乙酸中的萘甲酸(50g)(ex Aldrich)加入几滴溴(ex BDH),然后加入碘(0.5g)(ex BDH),在1小时内逐滴加入溴(15ml),将该混合物冷却至25℃,搅拌18小时,滤去生成的白色沉淀物,将其在热水中溶解,并用浓盐酸处理,沉淀物滤出并干燥(用五氧化磷ex BDH),得到5-溴-2-萘甲酸(从乙醇中重结晶)(28g),溶点:261-2℃。NMR′H:(DMSO,CDCl3),8.60(1H,S),8.00(5H,m),7.40(1H,m)。
上述酸(34g)用乙醇(240ml)中的浓硫酸(0.5ml)处理,回流6小时,用常规方法处理,得到乙基5-溴-2-萘甲酯(23g),溶点:52-54℃,NMR′H:8.68(1H,S),7.80-8.35(4H,m),7.43(1H,dd),4.50(2H,q),1.48(3H,t)。
实施例1
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(4-溴苯基)环丙基〕戊-2,4-二烯酰胺(化合物1)
(ⅰ)在25℃氮气压力下,将4-溴苯甲醛(9.25g)溶于干二氯甲烷(250ml)中,加入甲酯基亚甲基三苯基正膦(17.4g)(ex Lancaster),在25℃搅拌该溶液18小时,真空除去溶剂,用己烷洗涤残余物并过滤,真空除去己烷,得到4-溴肉桂酸乙酯(12.12g)。NMR′H:7.35(5H,m),6.38(1H,d)4.1(2H,q),1.35(3H,t)。
(ⅱ)在氮气压力下将4-溴肉桂酸乙酯(12.12g)溶于干二氯甲烷(50ml)中,并冷却至-20℃,逐滴加入二异丁基氢化铝(100ml,1M在二氯甲烷中的溶液)(ex Aldrich),将该溶液加热至25℃,然后搅拌18小时,再在乙醚和稀盐酸之间分配。有机相用饱和碳酸氢酸、盐水洗涤,用硫酸镁干燥,真空浓缩,得到3-(4-溴苯基)丙-2-烯-1-醇(8.9g)。NMR′H:7.28(2H,d),7.05(2H,d),6.45(1H,d),6.25(1H,t),4.25(2H,d),2.0(1H,S)。
(ⅲ)在室温将上述醇(1.07g)悬浮在己烷(50ml)中,并在氮气中冷却至-20℃,逐滴加入二乙基锌(ex Aldrich)(22.7ml,1.1M在己烷中的溶液),然后加入二碘甲烷(ex Aldrich)(4.1ml),将混合物慢慢加热至25℃,然后搅拌18小时,加入饱和氯化铵,并用乙醚萃取该混合物,用饱和的硫代硫酸钠溶液洗涤收集的醚萃取物,用硫酸镁干燥,真空除去溶剂,色谱分离(硅石、乙醚/己烷)提纯,得到(±)-反-2-(4-溴苯基)-1-羟甲基环丙烷(0.53g)。NMR′H:7.38(2H,d),6.95(2H,d),3.65(2H,d),1.8(1H,m),1.55(1H,s),1.44(1H,m),0.95(2H,m)。
(ⅳ)将草酰氯(ex Aldrich)溶于二氯甲烷(3ml)中,并在氮气中冷却至-70℃,逐滴加入在二氯甲烷(1ml)中的二甲基亚砜(ex BDH)(0.36ml),5分钟后,加入在二氯甲烷4ml中的上述醇(0.53g),在-70℃搅拌悬浮液30分钟,加入三乙胺(ex Aldrich)(1.6ml),在一小时内将混合物加热至0℃,用常规方法处理,得到(±)-反-〔2-(4-溴苯基)环丙基〕-甲醛,它可以被直接使用。NMR′H:9.4(1H,d),7.33(2H,d),6.9(2H,d),2.54(1H,m),2.20(1H,m),1.0-1.9(2H,m)。
(ⅴ)在-60℃,用四氢呋喃中的4-膦酰基巴豆酸三乙酯(0.58g),于氮气压力下对由正-丁基锂(ex Aldrich)(1.61ml)和二异丙基胺(ex Aldrich)(0.4ml)制备的二异丙基胺锂在干燥四氢呋喃中的溶液进行处理,2小时后,在-60℃加入上述醛(0.52g),18小时后,在25℃将混合物分布在醚和水之间,按上述方法处理醚萃取液,色谱分离提纯(硅石;乙醚/己烷),得到(±)-乙基-5-〔反-2-(4-溴苯基)-环丙基〕戊-2,4-二烯酸酯。NMR′H:7.4(2H,d),7.26(1H,dd),6.93(2H,d),6.28(1H,dd),5.80(1H,d),5.76(1H,dd),4.20(2H,q),2.05(1H,m),1.75(1H,m),1.35(2H,m),1.30(3H,t)。
(ⅵ)在-10℃将在干燥甲苯中的上述酯(0.18g)加入到由三甲基铝(ex Aldrich)(0.62ml 2M在甲苯中的溶液)和1,2-二甲基丙胺(ex Aldrich)(0.055g在干甲苯中)制备的复合物中,回流加热3小时,用2N-盐酸处理,分离有机层,按上述方法处理。色谱分离提纯(硅石,乙醚/己烷)得到标题化合物(0.096g)。TLC(硅石,乙酸乙酯∶己烷,3∶7)Rf0.25m:Pt141.9-143.2℃。
化合物2-17,63,64,99和100按照类似方法,使用特定的醛、维梯希试剂和胺来制备。
化合物编号 化合物名称
2 (±)-(2E,4E)N-异丁基-5-〔反-2-(4-溴苯基)环丙基〕戊-2,4-二烯酰胺
3 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3,5-双三氟甲基苯基)环丙基〕戊-2,4-二烯酰胺
4 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(2-萘基)环丙基〕戊-2,4-二烯酰胺
5 (±)-(2E,4E)N-新戊基-5-〔反-2-(2-萘基)环丙基〕戊-2,4-二烯酰胺
6 (±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔反-2-(2-萘基)环丙基〕戊-2,4-二烯酰胺
7 (±)-(2E,4E)N-新戊基-5-〔反-2-(4-溴苯基)环丙基〕戊-2,4-二烯酰胺
8 (±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔反-2-(4-溴苯基)环丙基〕戊-2,4-二烯酰胺
9 (±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔反-2-(3,5-双三氟甲基苯基)环丙基〕戊-2,4-二烯酰胺
10 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(4-三氟-甲基苯基)-环丙基〕-戊-2,4-二烯酰胺
11 (±)-(2E,4E)N-异丁基-5-〔反-2-(4-三氟甲基苯基)-环丙基〕-3-甲基-戊-2,4-二烯酰胺
12 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(4-甲氧基-苯基)环丙基〕戊-2,4-二烯酰胺
13 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(4-三氟甲氧基苯基)-环丙基〕-戊-2,4-二烯酰胺
14 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(4-溴-2-氟苯基)环丙基〕戊-2',4-二烯酰胺
15 (±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(2-氟-4-溴苯基)环丙基〕戊-2,4-二烯酰胺
16 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(4-溴-3-氟苯基)环丙基〕戊-2,4-二烯酰胺
17 (±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(4-溴-3-氟苯基)环丙基〕戊-2,4-二烯酰胺
63 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(4-氯-3-三氟甲基苯基)环丙基〕戊-2,4-二烯酰胺
64 (±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(4-氯-3-三氟甲基苯基)环丙基〕戊-2,4-二烯酰胺
99 (±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(5-溴-2-萘基)环丙基〕戊-2,4-二烯酰胺
100 (±)-(2E,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔反-2-(5-溴-2-萘基)环丙基〕戊-2,4-二烯酰胺
化合物 醛/RCHO 维悌希 胺
编号 其中R是 * 试剂
2 4-BrPh 1 异丁胺
3 3.5-CF3Ph 1 1,2-二甲基丙基胺
4 2-萘基 1 1,2-二甲基丙基胺
5 2-萘基 1 新戊胺
6 2-萘基 2 异丁胺
7 4-BrPh 1 新戊胺
8 4-BrPh 2 异丁胺
9 3.5-CF3Ph 2 异丁胺
10 4-CF3Ph 1 1,2-二甲基丙基胺
11 4-CF3Ph 2 异丁胺
13 4-CF3OPh 1 1,2-二甲基丙基胺
14 2-F,4-BrPh 1 1,2-二甲基丙基胺
15 2-F,4-BrPh 2 异丁胺
16 4-Br,3-FPh 2 1,2-二甲基丙基胺
17 4-Br,3-FPh 2 异丁胺
63 4-Cl,3-CF3Ph 1 1,2-二甲基丙基胺
64 4-Cl,3-CF3Ph 2 异丁胺
99 5-Br-2-萘基 2 异丁胺
100 5-Br-2-萘基 2 2-甲基丙基-2-烯基
Ph=苯基
维悌希试剂 1=4-膦酰巴豆酸三乙酯
2=3-甲基-4-膦酰巴豆酸三乙酯
实施例2
(±)-(2E,4E)N-异丁基-5-〔反-2-(3-三氟甲基苯基)-环丙基〕戊-2,4-二烯酰胺(化合物18)
(ⅰ)在硫酸(6ml)存在下,将乙醇(120ml)中的m-三氟甲基肉桂酸(10.4g)加热回流8小时,真空除去溶剂,用常规方法进行处理,得到乙基-m-三氟甲基肉桂酸酯(12.1g)
NMR′H:7.58(4H,m),6.4(1H,d),
4.25(2H,q),1.3(3H,t)。
(ⅱ-ⅵ)通过类似实施例1的步骤(ⅱ)至(ⅵ),但使用异丁胺代替1,2-二甲基丙基胺,将该化合物转化成最终产品。
按类似方法,使用指定的肉桂酸、维梯希试剂和胺制备化合物19-43和95-98。
化合物编号 化合物名称
19 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3-三氟甲基苯基)环丙基〕戊-2,4-二烯酰胺
20 (±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔反-2-(3-三氟甲基苯基)环丙基〕戊-2,4-二烯酰胺
21 (±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)3-甲基-5-〔反-2-(3-三氟甲基苯基)环丙基〕戊-2,4-二烯酰胺
22 (±)-(2E,4E)N-异丁基-5-〔反-2-(2-氯苯基)环丙基〕戊-2,4-二烯酰胺
23 (±)-(2E,4E)N-(1,2-二甲基丙基)5-〔反-2-(2-氯-苯基)环丙基〕戊-2,4-二烯酰胺
24 (±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔反-2-(2-氯苯基)环丙基〕戊-2,4-二烯酰胺
25 (±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔反-2-(2-氯苯基)环丙基〕戊-2,4-二烯酰胺
26 (±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-苯基环丙基〕戊-2,4-二烯酰胺
27 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-苯基环丙基〕戊-2,4-二烯酰胺
28 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3-氯苯基)环丙基〕戊-2,4-二烯酰胺
29 (±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3-氯苯基)环丙基〕戊-2,4-二烯酰胺
30 (±)-(2E,4E)-N-异丁基5-〔反-2-(3',4-二氯苯基)环丙基〕戊-2,4-二烯酰胺
31 (±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺
32 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺
33 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(4-氯-苯基)环丙基〕戊-2,4-二烯酰胺
34 (±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔反-2-(4-氯苯基)环丙基〕戊-2,4-二烯酰胺
35 (±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺
36 (±)-(2E,4E)N-环丙基甲基-5-〔反-2-(3,4-二氯苯基)环丙基〕-3-甲基-戊-2,4-二烯酰胺
37 (±)-(2E,4E)N(2,2-二甲基丙基)-3-甲基-5-〔反-2-(3,4-二氯苯基)环丙基〕-3-甲基-戊-2,4-二烯酰胺
38 (±)-(2E,4E)N-(1,1,2-三甲基丙基)-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺
39 (±)-(2E,4E)N-(2-丁基)-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺
40 (±)-(2E,4E)N-(2-甲氧基-2-甲基丙基)-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺
41 (±)-(2E,4E)N-(2-甲基-1,3-二氧戊环-2-基甲基)5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺
42 (±)-(2E,4E)N-(三甲基甲硅烷基甲基)-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺
43 (±)-(2E,4E)N-(环丙基甲基)-5-〔反-2(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺
95 (±)-(2E,4E)N-(2,2-二甲基丙基)-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺
96 (±)-(2E,4E)N-环己基-5-〔反-2-(3,4-二氯苯基)-环丙基〕-2,4-二烯酰胺
97 (±)-(2E,4E)N-(2-丁基)-3-甲基-5'-〔反-2-(3,4-二氯苯基〕戊-2,4-二烯酰胺
98 (±)-(2E,4E)N-(2-甲基-1,3-二氧戊环-2-基甲基)-3-甲基-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺
化合物 肉桂酸 维悌希 胺
编号 试剂
19 间-三氟甲基 1 1,2-二甲基丙胺
20 间-三氟甲基 2 异丁胺
21 间=三氟甲基 2 2-甲基烯丙基胺
22 2-氯 1 异丁胺
23 2-氯 1 1,2-二甲基丙胺
24 2-氯 2 异丁胺
25 2-氯 2 2-甲基烯丙基胺
26 不饱和的 2 异丁胺
27 不饱和的 1 1,2-二甲基丙胺
28 3-氯 1 1,2-二甲基丙胺
29 3-氯 2 异丁胺
30 3,4-二氯 1 异丁胺
31 3,4-二氯 2 异丁胺
32 3,4-二氯 1 1,2-二甲基丙胺
33 4-氯 1 1,2-二甲基丙胺
34 4-氯 2 异丁胺
35 3,4-二氯 2 2-甲基烯丙基胺
36 3,4-二氯 2 环丙基甲基胺
37 3,4-二氯 2 新戊胺
38 3,4-二氯 1 1,1,2-三甲基丙胺
39 3,4-二氯 1 仲-丁胺
40 3,4-二氯 1*2-甲氧基-2-甲基丙胺
41 3,4-二氯 1 2-甲基-1,3-二氧戊环
-2-基甲胺
42 3,4-二氯 1 三甲基硅甲烷基甲胺
43 3,4-二氯 1 环丙基甲胺
95 3,4-二氯 1 1,2-二甲基丙胺
96 3,4-二氯 1 环已胺
97 3,4-二氯 2 仲丁胺
98 3,4-二氯 2 2-氨基甲基-2-甲基-1,
3-二氧戊环
*2-甲氧基-2-甲基丙胺(ref:V.Harder,E.Pfeil和K.F.Zenner,Ber.,97(2),5101964)通过氢化锂铝还原2-甲氧基-2-甲基丙腈(ref:R.A.Navdo Kina,E.N.Zilberman,Zh,Org.Khim.,1980,16(8),1629)。
实施例3
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔顺/反-2-(2,2-二溴乙烯基)环丙基〕戊-2,4-二烯酰胺(化合物44)
(ⅰ)在室温氮气压力下,向顺/反(3∶1)乙基-2-甲酰基环丙基-羧酸酯(1.42g)(ex Aldrich)在二氯甲烷中的溶液加入三苯磷(ex Aldrich)(12g)和四溴化碳(6.6g)(ex Aldrich)。
在室温下搅拌该溶液3小时,然后分配于醚和水,用常规方法处理,然后过滤除去三苯基氧化磷,进行色谱分离,得到乙基-2-(2,2-二溴乙烯基)环丙基羧酸酯(2.9g)。NMR′H:5.92(1H,d),4.16(2H,q),2.44-0.95(4H,m),1.26(3H,t)。
(ⅱ)将在二氯甲烷(12ml)中的上述酯(1.8g)冷却至-20℃,逐滴加入二异丁基氢化铝(12ml 1M在己烷中的溶液),将溶液加热至0℃并保持该温度直至加入2N盐酸,用常规方法处理得到2-(2,2-二溴乙烯基)-1-羟甲基环丙烷(1.58g)。NMR:′H6.0,5.7(1H,d),3.44(2H,d),2.52(1H,s),1.8-1.0(2H,m),0.8(2H,m)。
(ⅲ)使用在二氯甲烷中的Swern(草酰氯,0.6ml;二甲基亚砜。1.0ml;三乙胺,4ml)氧化上述醇(1.58g)得到2-(2,2二溴乙烯基)环丙基-甲醛,在下步直接使用。
NMR:′H 9.6,9.43(1H,d),5.80(1H,d),2.46-1.82(2H,m),1.82-1.0(2H,m)。
(ⅳ)由正-丁基锂(2.3ml 1.6M在己烷中的溶液)和二异丙胺(0.55m'l)制备的二异丙基酰胺锂在干燥四氢呋喃中的溶液用THF的三乙基膦酰基巴豆酸酯(0.85g)在-60℃于氮气压力下处理,2小时后,在-60℃下加入上述醛,在温度保持在25℃下的18小时后,将该混合物在醚和水之间进行分配,用常规的方法进行处理,色谱分离(硅石,醚/己烷)提纯,得到(±)-(2E,4E)-乙基-5-〔顺/反-2-(2,2-二溴乙烯基)环丙基〕-戊-2,4-二烯酰胺(1.223g)。
NMR:′H 7.24(1H,dd),6.28(1H,dd),5.87(1H,d),5.80(1H,d),5.67(1H,dd),4.20(2H,q),1.75(2H,m),1.30(3H,t),1.15(m)。
(ⅴ)向在乙醇(5ml)和水(2ml)中的上述酯
(1.233g)溶液加入氢氧化钾(0.25g),搅拌该溶液18小时,然后真空除去乙醇,加入稀2N盐酸,用乙醚萃取,用硫酸镁干燥,真空浓缩得到(±)-(2E,4E)-5-(顺/反-(2,2-二溴乙烯基)环丙基〕戊-2,4-二烯酸(0.74g)。NMR(CD3OD):7.3C(1H,dd),6.45(1H,dd),6.15(1H,d),5.88(1H,d),5.00(1H,s),1.92(2H,m),1.28(2H,m)。
(ⅵ)将上述酸(0.32g)溶于二氯甲烷(5ml),加入三乙胺,加入苯基N-苯基磷酰胺基氯化物(ex Lancaster),30分钟后,在室温加入1,2-二甲基丙胺(0.087g)和三乙胺(0.14ml),在室温下搅拌该溶液18小时,然后用常规方法处理,色谱分离(硅石;乙醚/己烷)提纯,得到标题化合物。
实施例4
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-(反-2,2-二氟-3-苯基环丙基)戊-2,4-二烯酰胺(化合物45)
用普通方法(乙醇,120ml;浓硫酸,6ml)酯化肉桂酸(7.4g),得到肉桂酸乙酯(8.5g)。NMR:′H 7.55(1H,d),7.15(5H,m),6.2(1H,d),4.05(2H,q),1.15(3H,t)。
用普通方法使用在二氯甲烷(40ml)中的二异丁基氢化铝(40ml 1M在己烷中的溶液)处理上述酯(3.52g),得到3-苯基丙-2-烯-1-醇(2.8g)。NMR′H:7.2(5H,m),6.55(1H,d),6.35(1H,t),4.25(2H,d),1.97(1H,s)。
含乙酐(1.8g)的在吡啶(1.6ml)中的上述醇(2.05g)在25℃搅拌3小时,然后分布在醚和稀盐酸之间,用常规方法处理,得到3-苯基丙-2-烯基乙酸酯(2.2g),NMR′H:7.15(5H,m),6.52(1H,d),6.22(1H,t),4.57(2H,d),2.00(3H,s)。
将上述乙酸酯(1.65g)溶于二甘醇二甲醚(ex Aldrich),25℃氮气压力下加入氯二氟乙酸钠(8.4g),将溶液加热至180℃,并保持该温度半小时,冷却至40℃,再加入氯二氟乙酸钠(6.2g),该混合物加热至180℃又半小时,冷却该混合物并用己烷稀释,有机相用水洗涤,用硫酸镁干燥,真空除去溶剂,色谱分离(硅石;乙醚/己烷)提纯,得到反-2,2-二氟-3-苯基环丙基甲基乙酸酯(1.56g)。NMR′H:7.30(5H,m);4.37(1H,dd),4.26(1H,dd),2.67(1H,dd),2.29(1H,ddd),2.13(3H,s)。
上述乙酸酯(1.56g)在含有碳酸钾(2.94g)的含水甲醇(10ml)中搅拌18小时,用常规方法处理,得到2,2-二氟-3-苯基环丙基甲醇(1.08g)。NMR′H:7.30(5H,m),3.94(2H,m),2.63(1H,m),2.24(1H,m),1.67(1H,s)。
在25℃,上述醇(0.55g)在二氯甲烷(6ml)中搅拌,加入吡啶嗡重铬酸盐(2g)(ex Aldrich)和3°A分子筛(ex BDH)(1.5g),3小时后,在室温下用乙醚稀释该混合物,通过硅石过滤,用乙醚洗涤,真空除去溶剂,得到2,2-二氟-3-苯基环丙基甲醛(0.255g)。NMR′H:9.49(1H,dd),7.2-7.65(5H,m),3.61(1H,ddd),2.955(1H,ddd)。
在-60℃,将由正-丁基锂(1ml 1.6M在己烷中的溶液)和二异丙胺(0.24ml)制备的二异丙胺锂在干四氢呋喃中的溶液,在氮气压力下用在THF中的膦酰基巴豆酸三乙酯0.375g处理,2小时后,在-60℃加入上醛(0.255g),18小时后,在25℃,将该混合物分布在醚和水之间,用常规方式处理。
色谱分离(硅石;乙醚/己烷)提纯,得到(±)-(2E,4E)-乙基-5-〔反-2,2-二氟-3-苯基环丙基〕戊-2,4-二烯酸酯,通过类似实施例3步骤(ⅵ),将其转化为标题化合物。
实施例5
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-(反-2,2-二氟-3-(4-溴-苯基)环丙基〕戊-2,4-二烯酰胺(化合物46)
3-(4-溴苯基)丙-2-烯-1-醇(2.13g)(参见实施例1)与乙酐按通常方式反应,得到了3-(4-溴-苯基)丙-2-烯基乙酸酯(2.25g)NMR′H:7.35(2H,d),7.08(2H,d),6.52(1H,d),6.10(1H,dt),4.65(2H,d),2.1(3H,s)。
上述乙酸酯(2.25g)按通常方式与氯二氟乙酸钠(12.6g)反应,得到反-2,2-二氟-3-(4-溴苯基)环丙基甲基乙酸酯(2.39g)。NMR′H:7.48(2H,d),7.1(2H,d),4.30(2H,m),2.62(1H,dd),2.23(2H,m),2.12(3H,s)。
上述乙酸酯(2.39g)以普通方式与碳酸钾(2.36g)反应,得到2,2-二氟-3-(4-溴苯基)环丙基甲醇(1.93g)。NMR′H:7.3(2H,d),7.0(2H,d),3.8(2H,m),3.18(1H,s),2.55(1H,m),2.1(1H,m)。
通过类似于实施例3步骤(ⅲ)至(ⅵ)的方法,将上述醇(1.93g)转化为标题化合物。
使用了3-甲基膦基巴豆酸三乙酯和异丁胺按类似方法制备(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2,2-二氟-3-(4-溴苯基)环丙基〕戊-2,4-二烯酰胺(化合物47)。
实施例6
(±)-(2E,4E)N-(1,2-二甲基丙基)-6-〔顺,反-2,(3-三氟甲基-苯基)环丙基〕己-2,4-二烯酰胺(化合物48)
(ⅰ)在60°下,三丁基氢化锡(ex.Aldrich)(1.6g)和偶氮双异丁腈(0.01g)(ex.Aldrich)与丁炔-4-醇(0.31g)反应1小时,冷却并蒸馏(kugelr
hr,150°,1mmHg),得到4-三丁基锡丁-3-烯-1-醇(1.17g),其混合物中烯烃反式异构体与顺式异构体之比为1∶1。(参见J.K.Stille,Ang.Chem,Int.Ed.Engl.1986,25,508)。NMR′H:5.95(2H,m),3.60(2H,m),2.3(2H,m),0.9-2.0(2H,m)。
(ⅱ)在25℃,氩压力下,将钯双乙腈二氯化物(0.01g)溶于干的二甲基甲酰胺(10ml)中,在DMf中加入了-三氟甲基碘苯(1.03g)(ex.Fluorochem),然后加入上述醇(1.17g),72小时后,该溶液分布在醚和10%氢氧化铵溶液之间,用普通方式进行处理。
色谱分离(硅石;乙醚/己烷)提纯,得到4-(3-三氟甲基苯基)丁-3-烯-1-醇(0.67g),其顺∶反烯烃异构体之比为1∶1(参见J.K.Stille和B.L.Groh,J.Am.Chem.Soc,109,1987,815)。
NMR′H:7.5(4H,m),6.55(1H,d),6.32(1H,dt),3.78(2H,m),2.55(2H,m),1.50(1H,s)。
(ⅲ-ⅵ)通过类似于实施例1步骤(ⅲ)至(ⅵ)的方法,将上述醇转化成标题化合物。
实施例7
(±)-(E)N-(1,2-二甲基丙基)-3-〔顺-2,(3-三氟甲基苯基)环丙基〕丙-2-烯酰胺(化合物49)
(ⅰ)将丙炔酸乙酯(0.98g)(ex Lancaster)、三丁基氢化锡(3.01g)和偶氮二异丁腈(azobisisobuty-ronitrile)(0.01g)在60°下加热18小时。冷却并用色谱分离(二氧化硅;乙醚/己烷)提纯,得到(Z)-乙基-3-三丁基锡丙烯酸酯(1.9g)(参考J.K.Stille等人的J.Amer.Chem.Soc.,109,1987,815)。NMR′H:7.14(1H,d),6.73(1H,d),4.22(2H,q),1.38(18H,m),0.9(12H,m)。
(ⅱ)将上述酯(0.78g)溶于二氯甲烷(4ml)中,并在氮气下冷却至-20°,逐滴加入二异丁基氢化铝(4ml 1M在己烷中的溶液)。在25°下18小时后,小心地加入稀盐酸,然后用通常方式处理,得到3-三丁基锡-丙-2-烯-1-醇(0.75g)。NMR′H:6.72(1H,dt),6.10(1H,d),4.15(2H,dd),1.40(18H,m),0.90(9H,m)。
(ⅲ)至(ⅴ)用类似于实施例6(ⅱ)和实施例1步骤(ⅲ)和(ⅳ)的方法,将上述醇(0.75g)转化成(±)-顺式-2,3-三氟甲基苯基)-1-甲酰环丙烷(0.2g)。NMR′H:8.95(1H,d),7.50(4H,m),1.0-2.5(4H,m)。
(ⅵ)在氮气压力下上述醛(0.2g)和碳化乙氧基亚甲基三苯基正膦在二氯甲烷(5ml)中在25°下搅拌18小时,真空浓缩,然后用己烷洗涤残余物,在真空下除去己烷,得到(±)-(E)-乙基-3-〔顺-2-(3-三氟甲基苯基)环丙烷〕丙-2-烯酸酯(0.18g)。NMR′H:7.43(4H,m),6.18(1H,dd),5.94(1H,d),4.06(2H,q),2.62(1H,m),2.09(1H,m),1.55(1H,m),1.34(1H,m),1.22(3H,t)。
(ⅶ)用类似于实施例1(ⅵ)的方法将上述酯转化成标题化合物。
实施例8
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔顺,反-2,(3-三氟甲基苯基)环丙基〕戊-2,4-二烯酰胺(化合物(50)
将(±)-(E)-乙基-3-〔顺-2-(3-三氟甲基苯基)环丙基〕丙-2-烯酸酯(0.18g)(实施例7)溶于二氯甲烷(3ml)中,然后在氮气下冷却至-20°,加入二异丁基氢化铝(1.3ml 1M在己烷中的溶液),在25°下搅拌该溶液18小时,小心地加入稀盐酸,然后用通常的方法处理,得到顺-2-(3-三氟甲基苯基)-1-(3-羟基丙-2-烯-1-基)环丙烷(0.15g)。NMR′H:7.43(4H,m),5.79(1H,dt),4.98(1H,dd),3.95(2H,d),2.40(1H,m),1.94(1H,m),1.33(1H,m),1.10(2H,m)。
用Swern(草酰氯,0.54ml;二甲基亚砜,0.86ml;三乙胺,3.8ml)方法在二氯甲烷中将上述醇(1.35g)氧化,得到顺-2-(3-三氟甲基苯基)-1-(1-丙烯-3-醛基)环丙烷(1.3g)。NMR′H:9.21(4H,d),7.50(4H,m),6.28(1H,dd),5.98(1H,dd),2.79(1H,m),2.12(1H,m),1.68(1H,m),1.42(1H,m)。
用类似于实施例7(ⅵ)的方法将上述醛(1.3g)与碳化乙氧基亚甲基三苯基正磷(1.74g)反应,得到(±)-(2E,4E)-乙基-5-〔顺-2,(3-三氟甲基苯基)环丙基〕戊-2,4-二烯酸酯(1.1g)。NMR′H:7.42(4H,m),7.05(1H,dd),6.31(1H,dd),5.73(1H,d),5.31(1H,dd),4.17(2H,q),2.56(1H,m),2.03(1H,m),1.48(1H,m),1.25(4H,m)。
用类似于实施例1(ⅵ)的方法将上述酯转化成标题化合物,得到顺∶反环丙基异构体为6∶1的混合物。
在类似的方法中,用异丙胺代替1,2-二甲基丙胺,制得(±)-(2E,4E)N-异丁基-5-〔顺,反-2,(3-三氟甲基苯基)-环丙基〕戊-2,4-二烯酰胺(化合物51),其顺∶反式环丙基异构体为4∶1的混合物。
实施例9
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔顺,反-2,(4-氯苯基)-2-甲基环丙基〕戊-2,4-二烯酰胺(化合物52)
将乙基三甲基甲硅烷基乙酸酯(3.6ml)(ex Fluka)在-60°下加入到异丙基环己基氨基化锂〔由12.5ml正-丁基锂 1.6M的溶液和异丙基环己基胺(3.3ml)(ex Aldrich)在TMF中制得〕溶液中。在-60°下30分钟后,加入4-氯乙酰苯(ex Aldrich)(1.55g)。在25°下18小时后,该混合物分布在醚和水之间,然后用通常的方法处理,通过色谱分离(二氧化硅;乙醚/己烷)提纯,得到乙基-3-(4-氯苯基)-丁-2-烯酸酯(1.22g),其E∶Z烯烃异构体为1∶1的混合物。NMR′H:7.2(4H,m),6.0 & 5.0(1H,m),4.12(2H,m),2.51 & 1.90(3H,s),1.25(3H,m)。
将上述酯(1.44g)溶于二氯甲烷(13ml)中,并冷却至-20°。逐滴加入二异丁基氢化锂(12.8ml 1M在己烷中的溶液)。在25°下18小时后,小心地加入稀盐酸,并用通常的方法处理混合物,得到3-(4-氯苯基)丁-2-烯-1-醇(0.44g)。NMR′H:7.18(4H,s),5.85(1H,t),4.25(2H,d),3.05(1H,s),2.05(3H,s)。
用类似于实施例1的步骤(ⅲ)至(ⅵ)的方法将上述醇转化成标题化合物。
实施例10
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-(反-2,2-二甲基-3-(3-三氟甲基苯基)环丙基〕戊-2,4-二烯酰胺(化合物53)
氮气压力下,在四氢呋喃中的乙基-3-三氟甲基肉桂酸酯(0.98g)(实施例2)用由异丙基三苯基碘化鏻(2.12g)和正-丁基锂(2.8ml)制得的内鎓盐处理,在80°下20小时后,用通常的方法处理该混合物,通过色谱分离(二氧化硅,乙醚/己烷)提纯,得到(±)-正-丁基-〔反-3-(3-三氟甲基苯基)-2,2-二甲基环丙基〕-甲酸酯(0.78g)。NMR′H:7.22(4H,m),4.20(2H,m),2.72(1H,m),2.00(1H,m),1.40(7H,m),0.89(6H,m)。
在氮气下将上述酯(0.78g)溶于二氯甲烷(12ml)中,然后冷却至-20°,逐滴加入二异丁基氢化铝(7.4ml),然后在25°下搅拌该溶液18小时,小心地加入稀盐酸,然后用通常的方法处理,得到(±)-〔反-3-(3-三氟甲基苯基)-2,2-二甲基环丙基〕甲醇(0.31g)。NMR′H:7.5(4H,m),3.65(2H,d),2.55(1H,6s),1.62(1H,d),1.14(1H,m),1.15(3H,s),0.90(3H,s)。
用类似于实施例1步骤(ⅳ)至(ⅵ)的方法将上述醇转化成标题化合物。
用类似的方法,但用乙基-3,4-二氯肉桂酸酯作起始物制得(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2,2-二甲基-3-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺(化合物54)。
实施例11
(±)-(2E,4E)N-1,2-二甲基丙基)-5-〔反-2-(4-氯苯基)-1-甲基环丙基〕戊-2,4-二烯酰胺(化合物55)
在25°下二氯甲烷(250ml)中的4-氯苯甲醛(6.8g)(ex Aldrich)与碳化乙氧基亚甲基三苯基正膦(17.5g)(ex Lancaster)反应18小时,真空浓缩,然后用大量的己烷洗涤残余物,浓缩混合的己烷洗涤物,得到(E)-乙基-3-(4-氯苯基-2-甲基丙-2-烯酸酯(11.6g)。NMR′H:7.35(4H,m),4.25(2H,q),2.05(3H,s),1.31(3H,t)。
将上述酯(11.6g)溶于二氯甲烷(100ml)中,并冷却至-20°,逐滴加入二异丁基氢化铝(100ml),在25°下18小时后,小心地加入稀盐酸,用通常的方法处理该混合物,得到(E)-3-(4-氯苯基)-2-甲基丙-2-烯-1-醇(8.6g)。NMR'′H:7.34(2H,d),7.22(2H,d),6.49(1H,s),4.18(2H,s),1.90(3H,s),1.66(1H,s)。
用通常的方法,在己烷中用二乙基锌(45.5ml)和二碘甲烷(8.1ml)处理上述醇,得到(±)-〔反-〔2-(4-氯苯基)-1-甲基环丙基〕甲醇(1.94g)。NMR′H:8.94(1H,s),7.30(2H,d),7.06(2H,d),2.68(1H,dd),2.24(1H,dd),1.46(1H,dd),0.98(3H,?)。用类似于实施例3步骤(ⅳ)至(ⅵ)的方法将该醇转化成标题化合物。
实施例12
(-)N-异丙基-5-〔(1S,2R)-反-2-(3,4-二氯苯基)环丙基〕-戊-2,4-二烯酰胺(化合物56)
用Swern(草酰氯,0.5ml;二甲基亚砜,0.7ml;三乙胺,3.4ml)方法氧化3-(3,4-二氯苯基)丙-2-烯-1-醇(1.0g)〔用类似于实施例2(ⅰ)和实施例1(ⅱ)的方法制得〕,得到3-(3,4-二氯苯基)-丙-2-烯醛(0.9g)。NMR′H:9.76(1H,d),7.53(3H,m),7.41(1H,d),6.68(2H,dd)。
在25°下在乙醇(5ml)中上述醛(0.66g)与原甲酸三乙酯(0.6ml)(ex Aldrich)和硝酸铵(ex Aldrich)(0.01g)搅拌3.5小时,真空浓缩,然后用通常的方法处理,得到E-1-(3,4-二氯苯基)-3,3-二乙氧基丁-1-烯(0.97g)。NMR′H:7.32(3H,m),6.79(1H,d),6.19(1H,dd),5.08(1H,d),3.69(4H,m),1.29(6H,m)。
将上述乙缩醛(0.67g)溶于苯(25ml)中,然后用(+)-L-二异丙基酒石酸酯(0.7g)(ex Aldrich)和对-甲苯磺酸(0.01g)(ex Aldrich)处理。用Dean-Stark装置将该混合物在80°下加热6小时。冷却该溶液,用通常的方法处理,得到(-)-4,5-二碳化异丙氧基-2-〔(E)-2-(3,4-二氯苯基)乙烯基〕-1,3-二氧戊环(0.92g)。NMR′H:7.50(1H,d),7.40(1H,d),7.25(1H,dd),6.74(1H,d),6.25(1H,dd),5.81(1H,d),5.14(2H,m),4.77(1H,d),4.69(1H,d),1.33(12H,m)。
用通常的方法,在己烷中将上述乙缩醛(0.9g)与二乙基锌(11ml)和二碘甲烷(1.8ml)反应,得到(-)-4,5-二碳化异丙氧基-2-〔反-(2R,3R)-2-(3,4-二氯苯基)环丙-1-基〕-1,3-二氧戊环(0.8g)。〔α〕D-96.1°(c0.96,乙醇)。NMR′H:7.21(1H,d),7.13(1H,d),6.85(1H,dd),5.05(1H,d),5.02(2H,m),4.65(1H,d),4.52(1H,d),2.08(1H,m),1.47(1H,m),1.21(12H,m),1.14(1H,m),0.92(1H,m)。
将上述乙缩醛(0'.8g)在70°下在四氢呋喃(5ml)中,并有稀盐酸(3ml)存在下加热12小时,用通常的方法处理,得到(-)-〔反-(2R,3S)-2-(3,4-二氯苯基)环丙基〕-甲醇(0.23g)。NMR′H:9.39(1H,d),7.39(2H,m),6.94(1H,dd),2.56(1H,m),2.09(1H,m),1.65(2H,m)。
在-60°和氮气下,在四氢呋喃中用四氢呋喃中的三乙基-4-膦酰基丁烯酸酯(0.21g)处理二异丙基氨基化锂〔由正-丁基锂(0.6ml)和二异丙胺(0.14ml)制得〕。在-60°下2小时后,加入上述醛,在25°下18小时后,加入水,然后用通常的方法处理该混合物,通过色谱分离(二氧化硅,己烷/乙醚)提纯,得到(-)-(2E,4E)-乙基-5-〔反-(2R,3S)-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酸酯(0.16g)〔α〕D-304.7°(c0.9,乙醇)。NMR′H:7.28(3H,m),6.88(1H,dd),6.18(1H,dd),5.84(1H,dd),5.78(1H,d),4.10(2H,q),1.90(2H,m),1.20(5H,m)。
用类似于实施例1(ⅵ)的方法,将上述酯转化成标题化合物。
用类似的方法,用(-)-D-二异丙基酒石酸酯(ex Aldrich)制得(+)-N-异丁基-5-〔(1R,2S)-反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺(化合物57)。
实施例13
(+)-(2E,4E)N-异丁基-5-〔反-2-(2,6-二氯-4-吡啶基)环丙基〕-3-甲基戊-2,4-二烯酰胺(化合物58)
将2,6-二氯异烟酸(4.0g)(根据M.M.Robinson,J.Amer.Chem.Soc.80,5481,1958制得)溶于乙醇(20ml)和浓硫酸(1ml)中,在80°下6小时后,冷却该溶液,真空浓缩,用通常的方法处理残余物,得到乙基-2,6-二氯异烟酸酯(3.7g)。NMR′H:7.84(2H,s),4.48(2H,q),1.48(3H,t)。
将上述酯溶于二氯甲烷(60ml)中,并在氮气下冷却至-20°,逐滴加入二异丁基氢化铝(38ml)。在0°下2小时后,小心地加入稀盐酸,然后用通常的方法处理该混合物,得到2,6-二氯-4-羟基甲基吡啶。NMR′H:7.64(2H,s),4.98(2H,s)。
用Swern(草酰氯,0.33ml;二甲基亚砜,0.54ml;三乙胺,2.35ml)方法氧化上述醇(1.2g),得到(2,6-二氯-4-吡啶基)甲醛(1.2g)。NMR′H:10.02(1H,s),7.68(2H,s)。
将上述醛(1.2g)溶于二氯甲烷(40ml)中,然后加入碳化乙氧基亚甲基三苯基正膦(2.4g)。在25°下18小时后,真空浓缩该溶液,然后用己烷洗涤残余物,真空浓缩混合的己烷洗涤物,得到乙基-3-(2,6-二氯-4-吡啶基)丙烯酸酯(1.2g)。NMR′H:7.50(2H,d),2.28(2H,s),6.52(2H,d),4.29(2H,q),1.32(3H,t)。
在25°和氮气下,将上述酯(0.25g)加到二甲基亚砜(4ml)中的内鎓盐(由碘化三甲基氧化锍(0.24g)和氢化钠(0.044g 60%在矿物油中的分散体)中。在25°下18小时后,小心地加入水,用通常的方法处理该混合物。通过色谱分离(二氧化硅,乙醚/己烷)提纯,得到(±)-乙基-〔反-2-(2,6-二氯-4-吡啶基)环丙基〕甲酸酯(0.12g)。NMR′H:6.93(2H,s),4.16(2H,q),2.42(1H,ddd),1.99(1H,ddd),1.69(1H,ddd),1.30(2H,m),1.25(3H,t)。
在氮气下将上述酯(0.34g)溶于二氯甲烷(7ml中),然后冷却至-20°,逐滴加入二异丁基氢化铝(2.8ml),0.5小时后,小心地加入甲醇(0.5ml),然后加入2M氢氧化钠溶液(5ml)。用通常的方法处理该混合物。NMR′H:6.98(2H,s),3.64(2H,m),3.30(1H,bs),0.9-2.0(4H,m)。
用Swern(草酰氯,0.1ml;二甲基亚砜0.15ml;三乙胺,0.66ml)的方法氧化上述醇(0.21g),得到(±)-〔反-2-(2,6-二氯-4-吡啶基)环丙基〕甲醛(0.2g)。NMR′H:9.44(1H,d),6.96(2H,s),1.0-2.6(4H,m)。
在-60°下用三乙基4-膦酰基-3-甲基丁烯酸酯(0.26g)处理在四氢呋喃('2ml)中的二异丙基氨基化锂〔由正-丁基锂(0.7ml)和二异丙基胺(0.16ml)制得〕溶液。在-60°下2小时后,加入上述醛(0.2g)。在25°下2.5小时后,加入水,并用通常的方法处理该混合物。通过色谱分离(二氧化硅;乙醚/己烷)提纯,得到(±)-(2E,4E)-乙基-3-甲基-5-〔反-2-(2,6-二氯-4-吡啶基)环丙基〕戊-2,4-二烯酸酯(0.18g)。NMR′H:6.92(2H,s),6.22(1H,d),5.75(2H,m),4.13(2H,q),2.24(3H,s),1.94(2H,m),1.41(1H,m),1.28(1H,m),1.22(3H,t)。
用类似于实施例1(ⅵ)的方法将上述酯转化成标题化合物。
实施例14
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺(化合物59)
将在水中的3-硝基-4-溴甲苯(54g)(ex Lancaster)和乙醇溶液(100ml,1∶1)迅速搅拌,然后在25°下加入铁粉(84g)(ex BDH)。将该混合物加热至回流,然后在30分钟内逐滴加入在水中的浓盐酸(2.19g)和乙醇(50ml,1∶1)。回流4小时后,冷却该混合物。并用含15%氢氧化钾溶液使其具有碱性,然后通过硅藻土过滤,并用乙醇(2×50ml)洗涤。得到的混合物用水(1000ml)稀释,用通常的方法处理,得到3-氨基-4-溴甲苯(43.6g)。NMR′H:7.25(1H,d),6.40(2H,m),3.96(2H,bs),2.2(3H,s)。
在0℃将上述氨基甲苯(24g)在浓氢溴酸(230ml)中搅拌。加入在水(35ml)中的硝酸钠(9.8g)(ex BDH),并使反应温度保持在0°和5°,在50°下将该混合物倒入在水(230ml)中的溴化亚铜(37g)和氢溴酸上。在50°下2小时后和25°下18小时后,加入水,然后用通常的方法处理混合物,通过蒸馏(100°,0.5mmHg)提纯,得到3,4-二溴甲苯(12.7g)。NMR′H:7.53(2H,m),6.95(1H,dd),2.30(3H,s)。
将在冰醋酸(20ml)(ex BDH)和乙酸酐(32.6g)中的上述甲苯(5g)冷却至-10°。在温度保持在低于-5°下逐滴加入硫酸(7.8g),在温度保持在-5°~0°时分批加入三氧化铬(ex BDH)(6g)。在0°下15分钟后,将混合物倒在冰(150g)上,然后用通常的方法处理,得到二乙酸基甲基-3,4-二溴苯。NMR′H:7.53(2H,m),6.95(1H,dd),2.30(6H,s)。
将上述双乙酸酯溶解于乙醇(15ml)和水(15ml)中,然后加入浓硫酸(1.5ml)。回流1小时后,用通常的方法处理该溶液,得到3,4-二溴苯甲醛(2.25g)。NMR′H:10.04(1H,s),7.53(2H,m),6.95(1H,dd)。
将上述醛(2.25g)溶于二氯甲烷(25ml)中,然后加入碳化乙氧基亚甲基三苯基正膦(2.96g)。在25°下18小时后,真空浓缩该溶液,用己烷洗涤残余物,真空浓缩混合的己烷洗涤物,得到乙基-3-(3,4-二溴苯基)丙酸酯(2.4g)。NMR′H:7.7(2H,m),7.50(1H,d),7.15(1H,dd),6.32(1H,d),4.26(2H,q),1.33(3H,t)。
在氮气下将在二氯甲烷(25ml)中的上述酯(2.4g)冷却至-20°,然后逐滴加入二异丁基氢化铝(14.5ml)。在25°下18小时后,小心地加入稀盐酸,用通常的方法处理该混合物,得到3-(3,4-二溴苯基)丙-2-烯-1-醇(2.04g)。NMR′H:7.53(2H,m),7.13(1H,dd),6.56(1H,d),6.20(1H,dt),4.30(2H,d),1.98(1H,s)。
按照通常的方法,用在己烷中的二乙基锌(35ml)和dioodomethy(15.52ml)处理上述醇(2g),得到(±)-〔反-2-(3,4-二溴苯基)环丙基〕甲醇(1.3g)。NMR′H:7.40(1H,d),7.30(1H,d),6.76(1H,dd),3.53(2H,d),2.30(1H,s),1.68(1H,m),1.33(1H,m),0.87(2H,m)。
用类似于实施例1步骤(ⅳ)至(ⅵ)的方法,将上述醇转化化成标题化合物。
用类似的方法,分别用三乙基-3-甲基膦酰基丁烯酸酯和(ⅰ)异丁胺和(ⅱ)2-甲基丙-2-烯基胺制备(ⅰ)(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3,4-二溴苯基)-环丙基〕戊-2,4-二烯酰胺(化合物60)和(ⅱ)(±)-(2E,4E)N-(2-甲基丁-2-烯基)-3-甲基-5-〔反-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺(化合物93)。
实施例15
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3,5-二氯-4-溴苯基)环丙基〕戊-2,4-二烯酰胺(化合物61)。
在反应温度保持在低于35°和氮气下,用硫酰氯(4.05g)(ex BDH)处理在无水氯仿(250ml)中的对-氨基苄腈(11.8g)(ex Aldrich)。加热回流2小时后,将该混合物倒在冰上,并用2M氢氧化钠溶液使其具有碱性,用通常的方法处理,得到3,5-二氯-4-氨基苄腈(18.2g)。NMR′H:7.35(2H,s),4.70(2H,bs)。
在0°下用在水(30ml)中的硝酸钠(7.6g)处理在浓氢溴酸(190ml)中的上述氨基腈(18.7g)。在50°下将得到的混合物倒入在水(180ml)中的溴化亚铜(28.7g)和氢溴酸(30ml)。在50°下2小时和25°下18小时后,用水稀释该混合物,用通常的方法处理,得到3,5-二氯-4-溴苄腈(9.2g)。NMR′H:7.63(2H,s)。
在氮气下用二异丁基氢化铝(22ml,在甲苯中的1M溶液)处理在乙醚(100ml)中的上述腈(5g)。在25°下18小时后,加入1,4-二恶烷(150ml)和水(10ml),接着加入稀盐酸(250ml)。在25°下30分钟后,用通常的方法处理该混合物,得到3,5-二氯-4-溴苯甲醛(4.52g)。NMR′H:9.89(1H,s),7.85(2H,s)。
用类似于实施例1的方法将上述醛转化成标题化合物。
用类似的方法,用三乙基-4-膦酰基-3-甲基-丁烯酸酯和异丁胺制备(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(4-溴-3,5-二氯苯基)环丙基〕戊-2,4-二烯酰胺(化合物62)。
实施例16
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(4-(2,2-二溴乙烯基)苯基)环丙基〕戊-2,4-二烯酰胺(化合物65)
在0°和氮气下,用三苯基膦(15.7g)和四溴化碳(9.9g)处理在二氯甲烷(30ml)中的乙基-4-甲酰苯甲酸酯(2.46g)(ex Lancaster)。在25°下1.5小时后,加入水,然后用通常的方法处理该混合物,通过色谱分离(二氧化硅,乙醚/己烷)提纯,得到乙基-4-(2,2-二溴乙烯基)苯甲酸酯(3.32g)。NMR′H:8.0(2H,d),7.50(2H,d),7.45(1H,s),3.85(3H,s)。
在0.20°和氮气下用二异丁基氢化铝(21ml)处理在二氯甲烷(10ml)中的上述酯(3.32g)。在0℃下1小时后,加入稀盐酸,用通常的方法处理该混合物,得到4-(2,2-二溴乙烯基)苄基醇(3.18g)。NMR′H:7.50(2H,d),7.41(1H,s),7.20(2H,d),4.33(2H,s),3.65(1H,s)。
用Swern的方法(草酰氯,0.96ml;二甲基亚砜,1.56ml;三乙胺,6.9ml)在二氯甲烷中氧化上述醇(3.18g),得到4-(2,2-二溴乙烯基)苯甲醛(2.04g)。NMR′H:10.94(1H,s),7.86(2H,d),7.61(2H,d),7.45(1H,s)。
用类似于实施例1步骤(ⅰ)至(ⅴ)的方法,将上述醛转化成(±)-(2E,4E)-乙基-5-〔反-(4-(2,2-二溴乙烯基)苯基)环丙基〕戊-2,4-二烯酸酯。用类似于实施例3步骤(ⅴ)和(ⅵ)的方法将上述酯转化成标题化合物。
实施例17
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(4-乙炔基苯基)环丙基〕戊-2,4-二烯酰胺(化合物66)
在-40°和氮气下,用正-丁基锂(8.1ml)处理在无水四氢呋喃中的(±)-反-2-〔4-(2,2-二溴乙烯基)苯基〕环丙基甲醇(1.43g)(由实施例16制备)。在25°下4小时后,加入水,然后用通常的方法处理该混合物,通过色谱分离(二氧化硅,乙醚/己烷)提纯,得到(±)-反-2-(4-乙炔基苯基)环丙烷甲醇(0.62g)。NMR′H:7.41(2H,d),6.90(2H,d),3.30(2H,d),2.95(1H,s),2.59(1H,s),1.85(1H,m),1.34(1H,m),0.90(2H,m)。
用类似于实施例1的方法,将上述醇转化成标题化合物。
实施例18
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-(反-2-(3,4-5-三苯基)环丙基〕戊-2,4-二烯酰胺(化合物67)
用类似于实施例15的方法,用氢氯酸和氯化亚铜(ex BDH)代替氢溴酸和溴化亚铜,使4-氨基-3,5-二氯苄腈转化成标题化合物。
用类似的方法,用三乙基-3-甲基膦酰基丁烯酸酯和异丁胺制备(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3,4,5-三氯苯基)环丙基〕戊-2,4-二烯酰胺(化合物68)。
实施例19
(±)-(2E,4Z)N-(1,2-二甲基丙基)-4-氟-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺(化合物69)
用氟乙酸乙酯(2.7ml)(ex Lancaster)和草酸二乙酯(ex BDH)(3.8ml)处理在THF(30ml)中的氢化钠(0.74g,60%在矿物油中的分散体)(ex BDH)。在80℃下4小时后,加入(±)-反-2-(3,4-二氯苯基)环丙基甲醛(6g)〔实施例2(ⅰ)和实施例1(ⅱ)至(ⅳ)〕。在25°下18小时后,加入水,用普通方法处理该混合物,然后通过色谱分离(二氧化硅,己烷/乙醚)提纯,得到(±)-乙基-(2Z)-3-〔反-2-(3,4-二氯苯基)环丙基〕-2-氟戊-2-烯酸酯(4g)。NMR′H:7.30(1H,d),7.15(1H,d),6.90(1H,dd),5.70(1H,dd),4.30(2H,q),2.08(2H,m),1.35(2H,m),1.30(3H,t)。
在氮气下,将上述酯(4g)溶于二氯甲烷(30ml)中,并冷却至-20°。逐滴加入二异丁基氢化铝(26ml)。在25°下18小时后小心地加入稀盐酸,然后用通常的方法处理该混合物,得到(±)-(2Z)-3-〔反-2-(3,4-二氯苯基)环丙基〕-2-氟丙-2-烯-1-醇(3.3g)。NMR′H:7.32(1H,d),7.17(1H,d),6.90(1H,dd),4.10(2H,dd),3.60(1H,t),1.90(2H,m),1.20(2H,m)。
用Swern的方法(草酰氯,1.2ml;二甲基亚砜,2.0ml;三乙胺,8.8ml)在二氯甲烷中将上述醇(3.3g)氧化,得到(±)-(2Z)-3-〔反-2-(3,4-二氯苯基)环丙基〕-2-氟丙-2-烯醛(3.25g)。NMR′H:9.20(1H,d),7.39(1H,d),7.22(1H,d),6.95(1H,dd),5.60(1H,dd),2.20(2H,m),1.50(2H,m)。
在氮气下将上述醛(0.5g)溶于二氯甲烷(5ml)中,然后,在25°下用碳化乙氧基亚甲基三苯基正膦(0.67g)处理。在25°下18小时后,真空浓缩该溶液,并用己烷洗涤残余物。真空浓缩混合的己烷洗涤物,得到(±)-(2E,4Z)-乙基-4-氟-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酸酯(0.58g)。NMR′H:7.30(1H,d),7.00(3H,m),6.05(1H,d),5.90(1H,m),4.20(2H,q),2.00(2H,m),1.30(3H,t),1.30(2H,m)。
用类似于实施例1(ⅵ)的方法将上述酯转化成标题化合物。
实施例20
(±)-(2E,4Z)N-异丁基-3-甲基-4-氟-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺(化合物70)
在0°和氮气下,用甲基碘化镁〔由镁切屑(0.26g)和甲基碘(0.7ml)在乙醚(20ml)中制得〕处理在乙醚(10ml)中的(±)-(2Z)-2-氟-3-〔反-2-(3,4-二氯苯基)环丙基〕丙-2-烯醛(2.59g)(实施例19),在25°下18小时后,用通常的方法处理混合物,通过色谱分离(二氧化硅,乙醚/己烷)提纯,得到(±)-(3Z)-4-〔反-2-(3,4-二氯苯基)环丙基〕丁-3-烯-2-醇(2.0g)。NMR′H:7.23(1H,d),7.05(1H,d),6.90(1H,dd),4.52(1H,m),4.23(1H,m),3.0(1H,s),1.80(2H,m),1.35(3H,d),1.18(2H,m)。
用Swern的方法(草酰氯,0.7ml;二甲基亚砜,61ml;三乙胺,5.1ml)在二氯甲烷中氧化上述醇(2.0g),得到(±)-3Z)-3-氟-4-〔反-2-(3,4-二氯苯基)环丙基〕丁-3-烯-2-酮(1.5g)。NMR′H:7.30(1H,d),7.10(2H,d),6.95(1H,dd),5.70(1H,dd),2.32(3H,d),2.10(2H,m),1.43(2H,m)。
在0°和搅拌下,将氯乙酰氯(ex.Aldrich)(50g)逐滴加入到在无水乙醚(250ml)中的异丁胺(ex.Aldrich)(70ml)中。当该混合物的温度达到室温时,用通常的方法处理混合物,得到N-异丁基二-氯乙酰胺。将N-异丁基2-氯乙酰胺(20g)和亚磷酸三乙酯(23g)一起在120℃下加热3小时,真空蒸馏该混合物,得到N-异丁基二乙基膦酰基乙酰胺(22.5g,在0.1mm下沸点为140-142.5℃)。
在-70℃和氮气下,用在无水四氢呋喃中的二乙基-N-异丁基膦酰基乙酰胺(0.46g)处理在四氢呋喃中的二异丙基氨基化锂〔由正-丁基锂(2.3ml)和二异丙胺(0.51ml)制得〕溶液。在25°下2小时后,加入上述酮(0.5g)。在25°下18小时后加入水,然后用通常的方法处理该混合物,通过色谱分离(二氧化硅,乙醚/己烷)提纯,得到标题化合物(0.24g)。
用类似的方法,用2-甲基丙-2-烯基胺代替异丁胺,制备(±)-(2Z,4E)N-(2-甲基丙-2-烯基)-3-甲基-4-氟-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺(化合物94)。
实施例21
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3-氯-4-溴苯基)环丙基〕戊-2,4-二烯酰胺(化合物71)
该化合物是用类似于实施例14的方法,用氢氯酸和氯化亚铜代替氢溴酸和溴化亚铜制备的。
用类似的方法,用3-甲基-4-膦酰基丁烯酸三乙酯和异丁胺代替4-膦酰基丁烯酸三乙酸和1,2-二甲基丙胺,制备(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3-氯-4-溴苯基)环丙基〕戊-2,4-二烯酰胺(化合物72)。
用类似的方法,用4-氯-3-硝基甲苯作为起始物,制备(±)-(2E,4E)-(1,2-二甲基丙基)-5-〔反-2-(3-溴-4-氯苯基)环丙基〕戊-2,4-二烯酰胺(化合物73)和(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3-溴-4-氯苯基)环丙基〕戊-2,4-二烯酰胺(化合物74)。
实施例22
(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(4-苄基苯基)环丙基〕戊-2,4-二烯酰胺(化合物75)
用氯化汞(1.25g)(ex Aldrich)处理25°时在水(15ml)中的粉末锌(12.5g)(ex BDH)。加入浓盐酸,然后滗析去过量水,再加入4-苯甲酰苯甲酸(5g)(ex Lancaster),接着加入水(15ml),冰醋酸(2ml)和甲苯(15ml)。再加入20ml浓盐酸,加热回流7小时后,过滤混合物,并用稀盐酸洗涤,用通常的方法处理,得到4-苄基苯甲酸(4g)。
将上述酸(4g)溶于乙醇(50ml)中,然后用浓硫酸(0.5ml)处理,加热回流3小时后,真空浓缩该混合物,用通常的方法处理残余物,得到乙基-4-苄基苯甲酸酯(4g)。NMR′H:8.00(2H,dd),7.28(7H,m),4.39(2H,q),4.04(2H,s),1.40(3H,t)。
在0°和氮气下,用氢化铝锂(0.9g)处理在无水乙醚中的上述酯(4g)。在0°下1小时后和25°下18小时后,小心地加入水,然后用通常的方法处理该混合物,得到4-苄基苄醇(2.52g)。NMR′H:7.21(9H,m),4.53(2H,s),3.95(2H,s),2.10(1H,bs)。
用Swern的方法(草酰氯,1.2ml;二甲基亚砜,1.8ml;三乙胺,8.8ml)在二氯甲烷中氧化上述醇(2.52g),得到4-苄基苯甲醛(1.33g)。NMR′H:9.93(1H,s),7.78(2H,d),7.33(2H,d),7.20(5H,s),4.40(2H,s)。
用类似实施例15的方法将上述醛转化成标题化合物。
用类似的方法,用三乙基-4-膦酰基丁烯酸酯和1,2-二甲基丙胺制备(±)-(2E,4E)N-(1,2-二甲基丙基)-5-反-2-(4-苄基苯基)环丙基〕戊-2,4-二烯酰胺(化合物76)。
实施例23
(±)-(2Z,4E)N-异丁基-2-氟-3-甲基-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺(化合物77)
在安装有蒸馏柱的容器中将溴氟乙酸乙酯(ex Fluorochem)(25g)和亚磷酸三乙酯(ex Aldrich)(29g)一起在140-5°下加热6小时。当所有的乙基溴蒸馏出时,蒸馏剩余物,得到2-氟-2-磷酸乙酸三乙酯(22g)(在0.8mm下沸点为98~108°)。将该化合物(20g)逐滴加入到在无水乙醚(85ml)中的己烷洗涤过的氢化钠(3.3g,60%的分散体)中。在室温下3小时后和加热回流30分钟后,加入丙酮(6.1ml),在室温和氮气下搅拌该混合物4天。用通常的方法处理后,蒸馏粗产物,得到2-氟-3-甲基-丁-2-烯酸乙酯(4g)(在15mm下沸点为60-2°)。(参考Machleidt和Wessendorf,Ann,674,1,(1964))。
在回流和亮光照射下,将2-氟-3-甲基-丁-2-烯酸乙酯(4克,27.4mmol),N-溴琥珀酰亚胺(5.36克,30mmol)(ex Aldrich)和过氧化苯甲酰(30毫克)在四氯甲烷(60ml)中一起回流加热。2小时后除去溶剂,然后将残余物溶解于己烷中,通过“硅藻土”过滤并浓缩,短程蒸馏得到(E)和(Z)4-溴-2-氟-3-甲基丁-2-烯酸乙酯(4克)的混合物。在140-150°下和Vigreaux长颈瓶中,该混合物与亚磷酸三乙酯(3.82克,23.07mmol)在回流下加热。2小时后,通过bulbtobulb蒸馏提纯粗产品,得到2-氟-3-甲基-4-膦酰基丁烯酸三乙酯(3.5克,在0.5mm下沸点为160-70°)。
在-70°和氮气下,用上述膦酰基丁烯酸酯(2.82克)处理在四氢呋喃(10ml)中的二异丙基氨基化锂(由正-丁基锂(6.25ml)和二异丙胺(1.4ml)制得)的溶液。在-70°下2小时后,加入(±)-反-2-(3,4-二氯苯基)环丙基甲醛(2.15克)。在25°下18小时后,加入水,然后用通常的方法处理该混合物,通过色谱分离(二氧化硅,乙醚/己烷)提纯,得到(±)-(2E,4E)-乙基-2-氟-3-甲基-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酸酯(2.4克)。NMR′H:7.23(1H,d),7.10(1H,d),6.83(1H,dd),6.75(1H,dd),5.77(1H,dd),4.28(2H,q),2.27(3H,d),1.87(2H,m),1.33(3H,t),1.33(2H,m)。
用类似于实施例1的方法将上述酯转化成标题化合物。
用类似的方法,用2-甲基丙-2-烯基胺代替异丁胺,制备(±)-(2Z,4E)N-(2-甲基丙-2-烯基)-2-氟-3-甲基-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-乙烯酰胺(化合物78)。
实施例24
用类似于实施例23的方法,由酯(Z)-乙基-3-(3,4,5-三氯苯基)-2-氟丙-2-烯酸酯制备(±)-(2E,4E)N-(1,2-二甲基丙基)-5-(r-1-氟-C-2-(3,4,5-三氯苯基环丙基〕戊-2,4-二烯酰胺(化合物79)。在氮气下用草酸二乙酯(1.83克)和氟乙酸乙酯(1.33克)处理在四氢呋喃(10ml)中的氢化钠(0.33克)悬浮液,制得上述酯。加热回流4小时后,将3,4,5-三氯苯甲醛(2.62克)(由实施例18制备)加到冷却的混合物中。在25°下18小时后,加入水,然后用通常的方法处理该混合物。通过色谱分离(二氧化硅,己烷/乙醚)提纯,得到化合物79(2.5克),NMR′H:7.63(2H,s),6.77(1H,d),4.35(2H,q),1.38(3H,t)。
用类似的方法,用下列所示的醛,维悌希试剂和胺作为起始物制备下列化合物
化合物序号 化合物名称
80 (±)-(2E,4E)N-异丁基-3-甲基-5-〔r-1-氟-C-2-(3,4,5-三氯苯基)环丙基〕戊-2,4-二烯酰胺。
81 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔r-1-氟-C-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺。
82 (±)-(2E/Z,4E)N-(2-甲基丙-2-烯基-3-甲基-5-〔r-1-氟-C-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺,2'E∶2Z异构体为5∶4的混合物。
83 (±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔r-1-氟-C-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺,2E∶2Z异构体为1∶1的混合物。
84 (±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔r-1-氟-C-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺。
85 (±)-(2E/Z,4E)N-异丁基-5-〔r-1-氟-C-2-(3,4-二氯苯基)环丙基〕-3-甲基戊-2,4-二烯酰胺,2E,4E∶2Z,4E异构体为4∶1的混合物。
86 (±)-(2E/Z,4E)N(2,2-二甲基丙基)-3-甲基-5-〔r-1-氟-C-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺,2E,4E∶2Z,4E异构体为2∶1的混合物。
87 (±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔r-1-氟-C-2(3,4,5-三氯苯基)环丙基〕戊-2,4-二烯酰胺。
88 (±)-(2Z,4E)N-异丁基-3-甲基-5-〔r-1-氟-C-2-(3,4,5-三氯苯基)环丙基〕戊-2,4-二烯酰胺。
101 (±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔r-1-氟-C-2-(3-氯-4-溴苯基)环丙基〕戊-2,4-二烯酰胺,2E,4E∶2Z,4E异构体为1∶1的混合物。
102 (±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔r-1-氟-C-2-(3-氯-4-溴苯基)环丙基〕戊-2,4-二烯酰胺,2E,4E∶2Z,4E异构体为2∶1的混合物。
103 (±)-(2Z,4E)N-(2-甲基丙-2-烯基-3-甲基-5-〔r-1-氟-C-2-(3-氯-4-溴苯基)环丙基〕戊-2,4-二烯酰胺。
104 (±)-(2E,4E)N-异丁基-2-氟-3-甲基-5-〔r-1-氟-C-2(3-氯-4-溴苯基)环丙基〕戊-2,4-二烯酰胺。
105 (±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-2-氟-3-甲基-5-〔r-1-氟-C-2-(3-氯-4-溴苯基)环丙基〕戊-2,4-二烯酰胺。
92 (±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔r-氟-C-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺。
109 (±)-(2E/Z,4E)N-(2-丁基)-2-氟-3-甲基-5-〔r-1-氟-C-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺,2Z∶'2E异构体为7∶1的混合物。
110 (±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-2-氟-3-甲基-5-〔r-1-氟-C-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺,2Z∶2E异构体为6∶1的混合物。
111 (±)-(2E/Z,4E)N-异丁基-2-氟-3-甲基-5-〔r-1-氟-C-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺,2Z∶2E异构体为3∶1的混合物。
112 (±)-(2E/Z,4E)N-(2-丁基)-3-甲基-5-〔r-1-氟-C-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺,2E∶2Z异构体为3∶2的混合物。
113 (±)-(2Z,4E)N-(2-丁基)-3-甲基-5-〔r-1-氟-C-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺。
114 (±)-(2E/Z,4E)N-(2-丁基)-3-甲基-5-〔r-1-氟-C-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺,2E∶2Z异构体为5∶1的混合物。
115 (±)-(2E/Z,4E)N-异丁基-1-氟-3-甲基-5-〔r-1-氟-C-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺,2Z∶2E异构体为6∶1的混合物。
116 (±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-2-氟-3-甲基-5-〔r-1-氟-C-2-(3,4-二溴苯基)环丙基〕戊-2,4二烯酰胺,2Z∶2E异构体为5∶1的混合物。
117 (±)-(2E/Z,4E)N-(2-丁基)-2-氟-3-甲基-5-〔r-1-氟-C-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺,2Z∶2E异构体为5∶1的混合物。
118 (±)-(2E,4E)N-异丁基-5-〔r-1-氟-C-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺。
化合物 醛RCHO其中R= 维悌希 胺
序号 试剂
80 3,4,5-Cl3Ph (2) 异丁胺
81 3,4-Cl2Ph (1) 1,2-二甲基丙胺
82 3,4-Br2Ph (2) 2-甲基丙-2-烯
基胺
83 3,4-Br2Ph (2) 异丁胺
84 3,4-Br2Ph (1) 1,2-二甲基丙胺
85 3,4-Cl2Ph (2) 异丁胺
86 3,4-Cl2Ph (2) 2,2-二甲基丙胺
87 3,4,5-Cl3Ph (2) 2-甲基丙-2-烯
基胺
88 3,4,5-Cl3Ph (2) 异丁胺
101 3-Cl,4-BrPh (2) 异丁胺
102 3-Cl,4-BrPh (2) 2-甲基丙-2-烯
基胺
103 3-Cl,4BrPh (2) 2-甲基丙-2-烯
基胺
104 3-Cl,4-BrPh (3) 异丁胺
105 3-Cl,4-BrPh (3) 2-甲基丙-2-烯
基胺
92 3,4-Cl2Ph (2) 2-甲基丙-2-烯
基胺
109 3,4-Cl2Ph (3) 仲-丁胺
110 3,4-Cl2Ph (3) 2-甲基丙-2-烯
基胺
111 3,4-Cl2Ph (3) 异丁胺
112 3,4-Cl2Ph (2) 仲-丁胺
113 3,4-Cl2Ph (2) 仲-丁胺
114 3,4-Br2Ph (2) 仲-丁胺
115 3,4-Br2Ph (3) 异丁胺
116 3,4-Br2Ph (3) 2-甲基丙-2-烯基胺
117 3,4-Br2Ph (3) 仲-丁胺
118 3,4-Cl2Ph (1) 异丁胺
维悌希试剂3=2-氟-3-甲基膦酰基丁烯酸三乙酯
实施例25
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔r-1-氯-C-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺(化合物89)
在-70°和氮气下,用三乙胺(10.1克)处理在二氯甲烷(100ml)中的碳化乙氧基亚甲基三苯基正膦(34.8克),然后在60分钟内用溶于四氯化碳(100ml)的氯溶液(7克)处理。将该溶液加热到25°,然后加入水,用通常的方法处理混合物,产物从丙酮/己烷中重结晶后,得到碳化乙氧基氯亚甲基三苯基正膦(18.9克)。(参考:Denney和Ross,J.Org.Chem.,1962,27 998)。
在25°和氮气下,用3,4-二氯苯甲醛处理在二氯甲烷(100ml)中的碳化乙氧基氯亚甲基三苯基正膦(8.74克)。在25°下18小时后,真空除去溶剂,然后在己烷中磨成粉,真空浓缩己烷洗涤液,通过色谱分离(二氧化硅;乙醚/己烷)提纯得到乙基-3-(3,4-二氯苯基,-2-氯丙-2-烯酸酯(6.3克)。
用类似于实施例24的方法,将上述酯转化成标题化合物。
用类似的方法,用三乙基-4-膦酰基-3-甲基丁烯酸酯和异丁胺代替三乙基-4-膦酰基丁烯酸酯和1,2-二甲基丙胺,制备(±)-(2E,4E)N-异丁基-3-甲基-5-〔r-1-氯-C-2-(3,4-二氯-苯基)环丙基〕戊-2,4-二烯酰胺(化合物90)和(±)-(2Z,4E)-N-异丁基-3-甲基-5-〔r-1-氯-C-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺(化合物91)。
实施例26
(±)-(2E,4E)N-异丁基-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯硫代酰胺(化合物106)。
用在二氯甲烷(30ml)中的碳化乙氧基亚甲基三苯基正膦(4.85克)处理反-2-(3,4-二氯苯基,环丙烷甲烷甲醇(3克)(由实施例18制备)。真空浓缩,然后过滤,再浓缩得到(±)-乙基-3-〔反-2-(3,4-二氯苯基)环丙基〕丙-2-烯酸酯(1.8克)。
在二氯甲烷(100ml)中,用二异丁基氢化铝(12.6ml,1M在己烷中的溶液)处理上述酯(1.8克),然后用通常的方法处理,得到(±)-3-〔反-2-(3,4-二氯苯基)-环丙基〕丙-2-烯-1-醇(1.33克)。
用Swern的方法(草酰氯,0.7ml;二甲基亚砜,1.15ml;三乙胺,3.8ml)在二氯甲烷中氧化上述醇(1.33克),得到(±)-3-〔反-2-(3,4-二氯苯基)环丙基〕丙-2-烯-1-醛,该化合物可直接用于下一步骤。
在-70°下将N-丁基锂(62.5ml,0.1mol)加入到在四氢呋喃(200ml)中的甲烷磷酸二乙酯(15.2克,0.1mol)中。30分钟后,加入在四氢呋喃(50ml)中的异硫氰酸异丁酯(5.8克,0.05mol)中。将该混合物在室温下放置一整夜,然后倒在冰-水上,并用乙醚萃取。用盐水洗涤乙醚溶液,干燥,除去溶剂,得到N-异丁基-2-(二乙氧基磷酰基)乙酰硫代酰胺。
在-70°下将在四氢呋喃(5ml)中的N-异丁基-2-(二乙氧基磷酰基)乙酰硫代酰胺(0.7克)加入到四氢呋喃(15ml)中的二异丙基氨基化锂(5.4mol)中。使混合物的温度达到-20℃,然后再冷却到-40℃。
加入前制备的在四氢呋喃(5ml)中的(±)-3-〔反-2-(3,4-二氯苯基)环丙基〕丙-2-烯醛。将混合物在室温下放置1整夜,并用标准方法处理该混合物,通过柱色谱分离(二氧化硅;己烷∶乙醚为7∶3)提纯粗产物,得到标题化合物。
用类似的方法,用N-(1,2-二甲基丙基)-2-(二乙氧基磷酰基)-乙酰硫代酰胺代替N-异丁基-2-(二乙氧基磷酰基)乙酰硫代酰胺,制备(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯硫代酰胺(化合物107)。
用类似于实施例24的方法,用(C-2-(3,4-二氯苯基)-r-1-氟-环丙基)甲烷甲醇代替反-2-(3,4-二氯苯基)-环丙基)甲烷甲醇,制备(±)-(2E,4E)N-(1,2-二甲基丙基)-5-(C-2-(3,4-二氯苯基)-r-1-氟环丙基〕戊-2,4-乙烯硫代酰胺(化合物108)。
化合物 表2的-H' NMR数据
序号
1 7.40(2H,d),7.20(1H,dd),6.95(2H,d),6.27(1H,dd),5.75(1H,d),5.70(1H,dd),5.25(1H,d),3.98(1H,m),2.00(1H,m),1.74(2H,m),1.35(1H,m),1.25(1H,m),1.11(3H,d),0.91(6H,dd).
2 7.48(2H,d),7.19(1H,dd),6.94(2H,d),6.25(1H,dd),5.75(1H,d),5.71(1H,dd),5.50(1H,m),3.18(2H,dd),2.02(1H,m),1.81(1H,m),1.70(1H,m),1.32(1H,m),1.23(1H,m),0.94(6H,d).
3 7.68(1H,s),7.50(2H,s),7.20(1H,dd),6.29(1H,dd),5.77(1H,d),5.73(1H,dd),5.25(1H,d),3.98(1H,m),2.19(1H,m),1.86(1H,m),1.74(1H,m),1.44(1H,m),1.37(1H,m),1.13(3H,d),0.93(6H,dd).
4 7.79(3H,m),7.55(1H,d),7.45(2H,m),7.23(2H,m),6.27(1H,dd),5.78(1H,dd),5.74(1H,d),5.24(1H,d),3.98(1H,m),2.21(1H,m),1.87(1H,m),1.72(1H,m),1.51(1H,m),1.28(1H,m),1.10(3H,d),0.91(6H,dd).
5 7.82(3H,m),7.58(1H,d),7.46(2H,m),7.26(2H,m),6.30(1H,dd),5.79(1H,dd),5.75(1H,d),5.48(1H,m),3.19(2H,d),2.23(1H,m),2.88(1H,m),1.56(1H,m),1.28(1H,m),0.98(9H,s).
6 7.80(3H,m),7.54(1H,d),7.45(2H,m),7.22(1H,m),6.20(1H,d),5.77(1H,dd),5.60,5.51(1H,s),5.50(1H,m),3.15(2H,dd),2.31,1.97(3H,s),2.22(1H,m),1.86(2H,m),1.47(1H,m),1.25(1H,m),0.93(6H,dd).
7 7.40(2H,d),7.21(1H,dd),6.96(1H,d),6.27(1H,dd),5.81(1H,d),5.71(1H,dd),5.47(1H,m),3.17(1H,d),2.02(1H,m),1.73(1H,m),1.36(1H,m),1.24(1H,m),0.93(9H,s).
8 7.41(2H,d),6.98(2H,d),6.18(1H,d),5.68(1H,dd),5.62,5.50(1H,s),5.50(1H,m),3.16(2H,dd),2.28,1.98(3H,s),2.00(1H,m),1.79(2H,m),1.27(2H,m),0.94(6H,d).
9 7.69(1H,s),7.51(2H,s),6.20(1H,d),5.68(1H,dd),5.63,5.50(1H,s),5.50(1H,m),3.15(2H,dd),2.28,1.98(3H,s),2.17(1H,m),1.82(2H,m),1.40(2H,m),0.94(6H,d).
10 7.56(2H,d),7.28(1H,dd),7.17(2H,d),6.27(1H,dd),5.75(1H,d),5.72(1H,dd),5.28(1H,d),3.97(1H,m),2.08(1H,m),1.74(2H,m),1.41(1H,m),1.30(3H,m),1.11(3H,d),0.92(6H,d).
11 7.53(2H,d),7.18(2H,d),6.19(1H,d),5.68(1H,dd),5.61(1H,s),5.51(1H,bt),3.14(2H,t),2.28(3H,s),2.08(1H,m),2.83(2H,m),1.40(1H,m),1.31(H,m),0.93(6H,d).
12 7.19(1H,dd),7.02(2H,d),6.83(2H,d),6.21(1H,dd),5.73(1H,dd),5.71(1H,d),5.20(1H,d),3.98(1H,m),3.79(3H,s),2.01(1H,m),1.69(2H,m),1.29(1H,m),1.15(1H,m),1.08(3H,d),0.91(6H,d).
13 7.21(1H,dd),7.12(4H,m),6.29(1H,dd),5.77(1H,d),5.73(1H,dd),5.30(1H,d),4.00(1H,m),2.11(1H,m),1.75(2H,m),1.37(1H,m),1.26(1H,m),1.10(2H,d),0.91(6H,d).
14 7.14(3H,m),6.79(1H,dd),6.25(1H,dd),5.75(1H,d),5.75(1H,dd),5.21(1H,d),3.98(1H,m),2.15(1H,m),1.72(2H,m),1.32(1H,m),1.21(1H,m),1.09(3H,d),0.91(6H,d).
15 7.25(1H,s),7.19(1H,d),6.80(1H,dd),6.17(1H,d),5.69(1H,dd),5.61(1H,s),5.46(1H,t),3.12(2H,t),2.23(3H,s),2.11(1H,m),1.73(2H,m),1.28(1H,m),1.20(1H,m),0.91(6H,d).
16 7.43(1H,t),7.18(1H,dd),6.78(2H,m),6.23(1H,dd),5.72(1H,d),5.70(1H,dd),5.23(1H,d),4.00(1H,m),2.02(1H,m),1.75(2H,m),1.28(2H,m),1.12(3H,d),0.91(6H,d).
17 7.41(1H,t),6.79(2H,m),6.18(1H,d),5.63(1H,dd),5.68(1H,s),5.46(1H,m),3.10(1H,t),2.22(3H,s),2.00(1H,m),1.75(2H,m),1.28(2H,m),0.91(6H,d).
18 7.14-7.48(5H,m),6.27(1H,dd),5.75(1H,d),5.71(1H,dd),5.49(1H,m),3.14(2H,d),2.10(1H,m),1.80(1H,m),1.40(1H,m),1.30(1H,m),0.91(6H,dd).
19 7.15-7.5(5H,m),6.28(1H,d),5.77(1H,d),5.73(1H,dd),5.28(1H,d),3.99(1H,m),2.12(1H,m),1.78(2H,m),1.41(1H,m),1.28(1H,m),1.11(3H,d),0.92(6H,dd).
20 7.32-7.48(1H,m),6.20(1H,d),5.68(1H,dd),5.62-5.50(1H,m),5.50(1H,m),3.16(2H,dd),2.28-1.96(3H,s),2.10(1H,m),1.81(2H,m),1.41(1H,m),1.28(1H,m),0.95(6H,d).
21 7.24-7.60(4H,m),6.22(1H,d),5.21(1H,dd),5.73-5.51(1H,s),5.51(1H,m),4.86(2H,s),3.88(2H,d),2.29-1.98(3H,s),2.10(1H,m),1.80(1H,m),1.75(3H,s),1.40(1H,m),1.29(1H,m).
22 7.34(1H,dd),7.15(3H,m),6.97(1H,dd),6.28(1H,dd),5.81(1H,dd),5.76(1H,d),5.50(1H,m),3.18(2H,dd),2.33(1H,m),1.78(1H,m),1.62(1H,m),1.36(1H,m),1.22(1H,m),0.93(6H,d).
23 7.33(1H,dd),7.14(3H,m),6.95(1H,dd),6.27(1H,dd),5.78(1H,dd),5.73(1H,d),5.24(1H,d),3.99(1H,m),2.43(1H,m),1.68(2H,m),1.37(1H,m),1.23(1H,m),1.10(3H,d),0.92(6H,dd).
24 7.37(1H,dd),7.26(2H,m),6.97(1H,dd),6.21(1H,d),5.78(1H,dd),5.10-5.00(1H,s),5.00(1H,m),3.15(2H,dd),2.32(1H,m),2.30-1.96(3H,s),1.81(1H,m),1.71(1H,m),1.28(2H,m),0.94(6H,d).
25 7.31-6.24(1H,d),7.47(1H,m),7.16(2H,m),6.99(1H,m),5.78(1H,dd),5.65,35 5.52(1H,s),5.50(1H,m),4.85(2H,s),3.87(2H,d),2.35(1H,m),2.30-1.97(3H,s),1.83(1H,m),1.60(1H,m),1.75(3H,s),1.35(1H,m),1.25(1H,m).
26 7.13-7.32(3H,m),7.07(2H,dd),6.17(1H,d),5.69(1H,dd),5.59,5.50(1H,s),5.50(1H,m),3.12(2H,dd),2.27,1.94(3H,s),2.02(1H,m),1.78(2H,m),1.47(1H,m),1.20(1H,m),0.91(6H,d).
27 7.12-7.36(4H,m),7.06(2H,dd),6.23(1H,d),5.72(2H,d&dd),5.25(1H,d),3.98(1H,m),2.06(1H,m),1.75(2H,m),1.35(1H,m),1.22(1H,m),1.11(3H,d),0.91(6H,dd).
28 7.15(3H,m),7.02(1H,d),6.95(1H,dd),6.23(1H,dd),5.72(1H,d),5.67(1H,dd),5.21(1H,d),3.98(1H,m),2.01(1H,m),1.73(2H,m),1.35(1H,m),1.22(1H,m),1.11(3H,d),0.92(6H,dd).
29 7.20(2H,m),7.07(1H,d),6.97(1H,dd),6.17(1H,d),5.65(1H,dd),5.58-5.46(1H,s),5.46(1H,m),3.16(2H,dd),2.28,1.93(3H,s),2.00(1H,m),1.75(2H,m),1.32(1H,m),1.24(1H,m),0.92(6H,d).
30 7.32(1H,d),7.26(1H,dd),7.15(1H,d),6.91(1H,dd),6.25(1H,dd),5.78(1H,d),5.69(1H,dd),5.47(1H,m),3.21(1H,dd),2.00(1H,m),1.80(1H,m),1.70(1H,m),1.38(1H,m),1.25(1H,m),0.92(6H,d).
31 7.35(1H,d),7.16(1H,d),6.93(1H,dd),6.17(1H,d),5.66(1H,dd),5.61(1H,s),5.49(1H,m),3.14(1H,dd),2.28 1.94(3H,s),1.98(1H,m),1.82(1H,m),1.74(1H,m),1.73(1H,m),1.68(1H,m),0.93(6H,d).
32 7.32(1H,d),7.18(1H,dd),7.15(1H,d),6.92(1H,dd),6.26(1H,dd),5.85(1H,d),5.69(1H,dd),5.27(1H,dd),3.98(1H,m),2.00(1H,m),1.73(2H,m),1.37(1H,m),1.28(1H,m),1.13(3H,d),0.91(6H,dd).
33 7.25(2H,d),7.23(1H,dd),7.02(2H,d),6.24(1H,dd),5.75(1H,d),5.71(1H,dd),5.24(1H,d),4.00(1H,m),2.02(1H,m),1.71(2H,m),1.34(1H,m),1.26(1H,m),1.11(3H,d),0.93(6H,dd).
34 7.25(2H,d),7.01(2H,d),6.15(1H,d),5.66(1H,dd),5.58,5.50(1H,s),5.50(1H,m),3.13(2H,dd),2.29,1.97(3H,s),2.02(1H,m),1.75(2H,m),1.28(2H,m),0.92(6H,d).
35 7.30(1H,d),7.30(1H,dd),7.12(1H,d),6.89(1H,dd),6.16(1H,d),5.62(1H,dd),5.57-5.47(1H,s),5.47(1H,m),4.83(2H,s),3.83(2H,d),2.27-1.93(3H,s),1.97(1H,m),1.72(3H,s),1.21(2H,m),1.72(1H,m).
36 7.31(1H,d),7.14(1H,d),6.89(1H,dd),6.16(1H,d),5.63(1H,dd),5.59(2H,m),3.17(2H,dd),2.24(3H,s),1.95(2H,m),1.70(1H,m),1.25(2H,m),0.98(1H,m),0.52(2H,m),0.21(2H,m).
37 7.30(1H,d),7.15(1H,d),6.92(1H,dd),6.15(1H,d),5.61(1H,dd)5.60(1H,s),5.43(1H,bt),3.09(2H,d),2.26(3H,s),1.98(1H,m),1.71(1H,m),1.25(2H,m),0.91(9H,s).
38 7.29(1H,d),7.12(1H,d),7.12(1H,dd),6.88(1H,dd),6.20(1H,dd),5.70(1H,d),5.66(1H,dd),5.14(1H,s),2.37(1H,h),1.98(1H,m),1.71(1H,m),1.29(6H,s),1.25(2H,d),0.86(6H,d).
39 7.31(1H,d),7.19(1H,dd),7.11(1H,d),6.91(1H,dd),6.23(1H,dd),5.73(1H,d),5.67(1H,dd),5.21(1H,d),4.01(1H,m),2.01(1H,m),1.71(1H,m),1.48(2H,m),1.30(2H,m),1.13(3H,d),0.91(3H,t).
40 7.31(2H,d),7.20(2H,dd),7.11(1H,d),6.88(1H,dd),6.23(1H,dd),5.78(2H,d),5.73(1H,m),5.69(1H,dd),3.35(2H,d),3.19(3H,s),1.99(1H,m),1.69(1H,m),1.23(2H,m),1.13(6H,s).
41 7.29(1H,d),7.21(1H,dd),7.13(1H,d),6.88(1H,dd),6.22(1H,dd),5.73(1H,d),5.68(1H,dd),5.60(1H,m),3.94(4H,m),3.48(2H,d),1.98(1H,m),1.73(1H,m),1.32(3H,s),1.28(2H,m).
42 7.29(1H,d),7.21(1H,dd),7.13(1H,d),6.88(1H,dd),6.10(1H,d),6.05(1H,dd),5.55(1H,m),3.00(2H,d),1.98(1H,m),1.73(1H,m),1.28(2H,m),0.10(9H,s).
43 7.29(1H,d),7.21(1H,dd),7.13(1H,d),6.88(1H,dd),6.25(1H,dd),5.76(1H,d),5.70(1H,d),5.54(1H,m),3.18(2H,dd),1.98(1H,m),1.68(1H,m),1.28(2H,m),0.94(1H,m),0.48(2H,m),0.20(2H,m).
44 7.19(1H,dd),6.26(1H,dd),5.88(1H,d),5.76(1H,d),5.63(1H,dd),5.25(1H,d),3.99(1H,m),1.73(3H,m),1.13(3H,d),1.13(1H,m),0.9(6H,dd),0.90(1H,m).
45 7.27(6H,m),6.39(1H,dd),5.89(1H,d),5.86(1H,dd),5.68(1H,d),3.96(1H,m),2.76(1H,dd),2.58(1H,ddd),1.72(1H,m),1.12(3H,d),0.92(6H,dd).
46 7.46(2H,d),7.18(1H,dd),7.10(2H,d),6.37(1H,dd),5.89(1H,d),5.82(1H,dd),5.67(1H,d),3.93(1H,m),2.70(1H,dd),2.52(1H,m),1.72(1Hm,),1.10(3H,d),0.91(6H,dd).
47 7.46(2H,d),7.12(2H,d),6.30(1H,d),5.80(2H,dd),5.71(1H,s),5.71(1H,bt),3.14(1H,t),2.70(1H,dd),2.54(1H,ddd),2.30(3H,s),1.80(1H,m),0.93(6H,d).
48 7.30(5H,m),6.17(1H,m),5.97(1H,dd),5.75(1H,dd),5.31(1H,m),3.98(1H,m),2.27(1H,m),1.78(2H,m),1.20(2H,m),1.11(3H,d),1.00(2H,m),0.93(6H,dd).
49 7.40(4H,m),6.09(1H,ddd),5.87(1H,dd),5.10(1H,d),3.83(1H,m),2.55(1H,m),2.15(1H,m),1.66(1H,m),1.47(1H,m),1.27(1H,m),1.05(3H,d),0.85(6H,dd).
50 7.40(4H,m),6.94(1H,dd),6.26(1H,dd),5.73(1H,d),5.62(1H,m),5.23(1H,dd),3.90(1H,m),2.49(1H,dd),1.97(1H,ddd),1.66(1H,),1.41(1H,ddd),1.17(1H,dd),1.04(3H,d),0.86(6H,dd).
51 7.40(4H,m),6.95(1H,dd),6.26(1H,dd),6.03(1H,bt,5.78(1H,d),5.25(1H,dd),3.10(2H,m),2.49(1H,dd),1.98(1H,m),1.77(1H,m),1.42(1H,m),1.19(1H,m),0.89(6H,d).
52 7.21(4H,m),7.21-6.93(1H,dd),6.3-6.18(1H,dd),5.92-5.10(1H,dd),5.71(1H,dd),5.26(1H,m),3.95(1H,m),1.73(2H,m),1.45(1H,m),1.13(1H,m),1.08(3H,d),0.90(1H,m),0.89(6H,dd).
53 7.40(4H,m),7.25(1H,dd),6.88(1H,dd),5.94(1H,dd),5.78(1H,d),5.30(1H,d),4.00(1H,m),2.16(1H,d),1.88(1H,dd),1.72(1H,m),1.28(3H,s),1.11(3H,d),0.90,6H,dd),0.89(3H,s).
54 7.37(1H,d),7.25(1H,d),7.23(1H,dd),7.03(1H,dd),6.85(1H,dd),5.94(1H,dd),5.77(1H,d),5.78(1H,d),4.0(1H,m),2.06(1H,d),1.89(1H,dd),1.75(1H,m),1.25(3H,s),1.12(3H,d),0.92(6H,dd),0.90(3H,s).
55 7.28(2H,d),7.28(1H,dd),7.10(2H,d),6.14(1H,dd),6.82(1H,d),6.79(1H,d),5.37(1H,bd),4.00(1H,m),2.24(1H,dd),1.73(1H,m),1.24(1H,m),1.11(3H,d),0.93(6H,dd),0.91(3H,s).
56 7.34(1H,d),7.15(1H,d),6.94(1H,dd),6.26(1H,dd),5.26(1H,d),5.72(1H,dd),5.47(1H,bt),2.18(2H,t),2.03(1H,m),1.81(1H,m),1.74(1H,m),1.34(1H,m),1.27(1H,m),0.93(6H,d).
57 7.34(1H,d),7.15(1H,d),6.94(1H,dd),6.26(1H,dd),5.26(2H,d),5.72(1H,dd),5.47(1H,bt),2.18(2H,t),2.03(1H,m),1.81(1H,m),1.74(1H,m),1.34(1H,m),1.27(1H,m),0.93(6H,d).
58 6.91(2H,s),6.21(1H,d),5.60(1H,s),5.58(1H,dd),5.48(1H,bt),3.11(2H,t),2.23(3H,s),1.94(1H,m),1.83(1H,m),1.80(1H,m),1.40(2H,m),0.90(6H,d).
59 7.50(1H,d),7.33(1H,d),7.19(1H,dd),6.90(1H,dd),6.26(1H,dd),5.76(1H,d),5.70(1H,dd),5.22(1H,bd),4.00(1H,m),2.00(1H,m),1.87(2H,m),1.30(2H,m),1.11(3H,d),0.93(6H,dd).
60 7.50(1H,d),7.33(1H,d),6.89(1H,dd),6.18(1H,d),5.64(1H,dd),5.60(1H,s),5.43(1H,m),3.17(2H,t),2.28(1H,s),1.96(1H,m),1.81(2H,m),1.29(2H,m),0.94(6H,d).
61 7.22(2H,s),6.29(1H,d),5.78(1H,d),5.69(2H,dd),5.24(1H,bd),4.00(1H,m),1.95(1H,m),1.73(1H,m),1.29(2H,m),1.12(3H,d),0.93(6H,dd).
62 7.06(2H,s),6.15(1H,d),5.62(1H,dd),5.60(1H,s),5.46(1H,m),3.11(2H,t),2.21(3H,s),1.93(1H,m),1.73(2H,m),1.28(2H,m),0.92(6H,d).
63 7.40(2H,m),7.20(1H,dd),7.18(1H,d),6.30(1H,dd),5.78(1H,d),5.71(1H,dd),5.27(1H,bd),4.00(1H,m),2.10(1H,m),1.75(2H,m),1.32(2H,m),1.11(3H,d),0.93(6H,dd).
64 7.38(2H,m),7.13(1H,dd),6.13(1H,d),5.61(1H,dd),5.58(1H,s),5.50(1H,m),3.09(2H,t),2.22(3H,s),2.02(1H,m),1.75(2H,m),1.30(2H,m),0.90(6H,d).
65 7.47(2H,d),7.43(1H,s),7.20(1H,dd),7.06(2H,d),6.26(1H,dd),5.74(1H,d),5.72(1H,dd),5.27(1H,d),3.99(1H,m),2.06(1H,m),1.80(2H,m),1.42(1H,m),1.29(1H,m),1.11(3H,d),0.91(6H,dd).
66 7.39(2H,d),7.20(1H,dd),7.03(2H,d),6.26(1H,dd),5.76(1H,d),5.71(1H,dd),5.27(1H,d),3.99(1H,m),3.08(1H,s),2.07(1Hm,),1.78(2H,m),1.40(1H,m),1.29(1H,m),1.11(3H,d),0.92(6H,dd).
67 7.15(1H,dd),7.08(2H,s),6.25(1H,dd),5.72(1H,d),5.63(1H,dd),5.22(1H,d),3.99(1H,m),1.98(1H,m),1.70(2H,m),1.30(2H,m),1.12(3H,d),0.90(6H,dd).
68 7.23-6.6(1H,d),7.06(2H,s),6.14(1H,dd),5.58-5.20(1H,dd),5.58(2H,m),3.10(2H,2t),2.23-2.01(3H,s),1.95(1H,m),1.75(2H,m),1.28(2H,m),0.91(6H,2d).
69 7.30(1H,d),7.14(1H,d),6.94(1H,dd),6.91(1H,dd),6.01(1H,d),5.36(1H,d),4.76(1H,dd),3.97(1H,m),2.02(2H,m),1.71(1H,m),1.37(1H,m),1.21(1H,m),1.10(3H,d),0.91(6H,dd).
70 7.31(1H,d),7.16(1H,d),6.92(1H,d),6.00(1H,d),5.58(1H,m),4.83(1H,dd),3.13(2H,t),2.23(3H,s),2.04(2H,m),1.79(1H,m),1.33(1H,m),1.08(1H,m),0.91(6H,d).
71 7.48(1H,d),7.18(1H,dd),7.10(1H,d),6.82(1H,dd),6.23(1H,dd),5.72(1H,d),5.67(1H,dd),5.22(1H,d),3.98(1H,m),1.98(1H,m),1.72(2H,m),1.28(2H,m),1.10(3H,d),0.90(6H,dd).
72 7.43(1H,d),7.13(1H,d),6.82(1H,dd),6.15(1H,d),5.61(1H,dd),5.59(1H,s),5.48(1H,m),3.11(2H,t),2.23(3H,s),1.97(1H,m),1.88(2H,m),1.25(2H,m),0.90(6H,d).
73 7.31(1H,d),7.23(1H,d),7.15(1H,dd),6.92(1H,dd),6.23(1H,dd),5.71(1H,d),5.63(1H,dd),5.27(1H,d),3.94(1H,m),1.98(1H,m),1.70(2H,m),1.25(2H,m),1.10(3H,d),0.89(6H,dd).
74 7.31(2H,m),6.92(1H,dd),6.12(1H,d),5.61(1H,dd),5.60(1H,s),5.49(1H,m),3.12(2H,t),2.25(3H,s),1.96(1H,m),1.75(2H,m),1.30(1H,m),1.22(1H,m),0.91(6H,d).
75 7.10(9H,m),6.11(1H,d),6.63(1H,dd),5.57(1H,s),5.43(1H,m),3.91(2H,s),3.10(2H,t),2.26(3H,s),1.99(1H,m),1.78(2H,m),1.30(1H,m),1.17(1H,m),0.90(6H,d).
76 7.10(10H,m),6.20(1H,dd),5.69(1H,dd),5.65(1H,d),5.19(1H,m),3.93(2H,s),2.01(1H,m),1.71(2H,m),1.32(1H,m),1.19(1H,m),1.13(3H,d),0.90(6H,dd).
77 7.31(1H,d),7.12(1H,d),6.89(1H,dd),6.63(1H,d),6.32(1H,m),5.62(1H,dd),3.14(2H,t),2.24(3H,s),1.99(1H,m),1.82(2H,m),1.28(2H,m),0.92(6H,d).
78 7.31(1H,d),7.12(1H,d),6.89(1H,dd),6.67(1H,dd),6.40(1H,m),5.66(1H,dd),4.88(2H,s),3.88(2H,d),2.25(3H,s),2.00(1H,m),1.80(1H,m),1.57(3H,s),1.28(2H,m).
79 7.21(2H,s),7.21(1H,dd),6.44(1H,dd),5.85(1H,d),5.81(1H,dd),5.27(2H,d),3.96(1H,m),2.24(1H,ddd),1.73(2H,m),1.54(1H,m),1.09(3H,d),0.89(6H,dd).
80 7.24(2H,s),6.33(1H,d),5.79(1H,dd),5.70(1H,s),5.49(1H,m),3.11(2H,t),2.28(3H,s),2.22(1H,m),1.79(1H,m),1.70(1H,m),1.53(1H,m),0.91(6H,d).
81 7.35(1H,d),7.30(1H,d),7.23(1H,dd),7.07(1H,dd),6.43(1H,dd),5.83(1H,d),5.81(1H,dd),5.31(1H,d),3.94(1H,m),2.28(1H,m),1.72(2H,m),1.53(1H,ddd),1.09(3H,d),0.90(6H,dd).
82 7.80&6.35(1H,d),7.53(2H,m),7.02(1H,dd),6.09(1H,dd),5.85(1H,dd),5.72&5.60(1H,s),5.60(1H,m),4.81(2H,s),3.85(2H,d),2.38&2.00(3H,s),2.30(1H,m),1.68(3H,s),1.65(1H,m),1.59(1H,m).
83 7.80&6.30(1H,d),7.50(2H,m),7.00(1H,dd),6.00(1H,dd),5.80(2H,m),5.70&5.60(1H,s),3.05(2H,m),2.24&1.90(3H,s),2.23(1H,m),1.60(3H,m),0.90(6H,d).
84 7.50(2H,m),7.20(1H,dd),7.00(1H,dd),6.40(1H,dd),5.85(1H,d),5.83(1H,dd),5.28(1H,m),3.95(1H,m),2.25(1H,m),1.25(2H,m),1.55(1H,m),1.10(3H,d),0.90(6H,dd).
85 7.75&6.35(1H,d),7.38(2H,m),7.05(1H,dd),5.80(1H,dd),5.70&5.61(1H,s),5.40(1H,m),3.15(2H,m),2.30&1.95(3H,s),2.30(1H,m),1.41-1.83(3H,m),0.91(6H,d).
86 7.75&6.35(1H,d),7.34(3H,m),7.04(1H,dd),6.08&5.81(1H,dd),5.71&5.63(1H,s),5.44(1H,m),3.13(2H,d),2.28&1.96(3H,s),2.28(1H,m),1.44-1.80(2H,m),0.91(9H,s).
87 7.25(2H,s),6.37(1H,d),5.80(1H,dd),5.74(1H,s),5.54(1H,m),4.85(2H,s),3.88(2H,d),2.32&1.98(3H,s),2.24(1H,m),1.75(3H,s),1.75(2H,m),1.55(1H,m).
88 7.82(1H,d),7.27(2H,s),6.09(1H,dd),5.63(1H,s),5.52(1H,m),3.12(2H,t),2.30(1H,m),1.98(3H,s),1.80(1H,m),1.65(2H,m),0.93(6H,d).
89 7.38(1H,d),7.28(1H,dd),7.22(1H,d),7.15(1H,dd),6.51(1H,dd),5.84(2H,dd),5.23(1H,d),3.95(1H,m),2.47(1H,dd),1.73(3H,m),1.09(3H,d),0.89(6H,dd).
90 7.38(1H,d),7.32(1H,d),7.05(1H,dd),6.40(1H,d),5.83(1H,d),5.73(1H,s),5.43(1H,m),3.14(2H,t),2.44(1H,dd),2.27(3H,s),1.72(3H,m),0.91(6H,d).
91 7.89(1H,d),7.35(2H,m),7.07(1H,dd),6.05(1H,d),5.61(1H,s),5.49(1H,m),3.10(2H,t),2.46(1H,dd),1.98(3H,s),1.81(2H,m),1.75(1H,m),0.92(6H,d).
92 7.81&6.35(1H,d),7.35(2H,m),7.07(1H,dd),6.11&5.81(1H,dd),5.72&5.64(1H,s),5.55(1H,m),4.85(2H,s),3.87(2H,m).
93 7.50(1H,m),7.32(1H,d),6.88(1H,dd),6.17(1H,d)5.64(1H,dd),5.61(1H,s),5.46(1H,m),4.82(2H,s),3.88(2H,d),2.25&2.04(3H,s),1.93(1H,m),1.73(3H,s),1.70(1H,m),1.25(2H,m).
94 7.32(1H,d),7.18(1H,d),6.92(1H,dd),6.03(1H,s),5.61(1H,m),4.98(1H,dd),4.84(1H,s),3.86(1H,d),2.22(3H,s),2.00(2H,m),1.73(3H,s),1.34(1H,m),1.20(1H,m).
95 7.39(1H,d),7.21(1H,dd),7.18(1H,d),6.97(1H,dd),6.30(1H,dd),5.84(1H,d),5.20(1H,dd),5.42(1H,m),3.21(2H,d),2.03(1H,m),1.87(1H,m),1.19(2H,m),0.98(9H,s).
96 7.30(1H,d),7.13(1H,dd),7.09(1H,d),6.89(1H,dd),6.20(1H,dd),5.69(1H,d),5.65(1H,dd),5.28(1H,m),3.80(1H,m),1.90(2H,m),1.68(2H,m),1.25(10H,m).
97 7.30(1H,d),7.13(1H,d),6.89(1H,dd),6.14(1H,d),5.62(1H,dd),5.57(1H,s),5.20(1H,m),3.98(1H,m),2.24(3H,s),1.97(1H,m),1.71(1H,m),1.47(2H,dq),1.25(2H,m),1.11(3H,d),0.90(3H,t).
98 7.32(1H,d),7.16(1H,d),6.91(1H,dd),6.17(1H,d),5.66(1H,dd),5.65(1H,m),5.58(1H,s),3.98(4H,m),3.48(2H,d),2.28(3H,s),1.98(1H,m),1.73(1H,m),1.32(3H,s),1.25(2H,m).
99 8.13(1H,d),7.66(2H,m),7.50(1H,d),7.27(2H,m),6.16(1H,d),5.72(1H,dd),5.55(1H,s),5.43(1H,m),3.12(2H,t),2.16&1.95(3H,s),2.20(1H,m),1.84(2H,m),1.49(1H,m),1.30(1H,m),0.91(6H,d).
100 8.13(1H,d),7.66(2H,m),7.50(1H,d),7.27(2H,m),6.16(1H,d),5.72(1H,dd),5.58(1H,s),5.45(1H,m),4.82(2H,s),3.82(2H,d),2.29&1.93(3H,s),2.28(1H,m),1.85(2H,m),1.72(3H,s),1.50(1H,m),1.25(1H,m).
101 7.70&6.35(1H,d),7.5(1H,d),7.38(1H,d),6.99(1H,dd),5.80&6.10(1H,dd),5.73&5.64(1H,s),5.52(1H,m),3.15(1H,m),2.31&2.01(3H,s),2.30(1H,m),1.4-1.9(3H,m),0.92(3H,d).
102 7.82&6.40(1H,d),7.57(1H,d),7.39(1H,d),7.04(1H,dd),6.17&5.87(1H,dd),5.74&5.67(1H,s),5.57(1H,m),4.88(2H,s),3.89(2H,d),2.35&2.01(3H,s),2.30(1H,m),1.48-1.84(2H,m),1.60(3H,s).
103 7.81(1H,d),7.50(1H,m),7.31(1H,m),6.99(1H,dd),6.13(1H,dd),5.67(1H,s),5.60(1H,m),5.38(1H,d),4.88(2H,s),3.99(2H,d),2.28(1H,m),2.00(3H,s),1.77(3H,s),1.60-1.80(2H,m).
104 7.59(1H,d),7.39(1H,d),7.04(1H,dd),6.89(1H,d),6.41(1H,m),5.85(1H,dd),3.19(2H,t),2.36(3H,d),2.30(1H,m),1.70-1.90(2H,m),1.60(1H,m),0.98(6H,d).
105 7.54(1H,d),7.38(1H,d),7.00(1H,dd),6.88(1H,d),6.46(1H,m),6.87(1H,dd),4.89(2H,s),3.91(2H,d),2.39(3H,d),2.35(1H,m),1.50-1.90(2H,m),1.79(3H,s).
106 7.48(1H,dd),7.34(1H,d),7.08(1H,m),6.93(1H,dd),6.29(1H,dd),6.19(1H,d),5.79(1H,dd),3.62(2H,t),2.03(2H,m),1.74(1H,m),1.29(2H,m),0.98(6H,d).
107 7.48(1H,dd),7.35(1H,d),6.93(1H,dd),6.90(1H,m),6.30(1H,dd),6.15(1H,d),5.80(1H,dd),4.70(1H,m),2.00(2H,m),1.75(1H,m),1.30(2H,m),1.20(3H,d),0.95(6H,2xd).
108 7.55(1H,dd),7.45(1H,d),7.38(1H,d),7.11(1H,dd),6.97(1H,m),6.50(1H,dd),7.28(1H,d),5.95(1H,dd),4.78(1H,m),2.32(1H,m),1.98(1H,m),1.86(1H,m),1.55(1H,m),1.20(1H,m),1.20(2H,d),0.98(6H,2xd).
109 79&6.88(1H,d),7.39(2H,m),7.12(1H,dd),6.16(1H,m),5.89(1H,dd),4.03(1H,m),2.38(1H,m),2.33&1.97(3H,d),1.80(1H,ddd),1.60(4H,m),1.20(3H,d),0.94(3H,t).
110 7.9&6.89(1H,d),7.39(2H,m),7.11(1H,dd),6.47(1H,m),6.12&5.90(1H,dd),4.90(2H,s),4.93(2H,d),2.32(1H,m),2.32&1.96(3H,d),1.78(3H,s),1.80(1H,ddd),1.60(2H,m).
111 7.9&6.89(1H,d),7.33(2H,m),7.09(1H,dd),6.40(1H,m),6.10&5.88(1H,dd),3.21(2H,t),2.33&2.00(3H,d),2.32(1H,m),1.80(2H,m),1.56(1H,m),0.94(6H,d).
112 7.80&6.36(1H,d),7.38(2H,m),7.08(1H,dd),6.09&5.82(1H,dd),5.69&5.62(1H,s),5.77(1H,d),3.99(1H,m),2.32&1.99(3H,s),1.73(1H,ddd),1.50(4H,m),1.17(3H,d),0.93(3H,t).
113 7.80(1H,d),7.35(2H,m),7.09(1H,dd),6.11(1H,dd),5.63(1H,s),5.29(1H,d),4.00(1H,m),2.32(1H,m),2.00(1H,s),1.40-1.80(5H,m),1.16(3H,d),0.96(3H,t).
114 7.80&6.38(1H,d),7.54(2H,m),7.08(1H,dd),6.11&5.83(1H,dd),5.69&5.62(1H,s),5.29(2H,d),4.02(1H,m),2.29&2.00(3H,s),2.30(1H,m),1.80(1H,ddd),1.42-1.72(4H,m),1.16(3H,d),0.93(3H,t).
115 7.56(2H,m),7.08(1H,dd),6.88(1H,d),6.40(1H,m),6.12&5.88(1H,dd),3.18(2H,t),2.33&2.00(3H,d),2.31(1H,m),1.85(2H,m),1.58(1H,m),0.96(6H,d).
116 7.90&6.92(1H,d),7.55(2H,m),7.04(1H,dd),6.46(1H,m),6.09&5.89(1H,dd),4.89(2H,s),3.93(2H,d),2.34&2.00(3H,d),2.32(1H,m),1.80(2H,m),1.77(3H,s),1.60(1H,m).
117 7.90&6.87(1H,d),7.53(2H,m),7.06(1H,dd),6.13(1H,m),6.08&5.87(1H,dd),4.01(1H,m),2.34&1.99(3H,d),2.32(1H,m),1.80(1H,ddd),1.50-1.80(4H,m),1.18(3H,d),0.93(3H,t).
118 7.39(2H,m),7.32(1H,dd),7.10(1H,dd),6.46(1H,dd),5.90(1H,d),5.87(1H,d),5.08(1H,m),3.21(2H,t),2.31(1H,m),1.80(2H,m),1.58(1H,m),0.99(6H,d).
方案1.制备结构式Ⅰ的化合物
(ⅰ)过程(a) Z1=OR,X=O
(ⅱ)过程(a) Z1=OH,X=O
(ⅲ)过程(b) X=O,S
(ⅳ)过程(b) X=O,S
(ⅴ)过程(b) X=O,S
方案2.制备酯中间产物
(ⅰ)至(ⅴ)代表前面所述的制备酯中间产物的过程
方案3.制备醇和醛中间产物
生物数据
下列实施例非限定性说明了结构式(Ⅰ)化合物的杀虫活性:
实施例A-喷雾试验
本发明化合物的活性可用下述方法试验:将该化合物溶于丙酮(5%)中,然后在水:“Synperonic”(94.5%∶0.5%)中稀释,得到水乳液。然后将该溶液用来处理下列昆虫,在下列喷雾量下现察化合物的活性:
家蝇(Musca domestica)
将20只雌性家蝇装入两端装有纱布的纸板园筒内,将含有化合物的溶液喷雾到关在园筒内的昆虫上,在25℃下48小时后确定死亡率。
下列化合物在1000ppm或更低浓度下有效:1,2,3,5,6,7,8,10,11,14,15,19,20,21,36,37,38,39,40,41,96,48,55,57,65,66,78。
下列化合物在200ppm或更少浓度下有效:4,9,13,16,17,100,30,31,32,33,34,35,42,95,97,56,59,60,61,62,63,64,67,68,69,70,71,72,73,74,77,93,94,79,80,81,82,83,84,86,89,90,92,87。
Pluetella xylostella
传染有8只第二龄期的菜蛾属幼虫的中国卷心菜叶片用含有化合物的溶液喷雾,在25°下2天后确定死亡率。
下列化合物在1000ppm或更低浓度下有效:12,22,25,26,45,46,47,48,51,52,53,54,58,65,76。
下列化合物在200ppm或更低浓度下有效:1,2,3,4,5,6,7,9,11,13,14,15,18,19,20,21,23,24,27,28,29,30,31,32,34,36,41,42,95,44,50,57,61,66。
下列化合物在40ppm或更低浓度下有效:8,10,16,17,33,35,37,38,39,40,97,55,56,59,60,62,63,64,67,68,69,70,71,72,73,74,77,78,93,79,80,81,90,92,87。
棉叶螨(Tetranychus urticae)
用含有化合物的溶液喷雾受传染的法国豆叶片,在25℃下2天后确定死亡率。
下列化合物在1000ppm或更低浓度下有效:8,12,13,16,17,18,21,26,28,31,33,34,37,54,56,57,59,60,61,63,67,69,70,77,78,93,80,82,83,84,85,92,87。
Spodoptera littoralis
用含有化合物的试验溶液喷雾未受传染的叶子,放置干燥,然后用10只新孵化的幼虫传染,3天后确定死亡率。
下列化合物在1000ppm或更低浓度下有效:1,5,6,7,13,14,15,100,18,20,21,29,34,36,37,38,40,41,42,95,44,46,49,50,51,53,55,63,65,66,67,91。
下列化合物在200ppm或更低浓度下有效:3,4,8,9,10,11,16,17,19,30,31,32,33,35,39,96,97,56,57,59,60,61,62,64,68,69,70,71,72,73,74,77,78,93,94,79,80,81,82,83,84,85,86,89,90,92,87。
桃蚜(Myzus Persicae)
将10只成年瘤额蚜放在中国卷心菜的叶片上,24小时后,用含有化合物的溶液喷雾叶片,在25℃下2天后确定死亡率。
下列化合物在1000ppm或更低浓度下有效:8,9,13,18,19,20,22,24,30,31,34,35,95,44,50,59,60,61,66,72,75,77,78,93,94,82,83,84,85,86,92,87。
Diabrotica undecimpunctata
将第2龄期幼虫和它们的食物喷雾在含有化合物溶液的滤纸上,2天后确定活性。
下列化合物在1000ppm或更低浓度下有效:3,6,9,11,12,13,14,17,28,29,30,31,32,33,35,37,39,95,96,97,44,54,55,56,59,61,62,63,67,69,71,72,74,77,78,94,80,81,82,83,86,92。
下列化合物在200ppm或更低浓度下有效:10,16,68,73,79,84,85,89。
实施例B-某一地方的应用试验
德国小蠊(Blattella germanica)
将0.5μl在丁酮(有或没有故椒基丁氧金属)中的该化合物的溶液在某一地方用于雄性德国小蠊上,6天后确定死亡率。
下列化合物在10μg或更少(+胡椒基丁氧金属)的情况下有效:10,11,13,15,16,17,30,35,36,37,39,40,41,42,55,56,57,59,60,61,63,64,67,68,69,70,71,72,73,74,77,78,94,79,80,81,82,83,84,85,86,92,87。
下列化合物仅在10μg或更少的情况下有效:1,8,9,20,21,30,31,32,33,34,95。
Claims (11)
1、一种杀虫或杀螨剂组合物,其特征在于,该组合物含有杀虫或杀螨有效量的以下所示的式(Ⅰ)化合物或它们的盐作为其活性成分,以及含有载体或稀释剂,在需要时还可以含有有助于式(Ⅰ)化合物作用的增效剂
其中Q是各自任意选择地被一个至四个选自各任意选择地被一个至三个卤原子取代的C1-6烃基、C1-6烷氧基或亚甲二氧基取代的苯基、吡啶基、噻嗯基或萘基,或者是各自任意选择地被一个至四个选自卤原子、氰基或硝基取代的苯基、吡啶基、噻嗯基或萘基或者Q是二卤代乙烯基或R6-C≡C-基团,其中R6为C1-4烷基,三C1-4烷基甲硅烷基、卤素或氢;Q1为被一个或多个选自C1-3烷基,卤素,C1-3卤代烷基,链炔基或氰基任意选择地取代的1,2-环丙基环;R2,R3,R4和R5可以相同或不同,其中至少有一个为氢,而其他的则为独立地选自氢,卤素,C1-4烷基或C1-4卤代烷基的基团;X为氧或硫;R1选自氢和任意选择地被二氧戊环基,卤素,氰基,三氟甲基,三氟甲硫基或C1-6烷氧基的基团取代的C1-8烃基。
2、按照权利要求1的组合物,其特征在于式(Ⅰ)化合物的R2,R3,R4和R5是选自氢,甲基或氟。
3、按照权利要求1的组合物,其特征在于式(Ⅰ)化合物的环丙基环Q1的1位和3位未被取代和2位未被取代或被氟或氯取代。
4、按照权利要求1的组合物,其特征在于式(Ⅰ)化合物的R1为异丁基,1,2-二甲基丙基,1,1,2-三甲基丙基,2,2-二甲基丙基,2-甲基丙-2-烯基或(2-甲基-1,3-二氧丙环-2-基)甲基。
5、按照权利要求2的组合物,其特征在于式(Ⅰ)化合物的R1为异丁基,1,2-二甲基丙基,1,1,2-三甲基丙基,2,2-二甲基丙基,2-甲基丙-2-烯基或(2-甲基-1,3-二氧丙环-2-基)甲基。
6、按照权利要求3的组合物,其特征在于式(Ⅰ)化合物的R1为异丁基,1,2-二甲基丙基,1,1,2-三甲基丙基,2,2-二甲基丙基,2-甲基丙-2-烯基或(2-甲基-1,3-二氧丙环-2-基)甲基。
7、按照权利要求1的组合物,其特征在于式(Ⅰ)化合物是下列化合物或它们的盐中选出的一种化合物
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(4-溴苯基)-环丙基〕戊-2,4-二烯酰胺;
(±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔反-2-(3,5-双三氟甲基苯基)-环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3,5-双三氟甲基苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3,5-二氯苯基)环丙基)戊-2,4-二烯酰胺;
(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3,4-二氯苯基)环丙基)戊-2,4-二烯酰胺;
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(4-氯苯基)环丙基)戊-2,4-二烯酰胺;
(±)-(2E,4E)-(1,2-二甲基丙基)-5-〔反-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰按;
(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-异丁基-3-甲基-5-甲基-5-〔反-2-(4-氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔反-2-(3,4-二溴苯基)-环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3-三氟甲基-4-氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3,5-二氯-4-溴苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3,4,5-三氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-异丁基-3-甲基-4-氟-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3-氯-4-溴苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-异丁基-3-甲基-5-〔反-2-(3-氯-4-溴苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔反-2-(3-溴-4-氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔r-1-氟-c-2-(3,4,5-三氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-异丁基-3-甲基-5-〔r-1-氟-c-2-(3,4,5-三氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2Z,4E)N-异丁基-2-氟-3-甲基-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2Z,4E)N-(2-甲基丙-2-烯基)-2-烯基)-2-氟-3-甲基-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-(仲丁基)-5-〔反-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔r-1-氟-c-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔r-1-氟-c-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔r-1-氟-c-(3,4-二溴苯基)环丙基)戊-2,4-二烯酰胺;
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔r-1-氟-c-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰按;
(±)-(2E/Z,4E)N-异丁基-3-甲基-5-〔r-1-氟-c-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-(1,2-二甲基丙基)-5-〔r-1-氟-c-2-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4Z)N-(2-甲基丙-2-烯基)-3-甲基-4-氟-5-〔反-2-(3,4-二氯苯基)-环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-异丁基-3-甲基-5-〔r-1-氯-2-c-(3,4-二氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔r-1-氟-2-c-(3,4,5-二氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E/Z,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔r-1-氟-2-c-(3,4,5-三氯苯基)环丙基〕戊-2,4-二烯酰胺;
(±)-(2E,4E)N-(2-甲基丙-2-烯基)-3-甲基-5-〔反-2-(3,4-二溴苯基)环丙基〕戊-2,4-二烯酰胺。
8、权利要求1-7之一的组合物的制备方法,该方法包括将作为活性成分的杀虫或杀螨有效量的式(Ⅰ)化合物与适量的载体或稀释剂相混合。
9、权利要求1-7之一的组合物的制备方法,该方法包括将作为活性成分的杀虫或杀螨有效量的式(Ⅰ)化合物与适量的载体或稀释剂以及有助于式(Ⅰ)化合物作用的适量的增效剂相混合。
10、权利要求1-7之一的组合物的用途,该用途包括将该组合物用于其他适合的杀虫剂相混合组成混合杀虫剂。
11、权利要求1-7之一的组合物的用途,该用途包括将该组合物施用于害虫或有可能受害虫侵袭的环境中。
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IE (1) | IE64377B1 (zh) |
IL (1) | IL92317A (zh) |
MC (1) | MC2070A1 (zh) |
OA (1) | OA09145A (zh) |
PL (3) | PL162284B1 (zh) |
PT (1) | PT92323B (zh) |
RU (3) | RU2010025C1 (zh) |
SK (1) | SK646189A3 (zh) |
TR (1) | TR25218A (zh) |
ZA (1) | ZA898725B (zh) |
ZW (1) | ZW15189A1 (zh) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9113624D0 (en) * | 1991-06-25 | 1991-08-14 | Wellcome Found | Pesticides |
GB9126955D0 (en) * | 1991-12-19 | 1992-02-19 | Wellcome Found | Pesticides |
EP0549418A3 (en) * | 1991-12-23 | 1993-10-20 | Roussel Uclaf | Unsaturated amides with pesticidal activity |
FR2729945B1 (fr) * | 1995-01-26 | 1997-04-25 | Hoechst Schering Agrevo Sa | Nouveaux amides aromatiques, leur procede de preparation, les compostions les contenant et leur utilisation comme pesticides |
US6403638B1 (en) | 1998-10-01 | 2002-06-11 | Allergan Sales, Inc. | 2,4-pentadienoic acid derivatives having selective activity for retinoid X (RXR) receptors |
US6147224A (en) * | 1998-10-01 | 2000-11-14 | Allergan Sales, Inc. | 2,4-pentadienoic acid derivatives having selective activity for retinoid X (RXR) receptors |
DE10018370A1 (de) | 2000-04-14 | 2001-10-18 | Bayer Ag | Wirkstoffkombinationen mit insektiziden und akariziden Eigenschaften |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4855086A (en) * | 1982-10-15 | 1989-08-08 | Burroughs Wellcome Co. | Novel pesticides, preparation and use |
GB8504097D0 (en) * | 1985-02-18 | 1985-03-20 | Wellcome Found | Pesticidal compounds |
CA1268467A (en) * | 1985-02-18 | 1990-05-01 | Robert John Blade | Pesticidal compounds |
-
1988
- 1988-11-16 GB GB888826760A patent/GB8826760D0/en active Pending
-
1989
- 1989-11-15 PL PL89284065A patent/PL162284B1/pl unknown
- 1989-11-15 IL IL9231789A patent/IL92317A/en not_active IP Right Cessation
- 1989-11-15 EP EP89311815A patent/EP0369762B1/en not_active Expired - Lifetime
- 1989-11-15 IE IE365789A patent/IE64377B1/en not_active IP Right Cessation
- 1989-11-15 JP JP1297232A patent/JP2667916B2/ja not_active Expired - Lifetime
- 1989-11-15 ES ES89311815T patent/ES2062036T3/es not_active Expired - Lifetime
- 1989-11-15 PL PL89282310A patent/PL163550B1/pl unknown
- 1989-11-15 TR TR89/0964A patent/TR25218A/xx unknown
- 1989-11-15 CN CN89109195A patent/CN1027692C/zh not_active Expired - Fee Related
- 1989-11-15 AT AT89311815T patent/ATE99286T1/de active
- 1989-11-15 FI FI895433A patent/FI895433A0/fi not_active IP Right Cessation
- 1989-11-15 CN CN93117309A patent/CN1091423A/zh active Pending
- 1989-11-15 HU HU895912A patent/HU209286B/hu unknown
- 1989-11-15 CZ CS896461A patent/CZ646189A3/cs unknown
- 1989-11-15 CA CA002003052A patent/CA2003052A1/en not_active Abandoned
- 1989-11-15 DD DD89334602A patent/DD298926A5/de not_active IP Right Cessation
- 1989-11-15 AU AU44716/89A patent/AU630123B2/en not_active Ceased
- 1989-11-15 SK SK6461-89A patent/SK646189A3/sk unknown
- 1989-11-15 DE DE89311815T patent/DE68911876T2/de not_active Expired - Fee Related
- 1989-11-15 ZA ZA898725A patent/ZA898725B/xx unknown
- 1989-11-15 PT PT92323A patent/PT92323B/pt not_active IP Right Cessation
- 1989-11-15 RU SU894742606A patent/RU2010025C1/ru active
- 1989-11-15 ZW ZW151/89A patent/ZW15189A1/xx unknown
- 1989-11-15 PL PL89297791A patent/PL163669B1/pl unknown
- 1989-11-15 HU HU9300081A patent/HU9300081D0/hu unknown
- 1989-11-15 KR KR1019890016642A patent/KR0140890B1/ko not_active IP Right Cessation
- 1989-11-15 MC MC892076A patent/MC2070A1/xx unknown
- 1989-11-15 DK DK571489A patent/DK571489A/da not_active Application Discontinuation
- 1989-11-15 OA OA59682A patent/OA09145A/xx unknown
- 1989-11-16 BR BR898905808A patent/BR8905808A/pt not_active IP Right Cessation
-
1990
- 1990-05-15 RU SU904743786A patent/RU2055476C1/ru active
-
1992
- 1992-09-16 RU SU925052551A patent/RU2072351C1/ru active
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