CN1014061B - 嘧啶衍生物的制备方法 - Google Patents
嘧啶衍生物的制备方法Info
- Publication number
- CN1014061B CN1014061B CN86108825A CN86108825A CN1014061B CN 1014061 B CN1014061 B CN 1014061B CN 86108825 A CN86108825 A CN 86108825A CN 86108825 A CN86108825 A CN 86108825A CN 1014061 B CN1014061 B CN 1014061B
- Authority
- CN
- China
- Prior art keywords
- methyl
- benzyl
- pyrimidine
- ptfe
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000002360 preparation method Methods 0.000 title abstract description 122
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 title abstract description 3
- 150000003230 pyrimidines Chemical class 0.000 title abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 110
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 88
- -1 methoxyl group Chemical group 0.000 claims description 81
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 64
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000460 chlorine Substances 0.000 claims description 24
- 229910052801 chlorine Inorganic materials 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 3
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 3
- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- XDEPVFFKOVDUNO-UHFFFAOYSA-N pentafluorobenzyl bromide Chemical compound FC1=C(F)C(F)=C(CBr)C(F)=C1F XDEPVFFKOVDUNO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 13
- 230000000749 insecticidal effect Effects 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 125000003158 alcohol group Chemical group 0.000 abstract description 4
- ZXQYGBMAQZUVMI-UNOMPAQXSA-N cyhalothrin Chemical compound CC1(C)C(\C=C(/Cl)C(F)(F)F)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-UNOMPAQXSA-N 0.000 abstract description 4
- LLMLSUSAKZVFOA-UHFFFAOYSA-N 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(O)=O LLMLSUSAKZVFOA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000642 acaricide Substances 0.000 abstract description 3
- 125000005843 halogen group Chemical group 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 93
- 238000005160 1H NMR spectroscopy Methods 0.000 description 87
- 238000002329 infrared spectrum Methods 0.000 description 86
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 62
- 239000000203 mixture Substances 0.000 description 61
- 239000000243 solution Substances 0.000 description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 56
- 239000011541 reaction mixture Substances 0.000 description 41
- 238000010025 steaming Methods 0.000 description 35
- 239000000047 product Substances 0.000 description 34
- 239000002904 solvent Substances 0.000 description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 33
- 238000001035 drying Methods 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000003921 oil Substances 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 26
- 241000238631 Hexapoda Species 0.000 description 26
- 230000014759 maintenance of location Effects 0.000 description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 238000009835 boiling Methods 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 20
- 150000001793 charged compounds Chemical class 0.000 description 20
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 239000002585 base Substances 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000000470 constituent Substances 0.000 description 14
- 239000012044 organic layer Substances 0.000 description 14
- 241000607479 Yersinia pestis Species 0.000 description 13
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- PPXUHEORWJQRHJ-UHFFFAOYSA-N isovaleric acid ethyl ester Natural products CCOC(=O)CC(C)C PPXUHEORWJQRHJ-UHFFFAOYSA-N 0.000 description 12
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- 238000003810 ethyl acetate extraction Methods 0.000 description 11
- 238000000605 extraction Methods 0.000 description 11
- 150000004702 methyl esters Chemical class 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 235000002639 sodium chloride Nutrition 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000004293 19F NMR spectroscopy Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000003814 drug Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 150000003527 tetrahydropyrans Chemical class 0.000 description 7
- 241001124076 Aphididae Species 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 150000001409 amidines Chemical class 0.000 description 6
- VNXBKJFUJUWOCW-UHFFFAOYSA-N methylcyclopropane Chemical compound CC1CC1 VNXBKJFUJUWOCW-UHFFFAOYSA-N 0.000 description 6
- 150000002825 nitriles Chemical class 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- CWPBWQMSTGAQSS-UHFFFAOYSA-N 3-benzyl-4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1CC1=CC=CC=C1 CWPBWQMSTGAQSS-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
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- 238000004440 column chromatography Methods 0.000 description 4
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- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
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- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 3
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- ATROHALUCMTWTB-OWBHPGMISA-N phoxim Chemical compound CCOP(=S)(OCC)O\N=C(\C#N)C1=CC=CC=C1 ATROHALUCMTWTB-OWBHPGMISA-N 0.000 description 1
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- 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
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- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical class [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- JXHJNEJVUNHLKO-UHFFFAOYSA-N sulprofos Chemical compound CCCSP(=S)(OCC)OC1=CC=C(SC)C=C1 JXHJNEJVUNHLKO-UHFFFAOYSA-N 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- MLGCXEBRWGEOQX-UHFFFAOYSA-N tetradifon Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC(Cl)=C(Cl)C=C1Cl MLGCXEBRWGEOQX-UHFFFAOYSA-N 0.000 description 1
- 229960005199 tetramethrin Drugs 0.000 description 1
- OPASCBHCTNRLRM-UHFFFAOYSA-N thiometon Chemical compound CCSCCSP(=S)(OC)OC OPASCBHCTNRLRM-UHFFFAOYSA-N 0.000 description 1
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- 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
- 230000000699 topical effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
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- XAIPTRIXGHTTNT-UHFFFAOYSA-N triflumuron Chemical compound C1=CC(OC(F)(F)F)=CC=C1NC(=O)NC(=O)C1=CC=CC=C1Cl XAIPTRIXGHTTNT-UHFFFAOYSA-N 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
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- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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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
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/30—Halogen atoms or nitro radicals
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- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
本发明叙述了一些具有通式I的新型嘧啶衍生物及其制备方法:其中R1是氢或卤素;R2是支链的烷基或环烷基,Q是-OR基,R是具有化学式ROH的醇类残基,这醇和permethrin酸或者cyhalothrin酸化合时可形成具有杀虫活性的酯。这些嘧啶衍生物可用作杀螨剂和杀虫剂。本发明也叙述了具有通式I的一些新化合物,其中Q是卤素,羟基或低级烷基,它们可用作中间体。
Description
本发明涉及作为中间体新的羧酸及其衍生物,以及这些羧酸的具有杀虫活性的酯和包含这些酯的组合物。本发明也涉及制备这些新的羧酸及其衍生物的方法,和在这些方法中用到的一些新化合物。
首先,本发明提供具有通式Ⅰ的新化合物:
其中R1代表氢或卤素,R2代表含有3至6个碳原子的α-支链的烷基或环烷基,Q可以(a)代表羟基、卤素(尤其是氯)或者含有多至6个碳原子的烷氧基,这类化合物用作杀虫剂的中间体,或者(b)Q代表-OR基,其中R是具有化学式ROH的醇的残余,上述醇ROH与菊酸、permethrin酸或cyhalothrin酸化合时可形成有杀虫作用的酯。permethrin酸是3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷羧酸,cyhalothrin酸的学名是3-(2-氯-3,3,3-三氟丙-1-烯-1-基)-2,2-二甲基环丙烷羧酸。
更具体地说,Q代表具有下列通式的基团:
其中X是氧、硫、1,2-亚乙烯基或具有通式-
=Y-的基团,其中Y是氮或CR5,R4代表氢、甲基、氰基或乙炔基,每个R5可以选自氢、卤素、至多4个碳原子的烷氧基、至多4个碳原子并可被卤素任意地取代的烷基;n可以是0、1或2,R6代表氢、卤素、至多4个碳原子的烷基、至多4个碳原子的烷氧基、至多6个碳原子的烯基、至多6个碳原子的卤代烯基、至多4个碳原子的炔基、总数至多4个碳原子的烷氧基烷基、苯基、苯氧基或苄基,或被卤素或烷基取代了的苯基、苯氧基或苄基。
可以看到通式Ⅰ的化合物能以各种异构体的形式存在,或者以各种异构体的混合物存在。由于存在一个或两个手性中心而使有可能形成立体异构体或非对映异构体而产生旋光异构体。此外,当醇的部分含有取代的烯基时有可能形成几何异构体。所有这些各个异构体形式和它们的混合物,包括外消旋体,都属于本发明范围之内。
按照通式Ⅰ作为中间体的那些具体化合物是那些Q代表至多6个碳原子的烷氧基的化合物,包括通式Ⅰ羧酸的甲基、乙基、丙基和丁基酯,其中R1是氢、氯或氟;R2是下列基团之一:丙-2-基、丁-2-基、戊-2-基、戊-3-基、2-甲基-丙-2-基、2-甲基-丁-2-基、环丙基、1-甲基环丙基和环己基。
用作中间体的具体化合物包括:
RS-2-〔2-(丙-2-基)嘧啶-5-基〕-3-甲基-丁酸乙酯
RS-2-〔2-(1-甲基环丙-1-基)嘧啶-5-基〕-3-甲基-丁酸乙酯
RS-2-(2-丙-2-基)嘧啶-5-基)-3-甲基-丁酸乙酯
RS-2-〔2-(2-甲基丁-2-基)嘧啶-5-基〕-3-甲基-丁酸乙酯
RS-2-(2-环丙基嘧啶-5-基)-3-甲基-丁酸乙酯
RS-2-〔4-氯-2-(2-甲基-丙-2-基)嘧啶-5-基〕-3-甲基-丁酸乙酯
RS-2-〔4-氟-2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基-丁酸乙酯
还有和上述这些化合物相应的羧酸及酰氯衍生物。
具有通式Ⅰ的化合物,其中R1是氢或卤素、R2规定如上、Q代表-OR基,这里-OR是至多6个碳原子的烷氧基,可以在碱存在下,用2-卤代丙烷与具有式A的相应的化合物进行烷基化反应来制备。
在这方法中用2-碘丙烷特别好,而合适的碱是六甲基二甲硅烷基酰胺锂(LHMDS)。例如,式(A)化合物的制备可以通过用适当的脒
和1-甲酰基丁二酸二烷基酯反应,然后把4位的羟基转化为通式(A)的4-卤或4-氢化合物。
下面以图解方式来描述制备式Ⅰ化合物的方法,其中R1是氢或卤素,R2为前述的任意种含意,Q代表-OR,这里-OR是至多6个碳原子的烷氧基。
在当R1是氢时的特定的情况下,这些烷氧基酯也可按下述路线制备。
式Ⅰ中Q代表羟基的化合物,可通过上述的烷基酯水解而制得,最好是碱水解,例如,可用氢氧化钠的醇水溶液或氢氧化锂/四氢呋
喃/水混合物。这些酸可以进一步转化成Q代表卤素、最好是氯的式Ⅰ化合物,这可以用适当的卤化剂如亚硫酰氯或草酰氯和酸进行反应制得。
按照本发明用作杀螨剂和杀虫剂的化合物的具体例子列于下面表Ⅰ中,这些化合物符合下式:
而对每一个化合物给出了R1、R2和R的具体含意。R是以E-01到E-31编号,它们的含意列于下面:
E-01=3-苯氧基苄基
E-02=1-氰-1-(3-苯氧基苯基)甲基
E-03=2-甲基-3-苯基苄基
E-04=4-甲基-2,3,5,6-四氟苄基
E-05=4-烯丙基-2,3,5,6-四氟苄基
E-06=N-3,4,5,6-四氢苯二甲酰亚胺基甲基
E-07=1-乙炔基-1-(3-苯氧基苯基)甲基
E-08=5-苄基呋喃-3-基甲基
E-09=6-苯氧吡啶-2-基甲基
E-10=1-氰-1-(6-苯氧吡啶-2-基)甲基
E-11=1-〔1-(6-苯氧吡啶-2-基)〕乙基
E-12=4-(丙-2-炔-1-基)-2,3,5,6
-四氟苄基
E-13=4-(丁-2-炔-1-基)-2,3,5,6
-四氟苄基
E-14=4-(3-氯丙-2-烯-1-基)-2,3,
5,6-四氟苄基
E-15=4-甲氧甲基-2,3,5,6-四氟苄基
E-16=2-甲氧基-4-甲氧基甲基-3,5,6-三
氟苄基
E-17=4-苄基-2,3,5,6-四氟苄基
E-18=3-苄基-4-氟苄基
E-19=4-(3-三甲基硅基丙-2-炔-1-基)-
2,3,5,6-四氟苄基
E-20=4-(2-甲基丙-2-烯-1-基)-2,3,
5,6-四氟苄基
E-21=4-乙氧基-2,3,5,6-四氟苄基
E-22=4-三甲基硅基-2,3,5,6-四氟苄基
E-23=4-(丁-2-烯-1-基)-2,3,5,6
-四氟苄基
E-24=4-(2-氯丙-2-烯-1-基)-2,3,
5,6-四氟苄基
E-25=4-氟-3-苯氧基苄基
E-26=2-氯-6-氟苄基
E-27=1-氰-1-(3-苄基-4-氟苯基)甲基
E-28=3-苯基氨基苄基
E-29=4-(2,3-二氯丙-2-烯-1-基)-
2,3,5,6-四氟苄基
E-30=五氟苄基
E-31=1-氰-1-(4-氟-3-苯氧基苯基)甲基
见第9-11页表1
本发明中具有通式ⅠA的有杀虫活性的化合物是一些酯类化合物,它们可由上述的烷基酯、羧酸和酰氯按照通常的酯化方法制备,例如下面所述的一些方法:
(a)具有通式Ⅱ的羧酸
这里Q代表羟基,R1和R2具有上面给出的任何一种含意,可以直接和具有通式(Ⅲ)ROH的醇反应,这里R的含意如前所述。进行反应时最好存在一种酸性催化剂,例如干燥的氯化氢气,或者存在一种脱水剂,例如二环己基碳二亚胺。
(b)Q为卤原子,最好是氯原子,R1和R2具有上面给出的任何一种含意的通式(Ⅱ)的酰卤,可以和具有通式(Ⅲ)的醇反应,进行反应时最好有碱存在,例如吡啶、碱金属氢氧化物、碳酸盐或碱金属烷氧化物。
(c)Q代表羟基,最好是它的碱金属盐的上述通式(Ⅱ)的羧酸,可以和Q′代表卤原子,最好是氯原子,R具有上面给出的任何
表 Ⅰ
化合物编号 R2R1R
Ⅰ (CH3)3C H E-01
Ⅱ (CH3)3C H E-02
Ⅲ (CH3)3C H E-03
Ⅳ (CH3)3C H E-04
Ⅴ (CH3)3C H E-05
Ⅵ (CH3)3C H E-06
Ⅶ (CH3)3C H E-07
Ⅷ (CH3)3C H E-08
Ⅸ (CH3)3C H E-09
Ⅹ (CH3)3C H E-10
Ⅺ (CH3)3C H E-11
Ⅻ (CH3)3C H E-12
ⅩⅢ (CH3)3C H E-13
ⅩⅣ (CH3)3C H E-14
ⅩⅤ (CH3)3C H E-15
ⅩⅥ (CH3)3C H E-16
ⅩⅦ (CH3)3C H E-17
ⅩⅤⅢ (CH3)3C H E-18
ⅩⅨ (CH3)3C H E-19
ⅩⅩ (CH3)3C H E-20
ⅩⅪ (CH3)3C H E-21
ⅩⅫ (CH3)3C H E-22
ⅩⅩⅢ (CH3)3C H E-23
ⅩⅩⅣ (CH3)3C H E-24
ⅩⅩⅤ (CH3)3C H E-25
ⅩⅩⅥ (CH3)3C H E-26
表 Ⅰ(续)
化合物编号 R2R1R
ⅩⅩⅦ (CH3)3C H E-27
ⅩⅩⅤⅢ (CH3)3C H E-28
ⅩⅩⅨ (CH3)3C H E-29
ⅩⅩⅩ (CH3)3C H E-30
ⅩⅩⅩⅠ (CH3)3C Cl E-05
ⅩⅩⅩⅡ (CH3)3C Cl E-12
ⅩⅩⅩⅢ (CH3)3C Cl E-02
ⅩⅩⅩⅣ (CH3)3C Cl E-10
ⅩⅩⅩⅤ (CH3)3C F E-05
ⅩⅩⅩⅥ (CH3)3C F E-04
ⅩⅩⅩⅦ (CH3)3C F E-25
ⅩⅩⅩⅤⅢ (CH3)2CH H E-04
ⅩⅩⅩⅨ (CH3)2CH H E-05
ⅩL (CH3)2CH H E-30
ⅩLⅠ (CH3)2CH H E-12
ⅩLⅡ C2H5(CH3)2C H E-05
ⅩLⅢ C2H5(CH3)2C H E-12
ⅩLⅣ C2H5(CH3)2C H E-15
ⅩLⅤ
H E-05
ⅩLⅥ
H E-12
表 Ⅰ(续)
一种含意的通式Q′R(Ⅳ)的卤代烷反应。或者和由这种卤代烷与三级胺衍生的四级铵盐反应,这类三级胺可以是例如吡啶或者三烷基胺和三乙胺。
(d)一种具有上述通式(Ⅱ)的低级烷基酯,这里Q表示含有至多6个碳原子的低级烷氧基,最好是甲氧基或乙氧基,R1和R2具有上面给出的任何一种含意,和具有通式(Ⅲ)的醇一起加热以发生酯交换反应。进行反应时最好有一种适当的催化剂存在,例如碱金属烷氧化物如甲氧化钠,或一种烷基化的钛衍生物如钛酸四甲酯或钛酸四乙酯。
所有上述这些制备酯的一般方法在对于各种反应物合适时,在反应时可以使用溶剂和稀释剂,也可以升高温度或者在适当的催化剂,例如相转移催化剂存在下进行反应,以加速反应或提高反应的收率。
可以用相同的方法制备上述各化合物的异构体,但是所用的原料要用具有通式(Ⅱ)各化合物相应的异构体。这些异构体可应用通常分离异构体的技术从异构体的混合物中把它们分离出来。因此可以把羧酸和光活性的胺(例如(-)-α-甲基苄胺)形成盐,经分部结晶分离后,再重新析出光活性纯的羧酸,而得到各种光活性羧酸异构体。光活性纯净的羧酸异构体(或它们等价的酰氯或酯的异构体)再和适当的醇反应,就得到具有通式ⅠA的各个纯净立体异构体型式的化合物。
当具有通式ⅠA的化合物以两对外消旋异构体,即四种非对映异构体的混合物形式时,可以用例如高压液相层档或者当它们的物理性质合适时,用选择性结晶的方法,把两对外消旋异构体彼此分离。
用于制备具有通式ⅠA化合物方法的更详细内容,可参看下面给
出的具体实施例。
许多在制备通式ⅠA化合物时用到的醇ROH以前曾有过描述。特别是那些R代表取代的四氟苄基的醇类,在美国专利4405640号和4370346号以及公开的欧洲专利申请0196156A1号中均已叙述过。有一些未被公开文件报导过的新的醇,它们的制备方法将在后面的实施例中叙述。
具有通式ⅠA的化合物,可用来消灭或控制害虫及别的无脊椎害虫如螨类害虫的侵扰。通过施用本发明的化合物所消灭或控制的害虫和螨类害虫包括与农业(包括粮食和纤维作物的生长园艺和畜牧业),林业和植物来源的产品如水果、谷物和木材的储存有关的害虫,还有与人类和动物传染疾病有关的害虫。
人们通常配制成药剂配方把这些化合物施用于害虫侵扰的地区,配方中除了含有一种或多种通式ⅠA杀虫活性组份以外,还包括一些合适的没有杀虫活性的稀释剂或载体,和/或表面活性剂。
本发明的化合物可以作为配方的单独活性组份,在合适时也可以和一种或多种别的活性组份混合使用,例如和其它杀虫剂、杀虫剂的增效剂、除莠剂、杀真菌剂,或植物生长调节剂一起混合使用。
和本发明化合物一起混合使用的合适其它活性成份,是一些能扩展本发明化合物的活性应用范围,或增长它们在虫害地区维持药效时间的化合物。它们可增加本发明化合物的药效或补充活性,例如增快药物起作用的速度、改进杀伤率或克服抗药性。此外,这种多组份的混合物能帮助克服或防止害虫对个别组份的抗药性。
具体用于混合物中的杀虫剂、除莠剂或杀真菌剂将决定于想要应用的目的和所需的补充作用的类型。
合适的杀虫剂的实例包括下面这些:
(a)拟除虫菊酯类,如二氯苯醚菊酯、esfenvalerate、deltamethrin、cyhalothrin、联苯菊酯、2,4,5-涕丙酸菊酯、cyfluthrin、tefluthrin、对鱼类是安全的拟除虫菊酯类如ethofenprox、天然的除虫菊酯、tetramethrin、s-biollethrin,fenfluthrin、prallethrin、和5-苄基-3-呋喃甲基-(E)-(1R,3S)-2,2-二甲基-3-(2-氧杂硫戊环-3-亚甲基甲基)环丙烷羧酸酯。
(b)有机膦酸酯类,如profenofos、sulprofos、甲基一六○五、谷硫磷、异吸硫磷Ⅱ、heptenophos、甲基乙拌磷、克线磷、久效磷、profenophos、三唑硫磷、甲胺磷、dimethoate、磷胺、马拉硫磷、氯蜱硫磷、伏杀硫磷、fensulfothion、地虫硫膦、三九一一、phoxim、pyrimiphosmethyl、杀螟松、地亚农。
(c)氨基甲酸酯类(包括芳基氨基甲酸酯类),例如灭定威、cloethocarb、呋喃丹、二硫甲威、丁醛肟威、thiofurox、carbosulfan、苯噁威、fenobucarb、残杀威、草肟威;
(d)苯甲酰基脲类例如triflumuron、chlorofluazuron;
(e)有机锡化合物,例如三环锡、螨完锡、azocyclotin;
(f)大环内酯类,例如avermectins或milbemycins例如abamectin、avermectin和milbemycin;
(g)激素类,例如环壬保幼素、保幼生物素或蜕皮素;
(h)信息素类;
(i)有机氯化合物,如六氯苯、DDT、氯丹(八氯化甲桥茚)或狄氏剂(氧桥氯甲桥萘)。
除上面已列出的杀虫剂的主要化学种类以外,在使用需要时,在混合物中还可以加一些有特殊作用的杀虫剂。例如对特定的作物用有选择性的杀虫剂,例如专为稻科茎杆用的杀虫剂巴丹或buprofezin。另外,专为某种害虫或害虫的某一发育阶段的杀虫剂,例如杀卵剂clofentazine、flubenzimine、hexythiazox、和三氯杀螨砜,杀虫剂三氯杀螨醇或克螨特,杀螨剂溴螨酯、乙酯杀螨醇,或昆虫生长调节剂如hydramethylon、cyromazim、甲氧保幼素、chlorofluazuron和伏虫脲。
用于配方中合适的杀虫剂的增效剂实例有胡椒基丁醚、增效菊和十二烷基咪唑。
用于配方中合适的除莠剂、杀真菌剂和植物生长调节剂的选择,将依赖于想达到的目的和所需要的效果。用于稻科植物的选择性除莠剂的一个实例是敌稗;用于棉花的植物生长调节剂的一个实例是“pix”,用于稻科植物的杀真菌剂的一个实例是杀稻瘟菌素,例如杀稻瘟菌素s。和活性组份混合一起使用的其它组份的选择常是
配方者所熟知的,这将视所要达到的总效果而在已知的种类中选择。
在配方中本发明的化合物对任何其它活性组份的相对比例与许多因素有关,包括要控制的害虫种类和要求该混合物达到的效果。但一般说来,配方中其它活性组份所占的比例,应相当于它们单独使用时的用量,如存在增效剂,则可稍低些。
本配方可制成粉剂的形式,其中活性组份和一种固体稀释剂或载体混合在一起,如高岭土、膨润土、硅藻土或滑石;它们也可以制成粒剂的形式,这时活性组份被吸附在一种多孔粒状材料如浮石上。
此外,配方也可制成液体制剂,以浸渍或喷雾的方式应用。这种液体制剂一般是用一种或多种已知的湿润剂、分散剂或乳化剂(表面活性剂),把活性组份制成在水中的分散液或乳液。
湿润剂、分散剂和乳化剂可以是阳离子型的、阴离子型的或非离子型的。合适的阳离子型试剂例如有四级铵盐,如鲸腊基三甲基溴化铵。合适的阴离子型试剂包括例如皂类、脂肪族单酯的盐或硫酸盐,例如硫酸十二烷基酯钠盐,磺化芳香族化合物的盐,例如十二烷基苯磺酸钠、木素磺酸或丁基萘磺酸的钠盐、钙盐或铵盐,以及二异丙基和三异丙基萘磺酸钠盐的混合物。合适的非离子型试剂包括例如环氧乙烷和脂肪醇如油醇或鲸蜡醇(十六烷醇)的缩合产物,或者和烷基酚如辛基酚、壬基酚和辛基甲酚的缩合产物。别的非离子型试剂有由长链脂肪酸衍生的部份酯和己糖醇酐、以及所说的长链脂肪酸的部分酯和环氧乙烷的缩合产物,和卵磷脂。
制备配方时可将活性组份溶解在合适的溶剂如酮类溶剂(如二丙酮醇)中,或芳香溶剂(如三甲基苯)中,然后把制得的混合物加到含有一种或多种已知的湿润剂、分散剂或乳化剂的水中。
其它合适的有机溶剂有二甲基甲酰胺、二氯乙烷、异丙醇、丙二醇和别的二元醇类、二丙酮醇、甲苯、煤油、轻油、甲基萘、二甲苯、三氯乙烯、N-甲基-2-吡咯烷酮和四氢呋喃醇(THFA)。
以水的分散液或乳液形式使用的配方,一般以含有高浓度活性组份的浓缩液形式供应,在使用前将此浓缩液用水稀释。常常要求这些浓缩液能够长期储存,并在这样的长期储存之后能够用水稀释成水溶液制剂,后者能在足够长的时间内保持均相,以使它们能用通常的喷雾装置喷洒。浓缩液可包含10-85%重量百分数的一种或多种活性组份。在稀释制成水溶液制剂时,根据使用它们的不同目的,可制成含有不同量的活性组份的制剂。当用于农业或园艺时,水制剂中活性组份的含量在0.0001%至0.1%(重量)之间是特别有用的。
在应用时,可通过任何一种已知的施用杀虫药剂的方法,例如撒粉或喷雾的方法,把本配方制剂施用于害虫、害虫出没地区、害虫栖息区或易于被害虫侵扰的生长着植物上。
本发明的药物配方对多种害虫和其它无脊椎害虫都是剧毒的,这些害虫包括举例如下:
桃(赤)蚜 (蚜虫)
豆卫矛蚜 (蚜虫)
巢菜修尾蚜 (蚜虫)
埃及伊蚊 (蚊子)
棉带纹红蝽 (病毒的衣壳)
家蝇 (家蝇)
大菜粉蝶 (白蝴蝶,幼虫)
菜蛾 (菱纹背蛾,幼虫)
辣根猿叶虫 (芥末甲虫)
朱砂叶螨 (洋红蜘蛛螨)
普通红叶螨 (红蜘蛛螨)
红圆蚧 (介壳虫)
粉虱 (白蝇)
德国小蠊 (蟑螂)
斜纹夜蛾 (棉叶虫)
棉铃虫 (烟草芽虫)
澳洲疫蝗 (蝗虫)
玉米幼芽根叶甲 (根虫)
榆(苹)全爪螨 (柑桔螨)
稻褐飞虱 (植物跳虫)
切根虫 (夜盗蛾)
玉米禾螟 (玉米茎螟虫)
通式ⅠA的化合物以及含有它们的药剂配方已表明它们在控制植物上的蜱螨如红螨、叶刺瘿螨,以及棉株上的鳞翅目害虫如斜纹夜蛾棉铃虫,还有一些植物上的叶螨如Tetranychus spp.和panonychus spp.方面是特别有用的。具有通式ⅠA的化合物不仅对游动着的害虫(成虫和蛹),而且对虫卵都是起作用的。同一个化合物同时具有杀灭成虫和卵的活性,是非常吸引人的,它避免了为达到这两种效果而必须应用几种化合物组成的混合物,而后者是迄今所用的其它产品常用的方法。本发明化合物的另一个优点是,在用于控制蜱螨所用的药物用量水平上,常常能够同时达到在同一区域控制
其它虫害的目的,例如鳞翅目、鞘翅目和半翅目害虫的幼虫期如蚜虫虫害。这些化合物也可用来消灭栖息在土壤中的害虫如玉米幼芽根叶甲,也可用于消灭侵扰家畜的害虫和蜱螨如三鬃绿蝇和蜱如微小牛蜱、燕雀硬蜱、美洲花蜱、血红扇头蜱、美洲犬革蜱。它们不仅对那些药物敏感的害虫有效,也对那些有抗药性的害虫有效,而且对成虫、幼虫和害虫发育的中间阶段都起作用,并可通过局部给药、口服或非肠道用药给被侵染的宿主动物施药。
下面的实施例说明了本发明的各个方面。在制备的实例中,产物通常是借助核磁共振光谱和红外光谱来鉴定的。在每种产物具有具体名称时,它的光谱特性和名称所指定的结构是一致的。
在这些实施例中,气液色谱(GLC)的保留时间是用Hewlett packavd 5890气相色谱仪,用内径0.2毫米,长12.5米的Chromopak,C.P.Sil 5 C.B.柱测定的。除非特别说明,进样温度都是100℃,用15℃/分的温度梯度,最高温度达280℃,维持4分钟。用氦气作载气,柱前气压维持在11psi。在需要时,在一些实例中另指明了别的进样温度和最高温度。
除非特别指明,1H核磁共振(NMR)谱都是在270MHz频率的Jeol FX 270 NMR仪器上做的。90 MHz和60 MHz1HNMR谱分别用Jeol FX 90A和Jeol PMX 60型仪器完成。
19FNMR谱是在一台Jeol FX90Q型仪器上,在84.26MHz频率做的。所有NMR的位移值都是相对于标准物质(TMS或CFCl3)的ppm值。
实施例1
本例说明了制备2,2-二甲基丙脒盐酸盐的方法。
在0℃将干燥的氯化氢气体(约59克)通入2-氰-2-甲基丙烷(86克)在乙醇(60毫升)中的溶液,并在室温(约20℃)保持60小时,用乙醚(1000毫升)稀释,过滤收集沉淀的1-乙氧基-1-亚胺基-2,2-二甲基丙烷盐酸盐,在过滤器上用乙醚洗涤沉淀,并干燥。产物用乙醇(150毫升)调成浆状,并在室温往其中通入氨气,直到固体完全溶解。
混合物在此室温保持40小时,用乙醚(500毫升)稀释,过滤收集沉淀的固体,干燥,得到熔点为192-194℃的2,2-二甲基丙脒盐酸盐(25.75克)。将滤液蒸发还可得到第二批产品(50.29克)。
红外光谱(液体石腊):3300,3100,1680,1520
1230,995,980cm-1
实施例2
本例说明了制备(RS)-甲酰基丁二酸二乙酯的方法。
把乙醇(20毫升)分批加到金属钠(10.0克)很细地分散在无水甲苯(100毫升)的悬浮液中。加完后,将混合物在80℃加热3.5小时,然后把这黄色的悬浮液冷到20℃,在1小时内往其中滴加丁二酸二乙酯(70.0克)和甲酸乙酯(35.0克)的混合物,滴加时维持混合物温度在20至30℃。反应混合物在室温保持16小时,然后小心地加入水(100毫升)。
分出水层,用50%硫酸水溶液中和,用乙醚提取。提取醚液用
水洗,用无水硫酸镁干燥,减压蒸去溶剂而浓缩。残余的液体(66克)进行减压分馏,即得到所需的(RS)-甲酰基丁二酸二乙酯(46.0克),沸程82-86℃/0.53毫米汞。
核磁共振谱指出产物是以约1∶1的酮式和烯醇式的混合物存在。
1H NMR(CDCl3)δ:1.10-1.40(m,3H);2.90(d,J=7Hz,1H);
3.05(s,1H);3.75(t,J=7Hz,0.5H);
4.00-4.40(m,4H);7.10(d,J=11Hz,0.5H);
9.92(s,0.5H);11.5(d,J=11Hz,0.5H).
红外光谱(液膜):3300,2980,1735,1665,1175,
1030cm-1
实施例3
本例说明了制备5-乙氧羰甲基-4-羟基-2-(2-甲基丙-2-基)嘧啶的方法。
将金属钠(6.9克)溶解在乙醇(120毫升)中所得到的乙醇钠溶液,分批加到搅拌着的2,2-二甲基丙脒盐酸盐(41.0克)在乙醇(150毫升)的悬浮液中。过滤除去沉淀的氯化钠。在室温往搅拌着的滤液中滴入(RS)-甲酰基丁二酸二乙酯,在室温搅拌16小时后在回流温度加热1小时,然后减压蒸去溶剂,得到的固体残余物用石油醚(沸程60-80℃)洗,得到熔点为98-102℃的5-乙氧羰甲基-4-羟基-2-(2-甲基丙-2-基)嘧啶(40克)。把石油醚洗涤液蒸干,并将残余物用硅胶柱层析提纯,用乙酸乙酯和石油醚(沸程60-80℃)混合物(体积比1∶1)洗脱,还可以回收另一批产物(15克)。
1H NMR(CDCl3)δ:1.27(t,J=7Hz,3H);1.39(s,9H);
3.44(s,2H);4.13(q,J=7Hz,2H);
7.92(s,1H);12.5(bs,1H).
红外光谱(液体石腊):3400,1735,1660,1570,1460,
1375,1335,1275,1155,1030,
980cm-1.
实施例4
本例说明了制备4-氯-5-乙氧羰甲基-2-(2-甲基丙-2-基)嘧啶的方法。
把三氯氧磷(30毫升)分批加到5-乙氧羰甲基-4-羟基-2-(2-甲基丙-2-基)嘧啶(15.0克)中。这时发生放热反应,将得到的混合物倾入冰中。用碳酸钠中和后用乙酸乙酯提取,提取液用水洗,用无水硫酸钠干燥,减压蒸去溶剂得4-氯-5-乙氧羰甲基-2-(2-甲基丙-2-基)嘧啶(11.35克,油状物,放置后固化,熔点42-44℃)。
1H NMR(CDCl3)δ:1.29(t,J=7Hz,3H);1.40(s,9H);3.71
(s,2H);4.20(q,J=7Hz,2H);8.51
(s,1H)
红外光谱(液膜):2960,1735,1580,1520,1420,
1250,1180,1025,880cm-1
实施例5
本例说明了制备5-乙氧羰甲基-2-(2-甲基丙-2-基)嘧啶的方法。
将4-氯-5-乙氧羰基甲基-2-(2-甲基丙-2-基)嘧啶(18克)、甲苯(180毫升)、锌粉(36克)及饱和氯化钠的3摩尔氢氧化铵溶液(180毫升)所形成的混合物在100℃加热120小时。冷却后过滤除去固体组份,分出有机相。水相用乙酸乙酯洗,并把洗涤液与有机相合并。用水洗有机相,用无水硫酸镁干燥后减压蒸去溶剂,残余的油状物(16克)用硅胶柱进行柱色谱法层析提纯,用二氯甲烷洗脱,得黄色油状的5-乙氧羰甲基-2-(2-甲基丙-2-基)嘧啶(12克)。
1H NMR(CDCl3)δ:1.25(t,J=7Hz,3H);1.40(s,9H);
3.55(s,2H);4.2(q,J=7Hz,2H);
8.6(s,2H)
红外光谱(液膜):2960,1735,1480,1430,1260.
1180,1025cm-1
实施例6
本例说明了制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸乙酯的方法。
将二(三甲基硅烷基)酰胺锂(10.8毫升1摩尔无水氢呋喃溶液)滴加到维持温度在-78℃的5-乙氧羰甲基-2-(2-甲基丙-2-基)嘧啶(1.2克)在无水四氢呋喃(30毫升)的溶液中,形成的溶液在-78℃再搅拌90分钟,然后滴加2-碘丙烷(2.7毫升),反应混合物可以升到室温。将混合物倾入水中,用乙酸乙酯提取,合并提取液并用水洗,用无水硫酸镁干燥,减压蒸去溶剂而浓缩。将残余的油状物(1.48克)减压蒸馏,即得到(RS)-
2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸乙酯,为一无色油状物,(0.9克)沸点130℃/0.08毫米汞。
1H NMR(CDCl3)δ:0.8,1.05(2d,J=7Hz,6H);1.25(t,J=7
Hz,3H);1.4(s,9H);2.2-2.5(m,1H);
3.1(d,J=9Hz,1H);4.2(q,J=7Hz,2H);
8.6(s,2H)
红外光谱(液膜):2960,1725,1585,1430,1180,
1150,1020cm-1
实施例7
本例说明了制备(RS)-2-〔2-(2-甲基丙-2-基)-4-氯嘧啶-5-基〕-3-甲基丁酸乙酯的方法。
4-氯-5-乙氧羰甲基-2-(2-甲基丙-2-基)嘧啶在二(三甲基硅烷基)酰胺锂存在下,按照实施例6的实验程序与2-碘丙烷反应,即得(RS)-2-〔2-(2-甲基丙-2-基)-4-氯-嘧啶-5-基〕-3-甲基丁酸乙酯。
1H NMR(CDCl3)δ:0.8,1.1(2d,6H);1.25(t,3H);1.4(s,
9H);2.4(m,1H);3.8(d,1H);4.2(q,
2H);8.8(s,1H)
红外光谱(液膜):2980,1740,1425and1190cm-1
GLC保留时间:4.58分。
实施例8
本例说明了制备(RS)-2-〔2-(2-甲基丙-2-基)-
4-氟嘧啶-5-基〕-3-甲基丁酸乙酯的方法。
在干燥氮气保护下,将干燥的氟化钾(1.41克)和(RS)-2-〔2-(2-甲基丙-2-基)-4-氯嘧啶-5-基〕-3-甲基丁酸乙酯(1.88克)在无水环丁砜(14毫升)的悬浮液,在18-冠醚-6(0.38克)存在下于150℃搅拌加热24小时。冷却到室温(约22℃)后,把反应混合物倾入水中,用乙酸乙酯提取。有机相用水和盐水洗,干燥后减压蒸去溶剂。残余的棕色液体用硅胶柱层析提纯,用二氯甲烷作洗脱剂,即得到(RS)-2-〔2-(2-甲基丙-2-基)-4-氟嘧啶-5-基〕-3-甲基丁酸乙酯(0.8克),为一橙黄色液体。
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.3(t,3H);1.4(s,
9H);2.4(m,1H);3.55(d,1H);4.2(q,
2H);8.8(d,1H);
GLC保留时间:3.82分。
实施例9
用相似于实施例1所描述的实验程序,由适当的起始原料腈,制备了下列化合物;当所用的原料不容易得到时,它们的制备叙述于实施例16和17。在下面各情况下,当与氯化氢反应的时间(以产生中间体亚胺醚)和后来与氨气反应的时间(以产生脒)与实施例1中所述的不相同时,都已加以注明。
(Ⅰ)由2-甲基丙腈制备2-甲基丙脒
氯化氢反应时间:18小时(为引发反应,最初需温热至30℃)
氨反应时间:48小时
红外光谱(液体石腊):3300,3100,1680,1520cm-1
(Ⅱ)由环丙烷基腈制备环丙烷基脒盐酸盐
氯化氢反应时间:6天
氨反应时间:16小时
熔点:55-58℃
1H NMR(CDCl3)δ:0.85(m);1.2(m);1.7(m)
红外光谱(液体石腊):3400,3200,1650,1460,
1380,1310,1150,1040,
940cm1
(Ⅲ)由2,2-二甲基丁腈制备2,2-二甲基丁脒盐酸盐
熔点:128-129℃
红外光谱(液体石腊):3350-2630,1670,1510,1460,
1380,1300,1210,1085cm-1
(Ⅳ)由1-甲基环丙烷基腈制备1-甲基环丙烷基脒盐酸盐
氯化氢反应时间:1小时
氨反应时间:48小时
1H nmr(CDCl3)δ:0.84(m,2H);1.16(m,2H);1.26(s,
3H);8.40-9.00(宽峰,3H)
红外光谱(液体石腊):3200(宽峰),1670,1530,
1085,960,890cm-1
实施例10
本例说明了制备(RS)-4-二甲胺基-3-甲酰基-2-(1-甲基乙基)-3-丁烯酸乙酯、(RS)-4-乙氧基-3-甲酰基-2-(1-甲基乙基)-3-丁烯酸乙酯以及它们的混合物的步骤。
(Ⅰ)制备2-(1-甲基乙基)-2-(2,2-二乙氧基乙基)丙二酸二乙酯(参看Bull.Soc.Chim.France,1965,1761页)
用沸程为40-60℃的石油醚洗净氢化钠(4.8克50%的油悬浮体)上粘附的油,并把它悬浮于无水二甲基甲酰胺中;外部冷却将此悬浮液冷至0℃。往其中分批加入2-(1-甲基乙基)丙二酸二乙酯(21.2克)在干燥的二甲基甲酰胺(25毫升)的溶液,并将反应混合物在10℃搅拌15分钟,这时已检测不到再有氢气放出。往反应混合物中加入溴代乙醛二乙缩醛(19.7克,可由英国Gillingham的Aldrich化学有限公司,买到)在二甲基甲酰胺(25毫升)的溶液,得到红棕色的反应液,将它在120-130℃搅拌加热20小时。将反应混合物冷至0℃后,小心地加入冰/水混合物(总体积为1000毫升)。产物用乙醚提取(3×250毫升),合并,用水洗(2×300毫升)的有机层,用无水硫酸镁干燥,减压蒸去溶剂而浓缩。残余液体通过一个短的维氏分馏柱进行分馏,即得到沸程为94-98℃/0.1mmHg的2-(1-甲基乙基)-2-(2,2-二乙氧基乙基)丙二酸二乙酯(10.5克)。
1H NMR(CDCl3)δ:1.0(d,6H);1.2(t,6H);1.3(t,6H);
2.25(d,2H);2.3(m,1H);3.4-3.75
(m,4H);4.2(m,4H);4.65(m,1H).
红外光谱(液膜):2990,1730,1230,1120,1070cm-1
(Ⅱ)制备(RS)-4,4-二乙氧基-2-(1-甲基乙基)丁酸乙酯
把2-(1-甲基乙基)-2-(2,2-二乙氧基乙基)丙二酸二乙酯(60克)加入到含有醋酸钾(37克)和水(6.8毫升)的二甲基亚砜(450毫升)中。在氮气下在130-140℃搅拌加热18小时。气液色谱分析指出反应已完成40%。把反应温度升高到160-170℃再加热18小时。反应混合物冷至室温后用水(3000毫升)稀释。产物用乙醚提取(3×800毫升),合并的有机层用水洗(3×800毫升),用无水硫酸镁干燥。减压蒸去溶剂得到一种棕色液体。将它减压分馏,即得(RS)-4,4-二乙氧基-2-(1-甲基乙基)丁酸乙酯(31.8克),为一淡黄色液体,沸点68-70℃/0.2mmHg。
1H NMR(CDCl3)δ:0.9(d,6H);1.0(m,9H);1.75(m,1H);
1.8-2.05(m,2H);2.15(m,1H);3.4-3.7
(m,4H);4.05-4.2(m,2H);4.45(m,1H)
红外光谱(液膜):2990,1730,1375,1180,
1120,1060cm-1
这化合物也可按照化学摘要59,5012g(1963)和51,12086c(1957)所述的方法来制备。
(Ⅲ)制备(RS)-4-二甲胺基-3-甲酰基-2-(1-甲基乙基)-3-丁烯酸乙酯、(RS)-4-乙氧基-3-甲酰基-2-(1-甲基乙基)-3-丁烯酸乙酯和它们的混合物
在5℃,将三氯氧磷(5.50毫升)滴加到无水的二甲基甲酰胺(4.64毫升)。最初得到粘稠溶液,不久即固化。往其中加入1,2-二氯乙烷(10毫升),然后把反应混合物在60℃搅拌45分钟以制成Vilsmeyer-Haack试剂。
往上述反应混合物中滴加(RS)-4,4-二乙氧基-2-(1-甲基乙基)丁酸乙酯(5克)在1,2-二氯乙烷(10毫升)的溶液,然后再在60℃加热1小时。
将反应混合物取样分析,将等分试样加到固体碳酸钾中,用水稀释,在50-60℃加热5分钟。用乙酸乙酯作溶剂提取,用气液色谱分析说明反应完成了30%。
将反应混合物在70℃再加热1小时,将它冷至室温后,再在70℃加热1小时。将反应混合物冷至0℃后小心地加入到过量的固体碳酸钾中。浆状物小心地用冰/水稀释,并把混合物在蒸汽浴上加热10分钟。将混合物冷至室温并加入饱和的氯化钠溶液。产物用乙酸乙酯提取(2×750毫升),用无水硫酸镁干燥,减压蒸去溶剂。残余的棕色液体置于真空(0.5-1.0mmHg)下加热到50℃以除去挥发性的杂质。
得到的产物为一棕色液体(3.4克),不必进一步提纯即可使用。
用气相色谱/质谱分析产物,指出产物中包含68%的(RS)-4-二甲胺基-3-甲酰基-2-(1-甲基乙基)-3-丁烯酸乙酯(Ⅰ),12%的(RS)-4-乙氧基-3-甲酰基-2-(1-甲基乙基)-3-丁烯酸乙酯(Ⅱ)和17.5%的3-(1-甲基乙基)-5-羟基-四氢呋喃-2-酮(Ⅲ)杂质。随着反应条件和分离方法的变化,(Ⅰ)和(Ⅱ)的相对比例也有所变化,但所有这些混合物都适合于进一步转化成以后的实施例中所述的衍生物。
产物(Ⅰ)的分子离子峰:227
产物(Ⅱ)的分子离子峰:228
产物(Ⅲ)的分子离子峰:144
实施例11
本例说明了制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸乙酯的方法。
把按照实施例1制得的2,2-二甲基丙脒盐酸盐(0.14克),加到按照实施例10制得的(RS)-4-二甲胺基-3-甲酰基-2-(1-甲基乙基)-3-丁烯酸乙酯和(RS)-4-乙氧基-3-甲酰基-2-(1-甲基乙基)-3-丁烯酸乙酯的4∶3的混合物(0.2克)在乙醇(2毫升)的溶液中。往此搅拌着的混合物中加入甲氧化钠(0.06克)在乙醇(1毫升)的溶液,然后在回流温度加热2小时。冷却后,减压蒸去乙醇。残余的油状物用硅胶(Merck7729)柱层析提纯,先用二氯甲烷,再用含2%(体积)乙酸乙酯的二氯甲烷洗脱,即得到(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸乙酯(0.068克),为一淡黄色油状物。
产物的NMR和红外光谱与按实施例6制得的产物完全一致。
实施例12
按照相似于实施例11所述的实验程序,用适当的脒盐酸盐制备了下列化合物。脒盐酸盐的制备已在实施例1和9中叙述过。
(Ⅰ)由2-甲基丙脒盐酸盐制备(RS)-2-〔2-(1-甲基乙基)嘧啶-5-基〕-3-甲基丁酸乙酯。
1H NMR(CDCl3)δ:0.76(d,3H);1.06(d,3H);1.28(t,
3H);1.36(d,6H);2.34(m,1H);3.12
(m,2H);4.16(q,2H);8.68(s,2H);
分子离子峰:250
(Ⅱ)由环己烷基脒盐酸盐制备(RS)-2-(2-环己基嘧啶-5-基)-3-甲基丁酸乙酯。
1H NMR(CDCl3)δ:0.76(d,3H);1.16(m,10H);2.24(m,
2H);3.10(d,1H);4.12(q,2H);8.56
(s,2H)
分子离子峰:248
(Ⅲ)由1-甲基环丙烷基脒盐酸盐制备(RS)-2-〔2-(1-甲基环丙基)嘧啶-5-基〕-3-甲基丁酸乙酯。
1H NMR(CDCl3)δ:1.04(m,13H);1.60(s,3H);2.36(m,
1H);3.21(d,1H);4.12(q,2H);8.58(s,2H)
分子离子峰:262
(Ⅳ)由2,2-二甲基丁脒盐酸盐制备(RS)-2-〔2-(1,1-二甲基丙-1-基)嘧啶-5-基〕-3-甲基丁酸乙酯。
1H NMR(CDCl3)δ:1.00(m,18H);1.80(q,2H);2.34(m,
1H);3.16(d,1H);4.16(q,2H);8.68
(s,2H).
分子离子峰:278
实施例13
本例说明了另外两种制备本发明酯的途径-方法A和方法B。
方法A
(Ⅰ)制备(RS)-2-〔2-(2-甲基丙-1-基)嘧啶-5-基〕-3-甲基丁酸
将(RS)-2-〔2-(2-甲基丙-2-基)-嘧啶-5-基〕-3-甲基丁酸乙酯(5.4克)、氢氧化锂-水合物(2.16克)、四氢呋喃(108毫升)和水(108毫升)组成的混合物在80℃加热8小时。冷却后倾入稀盐酸中,混合物用乙酸乙酯提取,合并提取液用水洗,用无水硫酸镁干燥,减压蒸去溶剂而浓缩。
残余的油状物加入石油醚(沸程40-60℃)研磨,得到(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸(2.6克),为一白色固体。
1H nmr(CDCl3)δ:0.8,1.1(2d,J=7Hz,6H);1.4(s,9H);
2.0-2.5(m,1H);3.2(d,J=9Hz,1H);
8.6(s,2H);9.5(s,1H)
红外光谱(液体石腊):2600,1710,1550,1470,1375,
1305,720,650cm-1
(Ⅱ)制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-(RS)-1-乙炔基-1-(3-苯氧基苯基)甲基酯(化合物Ⅶ)
把N,N′-二环己基碳二亚胺(0.2克)在二氯甲烷(5毫升)的溶液,加到一个搅拌着的、由(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸(0.26克)、(RS)-α-乙炔基-3-苯氧基苄醇(0.224克)、4-二甲胺基吡啶(0.02克)和无水的二氯甲烷(5毫升)所组成的溶液中。将得到的混合物搅拌2小时。过滤除去形成的沉淀,滤液减压蒸去溶剂而浓缩,残余的油状物用硅胶柱层析提纯,用乙酸乙酯(1份体积)和石油醚(沸程60至80℃,1份体积)的混合物洗脱,得到(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-(RS)-1-乙炔基-1-(3-苯氧基苯基)甲基酯(0.4克),为非对映异构体的混合物。
1H nmr(CDCl3)δ:0.70,0.75,0.95,1.00(4d,J=7Hz,6H);
1.41(s,9H);2.30(m,1H);
2.60,2.55(2d,J=2Hz,1H);
3.19(d,J=9Hz,1H);6.39,6.35(2d,J=
2Hz,1H;)
6.80-7.50(m,9H);8.60(s,2H)
红外光谱(液膜):3280,2960,2920,2890,2120,
1740,1585,1540,1480,1430,
1245,1210,1140,690cm-1
方法B
制备(RS)-2-〔2-(1-甲基环丙基)嘧啶-5-基〕-3-甲基丁酸-3-苯氧基苄酯(化合物ⅩLⅨ)
把催化量的乙氧化钛(Ⅳ)加到一个由(RS)-2-〔2-(1-甲基环丙-1-基)嘧啶-5-基〕-3-甲基丁酸乙酯(0.2克)3-苯氧基苄醇(0.305克)在无水的甲苯(6毫升)的溶液中,反应混合物在回流温度搅拌18小时。不时由反应容器中取样,在乙酸乙酯和水之间分配,然后用气液色谱对有机相进行分析以监测反应的进展情况。如果18小时后反应仍未进行完全,可将反应混合物冷却,减压蒸去溶剂和反应中生成的乙醇,然后将残余物重新溶解在甲苯中,再加入催化量的乙氧化钛(Ⅳ),然后把反应混合物重新加热回流温度,一直到反应进行完全。
反应完成后,减压蒸去挥发性组份,残余物在乙酸乙酯和水之间进行分配。合并有机层,用无水硫酸镁干燥,减压蒸发。残余的油状物用硅胶柱层析提纯,用含有2%体积乙酸乙酯的二氯甲烷洗脱,得到(RS)-2-〔2-(1-甲基环丙基)嘧啶-5-基〕-3-甲基丁酸-3-苯氧基苄基酯。
1H NMR(CDCl3)δ:0.75(d,3H);0.92(m,2H);0.98(d,3H);
1.36(m,2H);1.58(s,3H);2.34(m,1H);
3.18(d,1H);5.08(q,2H);7.16(m,9H);
8.54(s,2H)
红外光谱(液膜):2970,1735,1590,1545,1445,
1370,1260,1020cm-1
实施例14
应用实施例13中的方法A或方法B,由适当的原料制备了下列化合物。在方法A中涉及的以前实施例中未叙述过的中间体酸的物理性质,将在实施例15中给出。那些不容易得到的醇中间体的制备方法,将在实施例18至25中描述。
(ⅰ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-3-苯氧基苄酯(化合物Ⅰ)
1H NMR(CDCl3)δ:0.75,1.00(d,J=7Hz,6H);1.41
(s,9H);2.30(m,1H);3.15(d,J=9Hz,
1H);5.08(s,2H);6.80-7.40(m,9H);
8.64(s,2H)
红外光谱(液膜):2960,1735,1580,1480,1425,
1250,1210,1140cm-1
(ⅱ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-(RS)-1-氰-1-(3-苯氧基苯基)甲基酯(化合物Ⅱ)
1H NMR(CDCl3)δ:0.95-1.20(4d,J=7Hz,6H);1.33(s,9H);
2.30(m,1H);3.30(d,J=9Hz,1H);6.35,
6.40(2s,1H);7.00-7.60(m,9H);8.55,
8.57(2s,2H)
红外光谱(液膜):2960,1740,1580,1480,1430,
1240,685cm-1
(ⅲ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-2-甲基-3-苯基苄基酯
(化合物Ⅲ)
1H NMR(CDCl3)δ:0.75,1.00(2d,J=7Hz,6H);1.41(s,
9H);2.13(s,3H);2.30(m,1H);3.20
(d,J=9Hz,1H);5.19(s,2H);7.20-7.45
(m,8H);8.67(s,2H)
红外光谱(液膜):2960,1735,1660,1585,1480,
1430,1175,1145,760,700cm-1
(ⅳ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-2,3,5,6-四氟-4-甲基苄基酯(化合物Ⅳ)
1H NMR(CDCl3)δ:0.75,1.00(2d,J=7Hz,6H);1.41(s,
9H);2.25(m,1H);2.28(t,J=2Hz,3H);
3.18(d,J=9Hz,1H);5.20(bs,2H);8.67
(s,2H)
红外光谱(液膜)1740,1490,1430,1285cm-1
(ⅴ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-烯-1-基)-2,3,5,6-四氟苄基酯(化合物Ⅴ)
1H NMR(CDCl3)δ:0.78,1.05(2d,J=7Hz,6H);1.41(s,
9H);2.30(m,1H);3.18(d,J=9Hz,1H);
3.45(bd,J=6.5Hz,2H);4.80-5.25(m,
4H);5.60-6.10(m,1H);8.65(s,2H)
红外光谱(液膜):2960,1740,1490,1430cm-1
(ⅵ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-N-(3,4,5,6-四氢苯二甲酰亚胺基)甲基酯(化合物Ⅵ)
1H NMR(CDCl3)δ:0.75,1.00(2d,6H);1.41(s,9H);1.78
(m,4H);2.35(m,5HH);3.10(d,J=9Hz,
1H);5.50(d,J=14Hz,1H);5.58(d,
J=14Hz,1H);8.62(s,2H)
红外光谱(液膜):2960,1730,1590,1550,1480,
1430,1140cm-1
(ⅶ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-5-苄基-呋喃-3-基-甲酯(化合物Ⅷ)
1H NMR(CDCl3)δ:0.75,1.00(2d,J=7Hz,6H);1.41(s,
9H);2.30(m,1H);3.17(d,J=9Hz,1H);
4.92(bs,2H);6.00(bs,1H);7.20-7.38
(m,6H);8.65(s,2H)
红外光谱(液膜):2960,1735,1590,1550,1430,
1175,1150,950cm-1
(ⅷ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-6-苯氧基吡啶-2-基-甲酯(化合物Ⅸ)
1H NMR(CDCl3)δ:0.75,1.00(2d,J=7Hz,6H);1.41(s,
9H);2.30(m,1H)3.25(d,J=9Hz,1H);
5.08(s,2H);6.70-7.70(m,8H);8.66
(s,2H)
红外光谱(液膜):2960,1735,1590,1570,1490,
1480,1450,1430,1150,690cm-1
(ⅸ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-(RS)-1-氰-1-(6-苯氧吡啶-2-基)甲酯(化合物Ⅹ)
1H NMR(CDCl3)δ:0.75-1.00(4d,J=7Hz,6H);1.41(s,9H);
2.30(m,1H);3.28,3.30(2d,J=7Hz,
1H);6.32,6.34(2s,1H);6.80-7.80(m,8H);8.63(8,2H)
红外光谱(液膜):2960,1735,1590,1490,1440cm-1
(ⅹ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-(RS)-1-〔1-(6-苯氧吡啶-2-基)〕乙酯(化合物Ⅺ)
1H NMR(CDCl3)δ:0.75-1.15(4d,J=7Hz,6H);1.41(s,9H);
1.45,1.55(2d,J=6.5Hz,3H);2.30(m,
1H);3.23(d,J=9Hz,1H);5.78,5.80
(2q,J=6.5Hz,1H);6.60-7.80(m,8H);
8.63(s,2H)
红外光谱(液膜):2960,1735,1590,1570,1440,
1255cm-1
(ⅹⅰ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-炔-1-基)-2,3,5,6-四氟苄基酯(化合物Ⅻ)
1H NMR(CDCl3)δ:0.95,1.05(2d,6H);1.4(s,9H);2.1
(t,1H);2.2-2.5(m,1H);3.25(d,1H);
3.65(d,2H);5.25(s,2H);8.6(s,2H)
红外光谱(液膜):3320,2965,1745,1490,1435
1280,1150,1050,860cm-1
(ⅹⅱ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-(丁-2-炔-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩⅢ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);1.8(t,
3H);2.35(m,1H);3.2(d,1H);3.6
(宽的s,2H);5.2(AB四重峰2H);8.6(s,
2H);8.6(s,2H)
红外光谱(液膜):1750,1495,1440,1285,1150,
1050cm-1
GLC保留时间:9.25分
(ⅹⅲ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-Z-4-(3-氯丙-2-烯-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩⅣ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);2.35
(m,1H);3.2(d,1H);3.65(d,2H);5.2
(AB四重峰2H);5.8(dt,1H);6.2(d,1H);
8.6(s,2H);
红外光谱(液膜):1750,1490,1440,1300,1150,
1055cm-1
GLC保留时间:9.63分
(ⅹⅳ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-(甲氧基甲基)-2,3,5,6-四氟苄基酯(化合物ⅩⅤ)
1H NMR(CDCl3)δ:0.75,1.05(2d,6H);1.4(s,9H);2.3
(m,1H);3.2(d,1H);3.4(s,3H);4.6
(宽的s,2H);5.25(s,2H);8.6(s,
2H)
红外光谱(液膜):1745,1495,1290,1150,1115,
1060cm-1
19F NMR(CDCl3)δ(相对于CFCl3):-143.516
GLC保留时间:8.7分
(ⅹⅴ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-2-甲氧基-4-(甲氧基甲基)-3,5,6-三氟苄基酯(化合物ⅩⅥ)
1H NMR(CDCl3)δ:0.75,1.05(2d,6H);1.4(s,9H);2.2-
2.4(m,1H);3.2(d,1H);3.4(s,3H);
3.8(d,3H);4.55(t,2H);5.2(宽的
s,2H);8.6(s,2H);
19F NMR(CDCl3)δ(相对于CFCl3):-137.193(d);-144.247(m);145.462(d).
红外光谱(液膜):1745,1490,1440,1285,1155,
1115,1070,990cm-1
GLC保留时间:9.42分
(ⅹⅵ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-苄基-2,3,5,6-四氟苄基酯(化合物ⅩⅦ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);2.35
(m,1H);3.2(d,1H);4.05(s,2H);5.2
(AB四重峰2H);7.2-7.3(m,5H);8.6(s,2H)
红外光谱(液膜):1745,1490,1440,1280,1150,
1050,980,705cm-1
GLC保留时间:11.27分
(ⅹⅶ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-3-苄基-4-氟苄基酯(化合物ⅩⅤⅢ)
1H NMR(CDCl3)δ:0.8,1.0(2d,6H);1.4(s,9H);
2.2-2.4(m,1H);3.2(d,1H);
4.0(d,2H);5.05(AB四重峰,2H);
7.0-7.4(m,8H);8.65(s,2H)
19F NMR(CDCl3)δ(相对于CFCl3):-118.517(s).
红外光谱:1740,1505,1440,1250,1180,
1155,1115,820,730,700cm-1
GLC保留时间:11.26分
(ⅹⅴⅲ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-(3-(三甲基硅烷基)丙-2-炔-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩⅨ)
1H NMR(CDCl3)δ:0.2(s,9H);0.8,1.05(2d,6H);
1.4(s,9H);2.3(m,1H);3.2
(d,1H);3.65(宽的s,2H);
0.2(AB四重峰2H);8.6(s,2H)
19F NMR(CDCl3)δ(相对于CFCl3):-143.466(s)
红外光谱(液膜):1745,1495,1440,1255,1240,
1150,1050,850cm-1
GLC保留时间:9.79分
(ⅹⅸ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-(2-甲基丙-2-烯-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩⅩ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);
1.8(s,3H);2.35(m,1H);
3.2(d,1H);3.4(s,2H);
4.6(s,1H);4.85(s,1H);5.2
(AB四重峰2H);8.6(s,2H)
红外光谱(液膜):1745,1490,1430,1285,1145,
1050cm-1
GLC保留时间:8.84分
(ⅹⅹ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-乙氧基-2,3,5,6-四氟苄基酯(化合物ⅩⅪ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);
1.4(t,3H);2.35(m,1H);
3.2(d,1H);4.3(q,2H);5.2
(AB四重峰2H);8.6(s,2H)
红外光谱(液膜):1740,1590,1500,1435,1390,
1145,940cm-1
GLC保留时间:8.42分
(ⅹⅹⅰ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-(三甲基硅烷基)-2,3,5,6-四氟苄基酯(化合物ⅩⅫ)
1H NMR(CDCl3)δ:0.4(s,9H);0.8,1.05(2d,6H);
1.4(s,9H);2.35(m,1H);3.2(d,1H);
5.2(AB四重峰2H);8.6(s,2H)
红外光谱(液膜):1745,1450,1270,1145,865,
850cm-1
GLC保留时间:8.80分
(ⅹⅹⅱ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-E,Z-4-(丁-2-烯-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩⅩⅢ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);
1.65(d,3H);2.4(m,1H);
3.2(d,1H);3.4(d,2H);5.2
(AB四重峰2H);5.5(m,2H);
8.6(s,2H)
红外光谱(液膜):1745,1490,1435,1290,1145,
1170,1040,960cm-1
(ⅹⅹⅲ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-(2-氯丙-2-烯-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩⅩⅣ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);
2.3-2.4(m,1H);3.2(d,1H);
3.75(s,2H);5.2(AB四重峰,2H)
5.2(s,1H);5.3(s,1H);8.6(s,2H)
红外光谱(液膜):1740,1490,1430,1280,1145,
1115,1050cm-1
GLC保留时间:9.30分
(ⅹⅹⅳ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-氟-3-苯氧基苄基酯(化合物ⅩⅩⅤ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);
2.3(m,1H);3.2(d,1H);5.0
(AB四重峰2H);6.9-7.4(m,8H)
8.65(s,2H)
19F NMR(CDCl3)δ(相对于CFCl3):-131.4(m)
红外光谱(液膜):1740,1590,1515,1490,1430,
1280,1210,1150,1115,815cm-1
(ⅹⅹⅴ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-2-氯-6-氟苄基酯(化合物ⅩⅩⅥ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);2.35
(m,1H);3.2(d,1H);5.25(AB四重峰2H);7.0
(t,1H);7.2-7.3(m,2H);8.6(s,2H).
红外光谱(液膜):1740,1610,1585,1486,1455,
1430,1250,1180,1160,990,
780cm-1
(ⅹⅹⅵ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-(RS)-1-氰-1-(3-苄基-4-氟苯基)甲基酯(化合物ⅩⅩⅦ)
1H NMR(CDCl3)δ:0.75-1.05(4d,6H);1.4(s,9H);2.35
(m,1H);3.2(2d,1H);4.0(宽的s,2H);
6.3,6.35(2S,1H);7.0-7.4(m,8H);8.6
(2s,2H)
19F NMR(CDCl3)δ(相对于CFCl3):-114.289(s)
红外光谱(液膜):1750,1590,1550,1500,1435,
1245,1135,1105,820,730,
700cm-1
(ⅹⅹⅶ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-3-(苯胺基)苄基酯(化合物ⅩⅩⅤⅢ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);
2.35(m,1H);3.2(d,1H);
四重峰2H);5.7(宽的S,1H);
6.8-7.4(m,8H);8.6(s,2H)
红外光谱(液膜):3400,1735,1595,1500,1435,
1180,1150,745,680cm-1
GLC保留时间:13.24分
(ⅹⅹⅷ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-E-4-(2,3-二氯丙-2-烯-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩⅩⅨ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);
2.35(m,1H);3.2(d,1H);
3.95(s,2H);5.2(AB四重峰,2H)
6.35(s,1H);8.6(s,2H)
GLC保留时间:10.26分
(ⅹⅹⅸ)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-五氟苄基酯(化合物ⅩⅩⅩ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);2.35
(m,1H);3.2(d,1H);5.2(ABAB四重峰,2H)
8.6(s,2H).
红外光谱(液膜):1750,1530,1515,1440,
1140,950,cm-1
(ⅹⅹⅹ)用方法A制备(RS)-2-〔4-氯-2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-烯-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩⅩⅪ)
1H NMR(CDCl3):0.85,1.1(2d,6H);1.4(s,9H);2.3
(m,1H);3.5(d,2H);3.8(d,1H);5.2
(d,2H);5.0(d,1H);5.2(d,1H);5.9
(m,1H);8.75(s,1H).
红外光谱(液膜):1750,1580,1490,1425,1155
cm-1.
(ⅹⅹⅹⅰ)用方法A制备(RS)-2-〔4-氯-2-(2-甲基丙-2-基)嘧啶-5-基)-3-甲基丁酸-4-(丙-2-炔-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩⅩⅫ)
1H NMR(CDCl3)δ:0.8,1.1(2d,6H);1.4(s,9H);2.05(t,
1H);2.35(m,1H);3.6(d,2H);3.8(d,
1H);5.25(d,1H);8.8(s,1H).
红外光谱(液膜):1750,1580,1495,1425,1155,
1050cm-1.
(ⅹⅹⅹⅱ)用方法A制备(RS)-2-〔4-氯-2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-(RS)-1-氰-1-(3-苯氧基苯基)甲基酯(化合物ⅩⅩⅩⅢ)
1H NMR(CDCl3)δ:0.8,0.85,1.0,1.1(4d,6H);1.4(s,
9H);2.4(m,1H);3.9(d,1H);6.35
(2s,1H);7.0-7.4(m,9H);8.75(s,
1H).
红外光谱(液膜):1760,1710,1590,1490,1425,
1250,700cm-1.
(ⅹⅹⅹⅲ)用方法A制备(RS)-2-〔4-氯-2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-(RS)-1-氰-(6-苯氧基吡啶-2-基)-甲基酯(化合物ⅩⅩⅩⅣ)
1H NMR(CDCl3)δ:0.8,0.85,1.0,1.15(4d,6H);1.4(s,
9H);2.4(m,1H);3.9(2d,1H);6.3
(2s,1H);6.95(t);7.2(m);7.4(m);
7.75(m);8.75(s,1H).
红外光谱(液膜):1745,1600,1580,1450,1430,
1250cm-1.
(ⅹⅹⅹⅳ)用方法B制备(RS)-2-〔4-氟-2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-烯-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩⅩⅩⅤ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);2.4
(m,1H);3.45(d,2H);3.6(d,1H);5.2
(AB四重峰2H);5.05(d,1H);5.1(d,1H);
5.9(m,1H);8.8(d,1H).
红外光谱(液膜):1745,1610,1490,1440cm-1.
(ⅹⅹⅹⅴ)用方法B制备(RS)-2-〔4-氟-2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-甲基-2,3,5,6-四氟苄基酯(化合物ⅩⅩⅩⅥ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);2.3
(m,1H);2.3(t,3H);3.6(d,1H);5.2
(d,2H);8.8(d,1H).
红外光谱(液膜):1745,1610,1490,1440,1290,
1075,940cm-1.
19F NMR(CDCl3)δ(相对于 CFCl3):-66.3(d)
-143.6(m)
-145.2(m)
(ⅹⅹⅹⅵ)用方法B制备(RS)-2-〔4-氟-2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-氟-3-苯氧基苄基酯(化合物ⅩⅩⅩⅦ)
1H NMR(CDCl3)δ:0.8,1.05(2d,6H);1.4(s,9H);2.2-
2.4(m,1H);3.6(d,1H);5.2(2d,2H);
6.9-7.4(m,8H);8.6(d,1H).
红外光谱(液膜):1735,1610,1590,1510,1490,
1430,1280,1210cm-1.
(ⅹⅹⅹⅶ)用方法B制备(RS)-2-〔2-(1-甲基乙基)嘧啶-5-基〕-3-甲基丁酸-4-甲基-2,3,5,6-四氟苄基酯(化合物ⅩⅩⅩⅤⅢ)
1H NMR(CDCl3)δ:0.76(d,3H);1.04(d,3H);1.36(d,
6H);2.52(m,4H);3.20(m,2H);5.22
(q,2H);8.62(s,2H).
红外光谱(液膜):2980,2880,1745,1590,1550,
1490,1440,1290,1150,1075
cm-1.
分子离子峰:398
(ⅹⅹⅹⅷ)用方法B制备(RS)-2-〔2-(1-甲基乙基)嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-烯-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩⅩⅩⅨ)
1H NMR(CDCl3)δ:0.76(d,3H);1.04(d,3H);1.36(d,
6H);2.34(m,1H);3.20(m,2H);3.48(
d,2H),5.18(m,4H);5.90(m,1H);
8.62(s,2H).
红外光谱(液膜):2975,2880,1740,1590,1550,
1490,1440,1150,1115cm-1.
分子离子峰:424
(ⅹⅹⅹⅸ)用方法A制备(RS)-2-〔2-(1-甲基乙基)嘧啶-5-基〕-3-甲基丁酸五氟苄基酯(化合物ⅩL)
1H NMR(CDCl3)δ:0.76(d,3H);1.01(d,3H);1.36(d,
6H);2.30(m,1H);3.20(m,2H);5.16
(宽峰,2H);8.62(s,2H).
红外光谱(液膜):2970,1745,1520,1510,1440,
1310,1130,1160,940cm-1.
分子离子峰:402
(ⅹl)用方法A制备(RS)-2-〔2-(1-甲基乙基)嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-炔-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩLⅠ)
1H NMR(CDCl3)δ:0.76(d,3H);1.02(d,3H);1.36(d,6H);
2.08(m,1H);2.34(m,1H);3.20(m,2H);
3.04(宽峰,2H);5.23(q,2H);8.60(s,
2H).
红外光谱(液膜):3320,2980,2880,1745,1590,
1550,1490,1440,1285,1150,
1050,860cm-1.
分子离子峰:422
(ⅹlⅰ)用方法B制备(RS)-2-〔2-(1,1-二甲基丙-1-基)嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-烯-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩLⅡ)
1H NMR(CDCl3)δ:0.69(t,3H);0.76(d,3H);1.03(d,
3H);1.36(s,6H);1.80(q,2H);2.34
(m,1H);3.18(d,1H);3.48(m,2H);
5.18(m,4H);5.90(m,1H);8.64(s,
2H).
红外光谱(液膜):2970,1745,1640,1590,1545,
1485,1430,1280,1140cm-1.
分子离子峰:452
(ⅹlⅱ)用方法A制备(RS)-2-〔2-(1,1-二甲基丙-1-基)嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-炔-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩLⅢ)
1H NMR(CDCl3)δ:0.68(t,3H);0.75(d,3H);1.02(d,
3H);1.36(s,6H);1.80(q,2H);2.06
(m,1H);2.34(m,1H);3.18(d,1H);
3.62(宽峰,2H);5.22(q,2H);8.60
(s,2H).
红外光谱(液膜):3320,2970,1745,1590,1550,
1495,1430,1280,1150,1050
cm-1.
分子离子峰:450
(ⅹlⅲ)用方法A制备(RS)-2-〔2-(1.1-二甲基丙-1-基)嘧啶-5-基〕-3-甲基丁酸-4-(甲氧基甲基)-2,3,5,6-四氟苄基酯(化合物ⅩLⅣ)
1H NMR(CDCl3)δ:0.68(t,3H);0.76(d,3H);1.00(d,
3H);1.34(s,6H);1.80(q,2H);2.32
(m,1H);3.18(d,1H);3.38(s,3H);
4.58(s,2H);5.24(q,2H);8.64(s,2H).
红外光谱(液膜):2970,1745,1590,1550,1495,
1440,1290,1150,1120,1060.cm-1
分子离子峰:456
(ⅹlⅳ)用方法B制备(RS)-2-〔2-环丙基嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-烯-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩLⅤ)
1H NMR(CDCl3)δ:0.76(d,3H);1.06(m,7H);2.28(m,
2H);3.14(d,1H);3.48(m,2H);5.16
(m,4H);5.88(m,1H),8.50(s,2H).
红外光谱(液膜)::2970,1740,1590,1545,1485,
1450,1290,1150.cm-1
分子离子峰:422
(ⅹlⅴ)用方法B制备(RS)-2-〔2-环丙基嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-炔-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩLⅥ)
1H NMR(CDCl3)δ:0.78(d,3H);1.04(m,7H);2.06(m,
1H);2.24(m,2H);3.16(d,1H);3.66
(m,2H);5.20(宽峰,2H);8.52(s,
2H).
红外光谱(液膜):3320,2970,1745,1590,1550,
1495,1455,1280,1150,1050
cm-1.
分子离子峰:420
(ⅹlⅵ)用方法A制备(RS)-2-〔2-环丙基嘧啶-5-基〕-3-甲基丁酸-4-氟-3-苄基-苄基酯(化合物ⅩLⅦ)
1H NMR(CDCl3)δ:0.72(d,3H);0.92(d,3H);1.08(m,
4H);2.24(m,2H);3.12(d,1H);3.96
(s,2H);5.02(q,2H);7.16(m,8H);
8.48(s,2H).
红外光谱(液膜):2970,1740,1590,1550,1500,
1455,1250,1180,1110cm-1.
分子离子峰:418
(ⅹlⅶ)用方法B制备(RS)-2-〔2-(1-甲基环丙-1-基)嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-烯-1-基)-2,3,5,6-四氟苄基酯(化合物ⅩLⅤⅢ)
1H NMR(CDCl3)δ:0.76(d,3H);0.92(m,2H);1.02(d,
3H);1.36(m,2H);1.56(s,3H);2.34
(m,1H);3.16(d,1H);3.48(m,2H);
5.16(m,4H);5.90(m,1H);8.52(s,
2H).
红外光谱(液膜):2970,1740,1590,1545,1490,
1470,1440,1300,1280,1150
cm-1.
分子离子峰:436
(ⅹlⅷ)用方法A制备(RS)-2-〔2-(1-甲基环丙-1-基)嘧啶-5-基〕-3-甲基丁酸-4-氟-3-苄基-苄
基酯(化合物L)
1H NMR(CDCl3)δ:0.72(d,3H);0.92(m,5H);1.36(m,
2H);1.66(s,3H);2.30(m,1H);3.14
(d,1H);4.96(s,2H);5.00(q,2H);
7.15(m,8H);8.52(s,2H).
红外光谱(液膜):2970,1735,1590,1550,1500,
1470,1440,1250,1150,1100
cm-1.
分子离子峰:432
(ⅹlⅸ)用方法A制备(RS)-2-〔2-(1-甲基环丙-1-基)嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-炔-1-基)-2,3,5,6-四氟苄基酯(化合物LⅠ)
1H NMR(CDCl3)δ:0.76(d,3H);0.86(m,5H);1.36(m,
2H);1.60(s,3H);2.08(m,1H),2.32
(m,1H);3.16(d,1H);3.64(宽峰,
2H);5.20(宽峰,2H);8.56(s,2H).
红外光谱(液膜):3320,2970,1745,1590,1550,
1495,1470,1440,1150cm-1.
分子离子峰:434
(l)用方法A制备(RS)-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-(RS)-1-氰-1-(4-氟-3-苯氧苯基)甲基酯(化合物LⅡ)
1H NMR(CDCl3)δ:0.7-1.1(4d,6H);1.4(s,9H);2.35
(m,1H);3.25(2d,1H);6.25,6.30
(2s,1H);6.9-7.4(m,8H);8.6(2s,1H)
红外光谱(液膜):2980,1755,1595,1435,1230,
740cm-1
实施例15
本例记录了实施例14中方法A的中间体羧酸的物理性质(参看实施例13)
(ⅰ)(RS)-2-〔2-(2-甲基丙-2-基)-4-氯嘧啶-5-基〕-3-甲基丁酸
1H NMR(CDCl3)δ:0.85,1.15(2d,6H);1.4(s,9H);
2.4(m,1H);3.85(d,1H);9.0
(s,1H)
GLC保留时间:5.21分
(ⅱ)(RS)-2-〔2-(1-甲基乙基)嘧啶-5-基〕-3-甲基丁酸
1H NMR(CDCl3)δ:0.80(d,3H);1.12(d,3H);
1.33(d,6H);2.33(m,1H);
3.23(m,2H);8.20(宽的s,1H);
8.77(s,2H)
红外光谱(石腊油糊):2970,1720,1595,1555,
1475,1440,1190,
910cm-1
(ⅲ)(RS)-2-〔2-环丙基嘧啶-5-基〕-3-甲基丁酸
1H NMR(CDCl3)δ:0.76(d,3H);1.07(m,7H);2.20
(m,2H);3.13(d,1H);8.53
(s,2H);9.47(宽峰,1H)
红外光谱(液膜):2970,1720,1595,1550,
1460,1190,910cm-1
(ⅳ)(RS)-2-〔2-(1-甲基环丙基)嘧啶-5-基〕-3-甲基丁酸
1H NMR(CDCl3)δ:1.05(m,10H);1.53(s,3H);
2.36(m,1H);3.18(d,1H);8.60
(s,2H);8.93(宽的s,1H)
红外光谱(液膜):2980,2570,1720,1595,
1550,1470,1440,1160,
735cm-1
(ⅴ)(RS)-2-〔2-(1,1-二甲基丙-1-基)嘧啶-5-基〕-3-甲基丁酸
1H NMR(CDCl3)δ:0.70(t,3H);0.78(d,3H);1.10
(d,3H);1.37(s,6H);1.87
(m,2H);2.34(m,1H);3.23(d,1H);
7.30(宽峰,1H);8.73(s,2H)
红外光谱(液膜):2970,1715,1595,1550,
1465,1435,1190cm-1
实施例16
本例说明了2,2-二甲基丁腈的制备方法
通过外部冷却,把正丁腈(5克)在无水四氢呋喃(50毫升)
的溶液冷却到-78℃。往其中慢加入六甲基硅烷迭氮锂(220毫升1摩尔的四氢呋喃溶液)溶液,反应混合物的温度维持在约-70℃;然后在-70℃搅拌1.25小时,再慢慢加入碘甲烷(31克)。将反应混合物升到室温(约20℃),放置18小时。把反应混合物小心地加到水中去,并用乙醚提取产物。合并的有机层用无水硫酸镁干燥,减压蒸去溶剂。残余的油状物在常压进行分馏提纯,得到2,2-二甲基丁腈(1.1克)
沸点128-129℃
1H NMR(CDCl3)δ:0.98(t,3H);1.24(s,6H);1.47(q,
2H).
红外光谱(液膜):2990,2950,2790,2240,1470
1390,1370,1015cm-1.
实施例17
本例说明了制备1-甲基环丙烷基腈的步骤
(ⅰ)制备1-甲基-环丙烷甲酰氯
把草酰氯(59.7克)分批加到搅拌着的1-甲基环丙烷甲酸(40克,可从Aldrich化学药品有限公司买到)在氯仿(300毫升)的溶液中。反应混合物在回流温度加热3小时。然后,在常压蒸馏除去挥发性组份,得到一个淡黄色液体(49克),通过气液色谱指出其中含有少量未反应的草酰氯。产物无需进一步提纯即可使用。
红外光谱(液膜):2980,1850,1780,1430,
1300,1285,1055,1080,
930cm-1.
(ⅱ)制备1-甲基环丙烷甲酰胺
把1-甲基环丙烷甲酰氯(49克)在氯仿(300毫升)的溶液慢慢地加到事先由外部冷却到0℃的浓氨水溶液(300毫升)中。反应混合物自行升温到20℃,并析出白色固体沉淀;再加入氯仿使这沉淀重新溶解。分出有机层,用无水硫酸镁干燥,减压蒸去溶剂。残余的固体用氯仿和正己烷的混合物重结晶,即得1-甲基环丙烷甲酰胺(17.6克),为一无色结晶。
熔点:148℃
红外光谱(石腊油糊):3390,3200,1660,1615,
1405,1245,1110,880
cm-1.
(ⅲ)制备1-甲基环丙烷基腈
把1-甲基环丙烷甲酰胺(7.0克)和过量五氧化二磷的混合物加热到200℃。在加热过程中1-甲基环丙烷基腈即由反应瓶中连续蒸出,并被冷凝收集(2.3克)。
沸点:126℃
红外光谱(液膜):2980,2950,2250,1465,
1430,1035,955,895
cm-1.
1H NMR(CDCl3)δ:0.76(m,2H);1.24(m,2H);1.40
(s,3H).
实施例18
本例说明在制备化合物Ⅻ中的一个中间体4-(丙-2-炔-1-基)-2,3,5,6-四氟苄醇的制备方法。
(a)把五氟苯甲醛(17.7克)、无水溴化锂(8.9克)和N-甲基吡咯烷酮(50毫升)形成的混合物在160℃,氮气下搅拌加热2小时,然后将它冷却并倾入水中。过滤收集固体沉淀,在过滤器上用水洗,然后在装有五氧化二磷的保干器中干燥。用乙醚研磨后收集残留的固体,即得4-溴-2,3,5,6-四氟苯甲醛(8.4克),熔点:105-108℃
红外光谱(石腊油糊):1700cm-1
(b)把硼氢化钠(1.0克)在30分钟内分批加到搅拌着的4-溴-2,3,5,6-四氟苯甲醛(8.2克)在甲醇(80毫升)中的溶液中,同时维持温度在-5℃至+5℃之间。然后把混合物在室温(约18℃)搅拌2小时。将混合物倾入水中,过滤收集沉出的白色固体,用水洗,空气干燥,即得4-溴-2,3,5,6-四氟苯甲醇(7.5克),熔点60-62℃
红外光谱(石腊油糊):3400(b),1500(b)cm-1
(c)把二氢吡喃(3.0克)和浓盐酸(0.3毫升)相继加到一个搅拌着的4-溴-2,3,5,6-四氟苄醇(8.4克)在无水的乙醚(50毫升)的溶液中,反应混合物继续搅拌15分钟后,减压蒸去较易挥发的组份。残余的油状物通过光谱分析证实是2-(4-溴-2,3,5,6-四氟苄氧基)四氢吡喃(9.5克),纯度大约95%。
1HNMR(CDCl3)σ:4.6(m、3H);3.9(m,2H);1.6(m,
6H)。
(d)在氮气保护下,维持温度在-70℃,把正丁基锂(2.3毫升2.5摩尔正己烷溶液)滴加到2-(4-溴-2,3,5,6
-四氟苄氧基)四氢吡喃(1.7克)的无水四氢呋喃(50毫升)溶液中,反应混合物继续搅拌2小时。往此混合物中加入溴化亚铜-二甲硫醚复合物(1.1克),再搅拌2小时,然后往这清亮的棕黄色溶液中滴加炔丙基氯(0.4克),反应混合物在-70℃保持1小时后,让它在4小时内慢慢升到室温。将此反应混合物在乙醚和饱和的氯化铵水溶液之间进行分配,分出醚相,用水洗,用无水硫酸镁干燥。减压蒸去溶剂,得到残余的油状物(1.4克),包含约60%所需的产物和大约20%的2-(2,3,5,6-四氟苄氧基)四氢吡喃,以及大约20%的其它尚未被鉴定的物质。产物可用硅胶柱借助高压液相层析(用Gilson仪器)进行分离提纯,用正己烷(9份体积)和乙醚(1份体积)的混合物洗脱,得到纯净的2-〔4-(丙-2-炔-1-基)-2,3,5,6-四氟苄氧基〕四氢吡喃(0.8克)。
1H NMR(CDCl3)δ:4.6(m,3H);3.9(m,2H);3.6(d,
2H);2.0(t,1H);1.6(m,6H).
红外光谱(液膜):3300,2700cm-1.
(e)把2-〔4-(丙-2-炔-1-基)-2,3,5,6-四氟苄氧基〕-四氢吡喃(0.8克)、稀盐酸(2N,5毫升)和甲醇(30毫升)的混合物在室温搅拌2小时,然后减压蒸发除去比较易挥发的组份。残余物用乙醚提取,合并的提取液用水洗,用无水硫酸镁干燥。减压蒸去溶剂,得一油状物,在放置时即结晶,得到4-(丙-2-炔-1-基)-2,3,5,6-四氟苄醇(0.5克),由石油醚(沸程60-80℃)重结晶后,熔点51-52℃。
1H NMR(CDCl3)δ:4.8(s,2H);3.6(m,2H);2.3
(宽的s,1H);1.0(t,1H).
红外光谱(石腊油糊):3400cm-1.
实施例19
本例说明了在制备化合物ⅩⅤⅢ、ⅩLⅦ和L的中间体3-苄基-4-氟苄醇的制备步骤。
第一步:制备3-溴-4-氟苯甲醛
把4-氟苯甲醛(49.6克)在干燥的二氯甲烷(20毫升)的溶液,加到一个冷的(0℃)粉状三氯化铝(90.4克)在干燥的二氯甲烷(100毫升)中的悬浮液中。加入溴(70.4克),并把混合物在回流温度加热16小时。冷却后,将反应混合物小心地倾入冰中,并用二氯甲烷提取。合并的有机层用饱和的偏亚硫酸钠溶液、水和盐水相继洗涤,然后用无水硫酸镁干燥。减压蒸去溶剂,得一暗红色油状物,用一支4″维氏分馏柱进行减压蒸馏提纯,给出3-溴-4-氟苯甲醛(45.7克),为一油状物,沸程85-108℃/8mmHg。
第二步:制备2-(3-溴-4-氟苯基)-1,3-二氧戊环
把3-溴-4-氟苯甲醛(45.7克)、乙二醇(27.39克)、对甲苯磺酸(0.225克)和无水甲苯(110毫升)的混合物用迪安-斯达克装置在回流温度加热。4.5小时后可分出约12毫升水,用气液色谱分析反应混合物指出没有原料醛存在。用碳酸氢钠溶液和盐水相继洗涤反应液后,用无水硫酸镁干燥。减压蒸去溶剂得一黄色油状物,减压蒸馏提纯后,得到2-(3-溴-4-氟苯基)-1,3-二氧戊环(43.56克),沸程68-106℃/0.04mmHg。
90 MHz1H NMR(CDCl3)(ppm):4.1(4H,m);
5.8(1H,s);7.0-7.7(3H,m)。
第三步:制备2-(3-苄基-4-氟苯基)-1,3-二氧戊环
这化合物是按照类似于Minato等人在Tetrahedron Letters,21 845页(1980年)发表的方法制备。
在氮气下,把溴化苄(2.77克)一次加到活化了的锌粉(2.1克)在无水四氢呋喃(20毫升)中的悬浮液中。反应混合物用超声波处理2小时,放置30分钟后在氮气下小心过滤。把滤液在氮气下加到2-(3-溴-4-氟苯基)-1,3-二氧戊环(1克)和四(三苯基膦)化钯(0)(0.05克)在无水四氢呋喃(10毫升)的混合物中。把混合物在回流温度加热搅拌48小时,这时通过气液色谱分析表明没有原料存在。冷却反应混合物并倾入乙醚中。分出有机层,用氯化铵溶液、水和盐水相继洗涤,用无水硫酸镁干燥。减压蒸去溶剂,得一黄色油状物,通过硅胶柱层析提纯,用石油醚(沸程40-60℃)乙醚混合物洗脱(含乙醚由10%逐渐增加到20%体积),得到2-(3-苄基-4-氟苯基)-1,3-二氧戊环(0.7克),产物不必进一步提纯即可应用。
60HMz1H NMR(CDCl3)δ(ppm):4.0(6H,m);5.7(1H,s);6.8-
7.5(8H,m).
第四步:制备3-苄基-4-氟苯甲醛
把2-(3-苄基-4-氟苯基)-1,3-二氧戊环(0.7克)、丙酮(10毫升)、水(1毫升)和浓硫酸(5滴)的混合物
搅拌16小时。把反应混合物倾入乙醚中,用碳酸氢钠溶液、水和盐水相继洗涤有机层,用无水硫酸镁干燥,减压蒸去溶剂即得3-苄基-4-氟苯甲醛(0.59克),它不必进一步提纯即可应用。
1H NMR(CDCl3)δ(ppm):4.10(2H,s);7.20(6H,m);7.75
(2H,m);9.90(1H,s).
红外光谱(液膜):1700cm-1(C=O)
第五步:制备3-苄基-4-氟苄醇
把3-苄基-4-氟苯甲醛(5克)在甲醇(75毫升)的溶液冷却到0℃。分部加入硼氢化钠(1.34克),并把反应混合物搅拌1小时。然后将反应混合物小心地倾入水和乙醚的混合物中,分出有机层,用水和盐水洗涤,用无水硫酸镁干燥,减压蒸去溶剂,得一淡黄色油状物,在Kugelrohr装置中蒸馏提纯,得到3-苄基-4-氟苄醇(4.0克)
沸点:120℃/0.02mmHg
1H NMR(CDCl3)δ(ppm):1.7(1H,宽的 s);4.0(2H,s);4.6
(2H,s);7.0-7.3(8H,m).
红外光谱(液膜):3600-3100cm-1(OH).
实施例20
本例说明在制备4-甲氧基甲基-2,3,5,6-四氟苯甲酸甲酯时作为副产物生成的2-甲氧基-4-甲氧基甲基-3,5,6
-三氟苯甲酸甲酯的制备方法,以及把它转化成在制备化合物ⅩⅥ时的中间体2-甲氧基-4-甲氧基甲基-3,5,6-三氟苄醇的方法。
(ⅰ)把按照美国专利No·4370346所述方法制得的4-溴甲基-2,3,5,6-四氟苯甲酸甲酯(10克),溶于无水甲醇(10毫升)中,在室温下(约22℃)把这溶液滴加到由金属钠(1.5克)溶于无水甲醇(20毫升)所形成的甲醇钠甲醇溶液中。加完后减压蒸去过量甲醇,加入水,用稀盐酸酸化,然后用乙酸乙酯提取。提取液用无水硫酸镁干燥后,减压蒸去溶剂。剩下有部份固化的残余物用石油醚(40-60℃沸程)研磨,过滤出固体。这固体(4.0克)通过NMR和红外光谱分析可知是4-甲氧基甲基-2,3,5,6-四氟苯甲酸,用石油醚/氯仿混合溶剂重结晶后的熔点为92-95℃。滤液用稀氢氧化钠溶液和水相继洗涤、分离、用无水硫酸镁干燥,减压浓缩,得一残余物(1.4克),经用硅胶柱高压液相层析(Gilson仪器)提纯,用3份体积沸程为40-60℃的石油醚、1份体积乙醚的混合物作洗脱剂,可分得一种在层析柱上走得较慢的产品(600毫克)和另一种走得较快的产品(650毫克)。通过NMR谱分析指出它们分别是4-甲氧基甲基-2,3,5,6-四氟苯甲酸甲酯和2-甲氧基-4-甲氧基甲基-3,5,6-三氟苯甲酸甲酯。
(ⅱ)把2-甲氧基-4-甲氧基甲基-3,5,6-三氟苯甲酸甲酯(600毫克)、硼氢化锂(50毫克)和无水乙醚(20毫升)的混合物搅拌2小时,再在室温保持16小时,然后按照实施例4中所述的方法分离所需的产物。通过NMR和红外光谱鉴定产物是
2-甲氧基-4-甲氧基甲基-3,5,6-三氟苄醇(370毫克)。
实施例21
本例说明了在制备化合物ⅩⅩⅦ时的中间体的(RS)-α-氰-3-苄基-4-氟苄醇的合成方法。
把氰化钾(0.26克)在水(2毫升)中的溶液,分批加到3-苄基-4-氟苯甲醛(0.5克)在冰醋酸(10毫升)中的悬浮液中,同时保持温度在0℃。30分钟以后,将反应混合物升到室温(大约25℃),并放置16小时。再加入一些冰醋酸(5毫升),继续在室温搅拌8小时。放置16小时后,又加入氰化钾(0.26克)在水(1毫升)中的溶液,把反应混合物放置7天后,用水稀释,用乙醚提取,醚层用碳酸氢钠水溶液、盐水相继洗涤后,干燥,减压蒸去溶剂。残余物用硅胶柱层析提纯,用含有乙醚(40%体积比)的己烷作洗脱剂,先洗脱下来的是回收的3-苄基-4氟苯甲醛(0.2克),然后下来的是α-氰-3-苄基-4-氟苄醇(0.24克),为一白色固体。
30 90 MHz1H NMR(CDCl3)δ:4.05(2s,2H);5.45(s,1H);7.1-
7.4(m,7H);7.9-8.0(m,1H)
实施例22
本例说明了在制备化合物ⅩⅣ时的中间体Z-4-(3-氯丙-2-烯-1-基)-2,3,5,6-四氟苄醇的制备步骤。
(ⅰ)制备Z-1-氯-3-碘丙-1-烯
把Z-1,3-二氯丙烯(4.05克)和碘化钾(6.0克)在
无水丙酮(75毫升)中的溶液加热至回流温度两小时。冷却到室温(约25℃)后把反应混合物倾入硫代硫酸钠水溶液中,然后用乙醚提取。有机层用水、盐水相继洗涤后,干燥,减压蒸去溶剂,即得Z-1-氯-3-碘丙-1-烯,为一橙黄色油状物(2.4克)。这化合物要立即用于下一步合成中。
GLC保留时间:1.04分
(ⅱ)制备2-〔Z-4-(3-氯丙-2-烯-1-基)-2,3,5,6-四氟苄氧基〕四氢吡喃。
在干燥氮气下,把正丁基锂(3毫升2.5M己烷溶液)分批加到2-〔4-溴-2,3,5,6-四氟苄氧基〕-四氢吡喃(1.7克)在无水四氢呋喃(10毫升)的溶液中。同时维持温度在-70℃。30分钟后一次加入溴化亚铜-二甲硫醚复合物(1.54克),反应温度可以升到0℃,再反应15分钟。重新冷却到-70℃后,分批加入Z-1-氯-3-碘丙-1-烯(2.03克)在无水四氢呋喃(3毫升)中的溶液,并在-70℃再搅拌1小时。待升到室温(约25℃)后,往反应混合物中加入氯化铵水溶液,然后用乙酸乙酯提取。干燥后,减压蒸去溶剂,得一橙黄色油,把它用硅胶柱进行中压柱层析(用Gilson仪器),用含有乙醚(5%体积)的石油醚(沸程40-60℃)洗脱,即得2-〔4-(3-氯丙-2-烯-1-基)-2,3,5,6-四氟苄氧基〕四氢吡喃,是一个主要含Z型异构体的顺反异构体混合物。
1H NMR(CDCl3)δ:1.5-1.8(m,6H);3.5(m,1H);3.65
(d,2H);3.90(m,1H);4.60(d,1H);
4.8(m,2H);5.8(q,1H);6.15
(m,1H)
GLC保留时间:5.98分
(ⅲ)制备Z-4-(3-氯丙-2-烯-1-基)-2,3,5,6-四氟苄醇
把第(ⅱ)步中制备的四氢吡喃醚溶于甲醇(30毫升),在搅拌下加入催化量的浓盐酸。搅拌2小时后,把反应混合物用水稀释,用乙酸乙酯提取。有机层经洗涤干燥后,减压蒸去溶剂,即得Z-4-(3-氯丙-2-烯-1-基)-2,3,5,6-四氟苄醇(0.6克),为一无色油状物,放置后固化。
1H NMR(CDCl3)δ:3.65(d,2H);4.8(s,2H);5.85
(q,1H);6.2(m,1H)
红外光谱(液膜):3640,1490,1300,1250
和1040cm-1
GLC保留时间:3.08分
实施例23
本例说明了在制备化合物ⅩⅩⅣ时的中间体4-(2-氯丙-2-烯-1-基)-2,3,5,6-四氟苄醇的制备步骤。
(ⅰ)制备2-〔4-(2-氯丙-2-烯-1-基)-2,3,5,6-四氟苄氧基〕-四氢吡喃。
把正丁基锂(2.3毫升2.5M的己烷溶液)在干燥氮气下分批加到2-〔4-溴-2,3,5,6-四氟苄氧基〕-四氢吡喃(1.7克)在无水四氢呋喃(10毫升)的溶液中,同时维持反应温度在-30至-20℃之间。15分钟后一次加入溴化亚铜-二甲硫醚复合物(1.2克),并将反应混合物在-10℃保持1小时,
然后加入1,2-二氯丙-2-烯(1毫升),然后让反应温度升到+15℃。3小时后,往反应混合物中加水,再加饱和的氯化铵水溶液,再用乙醚提取。有机层用水、盐水相继洗涤,干燥,减压蒸去溶剂,残余物在硅胶桂上进行中压柱层析(用Gilson仪器),用含有乙醚(10%体积)的石油醚(沸程30-40℃)洗脱,即得2-〔4-(2-氯丙-2-烯-1-基)-2,3,5,6-四氟苄氧基〕四氢吡喃(1.5克)。
90 MHz1H NMR(CDCl3)δ:1.4-1.9(m,6H);3.4-4.0
(m,2H);3.8(s,2H);4.45-
5.0(m,3H);5.2(m,2H)
红外光谱(液膜):2950,1630,1470,1260,
and1050cm-1
GLC保留时间:6.26分
(ⅱ)制备4-(2-氯丙-2-烯-1-基)-2,3,5,6-四氟苄醇
把第(ⅰ)步中制得的四氢吡喃醚(0.2克)溶于甲醇(6毫升)中,在搅拌下加入浓盐酸(几滴)。搅拌6小时后再放置14小时,将反应混合物倾入水中,用乙酸乙酯提取。有机层用水、盐水相继洗涤、干燥,减压蒸去溶剂,即得4-(2-氯丙-2-烯-1-基)-2,3,5,6-四氟苄醇,为一橙黄色油状物(0.15克)。
90 MHz1H NMR(CDCl3)δ:3.8(宽的s,2H);4.8
(宽的s,2H);5.2,5.25
(2s,2H)
GLC保留时间:2.45分
实施例24
本例说明了在制备化合物ⅩⅩⅡ时的中间体4-三甲基硅烷基-2,3,5,6-四氟苄醇的制备步骤。
(ⅰ)制备2-〔4-三甲基硅烷基-2,3,5,6-四氟苄氧基〕-四氢吡喃
在干燥氮气保护下,把正丁基锂溶液(2.9毫升1.5M的己烷溶液)分批加入4-溴-2,3,5,6-四氟苄氧基〕-四氢吡喃(1.5克)在无水四氢呋喃(43毫升)的溶液中,同时维持反应温度在-70℃。当加完最后一份正丁基锂时,出现很强的紫色。分批加入氯代三甲基硅烷(1.6毫升,用氧化铝干燥过),紫色立即消失。然后把反应混合物倾入水中,用乙酸乙酯提取。有机层相继用水和盐水洗涤、干燥、减压蒸去溶剂,即得2-〔4-三甲基硅烷基-2,3,5,6-四氟苄氧基〕-四氢吡喃。这粗产物(经气相色谱分析纯度为94%)不必进一步提纯而立即用于下一步反应。
90 MHz1H NMR(CDCl3)δ:0.5(s,9H);1.4-2.1
(m,6H);3.4-4.4(m,2H);
4.5-5.2(m,3H)
GLC保留时间:5.07分
(ⅱ)制备4-三甲基硅烷基-2,3,5,6-四氟苄醇
把在第(ⅰ)步中制得的四氢吡喃醚粗品溶解在甲醇(20毫升)中,在搅拌下加入浓盐酸(3滴)。在室温(约25℃)搅拌16小时后把反应混合物倾入乙酸乙酯中,用水和盐水洗涤,干燥。减压蒸去溶剂,得一黄色油状物,用硅胶柱层析提纯,用含有乙醚(从10%体积逐渐增加到40%体积)的石油醚(沸程40-60℃)作洗脱
剂,即得4-三甲基硅烷基-2,3,5,6-四氟苄醇(0.79克)。
90 MHz1H NMR(CDCl3)δ:0.4(s,9H);1.9(t,1H);
4.8(m,2H)
19F NMR(CDCl3)ppm(相对于CFCl3)δ:-128.75(dd);-145.90(dd)
红外光谱(液膜):3640,1450,1275,and850cm-1
GLC保留时间:2.24分
实施例25
本例说明了在制备化合物ⅩⅩⅨ时的中间体Z-4-(2,3-二氯丙-2-烯-1-基)-2,3,5,6-四氟苄醇的制备方法。
把4-(丙-2-炔-1-基)-2,3,5,6-四氟苄醇(0.1克)、氯化铜(Ⅱ)(1.3克)和氯化锂(0.62克)在无水乙腈(23毫升)中的溶液在回流温度加热40小时。把得到的深色溶液倾入稀盐酸中,用乙酸乙酯提取。有机相用更稀的盐酸洗涤,干燥,减压蒸去溶剂,即得Z-4-(2,3-二氯丙-2-烯-1-基)-2,3,5,6-四氟苄醇(0.1克),为一橙黄色油状物。
1H NMR(CDCl3)δ:1.95(宽的s,1H);3.95(s,2H);4.8
(s,2H);and6.35(s,1H)
红外光谱(液膜):3400,1490,1285,1055and820cm-1
GLC保留时间:3.82分
实施例27
本例说明本发明产物的杀虫性质。
本发明产物的杀虫活性是用许多害虫来测定的。产物是以液体制剂形式来使用。此液体制剂中含有产物按重量计为百万分之500、250、或100(p.p.m)。配制时是先将产物溶于丙酮中,然后用含有0.01%(重量)的湿润剂(以商品名称为“LISSAPOL”NX,“Lissapol”是注册商标)的水稀释到液体制剂含有所需的浓度。
对各种害虫所采用的试验操作基本相同,包括把一些害虫放在通常它们食用的食料或宿主植物介质上,然后对害虫或对介质或同时对二者施用药剂。在施药后一到三天估计害虫的死亡率。
对于家蝇(Musca domestica),还需要进行测定药剂使它们昏倒效果的试验。详细结果列于表Ⅲ。
表Ⅳ中列出了各种本发明的产物的试验结果,表中第二列的浓度比率是百万分之几,表中死亡率的等级分别用字母A,B或C来表示,A代表80-100%的死亡率或昏倒率,B代表50-79%的死亡率或昏倒率,C代表不到50%的死亡率或昏倒率。
在表Ⅳ中所用的害虫用字母代号来表示而所用的害虫种类,支持介质或食料以及试验方式和试验持续时间均列于表Ⅲ中。
表 Ⅳ
化合物 制剂浓
编号 度比率 TUATUEMP NL MD/ MD BG HV SP DB
(ppm) KD
Ⅰ 500 A C A C - B A A - C
Ⅱ 500 A C A C - A C A - B
Ⅲ 500 A A A C A A C A - C
Ⅳ 500 A A A C A A C A - C
Ⅴ 500 A A A C A A B A - C
Ⅵ 500 A A B C C C C C - C
Ⅶ 500 A A A B A A B B - C
ⅤⅢ 500 A C B C B C C B - C
Ⅸ 500 A A A C A B C A - C
Ⅹ 500 A A A C A A C A - C
Ⅺ 500 A A A C A A B A - A
Ⅻ 500 A A A C A A B A - A
ⅩⅢ 500 A A A B A A B - - A
ⅩⅣ 500 A A A B A B C - - B
ⅩⅤ 500 A A A A A A C A A C
ⅩⅥ 500 A A A A A A C A A A
ⅩⅦ 500 A A C C C C C C C C
ⅩⅤⅢ 500 A A A B A A C A A C
ⅩⅨ 500 A A C C A A C C A C
ⅩⅩ 500 A A A A C C C A A C
ⅩⅪ 500 A A A C B A C A A A
ⅩⅫ 500 A A B C A A C A A A
ⅩⅩⅢ 500 A C A A C C C A C A
ⅩⅩⅣ 500 A A A C A C C C C C
ⅩⅩⅤ 500 A A A C C C C A A A
ⅩⅩⅥ 500 A A C C C C B B A A
表 Ⅳ(续)
化合物 制剂浓
编号 度比率 TUATUEMP NL MD MD BG HV SP DB
(ppm) KD
ⅩⅩⅦ 500 A C A B A A C A B C
ⅩⅩⅤⅢ 500 A C C A A C C C C C
ⅩⅩⅨ 500 A A A C A A C C B B
ⅩⅩⅩ 500 A A A C A A - A A A
ⅩⅩⅪ 500 A A A C A C C B A C
ⅩⅩⅫ 500 A A A A A A C B A A
ⅩⅩⅩⅢ 500 A C A C A A C C A B
ⅩⅩⅩⅣ 500 B C C C A C C C C C
ⅩⅩⅩⅤ 500 A A A A A A B A A A
ⅩⅩⅩⅥ 500 A C C C B B C C A C
ⅩⅩⅩⅦ 250 C A A B C C C A A C
ⅩⅩⅩⅤⅢ 500 A C A C A A A A A A A
ⅩⅩⅩⅨ 500 A A A A A A B A A A
ⅩL 500 A C A B A A A A A A
ⅩLⅠ 500 A B A A A A A B A A
ⅩLⅡ 500 A A A A A A C B A C
ⅩLⅢ 500 A A A A A A C B A A
ⅩLⅣ 500 A A A C A B C A B C
ⅩLⅤ 500 A A A A A A B C A B
ⅩLⅥ 100 A C A C C A B C A A
ⅩLⅦ 500 C C A C C A C A A C
ⅩLⅤⅢ 500 A A A A A A A C A A
ⅩLⅨ 500 B B A C A A C A A A
L 500 C A B C C A C A A C
LⅠ 100 A A A C C A C B A A
LⅡ 500 A A A A A A C A A A
PID/jc
pp 33718
3 Dec 86
Claims (3)
1、一种制备式(Ⅰ)化合物的方法,
式中R1代表氢或卤素,R2选自丙-2-基、丁-2-基、戊-2-基、戊-3-基、2-甲基丙-2-基、2-甲基丁-2-基、环丙基、1-甲基环丙基和环己基,Q代表式-OR基,式中R代表下式基团
式中X是氧、1,2-亚乙烯基或具有通式
基团,其中Y是氮或CR5,R4代表氢、甲基、氰基或乙炔基,每个R5可选自氢、甲基、氟和甲氧基,n值可选自0,1和2,和R6选自氢、氟、氯、甲基、苯基、苯氧基、至多4个碳原子的烯基、至多3个碳原子的囟代烯基、至多4个碳原子的炔基、至多2个碳原子的烷氧基、甲氧基甲基、苄基、三甲基硅烷基、3-三甲基硅烷基丙-2-炔-1-基和苯胺基,此方法包括使式Ⅰ化合物进行如下反应:
(a)当Q代表羟基时,与式ROH的醇反应,或
(b)当Q代表囟原子时,与式ROH的醇反应,或
(c)当Q代表羟基时,与式Q′-R的囟化物反应,其中Q′代表囟原子,或
(d)当Q代表至多6个碳原子的烷氧基时,与式R-OH的醇反应。
2、根据权利要求1所述的方法,其中Q代表-OR基团,式中R选自3-苯氧基苄基、1-氰-1-(3-苯氧基苯基)甲基、2-甲基-3-苯基苄基、4-甲基-2,3,5,6-四氟苄基、4-烯丙基-2,3,5,6-四氟苄基、N-3,4,5,6-四氢苯二甲酰亚胺基-甲基、1-乙炔基-1-(3-苯氧基苯基)甲基、5-苄基呋喃-3-基甲基、6-苯氧基吡啶-2-基甲基、1-氰-1-(6-苯氧基吡啶-2-基)甲基、1-〔1-(6-苯氧基吡啶-2-基)〕乙基、4-(丙-2-炔-1-基)-2,3,5,6-四氟苄基、4-(丁-2-炔-1-基)-2,3,5,6-四氟苄基、4-(3-氯丙-2-烯-1-基)-2,3,5,6-四氟苄基、2-甲氧基-4-甲氧基-3,5,6-三氟苄基、4-甲氧基甲基-2,3,5,6-四氟苄基、4-苄基-2,3,5,6-四氟苄基、3-苄基-4-氟苄基、4-(3-三甲基硅烷基丙-2-炔-1-基)-2,3,5,6-四氟苄基、4-(2-甲基丙-2-烯-1-基)-2,3,5,6-四氟苄基、4-乙氧基-2,3,5,6-四氟苄基、4-三甲基硅烷基-2,3,5,6-四氟苄基、4-(丁-2-烯-1-基)-2,3,5,6-四氟苄基、4-(2-氯丙-2-烯-1-基)-2,3,5,6-四氟苄基、4-氟-3-苯氧基苄基、2-氯-6-氟苄基、1-氰-1-(3-苄基-4-氟苯基)甲基、3-苯胺基苄基、4-(2,3-二氯丙-2-烯-1-基)-2,3,5,6-四氟苄基、五氟苄基和1-氰-1-(4-氟-3-苯氧基苯基)甲基。
3、根据权利要求2所述的方法,其中式(Ⅰ)化合物选自下列化合物:
RS-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-甲基-2,3,5,6-四氟苄基酯
RS-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-烯丙基-2,3,5,6-四氟苄基酯
RS-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-炔-1-基)-2,3,5,6-四氟苄基酯
RS-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-4-甲氧基甲基-2,3,5,6-四氟苄基酯
RS-2-〔2-(2-甲基丙-2-基)嘧啶-5-基〕-3-甲基丁酸-2-甲氧基-4-甲氧基甲基-3,5,6-三氟苄基酯
RS-2-(2-丙-2-基-嘧啶-5-基)-3-甲基丁酸-4-(丙-2-炔-1-基)-2,3,5,6-四氟苄基酯
RS-2-〔2-(2-甲基丁-2-基)嘧啶-5-基〕-3-甲基丁酸-4-(丙-2-炔-1-基)-2,3,5,6-四氟苄基酯
RS-2-(2-环丙基嘧啶-5-基)-3-甲基丁酸-4-(丙-2-炔-1-基)-2,3,5,6-四氟苄基酯,以及
RS-2-〔2-(1-甲基环丙基)嘧啶-5-基)-3-甲基丁酸-4-(丙-2-炔-1-基)-2,3,5,6-四氟苄基酯。
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US4962109A (en) * | 1985-12-23 | 1990-10-09 | Imperial Chemical Industries Plc | Insecticidally and acaricidally active pyrimidine esters and intermediates therefor |
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GB8626520D0 (en) * | 1986-11-06 | 1986-12-10 | Ici Plc | Halogenated esters |
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US5601098A (en) * | 1995-06-02 | 1997-02-11 | Dimon Incorporated | Method and apparatus for applying methoprene to oriental tobacco |
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- 1986-12-16 EP EP86309808A patent/EP0227415A3/en not_active Ceased
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JPS62158262A (ja) | 1987-07-14 |
AR242785A1 (es) | 1993-05-31 |
US4762835A (en) | 1988-08-09 |
EP0227415A2 (en) | 1987-07-01 |
HUT42453A (en) | 1987-07-28 |
HU201529B (en) | 1990-11-28 |
HU206202B (en) | 1992-09-28 |
CN86108825A (zh) | 1987-07-22 |
AP8600051A0 (en) | 1986-11-01 |
OA08565A (en) | 1988-09-30 |
KR870006015A (ko) | 1987-07-08 |
PT84010B (pt) | 1989-07-31 |
ZA869480B (en) | 1987-08-26 |
HU904110D0 (en) | 1990-12-28 |
AU6680986A (en) | 1987-06-25 |
CA1269662A (en) | 1990-05-29 |
GB2184441B (en) | 1990-05-09 |
GB8630011D0 (en) | 1987-01-28 |
AP35A (en) | 1989-02-15 |
PT84010A (en) | 1987-01-01 |
GB2184441A (en) | 1987-06-24 |
GB8531637D0 (en) | 1986-02-05 |
EP0227415A3 (en) | 1988-03-23 |
BR8606428A (pt) | 1987-10-20 |
IL81016A (en) | 1992-03-29 |
IL81016A0 (en) | 1987-03-31 |
CS970186A2 (en) | 1989-09-12 |
AU604663B2 (en) | 1991-01-03 |
HUT45290A (en) | 1988-06-28 |
CS269991B2 (en) | 1990-05-14 |
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