CN1293672A - 硝基胍类衍生物的制备方法 - Google Patents
硝基胍类衍生物的制备方法 Download PDFInfo
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- CN1293672A CN1293672A CN99804095A CN99804095A CN1293672A CN 1293672 A CN1293672 A CN 1293672A CN 99804095 A CN99804095 A CN 99804095A CN 99804095 A CN99804095 A CN 99804095A CN 1293672 A CN1293672 A CN 1293672A
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- -1 C2-C6-alkinyl Chemical group 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 125000000335 thiazolyl group Chemical group 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims abstract description 5
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims abstract description 3
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 51
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 32
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 18
- 150000003839 salts Chemical group 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000004414 alkyl thio group Chemical group 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 150000001345 alkine derivatives Chemical class 0.000 claims description 5
- 125000005336 allyloxy group Chemical group 0.000 claims description 5
- 125000004455 (C1-C3) alkylthio group Chemical group 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229940074654 diuril Drugs 0.000 claims description 4
- 239000003205 fragrance Substances 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000001424 substituent group Chemical group 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract 3
- 125000003118 aryl group Chemical class 0.000 abstract 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 125000002950 monocyclic group Chemical group 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 50
- 239000000460 chlorine Substances 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 229910052794 bromium Inorganic materials 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 5
- 125000004076 pyridyl group Chemical group 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 235000011167 hydrochloric acid Nutrition 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- XVGVNOVEJAWYEO-UHFFFAOYSA-N 3,4-dihydro-2h-oxadiazine Chemical compound C1NNOC=C1 XVGVNOVEJAWYEO-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JSLZUBLGGPEVQN-DIPNUNPCSA-N (2r)-4-methyl-2-propan-2-yl-2-[2-[4-[4-[2-(3,4,5-trimethoxyphenyl)ethyl]piperazin-1-yl]butoxy]phenyl]-1,4-benzothiazin-3-one Chemical compound COC1=C(OC)C(OC)=CC(CCN2CCN(CCCCOC=3C(=CC=CC=3)[C@@]3(C(N(C)C4=CC=CC=C4S3)=O)C(C)C)CC2)=C1 JSLZUBLGGPEVQN-DIPNUNPCSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 241001414720 Cicadellidae Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000002618 bicyclic heterocycle group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000000232 haloalkynyl group Chemical group 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229950001891 iprotiazem Drugs 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 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
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KHEZAZQZWQJLAE-UHFFFAOYSA-N nitrothiourea Chemical compound [O-][N+](=O)NC(S)=N KHEZAZQZWQJLAE-UHFFFAOYSA-N 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 125000001544 thienyl group Chemical group 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
- 235000013311 vegetables Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pyridine Compounds (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Furan Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
本发明描述了一种制备式(Ⅰ)化合物的方法。其中:R1为氢或C1-C4烷基;R2为氢、C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基或-CH2B基团;A为未取代或一至五取代的芳香的或非芳香的单环或双环的杂环基;和B为可任选被一至三个取代基取代的苯基、3-吡啶基或噻唑基;其特征在于用强酸水解式(Ⅱ)化合物,其中R1,R2,A如式(Ⅰ)中所定义,且X为氧或硫;式(Ⅰ)化合物适合于制备杀虫剂。同时还要求保护了中间体(Ⅱ)。
Description
本发明涉及一种制备式(Ⅰ)化合物的方法
其中:
R1为氢或C1-C4烷基;
R2为氢、C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基或-CH2B基团;
A为未取代的芳香的或非芳香的单环或双环杂环基团或者-根据环系的取代可能性-其被选自如下的取代基1-5取代:卤素、C1-C3烷基、C1-C3烷氧基、卤代-C1-C3烷基、C1-C3-卤代烷氧基、环丙基、卤代环丙基、C2-C3链烯基、C2-C3炔基、C2-C3卤代链烯基和C2-C3卤代炔基、C1-C3烷硫基、C1-C3卤代烷硫基、烯丙氧基、炔丙氧基、烯丙硫基、炔丙硫基、卤代烯丙氧基、卤代烯丙硫基、氰基和硝基;和
B为苯基、3-吡啶基或噻唑基,它们可任选被1-3个选自如下的取代基取代:C1-C3烷基、C1-C3-卤代烷基、环丙基、卤代环丙基、C2-C3链烯基、C2-C3炔基、C1-C3烷氧基、C2-C3卤代链烯基、C2-C3卤代炔基、C1-C3-卤代烷氧基、C1-C3烷硫基、C1-C3卤代烷硫基、烯丙氧基、炔丙氧基、烯丙硫基、炔丙硫基、卤代烯丙氧基、卤代烯丙硫基、卤素、氰基和硝基
以及任选可能的它们的E/Z异构体、E/Z异构体混合物和/或互变异构体,在每种情况下均为游离或盐形式;
其中R1,R2和A如式(Ⅰ)中所定义,且
X为氧或硫;
式(Ⅰ)化合物可存在E/Z异构体,例如可存在下面两种异构体形式
相应地,下文中提及式(Ⅰ)化合物时应理解为也适用于相应的E/Z异构体,即使后者在每一情况下未特别提及。
相应地,上下文中提及式(Ⅰ)化合物时,应理解为也适用于相应的互变异构体,即使后者在每一情况下未特别提及。
式(Ⅰ)化合物,以及任选它们的E/Z异构体和互变异构体,可以以盐的形式存在。至少有一个碱性中心的式(Ⅰ)化合物,可以形成例如酸加成盐。例如与强无机酸,如无机酸:硫酸、磷酸或氢卤酸形成盐;与强有机酸,例如可任选被例如卤素取代的C1-C4链烷羧酸,如乙酸;例如任选不饱和的二元羧酸,如草酸、丙二酸、马来酸、富马酸或(邻)苯二甲酸;例如羟基羧酸,如抗坏血酸、乳酸、苹果酸、酒石酸或柠檬酸,或例如苯甲酸形成盐,或与有机磺酸;例如可任选被如卤素取代的C1-C4烷基或芳基磺酸;如甲磺酸或对甲苯磺酸形成盐,式Ⅰ化合物与所提到的类型的酸形成的盐优选在反应混合物的后处理中得到。
此外,具有至少一个酸性基团的式(Ⅰ)化合物可以与碱形成盐,与碱形成的合适的盐有例如金属盐,如碱金属盐或碱土金属盐,如钠、钾或镁盐;或与铵或有机胺,例如吗啉、哌啶、四氢吡咯;一、二、三-低级烷基胺,如乙基、二乙基、三乙基或二甲基丙胺;或与一、二、或三羟基低级烷基胺,例如单、二或三乙醇胺形成盐,而且,如果需要的话,可以形成相应的内盐。在本发明的范围内,优选可农用盐。上下文所提及式(Ⅰ)的游离化合物或其盐,应理解为也适用于式(Ⅰ)的相应盐或游离化合物,这也同样适用于式(Ⅰ)化合物及其盐的E/Z异构体和互变异构体,优选游离形式。
在式(Ⅰ)和式(Ⅱ)的定义中,单个通用术语应如下理解:
作为取代基的卤素原子为氟、氯,并且也可为溴和碘,优选氟、氯和溴,尤其是氯,这里卤素应理解为独立的取代基或如下取代基的一部分:卤代烷基、卤代烷硫基、卤代烷氧基、卤代环烷基、卤代链烯基、卤代炔基、卤代烯丙氧基或卤代烯丙硫基。作为取代基的烷基、烷硫基、链烯基、炔基和烷氧基可以是直链或支链的,烷基的例子有甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基或叔丁基,可提及的合适烷氧基尤其是甲氧基、乙氧基、丙氧基、异丙氧基或丁氧基和其异构体,烷硫基为例如甲硫基、乙硫基、异丙硫基、丙硫基或丁硫基异构体,如果作为取代基的烷基、烷氧基、链烯基、炔基或环烷基被卤素取代,它们可以是仅部分卤代或者甚至全卤代。上述提及的定义适用于卤素、烷基和烷氧基。这些基团的烷基部分的例子是被氟、氯和/或溴1-3取代的甲基,例如CHF2或CF3;被氟、氯和/或溴1-5取代的乙基,例如CH2CF3,CF2CF3,CF2CCl3,CF2CHCl2,CF2CHF2,CF2CFCl2,CF2CHBr2,CF2CHClF,CF2CHBrF或CClFCHClF;或被氟、氯和/或溴1-7取代的丙基或异丙基,例如CH2CHBrCH2Br,CF2CHFCF3,CH2CF2CF3或CH(CF3)2;或被氟、氯和/或溴1-9取代的丁基或其异构体,例如CF(CF3)CHFCF3或CH2(CF2)2CF3、2-氯环丙基或2,2-二氟环丙基、2,2-二氟乙烯基、2,2-二氯乙烯基、2-氯烷基、2,3-二氯乙烯基或2,3-二溴乙烯基。
如果所定义的烷基、烷氧基或环烷基被其它取代基取代,那么它们可被所列出的相同或不同取代基取代一次或多次。在被取代的基团中,优选还具有一个或两个其它取代基,作为取代基的环烷基为例如环丙基、环丁基、环戊基或环己烷基。链烯基和炔基含有不饱和碳-碳键,典型的代表是烯丙基、甲基烯丙基或炔丙基,还有乙烯基或乙炔基。烯丙氧基、炔丙氧基、烯丙硫基或炔丙硫基中的双键或三键与连接杂原子(氧或硫)位置之间优选被饱和碳原子分开。
为生产1,3-二取代的2-硝基胍,可以在单取代的2-硝基胍中进一步引入取代基(例如:通过烷基化引入),这些已经公开(例如参见EP专利申请0375907,0376279和0383091)。由于在这些反应中作为起始原料的单取代的2-硝基胍中存在三个活泼氢原子,前面提到的这类取代反应通常是没有选择性的,并得到不需要的取代产品。所提到的EP专利中请描述了通过单取代的硝基异硫脲与伯胺反应同时裂解硫醇制备1,3-二取代的2-硝基胍的方法。然而这些含有烷硫基离去基团并在该方法中建议用作起始化合物的硝基异硫脲的获得是比较困难的。
此外,EP-A-0483062中描述了一种制备式(Ⅰ)化合物的方法,其中水解三氮杂化合物,这种方法不能完全令人满意,特别是在环保方面。
可见上述制备式(Ⅰ)化合物的方法不能满足有关纯度和产率的要求,为此,有必要提供一种从易得的原料开始制备这些化合物的改进方法。
现在令人惊奇地发现,根据本发明的方法能满足这些要求。
根据本发明的水解方法优选在pH值为2或更低,常压和0-120℃,优选50-100℃的温度下进行。优选在无机酸,尤其是氢氯酸、氢溴酸、硫酸或磷酸,或在烷基羧酸、卤代烷基羧酸和磺酸的水溶液中进行操作,尤其是浓盐酸中进行操作。
所述反应在对反应组份呈惰性的溶剂或稀释剂中进行。合适的溶剂是,特别是醇例如甲醇、乙醇、丙醇和异丙醇,尤其是水。其它合适的溶剂为例如醚,如四氢呋喃和二氧六环以及其它对反应没有不利影响的溶剂。所述溶剂也可混合使用。式(Ⅱ)化合物的水解优选在水性介质或水与醇的混合物中进行。
根据本发明的方法优选用于生产这样的式(Ⅰ)化合物,其中杂环基团A是不饱和的并且通过作为环的一员的碳原子与该碱性物质(basic substance)相连。优选的基团A为吡啶基、噻唑基、四氢呋喃基、二氢呋喃基、呋喃基、n-氧化-吡啶基、噁唑基、异噁唑基、噻吩基、吗啉基、哌啶基、吡啶基和吡嗪基,最优选吡啶基、噻唑基、四氢呋喃基和n-氧化-吡啶基,尤其是3-吡啶基、2-卤代吡啶-5-基、2,3-二卤代吡啶-5-基、2-卤代噻唑-5-基,四氢呋喃-3-基、5-甲基-四氢呋喃-3-基、1-氧吡啶-3-基、1-氧-2-卤代-吡啶-5-基和1-氧-2,3-二卤代吡啶-5-基。
类似地还优选所述杂环A带有1-3个选自如下的取代基:卤素、C1-C3烷基、C1-C3卤代烷基、C1-C3卤代烷氧基和C1-C3烷氧基。
此外,优选生产这样的本发明式(Ⅰ)化合物:其中B为未取代或可以被1-2个选自卤素、C1-C3烷基、C1-C3卤代烷基、C1-C3卤代烷氧基和C1-C3烷氧基的取代基取代的苯基、吡啶基或噻唑基。
根据本发明生产式(Ⅰ)化合物中,这些是值得注意的,其中:R1为氢,R2为甲基、乙基、正丙基、正丁基、烯丙基、炔丙基或环丙基并且A为吡啶基、1-氧吡啶基、四氢呋喃基、噻唑基或为被1-3个选自卤素、C1-C3烷基、C1-C3卤代烷基、C1-C3卤代烷氧基和C1-C3烷氧基的取代基取代的吡啶基、1-氧吡啶基、四氢呋喃基或噻唑基。从这种意义上讲,各取代基如下定义的那些式(Ⅰ)化合物的生产也是有价值的,其中:
a)R1为氢
b)R2为甲基
c)A为2-氯吡啶-5-基、四氢呋喃-3-基、2-甲基-四氢呋喃-4-基或2-氯噻唑-5-基;和
d)X为氧
根据本发明生产的式(Ⅰ)化合物在虫害防治中是有价值的活性成分,并对哺乳动物、鱼、植物具有很好的耐受性。式(Ⅰ)化合物尤其适合于农业上的作物和观赏植物,尤其是棉花、蔬菜和果园、林场、存料和材料的保护以及卫生保健领域,特别是家养的或农场动物中存在的昆虫和蜱螨的防治。这些化合物对吮吸、损害植物的昆虫,尤其是蚜虫和叶蝉特别有效。可根据本发明生产的类型的具有杀虫活性的取代的2-硝基胍类化合物描述在例如EP专利申请376279、375907和383091中。
可以作为本发明制备方法的式(Ⅱ)的起始原料或起始产物,是部分已知的或可以通过已知方法生产,如果它们是新的,那么它们同样是本发明的目标。
表C:化合物通式
No. | R1 | R2 | X |
C.1C.2C.3C.4C.5C.6C.7C.8C.9C.10C.11C.12C.13C.14C.15 | HCH3HHCH3HHCH3C2H5C2H5HHHHH | HHHCH3CH3CH3C2H5C2H5C2H5HC2H5正丙基正丙基正丁基异丙基 | OOSOOSOOOOSOSOO |
表3:通式(Ⅱa)的化合物,其中A为
且R1,R2和X各与表C中的任一行相对应。
表4:通式(Ⅱa)的化合物,其中A为
且R1,R2和X各与表C中的任一行相对应。
表5:通式(Ⅱa)的化合物,其中A为
且R1,R2和X各与表C中的任一行相对应。
表7:通式(Ⅱa)的化合物,其中A为
且R1,R2和X各与表C中的任一行相对应。
表8:通式(Ⅱa)的化合物,其中A为
且R1,R2和X各与表C中的任一行相对应。
表9:通式(Ⅱa)的化合物,其中A为
且R1,R2和X各与表C中的任一行相对应。
制备实施例
实施例1:1-(2-氯吡啶-5-基甲基)-2-硝基-3-甲基-胍的制备
将4.0克5-(2-氯吡啶-5-基-甲基)-3-甲基-4-硝基亚胺基-全氢-1,3,5-噁二嗪和20毫升浓盐酸的混合物在80℃下搅拌2小时。反应混合物冷却至5℃,用浓苛性钠溶液调节到pH为约5,然后过滤,残余物与乙醚/乙酸乙酯(1∶1)混合并再过滤。这样就获得了标题化合物。
实施例2:1-(2-氯噻唑-5-基甲基)-2-硝基-3-甲基-胍的制备
将5.0克5-(2-氯噻唑-5-基-甲基)-3-甲基-4-硝基亚胺基-全氢-1,3,5-噁二嗪和20毫升浓盐酸的混合物在80℃下搅拌2小时。反应混合物冷却至5℃,用浓苛性钠溶液调节到pH为约5,然后过滤,残余物与乙醚/乙酸乙酯(1∶1,V∶V)混合并再过滤。这样就获得了标题化合物。
表13列出的下列化合物也可以用与上述实施例1和实施例2中的类似方法获得。c-propyl为环丙基。
表13:式(Ⅰ)化合物化合物号 A R1 R2
13.1 2-氯-吡啶-5-基 H H
13.2 2-氯-吡啶-5-基 H -CH3
13.3 2-氯-吡啶-5-基 H -C2H5
13.4 2-氯-吡啶-5-基 H -C3H7(n)
13.5 2-氯-吡啶-5-基 H 环丙基
13.6 2-氯-吡啶-5-基 H -C4H9(n)
13.7 2-氯-吡啶-5-基 H -CH(CH3)213.8 2-氯-吡啶-5-基 -CH3 -CH313.9 2-氯-吡啶-5-基 -C2H5 -CH313.10 2,3-二氯-吡啶-5-基 H H13.11 2,3-二氯-吡啶-5-基 H -CH313.12 2,3-二氯-吡啶-5-基 H -C2H513.13 2,3-二氯-吡啶-5-基 -CH3 -CH313.14 2,3-二氯-吡啶-5-基 -C2H5 -CH313.15
H H13.16
H -CH313.17
H -C2H513.18
H 环丙基13.19
H 环丙基13.20
-CH3 -CH313.21 2-氯-噻唑-5-基 H H13.22 2-氯-噻唑-5-基 H -CH313.23 2-氯-噻唑-5-基 -CH3 -CH313.24 2-氯-噻唑-5-基 -C2H5 -CH313.25 2-氯-噻唑-5-基 H -C2H513.26 2-氯-噻唑-5-基 H 环丙基13.27 2-氯-噻唑-5-基 -CH3 环丙基13.28 四氢呋喃-3-基 H H13.29 四氢呋喃-3-基 H -CH313.30 四氢呋喃-3-基 H -C2H513.31 四氢呋喃-3-基 H 环丙基13.32 四氢呋喃-3-基 -CH3 -C2H513.33 四氢呋喃-3-基 -CH3 环丙基13.34 5-甲基-四氢呋喃-3-基 H H13.35 5-甲基-四氢呋喃-3-基 H -CH313.36 5-甲基-四氢呋喃-3-基 H -C2H513.37 5-甲基-四氢呋喃-3-基 H 环丙基13.38 5-甲基-四氢呋喃-3-基 -CH3 -CH3
Claims (11)
1制备式(Ⅰ)化合物的方法
其中:
R1为氢或C1-C4烷基;
R2为氢、C1-C6烷基、C2-C6链烯基、C2-C6炔基、C3-C6环烷基或-CH2B基团;
A为未取代的芳香或非芳香的单环或双环的杂环基团或者-根据环系的取代可能性-其被选自如下的取代基1-5取代:卤素、C1-C3烷基、C1-C3烷氧基、卤代-C1-C3烷基、C1-C3-卤代烷氧基、环丙基、卤代环丙基、C2-C3链烯基、C2-C3炔基、C2-C3卤代链烯基和C2-C3卤代炔基、C1-C3烷硫基、C1-C3卤代烷硫基、烯丙氧基、炔丙氧基、烯丙硫基、炔丙硫基、卤代烯丙氧基、卤代烯丙硫基、氰基和硝基;和
B为苯基、3-吡啶基或噻唑基,它们可任选被1-3个选自如下的取代基取代:C1-C3烷基、C1-C3-卤代烷基、环丙基、卤代环丙基、C2-C3链烯基、C2-C3炔基、C1-C3烷氧基、C2-C3卤代链烯基、C2-C3卤代炔基、C1-C3-卤代烷氧基、C1-C3烷硫基、C1-C3卤代烷硫基、烯丙氧基、炔丙氧基、烯丙硫基、炔丙硫基、卤代烯丙氧基、卤代烯丙硫基、卤素、氰基和硝基;
以及任选可能的它们的E/Z异构体、E/Z异构体混合物和/或互变异构体,在每种情况下均为游离或盐形式;
其中R1,R2和A如式(Ⅰ)中所定义,且X为氧或硫。
2.如权利要求1所述的制备游离形式的式(Ⅰ)化合物的方法。
3.如权利要求1或2所述的制备式(Ⅰ)化合物的方法,其中R1为H。
4.如权利要求1-3任一项所述的制备式(Ⅰ)化合物的方法,其中R2为氢、C1-C3烷基或环丙基。
5.如权利要求l-4任一项所述的制备式(Ⅰ)化合物的方法,其中A为2-氯吡啶-5-基、四氢呋喃-3-基、5-甲基-四氢呋喃-3-基或2-氯噻唑-5-基。
6.如权利要求1-5任一项所述的制备式(Ⅰ)化合物的方法,所述式(Ⅰ)化合物由其中X为氧的式(Ⅱ)化合物制备。
7.如权利要求1-6任一项所述的方法,其特征在于使用无机酸。
8.如权利要求1-7任一项所述的方法,其特征在于该方法在水、醇或水与醇的混合物中进行。
9.如权利要求1-8任一项所述的方法,其中温度为50-100℃。
10.如权利要求1-9任一项所述的方法,其特征在于该方法在pH低于2条件下进行。
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CN (1) | CN1293672A (zh) |
AU (1) | AU748713B2 (zh) |
BR (1) | BR9908864A (zh) |
CA (1) | CA2321678A1 (zh) |
HU (1) | HUP0102089A3 (zh) |
ID (1) | ID26225A (zh) |
IL (1) | IL138343A0 (zh) |
PL (1) | PL343270A1 (zh) |
WO (1) | WO1999047520A1 (zh) |
ZA (1) | ZA200004179B (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102344394A (zh) * | 2011-07-26 | 2012-02-08 | 河北克尔化工有限公司 | 硝基胍及其衍生物n-甲基硝基胍、噁二嗪的制备方法 |
CN109053747A (zh) * | 2018-08-30 | 2018-12-21 | 广州大学 | 一种化合物及其制备方法和应用 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
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IE71183B1 (en) | 1988-12-27 | 1997-01-29 | Takeda Chemical Industries Ltd | Guanidine derivatives their production and insecticides |
TW198724B (zh) | 1990-10-24 | 1993-01-21 | Ciba Geigy Ag | |
JP3159859B2 (ja) * | 1994-02-09 | 2001-04-23 | 日本バイエルアグロケム株式会社 | 殺虫性ニトロ化合物 |
AU717868B2 (en) * | 1996-04-29 | 2000-04-06 | Syngenta Participations Ag | Pesticidal composition |
DE19712411A1 (de) | 1997-03-25 | 1998-10-01 | Bayer Ag | Verfahren zur Herstellung von 1,3-disubstituierten 2-Nitroguanidinen |
US6118007A (en) * | 1997-03-31 | 2000-09-12 | Mitsui Chemicals, Inc. | Preparation process of nitroguanidine derivatives |
IL133346A0 (en) * | 1997-06-09 | 2001-04-30 | Novartis Ag | Method for producing nitroguanidine derivatives |
CA2301172A1 (en) * | 1997-08-20 | 1999-02-25 | Peter Maienfisch | Method for the producing substituted-2-nitroguanidine derivatives |
-
1999
- 1999-03-17 JP JP2000536715A patent/JP2002506866A/ja active Pending
- 1999-03-17 WO PCT/EP1999/001781 patent/WO1999047520A1/en not_active Application Discontinuation
- 1999-03-17 AU AU35180/99A patent/AU748713B2/en not_active Ceased
- 1999-03-17 US US09/646,441 patent/US6518433B1/en not_active Expired - Fee Related
- 1999-03-17 CN CN99804095A patent/CN1293672A/zh active Pending
- 1999-03-17 KR KR1020007010324A patent/KR20010041996A/ko not_active Application Discontinuation
- 1999-03-17 ID IDW20001775A patent/ID26225A/id unknown
- 1999-03-17 HU HU0102089A patent/HUP0102089A3/hu unknown
- 1999-03-17 IL IL13834399A patent/IL138343A0/xx not_active IP Right Cessation
- 1999-03-17 CA CA002321678A patent/CA2321678A1/en not_active Abandoned
- 1999-03-17 EP EP99916827A patent/EP1068203A1/en not_active Withdrawn
- 1999-03-17 BR BR9908864-9A patent/BR9908864A/pt not_active Application Discontinuation
- 1999-03-17 PL PL99343270A patent/PL343270A1/xx not_active Application Discontinuation
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2000
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102344394A (zh) * | 2011-07-26 | 2012-02-08 | 河北克尔化工有限公司 | 硝基胍及其衍生物n-甲基硝基胍、噁二嗪的制备方法 |
CN109053747A (zh) * | 2018-08-30 | 2018-12-21 | 广州大学 | 一种化合物及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
HUP0102089A2 (hu) | 2001-10-28 |
JP2002506866A (ja) | 2002-03-05 |
HUP0102089A3 (en) | 2004-09-28 |
ZA200004179B (en) | 2001-04-25 |
AU748713B2 (en) | 2002-06-13 |
PL343270A1 (en) | 2001-08-13 |
ID26225A (id) | 2000-12-07 |
US6518433B1 (en) | 2003-02-11 |
WO1999047520A1 (en) | 1999-09-23 |
CA2321678A1 (en) | 1999-09-23 |
EP1068203A1 (en) | 2001-01-17 |
BR9908864A (pt) | 2000-11-21 |
AU3518099A (en) | 1999-10-11 |
KR20010041996A (ko) | 2001-05-25 |
IL138343A0 (en) | 2001-10-31 |
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