CN1423650A - 制备杂环化合物的方法 - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 17
- SKCNYHLTRZIINA-UHFFFAOYSA-N 2-chloro-5-(chloromethyl)pyridine Chemical compound ClCC1=CC=C(Cl)N=C1 SKCNYHLTRZIINA-UHFFFAOYSA-N 0.000 claims abstract description 8
- VXLYOURCUVQYLN-UHFFFAOYSA-N 2-chloro-5-methylpyridine Chemical compound CC1=CC=C(Cl)N=C1 VXLYOURCUVQYLN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011541 reaction mixture Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 150000003840 hydrochlorides Chemical class 0.000 abstract 1
- 239000012749 thinning agent Substances 0.000 abstract 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
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- 238000003756 stirring Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 5
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- -1 benzylalcohol, secondary alcohol Chemical class 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 235000015320 potassium carbonate Nutrition 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- WTUAWWLVVCGTRG-UHFFFAOYSA-N 4,5-dihydro-1,3-thiazol-2-ylcyanamide Chemical compound N#CNC1=NCCS1 WTUAWWLVVCGTRG-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 230000006837 decompression Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- LFIAJUBCDMNWEC-UHFFFAOYSA-N 1-ethylidene-2-nitroguanidine Chemical class CC=NC(N)=N[N+]([O-])=O LFIAJUBCDMNWEC-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000004476 plant protection product Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
Abstract
本发明涉及制备式(I)化合物的方法,其中R1、A、D、X和Z如说明书中所定义,该方法通过式(II)化合物,其中A、D和X如上述定义,与碱在稀释剂存在下反应。然后将该反应混合物与CCMP/CMP(2-氯-5-氯甲基吡啶/2-氯-5-甲基吡啶)和相应的盐酸盐的混合物反应。
Description
本发明涉及制备已知杂环化合物的新的方法。
特别是可在醇中通过烷基化未取代的环原子制备不饱和的杂环化合物的制备是已知的(EP-A-259 738)。
在质子惰性溶剂中进行的烷基化反应同样是已知的(EP-A-259738)。
在这些情况下接下来需要对产物进行纯化,以达到足够的纯度,此外用这些已知方法得到的收率不能令人满意。
R3为氢原子或烷基,以及Z为任选取代的5-或6-元杂环基,其至少含有两个选自氧、硫和氮原子的杂原子,或为任选取代的3-或4-吡啶基,通过式(II)化合物其中A、D和X具有上面给出的含义,与碱在稀释剂存在下反应,且随后使该反应混合物与具有相应盐酸盐的CCMP/CMP(2-氯-5-氯甲基吡啶/2-氯-5-甲基吡啶)混合物反应。
令人惊奇的是按照本发明方法可较简单、用较少的反应步骤以及较高地收率制得上述化合物。
在通式(I)和(II)中变量R1优选表示氢或C1-C3-烷基,特别优选表示氢;A优选表示亚乙基或三亚甲基,其各自可被C1-C3-烷基取代,特别优选表示亚乙基;D为硝基或氰基,X优选为氧或硫原子或为基团特别优选为氧原子或基团Z优选表示卤代的5-或6-元杂环基,其含有两个选自氧、硫和氮原子的杂原子,或为卤代的3-或4-吡啶基,特别优选表示卤代噻唑基或3-吡啶基,最优选表示2-氯吡啶-5-基。
所用的溶剂是质子性和偶极质子惰性溶剂,尤其是水、醇类、酮类(优选MIHK)、酯类(优选乙酸丁酯)、腈类(优选乙腈、正丙腈、丁腈)、吡啶类(优选CMP)、酰胺类(DMF)、DMSO或碳酸酯类,或其与水的混合物。在使用醇类作为溶剂的情况下,可以直接得到用作植物保护剂使用有利的变体和必需纯度的式(I)化合物。
可以应用的醇类举例是:伯醇类如甲醇、乙醇、丙醇、丁醇、2-甲基-1-丙醇、1-戊醇、苄醇,仲醇类如异丙醇、仲丁醇、2-戊醇,叔醇类如叔丁醇。
作为溶剂特别优选与水不混溶或只部分混溶的醇类,如正丁醇、戊醇,特别是正丁醇或腈类,如正丙腈或丁腈,特别是正丙腈。
该方法任选在碱存在下进行,作为举例可提及的有:碱金属和碱土金属氢氧化物,如NaOH、KOH、Ca(OH)2,碱金属碳酸盐类或碳酸氢盐类,如Na2CO3、Li2CO3、K2CO3、Cs2CO3或NaHCO3和KHCO3。优选可提及K2CO3、NaOH和KHCO3,特别是K2CO3。
通式(II)化合物也可作为碱金属盐或碱土金属盐以固体或溶解形式应用。
当该方法在水、水-醇-或水-腈-混合物中进行时,pH范围为6-13。
作为催化剂可使用相转移催化剂,任选季铵卤化物,如溴化四丁基铵或氯化四丁基铵或Cs盐等。
该反应也可以如下进行:首先,通式(II)化合物任选作为碱金属或碱土碱金属盐存在并在碱存在下,在40℃-130℃,任选在减压下,优选在100-500mbar下加热,随后在50-90℃,任选在减压下,优选在60℃-80℃加入CCMP/CMP混合物。
该反应适当地在常压下进行,但也可以在减压或加压下进行。特别优选在减压下进行。
在该方法的实际实施中,例如1摩尔CCMP/CMP混合物与0.95-3摩尔,优选1.0-约2.5摩尔式(II)化合物在溶剂如丁醇中,在1-3摩尔,优选1.5-2.5摩尔碱,例如碳酸钾存在下和任选在催化剂如四丁基溴化铵或碳酸铯存在下反应。
如果在两相体系中使用水,优选在pH8-10进行。
反应时间为3-12小时,优选5-10小时。在反应结束后可任选更换溶剂。对此在减压(1-1000mbar)下蒸出大部分反应稀释剂并补充等量的上述稀释剂之一。溶剂的替换可以在水解前或后进行。
在50℃-100℃下水解反应的悬浮液并且在50℃-80℃分出有机相,冷却、分出沉淀的活性组分、洗涤并重结晶。
存在于母液中的CMP(温度范围50℃-130℃,压力范围1-1000mbar)可回收并循环回反应过程中:可将得到的母液与结晶稀释剂混合(1份母液/4份溶剂-1份母液/0.5份溶剂),冷却该悬浮液并过滤出沉淀的活性组分。
式(II)的原料是已知的和/或可按本身已知的方法制备(参见JACS
79,(1957),3565;Arch.Pharm.
305,(1972),731-736;Heterocycles
31(1990),1601-1604;Biosci.Biotechnol.Biochem.57,(1993),127-128;Biosci.Biotechnol.Biochem.
56,(1992),364-365)。
2-氯-5-氯甲基吡啶的制备类似于(EP-A-458109,EP-A-260485)公开的方法进行。在有机溶剂(乙腈、四氯化碳,控制pH的水)中用自由基引发剂(AIBN)在沸点下氯化2-氯-5-甲基吡啶。在约40%的转化率时终止该反应,以得到高选择性的2-氯-5-氯甲基吡啶。然后在减压下蒸馏有机溶剂。
在蒸馏有机溶剂之后得到含有5-15%的残余溶剂、30-50%的CMP和25-45%的具有相应盐酸盐的CCMP的CCMP/CMP混合物。
由2-氯-5-甲基吡啶和2-氯-5-氯甲基吡啶及相应的盐酸盐组成的混合物用作用于活性组分反应的加料。该混合物可以不稀释的形式或在稀释剂(该稀释剂也适合在活性组分反应中使用)中用于反应中。
式(I)化合物适合例如用作杀虫剂(EP A20235752,EP A20259738)。
下列实施例用于解释本发明的主题,并不构成对本发明的任何限制。实施例1
将0.615摩尔碳酸钾和0.3摩尔2-氰基亚氨基噻唑烷悬浮于100ml正丁醇中并在60℃搅拌1h。在2h内,在70℃下加入0.315摩尔2-氯-5-氯甲基吡啶/2-氯-5-甲基吡啶(CCMP/CMP,混合物中含23%的CCMP)的100ml正丁醇的悬浮液并在72℃下搅拌2h。冷却至65℃后加入400g水并将相分离,然后在50℃下搅拌该有机相3h,随后在-5℃下搅拌18h。过滤出沉淀的产物并干燥;59.6g(理论量的78%)。实施例2
将0.615摩尔碳酸钾和0.3摩尔2-氰基亚氨基噻唑烷悬浮于100ml正丁醇中并在60℃搅拌1h。在2h内,在70℃下加入0.315摩尔2-氯-5-氯甲基吡啶/2-氯-5-甲基吡啶(CCMP/CMP,混合物中含23%的CCMP)的100ml正丁醇的悬浮液并在72℃下搅拌2h。冷却至65℃后加入400g水并将相分离,然后在50℃下搅拌该有机相3h,随后在-5℃下搅拌18h。过滤出沉淀的产物并干燥;将该母液与丁醇1∶1混合并冷却至0℃,过滤出冷却期间沉淀出的固体并干燥:总产量66.1g(85%的分离出的产物)。实施例3
将0.3摩尔2-氰基亚氨基噻唑烷和4.2g溴化四丁基铵悬浮于300m水中并加热至70℃,加入0.315摩尔CMP/CCMP混合物,用NaOH连续调节反应混合物的pH值保持为8-8.5。在60℃下反应2h后在该温度下进行相分离,有机相用150ml丁醇稀释并搅拌。在3h内将混合物冷却至3℃并抽滤沉淀的产物:得到58.5g(理论量的76%)。实施例4
将1.5摩尔亚乙基硝基胍(含16.5%的H2O)加到600g正丙腈中并共沸蒸水,然后在95℃下加入342g碳酸钾(2.5摩尔),随后加入2g碳酸铯。在95-100℃下,在30分钟内加入521g CMP/CCMP(31%CCMP),在100-105℃反应5h后加入1.2升水,用HCl调节反应混合物的pH值保持在6-7。在180mbar下从有机相中蒸出丙腈,然后加入500g正丁醇并将该混合物加热到80℃,将相分离,将有机相冷却至0℃,过滤出沉淀的产物并干燥;187.4g(理论量的73%)。
Claims (1)
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DE10002049.6 | 2000-01-19 | ||
DE10002049 | 2000-01-19 |
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CN1423650A true CN1423650A (zh) | 2003-06-11 |
CN1182135C CN1182135C (zh) | 2004-12-29 |
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US (1) | US6667401B2 (zh) |
EP (1) | EP1252159B1 (zh) |
JP (1) | JP5078211B2 (zh) |
KR (1) | KR100740983B1 (zh) |
CN (1) | CN1182135C (zh) |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101503406B (zh) * | 2008-12-17 | 2011-03-23 | 武汉工程大学 | 1-(2,3-环氧丙基)-n-硝基亚咪唑烷-2-基胺及其制备方法和应用 |
CN107629045A (zh) * | 2017-11-10 | 2018-01-26 | 上海生农生化制品股份有限公司 | 一种噻虫啉的水相合成方法 |
CN109311866A (zh) * | 2016-06-06 | 2019-02-05 | 拜耳作物科学股份公司 | 用于制备杂环化合物的方法 |
Families Citing this family (1)
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JP2014525422A (ja) * | 2011-09-02 | 2014-09-29 | バイエル・インテレクチユアル・プロパテイー・ゲー・エム・ベー・ハー | [3−[(6−クロロ−3−ピリジニル)メチル]−2−チアゾリジニリデン]シアナミドを製造する方法 |
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ZW5085A1 (en) | 1984-04-13 | 1985-09-18 | Nihon Tokushu Noyaku Seizo Kk | Nitromethylene derivatives,intermediates thereof,processes for production thereof,and insecticides |
DE3681465D1 (zh) * | 1985-02-04 | 1991-10-24 | Nihon Bayer Agrochem K.K., Tokio/Tokyo, Jp | |
JPH0730070B2 (ja) * | 1985-10-03 | 1995-04-05 | 日本バイエルアグロケム株式会社 | 新規複素環式化合物 |
PH23283A (en) | 1986-02-26 | 1989-06-30 | Eisai Co Ltd | Piperidine derivative, pharmaceutical composition containing the same and method of use thereof |
US5179095A (en) | 1986-02-26 | 1993-01-12 | Eisai Co., Ltd. | Piperidine derivative and pharmaceutical composition containing the same |
JPH0717621B2 (ja) * | 1986-03-07 | 1995-03-01 | 日本バイエルアグロケム株式会社 | 新規ヘテロ環式化合物 |
DE3630046A1 (de) * | 1986-09-04 | 1988-03-17 | Bayer Ag | Verfahren zur herstellung von 5-chlormethylpyridinen |
JPH07121909B2 (ja) | 1986-09-10 | 1995-12-25 | 日本バイエルアグロケム株式会社 | 新規複素環式化合物及び殺虫剤 |
DE3830238A1 (de) * | 1988-09-06 | 1990-03-15 | Bayer Ag | Verfahren zur herstellung von 1-substituierten 2-(nitroimino)-1,3-diazacycloalkan-derivaten |
DE4016175A1 (de) | 1990-05-19 | 1991-11-21 | Bayer Ag | Seitenkettenchlorierung von alkylierten stickstoff-heteroaromaten |
DE19710613A1 (de) * | 1997-03-14 | 1998-09-17 | Bayer Ag | Verfahren zur Herstellung von 5-Aminomethyl-2-chlorpyridinen |
DE19904310A1 (de) * | 1999-01-28 | 2000-08-03 | Bayer Ag | Verfahren zur Herstellung heterocyclischer Verbindungen |
US6307053B1 (en) | 2000-12-29 | 2001-10-23 | Sinon Corporation | Process for preparing imidacloprid |
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2001
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101503406B (zh) * | 2008-12-17 | 2011-03-23 | 武汉工程大学 | 1-(2,3-环氧丙基)-n-硝基亚咪唑烷-2-基胺及其制备方法和应用 |
CN109311866A (zh) * | 2016-06-06 | 2019-02-05 | 拜耳作物科学股份公司 | 用于制备杂环化合物的方法 |
TWI750181B (zh) * | 2016-06-06 | 2021-12-21 | 德商拜耳作物科學股份有限公司 | 製造雜環化合物之方法 |
CN109311866B (zh) * | 2016-06-06 | 2022-12-09 | 拜耳作物科学股份公司 | 用于制备杂环化合物的方法 |
CN107629045A (zh) * | 2017-11-10 | 2018-01-26 | 上海生农生化制品股份有限公司 | 一种噻虫啉的水相合成方法 |
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