CN101155795B - 生产经取代的噻吩磺酰基异氰酸酯的方法 - Google Patents

生产经取代的噻吩磺酰基异氰酸酯的方法 Download PDF

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CN101155795B
CN101155795B CN2005800451560A CN200580045156A CN101155795B CN 101155795 B CN101155795 B CN 101155795B CN 2005800451560 A CN2005800451560 A CN 2005800451560A CN 200580045156 A CN200580045156 A CN 200580045156A CN 101155795 B CN101155795 B CN 101155795B
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T·格勒
J·斯托尔丁
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Bayer CropScience AG
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    • C07D333/00Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur 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
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    • C07D333/02Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur 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
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Abstract

本发明涉及生产通式(I)的化合物的方法,其中R1和R2具有说明书所描述的含义,该方法通过与光气,反应在没有碱而有一种或多种稀释剂以及任选地催化剂的存在下,生成式(II)的化合物,其中R1和R2具有说明书所描述的含义。

Description

生产经取代的噻吩磺酰基异氰酸酯的方法
本发明涉及一种生产2,4-二取代的噻吩-3-磺酰基异氰酸酯的新方法,所述物质作为农用有效成分,特别是经取代的有除草活性的噻吩氨基羰基三唑啉酮(参见WO 01/05788)和磺酰脲(WO 01/10863)的中间产物。
已知一些经取代的噻吩磺酰基异氰酸酯可以在有机碱,特别是DABCO碱的条件下,通过光气由相应的磺酰胺生产(EP-A 30 142,US-A 4,481,029)。这种方法的缺点是,必须使用昂贵的有机碱。
根据本发明发现,以很好的产率生产这种特殊的经取代的2-烷基-4-烷氧羰基-二取代的噻吩-3-磺酰基异氰酸酯而没有形成值得一提的副产物、没有通常使用的碱是可行的。
据此发现,通式(I)的化合物可以很好的产率和高纯度获得,
Figure S2005800451560D00011
其中
R1为具有1至4个碳原子的烷氧基,且
R2为具有1至4个碳原子的烷基,
当式(II)的化合物
Figure S2005800451560D00012
其中,R1和R2具有上述含义,
在没有碱而有一种或多种稀释剂以及任选地催化剂的存在下,与光气反应。
在式(I)中,R1优选为甲氧基、乙氧基、正-或异-丙氧基。R2优选为甲基、乙基、正-或异-丙基。R1特别优选为甲氧基。R2特别优选为甲基。
在不使用有机碱的条件下,通过转化磺酰胺可以惊喜地发现一种反应时间短、以很好的产率和高纯度生产2,4-二取代的噻吩基-3-磺酰基异氰酸酯的新方法。
由此根据本发明的方法是对现有技术的丰富,因为它可以非常有利地生产2,4-二取代的噻吩基-3-磺酰基异氰酸酯。因此使基于这种中间产物的除草的噻吩氨基羰基三唑啉酮和磺酰脲的获得更容易。
式(II)的化合物是已知的并且可以按照WO01/05788所给出的方法或根据原则上已知的方法生产(参见,如:EP-A 30 412,US-A 4,481,029)。
在根据本发明的经取代的磺酰胺与光气的反应中,一般工作温度介于2 0℃和170℃,优选介于100℃和150℃,特别优选介于125℃和135℃。反应时的稀释剂优选使用任选卤化的芳香烃,例如氯苯、甲苯、二甲苯。二甲苯和氯苯是特别优选的稀释剂。
根据本发明的磺酰胺与光气的反应中,反应时间一般介于30分钟和6小时,优选介于2和4小时。
用于实施根据本发明的方法,用于生产式(I)的化合物优选使用等摩尔或过量的试剂。一般每摩尔式(II)的磺酰胺使用介于1.0和10摩尔,优选介于1.0和3摩尔的光气。但也可以根据本发明使用较多过量的光气。
根据本发明的方法一般在常压下进行,也可以在增压或减压下进行,一般介于0.1巴和10巴。
根据本发明的方法有利地在有一种催化剂的存在下进行。具有催化有效量的异氰酸丁酯或异氰酸戊酯可以作为催化剂使用。反应中,优选浓度为每摩尔磺酰胺0.1至5摩尔、优选0.7至1.3摩尔这种异氰酸酯。
依据其性质,经取代的磺酰胺也与作为催化剂使用的异氰酸酯反应生成相应的脲类。该脲类同样地可以在第二步骤中与光气反应生成相应的异氰酸酯。
根据本发明的方法获得的式(I)的化合物可以在用作生产除草终产物之前分离。所获得的化合物也可以不经过中间分离直接转化。基至优选,为生产除草的噻吩基磺酰胺基氨基羰基三唑啉酮,将所获得的式(I)的化合物直接与胺类(例如,三唑啉酮)反应。
因此根据本发明,还有一种方法,其中式(I)的化合物在下述反应步骤中不经中间分离而直接与三唑啉酮反应(“单罐法”,参见制备实施例3)。
制备实施例:
实施例1
Figure S2005800451560D00031
23.5克4-(氨基磺酰基)-5-甲基噻吩-3-羧酸甲酯(1)(100mmol)预置于250毫升二甲苯中。用水分离器可以从该混合物中蒸馏出大约70毫升的二甲苯。加入9.9克异氰酸正-丁酯(100mmol)后,将反应混合物加热至回流。经过三小时,随即通入24克光气,使温度保持在大约130℃(过量的光气会通过光气冷却器保留在系统中)。用于加工将反应物冷却至室温并将过量的光气通过氩气流除去。接着进行蒸馏提纯,其间回收异氰酸丁酯。经过蒸馏后,可在减压下得到呈无色固体的4-(异氰酸磺酰基)-5-甲基噻吩-3-羧酸甲酯(2)。获得22克的4-(异氰基磺酰基)-5-甲基噻吩-3-羧酸甲酯(2)(理论值的83%,含量:98%,沸点:120℃,0.4毫巴)。化合物鉴定和含量确定通过用甲醇衍生成相应的氨基甲酸酯进行。(1H NMR(400MHz,d6DMSO):2.72(s),3.61(s),3.79(s),8.00(s),11.96(s))。
实施例2
在上述条件下,将23.5克的4-(氨基磺酰基)-5-甲基噻吩-3-羧酸甲酯(1)与11.3克的异氰酸戊酯(100mmol)在光气的条件下转化成4-(异氰基磺酰基)-5-甲基噻吩-3-羧酸甲酯(2)。同样获得22克这种异氰酸酯(理论值的83%,含量:99%,沸点:120℃,0.4毫巴)。化合物鉴定和含量确定通过用甲醇衍生成相应的氨基甲酸酯进行。(1H NMR(400MHz,d6DMSO):2.72(s),3.61(s),3.79(s),8.00(s),11.96(s))。
实施例3
12.9克的5-甲氧基-4-甲基-2,4-二氢-3H-1,2,4-三唑-3-酮(3)(100mmol)预置于200毫升的二甲苯中并加温至70℃。在此温度下,将119克22%的4-(异氰基磺酰基)-5-甲基噻吩-3-羧酸甲酯(2)(100mmol)溶液计量加入干燥的二甲苯。在70℃的温度下,搅拌该混合物5.8小时。在室温下通过过滤所析出的产物进行加工。用50毫升二甲苯洗涤并随后干燥获得36.4克的4-({[3-甲氧基-4-甲基-5-氧代-4,5-二氢-1H-1,2,4-三唑-1-基]羰基}氨基)磺酰基)-5-甲基噻吩-3-羧酸甲酯(4)(理论值的91%,相对于标准含量:97.5%),熔点201℃。
第二步骤(分开地生产异氰酸酯和随即与胺类的反应)的可替代方法是,在去除光气(生产异氰酸酯)和馏去作为催化剂使用的异氰酸酯后,将从4-(异氰基磺酰基)-5-甲基噻吩-3-羧酸甲酯(2)的生产中产生的二甲苯溶液直接与胺类反应。去除作为催化剂使用的异氰酸酯对于成功地与胺类反应而言不是必须的。

Claims (5)

1.生产通式(I)的化合物的方法,
Figure FSB00000292301400011
其中
R1为具有1至4个碳原子的烷氧基,且
R2为具有1至4个碳原子的烷基,
且其中式(II)的化合物,
其中R1和R2具有上述的含义,
在没有碱而有一种或多种稀释剂以及任选地在催化有效量的异氰酸丁酯或异氰酸戊酯的存在下,与光气反应。
2.如权利要求1的方法,其特征在于,所述反应在介于100℃和150℃的温度下进行。
3.如权利要求1的方法,其特征在于,稀释剂选自溶剂氯苯或二甲苯。
4.如权利要求1至3中的任一项的方法,其特征在于,式(I)的化合物在后续反应步骤中,不经过中间分离而与胺反应。
5.如权利要求4的方法,其特征在于,所使用的胺是5-甲氧基-4-甲基-2,4-二氢-3H-1,2,4-三唑-3-酮。
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TWI668211B (zh) 2017-02-23 2019-08-11 德商拜耳作物科學公司 製備4-[(4,5-二氫-3-甲氧基-4-甲基-5-側氧-1h-1,2,4-三唑-1-基)羰基)胺磺醯基]-5-甲基噻吩-3-羧酸甲酯之方法
CN112552214A (zh) * 2020-12-09 2021-03-26 安徽广信农化股份有限公司 一种提高磺酰基异氰酸酯品质的生产工艺

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BRPI0519785A2 (pt) 2009-03-17
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