CN110818601A - 一种硝磺草酮的制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title abstract description 6
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 33
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- 238000007599 discharging Methods 0.000 claims abstract description 17
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 17
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/18—Salts thereof
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
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- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
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Abstract
本发明公开了一种硝磺草酮的制备方法，包括以下步骤：将100重量份2‑硝基‑4‑甲磺酰基苯甲酰氯溶解在有机溶剂中，加入150～170重量份1,3‑环己二酮后均匀滴加150～160重量份吡啶，进行酯化缩合；再加入30～40重量份4‑二甲氨基吡啶、2‑3重量份四丁基溴化铵以及150～180重量份吡啶的混合液进行重排反应，再加盐酸调至pH为1～2，分液水洗，加水蒸馏以回收二氯甲烷，然后放料、抽滤得粗品磺草酮；趁热将抽滤出的粗品磺草酮投入精制反应釜中，在50～55℃下搅拌20～40分钟，放料后抽滤，母液进甲醇蒸馏釜蒸馏精制以回收甲醇，将固体产物经干燥、气流粉碎后得硝磺草酮成品。该方法提高了产品的收率和纯度，还避免了使用三乙胺造成的水体污染。
Description
技术领域
本发明属于有机化学领域，具体涉及一种硝磺草酮的制备方法。
背景技术
硝磺草酮作用靶标为对羟基苯基丙酮酸双氧化酶(HPPD)，主要用于防除玉米田的阔叶杂草和禾本科杂草，具有除草谱广、环境相容性好、对哺乳动物和水生生物毒性很低，对玉米十分安全及对后茬轮作作物无药害等特性，具有很大的市场需求和良好的应用前景。此外，硝磺草酮防除抗三氮苯与抗磺酰脲的杂草特别有效，杂草在它与这些类型除草剂之间不存在交互抗性，这就给轮作中除草剂品种选择提供了便利。在硝磺草酮的生产工艺中，会产生大量的碱性有机废水，这些碱性有机废水中含有大量的三乙胺，若直接排放至河流中，会对河流中的鱼虾造成严重影响。
发明内容
针对现有技术中存在的问题，本发明提供一种硝磺草酮的制备方法，避免了使用三乙胺带来的环境污染，同时提高了产品的纯度和产率。
本发明提供的技术方案具体如下：
一种硝磺草酮的制备方法，包括以下步骤：
将100重量份2-硝基-4-甲磺酰基苯甲酰氯溶解在有机溶剂中，投入150～170重量份1,3-环己二酮，均匀滴加150-160重量份吡啶进行酯化缩合；再加入30-40重量份4-二甲氨基吡啶、2-3重量份四丁基溴化铵以及150～180重量份吡啶的混合液进行重排反应，再加盐酸调至pH为1～2，分液水洗，加水蒸馏以回收二氯甲烷，然后放料、抽滤得粗品磺草酮；趁热将抽滤出的粗品磺草酮投入精制反应釜中，在50～55℃下搅拌20～40分钟，放料后抽滤，母液进甲醇蒸馏釜蒸馏精制以回收甲醇，将固体产物经干燥、气流粉碎后得硝磺草酮成品。
在上述技术方案的基础上，有机溶剂为二氯甲烷。
在上述技术方案的基础上，相转移剂为四丁基溴化铵。
在上述技术方案的基础上，酯化缩合的温度为至15～40℃，时间为60-80分钟。
在上述技术方案的基础上，重排反应的温度为50℃，时间为30分钟酯化缩合的温度为至15～40℃，时间为60-80分钟。
与现有技术相比，本发明具有以下优点和有益效果：
(1)本发明采用弱碱性的吡啶替代传统的三乙胺，吡啶与2-硝基-4-甲磺酰基苯甲酰氯和1,3-环己二酮的副产物HCl反应生成不易挥发的盐酸吡啶盐，避免了使用三乙胺带来的气体污染，吡啶盐酸盐用途较广，可直接销售，也较易回收变成吡啶。
(2)本发明采用4-二甲氨基吡啶和四丁基溴化铵替代剧毒的丙酮氰醇作为催化剂，提高了生产的安全性。
(3)本发明收率能达到91％以上，相对于现有技术提高了3个百分点。
具体实施方式
下面将结合本发明的实施例，对本发明的技术方案进行清楚和完整的描述。如无特别说明，所用的试剂和原材料都可通过商业途径购买。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
实施例1：硝磺草酮的生产工艺：
在硝化反应釜加入98％浓硫酸500重量份、对甲砜基甲苯350重量份及氧化含水母液1100重量份后，5小时内均匀滴加180重量份的98％硝酸进行硝化反应，滴加完毕后保温70min，得到硝化液；将硝化液导入氧化反应釜后再加入5重量份催化剂V2O5，升温至142℃后，在19小时内均匀滴加68％硝酸890重量份，同时控制反应温度为146℃；再在14.5小时内均匀滴加350重量份的50％硝酸，同时控制反应温度为144℃；滴加结束后保温1小时。将反应液降温至50℃，然后压滤得到氧化产物和氧化含水母液，用水1100重量份循环漂洗氧化产物；向氧化产物中加入NaOH溶液调pH值至9.0，以溶解氧化产物，在加入过程中控制温度为60℃；然后趁热放料离心，滴加盐酸调pH值至2，在温度60℃下保持30min，降温至35℃后离心、漂洗，即得精制的2-硝基-4-甲磺酰基苯甲酸；将其在55℃下干燥得到2-硝基-4-甲磺酰基苯甲酸；酰氯化：在酰氯化反应釜中加入氯化亚砜，再投入2-硝基-4-甲磺酰基苯甲酸、DMF以进行升温回流反应，反应11～12小时后蒸馏分离出氯化亚砜，得到2-硝基-4-甲磺酰基-苯甲酰氯。
对比例1
取100重量份2-硝基-4-甲磺酰基苯甲酰氯溶解在二氯甲烷中，降温至15℃，投入165重量份的1,3-环己二酮，在80min内均匀滴加175重量份三乙胺进行酯化缩合；再加入15重量份丙酮氰醇，滴加160重量份三乙胺进行重排反应，再加盐酸调至pH为1.0左右，分液水洗，加水蒸馏以回收二氯甲烷，然后放料、抽滤得粗品磺草酮；趁热将抽滤出的粗品磺草酮投入精制反应釜中，在55℃下搅拌40min，放料后抽滤，母液进甲醇蒸馏釜蒸馏精制以回收甲醇，将固体产物经干燥、气流粉碎后得硝磺草酮成品，得到的硝磺草酮产品纯度为98.15％，收率为88.08％。
实施例2
将100重量份2-硝基-4-甲磺酰基苯甲酰氯溶解在有机溶剂中，投入160重量份1,3-环己二酮，均匀滴加150-160重量份吡啶进行酯化缩合；再加入30重量份4-二甲氨基吡啶、2重量份四丁基溴化铵以及150重量份吡啶的混合液进行重排反应，再加盐酸调至pH为2，分液水洗，加水蒸馏以回收二氯甲烷，然后放料、抽滤得粗品磺草酮；趁热将抽滤出的粗品磺草酮投入精制反应釜中，在50℃下搅拌30分钟，放料后抽滤，母液进甲醇蒸馏釜蒸馏精制以回收甲醇，将固体产物经干燥、气流粉碎后得硝磺草酮成品。得到的硝磺草酮产品纯度为98.15％，收率为91.8％。
实施例3
将100重量份2-硝基-4-甲磺酰基苯甲酰氯溶解在有机溶剂中，投入150重量份1,3-环己二酮，均匀滴加150重量份吡啶进行酯化缩合；再加入40重量份4-二甲氨基吡啶、3重量份四丁基溴化铵以及180重量份吡啶的混合液进行重排反应，再加盐酸调至pH为2，分液水洗，加水蒸馏以回收二氯甲烷，然后放料、抽滤得粗品磺草酮；趁热将抽滤出的粗品磺草酮投入精制反应釜中，在50℃下搅拌30分钟，放料后抽滤，母液进甲醇蒸馏釜蒸馏精制以回收甲醇，将固体产物经干燥、气流粉碎后得硝磺草酮成品。得到的硝磺草酮产品纯度为98.2％，收率为92.5％。
实施例4
将100重量份2-硝基-4-甲磺酰基苯甲酰氯溶解在有机溶剂中，投入170重量份1,3-环己二酮，均匀滴加165重量份吡啶进行酯化缩合；再加入35重量份4-二甲氨基吡啶、2重量份四丁基溴化铵以及170重量份吡啶的混合液进行重排反应，再加盐酸调至pH为1，分液水洗，加水蒸馏以回收二氯甲烷，然后放料、抽滤得粗品磺草酮；趁热将抽滤出的粗品磺草酮投入精制反应釜中，在50℃下搅拌30分钟，放料后抽滤，母液进甲醇蒸馏釜蒸馏精制以回收甲醇，将固体产物经干燥、气流粉碎后得硝磺草酮成品，得到的硝磺草酮产品纯度为98.13％，收率为92.0％。
实施例5
将100重量份2-硝基-4-甲磺酰基苯甲酰氯溶解在有机溶剂中，投入140重量份1,3-环己二酮，均匀滴加155重量份吡啶进行酯化缩合；再加入35重量份4-二甲氨基吡啶、2重量份四丁基溴化铵以及170重量份吡啶的混合液进行重排反应，再加盐酸调至pH为1，分液水洗，加水蒸馏以回收二氯甲烷，然后放料、抽滤得粗品磺草酮；趁热将抽滤出的粗品磺草酮投入精制反应釜中，在50℃下搅拌30分钟，放料后抽滤，母液进甲醇蒸馏釜蒸馏精制以回收甲醇，将固体产物经干燥、气流粉碎后得硝磺草酮成品，得到的硝磺草酮产品纯度为98.13％，收率为92.6％。
上述对实施例的描述是为了便于本领域普通技术人员能理解和应用本发明。熟悉本领域技术人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其它实施例中而不必付出创造性的劳动。因此，本发明不限于这里的实施例，本领域技术人员根据本发明披露的内容，在不脱离本发明范围和精神的情况下做出的改进和修改都在本发明的范围之内。
Claims (5)
1.一种硝磺草酮的制备方法，其特征在于，包括以下步骤：将100重量份2-硝基-4-甲磺酰基苯甲酰氯溶解在有机溶剂中，加入150～170重量份1,3-环己二酮后均匀滴加150～160重量份吡啶，进行酯化缩合；再加入30～40重量份4-二甲氨基吡啶、2-3重量份相转移剂以及150～180重量份吡啶的混合液进行重排反应，再加盐酸调至pH为1～2，分液水洗，加水蒸馏以回收二氯甲烷，然后放料、抽滤得粗品硝磺草酮；趁热将抽滤出的粗品硝磺草酮投入精制反应釜中，在50～55℃下搅拌20～40分钟，放料后抽滤，母液进甲醇蒸馏釜蒸馏精制以回收甲醇，将固体产物经干燥、气流粉碎后得硝磺草酮成品。
2.根据权利要求1所述的硝磺草酮的制备方法，其特征在于：所述的有机溶剂为二氯甲烷。
3.根据权利要求1所述的硝磺草酮的制备方法，其特征在于：所述的相转移剂为四丁基溴化铵。
4.根据权利要求1所述的硝磺草酮的制备方法，其特征在于：酯化缩合的温度为至15～40℃，时间为60-80分钟。
5.根据权利要求1所述的硝磺草酮的制备方法，其特征在于：重排反应的温度为50℃，时间为30分钟。
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