CN115073291A - 调环酸钙生产中间体丙酮基丁二酸二乙酯的生产工艺 - Google Patents
调环酸钙生产中间体丙酮基丁二酸二乙酯的生产工艺 Download PDFInfo
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Abstract
调环酸钙生产中间体丙酮基丁二酸二乙酯的生产工艺,包括以下步骤:步骤1:在室温下向低温混合釜内加入丙酮、顺丁烯二酸二乙酯,再加入苄胺作为催化剂以及N,N‑二甲基甲酰胺;步骤2:将步骤1所得混合物料经原料泵泵入带蒸汽夹套的管式反应器;步骤3:将步骤2中管式反应器内反应结束后的母液打入蒸馏釜进行常压蒸馏,将丙酮蒸出;步骤4:升温进行减压蒸馏,收集蒸馏出的馏出液,得到丙酮基丁二酸酯。本发明提供了一种丙酮基丁二酸二乙酯的生产工艺,其反时间短,可以连续生产,可明显减少调环酸钙的生产时间,提高生产效率,降低生产成本。
Description
技术领域
本发明涉及一种用于调环酸钙生产的中间体丙酮基丁二酸二乙酯的生产工艺,属于农药生产技术领域。
背景技术
调环酸钙的化学名称为3,5一二氧代一4一丙酰基环己烷羧酸钙,其结构式为,是日本组合化学工业公司1983首先开发合成的一种新型的植物生长抑制剂,主要用于控制禾谷类作物生长,能缩短作物的茎杆长度,又能增强植株的抗病害、抗寒冷、抗逆性能力,具有明显的抗倒伏作用。调环酸钙的工业生产路线目前通常采用以马来酸二乙酯做为起始原料,与丙酮在高压反应釜中进行Michael加成得到丙酮基丁二酸二乙酯;丙酮基丁二酸二乙酯再通过Claisen缩合反应得到3-羟基-5-乙氧羰基-环己-2-烯-1-酮;3-羟基-5-乙氧羰基-环己-2-烯-1-酮经过缩合、重排后生成3,5.二氧代-4-丙酰基环己烷羧酸乙酯;3,5.二氧代-4-丙酰基环己烷羧酸乙酯经水解并酸化后制得调环酸,调环酸与氢氧化钙反应获取最终产品调环酸钙。
发明内容
本发明的目的在于:提供一种丙酮基丁二酸二乙酯的生产工艺,其反时间短,可以连续生产,可明显减少调环酸钙的生产时间,提高生产效率,降低生产成本。
为实现以上目的,本发明采用的技术方案为: 调环酸钙生产中间体丙酮基丁二酸二乙酯的生产工艺,包括以下步骤:
步骤1:在室温下向低温混合釜内加入丙酮、顺丁烯二酸二乙酯,再加入苄胺作为催化剂以及N,N-二甲基甲酰胺,在低温下搅拌均匀;
步骤2:将步骤1所得混合物料经原料泵泵入带蒸汽夹套的管式反应器,泵入物料前管式反应器的蒸汽夹套通入蒸汽开始预热,物料泵入管式反应器后持续加热至物料温度达到110℃以上;
步骤3:将步骤2中管式反应器内反应结束后的母液打入蒸馏釜进行常压蒸馏,将丙酮蒸出;
步骤4:步骤3常压蒸馏无液体馏出后,开始升温进行减压蒸馏,收集蒸馏出的馏出液,得到丙酮基丁二酸酯;
进一步的,步骤1中丙酮:顺丁烯二酸二乙酯:苄胺:N,N-二甲基甲酰胺的投料摩尔比为1:8-10:0.02-0.06:0.02-0.06;
进一步的,步骤1中,低温混合釜内的温度控制在5-15℃之间;步骤2中,管式反应器内反应温度控制在110-150℃之间;步骤3中,常压蒸馏温度在56-58℃,将丙酮蒸出;步骤4中,减压蒸馏釜内真空度为11-18mmHg,收集125-130℃的馏份为丙酮基丁二酸二乙酯成品;
进一步的,步骤2中,管式反应器为盘管式管式反应器,物料通过盘管式管式反应器的时间在3-5hour之间。
本发明的积极有益技术效果在于:本发明在顺丁烯二酸二乙酯与丙酮的Michael加成反应中使用苄胺作为催化剂,并加入N,N-二甲基甲酰胺作为辅助溶剂,使得反应条件更为温和,并且正向反应速度加大,可以使用管式反应器作为反应容器进行连续反应,大大减少了反应时间及反应能耗,提高了生产效率及经济效益。
具体实施方式
为了更充分的解释本发明的实施,提供本发明的实施实例,这些实施实例仅仅是对本发明的阐述,不限制本发明的范围。
实施例:
向混合釜夹套内通入冷盐水使釜内温度降至10℃以下,向混合釜中加入160L(1000mol)的顺丁烯二酸二乙酯和590L(8000mol)丙酮,再加入5.5L(50mol)的苄胺,3.9L(50mol)的N,N-二甲基甲酰胺,开启搅拌将物料搅拌均匀;将搅拌均匀后的物料泵入盘管式反应器,升温开始反应,本实施例中,盘管式反应器反应管长度为50m,调节反应器出口流量使反应釜内物料流速为12.5m/hour,反应器出口的反应母液泵入蒸馏釜,在57℃左右温度进行蒸馏,至无液体馏出后,开始升温进行减压蒸馏,减压蒸馏真空度为15mmHg,收集128℃时的馏份,为黄色透明溶液丙酮基丁二酸酯,收率为92.3%,气相色谱检测得含量为94.2%。
本发明是发明人在寻找更合适的催化剂时,将苄胺及N,N-二甲基甲酰胺配合使用时发现该混合物对顺丁烯二酸二乙酯与丙酮的Michael加成反应具有更好的促进作用,从而可以采用管式反应器进行连续反应,替代了现有技术中的反应釜间隔式反应。本发明以苄胺替代了现有技术中的乙二胺作为催化剂,并且加入N,N-二甲基甲酰胺作为丙酮之外的补充溶剂,使得反应温度从150度降至110度左右即可反应,并且反应时间也从24小时以上缩短至5小时以内,这种加速作用机理尚不完全明确,发明人初步判断苄胺虽然与乙二胺同为脂肪胺的一种,但相较于乙二胺多了苯环结构,在加成反应中提供了更稳定的碳负离子,并且作为比丙酮更强的强极性溶剂,N,N-二甲基甲酰胺在Michael加成反应体系中增大了碳负离子和羰基周围的立体阻碍,使1,2-加成的竞争趋向最小,作为弱有机碱,N,N-二甲基甲酰胺应该也作为催化剂参与了反应,其同苄胺共同作用促进了加成反应的速度。
在详细说明本发明的实施方式之后,熟悉该项技术的人士可清楚地了解,在不脱离上述申请专利范围与精神下可进行各种变化与修改,凡依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均属于本发明技术方案的范围,且本发明亦不受限于说明书中所举实例的实施方式。
Claims (4)
1.调环酸钙生产中间体丙酮基丁二酸二乙酯的生产工艺,其特征在于:包括以下步骤:
步骤1:在室温下向低温混合釜内加入丙酮、顺丁烯二酸二乙酯,再加入苄胺作为催化剂以及N,N-二甲基甲酰胺,在低温下搅拌均匀;
步骤2:将步骤1所得混合物料经原料泵泵入带蒸汽夹套的管式反应器,泵入物料前管式反应器的蒸汽夹套通入蒸汽开始预热,物料泵入管式反应器后持续加热至物料温度达到110℃以上;
步骤3:将步骤2中管式反应器内反应结束后的母液打入蒸馏釜进行常压蒸馏,将丙酮蒸出;
步骤4:步骤3常压蒸馏无液体馏出后,开始升温进行减压蒸馏,收集蒸馏出的馏出液,得到丙酮基丁二酸酯。
2.根据权利要求1所述的调环酸钙生产中间体丙酮基丁二酸二乙酯的生产工艺,其特征在于:步骤1中丙酮:顺丁烯二酸二乙酯:苄胺:N,N-二甲基甲酰胺的投料摩尔比为1:8-10:0.02-0.06:0.02-0.06。
3.根据权利要求1所述的调环酸钙生产中间体丙酮基丁二酸二乙酯的生产工艺,其特征在于:步骤1中,低温混合釜内的温度控制在5-15℃之间;步骤2中,管式反应器内反应温度控制在110-150℃之间;步骤3中,常压蒸馏温度在56-58℃,将丙酮蒸出;步骤4中,减压蒸馏釜内真空度为11-18mmHg,收集125-130℃的馏分为丙酮基丁二酸二乙酯成品。
4.根据权利要求1所述的调环酸钙生产中间体丙酮基丁二酸二乙酯的生产工艺,其特征在于:步骤2中,管式反应器为盘管式管式反应器,物料通过盘管式管式反应器的时间在3-5hour之间。
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JPH0558996A (ja) * | 1990-12-25 | 1993-03-09 | Chugai Pharmaceut Co Ltd | 新規な3,5−シクロヘキサンジオン−1−カルボン酸エステル類 |
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JPH0558996A (ja) * | 1990-12-25 | 1993-03-09 | Chugai Pharmaceut Co Ltd | 新規な3,5−シクロヘキサンジオン−1−カルボン酸エステル類 |
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