WO2021103614A1 - 一种n-双(二甲胺基)-1,3-二甲基咪唑啉制备方法及用途 - Google Patents

一种n-双(二甲胺基)-1,3-二甲基咪唑啉制备方法及用途 Download PDF

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WO2021103614A1
WO2021103614A1 PCT/CN2020/104736 CN2020104736W WO2021103614A1 WO 2021103614 A1 WO2021103614 A1 WO 2021103614A1 CN 2020104736 W CN2020104736 W CN 2020104736W WO 2021103614 A1 WO2021103614 A1 WO 2021103614A1
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bis
dimethylamino
dimethyl
reaction
dimethylimidazoline
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PCT/CN2020/104736
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French (fr)
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钱继东
黄定乾
盛蕊
闫伟伟
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济宁康盛彩虹生物科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D233/44—Nitrogen atoms not forming part of a nitro radical
    • C07D233/52—Nitrogen atoms not forming part of a nitro radical with hetero atoms directly attached to said nitrogen atoms
    • 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
    • B01J31/0237—Amines
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/46—C-H or C-C activation

Definitions

  • the invention relates to the field of preparation methods and uses of compounds, in particular to a preparation method and uses of N-bis(dimethylamino)-1,3-dimethylimidazoline.
  • the reaction is a heterogeneous reaction
  • a phase transfer catalyst needs to be added as a medium for the transfer of F- in the solid-liquid two-phase to increase the solubility of F- in the liquid phase. Promote the fluorination reaction. Due to the electricity absorption of the cyano group, the ortho-para position chlorine atom of the benzene ring is easier to fluorinate, but the meta-substituted chlorine atom is inert and difficult to activate the fluorination. It needs a higher temperature to proceed.
  • Ordinary phase transfer catalysts Low catalytic activity, poor temperature resistance, easy to decompose at high temperature, resulting in excessively high temperature for fluorination, slow reaction rate, long time at high temperature, resulting in serious polymerization, dehalogenation, and coking, and fluorinated reaction yield Low energy consumption in the production process and serious pollution.
  • Common phase transfer catalysts include: quaternary ammonium salts, quaternary phosphonium salts, crown ethers and polyethers.
  • the quaternary ammonium salt will decompose when the temperature is slightly higher, and cannot play the role of catalyzing fluorination at higher temperatures.
  • the thermal stability of quaternary phosphonium salt and crown ether is better than that of quaternary ammonium salt, the catalytic activity is not high.
  • the substitution effect of chlorine on the meta position is small at high temperature.
  • the present invention produces a novel phase transfer catalyst, which is suitable for the synthesis of aromatic fluorine-containing compounds that are difficult to fluorinate. It is a preparation method of phase transfer catalyst N-bis(dimethylamino)methylene-1,3-dimethyl-2-chloroimidazoline ammonium chloride with good high temperature thermal stability and high activity .
  • a N-bis(dimethylamino) -1,3-Dimethylimidazoline is characterized in that its chemical formula is: C 9 H 23 N 5 ; its chemical molecular structure is:
  • a preparation method of N-bis(dimethylamino)-1,3-dimethylimidazoline which is characterized in that it comprises the following steps:
  • N-bis(dimethylamino)-1,3-dimethylimidazoline which is characterized in that it is used as a catalyst.
  • the said is suitable for use as a catalyst in the synthesis of aromatic fluorine-containing compounds which are difficult to fluorinate.
  • N-bis(dimethylamino)methylene-1,3-dimethyl-2-chloroimidazoline ammonium chloride salt is a novel phase transfer catalyst, which has high temperature With good thermal stability and high activity, it is especially suitable for the synthesis of aromatic fluorine-containing compounds that are difficult to fluorinate.
  • the use of the catalyst for fluorination reaction can reduce the reaction temperature and shorten the reaction time (less than 10 hours), thereby reducing polymerization, dehalogenation and coking phenomena, increasing the product yield (90%), and reducing environmental protection pressure to the greatest extent.
  • the catalyst has high activity, which can effectively reduce the reaction temperature and shorten the reaction time, thereby reducing the phenomenon of polymerization, dehalogenation, and coking, increasing the product yield, reducing environmental protection pressure to the greatest extent and reducing production costs.
  • This compound is a phase transfer catalyst N-bis(dimethylamino)methylene-1,3-dimethyl-2-chloroimidazoline ammonium chloride with good high temperature thermal stability and high activity, and its preparation Method Preparation method: firstly take 1,3-dimethyl-2-imidazoline and bis(trichloromethyl) carbonate as raw materials, carry out chlorination reaction to synthesize chloro 1,3-dimethyl-2-chloroimidazole Then, tetramethylguanidine was added dropwise to the resulting chloride salt, and the condensation reaction was carried out, and then the neutralization reaction was carried out to obtain N-bis(dimethylamino)methylene-1,3-dimethyl-2- Chlorimidazoline ammonium chloride salt.
  • This process uses bis(trichloromethyl) carbonate as the chlorinating reagent to replace oxalyl chloride, highly toxic phosgene, diphosgene, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and other chlorinating reagents.
  • the source greatly reduces the safety and environmental hazards of catalyst synthesis, and effectively solves the problem that phosgene is difficult to accurately quantify in the reaction process, and phosphoric acid is generated in the reaction of phosphorus-containing chlorinating reagents, which makes the reaction unable to proceed fully and product separation is difficult. The problem.
  • the purity of the reaction product is as high as 99%, and it can be used in the halogen exchange reaction of aromatic fluorine-containing compounds that are difficult to fluorinate.
  • the process has strong operability and mild reaction conditions. Except for the generation of high-content potassium chloride as a by-product, almost no other impurities are generated.
  • the process is safe, green and environmentally friendly, and the product has a good catalytic effect and a wide range of applications.
  • a kind of N-bis(dimethylamino)-1,3-dimethylimidazoline characterized in that: its chemical molecular formula is: C 9 H 23 N 5 ; chemical molecular structure is:
  • a preparation method of N-bis(dimethylamino)-1,3-dimethylimidazoline which is characterized in that it comprises the following steps:
  • N-bis(dimethylamino)-1,3-dimethylimidazoline which is characterized in that it is used as a catalyst.
  • the said is suitable for use as a catalyst in the synthesis of aromatic fluorine-containing compounds which are difficult to fluorinate.
  • Chlorination reaction pump 500 kg of toluene into the high tank, dissolve 200 kg of bis(trichloromethyl) carbonate, pump 200 kg of DMI into the reactor, add dropwise at 10-20 degrees, keep warm for 1 hour after dropping, and warm up To 40 degrees, keep for 5 hours, distill to recover toluene, and cool down. 284 kg of white crystalline product chloro 1,3-dimethyl-2-chloroimidazoline was obtained, the HPLC purity was 99.70%, and the yield was 96%.
  • Chlorination reaction pump 500 kg of toluene into the high tank, dissolve 200 kg of bis(trichloromethyl) carbonate, pump 200 kg of DMI into the reactor, add dropwise at 10-20 degrees, keep warm for 1 hour after dropping, and warm up To 40 degrees, keep for 5 hours, distill to recover toluene, and cool down. 287 kg of white crystalline product chloro 1,3-dimethyl-2-chloroimidazoline was obtained, the HPLC purity was 99.72%, and the yield was 97%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

本发明涉及化合物制备方法及用途领域，尤其是一种N-双(二甲胺基)-1,3-二甲基咪唑啉制备方法及用途，化学分子式为：C 9H 23N 5；制备方法包括如下步骤：S1：以1,3-二甲基-2-咪唑啉、双(三氯甲基)碳酸酯为原料，进行氯代反应合成氯代1,3-二甲基-2-氯咪唑啉；这既解决了其他氯代试剂的安全、环保问题，也极大的提高了产品收率(87％以上)。S2：向上述生成的氯盐中滴加四甲基胍，进行缩合反应；S3：再对上述产物进行中和反应，得N-双(二甲胺基)亚甲基-1，3-二甲基-2-氯咪唑啉氯化铵盐。本工艺可操作性强，反应条件温和，除生成高含量的氯化钾作为副产物外，几乎没有其他杂质生成，安全、绿色环保，产品催化效果好、适用范围广。

Description

一种N-双(二甲胺基)-1,3-二甲基咪唑啉制备方法及用途
技术领域
本发明涉及化合物制备方法及用途领域，尤其是一种N-双(二甲胺基)-1,3-二甲基咪唑啉制备方法及用途。
背景技术
在用卤交换法制备芳香族含氟化合物时，由于反应为非均相反应，需加入相转移催化剂，作为F-在固液两相传递的介质，增加F-在液相中的溶解度，从而促进氟化反应的进行。由于氰基的吸电性，使苯环的邻对位氯原子比较容易氟化，但间位取代氯原子呈现惰性，难以活化氟代，需要较高的温度才可以进行，普通的相转移催化剂催化活性低、耐温性能不好，高温下易分解，导致氟化需要过高的温度，反应速率慢、体系在高温下时间长，导致聚合、脱卤、焦化现象严重，氟代反应产率较低，生产过程能耗高，污染严重。
普通的相转移催化剂有：季铵盐、季磷盐、冠醚和聚醚等。季铵盐温度稍高时就会分解，无法起到较高温下催化氟化的作用，季磷盐、冠醚虽然热稳定性较季铵盐要好些，但催化活性不高，聚醚在较高温度下对间位上氯的取代作用很小。
在进行氯代反应时，早期以光气、双光气、草酰氯等为氯化试剂制备氯代1，3-二甲基-2-氯咪唑啉的方法，该三种方法收率低，而且光气、双光气剧毒，草酰氯为强腐蚀性液体，生产与运输都有很大的安全隐患。
也有以三氯化磷、五氯化磷、三氯氧磷等氯化试剂制备氯代1，3-二甲基-2-氯咪唑啉的报道，但此类试剂的使用使反应体系呈两相状态，并且反应中副产物磷酸的存在，至使反应难以充分进行，并且在产品分离时很困难。
发明内容
本发明为解决上述技术问题之一，本发明制造了一种新颖相转移催化剂，适用于较难氟代的芳香族含氟化合物的合成。其是，一种高温热稳定性好、活性高的相转移催化剂N-双(二甲胺基)亚甲基-1，3-二甲基-2-氯咪唑啉氯化铵盐的制备方法。旨在以一种绿色环保的方案，解决催化剂合成过程中的安全问题，同时高收率的获得高品质的相转移催化剂；所采用的技术方案是：一种N-双(二甲胺基)-1,3-二甲基咪唑啉，其特征在于：其化学分子式为：C 9H 23N 5；化学分子结构为：
Figure PCTCN2020104736-appb-000001
一种N-双(二甲胺基)-1,3-二甲基咪唑啉的制备方法，其特征在于：包括如下步骤：
S1：以1,3-二甲基-2-咪唑啉、双(三氯甲基)碳酸酯为原料，进行氯代反应合成氯代1,3-二甲基-2-氯咪唑啉；这既解决了其他氯代试剂的安全、环保问题，也极大的提高了产品收率(87％以上)。
S2：向上述生成的氯盐中滴加四甲基胍，进行缩合反应；
S3：再对上述产物进行中和反应，得N-双(二甲胺基)亚甲基-1，3-二甲基-2-氯咪唑啉氯化铵盐。
一种N-双(二甲胺基)-1,3-二甲基咪唑啉的用途，其特征在于：所述用作催化剂使用。
优选地，所述适用于较难氟代的芳香族含氟化合物的合成中作为催化剂使用。
本发明的有益效果体现在：N-双(二甲胺基)亚甲基-1，3-二甲基-2-氯咪唑啉氯化铵盐是一种新颖相转移催化剂，该催化剂有高温热稳定性好、活性高的特点，特别适用于较难氟代的芳香族含氟化合物的合成。使用本催化剂进行氟代反应，可以降低反应温度、缩短反应时间(10小时以下)，从而减少聚合、脱卤、焦化现象，提高了产品收率(90％)，最大限度地减轻环保压力。
1、以双(三氯甲基)碳酸酯为氯化试剂，避免了使用剧毒品光气、双光气、草酰氯、三氯化磷、五氯化磷、三氯氧磷等氯化试剂制备氯代1，3-二甲基-2-氯咪唑啉的不足。
2、以1,3-二甲基-2-咪唑啉、双(三氯甲基)碳酸酯、四甲基胍为原料，可操作性强，安全环保，经济效益高。获得的催化剂纯度高于99.5％，收率高于87％。
3、催化剂活性高，可以有效降低反应温度、缩短反应时间，从而减少聚合、脱卤、焦化现象，提高了产品收率，最大限度地减轻环保压力，降低生产成本。
本化合物是一种高温热稳定性好、活性高的相转移催化剂N-双(二甲胺基)亚甲基-1，3-二甲基-2-氯咪唑啉氯化铵盐，其制备方法制备方法：首先以1,3-二甲基-2-咪唑啉、双(三氯甲基)碳酸酯为原料，进行氯代反应合成氯代1,3-二甲基-2-氯咪唑啉，再向生成的氯盐中滴加四甲基胍，进行缩合反应，然后进行中和反应，得N-双(二甲胺基)亚甲基-1，3-二甲基-2-氯咪唑啉氯化铵盐。本工艺用双(三氯甲基)碳酸酯作为氯化试剂，替代草酰氯、剧毒 光气、双光气，三氯化磷、五氯化磷、三氯氧磷等氯化试剂，从源头上大大降低了催化剂合成的安全和环保隐患，并有效的解决了光气在反应过程中难以准确定量的问题，以及含磷氯化试剂反应中生成磷酸，使反应不能充分进行及产物分离困难的问题。反应产物纯度高达99％，可用于较难氟代的芳香族含氟化合物的卤交换反应。本工艺可操作性强，反应条件温和，除生成高含量的氯化钾作为副产物外，几乎没有其他杂质生成，安全、绿色环保，产品催化效果好、适用范围广。
具体实施方式
以下实施例仅用于更加清楚地说明本发明的技术方案，因此只作为示例，而不能以此来限制本发明的保护范围。
一种N-双(二甲胺基)-1,3-二甲基咪唑啉，其特征在于：其化学分子式为：C 9H 23N 5；化学分子结构为：
Figure PCTCN2020104736-appb-000002
一种N-双(二甲胺基)-1,3-二甲基咪唑啉的制备方法，其特征在于：包括如下步骤：
S1：以1,3-二甲基-2-咪唑啉、双(三氯甲基)碳酸酯为原料，进行氯代反应合成氯代1,3-二甲基-2-氯咪唑啉；这既解决了其他氯代试剂的安全、环保问题，也极大的提高了产品收率(87％以上)。
S2：向上述生成的氯盐中滴加四甲基胍，进行缩合反应；
S3：再对上述产物进行中和反应，得N-双(二甲胺基)亚甲基-1，3-二甲基-2-氯咪唑啉氯化铵盐。
一种N-双(二甲胺基)-1,3-二甲基咪唑啉的用途，其特征在于：所述用作催化剂使用。
优选地，所述适用于较难氟代的芳香族含氟化合物的合成中作为催化剂使用。
实施例1：
氯代反应：高位槽泵入500公斤甲苯，溶入双(三氯甲基)碳酸酯200公斤，反应釜内泵入DMI200公斤，在10-20度下滴加，滴完保温1小时，升温至40度，保持5小时，蒸馏回收甲苯，降温。得白色结晶产物氯代1,3-二甲基-2-氯咪唑啉284公斤，HPLC纯度99.70％，收率96％。
缩合反应：高位槽吸进二氯乙烷480公斤滴至上步氯代反应釜内，再滴加四甲基胍370公斤，控制釜内温度于40度下，滴完后，40度保温1小时，升温回收二氯乙烷，再滴加碱液，至反应液中性，离心得产品N-双(二甲胺基)亚甲基-1，3-二甲基-2-氯咪唑啉氯化铵盐462公斤，收率87.5％。
实施例2
氯代反应：高位槽泵入500公斤甲苯，溶入双(三氯甲基)碳酸酯200公斤，反应釜内泵入DMI200公斤，在10-20度下滴加，滴完保温1小时，升温至40度，保持5小时，蒸馏回收甲苯，降温。得白色结晶产物氯代1,3-二甲基-2-氯咪唑啉287公斤，HPLC纯度99.72％，收率97％。
缩合反应：高位槽吸进二氯乙烷480公斤滴至上步氯代反应釜内，再滴加四甲基胍370公斤，控制釜内温度于40度下，滴完后，40度保温1小时，升温回收二氯乙烷，再滴加碱液，至反应液中性，离心得产品N-双(二甲胺基)亚甲基-1，3-二甲基-2-氯咪唑啉氯化铵盐464公斤，收率87.9％。
以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围，其均应涵盖在本发明的权利要求和说明书的范围当中；对于本技术领域的技术人员来说，对本发明实施方式所做出的任何替代改进或变换均落在本发明的保护范围内。
本发明未详述之处，均为本技术领域技术人员的公知技术。

Claims (4)

  1. 一种N-双(二甲胺基)-1,3-二甲基咪唑啉，其特征在于：其化学分子式为：C 9H 23N 5；化学分子结构为：
    Figure PCTCN2020104736-appb-100001
  2. 一种N-双(二甲胺基)-1,3-二甲基咪唑啉的制备方法，其特征在于：包括如下步骤：
    S1：以1,3-二甲基-2-咪唑啉、双(三氯甲基)碳酸酯为原料，进行氯代反应合成氯代1,3-二甲基-2-氯咪唑啉；这既解决了其他氯代试剂的安全、环保问题，也极大的提高了产品收率(87％以上)。
    S2：向上述生成的氯盐中滴加四甲基胍，进行缩合反应；
    S3：再对上述产物进行中和反应，得N-双(二甲胺基)亚甲基-1，3-二甲基-2-氯咪唑啉氯化铵盐。
  3. 一种N-双(二甲胺基)-1,3-二甲基咪唑啉的用途，其特征在于：所述用作催化剂使用。
  4. 根据权利要求3所述的一种N-双(二甲胺基)-1,3-二甲基咪唑啉的用途，其特征在于：所述适用于较难氟代的芳香族含氟化合物的合成中作为催化剂使用。
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