WO2021103614A1 - Procédé de préparation et d'utilisation de n-bis(diméthylamino)-1,3-diméthylimidazoline - Google Patents

Procédé de préparation et d'utilisation de n-bis(diméthylamino)-1,3-diméthylimidazoline Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
bis
dimethylamino
dimethyl
reaction
dimethylimidazoline
Prior art date
Application number
PCT/CN2020/104736
Other languages
English (en)
Chinese (zh)
Inventor
钱继东
黄定乾
盛蕊
闫伟伟
Original Assignee
济宁康盛彩虹生物科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 济宁康盛彩虹生物科技有限公司 filed Critical 济宁康盛彩虹生物科技有限公司
Publication of WO2021103614A1 publication Critical patent/WO2021103614A1/fr

Links

Classifications

    • 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%.

Landscapes

  • 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

La présente invention relève du domaine des procédés de préparation et des utilisations de composés, et concerne en particulier un procédé de préparation et d'utilisation de N-bis(diméthylamino)-1,3-diméthylimidazoline, ayant la formule chimique : C9H23N5. Le procédé de préparation comprend les étapes suivantes consistant à : S1 : Synthétiser du 1,3-diméthyl-2-chloroimidazoline chlorée à l'aide de 1,3-diméthyl-2-imidazoline et de bis(trichlorométhyl) carbonate comme matières premières pour une réaction de chloration, ce qui résout les problèmes de sécurité et de respect de l'environnement d'autres réactifs chlorés, et améliore également de manière considérable le rendement en produit (87 % ou plus) ; S2 : ajouter du tétraméthylguanidine goutte à goutte au sel de chlorure généré pour effectuer une réaction de condensation ; et S3 : réaliser une réaction de neutralisation sur le produit décrit pour obtenir du chlorure de N-bis(diméthylamino)méthylène-1,3-diméthyl-2-chloroimidazoline ammonium. Le présent procédé présente une bonne aptitude au fonctionnement, les conditions de réaction sont modérées, presque aucune autre impureté n'est générée à l'exception de la génération de chlorure de potassium à haute teneur en tant que sous-produit, le procédé est sûr et respectueux de l'environnement, l'effet catalytique du produit est bon, et la plage d'application est large.
PCT/CN2020/104736 2019-11-27 2020-07-27 Procédé de préparation et d'utilisation de n-bis(diméthylamino)-1,3-diméthylimidazoline WO2021103614A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201911178343.6 2019-11-27
CN201911178343.6A CN110845414A (zh) 2019-11-27 2019-11-27 一种n-双（二甲胺基）-1,3-二甲基咪唑啉制备方法及用途

Publications (1)

Publication Number Publication Date
WO2021103614A1 true WO2021103614A1 (fr) 2021-06-03

Family

ID=69604948

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/104736 WO2021103614A1 (fr) 2019-11-27 2020-07-27 Procédé de préparation et d'utilisation de n-bis(diméthylamino)-1,3-diméthylimidazoline

Country Status (2)

Country Link
CN (1) CN110845414A (fr)
WO (1) WO2021103614A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110845414A (zh) * 2019-11-27 2020-02-28 济宁康盛彩虹生物科技有限公司 一种n-双（二甲胺基）-1,3-二甲基咪唑啉制备方法及用途
CN115108971A (zh) * 2022-06-30 2022-09-27 杭州凯氟科技有限公司 一种2,3-二氟-5-氯吡啶的制备方法

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998030533A1 (fr) * 1997-01-14 1998-07-16 Ppg Industries Ohio, Inc. Procede de preparation de chloroformates alpha-chlores
WO2005007634A1 (fr) * 2003-07-18 2005-01-27 Frutarom Ltd. 3-hydroxy-4-oxo-1,2,3-triazines et leurs derives pour la formation de liaisons amide et ester
CN1718572A (zh) * 2004-07-08 2006-01-11 兰克赛斯德国有限公司 制备环－氟化的芳香族化合物的改进方法
CN1927842A (zh) * 2006-06-15 2007-03-14 渤海大学 氯代1,3－二甲基－2－氯咪唑啉的合成工艺
CN101268055A (zh) * 2005-09-17 2008-09-17 拜尔农作物科学股份公司 制备5-氟-1,3-二烷基-1h-吡唑-4-羰基氟化物的方法
CN102690214A (zh) * 2012-05-31 2012-09-26 泰兴市远东化工有限公司 一种3，4-二氟苯腈的工业化制备工艺
CN102702087A (zh) * 2012-05-31 2012-10-03 泰兴市远东化工有限公司 一种2，3-二氟-5-氯吡啶的合成方法
CN103539699A (zh) * 2013-10-30 2014-01-29 上海华谊（集团）公司 一种3，4-二氟苯腈的合成工艺
CN103934020A (zh) * 2013-01-22 2014-07-23 福建博特化学品有限责任公司 八取代的双胍盐作为氟甲基六氟异丙基醚的合成催化剂的应用及催化合成方法
CN104151196A (zh) * 2014-07-16 2014-11-19 上海华谊（集团）公司 2,3,4,5,6-五氟苯腈的制备方法
CN105693614A (zh) * 2014-11-28 2016-06-22 青岛首冠企业管理咨询有限公司 氯代1,3-二甲基-2-氯咪唑啉的合成工艺
CN107488098A (zh) * 2017-07-21 2017-12-19 淄博飞源化工有限公司 一种工业化制备2,3‑二氟三氟甲苯、3,4‑二氟苯腈的连续生产方法
CN107848963A (zh) * 2015-07-24 2018-03-27 和光纯药工业株式会社 具有耐酸性的产碱剂或/和自由基产生剂、以及含有该产碱剂或/和自由基产生剂的固化性树脂组合物
CN108409605A (zh) * 2018-03-30 2018-08-17 江苏丰山集团股份有限公司 一种3,4-二氟苯腈的制备方法
CN110804001A (zh) * 2019-11-27 2020-02-18 济宁康盛彩虹生物科技有限公司 一种3,4-二氟苯腈工艺生产方法
CN110845414A (zh) * 2019-11-27 2020-02-28 济宁康盛彩虹生物科技有限公司 一种n-双（二甲胺基）-1,3-二甲基咪唑啉制备方法及用途
CN111018755A (zh) * 2019-12-30 2020-04-17 江苏傲伦达科技实业股份有限公司 一种利用4，4’-二异丙氧基二苯砜制备4-羟基-4’-异丙氧基二苯砜的方法

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998030533A1 (fr) * 1997-01-14 1998-07-16 Ppg Industries Ohio, Inc. Procede de preparation de chloroformates alpha-chlores
WO2005007634A1 (fr) * 2003-07-18 2005-01-27 Frutarom Ltd. 3-hydroxy-4-oxo-1,2,3-triazines et leurs derives pour la formation de liaisons amide et ester
CN1718572A (zh) * 2004-07-08 2006-01-11 兰克赛斯德国有限公司 制备环－氟化的芳香族化合物的改进方法
CN101268055A (zh) * 2005-09-17 2008-09-17 拜尔农作物科学股份公司 制备5-氟-1,3-二烷基-1h-吡唑-4-羰基氟化物的方法
CN1927842A (zh) * 2006-06-15 2007-03-14 渤海大学 氯代1,3－二甲基－2－氯咪唑啉的合成工艺
CN102690214A (zh) * 2012-05-31 2012-09-26 泰兴市远东化工有限公司 一种3，4-二氟苯腈的工业化制备工艺
CN102702087A (zh) * 2012-05-31 2012-10-03 泰兴市远东化工有限公司 一种2，3-二氟-5-氯吡啶的合成方法
CN103934020A (zh) * 2013-01-22 2014-07-23 福建博特化学品有限责任公司 八取代的双胍盐作为氟甲基六氟异丙基醚的合成催化剂的应用及催化合成方法
CN103539699A (zh) * 2013-10-30 2014-01-29 上海华谊（集团）公司 一种3，4-二氟苯腈的合成工艺
CN104151196A (zh) * 2014-07-16 2014-11-19 上海华谊（集团）公司 2,3,4,5,6-五氟苯腈的制备方法
CN105693614A (zh) * 2014-11-28 2016-06-22 青岛首冠企业管理咨询有限公司 氯代1,3-二甲基-2-氯咪唑啉的合成工艺
CN107848963A (zh) * 2015-07-24 2018-03-27 和光纯药工业株式会社 具有耐酸性的产碱剂或/和自由基产生剂、以及含有该产碱剂或/和自由基产生剂的固化性树脂组合物
CN107488098A (zh) * 2017-07-21 2017-12-19 淄博飞源化工有限公司 一种工业化制备2,3‑二氟三氟甲苯、3,4‑二氟苯腈的连续生产方法
CN108409605A (zh) * 2018-03-30 2018-08-17 江苏丰山集团股份有限公司 一种3,4-二氟苯腈的制备方法
CN110804001A (zh) * 2019-11-27 2020-02-18 济宁康盛彩虹生物科技有限公司 一种3,4-二氟苯腈工艺生产方法
CN110845414A (zh) * 2019-11-27 2020-02-28 济宁康盛彩虹生物科技有限公司 一种n-双（二甲胺基）-1,3-二甲基咪唑啉制备方法及用途
CN111018755A (zh) * 2019-12-30 2020-04-17 江苏傲伦达科技实业股份有限公司 一种利用4，4’-二异丙氧基二苯砜制备4-羟基-4’-异丙氧基二苯砜的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FRANK WÜRTHNER ET AL.: "Synthesis and Optical and Electrochemical Properties of Core-Fluorinated Perylene Bisimides", ORGANIC LETTERS, vol. 8, no. 17, 25 July 2006 (2006-07-25), XP002430943, ISSN: 1523-7060, DOI: 10.1021/ol0613416 *
MARIELOUISE HENRICH ET AL.: "A new family of delocalized lipophilic cations", TETRAHEDRON LETTERS, vol. 44, no. 31,, 4 July 2003 (2003-07-04), XP004435077, ISSN: 0040-4039, DOI: 10.1016/S0040-4039(03)01422-9 *

Also Published As

Publication number Publication date
CN110845414A (zh) 2020-02-28

Similar Documents

Publication Publication Date Title
CN109970508B (zh) 1-氯-2,3,3-三氟丙烯的制造方法
WO2021103614A1 (fr) Procédé de préparation et d'utilisation de n-bis(diméthylamino)-1,3-diméthylimidazoline
JP2006022105A (ja) 含フッ素環芳香環の改善された製造方法
CN108069994B (zh) 一类含硼化合物及其在催化氟化反应中的应用
CN107188777B (zh) 一种氯代五氟苯的制备方法
CN104557683B (zh) 2，3-二氯-5-三氟甲基吡啶的制备方法
CN110804001A (zh) 一种3,4-二氟苯腈工艺生产方法
CN104892371B (zh) 一种乙二醇二甲醚的制备方法
CN108530380B (zh) 一种n-甲基-1,2-苯并异噻唑啉-3-酮的合成方法
CN106029620A (zh) 2’-三氟甲基取代芳香族酮的制造方法
CN105536873A (zh) 一种复合催化剂及其应用
JP6779468B2 (ja) ペンタフルオロスルファニルピリジン
KR101363583B1 (ko) 2-브로모-6-플루오르나프탈렌의 제조방법
CN115490622A (zh) 一种三氟甲基苯硫酚化合物
WO2014114110A1 (fr) Application du sel de biguanide substitué en 8 comme catalyseur synthétique de l'éther hexafluoroisopropylique de méthylfluor et procédé de synthèse du catalyseur
JP6003896B2 (ja) クロロアルキルスルホニルクロリドの製造方法
TWI705055B (zh) 製備5-氟-1h-吡唑-4-羰基氟化物之方法
JP2016528224A (ja) ハロゲン化有機非ポリマー化合物の脱ハロゲン化水素化のための方法
TW201943708A (zh) 製備３，４－二氯－ｎ－（２－氰苯基）－５－異噻唑羧醯胺之方法
CN109704987B (zh) 一种合成2-氟苯胺化合物的方法
TWI648263B (zh) 藉由２，２－二氟乙胺之烷基化製備ｎ－［（６－氯吡啶－３－基）甲基］－２，２－二氟乙－１－胺
JPH01238564A (ja) 芳香族ニトリルの製造方法
JPS6011986B2 (ja) ジオキサジン系化合物の製造方法
JPH04120050A (ja) 芳香族スルホンの製造方法
Moilliet Industrial routes to ring-fluorinated aromatic compounds

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20893099

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20893099

Country of ref document: EP

Kind code of ref document: A1