CN110845414A - Preparation method and application of N-bis (dimethylamino) -1, 3-dimethylimidazoline - Google Patents
Preparation method and application of N-bis (dimethylamino) -1, 3-dimethylimidazoline Download PDFInfo
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- CN110845414A CN110845414A CN201911178343.6A CN201911178343A CN110845414A CN 110845414 A CN110845414 A CN 110845414A CN 201911178343 A CN201911178343 A CN 201911178343A CN 110845414 A CN110845414 A CN 110845414A
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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
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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
- B01J31/0237—Amines
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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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- 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
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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
- 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
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Abstract
The invention relates to the field of compound preparation methods and applications, in particular to a preparation method and application of N-bis (dimethylamino) -1, 3-dimethylimidazoline, wherein the chemical molecular formula is as follows: c9H23N5(ii) a The preparation method comprises the following steps: s1: taking 1, 3-dimethyl-2-imidazoline and bis (trichloromethyl) carbonate as raw materials, and carrying out chlorination reaction to synthesize chloro-1, 3-dimethyl-2-chloroimidazoline; the method solves the problems of safety and environmental protection of other chlorinated reagents, and greatly improves the product yield (more than 87%). S2: dropwise adding tetramethylguanidine into the generated chloride salt for condensation reaction; s3: then the above-mentioned product is undergone the process of neutralization reaction so as to obtain N-bis (A)Dimethylamino) methylene-1, 3-dimethyl-2-chloroimidazoline ammonium chloride salt. The process has strong operability, mild reaction conditions, safety, environmental protection, good catalytic effect of the product and wide application range, and almost no other impurities are generated except the high-content potassium chloride which is generated as a byproduct.
Description
Technical Field
The invention relates to the field of compound preparation methods and applications, in particular to a preparation method and application of N-bis (dimethylamino) -1, 3-dimethylimidazoline.
Background
When the halogen exchange method is used for preparing the aromatic fluorine-containing compound, because the reaction is heterogeneous, a phase transfer catalyst is required to be added as a medium for transferring F & lt- & gt in a solid-liquid two-phase manner, so that the solubility of the F & lt- & gt in a liquid phase is increased, and the fluorination reaction is promoted. Because of the electric absorption property of the cyano-group, the o-para chlorine atom of the benzene ring is easier to fluorinate, but the meta-substituted chlorine atom is inert and difficult to activate and fluorinate, the fluorination can be carried out only at a higher temperature, and the common phase transfer catalyst has low catalytic activity, poor temperature resistance and easy decomposition at a high temperature, so that the fluorination needs an overhigh temperature, the reaction rate is slow, the system is long at a high temperature, the phenomena of polymerization, dehalogenation and coking are serious, the fluorination reaction yield is lower, the energy consumption in the production process is high, and the pollution is serious.
Common phase transfer catalysts are: quaternary ammonium salts, quaternary phosphonium salts, crown ethers, polyethers, and the like. The quaternary ammonium salt can be decomposed when the temperature is slightly higher, and cannot play a role in catalyzing fluorination at higher temperature, the thermal stability of the quaternary phosphonium salt and crown ether is better than that of the quaternary ammonium salt, but the catalytic activity is not high, and the polyether has small substitution effect on meta-chlorine at higher temperature.
During the chlorination reaction, the method for preparing the chloro-1, 3-dimethyl-2-chloroimidazoline by taking phosgene, diphosgene, oxalyl chloride and the like as chlorinating agents in the early stage has low yield, and the phosgene, the diphosgene and the oxalyl chloride are highly toxic and are strong corrosive liquid, so the production and the transportation have great potential safety hazards.
There has been also a report on the production of chloro-1, 3-dimethyl-2-chloroimidazoline using a chlorinating agent such as phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride or the like, but the use of such an agent causes the reaction system to be in a two-phase state, and the presence of phosphoric acid as a by-product in the reaction makes it difficult to sufficiently proceed the reaction and makes it difficult to separate the product.
Disclosure of Invention
The present invention is made to solve one of the above-mentioned problemsA novel phase transfer catalyst is provided, which is suitable for synthesizing the aromatic fluorine-containing compound which is difficult to be fluorinated. The preparation method of the phase transfer catalyst N-bis (dimethylamino) methylene-1, 3-dimethyl-2-chloroimidazoline ammonium chloride salt has good high-temperature thermal stability and high activity. Aims at solving the safety problem in the catalyst synthesis process by a green and environment-friendly scheme and obtaining a high-quality phase transfer catalyst with high yield; the adopted technical scheme is as follows: an N-bis (dimethylamino) -1, 3-dimethylimidazoline, characterized in that: the chemical molecular formula is as follows: c9H23N5(ii) a The chemical molecular structure is as follows:
a preparation method of N-bis (dimethylamino) -1, 3-dimethylimidazoline is characterized by comprising the following steps: the method comprises the following steps:
s1: taking 1, 3-dimethyl-2-imidazoline and bis (trichloromethyl) carbonate as raw materials, and carrying out chlorination reaction to synthesize chloro-1, 3-dimethyl-2-chloroimidazoline; the method solves the problems of safety and environmental protection of other chlorinated reagents, and greatly improves the product yield (more than 87%).
S2: dropwise adding tetramethylguanidine into the generated chloride salt for condensation reaction;
s3: and then carrying out neutralization reaction on the product to obtain N-bis (dimethylamino) methylene-1, 3-dimethyl-2-chloroimidazoline ammonium chloride salt.
The application of N-bis (dimethylamino) -1, 3-dimethylimidazoline is characterized in that: the catalyst is used.
Preferably, the catalyst is suitable for synthesizing aromatic fluorine-containing compounds which are difficult to fluorinate.
The invention has the beneficial effects that: the N-bis (dimethylamino) methylene-1, 3-dimethyl-2-chloroimidazoline ammonium chloride salt is a novel phase transfer catalyst, has the characteristics of good high-temperature thermal stability and high activity, and is particularly suitable for synthesizing difficult-to-fluorin aromatic fluorine-containing compounds. The catalyst is used for carrying out the fluorination reaction, the reaction temperature can be reduced, and the reaction time (less than 10 hours) can be shortened, so that the phenomena of polymerization, dehalogenation and coking are reduced, the product yield (90 percent) is improved, and the environmental protection pressure is reduced to the maximum extent.
1. The bis (trichloromethyl) carbonate is taken as a chlorination reagent, so that the defect of preparing the chloro-1, 3-dimethyl-2-chloroimidazoline by using chlorination reagents such as hypertoxic phosgene, diphosgene, oxalyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like is overcome.
2. The 1, 3-dimethyl-2-imidazoline, the bis (trichloromethyl) carbonate and the tetramethylguanidine are used as raw materials, so that the operability is strong, the safety and the environmental protection are realized, and the economic benefit is high. The purity of the obtained catalyst is higher than 99.5%, and the yield is higher than 87%.
3. The catalyst has high activity, and can effectively reduce the reaction temperature and shorten the reaction time, thereby reducing the phenomena of polymerization, dehalogenation and coking, improving the product yield, furthest reducing the environmental protection pressure and reducing the production cost.
The compound is a phase transfer catalyst N-bis (dimethylamino) methylene-1, 3-dimethyl-2-chloroimidazoline ammonium chloride salt with good high-temperature thermal stability and high activity, and the preparation method comprises the following steps: firstly, taking 1, 3-dimethyl-2-imidazoline and bis (trichloromethyl) carbonate as raw materials, carrying out chlorination reaction to synthesize chlorinated 1, 3-dimethyl-2-chloroimidazoline, then dripping tetramethylguanidine into the generated chloride salt, carrying out condensation reaction, and then carrying out neutralization reaction to obtain N-bis (dimethylamino) methylene-1, 3-dimethyl-2-chloroimidazoline ammonium chloride salt. The process uses bis (trichloromethyl) carbonate as a chlorinating reagent to replace oxalyl chloride, virulent phosgene, diphosgene, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and other chlorinating reagents, so that the potential safety and environmental protection hazards of catalyst synthesis are greatly reduced from the source, the problem that phosgene is difficult to accurately quantify in the reaction process is effectively solved, and the problems that phosphoric acid is generated in the reaction of the phosphorus-containing chlorinating reagent, the reaction cannot be fully carried out and the product is difficult to separate are solved. The purity of the reaction product reaches up to 99 percent, and the method can be used for halogen exchange reaction of the aromatic fluorine-containing compound which is difficult to fluorinate. The process has strong operability, mild reaction conditions, safety, environmental protection, good catalytic effect of the product and wide application range, and almost no other impurities are generated except the high-content potassium chloride which is generated as a byproduct.
Detailed Description
The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
An N-bis (dimethylamino) -1, 3-dimethylimidazoline, characterized in that: the chemical molecular formula is as follows: c9H23N5(ii) a The chemical molecular structure is as follows:
a preparation method of N-bis (dimethylamino) -1, 3-dimethylimidazoline is characterized by comprising the following steps: the method comprises the following steps:
s1: taking 1, 3-dimethyl-2-imidazoline and bis (trichloromethyl) carbonate as raw materials, and carrying out chlorination reaction to synthesize chloro-1, 3-dimethyl-2-chloroimidazoline; the method solves the problems of safety and environmental protection of other chlorinated reagents, and greatly improves the product yield (more than 87%).
S2: dropwise adding tetramethylguanidine into the generated chloride salt for condensation reaction;
s3: and then carrying out neutralization reaction on the product to obtain N-bis (dimethylamino) methylene-1, 3-dimethyl-2-chloroimidazoline ammonium chloride salt.
The application of N-bis (dimethylamino) -1, 3-dimethylimidazoline is characterized in that: the catalyst is used.
Preferably, the catalyst is suitable for synthesizing aromatic fluorine-containing compounds which are difficult to fluorinate.
Example 1:
chlorination reaction: pumping 500 kg of toluene into the elevated tank, dissolving 200 kg of bis (trichloromethyl) carbonate, pumping 200 kg of DMI into the reaction kettle, dripping at 10-20 ℃, keeping the temperature for 1 hour after dripping, heating to 40 ℃, keeping the temperature for 5 hours, distilling and recovering the toluene, and cooling. 284 kg of white crystalline product chloro-1, 3-dimethyl-2-chloroimidazoline is obtained, the HPLC purity is 99.70 percent, and the yield is 96 percent.
Condensation reaction: 480 kilograms of dichloroethane are sucked into the overhead tank and dripped into the chlorination reaction kettle, 370 kilograms of tetramethylguanidine are dripped, the temperature in the kettle is controlled to be 40 ℃, after dripping is finished, the temperature is kept at 40 ℃ for 1 hour, dichloroethane is recovered by heating, alkali liquor is dripped until the reaction solution is neutral, and the product N-bis (dimethylamino) methylene-1, 3-dimethyl-2-chloroimidazoline ammonium chloride salt is obtained by centrifugation with 462 kilograms of yield of 87.5 percent.
Example 2
Chlorination reaction: pumping 500 kg of toluene into the elevated tank, dissolving 200 kg of bis (trichloromethyl) carbonate, pumping 200 kg of DMI into the reaction kettle, dripping at 10-20 ℃, keeping the temperature for 1 hour after dripping, heating to 40 ℃, keeping the temperature for 5 hours, distilling and recovering the toluene, and cooling. The white crystal product chloro-1, 3-dimethyl-2-chloroimidazoline is obtained with 287 kg, the HPLC purity is 99.72 percent and the yield is 97 percent.
Condensation reaction: 480 kilograms of dichloroethane are sucked into the overhead tank and dripped into the chlorination reaction kettle, 370 kilograms of tetramethylguanidine are dripped, the temperature in the kettle is controlled to be 40 ℃, after dripping is finished, the temperature is kept at 40 ℃ for 1 hour, dichloroethane is recovered by heating, alkali liquor is dripped until the reaction solution is neutral, and the product N-bis (dimethylamino) methylene-1, 3-dimethyl-2-chloroimidazoline ammonium chloride salt is obtained by centrifugation at 464 kilograms with the yield of 87.9 percent.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; the modifications or the substitutions do not cause the essence of the corresponding technical solutions to depart from the scope of the technical solutions of the embodiments of the present invention, and the technical solutions are all covered in the scope of the claims and the specification of the present invention; it will be apparent to those skilled in the art that any alternative modifications or variations to the embodiments of the present invention may be made within the scope of the present invention.
The present invention is not described in detail, but is known to those skilled in the art.
Claims (4)
1. An N-bis (dimethylamino) -1, 3-dimethylimidazoline, characterized in that: the chemical molecular formula is as follows: c9H23N5(ii) a The chemical molecular structure is as follows:
2. a preparation method of N-bis (dimethylamino) -1, 3-dimethylimidazoline is characterized by comprising the following steps: the method comprises the following steps:
s1: taking 1, 3-dimethyl-2-imidazoline and bis (trichloromethyl) carbonate as raw materials, and carrying out chlorination reaction to synthesize chloro-1, 3-dimethyl-2-chloroimidazoline; the method solves the problems of safety and environmental protection of other chlorinated reagents, and greatly improves the product yield (more than 87%).
S2: dropwise adding tetramethylguanidine into the generated chloride salt for condensation reaction;
s3: and then carrying out neutralization reaction on the product to obtain N-bis (dimethylamino) methylene-1, 3-dimethyl-2-chloroimidazoline ammonium chloride salt.
3. The application of N-bis (dimethylamino) -1, 3-dimethylimidazoline is characterized in that: the catalyst is used.
4. The use of N-bis (dimethylamino) -1, 3-dimethylimidazoline according to claim 3, wherein: the catalyst is suitable for synthesizing the aromatic fluorine-containing compound difficult to fluorinate.
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| CN201911178343.6A CN110845414A (en) | 2019-11-27 | 2019-11-27 | Preparation method and application of N-bis (dimethylamino) -1, 3-dimethylimidazoline |
| PCT/CN2020/104736 WO2021103614A1 (en) | 2019-11-27 | 2020-07-27 | Preparation method for and use of n-bis(dimethylamino)-1,3-dimethylimidazoline |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021103614A1 (en) * | 2019-11-27 | 2021-06-03 | 济宁康盛彩虹生物科技有限公司 | Preparation method for and use of n-bis(dimethylamino)-1,3-dimethylimidazoline |
| CN115108971A (en) * | 2022-06-30 | 2022-09-27 | 杭州凯氟科技有限公司 | Preparation method of 2, 3-difluoro-5-chloropyridine |
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