CN103553974A - Preparation method of N-alkyl conjugated ion type quaternary ammonium salt - Google Patents
Preparation method of N-alkyl conjugated ion type quaternary ammonium salt Download PDFInfo
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Abstract
The invention discloses a preparation method of N-alkyl conjugated ion type quaternary ammonium salt. Dialkylamine, bis(trichloromethyl)carbonate and tetramethyl guanidine are used as raw materials which are subjected to carbonylation, chlorination, condensation and neutralization reactions to synthesize an alkyl quaternary ammonium salt phase transfer catalyst, namely the N-alkyl conjugated ion type quaternary ammonium salt. In the process, since the bis(trichloromethyl)carbonate replaces highly-toxic phosgene, the safety and environmental protection hidden danger in catalyst synthesis are greatly reduced from the source, and the problem that phosgene is hard to accurately quantify in a reaction process is effectively solved; the reaction product alkyl quaternary ammonium salt is directly crystallized in toluene and separated out, has the purity of as high as 99%, and can be applied to a halogen exchange reaction. The reaction conditions of the process are mild, the process is safe and environment-friendly, the yield is high, the cost is low, and the activity of a finished product of the catalyst is good.
Description
Technical field
The present invention relates to a kind of preparation method of quaternary ammonium salt phase transfer catalyst, particularly, the preparation method who relates to a kind of N-alkyl conjugate ion type quaternary ammonium salt, can be used for halogen exchange process and prepares aromatic series fluorochemicals, is specially adapted to the synthetic of some aromatic series fluorochemicalss that need pyroreaction.
Background technology
N-alkyl conjugate ion type quaternary ammonium salt is a kind of novel phase-transfer catalyst that new development is in recent years got up, and can be applied to halogen exchange process and prepare aromatic series fluorochemicals.Compare other conventional phase-transfer catalyst as the labile shortcoming of the active low and high temperature of quaternary ammonium salt, quaternary alkylphosphonium salt, crown ether and polyethers phase-transfer catalyst, N-alkyl conjugate ion type quaternary ammonium salt has high reactivity, resistant to elevated temperatures feature, is specially adapted to the synthetic of some aromatic series fluorochemicalss that need pyroreaction.
The fluorine-containing aromatic hydroxy compound that the introducing of this catalyzer can reduce temperature of reaction, simplifies the operation, thereby Reaction time shorten obtains highly selective and high yield.
In prior art about N-alkyl conjugate ion type quaternary ammonium salt preparation method, its catalyzer synthesis technique step is tediously long, and particularly halohydrocarbon usage quantity is large for reaction solvent, and uses hypertoxic gas (phosgene), it is larger that reaction yield is affected by ambient moisture, is difficult to realize safety and stability and produces.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of N-alkyl conjugate ion type quaternary ammonium salt, solve the safety and environmental protection hidden danger existing in catalyzer building-up process, simplify reaction process, obtain the catalyzer of high purity, high yield.
For achieving the above object, the present invention mainly adopts following technical scheme:
A preparation method for N-alkyl conjugate ion type quaternary ammonium salt, is characterized in that, the general structure of described N-alkyl conjugate ion type quaternary ammonium salt is:
In above formula, R
1～R
2for C
1～C
16identical or different saturated or undersaturated straight chained alkyls, saturated or undersaturated branched-chain alkyl; A
-for chlorion;
The preparation feedback route of described N-alkyl conjugate ion type quaternary ammonium salt is as follows:
The preparation method of described N-alkyl conjugate ion type quaternary ammonium salt comprises the steps:
1) carbonylation reaction: at 5～10 ℃, the toluene solution of two (trichloromethyl) carbonic ethers is splashed in dialkylamine, and add acid binding agent, after dropwising, rise to stirring at room reaction 4～10 hours, separation, extraction, after underpressure distillation, obtains tetraalkyl ureas;
The mol ratio of described two (trichloromethyl) carbonic ether and dialkylamine is 1:2～1:15;
The mol ratio of described acid binding agent and dialkylamine is 1:1～2:1;
2) chlorination: at 5～10 ℃, the tetraalkyl ureas obtaining is made to toluene solution, the toluene solution of two (trichloromethyl) carbonic ethers is splashed in the toluene solution of tetraalkyl ureas, rise to stirring at room reaction, time for adding and churning time totally 2～10 hours, filter, washing leaching cake, obtains chloro salt;
Described tetraalkyl ureas is 1:1～1:5 with the mol ratio of two (trichloromethyl) carbonic ethers;
3) condensation neutralization reaction: the chloro salt obtaining is dissolved in methylene dichloride or chloroform, drips tetramethyl guanidine at 5～10 ℃, dropwise, rise to stirring at room reaction, time for adding and churning time totally 2～8 hours, obtain guanidine salt mixture; In the guanidine salt mixture obtaining, add dissolve with methanol, under room temperature, drip sodium methoxide solution, react 2～8 hours, filter desalination, distillation for removing methanol, adds toluene, crystallization at 0～25 ℃, suction filtration, obtains described N-alkyl conjugate ion type quaternary ammonium salt;
The mol ratio of described chloro salt and tetramethyl guanidine is 1:2～1:5; The consumption of described methylene dichloride or chloroform is 2～5 times of chloro salt weight.
Further, the structure of described dialkylamine is:
In above formula, R
1, R
2for C
1～C
16identical or different saturated or undersaturated straight chained alkyls, saturated or undersaturated branched-chain alkyl.
In step 1), in the toluene solution of two (trichloromethyl) carbonic ether, the consumption of toluene solvant is 1～6 times of dialkylamine weight; Step 2), in, in the toluene solution of two (trichloromethyl) carbonic ether and the toluene solution of tetraalkyl ureas, the consumption of toluene solvant is 1～6 times of tetraalkyl ureas weight.
Step 2) under dry inert gas protection, carry out.
In step 3), the consumption of methanol solvate is 2～5 times of guanidinesalt mixture weight, and the mol ratio of sodium methylate and chloro salt is 1:1～1:3, and the strength of solution of sodium methylate is 10%～30%.
In step 3), chloro salt is dissolved in methylene dichloride.
Described acid binding agent is triethylamine or pyridine.
Compared with prior art, beneficial effect of the present invention is:
1. take two alkylamines, two (trichloromethyl) carbonic ether, tetramethyl guanidine is waste N-alkyl conjugate ion type quaternary ammonium salt phase transfer catalyst, avoid using the danger of highly toxic product phosgene, and effectively solved the problem that phosgene is difficult to accurate quantitative analysis in reaction process.
2. the catalyzer purity obtaining is higher than 99.5%, and yield is higher than 85%.
And catalyzer in use, can significantly shorten reaction duration, promote speed of reaction, reduce production costs.
Embodiment
Below by specific embodiment, the present invention is described further, should be clear and definite, and embodiment only, for the description to optimal way of the present invention, does not limit the scope of the invention.
Embodiment 1
Carbonylation reaction: in the flask of agitator, reflux condensing tube, constant pressure funnel is housed, the aqueous solution (40%) that adds 225g dimethylamine, drips the toluene solution containing two (trichloromethyl) carbonic ethers of 118.7g at 10 ℃, and adds acid binding agent triethylamine 220g under vigorous stirring, after dropwising, rise to stirring at room 4h, separated organic phase, uses toluene aqueous phase extracted, merge organic phase, underpressure distillation obtains tetramethyl-urea 95g, yield 80%, purity 98%.
Chlorination: in the flask of agitator, reflux condensing tube, constant pressure funnel is housed, add above-mentioned tetramethyl-urea 30g, toluene 30g, drips the toluene solution containing two (trichloromethyl) carbonic ethers of 30g at 5 ℃, drips 4h, rises to stirring at room 2h.Filter, filter cake toluene wash, obtains chloro salt 50g.
Condensation neutralization reaction: chloro salt is dissolved in 60g methylene dichloride, drips 50g tetramethyl guanidine at 10 ℃, dropwise, rise to stirring at room 1h, revolve and steam except desolventizing, add 80g dissolve with methanol, drip 25% sodium methoxide solution under room temperature, remove by filter salt.Mother liquor is spin-dried for methyl alcohol, adds toluene 100g, stirs crystallization at 10 ℃.Suction filtration obtains two-(two (dimethylin) methylene radical of N-)-protochloride ammonium salt in catalysis agent 57.6g, HPLC purity 99.7%, yield 90%.
Embodiment 2
In the flask of agitator, reflux condensing tube, constant pressure funnel is housed, add 146g diethylamine, at 5 ℃, under vigorous stirring, slowly drip the toluene solution that contains two (trichloromethyl) carbonic ethers of 120g, and add acid binding agent pyridine 185g, after dropwising, rise to stirring at room 4h, underpressure distillation obtains tetraethyl urea.Yield 91%, purity 98%.
In the flask of agitator, reflux condensing tube, constant pressure funnel is housed, add above-mentioned tetraethyl urea 43g, toluene 40g, drips the toluene solution containing two (trichloromethyl) carbonic ethers of 30g at 5 ℃, drips 4h, rises to stirring at room 2h.Filter, filter cake toluene wash, obtains chloro salt 41g.
Chloro salt is dissolved in 60g methylene dichloride, drips 50g tetramethyl guanidine at 10 ℃, dropwise, rise to stirring at room 1h, revolve and steam except desolventizing, add 80g dissolve with methanol, under room temperature, drip 20% sodium methoxide solution, remove by filter salt.Mother liquor is spin-dried for methyl alcohol, adds toluene 100g, stirs crystallization at 10 ℃.Suction filtration obtains two (dimethylin) methylene radical-protochloride ammonium salt in catalysis agent 77g of two (diethylin) methylene radical-N-of N-, HPLC purity 99.5%, yield 85%.
Embodiment 3
In the flask of agitator, reflux condensing tube, constant pressure funnel is housed, add 130g dibutylamine, at 5 ℃, under vigorous stirring, slowly drip the toluene solution that contains two (trichloromethyl) carbonic ethers of 60g, and add acid binding agent triethylamine 125g, after dropwising, rise to stirring at room 4h, underpressure distillation obtains tetrabutyl urea.Yield 90%, purity 98%.
In the flask of agitator, reflux condensing tube, constant pressure funnel is housed, add above-mentioned tetrabutyl urea 73g, toluene 40g, drips the toluene solution containing two (trichloromethyl) carbonic ethers of 30g at 5 ℃, drips 4h, rises to stirring at room 2h.Filter, filter cake toluene wash, obtains chloro salt 70g.
Chloro salt is dissolved in 60g methylene dichloride, drips 50g tetramethyl guanidine at 10 ℃, dropwise, rise to stirring at room 1h, revolve and steam except desolventizing, add 80g dissolve with methanol, under room temperature, drip 15% sodium methoxide solution, remove by filter salt.Mother liquor is spin-dried for methyl alcohol, adds toluene 100g, stirs crystallization at 10 ℃.Suction filtration obtains two (dimethylin) methylene radical-protochloride ammonium salt in catalysis agent 122g of two (dibutyl amino) methylene radical-N-of N-, HPLC purity 99.5%, yield 80%.
Embodiment 4
In the flask of agitator, reflux condensing tube, constant pressure funnel is housed, the aqueous solution (40%) that adds 225g dimethylamine, drips two (trichloromethyl) carbonic ether toluene solutions of 118.7g at 10 ℃, and adds acid binding agent triethylamine 223g under vigorous stirring, after dropwising, rise to stirring at room 4h, separated organic phase, uses toluene aqueous phase extracted, merge organic phase, underpressure distillation obtains tetramethyl-urea 95g, yield 80%, purity 98%.
In the flask of agitator, reflux condensing tube, constant pressure funnel is housed, add above-mentioned tetramethyl-urea 30g, toluene 30g, drips the toluene solution containing two (trichloromethyl) carbonic ethers of 30g at 80 ℃, drips 4h, rises to stirring at room 2h.Filter, filter cake toluene wash, obtains chloro salt 53g.
Chloro salt is dissolved in 60g methylene dichloride, drips 50g tetramethyl guanidine at 10 ℃, dropwise, rise to stirring at room 1h, revolve and steam except desolventizing, add 80g dissolve with methanol, under room temperature, drip 30% sodium methoxide solution, remove by filter salt.Mother liquor is spin-dried for methyl alcohol, adds toluene 100g, stirs crystallization at 10 ℃.Suction filtration obtains two-(two (dimethylin) methylene radical of N-)-chlorimide salt catalyst 61g, HPLC purity 99.7%, yield 95%.
Embodiment 5
In the flask of agitator, reflux condensing tube, constant pressure funnel is housed, add 254g pentanoic, at 5 ℃, under vigorous stirring, slowly drip the toluene solution that contains two (trichloromethyl) carbonic ethers of 89g, and add acid binding agent triethylamine 196g, after dropwising, rise to stirring at room 4h, underpressure distillation obtains tetraphenyl urea.Yield 65%, purity 98%.
In the flask of agitator, reflux condensing tube, constant pressure funnel is housed, add above-mentioned tetraphenyl urea 94g, toluene 40g, drips the toluene solution containing two (trichloromethyl) carbonic ethers of 30g at 5 ℃, drips 4h, rises to stirring at room 2h.Filter, filter cake toluene wash, obtains chloro salt 80g.
63g chloro salt is dissolved in 100g methylene dichloride, drips 35g tetramethyl guanidine at 10 ℃, dropwise, rise to stirring at room 1h, revolve and steam except desolventizing, add 80g dissolve with methanol, under room temperature, drip 30% sodium methoxide solution, remove by filter salt.Mother liquor is spin-dried for methyl alcohol, adds toluene 100g, stirs crystallization at 10 ℃.Suction filtration obtains two (dimethylin) methylene radical-protochloride ammonium salt in catalysis agent 65g of two (hexichol amido) methylene radical-N-of N-, HPLC purity 98.5%, yield 90%.
Embodiment 6
In the flask of agitator, reflux condensing tube, constant pressure funnel is housed, add 107g aminomethyl phenyl amine, at 5 ℃, under vigorous stirring, slowly drip the toluene solution that contains two (trichloromethyl) carbonic ethers of 60g, and add acid binding agent pyridine 135g, after dropwising, rise to stirring at room 4h, underpressure distillation obtains two (N-methyl-N-phenyl) urea.Yield 85%, purity 98%.
In the flask of agitator, reflux condensing tube, constant pressure funnel is housed, add abovementioned alkyl urea 102g, toluene 100g, drips the toluene solution containing two (trichloromethyl) carbonic ethers of 51g at 5 ℃, drips 4h, rises to stirring at room 2h.Filter, filter cake toluene wash, obtains chloro salt 100g.
100g chloro salt is dissolved in 150g methylene dichloride, drips 78g tetramethyl guanidine at 10 ℃, dropwise, rise to stirring at room 1h, revolve and steam except desolventizing, add 80g dissolve with methanol, under room temperature, drip 30% sodium methoxide solution, remove by filter salt.Mother liquor is spin-dried for methyl alcohol, adds toluene 250g, stirs crystallization at 10 ℃.Suction filtration obtains two (dimethylin) methylene radical-protochloride ammonium salt in catalysis agent 139g of two (N-methyl-N-phenyl amido) methylene radical-N-of N-, HPLC purity 98.5%, yield 86%.
Example 1
With the example that is prepared as of 3,4-difluorobenzonitrile, the N-alkyl conjugate ion type quaternary ammonium salt phase transfer catalyst that adopts the embodiment of the present invention 1 to make is carried out to catalytic performance test.
In the 2000ml reactor of belt stirrer, reflux water-dividing device, thermometer, add 300g3,4-dichlorobenzonitrile, 900g DMI, 130g hexanaphthene, is warming up to 120 ℃, reflux water-dividing.After anhydrous separating in water trap, the method in the dry Potassium monofluoride of 300g spraying, above-described embodiment 1 of dropping into synthetic two-(two (dimethylin) methylene radical of N-)-protochloride amine salt 45g, be warming up to 150 ℃ of reaction 3h.Continue to be warming up to 190 ℃, reaction 5h finishes.After post-reaction treatment pure 3,4-difluorobenzonitrile 193g, purity 99.3%, yield 85%.
The catalyst that adopts present method to make prepares 3,4-difluorobenzonitrile, total reaction time is only 8 hours, in conventional art, adopt the phase-transfer catalysts such as Tetraphenylphosphonium Bromide to prepare 3 as catalyzer, the total reaction time of the method for 4-difluorobenzonitrile surpasses to be compared for 20 hours, has significantly promoted reaction efficiency, and product purity is high, yield is high.
Example 2-6
Use the N-alkyl conjugate ion type quaternary ammonium salt making in embodiment 2-6 as catalyzer, with 2,6-dichlorobenzonitrile, 2,3,4,5,6-penta fluoro benzene formonitrile HCN, 2,3,5,6-tetrachloro-p-phenylene dimethoxy nitrile, 4-chloronitrobenzene, 4-chlorobenzaldehyde are reaction substrate, take DMI as solvent, hexanaphthene be band aqua, carry out fluorine chlorine permutoid reaction, corresponding fluoro product purity, yield and the temperature of reaction obtaining after reaction treatment, total duration see table.
In sum, the N-alkyl conjugate ion type quaternary ammonium salt catalyst of producing by method provided by the present invention, can be for the synthetic fluorine-containing aromatic hydroxy compound of halogen exchange process.Take two alkylamines, two (trichloromethyl) carbonic ether, tetramethyl guanidine is waste N-alkyl conjugate ion type quaternary ammonium salt phase transfer catalyst, avoid using the danger of highly toxic product phosgene, and effectively solved the problem that phosgene is difficult to accurate quantitative analysis in reaction process.Meanwhile, the catalyzer purity of acquisition is higher than 99.5%, and yield is higher than 85%.And catalyzer is in use, can significantly shorten reaction duration, promote speed of reaction, reduce production costs.
Be noted that above embodiment is only unrestricted in order to technical scheme of the present invention to be described.Although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement the technical scheme of invention, and not depart from the scope of technical solution of the present invention, it all should be encompassed in claim scope of the present invention.
Claims (7)
1. a preparation method for N-alkyl conjugate ion type quaternary ammonium salt, is characterized in that, the general structure of described N-alkyl conjugate ion type quaternary ammonium salt is:
In above formula, R
1～R
2for C
1～C
16identical or different saturated or undersaturated straight chained alkyls, saturated or undersaturated branched-chain alkyl; A
-for chlorion;
The preparation feedback route of described N-alkyl conjugate ion type quaternary ammonium salt is as follows:
The preparation method of described N-alkyl conjugate ion type quaternary ammonium salt comprises the steps:
1) carbonylation reaction: at 5～10 ℃, the toluene solution of two (trichloromethyl) carbonic ethers is splashed in dialkylamine, and add acid binding agent, after dropwising, rise to stirring at room reaction 4～10 hours, separation, extraction, after underpressure distillation, obtains tetraalkyl ureas;
The mol ratio of described two (trichloromethyl) carbonic ether and dialkylamine is 1:2～1:15;
The mol ratio of described acid binding agent and dialkylamine is 1:1～2:1;
2) chlorination: at 5～10 ℃, the tetraalkyl ureas obtaining is made to toluene solution, the toluene solution of two (trichloromethyl) carbonic ethers is splashed in the toluene solution of tetraalkyl ureas, rise to stirring at room reaction, time for adding and churning time totally 2～10 hours, filter, washing leaching cake, obtains chloro salt;
Described tetraalkyl ureas is 1:1～1:5 with the mol ratio of two (trichloromethyl) carbonic ethers;
3) condensation neutralization reaction: the chloro salt obtaining is dissolved in methylene dichloride or chloroform, drips tetramethyl guanidine at 5～10 ℃, dropwise, rise to stirring at room reaction, time for adding and churning time totally 2～8 hours, obtain guanidine salt mixture; In the guanidine salt mixture obtaining, add dissolve with methanol, under room temperature, drip sodium methoxide solution, react 2～8 hours, filter desalination, distillation for removing methanol, adds toluene, crystallization at 0～25 ℃, suction filtration, obtains described N-alkyl conjugate ion type quaternary ammonium salt;
The mol ratio of described chloro salt and tetramethyl guanidine is 1:2～1:5; The consumption of described methylene dichloride or chloroform is 2～5 times of chloro salt weight.
2. the preparation method of a kind of N-alkyl conjugate ion type quaternary ammonium salt according to claim 1, is characterized in that, the structure of described dialkylamine is:
In above formula, R
1, R
2for C
1～C
16identical or different saturated or undersaturated straight chained alkyls, saturated or undersaturated branched-chain alkyl.
3. the preparation method of a kind of N-alkyl conjugate ion type quaternary ammonium salt according to claim 1, is characterized in that,
In step 1), in the toluene solution of two (trichloromethyl) carbonic ether, the consumption of toluene solvant is 1～6 times of dialkylamine weight;
Step 2), in, in the toluene solution of two (trichloromethyl) carbonic ether and the toluene solution of tetraalkyl ureas, the consumption of toluene solvant is 1～6 times of tetraalkyl ureas weight.
4. the preparation method of a kind of N-alkyl conjugate ion type quaternary ammonium salt according to claim 1, is characterized in that described step 2) under dry inert gas protection, carry out.
5. the preparation method of a kind of N-alkyl conjugate ion type quaternary ammonium salt according to claim 1, it is characterized in that, in described step 3), the consumption of methanol solvate is 2～5 times of guanidinesalt mixture weight, the mol ratio of sodium methylate and chloro salt is 1:1～1:3, and the strength of solution of sodium methylate is 10%～30%.
6. the preparation method of a kind of N-alkyl conjugate ion type quaternary ammonium salt according to claim 1, is characterized in that, in described step 3), chloro salt is dissolved in methylene dichloride.
7. the preparation method of a kind of N-alkyl conjugate ion type quaternary ammonium salt according to claim 1, is characterized in that, described acid binding agent is triethylamine or pyridine.
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| CN108558706A (en) * | 2018-03-28 | 2018-09-21 | 苏州昊帆生物股份有限公司 | Tetramethylurea and preparation method thereof |
| CN109251167A (en) * | 2018-10-25 | 2019-01-22 | 浙江工业大学上虞研究院有限公司 | The preparation method of the fluoro- 2,6- diamino-pyridine of 3,5- bis- |
| JP2020508209A (en) * | 2017-02-16 | 2020-03-19 | コリア・インスティテュート・オブ・サイエンス・アンド・テクノロジー | Catalyst for producing alkylene carbonate, method for producing the same, and method and apparatus for producing alkylene carbonate using the catalyst |
| CN112409209A (en) * | 2020-09-28 | 2021-02-26 | 济宁康盛彩虹生物科技有限公司 | Preparation method and application of N-bis (diphenylamino) methylene-N-bis (dimethylamino) methylene-iminium chloride |
| CN114014801A (en) * | 2021-12-13 | 2022-02-08 | 江苏丰山集团股份有限公司 | Green production process of 2, 3-difluoro-5-chloropyridine with low single impurity content |
| 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 |
| CN117776980A (en) * | 2023-12-18 | 2024-03-29 | 江苏丰山生化科技有限公司 | Preparation method of bis- (N-bis (dimethylamino) methylene) -chloride iminium salt |
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| JP2020508209A (en) * | 2017-02-16 | 2020-03-19 | コリア・インスティテュート・オブ・サイエンス・アンド・テクノロジー | Catalyst for producing alkylene carbonate, method for producing the same, and method and apparatus for producing alkylene carbonate using the catalyst |
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| CN114014801A (en) * | 2021-12-13 | 2022-02-08 | 江苏丰山集团股份有限公司 | Green production process of 2, 3-difluoro-5-chloropyridine with low single impurity content |
| 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 |
| CN117776980A (en) * | 2023-12-18 | 2024-03-29 | 江苏丰山生化科技有限公司 | Preparation method of bis- (N-bis (dimethylamino) methylene) -chloride iminium salt |
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