CN116178336A - Method for synthesizing N-aryl ketimine by acid catalytic ketal method and application - Google Patents
Method for synthesizing N-aryl ketimine by acid catalytic ketal method and application Download PDFInfo
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- CN116178336A CN116178336A CN202211678887.0A CN202211678887A CN116178336A CN 116178336 A CN116178336 A CN 116178336A CN 202211678887 A CN202211678887 A CN 202211678887A CN 116178336 A CN116178336 A CN 116178336A
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- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
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Abstract
The invention discloses a method for synthesizing N-aryl ketimine by an acid catalytic ketal method and application thereof. The method has the advantage that the condensation reaction of aromatic amine and alkyl ketone with poor nucleophilicity caused by electrical property or steric hindrance still has excellent reaction effect. The method has the advantages of simple operation, high raw material conversion rate, good reaction selectivity, high product yield and good quality. Can be applied to the efficient synthesis of the herbicide dimethenamid.
Description
Technical Field
The invention belongs to the field of organic synthesis methodologies, and particularly relates to a method for synthesizing N-aryl ketimine by an acid catalytic ketal method and application thereof.
Background
N-aryl ketimines as an important organic intermediate can participate in various types of reactions, such as: aza-diels-alder reaction to give tetrahydropyridine, reaction with meta-chloroperoxybenzoic acid to give oxaaziridine, povarov reaction to give quinoline, and important intermediates for reductive amination reactions. In addition, the N-aryl ketimine is used as the most common ligand in ligand chemistry, can form metal complexes with various metal elements widely, and has important application value in the field of metal catalysis. The asymmetric reductive amination reaction involving N-aryl ketimine is one of the most commonly used methods in industry for preparing chiral secondary amines, and is widely used in the synthesis of pharmaceutical and pesticide intermediates, for example: synthesis of the chiral pesticide, metolachlor (Metropoli) (WO 9521151,WO 9705095). Typical methods for preparing ketimines are by dehydration condensation of primary amines with ketones, which require azeotropic reflux for water separation during the reaction or molecular sieve based dehydrating agents because the equilibrium is more prone to ketone and amine sides. In the case of N-aryl ketimines, the nucleophilicity is reduced due to the conjugation of the lone pair of the nitrogen atom and the aromatic ring, and particularly when the ortho position of the aromatic amine has a substituent with large steric hindrance, the condensation reaction is generally difficult to proceed. Even if an activating reagent (Org.Lett.2019, 21,9699;Dalton Trans.2007,40,4565) such as tetra (ethoxy) titanium or titanium tetrachloride or a stoichiometric dehydrating agent (j. Organomet. Chem.2009,694,1380; new j. Chem.2005,29,385) is added, the condensation reaction efficiency is still low, the post-treatment is complicated, the yield of imine is low, and the method is not suitable for large-scale production.
Disclosure of Invention
The invention aims at solving the problem that the N-aryl ketimine compound is difficult to generate by dehydration condensation of aromatic amine with ketone compound due to poor nucleophilicity of aromatic amine caused by electrical property or steric hindrance, and provides a method for synthesizing N-aryl ketimine by a ketal method catalyzed by Lewis acid or organic acid and application thereof.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the method takes Lewis acid or organic acid as a catalyst, and under the heating condition, N-aryl ketimine is formed by condensation of aromatic amine and ketal, wherein the reaction formula is as follows:
in the reaction formula: ar is selected from phenyl, thienyl, pyridyl, furyl, pyrrolyl, or the aromatic ring carries one or more of the following substituents: halogen, alkyl, alkoxy, phenyl or benzyl;
wherein R is 1 And R is 2 Respectively selected from alkyl, phenyl, benzyl, thienyl, pyridyl, furyl and pyrrolyl, or the aromatic ring is provided with the following substituent groups: halogen, alkyl, alkoxy, phenyl or benzyl, R 1 、R 2 The same or different;
R 3 selected from methyl, ethyl, propyl, butyl or 1, 2-disubstituted ethyl, 1, 3-disubstituted propyl.
Further, the solvent used in the process is selected from toluene, xylene, 1, 2-dichloroethane, chloroform, ethyl acetate, acetonitrile, dioxane or tetrahydrofuran.
Further, the molar ratio of the aromatic amine to the ketal is 1 (1.0-3.0).
Further, the molar ratio of the acid catalyst to the aromatic amine is (0.1% -5%) 1.
Further, the lewis acid or organic acid catalyst comprises tin dichloride, ferric chloride, bismuth triflate, scandium triflate or p-toluenesulfonic acid;
the mol ratio of the acid catalyst to the aromatic amine is (0.5% -5%) 1.
Further, ar is selected from phenyl, thienyl, or the aromatic ring has the following substituents: chlorine, alkyl or alkoxy;
the R is 1 And R is 2 Respectively selected from alkyl, phenyl, benzyl or the aromatic ring, and has the following substituent groups: halogen, alkyl or alkoxy, R 1 、R 2 The same or different;
the R is 3 Selected from methyl or ethyl.
Further, the aromatic amine is selected from 2, 4-dimethyl-3-aminothiophene, 2, 6-dimethylaniline or 2-methyl-6-ethylaniline;
the molar ratio of the aromatic amine to the ketal to the acid catalyst to the solvent is 1:1.1-2.0:0.005-0.05:3-10.
Further, the solvent is selected from toluene, 1, 2-dichloroethane, chloroform or tetrahydrofuran;
the heating reaction temperature is (60-120).
The invention also discloses the N-aryl ketimine synthesized by the method for synthesizing the N-aryl ketimine by the acid catalytic ketal method.
The invention also discloses a method for synthesizing the N-aryl ketimine by the acid catalytic ketal method, which is applied to the synthesis of the herbicide dimethenamid
Compared with the prior art, the invention has the beneficial effects that:
the invention takes Lewis acid or organic acid as catalyst, and under the heating condition, N-aryl ketimine is generated by condensation of aromatic amine and ketal. The method has the advantages that the method is not only suitable for the condensation of common aromatic amine and alkyl ketone, but also has excellent reaction effect for the condensation reaction of aromatic amine and alkyl ketone with poor nucleophilicity caused by electrical or steric hindrance reasons. The method has the advantages of simple operation, high raw material conversion rate, good reaction selectivity, high product yield, good quality, simple operation and less three wastes, is suitable for large-scale preparation, and can be applied to organic synthesis methodologies and synthesis of medical and pesticide intermediates.
The present invention will be further described with reference to the following examples, which should not be construed as limiting the scope of the invention, in order to better understand the essential characteristics of the present invention.
The experimental steps of the invention are as follows:
(1) Preparing ketal: adding ketone, trialkyl orthoformate, p-toluenesulfonic acid and alkyl alcohol solvent into a round bottom flask with a reflux condenser, and heating for 2-4 hours at 60-100 ℃; the reaction was monitored in the gas phase, the starting ketone was less than 5%, and the reaction was stopped. The reaction formula is shown as formula (2):
r of ketone 1 、R 2 The groups are the same or different and are respectively selected from alkyl, phenyl and benzyl, or the aromatic ring is further provided with the following substituent groups: halogen, alkyl, alkoxy; r in the trialkyl orthoformate 3 The group is selected from methyl and ethyl;
the alkyl alcohol is selected from methanol and ethanol; the molar ratio of ketone to orthoformic acid trialkyl ester to p-toluenesulfonic acid to alkyl alcohol is 1:1-3:0.005-0.05:3-10.
And cooling the reaction liquid to room temperature, distilling to separate out solvent and excessive orthoformate for the alkyl ketone substrate which is liquid at room temperature, and then decompressing and distilling to obtain a ketal product. For aryl ketone substrates which are solid at room temperature, the product ketal is separated out in the reaction liquid, filtered and leached by methanol, and the obtained solid is the ketal product.
(2) Preparation of N-aryl ketimine: adding aromatic amine, ketal, acid catalyst and solvent into a round bottom flask with a reflux condenser, and heating for 2-4 hours at 70-110 ℃; the reaction is monitored in a gas phase, the aromatic amine as a raw material is less than 5%, and the reaction is stopped. The reaction formula is shown as formula (1):
the Ar group of the aromatic amine is selected from phenyl or thienyl, or the aromatic ring carries the following substituent groups: chlorine, alkyl, alkoxy; the Lewis acid or organic acid catalyst is selected from tin dichloride, bismuth triflate or p-toluenesulfonic acid; the solvent is selected from toluene, 1, 2-dichloroethane, chloroform, and tetrahydrofuran; the molar ratio of the aromatic amine to the ketal to the acid catalyst to the solvent is 1:1.1-2.0:0.005-0.05:3-10.
And cooling the reaction liquid to room temperature, distilling the N-aryl ketimine which is liquid at room temperature to separate out solvent and excessive ketal, and then distilling under reduced pressure to obtain an N-aryl ketimine product. For N-aryl ketimine which is solid at room temperature, a rotary evaporator is used for concentrating the solvent, and the obtained solid crude product is recrystallized by using solvents such as chloroform, toluene, ethyl acetate and the like according to different physical and chemical properties of the product, so that the N-aryl ketimine product can be obtained.
Examples 1 to 4 give examples of the preparation of different ketals, examples 5 to 7 give examples of the preparation of different N-aryl ketimine products, respectively, and examples 8 and 9 give examples of the preparation of the herbicide dimethenamid in combination.
Example 1
This example gives the preparation of ketals: examples of 1, 2-trimethoxypropane (1 a):
comprising the following steps: 8.8g of methoxyacetone, 11.7g of trimethyl orthoformate, 190mg of p-toluenesulfonic acid monohydrate and 20mL of methanol were charged into a 100mL round bottom flask equipped with a reflux condenser, the reaction was heated for 2.5 hours, the reaction was monitored by gas phase, the conversion of the raw material methoxyacetone was 98%, and the reaction was stopped. Methanol and excessive trimethyl orthoformate are distilled off, and then 12.6g of ketal product 1, 2-trimethoxypropane is obtained by reduced pressure distillation, the yield is 94.0%, and the content is 98.0%.
Example 2
This example gives the preparation of ketals: examples of 2, 2-diethoxy-1-methoxypropane (1 b):
comprising the following steps: 8.8g of methoxyacetone, 17.7g of triethyl orthoformate, 190mg of p-toluenesulfonic acid monohydrate and 20mL of ethanol were added to a 100mL round bottom flask equipped with a reflux condenser, the reaction was heated for 4 hours, the reaction was monitored by gas phase monitoring, the conversion of the raw material methoxyacetone was 96%, and the reaction was stopped. Methanol and excessive triethyl orthoformate are distilled and distilled under reduced pressure to obtain 15.0g of ketal product 2, 2-diethoxy-1-methoxypropane, the yield is 92.5%, and the content is 97.6%.
Example 3
This example gives the preparation of ketals: examples of bis (3, 5-di-tert-butylphenyl) dimethoxymethane (1 c):
comprising the following steps: 8.2g of bis (3, 5-di-t-butylphenyl) methanone, 2.4g of trimethyl orthoformate, 38mg of p-toluenesulfonic acid monohydrate and 20mL of methanol were charged into a 50mL round bottom flask equipped with a reflux condenser, the reaction was heated for 2 hours, the reaction was monitored by gas phase, the conversion of the starting bis (3, 5-di-t-butylphenyl) methanone was 97%, and the reaction was stopped. Cooling the reaction solution to room temperature, separating out ketal product in the reaction solution, filtering, leaching with methanol, and obtaining solid, namely ketal product bis (3, 5-di-tert-butylphenyl) dimethoxymethane 8.6g, wherein the yield is 95.0% and the content is 95.0%.
Example 4
This example gives the preparation of ketals: examples of 1, 3-bis (4-methoxyphenyl) -2, 2-dimethoxypropane (1 d):
comprising the following steps: 5.4g of 1, 3-bis (4-methoxyphenyl) acetone, 2.4g of trimethyl orthoformate, 38mg of p-toluenesulfonic acid monohydrate and 20mL of methanol were charged into a 50mL round bottom flask equipped with a reflux condenser, the reaction was heated for 2 hours, the reaction was monitored by gas phase, the conversion of the starting bis (3, 5-di-t-butylphenyl) methanone was 98%, and the reaction was stopped. Cooling the reaction solution to room temperature, separating out ketal product in the reaction solution, filtering, eluting with methanol, wherein the obtained solid is ketal product 1, 3-bis (4-methoxyphenyl) -2, 2-dimethoxypropane 6.0g, the yield is 96.5%, and the content is 96.2%.
Example 5
This example shows the preparation of N-aryl ketimine 2 a:
comprising the following steps: 8.9g of 2, 4-dimethyl-3-aminothiophene, 11.3g of ketal 1a, 265.4mg of tin dichloride and 20mL of 1, 2-dichloroethane were charged into a round bottom flask equipped with a reflux condenser, the reaction was heated for 4 hours, the reaction was monitored in a gas phase, and the reaction was stopped with less than 5% of the starting 2, 4-dimethyl-3-aminothiophene. The reaction solution is cooled to room temperature, the solvent is distilled and separated, and then the reduced pressure distillation is carried out to obtain the 12.5-g N-aryl ketimine product 2a, the yield is 90.2 percent, and the content is 94.6 percent.
Example 6
This example shows the preparation of N-aryl ketimine 2 b:
1.5g of 2-methylaniline, 7.6g of ketal 1c, 53.1mg of tin dichloride and 5mL of 1, 2-dichloroethane were charged into a 25mL pressure-resistant tube, the reaction was heated for 2 hours, the reaction was monitored by gas phase, and the reaction was stopped with less than 5% of the starting 2-methylaniline. The reaction solution was cooled to room temperature, the solvent was concentrated by using a rotary evaporator, and the obtained solid crude product was recrystallized by using ethyl acetate to obtain 6.4. 6.4g N-aryl ketimine product 2b, yield 92.0%, content 97.0%.
Example 7
This example shows the preparation of N-aryl ketimine 2c
1.2g of 2, 6-dimethylaniline, 3.8g of ketal 1d, 37.9mg of tin dichloride and 5mL of 1, 2-dichloroethane were charged into a 25mL pressure-resistant tube, the reaction was heated for 2.5 hours, the reaction was monitored in the gas phase, and the reaction was stopped with less than 5% of 2-methylaniline as the starting material. The reaction solution was cooled to room temperature, the solvent was concentrated by using a rotary evaporator, and the obtained solid crude product was recrystallized by using ethyl acetate to obtain 3.4-g N-aryl ketimine product 2c, yield 91.0%, content 96.0%.
Example 8
This example shows the preparation of 2, 4-dimethyl-3-aminothiophene derivative (3)
The imine 2a 3.9g obtained in example 5 was dissolved in 20mL of methanol, 1.1g of sodium borohydride was added in portions at 0℃and reacted at room temperature for 3 hours, and TLC was used to monitor the reaction, and the reaction was stopped after the complete conversion of the starting imine 2 a. Slowly adding ice water for quenching reaction, extracting with dichloromethane, concentrating organic phase, and distilling under reduced pressure to obtain 3.7g of product 3 with yield of 92.0% and content of 98.5%.
The product nuclear magnetic data are as follows: 1 H NMR(500MHz，CDCl 3 )：δppm 6.604(s，1H)，3.360(s，1H)，3.323－3.312(dd，2H),3.281－3.234(m，1H),2.992(s，1H)，2.288(s，3H)，2.099(s，3H)，1.144－1.131(d，3H)。 13 C NMR(125MHz，CDCl 3 )：δppm 141.650,133.338,121.919,115.911,76.328,59.034,53.042,18.539,14.439,12.695。
example 9
This example gives the preparation of the herbicide dimethenamid:
3.0g of the product obtained in example 8 and 2.0g of triethylamine were dissolved in 30mL of dichloromethane, 1.9g of chloroacetyl chloride was added dropwise at 0℃and reacted at room temperature for 4 hours, the reaction was monitored by TLC and the reaction was stopped after complete conversion of the starting material 3. Adding sodium bicarbonate solution for quenching reaction, extracting with dichloromethane, concentrating an organic phase, and distilling under reduced pressure to obtain 3.4g of the dimethenamid, wherein the yield is 82.0% and the content is 99.0%.
The product nuclear magnetic data is as follows, the product is a pair of diastereomers: 1 H NMR(500MHz，CDCl 3 )：δppm 6.795(s，1H)，6.794(s，1H)，4.554－4.515(m，1H)，4.455－4.416(m，1H)，3.670－3.630(m，4H),3.603－3.509(m，2H),3.387－3.313(m，2H),3.282(s，3H)，3.252(s，3H)，2.336(s，3H)，2.321(s，3H)，2.065(s，3H)，2.048(s，3H)，1.199－1.185(d，3H)，1.118－1.104(d，3H)。 13 C NMR(125MHz，CDCl 3 )：δppm 167.080,167.035，137.073,136.797,135.169,135.147,134.381,133.886,118.283,118.254,74.443,74.240,58.528,58.480,54.833,54.090,42.676,15.583,15.060,14.554,14.278,13.825,13.351。
the above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The method is characterized in that Lewis acid or organic acid is used as a catalyst, and under the heating condition, the N-aryl ketimine is generated by condensation of aromatic amine and ketal, and the reaction formula is as follows:
in the reaction formula: ar is selected from phenyl, thienyl, pyridyl, furyl, pyrrolyl, or the aromatic ring carries one or more of the following substituents: halogen, alkyl, alkoxy, phenyl or benzyl;
wherein R is 1 And R is 2 Respectively selected from alkyl, phenyl, benzyl, thienyl, pyridyl, furyl and pyrrolyl, or the aromatic ring is provided with the following substituent groups: halogen, alkyl, alkoxy, phenyl or benzyl, R 1 、R 2 The same or different;
R 3 selected from methyl, ethyl, propyl, butyl or 1, 2-disubstituted ethyl, 1, 3-disubstituted propylCyclic ketals of either meta or hexameta.
2. The method for synthesizing N-aryl ketimine by acid-catalyzed ketal process according to claim 1, wherein the solvent used in the method is selected from toluene, xylene, 1, 2-dichloroethane, chloroform, ethyl acetate, acetonitrile, dioxane or tetrahydrofuran.
3. The method for synthesizing N-aryl ketimine by acid catalysis ketal method according to claim 1, wherein the molar ratio of the aromatic amine to ketal is 1 (1.0-3.0).
4. The method for synthesizing N-aryl ketimine by acid catalysis ketal method according to claim 1, wherein the molar ratio of the acid catalyst to the aromatic amine is (0.1% -5%): 1.
5. The method for synthesizing N-aryl ketimine by acid-catalyzed ketal process according to claim 1, wherein the Lewis acid or organic acid catalyst comprises tin dichloride, ferric chloride, bismuth triflate, scandium triflate or p-toluenesulfonic acid;
the mol ratio of the acid catalyst to the aromatic amine is (0.5% -5%) 1.
6. The method for synthesizing N-aryl ketimine by acid-catalyzed ketal process according to claim 1, wherein Ar is selected from phenyl, thienyl, or the aromatic ring has the following substituents: chlorine, alkyl or alkoxy;
the R is 1 And R is 2 Respectively selected from alkyl, phenyl, benzyl or the aromatic ring, and has the following substituent groups: halogen, alkyl or alkoxy, R 1 、R 2 The same or different;
the R is 3 Selected from methyl or ethyl.
7. The method for synthesizing N-aryl ketimine by acid-catalyzed ketal process according to claim 1, wherein the aromatic amine is selected from 2, 4-dimethyl-3-aminothiophene, 2, 6-dimethylaniline or 2-methyl-6-ethylaniline;
the molar ratio of the aromatic amine to the ketal to the acid catalyst to the solvent is 1:1.1-2.0:0.005-0.05:3-10.
8. The method for synthesizing the N-aryl ketimine by an acid-catalyzed ketal process according to claim 1, wherein the solvent is selected from toluene, 1, 2-dichloroethane, chloroform or tetrahydrofuran;
the heating reaction temperature is (60-120).
9. An N-aryl ketimine synthesized by the method for synthesizing an N-aryl ketimine by the acid-catalyzed ketal method according to any one of claims 1 to 8.
10. The method for synthesizing N-aryl ketimine by using the acid-catalyzed ketal method according to any one of claims 1 to 8, which is applied to the synthesis of herbicide dimethenamid.
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