A method for synthesizing 2-halo-3-substituted hydrocarbylsulfonylpyridines and intermediates thereof by ionic liquid method

A technology for hydrocarbyl sulfonyl pyridine and hydrocarbyl, which is applied in the field of ionic liquid synthesis of 2-halogenated-3-substituted hydrocarbyl sulfonyl pyridine and its intermediates, and can solve the problems of difficult large-scale production, difficult treatment, and many three wastes.

Inactive Publication Date: 2019-09-24
SHANDONG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0008] But the shortcoming of this synthesis method is: the yield is low, the three wastes are more, and it is difficult to handle
[0014] This method is the improvement to method (2), and compound pentadiene nitrile is substituted with N-methylaniline, and the cyclization reaction yield improves slightly, and total yield is still not very ideal, and yield is 65%; many and difficult to handle
[0015] It can be seen that the existing sulfonylpyridine preparation methods generally have problems such as many "three wastes" and low yields, which are difficult to scale production; It is carried out in a traditional organic solvent, and there is no report on the preparation of 2-halo-3-ethylsulfonylpyridine by the ionic liquid method

Method used

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  • A method for synthesizing 2-halo-3-substituted hydrocarbylsulfonylpyridines and intermediates thereof by ionic liquid method
  • A method for synthesizing 2-halo-3-substituted hydrocarbylsulfonylpyridines and intermediates thereof by ionic liquid method
  • A method for synthesizing 2-halo-3-substituted hydrocarbylsulfonylpyridines and intermediates thereof by ionic liquid method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0078] Example 1: Preparation of 2-methylsulfonyl-5-(N,N-dimethyl)amino-2,4-pentadienenitrile

[0079] Add 59.6g (0.5mol) of methylcyanoethylsulfone, 50mL of N-butyl-N-ethylpiperidinium bromide, and 62mL (0.5mol) of 3-dimethylaminoacrolein into the reactor, mix well, and heat in microwave Reaction at a temperature of 55°C and incubated for 1 hour, TLC detection (petroleum ether:dichloromethane 1:2 development, sublimation iodine color development) 3-dimethylaminoacrolein has completely reacted, cooled to room temperature, organic solvent dichloromethane extraction 60mL ×3, the remaining phase ionic liquid was washed with water, dried in vacuum and reused. The organic phase was distilled off and the solvent dichloromethane was recovered to obtain 95.7 g of a light yellow solid with a melting point of 169-171° C. and a product yield of 95.6%. After HR-MS, 1 H NMR, 13 According to CNMR spectrum, the product is 2-methylsulfonyl-5-(N,N-dimethyl)amino-2,4-pentadienenitrile.

[00...

Embodiment 2

[0084] Example 2: Preparation of 2-ethylsulfonyl-5-(N,N-diethyl)amino-2,4-pentadienenitrile

[0085] Add 66.6g (0.5mol) of ethyl cyanoethyl sulfone, 50mL of N-ethyl-N-ethylpiperidinium chloride salt, and 124mL (1.0mol) of 3-diethylaminoacrolein into the reactor, mix well, and heat in a water bath Reaction at a temperature of 65°C and incubated for 10 hours, TLC detection (petroleum ether:dichloromethane 1:3 development, sublimation iodine color) ethyl cyanoethyl sulfone reaction is complete, cooled to room temperature, organic solvent toluene extraction 60mL×3, The remaining phase ionic liquid was washed with water, vacuum dried and reused. The organic phase was distilled off under reduced pressure to recover the solvent toluene to obtain 113.3 g of a light yellow solid with a melting point of 155-157° C. and a yield of 93.5%. The product was characterized by HR-MS, that is, 2-ethylsulfonyl-5-(N,N-diethyl)amino-2,4-pentadienenitrile. HR-MS(ESI):m / z Calcd for C 11 h 18 N 2 ...

Embodiment 3

[0086] Example 3: Preparation of 2-isopropylsulfonyl-5-(N,N-diethyl)amino-2,4-pentadienenitrile

[0087] Add 61mL (0.5mol) of isopropylcyanoethylsulfone, 50mL of N-ethyl-N-ethylpiperidinium chloride salt, and 62mL (0.5mol) of 3-diethylaminoacrolein into the reactor, mix well, and heat Reaction at a temperature of 63°C and incubated for 6 hours, TLC detection (petroleum ether:dichloromethane 1:2 development, sublimation iodine color development) 3-diethylaminoacrolein has completely reacted, cooled to room temperature, organic solvent toluene 60mL extraction 3 times , the remaining phase ionic liquid was washed with water, dried in vacuum and reused. The organic phase was evaporated under reduced pressure to remove the solvent toluene and recovered to obtain 118.2 g of light brown oil with a yield of 92.2%. The product was characterized by HR-MS, that is, 2-isopropylsulfonyl-5-(N,N-diethyl)amino-2,4-pentadienenitrile. HR-MS(ESI):m / z Calcd for C 12 h 20 N 2 o 2 S 279.3542[M...

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Abstract

The invention discloses a method for synthesizing 2-halo-3-substituted alkyl sulfonyl pyridine and an intermediate thereof by using an ionic liquid method. The method comprises the following steps: adding substituted amino acraldehyde, an ionic liquid and substituted cyanoethyl sulphone into a reactor, uniformly mixing, performing reaction, and tracking the reaction till the substituted amino acraldehyde or the substituted cyanoethyl sulphone is completely reacted so as to obtain an intermediate; adding halogen hydride into a reaction liquid for continuous reaction, and tracking detection till the reaction is completed; adding an alkali liquid into the reaction liquid to adjust the pH value to 7-8, leaving to stand and layer so as to obtain a water layer and an organic layer, extracting the water layer by using an organic solvent, combining the organic layer, and refining, thereby obtaining the 2-halo-3-substituted alkyl sulfonyl pyridine. The method for synthesizing the 2-halo-3-substituted alkyl sulfonyl pyridine, which is disclosed by the invention, has the advantages of being green and environment-friendly, short in reaction time, simple to operate, high in product yield and relatively good in bactericidal activity of products.

Description

technical field [0001] The invention relates to the field of organic chemistry, in particular to a method for synthesizing 2-halo-3-substituted hydrocarbylsulfonylpyridine and its intermediate by an ionic liquid method. Background technique [0002] In the production of organic chemical products, it is often necessary to use a large amount of organic solvents, but organic solvents are highly volatile and easily cause environmental pollution. Compared with traditional organic solvents and electrolytes, ionic liquids have a series of outstanding advantages: (1) almost no vapor pressure, non-volatile, colorless, and odorless; (2) a larger stable temperature range, better chemical stability (3) Its solubility to inorganic substances, water, organic substances and polymers can be adjusted through the design of anions and cations, and its acidity can be adjusted to superacid; (4) It is easy to mix with Other substances are separated and can be recycled; (5) show good solubility f...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D213/71C07C309/22A01P3/00
Inventor 刘玉法孙琳张彦春徐家丽李硕鑫
Owner SHANDONG NORMAL UNIV
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