JPH03215469A - 5,6-dihydro-4(1H)-pyridinone derivative - Google Patents

Abstract

NEW MATERIAL:The 3-chloro-5,6-dihydro-4(1H)-pyridinone derivative of formula I (X is halogen; Y is halogen or lower alkoxy; Z is H or halogen). EXAMPLE:3-Chloro-1-(2-chloro-3,5-dimethoxyphenyl)-2-(4-fluorophenyl)-6 -phenyl-5,6- dihydro-4(1H)-pyridinone. USE:Useful as a synthetic intermediate for a 3-chloro-4(1H)-pyridinone derivative having activities as agricultural chemicals or pharmaceuticals. PREPARATION:The compound of formula I can be produced by reacting a 5,6-dihydro-4(1H)-pyridinone derivative of formula II with a chlorination agent, thereby selectively chlorinating the 3-site. The reaction temperature is below the boiling point, preferably 0-30 deg.C. The chlorination agent is chlorine, N- chlorosuccinimide, etc.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to the use of 3-chloro-4( 1H) A novel intermediate of monopyridinone derivatives, 3-chloro-5,6-dihydro-4
(IH) This relates to a pyridinone derivative.

(Problems to be Solved by the Invention) Conventionally, when the 2- and 6-positions of the 4(IH)-pyridinone skeleton are asymmetrically substituted phenyl groups, direct chlorination produces the 5-chloro form or 5-chloro form as well as the 3-chloro form of the target product. 3.5-dichloromethane was produced as a by-product and reduced the purity. Moreover, it is very difficult to separate the 3-chloro form of these by-products by recrystallization, distillation, column chromatography, or the like.

(Means for Solving the Problem) As a result of many years of research, the present inventor has found that the general formula (I)
3-chloro-5.6-dihydro-4 (L
H) The present invention was completed based on the recognition that the monopyridinone derivative is a new compound that has not been described in any literature, and that conventional problems can be solved by using it. That is, the present invention provides 3-chloro5,6-dihydro-4 represented by (wherein, X represents a halogen atom, Y represents a halogen atom or a lower alkoxy group, and Z represents a hydrogen atom or a halogen atom).
(LH) is a monopyridinone derivative.

The compound of the present invention consists of a 5,6-dihydro-4(IH) monopyridinone derivative [general formula (■)] represented by (wherein, χ, Y, and Z have the same meanings as above) and a chlorinated By reacting with the agent, the 3-position is selectively chlorinated and can be obtained with high purity and high yield. As the chlorinating agent to be used, there is no problem in using any normally named chlorinating agent. For example, chlorine or N-chlorosuccinimide can be used.

Further, any solvent that is inert to the reaction may be used. Examples include benzene, toluene, chlorobenzene, silane, dioxane, chloroform, carbon tetrachloride, and acetic acid. Moreover, the reaction temperature can be below the boiling point, preferably at a temperature of 0 to 30°C. In addition, the 5,6 dihydro-4 (LH) monopyridinone derivative [general formula (■)] used above can be used in synthesis.
), 777 (1977), by reacting the 1-penten-4-yn-3-one derivative with anilines. Specific examples of the 3-chloro-5,6-dihydro-4(IH)-pyridinone derivative [general formula (I)] of the present invention obtained in this way and the results of confirmation data such as IR or NMR are shown below. Shown in 1. Also 3-chloro-5
．． A 6-dihydro-4(LH)pyridinone derivative [general formula (I)] can be easily derived into a 3-chloro-4(IH)-pyridinone by reacting with a dehydrogenating agent.

(Effect of the invention) The 3-chloro-5,6-dihydro-4(IH) monopyridinone derivative [general formula (I)] of the present invention is a novel compound that has not been described in any literature, and according to the above method, The target product can be obtained with high purity without the need for reconsolidation or distillation. In addition, the compound of the present invention can be easily reacted with a dehydrogenating agent to
It is a compound that is highly effective as an intermediate, as it can be derived into 3-chloro-4(1M)-pyridinone derivatives having agricultural or pharmaceutical activity.

(Example) The present invention will be specifically described below with reference to Reference Examples and Examples.

Reference example 1 ■-(2-chloro-3.5-dimethoxyphenyl)-2
-(4-fluorophenyl)-6-phenyl 5.6-
Synthesis of dihydro-4(IH)-pyridinone (synthesis of raw materials) 5.28 g of 1-phenyl-5-(4-fluorophenyl)-1-penten-4-yn-3one in 100 ml of acetic acid
, 4.71 g of 2-chloro-3,5-dimethoxyaniline
was added and refluxed for 5 hours.

After cooling, the reaction solution was poured into water, made weakly alkaline with 1N caustic soda, extracted with ether, concentrated, and purified by column chromatography (solvent: hexane/ethyl acetate - 2/1). 6.06 g of the target compound having a melting point of 143-144°C was obtained. The yield was 65.7%.

Example 1 Synthesis of 3-chloro-1-(2-chloro-3,5-dimethoxyphenyl)-2-(4-fluorophenyl)6-phenyl-5,6-dihydro-4(LH)pyridinone ( Compound 1) 1-(2-chloro-3,5-dimethoxyphenyl-2-(4-phenoleophenyl)- obtained in Reference Example 1)
2.3 g of 6-phenyl-5.6-dihydro-4(IH)-pyridinone is dissolved in 100-chlorobenzene.

0.38 g of chlorine was added to this solution, and the mixture was stirred at room temperature for 30 minutes. Add 100mf of chloroform to the reaction solution to make 10%
Washed with caustic potassium aqueous solution, concentrated and dried to a melting point of 178-1
1.51 g of the target compound was obtained at 79°C. Yield is 61.1
%Met.

Example 2 Synthesis of 3-chloro-1-(2-chloro-3,5-dimethoxyphenyl)-2-(4-methoxyphenyl)6-phenyl-5,6-dihydro-4(IH)pyridinone (
Compound 2) 1-(2-chloro 3,5-
dimethoxyphenyl)-2-(4-methoxyphenyl)
2.3 g of -6-phenyl-5,6-dihydro-4(LH)-pyridinone is dissolved in 100 g of chlorobenzene. 0.69 g of N-chlorosuccinimide was added to this solution, and the mixture was stirred at room temperature for 30 minutes. Add 10% chloroform to the reaction solution.
0 ml was added thereto, washed with a 10% aqueous potassium hydroxide solution, concentrated and dried to obtain 1.48 g of the target compound having a melting point of 181-182°C. The yield was 60.0%.

Example 3 3-chloro-1-(2-c4-3.5-dimethoxyphenyl)-2-(4-methoxyphenyl)6-(2-
Synthesis of pyridinone (compound 3) 1-(2-chloro3,5-dimethoxyphenyl)- obtained in the same manner as in Reference Example 1
100ml of 2.39g of 1-(4-fluorophenyl)-6-(4-methoxyphenyl)5,6-dihydro-4(LH)-pyridinone! dissolved in chlorobenzene.

0.69 g of N-chlorosuccinimide was added to this solution, and the mixture was stirred at room temperature for 30 minutes. Add 10% chloroform to the reaction solution.
0mj! was added, washed with a 10% caustic potassium aqueous solution, concentrated and dried to obtain 1.86 g of the target compound with a melting point of 184-185°C.
I got it. The yield was 72.5%.

Reference Example 2 3-chloro-1- described in JP-A-1-156918
(2-chloro-3,5-dimethoxyphenyl)-2-(
Synthesis of 4-chloro-1-pyridinone (4-fluorophenyl)-6-phenyl-4(LH)-3-chloro-1-obtained in Example 1
(2-k4-4-3,5-dimethoxyphenyl)-2-(
4-fluorophenyl)-6-phenyl5. 100ml of 1.40g of 6dihydro-4(IH)-viridinone
of dioxane, and in this solution pchloranil 1.4
5 g was added and refluxed for 10 hours.

Add 100mf of chloroform to the reaction solution! was added, washed with 10% caustic potassium aqueous solution, dried and concentrated to obtain a melting point of 276-277.
0.82 g of the target compound was obtained. The yield was 59.3%.

Rin Iro patent applicant Kumiai Chemical Industry Co., Ltd.

Claims (1)

[Claims] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents a halogen atom, Y represents a halogen atom or a lower alkoxy group, and Z represents a hydrogen atom or a halogen atom.) 3-chloro-5,6-dihydro-
4(1H)-pyridinone derivative.