SU791229A3 - Method of preparing dihydropyridine derivatives - Google Patents

Description

where the values of R and K are given, are reacted with an aldehyde of the general formula i | 1, where the values of R are given, and with ammonia, and the desired product is given. The starting compounds of the general formulas. ll, in which R is methyl, is obtained by reacting compounds of the formulas Hj C-CSsO about -CH-fi-OCMj si, -y with an alcohol of general formula K2. Compounds of the general formula u, in which X represents CjL-C j-alkyl, are obtained by reacting the compound RgHal, where Rj - has the same meaning that R but contains one atom less than R, with the compound of the general formula (1) R is methyl Example 1. 2,6-Dimethyl-3,5-dicarboallylloxy-1, 4-dihydropyridium 28.4 g (0.2 mol) of allyl acetoacetate and 0.2 are introduced into the reactor, cooled in an ice bath. g of diethylamine. The resulting solution is cooled to 0 s and 7.5 g (0.1 mol) of a 40% aqueous solution of formic aldehyde is added dropwise over 90 minutes while maintaining the temperature below or equal. The reaction mass is maintained for 6 hours and then at room temperature for 40 hours. The resulting solution is decanted and the aqueous phase is extracted with ether. The ether phase is added to the oil phase and dried over anhydrous sodium sulfate. The resulting solution is filtered and the ether the residue is distilled off with one part methanol. Ammonia is bubbled through the resulting solution while maintaining the temperature equal to OC, and the solution is saturated with ammonia and left to stand at room temperature for 12 hours. the solution is filtered on a Buchner funnel and the resulting solid residue is recrystallized from acetone to form 2, b-dimethyl-3,5-diYarboallylloxy-1, 4-dihydropyridine. 75% yield. T.SH1. 167 ° C. According to the described method, using the corresponding starting products, the products listed in Table 1 are obtained. Table 1

2,6-Dimethyl-3, 5-dicarbopropargyloxy-1, 4-dihydropyridine

2,6-Dimethyl-3,5-di- (2-carbochloroethoxy) -1,4-dihydropyridine

2,6-Dimethyl-3, 5-di- (4-carbomethoxybenzyloxy) -1,4-dihydropyridine

2,6-Dimethyl-3, 5-dicarbobenzyloxy-1, 4-dihydropyridine 2, b-Dimethyl-3,5-dicarbocinamine-1, 4-dihydropyridine

2, b-Dimethyl-3,5-di- (2-carbochlorobenzyl-oxy) -1,4-dihydropyridine

2,6-Dimethyl-3, 5-di- (2-carbomethylbenzyl-oxy-1,4-dihydropyridine Example 2. 2, b-Dimethyl-3,5-dicarbopropargyloxy-1, 4-dihydropyridine. Into the reactor load 14 g (0.1 mol) propargylacetoacetate, 10.5 g (0.075 mol) of hexamethylenetetramine.

60 202-203 (acetone)

31,158 (acetone)

18,143 (benzene 55 C)

57 122 (benzene).

156 (benzene over 37 that acetone)

44,190 (acetone) 47,140 (acetone) 60 2.9 g (0.038 mol) of ammonium acetate, 36 g of methanol and 5 g of water. In a weak stream of nitrogen, the reaction medium is boiled for one hour and cooled to room temperature and poured into a mixture of ice-water.

The resulting residue is filtered and washed with hot acetone to remove excess hexamethylenetetramine.

The resulting precipitate is dried with a constant weight ds, washed with hot aceto2, b-dimethyl-3,5-dicarboyalyloxy-1, 4-dihydropyridine

2, 6-Dimethyl-3,5-di- (4-gcarbochlorobenzyloxy) -, 4-dihydropyridine

2,6-Dimethyl-3, 5-dicarbobenzyloxy-1, 4-dihydropyridine

2,6-Dimethyl-3,5-di- (2-carbobutoxy-ethoxy) -1,4-dihydropyridine

2,6-Dimethyl-3,5-di- (2-carbomethoxyethoxy) -1,4-dihydropyridine

2, b-Dimethyl-3,5-di- (2-carboethoxyethoxy) -, 4-dihydropyridine

2,6-Dimethyl-3,5-di- (2-carbophenoxyethoxy) -, 4-dihydropyridine

2, b-Diphenyl-3, 5-dicarbo ;; to-1, 4-dihydropyridine

2, b-Dibenzyl-3,5-dicarboethoxy-1, 4-dihydropyrin

2,6-Di-butenyl-3, 5-dicarbomethoxy-1, 4-dihydropyridine

2,6-Dimethyl-3,5-di / 2-carboxy-2-ethoxy-ethoxy / 1/4-dihydropyridine.

2,6-Ditridecyl-3, 5-dicarbomethoxy-1, 4-dihydropyridine

Example 3. 2,4,6-Trimethyl-3, 5-dicarbomethoxy-1,4-dihydropyridine.

232 g (2 mol) of methyl acetoacetate and 160 g of methanol are introduced into the reactor. With stirring, dropwise added at 44 g (1 mol) of freshly distilled acetaldehyde.

Stirring is continued at the same temperature for 15 minutes in a: nitrogen stream and 90 g is added.

nom and get 2,6-dimethyl-3,5-dicarbopropargyloxy-1, 4-dihydropyridine. 75% yield, m.p. 206 ° C.

According to the described procedure and using the corresponding starting material, the compounds listed in Table 2 are obtained. 2

table 2

168 (rinsing with hot acetone)

171 (acetone) 120 (methanol)

95 (methanol) 107 (methanol) 109 (methanol)

132 (acetone)

142 (ethyl ether)

118 (methanol)

79 (benzene / pentane, 10/30)

156 (methanol-acetone 80/20)

61 (acetone)

20% ammonium hydroxide solution (1.15 mol). The temperature is raised to and the mixture is heated to the boiling point of methanol for one hour.

After cooling, the reaction mass is poured into a mixture of water and ice, and the resulting precipitate is filtered on a Buchner funnel.

The resulting precipitate is thoroughly protruded with water and recrystallization

From methanol and get 2,4, b-trimethyl-3/5-dicarbomethoxy-1, 4-ligylopyril-. Yield 69% / m. Pl, 155.

2,6-Dimethyl-3/5-icarbomethoksn-4-hexyl-1, 4-dihydropyridine

2, b-Dnmethyl-3/3 dicarbomethoxy-4-propyl-1 f 4-dihydropyridine

2,4,6-Trimethyl-3, 5-di- {4-carbomethyl-phenoxy) 1,4-dihydropyridine

2,4,6-Trimet L-3, 5-dicarbobenzyloxy-1, 4-dihydropyridine

2,4, b-rimethyl-3,5-gdikarboal liloksi-1,4-dihydropiEa1 d

2,4,6-TRIMETH-3, 5-di- {4-carbochlorobenzyloxy) -, 4-dihydropyridineN

2,4, b-Trimethyl-3,5-dicarbophenoxy-1, 4-dihydropyrida 1H

2, b-Dimvtil-3,5-dicarbomethoxy-4-phenyl-1, 4-dihydropyridine Example 4. 2,6-Dimethyl-3,5.-Dicarbomethoxy-4- (1-propenyl) -1, 4-di hydropyridine; 23.2 g (0.2 mol) of methyl acetoacetate and 7 g (0.1 mol) of crotonic aldehyde are introduced into the reactor at room temperature. With stirring, a solution of 40 g (t), 42 mol of carbonate a f in 400 g of water is added and stirring is continued for 20 hours at room temperature. The viscous precipitate is dissolved in ether and the ether solution is sieved with water, dried over sodium sulfate and the ether is distilled off. The crude product is recrystallized from a mixture of ethanol and hexane and 2, b-dimethyl-3,5-dicarbomethoxy-4- (1-propenyl) -1,4-dihydropyridine is obtained. Yield 60%, T.Sh1. 176 C. Compounds of general formula I can be used to stabilize vinyl polymers and copolymers. These compounds have low toxicity and have antioxidant properties.

Using the described procedure, using the corresponding starting material, the compounds listed in Table 2 are obtained. L,

Table

100 (cyclohexane)

140 (acetone)

192 (acetone)

123 (methanol)

100 (beneolhexane)

151 (methanol) 186 (methanol) 194 (acetone) of the invention of the dibush derivatives of the formula 7 / R C-OR, straight chain alkyl, lower alkenyl, phenyl or lower alkyl phenyl} lower straight chain alkyl, lower alkenyl, lower skinil, 2-chloroethyl, benzyl or benzyl, substituted in the position by chlorine ortho- or para-atom, methyl. or methoxy, phenylalkenyl, in which alkenyl contains 2 or 3 carbon atoms; phenyl or phenyl substituted in the p-position with methyl or radical (CH.) -, in which v is 2.3 or 4, and lower straight chain alkyl is unsubstituted or substituted. or phenyl; provided that R is methyl and Rj is a hydrogen atom, then it is alkyl or phenyl. characterized in that with. the purpose of developing a process for the preparation of new compounds is that the compound of the general formula H "R-C-CHj-cOOQ 979122910 In the position of ow is an atom where C and R values are given, subchloro, phenyl; hydrogen or the general formula tu. -alkyl with pr Myr pus chain, lower alkenyl. where R is given, and ammonia is given, and the desired product is isolated. Sources of information taken into account in the examination of 1 Joel J., Smith. Fundamentals of Chemistry of Heterocyclic Compounds, M., Mir, 1975, p. 88

Claims (2)

Claim A method of obtaining derivatives of di / idropyridine of the general formula ί ^th 2 ° ~. ^with where R about. straight chain alkyl, lower alkenyl, phenyl or lower alkylphenyl} straight chain lower alkyl, lower alkenyl, lower alkynyl, 2-chloroethyl, benzyl or benzyl substituted at the position of the chloro ortho or para atom, methyl. or a methoxy group, phenylalkenyl in which alkenyl contains 2 or 3 carbon atoms; phenyl or phenyl substituted in the η position with methyl or the radical H ^ —O (CH ₁ ) _I -, in which r is 2.3 or 4, and id.- lower straight chain alkyl unsubstituted or substituted in position si chlorine atom, phenyl; R. is a hydrogen atom or C., ~ C _g ~ straight chain alkyl, lower alkenyl .. or phenyl; with the proviso that R ₁ _ denotes Me- til ^e and R ₃ - hydrogen, then W does not represent alkyl or phenyl, characterized in that, with an object of providing a process for preparing the novel compounds, a compound of general formula I]% ^. -C-CHj-coOy ^, where the values and are given, are reacted with an aldehyde of the general formula tfi R ₃ CH0, where Rj values are given, and with ammonia, and the target product is isolated.