The chloride chloropyridine and method of production thereof

 

(57) Abstract:

The chloride chloropyridine General formula I, where R1-C1-6-alkyl, C1-6alkenyl, benzyl, possibly substituted by halogen or C1-4-alkyl; R2is unsubstituted or substituted WITH1-6-alkyl; R3is hydrogen or halogen, can be used as intermediates for obtaining agrochemical or pharmaceutical active substances or to obtain their predecessors. 2 S. p. f-crystals, 1 table.

The invention relates to new chloride chloropyridine, which can be used as intermediates for obtaining agrochemical or pharmaceutical active substances, in particular the chlorides chloropyridine General formula (I)

< / BR>
where

R1is unsubstituted or substituted C1-C6-alkyl or C3-C6alkenyl, benzyl which may be substituted with halogen or C1-C4-alkyl,

R2is unsubstituted or substituted C1-C6-alkyl,

R3is hydrogen or halogen.

New chloride chloropyridine the General formula (I) is produced by interaction of enamide the General formula (II)

< / BR>
where R1, R2and R3have the above knowledge and R5each signifies alkyl,

and, if necessary, in the presence of a diluent at a temperature from minus 30oC to + 100oC.

This method is another object of the invention. New chloride chloropyridine formula (I) are the original product to obtain chloropyridine formula (IV)

< / BR>
where R2and R3have the above meaning,

by thermal cleavage.

According to the proposed method are preferably the compounds of formula (I), in which

R1is unsubstituted or substituted by halogen (in particular fluorine, chlorine or bromine) or alkoxygroup with 1 to 4 carbon atoms (in particular methoxy - or ethoxypropane) alkyl with 1 to 6 carbon atoms, unsubstituted or substituted with halogen (in particular fluorine, chlorine or bromine) alkenyl, unsubstituted or substituted by fluorine, chlorine, stands, ethyl, propylene or bootrom benzyl,

R2is unsubstituted or substituted by halogen (in particular fluorine, chlorine or bromine) or alkoxygroup (in particular methoxy - or ethoxypropane) alkyl with 1 to 6 carbon atoms,

R3is hydrogen, fluorine or chlorine.

According to the proposed method are, in particular, the compounds of formulas is nesennye or substituted by chlorine, the stands, ethyl, n - or ISO-propylene, n-, ISO-, sec - or tert-bootrom benzyl,

R2is unsubstituted or zameshannye fluorine, chlorine, bromine, methoxy - or ethoxypropane methyl, ethyl, n - or ISO-propyl, n-, ISO-, sec - or tert-butyl,

R3is hydrogen or chlorine.

If used as starting compounds, for example, N-ethyl-N-(1-propen-1-yl)-ndimethylacetamide, phosgene and N,N-dimethylformamide, then the course of the reaction according to the invention can be represented by the following scheme:

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The initial compounds of General formula (II) are known and/or can be obtained by known methods (see application EP No. 546 418; J. Chem. Soc. Perkin Trans.I 1984, pages 1173 - 1182). The method according to the invention is carried out with application glorieuses agent. This may be a normal gloriouse agents, such as, for example, phosphorylchloride (phosphorus oxychloride), phosphorus (V) chloride, phosgene, oxalicacid, thionyl chloride, the acid chloride perchloroethane acid, dichlorobenzothiazole, N,N-dimethyl - chlorotrimethylsilane or N,N-diethyl-chlorotrimethylsilane.

Especially preferred gloriouse agent according to the method according to the invention is phosgene. Derivatives of formamide of the formula (III) are known substances.

As a particularly preferred derivatives of formamide should be called N,N-dimethylformamide and N,N-dibutylformamide.

As a diluent in the process according to the invention can be applied to conventional organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, possibly substituted halogenated hydrocarbons, such as benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as, for example, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or dimethyl or diethyl ether of ethylene glycol, NITRILES, such as, for example, acetonitrile, propionitrile or butyronitrile, amides, such as, for example, N,N-dimethylformamide, N, N-dimethylated-amide, N-methylformamide, N is an organic or triamide hexamethylphosphoric acid; sulfoxidov, such as, for example, dimethyl sulfoxide and sulfones, such as, for example, tetramethylsilane.

Especially preferred solvents are chlorobenzene and acetonitrile.

The method according to the invention Ave the equipment is temperature from minus 19oC to plus 40oC, and in the end from the 40oC to 75oC.

The method according to the invention is usually at atmospheric pressure. However, you can also work at elevated or reduced pressure, typically from 0.1 bar to 10 bar.

For carrying out the method of obtaining compounds of formula (I) is usually introduced on 1 mol of enamide formula (II), 1 to 10 mol, preferably 1.5 to 5.0 mol, in particular 2.0 to 3.0 mol glorieuses funds and 1 to 10 mol, preferably 1.0 to 2.0 mol derived formamide of the formula (III).

When carrying out the method according to the invention the components of the reaction may be subjected to transformation in any order.

According to a preferred form of the method first make the diluent derived formamide of the formula (III) and gloriouse agent and then add UNAMID formula (II) at a temperature of from -10oC to +50oC; then add gloriouse agent. Then complete the interaction of one or many hours of stirring at slightly elevated temperature.

Processing of the reaction mixture is carried out in the usual way. For example, dilute with water to two - three times the volume. By adding a base, for example, caustic soda, ustanny as the residual crude product is purified further by standard techniques, however, it can be used for further transformations and as such.

Obtained according to the method according to the invention, the chloride chloropyridine formula (I) can be used as intermediates for obtaining agrochemical or pharmaceutical active substances or to obtain their predecessors; for example, thermal decomposition receive chloropyridine formula (IV)

< / BR>
and the chlorides of the formula R1- Cl.

Depending on the substituent R require different temperature thermolysis, usually from 75oC to 200oC. Both components can be separated by distillation.

The following examples explain the invention.

Example 1.

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In 800 ml of chlorobenzene make 345,4 g (2.2 mol) of N,N-dibutylformamide. Miss 396 g (4 mol) of phosgene, the mixture is heated to a temperature of 40oC and when the internal temperature of 35 - 40oC was added dropwise 388 g (2 mol) of 97.4% N-benzyl - N-(1 - propen-1-yl)-ndimethylacetamide. When the internal temperature of 45oC pass additional 99 g (0.5 mol) of phosgene. The mixture is heated to a temperature of 70oC and stirred for 1 hour at a temperature of 70oC. Then cooled to room temperature (20oC), add 500 ml of water and prikaspian the Ura is a maximum of 30oC. the Phases are separated and the aqueous phase is evaporated to dryness when the internal temperature maximum 50oC. Receive 590 g of a light beige solid, which according to HPLC and1H-NMR consists of 65 % N-benzyl-2-chloro-5 - metilprednisolona, representing 75.5 % of theory.

By stirring with ethyl ether acetic acid pure salt (so pl.: 71 - 74oC.

1H-NMR (D2O): 2.5 h/mill (s; CH3) 5,9 h/mill (s; CH3that 7.4 and 7.5 h/mill (m, C6H5), 8,07 and 8.1 (d, CH), at 8.36 and 8,39 (DD, CH), and 8.8 (s, CH).

Example 2.

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15,5 r (0.1 mol) N-butyl-N-(1-propen-1-yl)ndimethylacetamide and 8 g (0.11 mol) of dimethylformamide are dissolved in 80 ml of dry acetonitrile and added dropwise with stirring (0.2 mol) of oxalicacid for 30 minutes at a temperature of 15oC. Then the reaction mixture is heated to a temperature of 40oC and again added dropwise 12.7 g (0.1 mol) of oxalicacid within 15 minutes. Then stirred for 10 hours at a temperature of 40 - 45oC. Distilled off in vacuum acetonitrile and vmeshivat the remaining oil in 350 ml of water, set with caustic soda pH = 5 and extracted three times with methylene chloride. The aqueous phase is evaporated to dryness in a vacuum. To staticstatic (so pl. 132-136oC with decomposition).

Analogously to examples 1 and 2 and in accordance with the General description of the proposed method can be obtained are listed in the table below, the compounds of formula (I).

Example 9.

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25,4 r (0.1 mol) of N-benzyl-2-chloro-5-metilprednisolona heated in a distillation apparatus to a temperature of 80 - 140oC in a water-jet vacuum pump. Argonauts a mixture of 2-chloro-5-methylpyridine and benzylchloride, which can be divided clear rectification.

Yield: almost quantitative.

Decomposition temperature N-n-butyl-2-chloro-5 - metilprednisolona is 130 - 160oC, N-propenyl - 2 - chloro-5-methyl-pyridinylamino is 145 - 180oC. the Yield of 2-chloro-5-methylpyridine also quantitative.

1. The chloride chloropyridine General formula I

< / BR>
where R1is unsubstituted or substituted WITH1-C6-alkyl or C3-C6alkenyl, benzyl which may be substituted with halogen or1-C4-alkyl;

R2is unsubstituted or substituted WITH1-C6-alkyl;

R3is hydrogen or halogen.

2. A method of obtaining a chloride chloropyridine General formula I

< / BR>
where R1- illegal is Eden halogen or1-C4-alkyl,

R2is unsubstituted or substituted WITH1-C6-alkyl,

R3is hydrogen or halogen, characterized in that UNAMID General formula II

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where R1, R2and R3have the above values,

subjected to interaction with gloriouse agent in the presence of a derivative of formamide of the General formula III

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where R4and R5each signifies alkyl,

and, if necessary, in the presence of a diluent at a temperature ranging from -30°C to + 100°C.

 

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Ionic liquids ii // 2272043

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