DE2608094C2 - - Google Patents

Description

or

J-O

J (OCOCH ₃ J ₂

reacts together and (2) the product of stage (1) treated with HCl

2. Di- or trichloroacetoxyiodobenzenes of the general formula

in which Z represents H or Cl.

The method described in the patent is that when carrying out the first stage, a reaction time from 16 to 17 hours is required. Another disadvantage is the price of trifluoroacetic acid.

The invention relates to a process for the preparation of a phenyliodonium chloride compound the general formula

[R-J-RTClo

in which R is 2-thienyl, phenyl, lower-alkylphenyl or lower-alkoxyphenyl and R 'denotes the remainder

means, characterized in that (1) thiophene, benzene, lower-alkylbenzene or lower alkoxybenzene with

(a) a compound of the general formula

-J (OCOCZCl ₂ J ₂

in which Z is H or Cl, or

(b) Di- or trichloroacetic acid and a compound of the general formula

The invention relates to a process for the preparation of phenyl iodonium chloride compounds.

In CA-PS 9 13 109 iodonium salts are described as antimicrobial agents or as microbiocides for the control of bacterial organisms such as gram-negative and gram-positive species, Mold, powdery mildew or powdery mildew blight, fungi or slime are effective. The salts are special for the preservation of paper, plaster or plaster or mortar, flat structures, cooling water, resins, Adhesives, paints, paints, oils, terrestrial plants, detergents, soaps, shampoos and wood. The salts of greatest value and interest are the chlorides.

In the process for the preparation of phenyliodonium chloride compounds described in the cited patent two stages are carried out: (1) reaction of (diacetoxyiodine) benzenes with (a) thiophene, benzene or a substituted benzene fts and (b) trifluoroacetic acid to produce phenyliodonium trifluoroacetates and (2) treatment of the trifluoroacetates with HCl. A disadvantage of the

«5 C!

means that is characterized in that one (1) thiophene, benzene, lower alkylbenzene or lower alkoxybenzene with

(a) a compound of the general formula

-J (OCOCZCl ₂ ) Z

in which Z is H or Cl, or

(b) Di- or trichloroacetic acid and a compound of the general formula

or

CIH ^ -J (OCOCH ₃ J ₂

reacts together and (2) the product of stage (1) treated with HCl.

The invention also relates to di- and trichloroacetoxyiodobenzenes of the general formula

40 -J (OCOCZCl _{2 I 2}

in which Z represents H or Cl.

In the first stage of the process according to the invention, essentially thiophene, benzene, lower-alkylbenzene or lower-alkoxybenzene is reacted with a compound of the formula R ¹ J (OCOCZCl ₂ J _2. The latter is new and can be preformed or formed in situ by joint reaction of (a) thiophene, benzene, lower-alkylbenzene or lower-alkoxybenzene, (b) di- or trichloroacetic acid and (c) a compound of the formula R'-J = O or R'-J (OCOCH ₃ J ₂ . It has surprisingly been found that reaction times of only 15 minutes to 2 hours are sufficient for carrying out the first stage of the process according to the invention.

It is generally desirable to carry out the reaction in the presence of an inert organic solvent perform. Appropriate solvent door include performing the first stage of the procedure halogenated hydrocarbon solvents such as methylene chloride, chloroform, perchlorethylene, 1,1,1-trichloroethane. Carbon tetrachloride or similar compounds; saturated hydrocarbons such as hexane, Octane or the like; aliphatic ethers; aliphatic and aromatic carboxylic acid esters and amides; and deactivated aromatic hydrocarbons such as chlorobenzene !, nitrobenzene or similar. The halogenated carbon

Hydrogen solvents, especially methylene chloride or chloroform, are preferred. Preferred solvents for the last stage of the process are such as acetone, ethyl acetate or formic acid, wherein the products of the first stage are soluble, but wherein the chloride salt is insoluble, so that the separation of the desired product is facilitated.

The process according to the invention is usually carried out at a temperature in the range from 0 to 100 ° C, preferably 15 to 50 ° C carried out. In some cases ι ο the first stage of the process can expediently be carried out at the boiling point of the solvent.

The first stage of the process according to the invention can expediently be carried out by adding> s thiophene, benzene or substituted benzene in portions to a dispersion of the other reactant or participants in a solvent. The reaction is somewhat exothermic and the temperature can be controlled by regulating the rate of addition of thiophene, benzene or substituted benzene. The reaction is essentially complete by the end of the addition, but some improvement in the yield can be obtained when allowed to stand the reaction mixture for a short time at a temperature up to about 50 ⁰ C. When the reaction is complete, the volatiles can be removed by distillation and the product can be crystallized by adding a non-polar solvent such as hexane. The product of the first stage corresponds to the formula

[R-J—

35

However, the separation of this product from the reaction mixture is not essential.

In the second stage of the process according to the invention the di- or trichloroacetate salt prepared in the first stage with gaseous or aqueous Treated HCl. If the treatment is carried out in the presence of a solvent, as described above, so the chloride salt precipitates as a crystalline solid. After the implementation, low-boiling components can be distilled off from the reaction mixture. The desired chloride salt can be decanted off or filtered off and further by recrystallization from an organic or aqueous organic Solvents such as acetone, ethyl acetate, pentane or hexane can be cleaned.

The following examples illustrate the invention without restricting it.

example 1
4-chloro-bis (trichloroacetoxy) iodobenzene

55

135 g (0.53 mol) of p-chloroiodosobenzene are in 800 ml of methylene chloride in a 2-1 Erlenmeyer flask is suspended. 190 g (1.16 mol) of trichloroacetic acid, dissolved in, are added to the suspension 5ÖÖ methylene chloride, with stirring over the course of 5 minutes. The reaction temperature becomes at room temperature held. After 30 minutes the solution is filtered and the solvent is reduced under reduced pressure Pressure removed. The solid residue is with f> 5 Ether triturated and filtered. The solid is collected on the filter, washed with ether and dried. The almost colorless, crystalline solid melt obtained with decomposition at 155 to 157 "C, The Yield is .80 to 85%. The substitution of dichloroacetic acid for trichloroacetic acid gives that corresponding 4-chloro-bis (dichloroacetoxy) iodobenzene, which melts at 111 to 112 ° C (decomp.).

Example 2
^ Chlorophenyl ^ -thienyliodonium dichloroacet,:!

3.6 g (0.01 mol) of 1-chloro-4- (diacetoxyiodine) benzene and 5.2 g (0.04 mol) of dichloroacetic acid in 50 ml of methylene chloride are mixed with 1.6 g (0.02 mol) of thiophene treated and 30 minutes under reflux, about 40 ⁰ C, with stirring, heated grazing the volatiles at reduced pressure and a temperature of 40 to 5O ⁰ C removed and the residual brown oil with about 100 ml ether and η-hexane treated. Crystallization is induced by scratching the inner walls of the flask with a glass rod. The resulting suspension is cooled and filtered. The product on the filter is washed with a small volume of ether and dried in vacuo at room temperature. The resulting ivory-colored, crystalline solid weighing 3.0 g (66.6% yield) and melts at 123 to 125 ⁰ C (dec.).

Example 3
4-chlorophenyl-2-thienyliodonium chloride

A suspension of 3.6 g (O ₁ OlMoI) 1-chloro-4- (diacetoxyiodine) benzene and 6.5 g (0.04 mol) trichloroacetic acid in 50 ml methylene chloride is stirred and 1.6 g (0, 02 mol) treated thiophene, which is added dropwise at room temperature over 5 minutes. The reaction mixture is then refluxed for 25 minutes. The volatile constituents are removed under reduced pressure and at a temperature of 40 to 50 ° C. The brown, oily residue is treated with 150 ml of ether, and a colorless, crystalline solid soon crystallizes out of the solution. It is filtered off, washed with ether and dried in vacuo at room temperature. A yield of 4.6 g (95%) (4 - chlorophenyl) - (2 - thienyl) - iodonium - trichloroacetate, F. 100-101 ⁰ C. After recrystallization from chloroform observed no change in the melting point.

Analysis door C ₁₂ H ₇ Cl ₄ JO ₂ S:

Calculated ... C 29.77, H 1.46, J 26.22%;
found .... C 30.0, H 1.62, J 25.9%.

1 g of the above trichloroacetate is dissolved in 35 ml of acetone at about 40 ° C and concentrated with 0.2 ml. Treated HCl. Colorless needles will gradually form. After cooling, the suspension is filtered and the Solid is washed with acetone and dried. A yield of about 80% (0.6 g) is obtained ^ -ChlorphenylJ-OthienylJ-iodonium chloride.

Example 4
4-chlorophenyl-2-thieny! Iodonium chloride

135 g (0.53 mol) of l-chloro-4-iodosobenzene are in Dissolve 800 ml of methylene chloride and add 347 g (2.12 mol) of trichloroacetic acid in 500 ml of methylene chloride to this solution added over 5 minutes with stirring at room temperature. Then 53.4 g

5 6

(0.636 Mo)) Thiophene over 5 minutes at Zim-HCl is added and the mixture becomes 20 minutes

mertemperature admitted. The resulting mixture is left to stand. The solid product that separates out

Stirred for 10 minutes at room temperature, the temperature is filtered off and mixed with two 500 ml parts of acetone

temperature is increased to 40 ° C. over 15 minutes, washed and dried. 129 g (68.4%

and then 3 l of acetone are added. 83 ml conc. s yield) of the desired product.

Claims (1)

Patent claims: 1. Process for the preparation of phenyliodonium chloride compounds the general formula [RJ-R /] CI ^e in which R 2-thienyl, phenyl, low-alkylphenyl or lower-alkoxyphenyl and R 'denotes the remainder