DE3142654A1 - Process for the preparation of triiodovinyl compounds - Google Patents

Abstract

The present invention relates to a novel process for the preparation of triiodovinyl compounds by reacting the corresponding alkyne derivatives with alkali metal iodide in the presence of alkali metal hypochlorite.

Description

"Process for the preparation of triiodo-vinyl compounds"

The present invention relates to a new method of preparation of triiodovinyl compounds. A number of known trihalovinyl compounds have fungicidal, bactericidal and insecticidal effects. In DE-OS 30 26 431 are Triiodhalogenallyl compounds are described which have high preservative effects to plastic materials, wood, paper, fibers, leather, adhesives and the like demonstrate.

Some triiodovinyl compounds have a very broad microbial static Spectrum of activity and such a high effectiveness that already with one concentration of active ingredient of e.g. 0.005%, based on the weight of the entire preparation to be preserved, a sufficient preservation against bacteria and fungi is achieved.

Many of these compounds known from DE-OS 30 26 431 have also excellent compatibility with humans and animals, so that they are used for preservation of cosmetic and topical pharmaceutical preparations are more useful than conventional preservatives.

So far, these triiodovinyl compounds have been prepared, for example, by reacting the corresponding iodoacetylene compounds (Houben-Weyl, Methods * der Organischen Chemie, Vol. 5/4, pp. 534 and 554 (1960)). Another production process is described in DE-OS 30 26 431 '. All these known processes have the disadvantage that they are carried out with elemental iodine, which is very difficult to handle. In the following production method described in DE-OS 23 20 415 HC = - C-R1 In addition, two equivalents of iodine per alkyne derivative must be used, since one equivalent of alkali iodide remains in the wastewater.

The object of the present invention is to provide an improved method for the production of triiodovinyl compounds, in which the use of elementary Iodine can be avoided and practically no iodide remains in the wastewater.

According to the invention, triiodallyl compounds can be produced in a one-pot process from the corresponding alkyne derivatives (2) and alkali iodide as the iodine-yielding component: UC = CR 1) 3 KI / NaOC1 / NaOIi 2) acid pH 6 3) NaOCl (2) where R is optionally substituted by a hydroxyl, amino, cyano, alkoxy, aryloxy, thioether, carboxyl, amide, carbamoyl, quart. Ammonium group or halogen-substituted alkyl, cycloalkyl, aryl, aralkyl, heteroaryl radical or a nitrile, formyl, acyl or amide radical; R preferably represents where R¹, R², R³ is hydrogen, alkyl having 1 to 12, preferably 1 - 6 carbon atoms, aryl, heteroaryl, the group - (CH2) n - CO-X, where n = 0 - 7 and X is -oR4 or - NR4R4 ', where R and R4' denote hydrogen, alkyl or hydroxyalkyl with 1 to 6 carbon atoms, the group 5 or the group (CH2) mYR where m = 0 - 8 and Y is an oxygen or sulfur atom and R5 and R6 are hydrogen, alkyl or hydroxyalkyl with 1 to 6 carbon atoms, alkoxy, alkoxyalkyl, alkoxyether, aryl, acyl, carbamoyl, Alkylsulfonyl or arylsulfonyl are, with the condition that a maximum of two of the radicals R1, R2 ,. R3 stand for hydrogen. In particular, those compounds in which two of the radicals R1, R2, R3 are hydrogen are preferred.

In the case of water-soluble alkynes (2), the reaction takes place in water Alkynes (2), which are sparingly soluble or insoluble in water, in the presence of another 1 water-miscible solvent that acts as a solubilizer, worked. Suitable solubilizers are, for example, alcohols or ethers.

In detail, the following applies to the conditions of the new procedure: Alkali hydroxide is added to a solution containing the alkyne compound and cooled with ice. preferably sodium hydroxide, and alkali iodide, preferably potassium iodide, added and at a temperature of about 2 -50 C, for a longer period of time, e.g. 1 - 4 hours, alkali hypochlorite solution, preferably sodium hypochlorite pochlorite, added dropwise. In this first sub-step of the process, the implementation of the system takes place Alkyne to the corresponding 2-iodo-1-ethynyl compound. Without this intermediate to isolate, the reaction mixture is then added in portions while cooling. Protonic acid added until a pII value ton.,. <6 is established.

Then at a temperature of about 10 -20 ° C over a longer period, e.g. 1 - 4 hours, additional alkali hypochlorite solution and at the same time additional protic acid added. It is left for a few hours at room temperature react. The triiodovinyl compound is obtained as a solid and is in itself separated in a known manner, optionally recrystallized and dried.

The following examples are intended to explain the present invention in more detail: example 1 Production of 2,3,3-TriioRællylalkohol For a solution of 14.0 g (0.25 mol) of propargyl alcohol in 100 ml of water are successively 10.0 g (0.25 Mol) sodium hydroxide and 124.5 g (0.75 mol) potassium iodide added; To do this, in 2 h at a temperature of 2-50 C gradually 155 g (0.25 mol) of 12.0% sodium hypochlorite solution dripped. The reaction mixture is then poured in portions with cooling Addition of 50% or acidified sulfuric acid and at a temperature of 10 -200 C in 2 h simultaneously with 155 g (0.25 mol) of 12.0 tiger sodium hypochlorite solution and the remaining amount of a total of 140 g (0.7 mol) 50 pointers sulfuric acid added.

To complete the iodine addition, the mixture is left at room temperature for a further 2 hours react. The precipitated solid is filtered off with suction and washed twice with water and dried (crude yield 100.1 g; 92 »- d.Th '); the last wash water a few crystals of sodium thiosulphate were added to remove the color. By recrystallization from 500 ml of acetone and concentrating the mother liquors twice, the total is isolated 88.6 g (81% of theory) 2,3,3-triiodallyl alcohol with a melting point of 145-8 ° C.

Example 2 Preparation of 2 - [(2,3,3-triiodo-2-propenyl) -oxy] -ethanol To the solution, cooled with ice / water, of -25.0 g (0.25 mol) 2- (2-propinyloxy) -ethanol in 100 ml of water successively 10.0 g (0.25 mol) sodium hydroxide and 124.5 grams (0.75 moles) of potassium iodide. To do this, in 2 h. At a temperature from 5 - 8 ° C gradually 145 g (0.25 mol) of 12.8% sodium hypochlorite solution dripped. The reaction mixture is then mixed in portions with cooling Addition of 50% or acidified sulfuric acid and at 10 - 200C in 2 hours at the same time with 145 g (0.25 mol.) 12.8 iger sodium hypochlorite solution and the remainder of a total of 140 g (0.7 mol) of 50% strength sulfuric acid were added.

To complete the iodine addition, approx.

React for 15 h at room temperature. The excreted oil will dissolved in methylene chloride and separated.

After the aqueous phase has been extracted twice with methylene chloride the combined organic phases are washed three times with water and washed over Magnesium sulfate dried; the second wash water will be used to decolorize a few crystals of sodium thiosulphate were added. After distilling off the solvent one obtains 111.5 g (93% of theory) 2- E (2,3,3-triiodo-2-propenyl) -oxy] -ethanol as an oil, which crystallizes through on rubbing to a yellowish solid with a melting point of 41-50C.

Claims (5)

Claims 1. A process for the preparation of tri-vinyl compounds of the general formula where R is optionally substituted by a hydroxyl, amino, cyano, alkoxy, aryloxy, thioether, carboxyl, amide, carbamoyl, quart. Ammonium group or halogen-substituted alkyl, cycloalkyl, aryl, aralkyl, heteroaryl radical or a nitrile, formyl, acyl or amide radical, in which one denotes an alkyne derivative of the formula (2) in which R has the meaning given above, reacts with alkali iodide in the presence of alkali hypochlorite. 2. The method according to claim 1, characterized in that R for where R1, R, R are hydrogen, alkyl having 1 to 12 carbon atoms, aryl, heteroaryl, the group - (CH2) n -CO-X, where n = 0-7 and X is -oR4 or'-NR4R4 , where R4 and R4 'are hydrogen, alkyl or hydroxyalkyl having 1 to 6 carbon atoms, the group or the group (CH2) m-YR5, where m = 0 - 8 and Y denotes an oxygen or sulfur atom and R5 and .R6 denote hydrogen, alkyl or hydroxyalkyl with 1 to 6 carbon atoms, alkoxy, alkoxyalkyl, alkoxyether, aryl, Acyl, carbamoyl, alkylsulphonyl or arylsulphonyl, with the proviso that a maximum of two of the radicals R11, R2, R3 are hydrogen. 3. The method according to claim 1 - 2, characterized in that one the alkyne derivatives (2) are reacted with potassium iodide in the presence of sodium hypochlorite. 4. The method according to claim 1-3, characterized in that one first in an alkaline aqueous medium with alkali iodide in the presence of alkali hypochlorite Reacts 1 to 4 hours and then at a pH <6 with the addition of further alkali hypochlorite can react. 5. The method according to claim 4, characterized in that the a solubilizer is added to the aqueous medium.