DE2304871A1 - 3,5-Dintro-4-amine phenyl alkyl sulphones - herbicides - Google Patents

Abstract

Sulphones of formula (I) (where R1 and R2 are H, alkyl, aryl, aralkyl, heteroalkyl or cycloalkyl or may be joined so as to form a ring, and R is alkyl aralkyl or cycloalkyl) which are herbicides, are prepd. by reacting sulphinates of formula (III) (where A is an alkali metal atom) with a halide of formula R-Z (where Z is halogen). The starting materials (III) are prepd. by redn. of sulphonyl halides of formula (III: A = halogen) and are pref. not isolated before reacting with R-Z.

Description

METHOD FOR MANUFACTURING 3,5-DINITRO - SUBSTITUTED - AMINO-PHENYL-ALKYL-SULPHONES The use of dialkyl or dialkenyl anilines in different positions are substituted, as herbicidal agents is known and is in various patents described. One of the best-known representatives of this group of compounds is 4-methylsulphonyl-2,6 - di-nitro-N, N-dipropylaniline. This compound - known as the herbicide nitraline - is in the US patent No. 3,321,292. Other derivatives of 2,6-dinitro -anilines are mentioned in the following patents: Belgian patent no. 611.387, French Patent No. 1,298,717, and USA Patent No. 3,111,403 3,257,190 and 3,227,734.

According to the USA patent specification No. 3,321,292 i8t the final phase of the Preparation of nitraline dissolved as follows: The halogen of 2,6-dinitro-4-methylsulphonyl - chlorobenzene is obtained by heating in a polar or non-polar solvent through the di-n-propylamino group replaced. To neutralize the released hydrochloric acid, an excess of di-n-propylamine or other acid binding agents are used.

The invention relates to a new method of production of 3, 5-dinitro-4-substituted-amino- ~ phenyl-alkyl sulfones.

It has been found that 3,5-dinitro-4-substituted-aminophenyl-alkylsulphones of the general formula 1 wherein R1 is hydrogen, alkyl, aryl, heteroalkyl, aralkyl or cycloalkyl group, R2 is hydrogen, alkyl, aryl, heteroalkyl, aralkyl or cycloalkyl group or R1 and R2 together form a ring, R is Alkyl group or an alkyl, aralkyl or cycloalky} group, can be very advantageously prepared by adding a7 sulphinates of the general formula III Reacts with a compound of the general formula II RZ II, in which R1, R2 and R are given above, A is alkali metal and Z is halogen, or bj 3,5-dinitro-4-substituted-aminobenzenesulphohalides of the general formula IV reduced [in which R1 and R2 are as stated above and X is halogen], after which the sulphinate of the general formula ITI formed in this way reacts with a compound of the general formula II without isolation.

The alkyl group is a group containing 1-6 carbon atoms, which can be straight-chain or branched, preferably methyl, ethyl or n-butyl group.

The aryl group and the aralkyl group preferably contain 6-8 and the cycloalkyl group has 5-7 carbon atoms.

The starting materials of the general formula III of the invention Procedures are new. The starting materials are from the corresponding sulphonic acid or prepared from a salt thereof by adding the acid or salt to the corresponding Sulnllohalogenid transferred and reduced the compound thus obtained.

According to an advantageous embodiment of the invention, the alkali salt of 3,5-dinitro-4-substituted-aminobenzenesulphinic acid [sodium or potassium salt] with an alkyl halide £ rethyl chloride, methyl bromide or especially with methyl iodide] converted into a sulpho group, the reaction being carried out in dimethylformamide at room temperature, resp. at 40 ° C or at a higher temperature, optionally carried out in an autoclave will. The reaction can also be carried out in the solvent, preferably in dimethylformamide be performed.

According to another embodiment of the invention, the above reaction from 3,5-dinitro-4-substituted- -aminobenzenesulphinic acid halogens starting without isolation of the SulphinaLe in the solvents specified above, be carried out at the same temperatures, with the same halogenating agents. The reduction of the acid halides can be realized as follows: a7 Das Mixture is boiled in water-benzene medium with sodium sulfite, thereby being through continuous addition of sodium hydrogen carbonate or through the use of other reducing agents, such as sodium thiosulphate, sulfur dioxide the alkaline Maintain pH, bJ The reaction mixture is dissolved in benzene solution with hydrazine hydrate Expediently further processed in alcohol at 0-4O0C.

cg The mixture is heated in a solution of acetone with sodium iodide, after evaporation, the sulphinate formed is treated with a suitable solvent extracted.

Further details of the invention can be found in the examples: Preparation of the starting material: a7 In a mixture of 750 ml of 96% alcohol and 450 ml of water are 160.3 g of Ob.5 mol7 potassium salt of 3,5-dinitro-4-chlorobenzenesulphonic acid dissolved, there are 68.5 ml of LD, 5 Mol7 triethylamine and 75 ml / a, 55 Mol7 on heating di-n-propylamine added. The mixture is heated with stirring for 3 hours. The alcohol is distilled and, after cooling, the product is obtained in the form of yellow precipitate. After filtration and Drying will do that Potassium salt of 3> 5-dinitro-4-di-n-propyl-benzenesulphonic acid with a yield 90-96% get C170-185 g7. M.p .: 223-225 ° C.

bJ 192.5 g [0.5 mol] of the potassium salt of 3,5-dinitro-4-di-n-propylaminobenzene-sulphonic acid are with constant stirring with 91.7 ml to 0.1 mol] of phosphorus oxychloride for 3 hours heated for a long time. The remainder of the phosphorus oxychloride is distilled at 10 Hgmm, for The rest is given to 250 g of icy water. The excreted product is after one hour standing filtered. Yield: 176 g [96%]. After a recrystallization 200 ml of carbon tetrachloride give 153 g of [83.8%] 3,5-dinitro-4-di-n-propylamino-benzenesulphochloride obtain. M.p .: 107-1o90C.

c] 7.3 g [0.04 mol] of 3,5-dinitro-4-di-n-propylamino-benzenesulphochloride are dissolved in 60 ml of benzene. The solution becomes a previously prepared, 9.4 g LO, 0375 mol] sodium sulfite, 3.4 g Lö, 04 Mot7 sodium hydrogen carbonate and 60 ml Water containing solution and the mixture is 4-5 hours at 70 OC intensely stirred. The pH value is 8-9 by adding 1-1 g of sodium carbonate secured in every hour. The suspension obtained is at cca. 100 Hgmm evaporated, so that the suspension becomes benzene-free. The residue is extracted with 3xlOO ml of ethyl acetate, after which the solvent is removed and the crude product is obtained with a yield 97-98% get LL-9 g7. M.p .: 230-232 ° C. The crude product is made from 35 ml of methanol recrystallized, and the sodium salt of the, 5-Dini4r-4-di-n-propylamino-sulphinic acid is obtained with a yield of 94-958. The product melts with decomposition at 2050C.

Example 1 7.06 g / 0.02 Mot7 sodium salt of 3,5-dinitro-4-di-n-propylamino-benzenesulphinic acid are dissolved in 50 ml dimethylformamide and 3.2 g L1.5 ml, 0.024 mol% methyl iodide are admitted. Thereafter, the reaction mixture is 60-68 hours stern at room temperature sen leather for example 6-8 hours at 40 ° C, respectively. in an autoclave at 1.1-1.2 atm. Stirred for 2 hours 7. The mixture is then evaporated at 20-40 Hgmm, the residue is washed with 100-200 mm of hot water, filtered and dried. 5.9-6.4 g of 4-methylsulphonyl-2,6-dinitro-N, N-di-n-propylaniline are obtained with a yield of 85-94 t.

M.p .: 148-151 OC.

Example 2 7.06 g [0.02 mol] of the sodium salt of 3,5-dinitro-4-di-n-propylamino-benzenesulphinic acid are dissolved in 50 ml of dimethylformamide and 2.4 g [0.022 mol] of ethyl bromide admitted. The mixture is according to the method described in Example 1 further treated. There are 4.4-4.9 g of ethylsulphonyl-2,6-dinitro-N, N-di-n-propylaniline obtained with a yield of 60-62%. M.p .: 147-149 ° C.

Example 3 7.06 g [0.02 mol] of the sodium salt of 3,5-dinitro-4-di-n-propylamino-benzenesulphonic acid are dissolved in 50 ml of dimethylformamide, and there are 3 g [0.022, mol] of n-butyl bromide admitted. The further treatment of the mixture is as in Example 1. There will be 5-6.1 g of 4-n-butylsulphonyl-2,6-dinitro-N, N-di-propylaniline with a yield of 70-76% received. Bp: 107-108 ° C.

Example 4 7.3 g [0.02 Mot7 3,5-dinitro-4-di-n-propylamino-benzene-sulphochloride are dissolved in 60 ml of benzene. The solution becomes a 9.4 previously prepared g [0.0375 mole] sodium sulfite and 3.4 g [0.04 mole] sodium hydrogen carbonate and 60 ml of solution containing water is added and the mixture is at mild reflux 4-5 Vigorously stirred for hours at 700C. Every hour, 1-1 g of sodium hydrogen carbonate is added added to the mixture to maintain pH: 8-9. After that, the received The suspension is evaporated at 100 Hg mm until the suspension becomes benzene-free. The aqueous residue is extracted with 300 ml of ethyl acetate and, after removal of the The sulfinate is obtained using a solvent. The sulfinate is in 50 ml of dimethylformamide dissolved and by the addition of 3.2 g [0.0245 mol) methyl iodide is after the im Example 1 described method obtained the product. 5.8-6.4 g of 4-methylsulphonyl-2,6-dinitro-N, N-di-n-propylaniline are obtained with obtained in a yield of 86-94%. Schm.P: 148-1510C.

Example 5 7.3 g of 0.02 Mot7 3,5-dinitro-4-di-n-propylamino-benzenesulphochloride are dissolved in 50 ml of benzene and 3 ml of 99.5% strength are obtained with vigorous stirring Hydrazine hydrate in a maximum of 40 ml abs. Dissolved methanol, added.

During the addition, the temperature was kept at a maximum of + 10oC. The reaction mixture was then stirred for a few hours at room temperature and left for one night. After adding 100 ml of water and 4 g of Na trium hydrogen carbonate, the hydrazine hydrate was distilled at 35-40 Hgmm. In addition The remainder are given 100 ml of water and the mixture is washed with 2x120 ml of ethyl acetate shaken out. The solvent is removed from the solution containing ethyl acetate and thus obtain the desired sulphinate. The product obtained is dissolved in 50 ml of dimethylformamide dissolved, and 3.2 g [0.0245 mol] of methyl iodide are added. According to the example 1 method described 5.9-6.4 g of 4-methylsulphonyl-2,6-dinitro-N, N-di-n-propylaniline obtained with a yield of 85-94%. M.p .: 148-1510C.

Example 6 7.3 g [0.02 mol7 of 3,5-dinitro-4-di-n-propylamino-benzenesulphochloride are dissolved in 200 ml of acetone, there are 6.3 g of f, 042 mol2 sodium iodide and 3.4 g [0.04 mo Sodium hydrogen carbonate is added to the reaction mixture is heated for a while, after evaporation the remainder becomes 100 ml of water and 5.3 added g [0.025 mol] of sodium thiosulfate dissolved in 50 ml of water. The mixture will extracted with 3x70 ml of ethyl acetate. The solvent is removed and thereby obtain the desired sulfinate. The product is dissolved in 50 ml of dimethylformamide 1 and 3.2 g of 0.0245 molar methyl iodide are added. The reaction mixture is treated according to the method described in Example 1 further. It will be 5.9-6.4 g of 4-methylsulphonyl-2,6-dinitro-N, N-di-n-propylaniline in a yield of 85-94 % obtain. Schm @ p .: 148-1510C.

Example 7 The sulfinate is made according to that described in Example 4 Method received. The product is dissolved in 50 ml of dimethylformamide and there will be 2.4 g [0.022 mol] of ethyl bromide were added. The reaction mixture is according to the example 1 method described further. There are 4.4-4.9 g of 4-ethylsulphonyl-2,6-dinitro-N, N-di-n-propylaniline obtained in a yield of 60-628. M.p .: 147-149 ° C.

Example 8 The corresponding sulfinate is described according to Example 4 Method received. The product is dissolved in 50 ml of dimethylformamide and there will be 3 g [0.022 Moll n-butyl bromide were added. According to that described in Example 1 method is 4-n-butylsulphonyl-2,6-dinitro-N, N - di-n-propylaniline with a yield of voii 70-76% received.

Example 9 The sulfinate is made according to that described in Example 5 Method received. The product is dissolved in 50 ml of dimethylformamide and there will be 2.4 g of LD, 022 mol) of ethyl bromide were obtained. According to the method described in Example 1 4.4-4.9 g of 4-ethylsulphonyl-2,6-dinitro-N, N - di-n-propylaniline with a yield obtained from 60-628.

M.p .: 147-149 ° C.

Example 10 According to the method described in Example 9, for Sulfinate, which is dissolved in 50 ml of dimethylformamide, 3 g [0.022 mol) of n-butyl bromide admitted. According to the method described in Example 1, 5-6.1 g of 4-n-butylsulphonyl-2,6-dinitro-N, N-di-n-propylaniline are obtained obtained with a yield of 70-768. M.p .: lo7-1o80C.

Example 11 The sulphinate is made according to that described in Example 6 Method prepared and dissolved in 50 ml of dimethylformamide, there are 2.4 g [0.022 Mol) ethyl bromide added. There are 4.4-4.9 g of 4-ethylsulphonyl-2,6-dinitro - N, N-di-n-propylaniline obtained with a yield of 60-62%. M.p .: 147-149 ° C.

Example 12 The sulphinate is made according to that described in Example 6 Method prepared and dissolved in 50 ml of dimethylformamide, there are 3 g [0.022 Mot7 n-butyl bromide added. There are 5-6.1 g of 4-n-butylsulphonyl-2,6-dinitro - N, N-di-n-propylaniline obtained with a yield of 70-76 8. M.p .: 107-1080C.

Claims (8)

PATENT CLAIM Process for the production of 3,5-dinitro-4-substituted-aminophenyl-alkylsulphones of the general formula I. wherein heteroalkyl-R1 is hydrogen, alkyl, aryl, aralkyl, # or cycloalkyl group, heteroalkyl-R2 is hydrogen, alkyl, aryl, aralkyl, # or cycloalkyl group or R1 and R2 together form a ring; R denotes an alkyl group, aralkyl or cycloalkyl group, characterized in that a] sulphinates of the general formula III with alkyl halides of the general formula II RZ II, in which R, R1 and R2 are indicated above, A is alkali metal atom and Z is halogen, b] or a 3,5-dinitro-4-substituted-aminobenzene-sulphohalide of the general formula IV where R1, R2 are given above and X is halogen, reduced and the resulting sulphinate of the general formula III is reacted without isolation with the compound of the general formula II. 2. The method according to claim 1, d a d u r c h g e k e n n z e i c h n e t that compounds of the general formulas III and IV are used as starting materials used, which contain alkyl groups in place of R1 and R2 £ where the meaning of A and X are as given above]. 3. The method according to claim 1, for the preparation of 4-methylsulphonyl-2,6-dinitro-N, N-di-n-propylaniline, it is not stated that aj is the sodium salt of 3,5-dinitro-4-di-n-propylanilinebenzenesulfinic acid alkylated with methyl halide or b] 3,5-dinitro-4-di-n-propylaniline-benzenesulfinic acid halide reduced and the resulting sulfinate without Isolation with one Methyl halide alkylated. 4. Verfahrxl according to claims 1 to 3, d a d u r c h g e k It is noted that the alkyl halides of the general formula II are methyl iodide, Methyl bromide or methyl chloride is used. 5. The method according to claims 1 to 3, d a -d u r c h g e k e n n note that the alkylation can be carried out in an organic solvent, preferably carried out in dimethylformamide. 6. The method according to method b7 of the method according to claim 1 and according to claims 2 and 3, d a -d u r c h g e k e n n z e i c h n e t that the reduction of the acid halides of the general formula IV in a water-benzene Mixture as a medium in the presence of an alkali metal hydrogen carbonate with a reducing agent, preferably with sodium sulphite, sodium hydrogen sulphite, sodium thiosulphate or Performs sulfur dioxide. 7. The method according to the method bg of claim 1 and according to the claims 2 and 3, d u r c h ek e n n z e i c h n e t, that one can reduce the acid halides of the general formula IV in a benzene solution with hydrazine hydrate in alcohol 0-400C. 8. Procedure according to method b7 and after response 2 and 3, thereby it is not noted that one can reduce the acid halides of the general purity Formula IV is carried out in acetone solution with heating with an alkali metal iodide.