DE2036314A1 - Sulphonyl-n-chlor-formimidoyl chlorides - plnant protection agents - Google Patents

Abstract

Sulphonyl-N-chloro-formimidoyl chlorides - plant protection agents. Cpds. of formula: RSO2CCl=NCl (where R is an opt. substd. aliphatic, araliphatic, aromatic or adamantyl gp.) are plant protection agents or intermediates thereof, and may be prepd. by reacting RSO2CN with at least the stoichiometric amt. of Cl2 at 0-250 degrees C, pref. in an inert solvent.

Description

Sulfonvisubstituierte N-Chl or-formimidoylchloride subject of Invention are new sulfonyl-substituted N-chloroformimidoyl chlorides and a process for their manufacture.

It has been found that new sulfonyl-substituted N-chloro-formimidoyl chlorides can be obtained obtained when sulfonyl cyanides of the formula R - S02 - CN in which R is optionally substituted aliphatic, araliphatic or aromatic, as well as an adamantyl The remainder is with at least the stoichiometrically required amount of halogen 0 to 2500C converts.

Optionally substituted aliphatic radicals contain 1 - 18, preferably 11-6 carbon atoms. As aliphatic radicals are of course also cycloaliphatic radicals with preferably 5 or 6 carbon atoms in the ring system to to understand. Araliphatic radicals preferably contain 1-4t in the al @ -phatic chain -1 or 2 * carbon atoms and, as the aromatic radical, naphhyl, sorcery but the phenyl radical. In addition to the naphthyl radical, the preferred aromatic radical is called the phenyl radical.

Halogens (preferably Fluorine, chlorine, bromine), CN, O-alkyl (Cl -SO2Cl as well as in the case of the aromatic and araliphatic Residues also called alkyl radicals with 1 - 4 carbon atoms and a nitro group. The cycloaliphatic radical can optionally also be replaced by lower alkyl groups (c1 - 4) be substituted.

The sulfonyl cyanides used for the process are known (German Offenlegungsschrift 1930 014) l resp.

can be obtained by known methods. As radicals R of the sulfonyl cyanide Examples include: methyl, ethyl, hexyl, cyclohexyl, adamantyl (1 or 2), phenyl, 4-methoxyphenyl, 4-methylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-cyanophenyl, 4-nitrophenyl, 2,6-dichlorophenyl, 2,4,5-trichlorophenyl, 4-chloro-3-nitrophenyl.

In addition to bromine, the halogen used for the process is preferably called chlorine. The reaction is preferably carried out at 20 ° -1500 ° C., in particular 60 - 1200C.

In general, the reaction takes place in a closed vessel in which adjusting pressure carried out. But you can also work without pressure, the upper temperature range is then preferred. The implementation in Presence of an inert organic solvent customary for chlorination reactions for example methylene chloride, carbon tetrachloride, chlorinated hydrocarbons such as, for example, o-dichlorobenzene, trichlorobenzene or perchlorindane.

In general, the stoichiometrically required amount of halogen becomes used; Of course there can be an excess Find use especially when working in an inert solvent (up to about 100%).

The batches are worked up in the customary manner.

The new compounds obtainable by the process correspond to the general formula wherein has the meaning given above.

They can be used as intermediates in the manufacture of pesticides but can also be used directly as such.

The temperature data in the examples relate to 0C.

Example 21.0 g of methanesulfonyl cyanide (0.2 mol) are added to 21.3 g (0.3 Mol) chlorine heated to 1100 in a closed vessel for 15 hours. Afterward is processed as usual.

The N-chloromethylsulfonylformimidoyl chloride of the formula is obtained in quantitative yield. The connection melts at 46 - 48 °. It boils at 70-70.50 / 0.5 Torr.

Example 2 If Example 1 is repeated and the methanesulfonyl cyanide is replaced by the corresponding amount of benzenesulfonyl cyanide BO, the compound of F @ rrel is obtained after a reaction time of 15 hours at 800 in likewise quantitative yield The melting point of the compound is. at 46 - 48 °. Bp: 124-125 ° / 0.5 Torr.

Example 3 0.2 mol of p-toluenesulfonyl cyanide and 0.3 mol of chlorine are allowed to react for 1 hour at room temperature in a closed vessel and then heated to 700 for 1 hour to complete the reaction. Chloro-4-toluylsulfonylformimidoyl chloride of the formula F: 67-90 ° Example 4 If p-chlorobenzenesulfonyl cyanide (0.2 mol) is heated with chlorine (0.3 mol) to 700 for 15 hours in a closed vessel, N-chloro-4-chlorophenylsulfonylformimide-doyl chloride of the formula is obtained F: 83840 (from petroleum ether, b.p. 40-60 °) in quantitative yield. The methanesulfonyl cyanide used for the process was obtained as follows: 114.5 g (1 mol) of methanesulfonyl chloride are converted into a solution of 252 g of sodium sulfite in 500 in the course of 45 minutes ml of water was added dropwise. The pH value is kept at 7-8 by adding 160 ml of a 50% strength by weight sodium hydroxide solution. The temperature is kept below 30 °. After the end of the dropping in, the pH is kept at 7-8 for a further 30 minutes by adding NaOH; then it is cooled to 15 ° C. 75 ml (excess) of cyanogen chloride (liquid) are then added dropwise within 5 minutes. The reaction mixture is then immediately placed in a separatory funnel, 250 ml of benzene are added, and the two layers are separated. The benzene solution of the sulfonyl cyanide is dried (calcium chloride) and the benzene is distilled off. The remaining, lastingly pure methanesulfo-20 cyanide is distilled. Bp: 72-13 ° / 15 torr; n20 = 1.4300.

Yield: 58.6 g. The benzenesulfonyl cyanide is obtained in an analogous manner from bp: 91 - 92 ° / 2.6 Torr. nD20 1.5300.

Also the other compounds used for the process were obtained analogously.

Claims (4)

Claims Sulphonyl-substituted N-chloroformimidoylchloride cer formula where R is an optionally substituted aliphatic, araliphatic or aromatic, as well as an adamantyl radical. 2. Compounds according to claim 1, wherein the radicals R are replaced by halogens, CN, lower O-alkyl radicals, SO2Cl, as well as in the case of the aromatic and araliphatic radicals Rests can be substituted by lower alkyl radicals and a nitro group and the cycloaliphatic radical can also contain lower alkyl groups. 3. Process for the production of sulfonyl-substituted N-chloroformimidoyl chlorides, characterized in that sulfonyl cyanides of the formula R - S02 - CN wherein R for an optionally substituted aliphatic, araliphatic or aromatic, as well as an adamantyl radical, with at least the stoichiometrically required Reacts amount of halogen at 0 to 250 °. 4. The method according to claim 3, characterized in that the Implementation of the reaction in the presence of an inert organic solvent.