DE1940625A1 - N-haloalkylthio-carbamic acid alkyl ester - Google Patents

Abstract

N-haloalkylthio-carbamic acid alkyl ester Microbicidal and algicidal cpds. formula: (where R is opt. substd. aliphatic, cycloaliphatic or aromatic gp., and R' is 1-6C alkyl or 2-4C alkenyl) may be prepd. by reacting a cpd. Cl2FC-S-N(R)-COF with a glycol monoether HO-CH2CH2-OR' in the presence of an acid binder.

Description

Alkyl N-haloalkylthio-carbamic acid esters, process for their preparation and their microbicidal and algicidal use. The present invention relates to new N-haloalkylthiocarbamic acid alkyl esters, which are microbicidal and algicidal Have properties and a method for their manufacture.

It is already known that N-fluorodichloromethylthio compounds are used as microbicides (cf.

Angewandte Chemie 76, 807 964J). The N-fluorodiohlomethylthio) phthalimide has already found its way into practice (see German Auslegeschrift 1 180 486).

It has now been found that the new N-haloalkylthiocarbamic acid alkyl esters of the general formula in which R stands for an optionally substituted, aliphatic, cycloaliphatic or aromatic radical and R 'stands for alkyl with 1-6 or alkenyl with 2-4 carbon atoms, have strong microbicidal and algicidal properties. It has also been found that the N-haloalkylthiocarbamic acid alkyl esters of the formula (I) are obtained when N-haloalkylthio-carbamic acid fluorides of the formula in which R has the meaning given above with glycol monoalkyl ethers of the formula HO-CH2-CH2-OR '(III) in which R' has the meaning given above, in the presence of acid binders.

Surprisingly, the compounds according to the invention show one higher microbicidal effect than the N-fluorodichloromethylthio compounds known from the prior art. The substances according to the invention thus represent an etherification of technology.

When using N- (fluorodichloromethylthio) -N-methylcarbamic acid fluoride and ethylene glycol monoethyl ether, the course of the reaction can be represented by the following equation: CH3-N-C0-F + HO-CH2-CH2-O-C2H5 triethyl- amine amine CH3-N-CO-OOH2-CH2-O-02H5 - CFCl2 The N-haloalkylthio-carbamic acid fluorides are generally characterized by the formula (II). In formula (II), R preferably represents aliphatic radicals with 1 to 3 carbon atoms, cycloaliphatic radicals with 6 carbon atoms and aromatic radicals with 6 to 10 carbon atoms. The radicals can in each case be substituted, preferably by chlorine atoms. Specific examples of the N-haloalkylthio-carbamic acid fluorides which can be used according to the invention are: N-methyl-N- (fluorodiohlomethylthio) -carbamic acid fluoride N-chloromethyl-N N-ethyl-N- "-" - "N-2 -Chloräthyl-N- "-" - "N-Propyl-N" - "-" N-Isopropyl-N "-" - "N-Cyclohexyl-N-" - "-" N-Phenyl-N "-" - "N-2-chlorophenyl-N- lt n" - n N-4-chlorophenyl-N- "-" - "N-3-" -N- "-" - "N-3,4-dichlorophenyl-N- "-" - "N-2,4-" -N- n - n N-2,4,6-trichlorophenyl-N- "-" - "N-4-methylphenyl-N-" - "-" N- Naphthyl-N- "-" - "The N-haloalkylthiocarbamic acid fluorides used as starting materials can be prepared from N-monosubstituted carbamic acid fluorides and fluorodinchloromethanesulfenyloride (cf. Deutsche Auslegeschrift 1 297 095).

The glycol monoalkyl ethers are defined by the formula (III). In of the formula (III), R 'preferably represents alkyl from 1 to 4 and alkenyl from 2 to 3 3 carbon atoms. as Examples are mentioned in detail: glycol monomethyl ether, Glycol monoethyl ether, glycol monoisopropyl ether, glycol monobutyl ether, glycol monovinyl ether and glycol monoallyl ether.

The compounds are well known.

All inert organic solvents can be used as diluents in question. These include ethers such as dioxane, hydrocarbons such as toluene and chlorinated hydrocarbons, like chlorobenzene. But you can also use excess glycol monoalkyl ethers as a solvent insert.

To bind the hydrogen fluoride formed in the reaction, you can all common acid binders can be used. These include tertiary bases, such as triethylamine, alkali hydroxides such as sodium hydroxide and alkali carbonates such as Sodium. Finally, the method according to the invention can also be used with the Carry out alkali salts of the glycol monoalkyl ethers.

The reaction temperatures can be varied within a relatively wide range are, in general, one works between 0 and 1000C, preferably between 20 and 500C.

When carrying out the process according to the invention, one sets up 1 mole of the carbamic acid fluoride contains 1 to 1.5 moles of acid binder. The glycol monoalkyl ether is preferably used in larger amounts, about 1.5 to 15 moles per mole of carbamic acid fluoride.

Due to their superior antimicrobial effect, which extends to a wide range Extending the scale of microorganisms, the compounds according to the invention are for many purposes of deinfection preservation and antimicrobial finishing very much Well suited, some of the substances according to the invention also prove to be used in crop protection effective as an insecticide and acaricide, There is also an effectiveness against phytopathogenic fungi, e.g. against Piricularia oryzae, Aolletotricham coffeanum and also against soil fungi and Fusicladium species. Also an effectiveness as Seed dressing should be mentioned.

Example A: Microbicidal and algicidal action / reciprocal germ inhibition values The microbicidal and algicidal action of the compounds according to the invention the previously known N- (fluorodichloromethylthio) phthalimide is shown in Table 1 see.

For some bacteria, molds and yeasts are the reciprocal of these Germ inhibition values entered. It is expressed with which Dilutions of the compounds mentioned promote the growth of the selected microorganisms is completely inhibited when these compounds are optimal for the organisms Nutrient medium can be added. The microorganisms used for this inhibition test belong to different generally very common groups. It was worked with microorganisms that are more difficult than conventional chemical preservatives and disinfectants are known to be particularly resistant.

Aspergillus niger, Penicillium camerunense and Paecilomyces are representatives very resistant mold.

Trichophyton mentagrophytes is the very common athlete's foot.

Candida and Saccharomyces are among the yeasts that are widely considered pathogenic Forms occur.

Escherichia coli, Bacterium proteus, Pseudomonas pyocyanea and Staphylococcus aureus belong to the gram-negative or .. gram-positive germs, some of them are pathogenic.

The above selected molds, yeasts and bacteria when the active ingredients according to the invention are added, result in germ inhibition values as experience has shown also to be expected in many other microorganisms of these three groups mentioned would be.

T able 1 Microbicidal and algicidal effects / reciprocal germ inhibition values Active ingredient Asperg. Penic. Paecilo- Trichoph. Candida Saccha- Paeudom. Bact. Echer.Stc. niger cameroon. myces mentagr. albic. romyces procyan. proteus coli aureus # -S-CCl2F 8,000 5,000 5,000 5,000 5,000 5,000 4,000 <4,000 <4,000 5,000 (known) (2) O C-OCH2CH2OCH3 Cl # -N S-CFCl2 24,000 -72,000 -72,000 -72,000 56,000 56,000 15,000 7,000 5,000 -72,000 (3) O Cl C-OCH2CH2OCH3 CL # -N S-CFCl2 24,000 -72,000 -72,000 72,000 56,000 56,000 15,000 6,000 6,000 40,000 A good algicidal effect against green, blue and diatoms was also found.

The following further examples are intended to make the subject matter of the invention still explain in more detail: Example B: In the circulated and for the stock preparation used manufacturing water from a paper or cardboard factory, which in strong The extent to which the growth of slime-forming bacteria was exposed was determined by use the connection (1) or (2) in particularly slimy places, such as funnels, laid paper, White water cards and headbox, in concentrations of 1: 50,000 and 1: 75,000 (based on the circulating water) the number of germs is reduced very far, as follows Compilation shows.

Germ counts per 1 ccm before adding 10 million 15 minutes after "75 30 n n fl 1,000 60 "n n 2,500 24 hours n n 120,000 through a 3 times weekly Adding it as a shock, the formation of slime could be suppressed.

Side effects on the paper machine were not noticed.

Example C: Natural tanning solutions that are highly susceptible to mold, were by adding the compounds (2) and (3) according to the invention even in high dilution protected against mold growth.

The effect of these compounds considerably exceeds that of the Oxydiphenyl otherwise used for this preservation, as shown in the following table The following can be seen: active ingredient concentration mold growth (2) 0.05% (3) 0.07% % o-Oxydiphenyl 0.1% + (known) 0.5% + 1.0 Example Dt coating colors, from pure organic or organic / inorganic materials, spoil in the storage containers within a few hours.

By adding 0.1 ffi of the compound (2), these materials become Protected against the growth of decomposing bacteria.

an addition of even 0.5% of the previously known N- (fluorodichloromethylthio) phthalimide, as well as conventional preparations such as benzoic acid or p-chlorometacresol, can Bacterial development and thus the microbial decomposition of the lubricant does not to prevent.

Example: The circulating water of a cooling tower is with the compound (4) added. It is added to the running water 3 times a day in spurts 20 ccm / cbm too. The cooling tower remains free of algae.

Example F: To prevent mold from growing in damp Eolzschliff are 0.05% preparations of the compounds (2) and (3) in ethyl glycol brought on the material. In this task, based on absolutely dry material, no mold formation occurs.

The following examples explain the manufacturing process: Example 1: 13 g (0.13 mol) of triethylamine are added dropwise at room temperature to the solution of 21 g (0.1 mol) of N-methyl-N- (fluorodichloromethylthio) carbamic acid fluoride in 100 ml of glycol monomethyl ether and the temperature is allowed to rise to 35.degree. After adding toluene, the batch is shaken with water, dried over sodium sulfate, the diluent is stripped off in vacuo and the methoxyethyl N-methyl-N- (fluorodichloromethylthio) carbamate is distilled at a boiling point of 0.1 mm Hg / 73-7500.

The yield is 15 g, which is 57% of theory.

Example 2: The representation takes place according to the information in Example 1, boiling point 0t02 mm Hg / 148 - 1520C.

Example 3: The representation is based on the information in Example 1. Boiling point 0.03 mm Hg / 168-172 ° C.

Example 4: The representation takes place according to the information in example 1.

sieving point 0.03 mm Hg / 103 - 108 ° C.

Claims (6)

Patent claims: N-haloalkylthio-carbamic acid alkyl esters of the formula in which R stands for an optionally substituted aliphatic, cycloaliphatic or aromatic radical and R 'stands for alkyl with 1 to 6 carbon atoms or alkenyl with 2 to 4 carbon atoms. 2) Process for the preparation of N-haloalkylthtocarbamic acid alkyl esters, characterized in that men N-haloalkylthio-carbamic acid fluorides of the formula in which R has the meaning given above, with glycol monoalkyl ethers of the formula HO-CH2-CH2-OR 'in which R' has the meaning given above, in the presence of acid-binding agents. 3) Microbicidal and algicidal agents, characterized by a content of N-haloalkylthio-carbamic acid alkyl esters according to claim 1, 4) Procedure for Combating microbes and algae, characterized in that one N-haloalkylthiocarbamic acid alkyl ester according to claim 1 can act on microbes and algae or their habitat. 5) Use of N-haloalkylthio-carbamic acid alkyl esters for Combating microbes and algae. 6) processes for the production of microbicidal and algicidal agents, characterized in that one N-haloalkylthio-carbamide acid alkyl ester according to Claim 1 mixed with extenders and / or surface-active agents,