CH502302A - Microbicidal quaternary ammonium cpds - Google Patents

Abstract

Microbicidal quaternary ammonium cpds. Title cpds. of formula (I): (where R1-R3 are opt. substd. aliphatic hydrocarbyl residues at least one of which 8-24 C; R4 is not 2 C alkanoyl; R5 is H, F, Cl or Br; R6 is H, F, Cl, Br, NO2, NH2, CN, opt. substd. aliphatic hydrocarbyl opt. linked via O or S, mono- or dialkylamino or acylamino, or R5 + R6 is a fused-on benzene nucleus; X is O or S; Z is an aliphatic 2-6 C hydrocarbon chain of which is not 2 are in the direct chain, and A is 1 equiv. of the anion of an acid), which are non-phytotoxic microbicides esp. active against phytopathogenic fungi, are prepd. by reacting corr. cpds. from which the substituent R4 is absent with a halide or anhydride of a is not 2 C alkanoic acid in the presence of an inert solvent and of a Lewis acid.

Description

  

  
 



  Process for the preparation of new quaternary ammonium salts
The present invention relates to a process for the preparation of new quaternary ammonium salts with valuable microbiocidal properties.



   Quaternary tetraalkylammonine salts are well known as antimicrobial active ingredients in the protection of plants and materials, as in human medicine. In contrast, aralkyl and aryloxyalkyl-tnalkylammonium salts have only gained importance in the protection of materials and for medical disinfection. These quaternary ammonium salts are not suitable for plant protection because of their phytotoxicity and their poor weather resistance.



     Surprisingly, it has now been found that quaternary ammonium salts of the formula I
EMI1.1
 have excellent microbicidal properties, and are particularly suitable for controlling phytopathogenic fungi. These active ingredients are not phytotoxic and are largely resistant to the effects of the weather. They also have a good effectiveness against those fungi and bacteria that damage and destroy organic materials and everyday objects.



   In formula I, the symbols: R1, Ru, each denote an unsubstituted or substituted aliphatic hydrocarbon radical; where at least one of these radicals has 8 to 24 carbon atoms, R4 is an alkanoyl group with at least 2 carbon atoms, R5 is hydrogen or a halogen atom with an atomic weight of less than 100, R6 is hydrogen, a halogen atom with an atomic weight of less than 100, the nitro, amino, Cyano or hydroxyl group, an unsubstituted or substituted aliphatic hydrocarbon radical, an unsubstituted or substituted aliphatic hydrocarbon radical bonded via oxygen or sulfur, an alkylamino, dialkylamino or acylamino group,

   or R5 and R6 together form a fused-on benzene nucleus, X is an oxygen or sulfur atom, Z is an aliphatic hydrocarbon chain link with 2 to 6 carbon atoms, of which at least 2 are in the direct chain, and A is an equivalent of an anion of an organic or inorganic acid.



   The hydrocarbon radicals R1, R2 and R3 are straight-chain or branched alkyl or alkenyl radicals.



  These residues can e.g. B. be substituted by halogen, the hydroxyl, mercapto, amino or cyano group and / or alkoxy, alkylthio, alkyl or dialkylamino group. The alkanoyl group R4 means in particular the acetyl, propionyl or butyryl radical. The aliphatic bridge member via which the alkanoyl groups mentioned can be bound is in particular a lower alkylene or alkenylene radical. An aliphatic hydrocarbon radical RG preferably has 1 to 4 carbon atoms; he can z. B. be substituted by halogen. Several substituents can be the same or different from one another.

  Z as an aliphatic hydrocarbon chain link denotes in particular an alkylene or alkenylene radical. The symbol A stands for an anion of an inorganic or organic acid. For example, the anions of the following acids come into consideration:
Hydrogen halides, sulfuric acids,
Phosphoric acid, perchloric acid, alkyl sulfuric acids, naphthoic acids,
Benzoic acids, acetic acid, aminoacetic acid,
Butyric acid, stearic acid, oxalic acid,
Adipic acid, maleic acid,
Tartaric acid, lactic acid, etc.



   The process according to the invention for the preparation of quaternary ammonium salts of the formula I is characterized in that a quaternary ammonium salt of the formula II
EMI2.1
 wherein R1, R2, Rs, R5, Ru, X, Z and A have the meanings given under formula I, in the presence of a solvent or diluent which is inert towards the reactants and in the presence of a Lewis acid with a halide or anhydride of at least 2 Alkanoic acid containing hydrocarbon atoms according to Friedei-Craft or a similar reaction.



   The quaternary salts obtained in this way can be reacted with other non-phytotoxic inorganic or organic acids in order to exchange the anion.



   The following Lewis acids come into consideration, for example, for the process mentioned: aluminum chloride, antimony pentachloride, ferric chloride, tellurium chloride, tin chloride, titanium tetrachloride, bismuth chloride, zinc chloride and the corresponding bromides and iodides, also boron trifluoride, boron trichloride, hydrogen fluoride, Sulfuric acid, phosphorus pentoxide or polyphosphoric acids. The Lewis acid is usually added to the reaction mixture in an amount of 1 to 5 moles. The reaction temperatures with the Lewis acid are between 40 and 2000 C.



   The quaternary ammonium compounds of the formula II which are used as starting material can be obtained, for example, by adding a tertiary amine of the formula III
EMI2.2
 with a hydrocarbon ester of the formula IV
R3-A (IV) can react. A quaternary ammonium compound thus obtained
EMI2.3
 can for the purpose of exchanging the anion with an organic or inorganic acid of the formula VI
H-A '(VI) are reacted; in the formulas III-VI the radicals R1, R. "Rg, R5, R6, A, X and Z have the above meaning.



   The compounds of the formulas III and V can for their part by condensation in an inert organic solvent of a halogenated hydrocarbon ether of a phenol or thiophenois of the formula VII
EMI2.4
 in which Hal is chlorine or bromine and Rj, Rs, X and Z have the above meaning, can be obtained with a secondary or tertiary amine. The preparation of tertiary amines according to formula III and that of halogenated hydrocarbon ethers of phenols or thiophenols according to formula VII is z. As described in British Patent No. 924961, see in particular Tables II and III of the patent.



   For use in crop protection, the new active ingredients are worked up in the customary manner with distribution and / or carrier substances and applied in such a way that the active ingredient concentration is in the range from 0.01 to 2%.



   The following example describes the preparation of the new active ingredients of the formula I. Unless otherwise stated, parts are parts by weight and the temperatures are given in degrees Celsius.



   example
4.14 parts of N-ß-phenoxyethyl-N, N-dimethyl-N-dodecylammonium bromide are dissolved in 75 parts by volume of carbon disulfide and 2 parts by volume of acetic anhydride. At 460, 3.5 parts of aluminum chloride are added to the boiling reaction mixture within 15 minutes with vigorous stirring, with vigorous evolution of hydrochloric acid. The vigorous evolution of gas has ceased after 90 minutes; then the cooled mixture is poured onto ice and water, the carbon disulfide is distilled off under reduced pressure and the remaining aqueous solution is extracted three times with 50 parts by volume of chloroform each time. After the chloroform solution has been dried with a little calcium chloride, the chloroform is evaporated.

  The crude product is purified over a silica gel column; you get that
N- (4-Acetyl-phenoxy-ethyl) -N, N-dimethyl-N-dodecylammonium bromide with a melting point of 78 to 810.



   The compounds listed in the table below are obtained in an analogous manner.



   Compounds Melting point N- (2-Acetyl4, 6-dichloro-phenoxy-ethyl) -
N, N-dimethyl-N-decyl-ammonium bromide hydrate 20-230 N- (2-acetyl-4, 6-dichloro-phenoxy-ethyD-N, N-dimethyl-N-dodecyl-ammonium bromide 92-940 N- (2-Acetyl-4,6-dibromophenoxyethyl) -N, N dimethyl-N-dodecylammonium bromide 105-106 N- (2-Acetyl-4-chloro-5-methyl-phenoxy- ethyl) -N, N-dimethyl-N-octyl-ammonium bromide hydrate 61-620 N- (2-acetyl-4-chloro-5-methyl-phenoxy) -ethyl) -N, N-dimethyl-N-dodecyl ammonium bromide 75-770 N- (4-acetyl-phenoxy-ethyl) -N, N-dimethyl-
N-octyl ammonium bromide 109-1110

    N- (4-acetyl-phenoxy-ethyl) -N, N-dimethyl
N-dodecyl ammonium bromide 76-780
Compounds Melting point N- (P-acetyl-6-methoxyphenoxy-ethyl) -N, N-dimethyl-N-dodecyl-ammonium bromide 88-900 N- (2-acetyl-phenoxypropyl) -N, N-dimethyl
N-decyl-ammonium bromide 113-1140 N- (2-acetyl-phenoxy-propyl) -N, N-dimethyl
N-dodecyl-ammonium-bromide 95-97 N- (2-propionyl-phenoxy-ethyl) -N, N- dimethyl-N-octyl-ammonium-bromide 1060 N- (2-propionyl-phenoxy-ethyl) -N, N- dimethylwN-dodecyl-ammonium-bromide 103-104 N- (2-butyryl-phenoxy-ethyl) -N, N dimethyl-N-dodecyl-ammonium bromide 109-1100 N- (4-propionyl-phenoxy-ethyl) -N, N dimethyl-N-dodecyl-ammonium bromide 88-890

    N- (4-butyryl-phenoxy-ethyl) -N, N-dimethyl
N-dodecyl-ammonium-bromide 100-1030 N- (2-acetyl-phenoxy-ethyl) -N, N-dimethyl-
N-octyl-ammonium bromide 84- & 0 N- (2-acetyl-phenoxy-ethyl) -N, N-dimethyl
N-dodecyl-ammonium-bromide 90-910 N- (2-acetyl-4-chlorophenoxy-ethyl) -N, N-dimethyl-N-dodecyl-ammonium-bromide 94-960 N- (2-acetyl-4- methyl-phenoxy-ethyl) -N, N-dimethyl-N-dodecyl-ammonium-bromide 91-930 N- (2-acetyl-5-methoxy-phenoxy-ethyl) -N, N-dimethyl-N-octyl-ammonium- bromide 1014030 N- (2-acetyl-5-methoxy-phenoxy-ethyl) -N, N-dimethyl-N-dodecyl-ammonium bromide 7O7 10 N- (2-acetyl-1-naphthoxy-ethyl) -N, N dimethylwN-decyl-ammonium iodide 1054080

    N- (2-Acetyl-4-cyano-phenoxy-ethyl) -N, N-dimethyl-N-dodecyl-ammonium-bromide 93950 N- (2-Acetyl-4,6-dichloro-phenoxy-ethyl) -
N, N-dimethyl <N-octyl-ammonium bromide 62650

 

Claims (1)

PATENT CLAIM Process for the preparation of new quaternary ammonium salts of the formula I. EMI3.1 in which Rr, R2, R3 each have an unsubstituted or substituted aliphatic hydrocarbon radical, at least one of these radicals having 8 to 24 carbon atoms, R4 an alkanoyl group with at least 2 carbon atoms, R5 hydrogen or a halogen atom with an atomic weight below 100, R6 hydrogen, a halogen atom with an atomic weight below 100, the nitro, amino, cyano or hydroxyl group, an unsubstituted or substituted aliphatic hydrocarbon radical, an unsubstituted or substituted aliphatic hydrocarbon radical bonded via oxygen or sulfur, an alkylamino, dialkylamino or acylamino group, or R5 and R6 together form a fused benzene nucleus, X is an oxygen or sulfur atom, Z is an aliphatic hydrocarbon chain link with 2 to 6 carbon atoms, of which at least 2 are in the direct chain, and A is an equivalent of an anion of an organic or inorganic acid, characterized in that that a quaternary ammonium salt of the formula II EMI3.2 wherein R1, R2, RQ, R5, R6, X, Z and A have the meanings given above, in the presence of a solvent or diluent which is inert towards the reactants and in the presence of a Lewis acid with a halide or anhydride of an alkanoic acid having at least 2 carbon atoms implements. SUBClaim Process according to patent claim, characterized in that the quaternary salt thus obtained is reacted with another, non-phytotoxic organic or inorganic acid for the purpose of exchanging the anion.