NO137136B - PROCEDURES FOR REPLACING A LIQUID REACTIVE WITH A GASY REACTIVE - Google Patents

Description

Process for the production of fungicidally active succinimidomethyl-substituted quaternary ammonium compounds.

The present invention relates to a

process for the production of succinimidomethyl substituted quaternary ammonium compounds which are fungicidally active,

but which has low phytotoxicity just opposite

growing plants.

When a quaternary ammonium compound is produced from trimethylamine, dimethyl-benzylamine or N-methylmorpholine by reaction with chloromethylsuccinimide, the quaternary ammonium compound formed lacks action against unwanted organisms. However, it is now Mitt found that

when a lipophilic group is introduced 'either at the nitrogen atom or in another position therein

molecular structure of the diene quaternary

ammonium compound, the latter acquires a significant value equally against fungi and bacteria.

Furthermore, they have the advantage that they are relatively non-phytotoxic to sensitive plants.

Previously known surfactant quaternary ammonium salts have been used

as bactericides for such purposes as sanitary treatment of stoneware, glassware, machines and equipment for food processing and

manufacturing, floors, walls, clothes etc. In general, these are previously known Quaternary

ammonium compounds have been found to be

fairly phytotoxic to sensitive plants

plants. When young tomato plants in greenhouse

are sprayed with a 1% solution of such

compounds such as undecyl dimethylbenzylammonium chloride, hexadecyldimethylbenzylammonium chloride, tertiary octylphenoxy

ethoxyethyldimethylbenzylammonium chloride

and tertiary dodecylmethylbenzyltrimelsylammonium chloride, the plants were killed. Even at concentrations of 0.1%, the phytotoxic effect was intolerable for greenhouse samples.

A new group of quaternary ammonium compounds has now been found which are effective against plant diseases and which can be used relatively safely on plants with the concentrations required to control these diseases.

These compounds can be represented by the following general formula

wherein R and R<*> each represent a hydrogen atom, an alkyl group with 1 to 7 carbon atoms, an alkenyl group with 2-7 carbon atoms or a lipophilic alkyl or alkenyl group with 8-12 carbon atoms. R<1> means an alkyl group having 1 or 2 carbon atoms, the 2-hydroxy-ethyl group, the beozyl group or a lipophilic group consisting of a lipophilic alkyl group with 10-20 carbon atoms, a lipophilic alkenyl group with 11-18 carbon atoms or a lipophilic aryl-aliphatic group with 12 to 25 carbon atoms.

*R<2> and R<3> can each be an alkyl group having 1-2 carbon atoms, the 2-hydroxy-ethyl group or 1 benzyl group or together divalent allphatic compounds consisting of -C<H>2CH.,CH2CH2-, CH2CH2CH2CH ,,CH2-,

-CH2CH2OCH2CH,-^ and methyl-substituted derivatives which form a heterocyclic ring with the nitrogen atom such as morpholine, piperidine, pyrrolidine and

An- is a halogen anion or another anion which can be either inorganic or organic.

According to the present invention, a method is provided for the production of the new succinimidomethyl quaternary ammonium compounds with the above formula, and. it is characterized by an N-halomethyl-succinimide of the general formula

wherein R and R<*> have the meanings given above and X means a halogen atom, is reacted with a tertiary amine of the general formula

in which R<1>, R<2> and R<3> have the meanings given above, by mixing the two reaction participants in approximately equivalent amounts under the assumption that at least one of the reaction participants has a lipophilic group, the lipophilic group being a lipophilic alkyl or alkenyl group of 8 to 12 carbon atoms, when encompassed by an N-halomethyl succinamide reactant, and a lipophilic group consisting of a lipophilic alkyl group of 10 to 20 carbon atoms, a lipophilic alkenyl group of 11 to 18 carbon atoms or a lipophilic aryl aliphatic group with 12 to 25 carbon atoms when included in the tertiary amine reaction participant, the reaction being carried out at a temperature between 25 and 150° C and, if desired, the X— halogen anion present in the structure for the succinimidomethyl substituted quaternary ammonium compound is replaced at the end of the reaction with another anton which can be either inorganic or organic.

In this connection, it is known that a

halide ion such as chloride ion or bromide ion can be replaced in a known manner with other anions. Thus, a concentrated solution of a quaternary ammonium chloride can be treated with a sodium phosphate solution to exchange anions with the formation of quaternary ammonium phosphate. By converting halide to hydroxide and subsequent neutralization, any anion can be introduced, including acetate or propionate as typical anions for organic acids. It is thus possible to have any desired anion present in the structures of the new quaternary ammonium compounds.

The reaction participants were suitably mixed in an organic solvent. This, if used, is distilled off to leave a residue in the form of an oil, paste or solid which can be used without further purification if this is desired. However, the residue can be purified by treatment with charcoal or extraction or, in the case of solids, by crystallization from a suitable solvent.

Acetone, methyl ethyl ketone, methyl hexyl ketone, diethyl ketone, acetonitrile, nitromethane, ethyl acetate, naphtha benzene, tom-ene or xylene can be used as solvents for the reaction.

Typical tertiary amines that can be reacted with succinimidomethyl halide include n-dodecylbenzylmethylamine, cetyldimethylarnine, decyldimethylamine, dodecylbenzylmethylamine, dodecyldibenzylamine, N-dodecylmorpholine, N-octadecylmorpholine, D-dodecylbenzylmorpholine, N-nonylmethylbenzylmorpholine, N- myristylpyrrolidiine, N-cetylpiperidine, oleyldimethylamine, (5,5,7,7-tetramethyl-2-octenyl)-dimethylamine, oc-tyloxypentenyldimethylamine, octylphenoxyethoxyethyldimethylamine, nonylphenoxyethoxyethylbenzylmethylamine, nonylphenoxyethyldi(hydroxyethyl)amine, octylphenoxyethoxyethylmorpholine, nonylphenoxyethoxyethylpiperidine din, (diethylphenyl-2-pententyl)dimethylamine or N-methylmorpholine.

As halomethylsuccinimides, N-chloromethyl or N-bromomethyl derivatives of succinimides, a mono- or di-substituted succinimide, such as α-methyl-, α,α'-dimethyl-, α-butenyl-α-butyl-, α-dodecenyl-, or α-dodecylsuccinimide or compounds such as (N-chloromethyl)dodecenylsuccinimide and (N-chloromethyl)dodecylsuccinimide.

Further details of the preparation of the compound according to the present invention are given in the following examples. Parts are given as parts by weight if nothing else is stated.

Example 1:

A mixture of 12 parts of N-chloromethylsuccinimide, 17.3 parts of dodecyldimethylamine and 80 parts of acetone was heated with an additional reflux condenser for 2.5 hours. The solid that separated was collected, washed with acetone and air dried. The product thus obtained amounted to 23 parts and melted at 171-173° C during decomposition. This is dodecyldimethyl (succinimidomethyl) ammonium chloride and has the formula

Analysis: Calculated for C1()H.!7C1N;)O2 : Cl, 9.9; N, 7,8

Found: Cl, 9.7; N, 7.4

In floating sprout samples, this compound gave ED3(I values of 1-10 ppm. against Alter-

maria solani and Stefylium sacinaeforme and at 105 ppm. against Monolinia fructicola.

Similarly, N-octadecyl-morpholin (27 parts) is reacted with N-chloro-methylsuccinimide instead of the above-mentioned dodecyldimethylamine. The product is available as a paste and corresponds in composition to octadecyl (succinimidomethyl) morpholinium chloride. It gives ED-)0 values of 10-50 against standard test organisms. It is not phytotoxic at 1% or 0.1% to young tomato plants or lima bean plants.

Example 2:

A mixture of 12 parts of N-chloromethylsuccinimide, 17.2 parts of dimethyl-(5,5,7,7-tetramethyl-2-octenyl)amine and 80 parts of acetone was refluxed for 2 hours. The product was isolated in the usual way. 24 parts of dimethyl-(succinimidomethyl)-5,5,7,7-tetramethyl-2-octenyl-ammonium chloride were obtained with the structure

which is a white solid melting at 188-190° C during decomposition.

Analysis: Calculated for CinHSi-ClN,02 : Cl,

9.9; N, 7.8

Found: Cl, 9.7; N, 7.6.

Against Moinolinia fructicola this compound gave an > ED-,, value of one ppm. It was not phytotoxic at 1% or 0.1% to Idma bean plants.

Example 3:

A mixture of 14.8 parts of N-chloromethylsuccinimide, 30.3 parts of dodecylbenzyldimethylamine and 80 parts of acetone was heated under reflux for 1 hour. The product was isolated in the usual way as a solid (35.2 parts) melting at 193-194° C. with decomposition. This is dodecyl-dlmethyl-stucciinimldomethyl-ammonium chloride with formula

Analysis: Calculated for C0(iH43ClH202: Cl, 7.9; N, 6.2

Found: Cl, 8.3; N, 6.2

In slide sprout tests, this compound gave ED-0 values of 1-10 ppm. against Alternaria solanii, Mono llniia frukciticola and Stemfylium sarcinaeforme.

On tender, young tomato plants it showed slight damage at 1% and no damage at 0.1%. On lime bean plants it showed no damage even at 1%.

In the same way as above, 31.5 parts of N-dodecylbenzylpyrroli-

your instead of the above-mentioned dodecylbenzyldimethylamine with N-chloromethylsuccinimide so that it gives dodecylbenzylsuccinimidomethylpyrrolidine chloride having ED.-n values of approx. 10 ppm. against standard test organisms and is not phytotoxic at 1% or 0.1% against young tomato or lima bean plants.

N-dodecylbenzylpiperidin is reacted in the same way with N-chloro-methylsuccinimide and gives dodecylbenzyl-succimimidomethyl-piperidinium chloride which gives ED-0 values also of approx. 10 ppm. and are non-phytotoxic in these tests against young tomato and lima bean plants.

Example 4:

A mixture of 14.8 parts of N-chloromethyl succinimide, 32.2 parts of tertiary octylphenoxyethoxyethyldimethylamine and 160 parts of ace-

ton was heated with a reflux condenser for 3 hours. The solid matter that is secreted by

cooling was collected and dried. 38.1 parts of dimethyl-tertiaryoctylphen-oxyethoxyethyl-succinimiidomethylammonium chloride were obtained which melts at 154-157° C during decomposition.

This has a formula

Analysis: Calculated for C^H^CIN^O^ : Cl,

7.6; N, 6.0

Found: Cl, 7.6; N, 5.7

In the sliding sprout test, this compound gave the following ED-0 values: 1-10 ppm. against both Alternaria solani and Stemfylium sarcinaeforme and 10-50 ppm. against Monolinla fructicola.

On lima bean plants it showed no damage even at 1%.

Example 5:

a. (N-Chloromethyl)-dodecenyl succinimide was prepared as follows: A mixture of 105 parts dbdecenyl succinimide, 36 parts (37%) formaldehyde and 200 parts dloxane was refluxed for 3 hours. The mixture was concentrated under reduced pressure. 260 parts of benzene were added to the residue and the water in the mixture was removed by azeotropic distillation. The dry benzene solvent was then evaporated in vacuo to give 108 parts of a viscous oil which was N-hydroxymethyl-dodecenylsuccinim.

The crude N-hydroxymethyl-dodecenylsuccinimide (58 parts) was dissolved in chloroform (180 parts) and treated with thionyl chloride (28.7 parts). The mixture was stirred at room temperature for 1.5 hours and then heated with a reflux condenser for 30 minutes. The mixture was concentrated in vacuo to give 51 parts of a thick oil. Distillation of this material gave 31.5 parts of pure (N-chloromethyl)-dodcenylsuccinimide, boiling at 151-173°C (0.2 mm) and

25

had n— 1.4962.

Analysis: Calculated for CI7H2801N02 : N, 4.4 Found: : N, 4.2.

b. A mixture of N-chloromethyl-dodecenylsuccinimide (13.5 parts), 5.8 parts benzyldimethylamine and 60 parts acetone was heated under reflux for 2 hours. The solid matter that separates on cooling was collected and dried. 5.3 parts of benzyl-dodecenylsuccinimidomethyl-dimethylammonium chloride were obtained,

which melted at 161-163° C.

Analysis: Calculated for C20HJIClN2O2 : Cl, 7.9; N, 6.3

Found: Cl, 7.7; N, 6.1

This compound gave EDr)() values against Monollnia fructicola of 10-50 ppm in standard gli-despire samples. against Alternaria solani at 1-10 ppm. and against Stemfylium aarcinaeforme at less than 1 ppm.

It was not phytotoxic to young tomato plants or lima beans at 1% or 0.1%•

Example 6:

A mixture of 15 parts of N-chloromethyl-dodecenylsuccinimide, 14.5 parts of dodecylbenzyl-dimethylamine and 80 parts of acetone was heated under reflux for 4.5 hours. The mixture was distilled to give 25 parts of a viscous oil. This has a formula

which was identified as dodecenylsuccinimidomiethyl-dodecyltenziyl-dimacphylammonium chloride.

Analysis: Calculated for C. 18 Hlir)ClN 2 O 2 : Ol, 5.8; N, 4.6

Found: Cl, 5.1; N, 4.2.

In the slide sprout test, this compound gave the following ED,-(l) values: 1-10 ppm. against Monollnia fructicola and 10-50 ppm. against both Alternaria solani and Stemfylium sarcinaeforme.

By reacting the equivalent weight of N-chloro-methyldodecylsuccinimide with dodecylbenzyl-dimethylammonium chloride by the above procedure, the corresponding dodecylsuccinimidomethyl-dodeoylbenzyldimethylammonium chloride is obtained. It has an EDS0 value of approx. 1-10 ppm. against the three test organisms mentioned above.

On tomato and lima bean plants, it showed no damage even at 1%.

Example 7:

a. N-'chloromethyl-αα'-dimethylsuccinimide was prepared as follows: A mixture of 15 parts αα'-dimethylsuccinimide, 11 parts (37%) formaldehyde and 10 parts water was refluxed for 2 hours. The mixture was concen-

evaporated under reduced pressure to about half its volume and benzene (50 parts) was added. The remaining water was removed by azeoptropic distillation. The dry benzene solution was then evaporated in vacuo to give 15.8 parts of a solid with a melting point of 45-50° C. This was an N-hydroxymethyl-α-dimethyl-succinimide.

The above crude N-hydroxymethyl-a'-dimethylsuccinimide was dissolved in 30 parts of chloroform and treated with 11.9 parts of thionyl chloride. The mixture was heated under reflux for 12 hours and then concentrated in vacuo to give 16.4 parts of a viscous oil which was N-chloromethyl-αα'-dimethylsuccinimide.

Analysis: Calculated for C7H1(lCIN02: N, 8.0 Found: N, 8.0

b. A mixture of 8 parts N-chloromethyl-α α'-dimethylsuccinimide, 14.4 parts (96.4%) dodecylbenzyldimethylamine and 40 parts acetone was heated under reflux for 3 hours. The acetone is then removed by evaporation under reduced pressure. The remaining oil was dissolved in ethanol and 64.7 parts of a solution found by AgNO,, titration and containing 24% dodecylbenzyl-dimethyl-a a'-dimethyl-succinimidomethylammonium chloride of the formula

This compound gave ED-n values of 1-10 ppm. against Alternaria solani and Mono-liniia fructicola and less than 1 ppm. against Stemphylium sarcirtaeforme.

For the sake of comparison, benzyldimethyl-succinimidomethyl-ammonium chloride was also prepared. First, N-chloromethylsuccinimide was formed by reacting N-hydroxymethylsuccinimide and phosphorus trichloride according to the method described by Cherbuliez and Sulzer, Heiv. Chim. Acta 8, 567 (1925). Then 14.8 parts of this product, 13.5 parts of benzyldimethylamine and 80 parts of acetone were heated to ten-bake cooling temperatures for 4 hours. The mixture was cooled in an ice bath. A solid formed and this was separated and washed with acetone and dried in air. The yield was 21.3 parts of benzyldimethylsuccinimidomethylammonium chloride with a melting point of 190-191.5° C during decomposition. It gave ED50 values against the standard test organisms greater than 1000 ppm.

Example 8:

31.4 parts of N-chloromethyldodecenyl succinimide, 10.1 parts of N-methylmorphoTin and 80 parts of acetone are mixed. The mixture is heated for 4 hours at reflux cooling temperature. The solubilizing agent was then removed from the reaction mixture by heating to leave a residue of 40 parts of a viscous oil. On analysis, this oil corresponds to dodecenylsuccinimidomethyl methylmorpholinium chloride.

The procedure was repeated by replacing the above-mentioned dodecenyl compound with 32 parts of N-chloromethyliodecyl succinimide. The product is dodecylsuccinimii-domethyl-methylmorpholinium chloride as an oil.

These compounds gave ED-0 values of 10-50 ppm. against the 3 standard test organizations. None of the compounds are phytotoxic! 1% equal to parent young tomato plants.

These compounds are of importance in

that it is established that the lipophilic group can

be attached not to the ■nltrogen atom, but to

a different position in the molecule and gives substantially equivalent results.

The compounds according to the present invention have been examined for bactericidal activity and were all found to be active in

varying degrees. The main value for these

compounds, however, are like fungicides.

Although in e.g. chloromethyl group has been used, the bromomethyl group can be used in the same way. The quaternary ammonium bromides formed are at least as effective as the corresponding chlorides and i

in some cases even more active.

Claims (1)

Procedure for the production of new fungicidally active succtaimidomethyl-substituted quaternary ammonium compounds of the formula wherein R and R<*> each represent a hydrogen atom, an alkyl group of 1 to 7 carbon atoms, an alkenyl group of 2 to 7 carbon atoms or a lipophilic alkyl or alkenyl group of 8 to 12 carbon atoms, R< 1> means an alkyl group having 1 or 2 carbon atoms, 2-hydroxyethyl group, benzyl group or a lipophilic group consisting of a lipophilic alkyl group of 10 to 20 carbon atoms, a lipophilic alkenyl group of 11 to 18 carbon atoms, or a lipophilic arylaliphatic group of 12 to 25 carbon atoms , R- and R'<1>, individually, means an alkyl group having 1 or 2 carbon atoms, 2-hydroxyethyl or benzyl group or together form a divalent chain consisting of -CH^CB^CHgCHg-, -CHgCHpOCHt, CHg-, -CH^CHg CH^CH^CH^- or methyl-substituted derivatives thereof, which forms a heterocyclic ring with the nitrogen atom, and An- is a halogen ion or other anion which can be either inorganic or organic, characterized by & ti N-halomethylsuccinimide with the general formula wherein R and R<*> have the meanings given above and X means a halogen atom, is reacted with a tertiary amine of the general formula in which R<1>, R<2> and R<8> have the meanings given above, by mixing the two reaction participants1 in approximately equivalent amounts under the condition that at least one of the reaction participants has a lipophilic group, as the lipophilic group is a lipophilic alkyl or alkenyl group of 8 to 12 carbon atoms when comprised by an N-halomethylsuccinimide reactant, and one lipophilic group consisting of a lipophilic alkyl group of 10 to 20 carbon atoms, a lipophilic alkenyl group of 11 to 18 carbon atoms or a lipophilic arylaliphatic group of 12 to 25 carbon atoms when encompassed by the tertiary amine reactant, the reaction being carried out at a temperature between 25 and 150°C, and, if desired, replacing the X halogen anlon present in the structure with succinimidomethyl substituted quaternary ammonium compound at the end of the reaction with another anion which can be either inorganic or organic.