CA1292882C - Synergist for biocide - Google Patents

Abstract

Abstract of the Disclosure A biocide is strengthened in the biocidal effect with a branched guaternary ammonium salt having a group of

Description

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This invention relates to a synergist for a biocide.
Biocides including insecticide, fungicide (also called as Bactericide), herbicide, and plant growth regulator are used in formulations such as emulsion,wettable powder, solution, flowable powder, granule, and dust.
It is noted in this connection that various measures are taken on properties of the formulations so that the principal ingredients thereof fully exhibit their activity. However, still more enhancement in the effect of the biocide cannot be attained by such measures.
Under present circumstances where the development of biocides is becoming more and more difficult, enhancing the activity of known biocides is greatly meaningful.
The present inventors have made extensive and intensive studies to find out that a specific compound acts so as to enhance the effect of various biocides.
A biocide composition of the invention comprises a biocidally effective amount of biocide and a branched quaternary ammonium salt having the ormula (I):

[R > < R ~ (I) (in which Rl, R2 and R3 are each Rs-CHCH2-, ~ CH2 or an alkyl having 1 to 4 carbon atoms, Y is hydrogen or a halo-gen, Rs is an alkyl or alkenyl having 4 to 18 carbon atoms, R6 is an alkyl or alkenyl having 2 to 16 carbon atoms, provided that at least one of Rl, R2 and R3 is Rs-fHCH2-; R4 is an alkyl having 1 to 4 carbon atoms or -CH2CH20H and X3 is a counter ion) in an amount sufficient to enhance the effect of the biocide.
The composition preferably comprises 0.1 to 20, more preferably 0.8 to 20, parts by weight of the quaternary ammonium salt per part of the biocide.
The invention further provides a method for strengthen-ing the effect of a biocide which comprises applying the biocide together with the branched quaternary ammonium salt as defined above.
The biocide composition may further contain a biocidally acceptable carrier or diluent.

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Specifically, in accordance with the present invention, there is provided a synergist for a biocide comprising a branched quaternary ammonium salt repre-sented by the following general formula (I):

[ R 2 > < R ~ ( I ) wherein Rl, R2, and R3 are each independently Rs-CHCHz, (whereln Y is a hydrogen or R ~ y ~ C H 2 halogen a~om) or an alkyl group having 1 to 4 carbon atoms, provided that at least one Or them is R5-CHCH2 where R5 is an alkyl or alkenyl group having 4 to 18 carbon atoms; R6 is an alkyl or alkenyl group having 2 to 16 carbon atoms; R4 is an alkyl group having 1 to 4 carbon atoms or -CH2CH20H; and X~ is a counter anion.
Although the counter anion ~ in the general formula (I) is not particularly limited, examples Or preferable counter anion include CH3S04, halogen atoms (e.g., C~, Br, and I), C2H5S04, HO(CH2)mCOO
(wherein m is an integer of 1 to 5), lZ~3Z882 O-P-H (wherein R is an alkyl group having 1 OR O
to 3 carbon atoms), and (R'-otA'o ~ qP~O (wherein (OH)2_q R' is an alkyl or alkenyl group having 8 to 22 carbon atoms, A' is an alkylene group having 2 to 4 carbon atoms, p is an integer of O to 20, and q is 1 or 2).
The compound represented by the general formula (I) can be produced by known methods. For example, it can be produced by quaternizing a tertiary amine represented by the following general formula (II) with a quaternizing agent such as methyl chloride, methyl bromide or dimethyl sulfate:

R, ~ N -R3 ( ~) wherein R1, R2, and R3 are as define~d above with respect to formula (I).
The tertiary amine represented by formula ~II) can also be prodU~ed by known methods. For example, it can be produced by directly aminating an alcohol represented by the following general formula (III) with ammonia, methylamine, or dimethylamine:

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Rs-CH-CHz-OH t m R~ .

wherein R5 and R6 are as defined above with respect to formula (I).
Preferable compounds among the compounds represented by the general formula (I) are those represented by the rollowing formulae (IV) to (VI):

ca3 ~ l CH3-~CHz~CH-CHz-N-CH3 X (~) (CH2) r.- Z CH3 i ~ CH3 wherein n ls an intger~of 3 to 17 and X is C~, Br 3 4;

CH3-~CHzt~CH- CH2- N- CH3 ~X (V ) tCH 2) n - z CHz l CH3 ~ l wherein n is an integer Or 3 to 17, Y is a hydrogen or halogen atom, and X is CQ, Br or CH3S04; and lZ~Z88Z

CH~
CH3 tCHz~-CH- CH2 - ~-CH3 tCHz)~ z CNz ;X (~) CH 3 CH ~CHz~ CH3 (CHz) m C~, wherein n and m are each independently an integer Or 3 to 17 and X is C~, Br or CH3S04. Among them the compounds represented by formula (IV) are particu-larly preferable.
The synergist for a biocide is characterized in that it has a branched alkyl group as opposed to conventional synergists which have a straight-chain alkyl group or a straight-chain alkenyl group.
Because of its structure, the synergist for a biocide Or the present invention is not only free rrom phytotoxicity even when it is used in combination with the biocide, but also can enhance by twice to thrice the efrect Or the biocide.
The synergist for a biocide of the present invention is used in an amount Or usually 0.1 to 5, preferably 0.2 to 4 in terms of a weight ratio relative to the princlpal ingredient of the biocide.
The form of the preparation is not particularly ?2~382 limited and may be any of emulsion, flowable powder, wettable powder, dust, etc. Therefore, other additives such as emulsifier, dispersant or carrier can be added according to the preparation.
The synergist of the present invention can be used by incorporating it in the above-mentioned various preparations or adding it to the above-mentioned preparations when they are diluted for use. The synergism can be attained by either of the above-mentioned methods.
Although the reason why the synergist for a biocide Or the present invention exhibits such a remarkable synergistic activity is not yet fully elucidated, it is believed that the synergist for a biocide of the present invention breaks the wax layer present on the surface Or plant and the wax present on insect, thereby promoting the penetration of the bioclde into the plant, insect and bacterium regardless Or the structure Or the biocide.
In view Or the above, it is preferred that the synerglst for a biocide of the present invention be used at 50 ppm or higher in terms of concentration in a diluted state.
Examples of the biocide for which the synergist of the present invention may be used will now be lZ~ 2 described, though the biocides are not limited to them. Further, it should be noted in this connection that the synergist of the present invention can be safely used for various crops without exhibiting phytotoxicity. Examples of the insecticide include pyrethroid insecticides such as fenvalerate (d-cyano-3-phenoxybenzyl 2-(4-chlorophenyl)-3-methyl-valerate) and Baythroid (cyano(4-fluoro-3-phenoxyphenyl-methyl-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopro-panecarboxylate); organophosphorus insecticides such as DDVP (2,2-dichlorovinyl dimethyl phosphate), Sumithion (dimethyl 4-nitro-m-tolyl phosphorothionate), Malathon (S-(1,2-bis(ethoxycarbonyl)ethyl) dimethyl phosphorothiolothionate), dimethoate (dimethyl S-(N-methylcarbamoylmethyl) phosphorothiolothionate), Elsan (S-(~-(ethoxycarbonyl)benzyl) dimethyl phosphoro-thiolothionate), and Baycide (O,O-dimethyl 0-(3-methyl-4-methylmercaptophenyl) thiophosphate); carbamate insecticides such as Bassa (o-butylphenyl methyl-carbamate), MTMC (m-tolylmethylcarbamate), Meobal (3,4-dimethylphenyl N-methylcarbamate), NAC (1-naphthyl N-methylcarbamate); methomyl (methyl N-((methylcarbamoyl)oxy)thioacetimidate); and cartap (1,3-bis(carbamoylthio)-2-(N,N-dimethylamino)-propane hydrochloride).
Examples Of the acarcide include Smite 1~2~38Z

(2-(2-p-tert-butylphenoxy)isopropoxy)isopropyl 2-chloroethyl sulfide), Acricid (2,4-dinitro-6-sec-butylphenyl dimethylacrylate), Chlormite (isopropyl 4,4-dichlorobenzilate), Akar (ethyl 4,4-dichloroben-zilate), Kelthane (l,l-bis(p-chlorophenyl)-2,2,2-trichloro)ethanol, Citrazon (ethyl O-benzoyl-3-chloro-2,6-dimethoxybenzohydroxamate), Plictran (tricyclohexyltin hydroxide), and Omite (2-(p-tert-butylphenoxy)cyclohexyl 2-propynyl sulfite).
Examples Or the bactericide include organosulfur bactericides such as Dithane (zinc ethylenebis(dithio-carbamate), maneb (manganese ethylenebis(dithiocarba-mate), and thiram (bis(dimethylthiocarbamoyl) disulride);
Benlate (methyl l-(butylcarbamoyl)-2-benzimidazolecar-bamate); Dirolatan (N-tetrachloroethylthio-4-cyclohexene-1,2-dicarboximide); Daconil (tetrachloroisophthalonitrile);
Pansoil (5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole);
thiophanate-methyl(1,2-bis(3-methoxycarbonyl-2-thioureido)benzene); Rabcide (4,5,6,7-tetrachloro-phthalide), Kitazin-P (O,O-diisopropyl S-benzyl phosphorothiolate); Hinosan (o-ethyl diphenyl phos-phorodithiolate); and probenazole (3-allyloxy-1,2-benzothiazole l,l-dioxide).
Examples Or the herbicide include Stam (3',4'-dichloropropionanilide), Saturn (S-4-chlorobenzyl lZ~ZE~2 N,N-diethylthiolcarbamate), DCMU (3-(3,4-dichlorophenyl)-l,l-dimethylurea), and Gramoxone (l,l'-dimethyl-4,4'-bipyridinium dichloride).
Examples of the plant growth regulator include MH (maleic hydrazide) and Ethrel (2-chloroethylphos-phonic acid).
(Examples) The synergist for a biocide of the present invention will now be described in more detail with reference to the following examples which should not be construed as limiting the scope of the present invention.
Synergist for a biocide:
Compound 1 according to the present invention CHJ ` I
¦ CaJ (CH2) JCHCH2-N-CHJ Cl CH2 CH~
CH~

Compound 2 according to the present invention ' CHJ
1~
CHJ (CH2) 7CHCH2-N-CHJ Cl (CH 2) s CH J
CHJ

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Compound 3 according to the present invention CH 3 (CH 2) IIC-HCH 2 - N-CH 3 Br (CHz) 9 CH3 Compound 4 according to the present invention , CH3(CHz)sCHCH2-N-CH3 . I I
(CHz)~ CH 2 CH3SO 4 CH 3 CH-(CH 2~ CH 3 (GHz)s Compound 5 according to the present invention CH2 ~ ~< CH3 GH~(GH~ CHGH: CH3 C!
I ; and (CH2) 4 Compound 6 according to the present invention Cl ~ CHz \ ~/ CH3 i CH3(CH2)7-CHCH2 / \ CH3 Cl (CHZ)s lZ~ZE~3Z

Example 1 Paraquat herbicide:
(Formulation No. 1) Paraquat 24 % (on the weight basis;
the same shall apply hereinafter) compound No. 1 accor- 20 %
ding to the present invention water 56 %
(Comparative formulation No. 1) paraquat 24 %
polyoxyethylene 20 %
alkylamine water 56 %
Crabgrasses (30 crabgrasses per pot) which were in a trifoliate stage were treated with the above herbicide in a predetermined concentration.
7 days after the treatment, the weight of survival at the aerical part and the percentage herbicidal effect relative to the untreated section (%) were calculated. 50 % herbicidal concentration was also determined. The results are shown in Table 1.

1~''3Z~3~2 Table 1 ActiveFormul. Comp. formul.
ingredientNo. 1 No. 1 concn.
herbicidal effect (%) 2000 ppm100 96 50 ~ herbicidal190 385 concn. (ppm) Example 2 Kelthane acaricide:
(Formulation No. 2) Kelthane 40 %
xylene 30 %
compound 2 according to 20 %
the present invention emulsifier 2* 10 %
(Comparatlve Formulatlon No. 2) Kelthane 40 %
xylene 30 %
lauryldlmethyl- 20 %
ammonlum chloride emulsifier 2 10 %
* emulsifier 2 alkylbenzenesulfonate 30 %
polyoxyethylene(15) 30 %
nonylphenol ether lZ~Z~Z

polyoxyethylene(20) 40 %
oleyl ether Female two-spotted spider mite imagoes were inoculated 30 imagoes per section in three-course system and incubated at 25 C for 24 hr. Thereafter, the acaricidal efrect was assayed by the leaf dipping method. The percentage acaricidal effect relative to an untreated section was determined 24 hr after the treatment with the acaricide. Further, the median lethal concentration was also determined.
Teh results are shown in Table 2.
Table 2 Active Formul. Comp. formul.
ingredient No. 2 No. 2 concn.

acaricidal efrect (%) 500 ppm 100 68 62.5 48 11 LC50 concn. (ppm)70 300 Example 3 Sumithion insecticide:
(Formulation No. 3) Sumithion 55 %

129213~2 xylene 15 %

compound 3 according to 20 %
the present invention emulsifier 3* 10 %
(Comparative Formulation No. 3) Sumithion 55 %
xylene 35 %
emulsifier 4* 10 %
* emulsifier 3 alkylbenzenesulfonate 30 %

polyoxyethylene(ll) 15 %
nonylphenyl ether polyoxyethylene(20) 55 %
styrenated phenol ether * emulsifier 4 alkylbenzenesulfonate 30 %

polyoxyethylene(ll) 30 %
nonylphenyl ether polyoxyethylene(20) 40 %
styrenated phenol ether Third-instar rice insect larvae were lncubated.
Thereafter, the insecticidal effect of the insecticide was assayed by the leaf dipping method using 10 larvae per section in three-course system. The percentage insecticldal effect relative to an untreated section was determined 24 hr after the treatment.
Further, the median lethal concentration was also 129Z~}82 determined. The results are shown in Table 3.
Table 3 Active Formul.Comp. formul.
ingredient No. 3 No. 3 concn.
insecticidal effect (%) lO0 ppm 92 55 41 lO

LC50 concn. (ppm) 35 95 Example 4 Thlophanate-methyl bactericide:
(Formulation No. 4) thiophanate-methyl 50 %
clay 25 %
compound 4 according to20 %
the present invention dispersant 1* 5 %
(Comparative Formulation No. 4) thiophanate-methyl 50 %
clay 45 %
dispersant l* 5 %
* dispersant l sodium sulfate Or a con-60 %
densate of naphthalene with formalin l~Zli~2 sodium lauryl sulfate 40 %
The above bactericide was applied to cucumbers which were in a pentafoliate stage. 3 days after the application, the leaves of the cucumbers were cut out and used for tests. Anthrax bacilli were previously incubated in a Petri dish and the agar medium was perforated with a cork borer to form bacillus-containing agar medium. This medium was placed on the center of the leaf which had been cut out, followed by incubation in a Petri dish for 4 days. Thereafter, the extent of spreading of the spot accompanying the disease was determined, and the protective valeu relative to an untreated section (%) was calculated. Further, the 50 % control concentration was also determined. The results are shown in Table 4.
Table 4 ActiveFormul. Comp. formul.
lngredient No. 4 No. 4 concn -protective value (%) 1000 ppm 100 90 62.530 11 50% control concn. 110 225 (ppm) Z

Example 5 Maleic hydrazide axillary bud inhibitor:
(Formulation No. 5) potassium salt of maleic hydrazide 22 %

compound 5 according to the 25 %
present invention water 53 %
(Comparative Formulation No. 5) potassium salt of maleic hydrazide 22 %
laurylbenzyldimethylammonium chloride 25 %
water 53 %
Tabacco belonging to the species Virginia was cultivated in a 4-"sun" (4.772-in.) flowerpot.
When tabacco was in 50 % bloom, it was sub~ected to topping. Immediately after the topping, the above axillary bud inhibitor having a predetermined concentration was applied. The tabacco was left as it was for 14 days. Thereafter, the weight of survival of the axillary buds was determined to calculate the percentage axillary bud inhibiting effect relative to an untreated section. The results are shown in Table 5.

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Table ~

ActiveFormul.Comp. formul.
ingredient No. 5 No. 5 concn.

axillary bud inhibit-ing effect (%) 600 ppm95 77 50 % axillary bud105 300 inhibition concn. (ppm) Example 6 Karmex D herbicide:
(Formulation No. 4) DCMU 5 %
clay 46 %
dispersant 2* 4 %
* dispersant 2 sodium sulfate Or a con-50 %
densate Or naphthale,ne with formalin sodium lauryl sulfate 50 %
The above-mentioned preparation was diluted with water to have a predeterm~n~d concentration.

Subsequently the compound 6 according to the present invention was added to the resulting diluted solution so that the concentration Or the compound is 2000 ppm.

12~2882 The herbicidal eff'ect of the resulting liquid herbicide was assayed in the same manner as in Example l.
The results are shown in Table 6.
Table 6 Active Section to which unadded ingredient compound 6 of the section concn. present invention has been added herbicidal effect (%) 2000 ppm lO0 95 lO00 91 82 125 39 ll 50 % herbicidal concn. 210 380 (ppm)

Claims (23)

1. THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
   PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
   
   l. A biocide composition which comprises a biocidally effective amount of a biocide and a branched quaternary ammonium salt having the formula (I):
   
   (I) (in which R1, R2 and R3 are each , or an alkyl having 1 to 4 carbon atoms, Y is hydrogen or a halo gen, R5 is an alkyl or alkenyl having 4 to 18 carbon atoms, R6 is an alkyl or alkenyl having 2 to 16 carbon atoms, provided that at least one of R1, R2 and R3 is ; R4 is an alkyl having 1 to 4 carbon atoms or -CH2CH2OH and X? is a counter ion) in an amount sufficient to enhance the effect of the biocide.
2. 2. A composition as claimed in Claim l, which comprises 0.1 to 20 parts by weight of the quaternary ammonium salt per part by weight of the biocide.
3. 3. A composition as claimed in Claim 1, which comprises 0.8 to 20 parts by weight of the quaternary ammonium salt per part by weight of the biocide.
4. 4. A biocide composition as claimed in claim 2, wherein X
   is Cl, Br, I, CH3SO4, C2H5SO4, HO(CH2)mCOO (where m is an integer of 1 to 5), or (where R' is an alkyl or alkenyl having 8 to 22 carbon atoms, A' is an alkylene group having 2 to 4 carbon atoms, p is an integer of 0 to 20 and q is an integer of 1 or 2).
5. 5. A biocidal composition as claimed in claim 1, 2 or 4, which further comprises a biocidally acceptable diluent or carrier.
6. 6. A biocide composition which comprises:
   (i) a biocidally acceptable diluent or carrier, (ii) a biocidally effective amount of a biocide selected from the group consisting of insecticide, fungicide, acaricide, herbi-cide and plant growth regulator, and (iii) a quaternary ammonium salt in an amount of 0.1 to 5 parts by weight per part by weight of the biocide, wherein the quaternary ammonium salt has a branched alkyl group and is repre-sented by the formula:
   
   (IV) (V) or (VI) (wherein n and m are each independently an integer of 3 to 17 and X
   is Cl, Br or CH3SO4).
7. 7. A biocide composition as claimed in claim 2, 4 or 6 wherein the biocide is herbicide.
8. 8. The biocide composition as claimed in claim 2, 4 or 6 wherein the biocide is DCMC (3-(3,4-dichlorophenyl)-1,1-dimethylurea) herbicide.
9. 9. A biocide composition as claimed in claim 2, 4 or 6 wherein the biocide is acaricide.
10. 10. A biocide composition as claimed in claim 2, 4 or 6 wherein the biocide is Kelthane (1,1-bis(p-chlorophenyl)-2,2,2-trichloroethanol) acaricide.
11. 11. A biocide composition as claimed in claim 2, 4 or 6 wherein the biocide is insecticide.
12. 12. A biocide composition as claimed in claim 2, 4 or 6 wherein the biocide is Sumithion (dimethyl 4-nitro-m-tolyl phosphorothionate) insecticide.
13. 13. A biocide composition as claimed in claim 2, 4 or 6 wherein the biocide is bactericide.
14. 14. A biocide composition as claimed in claim 2, 4 or 6 wherein the biocide is thiophanate-methyl bactericide.
15. 15. A biocide composition as claimed in claim 2, 4 or 6 wherein the biocide is plant growth regulator.
16. 16. A biocide composition as claimed in claim 2 4 or 6 wherein the biocide is potassium salt of maleic hydrazide plant growth regulator.
17. 17. A method for strengthening the effect of a biocide which comprises applying the biocide together with the branched quater-nary ammonium salt defined in claim 1.
18. 18. A biocide composition as claimed in claim 6 wherein the quaternary ammonium salt has the formula (IV).
19. 19. A biocide composition as claimed in claim 18 wherein n in the formula (IV) is 5 to 11.
20. 20. A biocide composition as claimed in claim 6 wherein the quaternary ammonium salt has the formula (V).
21. 21. A biocide composition as claimed in claim 20 wherein n in the formula (V) is 5 to 11.
22. 22. A biocide composition as claimed in claim 6 wherein the quaternary ammonium salt has the formula (VI).
23. 23. A biocide composition as claimed in claim 22 wherein n and m in the formula (VI) are 5 to 11 and 5 to 11 respectively.