SYNERGISTE POUR BIOCIDE

SYNERGIST FOR BIOCIDE

Abrégé anglais

5702-272
Abstract of the Disclosure
A biocide is strengthened in the biocidal
effect with a branched guaternary ammonium salt
having a group of <IMG>
in which R5 is an alkyl or alkenyl having 4 to
18 carbon atoms and R6 is an alkyl or alkenyl
having 2 to 16 carbon atoms.

Revendications

5702-272
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 <IMG> , <IMG>
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 <IMG> ; 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. 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.
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5702-272
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. 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),
<IMG> or <IMG>
(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. A biocidal composition as claimed in claim 1, 2 or 4,
which further comprises a biocidally acceptable diluent or
carrier.
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:
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65702-272
<IMG> (IV)
<IMG> (V)
or
<IMG>
(VI)
(wherein n and m are each independently an integer of 3 to 17 and X
is Cl, Br or CH3SO4).
7. A biocide composition as claimed in claim 2, 4 or 6
wherein the biocide is herbicide.
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65702-272
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. A biocide composition as claimed in claim 2, 4 or 6
wherein the biocide is acaricide.
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. A biocide composition as claimed in claim 2, 4 or 6
wherein the biocide is insecticide.
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. A biocide composition as claimed in claim 2, 4 or 6
wherein the biocide is bactericide.
14. A biocide composition as claimed in claim 2, 4 or 6
wherein the biocide is thiophanate-methyl bactericide.
15. A biocide composition as claimed in claim 2, 4 or 6
wherein the biocide is plant growth regulator.
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65702-272
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. 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. A biocide composition as claimed in claim 6 wherein the
quaternary ammonium salt has the formula (IV).
19. A biocide composition as claimed in claim 18 wherein n
in the formula (IV) is 5 to 11.
20. A biocide composition as claimed in claim 6 wherein the
quaternary ammonium salt has the formula (V).
21. A biocide composition as claimed in claim 20 wherein n
in the formula (V) is 5 to 11.
22. A biocide composition as claimed in claim 6 wherein the
quaternary ammonium salt has the formula (VI).
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.
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Description

1~$3Z~
5702-272
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

5702-272
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
R6
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.

~29Z88Z
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
R6
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),

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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:

lZ9Z8~Z
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
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

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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

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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
-- 10 --

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Compound 3 according to the present invention
- - CH3
CH 3 (CH 2) IIC-HCH 2 - N-CH 3 Br
(CHz) 9 CH3
CH3
Compound 4 according to the present invention
CH3
,
CH3(CHz)sCHCH2-N-CH3
. I I
(CHz)~ CH 2 CH3SO 4
CH 3 CH-(CH 2~ CH 3
(GHz)s
CH3
Compound 5 according to the present invention
CH2 ~ ~< CH3
GH~(GH~ CHGH: CH3 C!
I ; and
(CH2) 4
CH3
Compound 6 according to the present invention
Cl ~ CHz \ ~/ CH3 i
CH3(CH2)7-CHCH2 / \ CH3 Cl
(CHZ)s
CH3
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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
1000 90 82
500 81 60
250 58 38
125 41 13
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

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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
250 88 45
125 72 28
62.5 48 11
LC50 concn. (ppm)70 300
Example 3
Sumithion insecticide:
(Formulation No. 3)
Sumithion 55 %
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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
3
63 21
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
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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
500 93 71
250 78 54
125 55 32
62.530 11
50% control concn. 110 225
(ppm)
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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
300 85 5
150 63 41
43 10
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.
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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
5 77 63
250 55 40
125 39 ll
50 % herbicidal concn. 210 380
(ppm)
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