Note: Descriptions are shown in the official language in which they were submitted.
1~76ZO
This invention relates to methods and compositions
for controlling insect and acarid pests. In another aspect
this invention relates to unsymmetrical N-substituted
bis-carbamoyl sulfide compounds which are themselves
novel and to their production.
The compounds which are employed as the active
ingredients in the pesticidal compositions of this invention
are unsymmetrical bis-carbamoyl sulfide compounds of the
following general formula:
O R R10
~. . . .................................... .
Rl-OC-N-S-N-C-OR2
wherein:
R and R' are individually alkyl radicals having
from 1 to 4 carbon atoms;
Rl is 3 ~ =N- or A ~ = N-; or
Rl is alkynyl when R2 is other than alkenyl or alkynyl;
R2 is other than Rl and is alkenyl, alkynyl,
phenyl, benzofuranyl, benxothienyl, naphthyl or tetra- -
hydronaphthyl all of which may be either unsubstituted or
substituted with one or more halogen, nitro, nitrile,
alkyl, alkylthio, alkylthioalkyl, methylenedioxy, amino,
alkylamino, dialkylamino, alkoxycarbonylamino, dialkylamino-
alkylene-imino, alkylcarbonylamino, formylamino, dicyano-
ethylidene, alkoxy, alkynyloxy, phenoxy, phenyl, 2-di-
thianyl, 2-dithiolanyl, 2-dioxalanyl, 2-oxathianyl, 2-
oxathialanyl or 2-dioxanyl groups in any combination;
or R2 is: R ~ ~
~ = N- or A ~ = N-
R3 is hydrogen, alkyl, alkylthio or cyano;
R4 is alkyl, alkylthio, alkylthioalkyl, alkoxy
2.
: ~ : '
~q620
D-10 577-1
alkanoy~ aroyl or alkoxycarbonyl, all of which may be unsub-
stituted or aliphatically substituted in any combination
with one or more cyano, nitro, alkylthio, alkylsulfinyl,
alkylsulfonyl, alkoxy, aminocarbonyl, alkylaminocarbonyl,
or dialkylaminocarbonyl groups or R4 is phenyl, amino-
carbonyl, alkylaminocarbonyl, dialkylaminocarbonyl or an
R5CONH- or R5CON(alkyl)- group where R5 is hydrogen,
alkyl, or alkoxy; and
A is a divalent aliphatic chain completing a five
or six mumber ring, which includes one or two divalent oxygen,
sulfur, sulfinyl or sulfonyl groups and which may also
include one divalent amino, alkylamino or carbonyl group;
in any combination; or A may also complete a six membered
ring which includes three divalent sulfur, sulfinyl or
sulfonyl groups in any combination; provided that the total
number of aliphatic carbon atoms in R3,R4 and A individually,
may not exceed eight.
The preferred compounds of this invention are
those in which R and R' are methyl. The active compounds
of this invention exhibit a very high level of pesticidal
ac~ivity coupled with substantially reduced mammalian
toxicity and plant phytotoxicity as compared with other
known pesticidal compounds having a comparable spectrum
of activity against insect, nematode and arachnid pests.
The unsymmetrical bis-carbamoyl sulfides of this
invention can be prepared convenien~ly by the method shown
in the following general reaction scheme:
O R R'O O R R' O
ll l l ll ll l l ll
FC-N-S-N-CF + RlOH ` Rloc-N-s-N-c - F
acceptor
10577-1
~7620
O R R'O O R R'O
.. . . ....................... .. . .
RlOC-N-S-N-CF -~ R2OH~ RlOC-N-S-N-c-oR2
acid
acceptor
wherein R, R', Rl and R2 are as defined above.
One equivalent of an oxime or hydroxyl reactant
(RlOH or R20H) is reacted with the bis-carbamoyl halide
in the presence of one equivalent of an acid acceptor,
preferably in an inert solvent to produce the intermediate
carbamate-sulfenyl-carbamoyl halide compound which is then
reacted with the second oxime or hydroxyl reactant.
(RlOH if R20H was used in the first step; R20H if RlOH
was used first) in the presence of an acid acceptor to
yield the desired unsymmetrical bis-carbamate compound.
The production of the intermediate carbamate-sulfenyl-
carbamoyl halide compounds is described more fully in
Canadian Application Serial Number 266,788 filed
November 29, 1976, entitled "Carbamate-Sulfenyl Carbamoyl
Fluoride Compounds". The acid acceptor employed can be
either an organic or inorganic base such as triethylamine
or sodium or potassium hydroxide. A phase transfer agent
such as a crown ether may also be employed. Any conven-
tional inert solvent can be used, such as benzene, toluene,
dioxane, tetrahydrofuran, ethyl ether, methylene chloride or
the like.
This reaction may also be carried out in two phase
systems such as an aqueous solution of an inorganic base as
one phase and an aromatic solvent including a quaternary
ammonium salt as a phase transfer agent as the second phase.
The reaction temperature is not critical. The reaction goes
essentially to completion at room temperature. Elevated
temperatures may be employed if it is desired to reduce the
4.
~ 1'~'.. ...
~7 6 ZO
D-10577-1
reaction time.
The hydroxyl and oxime reactants employed in the
synthesis described above are known compounds which can be
prepared by conventional methods. See for example United
States Patents 3,752,841; 3,726,908; 3,843,669 and Belgian
Patents 813,206 and 815,513.
The bis-carbamoyl fluoride starting reactants are
prepared by reacting hydrogen fluoride with an appropriately
substituted alkylisocyante compound to form an alkylamino-
carbonylfluoride compound which may then be reacted with
sulfur dichloride to produce the desired bis-carbamoyl
fluoride starting material.
Representati~e of an unsymmetrical bis-carbamoyl
sulfide according to this invention is N-[2-Methylthio-2-
methylpropionaldehyde-0-(N-methylcarbamoyl)oxime~ N-ll-
methylthioacetaldehyde O-(N-methylcarbamoyl)oxime~ sulfide
which has the structure:
CH3 O CH3 ,CH3 ,, ,,,CH
CH3S-C C = N-O- C-N-S-N C-O-N=C 3
CH3 H 3
Other compounds illustrative of the new compounds of this
invention are:
N-Cl-Methylthioacetaldehyde O-(N-methylcarbamoyl)oxime] N-
~2-O-(N-methylcarbamoyl)oximino-1,4-dithiane] sulfide
N-~l-Methylthioacetaldehyde O-(N-methylcarbamoyl)oxime~
N- ~,3-dihydro-2,2-dimethyl-7-(N-methylcarbamoyloxy)ben~o-
furan~ sulfide
N-[l-Methylthioacetaldehyde O-(N-methylcarbamoyl)oxime~
N-(3-isopropylphenyl N-methylcarbamate) sulfide
.
1~376ZO
D-10,577-1
N-[l-Methylthioacetaldehyde O-(N-methylcarbamoyl)oxime]
N-(l-naphthyl N-methylcarbamate) sulfide
N-[2-Methylthio-2-methylpropionaldehyde O-(N-methycar-
bamoyl)oxime] ~-(l-naphthyl N-methylcarbamate) sulfide
N-[l-Methylthioacetaldehyde O-(N-methylcarbamoyl)oxime]
N-(2-isopropoxyphenyl N-methylcarbamate) sulfide
N~ Methylthioacetaldehyde O-(N-methylcarbamoyl)oxime
N-(4-dimethylamino-3, 5-xylyl N-methylcarbamate) sulfide
N-[2-Methylthio-2-methylpropionaldehyde O-(N-methyl-
carbamoyl)oxime] N-(3-isopropyl-4-methoxycarbonylaminophenyl
N-methylcarbamate) sulfide
N-[2-Methylthio-2-methylpropionaldehyde O-(N-methylcarbamoyl)-
oxime] N-[2,3-dihydro-2,2-dimethyl-7-(N-methylcarbamoyloxy)
benzofuran~ sulfide
N-[l-Methylthio-N', N'-dimethylcarbamoylformaldehyde O-(N-
methylcarbamoyl)oxime] N- E l-methylthioacetaldehyde O-(N-
methylcarbamoyl)oxime] sulfide
N-[2-Methylsulfonyl-2-methylpropionaldehyde O-(N-methyl-
carbamoyl)oxime] N-[2,3 dihydro-2,2-dimethyl-7-(N-methyl-
carbamoyloxy) benzofuran] sulfide
N-[2-0-(N-methylcarbamoyl)oximino-1,4-dithiane] N-(3-iso-
propylphenyl N-methylcarbamate) sulfide
N-rl-Methylthioacetaldehyde O-(N-methylcarbamoyl)oxime
N- Z4- (N' N'-dimethylformamidino)-3,5-xylyl N-methylcarbamate
sulfide
N-~l-Methylthioacetaldehyde O-(N-methylcarbamoyl)oxime
N-[(N',N'-dimethylamin~ethylenecarbamoyl)-l-methylthio-
formaldehyde O-(N-methylcarbamoyl)oxime~ sulfide
N-12-Methylthio-2-methylpropionaldehyde O-(N-methylcarbamoyl)
oxime] N-(4-dimethylamino-3,5-xylyl N-methylcarbamate)
sulfide
N-[3,3-Dimethyl-l-methylthiobutanone-2 O-(N-methylcarbamoyl)-
oxime] N-Tl-methylthioacetaldehyde O-(N-methylcarbamoyl)-
oxime] sulfide
N-[3,3-DimethYl-l-methylsulfonylbutanone-2 O-(N-methylcarbam-
oyl)oxime] N-~2 3-dihydro-2,2-dimethyl-7-(N-methylcarbamoyl-
oxy) benzofuran~ sulfide
N-r3-Methylsulfonylbutanone-2 O-(N-methylcarbamoyl)oxime]
N-~2,3-dihydro-2,2-dimethyl-7-(N-methylcarbamoyloxy)
benzofuran] sulfide
. .
1~37620
D-10,577-1
N-[3,3-Dimethyl-l-methylthiobutanone-2 0-(N-methylcarbamoyl)
oxime] N-[l-methylthioacetaldehyde 0-(N-methylcarbamoyl)-
oxime] sulfide
N-[2-C~ano-2-methylpropionaldehyde 0-(N-methylcarbamoyl)
oxime] N-(l-naphthyl N-methylcarbamate) sulfide
N-[l-Methylthio-N', N'-dimethylcarbamoylformaldehyde 0-(N-
methylcarbamoyl)oxime] N-[2,3-dihydro 2,2-dimethyl-7-(N-
methylcarbamoyloxy) benzofuran] sulfide
N-~l-Methylthiopyruvaldehyde 0-(N-methylcarbamoyl)oxime]
N-[l-methylthioacetaldehyde 0-(N-methylcarbamoyl)oxime]
sulfide
N-[2-0-(N^methylcarbamoyl)oximino-1,3-dithiolane] N-(l-
naphthyl N-methylcarbamate) sulfide
N-[5-Methyl-4 0-(N-methylcarbamoyl)oximino-1,3-dithiolane]
N-(l-naphthyl N-methylcarbamate) sulfide
N-[1-(2-cyanoethylthio)acetaldehyde 0-(N-methylcarbamoyl)
oxime] N-(l-naphthyl N-methylcarbamate) sulfide
N-[1-(2-cyanoethylthio)acetaldehyde 0-(N-methylcarbamoyl)-
oxime] N-[2,3-dihydro-2,2-dimethyl-7-(N-methylcarbamoyloxy)
benzofuran] sulfide
N-[4,5,5-Trimethyl-2 0-(N-methylcarbamoyl)oximino-thiazolidin-
3-one] N-[l-methylthioacetaldehyde 0-(N-methylcarbamoyl)-
oxime] ~ulfide
N-[4,5,5-Trimethyl-2 0-(N-methylcarbamoyl)oximino-
thiazolidin-3-one] N-[3,5,5-trimethyl-2 0-(N-methylcarbamoyl)-
oximinothiazolidin-4-one] sulfide
N-[4-Methyl-2, 0-(N-methylcarbamoyl)oximino-tetrahydro-
1,4-thiazine-3-one] N-(l-naphthyl N-methylcarbamate) sulfide
N-[4-Methyl-2 0-(N-methylcarbamoyl)oximino-tetrahydro-
1,4-thiazine-3-one] N-[1-(2-cyanoethylthio)acetaldehyde
0-(N-methylcarbamoyl)oxime] sulfide
N-~4-Methyl-2 0-(N-methylcarbamoyl)oximino-tetrahydro-
1,4-thiazine-3-one] N-[l-methylthioacetaldehyde 0-
(N-methylcarbamoyl)oxime sulfide
N-[5,5-Dimethyl-4 0-(N-methylcarbamoyl)oximino 1,3-dithio-
lane] N-(l-naphthyl N-methylcarbamate) sulfide
N-[2-(0-(N-methylcarbamoyl)oximino-1,4-dithiane] N-[4-
dimethylamino-3,5-xylyl N-methylcarbamate] sulfide
N-[2-(0-(N-methylcarbamoyl)oximino-1,4-dithiane] N-[3-
isopropyl-4-methoxycarbonylamino-(N-methylcarbamoyloxy)
benzene] sulfide
37620
D-10,577-1
N-[1-(2-cyanoethylthio) acetaldehyde O-(N-methylcarbamoyl)-
oxime] N-[2~2-dithiolanyl) phenyl N-methyl carbamate] sulfide.
N-[1-(2-cyanoethylthio)acetaldehyde O-(N-methylcarbamoyl)-
oxime] N-[2-(2-dioxalanyl) phenyl-N-methylcarbamate] sulfide.
N-[l-isopropylthioacetaldehyde O-(N-methylcarbamoyl)oxime]
N-[2-propynyloxy phenyl N-methylcarbamate~ sulfide
N-[2,3-dihydro-2,2~dimethyl-7-benzofuranyl-N-methyl-
carbamate] N-[propynyl N-methyl carbamate] sulfide.
N-[1-(2-cyanoethylthio) acetaldehyde O-(N-methylcarbamoyl)oxime]
N-[4-phenoxyphenyl N-methylcarbamate] sulfide.
N-[l-~ethylthio-N',N'-dimethylcarbamoylformaldehyde 0-
~N-methylcarbamoyl)oxime] N-[2-(2-dithiolarAyl) phenyl N-
methylcarbamate] sulfide
N-[1-(2-cyanoethylthioacetaldehyde O-[N-methylcarbamoyl)oxime]
N-[2-isopropoxyphenyl N-methylcarbamate~ sulfide
N-[2-0-(N-methylcarbamoyl)oximino-1,3,5-trithiane] N-
[2-isopropoxyphenyl N-methylcarbamate] sulfide
N-[2-0-(N-methylcarbamoyl)oximino-1,3,5-trithiane] N-[2-(2-
oxathiolanyl) phenyl N-methylcarbamate] sulfide.
N-[2-0-(N-methylcarbamoyl)oximino-1,4-dithiane] N-
[2-propynyloxy phenyl N-methylcarbamate] sulfide
N-~5-Methyl-4-0-(N-methylcarbamoyl)oximino-oxathiolane]
N-~4-phenoxyphenyl N-methylcarbamate] sulfide.
N-~4,5,5-Trimethyl-2-0-~N-methylcarbamoyl)oximino-
thiazolidin-3-one] N-~2-propynyloxy phenyl N-methylcarbamate]
sulfide
N-~3,5,5-Trimethyl-2-0-[N-methylcarbamoylJoximino-thiazolidin-
4-one] N-~2-(2-dithiolanyl)phenyl N-methylcarbamate] sulfide.
The following specific examples are provided to
illustrate the p~ocedures used for the preparation of the
compounds of this invention.
EXAMPLE I
Preparation of N-~2-Methylthio-2-methylpropionaldehyde
O-(N-methylcarbamoyl)oximel N-[l-methylthioacetaldehyde
O-~N-methylcarbamoyl)oximetsulfide
A. To a polypropylene reactor containing 80 g
(4.Om) of hydrogen fluoride in 1800 ml of toluene, cooled
1~76ZO
D-10577-1
to -40C was added dripwise with stirring 228 g (4.0m)
of methylisocyanate, over a period of 20 minutes. The
reaction mixture was allowed to warm to 0C and was main-
tained at this temperature for 1 hour. Then 206 g (2m) of
freshly distilled sulfur dichloride was added followed by
a slow addition of 346 g (4.4m) of pyridine at -20 to
0C. After stirring for 2 hours at -10C and for 16 hours
at ambient temperatures, the reaction mixture was diluted
with 500 ml of water. The toluene layer was further washed
with (3 x 500 ml? water dried and distilled to yield 244 g
(66 percent) of bis-(N-methyl-N-fluorocarbonylamino) sulfide.
~.p. 55-57C/0.25 mm. m.p. 40-41C.
Calc'd for C4H6F2N202S: C, 26.09; H, 3,28; N, 15.21
Found: C, 26.19; H, 3.20; N, 14.79.
B . To a solution of 0.714 g of l-methylthioacetald-
oxime and 1.36g of bis-(N-methyl-N-fluorocarbonylamino
sulfide in 15 ml dioxane was added dripwise 0.687g of
triethylamine. After the solution was allowed to stand
for 20 hours, it was diluted with water and extracted with
ethyl acetate. The organic extr~t was washed with water,
dried with magnesium sulfate and concentrated under vaccum
to yield 1:0 g of l-methylthioacetaldehyde ~-lN-methyl-N-
(N!-methyl-N'-fluoroformylaminosulfenyl)carbamoyl]
oxime which was crystallized from isopropyl ether-ethyl
acetate, m.p. 102-104C.
Calc d for C7H12FN33S2: C, 31.22; H, 4.49; N, 15.60
Found: C, 31.67; H, 4.69; N, 15.34
C. To a solution of 2.69 g of l-methylthioacetal-
dehyde 0-~N-methyl-N-(N'-fluoroformylaminosulfenyl) carba-
moy~ oxime and 1.33 g 2-methylthio-2-
.
.
1~376ZO
D-10,577-1
methylpropionalkoxime in 50 m dioxane was added dropwise
with stirring 1.01 g triethylamine. After 48 hours the
reaction mixture was diluted with water and extracted in
ethylacetate. The organic extract was washed with water,
dried and concentrated. The product, N-[2-Methylthio-2-
methylpropionaldehyde 0-(N-methylcarbamoyl)oxime] N-
[l-methylthioacetaldehyde 0-(N-methylcarbamoyl)oxime
sulfide, was crystallized from isopropyl ether. Wt. of
solid 1.87 g. m.p. 99-101C.
Calc d for C12H22N44S3: C, 37.68; H, 5.80; N, 14.65
Found: C, 37.68; H, 5.72; N, 14.51
EXAMPLE II
Preparation of N-[l-Methylthioacetaldehyde 0-(N-methyl-
carbamoyl)oxime] N-[2-(0-N-methylcarbamoyl)oximino)-1, 4-
dithiane] sulfide
To a solution of 2.69 g of l-methylthioacetaldehyde
0-[N-methyl N-(N'-methyl-N'-fluoroformylaminosulfenyl~
carbamoyl]oxime and 2-oximino-1,4-dithiane in 50 ml of dioxane
was added dropwise with stirring 1.01 g of triethylamine.
After stirring at ambient temFerature for 48 hours the solid
was collected by filtration. It was then dissolved in
methylene chloride, washed with water, dried and concentrated
to yield 2.2 g of N-[1-Methylthioacetaldehyde 0-(N-methyl-
carbamoyl)oxime] N-[2-0-(N-methylcarbamoyl)oximino-1, 4-
dithiane] sulfide. Crystallized from ethyl acetate chloro-
form. m.p. 164-165C.
Calc d for CllH18N44S4: C, 33-15; H, 4.55; N, 14.06
Found: C, 33.06; H, 4.55; N, 13.80
76ZO
D-10577-1
EXAMPLE 'I'II
Preparation of N-[2-(0-(N-methylcarbamoyl)oximinc)-1,4-
dithiane-~-[2-0-(N-methylcarbamoyl)oximino-3,5,5-
'trimethylthiazolidin-4-one]sulfide
. _ . .
To a suspension of 3.4 g of 2-~O~N-methyl-N-(N'-
methyl-N'-fluoroformylaminosulfenyl)carbamoyl)oximino~-3,
5,5-trimethylthiazolidin-4-one and 1.5 g of 2-oximino-1,
4-dithiane in 70 ml of toluene cooled to 15C, was added
dropwise with stirring 1.05 g of triethylamine over a
period of 20 minutes. After stirring for 17 hours at
room temperature the reaction mixture was concentrated
under reduced pressure. The solid was taken in methylene
chloride, washed with water. The organic layer was dried
and concentrated to yield 3.5 g of N-~2-(N-methylcarbamoyl)-
oximino-1,4-dithiane~ N-[2-O~N-methylcarbamoyl)oximino-3,
5,5-triethylthiazolidin-4-one] sulfide. Recrystallized from
ethyl acetate and isopropyl ether. m.p. 170-171C.
Calc d for C14H21N55S4: C, 35.96; H, 4.53; N, 14.98
Found: (., 35.90; ~, 4.94; N, 14.75
EXAMPLE IV
Preparation of N- ~-methyl-N-propargyoxycarbonylamino N-[3,5
5-trimethylthiazolidin-4-one-2 ~(N-methylcarbamoyl)oximl sulfide
To a solution of 1.7 g of 2~ N-methyl-N-(N'-
methyl-N'-fluoroformylaminosulfenyl)carbamoyljoximino]-3,
5,5-trimethylthiazolidin-4-one and 0.28 g of propargyl
alcohol in 20 ml of toluene cooled to 10-15C was added
dropwise 0.55 g of triethylamine dissolved in 5 ml of toluene.
After stirring for 20 hours at ambient temperature, the
reaction mixture was diluted with water and ethyl acetate.
The organic extract was washed with water, dried over
anhydrous magnesium sulfate and concentrated under reduced
pressure. The product, N-[N-methyl-N-propargyloxycarbonyl-
~m;no]N-[3,5,5-trimethylthiazolidin-4-one-2-
11. - ~ ,.
..... ., , ",.. , , .. .. ,.. , . .. .. ... . ...... . " .. i. .. , . . , , .. .. .. . . . ~
~3762~J
D-10,577-1
O(N -methylcarbamoyl)oxime~ sulfide, was crystallized
from isopropyl ether - ethylacetate.
Weight = 0.52 g m.p. 96-96.8C
Calc d for C13H18N45S2: C, 41.70; H, 4.84; N, 14.96
Found: C, 41.86; H, 5.06; N, 14.22
EXAMPLE V
Preparation of N-[l-Methylthioacetaldehyde 0-(N-methyl-
carbamoyl)oxime] N-[2,2-dimethyl-2,3-dihydro-7-
(N-methylcarbamoyloxy)benzofuran] sulfide
To a solution of 5.0 g of l-methylthioacetaldehyde
0-[N-methyl-N-(N'-methyl-N'-fluoroformylaminosulfenyl)
carbamoyl]oxime and 3.05 g of 2,2-dimethyl-2,3-dihydro- -
benzofuran-7-ol in 50 ml of dioxane was added dropwise
1.87 g of triethylamine. After allowing the reaction
mixture to stand for 18 hours, it was quenched with 200
ml of water and the product was extracted with ethyl
acetate. The organic extract was washed with water, dried
over magnesium sulfate and concentrated under reduced
pressure to yield an oil. The product, N-~l-methylthio-
acetaldehyde 0-(N-methylcarbamoyl)oxime] N-[2,2-dimethyl-2,
3-dihydro-7-(N-methylcarbamoyloxy)benzofuran] sulfide,
crystallized from ethylacetate-isopropyl ether. Weight
of solid 4.3 g m.p. 141-144C.
Calc d for ~17H23N35S2: C, 49.38; H, 5.60; N, 10.16
Found: C, 49.59; H, 5.63; N, 10.34
EXAMPLE VI
Preparation of N-[2-Methylthio-2-methylpropionaldehyde 0-
(N-methylcarbamoyl)oxime] N-[l-(N-methylcarbamoyloxy)
aa~hthalenel sulfide
To a solution of 6.5 g of l-[N-methyl-N-(N'-
methyl-N'-fluoroformylaminosulfenyl) carbamoyloxy] naphthalene
and 2.94 g of 2-methylthio-2-methylpropionaldoxime in
10E~7620
D-10577-1
100 ml of toluene was added 2.23 g of triethylamine
and the reaction mixture stirred for 18 hours. The
mixture was diluted with an additional 100 ml of toluene
and was washed with a 100 percent solution of sodium
carbonate and water. The organic phase was dried and
concentrated under vacuo to yield 7.7 g of the crude
N-l2- Methylthio-2-methylpropionaldehyde 0-(N-methyl-
carbamoyl)oxime~ N-~l-methylcarbamoyloxynaphtalene]
sulfide as a viscous oil. An aliquot was purified by
dry column chromatography.
Cl9H23N34S2: C~ 54-13; H, 5.50; N, 9.96
Found: C, 53.19; H, 5.56; N, 9.58
EXAMPLE VII
Preparation of N-[l-Methylthioacetaldehyde 0-(N-methyl- m~
carbamoYl)oxime~[N- 1- l-naPhthYl N-methylcqrbamatel sulfide
N-[l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)-
oxime] N-~l-naphthylmethylcarbamate] sulfide was pre-
pared by the procedure employed in Example VI by reacting
3.88 g of L-methylthioacetaldehyde 0-~N-methyl-N-(N'-methyl
N'-fluoroformylaminosulfenyl)carbamoyll oxime with 2.07 g
of l-naphthol and 1.45 g of triethylamine as an acid
acceptor.
Weight of product 4.1 g. m.p. 88-90C.
Calc d for Cl7Hl9N34S2: C, 51.89; H, 4.87; N, 10.68
Found: C, 52.35; H, 4.86; N, 10.31
.
. . .
76ZO
D
EXAMPLE VIII
Preparation of N-[l-Methylthioacetaldehyde 0-(N-mc
carbamoyl)oxime] N-[4-isopropylphenyl-(N-methylcarbam~
sulfide
N-[l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)-
oxime] N-[4-isopropylphenyl-(N-methylcarbamoyloxy)] sulfide
was prepared by the procedure employed in Example VI by
reacting 3.56 g of l-methylthioacetaldehyde 0-[N-methyl-
N-(N'-methyl-N'-fluoroformylaminosulfenyl)carbamoyl]oxime
with 2.04 g of 4-isopropylphenol and 1.51 g of triethylamine
as an acid acceptor.
Weight of the product 3.7 g m.p. 108-110C.
Calc d for C16H23N34S2: C, 49.85; H, 6.01; N, 10.90
Found: C, 49.22; H, 6.07; N, 10.97
EXAMPLE IX
Preparation of N-[l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)
oxime] N-[4-tert-butylphenyl-(N-methylcarbamoyloxy)] sulfide
N-[l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)
oxime] N-[4-tert-butylphenyl-(N-methylcarbamoyloxy)] sulfide
was prepared by the procedure employed in Example VI by
reacting 3.56 g of l-methylthioacetaldehyde 0-[N-methyl-N-
(N'-methyl-N'-fluoroformylaminosulfenyl)carbamoyl]oxime
with 2.25 g of 4-tert-butylphenol and 1.51 g of triethylamine
as an acid acceptor.Weight of the product was 3.8 g, m.p.
141-143C.
Weight for C17H2sN304S2: C, 51.10; H, 6.30; M, 10.51
Found: C, 50.69; H, 6.37; N, 10.59
EXAMPLE X
Preparation of N-[l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)
oxime] N-[1-(2-cyanoethylthio)acetaldehyde 0-(N-methylcarbamoyl)
oxime] sulfide
N-[l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)-
oxime] N-[1-(2-cyanoethylthio)acetaldehyde 0-(N-methylcarbamoyl)
oxime] sulfide was prepared by the procedure employed in
14.
~ 376ZO D-10,577-1
Example III by reacting 2.88 g of 1-(2-cyanoethyl)thioacetal-
doxime and 4.75 g of l-methylthioacetaldehyde 0-[N-
methyl-N-(N'-methyl-N'-fluoroformylaminosulfenyl)carbamoyl]-
oxime in 75 ml of toluene and 2.02 g of triethylamine as an
acid acceptor. Weight of the product ~.2 g m.p. 121-123C.
lc d for C12HlgN504S3: C, 36.62; H, 4.87; N, 17 80
Found: C, 36.48; H, 4.81; N, 17.44
EXAMPLE XI
Preparation of N-[l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)-
oxime] N-[l-methylthio-N', N'-dimethylcarbamoylformaldehyde
0-(N-methylca3bamoyl)oxime] sulfide
N-[l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)-
oximelN-[l-methylthio-N', N'-dimethylcarbamoylformaldehyde 0-
(N-methylcarbamoyl)oxime] sulfide was prepared by the procedure
employed in Example III by reacting 5.39 g of l-methylthio-
acetaldehyde 0-[N-methyl-N-(N'-methyl-N'-fluoroformylamino-
sulfenyl)carbamoyl] oxime with 3.24 g of l-methylthio-N,
N-dimethylcarbamoylformaldoxime in 100 ml of toluene and
2.02 g of triethylamine as an acid acceptor. Weight of re-
crystallized product 4.0 g m.p. 121-123C.
for C12H21N505S3: C, 35.02; H, 5.14; N, 17-02
Found: C, 35.00; H, 5.18; N. ~6.58
EXAMPLE XII
Preparation of N-[l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)-
oxime] N-[l-~N-methylcarbamoyloxy)-4-nitrobenzene] sulfide
N-[l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)-
oximelN-[l-(N-methylcarbamoyloxy)-4-nitrobenzene] sulfide was
prepared by the procedure employed in Example V by reacting
5.0 g of l-methylthioacetaldehyde 0-[N-methyl-N-(N'-methyl
N'-fluoroformylaminosulfenyl)carbamoyl]oxime with 2.59 g
of 4-nitrophenol in 75 ml of dioxane and 1.87 g of triethyl-
amine. Weight of the product 3.9 g. m.p. 164-165C.
r C13H16N406S2: C, 40.20; H, 4.15; N, 14 42
Found: C, 40.35; H, 4.05; N, 14.23
6ZO
D-10,577-1
,
EX~PLE XIII
Preparation of N-[l-Methylthioacetaldehyde 0-(N-methyl-
carbamoyl~oxime]N-Cl-methylthio-l-ethoxycarbonylformaldehyde
O-(N-'met~l'carbamby'l)o'xime]'sul'fide'' ''' ''
N-~l-Methylthioacetaldehyde 0-CN-methylcarbamoyl)oxime]
N-[l-methylthio-l-ethoxycarbonylformaldehyde O -(N-methyl-
carbamoyl~oxime] sulfide was prepared by the procedure employed
in E~ample III by reacting 5.38 g of l-methylthioacetaldehyde
0-[N-methyl-~-(N'-methyl-N'-fluoroformylaminosulfenyl)
carbamoyloxime'with 3.26 g of l-methylthio-l-ethoxycarbonyl-
formaldoxime in 75 ml of toluene and 2.02 g of triethylamine
as an acid acceptor. Weight of the product 6.02 g. m.p. 99-100C
d for C12H20N46S3: C, 34.94; H, 4.89; N, 13 58
Found: C, 34.76; H, 5.00; N, 13.41
EXAMPLE XIV
Preparation of N-~l-Methylthioacetaldehyde 0-(N-methyl-
cæbamoyl~oxime]N-~l-(N-methylcarbamoyloxy)-5,6,7,8-tetrahydro-
naphtXalene]''s'ul'fi'de. ' '' ' ''
N-~l-Methylthioacetaldehyde 0-(N-methylcarbamoyl~oxime]
N-[l-(N-methylcarbamoyloxy~5,6,7,8-tetrahydronaphthalene]
sulfide was prepared by the procedu~e employed in Example YI
by reacting 2.0 g of l-methylthioacetaldehyde 0-~N-methyl-N-
(N'-methyl-N t -fluoroformylaminosulfenyl~carbamoyl]oxime with
1.1 g of 5,6,7,8-tetrahydro-1-naphthol in 50 ml of toluene
and 0.75 g of triethylamine as an acid acceptor. Weight of the
product 2.3 ~. m.p. 119-120C.
alc d for C17H23N34S2: C, 51.36; H, 5.83; N, 10.57
Found: C, 51.16; H, 5.86; N, 10.44
15.
,
- .
.
6ZO
D-10,577-1
EXAMPLE XV
Preparation of N-[l-Methylthioacetaldehyde O-(N-methylcarbamoyl)-
oxime] N-~0-(N-methylcarbamoyl)-4-methylthio-3-methylphenyl]
.. .. ... ..
N-[l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)-
oxime] N-[O~(N-methylcarb~moyl~-4-methylthio-3-methylphenyl]
sulfide was prepared by the procedure employed in Example VI
by reacting 3.56 g of l-methylthioacetaldehyde O-(N-methyl-
N-(N'-methyl-N'-fluoroformylaminosulfenyl)carbamoyl]oxime with
2.77 g of 4-(methylthio)-m-cresol in 100 ml of toluene and
1.81 g of triethylamine as an acid acceptor. Weight of the
product 3.2 g. m.p. 98-99C.
Calc d for C15~21N34S3: C, 44.64; Hl 5.24; N. 10.
Found: C, 44.40; H, 5.08; N. 10.25
EXAMPLE XVI
Preparation of N-~l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)-
oxime] N-~4-methoxycarbonylæmino-(N-methylcarbamate)-3-iso-
proPylp~enyll sulfide
N-[l-Methylthioacetaldehyde O-(~-methylcarbamoyl)
oxime] N-[4-methoxycarbonylamino-(N-methylcarbamate)-3-iso-
propylphenyl] sulfide was prepared by the procedure employed
in Example VI by reacting 4.0 g of l-methylthioacetaldehyde
0-~N-methyl-N-CN'-methyl-N'-fluoroformylaminosulfenyl)carbamoyl]- -
oxime w~th 3.75 g of 4-methoxycarbonylamino-3-isopropylphenol
in 75 ml of toluene and 1.81 g of triethylamine as an acid
acceptor. Weight of the product 3.6 g. m.p. 113-115C.
c d for C18~26N46S2: C, 47-14; ~, 5.72; N, 12.22
Found: C, 46.86; ~, 6.05; N, 12.11
17.
~ . .
10876Z0 D-10,577-1
EXAMPLE XVII
Preparation of N-[l-Methylthioacetaldehyde 0-CN-methyl-
carbamoyl)oxime} N-~3-Cand 4)-isopropylphenyl-C.~-methyl-
carbamo~loxy)~- sulfide
N-[l-Methylthioacetaldehyde 0-(N-methy~-arbamoyl)- -
oximelN-~3-(and 4)-isopropylphenyl-(N-methylcarbamoyloxy)~
sulfide was prepared by the procedure employed in example VI
by reacting 2.69 g of l-methylthioacetaldehyde 0-[N-methyl-N-
(N'-methyl-N'-fluoroformylaminosulfenyl)carbamoyl]oxime with
1.36 g of meta/para-(60:40)-isopropylphenol in 50 ml of dioxane
and 1.01 g of triethylamine as an acid acceptor. Weight of
the crude product 2.18 g. An aliquot was purified by chromato-
graphy.
Calc'd for C16H23N304S2: C, 49.85; H, 6.01; N, 10.90
Found: C, 48.14; H, 5,90; N, 11.07
EXAMPLE XYIII
Preparation of N-[l-Methylthioacetaldehyde 0-(N-methyl-
carbamoyl)oxime] N-~3,4,5-trimethylphenyl-(N-methylcarbamoyl-
oxy)] su~fide
N-[l-Methylthioacetaldehyde O-(N-methylcarbzmoyl)-
oxime] N-~3,4,5-trimethylphenyl-CN-methylcarbamoyloxy)] sulfide
was prepared by the procedure employed in E~ample VI by reacting
3.55 g of l-methylthioacetaldehyde 0-~N-methyl-N-(N'-methyl-N'-
fluoroformylaminosulfenyl~carbamoyl]oxime with 2.72 g of 3,4,5-
trimethylphenol in 100 ml of toluene using 2.02 g of triethyl-
amine as an acid acceptor. Weight of the product 3.1 g.
m.p. 97-99C.
Calc'd for C16H23N304S2: C, 49.85; H, 6.01; N, 10.90
Found: C, 49.57; H, 5.97; N, 10.89
: .
18.
- , .. : . . . .
1~87620 D-10,577-1
EXAk~L~ XI~
Preparation of N-~-MethylthIoac~taldehyde O-(N-methylcarbamoyl)-
oxime] N-L~4-dinitro-6'-sec-butylphenyl-~N-methylcarbamoyloxy)]
sulfïde '' '''''' ' ' '
..... _
N-[l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)-
oxime] N-[2,4-dinitro-6-sec-butylphenyl-(N-methylcarbamoyloxy)]
sulfide was prepared by the procedure employed in Example VI
by reacting 3.56 g of l-methylthioacetaldehyde 0-[N-methyl-~-
(N'-me~hyl~N'-fluoroformylaminosulfenyl)carbamoyl]oxime with
1~ 4.3 g of 2,4-dinitro-6-sec-butylphenol in 100 ml of toluene
and 1.8 g of triethylamine as an acid acceptor. Crystallized
from methanol. m.p. 129-130C. - ,
lc d for C17H23N58S2: C, 41.71; H, 4.74; N, 14 31
Found: C, 41.60; H, 4.52; N, 14.22
EXAMPLE XX
Preparation of N-[l-Methylthioacetaldehyde 0-CN-methyl-
carbamoyl)oxime]N-~3-CN~,N'-dimethylamino)phenyl-(N-methyl
carbamo~loxy)~ sulfide
N~ Methylthioacetaldehyde O-~N-methylcarbamoyl)
oxime~ N-L3-(Nt,N~-dimethylamino)phenyl-CN-methylcarbamoyloxy)]
sulfide was prepared by the procedure employed in Example VI
by reacting 3.55 g of l-methylthioacetaldehyde 0-[N-methyl-
N-(N'-methyl-N'-fluoroformylaminosulfenyl)carbamoyl]oxime with
1.78 g of 3-dimethylaminophenol in 150 ml of toluene and 1.52 g '~
of triethylamine as an acid acceptor. The weight of the product ~ - -
after purification 1.3 g m.p. 108-109C. - -
Calc d for C15H22N44S2: C, 46.61; H, 5,74; N, 14.50
Found: C, 46.33; E, 5.52; N, 14.19
~';
19.'
87 62~D D-10,577-1
E~AMPLE XXI
Preparation of N~ Methylthioacetaldehyde O-CN-methyl-
carbamoyl~oxime]' N-~4-formylamino-3-methylphenyl-(N-methyl-
carbamo~lo-x~)']''s'ulfide
N-~l-Methylthioacetaldehyde O-(N-methylcarbamoyl)-
oæime] W-[4-formylamino-3-methylphenyl-(N-methylcarbamoyloxy)]
sulfide was prepared by the procedure employed in Example YI
by reacting 4.04 g of l-methylthioacetaldehyde 0-[N-methyl-
N-(N'-methyl-N'-fluoroformylaminosulfenyl)carbamoyl]oxime with
2.67 g of 4-~,N-dimethylformamidino-metacresol in 200 ml of
toluene and 1.56 g of triethylamine as an acid acceptor.
After usual work-up and purification by coll~n chromatography
0.7 g of the product was isolated. m.p. 143-145G.
Calc'd for Cl5H20N405S2: C, 44.98; H, 5.03; N, 13-99
Found: C, 44.87; H, 4.98; N, 13.79
' EXANPLE XXII
Preparation of N-[2~0-(N-methylcarbamoyl)oximino~1,4-dithiane]
N-~l-'naphthy~-cN-methylcarbamoyloxy)] sulfide
N-~2-0-(N-methylcar~amoyl~oximino-1,4-dithiane3
N-[l-naphthyl-(N-methylcarbamoyloxy)] sulfide was prepared
by the procedure employed in Example YI by reacting 5.0 g of
l-[N-methyl-N-CN'-methyl-N~-fluoroformylaminosulfenyl)
carbamoyloxy]-naphthalene with 2.42 g of 2-oximino-1,4-
tithiane in 100 ml of toluene and 1.64 g of triethylamine as
an acid acceptor. Weight of the product 5.0 g. m.p. 148-150C.
lc d for C18HlgN34S3: C, 49.41; H, 4.38; N, 9.60
Found: C, 48.70; ~, 4.28; N, 9.53
20.
10876ZO D-10,577-1
EXAMPLE XXIII
Preparation of N-[l-Methylthioacetaldehyde O-(N-methylcarbamoyl)- '~
oxime] N-~4-C2'-'cis,7~-octadienyl-cN-methylcarbamoyloxy~benzene]
sulfi'de ' '
N-[l-Methylthioacetaldehyde 0-(N-methylcarbamoyl)oxime] N-
[4-(2-cis,7)octadienyl-(N-methylcarbamoyloxy)benzene] sulfide
- was prepared by the procedure employed in Example VI by reacting
3.5 g of l-methylthioacetaldehyde 0-[N-methyl-N-(N'-methyl-N'-
fluoroformylaminosulfenyl)carbamoyl] oxime with 2.63 g of 4-
~ 2,7~-octadienylphenol in 150 ml of toluene and 1.31 g
of triethylamine as an acid acceptor. The oily residue was
purified by column chromatography to yield 1.9 g of an oil.
Calc'd for C21H29N3O4S2 C~ 55-8 ;
Found: C, 55.22; H, 6.39; N, 9.22
EXAMPLE XXIV
Preparation of N-[2-0-(N-methylcarbamoyl)oximino-1,4-dithiane]
N-[2,3-dihydro-2,2-dimethyl-7-(N-methylcarbamoyloxy)
benzofuran] sulfide ~ ~'
N-[2~'0-(N-methylcarbamoyl~oximino~1,4-dithiane]
N-[2,3-dihydro-2,2-dimethyl-7-(N-methylcarbamoyloxy)
benzofuran] sulfide was prepared by the procedure employed '
in Example VI by reacting 3.13 g of 2~ N-methyl-N-(N'-methyl-
N'-fl~oroformylaminosulfenyl)carbamoyl]oximin~}1,4-dithiane
with 1.65gof 2,3-dihydro-2,2-dimethyl-benzofuran-7-ol in
150 ml of toluene and 1.01 g of triethylamine as an acid
acceptor. The crude product was purified by dry-column
chromatography to yield an amorphous solid.
Calc'd for C18H23N35S3: C, 47.24; H, 5.07; N, 9.18
Found: C, 46.04; H, 5.03; N, 8.81
.
7620
D-10,577-1
EXAMPLE XXV
Preparation of N-[2-0-(N-methylcarbamoyl)oximino-1,4-dithiane]
N-[4-isoproPYl-(N-methylcarbamoyloxy) benzene] sulfide
N-[2-(0-(N-methylcarbamoyl)oximino~-1,4-dithiane]
N-[4-isopropyl-(N-methylcarbamoyloxy) benzene] sulfide was
prepared by the procedure employed in Example VI by reacting
3.13 g of 2-0-[N-methyl-N-(N'-methyl-N'-fluoroformylamino-
sulfenyl)carbamoyl]oximino-1,4-dithiane with 1.36 g of 4-
isopropylphenol in 150 ml of toluene and 1.01 g of tri-
ethylamine. Weight of the product after column chromatography
1.1 g. m.p. 129-131C.
c ~ for C17~25N3Q4S3 C, 47.53; H, 5.40; ~ 9^70
Found: C, 47.40; H, 5.27; N, 9.73
The compounds of EXAMPLES XXVI-XLI were prepared
by the methods of EXAMPLES I-XXV. The physical properties
of these compounds are listed in TABLE I below.
22.
: : ... ..
~087620
X X~3 X X X X
_ .
~n n n n n n~ ;8
cnn - Inln~ Inl~n - Inl n Inl un~ - ~n~ w
~ Z X Z ~ z ~ z
w I w I w I w I w ~ w
.. _ . . _
n~ ~ ~n n ~ ~
z
w n Z
~ _ D
e~ Wb wb wr wb `wb wr .~ z
_ ~ @i
b b b r b b b ~ n~o~ w
w w w w w w w Z- -~D ~
_ u~ D~Z 'r
W ~o~o ~ O - o~ ~ : :
~0 :d ~0
-- n
~ ."
n n n n n n n:3: o
~ :~ ~ ~ wZ z z e x~
w O ~ O ~ n
_ _ I U~
n n
w ~ o~ Di~
_ W g ~ 0 ~ ~D O 0~ C
= ~, .... ~ _ t
w ~n æ~ ~n 0O ~ c'
_
O O . . ~ . . .O O ~ ~ ~ ~ Z
00 w~ ~0~ ~ ~ .
.
37620
æ ~ æ cæ æ æ~
S X X X X X _
W ~ W .. , W W
n n n ~n ~ n ~n
'zX Z X ~I XZ :-: Z ~ ~:
. : -
~ r
Z .~
n X n ~ X n ~ ¦ Z
n n n n ~ n ~ ~ Z
:~ x :~ X x x~ :o rta
~ ~ ~Z - ~ ~ ~ ~ ,
~,o, ~ ~ ~ ~~ z ~ ~
n O D t
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H
n r rn ~, r ~F O
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n
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`J~`` ~ ~ ~~D~D ~ ~
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o o~o~_ _ C .:.
~11 ~I ~JI Ul ~ ~C` ~ ~ ~ ~1~ Ul ~Jl 3 C~
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1~376ZO
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W:~ Z ~X ~ ~:~ Z
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5~ o -- :
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~tDB7620
D-10,577-1
.
Selected species of the new compounds were
evaluated to determine their pesticidal activity against
mites and certain insects, including an aphid, a caterpillar,
a beetle and a fly.
- Suspensions of the test compounds were prepared by
dissolving one gram of compound in 50 milliliters of acetone
in which had been dissolved 0.1 gram (10 percent of the weight
of compound) of an alkylphenoxy polyethoxyethanol surfactant,
as an emulsifying or dispersing agent. The resulting solution
was mixed into 150 milliliters of water to give roughly
200 milliliters of a suspension containing the compound
in finely divided form. The thùs-prepared stock suspension
contained 0:~5 percent by weight of compound. The test
concentrations in parts per million by weight employed
in the tests described hereinbelow were obtained by appropriate
dilutions of the stock suspension with water. The test
procedures were as follows:
Bean APhid Foliage SPray Test
Adults and nymphal stages of the bean aphid
APhis fabae Scop.) reared on potted dwarf nasturtium
plants at 65-70F. and 50-70 percent relative humidity,
consistuted with test insects. For testing purposes, the
number of aphids per pot was standardized to 100-150 by
trimming plants containing excess aphids.
The test compounds were formulated by diluting
the stock suspension with water to give a suspension
containing 500 parts of test compound per million parts
of inal formulation.
:
26.
- . . ~ ,
: ., ~ ~ ~ ., ,
376ZO
D-10,577-1
The potted plants (one pot per compound tested)
infested with 100-150 aphids, were placed on a revolving
turntable and sprayed with 100-110 milliliters of test
compound formulation by use of a DeVilbiss spray gun set
at 40 psig. air pressure. This application, which lasted
25 seconds, was sufficient to wet the plants to run-off.
As a control, 100-110 milliliters of a water-acetone-
emulsifier solution containing no test compound were
also sprayed on infested plants. After spraying, the pots
were placed on their sides on a sheet of white standard
mimeograph paper which had been previously ruled to facilitate
counting. Temperature and humidity in the test room during
the 24 hour holding period were 65-70F. and 50-70 percent,
respectively. Aphids which fell onto the paper and were
unable to remain standing after being uprighted were
considered dead. Aphids remaining on the plants were
observed closely for movement and those which were
unable tc move the length of the body upon stimulation
by prodding were considered dead. Percent mortality
was recorded for various concentration levels.
. .
.
D-10577- L
1~7620
Southern Armyworm Leaf Spray Bait Test
Larvae of the southern armyworm (Spodopera
eridania, (Cram.~), reared on Tendergreen bean plants
-
at a temperature of 80+5F. and a relative humidity of
50+5 percent, constituted the test insects.
- The test compounds were formulated by diluting
the stock suspension with water to give a suspension
containing 500 parts of test compound per million parts
of final formulation. Potted Tendergreen bean plants of
standard height and age were placed on a revolving turn-
table and sprayed with 100-110 milliliters of test compound
formulation by use of a DeYilbiss spray gun set at 10 psig
air pressure. This application, which lasted 25 seconds, was
sufficient to wet plants to run-off. As a control, 100-110
milliliters of a water-acetone-emulsifier solution containing
no test compound were also sprayed on infested plants, When
dry, the paired leaves ~ere separated and each one was
placed in a 9 centimeter Petri dish lined with moistened
filter paper. Five randomly selected larvae were introduced into
each dish and the dishes were closed. The closed dishes were
labeled and held at 80-85F, for three days. Although the
larvae could easily consume the whole leaf within twenty-
four hours, no more food was added. Larvae which were unable
to move the length of the body, even upon stimulation by
prodding, were considered dead. Percent mortality was recorded
for various concentration levels,
Mexican Bean Beetle Leaf Spray Test
Fourth instar larvae of the Mexican bean beetle
(Epilachna varivestis, Muls.), reared on Tendergreen bean
plants at a temperature of 80+5F. and 50+5 percent relative
humidity, were the test insects.
,, .' :, ~ . ., - ,.
1~7620
D-10577-1
.
The test compounds were formulated by diluting
the stock suspension with water to give a suspension with
water to give a suspension containing 500 parts of test
compound per million parts of final formulation. Potted
Tendergreen bean plants of standard height and age were
placed on a revolving turntable and sprayed with 100-110
milliliters of test compound formulation by use of a
DeVilbiss strapy gun set at 10 psig air pressure. This
application, which lasted 25 seconds, was sufficient to
wet plants to run-off. As a control, 100-110 milliliters
of a water-acetone-emulsifier solution containing no test
compound were also strayed on infested plants. When dry, the
paired leaves were separated and each was placed in a 9
centimeter Petri dish lined with moistened filter paper.
Five randomly selected larvae were introduced into each
dish, and the dishes were closed. The closed dishes were
labeled and held at a temperature of 80+5F. for three days.
Although the larvae could easily consume the leaf within
24 to 48 hours, no more food was added. Larvae which were
unable to move the length of the body, even upon stimulation,
were considered dead.
Fly Bait Test
Four to 9iX day old adult house flies (Musca
domestica, L.), reared according to the specifications
of the Chemical Specialties Manufacturing Association
(Blue Book, McNair-Dorland Co., N.Y. 1954; pages 243-2$4, 261)
under controlled conditions of 80+5F. and 50+5 percent
relative humidity, were the test insects. The flies were
immobilized individuals, males and females, were transferred
to a cage consisting of a standard food strainer
29.
- , .' . ~' ''
1~37620
D-10577-1
about five inches in diameter which was inverted over a
wrapping-paper-covered surface. The test compounds were
formulated by diluting the stock suspension with a 10 percent
(by weight) sugar solution to give a suspension containing
500 parts of test compound per million parts of final
formulation, by weight. Ten milliliters of the test formula-
tion were added to a souffle cup containing a one-inch
square of an absorbent cotton pad. This bait cup was
introduced and centered on the blotting paper under the food
strainer prior to admitting the anesthetized flies. The
caged flies were allowed to feed on the bait for twenty-four
hours, at a temperature of 80+5F. and the relative humidity
of 50+5 percent. Flies which showed no sign of movement on
prodding were considered dead.
Mite Folia~e Spray Test
Adults and nymphal stage of the two-spotted
mite (Tetranychus urticae Koch), reared on Tendergreen
bean plants at a temperature of 80+5F and at a relative
humidity of 50+5 percent, were the test organisms. Infested
leaves from a stock culture were placed on the primary leaves
of two bean plants six to eight inches in height, growing in
a two-and-a-half inch clay pot. 150-200 Mites, a sufficient
number for testing, transferred from the excised leaves to
the fresh plants in a period of twenty-four hours. Following
the twenty-four hour transfer period, the excised leaves were
removed from the infested plants. The test compounds were
formulated by diluting the stock suspension with water to
give a suspension containing 500 parts of test compound per
million parts of final formulation. The potted plants (one
pot per compound~ were placed on a revolving ,urntable and
sprayed with 100-llO
.. ~ : , - . . . - , .
1~7620
D-10577-1
milliliters of test compound formulation by use of a DeVilbiss
spray gun set at 40 psig. air pressure. This application,
which lasted 25 seconds, was sufficient to wet the plants
to run-off. As a control, 100-110 milliliters of a water
solution containing acetone and emulsifier in the same
concentrations as the test compound formulation, but
containing no test compound, were also sprayed on inested
plants. The sprayed plants were held at a temperature of
80+5F and a 50+5 percent relative humidity for six days,
after which a mortality count of motile forms was made.
Microscopic examination for motile forms was made on the
leaves of the test plants. Any individual which was
capable of locomotion upon prodding was considered living. ~`-
` Nematocide Test
The test organism used was the infective
migratory larvae of the root-knot nematode, Meloido~yne
incognita var. acrita, reared in the greenhouse on
roots of cucumber plants. Infec~ed plants were removed
from the culture,` and the roots are chopped very finely.
A small amount of this inoculum was added to a pint jar
containing approximately 180 cc. of soil. The jars
were capped and incubated for one week at room temperature.
During this period eggs of the nematode were hatched, and
the larval forms migrated into the soil.
Ten ml. of the test formulation were added to
each of the two jars for each dosage tested. Following the
addition of chemical, the jars were capped, and the contents
thoroughly mixed on a ball mill for 5 minutes.
The test compounds were formulated by a
standard procedure of solution in acetone addition of an
31.
.
~0876~0 D-10,577-1
emulsifier, and dilution with water. Primary screening
tests were conducted at 3.33 m.g. of the test compound
per jar.
The jars were left capped at room temperature
for a period of 48 hours, and the contents then trans-
ferred to 3 inch pots. Subsequently, the pots were
seeded to cucumber as an indicator crop and placed in
the greenhouse where they were cared for in the normal
fashion for approximately 3 weeks.
The cucumber plants were then taken from the
pots, the soil removed from the roots; and the amount of
galling visually rated.
The results of these tests are set forth
in Table I below. In these tests the pesticidal activity
of the compounds at the indicated dosage rate against aphid,
mite, Southern Armyworm (SA), Mexican Bean Beetle (MBB),
and house fly was rated as follows:
A = excellent control
B s partial control
C - no control
In the test for activity against nematodes (nem)
activity was rated as follows:
1 3 severe galling, equal to untreated plants
2 = moderate galling
3 = light galling ;
4 = very light galling
5 = no galling, perfect control
Dashes indicate no test conducted.
32.
.
D-10577 -1
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1~)87620
PhytotQxicity Test
Experiments were also conducted to determine
the phytotoxicity of repres~ntatiYe compounds with respect
to healthy fresh plants, Solutions of the compounds were
prepared as described above to provide a concentration of
2500 parts per million of the test compound. The test plants
were sprayed in accordance with the procedure described
above for the Mite Foliage Spray Test so as to deliYer
approximately 100 milliliters of test solution to the leaves
of each plant tested. The sprayed plants and controls were
set aside for approx~mately one hour to allow the foliage to
dry and were then placed in the greenhouse. After ten days
the plants were visually inspected to determine the extent of
foliage injury. A rating of l indicates no perceptible
injury; 5 indicates the plant was dead and ratings of 2, 3
and 4 indicate intermediate degrees of injury based upon the
number and extent to which leaYes were injured.
- Mammalian ToxicitY
Certain compounds were also evaluated to
determine their peroral toxicity to mammals by conYen-
tional methods. The representatiYe animal selected for
this experiment was the rat, The test results o~tained are
expressed in terms of the number of milligrams of composition
per kilogram of weight of the animal required to achieve a
mortality rate of 50 percent CLD50~
The results of these experiments are also su~marized
in Table I below.
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It will be understood that the insect species
and other pests employed in the above tests are merely
representative of a wide variety of pests that can be
controlled by use of the novel compounds of this invention.
The compounds contemplated in this invention
may be applied as insecticides, miticides and namatocides
according to methods known to those skilled in the art.
~esticidal compositions containing the compounds as the
active toxicant will usually comprise a carrier and/or
- 10 diluent, either liquid or solid.
Suitable liquid diluents or carriers include
water, petroleum distillates, or other liquid carriers
with or without surface active agents. Liquid concentrates
may be prepared by dissolving one of these compounds with
a nonphytoxic solvent such as acetone, xylene, or nitro-
benzene and dispersing the toxicants in water with the
aid of suitable surface active emulsifying and dispersing
agents.
The choice of dispersing and emulsifying agents
and the amount employed is dictated by the nature of the
- composition and the ability of the agent to facilitate
the dispersion of the toxicant. Generally, it is desir-
able to use as little of the agent as is possible,
consistent with the desired dispersion of the toxicant
in the spray so that rain does not re-emulsify the toxicant
after it is applied to the plant and wash it off the
plant. ~onionic, anionic, or cationic dispersing and
emulsifying agents, for example, the condensation products ~ -
of alkylene oxides with phenol and organic acids, alkyl
. ~
49.
D- 10577_1
3762~
.
aryl sulfonates, complex eth~r alcohols, quaternary ammonium
compounds, and the like may be employed for this purpose.
In the preparation of wettable powder or dust
or granulated compositions, the active ingredient is
dispersed in and on an appropriately divided solid carrier
such as clay, talc, bentonite, diatomaceous earth,
fullers earth, and the like. In the formulation of the
wettable powders the aforementioned dispersing agents as
well as lignosulfonates can be included.
The required amount of the toxicants contemplated
herein may be applied per acre treated in from 1 to 200
gallons or more of liquid carrier and/or diluent or in
from about 5 to 500 pounds of inert solid carrier and/or
diluent. The concentration in the liquid concentrate
will usually vary from about 10 to 95 per cent by
weight and in the solid formulations from about 0.5 to
about 90 percent by weight. Satisfactory sprays, dusts,
or granules for general use contain from about 1/4 to 15
pounds of active toxicant per acre.
The pesticides contemplated herein prevent
attack by insects, mites and nematodes upon plants or other
material to which the pesticides are applied. With respect
to plants, they have a high margin of safety in that when used
in sufficient amount to kill or repel the insects, they do ~ -
not burn or injure the plant, and they resist weathering
which includes wash-off caused by rain, decomposition by
ultra-violet light, oxidation, or hydrolysis in the
presence of moisture or, at least, such decomposition,
oxidation, and hydrolysis as would materially decrease
the desirable pesticidal characteristic of the toxicants
50.
: .
D- 10577-
~ ~7 6Z~D
or impart undesirable characteristics, for instance,
phytotoxicity, to the toxicants~ The toxicants are
compatible with other constituents of the spray schedule,
and they may be used in the soil, upon the seeds, or the
roots of plants without injuring either the seeds or roots
of plants. Mixtures of the active compounds may be
employed if desired as well as combinations of the active
compounds of this invention with other biologically
active compounds.
:
