Note: Descriptions are shown in the official language in which they were submitted.
lC~691Z~ 9965-1
This invention relates to a novel class of carbamate-
sulfenyl-carbamoyl fluoride compounds and to their preparation. -
me novel compounds of this invention are com-
pounds corresponding to the following general formula:
O R R'O
ll l l ll
FC-N-S-N-C-R"
wherein: -
R and R' are the same or different and are
alkyl groups having from one to four carbon atoms;
R" is:
a) hydrogen; or
b) alkyl, cycloalkyl, phenyl, phenylalkyl, : -
naphthyl, alkenyloxy, alkynyloxy, phenoxy, 5,6,7,8-tetra-
hydronaphthoxy, naphthoxy, benzofuranoxy, benzothienoxy or
methylenedioxyphenoxy all of which may be unsubstituted or
~ubstituted with one or more chloro, bromo, fluoro, cyano,
nitro, alkyl, alkynyloxy, phenoxy, phenyl, 2-dithiolanyl,
2-dioxalanyl, alkoxy, haloalkyl, dialkylamino, cyanoalkyl
dicyanoethylidene or alkylthio groups in any combination; or
~. ~
~ : c) a group of the formula:
::~ Rl
: - ON - C or - ON - C A;
R2
~: wherein:
: ::
:~ Rl is hydrogen, alkyl or alkylthio or cyano;
~ i9 alkyl, alkylthio, alkoxy, alkanoyl,
: $
:
:- ,
9965 -
10691Z7
alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl or
tialkylaminocarbonyl, all of which may be unsubstituted
or aliphatically substituted in any combination with one or
more cyano, nitro, alkylthio, alkylsulfinyl, alkylsulfonyl,
alkoxy, aminocarbonyl, alkylaminocarbonyl, or tialkylamino-
carbonyl groups or R2 is phenyl, aminocarbonyl, alkylamino-
carbonyl, tialkylaminocarbonyl oran R3CONH- or R3CON(alkyl)-
group where R3 is hytrogen, alkyl or alkoxy; and
A is a tivalent aliphatic chain, completing a
five or 8iX member ring, which inclutes one or two
tivalent oxygen, sulfur, sulfinyl or sulfonyl groups ant
which may also inclute one tivalent amino, alkylamino or
carbonyl group; in any combination;
provided that the total number of aliphatic carbon -
atoms in Rl, R2 and A, individually, may not exceed eight.
Preferred compounds according to this invention
are those wherein R and R' are both methyl.
Many of th~se compounds are themselves useful
as insecticides, miticides, and nematocides. All of
these compounds are useful as intermediates in the p~epar-
ation of pesticidal compositions by reaction with oxime
compounds to form bis-carbamate compounds ~oined by a
sulfenyl radical. For example, l-methylthioacetaldehyde
O-[N-methyl-N-(N'-methyl-N'-fluoroformylaminosulfenyl)
.
: . .......... . . ~ ,
.
~0691Z7
carbamoyl]oxime may be reacted with 2-methylthio-2-
methylpropionaldoxime in the presence of an acid acceptor
to yield N-[2-methylthio-2-methylpropionaldehyde
0-(N-methylcarbamoyl)oxime]N-[l-methylthioacetaldehyde-O-
(N'-methylcarbamoyl)oxime]sulfide, which exhibits
outstanding insecticidal and miticidal properties. The
preparation and utility of such bis-carbamate compounds,
produced by reacting compounds according to this invention
with oxime compositions and other active hydrogen con-
taining compounds is more fully described in my co-
pending Canadian Application Serial No. 266,786, filed
November 29, 1976 entitled "Unsymmetrical Bis-Carbamate
Compounds."
The novel compounds of this invention can be
prepared in a variety of ways. One method of preparing
certain of the compounds of this invention is by the
process shown in the following general reaction scheme:
0 R R'0 0 R R'0
ll l l ll ll l l ll
I) FC-N-S-N-CF+HR ~ FC-N-S-N-CR"
acid
acceptor
In the above general reaction scheme and those
which are described below, R, R' and R" are as defined
above.
Another reaction which may be employed for the
preparation of compounds according to this invention is
shown by the following general reaction scheme:
~CN69127 9965-1
.
0 R R'0 0 R R'0
,, ................... - - -- .
II) FC-NH + ClS-N-C-R" acid ~ FC-N-S-N-CR"
acceptor
Procedure I is used for preparing compounds in ---
~l which R" is bound to the carbonyl group through a dival- --
¦ ent oxygen group while procedure II is preferred for
producing compounds in which R" is bound to the carbonyl
~ 10 group by a carbon atom and may also be used to prepare
I compounds in which R" is bound to ~he carbonyl group
through oxygen.
, These reactions are conducted in the presence
; ~ of at least one equivalent of an acid acceptor which may
be ither an organic or inorganic base such as triethyl- -~
¦ ~m~ne, tetraethylenediamine, pyridine or sotium or
~¦ pota~sium hydroxide.
These reactions are also normally conducted in
~i the presence of an inert solvent such as an ether,
~ 20 chlorinated hydrocarbon or aromatic solvent or any of
;;~; the many inert organic solvents commonly used for such
i reaction~, Illustrative of the inert solvents which may
~' be used are methylene chloride, chloroform, dioxane,
tetrahydrofuran, benzene, toluene, acetone, dimethoxy-
ethane, dimethylformamite, acetonitrile and the like.
Reaction temperatures are not critical in the
conduct of these reactions and may range from about -S0C
to about 100C. These reactions are preferably conducted
at a temperature ranging from about ~ C to about 40C.
~069127 9965 l
The bis-carbamoyl fluoride compounds employet
as the starting materialsin procedure I can be prepared
conven~ently by reacting hydrogen fluoride and an alkyl-
isocyanate to form N-alkylcarbamoYl fluoride which may
then be reacted with sulfur tichloride in the presence of
an acid acceptor to produce the de~ired bis-carbamoyl
fluoride compound. (See Example III).
The oxime compounds and chlorosulfenyl compounds
employed as starting materials in the procedures described
above are known compounds which can be prepared by con-
ventional means. See for example U.S. Patents 3,752,841,
3,726,908, 3,843,669, 3,843,689 and Belgian Patents
813,206 and 815,513.
The following representative examples are
presented to re clearly illustrate-the preparation of the
novel compounds of this invention:
,ExamPle I
PreParation of N-MethYl-N-(N'-methYl-N'-formYlamino-
sulfenyl~carbamoYl fluoride
To a solution of 9.0 g hydrogen fluoride in
100 ml toluene cooled to -50C was added 25.6g methyl
, isocyanate. After stirring for 45 minutes and allowing
the mixture to warm to -10C, 56.4g of N-methyl-N-formyl-
aminosulfenyl chloride dissolved in 300 ml toluene was
~dded. Triethylamine 45.4g was added dropwise over a
period of 0.5 hr while the temperature was maintained
i ~ 9965-1 -
~069127
between 0 to 8C by external cooling. After stirring
for 0.5 hr at ambient temperature, the reaction mixture
was diluted with 200 ml ice water. The organic layer was
i separated, washed with water, dried and concentrated.
! Di~tillation of the residue yielded 22.4g of product.
¦ b.p. 60-62C/0.2mm.
i Calcd- for c4H7FN2o2s: C, 28.91; H, 4.24; N, 16.86.
Found: C, 29.01; H, 4.43; N, 16.26.
ExamPle 11
PreParation of N-MethYl-N-(N'-methYl-N'-acetYlamino-
sulfenYl)carbamoYl fluoride
To a solution of 13.32g hydrogen fluoride in
~ 100 ml toluene, cooled to -50C, was added 38.05g of
¦ methyl isocyanate. The reaction mixture was allowed to
¦ wanm to approximately 8C and stirred at that temperature
for 1.5 hr. Then93.0g of N-methylacetylaminosulfenyl
chloride tissolvet in 250 ml toluene was added followed
by dropwise addition of 67.4g of triethylamine. The
temperature was maintained at 0-5C during the addition.
After stirring at ambient temperature for 0.5 hr, the
reaction mixture was diluted with 200 ml water. The
toluene extract was further washed with water, dried with
magnesium sulfate and evaporated in vacuo. Distillation
; of the residue yielded 40.0g of product; b.p. 70-74
C/0.5mm.
Calcd for C5HgFN202S: C, 33.32; H, 5.03; N, 15.55.
Found: C, 32.71; H, 5.02; N, 15.13.
7.
I 9965-1
- 1069127
I Example III
¦ Preparation of Bis-(N-MethYl-N-fluorocarbonYla~Lno)
¦ sulfide
I - To a polypropylene reactor containing 80 g
¦ (4.0 ~ of hydrogen fluoride in 1800 ml of toluene, cooled
to -4~ C was added dropwise with stirring 228 g (4.Q~ of
methylisocyanate, over a periot of 20 min. The reaction
mixture was allowed to warm to O~C and was maintained at
i . thi9 temperature for 1 hr. Then 206 g of freshly
¦ 10 distilled sulfur dichloride was added followed by a slow
¦ addition of 346g (4.4 m) of pyridine at -20 to -0C.
¦ Ater stirring for 2 hrs. at -10C and for 16 hrs. at
ambient temperature, 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 the product. B.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-J9.
Example IV
PreParation of l-MethYlthioacetaldehYde 0-[N-methYl-N-
. (N'-methYl-N'-fluoroformYlaminosulfenyl)carbamoYl] oxime
To a solution of 0.714g l-methylthioacetaldoxime
and 1.36g of bis-(N-methyl-N-fluorocarbonyl2mino) sulfide
in 15 ml dioxane was added dropwise 0.687g of triethyl-
amine. After the solution was allowed to stand for 20
hrs, it was diluted with water and extracted with ethyl
lCN69 i 2 ~ 9965-1
acetate. The organic extract was washed with water,
dried with magnesium sulfate and concentrated under
vacuum to yield l.Og of solid which was crystalli~ed
from isopropYl ether-ethyl acetate. m.p. 102-104C.
Calcd.~rc7Hl2FN3o3s2 C, 31.22; H, 4.49; N, 15.60. -
Found: C, 31.67; H, 4.69; N, 15.34.
Example V
.
Preparation of 2-MethYl-2-methylthioproPionaldehYde 0-
tN-methyl-N-(N'-methYl-N'-fluoroformYlaminosulfenYl)
carbamnYlloxime
To a solution of 8.63g bis-(N-methyl-N-fluoro-
-- carbonyl~minO~ sulfide-and 6.66g of 2-methyl-2-methyl-
thiopropionaldoxime in 40 ml dioxane and 40 ml toluene
was added dropwise at 0-5C, 5.06g of~triethylamine over
a period of 1 hr. The reaction mixture was allowed to
st~nd overnight, diluted with water, and extracted in
ethyl acetate. The organic extract was washed with water,
dried and concentrated under reduced pressure. The
residual sil crystallized on standing; weight of product
Z0 2.8 g, m.p. 70-71C.
Calcd ~r C9HlOFN303S2: C, 36.35; H, 5.42; N, 14.13.
Found: C, 36.60; H, 5.57; N, 13.39.
Example Vl
Preparation of 2,3-DihYdro-2.2-dimethYl-7-tN-methYl-N-
(N'-methYl-N'-fluorocarbonylaminosulfenyl) carbamoYloxrl
benzofuran
To a solution of 5.0g bis-(N-methyl-N-fluoro-
' ' ' ' - . ' .~ : . :
9965-1
~ ~ 9 ~ Z 7
carbonylamino) sulfide and 5.0g of`2,2-dimethyl-2,3-
dlhydrobenzofuran-7-~1 in 75 ml dioxane was added 4.0g
of triethylamine. After allowing the reaction mixture
to stand at ambient temperature for 6 days, it was
diluted with 200 ml water and extracted in ethyl acetate.
The ethyl acetate extract was washed with water, dried
and concentrated under Yacuo. Purification by silica gel
chromatography yielded 5.0g of product as a viscous oil.
Calcd-for C14H17FN24S: C, 51.21; H, 5.21; N, 8.53.
Found: C, 51.90; H, 5.34; N, 8.60.
ExamPle VII
PreParation of 2-lO-~N-Methyl-N-(N'-methyl-N'-fluoro-
formYlaminosulfenYl)carbamoYl] oximinol-3.5.5-trimethYl-
thiazolidin-4-one
To a suspension of 8.63g bis-(N-methyl-N-fluoro-
carbonylaminQ) sulfite and 8.71g of 3,5,5~trimethyl-2-
oximinothiazolidin-4-one in S0 ml toluene was added drop-
wise 5.06 g of triethylamine. The temperature of the
reaction solution was maintained between 0 to 5C.
After the addition of triethylamine all of the material
was in solution. After stirring for an additional 2 hrs,
the reaction product was isolated by the usual wor~-up.
Concentration of the ethyl acetate solution yielded 1.5g
of the less soluble bis-carbamate. Crystallization of
the mother liquor from isopropyl ether-hexane yielded
8.0g of product. m.p. 111-115C.
10.
9965-1
iCH69 ~ Z 7
Calcd- ~rClOHlsFN4o4s2 C, 35.49; H, 4.47; N, 16.56.
Found: C, 36.04; H, 4.99; N, 16.18.
ExamPle VIII
Preparation of l-[N-methvl-N-(N'-methYl-N'-fluoroformYl-
aminosulfenYl)carbamoYloxv] naphthalene.
To a solution of 4.32g ofvC-naphthol in 25 ml
of dioxane was added 6.0g of bis-(N-methyl-N-fluoro-
carbonylamin) ~ulfide. To this solution was added
dropwise with stirring 3.03g of triethylamine diluted
with 5.0 ml of dioxane. After stirring for 28 hrs. at
room temperature the solution was concentrated under
reduced pressure and taken in ethyl acetate, washed with
water, dried over magnesium sulfate and concentrated to
7.22g of an oil. The product crystallized from isopropyl
ether, m.p. 58-60C.
Calcd-for C14H13FN23S3: C, 54.53; H, 4.25; N, 9.09.
Found: C, 54.58; H, 4.32; N, 8.96.
ExamPle IX.
~ ration of 2-tO-lN-methYl-N-(N'-methYl-N~-fluoro-
ormYlaminosulfenYl)carbamoYl]oximino]-1.4-dithiane.
To a suspension of 3.68 g of bis-(N-methyl-N-
fluorocarbonylamino) sulfide and 2.98g of 2-ox~mino-
1,4-dithiane in 125 ml of toluene was added with stirring
2.02 g of triethylamine. After the addition of the amine
all the material was in solution. The reaction mixture
was stirred at room temperature for 20 hrs. The
insoluble bis-carbamate (1.0 g) was removed by filtration.
11.
l~9~Z7 9965-1
The filtrate was washed with water, dried over magnesium
sulfate and concentratet to yield 3.6 g of crystalline
product. It was recrystallized from isopropylalcojhol,
m.p. 124-126C.
cd- for C8H12FN303S3: C, 30-66; H, 3.86; N, 13 41.
Found: C, 30.71; H, 3.75; ~, 13 17.
lla.
.. . , - . ~ ... . .
.:: . . - . : -~
: :
9965-1
10691Z7
Example X
PreParation of 4-~;-ButYlPhenYl-N-methYl-N-(N'-methyl-N'-
fluoroformylaminosulfenyl)carbamate
4-tert-Butylphenyl-N-methyl-N-methyl-N-(N'-methyl-
N'-fluoroformylaminosulfenyl)carbamate was prepared by the
proceture of Example IX by reacting 34.99 of bis-(N-methyl-
N-fluorocarbonylami~) sulfide with 30 g of 4-tert-butylphenol
in 600 ml of toluene with 20.24 g of triethylamine as
acid acceptor. Weight of the product 29.54 g, m.p.
69-72C.
Analysis:
IR(KBr): S.6 (COF), 5.84 (CO)
NMR(CDC13): Sl.31 (s), 9H, C(CH3)3;
~3.44 (d), J s 1.0 Hz, 3H, CH3N;
5 3.49 (s), 3H, CH3N;
~;7.1 (d), JAB 8.5 Hz
)' JBA 8-5 Hz~4H (aromatic)
Example XI
Preparation of 3-IsoProPYlPhenyl-N-methyl-N-(N'-methyl-N~
20 fluoroformYlaminosulfenYl~carbamate
3-Isopropylphenyl-N-methyl-N-(N'-methyl-N'-
fluoroformylaminosulfenyl)carbamate was prepared by
the prooedure of Example IX by reacting 51.56 g of
bis-(N-methyl-N-fluorocarbonylamino)sulfide with 40 g
of 3-isoprcpylphenol in 600 ml of toluene with 29.34 g
of triethylamine as acid acceptor to yield 77 g of an oil.
9965-1
~0691Z7
Analysis:
IR (neat): 5.6 (COF), 5.8 (CO) ",~ .
NMR(CDC13): ~1.18 (d), J = 7.0 Hz, 6H, CH(CH3)2
S2.5-3.0 (m), J= 7.0 Hz, lH, CH
S3.27 (d), J = 1.0 Hz, 3H, NCH3
~3.32 (s), 3H, NCH3
S6.7-7.3 (m), 4H, aromatic
ExamPle XII
PreParation of 3.4~5-trimethylPhenyl-N-methyl-N-(Nl-meth
10 N'-fluoroformYlaminosulfenyl)carbamate
3,4,5-Trimethylphenyl-N-methyl-N-(N'-methyl-N'-
fluoroformylaminosulfenyl)carbamate was prepared by the
procedure of Example IX by reacting 38.67 g of bis-(N-
methyl-N-fluorocarbonylamino)sulfide with 30 g of 3,4,5-
trimethylphenol in 600 ml of toluene with 22.26 g of
triethylamine as acid acceptor to yield 58.7 g of an oil.
AnalYs-is:
IR (neat): 5.6 (COF), 5.81 (CO) ,~.
NMR(CDC13): ~ 2.0 (s), 3H, CH3;
~ 2.13 (s), 6H, CH3;
3.27 (s), 3H, NCH3;
~3.31 (s), 3H, NCH3;
~6.63 (s), 2H, aromatic
9965-1
1069127
Example XIII
Preparation of 4-NonYlPhenYl-N-methYl-N-(Nl-methyl-N
fluoroformylaminosulfenyl)carbamate
4-Nonylphenyl-N-methyl-N-(N'-methyl-N'-
fluoroformylaminosulfenyl)carbamate was prepared by the
procedure of Example IX by reacting 11.01 g of p-nonylphenol
with 9.21 g of bis-(N-methyl-N-flu~rocarbonylamino)
sulfide in 250 ml of toluene with 5.06 g of triethylamine
as acid acceptor to yield 16 g of an oil
Analysis:
IR (neat): 5.58 (COF), 5.77 (CO) ~.
NMR (CDC13): S 1.5-2.0 (m), l9H, (CgHlg)
~3.52 (s), 6H, -NCH3
~7.0-7.5 (m), 4H, aromatic
ExamPle XIV
Preparation of 3-DimethylaminoPhenYl-N-methYl-N-(N'-
methyl-N'-fluoroformYlaminosulfenyl)carbamate
3-Dimethylaminophenyl-N-methyl-N-(N'-methyl-N'-
fluoroformylaminosulfenyl)carbamate was prepared by
the procedure of Example IX by reacting 6.72 g of
bis-(N-methyl-N-fluorocarbonylamino)sulfide with 5 g
of 3-dimethylaminophenol in 100 ml of toluene with 3.69g
of triethylamine as acid acceptor to yield 10.43 g of
an oil.
14.
9965-1
1069~Z7
Analysis:
IR (neat): 5.6 (COF)~ 5.8 (GO) ~_
NMR (CDC13): ~ 2.86 (s), 6H, N(CH3)2;
3.40 (s), 3H, NCH3;
~3.43 (s), 3H, NCH3;
~6.3-7.3 (m), 4H, aromatic
ExamPle XV
PreParation of N-Methyl-N-(N'-methyl-N'-fluoroformyl-
aminosulfenyl~_ropynylcarbamate
N-Methyl-N-(N'-methyl-N'-fluoroformylamino-
sunfenyl)propynylcarbamate was prepared by the procedure
of Example IX by reacting 33.15 g of bis-(N-methyl-N-
fluorocarbonylamino)sulfide with 10 g of propargyl
alcohol in 100 ml of toluene with 18.2 g of triethylamine
as acid acceptor to yield 30 g of an oil.
Analysis:
IR (neat): 4.7 (C-C); 5.58 (COF), 5.8 (CO) ,4~_
NMR (CDC13): 2.63 (t), J 8 2.5 Hz, lH, C-C-H
3.41 (d), J 1'_1.0 Hz, 3H, N-CH3
3.43 (s), 3H, NCH3
4.82 (d), J = 2.5 Hz, 2H, CH2
:
15.
~: . :: . , ;:, : ~ . . - ,
9965-1
~069127
Example XVI
Preparation of 2-Isopro~poxYphenyl-N-methyl-N-(N'-methyl-
N'-fluoroformylaminosulfenyl)carbamate
2-Isopropoxyphenyl-N-methyl-N-(N'-methyl-N'
fluoroformylaminosulfenyl)carbamate was prepared by
the procedure of Example IX by reacting 46.04 g of
bis-(N-methyl-N-fluorocarbonylamino)sulfide with 40 g
of 2-isopropoxyphenol in 750 ml of toluene with 25.29 g
of triethylamine as acid acceptor to yield 73.64 g of
an oil.
Analysis:
Calc d for C13H17FN2O4S: C, 49.35; H, 5.42; N, 8.86
Found: C, 51.07; H, 5.57; N, 8.38
IR (neat): 5.6 (COF), 5.78 (CO) ~ _ .
Example XVII
Preparation of 5~6~7~8-TetrahYdronaPhthYl-N-methyl-N-(N'-
methYl-N'-fl,uoroformylaminosulfenyl)carbamate
5,6,7,8-Tetrahydronaphthyl-N-methyl-N-(N'-
methyl-N'-fluoroformylaminosulfenyl)carbamaté was prepared
by the procedure of Example IX by reacting 9.21 g of
bis-(N-methyl-N-fluorocarbonylamino)sulfide with 7.41 g
of 5,6,7,8-tetrahydro-1-naphthol in 300 ml of toluene
with 5.05 g of triethylamine as acid acceptor to yield
9.S g of an oil.
16.
.
9965-1
~06gl2~
Analysis:
IR (neat): 5.6 (COF), 5.8 (CO)~-
NMR (CDC13): ~1~6-lo9~ (m), 4H;
2.4-2.9, (m), 4H;
3.44, (s) 3H, NCH3;
~3.50, (s) 3H, NCH3;
~ 6 ~ 8-7.2, (m), 3H, aromatic
ExamPle XVIII
PreParation of 2-PropynYloxYphenyl-N-methyl-N-(N'-methyl-
10 N'-fluoroformYlaminosulfenYl)carbamate
2-Propynyloxyphenyl-N-methyl-N-(N'-methyl-N'-
fLuoroformylaminosulfenyl)carbamate was prepared by
the proceture of E~u~mple IX by reacting 10.12 g of
bis-(N-methyl-N-fluorocarbony]ami~) qulfide with 8.1 g
of 2-propargyloxyphenol in 200 ml of toluene with 5.3 g -
of triethylamine as acid acceptor. Weight of the product
was 6.9 g, m.p. 80-82C.
AnalYsi~:
Calc d for C13H13FN2O4S: C, 49.99; H, 4.19; N, 8.97
Found: C, 50.08; H, 4.21; N, 8.82
E m~le XIX
Preparation of 3-Phenoxyphenyl-N-methyl-N-(N'-methyl-N'-
fluoroformYlaminosulfenyl)carbamate
3-Phenoxyphenyl-N-methyl-N-(N'-methyl-N'-
fluoroformylaminosulfenyl)carbamate was prepared by the -
procedure of Example IX by reacting 2.58 g of bis-(N- -
methyl-N-fluorocarbony~minO) sulfide with 2.68 g of
:~:
17.
... ~.
~: . :. .. , ,. .: . . .. ~ ' . , .'', . .. -
... . , -. .. . ~ . .
`:
l~91Z7 9965-1
: ', I,
¦ 3-phenoxyphenol in 75 ml of toluene with 1.42 g of
l triethylamine as acid acceptor to yield 3.4 g of an
., 1,
: oil.
: AnalYsis: ~
: ~ ` rR (neat): 5.63 (COF), 5.82 (CO) ~,
,: .
.~. ~ NMR (CDC13): S3.4 (d), J ~ L.o Hz, 3H, NCH3;
3.44 (s), 3H, NCH3;
` . ~6.8-7.5 (m), 9H, aromatic
, ..... . . . , ,: . .. . .
: , . . , - -: : -
.` .. ~ ,. ' : : . . ':
. , .
.. ~ ,. ~ .. .
. . . .
- . .
:: . . . . ~ , .: . ...
.
. . :. : ' ' : :: . ~ : : . :
. , - , :- -~ - ~
9965-1
1069127
Illustrative of other new compounds which can be
prepared by the processes described above are the follow-
ing:
N-Methyl-N-(N'-propyl-N'-formylaminosulfenyl)carbamoyl
fluorite.
N-Methyl-N-(N'-butyl-N t -acetylaminosulfenyl)carbamoyl
fluoride.
2,3-Dihydro-2-methyl-7-lN-methyl-N-(N'-methyl-N'-fluoro-
formylaminosulfenyl)carbamoyloxy]benzofuran.
l-lN-Methyl-W-(N'-methyl-N'-fluoroformylaminosulfenyl)
carbamoyloxyl5,6,7,8-tetrahydronaphthalene.
2-Methyl-2-methylJulfonyl propionaldehyde 0-~N-methyl-N-
(N'-fluoroformylaminosulfenyl)carbamoyl]oxime.
l-lsopropylthioacetaldehyde 0-~N-methyl-N-(N'-methyl-N'-
fluoroformylaminosulfenyl)carbamoyl]oxime.
2-Methyl-2-methoxypropionaldehyde 0-~N-methyl-N-(N'-methyl-
N'-fluoroformylaminosulfenyl)carbamoyl]oxime.
1-(2-Cyanoethylthlo)acetaldehyde 0-lN-methyl-N-(N'-methyl-
N'-fluoroformyl~m~nosulfenyl)carbamoyl]oxime. ~;
2-Methyl-2-cyanopropionaldehyde O-[N-methyl-N-(N'-methyl- -
N'-fluoroformylaminosulfenyl)carbamoyl~oxime. -
-` 9965 -
~069lZ7
l-Methylthio-l-dimethylcarbamoylformaldehyde 0-[~-methyl-
N-(N'-methyl-N'-fluoroformylaminosulfenyl)carbamoyl)oxime.
2-[[O-tN-methyl-N-(N'-methyl-N'-fluoroformylamino~ulfenyl)
carbamoyl]oximinol]-4-methyl~etrahydro-1,4-thiazin-3-one.
l-Methylthio-3,3-dimethylbutanone-2 O-[N-methyl-N-(N'-
methyl-N'-fluoroformylaminosulfenyl)carbamoyl~ oxime.
2-[[0-tN-methyl-N-(N'-methyl-N'-fluoroformy?aminosulfenyl)
carbamoyl]oximino]]-1,3-dithiolane.
4-~[0-~N-methyl-N-(N'-methyl-N'-fluoroformyl~inosulfenyl)
carbamoyl]oximinol]-5,5-dimethyl-1,3-dithiolane.
4-t[0-[N-methyl-N-(N'-methyl-N~-fluoroformylaminosulfenyl)
carbamoyl~oximino]]-5-methyl-1,3-oxathiolane.
2-[[0-[N-methyl-N-(N'-methyl-N'-fluoroformylaminosulfenyl)
carbamoylloximino]]-3,3-dimethyl-1,4-dithiane.
2-[[0-[N-methyl-N-(N'-methyl-N'-fluoroformylaminosulenyl)
carbamoyl]oximino]]-3-isopropylthiazolidin-4-one.
2-[[0-[N-methyl-N-(N'-methyl-N'-fluoroformylaminoqulfenyl)
carbamoylIoximino I ] -4,5,5-trimethylthiazolidin-3-one.
4-Dimethylamino-3,5-xylyl-N~methyl-N-(N'-methyl-N'-fluoro~
for~ylaminosulfenyl)carbamate.
4-Methoxycarbonylamino-3,5-xylyl-N-methyl-N-(N'-methyl-N'-
fluoroformylaminosulfenyl)-carbamate.
2-Isopropoxy-phenyl_N-methyl-N-(N'-methyL-N'-fluoroformyl-
aminosulfenyl)carbamate.
3-sec-Butyl-phenyl-N-methyl-N-(~'-methyl-N'-fluoroformyl-
aminosulfenyl)carbamate.
20.
9965
10691Z7
3,4-~ylyl-N-methyl-N-(N'-methyl-N'-fluoroformylaminosulfenyl)
carbamate.
3,4-Methylenedioxyphenyl-N-methyl-N-(N'-methyl-N'-fluoroformyl-
aminosulfenyl)carbamate. ~
4-Methylthio-3,5-xylyl-N-methyl-N-(N'-methyl-N'-fluoroformyl-
aminosulfenyl)carbamate.
2-Dioxalanylphenyl-N-methyl-N-(N'-methyl-N'-fluoroformyl-
aminosulfenyl)carbamate.
l-Methylthioacetaldehyde 0-[N-butyl-N-(N'-methyl-N'-fluoro-
formylaminosulfenyl)carbamoyl]oxime.
2-Methyl-2-methylthiopropionaldehyde 0-[N-methyl-N-(N'- -
isopropyl-N'-fluoroformylaminosulfenyl~carbamoyl]oxime.
2-Methyl-2-methoxypropionaldehyde 0-[N-methyl-N-(N'-butyl-
N'-fluoroformylaminosulfenyl)carbamoyl]oxime.
2;,4-Dinitro-6-sec-butyl-phenyl-N-methyl-N-(N'-methyl-N'-
fluoroformylaminosulfenyl)carbamate
2,6-ti-tert-butyL-4-(2,2-dicyanoethylidene) phenyl-N-methyl-
N-(N'-methyl-N'-fluoroformylaminosulfenyl)carbamate.
3-Isopropyl phenyl-N-methyl-N-(N'-methyl-N'-fluoroformyl-
aminosulfenyl)carbamate.
4-Isopropyl phenyl-N-methyl-N-(N'-methyL-N'-fluoroformyl-
- aminosulfenyl)carbamate.
3,5-di-tert-butyl-4-[~-methyl-N-(N'-methyl-N'-methyl-N'-
fluoroformylaminosulfenyl)carbamoyloxylbenzylidene
malononitrile.
l-Cyano-2,2-dimethylpropionaldehyde 0-[N-methyl-N-(N'-methyl-
N'-fluoroformylaminosulfenyl)carbamoyl]oxime.
,
21.
-` ~0691Z7 9965 l
l-Methylsulfonyl-3,3-dimethylbutanone-2 O-[N-methyl-N-
(~'-methyl-N'-fluorofonmylaminosulfenyl)carbamoyl]oxime.
3-~ethylsulfonylbutanone-2 0-[N-methyl-N-(N'-met~ l-N'-
fluoroformylaminosulfenyl)carbamoyl]oxime.
N-Methyl-N-(N'-methyl-N'-dodecanoylamino-sulfenyl~
carbamoyl fluoride.
All of the compounds of this invention can be
produced simply and in excellent yield by the processes
described above by simply selecting the appropriate
reactants to produce the compound desired.
Selected species of the new compounds were
evaluated to determine their pesticidal activity against
mites, nematodes and certain insects, including an aphLd,
; 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 polyethoxy- -
ethanol surfactant, as an emulsifying or dispersing-
agent. The resulting solution was mixed into 150 milli-
liter3 of water to give roughly 200 milliliters of a
suspension containing the compound in finely divided form.
The thus-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:
22.
~069lZ7 9965 - 1
Bean APhid Folia~e SPraY Test
Adults and nymphal stages of the bean aphid
(A~his fabae Scop.) reared on pottet dwarf nastur~ium
plants at 65-70F. and 50-70 per cent relative humidity,
constituted the 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 suQpension con-
taining 500 parts of test compound per million parts offinal formulation.
The potted plants (one pot per compound tested) ;
infested with 100-150 aphids, were placed on a revolving
turntable ant 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 laQted
25 ~econds, was sufficient to wet the plants to run-off.
A~ a control, 100-110 milliliters of a water-acetone-
emulsifier solution containing no test compound were also
~prayed on infested plants. After spraying, the pots
were placed on their sides on a sheet of white standard
mlmeograph 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 per cent, respectively. Aphids which fell onto
the paper and were unable to remain standing after being
uprighted were considered dead. Aphids remaining on the
23.
.- . ~- ~ .. - :
. . . - : : :
~069lZ7 9965
plants were observed closely for movement and those
which were;-unable to move the length of the body upon
stimulation by prodding were considered dead. Pe~ cent
mortality was recorded for various concentration levels.
Southern Armvworm Leaf SpraY Test
Larvae of the southern armywonm (Prodenia
eridania~ (Cram.)), reared on Tendergreen bean plants
at a temperature of 80+5F. and a relative humidity of
50+5 per cent, constituted the test insects.
me test compounds were fonmulated 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 standart height and age were placed on a revolving
turntable and sprayed with 100-110 milliliters of test
compound formulation by use of a DeVilbiqs spray gun set
t 10 psig air pres~ure. This application, which lasted
25 ~econds, was sufficient to wet plants to run-off.
A~ a control, 100-110 milliliters of a water-acetone-
emulsifier solution containing no test compound werealso sprayed on infested plants. When dry, the paired
; leaves were 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
24.
9965
10691Z7
twenty-four hours, no more foot was added. Larvae
which were unable to move the length of the body, even
upon stimulation by prodding, were considered dea~. Per ;~
cent 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 Tentergreen bean
plants at a temperature of 80+5F. and 50+5 per cent
relative humidity, were the test insects.
The test compounds were formulated by diluting
the stock suspension with water to give a suspension con-
taining 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 DeVilbiss 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 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
25.
~069127 9965-1
three days. Although the larvae could easily consume
the leaf within 24 to 48 hours, no re food was added.
Larvae which were unable to move the length of th;e body,
even upon stimulation, were considered dead.
F1Y Bait Test
Four to six day old adult house flies (Musca
domestica. L.), reared according to the specifications
of the Ch~m~cal Specialties Manufacturing Association
(Blue Book, McNair-Dorland Co., N. Y. 1964; pages 243-
244, 261) under controlled conditions of 80~5F. and
50_5 per cent relati~e humidity, were the test insects.
The flies were i obilized by anesthetizing with carbon
dioxide and twenty five immobilized individuals, males
. .
and females, were transferred to a c-ge consisting of a
standard food strainer about five inches in diameter
which was inverted over a wrapping-paper-covered surface.
The test compounds were formulatet by diluting the stock
su~pension with a 10 per cent (by weight) sugar solution
to give a suspension containing 500 parts of test com-
pound per million parts of final formulation, by weight.Ten milliliters of the test formulation 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
26.
1069127 9965-l
temperature of 80+5F. and the relative hum~dity of
50+5 per cent. Flies which showed no sign of movement
on prodding were considered dead. .~,
Mite Folia~e SpraY Test
Adults and nymphal stages of the two-spotted
mite (Tetranychus urtlcae Koch), reared on Tendergreen -
bean plants at 80+5 per cent relative humidity, 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
re ved from the infested plants. The test compounds
were formulated by diluting the ~tock 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 turntable and sprayet with 100-110 milliliters
of test compound formulation by use of a DeVilbiss spray
gun ~et 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
27.
~CN69~27 9965-1
containing no test compound, were also sprayet on
infested plants. The sprayed plants were held at 80+5
per cent relative humidity for six days, after which a
mortality count of motile forms was mate. 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~vne
nco~nita var acrita, reared in the greenhouse on root~
of cucumber plants. Infected plants were removed from
the culture, and the roots are chopped very finely. A
small amount of this inoculum was added to a point ~ar
containing approximately 180 cc. of soil. The ~ars were
capped and incubatet 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 ~ars for each dosage tested. Following
the addition of chemical, the ~ars 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 emulsifier,
and dilution with water. Primary screening tests were
conducted at 3.33 m.g. of the test compound per jar.
~0~91Z7 9965-l
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 we~e seedet
to cucumber as an indicator crop and placed in the green- -
house where they were cared for in the nonmal fashion for
approxi~ately 3 weeks.
The cucumber plants were then taken from the
pots, *e 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 was rated as follows:
A - excellent control
B - partial control
C - no control
Dashes indicate no test conducted.
29.
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Th~ pe~ticidaLl~ aceive compou~d~ contemplated
in t6i~ in~ention may be ap~l~`ed a~ ~n-cect~cid~s, mieicides
aQd nematocid accor~ng to methods ~nown to ehose skilled
i~ the art Pesticidal compositions containing the compounds
as the activ~ toricanf wiLL usually comprise a carrier
i~ nd/or diluent, ~tber liquid or solid
Suitable liquid diLuents or carriers include water,
petroLeum distiLlates, or other liquid carriers with or
wiehout surface active agents Liquid concentrates may be
prlqpared by dis-olvlsg one of these compounds with a non-
pb~totorLc soLvent such as acetone, xyLene, or nitrobenzene
disp~rsing the toxicant~ in water with the aid of suit-
a61e -urface~active emulsifying and dispersing agents
Th~ch~ic~ of tispersing~and emul~lfying agents
and th~ amount employed~ls dictated by the nature of the
co po-ition and~the~ability~of the~agent to facilitate the
disper~ion~of~th~ oxicant GeneraLly, it l~ tesirable to
use as~ittle of the agent a8 i8 possible, consistent with
the d ired dispersio~ of the toxicant in the ~pray so that
20~ r ~n do not~re-emul-ify the toxicant after it is applied
to~th~pLant and wa~h~lt off the plant Non-ionic, anionic,
or~c tlonlc~disper~ing nd emulsifying agents may be employed,
for~e~ampLe, the condbn~ation products of alkylene oxides
h~phenol and~organic acids, alkyl aryl sulfonateQ, complex
et~r alcohoL~, quate~nary ammonium compounds, and the Like
In th~ preparation of wettable powder or dust or
grinuL ted compo-ltions, the active ingredient is dispersed
i~ and a~ an appropriateLy d~v~ded soLid carrier such as
clay, t lc, benton~te, diatQmaceous earth, fuLLers earth,
and the Li~e ~n the formuLation of the wettabLe powders
the aforeme~tioned dispersing agents as well as lignosuL-
32.
. . :
9965-
~0691Z7
fonates 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 Qolid carrier and/or diluent. The
concentration in t~e liquid concentrate will usually vary
from about 10 to 95 weight per cent by weight and in the solid
formulations from about 0.5 to about 90 per cent by weight.
Satisfactory sprays, dusts, or granules for general use contain
from about 1~4 to 15 pounds of active toxicant per acre.
The pesticide~ contemplated herein prevent attack
by insects, mites and nematodes upon plants or other material
to which the pesticides are applied, and they have relatively
high res~dual toxicity. 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
j caused by rain, decomposition by ultra-violet light, oxidation,
or hydrolysis in the presence of moisture or, at leaqt, such
decomposition, oxidation, and hydrolysis as would materially
decrea~e the desirable pesticidal characteristic of the
toxicants or impart undesirable characteristics, for instance,
phytotoxicity, to the toxicant~. The toxicants are so chem-
icaLLy inert that they are now compatible with substantially
any other constituents or the spray schedule, and they may be
used in the soiL, upon the seeds, or the roots of plants with-
out iniuring either the seeds or roots of plants.
As indicated above the compounds of this invention
are aLso usefuL as intermediates in the preparation of more
compLex pesticidally active compoundc.
33.
