CA1069127A - Carbamate-sulfenyl-carbamoyl fluoride compounds - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Carbamate-sulfenyl-carbamoyl fluoride compounds are valuable insecticidal compositions and are also use-ful intermediates in the production of bis-carbamate compounds.

Description

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;

~: wherein:
: ::
:~ Rl is hydrogen, alkyl or alkylthio or cyano;

~ i9 alkyl, alkylthio, alkoxy, alkanoyl, : $
:

:- , 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 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-' ' ' ' - . ' .~ : . :

~ ~ 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.

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.

.. . , - . ~ ... . .
.:: . . - . : -~

: :

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.

~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 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.

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.

~: . :: . , ;:, : ~ . . - , ~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.

.

~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 , ..... . . . , ,: . .. . .
: , . . , - -: : -.` .. ~ ,. ' : : . . ':
. , .
.. ~ ,. ~ .. .

. . . .
- . .
:: . . . . ~ , .: . ...
.
. . :. : ' ' : :: . ~ : : . :
. , - , :- -~ - ~

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.

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.

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.

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lO~91Z7 9965-l 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.

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~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.

Claims (8)

WHAT IS CLAIMED IS:

1. A compound of the formula:

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, naphthoxy, 5,6,7,8-tetrahydronaphthoxy, benzofuranoxy, benzothienoxy or methylenedioxyphenoxy, all of which may be unsubstituted with one or more alkyl, alkoxy; dialkylamino, alkynyloxy, or phenoxy substituents.
c) a group of the formula:

or wherein:
R1 is hydrogen, alkyl, alkylthio or cyano;
R2 is alkyl, alkylthio, said alkyl may be un-substituted or substituted with alkylthio.
A is a divalent aliphatic chain, completing a five or six member ring, which includes one or two divalent sulfur which may include one divalent amino, or carbonyl group; in any combination; provided that the total number of aliphatic carbon atoms in R1, R2 and A, individu-ally, may not exceed eight.

2. A compound according to claim 1 wherein R
and R' are methyl.

3. A compound according to claim 1 wherein R" is:

4. A compound according to claim 1 wherein R" is:

5. 1-Methylthioacetaldehyde O-[N-methyl-N-(N'-methyl-N'-fluoroformylaminosulfenyl)carbamoyl]oxime.

6. 2-Methyl-2-methylthiopropionaldehyde O-[N-methyl-N-(N'-methyl-N'-fluoroformylaminosulfenyl) carbamoyl]oxime.

7. 2-[O-[N-Methyl-N-(N'-methyl-N'-fluoro-formylaminosulfenyl)carbamoyl] oximino]-3,5,5-trimethyl-thiazolidin-4-one.

8. A method of preparing a compound of the formula:

which comprises reacting a compound of the formula:

with a compound of the formula HR"in the presence of an acid acceptor, 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, naphthoxy, 5,6,7,8-tetrahydronaphthoxy, benzofuranoxy, benzothienoxy or methylenedioxyphenoxy, all of which may be unsubstituted or substituted with one or more alkyl, alkoxy, dialkylamino, alkynyloxy, or phenoxy substituents; or c) a group of the formula:

or wherein:
R1 is hydrogen, alkyl, alkylthio or cyano;
R2 is alkyl, alkylthio, said alkyl may be unsubstituted or substituted with alkylthio; and A is a divalent aliphatic chain, completing a five or six member ring, which includes one or two divalent sulfur, which may include one divalent amino, or carbonyl group; in any combination;
provided that the total number of aliphatic carbon atoms in R1, R2 and A, individually, may not exceed eight.