CA1100981A - N-aminothio derivatives of n-methyl carbamates - Google Patents

N-aminothio derivatives of n-methyl carbamates

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Publication number
CA1100981A
CA1100981A CA267,127A CA267127A CA1100981A CA 1100981 A CA1100981 A CA 1100981A CA 267127 A CA267127 A CA 267127A CA 1100981 A CA1100981 A CA 1100981A
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Prior art keywords
group
carbon atoms
inclusive
alkyl
compound
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French (fr)
Inventor
Victor L. Rizzo
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Pharmacia and Upjohn Co
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Upjohn Co
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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D295/00Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/26Sulfur atoms
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D339/00Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/02Five-membered rings
    • C07D339/06Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates

Abstract

ABSTRACT OF THE DISCLOSURE

N-aminothio derivatives of certain H-methyl carbamate insecticides fire disclosed as insecticides.

Description

~ 8 1 3220 SUMMARY OF THE INVENTION
This invention pertains to new organic chemicals, to a process for prepar;ng them, and to formulations for insecticidal, miticidal, and nematocldal use. The inven-~ion is more p~rticularly directed to novel am;nothioderivatives of N-H carbamate insecticides, to a process for preparing them. and to formulations containing them and for use in controlling and preventing damaging infesta-tions by insect pests.
Other research objectiv~s include discovery of ef-fective chemical pesticides, more economic ones, those less toxic to desirable animals, and more persistent insecticides.
Hence, it is an ob~ective of this in~ention to pro-vide new organic chemicals that will be effective insectpest control agents. A further ob~ective is to provide a new means of prevent;ng damage by insect pests. A still further objective is to provide new organic chemicals that are more toxic to insects but less toxlc to desirable warm-blooded animals. An even more specific object is to pro-vide new organic chemicals oF the aminothio carbamate characteristic that are more persistent under certain en-vironmental conditions, advantageous ln formulation, and improved ;n spectrum. Still other objectives of the inven-tion are apparent to persons skilled in the chemical pestcontrol art.
It has now been found, in accordance with this inven-tion, that certain novel aminothio derivati~es of N-H
carbamate insecticides are new insectic;des, miticides, and nematocides. The new organic chemicals are effective
-2-- < ,. .., ~. . . : . .
~ . . .
- :. .. . ..

~ 9~ 3220 ' at low concentrations aga;nst various insect pests inclu-ding, For example, house flies, mosquitoes, mosquito lar-vae, thrips, bean beetles~ aphids, armyworms, alfalfa leaf weevils, bollworms, saltmarsh caterpillars, crickets, roaches, 1ice, ticks, fleas, root knot nematodes, spider mites, citr~s red mites, and Colorado potato beet'ies.
'The term "insec~ pest" ;s employed in its broad sense ln this descr;pt;on of the invent;on. The word "insect" is used in the same sense as in the Federal lQ Insecticide5 Fungicide, and Rodentic;de Act of 1~47. I'n general, "insect" refers to animals comprising the phylum Arthropoda, illustratively: class Insecta, for example, orders Isoptera, Thysanoptera, Mallophaga, Hemiptera, Anoplura, Homoptera, Coleoptera, Lepidoptera, Orthoptera, Diptera, and Hymenoptera; and class Arachnida, for example, orders Araneae and Acarina.
~ETAILED DESCRIPTION OF T~E INVENTiON
.
The novel insecticidal, miticidal, and nematocidal compounds of this invention are charac~eristically aminothio derivatives of N-H carbamate insecticides. The parent compounds, N-methylcarbamates, include a broad class of organic chemicals that have been synthesized and developed by numerous skilled artisans.
In accordance with the invention, there are pro-vided compounds of the formula o CH3 \S N/R2 ....
wherein Rl is selected from the group consisting of :; ,. - , , . -. :
.,. , . ~ - :

a.
Rs~, R6--~ I '1 ~
wherein R~, Rs, and R6 are the same or different and are selected from the group cons;sting o~ hydrogen, alkyl of one to five carbon atoms, inclusive, halogen, a1koxy of one to f;ve carbon atoms, inclusive, alkylthio of one to five carbon atoms, ;nclusive, dialkylamino w;th each alkyl the same or different and having one to three carbon atoms, ;nclusive, and -N~SHNd;-methyl, and b.
X\
C=N

wherein X and Y are the same or different and are selected from the group consisting of alkyl of one to five carbon atomsl inclus;ve, alkylth;o of one to five carbon atoms, inclusive, monocyano substituted alkylthio of one to f;ve ~.
carbon atoms, inclusive, phenylthio wherein phenyl is un-subs~ituted or substituted with one to three subst;tuents, Z5 same or d;fferent, selected from the group consisting of halogen and alkyl of one to four carbon atoms, inclusive, cyano, alkoxy having one to five carbon atoms, inclusive, phenyl and dialkylaminocarbonyl with alkyl be;ng the same or difFerent and having from one to three carbon atoms, ;nclusive, and when X ;s hydrogenj Y is of the formula .. ..

8~ : ~

R~- C - S _ R7 :-Rg 5: wherein R7 is selected from the group consi~sting of alky~l of one to thrPe carbon atoms, incius;vé, and pheny1; R8 is alkyl of one to three carbon atoms, inclusive; Rgis selected from the group consisting of alkyl of one to :~
: - ~
three carbon atoms, lnclusive, and SRIo wherein Rlo is alkyl and is the same alkyl;group as R7, and taking R7 and Rlo together with the atoms to which tney are at-tached form a dithio heterocyclic of the~formula ~( C H 2 )~ , ~ C S) wherein n is 2 or 3 and the alkylene / R~
portion of the r~ing is unsubstituted or subs~ituted with : one or:two methyl graupsi X and ~ taken together ~ ~
with the carbon atom to which they are attached form a ~ .
dithio heterocyclic of the formula :"
~(GH~3m~

~c-J ` .
wherein m is 2 or 3 and the alkylene portion of the ring is unsubstituted or substituted with one to two methyl ~5 groups;
R2 and R3 are the same or different and are selec-ted from the group consisting of alkyl of one to six carbon atoms, inclusive; cycloalkyl of three to six carbon atoms, ;nclusive;

wherein Q and R"are the same or dif`fer-Rll erent and are selected from the group consisting of hydro-gen, methyl, and chloro; and ~ CH2 ~ wherein .
D is 1 or 2j and taking R2 and R3 to~ether w~th the~nitro-gen atom to which they are attached, form an alkylene ring ~--R,2 `
of four or five~ring carbon atoms, - N à , :

R R,~ ;
~< 12 - N S , R~2 is selected from the group consistin~ of R,2 : of hydrogen and alkyl of one to three carbon atoms, inclu-sive, and 4-methylpiperazino.
This group of compounds i~s referred to as Group A.
Another group of compounds, hereafter referred to as Group B, arè those compounds of Group A wherein Rl is Rs selected from the group consisting of wherein R~ and Rs are hydrogen and R6 is defined as in Group A. R2 and R3 are defined as in Group Ai A further group of compounds, hereafter referred to as Group C, are those of Group A, wherein Rl is X
~=N -. y /

8~

wherein X and Y are the same or different nd are selectedfrom the group consisting of alkyl of one to five carbon atoms, inclus;ve, alkylthio of one to five carbon atoms, inclusive, monocyano substituted alkylthio of one to ~ive carbon atoms, inclusive, phenylthio wherein phenyl is un-substituted or substituted with one to three substituents, same or different, selected ~rom the group consisting of halogen and alk~l of one to four carbon atoms, inclusive, cyano, alkoxy having one to five carbon atoms~ inclusive, phenyl and dialkylaminocarbonyl w;th alkyl being the same or different and having from one to three carbon atoms, in-clusive; when X is hydrogen, Y is of the formula I

R 8 C ~ S - R7 Rg wherein R7 is selected from the group consisting of alkyl of one to three carbon atoms, inclusive, and phenyl, R8 is alkyl of one to three carbon atoms, inclusive; Rg is selected from the group consisting of alkyl of one to three carbon atoms, inclusive, and SRIo wherein Rlo is a1kyl and is the same alkyl group as R7, and tak~ng R7 and Rlo together with the atoms to which they are attached form a dithio-heterocyclic of the formula f (CH2)~ wherein \~C-- S
R~
n is 2 or 3 and the alkylene portion of the r;ng ;s unsub- -:
st;tuted or substituted with one or two methyl groupsj X and Y taken together with the carbon atom to which they are attached form a dithio heterocyclic of the formula , ~.

8~

~(CH2)m~
S S .:
~C~ ~;

wherein m ;s 2 and the alkylene portion of the ring is .
unsubstituted or substituted with one to two methyl groups;
R2 and R3 are deflned as in Group A.
Another group of compounds, hereafter referred to .;
as Group D, are those compounds o~f Group C wherein Rl is :~
~ X .:
C~N -y/
wherein X and Y taken together with the carbon atom to which they are attached, form a dithioheterocyclic of the formula :
S ~

=:C ~ ~CH 2 )m whcre;n m is 2 and the alkylene portion of the riny is unsubstituted or substituted with one or two methyl groups.
R2 and R3 are defined as in Group A. . .
A further group ~of compounds, hereafter referred to as Group E are those compounds of Group A wherein Rl is selected from the group cons;sting of Rs ~ ~ R2.

R6 '~
R3j R4, R5, and R6, defined as in Group A.
A further group of compounds, hereafter ~eferred to as Group F, are those compounds of Group E wherein ~4 is hydrogen or alkyl of one to five carbon atoms, 8~

inclusive, Rs is alkyl of one to five carbon atoms, inclusive, and R6 is selected from the group consisting of hydrogen, halogen, alkylthio of one to five carbon atoms9 inclusi~e, and dialkylamino with each a1kyl the same or different and having one to three carbon atoms, inclusive, R2 and R3 are defined as in Group A.
Another group of compounds, hereafter referred to as Group G, are those compounds of Group F wherein R2, R3, R4, and Rs are defined as in Group F and R6 is di-alkylamino with each alkyl the same or different and having one to three carbon atoms, inclusive.
A further group of compounds, hereafter referred to as Group H, are those compounds of Group F wherein R~, R3, R4 and R5 are defined as in Group A and R6 is alkylthio lS of one to five carbon atoms, inclusive.
A still further group of compounds, hereafter re~
ferred to as Group I, are those compounds of Group F
wherein R2, R3, R4, and Rs are defined as in Group F, and R6 is halogen.
A further subgroup of compounds, hereafter referred to as Group J are those compounds of Group F wherein R2, R3, R", and Rs defined as in Group F and R6 is hydrogen.
A further subgroup of compounds, hereafter referred to as Group K are those compounds of Group J wherein R4 is hydrogen.
A further group of compounds, hereafter referred to as Group L, are those cbmpounds of Group J wherein R4 is alkyl of one to five carbon atoms, inclusive.
Preferred of Groups F, G, H, I, J and L are those campounds wherein the alkyl groups are at the 3 and 5 g_ . ::
, ~ . , . ~ , . . .

1~ 98~

positions of the phenyl ring.
Preferred of Group K are those compounds ~herein the alkyl group is at the 3 position of the phenyl ring.
Another group of compounds, hereafter referred to as Group M~ are those compounds of Group C wherein X and Y are the same or different and are selected from the group consistiny of alkyl of one to five ~arbon atoms, inclusive, alkylthio of one to five carbon atoms, inclu-sive, monocyano substituted alkylthio of one to five car-bon atoms, inclusive, phenylthio wherein phenyl is un-substituted or substituted with one to three sùbstituents, same or different, selected from the group~consisting of halog`en and alkyl of one to four carbon atoms, inclusive, cyano, alkoxy of one to five carbon atoms, inclusive, phenyl, and dialkylamino carbonyl with alkyl the same or different and having one to three carbon atoms, inclusive.
R2 and R3 are defined as in Group C.
A further group of compounds, hereafter referred to as Group N, are those compounds of Group M wherein X
is alkyl of one to five carbon atoms, inclusive, Y is defined as in Group M, R2 and R3 are def;ned as in Group C.
A still further gr.oup of compounds, hereafter referred to as Group 0, are those compounds of Group N
wherein Y is selected from the group consist;ng of alkyl- -thio of one to five carbon atoms, inclusive, phenylthio wherein phenyl is unsubstituted or substituted with one to three substituents, same or different, selected from the group consisting of halogen and alkyl of one to four carbon atoms, inciusl ve, cyano, a1koxy havi ng one to - - . , - . ...................... -: . : .. . ~ ; . -8~

five carbon atoms, inclusive; R2 and R3 deFined as in Group C.
Anothe~ group of compounds, hereafter referred to as Group P5 are those compounds of Group N wherein Y is a monocyano substituted alkylthio of one to five carbon atoms, inclusive; R2 and R3 defined as in Group C.
A still further group of compounds, hereafter :
referred to as Group Q, are those compounds of Group N
wherein Y is dialkylaminocarbonyl with the alkyl group being the same or d;fferent and having one to three carbon atoms, inclusive; R2 and R3 defined as in Group C.
Another group of compounds, hereafter referred to as Group R, are those compounds of Group 0 wherein Y ;s phenylthio wherein phenyl is unsubst~tuted or substitu-ted with one to three substituents, same or different, selected from the group consisting of halogen and alkyl of one to four carbon atoms~ inclusive, cyano and alkoxy having one to five carbon atoms, inclusive; R2 and R3 defined as ;n Group C.
A further group of compounds, hereafter referred .
to as Group S, are those compounds of Group 0 wherein Y
is alkylthio of one to five carbon atoms, inclusive; R~
and R3 defined as in Group C.
Another group of compounds, hereafter referred to ~5 as Group T, are those compounds of Group C where~n Rl ;s X
C=N -yl ' ~ ~
and X and Y taken together w;~h the carbon atoms to which 1 1 , - ~ , ,:, . ~ ", . :

~ lLCl ~981 they are attacheel form a dithio heterocyclic of the formula :~

S S
'~C~ ~ '~
Il :
wherein m is 2 or 3 and the alkylene portion of the ring is unsubstituted or subs:tituted with one to two methy1 groups; R2 and R3 defined as in Group C. :-A furthér group of compounds, hereafter referred to as Gro~p U, are those compounds of Group~C wherein Rl -i s ..

/C-N - :

;
and X is hydrogen and Y is of the formula Rg wherein R7is selected from the group consisting of alkyl of one to three carbon atoms, inclusive, and phenyl; R8 : is alkyl of one to three carbon atoms, inclusive; Rg is selected from the group consisting of alkyl of one to three carbon atoms, inclusive, and SRIo wherein Rlo is a:lkyl and is the same alkyl group as R7, and taking R8 and R1o together with the atoms to which they are at-tached form a dithio heterocyclic of the formula ~(CH23n~
S S wherein n is 2 or 3 and the alkylene portion of the ring is unsubstituted or substituted with ;~

.. ..

one or two methyl yroups; R2 and R3 are defined as in Group C.
A further group of compounds, hereafter referred to as Group V, are those compounds of Group U where;n R7 is selected from the group consisting of alkyl of one:to three carbon atoms9 inclusi~e, and phenyl; R8 is alkyl of one to three carbon atoms, inclusive, and Rg is alkyl of one to three carbon atoms, inclusive; R2 and R3 are ;~
defined as in Group C.
Another group of compounds, hereafter referred to as Group W, are those compounds of Group U wherein R7 is ~ ;
selected from the group consisting of alkyl of one to three carbon atoms, inclusive, and phenyl; R8 is alkyl ~ of one to three carbon atoms, inclusive, Rg is SRIo where in Rlo is alkyl and is the same alkyl group as R7 and tak;ny Rg and Rlo together with thè atoms to which they are attached form a dithio heterocyclic of the~formula /(CH2 )~
~ S ~ S wherein n is 2 or 3 and the alkylene 2U ~ / RR
portion of the rlng is unsubstituted or substituted with one or two methyl groups; R2 and R3 defined as in Group C.
A further group of compounds, hereafter referred to as Group X, are those compounds of Group U wherein R7 is selec~ed from the group consisting of alkyl of one to ~hree carbon atoms, inclusive, and phenyl, R8 is alkyl of one to three carbon atoms~ inclusive, Rg ls SRio and taklng Rg and Rlo together with the carbon atoms to ~hich they are at-tached form a dithio heterocyclic of the formula , ~(CH2)n~ .
~ C wherein n is 2 or 3 and the alkylene portion of the ring is unsubstituted or substituted with one or two methyl groups; R2 and R3 defined as in Group C.
The phrase "alkyl of from one to six carbon atoms, inclusive" includes methyl, ethyl~ prapyl, butyl, pentyl, hexyl, and isomeric forms thereof. Alkyl of lower carbon atom limitat~on are to be interpreted in a similar manner.
The term "alky1thio" is intended to mean a moiety of the formula alkyl-S- wherein the attachment to the rest of the molecule is through the sulfur. "Ph~ny1thio" is to be interpret~d in a similar manner. "Dialkylamino" is a alkyl moiety represented in the formula ~ N - wherein alkyl the attachment to the rest of the molecule is through the nitrogen. "Halogen" includes fluoro, chloro, bromo, and ;odo.
The new organic chemicals of this invention are prepared from antecedent N-methylcarbamates by either of two conventional processes. In accordance with one process~
an amount of a selected N-methylcarbamate is dissolved in tetrahydrofuran along with an equivalent (or an excess if desired) of an acid acceptor such as a trialkylamine, e.g., triethylamine. This mixture is cooled to about 10C. in an ice-bath and an equivalent of an aminosulfenyl chloride, /N - S -Cl, is added with stirring. This reaction mix-ture is stirred until reaction is completed~ Stirring can - . . ..... : .... ,. : .
. . :: .. .: , , .

~ 9 8 extend over five to eight days~ after which interval the mixture is filtered~ and the solvent medium is removed from the filtrate by evaporation under reduced pressure.
The residue thus obtained is purified by chromatography, --advantageousiy adsorptlon chromatography with s;lica gel.
In accordance with another procedure~ a solution of a secondary amine, e.g., a dialkylamine, for example, dimethylam;ne in a suitable organic solvent medium, e.g., n-hexane, is slowly added ~dropwise) to a chilled solu-tion (e.g., -5C.) of sulfur dichloride in a similar sol-vent medium.
The chilled reaction mixture is stirred for an interva1, e.g.,-30 minutes, in order to obtain reasonable completion of the reaction. The mixture is filtered in order to remove prec;pitated salts, and the salts are r washed with, e.g., dieth~l ether. The desired secondary aminosulfenyl chloride is obtained in a concentrate by re-moving excess solvent by evaporation. This concentrate can then be added slowly, e.g., dropwise, to a solution of a selected N-methylcarbamate in a suitable organic sol-vent medium, e.g., dimethylformamide containing at the same time an acid acceptor, advantageously a tertiary amine, e.g., a trialkylamine such as tr1ethylamine. This reaction mixture is quenched with water, and the desired disubstitu-ted aminothio alkylcarbamate is recovered and purified by conventionai procedures such as solvent extraction, washing to remove traces of salts, drying, and removing the ex-tracting solvent.
The table below provides 1llustrative exa~ples of the compounds of the invention within Formula I.

R, :

Rs 2 R4 :

R6 ~ 6 R4 Rs R6 R2 R3
3-C4Hg 4-i-C3H7 5-C2Hs C2Hs i-C6HI3 2-C5Hl~ ~ H 6-i-CsH"
C2Hs 2-C3H7 4~ C3~7 6-C3H7 0 0 3-C2Hs 4.t~C4Hg. 6-CH3 CH3 i-C3H7 2-Cl H 4-Br CH 2~ ~C 1 3-Cl 5-C1 6-Cl t-C4Hg CH3 H 4-F H V / C6Hl3 2-I 4-Br 6-F -N
2-OCH3 3-OCH3 4-OCH3 CH3 -cH2cH2 ~

3-OC2Hs 5-O-t-C4Hg H O ~ Cl
4-oCsHll H~ 6-O-i-C3H7 iC4Hg ~
2-C4Hg 5-C,jH9 6-C4Hg CsHIl ~ CH3 3-SCH3 H 6-SC4Hg ~ C2Hs 3-SCH3 4-S-t-64Hg 5-SC2Hs O -CH
H H 4 SCsH
~ C3H
3-SC2Hs 5-SC2Hs 6-SC2Hs C2Hs C2H5 . H 3-n(CH3)2 -CH2 ~ CH3 .

::

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

8~

2-N(C3H7)2 H 5-N(C3H7)2 ~ O

/CH3 4-N(CH3)2 i-C3H7 -CH2CH

52 N(C2Hs)2 ~ 6-N(C2Hs)2 ~ CH3 H H 3-N=CHN(CH3)2 ~ ~ CH3 :~
H H 3-N-CHN(CH3)2 CH3 C2H5 3-N-GHN(CH3)2 H H V C4Hg H 2-C2Hs 4-Cl ~ ~

3-C~,H9 5-Br 6-OC2Hs O C2Hs ~, 2-i-C3H7 4-SCH3 ~ C2Hs i-C3H7 i-C3H7 CH3 : :
3~0C4Hg 5-SC2Hs 6-N=CHN(CH3)2 - N

2-Br 4~i-C3H7 6-N(CH3)2 ~ clH3 CH3 3-CH3 5-C2Hs 6-I i-CsH

~ 2-SC2Hs 4-SC3H7 5-N(C2Hs)2 -C-N -C2H5 C3H7 t-C4H9 C2Hs C4Hg CsHIl O
~~\ .
C2Hs t-C4Hg - N\~ N-CH3 ' ,:
, ~ lJ9~ :

Cl i-C3H7 CH
SCH3 SCsHIl ~ C2Hs SC2Hs SC2H5 ~a SC3H7 SC4Hg 1-C3H7 - ~ Cl S~t~4~ SCH3 -A
SCH2CN SC2H3(CN)C2Hs ~

SC2H4CN SCH3 ~ i-C4Hg SC6Hs SCsHs -CH2GH2 ~ C2H5 SCHg SC6Hs i-CsH~ CsHl I - `
SC6Hs sC2Hs Q CH3 SC6H5 CH3 ~2Hs C2H5 ~ CH3 SC6Hs SCH2CN ~ N S
2 3 C~13 both ~ ~ 4 substit~ents ;

4-C2H5 3-Cl -CH2CH2 ~-CH2CH
5-C6Hs 2-F C5HllCH3 3~CON(CH3)2 5-C3H7 ~ CH3 S ~ Y CH3 .
2-CH3 i-C3H7 -CH2 ~ CH, -~

~ 3220 4-Cl S-C4Hg C3H7 C3H

5-CN S ~ -N

4-OC3H7 i-C3H7 i-C4Hg X is H
Y is R8 - C - SR7 :

R7 R~3 Rg R2 R3 /--\
CH3 C3H7 C2Hs - N 0 CzHs C2H5 i-C3H7 C6HI3 C6Hl3 C3H7 CH3 CH3 O C2Hs / ~ C3H7 ~
i~-C3H7 C2Hs - N ~ ~0 ~:

C6Hs i-CgH7 C3H7 C4Hg CgH7 CH3 i-C3H7 S-CH3 ~ Cstl~
C2Hs C2Hs S~C2tls Cl t_c,lHg t-C~,Hg C3H7 CH3 S-C3H7 -CH2 ~ -CH

i-C3H7 C3H7 S-iC3H7 N ~ -CH3 , , ~

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

9~31 h2)n~

--c R

R8 n _~_ R2 CH3 2 H N ~
~:
: C2Hs 3 H -CH2CH2 ~ CH3 ~ ~-C3H7 ;-C3H7 3 H - N S
. i-C3H7 CH3 2 l-C~3 ~ C~H
C2Hs 2 2-CH3 C3H7 C3H, 3 l-CH3 i~Cs~ll -CH
i~C3H7 3 2,2-diCH3 CH3 t-C4Hg ~ ( CH2 )~

,~
~C ,v m P R2 R3 ~ .

2 l-CH

~ 98~ 3220 3 2-C~3 -CH2C~2 ~ C~Hs '' 2 l~l-diCH3 3 1,3-diCH3 ~ i-C"Hg 3 2,2-diCH3 C3H7 ~ ~, The scope of this invention is merely lndicated by the following exemplified embodiments. Those skilled in the art will readily recognize further ramifications of the invention.

E~ Preparation of 3-Is~r~e~F~ N~dimeth,yl-__ ~_ __ _ amino)th;o]-N-meth,vlcarbamate To a solution consisting of 1.93 gm. (0.01 mole) meta-isopropylphenyl N-methylcarbamate and 25 ml.
tetrahydrofuran was added 1.01 gm. tO.01 mole) triethyl-amine. This solutlon was cooled to 10C. and 1.115 gm. , (0.01 mole) dimethy1aminosulfenyl chioride was added drop by drop. The amount of triethylamine hydrochlarlde that precipitated did not appear to be quantitative, so the reaction mixture was set aside at 25C. for eight (8) days.
The precipitate was then collected on a filter, and the filtrate was saved. The tetrahydrofuran was then removed from the filtrate by evaporation under reduced pressure.
The residue thus obtained was transferred to a column (100 gm.~ of sil;ca gel for chromatograph;c purification.
The chromatogram was developed with a solvent system con-sisting of 5 percent ethyl aceta~e in benzene. The eluate ; !

~ 3220 was collected and after remov;ng the solvents by evapora-tion under reduced pressure, there was obtained 0.53 gm.
of 3-isopropylphenyl N-~dimethyla~ino)thio]~N ~ethylcarbamate as an oil, Analysis Calc'd for: Cl3H20N202S
C~ 58.18; H, 7.5i; N, 10.44 Found: C~ 58.00; H, 7.91; N, 10.09 Example 2 l~n~lth~ minD~ca~
thioate A solution of morpholine (7.8 gm., O.Q90 mole) in hexane (100 ml.) was added dropwise during thirty min-utes to a cold (-5C.) solution oF sulfur d~chloride (4.93 gm., 0.047 mole) ;n hexane (100 ml.). This react1On mix-ture was stirred for thirty minutes at -5C. and then filtered. The filtrate was concentrated by evaporàting off the hexane under reduced pressure. The concentrate as an orange liquid was added dropwise over fifteen minutes to a cold (~5C.)solution of methyl N-[[(methylamino)carbonyl]-oxy~ethanimidothioate ~4.87 gm., 0.03 mole) in dimethyl-Formamide (15 ml.) containing trlethylamine (5.6 ml., 0.04 mole). This mixture was in turn stirred for two (2) hours at 0C. It was diluted with cold water and a precipitate formed. The precipitate was collected on a filter, and the filter cake was washed with water and dried. There was thus obtained 8.35 gm. (99% yield) of object compound. Re-crystallization from ethyl acetate gave methyl N~ methyl-(4-morpholinylthlo)aminoJcarbonyl]oxy]ethan;midothioate as a white solid having a melting point at 128 to 129C.

..

~na_~is Calc'd_ror: C9HI7N303S2 C3 38.69; H, 6.14, N~ 15.0~; S, 22.95 '~
Found: C, 38.91; H, 6.1~; N, 15.25; S, 22.86 ' Representative aminothio carbamates according to Formula I and this ;nvention were prepared according to the process embodiments of Examples 1 and 2 and tested along with the parent N-monos~bstituted carbamates against vario~'s representative insect pests. Tlle pest species ' ,~
included southern armyworrn larvae (SAW) (Spodoptera eridania), nymph stage house crickets (HC) )Acheta domesti- ,~
_ cus); adult house flies (HF) (Musca domestica); adult boll weevils (B~) (Anthonomus grandis); yellow-fever mosquito ~'' larvae (YFM) (Aedes ae~ypti); and cabbage looper larvae ' (CL) ~Trichoplusia ni).
`
Example 3 ~
The details of the tests are as follows: Prepara- ' tion of tested chemicals - Analytical samples of each were dissolved in acetone. These acetone solutions were applied as such or portions of them were dilùted with a Tween 20 ' "wet water" or a 10% sucrose "wet water". The "wet water"
itself contained 0.132% vlv of Tween 20 (polyoxyethylene sorbitan monolaurate).
The southern armyworm and cabbage looper tests were 25~ effected with Henderson bush lima bean foliage characterized by two primary leaves per replicate. The leaves were dipped into a "wet water" emu1sion of a test chemical, allowed to dry, and then placed'on d moistened filter disk in a 9 cm ,~
plastic petr~ dish. Five larva of the respective test in-3~ sects were put on the leaves, the cover of'the petri dish -~
* Trademark - ~ 3 - -.... ' ' `:
... .

was replaced, and it was set aside for future evaluation.
Three replications for each treatment rate were prepared.
The house cricket test was effected`by pipetting 5 ml. portions of the acetone solutions into 9 cm petri dishes and allowing the acetone to evaporate. Ten nymphal house crickets were released into the treated dish and the cover was replaced. Three replicates for each treat-ment rate were prepared.
The house fly and boll weev;l tests were effected by saturating a golf-ball size wad of cotton with lO ml.
of a "10% wet sugar water" preparatian of the test chem;- `
cal. The saturated wad was placed in a portion cup wh;ch was attached to the ins;de surface of a 5-oz. waxed paper cup. Ten adult house fl;es or boll weevils were released in the 5-oz. cup and ;t was covered with a plastic l~d for future observation. Two replicates were prepared for each treatment rate.
The yello~ fever mosquito larvae test was effected by adding the appropri~te amount of a wet water and acetone solution of the test chemical to l00 ml. distilled water in a 5-oz. waxed paper cup. Ten mosquito larvae were added.
Dr;ed yeast was added after twenty-four hours. There were two repl;cates for each treatment rate.
The southern armyworm, house cr;cket, boll weev;l, house fly and cabbage looper tests were held at 22C., while the yellow fever mosquito larvae tests were held at 27C.
The tests were evaluated for insect kill (including moribund and knocked down) after twenty-four, forty-eight and sometimes seventy-two hours.

.

Tlle representa~ive new aminothio carbamates of this invention ha-le the following names, physical form and elemental analyses.

-~tdimethYlaminothio)methylamino]carbonyl~oxime of 2-methyl-2-(methylthio)propanal, m.p. 50-51C.
Analysis Calc'd for: C~HlgN302S2 C, 40.73; H, 7.22; N, 15.83; S, 24.16 Found: C, 40.53; H, 7.73, N, 15.35; S, 24.51 o-cr methyl(l-pyrrolidinylthio)amino]carbonyl]oxime of 2-methyl-2-(methylthio)propanal, m.p. 73-74C.
Analys;s Calc'd for: C,lH2lN3025 C, 45.33; H, 7.26; N, 14.42; S, 22.00 Fo~nd: C, 45.23; H, 7.77; N, 14.22; S, 22.01 O-[CmethYl(l-piperidinylthio)amino]carbonyl]oxime of 2-methyl-2-(methylthio)propanal, m.p. 51-53C.
Analysls Calc'd for: Cl2H23N302S2 C, 47.18; H, 7.59; N, 13.76; S, 21.00 Found: C, 47.38; H, 8.14; N, 13.81; S, 21.35 0-c~methyl(4-morpholinylthio)amino]carbonyl]oxime of 2-methyl-2-(methylthio)propanal, m.p. 75-76C. -Analysis Calc'd for: CIlH2lN303S2 .~ ~ .
C, 42.97; H, 6.89; N, 13.59; S, 20.86 Found: C, 43.38; H, 6.92; N, 13.55; S, 21.13 0-[~(2,6-dimethyl-4-morpholinylthio)methylam;no]oarbonyl]-oxime of 2-methyl-2-(methylthio)propanal, m.p. 61-62C.

- ,~

~0~9~1 Analysis Calc'd for: C13H25N303S2 C, 46.54; H, 7.51; N~ 12.53: S~ 19.12 Found: C, 46.97; W, 8.16; N, 12.52; S, 19.11 The compo~nd, when tes~ed as des~ribed in Fxample 3, gave the following resul~s:
Insect Rate . Mortal~
HC10 ~g./plate 100 -~
HF 30 ppm. 90 BW10 ~g./plate 100 Example 4 Starting with the known compound methyl N-~rtmethyl-amino)carbonyl]oxy]ethanimidothloate, the Follawlng new aminothio carbamate derivatives of this compound are pre-pared by procedures similar to Examples 1 and 2.

Methyl N-[[~[(dimethylamino)thio]methylamino~carbonyl]-oxy~ethanlmidothioate, m.p. 68-70C.
~nalysis Calc'd for: C~HIsN30252 C, 35.42; H, 6.37; N, 17.70 Found: C, 35.73; H, 6.45; N, 17.60 Methyl N-r[[~(diisopropylamino)thio]methylamino]carbonyl]-oxy~ethanimidothioate, m.p. 81-82C.
Analys~s Calc'd for: C,IH23N30252 C, 45.02; H, 7.90; N, 14.31; S, 21.85 Found: C, 45.26, H, 8.34i N, 14.08; S, 22.17 .

Methyl N-~[~methyl(l-piperidinylthio)amino~carbonyl]oxy]-ethanimidothioate, m.p. 53-54C.

, .. . . . . . . , .,, ~ ........ . . . . . . ..
.~. . . . .. .

9~l Analysis Calc'd for: CloHlsN3o~s2 .
C, 43.39; H, 6.90; N, 15.15; S, 23.12 Found:C, 43.20; H, 6.88; N, 15.25; S, 23.56 Methyl N-c~methyl(4-morpholinylthib)a~ino]carbonyl]oxy]
ethanimidothioate, m.p. 128-129C.
Analysis Calc'd_for: CgHl7N30352 C, 38.69, H9 6.13; N, 15.04; S, 22.95 ~, Found: C, 38.91; H, 6.18; N, 15.25; S, 22.86 '-~
10This compound, when tested as described in Example 3, gave the follow;ng results:
Insect Rate Mortality SAW 60 ppm 100 ~ HC 30 ~g./plate ~3 HF 30 ppm 95 BW 30 ppm 95 CL 180 ppm 93 :~ .
~ Methyl N~C(di-n-butylaminothio)methylamino]carbonyl]oxy]-20 ethanimidothioate as an oil. ~
Analysis Calc'd for: C~3H27N302S2 ~ ;-C, 48.56; H, 8.47; N, 13.07; S, 19.95 Found: C, 48.26; H, 9.06; N, 12.95; S, 19~93 r Methyl N~ 2,6-dimethyl-4-morphollnylthio)methylamino~-carbonyl]oxy~ethanimidothioate, m.p. 65-67C.
Analysis Calc'd for C~IH2lN303S2 C, 42.97; H, 6.89; N, 13.67; S, 20.86 Found: C, 42.92; H, 6.85; N, 13.45; S, 20.91 , ,- , , , ,, , ,. .: , , : , v ~ 3220 Using the known compound 3,5-diisopropylphenyl -N-methylcarbamate, the follow;ng new arn~nothiocarbamate derivatives were prepared by methods similar to Examples 1 and 2. .

3,5-di;sopropylphenyl N-methyl-N-(dime~hylamino)carbamate as an oil.
Analysis Calc'd For: CI~H26N202S
lo C, 61.90; H3 8.44i N, 9.03i 5, 10.33 ~:
Found: C, 61.68; H, 8.81; N, 8.91; S, 10.27 The compound, when tested as described in Example 3 gave the follo~ing results:
Insect Rate Mortality 15 HC 30 ~./plate 97 HF 90 ppm 95 ~ M 0.6 ppm lO0 :
3,5-Diisopropylphenyl N-methyl-N-(l-piperidinylthio)-carbamate as an oil.
Analysis Calc'd for- Cl9H30N202S
.

C, 65.10; H, 8.63; N~ 7.99; S, 9.15 Found: C, 64.94; H, 8.80; N, 7.66; S, 10.05 3,5-Diisopropylphenyl N-methyl-N-(4-morpholinylthio)-carbarnate as an o11.
Analysis Ca1c'd for Cl8H29N203S
C, 61.33; H, 8 01; N, 7.95; S, 9.10 Found: C, 61.04; H, 8.30; N, 7.83; S, 9.25 , . .. . :. . :

9~1 3,5-D;isopropylphenyl N-(dibuty1aminothio)-N-methyl-carbamate as an oil.
Analysis Oalc'd for: C22H33N202S ~ :
G, 6~.96, H, 9.71; N, 7.10; S~ 8,13 Found: C, 66.86; H, 10.06, N, 7.07; S, 9.85 , ,~.

3,5-~isopropylphenyl N-(diisopropylaminothio~ N-methylcarbamate as an oil.
Analysis Calc'd for: C20H34N202S
C, 65.53; H, 9.35; N, 7.~64, S, 8075 Found: C, 65.29; H, 9.07; N, 7.36; S, 13.40 ~ .' Example 6 Vsing the known compound meta-isopropylphenyl N-m`ethylcarbamate, the following aminothio carbamates were prepared by methods similar to Examples 1 and 2:

3--~sopropylphenyl N-methyl-N-(l-piperidinylthio)- .
carbamate as an oil.
Analysis Cal_id for: C~6H24N202S r C, 62.30; H, 7.84; N, 9.08; S, 10.40 Found: C, 62.33; H5 8.05; ~, 8.94; S, 10.31 3-Isopropylphenyl N-methyl-N-(4-morpholinylthio)carbamate as an oil.
Analysis Calc'd for- ClsH~2N203S
C, 58.03; H, 7.15; N, 9.03; S, 10.33 Found: C, 57.96i H,~6.95; N, 9.i5; S, 10.18 , . . . ~ .

3-Isopropylphenyl N-(dibutylaminothio)~N-methylcarbamate as an oil.
Analysis Calc'd for: ClgH32N202S
C, 64.73; H, 9.15; N, 7.95; S, 9.10 Found: C, 64.45; H, ~.81; N, 7.71; S, 9.29 3-Isopropylphenyl N-(dlisopropylaminoth;o)-N-methyl-carbamate as an oil.
Analys;s Calc'd for: C17H2~N202S
C, 62.92; Il, 8.7û; N, 8.64; S, 9.88 Found:C, 62.79; H, 8.67j N, 8.33; S, 11.61 The compound, when tes~ed as described`;n Example 3, gave the following results:
Insect Rate Mortality SAW 300 ppm lO0 HC 3.3 ~g./plate lO0 BW 30 ppm 95 YFM 0.067 pp~ 100 3-Isopropylphenyl-(dimethylaminothio)-N-~ethylcarbamate as an oil.
An~lc'd for: Cl3H20N202S
C, 58.18; H, 7.51; N, 10.44 Found: C, 58.00; H, 7.91; N, lO,09 xample 7 Using the known compound o-isopropoxyphenyl N-methy1carbamate, the followiny aminothio derivatives were prepared by methods similar to Examples l and 2.

~ 3220 o-Isopropoxyphenyl N-(diethylaminothio~-N-methylcarbamate as an oil.
, Analysis Cal`c'd for: ClsH24N203S
C, 57.66; N~ 7.74; N, 8.97 Found:C, 57.91; H, 7.57i N, 9.0S :

~, ~
o-Isopropoxyphenyl N-methyl-N-(l-piperidinylthio)-carbamate as`an oil.
Analysis ~alc'd _ or: Cl6H24N203S ~-~
C, 59.22; H~ 7.46; N, 8.64; S, 9.88 ~:
Found C, 59.81; H, 7.51; N, 8.52; 5, 9.58 .

o-Isopropoxyphenyl N-(ethyl-n-butylaminothio?-N-methyl~
carbamate as an oil.
15Analysis Calc'd for: Cl7H28N203S
C, 59.97; H, 8.79; N, 8.23; S, 9.42 , Found: C, 59.88; H, 8.09; N, 7.92; S, 9.19 The compound, when tested as described in Example ~`
39 gave the foll:owing results:
20 Insect Rate ~ .
HC30 ~g./plate 100 HF ~0 ppm 85 BW 30 ppm 80 YFM0.067 ppm 100 o-lsopropoxyphenyl N-(diisobutylaminothio)-N-methylcarba-mate as an oil.
~r~ alc'd for: ClgH32N203S
C, 61.92; H, 8.75; N~ 7.60; S, 8.70 Found: C, 61.76; H, 9.08, Ni 7.53; S,i3.18 ..

. ~- . . ~ .

9~3~ 3220 o-Isopropoxypheny'l N-(dimethylaminoth;o)-N-methylcarbamate as an oil.
Anal~s Calc'd for: C13H20N203S
Cg 54.90; H, 7.09; N~ 9.85, S, 11.28 F ound: C, 54.71, H~ 7.08; N, 9.61~ S, 11.11 o-Isopropoxyphenyi N-methy'l-N-(4 morpholinylthio)carbamate as an oil.
Analysis Calc'd for: Cl5H22N204S
C, 55.19; H, 6.79; N, 8.58; S, 9.82 F ound: C, 55.10; H, 6.93, N, 8.55; S, g.62 o-Isopropoxyphenyl N-(di-n-butylaminothio)-N-methylcarbalnate as an oil.
lS Analysis Calc'd for: ClgH32N203S
C, 61.92~ H, 8.75; N, 7.60; S, 8.70 Found: C, 62.26; H, 8.67; N, 7.37; S, 8.65 o-Isopropoxypherlyl N-(diisopropylaminothio)-N-methylcarba-mate, m.p. 32-34C, Ana~is_Calc'd for: Cl7H2~N203S
C, 59.97; H, 8.29; N~ 8.23;,S, 9.42 Found: C, 60.24, H, 8.30; N, 8.04; S, 9.42 25 Ex~8 Us;ng the known compound 0-[[methylaminolcarbonyl]-oxime of 1,3-clithiolan-2-one, the following aminothio com- ;~
pounds ~ere prepared by methods similar to Examples 1 and 2:



g~, 0-c~(dimethylaminothio)methylamino]carbonyl]oxime of ~ ;
1,3-dithiolan-2-one, m.p. 85~-86.5C.
Analysis Calc'd for: C7Hl3N302S3 C, 31.44, ~, 4.90; N, 15.77; S, 35.98 ~;
Fcund: C, 31.74; H~ 5.00; N, 15.54; S, 35.gl 0-t~methyl(l-piperidinylthio)amino]carbonyl]oxime of 1,3-dithiolan-2-one, m.p. 99-99.5C.
Analys;s Calc'd for: CloHl7N302S3 C, 39.06; H, 5.57; N, 13.67; S, 31.29 Found: C, 39.13; H, 5.gl; N, 13.57~ S, 31.05 The compound, when tested as described in Example 3, gave the following results~
Insect Rate Mortality SAW 100 ppm 100 ~;
HF 3.3 ppm 95 --BW lO ppm 100 CL 300 ppm 93 YFM 0.6 ppm 100 0-~methylt4-morpholinylthio)amino}carbonyl~oxime of 1,3-~ithiolan-2-one, m.p. 124-126C~
is Calc'd for: CgHI sN303S3 C, 34,93; H~ 4.89; ~, 13.58, S, 31.09 ~25 Found: C, 35.08, H, 5.15; N, 13.39; S, 30.81 0-~di-n~butylaminothio~methylamino~carbonyl~oxime of 1,3-dithiolan-2-one, m.p. 39-41C.
Analy~is Calc'd for: l 3H~5N302S3 ~ 3220 1~ 81 ,:

C, 44.41; H~ ~.17; N, 11.95; S, 27.36 Found C~ 44.42; H, 7.29;tt, 12.05; S, 27.55 ~
':
0-~[(~36-dimethyl-4-morpholinylthio)methylamino]carbonyl]-oxime of 1,3-dithiolan-2-one, m.p. 81-83C.
: CllHlgN303S3 C, 3g.15: Hi 5.67; N, 12.45: S, 28.:51 ~:
Found: C9 39.42; H, 5.86; N, 12.17; S, 28.62 E _ ple 9 Using the known compound 3-tert-bu~ylphenyl N-methylcarbamate, the following aminothio deriv~t1ves were prep~red by~met~hods similar to those of Examples 1 and 2:

3-tert-Butytphenyl N~methyl-N-(dimethyla~inothio)carbamate as an oil. : ' Analysis Calc'd ~or~ CI4H22N202S
: ~~ : C, 59.54; H, 7.B5; N~ 9.92 : ~ ~ Found:C, 59.77, H, 7.57; N, 9.73 20The compound, when tested as described in Example 3, ave the following results:
Insect Rate Mortality tlC 30 ~g./plate 100 : fFM 0.6 ppm 100 3-tert~Butyl~phenyl N-methyl-N~ piperldinylth~o)carbamate as an oil. j ~.
Ana~ysis _alc'd ~or: Cl7t-t26N202S
C, 63.33; H, 8.13, N, 8.69; S, 9.95 Found: C, 63.33; H, 8.09; N, 8.57; S, 10.33 --3~~

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

~ 8~ 3220 3~-tert-butylphenyl N methyl-N-(4-morpholinylthio)carba-mate as an oil. ~`
Analysis Ca'lc'd for: Cl6H2l,N203S
_ . --C, 59'.23; H, 7.46; N, 8.64; S, 9.88 Found: C, 59.00; H, 7.08; N, 8.56; S, 9.82 '' 3-tert-butylphenyl N-(di-n-butylaminoth;0-N-methylcarba-mate as an oil.
Analysis Cal'c'd for~ C20H34N202S
:
C, 65.53; H, 9.35; N, 7.64; S~ 8.75 :-~ound: C, 65.89; H, 9.47; N, 7,47; S, 9.08 '~

3-tert-butylphenyl N-(diisopropylaminothio)-N-methyl-carbamate as an o;l.
Analysis Calc'd For: Cl 8H3oN202S
C, h3.~6; H, 8.9i3 N, 8.28; S, 9.47 Found: C, 63.50; H, 9.32; N, 8.18; S, 9.72 Example 10 Uslng the known compound 3,5-dimethyl-4-dimethyl-am;nophenyl N-methylcarbamate, the aminothio derivatives were prepared following methods similar to those of Examples 1 and 2.

3,5-Dime~hyl 4-d;methylaminophenyl N-(diisobutylphenylthio)-N-methylcarbamate as an oil.
A~ sis Calc'd for: C20H35N302S
__. __ C, 62.95; H~ 9.25; N~'ll.01; S~ 8.40 Found: C, 62.61; H, 9.60; N, 10.75; S, 8.58 .0~338~L 3220 , ..

3,5-Dimethyl-4-dimethylaminophenyl N-(diethylaminothio)-N-methylcarbamate as an oil.
Analysis Calc'd for: Cl6H2~N3025 C, 59.04; H, 8.36; N, 12.91; S, 9.85 F ound: C, 59.03; H, 8.43: N, 12081; S~ 10.10 3,5-Dimethyl-4-dimethylaminophenyl N-(2,6-dimethyl-4- `
morpholinylthio)-N-methylcarbamate as an o;l.
_nalysis Calc'd for: C,8H29N303S
C, 58.82; H, 7.95; N, 11.43; S~ ~.73 F ound: C, 58.58; H, 7.82; N, 11.34; S5 8.96 The compound, when tested as descri bed i n Exampl e 3, gave the ~ol l ow; ng resul ts I ns ec tRa te Mortal i ty SAW 100 ppm 100 BW 30 ppm 95 Y FM ~0 . 6 ~ p pm 7 5 CL ~ 10~0 ppm 80 :
20 3,5-Dimethyl-4 -dimethylaminophenyl N-( Dimethylaminothio)-N-methylcarbamate as an oil.
Analysis Calc'd for: C~4~l23NgO2$
~ C, 56.53, H, 7.70; N, 14.13; S, 10.78 F ound: C, 56.48; H, 8.01; N, 14.28 3,5-Dimethyl 4-dimethylaminophenyl N-methyl-N-(l-piperi-dinylthio)carbamate as an oil.
Analysis Calc'd ~or: ~l7H27N3C2S
C, 60.50; H, 8.07; N, 12.45; S, 9.50 F ound: C, 60.51~ H, 8.25; N, 12.56; S, 9.89 3~5-Dimethyl-4 dimethylaminophenyl N-methyl-N-(4-morpho-linylthio)carbamate, m.p. 74-75C.
Analysis Calc'd for: Cl 6H2sN303S ;~;
C, 56.61; H, 7.42; H, 12.38; S~ 9.45 Found~ C, 56.30; H, 7.54; N, 12.123 S, 9.20 3,5-Dimethyl-4-dimethylaminophenyl N-(di-n-~uty1am1no-thio)-N-methylcarbamate as an oil.
Analysis Calc'd fo~: C20H35N302S
C~ 62.95, H, 9.25; N, ll.Oli S~ 8.40 Found: C, 62.84; H, 9.51; N, 10.75; S, 8.73 3,5-D;methyl-4-dimethylaminophenyl N-~diisopropylamino-thio)~N-methylcarbamate as an oil.
~ s Calc'd for: ClaH3lN3o2s C, 61.15i H, 8.84; N, 11.89; S, 9.07 :
~ Found: C, 60.93; H, 9.25; N, 11.64; S, 9.14 Ex~ple 11 __ IJsiny the known compound 2-cyanoethyl N-C~methyl-amino~carbonylJoxy~ethanimidothioate, the aminothio deri-vatives were prepared by methods s;milar to Examples 1 and 2, 2~ 2-cyanoethyl N ~(dimethylaminothio]methylamino~carbonyl]-oxy]ethanimidothioate, m.p. 78.5-80C.
Analysis Calc'd For: CgHl6N402S2 C, 39.11; H, 5.84; N, 20.27; Sj 23.20 Found: C, 38.96; H, 5.81; N, 19.87; S, 23.34 ~ 3220 2-Cyanoethyl N-~Ccmethyl(l-piperidinylthio)amino]carbonyl]-oxy~ethan;midothioate, m.p. 118-119C. :.
Ana~ Calc'd for: Cl2H20N402S2 C, 45.54; H, 6~37; N, 17.71; S, 20.27 Found: C, 45.36; H, 6.39; N3 17.71; Sj 20.36 2-Cyanoethyl N-[~methyi(4-morpholinylthio)am;no]carbonyl]-oxy3e~hanimidothioate, m.p. 121-123C.
Analysis Calc'd for: CIlHl8N403S
C, 41.49; H, 5.70; N, 17.60 S~ ~0.14 Found: C, 41.35; H, 5.99; N, 17.15i S, 19.91 2-Cyanoethyl N-[Cc(2,6-dimethyl-4-morpholinylthio)-methylamino]carbonyl3Oxy~ethanimidothioate, m.p. 64.5-
6~.5C.
Analysis Calc'd for: Cl3H22N403S2 :
C, 45.06, H, 6.40; N, 16.17; S, 18.51 Found: C,~44.73; H, 6.75; N, 16.09; S, 18.52 ~-.

2-Gyanoethyl N-C~E(di n-butylaminothio)methylcarbonyl]-oxy]ethanimidoth;oate~ m.p. 59.5-60.5C.
Analysis Calc'd for: ClsH28N4o2s2 ;~
C, 49.97; H, 7.83; N, 15.54; S, 17.79 Foùnd: C, 49.68; H, 7.83; N, 15.16; S, 17.73 The compound, when ~ested as described ;n Example 3, gaYe the following results:
Insect Rate Mortality SAW 33 ppm 100 ~ :
HF 10 ppm 100 B~ 10 ppm 85 .. .... . ...; .

YFM 0.02 ppm 100 CL 100 ppm 73 Exam le 12 The compound O-~r(dimethylamino)thio]methyl^
carbamoyl~oxime of 2-methyl 1,3~dithiolane-2-carbox~
aldehyde, m.p 66-6~C. - ;
Analy_is Calc'd for: CgH17N302S3 c, 36.59; H, s~8n; N, 14.22 .
Found: C, 36.43; H, 5.89; N, 14.19 O-~(diethylamino)thio]methylcarbamoyl~oxime of 2-methyl-1,3-dithio1ane-2-carboxaldehyde as an o~l.
Analy~ c'd for: CIlH21N30253 lS ~ ~ C, 40.84; H, 6.54; N, 12.99 Found: C, 40.99; H, 6.61; N, 13.10 :
A compo~und of particu1ar interest ls methyl N-~[rmethyl(-4 rnorpholinylthio)amino]carbonyl]oxy]ethan-imidothioate which has exhibited unexpectedl~y superiorpersistency agairlst soathern armyworms in a comparative laboratory test. For exampte, th;s compound gave 100 percent kills at 14 and 49 days when applied at 200 ppm.
Other compounds of this subclass have tile same or simi-lar act;~ity against insect pests and exhibit relativelylow phytotoxicity to plants such as cotton.
The new aminothio carbamates of Formula I can be used as the pure compounds, such as those described in the Examples, as technical grade compounds frorn commercial pr~duction, or as mixtures of individual pure compounds, ~ -39-~ 3220 but for practical reasons, the compounds are preferably formulated with a diluent carrier with or w1thout adju-vants for use against insects, mites, and nematodes.
There are many different k;nds of d~l~ent carriers suit-able for the method and formulation embodiments of thisinvention. Dispersible carriers are commonly used in the art. Such carriers may or may not include adjuvants such as wetting agents, emulsifying agents, stickers, and other components that indirectly promote efficacy. ;
The new am;nothio carbamates of Formula I are ;
useful against ;nsects, nematodes and m;tes 1n formula-tions, e.g., as dusts, wettable powders, emulsifiable concen-trates, aqueous dispersions, solutions, and flowable creams for application to a situs, soil, plants, and foliage, seeds or ot~her parts of plants. Granular formu-lations can be prepared and applied to soil or on surfaces.
Moreover~ the new compounds of Formula I of this invention can be the so~e ac~tive agent in a formulation or other insecticidal, miticidal, or nema~icidal components may be included.
The new solid compounds of Formula I can be readily formulated as dusts by grinding a mixture of the compound and a pulverulent carrier in the presence of each other.
C.rjn~ing is conveniently accomplished in a ball mill, a hammerm~ll, or by air-blast micronization. A suitable ultimate particle size is less than 60 microns. Prefer-ably, 95% of the particles are less than 50 microns, and about 75~0 are 5 ~o 20 microns. Dusts of that degree of comnlinution are conveniently free-flowing and can be ap-plied to animals~ inanimate matter, fruit trees, crop , . .. . .

~ 3220 plants, and soil so as to effect thorough distrib~tion and coverage. Dusts are p;articularly adapted for effec-tively controlling insects and mites over wide areas ~ ~`
when applied by airplane. They are also lndicated for application to the undersides of plant foliage. u Representative suitable pulver~lent carriers include the natural clays such as China, Georgia, Barden, attapulgus, kaol;n 9 and bentonite clays; minerals in their natural forms as they are obtained from the earth such as talc~ pyrophyllite, quartz, diatomaceous earth~
Fuller's earth, chalk, sulfur, si1ica and sil;cates;
chemically modified m;nerals sach as washed bentonite, and colloidal silica; and organic flours such as wood.
~alnut shell, soybean, cottonseed, and tobacco flours, and free-flowing, hydrophobic starches.
Dusts can also be prepared ~y dissolving an amino-thio carbamate of ~ormula I in a volatile so1vent such as methylene chloride, mixing the solution with a pu1veru-lent carrier and evaporating the solvent.
The proportions of pulverulent carrier and active cumpound ~Forrnula I) can vary over a wide range depending pon the use of It, nematode or mite pests to be controlled and the eonditions of treatment. In general, dust formu-lations can contain up to about 90~ (on a weight basis) of the active ingredient. A-generally preferred proportion is from about 0.50% to about 20% of active ingredient.
The ~ispersible powder formulations of this inven-tion are prepared by incorporating a surfactant in a dust formulation prepared as described above. When about 0.1%
to about 12% of a surfactant is incorporated in a dust, the 3~20 8~1L

dispersib1e powder thus obtalned ls partlcularly adapted for further admlxture with water for spraying on lnanimate .matter and productsg fruit trees, field crops, soil, and ltvestock. The dispersible powders can be admixed with water to obta;n any desired concentration of actlve ingre-dient, and the mixture can be applied in amounts suffi~
c;ent to obtain predeterm;ned rates of application and uniform distribution. With th;s flexibil;ty in. mind, the ~.
disperstble powders of the ;nvention can conveniently ~ -co~prise preferably about 5% to.about 80~O of act;ve ingre-dient..
. Representative surfactants useful for preparing dispersibie powder formulations of thls invention include alkyl sulfates and sulfonates~ alkyl aryl sulfonates~ ~:
suifosuccinate esters, polyoxyethylene sulfates, polyoxy-ethylenesorbitan ~onolaurate, alkyl.aryl polyether s.ulfates, alkyl aryl polyether alcohols, a~lkyl naphthalene sulfonates, alkyl quaternary ammonium salts, sulfated fatty.acids and . esters, sulfated fatty acid amides, glycerol mannitan laurate, polyalkylether condensates of fatty acids~ lignin sulfonates, and the like. The preferred class of surfac-tants includes blends of sulfonated oils and polyalcohol carboxylic acid esters (Emcol H-77)-, blends of polyethoxy ethanols ~Tritons X~151, X-161, X 171)9 e.g., about equal parts of sodium kerylbenzene sulfonate and isooctylphenoxy polyethoxy ethanol containtng about 12 ethoxy groups, and blends of calclum alkyl aryl sulfonates and polyethoxylated vegetable oils ~Agrimul N4S). Ie ~w~ll be understood, of course, that the sulfate and sulfonate surfactants sugges-ted above wtll preferably be used in the form of their ~42 '' ~

9~1.

soluble salts, for example, their sodium salts. All ofthese surfactants are capable of reducing the surface tens;on of water ~n concentrations of about 1% or less.
The dispersible powder formulations can be prepared with a mixture of sur~actants of the types ind;cated ;f de-sired.
A suitable dispersible powder formulation is obtain-ed by blend;ng and milling 327 lbs. of Georgia Clay, 4.5 lbs. of isooctylphenoxy polyethoxy ethanol (Triton~9X-lqO) as a wett;ng agent, ~ lbs. of a polymerized sodium salt ~ ) of substituted benzoid long-chain sulfonic acid (Daxad 27) as a dispersing agent, and 113 lbs. of the active ingredi-ent, e.g., the compound embodiment of Examples 2 and 5 The resulting formulatlon has the following percentage 15 co~position ~parts herein are by weight unless otherwise specif;ed).
Active ingred;ent 25%
Isooctylphenoxy polyethoxy ethanol1%
Polymerized sodium salt o~ substi-tuted benzo;d long-chain sulfonic acld 2%
Georgia Clay 72%
This formulation, when dispersed in water at the rate of 10 lbs. per 100 gallons, gives a spray formula-t~on containing about 0.3X (300~ ppm) aetive ingre~ient wh;ch can be applied against insects9 or mites, on p1ants, fruit trees, or other habitats, or can be used to spray so~l against nematodes.
If desired, dispersants such as methylcellulose, polyvinyl alcohol, sodium ligninsulfonates~ and the like , -43- :

~~

can be included in the dispersible powder formulat;ons of this invention. Adhesive or sticking agents such as vegetable oils, naturally occurring gums, casein, and others can also be incl~ded. Corrosion inhibitors such as epichlorohydrin and anti foaming agents such as stearic ac;d can also be included.
The new aminothio carbamates o F Formula I of this invention can also be applied to insects~ mites, objects, or situs ;n aqueous sprays without a solid carrier. Since, however, the compounds themselves are relatively insoluble in water they are preferably dissolved in a suitable inert organic solvent carrier. Advantageously, the solvent carrier is immiscible w;th water so that an emulsion of the solvent carr;er ;n water can be prepared. I F, for .:
example, a water-miscible solvent carrier such as ethanol is used, the solvent carrier w;ll dissolve in the water and any excess of compounds of Formula I will be thrown out oF solutlon, In an oil-in-water emulsion9 the solvent phase is dispersed in the water phase and the dispersed phase contains the act;ve ingredient. In this way, un;-Form distribution of a water insoluble active ingredient is achieved in an aqueous spray. A solvent carrier in which the new am;noth;o carbamates of Formula I are h;ghly soluble is des;rable so that relatively high concentrations of active ingredient can be obtained. Sometimes, one or more solvent carriers with or without a cosolvent can be used in order to obtain concentrated solutions of the active ingredient, the main consideration being to employ a water-immiscible solvent For the active ingredient that 30 will hold the compound in solution over the range of ~44-,. ~
concentrations useful for applying to insects and mites.
The emulsifiable concentrates of the invention are prepared, therefore, by dissolving the active ingredient and a surfactant in a substantially water-immiscible sol-vent carrier (i.e.~ a solvent carrier which is soluble in water to the extent of less than 2.5% by volume at temperatures of the order of 20 to 30C.), for example, cyclohexanone, methyl propyl ketone, summer oils, ethyl-ene dichloride, aromatic hydrocarbons such as benzene, toluene, and xylene, and high-boiling petroleum hydro-carbons such as kerosene, diesel oil, and the like. If desired, a cosolvent such as methyl ethyl ketone, acetone, isopropanol, and the like can be included with a solvent carrier in order to enhance the solubility of the active ;-ingred~ent. Aqueous emulsions are then prepared by mixing with water to give any desired concentration of active ingredient. The surfactants which can be employed in the aqueous emuls~ons of the invention are those t~ypes noted above. Mixtures of surfactants can be employed, if desired.
Advantageo~sly, the concentratlon of active ingredi-ent in the emulsifiable concentrates can range f~om about 5% to about 50% by weight, preferably from about 10~ to about 40%. A concentrate comprising 20% (by weight) of the compound dissolved in a water-;mmiscible solvent of the kind noted above can be admixed with an aqueous medium in the proportions of 13 ml. of concentrate with one gallon of medium to give a mixture containing 700 parts of active ingredient per million parts of liquid carrier. Similarly, one quart of a 20% concentrate mixed with 40 gallons of water provides about 1200 ppm (parts per million~ of active Q~

ingredient. In the same manner, more concentrated solu-tions of active ingredient can be prepared.
The concentrate formulations of the invention which are intended for use in the form of aqueous dispers;ons of emulsions can also comprise a humectant, that is to ~-say, an agent which will delay the drying of the composi-tion ;n contact with material to which it has been applied.
Suitable humectants include glycerol, diethylene glycol, solubil;zed lignins~ such as calcium ligninsulfonate, and the like.
The granular formulations of this invention are convenient for application to soil when persistence is desired. Granulars are readily applied broadcast or by localized, e.g., in-the-row applications. The indiv;dual granules may be any des;red size from 10 to 60 mesh, advantageously 20 to 40 mesh. Granulars are prepared by d;ssolving the active compound in a solvent such as methyi-ene chloride, xylene, or acetone and applying the solution to a quantity of a granulated absorbent carrier. Represen-tative granulated absorbent carriers include ground corn cobs, ground walnut shells, ground peanut hulls, and the l;ke. If desired, the impregnated granulated absorbent carrier can be coated with a coating that will preserve the integrity of thegranular until it is applied to an object or situs favorable for release of the active ln-gredient.
The rates of appl~cation to insects, mites, soil, or other situs will depend upon~the species of the pest organism to be controlled, the presence or absence of desirable liv;ng organ;sms, temperature cond;t;ons of ~-- .
-~6-, ., ,, , ~ .

~ 9 ~ ~

treatment, and the method and efficiency of application.
In general, insect;cidal and miticidal activity is ob-tained when the compounds are applied at concentrations of about 5 to about 2000 ppmj preferably at concentra-tions of about 30 to about lO00 ppm. For nematodes fromlO to 50 lbs./acre of the active comPound is necessary.
The formulations containing new aminothio carba-ates of Formula I according to the ;nvention, can be applied to insects, mites, nematodes, soil or other situs by conventional methods. For example, an area of soil, a building, or plants can be trea~ed by spraying wettable powder sprayers or from hand-operated knapsack sprayers.
Dips can be used for livestock. Dusts can be applied by power dusters, or by hand-operated dusters. Creams and ~`
ointment formulations can be applied to skin or objects for prolonge~ protection from insects~ or mites.
The active compounds of the invention can also be formulated in relatively dilute proportions ln a dis-persible insecticide carr~er for household applications.
Thus, the active compounds can be formulated in dusts having from about 0~1% to 5.0% active ingredient with deodorized kerosene for aerosol applications.
It will, of course, be appreciated that the con-ditions encountered when applying the method and formu-lations of th;s invention to actua1 practice can varywidely. Included among the variables that may be en-countered are the degree of infestation by pests, the particular pest to be controlled, the particular situs being treated, the type of plants, the prevailing weather conditions, such as temperature, relatiYe humidity, 3~20 rainfall, dews, and so forth.
The compounds of Formula I are effect;v~ pesticides that can be used to control invertebrate pests in agri-culture, industry, and around the home. The compounds have been found to be actiYe against invertebrate an;mals of.ill.ustra.tiYely Class I~secta, for example, order Coleo-ptera, more specifically, the cotton boll weevil (Anthon-omus 3randis Boheman), the confused flour beetle (Tri-bolium confusum Jacquelin deVal~, and the Mexican bean beetle (~E~lachna varivestis Mulsant), order Diptera, .
more specifically3 the housefly (Musca domestica Linnaeus), order Orthoptera, more speci~ically, the house cricket (Acheta dornes~icus Linnaeus), and the German cockroach (Blatella ~ermanica Linnaeus), and order Lepidoptera, more specifically, the Southern armyworm (Prodenia e da a Cramer), and more specifically, the two-spotted spider mite (letranychus urticae Koch).
Efficacy against invertebrate pests has been demon-stra~ed at concentrati.ons of 100~ 500, 75, 40, and even ZO 10 ppm depending upon the specific insect or mite used.
Some invertebrate animal pests will be more sensitive to the compounds than others~ and others might be quite re-sistant.
~11 mortalities in the ta~les are expressed in per cent A further aspect of the invention is compounds of ~ -Formula ~' CH ~ ,~H3 /R2 3 ~ - IClN - SN~R
II `

wherein R2 and R3 are as defined previously ;n this specification. These compounds are prepared in an analogous fashion as the previous compounds within this specification~ that~is, startin~ with the basic Furadan compound, the aminothio derivative is prepared. These compounds are used in the same manner as the previous compounds disc~osed and embodied in this speci~ication.
Below are examples of this aspect of the invention.
Example 13 Using the known compound 2,3-dihydro-2,2-dimethyl- ;
7-benzofuranyl methylcarbamate, the following new amino-th10 carbamate derivatives are prepared:

2,3-D;hydro-2,2-dimethyl-7-benzofuranyl methyl(l-piperi-dinyl~hio)carbamate, m.p. 62-63C.
Analysis _lc'd for: Cl7H24N203S
C, 63.71; H, 7.55; N, 8.74; 5, lO.01 Found: C, 63.75; H, 7.32; W, 8.61; S, 9.87 2,3-Dihydro-2~2-dimethyl-7-benzofura~yl-N-methyl(4-morpho-linylthio)oarbamate, m.p. 80-81C.
A _lysis CdlC 'd for: Cl6H22N204S
C, 56.78; H, 6.55; N, 8.28; S, 9.48 .

9~

Found: C, 5fi.60; H~ 6.84; N, 8.13, S, 9.58 ~ .
2,3~Dihydro-2,2-dimethyl-7-benzofuranyl(dibutylaminothio)-methylcarbamate as an oil.
Analysis Calc'd for: C20H32N203S
C, 63.12; H, 8.48; N, 7.36; S, 8.43 ~ ;
Found C, 62.87; H, 8.71; N, 7.30; S~ 8.69 2,3-Dihydro-2,2-dimethyl-7-benzofuranyl~(diethylamino)-~10 thio]tnethylcarbamate as~an oil.
Analysis Calc'd for: C16H24N203S
C, 59.23; H, 7.46; N, 8.63 Found: C, 59.14; H, 7.21; N, 8.65 This compound, when tested as described in Example 3, gave the follow;ng results: ~"
Insect Rate Mortality SAW 100 ppm 87 HC 1.3 ~g./plate 97 HF 30 ppm 100 BW 10 ppm 100 YFM 0.67 ppm 100 CL 100 ppm 93 ;' 2,3-Dihydro-2,2-d;methyl-7-benzofuranyl(diisopropylam;no-thio)methylcarbamate, m.p. 67-69C.
Analysi _Calc'd for: C,3H28N203S
C, 61.33; H, 8.01; N, 7.95; S, 9.10 Found: C, 61.27; H, 8.15; N, 7.98; S, 9.38 09 8 ~ 3220 It should be noted that all the compound sub-genera and compound species can be formulated into suit-able compositions and used for pesticidal activlty in accordance w;th the specif;cation.
l~ith respect to Example 12~ the aminothio deri-vatives were prepared from the known compound 0-~methyl-carbamoyl]oxime of 2-methyl-1,3-dithiolane-2-carboxalde-hyde by procedures similar to Examples 1 and 2. :

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

Claims (11)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the formula wherein R4, R5 and R6 are the same or different and are selected from the group consisting of hydrogen, alkyl of one to five carbon atoms, inclusive, halogen, alkoxy of one to five carbon atoms, inclusive, alkylthio of one to five carbon atoms, inclusive, dialkylamino with each alkyl the same or different and having one to three carbon atoms, inclusive, and -N=CHNdi-methyl;
R2 and R3 are the same or different and are selected from the group consisting of alkyl of one to six carbon atoms, inclusive; cycloalkyl of three to six carbon atoms, inclusive;

wherein Q and R11 are the same or different and are selected from the group consisting of hydrogen, methyl, and chloro; and wherein D is 1 or 2; and taking R2 and R3 together with the nitrogen atom to which they are attached, form the alkylene ring of four or five ring carbon atoms, wherein R12 is selected from the group consisting of hydrogen and alkyl of one to three carbon atoms, inclusive, and 4-methylpiperazino.
2. A compound in accordance with claim 1 wherein R4 and R5 are hydrogen.
3. A compound in accordance with claim 1 wherein R4 is hydrogen or alkyl of one to five carbon atoms, inclusive, R5 is alkyl of one to five carbon atoms, inclusive, and R6 is selected from the group consisting of hydrogen, halogen, alkylthio of one to five carbon atoms, inclusive, and dialkylamino with each alkyl the same or different and having one to three carbon atoms, inclusive.
4. A compound in accordance with claim 3 wherein R6 is dialkylamino with each alkyl the same or different and having one to three carbon atoms, inclusive.
5. A compound in accordance with claim 3 wherein R6 is alkylthio of one to five carbon atoms, inclusive.
6. A compound in accordance with claim 3 wherein R6 is halogen.
7. A compound in accordance with claim 3 wherein R6 is hydrogen.
8. A compound in accordance with claim 7 wherein R4 is hydrogen.
9. A compound according to claim 7 wherein R4 is alkyl of one to five carbon atoms, inclusive.
10. A method for controlling pests consisting of insects, nematodes and mites which comprises applying to a situs, a pest or a plant a pest-controlling effective amount of a compound of the formula wherein R2, R3, R4, R5 and R6 are defined as in claim 1 in association with a pesticidal carrier.
11. A method of preparing compounds of the formula wherein R2, R3, R4, R5 and R6 are defined as in claim 1 which comprises reacting a compound of the formula with a.
in an organic solvent or b.
in sulfur dichloride and an organic solvent, wherein R2, R3, R4, R5 and R6 are as previously defined.
CA267,127A 1976-01-02 1976-12-03 N-aminothio derivatives of n-methyl carbamates Expired CA1100981A (en)

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