CA1138885A - Acaricidal, insecticidal, and nematocidal phosphorodiamidothioates - Google Patents

Abstract

Abstract of the Disclosure Disclosed are compounds of the formula:

wherein R1 is a hydrogen atom;
an unsubstituted or substituted alkyl group;
an alkynyl group;
an alkenyl group;
an alkyldienyl group;
a cycloalkyl group:
an alkoxycarbonyl group;
an unsubstituted or substituted phenyl group;
an unsubstituted or substituted phenylalkyl group;
R2 is an unsubstituted alkyl group;
R3 is a hydrogen atom, an alkyl group, or an alkenyl group;
R4 is a hydrogen atom, an alkyl group or additionally when R3 and R5 are not taken together to form a heterocycle, an alkenyl group;

- ii -R5is a hydrogen atom;
an unsubstituted or substituted alkyl group;
an alkynyl group;
an alkenyl group;
a cycloalkyl group;
an unsubstituted or substituted phenyl group;
an unsubstituted or substituted phenyl (C1-C5) alkyl group, or R3 and R5 can be taken together to form a heterocyclic ring of the formula wherein Z is a -CH2CH2- group, a -CHCH2CH2- group, or a -CH2CH2CH2CH2- group;
X and X1 are independently an oxygen atom or a sulfur atom;
as well as compositions containing them, and to methods of using them to control certain harmful pests.

Description

~3~

ACARICIDAL, INSECTICIDAL, AND NEMATOCIDAL
PHOSPHORODIAMIDOTHIOATES
The Disclosure This invention relates to novel phosphorodi-amidothioates, to compositions containing them, and to methods of using them to control a variety of harmul pests.
The novel compounds of this invention can be represented by the formula 1 li -~' / NR3R
~P ~I~

wherein ~ is a hydrogen atom;
: 15 an unsubstituted (Cl-Cl2~ alkyl group, preferably (Cl-C6), more preferabty (Cl-C4), most preferably methyl or ethyl;
a (Cl-Cl2) alkyl group, substituted with up to three substituents selected from chloro, bromo, or fluoro, preferabl.y a tCl-C6) group substituted with up to three sub-stituents selected from chloro, bromo, and fluoro, more preferab1.y trifluoromethyl;
a (Cl-Cl2) alkyl group substituted .`, ' .

~1 3~

wi~h one substituent selected from cyano, nitro, ~C~-C61alkoxy, (Cl~C6)alkyl-thio, (Cl-C~) alkylsul~inyl, (Cl-C6) alkylsulfonyl, (Cl~C~) alkylcarbonyl, (Cl-C~ alkoxycarbonyl, (Cl-C6) alkglcarbony].oxy, (Cl-C6) mono- or dialkyLaminocarbonyl, phenoxy, phenylthio, phenyl~ulfinyl, phenylsulf onyl, phenyl-carbonyl, phenoxycarbonyl, phenylcarbonyl-oxy, phenylaminocarbonyl, (C3-C6) alkenyloxycarbanyl, (C3-C6~ alkenyl-carbonylo~y, aminoçarbonyl, and (Cl-C6) alkylcarbqnylamino groups, preferably a ~Cl-C~!alkyl group sub#tituted with one lS substituent selected from cyano, ~itro, ~Cl-C4~alkoxy, (Cl~C4)alkylthior (Cl-C4)alkylsulfinyl, ~Cl-C4)alkyl-sulfonyl, a~etyl, ~Cl-C4)al~o~ycarbonyl, ~Cl-C4) alkylcarbonyloxy ~ ~Cl~:4) mono or dialkylaminocarbonyl, ph~noxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylcarbonyl, phenoxycarbonyl, phenyl-carb~nylo~y, phenyla~inocarbonyl, (C3-C4)alkenyloxycarbonyl, (C3-C4)alkenyl-carbonylo~y, aminocarbonyl, and (Cl-C4)-alkylcarbonylamin~ groups; more pre~erably a (Cl-C4)alkyl gro~p su~stitute~ wi~h one substituent selected from cyano, nitro, ~ethoxy, ~ethylthio, methylsulfinyl, ~ethyl-sulfonyl, acetyl, methoxycarbonyl, ethoxy-carbonyl, methylc~rbcnyloxy, mono- or di-~ethylaminocarbonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenyl-carbonyl, pheno~ycarbanyl, phenylcarbonyl-oxy, pbenylaminocarbonyl, ~C3-C4) ~.3~

alkenyloxycarbonyl, (C3-C4) alkenyl-carbony].oxy, aminocarbonyl, and methyl-carbonylamino groups;
a (C3-Cl2)alkynyl group, preferably (C3-C6), more preferably (C3-C4);
a (C2-Cl2)alkenyl group, preferably (C3-C6), more preferably (C3-C4);
a (C4-C17) alkyldienyl, group;
a (C3-C6)cycloalkyl group;
a (Cl-C6) alkoxycarbonyl group, preferably ( 1 C4), more preferably (Cl-C );
an unsubstituted phenyl group;
an unsubstituted phenyl (Cl-C5) alkyl group preferably phenyl (C~-C3) alkyl, more preferably benzyl;
a phenyl or phenyl (Cl-C5) alkyl group, preferably phenyl (Cl-C3) alkyl, more preferably benzyl substituted w;th up to : three substituents selected ~rom cyano, nitro, halogen, (Cl-C6)alkyl, (Cl-C6)alkoxy, (Cl-C6) alkylthio, (Cl-: C6) alkylsulfinyl, ~Cl-C6) alkylsul-fonyl, phenoxy, (Cl-C6~haloalkyl, tri.-fluoromethyl, (Cl-C6)mono- or dia].kyl-aminocarbonyl, (Cl-C6)alkoxycarbonyl, (Cl-C6) alkylcarbonyl, (Cl-C6}a].kyl-carbonyloxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenyl-: 30 aminocarbonyl, (C3-C6)alkenyloxycarbonyl,(C3-C6)alkenylcarbonyloxy, aminocarbonyl, and (Cl-C6) alkylc~rbonylamino groups;
preferably a phenyl group substituted with : up to three substituents selected from cyano, nitro, methyl, methoxy, phenoxy, ~' .

,~,.,~ 3,,s~

acetoxy, ac~tyl, trifluoromethyl., chloro, fluoro, bromo, methylthio, methylsulfinyl, an~
methylsulfonyl;
~ is a (C2-CO)alkyl group, prefQra~ly (C2-C4), more preerably (C3-C4);
R i3 3 hydro~en atom, a ~Cl-C3) alkyl group, pre~erahly methyl or ethyl, ~ore preferably methyl or a ~C3~C~) alkenyl ~roup, pre~erably propenyl;
R4 is a hydroqen atom, a tCl-C3) alkyl group, prS~ferably ~ethyl or ethyl, ~ore preferably ~ethyl, or additionally when R3 or R5 are not taken together to form a heterocycle, a (C3-Co) alkenyl group, preferably propenyl;
R is a hydrogen a~om; an unsubstituted (Cl-Cl~) alkyl group, preferably ~Cl-C6),~ore : preferably (Cl-C4), most preerably methyl or ethyl;
a ~Cl-C12) al~yl gsoup substituted with one substitutent selected ~rom cyano, ni~rop ~Cl-C6)alksosy, (Cl-C6)alkyl~hio, (C -C6)alkylsulfinyl, (Cl-CO) alkylsulfonyl, (Cl-C~) alkylcarbonyl, (Cl-C6) alkylcarbonylo~y, ~Cl-C6) ~ono- or dialkylaminocarbonyl, phenoxy, phenylthio, pbenyl~ulfinyl, phenylsulfo~yl, : phenylcarbonyl~ phenoxycarbonyl~ phenyl--carbonyloxy, phenylaminocarbonyl, (C3-C~) alkeQylo~ycarbonyl, (C3-C6) alkenyl-carbSonylo~y~ aminocarbonyl, and ~Cl-C6) alkylcarbonylamino groups, preferably a (Cl-C6) al~yl group substituted with one substituent selected from oyano, nitro, (Cl-C4)alkoxy, (Cl-C4)alkylthio, (Cl~C4)alkylsul~inyl, (Cl-C4)alkyl--~s ', . ~ :

.

:, .1 . .

~l.3~

sulfonyl, acetyl, (Cl-C4)a]koxycarbonyl, (Cl-C4)al.kylcarbonyl.oxy, (Cl-C4!mono-or dialkyla~i.nocarbonyl, phenoxy, phenylthi.o, phenylsulfinyl, phenylsulfonyl, phenylcarb-onyl, phenoxycarbonyl, pheny~carbonyloxy, phenylaminocarbonyl, tC3-C~)alkenyl-oxycarbonyl, (C3-C~)alkenyl.carbonyloxy, aminocarbonyl, and (Cl-C4)alkylcarbonyl-amino groups; more preferably a (Cl-C4)-alkyl group substituted with one substituent selected from cyano, nitro, methoxy, methylthio, methylsulfinyl, methylsul-fonyl, acetyl, methoxycarbonyl, ethoxycarbonyl, methylcarbonyloxy, mono- or dimethy~.amino-carbonyl, phenoxy, phenylthio, phenyl-sulfinyl, phenylsulfonyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbony].oxy, phenyl-aminocarbonyl, (C3-C4) alkenytoxycarb-onyl, (C3-C4) alkenyl.carbonyloxy, amino-carbonyl, and methylcarbonylamino groups;
a (C3-C~2)alkynyl group, preferably ~C3-C6), more preferably (C3-C4);
a (C3-C12)alkenyl group, preferably ~C3-C6), more preferably (C3-C4);
a (C3-C6)cycloalkyl group, preferabl.y (C5-C~);
an unsubstituted phenyl group;
:`. an unsubstituted phenyl (Cl-C5) alkyl preferably phenyl (Cl-C3) alkyl; more preferably benzyl;
a phenyl or a phenyl (Cl-C5) alkyl group substituted with up to three substituents :~ selected from cyano, nitro, halogen, (Cl-C6)alk5~1~ (Cl-C6)al.koxy, (Cl-C6) alkyl.thio, (Cl-C6) alkyl.sulfinyl, (Cl-C6) alkylsulfonyl, phenoxy, (Cl-. .

. . .
:;
, .
. , .

C6 ~ haloa l kyl, tr if l uoromethyl, (Cl-C 6 ) mono or dialkylaminocarbonyl, (C~
alkoxycarbonyl, (Cl-C6! alkylcarbonyl, ~Cl-C6)alkylcarbonyloxy, phenylthio, phes~yl~ul~inyl, phenylsulfonyl, benzyl, phenylcarbonyl, phenoxyc:arbonyl, phenyl~
carbonyloxy, p~enylaminocarborlyl, ~C3 C6 ) alkenyloxyear bonyl, (C3-C6 1 alkenyl-carbonyloxy, aminocarbonyl, or (Cl-C6) alkylcarbonylamino groups; pref erably a ~henyl group subs~ituted with up ~o three ~u~stituents selected frolll cyano, nitro, methyl, metho~y, phenoxy, acetoxy, acetyl, triflaorornethyl, chloro, fluoro, bromo, methylthio, methylsulfinyl, and methylsul:Eonyl;
E~ and R can be taken together to ~orm a he~ero-cyclic r~ng of the formula X _ _ -Z _ R~ R4 p, : ~herein Z is a -C~2C~2- group, a -C~2C~2C~2- group, or a -C~2C~2-group, pseferably a -C~2C~2- group, or a 1 2C~2C~ ~ro~p; and X and X are independen~ly an oxygen ato~ or a sulfur atom, pre~erabty an oxygen atom.
As used i~ the s~eci~ication and elai~s, the terms alkyl, alkenyl and alk~nyl are meant to include branched as well as straight ~hain alkyl, alkenyt and alkynyl qroups.
Representa~ive examples of such groups include me'chyt, ethyl, propyl, isopropyl, e~c-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, allyl, 2-~utenyl, 3 methyl-l-pentenyl, 3-h~xenyl, propynyl, l-pentynyl, 4-methyl-l-pentynyl, hexynyl, and the 1ike.

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

,: .

3y a 3ubstituted phenyl, as used in the specification and claims, is meant aphenyl group substitu~ed wi~h one or more, bu~ preferably with one to three, suhsti~uents sele~ted ~rom cyano, nitro, halogen, alkyl, alkoxy, alkylthio, alkylsulfi~yl, alkylsulfonyl, phenoxy, halo-alkyl, ~ri1uoromethyl, mono- or dialkylaminocarbonyl, alkoxycarbonyl, alkylcarbonyl, alkylcarbonyloxy, phenyl-thlo, phen~lsulfnyl, phenylsul~onyl, benzyl, phenyl-ear~onyl, ph~noxycarbonyl, phenylcarbonylo~y, phenyl-amanocarbcnyl, alkenylo~ycarbonyl, alkenyl carbonyloxy,aminocarbonyl and alkylcarbonyla~ino and the like, wherein each alkyl $oiety i5 s~raight or branched chain and co~tain~ ~r~m ~ to 6, preferably from 1 to 4, more preferably 1 or 2 carbon atoms.
By a ~ubstituted alkyl group as u~ed in the ~pecificatio~ and claims i5 meant a (Cl-C12) alkyl ~roup, preferably (Cl-C6), more preferably tCl^C~, substituted with up to three substi~uents selected from halegen; or one substituent selected from ~yano, ni~ro, alkoxy, alkylth~o, alkylsulfinyl, alkylsulfonyl, alkyl~-carbonyl, ~lkoxycarbonyl, alkylcarbonyloxy, mo~o- or dlalkylamino~arbonyl, alkylcarbonylamino, and the like, ~herein each alkyl moiety is strai~ht or branched chain, and contains from 1 to 6, pre~erably from 1 to 4, ~ore preferahly I ~ 2, ~o t preferably 1 carbon ato~(s), alkenylo~ycarbonyl and alkenyl carbonylo~y wherein the alkenyl iety contains from 3 to 6 preferably from 3 to 4 carbon atoms; and phenoxy, phenyl~chio, phenylsulf inyl, phenyl~ulfenyl, ph~nylcarbonyl, phenyloxycarbonyl, 30 phen~lcarb~nylo~y, phenyla~inocarbon~l, and the like, wherein the phenyl is op~ionally ~ubstituted (but preferably unsubstituted) with sub~ti~uents such as defined : above for ~ubstituted phenyl; and aminocarbonyl.
By an alkenyl group, as used in the specif ication and ~; 35 clai~s, is ~eant an alkenyl group such as an allyl group, '"
:, .,~ .
`:~

or the like, with one cis or trans doub~e bond, or a s~yryl group.
By an alkynyl group, as used in the speci~ication and clai~s, is meant an alkynyl group, such as a propargyl S grou~, wi~h one triple bond.
By a substituted phenylalkyl group i~ meant an phe~ylalkyl group e.g., benzyl, phenethyl~ 3-phenyl-1-methyl~ropyl, etc., the aromatic rin~ of which i~
substituted with one or more, but preferably with one to three sub~ituents selected ~rom the group of substituents deined for subs~ituted phenyl above.
By a~ alkyldienyl, as used in the specif ication and clains, i3 aleaslt a diene such as 2,4-pentadienyl group with either cis or trans double bonds which can be either con~ugated ar isolated.
~y an acyl group as used in the ~pecification and clai~s is mean~ a group of the formula RCtX) whereln R i~ a hydrogen atom or an organic group and X is an oxygen or sulfur atom.
~y a ~B~ ring as used in the specification ~nd claims is meant the ben~ene ring of the fused benzene and pyridine ring system of ~uinc~line or isoquinoline.
The ~ost preferred compounds o~ thi~ invention possess e~pecially enhanGed nematocidal, acaricidal, ~ungicidal and ar~hropodicidal, particularIy nematocidal, acaricidal and insecticidal activity. They can be represented by the for~ula:.
X _" R
Rl-C-N \ ~X4 ~II) Xl~ SR2 wherein Rl i~ ~ hydrogen atom, methyl group, ethyl group, .` methoxymethyl group, a cyclopropyl group or a trifluoromethyl group;

.~.3~

R is a (C3-C~)alkyl group;
R4 i a methyl group;
R5 i a hydrogen atom, a me~hyl or ethyl group, preferably methyl; and X and Xl are independently a sulfur or an oxygen atom, preferably oxygen.
Particular preferred compou~ds have the ~ollowing formulas:

\ p /
\ SC~C~2C~3 ~3 S ~ C~3 ~-C-N \ ~ C~
0~ \SC~ 2C~3 c~3 / C~2CE[3 H-C-N \ ~ ~Ca3 ,. o~ ~ SC~C~2C~3 ~3 C~ -C N ~ 3 ~C~

0'7 ` SCI~C~2C~3 C~3 , .

O C~3 C~3 ~-N / / N~CH3 o~ ~ SC~C~2C~3 C~3 O / C~3 C~3oc~vc-~ \ ~ N~ca3 a~ ~ s IC~ 2C~13 - C~3 ~ C-N / 3 p ~ ~C~3 o ~ \ 3~C~C~3 c~3 / p / ~C~3 0~ \ SC~CEI
C~3 Typical ~ample~ o~ c~mpounds within the scope of this in~n~ion include the ~ollowing:
~-Ethyl ~'-methyl ~-methylcarbonyl S~ methylpropyl~
phosphorodiæmidothioate N-~e~yl ~-hexylcarb~nyl ~ '-dimethyl S-propyl pho~phor~diamidothioate N-~ydrogen~ar~onyl N,N'-di~ethyl S-ethyl pho~phorodiamidothioate N,N'-Diethyl N ethylearbonyl S (2-~ethylpropyl) : phosphorodiamid~thioate N-Ethylcarbonyl N,~'-dimethyl S-(l-methylethyl) ~3~

phosphorodiamidothioate N,N'-giethyl N~hydrogencarbonYl S-propyl phosphorodiamidothioate N-~ydrogenoarbonyl N,N'-dipropyl S-(l-~ethyl-5propyl) phosphorodiamidothioate S-Butyl ~',N'-diethyl ~-methylcarbonyl N-~propyl phosphorodiamidothioate N-Dcdecylcarbonyl ~,N'-dimethyl S-propyl phosphoro-aiamidothioate la ~-Chloro~ethylcarbonyl ~,N'-diethyl S-(l methylpropyl) phosphor~diamidothioate ~-~ydrogencarbonyl ~ '-dimethyl S-hexyl N-propyl phosphorodiamidothioate N~ydrogencarbonyl S-hexyl N',N'-dimethyl N-(3-15methyl~ul~onylpropyl) phosphorodiamidothloate N',N'-Diothy~ ~-methylcarbonyl S-~2-methylpropyl) N-(2--propenyl)phc~phorodiamidothioate ~-~2-Cyanoethyl) S;-ethyl N-e~hylcarbonyl N',~'-di~ethyl phospharodiamidothioate N-(2-3u~ynyl) N-hydrogencarbonyl N',~'-dim~thyl S-propyl phosphorodiamidothioate : N-~2-Metha~yethyl) ~ '-dime~hyl ~-methylcarbonyl S-propyl pho~phorcdiamidothioate ~ ',S-Triethyl N-hydrogencarbonyl N-(2-methyl-25thio~thyl) phosphorodiamidothioate ~-(2-~thoxycarbonylethyl) N'-ethyl N-hydrogencarbonyl S~2-~ethylbutyl)phosphorcdiamidothioate ~-Cyclohe2yl N',N',S-triethyl N-methylcarbonyl phosphorodiamidothioate Y-(2-Propenylcarbonyl) N,N',N',S-tetrapropyl phosphorod~amidothioate N-(3-Dcdecenyl)carbonyl N',N'-diethyl S-pentyl N-propyl phosphorodiamido~hioate S-~exyl N-(2-hexenylcarbonyl) N',N',N-trimethyl 35phosphorodia~idothioate ~l3~

N,N'-Diethyl N-(2-propynylcarbonyl) S-propyl pho~phorodlamidothioate S-~utyl N-(3-hexynyl)carbonyl N-pentyl N',N'-dipropy phosphorodiamidothioate N-Cyclopropylcarbonyl N,S-diethyl ~'tN'-dimethyl phosphorodiamidothioate _-Cyclohexylcarbonyl ~,N'-di~iethyl S-pentyl pho~phorodiamidothioate N,~'-Diethyl ~-ph~nylcarbonyl S-propyl pho~phorodia~iidothioate ~-~e~zylcarbonyl ~,N',5-tripropyl pho~phorodia~idothioate S-B~hyl N,N'-dimethyl ~-(5-phenylpentyl!car,bonyl pho~phorodiamidothioate N,N'-D~methyl S~ methylpropyl) N-~4-nitrophienyl)carbqnyl pho~ph~rodiamidothioate N-Dodoicylthiocarb~nyl N,~'-diethy~ S-propy~
phosphorodiamidothioate ~-~e~ylthiocarbonyl N,N'-dimethyl S-propyl phosphor~diamidothioate N-~(2-~thoxycarhonylpropyl)carbonyll N,N'-dimethyl S-(l-methylpropyL) phosphorodiamidothioate ~tN'~Diethyl ~-(2-methoxyethylcarbanyl) S-propyl phosphorodiamidothioate ~-~ydrogenthio~arb~nyl N~N'-dimethyl S-(l-methyl-propyl) phosphorodiamidothioate ~,N'-Di~ethyl S(l-methylpropyl) N-trifluoromethylthio-'. carbo~yl phosphorodi~midothioate 30 ~,~'-Dimethyl ~-methylthiocarbonyl S-propyl phosphoro-diamidothioate N,N'-Dimethyl S-propyl N-propylthiocarbonyl phosphoro-diamido~hioate N-Methylthiome~hylthiocarbonyl N,~',S-triproeyl phos-phorodiamidothioate .;

N-Cyanomethylcarbonyl N,N'-~imethyl S-(l-methylpropyl) phosphorodiamidodithioate ~-(4-~itrophenylcarbonyl) N,N',S-tripropyl phospharodi-amidod ithioate S ~-~exyloarb~nyl ~,N'-dimethyl S-(2-methylpropyl) phos-phor~diamidodithioate ~-Cyclopropylcarbonyl N,N'-dimethyl S-(l~-methylpentyl) phosphoroaiamidodithioate ~ (1,2-Ethanediyl) N-hydrogencarbonyl S~ methyl-propyl~phosphorodiamidothiaate ~,N'-(1,2-Ethanediyl) ~-methylc~rbonyl S~ methylethyl) p~osphorodia~idothioate ~-Chloromethylcarbonyl N,~'-(1,2-propanediyl) S-propyl pho~ph~r~diamidothioate 5 S-E~hyl N metho~ymethylc~rbonyl N-(1,3~propanediyl) pho~pharcdia~idothioate N-~ydrogencarbonyl N,N'-(1,3-propanediyl) S-propyl phos-~harodiamidothioate The c~mpounds o~ the present invention can be prepared

2~ by a.variety of methads.
One method involves acylation of an N,N'-di- or tri-~ubstituted S-alkyl phosphorodiamidothioate. For e~ample:

~3~8~

O O
Il il H-C o~C CH3 X1 O

R3R N-P-NHR5 R -C o C~R Xl SR 3 4 1l 5 R R -N-P - N-R
R ~ H SR C-R

AlC13+R -C-Cl xl ~ R3R4-N-$ - N-R5 R~ H SR C-R-wherein R1, R2, R3, R4 and R5 are as de:Eined for Formu 1 a I.
Another method where RJ a ~ or unsubsti.tuted alkyl involves the hydrolysis of a formamidine. The general reaction can be represented by the following equation:

X ~ N=C-N 3 4 +

o ~ \ SR ~2 I / R
H-C-N \ / SR2 -~ other products ~ \ 3 4 A third method of preparation, when Rl ~ hydrogen, involves the reaction of acyl halides with substituted or unsubstituted pyridines and the appropriate phosphorodi-.~3~

- l5 ~
amidothioate. The reaction proceeds through the inter-mediacy of an N-acylpyridinium salt. The general reaction can be represented by the foltowing equation:

Rl ~ R7 ~ R7 ~ ~ y~ +

RlJ~O
xl 1 R Xl NR3R4 R8 'l¦ ,NR3R4 R ~5 \ SR2 R

~5 . HY
wherein ;~ Rl, R2, R3, R4, R5 and X are as defined for Formula I and ~6 and R7 are hydrogen, or together form the "B"
lS ring of quinoline;
R7 and R8 together form the "B" ring of iso-quinoline; or i R8 is hydrogen, amino, mono or di(Cl-C6)alkyl-amino, or a nitrogen containing tC2-C6) heterocyclic ring bonaed at N; when R is not . a member of the B ring of isoquinoline; and Y is chlorine or bromine.
This aspect of the invention is more fully described in 25 Canadian Paten-t Application No. 365,749, Ollinger et al, filed November 28, 1980.
: The N'-mono- or di-alkyt. ~-alkyl or subs~i.tuted alkyl.
S-alkyl phosphorodiamidothioate intermediates can be prepared in one or two steps by the reaction of an S-a].kyl ~ 30 phosphorodichloridothioate with monoalkyl or dialkyl ami.nes.
: When the two amine groups are different, the S-alkyl ~ phosphorodichloridothioate is reacted with one of the amine .'' .
,, . ~

groups to form a monochloride intermediate. The second amine grouE3 i3 then added~
O O
C12--P--SR2 ~ F~3R4NE~ ~ R3R4N--P-SR2 ~ EECl O O
~3R4~ P--SR2 ~ ~5~ 3R4~--p_SR ~ ~ICl Cl ~5 When R3 alld R5 are the same (Cl-C3) monoalkyl, the inter~ediates are formed by adding two moles of amine to ~he S-alkyl pho~phoro2 ichlor idoth ioate .
O O
::12-P--SR~ ~ 2R5~2~ R5EIN--P--N~R5 ~ 2~C~
SR
The a~o~e reactions are pref erably carried out in~the p~e~ence of an aci~ binding reagent, ~uch as a dialkyl-aniline, pyridine or trialkyl amine. Two additional moles of R5~2 may serve a~ ~he acid bind Lng agen~ when R N~2 i9 the rea~tant.
~or prepara~ion of both intermediate and acyl phos-phorodiamidothioates, generally a substantially equimolarratio of reactants is pre~erred. While not required, ~he reaction i~ advan~a~eously carried out in the pre2ence of an inert organic so~ven~ such as an ether, aromatic hydrocarbon, halo~enated aromatic hydrocarbon, aliphatic hydrocarbon, alipha~ic nitrile, nitroalkyl or nitroaryl and the like, or mixtures thereof. Suitable solvents include, for example, ethyl eth~r, dioxane, methylene chloride, tetrahydrofuran, benzene, toluene, chlorobenzene, heptane, acetonitrile, nitromet~ane, nitrobenzene and the like. The rea~tion is generally conducted in a tempera~ure range of about -10C to 100~C or more, and preferably in the range of about 0 to about 60~C.
All of the starting materials used in the preparation of the compounds of this Lnvention are know~ compounds, are readily prepared by adap~ions of known routes or are herein de cribed. ~or e~ample, the ~ormamidine starting materials a~ prepared by condensa~ion of an aniline with an N-alkyl formamide. (~.S. Pate~t No. 3,502,720, 3elgian Patent No.
771,792, South African Patent No. 732,129.) ~he ~ollowing e~amples are given by way o~
illu~tration, and are not to ~e considered as limitations o~ ~he prese~t i~ention.
~ample 1) -~e~b= ' ERC SS ~e~hy}amine is bubbled into an i~e-cooled ~olution o S~ methy.l.propyl) phosphorodichloridothioate 11 g (0.054 mole), in 50 ml of ~etrahydro~uran (TEF~. The reaction is stirred 1~2 hour at room ~emperature, diluted with 200 ml o~ ether, filtered to remove the methylamine hydro::hloride, and evaporated to give 10 g (94~ of theory) Oe product a an orange oil.
}5xampte 2) ~

~ce~s methylEmine is bubbled into a solution of S-(2-~e~hylpropyl) pbosphorodichloridothioate, 50 g (0.2~
mole), in 300 ml o~ ether. The reaction is s~irred 2-1/2 hrs. at rocm ~emperature and f ilt~red. The e~her solution i~ ~ashed with 100 ~1 of wa~er, dried o~er 4A ~ole~ular ~ie~es, aNd evapora ed to an oil. The water wash is ~a~urated with sodium chloride and extracted ~th ether.
o This ether solution i~ dried o~er 4A molecular sieves and dried to an oil. The two oils~are combined, yiel~ing 41 g.
(85~ o~ theory).
The foll~wing intermediates are prepared in an analogous manner.
E~ample 3) ~ iethyl S-propyl phosphorodiamido-thioate E~ample 4) - N,~'-Diethyl S~ ethylpropyl) phosphorodiamidothioate .~3~

~ample 5) - S~ Me~hylpropyl) N,N'-(2-propenyl) pho~phorodiamido~hioate 1~2sample 6) - S- (l~lethylpropyl) N,N' -dipropyl pho~phorod iasnidoth ioate 5 ~a~pl~ Dimethyl S~ methylethyl)pho~phorodi-amidoth iaate i~sample 8) - ~ ~pyl) ~hc~Phorodiæ~idothioate A solution of d~m~thylamine, 5.8 g (0.13 mQle), and 10 triethylamine, 13.0 g. (0.13 mole), in 100 ml of TEF is added drop~ise to an ice-cooled solutio~ of S~ methyl-propyl) ~hosphorodichloriaothioate, 27 g. (0.13 mole), in 20U ml of T9F. The reac~ion is s~irred 1 hour at room te~perature. A ~olution of methylaminel 3~96 g. ~0.13 15 mole), and tri~thyl~mine, 13~0 9. ~0.13 mole), i5 adde`d at ic~-bath temperature. The reaction i5 stirred 2 hour~ at roGm temperature and stands overnight. The triethylamine hydrochloride i~ filtered and th~ T~F is evaporated.
Ether, lSO ml, and hexane, 100 ml are added, precipita~ing 2n ~ore ~riethylamine hydrochloride. The suspension is filtered through"Super-Cel"and the solvents are evaporated to give 26 g. (9S~ of theory) of oil.
~ample 9 1~ prepared in an analogous ~a~ner.
~xample 9) -diamidothioate ~ample 10) ~ N-~y~roqencarbonyl_~L~-dimethyl 5 m ~
Formic acia, 10 ml, and ace~iG anhydride, 20 ~1, are mi~ed at room ~eMperature and heated at 50 for 15 minutes, then rec~oled in ice. A solution of ~,N'-dimethyl S-ethylpropyl) phosphorodiamidothioate, 39.2 ~. (0.2 ~ole~, and 0'5 ml of 85% phosphoric acid in 30 ml of methylene ~hloride are added. The solution is warmed to 3S room temperature and s~irred 6 days at room temperature.

*Trademark for a type of diatomaceous earth ~ilter aid, specially processed to provide rapid filtration.

One half o~ ~he mixture is diluted in 100 ml of C~2C12 and extracted ~i~h three 100 ml portions of water. The methylene chloride is dried over 4A molecular ~ieves, filtered, and evaporated to give 12 9. (SO~ yield) of S product as an oil.
The foll~wing compounds are prepared in a manner analogous to ~xa~ple 10.
k~a~ple 11) ~ ydrogencarbonyl ~,N',N' tri~ethyl S~ methylpropyl) phosphorodiamidothioate 0 ~xample 12) ~ ydro~encarbanyl ~ di~lethyl S (2-~ethylpropyl) pho~phor~diamidothioate ~sa~ple 13) - ~-Hydroqencarbonyl N,N'-di~ethyl S-propy p~sphorcdiamidothioate ~3a~ple 14) ~ ydroge~carbonyl N,N'-di(2-propenyl) S-(l methylpropyl) phosphorodiamidothioate E~a~ple 15) ~ ~,N'-~iethyl N-hydrogencarbonyl S-~l-~ethylpropyl) phosphoroaiamidothioa~e E~ample 16) - N,N'-Di~thyl N-hydrogenoarbonyl S-propyl phosphorodiamidothioa~e ~ample 17) - N-aydrogencarbonyl N,N',N' trimethyl S-propyl phosphorodiamidothioate ~ple 18) - N-~ydrogen~arbonyl N,N'-dimethyl S-~ ethylethyl) phosphorodiamidothioate E~ample 19) ~ ydrogencarbonyl ~,N'-di~ethyl S-13-~ethylbutyl) pbosphorodiamidothioate E~ample 20) - S-Ethyl ~-~ydroqen~arbonyl ~,N'-dimethyl pbosphorodiamidothioate E~ample 21) - -EthYl N h~dro~encargonyl_N'-methyl_S~

~thyl ~'-methyl N-r ~4-methylphenylimino)methyl]
S-(l-methylpropyl) phosphorodiamido~hioate is hydrolyzed as 5% active ingredient on Celatom ~P-78"granular, which has a p~ of 5 and contains 3% water, over two to six weeks. The organic compounds are e~tracted by ctirring 20a 9. of the 5~ Celatom granular in 1200 ml of toluene for 3 mins. The *Trademark for a type of diatomaceous earth.
**Trademark, - 2~ -soLvent is iltered through"Super-Cel'`and evapora~ed to ~ive 6O7 g of oil. The product is isolated and purified by preparative li~uid chromatography used two"PrepPak-500"*
5ilica g~l column~ in ~eries and a mobile phase of 90 ethyl acetate/10 isooctane at a flow rate of 250 ml/min.
Recovery o~ product is 2.9 g.
; Example 2~A) -~th~l~ro~vl) ohos~horodiamidothloate ~,N'-D~ethyl 5~ ethylpropyl) phosphorodiamido-thioate, 7.1 g. ~0.036 mole), acetio anhydri.de, 7.4~ 9.
~0.073 mole), and 0.1 ml of 85~ phosphoric acid are heated for g hours at reflu~ ~n 10 ml of methylene chloride. The ~i2ture is extracted with two 50 ~1 portions of water, dxied with 4~ molec~lar ~ieve~, and evaporated to gi~e 7 g.
of oil. The product is puri~ied by column chr~matograpby on 20 g. o~ Biosil A. Blution with toluene ~3xlO0 ml por~ions) a~d 1~1 ether hexane (2S0 ml) gives 0.7 g. (8 yield) oE product a3 an oil.
E2ample ~2~
~ethylpropYl) Phosph-orodiamidothioate Aluminum chloride, 7.0 g. (0.052 moles), Is dissolved in 30 ~1. of nitrome~hane whi~h has been dried o~er 4A
~olecular ~ie~e~. The reaction exotherms to 35, and is cooled to room temperature. Acetyl chlar ide, 3 . 8 ml .
~0.052 ~ole), is added and the reaction i~ stirred 10 min.
a~ room temperat~tre. A solution of N~ dimethyl S (l-~ethylpropyl) phosphoroaiamiaothioate, 5 9 (0.026 ~ole), in 20 ml. of nitromethan2 is added and stirring is continued for 8 hr. at room temperature. After standing ~0 overnight, the raactic)n is diluted wi~h 100 ml. of ether, estracted with 50 of water, then 5~ 50dium bioarbcnate solution. Tbe ~ther layer is dried over 4A molecular sie~es, filtered~ and evaporated to yield 2. 6 g O ~40% of theory) o} product as a yell~w oil.

*Trademark.
**Trademark .

~L~3~ 3~i E~ample 2 b thioate N,~'-Dimethyl S~ methylpropyl) phosphorodiamido-tbioate, 15 g ~0.08 ~ole), trifluoroacetic anhydride, 25.2 g (0~12 ~ole) 0.2 ~1 of 85~ a3PO4 and 20 ml of ~hylene chlorid~ are ~eated 7 hours at reflux. The re~ction is sxtrac~ed with 100 ml of water, dried over 4A
lecular sieves, hea~ed, and e~aporated to glve 19.2 9 of 10 oil. Puriicatlan of 10 g. of ma~erial by preparative high pressure li~uid ohromato~raphy using ~wo PrepPak 500 silica gel columns in series and a mobile phase of 70 ethyl acl3tate/30 i~ooc~ane gives 2 g of product.
E2ample 24 A solution of N,Nt-dimethyl S~ methylpropyl) ~hosphorodlamidothloate, 10.6 g. (0.054 ~oLe), and pyridiner 4.3 9. (O.a54 mole) t in 40 ml of ~oluene i3 added to an ice-o~oled solution of decanoyl chlor ide, 10.3 g.
20 (0.054 mole), in 50 ml o~ ~oluene. A white solid fo~med after a fe~ mi~ut~s. The suspension is stirred 4 days at ambi~nt temperature. ~t is extracted se~uen~ially with 250 ml o~ 5~ sodium bicarbonate and 2~ hydrochloric acid. ~be organic layer is dried with 4~ molecular sie~es, evaporated to give 15 g. o yellcw oil. Chromatography on 60 g. of Bio~il A (elution with 10% ether in toluenel gives 3 g.
(11S yield) o product. E~) A solution of N,~'-d~methyl S~ ethylpropyl) phosphor~diamidothiaate, 5~3 g. (0.026 mole), and 4-pyrrolidino~yridine, 3.80 g.
30 ~û. 026 illole~, in 2û ml of toluene is ad2ed dropwise over 10 min. to an ice-cooled solution of decanoyl chloride, 5.13 g. (0.026 mcle), in 25 ml of toluene, maintaining a temperature of 10-13~C, for 1/2 hr. after completion of addition. The reaction is stirred 24 hrs., diluted witb 35 100 ml of ether, filtered, and evaporated to give 8.4 g. of ~.3~

crude produc~. ~he spectral data (nmr and ir3 were similar to those of ~ethod A.
The following e~amples are prepared in a manner analogous to 24~.
~xample 25) - ~,N'-~imethyl S~ methylpropyl) N-(4-nitrophenyl) carbonyl phosphorodiamldo-thioat~
}5~ample 26~ -t (2~etho~carbonyl) ethyl carbonyl~
di~ethyl S-tl ~ethylpropyl) phosphoro-diamidothioate E~ample 27) - ~-Methoxymethylcarbonyl ~,N'-dimethyl S-ethylpropyl) phosphorodiamidothloate ~ample 28 ) - ~-D i ~h loromethy lcar bonyl N,~'-dimethyl S
~ ethylpropyl) phosphorodiamidothioate ~xample 29) - N~ Bro~oethyl)carbonyl] N',~'-dimethyl S~ methylpropyl~ phospborodiamidothioate E~ample 30) - N~ Chloroethyl)carbonyl] ~,N'-dimethyl - S-(l-methylpropyl) phosphorodiamidothioate Example 31) - ~,N'-~imethyl S-(l-methylpropyl) N-phenyl-c~rbonyl phosphorodiamidothioate Example 32) - N,N'-Dimethyl S tl-methylpropyl) N-t(~-ph~nyle~hylene) carbonyl] phosphoro-dia~idothioate Æxample 33) - ~-Chloromethyl carbonyl N,~'-dimethyl ~5 S-(l-methyl-propyl) phosphorodiamidotbioate Example 34) - ~-Bromomethylcarbonyl N~'-dimethyl S-ethylpropyl) phosphorodiamidothioate ~sample 35) N- r ( E~hoxycar bony lmethy 1 ) car bonyl] N,N'-dimethyl S~ methylpropyl) phosphoro-diamidothioate Example 36) ~ N-CyclopropylGarbonyl ~,~'-dimethyl S-(l-methylpropyl) phosphorodiamidothioate Example 37) - ~ (MethosYcarbonyl)carbonYl N,N'-dimethYl S~ ethyl~rop~ hosphorodiamidothioate A solution of ,~'-dimethyl S-(l-methylpropyl) phosphorodiamido~hioa~e, lO g. tO.051 mo.l.es), and pyridine, .1 g. (0.10~ moles), in 50 ml o~ toluene is added dropwise to an ice-coaled s~lut~on o methyl oxalyl chloride, 12.5 g. (0.102 m~le~), in 50 ml. o~ toluene. The mixture i5 stlrred 48 hr. at room temperature, filtered to remove the pyridine hydrochloride, and e~aporated. The residual oil is diluted with 2ao ml of ether, precipitating additional pyridine hydrochlorid~, ~iltered, and evaporated to give 11 g. of oil~ Purification by preparative high pressure liquid chromatography using one PrepPak 500 silica gel colu~n and a mobile phase of ethyl aceta~e gives 2.0 g.
l14% of theor~) of product.
The following examples are prepared in an analoyous manner.
Example 3~) - N (3-Chloropropyl)carbonyl N,~'-dimethyl S-(l m~thylpropyl) phosphorodiamidothioate Ex~mple ~9) ~ a,ll-~eptadeca~ienyl)carbonyl Nr~'-di-methyl S (l-methylpropyl) pho~phorodia~ido-thioate : 20 Example 40) - N,N'-D~ethyl ~ propenecarbonyl) S-tl-~ethylpropyl) phosphorodiamidothioate ~ample 41) - W,N'-Di~e~hyl N-(phe~yl~ethyl)carbonyl S
(l-methylpropyl) phosphorodiamidothioate B~ple ~2) - N-(4-Chlorophenyl)carbonyl ~,N'-di~ethyl S-(l-~ethylpropyl) pho~phorodiamidothioate ~xample 43) - N-(2,4-Dichlorophenyl)carbonyl R,N'-dimethyl S-(l-methylpropyl) phosphoro-diamidothioate ~xample 44) - N-Cyclohexylcarbor~yl ~,N'-dimethyl S~
methylpropyl) phosphorodiamidothioate Example 45) - ~,N'-Dimethyl S-tl-methylpropyl) N-(pheno~ymethyl)carbonyl phosphoro-' diamidothioate E~ample 46) - ~-(2-Bromoethyl) N,N'-dimethyl S-~l-methyl-propyl) phosphorodiamidothioate ~3~

~ample 47) - ~-~enthiocarbonyl N~N'-dimethvl S-Pho~phorus pen~asulfide, 17.8 g. (0.08 moles~ is added to a ~olution of N-hydrogencarbonyl N,N'-dimethyl S S~ methylpropyl) phosphorodiamidothioate in Z00 ml. of pyridin~. The reaction exotherms to 5SC. Ater ~tirring 24 br. at room temperature the mixture is diluted with 300 ml. o~ ether and ~ ered through a 5 g. of ~iosil A"
~v~poeation of th~ solvent gives 3.1 g. oE oil.
P~rifica~ion by high pr~ssure liquid chromatography using one'PrepPak 500"~ilica gel column and a mobile phase of 70/30 ethyl acetate/i~ooctane gives 3 g. of product ~25% of theory).
~a~ple 48) - N-~dro~encarbonyl N,N'-Dimethyl S~
A~etio anhydride, 1.76 g. (~.017 ~ole), i9 added to a ~olution of N,N'-di~ethyl S~ methylpropyl) phospboro-dia~idothioate, 3.0 g. (0.014 moles) and formic acid, 0.69 g. (0.015 ~oles?, in 20 ml. of ~hylene chlorLde. After 7 aays at room te~perature, l.76 g. o~ acetic anhydride and 0~69 g. of formic acid are added. A~ter a~ additional 3 days at room te~perature the reac~ion ~ixture is ~oncen-trat~d, dil~ted with 50 ml o~ chloroform, extra~ted with thre~ 20 ml portion3 of 5% sodium bicarbona~e, aried over 4A mole~ular 3ieve, fil~ered, a~d evaporated to gi~e 2.8 g.
(83~ o~ theory) of product. The following example is prepared in an analogous man~er.
Exa~ple 49) - ~- ydrogencarbonyl ~IN'-dimethyl S-propyl phosphorod iamidod ithioate ~!.3~

TABLE I
Elemental Analysis E1emental Anal~sis Calc~.(Found) Ex. Emp. Formula C H N
1 C6H17N2 36.73(36.43) 8.67(9.02) 14.28(l4.09) 2 C6H17N2 36.73(36.32) 8.67(8.83) ]4.28(l4.04~

3 C7H19 2 39.98(39.4]~ 9.10(9.35) 13.32(12.77)

4 not avai1ab1e not avaiLable 10 6 not available 7 C5H15N2 32.96(32.61) 8.24(8.23) 15.38(15.40!
8 C8H1g 20 43.24(41.00) 8.55(8.65) 12.61(10.10) 9 not available 10 C7H19N22PS 37.50(38.21) 7.58(7.93) 12.50(12.52) 11 C8H17N2 2 40.33(40.98) 7.98(8.65) 11.76(10.05) 12 C7H17N2O2P 37.50(37=30) 7.58(7.94) 12.50(12.50) 13 C6H15N22 34.28(34.83) 7.19(7.51) 13.33(13.53) 14 C1~H21N2O2P 47.82(46.11) 7.60(7.63) lO.'L4(lO.08) C9H2LN2O2PS 42.85(41.81) 8.33(8.41) 11.L1(l1.92) 16 C8H19N2PS 40.33(39.66) 7.98(8.25) 11.76(10.82) 17 C7H17N2O2P 37.50(35.55) 7.58(7.60! 12.50~12.89) 18 C6~11s~2O2PS 34.28(35.05) 7.19(7.19) 13.33(l4.55) 19 C8H1gN2O 40.33(40.79) 7.98(8.50) 1].76(l].94) C5H13N22 30.76(31.04) 6.66(6.65) 14.35(l4.08) 21 C8H19N22PS 40.33(40.38) 7.98(8.12) 11.76(11.94) 22 C8H1g 2 2 40.33(39.52) 7.98(8.61) ll.76(11.98) 23 C8HlzF3N2o2p 32.87(31.98) 5.47(5.34) 9.58(9.60) 24 Cl6H25N2o2p 56.47(55.44) 7.35(7.97) 8.23(10.42) C13N20N3o4 45.21(45.34) 5.79(5.94) 12.17(12.19) 26 C11H23N24 39.05(38.43) 6.80(6.08) 8.23(10.81) 27 C9~21N23 40.29(40.59) 7.83(7.90) 10.~L4(9.84) 28 C8H17N2C~22 3l.27(32.10) 5.58(5.40) 9.]2(8.40) 29 C9H20 2 2 32.62(36.00) 6.04(6.98) 8.46(8.97 C9H20N2C12 37.69(40.27) 6.98(7.33) 9.77~11.44 31 C13 21 2 2 52.00(56.58) 7.05(7.23) 9.32(9.74) 32 Cl5H23N2o2p 55.21(55.42) 7.10(7.64) 8.58(8.41) 3~3~

TABLE I (continued) Elemental Analyses Elemental Analysis Calcd.tFound) Ex. Emp. Formula _ C H N
33 C8H18 2 2 35.33(35.21) 6.65(6.85) lO.28(9.8]) 34 C8Hl8BrN202PS 30.29(30.54) 5.71~(6.l7) 8.83(8.79) 35 CllH23N24 42~58(42.35) 7.47(7.64) 9.03(9.21) 36 CloH21N22 45.45(45.27) 8.01(8.lS) 10.59(10.49) 37 C9HI9N24 38.30(33.15) 6.78(6.21) 9.92(10.72) 38 ClOH22c 2 2 39.93(39.92) 7.37(7.74) 9.31(9.63) 39 C24H47N22 62.88(62.32) 10.26(lO.79~ 6.lO(6.31) 40 CloH21N22 45.45(46.18) 8.01(8.10) 10.60(10.40) 41 Cl9H23N22PS 53.50(53.79) 7.37(7-59) 8.91(8.77) 42 C13H20N2clo2 46.59(45.78) 6.02(5.94) 8.37(7.87) 43 C~3Hlgcl~N2o2ps 42.28(42.65) 5.1~(7.79) 7.59(]0.48) 44 Cl3H27N2o2p 50.98(50.24) 8.88(9.27) 9.l4(9.09) 45 C14H23N23P 50.91(50.83) 7.00(7.29) 8.S0(8.25) 46 CgH20BrN202PS 32.62(36.00) 6.10(6.98) 8.40(8.97) 47 C7H17N20PS2 35.00(35.25) 7.08(7.55) 11.70(12.22) 48 C7H17N~OPs2 35.00(35.30) 7.08(7.22) 11.70(11.47) 49 C6HlsN~OPs2 31.80(31.57) 6.68(6.90) 12.38(12.01) Initial evalua~lons are made on the following mite, insect, and nematode:
Code Symbol Common Name Latin Name 25 TSM Two-spotted spider Tetranychus mite urticae SAW Southern armyworm Spodoptera eridania nema Southern root-knot Meloido~yne in-nematode cognita A test solution containing 600 ppm of test compound can be made by dissolving the test compound ;n a solvent (acetone:methanol, 1:1), adding surfactant and then water to give an acetone:methanol:water system of 10:10:80. A
1:1 mixture of an alkylarylpolyetheralcohol (commercially &'~

available under the trademark Tri~on X-155) and a modified phthalic gly~erol alkyl resin ~co~mercially available u~der the trademark Triton B-1956! can be utili~ed at the equivalent of one ounce per 100 gallons S of test solution a~d a surfactant.
For the mite test, infested bean ~Phaseolus lim ) leaf discs ~1.25 inches in diameter) containing ab~u~ S0 mi~es are placed in a Petri dish lid on a moi~tened pieoe of cotton. The leaves are then sprayed ~ith the test solution using a rotating turntable. They are held ~or 24 hours and then the percent kill is determined .
For the'armywcrm test, detached bean lea~es on pieces o~ ~oistened ~ilter paper are sprayed as above ~or the ~ite test in ~i~ilar dishe~ and allowed to dry. The diqhes are inest~d with 10 third instar southern armyworm larvae. The dishes are covered . After holdiny ~or 43 hours, the percent kill i5 obtained.
Fcr the nematode teqt, sc~il is homogeneouqly 20 inoculated with a ~acarated blend of tomato ro~ts heavily knatted with the root knot nematode. Ten ~illilLters of the t~st solution are added to 200 milliliters of the i~oculated so~l in a 16 oz. jar to give a concentration by v~lume o~ about 30 ppm. The ~ar is then shaken to 2S i~sure thorough mi~lng, immediately uncapped, and allowed to air for 24 hours. The 50il iS then placed into a 3 inch plastic pot a~er which time 3 cucumber ~Cucumis sativus) seeds ase plant@d. A~out 23 days thereafter, the ~Ncumber plants are removed f rom the so il and the root system examined Eor the presence of knots. A total of 15 knots or less i5 considered as a ~ea~ure of control.
Table II gives the results of the foregalng biological evaluations~

~.3~

-- ~8 --TABLE I 1:
~b ~3~ TS~ a SAW a NEMA c 100 1.00 ~ 100 100 3 100 lO~J +

S -- _ _ I; ,, _ _ ` 7 100 0 8 -- .
9 ~
l~ 100 11 ~00 100 1~; 10~ 100 - 2t} 17 lU0 100 21~ 100 100 .- 21 100 100 ~5 22 100 100 23 lOt~ 100 2e; 100 40 27 100 l~(J
2~ 100 100 29 ' 100 lOa 3a lO~ lOO
31 10~ 100 ~L~.3~

TABLE II

333~æ~ TS~ a SAW a ~E~ c 3~ ~0 100 +
33 100 1~0 3~ lOa lO0 37 ~ ~ _ 38 lO0 lO0 +
39 lO~ +
l~0 o +
41 lO0 1~0 42 10~ 100 43 lO0 lO0 +
44 l~0 100 4S lO0 100 ~6 100 100 47 lO0 10~ +
4~ 100 lO0 +
49 100 lO0 +
100 lO0 a) TS~ two-~potted mite SA~ 3 sou~hern armywor~; nema nematode.
b) In~e~ idal screeQing results; % control at 600 p~
c) ~ means co~trol 15 knots or less (at 30 ppm in soil) ~sample~ 4, 5, 6, 8 and 9 are intermediate compounds or ~hich no biological data is included.

The c~mpounds of the invention are useful for the protection of plants and animals, including mammals, from the ravages af harmful and annoying pests. These compounds are particularly efective against ar~hropods ~in varying stages of development) and are especially effective against members o~ ~he Cla~s Arachnoidea, which includes the Order Acarina, a~ represented by mites and ticks, and the Class Insecta, the insects. Am~ng the arthropods which are

5 effectiv~ly controlled by the compounds of the present invention are the chewing insects, e.g., the southern armywor~ (SpodoPtera eridania), mi~es, e.g., the two-spotted ~pider ntite ~ urticae) and others.
The compounds o~ this invention are also active, as fungicides.
Furthermore, ~ompounds o this invention possess nema~ocidal activity. Among the nematodes which are e~fectively cc)ntrolled by the compounds o~ the present invention are soil nematodes, typi~ied by the southern root knot nematode ~M~a5~ y3~ inc~gnita)-Generally, control of pests is achieved in accordanc~with this inv~ntion by application of the compounds in pest~cidally effective amoun~s ~e.g., arthropodiciclally ~ectiv~ ~mounts) ~ither directly to the pests to be 20 con~rolled or to the loci ~o be ~reed of or protected ~rom attack by such pests. Plant protection loci may be de~ined as the ~erial and subterranean portion~ o plants ox propagatiYe subunits and their immediate or ~uture environs. For e~a~ple, food, iber, orage, forest, and orn~e~tal crops and stored products thereof represent plant protection loci. Treatment with compounds of this invention o domestic animals, and their immediate environs ~i~ilarly constitute representative loci for protection again~t variou3 annoying ec~oparasitic or endoparasitic Acarina (Acari) and Tnsecta. Many of the below formula-tions can be utilized on ani~als in the control of parasites. Thus, the compounds can be deposited on or in the soil, plants, insects, manmade structures, or other substrates as deposits, coatings, etc. Accordingly, compounds of the present invention provide utility as the ~.3~

essential active ingre~ient of pesticidal compositions suitable for agricultural and sanitary purposes.
The ter~ ~ontrol~ as employed in the specification and claim~s of ~hi~ application is to be construed as any means which adversely affects the existence or growth of a living organi~m. Such m~ans can comprise a complete killlng action, eradicatioa, arresting in growth, inhibition, redu~tion in number or any combination thereof.
~he term ~pe tY as employed in ~he specifieation and 10 claims o~ this a~plication refers ~o fungi, nemato~es and variou~ a.rthropoe3~ e~pecially insec~s and acarids.
The phosphorodi~midothioates of ~his in~ention possess general u~ility as arthropodicides, particularly as against ~embers of the clas3 Arachnoidea, which include~ the order I5 Acarina, as represen~ed by mites and tIcks, and In3ecta, the in~ects. Cer~airl compounds of this invention are also ac~i~e a3 ne~nato~:ide~ and fungicides, particularly nematocides .
Formulat ion ~or use as pesticides, the compounds of this invention can be used as solutions in organlc solvents or formula-'eion~ . For exaDIple, they can bs f ormulated as wettable powders, emul~i~iable concentrates, dusts, granular for~ulations or flowable emulsifiable concentrates. In ~uch ormulation~, the phosphorodiamidothioate~ are estended ~ith an agronomically acceptable liguid or solid carrier and, when desired, suitable surfactants are likewise incorp~rated. Surfactants commonly used in the art ~an be ~ound in the John W. ~cCutcheon, Inc.
publication ~Detergents and Emulsiiers Annual~.
The phosphorodiamidothioates can be taken up or ~i~ed with a finely particled olid carrier, as for e2ample, clay , inorganic silicates, carbonates, and silicas.
Organic carriers can also be employed. Dust concentrates are c~mmonly made wherein phosphorodiamidothioates are ~3~

present in the range of about 20 to about 80~. For ulti~ate applications, these concentrates are norma~ly e~tended with additional solid to give an active ingredient content of ~rom abou~ 1 to about 20~. Granular formula-S tions are ~ade using a qranuLar or pelletized form o~carrier, such a~ granular clays, vermiculi~e, char~oal or corn cobs, and can contain the active ingredient in ~rom about 1 to about 25~ by weigh~.
W~ttable powder fon~ulations are made by incorporating the compounds of this invention in an inert, finely di~ided ~olid carrier along with a surfactan~ which can be one or ~ore emulsifying, wetting, dispersing or spreading agen~s or blend of ~hese. The phosphorodiæmidothioa~es are u~ually present in the range of abou~ 10 ~o about 35% by weight and sur~actant~ from about 0.5 to about 10~ by weight.
One convenient ~ethod for preparing a ~olid fQrmul2ltion is tG l~pregnate the phosphorodiamidothioate onto the æolid carrier by mean~ of a volatile solvent ~ucb as ac:etone. ~n this ~anner, adjuvant~, ~uch as activators, adhesives, plant nutrients, synergists and various surfactan~s can also be incorporated.
~ ulsi~iable concentrate fonmulations can be prepare~
~y diY ol~ing the pho~phorodiamidothioates of this inv~ntion i~ a~ agronomically acceptable organ~c solvent and adding a solvent-soluble emulsiying agent. Suitable aol~ents axe usually water-immi3cible and ean be found in the hydroc~rbon, ketone, ester~ alcvhol and amide groups o~
organic solvents. ~ixtures of solvents are commonly employed~ The ~urfac~ants useful as emulsifying agents can constitute about 0.; to about 10~ by weight o emulsifiable concentrate and c:an be anionic, cationic or non-ionic in character. The ~ncentration of the active ingredients can vary f rom aboul: 20 to about 50% .
For use as pesticidal agents, ~hese co~pounds should be ~' :

~.3~

applied in an effective amount sufficient to exert the desired pesticidal activity by techniques well known in the art. ~sually, this will involve the application of the phosphorodiamidothioate to the loci to be protected from or freed of pa~ts in an effective amount when incorporated in ` an agrono~ically acceptable carrier. ~wever, in certain : situations, it may be desirable and advantageous to apply the c~mpounds directly onto the loci to be protected from ~r ~reed o pests without the benefit oE any substantial æmount o~ carrier. This is a particularly ef~ective method when the physical nature of the toxicants is suoh as to permit what is known as "low-volume" application, ~hat is, wben the compounds are in liquid form or subs~antially solu~le in higher boilin~ solvents.
The application rate will, of course, vary depending upon the purpcse for uch application, the phosphoro-diamidothloate being utilized, the frequency of dissemination and the like.
3y ~a~ronomically acceptable carrier n is meant any 3ubstanc~ which can be utilized to aissolve, disperse, or dlffuse the chemical incorporated therein without .impairing the effectiveness of the toxic agent and which does no permanent aamage to such environment as soil, equipment and a~ron~mic ~rops.
: 2S For use as insec~icides and acaricides, dilute sprays can be applied at c~ncentrations of about 0.01 to about 20 pounds of the phosphorodiamidothioate ingredient per 100 gallons of spray. They are usually applied at about 0~1 to about 5 pounds per 10~ gallon~. In more concentrated sprays, the active ingredient is increased by a factor of about 2 to about 12. ~ith dilute sprays, applications are usually made to the plants until run off is achieved, whereas with more concentrated low-volume sprays, the materials are applied as mists.
For use as a fungicide, the compounds of this invention ~3~

can be applied as fungicidal sprays by methods commonly employed, such as, conventional high-gallonage hydraulic sprays, low-gallonage sprays, air-blast sprays, aerial sprays and dusts. The dilution and rate of application will dep~nd upon the type of equipment employed, the method of application and dlseases to be controlled, but the pre~erred e~ective amoun~ is usually akout 0.1 lb. to a~ut S0 lbs. per acre of the active ingredient.
A3 a fungicidal ~eed protectant, the amount o~ toxicant coat~d on the seed is usually a~ a dosage rate of about 0.1 to about 20 ounc~s per hundred pounds of seed. As a soil fungicide the che~ical can be inoorporated in the soil or applied to ~he surface usually at a rate of a~out 0.1 to about 50 lbs. per acre. As a foliar fungicide, the toxicant is u~ually applied to growing plants a~ a rate of about ~.~5 to about 10 lbs. per acre.
For use as a nematocide, systemic agent, or as a soil insecticide, the phosphorodiamidothioates can be applied as a ~olid ormulati~n, preferably a granular formulation or as a diluted li~uid preparation, by broadcasting, sidedressin~ soil incorporation or seed treatment.
The ~ompositlon can also be added to transplant or irri~ation water or to units employed in propagation, such as seeds, tubers, roots, seedlings, etc. t 50 as to disinfect and/or pro~ide residual protection from ne~atodes, soil in~ects (and ~ites) and vi~ systemic uptake, oliar pests. The application rate can be from about 0.5 to abou~ 50 pounds per acre; however, higher rates can also be used. The preferred rate i5 from about 1 to about 25 pounds per acre. For soil incorporation, the compounds of this invent-on can be mixed with the soil or other growth medium at a rate of about 1 to about 100 ppm - of active ingredient.
The compounds of this invention can be utilized as the sole pesticidal agents or they can be employed in con-junction with other bactericides, fungicides, herbicides, insecticides, acaricides, nematocides and comparable pestioides.
T~e ~ollowing are example~ o~ formulations are given by way o~ illustration, and are no~ to be considered as limitation of the present invention.

a) 10~
10.0~ acti~e ingredient 0.5~ ~odium lauryl sulfate 3.0~ 3~dium lignosul~onate 86.5~ ~aolin (par~icle size 10-50 ~ierons) b) 35%
35.0~ ac~ive ingredient 0.5% ~odium lauryl ~ulfate 3.0% sodium lignosulfonate 20.0~ precipitated silica, particle size 1 micron 41.5~ Xaolin, particle size 10-50 microns Granulate a) 1~
13 ac~ive ingredient .. ..
99~ Celatom MP78 (diat~maceous earth) b) 25%
25% a~tlve ingredient 70~ attapulgite 5~ pyrogenic silica, particle size 1 micron (spray activ~ ingredient on granule, add pyrogenic silica) e~ 10~
10% ac~ive ingredient 9Q~6 ~gsorb MB (2~ontmorillani~e clay - Mississippi Brown) d) 10~
109~ ac:tive ingred ient 90% corn cob granule *Trademark.
. -. .. . .
, ~.
.

., ' .

~.3.~

e) 5 5~ active ingred ient 9596 walnut shell The above granular for~ulations can be prepared by 5 either of the two following methods or other suitable means.
The a~tive ingredien~ is dissolved in 3 parts xylene an~ thi3 solution i~ sprayed on the granular material~ The ~ylene i5 subsequently evaporated.
The ac~ive ingredlent is dissolved in~4 parts of toluen~ and this solution is dripped onto ~ranular ma~eria].
in a tumb~ing iar. ~he toluene is sub~equently evaporated.
Flowable Emulsion Conc~ntrate a~ 2Q~
2d~ a~tive ingredient 30% cyclohe~ane 42~ xylene 8~ mixture o~ calcium dodecylbenzenesul~onate and octylphenolethoxylate b~ 50~
5~ active ingredient 15~ xylene 25~ cyclohexanone 10% mixture of calcium dodec~.lbenzenesulfonate and octylphenolethoxylate Du~t Concentrate a) 10~
- 10% active ingredient ~0~ Montmorillonite b) 20%
-0% active ingredient 75% Montmorillonite , ~.3~

5~ ~recipitated silica, 20-80 microns, particle size 1 ~icron Table III
~ Active ~ Preferred ~ ~~
~ormulation Concentration Concen~r-ation Wettable Powder 1 - 35 10 - 35 ~3~ ~~~~~ncentrate --i ~Si---- = 0 - ~o Ylo~able Emulsion 10 . Coccentrate 1 - 40 - 2T
Du~t Concentrate 10 - ao _ 20 - 8 Granules 0.1 - 25 _ ~ - 15 Many variations of this invention are possible without departing from the spirit or scope thereof.

Claims (34)

Claims

1. A compound of the formula:

wherein R1 is a hydrogen atom, an unsubstituted (C1-C12)alkyl group;
a (C1-C12)alkyl group substituted with up to three substituents selected from chloro, bromo, and fluoro;
a (C1-C12)alkyl group substituted with one substituent selected from cyano, nitro, (C1-C6)alkoxy, (C1-C6) alkylthio, (C1-C6) alkylsulfinyl, (C1-C6) alkylsulfonyl, (C1-C6) alkylcarbonyl, (C1-C6) alkoxycarbonyl, (C1-C6) alkylcarbonyloxy, (C1-C6) mono- or dialkylaminocarbonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenylaminocarbonyl, (C3-C6) alkenyloxycarbonyl, (C3-C6) alkenylcarbonyloxy, aminocarbonyl, and (C1-C6) alkylcarbonylamino groups;
a (C3-C12)alkynyl group;
a (C2-C12)alkenyl group;
a (C4-C17) alkyldienyl;
a (C3-C6)cycloalkyl group;
a (C1-C6) alkoxycarbonyl;
an unsubstituted phenyl group;
an unsubstituted phenyl (C1-C5) alkyl group;

a phenyl or phenyl (C1-C5) alkyl group, substituted with up to three substituents selected from cyano, nitro, halogen, (C1-C6) alkyl, (C1- C6) alkoxy, (C1-C6)alkylthio, (C1-C6) alkyl-sulfinyl, (C1-C6) alkylsulfonyl, phenoxy, (C1-C6) haloalkyl, trifluoro-methyl, (C1-C6) mono- or dialkylamino-carbonyl, (C1-C6) alkoxycarbonyl, (C1-C6) alkylcarbonyl, (C1-C6) alkylcarbonyloxy, phenylthio, phenyl-sulfinyl, phenylsulfonyl, benzyl, phenyl-carbonyl, phenoxycarbonyl, phenylcarbonyl-oxy, phenylaminocarbonyl, (C3-C6) alkenyloxycarbonyl, (C3-C6) alkenyl-carbonyloxy, aminocarbonyl, and (C1-C6) alkylcarbonylamino groups;
R2 is a (C2-C6)alkyl group;
R3 is a hydrogen atom, a (C1-C3) alkyl group, or a (C3-C6) alkenyl group;
R4 is a hydrogen atom, a (C1-C3) alkyl group, or additionally when R3 and R5 are not taken together to form a heterocycle, a (C3-C6) alkenyl group;
R5 is a hydrogen atom;
an unsubstituted (C1-C12)alkyl group;
a (C1-C12)alkyl group substituted with one substituent selected from cyano, nitro, (C1-C6)alkoxy, (C1-C6) alkylthio, (C1-C6) alkylsulfinyl, (C1-C6) alkylsulfonyl, (C1-C6) alkylcarbonyl, (C1-C6) alkoxycarbonyl, (C1-C6) alkylcarbonyloxy, (C1-C6) mono- or dialkylaminocarbonyl, phenoxy, phenylthio, phenylsulfinyl, phenyl.sulfonyl, phenylcarbony1, pbenoxycarbonyl, phenyl-carbonyloxy, phenylaminocarbonyl, (C3-C6) alkenyloxycarbonyl, (C3-6) alkenylcarbonyloxy, aminocarbonyl, and (C1-C6) alkylcarbonylamino groups;
a (C3-C12)alkynyl group;
a (C3-C12)alkenyl group;
a (C3-C6)cycloalkyl group;
an unsubstituted phenyl group;
an unsubstituted phenyl (C1-C5) alkyl group;
a phenyl or phenyl (C1-C5) alkyl group, substituted with up to three substituents independently selected from cyano, nitro, halogen, (C1-C6) alkyl, (C1-C6) alkoxy, (C1-C6)alkylthio, (C1-C6) alkylsulfinyl, (C1-C6) alkylsulfonyl, phenoxy, (C1-C6) haloalkyl, trifluoro-methyl, (C1-C6) mono- or dialkylamino-carbonyl, (C1-C6) alkoxycarbonyl, (C1-C6) alkylcarbonyl, (C1-C6) alkylcarbonyloxy, phenylthio, phenyl-sulfinyl, phenylsulfonyl, benzyl, phenyl-carbonyl, phenoxycarbonyl, phenylcarbonyl-oxy, phenylaminocarbonyl, (C3-C6) alkenyloxycarbonyl, (C3-C6) alkenyl-carbonyloxy, aminocarbonyl, and (C1-C6) alkylcarbonylamino groups;
R3 and R5 can be taken together to form a hetero-cyclic ring of the formula _ 41 -wherein Z i5 a -CHCH2- group, a -CH2-CH2CH2- group, or -CH2CH2CH2-CH2- group; and X and X1 are an oxygen atom or a sulfur atom.

2. A compound according to claim 1 wherein R1 is hydrogen.

3. A compound according to claim 1 wherein R1 is a hydrogen atom;
an unsubstituted (C1-C6)alkyl group;
a (C1-C6)alkyl group substituted with one substituent selected from cyano, nitro, (C1-C4)alkoxy, (C1-C4) alkylthio, (C1-C4) alkylsulfinyl, (C1-C4) alkylsulfonyl, (C1-C4) alkylcarbonyl, (C1-C4) alkoxycarbonyl, (C1-C4) alkylcarbonyloxy, (C1-C4) mono- or dialkylaminocarbonyl, phenoxy, phenylthio, phenysulfinyl, phenyl-sulfonyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenylaminocarbonyl, (C3-C6) alkenyloxycarbonyl, (C3-C6) alkenylcarbonyloxy, aminocarbonyl, and (C1-C4) alkylcarbonylamino groups;
a trifluorometnyl group, a (C3-C6)alkynyl group;
a (C3-C6)alkenyl group;
a (C4-C17) alkyldienyl group;
a (C3-C6)cycloalkyl group;
a (C1-C4) alkoxycarbonyl group;
an unsubstituted phenyl group;
an unsubstituted phenyl (C1-C3) alkyl group:
a phenyl or phenyl (C1-C3) alkyl group, substituted with up to three substituents independently selected from cyano, nitro, halogen, (C1-C4) alkyl, (C1-C4) alkoxy, (C1-C4)alkylthio, (C1-C4) alkylsulfinyl, (C1-C4) alkylsulfonyl, phenoxy, (C1-C4) haloalkyl, trifluoro-methyl, (C1-4) mono- or dialkylamino-carbonyl, (C1-C4 ) alkoxycarbony1, (C1C4) alkylcarbonyl, (C1-C4) alkylcarbonyloxy, phenylthio, phenyl-sulfinyl, phenylsulfony], benzyl, phenyl-carbonyl, phenoxycarbonyl, phenylcarbonyl-oxy, phenylaminocarbonyl, (C3-C6) alkenyloxycarbonyl, (C3-C6) alkenyl-carbonyloxy, aminocarbonyl, and (C1-C4) alkylcarbonylamino groups;
R2 is a (C2-C4)alkyl group;
R3 is a hydrogen atom, a (C1-C3) alkyl group or a (C3-C4) alkenyl group;
R4 is a hydrogen atom, a (C1-C3) alkyl group, or additionally when R3 and R5 are not taken together to form a heterocycle, a (C3-C4) alkenyl group; and R5is a hydrogen atom, a (C1-C6)alkyl group;
a (C1-C6)alkyl group substituted with one substituent selected from cyano, nitro, (C1-C4)alkoxyt (C1-C4) alkylthio, (C1-C4) alkylsulfinyl, (C1-C4) alkylsulfonyl, (C1-C4) alkylcarbonyl, (C1-C4) alkoxycarbonyl, (C1-C4) alkylcarbonyloxy, (C1-C4) mono- or dialkylaminocarbonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenyl-carbonyl, phenoxycarbonyl, phenylcarbonyl-oxy, phenylaminocarbonyl, (C3-C6) alkenyloxyoarbonyl, (C3-C6) alkenyl-carbonyloxy, aminocarbonyl, and (C1-C4) alkylcarbonylamino groups:
a (C3-C6)alkynyl group;
a (C3-C6)alkenyl group;
a (C5-C6)cycloalkyl group;
an unsubstituted phenyl group;
an unsubstituted phenyl (C1-C3)alkyl group;
a phenyl or phenyl (C1-C3) alkyl group, substituted with up to three substituents selected from cyano, nitro, halogen, (C1-C4) alkyl, (C1-C4) alkoxy, (C1-C4)alkylthio, (C1-C4) alkyl-sulfinyl, (C1-C4) alkylsulfonyl, phenoxy, (C1-C4) haloalkyl, trifluoro-methyl., (C1-C4) mono- or dialkylamino-carbonyl, (C1-C4) alkoxycarbonyl, (C1-C4) alkylcarbonyl, (C1-C4) alkylcarbonyloxy, phenylthio, phenyl-sulfinyl, phenylsulfonyl, benzyl, phenyl-carbonyl, phenoxycarbonyl, phenylcarbonyl-oxy, phenylaminocarbonyl, (C3-C6) alkenyloxycarbonyl, (C3-C6) alkenyl-carbonyloxy, aminocarbonyl, and (C1-C6) alkylcarbonylamino groups; or R3 and R5 can be taken together to form a hetero-cyclic ring of the formula wherein Z is a -CH2CH2- group or a -CH2-CH2CH2- group.

4. A compound according to claim 3 wherein;
R1 is a hydrogen atom a (C1-C4) alkyl group; a (C1-C4) alkyl group substituted with one substituent selected from cyano, nitro, methoxy, ethoxy, methylthio, methylsulfinyl, methylsulfonyl, methylcarbonyl, methoxycarbonyl, ethoxycarbonyl, methylcarbonyloxy, (C3-C4)-alkenyloxycarbonyl, (C3-C4)alkenylcar-bonyloxy, mono or dimethylaminocarbonyl, methylcarbonylamino, phenoxy, and phenylthio;
a (C3-C4) alkynyl group; a (C3-C4) alkenyl group; a phenyl group; a benzyl group; or a trifluoromethyl group; or a cyclopropyl group;
R5 is independently a hydrogen atom; a (C1-C4) alkyl group, a (C1-C4) alkyl group substituted with one substituent selected from cyano, nitro, methoxy, ethoxy, methylthio, methylsulfinyl, methylsulfonyl, methylcarbonyl, methoxycarbonyl, ethoxycarbonyl, methylcarbonyloxy, (C3-C4) alkenyl-oxycarbonyl, (C3-C4)alkenylcarbonyloxy, mono or dimethylaminocarbonyl, methylcarbonyl-amino, phenoxy, and phenylthio; a (C3-C4) alkynyl group; a (C3-C4) alkenyl group; a phenyl group, or a benzyl group;
R3 is a hydrogen atom or a methyl group; and R4 is a methyl or ethyl group.

5. A compound of the formula:
wherein R1 is a hydrogen atom;

an unsubstituted (C1-C6) alkyl group;
a (C1-C6) alkyl group substituted with up to three substituents selected from fluoro, chloro and bromo groups;
a (C1-C6) alkyl group substituted with one substituent selected from (C1-C4) alkoxy, (C1-C4) alkoxycarbonyl, and phenoxy groups;
a (C3-C6) alkenyl group;
a (C4-C17) alkyldienyl group;
a (C3-C6) cycloalkyl group;
a (C1-C4) alkoxycarbonyl group;
an unsubstituted phenyl group;
an unsubstituted phenyl (C1-C3) alkyl group;
an unsubstituted phenyl (C2-C6) alkenyl group;
a phenyl or phenyl (C1-C3) alkyl group;
substituted with up to two substitutents selected from nitro and chloro groups;
R2 is a (C2-C4) alkyl group;
R3 is a hydrogen atom, a (C1-C3) alkyl group, or a (C1-C3) alkenyl group;
R4 is a hydrogen atom or a (C1-C3) alkyl group;
R5 is a hydrogen atom, a (C1-C3) alkyl group or a (C1-C3) alkenyl group; and X and X1 are an oxygen atom or a sulfur atom.

6. A compound according to claim 4 wherein, R2 is a (C3-C4)alkyl group;
R3 is a hydrogen atom;
R4 is a methyl group; and R5 is a hydrogen atom, a methyl group or an ethyl group.

7. A compound according to claim 6 having the formula:

8. A compound according to claim 6 having the formula:

9. A compound according to claim 6 wherein R1 is a hydrogen atom, a methyl group, an ethyl group, a methoxymethyl group, a cyclopropyl group or a trifluoromethyl group;
R5 is a mthyl group; and X is an oxygen atom.

10. A compound according to claim 9 having the formula:

11. A compound according to claim 9 having the formula:
.

12. A compound according to claim 9 having the formula:

13. A compound according to claim 9 having the formula:

14. A cmpound according to claim 9 having the formula:

15. A compound according to claim 9 having the formula:

16. A method of controlling pests which comprises applying directly to the pests or to the loci to be freed of, or protected from attack by, such pests, a pesticidally effective amount of the compound of claim 1, 2 or 3.

17. A method of controlling pests which comprises applying directly to the pests or to the loci to be freed of, or protected from attack by, such pests, a pesticidally effective amount of the compound of claim 4, 5 or 6.

18. A method of controlling pests which comprises applying directly to the pests or to the loci to be freed of, or protected from attack by, such pests, a pesticidally effective amount of the compound of claim 7, 8 or 9.

19. Amethod of controlling pests which comprises applying directly to the pests or to the loci to be freed of, or protected from attack by, such pests, a pesticidally effective amount of the compound of claim 10, 11 or 12.

20. A method of controlling pests which comprises applying directly to the pests or to the loci to be freed of, or protected from attach by, such pests, a pesticidally effective amount of the compound of claim 13, 14 or 15.

21. A method of controlling pests in plants through systemic pesticidal action which comprises applying a pesticidally effective amount of a compound according to claim 1, 2 or 3 to the growth medium.

22. A method of controlling pests in plants through systemic pesticidal action which comprises applying a pesticidally effective amount of a compound according to claim 4, 5 or 6 to the growth medium.

23. A method of controlling pests in plants through systemic pesticidal action which comprises applying a pesticidally effective amount of a compound according to claim 7, 8 or 9 to the growth medium.

24. A method of controlling pests in plants through systemic pesticidal action which comprises applying a pesticidally effective amount of a compound according to claim 10, 11 or 12 to the growth medium.

25. A method of controlling pests in plants through systemic pesticidal action which comprises applying a pesticidally effective amount of a compound according to claim 13, 14 or 15 to the growth medium.

26, A method of controlling pests which comprises applying directly to the pests or to the loci to be freed of or protected from attack by, such pests, a composition comprising a pesticidally effective amount of a compound according to claim 1 and an agronomically acceptable carrier.

27. A method according to claim 26 wherein the pests are phytopathogenic fungi.

28. A method according to claim 26 wherein the pests are acarids.

29. A method according to claim 26 wherein the pests are insects.

30. A method according to claim 26 wherein the pests are nematodes.

31. A method of controlling pests which comprises applying directly to the pests or to the loci to be freed of or protected from attack by, such pests, a composition comprising a pesticidally effective amount of a compound according to claim 7, 8 or 9 and an agronomically acceptable carrier.

32. A method of controlling pests which comprises applying directly to the pests or to the loci to be freed of or protected from attack by, such pests, a composition comprising a pesticidally effective amount of a compound according to claim 10, 11 or 12 and an agronomically acceptable carrier.

33. A method of controlling pests which comprises applying directly to the pests or to the loci to be freed of or protected from attack by, such pests, a composition comprising a pesticidally effective amount of a compound according to claim 13, 14 or 15 and an agronomically acceptable carrier.

34, A method for preparing a compound of the formula which comprises the formylation of a N,N'-di- or tri-substituted S-alkyl phosphorodiamidothioate by reacting a compound of the formula:

with a compound of the formula:
wherein R2, R3, R4 and R5 are as defined in claim 1.