CA1138883A - Lepidoptericidal isothiourea compounds - Google Patents

Abstract

Abstract of the Invention Lepidoptericidal and herbicidal active compounds having the generic formula wherein R, R1, R2 and R3 are as disclosed herein.
In general, these compounds show enhanced lepidoptericidal activity and show reduced phytotoxic effect on crops to be protected from the lepidoptera.

Description

L38~83 ~.

LEPIDOPll~RICIDAL ISOTHIOUREA COMPOUNDS

Bac~round of the Invention Lepidoptericidal isothiuronium compounds have been disclosed in the prior art particularly those described in U.S. Patents 3,969,511 and 4,062,892 and have the formula ~ .
j SR2 :
i These compounds have a major disadvantage in that they show high levels of phytotoxic activity and thus, although control-ling lepidoptera in the crop to be protected, are detrimental to the crop itself. To overcome this problem, applicants have discovered that substitution of the active hydrogen on ~ the above type of isothiuronium and urea compounds with j 10 certain specific, relatively easily cleaved groups can lessen or eli~inate phytotoxic efects of the parent compound while -~
I maintaining, and in some cases enhancingj the lepidoptericidal activity of the compound. - ;~

~ ~o prior art has been discovered which teaches ; 15 or suggests the result that applicants have achieved.
~, .
3~ :

,,' -- 11 3~ 8 3 . -2-. .
t,`, Description of the Invention , The present invention is a novel group of . .
, compounds which may generally be described as certain isothioureas which are active lepidoptericides. i~
Compounds of the present invention are represented by j 5 the generic formula ...
SR
. 1 2 L RN C NRl R

wherein R and Rl are independently selected from the group consisting of:
~';
.A .' C2-C10 alkyl, preferably C5-Cg alkyl, ~;
;i more preferably C6-C8 alkyl, ;l 10 C2-C10 alkoxyalkyl, preferably C5-C
alkoxyalkyl, more preferably l C6-C8 alkoxyalkyl and ;l phenyl and R and Rl together contain from 12 to 22 carbon atoms;
.~
wherein R2 is selected from the group consisting of:

Cl-C14 alkyl, preferably Cl-C6 alkyl, more preferably Cl-C3 alkyl, C3-C10 alkenyl, preferably C3-C5 alkenyl, ~ more preferably C2-C3 alkenyl, ~ 20 C3-C4 alkynyl, C2-C4 hydroxyalkyl, preferably C2-C3 hydroxyalkyl, C2-C6 alkylthioalkyl, preferably G2-C4 alkylthio- .
alkyl, ~1 ` , .

: .
.

, ~ . . , . . . ~ - . . ... , . ~ - , . ., -8~83 .,~ , C2-C6 alkyloxyalkyl, preferably C2-C4 : alkylthioalkyl, (CH2)n [X(CH2)n] y where n ~ 1 or 2, X is O or S and y = 1-4, preferably -~
5 1-2, ., O ~, - -(CH2)nCOH where n - 1-10, preferably 1-5, more preferably 1-3, phenyl and phenethyl;

wherein R3 is selected from the group consisting of~

~ carboalkoxyalkyl wherein the alkyl is s Cl-C4 alkyl, preferably Cl-C2 alkyl, :~
; alkylketoalkyl wherein the alkyl is Cl-C4 alkyl, preferably Cl-C2 alkyl, ; 15 hydroxyalkenyl wherein the alkenyl is C3-C4 alkenyl, ~ hydroxyalkyl wherein the alkyl is Cl-C12 j alkyl, preferably Cl-C6 alkyl, : `~
J more preferably Cl-C3 alkyl~
s 20 formylhydroxymethyl, .
hydroxyhaloethyl wherein the halo is chloro, :
bromo or iodo, preferably chloro or ~i bromo, more preferably chloroj -substituted phenoxyalkyl wherein the alkyl . 25 is Cl-C2 alkyl, preferably Cl alkyl and the substituents are p-methoxy, , . Cl, NO3 or CNj ~ :

~ wherein Rl is -OH, -NH2 or .
R
Cl-C4 alkoxy, preferably methoxy, .

`-` 113!~883 -4- :

~- ~H OIH ~R2 , -~ -CH-CHN-C-NRl wherein R, Rl and R2 are --R .~:~
as defined above, ,-- ~ N-C'NRl wherein R, Rl and R2 are OH R
: as defined above, ~:
o~
-PO3-B, -P02-B or -SO3-B wherein B is a basic catio~ preferably an organic ba~ic cation, more :
preferably an organic basic cation selected from the group consisting of -(CH3)3NH and l -~N ~ wherein R4 is selected from the group , R5 consisting of:
' -H, ; -Cl-C22 alkyl, preferably Cl-C12 alkyl, more preferably Cl-C8 alkyl and :: most preferably Cl-C6 alkyl, 1 15 hydroxyethyl, j naphthyl, phenyl, substituted phenyl wherein the substituents are independently selected from the group of halogen, preferably chlorine, Cl-C5 alkyl, .~ :
J

91~E~3 ;

preferably Cl-C2 al~yl Cl-C5 alkoxy preferably Cl-C2 alkoxy, nitro, cyano ~:
and -CF3, n , ,~ n3 0 1 2 ~ NHC~-C-N~l wherein R, Rl and R2 are as defined above, -(CH2)6NHC~-C~NRl wherein R, Rl and R2 are as defined above, g IR2 : :~
CH2NHCN-C~NR~
R wherein R, Rl and R2 ~ :;

CH3 are ~s defined above ~" o SR2 `
:'.
~ CH2 ~ CN-C-NRl wherein R, Rl and R :~
R2 are as defined above, O SR
.i NH~N-C~NR
R wherein R, Rl and R2 are :
i~ as deined above, ." , ., ;", ~:

:
.. ~ . . .
~, ... .
. `` :
... .
~'' "

.

'': ~ ~ . , ", .: ~ : : ~ ,. : , ., ~ . , :: . .

113~3 .
: -6-o ~ 2 O o NHC-N-C~
,~HC-O(cH2cH20~x-cN~

wherein x is 1 to 8 and R, Rl and ~ - -R2 are as defined above, R o~ NHC-N-C~

.. ' 5 wherein m is 2 or 3 and R, R
, and R2 are as defined above, ;!
,, o ~ R2 O o ,NHc-N-c~NR
NH~- ~ C ~ R

,1 .
.~ wherein R, Rl and R2 are as defined above, ,,~
,, , o SR2 O o NHC-N-C~NR
, ~ C-NH ~ N~C ~ R
i 10 ~ 3 CH3 wherein R, Rl and R2 are as defined above, ~, ; , . .
. . . ~ , , . . . ; .

~13 ,. o . ,.
' ~C~lo , .: ~, y , . wherein X is selected from the group consisting of: .;
O, NH, and NRll;
Y is hydrogen or methyl; and Rlo is selected from the group consisting of:
H, ~ ~ -Cl-C18 alkyl, preferably ~ ~:
~' Cl-C8 alkyl, more preferably Cl-C2 alkyl, C3-C4 alkenyl~ ~ ~
C3-C4 alkynyl, ~;
i C2-C6 haloalkyl, preferably !~' C2-C3 haloalkyl, :
C3-C8 cycloalkyl, C7-C20 polycycloalkyl, :
" ';

" .
.. . .
" .

:j , .~, .
... .

~ !L3~1~83 .

, -8 C2-C16 polyalkoxyalkyl, C2-C6 hydroxyalkyl~
- C3-Clo alkoxyalkyl, . C3-C8 carboalkoxyalkyl, - ~-C4-C8 cycloalkylalkylj `.
C4-C8 alkylcycloalkyl, preferably - C6-C8 alkylcycloalkyl, : C4-C7 cycloalkylimino C2-C10 alkylimino, o Cl-C3 alkylaminoj C4-C12 dialkylaminoalkyl, C -Cl cycloalkenyl phenyl, alkylphenyl wherein the alkyl is Cl-C4i parachioroalkylphenyl wherein the alkyl is Cl-C4, : -naphthylj ~:
~ anthracenyl, ril 20 benzamidocycloalkyl wherein :
the alkyl is Cl-C2, pyranylmethyl, j tetrahydrofurfuryl, thiophenemethyl, benzhydryl, halobenzhydryl, polycyclic alcohol, and substituted phenyl wherein the substituents are selected ;.. 30 from the group consisting of:
Cl-C4 alkyl, ~
,', halogen j : ' nitroj ,'t trifluoromethyl, formyl , . ~ . . : , . ~ -. ,, . . -:

~ 3~38 :
g chLoroacetyl, : Cl C4 alkoxy~ :
hydrogen, ; benzyl, chlorobenzyl, ~ -- S- :~:
phenethyl, and substituted phenethyl wherein -~ the substituents are , .
selected from the group Cl-C4 alkyl and halogen,` and ~ . -Rll is selected from the group consisting of: -. Cl-C4 alkyl~
C3-C6 alkoxyalkyl, and C3-C4 alkenylj .
Rlo and Rll taken together :. form heterocycllc compounds, ; 20 preferably herterocyclic I compounds selected from the 9 group consisting of: :
azepinyl, morpholinyl, . 25 piperdinyl, Cl-C3 alkyl substituted . peperdinyl, and . Y is hydrogen or methyl ; provided that when X - O or S
- then Rlo is other than hydrogen and su~stituted phenyl wherein the substituents are selected from the group ~ consis.ting of:
. 35 halogen, . ~ Cl-C4 alkoxy, . .

- , ~ . . .

~138~83 . .

.~ -10-phenoxy, :; trifluoromethyl, Cl-C6 thioalkyl, .
nitro, -5 isocyanato, C C polyalkoxy C3-C7 cycloalkyl, C3-C24 carboalkoxyalk~l, preferably C3-C10 carboalkoxyalkyl, ~ Cl-C8 haloalkyl, preferably Cl-C4 haloalkyl, C3-C12 alkenyl, preferably C3-C4 alkenyl, C2-C6 dialkylamino, :; phenylaminoj Cl-C24 alkyl, preferably Cl-C4 alkyl, 7 C3-C12 hydroxyalkylamidoalkyl C5-C10 N,N-hYrXYalkYl-ureidoalkyl, isocyanatoalkyl wherein the i alkyl is Cl-C5, ~! C3-C12 alkylamidoalkyl, : 25 polyalkoxyamidoalkyl wherein . .
the polyalkoxy moiety contains from 3-6 repeating C2-C3 alkoxy units and the amidoalkyl ~ 30 moiety contains from : 4-12 carbon atoms, ' -So2cl~ -~
;~. -S2 polyalkoxyamidoalkyl ; wherein the polyalkoxy moiety contains from '`` 1~38~383 5"
,' '~ ' ' ~': .

3-6 repeating C2-C3 ~ alkoxy units and the ;-~ amidoalkyl moietyi~, contains from 4-12carbon atoms, R5 is selected from the group consisting of~
hydrogen ~ Cl-C4 alkyl ,~ C3-C6 alkoxyalkyl, C3-C4 alken ~i hydroxyethyl, and -~
phenyl, :~
~, R4 and R5 taken together form heterocyclic :: :
compounds, preferably heterocyclic compounds selected from the group consisting of~
azepinyl, morpholinyl, piperdinylj and :
Cl-C3 alkyl substituted piperdinyl~
Il O
-CXnR6 wherein X is 0 or S, n is 0 or 1, R6 is selected from the group ' consisting of:
i Cl-C18 alkyl, preferably Cl-C12 alkyl, more preferably `~ Cl-C4 alkyl C2-C6 haloalkyl phenyl, and substituted phenyl wherein when N
,,~
= 1 the substituents are selected from the group consisting of:
nitro, :3 chloro .-7 .¦ Cl-C2 alkyl, C4-C6 polyalkoxyalkyl, ~,', "

. . .

r-1~L3~ 3 ,. . . .

C3-C8 cycloalkyl, ,, C3-C4 alkenylj ; C3-C6 alkoxyalkyl, C2-C6 hydroxyalkyl, ' ' Cl-C3 carboxyalkyl, and `~ :
i C5-C8 trialkylammoniumalkyl salts, and when n = 0 the substituents are selected from the group ', -' consisting of: ' '' , 10 chloroj thiopotassium, -Cl-C18 alkyl, preferably ' Cl-C12 alkyl, more preferably ' C -C alkyl ' :~ 15 benzyl, ' ~, Cl-C2 heteroalkylj ,l C2-C4 chlorocarboxyalkyl, C4-C6 polyalkoxyalkylj and acetylj O O ~:, -CR7CYdZ wherein R7 is selected fro~ the ::~
group c,onsis,ting of~
J -(CH2-?n wherein n - O to 8, ,~ -CH'CH-, ,:

~: ~/ : ~
,, ~ wherein M is H or Cl, M

i ': .

,' - .

1~3~9883 .

::
-CCl=CCl-j , . -CH20cH2-~ and -OCH2CH2O-, and .
d - O or l, and when d = l , 5 Y is selected from the group . - ~ :
consisting of:
o ~ :~
-S, and :
-NH, Z is selected from the group consisting of:
- Cl-C18 alkyl, preferably Cl-C12 alkyl, more : preferably Cl-C4 ~kyl, -~
hydrogen, - C4-C16 polyalkoxyalkyl~
C4-C8 dialkylaminoalkyl, C C lk phenyl, substituted phenyl, ~ organic salts, :i inorganic salts, and ~,j when d 2 0 ~ Z iS -,, Cl or . SR2 ., I . .
-N-C-NR wherein R~ ~
R ~ :
f Rl and R2 are as -:
defined above, 'J
"

.
, , .

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

1~3E~8~3 O
-P(R8)2 wherein R8 is selected Prom the ~ ~
group consisting of: :
Cl-C10 alkoxy, preferably , Cl C5 alkoxy~
amino, Cl-C10 alkoxyamin, ,, preferably Cl-C5 alkoxyamino, hydroxy, and -organic base :
-S0 ~ wherein w - 0-2 and ~ is selected from : the group consisting of~
;
amino, ~ :
Cl-C10 alkyl, preferably ~ ~
Cl-C5 alkyl, :: :
Cl-C4 haloalkyl~
phenylj :
Cl-ClO dialkylamino, Gl-Clo alkylaminoj Cl-ClO alkoxy, preferably ~::
Cl C5 alkoxy~
substituted phenyl wherein the substituents are selected from the group consisting of: :
nitroj chloro, . Cl-C4 alkylj and .,~ . methoxy. ~:
:: -~: ~
. . .
.. ~ .

. ~.

3 : ~:

1~3~33 -` :

General Methods of Preparation The compounds of the present invention are derivatives of isothioureas containing one free hydrogen ~
atom attached to nitrogen, that is~ as sho~ by the ---following formula:
' ; SR
I
R-N=CNHR

The formation of the prior art isothioureas is well known in the art. They are derived by the reaction of an isothiocyanate with a primary amine to form a thiourea followed by the reaction with an alkyl halide to produce an isothiourea salt. An unreactive solvent such as ethanol o can be used for both the formation of the thiourea and the alkylation step to form the isothiourea salt. Heat is usually used to speed both reactions. The preparation of the isothiourea salt is shown below:

S
R-NCS + H2N-R2 > RNHCNHR2 S*
R'X > R-N=CNHR2 HX
,, ~ .
X - I, Br or Cl , . . . - . . , ~ 1 ~ 3~8 8 3 ,,"
, -16-., The compounds of this invention are prepared by `; reacting the base of an isothiourea wi~h an isocyanate or acid chloride. The free base can either be prepared by neu-tralization of an isothiourea salt with a cold aqueous solution~
of ab~se ~uch as dilute sodium hydroxide, extracting the free isothiourea with a water insoluble solvent such as hexane, benze~e, toluene, etc., drying over a dehydrating agent such as magnesium sulfate, filtering and evaporation under vacuum.
An alternative procedure is to dissolve the isothiourea salt in a non-reactive solvent such as benzene or toluene then add-ing an equal molar amount of an isocyanate and the equivalent amount of a soluble tertiary base or an acid chloride and two equivalent amount~ of a soluble tertiary base such as tri-ethylamine, completing the reaction by stirring at ambient --temperature for several hours or refluxing for a shorter -~
period of time. An alternative method when using a base such `
~, as triethylamine is to treat the isothiourea salt in a solvent ~, such as benzene in which triethylamine hydrohalide is almost totally insoluble, filtering off the triethylamine hydrohalide - -and treating the filtrate with the isocyanate or acid chloride, completing the reaction as discussed previously. Solvents suitable for the condensation of the isothiourea with an isocyanate or acid chloride are those which are unreactive to any of the reactants. These include hexane, benzene, toluene, tetrahydrofuran, dioxane, methylenechloride, diethylether, and the like. Depending on the reactants, reaction temperatures are generally within the range of -20C to 80C and reaction times vary from 0.5 hours to 24 hours.

In some instances, it has been found that the con-densation of an isothiourea with an isocyanate or acid chloride ~~
~r `can be hastened by the addition of such catalysts as triethylamine and dibutyltindilaurate.
,.`.! ~
yj ~1 ' ' :'.' ' . Equations showing the reactions just discussed are as follows:

A) Using isothiourea base with an isocyanate ~, SR2 SR2 ~ ,., R-N'CNHRl ~ R3NCo > R-N=CN-Rl ." I :
o=CNHR3 ~, :
B) Using isothiourea salt + a base SR
~ R-NaCNHRl HX + Et3N + R3NCo -~ > -~
.s SR2 :
', R-~-CNRl + Et3N-HX ¦
OsCNHR V

i C) Using isothiourea base with an acid chloride . ~ ;

J/ SR2 11 Et N SIR2 RN~CNHRl + R3CC1 3 ~ RN=CNRl + Et3N HCl ;' ' ..
i ~. .

i . . ~ . .

-- 113!~8~33 , The isothiourea precursors of the prior art discussed above can in general be prepared by the methods disclosed in U.S. Patents 3,969,511 and 4,062,892.

These compounds are useful as lepidoptericides when used in a lepidoptericidally effective amount on insects of the order lepidoptera or their habitat or feedstuffs. Some of the compounds also show phytotoxic effects which could render them useful as herbicides as well as lepidoptericides if such efficacy was desired. In addition, some of these compounds show biocidal and/or fungicidal effects.

i; By l'lepidopteric~dally effective amountll is meant the amount of the herein disclosed lepidoptericidal compounds which when applied in any conventional manner to the habitat of the lepidoptera, the feedstuffs of lepidoptera, or the insects themselves, will llcontrolll by killing or substantially in~uring a significant portion of the lepidoptera.
s : ~
These compounds are useful in protecting food, fiber ~ forage crops and ornamental crops from damage by insects and i~ larva of other order lepidoptera. Examples of crops to be protected include forest trees such as oak and pine, fruit trees such as peach, apple and walnut, vegetables such as tomatoes, other crops such as tobacco, cotton, lettuce, cabbage, corn and rice and any crop which lepidoptera feed upon. ~ ~`

~ A .
The novel compounds of this present invention can be prepared from the above precursors by methods shown in the following examples.
i .

, ., .:

3~8~33 ,~ :
. ~ -19-` Example 1 . .
i 1~3-DihePtyl-2-ethyl-3-(0,0-dimethyl phosphoro)isothioure~
.. . . .
6.0 grams (g) (0.02 mole ) of 1,3-diheptyl-2-ethyl isothiourea and 200 milliliters (ml) of methylene chloride were combined in a 500 ml 3-neck flask fitted with a stirrer, thermometer and dropping funnel~ The solution was stirred and cooled to 0C. 2.0 g (0.02 mole ) of triethylamine was added to the flask. Next, 3.0 g - (0.02 mole ) of phosphorus oxychloride dissolved in 25 ml of methylene chloride was added at such a rate that the pot temperature was maintained at 0 to 5C. After the addition was complete, the reaction mass was stirred at 0C
for 30 minutes. Then, a solution of 8.7 g (0.04 mole ) of 25 percent sodium methoxide in methanol with 25 ml of methylenechloride was added over a period of 15 minutes while the pot temperature was maintained at 0 to 5Co The reaction mass was then stirred at 5C for 30 minutes i and then at room temperature for 30 minutes. The resulting mixture was then washed with two 200 ml portions of water , and phase separated. The methylene chloride phase was dried with anhydrous MgS04, filtered and evaporated ; 20 invacuo to yield 7.4 g of the desired product, 1,3-diheptyl-2-ethyl-3-(0,0-dimethylphosphoro) isothiourea which had a nD of 1.4528. The product identification ~ was confirmed by infrared (IR), H-nuclear magnetic r resonance (NMR) and C13-NMR spectra. Compound No. 229 in TableI.

,i ,,~
,ii , .......................................................................... .
.:
.,, '.;, -" . . ~

Example 2 1,3-diheptyl-2-ethyl-3- N-[4~methYl-3-(carbowax-350-carbamyl)l phenyl carbamyl isothiourea ,,s The title compound was formed as follows:
-.
Intermediate a) :, :
3.56 g (0.02 mole) of 2-methyl-5-nitrophenyl-isocyanate, 7.0 g (0.02 mole) of carbowax 350, 2 drops of triethylamine, 1 drop of di- butyltindilaurate and 25 ml of methylene chloride were combined with stirring in a 100 ml round bottom flask. After the exotherm had sub~
sided, the solvent was removed invacuo. The residue was dissolved in a 10:1 mixture of diethylether-toluene. A
white solid impurity was removed by filtration and ~ evaporation of the filtrate invacuo gave 10.5 g of the Ji 10 desired compound N-(2-methyl-5-nitrophenyl) carbowax (350) carbamate, n30 1.4810. The structure was confirmed by ~-~
C -NMR spectra. ~-Intermediate b) 3 - - ;
7 g (0.013 mole) of intermediate a) was dissolved , in 200 ml of ethanol in a Parr glass pressure bottle. 1 i 15 g of palladium on carbon catalyst was added and the mixture was shaken and reacted with hydrogen maintained at a pressure of 50 psi for 30 minutes. The reaction mass was then filtered and the filtrate was evaporated invacuo to yield 6.0 g of the desired compound N-(2-methyl-5-amino-phenyl) carbowax (350) carbamate. The structure was confirmed by C 3-NMR spectra.

i , :
'I " :

1~3~883 s, --21--,: :
Intermediate c) :.,, ~ 5.8 g (0.0116 mole) of intermediate b) was - ' -~ dissolved in 200 ml of toluene in a 250 ml 3-neck flask i fitted with a condenser, stirrer and gas inlet tube. The ~~
solution was stirred, heated to 70C and saturated with i 5 HCl gas. The mixture was then heated to reflux and phosgene was bubbled in for 30 minutes. The reaction mass became clear. N2 gas was then bubbled in to remove the excess phosgene. The solvent was removed invacuo to yield 6.1 g of N-(2-methyl-5-isocyanophenyl) carbowax (350) carbamate, n3 1.5848. The structure was confirmed by C 3-N~R spectra.
f~' ii 1~3-diheptyl-2-ethyl-3- N-[4-methyl-3-(carbowax-350-carbamYl)] phenYl carbam~rl isothiourea

2.0 g (0.004 mole) of intermediate c), 1.2 g (0.004 mole) of 1,3-diheptyl-2-ethylisothiourea, 2 drops of triethylamine and 15 ml of methylene chloride were combined-il a 100 ml round bottom flask. After the exotherm had subsided, the solvent was removed invacuo to yield 3.3 g of the desired product, 1,3-diheptyl-2-ethyl-3- N-[4-methyl-3-(carbowax-350-carbamyl) phenyl clarbamyl isothiourea. The structure was confirmed by 20C 3-NMR spectra. Compound No. 21~ in Table I.
, ~.
, ..... . . .

~:s.;~

.

~,, :~' ;~

-` 113!i3B~3 . -22-,. . .
` Example 3 , :
1 3-diheptyl-2-ethYl-3-[N-(3-tergitol (15-S-7) :' oxycarbamylphen~l) carbamyl] isothiourea The title compound was formed as follows:

Intermediate d) -~
i; .
i In the same manner as intermediate a) of ~ -i Example 2 above, 3.28 g (0.02 mole) of 3-nitrophenyliso- -''5, cyanate, 10.1 g of tergitol (15-S~7), 2 drops of tri-ethylamine and 25 ml of methylene chloride were combined ~;~
to yield 13.2 g of the desired compound, N-(3-nitrophenyl) tergitol (15-S-7) carbamate. Structure was confirmed by IR spectra.
"., . ~ ~
Intermediate e) ; In the same manner as intermediate b) of Example ~ ~
, 2 above, 11.2 g (0.0166 mole) of intermediate d) was ~ -reduced with H2 in ethanol using 1 g of palladium on carbon catalyst to yield 9.3 g of the desired compound, , N-(3-aminophenyl) tergitol (15-S-7) carbamate. Structure was confirmed by IR spectra.

Intermediate f) ~ In the same manner as intermediate c) of Example !~' 15 2 above, 9.3 g (0.0145 mole) of intermediate e) was treated;;~ w~th excess HCl ~s followed by excess phosgene to yield ~; 9.4 g of the desired compound, N-~3-isocyanophenyl) tergitol (15-S-7) carbamate. Structure was confirmed by IR spectra.

:1 .

.. . .

1~3~?~83 , 1,3-diheptyl-2-eth~1-3-~N-~3-ter~itol (15-S-7) oxycarbamylphenyl) carbamyl] isothiourea ~' ,, In the same manner as the title compound of --Example 2 above, was prepared 2 g (0.003 mole) of ;-.
intermediate f) was combined with 0.9 g (0.003 mole) of 1,3-diheptyl-2-ethylisothiourea, 2 drops of triethylamine and 10 ml of methylene chloride to yield 2.9 g of the desired product, 1,3-diheptyl-2-ethyl-3-[N-(3-tergitoi (15-S-7) oxycarbamylphenyl) carbamyl] isothiourea nD
1.5710. Structure was confirmed by IR spectra. Compound No.
219 in Table I.
Example 4 1~3-diheptyl-2-ethyl-3-(0.0-diethylphosphorodithioyl : acetyl) isothiourea Intermediate g) 30 g (0.1 mole) of 1,3-diheptyl-2-ethylisothiourea, 12.4 g (0.11 mole) of chloroacetylchloride and 250 ml of toluene were combined in a 500 ml 3-neck flask fitted with a stirrer, thermometer and dropping funnel. The solution was stirred and cooled to -30C with a dry-ice bath.
11.1 g (0.11 mole) of triethylamine was then added over a period of 30 minutes. After the addition was complete, the reaction mass was allowed to warm to room temperature "
and stirring was continued for 1 hour. The reaction mass was then washed in turn with two 200 ml portions of water, 100 ml of saturated sodium bicarbonate solution and ; finally with two 200 ml portions of water. The toluene phase was dried with anhydrous MgS04, filtered and evaporated invacuo to yield 3601 g of the desired compound, 1,3-diheptyl-2-ethyl-3-chloroacetylisothiourea. The structure was confirmed by IR and NMR spectra.

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

.
:

; -

3~8;~
, .

,'.:
- 1~3-diheptyl-2-ethyl-3-(0,0-diethylphosphorodithioyl acetyl isothiourea .'~ .... ' ~ "~
~'t 2.2 g (0.012 mole) of 0,0-diethyldithiophosphoric ~ ~-s acid was dissolved in 25 ml of acetone and was treated - ~
~ .
i with 5 g of anhydrous potassium carbonate. After neutraliza-, tion, the acetone phase was decanted into a 250 ml flask `
J 5 containing a solution of 3.0 g (0.008 mole) of intermediate g) in 75 ml of acetone. The resulting mixture was stirred at room temperature for 2 hours, then was poured into two 200 `~ -ml of toluene. The resulting mixture was washed ~ith t~o 200 ml portions of water. The toluene phase was then -~;~ 10 dried with anhydrous MgS04, filtered and evaporated invacuo to yield 3.6 g of the desired product, 1,3-diheptyl-2-ethyl~
3-(0,0-diethylphosphorodithioylacetyl) isothiourea. nD
1.5060. The structure was confirmed by IR and NMR spectra. `
.! Compound No- 261 in Table I.
Example 5 ,,i N.N'-dihePt~l-S-ethYl-N-proPane sulfonyl isothiourea 1.8 g (0.018 mole) of triethylamine was added to 4.5 g (0.015 mole) N,N'-diheptyl-S-ethyl-isothiourea ~, in 50 ml methylene chloride in a stirred round bottom `
flask. A solution of propanesulfonyl chloride (0.018 mole, 2.6 g) in 8 ml methylene chloride was added dropwise to ~3 the above solution at 0C. The mixture was stirred 1.5 ~; 20 hours at room temperature then at 30-35C for 1.5 hours. The ~; cooled solution was washed twice with 20 ml water, once with 25 ml saturated sodium bicarbonate solution and twice more with 20 ml of water. The organic phase was dried over magnesium sulfate and evaporated invacuo to yield the product as a yellow oil. n30 1.4805. Yield was 5.2 g `~
(85.4%of theory). The structure was confirmed by IR
t,',,~ spectrum. Compound No. 203 in Table I.
~F~

~13~ 3 Exam,ple 6 ~, N.N'-dihePtyl-S-ethyl-N'-p-toluene sulfonyl isothiourea ' The reaction was carried out with 0.018 mole -~~
(3.4 g) p-toluenesulfonyl chloride in the same manner as Example 5 above. The product had a n30 of 1.517. Yield was 6.0 g (88~/o of theory). IR, NMR spectra and mass spectroscopy confirmed the structure. Compound No. 206 in Table I.
Example 7 1,3-di-n-heptyl-l-trichloromethylthio-2-ethYl isothiourea .
3 g (0.01 mole) 1,3-di-n-heptyl-2-ethyl isothiourea was mixed with 50 ml tetrahydrofuran in a stirred round bottom flask and cooled in an ice bath. 1.4 ml (0.01 mole) triethylamine was added and the mixture stirred for 10 t~ 10 minutes. 1.1 ml (0.01 mole) trichloromethyl sulfenyl chloride was added to the mixture dropwise over 2 minutes.
A white precipitate formed and ~he mixture was stirred for 1 hour while coming to ambient temperature. The resultant reaction mixture was allowed to sit overnight. The mixture was suction filtered to remove the white solid which was rinsed twice with 10 ml of fresh tetrahydrofuran. The j filtrate was evaporated under vacuum resulting in 4.55 g of the title product at a yield of 101.2 percent. The resulting liquid had a n30 of 1.5084 and was identified as the title compound by IR spectrum and mass spectroscopy.
Compound No. 297 in TabLe I.

~~ 1 1 3~ 8 ~ 3 - ExamPle 8 1,3-di-n-heptyl-1-(2'-fluoro -1',1'.2' 2'-tetrachloroethylthio-. 2-ethylisothiourea , . . .
2.0 g (0.007 mole) 1,3-di-n-heptyl-2-ethyl iso-' thiourea was dissolved in 100 ml tetrahydrofuran and placed in a stirred round bottom flask and placed in an ice bath.
; 0.7 g (.0069 mole) triethylamine was added and the mixture - -stirred for 10 minutes. 1.68 g (.0068 mole) 2-fluoro-1,1,2,2-tetrachloroethylsulfenyl chloride dissolved in 20 ml of tetrahydrofuran was added over approximately 15 minutes.
A precipitate formed while the mixture was stirred for 2 hours.
The mixture was suction filtered and the precipitate was washed twice with 20 ml tetrahydrofuran. The filtrate was vacuum evaporated. The title product's yield was 3.53 g of a liquid having a nD of 1.5091. The product identity was confirmed by IR spectrum and mass spectroscopy. Compound No. 298 in Table I.

, Example 9 f 1.3-di-n-heptyl-1-o-nitrophenylthio-2-ethylisothiourea 1.9 g (0.01 mole) of 2-nitro benzene sulfenyl chloride was di~solved in 50 ml of tetrahydrofuran. A mixture of 3 g (0.01 mole) 1,3-di-n-heptyl-2-ethylisothiourea in 30 ml of tetrahydrofuran was added to the mixture in a glass round bottom stirred flask cooled in an ice bath. 1.05 g (0.01 mole) ;~ 20 of triethylamine in 10 ml of tetrahydrofuran was added over a period of 10 minutes. A white precipitate formed immediately and the reaction mixture was stirred in the bath for 3 hours while coming to ambient temperabure and then suction filtered.
The filtrate was vacuum evaporated to produce , ;-.
, ,i~- , : : .. .
, ~. , : -`" 1 1 3~8 ~ 3 - a light brown sticky residue which was redissolved in approximately 100 ml diethyl ether and filtered through magnesium sulfate and Dicalite 4200 by suction. The filtrate was vacuum stripped to produce 4.2 g of a liquid having -~
a n30 of 1.5463. The product was identified as the title product by IR spectrum. Compound No. 300 in Table I.

Example 10 , . . .
~' S-ethYl-1~3-dihePtYl-3-(2-carboethoxy) ethyl-2-isothiourea ., ,,~
3 g (0.01 mole) of S-ethyl-1,3-diheptyl-2-iso-thiourea and 3 g (0.03 mole) of ethyl acrylate were placed in a 100 ml glass flask. A catalytic amount of base (0.1 g NaH) was added and the mixture heated from 25 to 85C
;~ and held at 85C for 5 hours. The reaction mixture was cooled and 150 ml of ether was added.
, The ether was washed with 100 ml of water, then dried and stripped to yield 2 g of the title product. The structure was verified by IR and NMR spectra.
Compound No. 199 in Table I.
Example 11 S-eth~1-1.3-diheptyl-3-(3-oxobutyl)-2-isothiourea The procedure was the same as for Example 10 `
, except ethyl acrylate was replaced with methyl vinyl ketone and the reaction was run at room temperature for

4 hours. Work-up of the product ~as the same. 2 g j 20 of the title product was produced and identified by IR
; and NMR spectra. Compound No. 200 in Table I.
.~
,........................................................................... .

,, . ~ .

.
~, , . ~ .
~, ~

~ 3~ 3 ~, Example 12 .:
N,N-di-n-heptyl-N'-ethyloxalyl-S-ethyl-isothiourea ,

5.0 g (16.6 millimoles) of S-ethyl-1,3-diheptyl-2-isothiourea and 1.8 g (18.3 millimoles) of triethylamine in 50 ml of methylene chloride were mixed together in a 100 ml single necked round bottom flask equipped with a magnetic stirrer and stopper. The clear light yellow solution was cooled to 0C in an ice bath. To this stirred, cooled solution was added 2.50 g (18.3 millimoles) of ethyloxalyl chloride dropwise while maintaining the temperature between 5 to 15C. A large amount of a white precipitate formed within seconds and stirring was allowed to continue for 1 hour at 0C. The cooling bath was removed and the mixture stirred at room temperature for 3 hours. The precipitate was dissolved by the addition of 50 ml water and the mixture transferred to a separatory funnel containing 50 ml of methylene chloride. The layers were separated and the organic phase washed once with 10 ml of saturated NaHC03, 3 times with 10 ml portions of water, once with 10 ml of saturated sodium chloride and dried over Na2S04. The dried, clear yellow organic solution ~ 20 was filtered through Na2S04 and the solvent was removed 3 under vacuum to yield 6.63 g (99.770 yield~ of the title ~ product as a clear, yellow oil having a nD of 1.4757. The ¦ product was identified as the title product by IR and NMR
spectra and mass spectroscopy. Compound No. 671 in Table I.

,'. . ~ :
-' ~, ~ . . - -1~3~33 , .

J, -29-~ Bis-N'-(N,N'-n-heptyl-S-ethylisothioureyl)-oxalate ... . . .
The procedure for Example 13 is the same as for Example 12 above with the exception that a 200 ml single necked round bottom flask was used in place of -the 100 ml flask and 1.16 g (9.13 millimoles) of oxalyl chloride was substituted for the ethyloxalyl chloride af ~i the previous example. The reaction resulted in a clear yellow solution which was stirred at 0C for 1 hour and then stirred at room temperature for 20 hours. The clear yellow solution was then transferred to a separatory funnel containing 50 ml of water and 50 ml of methylene chloride.
The layers were phase separated and the organic phase ~ ;
washed once with 10 ml of 10 percent potassium carbonate, ~ -5 times with 10 ml portions of water, once with 10 ml of saturated sodium chloride and dried over Na2S04.
~ 15 The dried organic solution was filtered and the solvent -~
r,~,, removed as in Example 12 to yield 5.55 g (102.1Z of theory yield) of an orange oil having a nD of 1.4932.
The product was identified as the title product by IR
and NMR spectra and mass spectroscopy. Compound No. 688 in Table I.
Example 14 , .
~ N.N'-Di-(l-heptyl)-N'-(ethylmercapto carbonyl)-S-ethYl ,, .
isothiourea The procedure and equipment were the same as ;` in Example 12 above with the exception that 5.0 g (16.6 f millimoles) of N,NI-di-(l-heptyl)-S-ethyl isothiourea and ' 1.85 g (18.3 millimoles) of triethylamine and 50 ml of methylene chlorde were added to the flask followed by ~ 25 addition of 2.28 g (18.3 millimoles) of ethylthio ':! chloroformate. The resultant product was phase separated, .,~ . .

i, .
,........................................................................... .
. .
., ~;

1~3~ 3 :

~ washed and dried in a manner of Example 12. The :~ solvent was removed under vacuum to yield 6~55 g (101~5~/o of theory yield) of accrued yellow oil having a nD of 1.4922. The product was identified as the title-~
, 5 product by IR and NMR spectra and mass spectroscopy. ~ -.
Compound No. 300 in Table I.

~. "' :
;

,~ ~
" ~ ~:
.~

J, , ~-, ,, ' .'. , ~. .

., -~
.:
~ ! .

., .
., ~'' ' '' ~ : ' ' ~, ' , ', ' ' :'~ ' - ' ' ' \
1131~883 ,. . . .

:
Example 15 ~
, 1~3-diheptyl-2-ethYl-3-[3~-2 "-ethoxyethoxycarbonylamino~-4'-methylphenylaminocarbonyl) isothiourea ~~ -~

The title product was prepared as follows:

Step a) 1,3-diheptyl-2-ethyl-3-(3-isocyanato-4-methylphenyl-aminocarbonyl) isothiourea (Intermediate).
"
125 cubic centimeters (cc) of methylene chloride -~
was pipetted under argon flow into a 200 cc 3-neck stirred flask,l5.1 g (0.86 mole) of toluene - 2,4-diisocyanate was then added to the methylene chloride. Next, 25.8 g (0.086 mole) of 1,3-diheptyl-2-ethyl isothiourea was added without cooling over a period of 5 minutes. The temperature increased from 20 to approximately 30C during this addition.
! The reaction mixture was then heated to reflux (41C) and ~ held at reflux temperature for 1 hour. The resultant ;! reaction mixture was then concentrated on a rotary evaporator under high vacuum. The reaction produced 39.8 g ; 15 of product having a ~ of 1.5318 which was identified as the intermediate title product by IR and carbon 13 NMR
spectra.

Step b) Preparation of 1,3-diheptyl-2-ethyl-3-[3'-(2 "
ethoxyethoxycarbonylamino)-4'-methylphenylaminocarbonyl]
isothiourea.

~! 4.74 g (0.010 mole) of the intermediate of step a) 0.95 g (0.0105 mole) 2-ethoxyethanol, 2 drops of triethylamine, 1 drop of dibutyltindilaurate and 25 cc of tetrahydrofuran dried over a Linde Molecular Sieve 3A were chasged to a 3-neck flask. The mixture was brought to reflux (67 to 68C) and held at reflux for 2 hours. The solvent was then removed under high vacuum at a pressure of 0.3 mm or less and at a , :

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

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

1~3~ 3 :. -, . . .
bath temperature of 80 to 90 C. 5.6 g of a viscous oil was recovered and identified as the title product by IR
~ and carbon 13 NMR spectra analyses. Compound No. 419 in t !;'' Table I.
` Example 16 -'~
ç
1.3-diheptyl-2-eth~1-3-~3~-(3 "-chloro-4~-methYlphenyl-ureido)-4'-methylphenylaminocarbonyll isothiourea The reaction and reactants were identical to the reaction of Example 15 b) with the exception that 1.49 g (0.0105 mole) of 3-chloro-4-methylaniline is substituted for the 2-ethoxyethanol. An insoluble by-product was formed which was removed by filtering before ; evaporation of the solvent. The reaction produced 3.5 g , 10 of a product identified as the title product by IR and NMR
spectra analyses. Compound No. 429 in Table I.

~, Example 17 1.3^diheptyl-2-eth~1-3-~3'-propylureido-4'-methYlPhenyl-~J
aminocarbonyl] isothiourea 4.74 g (0.010 mole) of the intermediate as prepared in ~xample 15 a) and 25 cc of dry tetrahydrofuran were charged to a 3-neck flask. 0.62 g (0.0105 mole) of propylamine was added at room temperature without cooling.
The reaction was exothermic and the temperature rose about 10 to 20C. No heat was applied to the mixture and the ~ ~-reaction was completed in 1 hour. The mi~ture was filtered from a small amount of solid by-product and was worked up in the manner of Example 15 b). The reaction produced 5.0 g of a liquid having a n30 of 1.5312 and was identified , as the title product by IR and carbon 13 NMR spectra analyses~ Compound No. 431 in Table I.
,, . , .

.

, .

~13!~1~83 Example 18 l,3-diheptyl-2-ethyl-3[3'-p-chlorobenzylthiocarbonYlamino-, 4'-methylphenylaminocarbonyl] isothiourea The reactants were the same as in Example 15 b) with the exception that l.66 g (0.0105 mole) of 4-chloro-benzylmercaptan was substituted for the 2-ethoxyethanol.
The reaction produced 6.5 g of a viscous liquid which -was identified as the title product by IR and NMR
spectra analyses. Compound No. 433 in Table I.
Example l9 1.3-diheptvl-2-ethyl-3-(3'-phenoxy_arbonylamino-4'-methyl-phenylaminocarbonyl) isothiourea The reactants were the same as in Example 15 b) with the exception that 0.99 g (0.0105 mole) of phenol was subætituted for the 2-ethoxyethanol. The reaction produced 5.2 g of a liquid having a ~ of 1.5488 whi~h was identified as the title product by NMR and IR spectra analyses.
Compound No. 452 in Table I.
Example 20 l-octyl-2-ethyl-3-sec-heptyl-3-13-(l-octyl-2-propyl-3-sec-heptyl-3-carbonylamino)-4-methylphenylcarbonylamino isothiourea Step a) Preparation of l-octyl-2-ethyl-3-sec-heptyl-3-(3-isocyanato-4-methylphenylaminocarbonyl) isothiourea -(Intermediate).

This intermediate was prepared as was the intermediate of Example 15 a) with the exception that 27.2 g (0.086 mole) of l-octyl-2-ethyl-3-sec-heptyl-, - . - -. ~ -~ "

~3~383 .
~; -34-,.~
isothiourea was substituted for the thiourea reac~ant ` of step 25 a). The reaction produced 41.5 g (98.8 weight percent of theory) of a liquid having a nD of 1.5280 ~ which identified as the title intermediate by IR and 4, 5 carbon 13 NMR spectra analyses, 7. ' Step b) Preparation of l-octyl-2-ethyl-3-sec-heptyl-3-~- 13-(1-octyl-2-propyl-3-sec-heptyl-3-carbonylamino)-4- .
methylphenylcarbonylamino] isothiourea.
The title product was prepared in the manner of 1 step 15 b) with the exception of using 4.87 g (0.010 mole) of the intermediate prepared in step 20 a) and 3.29 g (0.010 mole) of 1-octyl-2-propyl-3-sec-heptyl isothiourea.
The reaction produced 7 9 g (96.3 weight percent of theory) of a liquid having a nD of 1.5185 which was identified as the title product by IR and carbon 13 NMR spectra analyses. ~ -Compound No. 558 in Table I.
Example 21 1.3-bis-n-heptyl-1-(carbamylsulfonylchloride)- ;~
2-S-eth~l isothiourea '~'3 50 ml of dry methylene chloride and 8.49 g of ~ chlorosulfonyl isocyanate (aldrich) were placed in a 200 ml ;:, flask provided with a magnetic stirrer, thermometer and ; dropping funnel. A solution of 18 g of the 1,3-diheptyl-2-ethyl isothiourea (in 100 ml dry methylene chloride)was added dropwise over 40-45 minutes. The reaction exhibited -a slight exotherm so the flask was cooled in a water bath !,`,~, to hold the temperature below 28C. The solution was then stirred at about 25C overnight.

~ The solution was then filtered and the filtrate ; 25 concentrated under reduced pressure. 26.2 g (99 weight s percent of theory) of a thick liquid having a nD of 1.4833 .,s !;' . .
`: ~

:` - : : :, :

113~ 3 .

was recovered. The product was identified as the title product by IR and NMR spectra analyses. Compound No. 635 in Table I.
Example 22 --1.3-bis-n-heptyl-1-chlorocarbonyl-2-ethyl isothiourea 100 ml of dry CH2C12 was placed in a 500 ml flask equipped with a thermometer and dropping funnel and coolëd to 5C in an ice bath. A solution of phosgene in benzene (170 g of 17.5 percent weight concentration) was then added.
Next, a solution of 100 ml of dry CH2C12, 10.1 g triethyl-amine and 30 g of 1,3-diheptyl-2-ethyl isothiourea was added dropwise over a one hour period at 5C. The mixture was then stirred overnight at ambient temperature.

The next morning the reaction mixture was warmed to about 40C for 2 1/2 - 3 hours to ensure completion of the reaction. The mixture was then sub~ected to reduced pressure to remove the CH2C12 solvent. 100 ml of dry ether was added and the mixture flltered by suction on a glass ~ frit. The solid was washed by a little more ether and the ; combined filtrates concentrated under reduced pressure to remove the ether. 38 g g of a liquid (106 weight percent , of theory) having a nD of 1.4613 was recovered. The ; 20 product was identified as the title product by mass spectra sn-ly~es. Co~pound No, 643 in Table I.

~

, ~

, c . .

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

- ~J.3~3~83 Example 23 1~3-bis-n-heptyl-1-diethylcarbamvl-2-ethyl i~othiourea , ;~
.~ , 100 ml of dry benzene and 5.44 g of 1,3-diheptyl-2-ethyl isothiourea carbamyl chloride were placed ~n a 200 ml flask equipped with a thermometer and dropping funnel.
- A solution of 12 ml dry benzene and 2.19 g diethyl amine was added dropwise over 10-12 minutes. An exotherm raised the temperature from 21 to 30C. The mixture was then ~
heated to 45-50C for 3 hours. The reaction mixture was ~-then cooled to 15C and wa~hed twice by 50 ml portions of cold water. The benzene phase was dried by MgS04, filtered and the solvent removed under reduced pressure. 5.75 g of a liquid (96 weight percent of theory) having a nD of 1.4568 was recovered. The structure was confirmed as the title compound by mass spectra analyses. Compound No. 644 in -~
Table I. ~-Example 24 ,~.
1.3-bis-n-heptyl-1-(propargyloxycarbonyl)-2-ethyl isothiourea 50 ml of dry tetrahydrofuran and 0.36 g of NaH were placed in a 200 ml flask equipped with a thermometer and dropping funnel. A solution of 10 ml dry THF and 0.84 g ' propargyl alcohol was added dropwise over 8-10 minutes. The reaction mixture liberated hydrogen and exhibited a slight exotherm. The mixture was then stirred for 3 hours to complete the reaction. -Then a solution of 15 ml dry THF and 5.44 g of the 1,3-diheptyl-2-ethyl isothiourea carbamyl chloride was ~ added dropwise over 10 minutes. The mixture was stirred ! and warmed to 45C for 2 hours. The reaction was cooled to 25C and filtered by suction on a glass frit and filter.

' :

', . . , ' ' ' ' ' ~ ' : /-1~3~ 3 The solvent was removed under reduced pressure, S.0 g of a liquid (88 weight percent of theory) having a n30 of 1.4553 was recovered. The structure was confirmed as the title compound by NMR and spectra analyses. Compound No. 648 in -~
Table I. ~7-Example 25 , - 1.3-bis(2-ethYlhexvl)-l-(succinic anhydride adduct)2-ethyl-isothiourea-Et3N salt 200 ml of dry CH2C12, 32.8 g of 1,3-(2-ethylhexyl)-2-ethyl isothiourea, 11 g of succinic anhydride and 11.1 g of Et3N were placed in a S00 ml flask. There was a slight exotherm upon mixing these components. The solution stood overnight.
.;~
The reaction mixture was then stripped under ~, reduced pressure. 47.3 g of a liquid (89 weight percent of theory) having a n30 of 1.4899 was recovered. The structure was confirmed as the title compound by IR and NMR spectra analyses. Compound No. 665 in Table I.
,j, , ', ~

. ' ~ .
, ~
.: .
, .
;. :
..
:
.
. ., ., ...
.
.~ . .

, :

: 1~3!~?~83 ,~
ExamPle 26 Reaction product of 2 moles of 1.3-di-(2'-ethylhexyl)-2-S-ethyl isothiourea + toluene-2,4-diisocYanate . . .
r. In a three-neck 200 ml flask equipped with a magnetic stirrer,3.28g (0.01 mole) of 1,3-di-(2'-ethyl-hexyl-2-S-ethyl isothiourea was mixed with 20 ml of tetra-hydrofuran. To this solution was added 0.87 g (0.005 mole) of toluene-2,4-diisocyanate. The temperature rose from 23C to 34C. The mixture was allowed to stand at ambient ~ ~-temperature overnight after which it was evaporated under --vacuum. Infrared analysis showed that the reaction was incomplete, therefore, the mixture was dissolved in 30 ml of methylenechloride and 1 drop of dibutyltindilaurate and 2 drops of triethylamine were added. The homogenous solution was stirred at ambient temperature for 1.5 hours.
The mixture was reevaporated under vacuum to obtain the product as a vigcous yellow liquid having a n30 of 1.5201.
The yield was 4.3 g. The product was identified as the title compound by both IR and NNR spectra analyses.
Compound No. 85 in Table I.

Example 27 .~ .
~ 1.3-di-n-heptyl-1-N-phenYlcarbamyl-2-S-n propyl isothiourea ~!
The equipment was as in Example 26 above. 6.2 g (0.014 mole) 1,3-di-n-heptyl-2-S-n-propyl isothiuronium-hydrogen iodide was dissolved in 35 ml of tetrahydrofuran and 1.68 g (0.014 mole) phenyl isocyanate was added followed by a portion-wise addition of 1.43 g (0.014 mole) triethylamine with cooling.
A solid precipitate formed on addition of the triethylamine.
The reaction was stirred at ambient temperature overnight.
The reaction mixture was then vacuum evaporated to remove , .. ~ . ' 1~3~ 33 tetrahydrofuran and the residue was dissolved in chloro-form and washed two times with 150 ml portions of water.
The organic phase was then dried over magnesium sulfate, filtered anduRcuum evaporated to remove the chloroform. -~
The product was 5.9 g (96.7 weight percent of theory yield) -of a yellow liquid having a nD of 1.5188. The product was identified as the title compound by IR and NMR spectra analyses. Compound No. 11 in Table I.
;.
; Example 28 . .
~3-di-n-heptyl-l-N-octadecylcarbamyl-2-s ethyl isothiourea The equipment was the same as in Example 26 above.
; 10 4.5 g (0.015 mole) 1,3-di-n-heptyl-2-S-ethyl~sothiourea was mixed with 40 ml tetrahydrofuran and 4.43 g (0.015 mole) N-octadecylisocyanate was added. Three drops of triethyl- ;-amine were added and the mixture stood overnight. The K, mixture was then warmed to 40C for 20 minutes to complete the reaction. A small amount of solid formed on cooling and was filtered off. The reaction mixture was then vacuu~ evaporated to produce 8.9 g (100 percent of theory yield) of a pale liquid having a nD of 1.4750. The product was identified as the title product by IR and NMR spectra analyses. Compound No. 29 in Table I.
,.. . Example 29 .
1.3-di^n-hept~l-1-N-4-methYlthiophenylcarbam~1-2-S--~thyl isothiourea The equipment was the same as in Example 26 above.
3.0 g (0.01 mole) 1,3-di-n-heptyl-2~ -ethyl isothiourea was mixed with 25 ml of methylene chloride. Two drops of triethylamine and 1 drop of dibutyltindilaurate were .,~ . . .
,, -,i.

,; ~ .
: ~

--- 113!!~3 - added and then 1.65 g (0.01 mole~ 4-methyl thiophenyl isocyanate was added. The temperature rose from 23~ to ~, 33. The reaction mixture was then vacuum evaporated - to remove the methylene chloride to produce 4.65 g (100 -~
percent of theory yield) of a yellow liquid having a _, nD of 1.5340. The liquid solidified on standing into a semi-solid. The product was identified a~ the title product by IR and NMR spectra analyses. Compound No.
; in Table 47 in Table I.
,', ; Example 30 1.3-di-n-heptyl-1-N-2-chloroethYlcarbamyl-2-s-ethYl isothiourea .
The procedure, equipment and reactants were the same as in Example 29 with the exception that 1.06 g (0.01 mole) of 2-chloroethylisocyanate was substituted for ; the 4-methylthiolphenyl isocyanate. The reaction produced 4.14 g (102 weight percent of theory yield) of a clear liquid having a nD of 1.4930. The product was confirmed as the title compound by IR and NMR spectra anlyses.
; Compound No. 48 in Table I.
i Example 31 .
l-sec-heptyl-3-n-heptYl-2-S-ethYl isothiourea tIntermediate) The equipment was the same as in Example 26 above.
11.5 g (0.1 mole) 2-aminoheptane was mixed with 50 ml ethanol 2B and 15.7 g (0.1 mole) N-heptyl isothiocyanate was added, resulting in an exothermic reaction during which the temperature rose from 25 to 65C. The reaction mixture was refluxed on a steam bath for 1.5 hours. 17.16 g (0.11 mole) ethyl iodide was then added to the thiourea and the mixture reauxed for 1.5 hours on a steam bath. The .: : .................. :
.

, 1~3~
.

product was vacuum evaporated to produce 44.0 g of an isothiuronium salt. The isothiuronium salt was dissolved in 200 ml of toluene and washed with 100 cc of 5 percent ~ sodium hydroxide. The toluene layer was then washed twice 5 with 150 cc portions of water, dried over magnesium sulfate,~
filtered and vacuum evaporated. The product was then stripped under high vacuum to produce 7.78 g (92.6 weight percent of theory yield) of a clear, yellow liquid having a nD of 1.4768. The product was identified as the title product by IR and NMR spectra analyses.

Example 32 l-sec-heptyl-3-n-hexyl-2-S-ethyl isothiourea (Intermediate) ; The equipment, procedure and reactants were the same as in Example 31 with the exception that 10.01 g (0.07 mole) of n-hexylisothiocyanate, 8.05 g (0.07 mole) 2-aminoheptane, 35 ml ethanol 2B, 11.7 g (0.075 mole) ethyl iodide, 200 ml of toluene and a one percent solution sodium hydroxide (0.08 mole) were used as reactants and reagents in the procedure. The reaction produced 19.6 g (98 weight percent of theory yield of a clear liquid having a n30 of 1.4765. The product was identified as the title product by IR and NMR spectra analyses.

Exam~le 33 . :.
1,3-di-n-heptyl-1-N-tert-butylcarbamyl-2-S-ethYl ~othiourea The equipment was the same as used in Example 26.
3.0 g (0.01 mole) 1,3-di-n-heptyl-2-S-ethyl isothiourea was mixed with 30 ml of methylene chloride. Two drops of tri- - -ethylamine and 1 drop of dibutyltindilaurate were added to the mixture followed by 1.0 g (0.01 mole) tert-butyl isocyanate.
The temperature rose from 24 to 39C. The reaction mixture was , ~:

~ '~ ~ ' `' , , - ~13E~3 .

stirred overnight at ambient temperature and then heated for one-half hour at 35 to 40C to complete the reaction. The reaction mixture was vacuum evaporated to produce 3.83 g (96 weight percent of theory yield) of a clear liquid having a nD of 1.4750. The product was identified as the title product by IR and NMR spectra analyses~ Compound No. 40 in Table I.

Example 34 1,3-di-n-heptyl-1-N-eth~lacetatecarbamyl-2-S-ethyl isothiourea The procedure, equipment and reactants were the same as in Example 33 with the exception that 1.29 g (0.01 mole) ethylisothiocyanato acetate was used in place of the tert-butyl isocyanate. The reaction produced 4.3 g (100 -~ weight percent of theory) of a clear liquid having a nD of 1.4800. The product was identified as the title product by IR and NMR spectra analyses. Compound No. 41 in Table I.

Example 35 ., ~ 3-di-n-heptYl-3-B-hYdroxyethYlcarbamYl methYlcarbamYl-2-S- ethYl isothiourea The equipment was the same as in Example 26.
9.0 g (0.03 mole) 1,3-di-n-heptyl-2-S-ethyl isothiourea was mlxed with 30 ml of methylene chloride to which 3.87 g (0.03 mole) ethylcyano acetate was added. The temperature rose from 23 to 45C during the reaction. The mixture was allowed to stand overnight. Then lO drops of additional isothiourea were added to react residual isocyanate. To the reaction mixture was then added 1.83 g (0.03 mole) of 2-aminoethanol and the reaction mixture was stirred overnight. The reaction mixture was vacuum evaporated to remove the methylene chloride and 25 ml of ethanol were added to the remaindeF of the ... ..

.~

.,. . ~ . . ~ . , .

reaction mixture. The reaction mixture was then allowed to stand for 3 days. The resultant cloudy mixture was then stirred at ambient temperature overnight, then vacuum evaporated to produce 13.7 g of a yellow, turbid liquid having a nD of 1.4800. The product was identified as the --title product by IR and NMR spectra analyses. Compound No. ~_ 64 in Table I.

ExamPle 36 Reaction product of 2 moles of 1~3-di-n-sec-heptyl-2-s-et~yl isothiourea + pp'-diphen~lmethane diisocyanate , :
; The equipment was the same as in Example 26.
3.0 g (0.01 mole) of 1,3-di-sec-heptyl-2-s-ethyl isothiourea 10 wa~ mixed with 30 ml of toluene. 1.25 g (0.005 mole) of s pp'-diphenylmethane diisocyanate was added to the mixture, i and the reaction mixture was heated and held for 2 hours at ~ - 75 to 80C. The IR showed a small isocyanate peak; so 10 drops of the isothiourea was added and heating continued for 30 minutes. The reaction mixture was then stirred at ambient temperature overnight. The reaction mixture was then vacuum evaporated to produce 4.5 g (104 weight percen~
of theory) of an amber colored liquid having a nD of 1.5310.
The product was identified as the title product by IR and NMR
~ 20 spectra analyses. Compound No. 127 in Table I. ~ -A ' Example 37 ; Reaction product of 2 moles of 1-N-sec-hept~1-3-N-n-hexy1-2-S-methYl-thiomethvl isothiourea I toluene 2,4-diisocyanate jJ
s The procedure and equipment were the same as in Example 36, but the reagents were 3.8 g (0.01 mole) l-sec-heptyl-3-N-n-hexyl-2-S-methyl-thiomethyl isothiourea, .87 g (0.005 mole) toluene-2,4-diisocyanate and 25 ml of -., .
. .

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, :
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: The product was identified as the title product by IR and NMR spectra analyses. Compound No. 138 in Table I.

Example 38 l-N-sec-heptyl-3-N-n-octyl-n-octadecylcarbamlrl-2-s-a isothiourea The procedure and equipment were the same as in Example 26. 1.9 g (0.006 mole) 1-sec-heptyl-3-n-octyl-2-S-allyl isothiourea was mixed with 25 ml of tetrahydrofuran to which 1.77 g (0.006 mole) n-octadecylisocyanate was added to the mixture. The reaction mixture was then stirred at ambient temperature overnight and then vacuum evaporated to produce 3.79 g (100 weight percent of theory yield) of a clear liquid ~ving a nDU of 1.4769. The product was identified as the title product by IR and NMR spectra analy~es. Compound No. 144 in Table I.

Exam~ple 39 Reaction product of 2 moles of 1-phenyl-3-n-heptyl-2-s-ethyl isothiourea + toluene-2,4-diisocyanate The equipment was the same as used in Example 26.
2.78 g (0.01 mole) 1-phenyl-3-n-heptyl-2-S-ethyl isothiourea ; in 35 ml of tetrahydrofuran were m~ed with 0.87 g (0.005 mole) toluene-2,4-diisocyanate. The reaction mixture was then refluxed on a steam bath for 1 hour, then 15 drops of the isothiourea was added, and the reaction mixture was refluxed for an additional hour to react all the isocyanate.

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113~8~3 The reaction mixture was vacuum evaporated to produce 4.1 g of a viscous, yellow liquid having a nD of 1.5737. The product was identified as the title product by IR and NMR
;~ spectra analyses. Compound No. 151 in Table I.
~, :
Example 40 ~-~
..
; N-(5-sila-5~5-dimethyl-1-heptyl)-N'-n-heptyl,n-octadecylcar-bamyl-2-s-ethyl isothiourea ,. . .
The equipment was the same as in Example 26. 2.4 g (0.007 mole~ l-(5'-sila-5',5'-dimethyl-N-heptyl)-3-n-heptyl-2-S-ethyl isothiourea in 25 ml tetrahydrofuran was mixed with 2.06 g (0.007 mole) N-octadecylisocyanate ant stirred at ambient temperature for 2 hours. The reaction mixture was vacuum evaporated to produce 4.51 g (100 weight percent of theory yield) of a clear liquid having a n30 of 1.4765.
The product was identified as the title product by IR and NMR spectra analyses. Compound No. 184 in Table I.

~ Example 41 r,, N-dichloroacetyl,N,N'-di-n-heptyl,S-ethyl isothiourea .
3.0 g (0.01 le) 1,3-di-n-heptyl-2-S-ethyl isothiourea dissolvet in 25 ml of methylene chloride was , placed in a three-neck 200 ml flask equipped with a magnetic ~tirrer. 1.1 g triethylamine was added to the mixture.
Then 1.5 g (0.01 mole) dichloroacetyl chloride in 10 ml of methylene chloride was added slowly while cooling the reaction mixture in an ice bath. The reaction m~xture was heated to and then held at 40C for one-half hour. The - reaction product was washed with water and the organic layer was dried with magnesium sulfate, filtered and vacuum stripped to yield 4.1 g of a liquid having a n30 of 1.4723. `~
The product was identified as the title product by NMR
spectra analysis. Compound No. 332 ~n Table I.

.

:` ~
- ~13~8~3 Example 42 , . .
Adduct of 1 mole 1,3-di-n-heptyl-2-S-eth~l isothiourea and 1 mole of di~lycolic anh~dride s, The equipment was the same as in Example 41.
3.0 g (0.01 mole) of 1,3-di-n-heptyl-2-S-ethyl isothiourea dissolved in 15 ml glycol and 1.2 g (0.01 mole) diglycolic anhydride dissolved in 10 ml glycol were added thereto.
The reaction was heated to reflux for 10 minutes and evaporated under vacuum to produce 4.1 g of a liquid having a nD of 1.4608. The product was identified as the title product by IR and NMR spectra analyses. Compound No. 321 in Table I.
. , .
r Example 43 Adduct of 1 mole 1~3-di-n-heptyl-2-s-ethyl isothiourea and 1 mole of succinic anhydride ', 10The equipment, procedures and reactants were the same as in Example 42 with the exception that L0 g (0.01 mole) succinic anhydride was substituted for the diglycolic anhydride. The reaction yield was 4.1 g of a semi-solid. The product was identified as the title product by NMR spectra -analysis. Compound No. 331 in Table I.

; Example 44 .
Adduct of 1 mole 1~3-di-n-heptyl-2-S-ethyl isothiourea and 1 mole of formaldehyde :!
~, The procedure, equipment and reactants were the ,i same as in Example 42 with the exception that 1.2 g formalde-hyde as a 37 percent solution in water (0.01 mole plus approximately 20 percent excess) was - ~

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substituted for the diglycolic anhydride. The reaction yield was 3.3 g of a semi-solid which was identified as the title product by NMR spectra analysis. ~, Compound No. 323 in Table I. ---- .
Example 45 Adduct of 1 mole 1,3-di-n-heptyl-2-S-ethyl isothiourea and 1 mole of p-anisaldehyde i~ 5 The equipment, procedure and reactants were the ;~
same as in Example 42 with the exception that 1.4 g (0.01 mole) anisaldehyde was substituted for the diglycolic an-hydr30de. The reaction yield was 4.3 g of a liquid having -a nD of 1.4825. The product was identified as the title product by NMR spectra analysis. Compound NoO 328 in Table I.

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~) -3~ 3 PIDOPT~RICIDAL EVALUATION
:

Lepidoptericidal activity of the above compounds were evaluated for efficacy on various lepidopterous species as follows:

I. Salt-Marsh Caterpillar ~Esti~mene acrea (Drury)~

A test solution is prepared by dissolv-ing the test compound in a 50-50 acetone-water solution. A
section of a curly dock (Rumex crispus) leaf, approxim~tely 2.5 cm wide and 4 cm long, is immersed in the test solution for 2-3 seconds, then placed on a wire screen to dry. The dried leaf is placed in a petri dish containing a moistened piece of filter paper, and infested with 5 second-instar salt-marsh caterpillar larvae. Mortality of the larvae is recorded 48 hours later. If surviving larvae are still present, a piece of synthetic media is added to the dish ~-~
and the larvae are observed for an additional 5 days in order to detect delayed effects of the test compound. The primary screening level for this test is 0.05 percent by weight of the test compound in the solution.

II. Cabbage Looper lTrichoPlusia ni (Hubner)l The procedure for cabbage looper larvae is the same as that used for salt-marsh caterpillar larvae, except that a cotyledon of hyzini squash (Calabacita abobrinha) of approximately the same size as the curly dock leaf section is used in place of the latter. The primary ~ -screening level for this test is 0.05 percent by weight of the test compound in the solution.

. ~ .

. , .

~` 1 ~ 3~ 8 8 3 III. Tobacco Budworm lHeliothis virescens (F.)l Larvae of the tobacco budworm are used in this test in a procedure identical to that used for salt-marsh caterpillar larvae, except that a Romaine lettuce (Latuca sativa) leaf section of approximately the same size .
as the curly dock leaf section is used in place of the latter. The primary screening level for this test is 0.1 percent by weight of the test compound in the solution.

Table II summarizes the results of the lepidop-tericidal tests performed on the compounds of Table I.
These test results are expressed as LD50 values, which represent the dose of test compound which was lethal to 50 percent of the insect population in the test. The entries in Table II were obtained as follows:

For a particular lepidoptera, each compound was anitially tested at the primary screening level. Those compounds showing less than 50 percent kill at this level are represented in the table by the primary screening level preceded by a "greater than" sign ( >). Those compounds showing approximately S0 percent kill are represented by the primary screening level alone. Those compounds showing greater than 50 percent kill were sub~ected to further testing at successively lower levels, until the level was found at which approximately 50 percent kill was achieved.
The latter level is listed as the LD50 for this group.

.

~` 1 ~ 3~ ~ ~ 3 Phvtotoxicity Tests Phytotoxicity tests are conducted on cotton (GossayPium hirsutum) and hyzini squash (Calabacita abobrinha) -seedlings. Plants are grown and treated in Kaiser No. 1059 ; ,' ;

6" x 9" x 3" aluminum flats. Each flat contains one row of cotton and one row of squash, with 6-8 plants per row. - ~ ' The plants are grown in the greenhouse and are treated when '~
they are approximately 8 days old and 2" tall.

Technical test compounds are diluted in a 50-50 acetone-water solution and formulated compounds are diluted ~ `
in water. These test solutions are then sprayed on the flats in a Ducon-Savko Model 3400 li,near spray table at rates of 1/2, 1, 2, and 4 lbs a.i./80 gallons/acre. The treated plants are then placed in the greenhouse and watered in such a way that the foliage is not wet.

One week later, the treated plants are inspected ~ ~`
and the degree of phytotoxicity is subjectively rated from O to 5 as follows~

O ~ no in3ury 1 - slight injury 2 - slight to moderate injury 3 - moderate injury 4 - moderate to severe injury 5 ~ severe in3ury or dead Table II also summarizes the results of the phyto-toxicity tests performed on the compounds of Table I.

~ - - ~. . ~ - . . .

/
~~ 1 ~ 3~ ~ ~ 3 .

The primary screening level in each of the above tests was selected for purposes of convenience only, and none of the figures in the table are to be understood as representing the highest level at which a viable test for lepidoptericidal activity can be conducted.

~3~8~3 ~ ;
~able II

Compound Lepidoptericidal Phytotoxicity No. Activity Cotton Squash .008 .01 ~,.05 0 0 2 0 0 2 2 .008 .003 .04 . 0 0 1 0 1 2 3 .0024 .006 .03 0 0 3 0 1 1 4 .016 .0016>.08 0 0 0 0 0 0 .003 .009 .15 1 4 4 1 4 4 6 .001 .005 .05 0 0 2 0 0 2

7 .002 . 0008 . 02 0 1 4 0 1 4

8 .0009 . ooog . 02 0 1 4 0 0 3

9 .0007 ,002 .01 1 3 5 0 2 5 .005 .0007 .02 ` 1 3 5 1 3 5 11 .008 .002 ~ . os o 2 s o 2 s 12 . ool .002 ~ . 05 0 1 5 0 2 5 13 .003 .003 > .05 1 2 5 1 2 5 14 .003 ~005 ? .05 1 3 5 0 2 4 .008 .008 > . 05 1 2 5 0 1 3 16 . 008 .008 ~ . os 1 3 4 0 2 4 17 .001 .002 ~ .05 1 2 4 0 1 4 18 . 05 .003 > .05 1 2 4 0 1 3 19 .003 .005 ~ .05 0 2 5 0 2 5 - 20 ~.008 .002 ~ . 05 1 2 4 0 1 3 21 .01 .003 ~.05 Q 1 2 0 1 2 22 .005 . 0008 ~ . 05 0 0 1 0 0 , "

; ~ ~

-22&-Compound Lepidoptericidal Phytotoxici~y No. ActivitY Cotton~~~~ Squash SMC CL ~ ~ 1/2 1 2 1/2 1 2 23 .003.0005 >.05 0 1 3 0 2 4 24 ~.05.01 >.05 0 1 3 0 1 2 .03.005 >.05 0 2 4 0 2 3 26 ~.05.01 >.05 1 2 3 0 1 2 27 .005.001 >.05 0 1 3 0 1 3 28 ~.05.003 .05 0 1 3 0 1 2 29 .002.002 >.05 0 0 0 0 0 .005.002 .05 0 1 2 0 0 31 .005.003 .05 0 1 2 0 1 3 32 .001.002 .01 0 1 3 0 1 3 33 .008.01 ~.05 0 0 1 0 0 1 34 .005.002 >.05 1 1 2 1 2 3 .01.0005 ~.05 0 1 2 1 2 3 36 .005.002 >.05 0 1 2 0 1 3 37 .002.002 .05 0 0 1 0 0 2 38 .003.005 ~.05 0 1 3 1 2 4 39 >.05.1 ~ .05 0 0 2 0 1 3 .001.001 .01 1 3 5 1 4 5 41 .003.03 >.05 0 0 1 0 1 2 42 .001.002 .OS 0 2 3 1 2 5 43 .002.002 ~.05 0 2 5 1 3 5 44 ~.05 .03 > .05 0 1 3 0 2 4 1~.3~l 383 Compound Lepidoptericidal Phytoto~icity No. Activity Cotton Squash .01 .0005.05 1 2 5 1 3 5 46 .01 .002 .05 0 0 1 0 1 2 47 .001 .001 .03 0 1 3 0 2 4 48 .005 .001 .03 1 2 4 1 3 5 49 .0003 .0002.05 l 2 5 1 3 5 .0003 .0003.05 1 3 5 1 / 3 5 51 .001 .001 .05 0 2 5 0 2 5 52 .005 .003 0 1 2 0 0 2 53 .008 .005 0 0 1 0 0 54 .008 .005 0 0 0 0 0 2 .002 .002 0 1 2 0 1 2 56 .001 .0003.02 1 2 3 1 3 4 57 .001 .0003.02 0 2 4 1 2 5 58 .002 .0005.05 0 2 3 0 3 5 59 .002 .0005.05 0 1 3 0 1 3 .003 .002 >.05 0 0 0 0 0 0 61 .008 .005 .05 0 2 5 0 3 5 62 .0008 .001 .05 0 1 2 0 1 2 63 .001 .005 ~ .05 0 0 1 0 0 2 64 .005 .008 ~ .05 0 0 1 0 0 1 .0002 .0005.02 1 2 5 1 3 5 66 .002 .03 .05 0 1 3 0 2 3 .. . . .. - . ~

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

:

~ 3~1~

~230-Compound Lepidoptericidal Phytotoxicity No. Activity Cotton Squash 67 .001 .002 .05 0 0 0 0 0 0 68 .0008 .005 .05 0 1 3 0 2 5 69 .0003.002 > .05 0 1 3 0 1 5 .001 .002 > .05 0 1 3 0 1 4 71 .001 .0005 .05 0 1 4 0 1 4 72 .0008 .002.05 0 0 1 0 1 2 73 .002 .003.06 0 0 1 0 0 74 .002 .002.03 - 0 0 0 0 1 0 7B .003 .03~ .05 0 0 0 0 0 0 76 .003 .03> .05 0 0 1 0 0 77 .01 .002 ~ .05 0 0 1 0 0 78 .002 `.0005 .05 0 1 2 0 1 3 79 .005 .002 > .05 .002 .0005 .01 0 0 1 0 0 1 81 .003 .002 .05 0 0 0 0 0 82 .008 .002 >.05 0 1 3 0 1 4 83 .005 .003 ~.05 0 0 1 0 0 1 84 .001 .0003 ~ .05 0 1 4 0 1 5 .005 .0003 .03 0 0 3 0 0 2 86 .002 .0008~.05 0 0 0 0 0 0 87 . ~02.002 > .05 0 0 3 0 1 4 88 .003 .0002 >.05 0 0 3 0 0 4 , : ~ ,:.. ~ . .

3~ ~ 3 ~-23`1-Compound Lepidoptericidal Phytotoxicit~ -No. Activi~v Cotton Squash :

89 .001 .002 .05 0 0 0 0 0 0 .001 .0002 .04 0 0 1 0 0 91 .0003 .0002 .01 0 0 0 0 0 1 92 .005 .03 >.05 0 0 0 0 0 0 93 .001 .001 ~.05 0 0 2 0 1 3 94 .005 .002 ~.05 0 0 1 0 0 1 .002 .0008 ~.05 0 0 0 0 0 96 .001 .0003 >.05 0 2 4 1 3 5 97 .0008 .0008 >.05 0 0 0 0 ~ 0 98 .001 .001 .05 0 1 3 0 1 3 99 .002 .0005 >.05 0 0 1 0 0 2 100 .003 .0005 .05 0 1 3 0 1 4 :
101 .001 .002 .05 1 2 4 1 3 5 102 .0003 .002 .06 0 0 0 0 0 103 ~.05 .002 .03 1 2 4 1 2 5 104 .003 .002 .05 0 0 0 0 0 0 105 .005 .002 .05 0 0 0 0 0 0 106 .005 .0005 .05 0 1 4 0 2 4 107 .003 .0008 .05 0 0 1 0 0 2 :
108 .002 .00~ >.05 0 1 2 0 1 3 109 .003 .002 .05 0 2 4 0 3 5 110 .01 .0005 >.05 0 0 2 0 0 2 ' ,' .

- 1~ 3~ 33 Compound Lepidoptericidal ~ PhYtotoxic~y No. Activit~ Cotton Squash 111 .008 .05 ~ .05 0 0 112 .001 .0003 .05 0 0 2 0 1 3 113 .005 .003.05 0 0 0 0 0 0 114 .002 .0005 .05 0 0 2 0 1 3 115 .003 .008 j.05 0 0 0 0 0~ 0 116 .002 .003 <.05 0 0 0 0 117 .002 .002 ~.05 0 0 0 0 0 1 118 .001 .0005 ~.05 0 0 1 1 2 ~3 119 .05 .002 ~.05 0 0 0 0 0 1 120 .002 .001.05 0 0 0 0 0 0 121 .0005 .0005.03 0 0 1 0 0. 2 122 .0001 .0005.03 0 1 3 1 3 5 123 .0003 .001.05 1 3 4 1 4 5 124 .05 .002.05 0 1 2 0 1 3 125 . 0008 .001<. 05 0 0 1 0 0 1 126 .0005 .0005 .03 0 1 3 1 2 4 127 .0008 005 ~.05 0 1 2 1 2 5 128 .001 .001~.05 0 0 0 0 0 0 129 .005 .0005 .05 0 0 1 0 1 2 130 .002 .002 ~.05 0 0 0 0 0 3 131 .008 .002.05 0 0 0 0 0 0 132 .003 .002 <.05 0 0 1 0 1 3 ., ' ' ~ ' ' 1~38~83 Compound Lepidoptericidal Ph~totoxicity No. - Activitv Cotton Squash 133 .001.005 <.05 0 0 1 0 0 2 134 .003.001 ~.1 0 0 0 0 0 135 .0008.0005 <.05 0 0 2 0 1 3 136 - .0002.003 .05 0 0 0 0 0 137 .001.03 >.1 0 0 0 0 0 0 138 .005.01 ~.05 0 1 2 0 1 2 139 .003.002 <.05 0 0 0 0 0 140 .002.001 <.05 0 0 1 0 0 0 141 .0005.0005 .05 0 0 2 0 0 142 .01.002 .05 0 0 0 0 0 0 143 ~.05 .03 .05 0 0 0 0 0 0 144 .001.002 <.05 0 0 0 0 0 0 145 .0003.0005 <.05 0 0 1 0 0 2 146 ~.05.005 .05 147 .005.002 ~.05 0 0 2 0 0 2 148 .005.0005 <.05 0 0 1 0 0 149 .005.002 .05 0 0 0 0 0 0 150 .0001.0003 ~.05 0 1 2 0 1 3 151 >.05.008 <.05 0 0 0 0 0 0 152 oO02 .0003 .05 0 1 3 0 -2 3 153 .002 .001 .08 0 0 0 0 0 0 154 .0003~.001 ~02 0 0 1 0 0 - . ~,......... . ~,.......... .. . .
.
. . , ~ , .

3~883 Compound Lepidoptericidal Ph~totoxicity No. Activit~ Cotton Squash SMC CL TBW 1~2 1 2 1/21 2 155>.05 ~.05>.05 0 0 0 0 0 0 156.03 .03>.05 0 0 0 0 0 1 157~05 ~.05.04 0 0 0 0 0 1 158>.05 ~.0505 159.05 .008>.05 0 0 0 0 0 160>.05 .05>.05 0 0 1 0 0 1 161>.05 .03.05 0 0 0 0 0 0 162>.05 ,1>-05 `
163~.05 .01.04 0 0 0 0 0 0 164 .008 ~.05.05 0 0 1 0 0 165~.05 ~.05.05 0 0 1 0 0 166~.05 ~.05>.05 0 0 1 0 0 167~.05 ~.05.05 0 1 2 0 0 1 168~.05 .01.05 0 0 0 0 0 0 169.03.005 >.05 0 0 0 0 0 0 170,~.05~.05 >-05 171~.05.4 >.05 0 0 0 0 0 0 172 .003 <.001 >.05 0 0 0 0 0 0 173.01.003 >.05 0 0 0 0 0 0 174>.05.03 >.05 0 0 1 0 0 0 175~.05~.05 >.05 0 0 1 0 1 2 176.05~.05 >.05 0 0 1 0 0 1 -... , ~ . ~ . . . . . . ... .. . :

~3~ ~ 8 3 Co~pound Lepidoptericidal Phytotoxicity No. _ Activity Cotton Squash 1?7 > .05 .2 >.05 0 0 1 0 0 178 >.05 .05 >.05 0 0 1 0 0 1 179 >.05 .01 >.05 0 0 1 0 0 180 .005 > .05>.05 0 1 3 0 1 2 181 .05 .01>.05 0 0 0 0 0 182 .03 .008>.05 1 2 4 1 2 4 183 > . 05 >.05.05 o o o o o o 184.01 .003 >.05 o o o o o o 185~.05 .5.05 0 o o o o o 18~>.05 .05>.05 0 0 0 0 0 0 187>.05 .01>.05 0 0 0 0 0 0 188>.05 .5>.05 0 0 1 0 0 0 189.003 .01>.05 0 0 1 0 0 190>.05 .008 >.05 0 0 0 0 0 0 191.01 .15~.05 0 2 3 0 2 4 192>.05 .01>.05 0 1 2 0 1 3 193 .4 0 0 1 0 0 - 2 194 .2 0 0 2 0 0 2 195 .001 .002>.05 0 1 2 0 1 3 196 >.05 .01~.OS 0 1 2 0 0 2 197 .2 0 0 1 0 1 2 198 .5 0 1 2 0 0 1 ~ ~ . . . ` . . . .

~3~t383 Compound Lepidoptericidal Ph~totoxicity No. _ Activit~ Cotton Squash _ SMC CL ll~W 1/2 1 2 1/2 1 2 199> .05 .2 > .05 1 2 4 1 3 5 200 .01 .0025 ~.05 1 3 5 2 3 5 201 .05 >.05 >.05 o 0 0 0 o 0 202 .05 ~.05 ~.05 o 0 0 o 0 0 203~ .05 ~ .05 .03 0 - 0 0 0 0 0 204 ~.05 .1 ~.05 0 0 0 0 0 0 205 ~.05 .1 ~.05 ` 0 0 0 0 0 0 206 .03 .03 ~.05 207 .03 .03~ .05 o 0 0 0 o 0 208 .03 .008 .05 0 0 0 0 0 0 209 .01 .01 ?.05 0 0 0 0 0- 0 210 >.05 ~.05 >-05 211 .05 ~.05 >.05 o 0 0 0 o 0 212 .01 .002 05 0 0 1 0 0 213 >.5 >.05 >.5 0 0 0 0 0 1 214 ~.05 0 0 0 0 0 1 215 ~ .05 0 0 0 0 0 0 216.008 .005~ .05 0 0 2 0 0 1 217 .05 ~ .05~ .05 0 0 1 0 1 2 218 .05 .003 ~.05 0 1 2 0 1 2 219.005 .008 ~.05 0 0 0 0 0 2 220 .03 .004 .05 0 0 1 0 0 1 .
:

~ :

3~ ~ 83 Compound Lepidoptericidal PhYtotoxici~y No. Activit~ Cotton Squash 221 .01.004 .05 0 0 1 0 1 2 222 >.05.3 ~.05 0 0 0 0 0 0 223 .003.008 ~.05 0 0 0 0 0 0 224 .03.002 ~.05 0 0 0 0 0 225 .01.03 ~.05 0 0 1 0 0 2 226 .005.005 ~.05 0 0 1 0 0 227 .03.0008 ~.05 0 1 2 0 1 3 228 .003.002 .05 0 1 2 0 1 2 - 229 .01.009 ~ .1 0 1 3 0 2 4 230 .003.001 ~.1 1 3 5 1 3 5 231 .001.0005 ~.1 2 5 5 1 5 5 232 .001.0005 ~.1 0 2 5 0 2 5 233 .003.0008 >.1 1 4 5 0 3 5 234 .002.002 .1 0 2 5 0 2 5 235 .003.0008 .1 1 4 5 0 3 5 236 .003.0005 ~.1 1 3 5 1 3 5 237 .002.0005 ~.1 1 5 5 1 5 5 238 .002.003 ~.05 0 0 0 0 0 239 .03.03 ~.05 0 0 2 0 0 2 240 .03.03 > .05 0 1 2 0 1 3 241 ~.05.005 ~.05 0 0 3 0 1 5 242 .01.005 ~.05 0 0 2 0 1 5 ;

, ~3~S~3 Compound Lepidoptericidal Phytotoxicity No. ActivitY Cotton ~9L~

243 .03 .005 ~.05 0 0 3 0 1 4 244 .03 .01 ~ .05 0 1 3 0 1 4 245.008 .03 .05 0 1 3 0 1 4 246 .05 .005 ~ .05 0 0 2 0 1 3 247 .01 .002 ~.05 0 0 1 0 0 2 248 .01 .01 ~.05 0 0 0 0 0 0 249> .05 ~ .05 .05 0 0 0 0 0 0 ~ - .
250~ .05 .2 ~ .05 0 0 0 0 0 0 -251 .01 .005 ~ .05 0 0 2 0 1 4 252~ .05 .03 .05 0 0 1 0 0 253~.05 .03 >.05 0 0 0 0 0 0 254~.05 .05 ~.OS 0 0 0 0 0 255~ .05 ~ .05 .05 0 0 0 0 0 0 ;
256~.05 .15 ~.05 0 0 0 0 0 1 257~.05 .1 ~.1 0 0 0 0 0 0 -~
258~.05 ~.05 ~.1 0 0 0 o 0 0 ~'~
259~ .05 ~ .05 .01 0 0 0 0 o 0 260.008 .03 ~ .05 0 0 0 0 0 1 - -261>~05 .05 ~.05 0 0 0 0 0 0 262.05 >.05 >.05 0 0 0 0 0 0 ~-263.005 .005 > .05 0 1 I 0 1 2 264.005 .005 > .05 0 0 1 0 0 ., ' ~

38~3~3 Compound Lepidoptericidal Phytotoxicity No . Activit~ Cotton Squash SMC CL 1~ 1/2 1 2 1/2 1 2 265 .03 .003~.05 0 0 2 0 1 3 266 ~.05 .4>.05 0 0 1 0 1 2 267 .005 .003~ .05 0 0 0 0 1 2 268 .03 .002~ .05 0 0 2 0 0 2 269 .03 ~.05~ .05 0 0 1 0 1 2 270 .003 .002.03 0 1 3 0 1 4 271 .003 .002.05 0 2 5 1 - 2 5 272 .002 .002.05 1 2 4 1 3 5 273 .005 .002.05 1 2 4 1 3 5 274 .002 .001.05 0 1 2 0 1 3 275 .001 .0005.05 0 0 2 0 1 3 276 .003 .0008 > .05 0 0 2 0 1 3 277 .001 .002 ~ . 05 0 1 2 0 1 2 278 .003 .001. 05 0 1 4 0 1 5 279 .003 ' .001 ~ . 05 0 1 2 0 1 3 280 .003 .0005 . 05 0 1 4 0 1 5 281 .001 .001 .06 1 2 4 0 2 5 282 .005 . 0005 . 05 1 2 4 0 1 5 283 .01 .002 .05 0 1 2 0 1 3 284 .001 .0008 .05 1 4 5 1 4 5 285 .001 .0002 > .05 0 1 3 0 3 5 286 .001 .0002 .05 0 0 2 0 0 3 , ., ~ ~ . ' , 3~ ~ 3 Compound Lepidoptericidal Phytotoxicity No. Activit~ Cotton Squash SMCCL TBW lt2 1 2 1/2 1 2 287 .005.0005 .02 0 0 3 0 0 4 288 .002.0005 .02 0 0 1 0 0 1 289 .002.001 ~.05 0 0 0 0 0 0 290 .002.0008 .03 0 0 0 0 0 0 291 .001.002 .05 0 0 0 0 0 0 292 .003.005 .01 0 0 0 0 0 0 293 .001.0005 .01 0 0 0 0 0 0 294 .001.0002 >.05 0 0 0 0 0 1 295 .002.03 ~.05 0 0 0 0 0 0 296 .0005.001 .05 0 0 0 0 0 0 297 .002.002 .05 0 0 0 0 0 1 298 .003.005 >.05 0 0 2 0 1 2 299 .008.003 >.05 0 1 3 0 2 3 300 .005 .003.05 0 0 0 0 0 0 301 .003 .001.05 0 0 0 0 0 1 302 .03 .03~.05 0 0 1 0 1 2 303 > .05 .03>.05 0 0 0 0 0 304 >.05 .01>.05 0 0 0 0 0 0 305 ~.05 ~.05.04 0 0 0 0 0 0 306>.05 ~.05 .05 0 0 1 0 1 2 307~.05 >.05 >.05 0 0 1 0 2 3 308 >.05 >.05 >.05 0 0 1 ~ 0 ~3~8~3 Compound Lepidopter~ cidal Phytotoxicity No. Activit~ Cotton Squash _ 309~ .05 ~ .05> .05 0 0 0 0 0 310~.05 ~.05.05 0 0 0 0 0 0 311 .05 ~.05>.05 o 0 0 0 0 0 312 .04 .05~.05 0 0 0 0 0 0 313.002 .003.04 0 2 4 1 3 5 314.002 .005 > .05 2 3 5 3 4 5 315~.008 <.008 .05 1 3 5 2 3 5 316 .04 .04~.05 0 0 0 0 0 0 317 .05 ~ .05 0 0 0 0 0 318>.05 ~.05 o 0 0 0 0 0 319.002 .002.04 1 2 3 1 2 4 320.005 ~008 ~.05 0 0 1 0 0 2 321.002 .002 .02 1 2 4 2 3 5 322.002 .003 .03 1 3 5 1 3 5 323.005 .01 .05 0 1 2 0 1 2 324> .05 .5 ~ .05 0 0 0 0 0 0 325 .03 .003 ~ .05 0 0 1 0 0 0 326.002 .001 .03 1 2 5 2 3 5 327.003 .002 .05 1 2 5 2 3 5 328.002 .003 .04 1 2 5 2 3 5 329.002 .003 > .05 0 1 3 1 2 3 330.002 .005 ~.05 3~ ~ ~ 3 `Compound Lepidoptericidal Phytotoxicity No. _ Activit~ Cotton Squash SMC CL TBW lt2 1 2 1/2 1 2 331 .001.003 ~ .05 0 0 0 0 0 0 332 .002.005 ~ .05 0 0 0 0 0 0 333 ~.05~.05 > .05 0 0 0 0 0 0 334 .03.008 ~.05 o o 0 o 0 335 >.05.1 ~ .05 0 0 0 2 4 5 336 ~ .05.1 ~.05 0 0 0 0 0 0 337 .03>.05 >.05 0 0 0 0 0 0 338 .005.002 ~.05 1 3 5 1 2 5 339 .005.002 >.05 1 3 4 1 2 3 340 .03.005 .03 0 1 3 1 2 3 341 .01.008 ~.05 0 2 3 1 2 3 342 .01.009 .05 0 0 1 0 1 2 343 .002.005 ~.05 0 2 3 1 2 4 344 ~.05.1 ~.05 0 0 0 0 0 0 345 .002.003 .03 0 1 3 1 2 3 346 .03.008 > .05 0 0 0 0 0 347 .03.009 ~.05 0 0 0 0 0 0 348 .005.002 .05 0 1 4 0 1 3 349 ~.05.05 ~.05 0 2 4 0 2 3 350 .005.005 .03 0 1 4 1 2 3 351 .03.005 ~.05 0 1 2 ~ 2 3 352 .005.003 ~.05 0 0 2 1 1 2 - .

. . . : .

38l~i83 Compound Lepidoptericidal Phytotoxicity No. Activitv Cotton Squash SMCCL 1~ 1/2 1 2 1/2 1 2 353 .03 .002 .05 0 0 0 0 0 0 354 .002.002 .01 0 0 0 0 0 0 355 .002.001 .05 0 3 4 1 2 5 356 .005.005 ~ .05 0 1 2 0 2 4 357 .03 .005 .05 0 0 0 0 0 0 358 .05 > .05 .05 0 0 0 0 0 0 359 .002.005 .05 0 2 3 1 2 2 360 .005.002 .05 0 1 3 1 2 3 361 .01 -.003 ~ .05 0 0 0 0 0 0 362 .008.008 ~ .05 0 0 0 0 0 0 363 .05 .002 .05 0 0 0 0 0 0 364 .005.002 .05 0 0 1 0 0 365 ~.05 .2 ~.05 0 0 0 0 0 0 366 ~ .05> .05 .05 0 0 0 0 0 0 367 .003.005 ~ .05 0 1 2 0 1 2 368 ~ .05 .03 .05 0 0 0 0 0 0 369 .003.003 .05 0 1 2 0 1 2 370 .005.005 .05 0 0 2 0 0 2 371 .003.008 .05 0 1 3 0 1 2 372 .002.002 ~ .05 0 0 1 0 1 2 373 .002 .005 ~.05 0 2 4 1 2 3 374 .001.002 ~ .05 0 1 2 0 1 2 - . . ~ . . ,, . -.. . . .
:. : . , - . ,: . . .
.. ~ . . . .

1~.388B3 ,,. '' ~.
-244- `
::
', .'.
Compound Lepidoptericidal Phytotoxicity No . Activitv Cotton Squash . . .__ ;

375 .002 .002 ~ .05 0 0 0 0 0 0 376 .003 .005 05 377 .002 .0005 .05 0 0 0 0 0 378 .003 .005 .05 0 0 0 0 0 1 --379 .002 .003 .05 0 0 0 0 0 0 380 .002 .0003 .05 0 0 0 0 0 0 ~ ~;
381 .002 .003 > .05 0 0 0 0 0 0 .
382 .002 .0005 .1 0 0 0 0 0 0 383 .001 .002 .05 0 1 2 1 2 3 384 .002 .0008 .05 0 0 0 0 0 1 385 .002 .0005 .05 0 0 1 0 0 2 386 .016 .0016 ~ .08 0 0 0 0 0 0 387 .003 .009 .15 1 4 4 1 4 4 388 .0024 .006 . Q3 0 0 3 0 389 .004 .0008 ~.1 0 0 2 0 0 2 390 .05 .03 .05 391 ~.05 >.05 ~05 392 ~ .05 ~ .05 05 393 .01 .01 ~ .1 0 0 0 0 0 0 394 .05 .03 >.1 0 0 0 0 0 0 395 .05 ~.05 ~.1 0 1 3 0 1 2 396 .01 .005 >.1 0 0 0 0 0 0 .

~3~8~3 Compound Lepidoptericidal Phytotoxici~y No. ActivitY Cotton Squa~h 397 .05 ~.05 >.1 0 0 0 0 0 2 398 .05't . 003> .1 0 1 3 0 2 3 399 .01 .01 .03 0 0 0 0 0 0 400 .05 .04 0 0 0 0 0 0 401 .002.002 1 2 5 1 3 5 402 .05 ~.05 0 0 0 0 0 0 403 .001.002 0 2 4 1 2 5 404 .03 .008 405 .03 .01 0 0 0 0 0 406 .03 .03 0 0 0 0 0 407 .03 .008 0 0 0 0 0 1 408 . 03 .03 >.05 0 0 o o o o 409 .003 .005 >.05 0 0 0 0 0 0 410 .0008.002 . 05 0 0 0 0 0 411 .005;~ .002 .04 0 1 3 1 3 4 412 .003.002 >.05 0 O 2 0 0 2 413 .003.001 .04 0 0 0 0 0 0 414 . 005. 003 .04 0 0 1 0 0 415 .002.001 .04 0 1 3 0 1 2 416 .005.002 .04 0 0 0 0 0 1 417 .003 .0025 >.05 0 0 0 0 0 0 418 .008 .003 > .05 0 0 0 0 0 0 :: .

3~3 -24~

Compound Lepidoptericidal Phytotoxicit lr No. Activitlr _ Cotton Squash SMC CL ll~W 1~2 1 2 1/2 1 2 419 .002 .0025 .05 0 0 0 0 0 0 420 .01 .003> .05 0 0 0 0 0 0 421 .002.005 .03 0 0 1 0 0 2 422 .005.002 .05 0 0 1 0 0 2 423 .008.003 ~.01 0 0 0 0 0 2 424 .03 .001 .05 0 0 0 0 0 0 425 .01 .002~ .05 0 0 2 0 0 2 426 .01 .005> .05 0 1 2 0 1 2 427 .01 .002 ~.05 0 0 0 0 0 0 428 .03 .005> .05 0 0 429 .002.001 >.05 0 0 0 0 0 0 430 .005.002> .05 0 0 0 0 0 431 .0} .002 >.05 0 0 0 0 0 2 432 .005.005~ .05 0 0 2 0 0 2 433 .005.005> .05 0 0 0 0 0 0 434 .01 .03 >.05 0 0 0 0 0 0 435 .01 .002~ .05 0 0 0 0 0 0 436 .003' .001.05 0 0 0 0 0 1 437 .005; .001> .05 o 0 0 o 0 0 438 .003.002> .05 0 0 1 0 0 439 .003.003~ .05 0 0 1 0 0 2 440 .003.003> .05 0 0 0 0 0 0 r ~8 8 ~ 3 Compound Lepidopteric~dal Phytotoxicit No. Activitr Cotton ~9L~

441 .005.002 ~.05 0 0 0 442 .003.005 >.05 0 0 0 0 0 2 443 .003.005 ~.05 0 0 0 0 0 0 444 .008.01 ~.05 0 0 0 0 0 0 445 .001.01 ~.05 0 0 446 .003.008 >.05 0 0 0 0 0 0 447 .008.01 >.05 0 0 0 0 0 0 448 .005.005 >.05 0 0 0 0 0 449 .008.005 >.05 0 0 0 0 0 0 450 .005.005 ~.05 0 0 0 0 451 .005.03 .05 0 0 0 0 0 0 452 .001.001 .05 0 0 0 0 0 0 453 .002.005 .05 0 0 0 0 0 0 454 .001'.003 ~.05 0 0 0 0 0 0 455 .008 .002.06 0 0 1 0 0 1 456 .002 .002.05 0 0 0 0 0 0 457 .005 .002.05 0 0 0 0 0 0 458 .005 .01~.05 0 0 0 0 0 0 459 .008 .01.05 0 0 0 o 0 0 460 .003.002 > .05 0 0 0 0 0 0 461 .005.002 >.05 0 0 0 0 0 0 462 .005.002 >.05 0 0 0 0 0 0 ~3~83 ~ :

i~

Compound Lepidoptericidal P~ytotoxicity No. Activit~ Cotton S-quash ~ -463 .005 .005 .05 0 0 0 0 0 0 464 .002 .005 .05 0 0 0 465 .005 .002 ~.05 0 0 0 0 0 0 466 .003 .002 .05 0 0 0 0 0 0 467 .003 .002 ~.05 0 0 1 1 0 2 468 .002 .002 ~.05 0 0 0 0 0 0 469 .002 .002 >.05 0 0 0 0 0 0 470 .002 .003 .05 471 .002 .005 ~.05 0 0 0 0 472 .003 .005 >.05 0 0 0 0 0 1 473 .002 .002 ~.05 0 0 0 0 0 0 474 .002 .002 .05 0 0 0 0 0 1 475 .002 .005 ~.05 0 0 0 0 0~
476 .002 .002 .05 '~ 0 0 0 0 0 477 .005 .002 >.05 0 0 0 0 0 0 478 .003 .002 ~.05 0 0 0 0 0 0 479 . .005 .01 .05 0 0 0 0 0 0 480 .003 .002 ~.05 0 0 0 0 0 0 481 .003 .002 .03 0 0 0 0 0 1 482 .008 .003 .05 0 0 0 0 0 483 .005 .002 ~.05 0 0 0 0 0 0 484 .003 .002 ~.05 0 0 0 0 0 0 - ~

.

~ 31!~383 Compound Lepidoptericidal PhqtxnhIaic~y No. Activity Cotton Squash 485 .003.002 ~ .05 0 0 0 0 0 0 486 .005.002 ~ .05 0 0 0 0 0 0 487- .001.005 ~ .05 0 0 0 0 o 0 488 .003.002 .05 0 0 0 0 0 1 489 .01.002 ~ .05 0 0 0 0 0 0 490 .002.002 > .05 0 0 0 0 0 0 491 .005.003 ~.05 0 0 0 0 0 0 492 .003.002 ~.05 0 0 0 0 0 0 493 .005.005 ~ .05 0 0 0 0 0 1 4~94 .01.005 ~ .05 ~ 0 0 0 0 0 495 .01.002 ~ .05 0 0 0 0 0 0 496 .003.001 ~ .05 0 0 0 0 0 0 497 .001 .002 .01 0 0 0 0 0 0 498 .0008 .005 .03 0 0 0 0 0 0 499 .002 .002 .01 0 0 0 0 0 0 500 .003 .002 .05 0 0 0 0 0 0 501 .002 .002 .03 0 0 0 0 0 0 502 .003.002 ~ .05 0 0 0 0 0 0 503 .002.001 ~ .05 0 0 0 0 0 0 504 .005.002 >.05 0 0 0 0 0 0 505 .008.001 > .05 0 0 0 0 0 0 506 .002 > .003 .01 0 0 0 0 0 0 : ~

~38~83 Compound Lepidoptericidal PhYtotoxicit No. Activity Cotton ~9L___ 507 .002.005 ~.05 508 .001.002 .03 0 0 0 0 0 0 509 .001.002 .05 0 0 0 510 .005.001 ~.05 0 0 0 0 0 0 511 .001.005 ~.05 0 0 0 0 0 0 512 .001.005 .05 0 0 1 0 0 1 513 .002.005 ~.05 0 0 1 0 0 1 514 .005.006 ~.05 0 0 0 0 0 0 515 .002.002 .05 0 0 0 0 0 0 516 .001.005 >.05 0 0 0 517 .002.002 ~.05 0 0 1 0 0 518 .003.005 ~.05 0 0 0 0 0 1 519 .001.005 >.05 0 0 0 o 0 0 520 .001.005 ~.05 0 0 0 0 o 0 521 .008.003 ~.05 0 0 0 0 0 522 .005.003 >.05 0 0 o 0 0 0 523 .005.005 >.05 0 0 0 0 0 0 524 .002.0002 >.05 0 0 0 0 0 0 525 .002.001 ~.05 0 0 0 0 0 0 526 .002.0005 ~.05 0 0 0 0 0 0 527 .002.0003 >.05 0 0 0 0 0 0 528 .002.0002 .05 0 0 1 0 1 3 ,' - .. . . . .. . .

'3 Compound Lepidopterlcidal Phytotoxicity _ No. ActivitY Cotton Squash SMCCL TBW 1/2 1 2 lJ2 1 2 529 .002.0002 ~.~5 0 0 0 0 530 .002.001 >.05 0 o o o o o 531 . 002. 001 ~ . 05 0 0 0 0 0 0 532 .001.0002 .05 0 0 0 0 0 2 533 .002,0001 <.05 534 . 002. 002 . 05 0 0 0 0 0 535 .002,0002 ~-05 536 .002,0005 ~.OS 0 0 0 0 0 0 537 .001 .0005 .05 0 0 0 0 0 0 538 .002 .002 .05 0 0 0 0 0 0 539 .001 .0005 .05 0 0 0 0 0 0 540 .002 .00~1 .05 541 .0002 .001 .05 0 0 0 0 0 0 542 .03 .002 .05 0 0 0 0 0 0 543 .00~5~0003 <.05 0 0 0 0 0 0 544 .002.0001 .05 545 ,03`.002 .05 546 .001.0001 ~05 547 .0005.0005 .05 0 0 1 0 0 3 548 .001.0003 ~.05 0 0 1 0 0 549 .002.0002 .05 0 0 0 0 0 0 550 .002.0002 .05 0 0 0 0 0 0 : ;

.

1~3t~B15 3 Compound Lepidoptericidal Phlrtotoxicit~
No . Activity Cotton Squash SMCCL ll~W 1/2 1 2 1/2 1 2 551 .03.001 .05 0 0 1 0 0 552 .0003.0002 .05 0 0 0 0 0 553 .001.0003 <.05 0 0 0 0 0 1 554 .001.0003 .05 0 0 0 0 0 0 555 .002.0008 ~ .05 0 0 0 0 0 0 556 .0005.0001 ~.05 0 0 0 0 0 557 .0005.0002 .05 0 0 0 0 0 2 558 .0002.0003 <.05 0 0 0 559 .003 .002.05 0 0 1 0 0 1 560 .003.002 ~ .05 0 0 0 0 0 561 .001 .002.03 0 1 3 0 1 5 562 .001 .001.05 0 0 2 0 0 2 563 .001.0003 .05 0 o 0 0 0 0 564 .003.0005 ~.05 0 0 2 0 1 3 565 .002.0005 ~.05 0 1 2 0 1 2 566 .0005 .0005.05 0 0 2 0 1 3 567 .0003 .0005.05 0 0 2 0 1 2 568 .0003 .0002>.05 0 0 1 0 1 2 569 .0008 .0003.02 0 0 o 0 0 1 570 .0003 .0003.05 0 0 1 0 0 571 .0005.0003 ~.05 0 0 2 0 1 2 572 .0002.0002 .05 0 0 2 0 1 3 ..

. .

~: . :. . .

3~ 3 Compound Lepidoptericital Phvtotoxicity No. _ ActivitY Cotton Squash 573 .001 .0005 ~.05 0 0 1 0 1 2 574 .001 .0005 ~.05 0 0 2 0 1 2 575 .01 .0008 ~.05 0 0 1 0 1 2 576 .0002 .0005 >.05 0 0 1 0 0 2 577 .0002 .0003 .05 0 0 1 0 0 2 578 .0005 .0005 >.05 0 0 1 0 0 2 579 .0005 .0005 >.05 0 0 0 0 1 2 580 .0005 .0008 >.05 0 0 0 0 0 581 .0002 .0005 .05 0 0 0 0 0 582 .0002 .0005 .005 0 0 1 0 0 2 583 .0003 .0003 ~.05 0 0 1 0 0 2 584 .002 .001.05 0 0 0 0 0 0 585 .003 .002.05 0 0 0 0 0 0 586 .03 .005.05 0 0 1 0 0 0 587 .01 .002.05 0 0 0 0 0 0 588 >.05 .05 .05 0 0- 0 0 0 0 589 > .05 .008.05 0 0 0 0 0 0 590 .05 .002>.05 0 1 3 0 1 2 591 .05 .01 .05 0 0 1 0 0 0 592 .01 .01>.05 0 0 0 0 0 0 593 .03 .01>.05 0 0 0 0 0 0 594 .005 .002.05 :

~ . . . .. .

1~381~33 Compound Lepidoptericidal . Phytotoxicity No. Activity Cotton Squash 595~ .05 .005 .05 0 0 0 0 0 0 596.002 .002 ~04 0 0 0 0 0 G
597.OOS .005 .05 0 0 0 0 0 598.005 .01> .05 0 0 0 0 0 599.001 .0002.02 0 0 0 0 0 1 600~.001 .0005.04 0 0 0 0 0 0 601<.001 .0003.005 0 0 1 0 0 602.002 .003>.05 0 1 2 0 1 2 603.002 .0003.08 . o 0 0 0 0 1 604.003 .003 .05 0 0 1 0 0 605.003 .05~.05 o 0 0 0 0 0 606~.05 .4 >-05 607~.05 .05 ~-05 0 0 0 0 0 0 608~.05 2 >-05 0 0 0 0 0 0 609.003 .0003.05 0 0 1 0 0 610.002 .0005 >.05 0 0 2 0 0 611.008 .0002 >.05 0 0 1 0 0 1 612.002 .001>.05 0 0 1 0 0 613.003 .001 .05 0 0 1 0 0 614.01 .003>.05 0 0 1 0 0 615.001 .002 04 0 0 . 2 0 0 2 616 O004 ~.001~-05 0 0 . 1 0 0 2 - ; ... . : .

3~3 .

Compound Lepidoptericidal Ph~toto~icity No. Activit~ Cotton S-quash 617 .003 .01 .05 0 0 1 0 0 2 618 .001,005 .05 0 0 2 0 0 619 .002.005 .05 0 0 l 0 0 2 620 .002.002 >.05 0 0 1 0 0 621 .01 .003.05 0 0 0 0 0 0 622 .03 .001>.05 0 0 1 0 0 623 .002 .01>.05 0 0 ~ 0 0 624 .001 .0008.03 0 0 0 0 0 625 .003 .001.05 0 0 0 0 o 0 626 .003 .0005.03 0 0 1 0 0 627 .005 .001.01 0 0 1 0 0 1 628 .003 .001>.05 0 0 0 0 0 0 629 .001.0005 >.05 o o 0 0 0 0 630 .003 ~.001 .05 0 1 2 0 1 2 631 >.05 .01>.05 0 0 1 0 0 632 .005 .0~ .05 0 0 1 0 1 2 633 .01 .01 .1 0 0 1 0 0 0 634 .002 ~003.05 1 2 4 1 2 3 635 .008 . 002 ~ . 05 0 0 1 0 0 636 >.OS .1 .05 0 0 0 0 ~ 0 637 .002 .003 ~.05 0 1 3 0 1 4 638 .003 .003 >.05 0 1 3 0 2 4 ,' : ~ , : : , 3~

Compound Lepidoptericidal Phytotoxicit No. _ Act~vit~ Cotton ~9~

639 ~.05 .1~ .05 0 0 0 0 0 0 640 .008 .05~.05 0 1 2 0 1 3 641 >.05 .15>.05 0 0 0 0 1 2 642 >.05 .2>.05 0 0 0 0 0 0 643 .003 .03~.05 0 0 1 1 2 3 644 .01 ~.05~,05 o 0 0 0 0 0 645 .01 >.05>.05 0 0 0 0 0 0 646 .03 .05>.05 647 .03 >.05>.05 0 0 0 0 0 0 648 .01 >.05> .05 0 o 0 0 0 0 649 .003 ~.05>.05 0 0 0 0 650 .003.003 >.05 0 1 2 0 1 3 651 .05 .03 ~.05 0 0 0 0 0 0 652 .05 .03 >.S 0 0 653 .002.002 ~.05 0 1 2 0 1 3 654 >.05 ~4 ~.05 0 0- 0 0 0 0 - 655 ~.05 .2 >.05 0 0 0 - 0 0 0 656 ~.05 .1 ~.05 0 0 0 0 0 0 ~57 .05 >.05>.05 0 0 0 0 0 0 658 .03>.05>.05 o 0 0 0 0 0 659 ~.05 .05 .03 0 0 0 0 0 0 660 ~.05 .03~.05 o 0 0 0 0 0 :....... ' ~13~ 3 Compound Lepidopterici~al Phytotoxicity No. Activity Cotton Squash 661 .03 .01 >.05 0 3 5 1 4 5-662 >.05 > .05 >.05 o 0 0 0 0 663 .002 .005 .05 0 0 1 0 1 2 664 ~.001 .002 >.05 0 0 0 0 0 665 ~.001 .005 .05 o 0 0 0 0 0 666 ~.001 .001 >.05 0 0 0 0 0 1 667 .03 ~.05 >.05 0 0 0 0 0 668 .03 .1 >.05 0 0 0 0 0 0 669 .002 .002 .05 0 1 2 1 3 4 670 .03 .oS ~.05 o 0 0 o 0 0 671.001 <.001 05 672 ~.05 ~.05 ~.05 0 0 0 0 0 673 >.05 ~5 ~.05 0 0 0 0 0 0 674 ~.05 ~.05 >.05 0 0 0 0 0 0 6~5 .05 >.05 ~.05 0 0 Q 0 0 0 676 >.05 >.05 >.05 0 0 0 0 0 0 677 ~.05 .2 ~.05 0 0 0 0 0 0 678 ~.05 .1 ~.05 0 o 0 0 0 0 679 .003 .003 >.05 0 0 1 0 1 2 680 .002 .002 ~.05 0 1 2 0 0 681 >.05 .1 ~.05 0 0 0 0 0 0 682 ~.05 ~.05 ~.05 o 0 0 o 0 o ':.~,' . ~ . . ~ ~ - .. , ... , ~ , , r -3~3 ,,~" ~:
Compound Lepidoptericidal Phytotoxic~ ty No. ActivitY Cotton Squash SMC CL TBW 1/2 1 2 ~ 1 2 683 > .05~ .05> .05 o 0 0 0 o 0 684 ~.05 .1 ~.05 0 0 0 0 0 0 685 ~.05 .15 ~.05 0 0 0 0 0 0 686 ~.05 >.05 ~.05 687 >.05 ~.05 ~.05 o 0 0 0 o 0 688 .03 .003 >.05 0 0 1 0 0 1 689 .01 .03>.05 0 1 2 0 1 2 690 ~ .05 .1> .05 0 0 0 0 1 2 691 .008 .002~ .05 0 0 0 0 0 0 692 .008 .008> .05 0 0 0 0 0 0 693 .03 .03~ .05 0 0 0 0 0 0 694 .0003 .002.03 0 0 0 0 0 o 695 .002 .005.03 0 0 0 0 0 0 696 .0005 .0008 ~.05 0 0 0 0 0 0 697 ~.05 .03~.05 0 0 0 0 0 0 698 ~.05 .03>.05 o 0 0 o 0 0 699 ~.05 .12~.05 0 0 0 0 1 2 700 .008 .03~ .05 0 0 0 0 0 0 701 ~.05 .4~.05 o 0 0 o 0- 0 702 ~.05 .4~.05 0 0 0 0 0 0 703 .005 .03~ .05 0 0 0 0 0 0 704 .002 .001~.05 0 0 0 ~ 0 0 .. .

- \' 1~8~3 -25g-Compound Lepidoptericidal PhYtotoxicitY
No, Activitv Cotton Squash - SMCCL TBW 1/2 1 2 1~2 1 2 705 .001.0008 .05 0 0 0 0 0 0 706 .01.005 ~.05 0 0 0 0 0 0 707 .001.03 ~ .05 0 - 0 0 0 0 io8 .0003.001 ~ .05 0 o o o o o 709 .003.008 ~.05 0 0 710 .005.005 > .05 0 0 0 0 0 0 711 .03.03 ~ .05 o o o o o o 712 .001.002 > .05 0 0 0 0 0 0 713 .002.002 >.05 0 0 0 0 0 714 .008.003 >.05 0 0 0 0 0 715 .0005`.003 ~.05 0 0 0 0 0 0 716 >.05~.05 >.05 0 0 0 0 0 717 .005.003 ~ .05 0 0 0 0 0 1 718 .001.0005 .03 0 0 0 0 o o 719 .002.001 < .05 0 0 0 0 0 0 720 .002 .003 <.05 0 0 0 0 0 721 .002 .01 <.05 0 0 0 0 0 0 722 .001 .005 .1 0 0 0 0 0 0 723 ~.05 ~.05 >.05 0 0 0 0 0 0 724 .002 .01 .05 0 0 o o o o 725 .002 .03 >.05 0 0 0 0 0 0 726 .0005 .0008 .04 0 0 0 0 0 0 1~38~3~3 Compound Lepidoptericidal . Phytotoxicity No. Act~vit~ Cotton - ~g~_h 727 .03 .01.05 0 0 0 0 0 O
728 ,03 .03.05 o O O , O O O
729 .001 .001 .01 0 0 0 0 0 0 730 .05 > .05> .05 o O O O Q O
731 .0005 .0005 >.05 0 0 0 0 0 0 732~.05 ~05 >.05 0 0 0 0 0 0 733~.05 ~.05 >.05 0 0 0 0 0 734~.003 .12 .05 0 0 0 0 0 0 735.01 .008 .l o O O o O O
736>.05 .4 >~l o O O O l 2 737.01 >.05 >.1 o O o O o O
738>.05 .2 .04 0 0 1 0 l 2 739>.05 >.05 05 0 0 1 0 0 740>.05 .1 04 0 0 0 0 l 2 ~41>.05 .03 04 0 0 0 0 0 0 7~2> .05 .03 .05 0 O O O O O
743.05 . OD5 04 0 O O O O O
744~.05 .1 ~.05 ' O O O O 1 2 745~ 05 05 .05 o O O O l 2 746.005 .005 .04 0 0 0 0 0 0 747.003 .0005 .05 0 0 0 0 0 0 748.05 .1 >.05 o O O O O o . .

- `~

- 1~3~981~3 Compound Lepidoptericidal Ph~totoxic~ ty No. ActivitY Cotton Squash 749>.05 .005 >-05 0 0 0 0 0 0 750.03 > .05 >.05 0 0 0 0 0 0 751.005 ~.001 05 0 0 0 0 0 0 752 .01 .008>-05 0 0 0 0 0 2 753 .03 .05>.05 o 0 0 0 0 0 754 .005 .03>.05 0 0 0 0 0 1 755 .003 .05>.05 0 0 0 0 0 756 .008 .03.05 0 o 0 0 0 1 757 .03 ,03.05 o 0 0 0 1 2 758 .008 .03.05 o 0 0 0 0 2 759 .01 .15>-05 0 0 760 .006 .0105 761 >.05 .5>.05 0 0 0 0 0 0 762 .05 .01>-05 0 763 .05 . 05>.05 0 0 0 0 0 0 764 >.05 .0305 0 0 0 0 0 0 765 >.05 .05>-05 0 0 0 0 0 0 766>.05 > .05 .05 0 0 0 0 0 0 767 >.05 .01 >-05 0 0 0 0 0 0 768 .05 .05 >.05 0 0 0 0 0 0 769>.05 ~ .05 >.05 0 0 0 0 0 0 770 >.05 .1>-05 0 0 0 0 0 0 h~ .~
-3 ~ ~3 Compound Lepidoptericidal ~h~lrtotoxicicy No. Activity Cotton Squash .:
SMC CL TBW 1/2 1 2 1/2 1 2 :: :
771 .01 .1 ~.05 0 ~:-772 .003 .005 .05 0 0 0 0 0 0 773 .01- .005 >.05 0 774 .0005 .0008 .01 0 0 1 0 0 0 775 .0003 .0004 .003 0 0 1 0 0 2 776 .0005 .001 .05. 0 0 1 0 0 777 .003 .005 >.05 ' 0. 1 3 0 1 2 778 .0003 .0003 .05 0 0 1 0 0 SYmbols for Table II
SMC : salt-marsh caterpillar CL : cabbage looper TBW : tobacco budworm > greater than < : less than - :

f ~ .
~3~3 :: `

Biocidal Tests In Vitro Vial Tests Tubes of sterilized nutrient and malt extract broth were prepared. Aliquots of the toxicant, dissoLved in an appropriate solvent, were in3ected through the stopper, into the broth, to provide concentrations ranging from 50 ppm downward. The test organisms consisted of one fungi, BotrYtus cinerea, and one bacteria, StaPh~lococcus aureus (S.a.) Roseenbach.
Three drops of a spore suspension of each of the fungi were in~ected into the tubes of malt broth and three drops of the bacteria were in~ected into the nutrient broth. One week later the growth of each organism was observed and effective-ness of the chemical was recorded as the lowest concentration in ppm which provided lO0 percent inhibition of growth as compared to untreated inoculated tubes. The results are shown in Table III.

Fun~icidal Tests Foliar Preventive SPrays ~.
Bean PowderY Mildew -- The chemicals were dissolved in an appropriate solvent and diluted with water containing several drops of a wetting agent. Test concentrations, ranging from 1000 ppm downward, were sprayed to runoff on the primary leaves of pinto beans (Phaseolus vulgaris L.).
After the plants were dry, the leaves were dusted with spores of the powdery mildew fungus (ErYsiPhe polygoni de Candolle) and the plants were retained in the greenhouse until the fungal growth appeared on the leaf surface. Effectiveness was recorded as the lowest concentration, in ppm, which will provide 75 percent or greater reduction in mycel-ial growth -~ ~ , . . .

3~ 3 on the leaf surface as compared to untreated, inoculated plants. The result~ are shown in Table III .

Table III

ComPound No. Biocides Fungicides -LC-100 (ppm~ LC-75-100 (ppm) StaPh aureus Botyrytus Bean Powder~ Mildew cinerea 155 - - 500 ~ ~:

170 ~ ~ 500 183 5 (10) 500 310 ~ 5 ( ) - partial control - 50% or greater The primary screening level in each of ehe above tests was selected for purposes of convenience only, and none of the figures in the table are to be understood as representing the highest level at which a viable test for lepidoptericidal activity can be conducted.

.

3~ ~ ~3 The compounds of this invention are generally used in formulations suitable for convenient application. In general, such fonmulations will contain inert or other active ingredients or diluent carriers in addition to the active compound. Examples of such ingredients or carriers are organic solvents, such as sesame oil, xylene range solvents, and heavy petroleum; water; emulsifying agents; surface active agents;
talc; pyrophyllite; diatomite; gypsum; clays; and propellants, such as dichlorodifluoromethane.

The active compounds can further be combined with dust carriers for application as dusts, with granular carriers for application by fertilizer spreaders or ground or airplane seeders. It also can be formulated as a wettable powder or a flowable for application as a water su~pension, or with sol-vents and surface active materials for application as sprays, aerosols, or emNlsions. The compounds or their formulated mixtures can be applied to any habitat of the pests. Examples of such habitats are insect dwellings, clothing, plant surfaces, and soil. If desired, however, the active compositions can be ~ ~-applied directly to organic matter, seeds or feedstuffs in general, upon which the pests feed, or directly to the pests themselves. When applied in such a manner, it will be advantageous to use a formulation which is not volatile.

Particularly preferred compositions are those com-prising an insecticidally effective amount-of t~e active~
compound in combination with an inert insoluble solid carrier vehicle. Examples of such compositions are wettable powders, dusts, and flowable formulations, in which the solid carrier is in finely divided form; and granular formulations, in which the solid carrier is a pre-formed granule.-.
-3~ ~ 3 -~66-These isothiourea compounds can also be fonmulated to include ~aits that induce feeding responses in the lepidoptera larva resulting in earlier ingestion of the lepidoptericidal isothioureas. Effective baits include cottonseed flour, cottonseed oil, extract of mature -cottonseed, sucrose, invert sugar, citrus molasses, soybean oil, soy flour, corn oil, extract of corn kernels, extract of corn silks, extract of corn seed and mixtures thereof --together with suitable emulsifiers and wetting agents.

The amount of active compound or formulation which i8 considered to be insecticidally effective is that amount which, when applied to the pest habitat or feedstuff, will kill or substantially in~ure a significant portion residing or feeding thereon. The active compounds of this invention can be employed either as the sole pesticide component of the formulations or as one of a mixture of compound~ in the formulation having similar utility. Furthermore, the presently disclosed pesticide compositions need not be active as such.
The purposes of this invention will be fully served by a composition which is rendered active by external influences, such as light, or by physiological action occurring when the preparation is ingested or penetrates into the body of the pest.

The precise manner in which the pesticide compounds of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticidal compound will be used as a component of a liquid composition; for example, an emulsion, suspension, or aerosol spray. While the concentration of the active pesticide compound in the present formulation can vary within rather wide limits, ordinarily, the pesticide composition will compri~e not more than about 50.0 percent by weight of-the formulation.

.. . ~ .

" " ~ " ~ . ~":, :

Claims (27)

WHAT IS CLAIMED:

1. A compound having the formula wherein R and R1 are independently selected from the group consisting of:

C2-C10 alkyl, C2-C10 alkoxyalkyl, and phenyl and R and R1 together contain from 12 to 22 carbon atoms;
wherein R2 is selected from the group consisting of:

C1-C14 alkyl, C3-C10 alkenyl, C3-C4 alkynyl, C2-C4 hydroxyalkyl, C2-C6 alkylthioalkyl, C2-C6 alkyloxyalkyl, (CH2)n[X(CH2)n] y where n = 1 or 2, X is O or S and y = 1-4, -(CH2)n?OH where n = 1-10, phenyl, and phenethyl;
wherein R3 is selected from the group consisting of:
carboalkoxyalkyl wherein the alkyl is C1-C4 alkyl, alkylketoalkyl wherein the alkyl is C1-C4 alkyl, hydroxyalkenyl wherein the alkenyl is C3-C4 alkyl, hydroxyalkyl wherein the alkyl is C1-C12 alkyl, formylhydroxymethyl, hydroxyhaloethyl wherein the halo is chloro, bromo or iodo, substituted phenoxyalkyl wherein the alkyl is C1-C2 alkyl, and the substituents are p-methoxy, Cl, NO3 or CN, wherein R1 is selected from the group consisting of:

-OH, -NH2 or -C1-C4 alkoxy, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above;

, or wherein B is a base;
wherein R4 is selected from the group consisting of:
-H, C1-C22 alkyl, hydroxyethyl, naphthyl, phenyl, substituted phenyl wherein the substituents are independently selected from the group consist-ing of halogen, C1-C5 alkyl, C1-C5 alkoxy, nitro, cyano and -CF3, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein x is 1 to 8 and R, R1 and R2 are as defined above, wherein m is 2 or 3 and R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein X is selected from the group consisting of:
O, S, NH and NR11;
Y is hydrogen or methyl; and R10 is selected from the group consisting of:

-H, C1-C18 alkyl, C3-C4 alkenyl, C3-C4 alkynyl, C2-C6 haloalkyl, C3-C8 cycloalkyl, C7-C20 polycycloalkyl, C2-C16 polyalkoxyalkyl, C2-C6 hydroxyalkyl, C3-C10 alkoxyalkyl, C3-C8 carboalkoxyalkyl, C4-C8 cycloalkylalkyl, C4-C8 alkylcycloalkyl, C4-C7 cycloalkylimino, C2-C10 alkylamino, C1-C3 alkylamino, C4-C12 dialkylaminoalkyl, C6-C10 cycloalkenyl, phenyl, alkylphenyl wherein the alkyl is C1-C4, parachloroalkylphenyl wherein the alkyl is C1-C4, naphthyl, anthracenyl, benzamidocycloalkyl wherein the alkyl is C1-C2, pyranylmethyl, tetrahydrofurfuryl, thiophenemethyl, benzhydryl, halobenzhydryl, polycyclic alcohol, and substituted phenyl wherein the substituents are selected from the group consisting of:
C1-C4 alkyl, halogen, nitro, trifluoroemthyl, formyl, chloroacetyl, C1-C4 alkoxy, hydrogen, benzyl, chlorobenzyl, phenethyl, and substituted phenethyl wherein the sub-stituents are selected from the group consisting of:
C1-C4 alkyl and halogen, and R11 is selected from the group eonsisting of:
C1-C4 alkyl, C3-C6 alkoxyalkyl, and C3-C4 alkenyl;

R10 and R11 taken together form heterocyclic compounds;
provided that when X =
O or S then R10 is other than hydrogen; and substituted phenyl wherein the sub-stituents are selected from the group consisting of:
halogen, C1-C4 alkoxy, phenoxy, trifluoromethyl, C1-C6 thioalkyl, nitro, isocyanato, C2-C4 polyalkoxy, C3-C7 cycloalkyl, C3-C24 carboalkoxy-alkyl, C1-C8 haloalkyl, C3-C12 alkenyl, C2-C6 dialkylamino, phenylamino, C1-C24 alkyl, C3-C12 hydroxyalkyl-amidoalkyl, C5-C10 N,N-hydroxy-alkylureidoalkyl, isocyanatoalkyl wherein the alkyl is C1-C5, C3-C12 alkylamido-alkyl, polyalkoxyamido-alkyl wherein the polyalkoxy moiety contains from 3-6 repeating C2-C3 alkoxy units and the amidoalkyl moiety contains from 4-12 carbon atoms, -SO2Cl, -SO2 polyalkoxy-amidoalkyl wherein the polyalkoxy moiety contains from 3-6 repeating C2-C3 alkoxy units and the amidoalkyl moiety contains from 4-12 carbon atoms;
R5 is selected from the group consisting of:
hydrogen, C1-C4 alkyl, C3-C6 alkoxyalkyl, C3-C4 alkenyl, hydroxyethyl, and phenyl;
R4 and R5 taken together form heterocyclic compounds; and -?XnR6 wherein X is O or S, n is O or 1, R6 is selected from the group consisting of:
C1-C18 alkyl, C2-C6 haloalkyl, phenyl, and substituted phenyl wherein when n 1 the substituents are selected from the group consisting of:
nitro, chloro, C1-C2 alkyl, C4-C6 polyalkoxyalkyl C3-C8 cycloalkyl, C3-C4 alkenyl, C3-C6 alkoxyalkyl, C2-C6 hydroxyalkyl, C1-C3 carboxyalkyl, and C5-C8 trialkylammoniumalkyl salts, and when n = 0 the substituents are selected from the group consisting of:
chloro, thiopotassium, C1-C18 alkyl, benzyl, C1-C2 heteroalkyl, C2-C4 chlorocarboxyalkyl, C4-C6 polyalkoxyalkyl, and acetyl;

-?R7?YdZ wherein R7 is selected from the group consisting of:

-(CH2-)n wherein n = 0 to 8, -CH=CH-, wherein M is H or Cl, , -CCl=CCl-, -CH2OCH2-, and -OCH2CH2O-;

d = 0 or 1, and when d = 1 Y is selected from the group consisting of:
-O, -S, and -NH;

Z is selected from the group consisting of:
-C1-C18 alkyl, hydrogen, C4-C16 polyalkoxyalkyl, C4-C8 dialkylaminoalkyl, C3-C5 alkynyl phenyl, substituted phenyl, organic salts, inorganic salts, and when d = O, Z is Cl or wherein R, R1 and R2 are as defined above;
-?(R8)2 wherein R8 is selected from the group consisting of:
C1-C10 alkoxy, amino, C1-C10 alkoxyamino, hydroxy, and organic base;

-SOwR9 wherein w = 0-2 and R9 is selected from the group consisting of:
amino, C1 C10 alkyl, C1-C4 haloalkyl, phenyl, C1-C10 dialkylamino, C1-C10 alkylamino, C1-C10 alkoxy, substituted phenyl wherein the substituents are selected from the group consisting of:

nitro, chloro, C1-C4 alkyl, and methoxy.

2. The compound of Claim 1 wherein R and R1 are independently selected from the group consisting of:

C5-C9 alkyl, C5-C9 alkoxyalkyl, and phenyl and R and R1 together contain from 12 to 22 carbon atoms;
wherein R2 is selected from the group consisting of:
C1-C6 alkyl, C3-C5 alkenyl, C3-C4 alkynyl, C2-C3 hydroxyalkyl, C2-C4 alkylthioalkyl, C2-C4 alkyloxyalkyl (CH2)n[X(CH2)n] y where n = 1 or 2, X is O or S and y = 1-2, -(CH2)n?OH where n = 1-5, phenyl, and phenethyl

3. The compound of Claim 1 wherein R and R1 are independently selected from the group consisting of:

C6-C8 alkyl and C6-C8 alkoxyalkyl, and phenyl and R and R1 together contain from 12 to 22 carbon atoms;

wherein R2 is selected from the group consisting of:

C1-C13 alkyl, C2-C3 alkenyl, C3-C4 alkynyl, C2-C3 hydroxyalkyl, C2-C4 alkylthioalkyl C2-C4 alkyloxyalkyl (CH2)n[X(CH2)n] y where n = 1 or 2, X is O or S and y = 1-2, -(CH2)n?OH where n = 1-3, phenyl, and phenethyl.

4. The compound of Claims 1, 2 or 3 wherein R3 is selected from the group consisting of:

carboalkoxyalkyl wherein the alkyl is C1-C2 alkyl, alkylketoalkyl wherein the alkyl is C1-C2 alkyl, hydroxyalkenyl wherein the alkenyl is C3-C4 alkyl, hydroxyalkyl wherein the alkyl is C1-C6 alkyl, formylhydroxymethyl, hydroxyhaloethyl wherein the halo is chloro or bromo, substituted phenoxyalkyl wherein the alkyl is C1 alkyl and the substituents are p-methoxy, Cl, NO3 or CN, wherein R1 is -OH, -NH2 or methoxy, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above;

, or wherein B is an organic base;

wherein R4 is selected from the group consisting of:

-H, -C1-C12 alkyl, hydroxyethyl, naphthyl, phenyl, substituted phenyl wherein the sub-stituents are independently selected from the group consisting of chlorine, C1-C2 alkyl, C1-C2 alkoxy, nitro, cyano and -CF3, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein x is 1 to 8 and R, R1 and R2 are as defined above, wherein m is 2 or 3 and R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein X is selected from the group consisting of:
O, S, NH, Y is hydrogen or methyl; and R10 is selected from the group consisting of:
-H, C1-C8 alkyl, C3-C4 alkenyl, C3-C4 alkynyl, C2-C3 haloalkyl, C3-C8 cycloalkyl, C7-C20 polycycloalkyl, C2-C16 polyalkoxyalkyl, C2-C6 hydroxyalkyl, C3-C10 alkoxyalkyl, C3-C8 carboalkoxyalkyl, C4-C8 cycloalkylalkyl, C6-C8 alkylcycloalkyl, C4-C7 cycloalkylimino, C2-C10 alkylimino, C1-C3 alkylamino, C4-C12 dialkylaminoalkyl, C6-C10 cycloalkenyl, phenyl, alkylphenyl wherein the alkyl is C1-C4, parachloroalkylphenyl wherein the alkyl is C1-C4, naphthyl, anthracenyl, benzamidocycloalkyl wherein the alkyl is C1-C2, pyranylmethyl, tetrahydrofurfuryl, thiophenemethyl, benzhydryl, halobenzhydryl, polycyclic alcohol, and substituted phenyl wherein the substituents are selected from the group consisting of:
C1-C4 alkyl, halogen, nitro, trifluoromethyl, formyl, chloroacetyl, C1-C4 alkoxy, hydrogen, benzyl, chlorobenzyl, phenethyl, and substituted phenethyl wherein the substituents are selected from the group consisting of:
C1-C4 alkyl, halogen, and R11 is selected from the group consisting of:
C1-C4 alkyl, C3-C6 alkoxyalkyl, and C3-C4 alkenyl;`
R10 and R11 taken together form heterocyclic compounds selected from the group consisting of:
azepinyl, morpholinyl, piperdinyl, C1-C3 alkyl substituted piperdinyl;
provided that when X = O or S
then R10 is other than hydrogen and substituted phenyl wherein the substituents are selected from the group consisting of:
halogen, C1-C4 alkoxy, phenoxy, trifluoromethyl, C1-C6 thioalkyl, nitro, isocyanato, C2-C4 polyalkoxy, C3-C7 cycloalkyl, C3-C10 carboalkoxyalkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C2-C6 dialkylamino, phenylamino, C1-C4 alkyl, C3-C12 hydroxyalkylamidoalkyl, C5-C10 N,N-hydroxyalkyl-ureidoalkyl, isocyanatoalkyl wherein the alkyl is C1-C5, C3-C12 alkylamidoalkyl, polyalkoxyamidoalkyl wherein the polyalkoxy moiety contains from 3-6 repeating C2-C3 alkoxy units and the amidoalkyl moiety contains from 4-12 carbon atoms, -SO2Cl, -SO2 polyalkoxyamidoalkyl wherein the polyalkoxy moiety contains from 3-6 repeating C2-C3 alkoxy units and the amidoalkyl moiety contains from 4-12 carbon atoms;

R5 is selected from the group consisting of:
hydrogen, C1-C4 alkyl, C3-C6 alkoxyalkyl, C3-C4 alkenyl, hydroxyethyl, and phenyl;
R4 and R5 taken together form hetero-cyclic compounds selected from the group consisting of:
azepinyl, morpholinyl, piperdinyl, and C1-C3 alkyl substituted piperdinyl;
-?XnR6 wherein X is O or S, n is 0 or 1, R6 is selected from the group consisting of:
C1-C12 alkyl, C2-C6 haloalkyl, phenyl, and substituted-phenyl wherein when n = 1 the substituents are selected from the group consisting of:
nitro, chloro, C1-C2 alkyl, C4-C6 polyalkoxyalkyl, C3-C8 cycloalkyl, C3-C4 alkenyl, C3-C6 alkoxyalkyl, C2-C6 hydroxyalkyl, C1-C3 carboxyalkyl, C5-C8 trialkylammoniumalkyl salts, and when n = 0 the substituents are selected from the group consisting of:
chloro, thiopotassium, C1-C12 alkyl, benzyl, C1-C2 heteroalkyl, C2-C4 chlorocarboxyalkyl, C4-C6 polyalkoxyalkyl, and acetyl;

wherein R7 is selected from the group consisting of:
-(CH2-)n wherein n = 0 to 8, -CH=CH-, wherein M is H or Cl, , -CCl=CCl-, -CH2OCH2-, -OCH2CH2O-, and d = 0 or 1, when d = 1 Y is selected from the group consisting of:
-O, -S, and -NH, and Z is selected from the group consisting of:
C1-C12 alkyl, hydrogen, C4-C16 polyalkoxyalkyl, C4-C8 dialkylaminoalkyl, C3-C5 alkynyl, phenyl, substltuted phenyl, organic salts, inorganic salts, and when d = 0, Z is Cl or wherein R, R1 and R2 are as defined above;

wherein R8 is selected from the group consisting of:
C1-C5 alkoxy, amino, C1-C5 alkoxyamino, hydroxy, and organic base;

-SOwR9 wherein w = 0-2 and R9 is selected from the group consisting of:
amino, C1-C5 alkyl, C1-C4 haloalkyl, phenyl, C1-C10 dialkylamino, C1-C10 alkylamino, C1-C5 alkoxy, substituted phenyl wherein the substituents are selected from the group consisting of:
nitro, chloro, C1-C4 alkyl, and methoxy.

5. The compound of Claims 1, 2 or 3 wherein R3 is selected from the group consisting of:

carboalkoxyalkyl wherein the alkyl is C1-C2 alkyl, alkylketoalkyl wherein the alkyl is C1-C2 alkyl, hydroxyalkenyl wherein the alkenyl is C3-C4 alkyl, hydroxyalkyl wherein the alkyl is C1-C3 alkyl, formylhydroxymethyl, hydroxyhaloethyl wherein the halo is chloro, substituted phenoxyalkyl wherein the alkyl is C1 alkyl and the substituents are p-methoxy, Cl, NO3 or CN, wherein R1 is -OH, -NH2 or methoxy, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, , or wherein B is an organic base selected from the group consisting of:

and , wherein R4 is selected from the group consisting of:
-H, C1-C8 alkyl, hydroxyethyl, naphthyl, phenyl, substituted phenyl wherein the substituents are independently selected from the group consisting of chlorine, C1-C2 alkyl, C1-C2 alkoxy, nitro, cyano and -CF3, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein x is 1 to 8 and R, R1 and R2 are as defined above, wherein m is 2 or 3 and R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein X is selected from the group consisting of:
O, S, NH, NR11, and Y is hydrogen or methyl, R10 is selected from the group consisting of:
-H, C1-C2 alkyl, C3-C4 alkenyl, C3-C4 alkynyl, C2-C3 haloalkyl, C3-C8 cycloalkyl, C7-C20 polycycloalkyl, C2-C16 polyalkoxyalkyl, C2-C6 hydroxyalkyl, C3-C10 alkoxyalkyl, C3-C8 carboalkoxyalkyl, C4-C8 cycloalkylalkyl, C6-C8 alkylcycloalkyl, C4-C7 cycloalkylimino, C2-C10 alkylimino, C1-C3 alkylamino, C4-C12 dialkylaminoalkyl, C6-C10 cycloalkenyl, phenyl, alkylphenyl wherein the alkyl is C1-C4, parachloroalkylphenyl wherein the alkyl is C1-C4, naphthyl, anthracenyl, benzamidocycloalkyl wherein the alkyl is C1-C2, pyranylmethyl, tetrahydrofurfuryl, thiophenemethyl, benzhydryl, halobenzhydryl, polycyclic alcohol, and substituted phenyl wherein the substituents ase selected from the group consisting of:
C1-C4 alkyl, halogen, nitro, trifluoromethyl, formyl, chloroacetyl, C1-C4 alkoxy, hydrogen, benzyl, chlorobenzyl, phenethyl, and substituted phenethyl wherein the substituents are selected from the group consisting of:
C1-C4 alkyl, halogen, and R11 is selected from the group consisting of:
C1-C4 alkyl, C3-C6 alkoxyalkyl, and C3-C4 alkenyl, R10 and R11 taken together form heterocyclic compounds preferably heterocyclic compounds selected from the group consisting of:
azepinyl, morpholinyl, piperdinyl, C1-C3 alkyl substituted piperdinyl, and provided that when X = O or S
then R10 is other than hydrogen and substituted phenyl wherein the substituents are selected from the group consisting of:
halogen, C1-C4 alkoxy, phenoxy, trifluoromethyl, C1-C6 thioalkyl, nitro, isocyanato, C2-C4 polyalkoxy, C3-C7 cycloalkyl, C3-C10 carboalkoxyalkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C2-C6 dialkylamino, phenylamino, C1-C4 alkyl, C3-C12 hydroxyalkylamidoalkyl, C5-C10 N,N-hydroxyalkyl-ureidoalkyl, isocyanatoalkyl wherein the alkyl is C1-C5, C3-C12 alkylamidoalkyl, polyalkoxyamidoalkyl wherein the polyalkoxy moiety contains from 3-6 repeating C2-C3 alkoxy units and the amidoalkyl moiety contains from 4-12 carbon atoms, -SO2Cl, -SO2 polyalkoxyamidoalkyl wherein the polyalkoxy moiety contains from 3-6 repeating C2-C3 alkoxy units and the amidoalkyl moiety contains from 4-12 carbon atoms;

R5 is selected from the group consisting of:
hydrogen, C1-C4 alkyl, C3-C6 alkoxyalkyl, C3-C4 alkenyl, hydroxyethyl, and phenyl;
R4 and R5 taken together form heterocyclic compounds selected from the group consisting of:
azepinyl, morpholinyl, piperdinyl, and C1-C3 alkyl substituted piperdinyl, wherein X is O or S, n is 0 or 1, R6 is selected from the group consisting of:
C1-C4 alkyl, C2-C6 haloalkyl, phenyl, and substituted phenyl wherein when n = 1 the substituents are selected from the group consisting of:
nitro, chloro, C1-C2 alkyl, C4-C6 polyalkoxyalkyl, C3-C8 cycloalkyl, C3-C4 alkenyl, C3-C6 alkoxyalkyl, C2-C6 hydroxyalkyl, C1-C3 carboxyalkyl, C5-C8 trialkylammoniumalkyl salts, and when n = 0 the substituents are selected from the group consisting of:
chloro, thiopotassium, C1-C4 alkyl, benzyl, C1-C2 heteroalkyl, C2-C4 chlorocarboxyalkyl, C4-C6 polyalkoxyalkyl, and acetyl;

wherein R7 is selected from the group consisting of:
-(CH2-)n wherein n = 0 to 8, -CH=CH-, wherein M is H or Cl, , -CCl=CCl-, -CH2OCH2-, -OCH2CH2O-, and d = 0 or 1, when d = 1 Y is selected from the group consisting of:
-O, -S, and -NH, and Z is selected from the group consisting of:
C1-C4 alkyl, hydrogen, C4-C16 polyalkoxyalkyl, C4-C8 dialkylaminoalkyl, C3-C5 alkynyl, phenyl, substituted phenyl, organic salts, inorganic salts, and when d = O, Z is Cl or wherein R, R1 and R2 are as defined above;

wherein R8 is selected from the group consisting of:
C1-C5 alkoxy, amino, C1-C5 alkoxyamino, hydroxy, and organic base;

-SOwR9 wherein w = 0-2 and R9 is selected from the group consisting of amino, C1-C5 alkyl, C1-C4 haloalkyl, phenyl, C1-C10 dialkylamino, C1-C10 alkylamino, C1-C5 alkoxy, substituted phenyl wherein the substituents are selected from the group consisting of:
nitro, chloro, C1-C4 alkyl, and methoxy.

6. The compound of Claim 1 wherein R is -secC7H15, R1 is -C6H13, R2 is -C2H5 and R3 is .

7. The compound of Claim 1 wherein R is -secC7H15, R1 is -C8H17, R2 is -CH3 and R3 is .

8. The compound of Claim 1 wherein R is -secC7H15, R1 is -C8H17, R2 is -C2H5 and R3 is .

9. The compound of Claim 1 wherein R is -secC7H15, R1 is -C8H17, R2 is -C2H5 and R3 is .

10. A method for controlling lepidoptera com-prising applying to said lepidoptera or the locus or feed-stuffs thereof a lepidoptericidally effective amount of the compound of Claim 1.

11. A method of controlling lepidoptera com-prising applying to said lepidoptera or the locus or feed-stuffs thereof a lepidoptericidally effective amount of the compound of Claim 2.

12. A method of controlling lepidoptera com-prising applying to said lepidoptera or the locus or feed-stuffs thereof a lepidoptericidally effective amount of the compound of Claim 3.

13. The method of Claims 10, 11 or 12 wherein R3 is carboalkoxyalkyl wherein the alkyl is C1-C2 alkyl, alkylketoalkyl wherein the alkyl is C1-C2 alkyl, hydroxyalkenyl wherein the alkenyl is C3-C4 alkyl, hydroxyalkyl wherein the alkyl is C1-C6 alkyl, formylhydroxymethyl, hydroxyhaloethyl wherein the halo is chloro or bromo, substituted phenoxyalkyl wherein the alkyl is C1 alkyl and the substituents are p methoxy, Cl, NO3 or CN, wherein R1 is -OH, -NH2 or methoxy, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above;
, or wherein B is an organic base;

wherein R4 is selected from the group consisting of:

-H, C1-C12 alkyl, hydroxyethyl, naphthyl, phenyl, substituted phenyl wherein the substituents are independently selected from the group consisting of halogen, C1-C5 alkyl, C1-C5 alkoxy, nitro, cyano and -CF3, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein x is 1 to 8 and R, R1 and R2 are as defined above, wherein m is 2 or 3 and R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein X is selected from the group consisting of:
O, S, NH, Y is hydrogen or methyl; and R10 is selected from the group consisting of:
-H, C1-C8 alkyl, C3-C4 alkenyl, C3-C4 alkynyl, C2-C3 haloalkyl, C3-C8 cycloalkyl, C7-C20 polycycloalkyl, C2-C16 polyalkoxyalkyl, C2-C6 hydroxyalkyl, C3-C10 alkoxyalkyl, C3-C8 carboalkoxyalkyl, C4-C8 cycloalkylalkyl, C6-C8 alkylcycloalkyl, C4-C7 cycloalkylimino, C2-C10 alkylimino, C1-C3 alkylamino, C4-C12 dialkylaminoalkyl, C6-C10 cycloalkenyl, phenyl, alkylphenyl wherein the alkyl is C1-C4, parachloroalkylphenyl wherein the alkyl is C1-C4, naphthyl, anthracenyl, benzamidocycloalkyl wherein the alkyl is C1-C2, pyranylmethyl, tetrahydrofurfuryl, thiophenemethyl, benzhydryl, halobenzhydryl, polycyclic alcohol, and substituted phenyl wherein the substituents are selected from the group consisting of:
C1-C4 alkyl, halogen, nitro, trifluoromethyl, formyl, chloroacetyl, C1-C4 alkoxy, hydrogen, benzyl, chlorobenzyl, phenethyl, and substituted phenethyl wherein the substituents are selected from the group consisting of:
C1-C4 alkyl, halogen, and R11 is selected from the group consisting of:
C1-C4 alkyl, C3-C6 alkoxyalkyl, and C3-C4 alkenyl;
R10 and R11 taken together form heterocyclic compounds selected from the group consisting of:
azepinyl, morpholinyl, piperdinyl, C1-C3 alkyl substituted piperdinyl;
provided that when X = O or S
then R10 is other than hydrogen and substituted phenyl wherein the substituents are selected from the group consisting of:
halogen, C1-C4 alkoxy, phenoxy, trifluoromethyl, C1-C6 thioalkyl, nitro, isocyanato, C2-C4 polyalkoxy, C3-C7 cycloalkyl, C3-C10 carboalkoxyalkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C2-C6 dialkylamino, phenylamino, C1-C4 alkyl, C3-C12 hydroxyalkylamidoalkyl, C5-C10 N,N-hydroxyalk ureidoalkyl, isocyanatoalkyl wherein the alkyl is C1-C5, C3-C12 alkylamidoalkyl, polyalkoxyamidoalkyl wherein the polyalkoxy moiety contains from 3-6 repeating C2-C3 alkoxy units and the amidoalkyl moiety contains from 4-12 carbon atoms, -SO2Cl, -SO2 polyalkoxyamidoalkyl wherein the polyalkoxy moiety contains from 3-6 repeating C2-C3 alkoxy units and the amidoalkyl moiety contains from 4-12 carbon atoms;

R5 is selected from the group consisting of:
hydrogen, C1-C4 alkyl, C3-C6 alkoxyalkyl, C3-C4 alkenyl, hydroxyethyl, and phenyl;

R4 and R5 taken together form hetero-cyclic compounds selected from the group consisting of:
azepinyl, morpholinyl, piperdinyl, and C1-C3 alkyl substituted piperdinyl;

wherein X is O or S, n is 0 or 1, R6 is selected from the group consisting of:
C1-C12 alkyl, C2-C6 haloalkyl, phenyl, and substituted phenyl wherein when n = 1 the substituents are selected from the group consisting of:
nitro, chloro, C1-C2 alkyl, C4-C6 polyalkoxyalkyl, C3-C8 cycloalkyl, C3-C4 alkenyl, C3-C6 alkoxyalkyl, C2-C6 hydroxyalkyl, C1-C3 carboxyalkyl, C5-C8 trialkylammonium salts, and when n = 0 the substituents are selected from the group consisting of:
chloro, thiopotassium, C1-C12 alkyl, benzyl, C1-C4 chlorocarboxyalkyl, C4-C6 polyalkoxyalkyl, and acetyl;
wherein R7 is selected from the group consisting of:
-(CH2-)n wherein n = 0 to 8, -CH=CH-, wherein M is H or Cl, , -CCl=CCl-, -CH2OCH2-, -OCH2CH2O-, and d = 0 or 1, when d = 1 Y is selected from the group consisting of:
-O, -S, and -NH, and Z is selected from the group consisting of:
C1-C12 alkyl, hydrogen, C4-C16 polyalkoxyalkyl, C4-C8 dialkylaminoalkyl, C3-C5 alkynyl, phenyl, substituted phenyl, organic salts, inorganic salts, and when d = O, Z is Cl or wherein R, R1 and R2 are as defined above;

wherein R8 is selected from the group consisting of:
C1-C5 alkoxy, amino, C1-C5 alkoxyamino, hydroxy, and organic base;

-SOwR9 wherein w = O-2 and R9 is selected from the group consisting of:
amino, C1-C5 alkyl, C1-C4 haloalkyl, phenyl, C1-C10 dialkylamino, C1-C10 alkylamino, C1-C5 alkoxy, substituted phenyl wherein the substituents are selected from the group consisting of:
nitro, chloro, C1-C4 alkyl, and methoxy.

14. The method of Claims 10, 11 or 12 wherein R3 is:
carboalkoxyalkyl wherein the alkyl is C1-C2 alkyl, alkylketoalkyl wherein the alkyl is C1-C2 alkyl, hydroxyalkenyl wherein the alkenyl is C3-C4 alkyl, hydroxyalkyl wherein the alkyl is C1-C3 alkyl, formylhydroxymethyl, hydroxyhaloethyl wherein the halo is chloro, substituted phenoxyalkyl wherein the alkyl is C1 alkyl and the substituents are p-methoxy, C1, NO3 or CN, wherein R1 is -OH, -NH2 or methoxy, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, , or wherein B is an organic base selected from the group consisting of:

and , wherein R4 is selected from the group consisting of:
-H, C1-C8 alkyl, hydroxyethyl, naphthyl, phenyl, substituted phenyl wherein the substituents are independently selected from the group consisting of chlorine, C1-C2 alkyl, C1-C2 alkoxy, nitro, cyano and -CF3, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein x is 1 to 8 and R, R1 and R2 are as defined above, wherein m is 2 or 3 and R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein R, R1 and R2 are as defined above, wherein X is selected from the group consisting of:
O, S, NH, NR11, and Y is hydrogen or methyl, R10 is selected from the group consisting of:
-H, C1-C2 alkyl, C3-C4 alkenyl, C3-C4 alkynyl, C2-C3 haloalkyl, C3-C8 cycloalkyl, C7-C20 polycycloalkyl, C2-C16 polyalkoxyalkyl, C2-C6 hydroxyalkyl, C3-C10 alkoxyalkyl, C3-C8 carboalkoxyalkyl, C4-C8 cycloalkylalkyl, C6-C8 alkylcycloalkyl, C4-C7 cycloalkylimino, C2-C10 alkylimino, C1-C3 alkylamino, C4-C12 dialkylaminoalkyl, C6-C10 cycloalkenyl, phenyl, alkylphenyl wherein the alkyl is C1-C4, parachloroalkylphenyl wherein the alkyl is C1-C4, naphthyl, anthracenyl, benzamidocycloalkyl wherein the alkyl is C1-C2, pyranylmethyl, tetrahydrofurfuryl, thiophenemethyl, benzhydryl, halobenzhydryl, polycyclic alcohol, and substituted phenyl wherein the substituents are selected from the group consisting of:
C1-C4 alkyl, halogen, nitro, trifluoromethyl, formyl, chloroacetyl, C1-C4 alkoxy, hydrogen, benzyl, chlorobenzyl, phenethyl, and substituted phenethyl wherein the substituents are selected from the group consisting of:
C1-C4 alkyl, halogen, and R11 is selected from the group consisting of:
C1-C4 alkyl, C3-C6 alkoxyalkyl, and C3-C4 alkenyl, R10 and R11 taken together form heterocyclic compounds preferably heterocyclic compound selected from the group consisting of:
azepinyl, morpholinyl, piperdinyl, C1-C3 alkyl substituted peperdinyl, and provided that when X = O or S
then R10 is other than hydrogen and substituted phenyl wherein the substituents are selected from the group consisting of:
halogen, C1-C4 alkoxy, phenoxy, trifluoromethyl, C1-C6 thioalkyl, nitro, isocyanato, C2-C4 polyalkoxy, C3-C7 cycloalkyl, C3-C10 carboalkoxyalkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C2-C6 dialkylamino, phenylamino, C1-C4 alkyl, C3-C12 hydroxyalkylamidoalkyl, C5-C10 N,N-hydroxyalkyl-ureidoalkyl, isocyanatoalkyl wherein the alkyl is C1-C5, C3-C12 alkylamidoalkyl, polyalkoxyamidoalkyl wherein the polyalkoxy moiety contains from 3-6 repeating C2-C3 alkoxy units and the amidoalkyl moiety contains from 4-12 carbon atoms, -SO2Cl, -SO2 polyalkoxyamidoalkyl wherein the polyalkoxy moiety contains from 3-6 repeating C2-C3 alkoxy units and the amidoalkyl moiety contains from 4-12 carbon atoms;

R5 is selected from the group consisting of:
hydrogen, C1-C4 alkyl, C3-C6 alkoxyalkyl, C3-C4 alkenyl, hydroxyethyl, and phenyl;
R4 and R5 taken together form heterocyclic compounds selected from the group consisting of:
azepinyl, morpholinyl, piperdinyl, and C1-C3 alkyl substituted piperdinyl, wherein X is O or S, n is 0 or 1, R6 is selected from the group consisting of:
C1-C4 alkyl, C2-C6 haloalkyl, phenyl, and substituted phenyl wherein when n = 1 the substituents are selected from the group consisting of:
nitro, chloro, C1-C2 alkyl, C4-C6 polyalkoxyalkyl, C3-C8 cycloalkyl, C3-C4 alkenyl, C3-C6 alkoxyalkyl, C2-C6 hydroxyalkyl, C1-C3 carboxyalkyl, C5-C8 trialkylamm?umalkyl salts, and when n = O the substituents are selected from the group consisting of:
chloro, thiopotassium, C1-C4 alkyl, benzyl, C1-C2 heteroalkyl, C2-C4 chlorocarboxyalkyl, C4-C6 polyalkoxyalkyl, and acetyl;

wherein R7 is selected from the group consisting of:
-(CH2-)n wherein n = 0 to 8, -CH=CH-, wherein M is H or Cl, , -CCl=CCl-, -CH2OCH2-, -OCH2CH2O-, and d = O or 1, when d = 1 Y is selected from the group consisting of:
-O, -S, and -NH, and Z is selected from the group consisting of:
C1-C4 alkyl, hydrogen, C4-C16 polyalkoxyalkyl, C4-C8 dialkylaminoalkyl, C3-C5 alkynyl, phenyl, substituted phenyl, organic salts, inorganic salts, and when d = O, Z is Cl or wherein R, R1 and R2 are as defined above;
wherein R8 is selected from the group consisting of:
C1-C5 alkoxy, amino, C1-C5 alkoxyamino, hydroxy, and organic base;

-SOwR9 wherein w = 0-2 and R9 is selected from the group consisting of:
amino, C1-C5 alkyl, C1-C4 haloalkyl, phenyl, C1-C10 dialkylamino, C1-C10 alkylamino, C1-C5 alkoxy, substituted phenyl wherein the substituents are selected from the group consisting of:
nitro, chloro, C1-C4 alkyl, and methoxy.

15. The method of Claim 10 wherein R is -secC7H15, R1 is -C6H13, R2 is -C2H5 and R3 is .

16. The method of Claim 10 wherein R is -secC7H15, R1 is -C8H17, R2 is -CH3- and R3 is .

17. The method of Claim 10 wherein R is -secC7H15, R1 is -C8H17, R2 is -C2H5 and R3 is .

18. The method of Claim 10 wherein R is -secC7H15, R1 is -C8H17, R2 is -C2H5 and R3 is .

19. The compound of Claim 1 wherein said R, R1, R2 and R3 groups are selected so that said compound is substantially non-phytotoxic and produces an LD50 effect on said lepidoptera when feedstuffs or habitat of said lepidoptera are contacted with up to a .05 weight percent solution of said compound.

20. The method of Claim 10 wherein said R, R1, R2 and R3 groups are selected so that said compound is substantially non-phytotoxic and produces an LD50 effect on said lepidoptera when feedstuffs or habitat of said lepidoptera are contacted with up to a .05 weight percent solution of said compound.

21. A compound having the formula wherein R and R1 are independently selected from the group consisting of C2-C10 alkyl, C2-C10 alkoxyalkyl, and phenyl and R and R1 together contain from 12 to 22 carbon atoms;
wherein R2 is selected from the group consisting of C1-C14 alkyl, C3-C10 alkenyl, C3-C4 alkynyl, C2-C4 hydroxyalkyl, C2-C6 alkylthioalkyl C2-C6 alkyloxyalkyl, (CH2)n[x(CH2)n] y where n = 1 or 2, X is O or S and y = 1-4, where n = 1-10, phenyl, and phenethyl; and wherein R3 is an organic group or a group containing phosphorus and oxygen or sulfur and oxygen; said R, R1, R2 and R3 groups being selected so that said compound is substantially non-phytotoxic and produces an LD50 effect on said lepidoptera when feedstuffs or habitat of said lepidoptera are contacted with up to a .05 weight percent solution of said compound.

22. A method for controlling lepidoptera comprising applying to said lepidoptera or the locus or feedstuffs thereof a lepidoptericidally effective amount of the compound of Claim 21.

23. The method of controlling lepidoptera comprising applying to said lepidoptera or the locus or feedstuffs thereof a lepidoptericidally effecting amount of a compound having the formula wherein R, R1 and R2 are organic groups which may be the same or different and R and R1 together contain from 12 to 22 carbon atoms; and wherein R3 is an organic group or a group containing phosphorus and oxygen or sulfur and oxygen;
said R, R1, R2 and R3 groups being selected so that said compound is substantially non-phytotoxic and produces an LD50 effect on said lepidoptera when feedstuffs or habitat of said lepidoptera are contacted with up to a .05 weight percent solution of said compound.

24. The compound of Claim 1 wherein R is -C7H15, R1 is -C7H15, R2 is -C2H5 and R3 is .

25. The compound of Claim 1 wherein R is -sec-C7H15, R is -C8H17, R2 is -CH3 and R3 is .

26. The method of Claim 10 wherein R is -C7H15, R1 is -C7H15, R2 is -C2H5 and R3 is .

27. The method of Claim 10 wherein R is -sec-C7H15, R1 is -C8H17, R2 is -CH3 and R3 is .