BIOCIDALLY-ACTIVE 1,3-BENZODITHIOLE-2-THIONE COMPOUNDS

TRADUCTION NON-DISPONIBLE

English Abstract

Abstract of the Disclosure
1,3-Benzodithiole-2-thione compounds are disclosed
including the novel method of preparing said compounds and
their biocidal activity.

Claims

WHAT IS CLAIMED IS:
1. A compound selected from the group consisting
of those of the formulae:
<IMG> I
and
<IMG> II
and
<IMG> III
wherein Y is selected from nitro and trifluoromethyl; X is
selected from alkyl and alkenyl of up to 6 carbon atoms, nitro,
trichloromethyl, trifluoromethyl, trifluoromethoxy, trifluoro-
methylthio, trifluoromethylsulfoxyl, trifluoromethylsulfonyl,
21

methoxymethyl, cyano, carboxy, halogen (F, Cl, Br, I),
hydroxy, acetylamino, amino, N-phenylamino, N,N-diallylamino,
alkoxy, N-morpholino, N-piperidino, N-piperazino, N-pyrrolidino
dimethylaminodithiocarbamyl, carboalkoxy, alkylthio, mono- an
dialkylamino, N-alkylcarbamyl, N,N-dialkylcarbamyl, alkyl-
sulfoxy, alkylsulfonyl, said alkyl groups containing from 1 to
4 carbon atoms; n is an integer from 0 to 3; and salts thereof
2. A compound as claimed in claim 1 of formula I
wherein Y is nitro and n is 1.
3. The compound as claimed in claim 2 which is
4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-thione.
4. A compound as claimed in claim 1 of formula I
wherein Y is trifluoromethyl and n is 1.
5. The compound as claimed in claim 4 which is
5-nitro-7-trifluoromethyl-1,3-benzodithiole-2-thione.
6. A compound as claimed in claim 1 having
formula I wherein Y is trifluoromethyl and n is 2,
22

7. The compound as claimed in claim 6 which is
7-diethylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-
2-thione.
8. The compound as claimed in claim 6 which is
7-dimethylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-
2-thione.
9. A compound as claimed in claim 1 of formula II
wherein Y is nitro and n is 1.
10. The compound as claimed in Claim 9 which is
4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-thione oxide.
11. A compound as claimed in claim 1 of formula II
wherein Y is CF3 and n is 2.
12. The compound as claimed in claim 11 which is
7-aminopropyl-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-
thione oxide.
13. The compound as claimed in claim 11 which is
7-dimethylamino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-
2-thione oxide.
23

14. A compound as claimed in claim 1 of formula III
wherein Y is CF3 and n is 2.
15. The compound as claimed in claim 14 which is S-tert.
butyl-S'-(2,4-dinitro-3-aminopropyl-6-trifluoromethylphenyl)-
trithiocarbonate.
16. A process for preparing compounds of the formula:
<IMG> I
wherein Y is selected from hydrogen, cyano, alkylsulfonyl, nitro
and trifluoromethyl; X is selected from alkyl and alkenyl of up
to 6 carbon atoms, nitro, trichloromethyl, trifluoromethyl, tri-
fluoromethoxy, trifluoromethylthio, trifluoromethylsulfoxyl,
trifluoromethylsulfonyl, methoxymethyl, cyano, carboxy, carbamyl,
halogen (F, Cl, Br, I), hydroxy, acetylamino, amino, N-phenyl-
amino, N,N-diallylamino, alkoxy, N-morpholino, N-piperidino,
N-piperazino, N-pyrrolidino, dimethylaminodithiocarbamyl,
carboalkoxy, alkylthio, mono- and dialkylamino, N-alkylcarbamyl,
N,N-dialkylcarbamyl, alkylsulfoxy, alkylsulfonyl, said alkyl
groups containing from 1 to 4 carbon atoms and n is an integer
from 0 to 3 which comprises reacting a nitrobenzene compound of
the formula:
<IMG> II .
wherein Z is halogen (F, Cl, Br, I) or alkoxy, Y, X and n are
as defined above;
with S-tertiarybutyl sodium trithiocarbonate to
provide an intermediate, which intermediate is decomposed to
provide the desired compound.
24

17. The process of claim 16 wherein said reaction is
carried out in a solvent at a temperature in the range from
-10°C to 200°C.
18. The process of claim 16 wherein said intermediate
is isolated prior to decomposition.
19. The process of claim 16 wherein said intermediate
is decomposed by heating in a solvent at a temperature in the
range from 20°C to 200°C.
20. The process of claim 16 for preparing compounds
having formula I wherein Y is nitro and n is 1 which comprises
reacting a nitrohalobenzene of formula II wherein Y is nitro
and n is 1 with said S-tertiarybutyl sodium tri-thiocarbonate,
decomposing said intermediate and recovering product.
21. The process of claim 20 for preparing 4-nitro-6-
trifluoromethyl-1,3-benzodithiole-2-thione wherein 2,6-dinitro-
4-trifluoromethyl-chlorobenzene is reacted with S-tertiarybutyl
sodium trithiocarbonate.
22. The process of claim 16 for preparing compounds
having formula I wherein Y is CF3 and n is 1 which comprises
reacting a nitrohalobenzene of formula II wherein Y is CF3
and n is 2 with said S-tertiarybutyl sodium trithiocarbonate,
decomposing said intermediate and recovering product.
23. The process of claim 22 for preparing 5-nitro-7-
trifluoromethyl-1,3-benzodithiole-2-thione wherein 2,4-dinitro
6-trifluoromethyl-chlorobenzene is reacted with S-tertiarybutyl
sodium trithiocarbonate.
24. The process of claim 20 for preparing compounds
having formula I wherein Y is trifluoromethyl and n is 2 which
comprises reacting a nitrobenzene of formula II wherein Y is
trifluoromethyl and n is 2 with said S-tertiarybutyl sodium
trithiocarbonate and recovering product.
25. The process of claim 24 for preparing 7-diethylamino-
6-nitro-4-trifluoromethyl-1,3-benzodithiole-2 thione wherein 2,

4-dinitro-3-diethylamino-6-trifluoromethyl-chlorobenzene is
reacted with said S-tertiarybutyl sodium trithiocarbonate.
26. The process of claim 24 for preparing 7-dimethyl-
amino-6-nitro-4-trifluoromethyl-1,3-benzodithiole-2-thione
wherein 2,4-dinitro-3-dimethylamino-6-trifluoromethyl chloro-
benzene is reacted with said S-tertiarybutyl sodium trithio-
carbonate.
27. The process defined in claim 16 including the step
of subjecting the product thus obtained to peroxidation conditions
to prepare a compound of the formula.
28. A method of treating pests associated with growing
plants selected from fungi, insects and mites to beneficially
enhance the growth and/or yield-potential of said growing plants
which comprises treating soil, seed or said plants with a
biocidally active amount of a compound selected from the group
consisting of those of the formulae:
<IMG> I
and
<IMG> II
and
<IMG> III
wherein Y is selected from hydrogen, cyano, alkylsulfonyl, nitro
and trifluoromethyl; X is selected from alkyl and alkenyl of up
to 6 carbon atoms, nitro, trichloromethyl, trifluoromethyl, tri-
fluoromethoxy, trifluoromethylthio, trifluoromethylsulfoxyl,
trifluoromethylsulfonyl, methoxymethyl, cyano, carboxy, carbamyl,
26

halogen (F, Cl, Br, Y), hydroxy, acetylamino, amino, N-phenyl-
amino, N,N-diallylamino, alkoxy, N-morpholino, N-piperidino, N-
piperazino, N-pyrrolidino, dimethylaminodithiocarbamyl, carbo-
alkoxy, alkylthio, mono- and dialkylamino, N-alkylcarbamyl,
N,N-dialkylcarbamyl, alkylsulfoxy, alkylsulfonyl, said alkyl
groups containing from 1 to 4 carbon atoms, n is an integer
from 0 to 3; and salts thereof.
29. The method as claimed in claim 28 wherein said com-
pound has formula I as shown in claim 28 in which Y is nitro
and n is 1.
30. The method as claimed in claim 29 in which the com-
pound is 4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-thione.
31. The method as claimed in claim 28 wherein said com-
pound has formula I as shown in claim 28 in which Y is CF3 and
n is 1.
32. The method as claimed in claim 31 in which the com-
pound is 5-nitro-7-trifluoromethy1-1,3-benzodithiole-2-thione.
33. The method as claimed in claim 28 wherein said com-
pound has formula I as shown in claim 28 in which Y is trifluoro-
methyl and n is 2.
34. The method as claimed in claim 33 in which the com-
pound is 7-diethylamino-6-nitro-4-trifluoromethyl-1,3-benzo-
dithiole-2-thione.
35. The method as claimed in claim 33 in which the com-
pound is 7-dimethylamino-6-nitro-4-trifluoromethyl-1,3-benzo-
dithiole-2-thione.
36. The method as claimed in claim 28 wherein said com-
pound has ormula II in which Y is nitro and n is 1.
37. The method as claimed in claim 36 in which the com-
pound is 4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-thione
oxide.
38. The method as claimed in claim 28 wherein said com-
pound has formula II in which Y is CF3 and n is 2.
27

39. The method as claimed in claim 38 in which the
compound is 7-aminopropyl-6-nitro-4-trifluoromethyl-1,3-benzo-
dithiole-2-thione oxide.
40. The method as claimed in claim 38 in which the
compound is 7-dimethylamino-6-nitro-4-trifluoromethyl-1,3-
benzodithiole-2-thione oxide.
41. The method as claimed in cliam 28 wherein said
compound has formula III in which Y is CF3 and n is 2.
42. The method as claimed in claim 41 in which the
compound is S-tert. butyl-S'-(2,4-dinitro-3-aminopropyl-6-
trifluoromethylphenyl)-trithiocarbonate.
28

Description

:llOZ;~Z6
; ,.
~, ,." . .
;' - :
~ . ~
~,
.
,
19~ ~ ~ Bac~ground oE the 1nventlon~
20 ~ This~ invention relates generally to new and useful
21 ii biocidally active~ compounds. ~ore speei~ically, it rela~es : ¦
22 1¦ to novel 1,3-benzodithiole-2-thione~compou~d:s:prep~ared by an .
23 ~1 t~usttaI but highly simple and convenient cyclization reaction.
~ ,
24 1 In fact, it is due to this synthesis that the numerous i -~
25 1l derivatives disclosed herein can be obtained so easily :and : ¦ :
26 i in good yields.
27 ,1
28 ll The novel compounds of this invention are useful
29 , in treating pests such as fungi, insects and mites associated ,,
30 ', with growing plants in order to beneficially enhance the growth
', ~
( _

'~8 ~2326
l and/or yield-potential of said growing plants. This is
2, accomplished by applying a biocidally active amount of the
3 subject compound to the growing plant.
il :
5l For purposes of this disclosure and for the sa~.e
6 of convenience and clarity, certain terms used herein are
7l, defined as follows:
8 l, The phrase "treating fungi, insects and mites
g l, associated with grvwing plants" signifies the application
!!
lOii of a compound as herein defined to combat fungi, insects
and mites associated with growing plants which embraces
l2 i germinating plants, e.g. sprouts, seedlings, and fully grown
13 ~ plants. The made of application will depend on the desired
. 14 il end use.
~ .,
~t ~ .
When treatment comprises foliar fungicidal, insec- ¦
17 l~ ticidal or miticidal application, the compound is administered,
18 as a spray, di~ectly onto the leaves and other above ground
~9 ~, portions of diseased plants.
20, ~
21 li All of ~he afor said treatments, whatever the
22 l objective, have a unitary result. That is, they beneficially
23 , enhance or improve the growth and/or yield potentia1 of the
24 ji treated plant. -~
!l
25 i,i . ,
The term '~biocidally active amount" means an amount
27 1, of compound which efectLvely permits the desired obieckive.
28
29 , Summary of the Invention
30 , Accordingly, this invention is concerned with
_ ~ i

-&~8 ~ 6
compounds of the formulae:
2 ~C~5 S~O S
4: S3 2~ S~ \ S~C-S-C(cH3~3 ~ :
5 ~ 5 ~ 2
8 (X)n I (X)n II (X)nIII
9 ' . '
wherein Y is selected from hydrogen, cyano, alkylsulfonyl,
11 nitro and trifluoromethy~; X is selected from alkyl and alkenyl ¦
12 o~ up to 6 carbon atoms, nitro, trichloromethyl, trifluoro- !
13 methyl, trifluoromethoxy, trifluoromethylthio, trifluoromethyl- .
14 sulfoxyl, trifluoromethylsulfon~l, methoxymethyl, cyano,
15 'l, earboxy, carbamyl, halogen (F, Cl, Br, I), hydroxy, acetyl~
16 . amino, amino, N-phenylamino, N,N-diallylamino, al~oxy,
1 17 , N-~Lorpholino, N-piperidino, N-piperazino, N-pyrrolidino,
~1 i
18 l dimethyla-minodithiocarbamyl, carboalkoxy, alkylthio, mono-
l9 ,' and dialkylamino, N-alkylcarbamyl7 N,N-dialkylcarbamyl,
20 , alkylsulfoxy, alkyl sulfonyl, said alkyl groups containing
21 ll from 1 to 4 carbon atoms; n is an integer from 0 to 3; and I :
: 22 l¦ saLts thereof.
,1 I
24 ~ 0 particular interes~ are compounds as shown having
25 l, formula I above wherein Y is nitro and n is 1, such as:
26 l, 4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-
27 '' thione and wherein ~ is trifluoromethyl and n is 1, e.g. ¦
28 ' 5-nitro-7-trifluoromethyl-1,3-benzodithiole-2-
29 , thione.
,:
--3--

~ 3 ~1~
:.-888
l Others which are preferred are those as shown above
2 having formula I wherein Y is trifluoromethyl and n is 2 such asl
3 4-diethylamino-5-nitro~7-trifluoromethyl-l,3-
4 benzodithiole 2-~hione
4-dimethylamino-5-nitro 7-trifluoromethyl-l,3-
6l benzodlthiole-2-thione.
.,
~ 7
~: i .
~ 8 " Also within the purview of this invention is the
.,
g novel process for preparing such compounds involving a unique
cyclization step as well as the use of such compounds to
l] bene~icia1ly enhance the growth and/or yield-potential of
12 plants.
13 `
14 1 Detailed Des-cription~of the Invention
15 , The novel~compounds of th:is invention having formula .
I6 I are prepared by a novel procedure~wh rein a unique cycIization
l7 step is involved. It is this synthetic~method which allows for
18 the formation of th~e numerous compounds disclosed herein. Com-
l9 pounds which would ordinarily be inaccessible or at best, 1,
tedious and difficult to make, are r~ndered available by an I ;
i .~,
21 1 unusually simple and mild synthesis.
~2 11
23 jl The process can be expressed by the ollowing
24 , reactions
26 , Z
27 1i Y ~ NO2 + O
29 ~ S-IC~-S-C(CH3)3 ____________~3
30 ' (~)n
'~
,

~8~ ;23~
~ . :
Sl ~. S
2~, 5-C-s-cCcH3~3 S
::~ 3~
6 (X)n C (X)n D
8~' wherein Y ~s selected from hydrogen, cyanol alkylsulfonyll nitro
g ll and tirfluoromethyl; X is selected from alkyl and alkenyl o up
10 , to 6 carbon atoms, nitro, trichloromethyl, trifluoromethyl,
11 ~ trifluoromethoxy, trifluoromethyl-thio, trifluoromethylsulfoxyl, ¦
,il .
12 i trifluoromethylsulfonyl, methoxymethyl, cyano, carboxy,
13 'i~ carbamyl, halogen (F, Gl, Br, I), hydroxy, acetylamino, amino, ! ~ :
14 I N-phenylamino, N,N-diallylan~ino, alkoxy, N-morpholino, I
15 , N-piperidino, N-piperazino, N~pyrrolidino, dimethylaminodithîo- ~ I
16 carbamyl, carboalko~y, alkylthio, mono~ and dialkylamino,
I7 N-alkylcarbam~l, N,N~dialkylcarbamyl., alkylsul~oxy, alkyl-
18 jl sulfonyl, said alkyl groups containing from 1 to 4 carbon atom3
19 ~ and n is an integer from O to 3; Z is halogen (F, Cl, Br, I~ j
20 i or alkoY.y, and R and R' are e~ch alkyl groups, straight- or
bra~ch-ehained, containing from l to 4 carbon atoms-~
22 11
23 il Starting material A is typically a haloben~ene
24 li derivative, many o~ which are commercially available. If
25 ¦ not, one can e~sily synthesize the desire~ compound using
26 ~I well-documented che~ical techniques. As is apparent, the
27 ,'l halo group (Z) and the adjacent nitro group both undergo
28 ~I substitution thereby effecting cyclization to form the
29 j heterocyclic 5-membered ring. The other reagent, B, is
S-tertiarybutyl sodium trithiocarbonate.
i,, 1
; -5-

j38 ~ 326;
1 The attractiveness of the above process is tha~
2 under relatively mild conditions, using generally available
1 3` or easily accessible reagen~s, one can obtain the desired
4 compounds in good yields. The intermediate product C of
5'~ this reaction is usually isolated. However, it is possible
6 ll to effect cyclization directly, to produce final product D
7 1 the substitu~ed 1,3-benzodithiole-2-thiones.
8 ,
g The novelty of this synthetic method is clearly
evident to one skilled in the art. It enables one to ~use
11 onto a benzene ring containing adjacent nitro and halo groups
12 a cyclic ring having the structure:
i; : I
13 ~ I
14 ~` ~ S ~,
15 , S ~ \
~16' ~ S
17 i l benzene
18 ~ ring
19i , I :
21 ii Importantly, it allows one to do thi5 under mild ¦
conditions and using various chlorobenzene derivatives so ¦ ~
23 that almost any desired substituted compound results. ! :~ I
24 il
25 I The first step in reaction process is carried out
26 1 in the temperature range o~ from -10C to 200C. In many
27 '~ instances, the reaction proceeds at room temperature or lower,
28 `` whereas, in some cases, elevated temperatures may be desired
~9 ', in order to accelerate the reaetion.
,;
'.
-6-

~88 ~ 2~2~
1 The reac~ion is usually carried out in a solvent,
2 al~hough the solvent may be omitted if effective dissolu-
3 ~ion of materials is possible. A solvent is generally
preferred, however, and it can be any solvent which dves
5~ not enter into the reaction and in which the reactants are
6l~ soluble to some extent. Suitable solvents are dimethyl-
formamide, dimethylsulfoxide, acetone and methyl isobutyl
8 ' ketone.
10 I The mole ratio of reagents A and B is normally
11l 1 to 1, however, it is generally preferred to use a slight
12 l excess o~ reagent B to ensure more complete-reaction.
13 Ill :
14 Intermediate~C can be isolated prior to conversion
15 ~, to product D or it can be decomposed-directly. If isol`at d,
16 1l the decomposition of C to D is typically effected in a solvent
17 ~I such as ethanol, acetone, dimethyl sulfoxlde or glacial acetic
18 ll acid. If decomposition is efected directly, the reaction
9 !i mixture containing intermediate C is treated to produce
20 ll, produ~t~D.
2 I l l
22 I The aforesaid decomposition reaction is accomplished
23 ~I generally by a heati.ng step at temperatures in the range from
24 1¦ 20C to 200C. In certain instances, that decompo~ition will
25 li occur at lower temperatures without the need for a heating
step.
27 ~~
28 i' The work-up is standard - product is obtained
29 l, by precipitation, washing, drying and recrystallization if
necessary.
,, i
-7- 1

~z326
:.~888
,
l Product D can be ~urther reacted under peroxidation
; 2, conditions to provide trithione oxides E as follows~
4 ~
5 ~ S ~ ~ ~ S-O ~ :
6 ~ ~ Peroxidation
12 ,' This reaction is effecred undel standard peroxidati n
13., conditions using any suitable peroxide catalyst,:e.g~ peracet-ic
: 14~1 acid.
16 ,. The biocidal:pro:oesses~of this:invention comprise ~: :
17'i ~applying~ a biocldally: fective am~unt~of:~a c~mpound dis:closed~
~ ~ 18 ~, herein~to growing plants. The compounds are ~ormulated ~or use:
:~ lg i either as sprays made;up by addlng~water to emulsifiable con- I
20 ' ;c.entrates or wettable:powders, as granule~ or as`dispersions
~ ~ 21 1! on carriers ~such~as;attapulgite clay granules, peat moss,~
22 1! ~ertilizer, vermiculite, etc~. ~The co~pounds~are quite insoluble ! ~
23 ,.¦ in water, a~d hence, for the preparatian of emulsions br I ~ ~`
24 11~ wetta~le powders, the comyounds are preferably form-ulated with
: 25 ~ wetting agents. : : ~ .
26-
27 I Since numerous compounds disclosed herein are free :~
28 , bases and acids, they can be converted to acid salts (~ree
29 .I bases) and base salts (free acids).
; 30 1',
,: 1 1'
'' . I
--8--

-~8
%~6
1 The acid-addi~ion and base-addition salts are
2 within the purview of this invention. The a~id~addition
3 salts are easily prepared by treating the amine base with
4,l a substantially equimolar amount of a chosen acid in an
5' aqueous solution or in a suitable organic solvent such as
~ 6l, methanol or ethanol. The only restriction on the acid used
-~ 7 ll is that it provides acceptable ions, i.e., those which do
8,~ not deleteriously affect the growing plants. The base-
9 addition salts are prepared in a similar manner except that
lOi base instead of acid is added. The same restriction with
respect to acceptable ions applies.
12
13i For foliar fung1cidal, insecticidal and miticidal
14 , useJ the compounds disclo~ed herein are applied at a rate ¦
` : 15 ll o~ about 200 to 5000 parts per million as an emulsion in
16l water.
17 ll
18'' EXAMPLE I
gi, 4-Nitro~6~tri~1uoromethyl-1,3-benzodithiole-2--thione
,l To a stirred and cooled (freezing mixture) solution
21 1 of 27.0 g (0.1 moLe) of 3,5-dinitro-4-chlorobenzotrifluoride
- 22ll (I) in 100 ml of acetone was added dropwise a solution of
;~ 23 l 24.7 g (0.11 mole~ o~ S-tert. butyl sodium trithiocarbonate
24l (II) in 150 ml of acetone. The temperature of the reaction ~`
25!I mixture was maintained at -10 to -5C during addition of
26¦ II. Mixture allowed-to stir at room temperature overnight,
27 ¦I poured into 1200 ml of water, and extracted with three lO0 ml
281 portions of methylene chloride. A~ter drying over anhy.
29~~ Na2S04, the methylene chloride extract was freed o~ solvent
by distilling in vac. on a rotary evaporator. The residual
,, , I
_g_

-888
fiff~;Z'~f : '~
', ' ,
l material was triturated with cold ethanol, suction ~iltered
2 and dried. This yielded 16.0 g (40/O theor.) of S-tert.
3' butyl-S'-(2,6f-dinitro-4-trifluoromethylphenyl)-trithiocarbonate
4f (III).
5' !
6 I,l 15 g (O. 037 mole3 of III was dissolved in 125 ml
7, of glacial acetic acid and heated to 90-100C for 45 minutes.
~! ~
8 The mixture was poured into 500 ml of water, extracted with
g , three 100 ml portions of methylene chloride. The organic ,
10l extract was dried {Ma2S04) and solvent removed by distillation ¦ ;
in ~ac. The residual solid-was recrystalli~ed from ethanol. ~ l ~
12 There was obtained 6.0 g (55% theor.) of 4-nitro-6-tri1uoro- l I
: 13 ,, me~hyl-1,3-benzodithiole-2-thione, m.p. 13-165C.~Analytical:
14 ' Calff^ffd. for CgH7F3NO2S3: C, 32.32; H, 0.67; S, 32.32. Found ~ ¦
I~ 15 , C, 32.18; H, 0.74; S, 32.21. Mass ;Spectrum mol. wt. = 297.
16 NMR(d6DMSO); 8.63f~ ,m) 8.73l1H,~m).~
18~ EXAME'LE II ~ f
19 ¦ The procedure of Example I is repeated wherein the
20 '' following chLorobenzene derivatives are used in place of
21 ,i 2j6-dinitro-4-trifluoromethylchlorobenzene to provide the
22 ¦ corre5ponding products: -
23 ii :
24 ' chlorobenzene derivative Product
2~ Ij 2,6-dinitro-4-cyano-chloro- 4-nitro-6-cyano-1,3-benzo-
¦I ben~ene dithiole-2-thione
Z7 l, _
Z8 ' 2,4-dinitro-3-dimethylamino- 7 dimethylamino-6-nitro-
6-tri~luoromethyl-chloro- 4-trifluorQmethyl-1,3-benzo-i
29 benzene dithiole-2-thione
-10-

-~88 ~ 3 ~
l chlorobenz~ne derivative Product
, . _ . ____
2 2,4-dinitro-6--trifluoromethyl- 5-nitro-7-tri~luoromethyl-
ll chlorobenzene l,3-benzodithiole-2~thione
5,,2,4-dinitro-3-diethylamino-6- 7-diethylamino-6-nitro-
~ l trifluoromethyl-chloro- 4-trifluoromethyl-1,3-
:: 6l benzene benzodithiole-2-thione
~ 7jl
.,i I -- ~ . ' I
8i, 2,6-dinitro-5-tri1uoromethyl-4-nitro-7-trifluoromethyl-
l chlorobenz2ne 1,3-benzodithiole-2-thione ¦
i~ !i
'- 10 11
~ 2,4-dinitro-3-monopropylamino-7-monoprop~lamino-6-nitro-
;li 6-trifluoromethyl-chloro-4-trifluoromethyl-1,3-
12', benzene benzodithiole-2-thione
13~1
14 1,l 2,4-dinitro-3-di-n-propylamino-7-di-n-propylamino-6-nitro-
: 1l 6-trifluoromethyl-chloro-4-trif1uoromethyl-1,3- 1
~i~ 15 ii benzene benzodithiole-2-thione t
'.! I . _
17¦~ 2,6-dinitro-4-methyl-chIoro- 6-methyl-4-nitro-1,3-benzo- l ~
~1 dithiole-2-thionel ~ ~
-~19,~ _ . I ' ' .
20 1 2,4,6-trinitro-chlorobenzene 4,6-dinitro-1,3-benzodithiole-
. l 2-thione
:~.21 i
22 11 _ _ _ .
231~ 2,6-dinitro-4-fluoro-chloro- 6-fluoro-4-nitro-1,3-benzQ-
¦ benzene dithiole-2-thione
251 _ _ . .............. _ ~ .
26l! 4-chloro-2,6-dinitro-chloro- 6-chloro-4-nitro-1,3-benzo-
: 27 !1 dithiole-2-thione
28 , . _
29', 1,4-dichloro-3-methyl-2,6- 6-chloro-7-methyl-4-nitro-
il dinitro chlorobenzene l,3-benzodithiole-2-thione
;i
ll l
- 11- ~

o ~ 8 11~ 23 ~6
1 chlorobenzene derivative Product
_ _ ,
2 3-chloro-2,6-dinitro-4- 7-chloro-4-nitro-6-tri1uoro-
: trifluoromethyl chloro- methyl-1,3-benzodithiole-2-
3 benzene thione
,1
4 Ij - -- . .
:. 5 1 2,6-dinitro-chlorobenzene 4-nitro-1,3-benzodithiole-2-
'. thione ! ~:
~ ..
7 ,
--~ ~ ~
; 8 ,3,5-dimethyl-2,4,6-trinitro- 5,7-dime~hyl-4,6-dinitro- 1 ~ -
chlorobenzene 1,3-benzodithiole-2-thione 1 .:
g ,, I ,:
10,
.-~ ,_ ~ . .. _
11 3-di-n-propylamino-2,4- 7-di-n-propylamino-6-nitro-
.dinitro-6-trifluoromethyl-4-trifluoromethyl-1,3-benzo- !
12 ,chlorobenzene dithiole-2-thione
13 ~ . :
;: 142,4-dinitro-3-monoisopropyl- ~ 7-monoisopropylamino-6-nitro~
: .amino-6-trifluoromethyl~ : 4-trifluoromethyl-1,3-ben~o- .~
i': lS ,chlorobenzene ~ ;dithiole-2-thione : I ::: -
16, ~
7 !2,4-dini-tro-3-mono-n-propyl- 7-~monopropylamino-:6-nitro-
a~ino-6-tri1uoromethyl- .4-trifluoromethyl-1,3-benzo~
18 ichlorobenz~ne ~ :dith~ole-2-thione
! ' I : ,
19 ''
. ', - _ ..... ___ _ - ----- . ,
3-dietkylamino-2,4-dinitro- 7-diethylamino-6-ni~ro-4-tri-
: 16-trifluoromethyI-chloro- 1uoromethyl-1,3-benzo-
21 ~i- benzene di-thiole-2-thione 1,
22 1'
23 i 2,4-dinitro-3-n-propylthio- 6-nitro-7-n-propylthio-4-tri-
6-trifluoromethyl-chloro- fluoromethyl-1,3-benzo-
24 1! benzene dithiole-2-thione
1~
- 25 1! - - -
2 6 'i I 2,4-dinitro-3~isopropylthio- 7-isopropylthio-6-nitro-4-
,, 6-tri1uoromethyl-chloro- trifluoromethyl-1,3-benzo-
27 benzene dithiole-2-thione
~, ~' .
28 i :
;30 '' I
' " ' i
-12-

-~88
l chlorobenzene derivative Product
. , . ~
2, 4-cyano-2,6~dinitro-chloro~ 6-cyano-4-nitro-1,3-benzo
3 benzene dithiole-2-thione
.,
. .... _
5ll 3-diallylamino-2,4-dinitro- 7-diallylamino-6-nitro~4- ¦
,, 6-trifluoromethyl-chloro- trifluoromethyl-1,3-benzo-
6 ~ benzene dithiole-2-thione
7'l . . .
8il 274-dinitro-3-methylamino- 7-methylamino-6-nitro-4-
1l 6-trifluoromethyl-chloro- trifluoromethyl-1l3 benzo-
9 ll benzene dithiole-2-thione
11l 2,4-dinitro-3-monobutylamino- 7-mono-n-butylamino-6 nitro-
i! 6-~rifluoromethyl-chloro- 4-tri~luoromethyl-1,3-benzo-
1 12,~ benzene dithiole-2-thione
l3 !1 .
.. . ~ _
: 14 ¦~ 3-dibutylamino-2,4 dinitro- 7-di-n-butylamino~6-ni~ro-4-
I 6-trifluoromethyl-chloro- tri~luoromethyl-1,3-benzo-
I-15 l, benzene dithiole-2-thione
:~- 16 ll __ :
:~ 17ll 2,4-dlnitro-3-monophenylamino- 7-monophenylamino-6-nitro-
6-tri1uoromethyl-chloro- 4-trifluoromethyl-1,3-benzo-
:18jl b,~nzene di~hiole-2-thione
~'19 !1.
j I
20 ll 2,4-dinitro-3-piperidino-6- 6-nitro-7-pip2ridino-4~
I! trifluoro~ethyl-chloro- trifluoromethyl-1,3-benzo-
21 l¦ benzene dlthiole-2-thione
2~ . . _
231! 2,4-dinitro-3-morpholino-6- 7-morpholino-6-nitro-4-
!! trifluoromethyl~chloro~ trifluoromethyl-1,3-benzo-
24jl benzene dithiole-2-thlone
2511 - _
25 ! 2,4-dinitro-3-pyrrolidino-6- 6-nitro~7-pyrrolidino-4-
¦ trifluoromethyl-chloro- tri~luoromethyl-1,3-benzo-
27 ,I benzene di-thiole-2-thione
28 j
29
: 30
" 1, i
1.
"
-13
,:

r ) ~ 6
3~
1chlorobenzene derivative Product
2,4-dini~ro- chlorobenz ene 5-nitro-1,3-b enzo dithiole- I
3 2-thione
~ .~
4,, . . . . _
5!l 2-nitro-4-trifluarometh~l- S-trifluoromethyl-l, 3-benzo-
1 chlorobenzene dithiole-2-one
7, In all instances, intermediate trithiocarbonate
8 ' is first isolated.
91, 1
10 , EXAMPI,E III j :-~
11 I The procedure of Example I is repeated wherein the t
- ::
12, followi~g solvents are used in place of acetone with comparable
13 results: I : :
14,' dimethylsulfoxide ¦
15 ~j dime~hylformamide ¦
16 l, ~ethylisobutyl ketone
17~1, glacial acetic acid
: ~
18
19 , ~ EXAMPLE IV ¦ :
20 i' The procedure of Example I is repeated wherein the
21l, following halobenzene derivatives are used:in place of
22 ',l 2,6-dinitro~ trifluoromethyl-chlorobenzene to provide corre-
23 il sponding products:
24'~
26 I Z ~ C\ S
~7 lY ~ 2 Y ~ S
29 Xl ~ X3 X ~ X3 1,
30 , X2 X2
'~ . I
, i
- 1 4 -
!

.- 888 ~ 23Z~
_ halobenzene derivative
,: , __
2l z Y xl x2 X3
" _ .. _~ . ._
~ ~ Cl N02 allyl H H
5 ,! _ _ ___
6, Br N02 hexyl H H
~ ~ 7 " - _ __ ____ ~ I
: ~ 8 " F N02 CC13 ~ ¦
:: 9 , ' . . _ . .. _ . . . . _ ._ , , ,
1~ 10 'I Cl N02 H ~ CF30 . . :~
11 - _ - ~ ~_ ----~
12 1~ Cl : CF3 H ~ CH3S2 H
I :
13 !, - _ _ ~ ~ _ __ _
14 Cl No2 ~ H ~ :~ ~1 3 . . .
~ ~
15 l l ~ _ : _
16 ~ ~ N2 ~ ~ ~ CF3SO ¦ ~
17 !~ ~ . - I :-
Cl N02 H CN ~ ....
19 ~ :. .. ~_ _. : _ ~ .
20 I Cl ~ N02 H CF3S02 ~
.. _ . . _ ~ . , -:
2 2 Cl NO2 H ; H H :: ;~
23 I _ _ ; ~ _ __
24 I Cl N02 H CH30CH2 H :
2 5 I . __ _ _ __ .
26 ¦ Cl CF3 H CN H
27 !i _ _ _
2 8 , CF3 H COOH H
29 I __ __ _ . __
30 I', CF3 H OH H
l -- --------- - -~------- -- ---- - - - -
31 'i Cl C~'3 H NH2 H
~ _ _ .. __ . . . _ _____~
- 15- ,

~8 1~L~2~
!
1 ~ EXAMPLE V
2; For determination of foliar ungicidal activity
3 for the herein disclosed co~pounds, the following scrPen was
4,, used.
j , .
6l Powdery Mildew of Cucumbers
7 ,, Cucumber plants of a suscepti.ble variety are
8 ,I grown in paper pots with 4 to 6 plants per pot. When the
g i first leaves have reached a size o about two inches in
10 I diameter, they are sprayed~with the test solutions (5~00 PPM) ¦ ;~
~,.
with two pots used for ~each treatment applied. After the
12 1 spraying treatm nts have dried thoroughly,~the plants are
13 ll dusted with spores of powdery mildew f~ngus, Erysiphe
14 l cichoracearum, reared on cucumber p:Lants.~ Observations I
IS~ are made for disease~symptoms through~ut a period of 15 ~ :~
16 days.
lB~ 1l The following compounds exhibited oliar fungicidal ¦
19 l' propertie
20~l~ 4-nitro-6~trifluoromethyl-1,3-benzodithiole-2-
21 ! i thione
22 ¦~ 4-dimethy.l~mino-5-nitro-7-tri1uoromethyl-1,3-
23 1I benzodithiole-2-thione
11 .
~4 ¦1 5-nitro-7-tri1uoro~ethyl-1,3-benzodithiole-2-
25 I t~ione
26 II 4-diethylamino-5-nitro-7-trifluoromethyl-1,3-
27 I benzodithiole~2-thione.
28
29 1 The following intermediate showed follar fungicidal
30 ,, activity: ¦
~! l
-16-

~8 3L~3~
. , .
1 S-tert. butyl-S'-(2,4-dinitro-3-aminopropyl~6-
2 trifluoromethylphenyl)-trithiocarbonate. I
, 1,
3 1i
4~ The following thione-oxides exhibited foliar
S fungicidal activity:
6,, 4-aminopropyl-5-nitro 7-trifluoromethyl-1,3-
7l, benzodithiole-2-thione oxide
8 4-dimethylamino-5-nitro-7-trifluoromethyl-1,3-
9l benzodithlole-2-thione oxide.
1~
111 EXAMPLE VI
12~ For determination-of insecticidal and miticidal
~ 13i, activity, th~ following screens were used.;
;~ 14~
1 15 i' The samples are tested at ~000 PPM with the ~ !
16l~ exception of the pea aphid systemic~test where lOO PPM is
17l, utilized. I !
~ ~ 18 ~
19 ¦ ~ ~ouseflies j
20 ¦' Fifty adult houseflies are sprayed in 2 x 5
21i~ inch diameter stainless steel cages faced on~top and bottom
22 ll with 14 mesh screen. The insects are retained in the same
1 23 1I cages for knockdown observations after 2 hours. The 24
24 1 hour mortality may be ~rom residual as well as from diract
25 i contact. .
~6 ,
27 I' Southern Armyworm and Mexican Bean Beetle
2~ l, Lima bean leaves dipped into test solutions are
29 1,l offered to ten larvae of the Southern Armyworm (late third
30 '
". ' I
-17-
.,~ ' ' ' .

-,38 ~ 26 - ~
1 instar) and the Mexican Bean Beetle (late second instar), li
Mortality is recorded after a 48 hour feeding period,
3 ,
4, Pea Aphid
5 ,, Ten adult pea aphids are sprayed and transerred
; 6 ' to sprayed pea plants and held for 48 hour mortality determina-
~ 7 i~l tions.
~ ~'',i , '
g ,~ Spider Mite
10 ' Excised lima bean plants are infested with 50 to
100 adults of the strawberry spider mite prior to testing. ¦
12 ~ Adult mortality presence~or absence of~nymphs and phytotoxicity
13 are noted, ; ~
j! :
14,
! : :: : `
Systemic Aphid Test
16 ,i Systemic insecticidal activity is evaluated by
17 , applying 25 milliliters of the sampl~ to the vermiculite
18 . sub~tratum of pot~ed pea seedlings. Three days after applica-
19 ' tion, the pea plants are infested with ten adult aphids.
2~ l Mortality determinations are made after 5 days.
21 i
22 ¦I The following compounds e~hibited insecticidal
23 ', and miticidal activity;
24 1, 4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-
25 1~ thione
26 ~l 4-dimethylamino-5-nitro-7-trifluoromethyl-1,3-
27 I benzodithiole-2-thione -
28 ' 5-nitro-7~tri1uoromethyl-1,3-benzodithiole-2-
29 ,~ thione
30 ,, 4-diethylamino-5-nitro-7-tri:Eluoromethyl-1,3-
31, benæ~dithiole~2-thione,
-1~- 1
, . :

.-S88 ~ 326
1 The following intermediate showed miticidal
2~,; activity: ¦
3 ' S-tert. butyl-S'-(2,4-dinitro-3-aminopropyl-6- ¦
4I trifluoromethylphenyl)-trithio~arbonate.
~ 5,l 1
6 1 The following thione oxides exhibited miticidal
7 '' and insecticidal activity: ! :
8i 4-aminopropyl-S-nitro~7-trifluoromethyl-1,3- ¦
9 1 benzodithiole-2~thione oxide ¦
10l 4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-thione
11 ; oxide
12 , 4-dimethylamino-5-nitro-7-trifluoromethyl~1,3- ~ ¦
I1 13 I benzodithiole-2-thione oxide.
14 ~
17 ¦' ~4-Nitro-6-trifluorometh~ 1,3-benzodithiol~e-2-thio e oxide
18 ¦' To a stirred solution o ~7.35 g.,(24.7 mmoles~ ¦
19 ,~ of.4-nitro-6-trifluoromethyl-1,3-benzodithiole-2-thione
20 ~ in lS0 ml.o~ chloroform was added dropwise a solution of
,
21 1 5.17 g.,(24.7 mmoles)of 40~/O peracetic acid in 50 ml. of I `
.~ ~2 ~I chloroform over a period of 20 minutes, the temperature being
, 23,li maintained at 8-12C.
24
25 ¦I The reaction mixture was allowed to stir at
: 26 i ambient temperature for 30 minutes, the resulting solution
27 I~ washed with two 150 ml. portions of water, dried lNa2SO4]
28 , and the solvent distilled .in vacuum.
,.,,,~ ~. I
29 ,l
30 ,I The residual crystalline material was recrystallized
:, 1'', .
~, ~ .

~23~6
~8~
;. I
1 from ethanol and yielded 4.18 g. [53%] of the thione oxide,
2 ' MP 163~C. dec. NMR (d6DMSO); 8.70~rlH, M3; 8.45 [lH, M]. The ~ :1
3 , mixed ~P wi~h s~arting material gave a depression o~ melting
4 'li polnt.
5 ,l
6 1i It should be understood by those skilled in the
7 l' art that various modifications may be made in the present ¦~
8 ~ inve~tion without departing from the spirit and scope
9 il thereof as described:in the specification and defined in
10 j, the appended claims.
11 il
12 I
11 :~.
13 ~ :
14 ,' ~ :
15 i~ : : ~;
I6 ~
17 11 ~ :
18 1'
19 ~ :
20 ~'1 , '`
21 j
22 Il :
23 i
24
26 1.
27
28
29
30 "
, 11 . . ':
"
-20-
":, ' , , , , I ,
!