Note: Descriptions are shown in the official language in which they were submitted.
105l~lS
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention is concerned with insecticidal compounds
which have morphogenetic hormonal mimetic activity. Compounds having morpho-
genetic hormonal mimetic activity exert a disrupting influence upon the
normal development of insects. These compounds interfere with the normal
metamorphosis of the pest insects and result in the formation of individual
insects of the treated species which develop abnormally and are nonviable or
sterile. This ultimately leads, indirectly at least, to the destruction of
the insect population.
Description of the Prior Art
Thioketal-substituted phenylhydrazones are disclosed by M.W.
Moon et al, "J. Agr. Food Chem.," 20, 888 ~1972). German patent No. 2,157,601
~ . 77 88470b (1972~] also disclose thio-substituted phenylhydrazones.
Phenylhydrazone compounds are also disclosed in "J. Agr. Food Chem.,"-20, 1187
(1972); "J. Org. Chem.," 37, 383, 386, 2005 (1972); and Netherlands patent
application No. 7,1139497.
DESCRIPTION OF THE INVENTION
-
The insecticidal phenylhydrazone sulfides of the invention are
represented by the formula:
Cl IR
Ar - NHN = C - IC2 (S)n ~I)
wherein Rl is hydrogen or alkyl of 1 to 6 carbon atoms, R2 is hydrogen or
alkyl of 1 to 6 carbon atoms, R is ArNHN = C(Cl)C(R )(R ) -, alkyl of 1 to
6 carbon atoms, haloalkyl of 1 to 6 carbon atoms and 1 to 5 fluoro, chloro or
bromo groups or phenyl unsubstituted, or substituted with up to 3 (0 to 3)
fluoro, chloro or bromo; Ar is phenyl unsubstituted or substituted with up to
5 (0 to 5), more preferably with up to 3 (0 to 3), fluoro, chloro or
- 2 - ~
. ,~,..,.,:~
~ ~35~
bro~o or with up to 2 (0 to 2)~ more preferably with up to 1 (0 77
to 1~ nitro; ana n is 1, 2 or 3O 78
Representative alkYl groups ~hich Rl, R2 an~ R3 may 79
represent include methyl, ethyl, n-propyl, isopropyl, n-hutyl, B0
sec-pentyl and isohexyl. Representative haloalkYl R3 groups 82
include trifluoramethyl, chloromethyl, trichloromethyl, 83
1,1,2,2-tetrachloroethyl, pentabromoethyl, pentachloroethyl, 4- 85
chlorobutyl, etc. Representative halophenyl R3 groups include 87
4-fluorophenyl, 4-chlorophenyl, 3-bromophenyl~ 2,4 dichloro- 90
phenyl, and 2,4,6-trichlorophenyl. Representative halophenyl 93
Ar groups include 2-fluorophenrl, 4-fluorophenyl, 4-chloro- 94
phenyl, 2j4-dichlorophenyl, 3,5-dichlorophenyl, 2,4- 96
dibromophenyl, 2,4,6-tribromophenyl and pentachlorophenyl. 97
~he preferred Rl and ~Z groups are alkyl of 1 to 3 98
carbon atoms. The preferred R~ qroup is alkyl of 1 to 6 carbon 100
atoms, haloalkyl of 1 to 2 carbon atoms and 1 to 5 chloro or 101
bromo, phenyl of up to 3 chloro or bromo or 102
ArNHN=C(Cl~C(~ R2~-. The most preferred ~3 group is alkyl of 103
1 to 6 carbon atoms or ArN~N=C(Cl)C(~)(R2)-. The preferred Ar 105
groups are phenyl and phenyl substituted with 1 to 5 chloro or 106
bromo groups, especially trichlorophenyl. 107
Representative compounds of formula (I) ~herein n is 10B
1, 2 or 3 are tabulated in Table I (0 represents phenyl~. 109
.
~8Z3~
TABLE I
Ar R1 R2 R3
H H C113
C~3 ~1 C113-
C~5 C1~3 C ~3
2-F~ C2~15 C2115 ClC1~2
3-Cl~ i-C3~17 i-C311~ ClzC11
4-Br~ C113 n-C411s CCl3
2,4-F2~ C~l3 n-C5l~ll C2Cl5
3,4-Cl2~ C113 n-C6~13 C113
3,5-Br2~ C113 C~13 C113
2,4,6-F3~ C~13 C113 . CCl3
2,4,6-Cl3~ C~115 C113 C113
2,4,6-Br3~ CH3 CH3 CH3
H H ~NI1N=CClCH2-
2,4-C12~ H H 2,4-Cl2~NHN=CClCH2-
m-02N~ H H m-02N~NHN=CClCH2~
H CH3 ~NHN=CClCH(CH3)-
3~5-Cl3~ ~ C2H5 ~NHN=CClCH(CzH5)-
2,4,6-Cl3~ H n-C3H7 2,4,6-Cl3~NHN=CClCH(n-C3H7)-
3,5-F2~ H sec-C4Hg 3,5-F2~NHN=CClCH(sec-C4Hg)-
2,4,6-Br3~ H n-csHll 2,4~6-Br3~NHN=CClCH(n-C5H11)-
2,4,6-Cl3~ E~ n-C6H13 2,4,6~Cl3~NHN=CClCH(n-C6Hl3)-
3t5-cl2~ CH3 CH3 3,5-Cl2~NHN=CClC(CH3)2-
2,4,6-Cl3~ CH3 CH3 2,4,6-Cl3~NHN=CClC(CH3)2-
2,4-(02N)2~ CH3 CH3 2,4-(02N)2~NHN=CClC(CH3)2-
2,6-Cl2-4-Br~ C2H5 C2H5 2~6-cl2-4-sr~NHN=cclc(c2H5)
2,4,6-Cl3~ n-C6H13 CH3 2,4,6-Cl ~NHN=CClC(CH3)2-
~ class of preferred phenylhydrazone sulfides of 113
formula ~l~ are those wherein R1 and R2 individually are alkyl 114
of 1 to 3 carbon atoms, R~ i5 alkyl of 1 to fi carbon atoms, 115
chloroalkyl of l to 2 carbon atoms and l to S chloro, or phenyl 117
of up to 2 chloro or bromo, Ar is phenyl substituted with up to 118
S chloro, bromo or fluoro, more preferably phenyl substituted 119
with up to ~i chloro, and n is 1, 2 or 3. 120
A preferred class of bis-phenylhydrazone sulfides of 121
:Formula (I) are those wherein Rl is hydrogen; ~2 is alkyl of 1 122
to 6 carbon atoms, more preferably 1 to 3 carbon atoms; and Ar 123
is phenyl substituted with up to 3 fluoro, chloro or bromo, 124
more preferably phenyl substituted with up to 3 chloro or 125
bromo. 126
Another preferred class of bis-phenylhydrazone sul- 127
fides of formula (T) are those wherein R1 or R2 individually 128
-- 4 --
1~)5~
are alkyl of 1 to 6 carbon atoms, preferably 1 to 3 carbon 129
atoms, and Ar is phenyl substituted with up to 3 fluoro, chloro 130
or bromo, more preferably phenyl substituted with up to 3 131
chloro or bromo. 132
The bis-phenylhydrazone compounds of the inYention 133
are prepared by reacting a bisalkanoyl acid chloride (II) with 134
a phenylhydrazine (~T~ and then reactina the resulting bis- 135
hydrazide (IV) with phosphorus pentachloride, as depicted in 136
reactions (1) and (2): 137
r ~
Lc1c_~5n + 2 ArNHNH2 ~ L~rNHNH~C~C~Sn ~ 2HCl (1)
(II) . (IV)
PC15~ , . 1
( IV ) ~ ArNHN=C - C--Sn ( 2 )
R2 2
1' .
~herein P~, RZ, Ar and n have the same significance as pre- 139
viously defined. 140
Reaction (1~ is conducted by reactinq about 2 mols of 141
the phenylhydrazine (111) with about 1 mol of the bisalkanoyl 142
acid chloride in the presence of about 2 mols of an acid 143
acceptor in an inert solvent at a temperature of from about 01 144
to 50C, by more-or-less conventional procedures. Suitable 146
acid acceptors are trialkylamines, such as triethylamine, or
yridine compounds, such as pyridine or alpha-picoline. 147
Reaction (2~ is conducted by reacting about 1 mol of 148
the bishydrazide ~IV) with about 2 mols of phosphorus penta- 149
chloride in the presence of an inert solvent at a temperature 150
of about 251 to 1001C, and then working up the product mixture 151
1~5~Z~S
with phenol. Suitable inert solvents are chlorinated hydrocarbons such as
carbon tetrachloride and methylene dichloride. Reaction (2) is a known
reaction for the chlorination of hydrazldes, as disclosed in Netherlands
Patent Application No. 71.13497 and in United States Patent 3,745,215.
The phenylhydrazone sulfides of the invention wherein n is 2
or 3 may be prepared by reacting a bishydrazone (V) with excess chlorine and
then reacting resulting sulfenyl chloride (VI) with a mercaptan as depicted
in the following reactions (3) and (4).
IH Rl C12 Cl Rl
[Ar - NHN = C - f - S~2 ~ Ar - NHN = C - C - (S)n_l (3)
(V) R2 (VI )
R3SH Cl Rl
I 1 3
(VI) - ~ Ar - NHN = C - Cl - (S)n - R (4)
(VII) (I) R
10wherein n is 2 or 3, and Rl, R2, R3 and Ar have the same significance as
previously defined, and R3 is alkyl, haloalkyl, phenyl or substituted phenyl.
Reaction (3) is conducted with about 2 to 11 mols, preferably
3 mols to 3.5 mols, of chlorine per mol of the bishydrazone (V) in an inert
solvent, e.g., chlorinated hydrocarbons such as methylene chloride and
Garbon tetrachloride, at a temperature of 0 to 50C. The resulting sulfenyl
chloride (VI) may be isolated and purified. However, it is generally more
convenient to react the sulfenyl chloride (VI), without purification, with
a substantially equimolar amount of the mercaptan (VII) at a temperature of
0 to 50C to produce the product (I). The product (I) is isolated and
purified by conventional procedures such as extraction, filtration,
crystalliz3tion and chromatography.
6 -
~-é ~i
. :~..,
2~L5
Ihe phenylhydrazone sulfides of the invention wherein n is 1
or 2 are prepared by reacting a hydrazide sulfide (VIII) with phosphorus
pentachloride as depicted in reaction (5):
O Rl Cl
Il 1 3 l l
Ar - NHNH - C - C - S - R ~ PCI5 --~ Ar - NHN = C - C - Sn - R3 (5)
R2 R2
(VIII) (I)
wherein n is 1 or 2, and Rl, R2 and Ar have the same significance as previous-
ly defined, and R3 is alkyl, haloalkyl, phenyl or substituted phenyl.
Reaction (5) is conducted by reacting substantially equimolar
amounts of the hydrazide sulfide (VIII) and phosphorus pentachloride in the
presence of an inert solvent at a temperature of about 0 to 100C, and then
working up the product mixture with phenol. Reaction (5) is a known reaction
for the chlorination of hydrazides, as disclosed in Netherlands Patent
Application No. 71.13497 and in United States Patent 3,745,215.
I~he hydrazide sulfide reactant (VIII) is suitably prepared by
reacting substantially equimolar amounts of an aryl hydrazine (III) and an
alkanoyl halide (IX) in the presence of an acid acceptor in an inert solvent
at 0C to 50C, as depicted in reaction (6):
O Rl O
Il l 3 11 1
Ar - NHNH2 ~ X - C - Cl Sn ArNHNH C - I - Sn - R3 (6)
(III) (IX) (VIII)
wherein n is 1 or 2, X is chloro or bromo, and Rl, R2, R3 and Ar have the
same significance as previously defined.
The hydrazide monosulfide reactant (VIII) (n = 1) is also
suitably prepared by alkylating a bromo-hydrazide of the formula
.
. ~
. . .
~5~2~
O Rl
ll l
Ar-NllNll~C-C-Br (X)
R2
with an alkali metal mercaptide of the formula R~SM wherein N 215
is an alkali metal and R~, ~Z and ar have the same significance 217
as previously defined, and ~ is alkyl, haloalkyl, phenvl or 218
substituted phenyl. The bromo-hydrazide reactant ~X) is 219
suitably prepared by reacting the aryl hydrazine (III) and an 220
alpha-bromoalkanoyl halide. 221
~he co~pounas of the invention are useful as morpho- 222
genetic hormonal mimetic insecticides, particularly, against 224
insects such as cabbage lcoper larvae, alfalfa weevil larvae, 225
yello~ mealworm, kissing bug and mosquitos. 226
The compounds are very potent and are used at 227
extremely low concentrations. For example, compositions 229
containing lO0 ppm to O.Ol ppm, preferably from 5 ppm to O.l 230
ppm, are effective for inhibitinq or interfering with the 231
normal metamorphasis of insects. However, the effective 233
concentration depends in part on the mode of applicatlon and 234
the particular insect.
The compounds may be applied in either liquid or 235
solid formulations to the pre-adult insects or their habitats. 236
For example, they may be sprayed or otherwise applied directly 237
to plants or aqueous bodies so as to effect control of insects 238
coming into contact therewith. 239
Formulations of the compounds of this invention will 240
comprise a metamorphosis-inhibitinq amount of one or more of 242
the compounds and a biologically inert carrier. Usually they 243
will also contain a wettin~ aqent. Solid carriers such as 244
cla~, talc, sawdust, alfalfa meal, and the like may be used in 245
such formulations. Liguid diluents which may be used with 246
~51~2~i
these compounds include water aliphatic and aromatic solvents. 247
In addition, these formulations may contain other compatible 248
pesticides, fillers, 5t~abilizers~ attractants and the like. 249
~ he concentration of the active ingre~ient to be used 250
with inert carriers, either solid or liquid carriers, will be 251
dependent upon many factors, such as the particular compound 252
which is used, the c~rrier in or upon ~hich it is incorporated, 253
the method and conditions of application, the insec~ species to 254
be controlled, e c., the proper consideration of these factors 255
beinq within the skill of those versed in the art. In general, 257
the toxic inqreaients of this invention will be effective in 258
concentrations from about O.OOOl~ b~ weight to as high as 50%
by weiqht or higher. Economically, of course, it is desirable -260
to use lower concentrations of this active ingredient. 261
The compounds of the invention are particularly 262
useful in combination with mosqui~o larvicidal petroleum oil 263
dispersions. Petroleum oils suitable as mosquito larvicidal 264
dispersions are known. Such hyarocarbon oils include mineral 265
oils such as naphthenic base and paraffinic base lubricating 266
oils, etc., as well as synthetic oils. Such hydrocarbons oils 268
are nonphytotoxic ana generally contain not more than a few 269
percent aromatics. ~articularly suitable hydrocarbon oils have 270
boiling points above 350 to 400F. and viscosities of frcm 271
about 33 to 200 SSIl at 100~.
The amount of the compound of the invention employed 272
in petroleum oil qenerally ranges from 0.1% to 10% by weiqht 273
based on weight of oil. The hydrocarhon oil dispersions 275
containinq the compounds of the invention are contacted with or 276
applied to the surface of the agueous bodies wherein ~osquito 277
control is desired hy conventional methods.
The terms "insecticide" and "insect" as used herein 278
refer to their broad and commonly understood usage rather than 279
_ g _
~0~
to those creatures which in the strict bioloqical sense are 280
classified as insects. Thus, the term "insect" is used not 281
only to include small invertebrate animals belonqing to the 282
clacs Tnsec a but also to other related classes of arthropoas 283
whose members are se~mented in~ertebrates havin~ more or fewer 2e4
than six leqs, such as spiders, mites, ticks, centipedes, ~orms 285
aDd the like.
~ x_mP~ 288
A mixture of 21.2 g. 2,4,6-trichlorophenylhydrazine, 291
10.3 g. 2i2'-dith;obisisobut~raldehyde and 100 ml. ethanol ~as 293
heated to re1ux and filtered hot. The solvent was evaporated 295
to leave a solid. The solid was washed with ~0 ml. hexane and 296
filtered to give l~.fi g~ of the bis-hydrazone product, m.p. 85- 297
110C. ~ecrystallization from hexane and then from ethanol 299
qave the proauct as a white solid, m.p. 116-117C. Elemental 301
analysis for C20H20Cl~N~S~ gave: ~S, calc. 10.8, found 10.8 302
~Cl, calc. 35.9, founa 34.5. 303
To a cooled (0C) and stirred mixture of 8.0 g. of 306
the bis-2,4,6-trichlorophenylhydrazone of 2,2'-dithiobis~
isobutyraldehyde (prepared above) was added 3.3 g. chlorine in 308
50 ml. carbon tetrachloride over a 30-minute period~ The 309
mixture was filtered and the excess chlorine was removed under 310
reduced pressure. To the reaction mixture was added 2 g. 311
methvl mercaptan. The solYent vas then stripped to leave 9.7 312
q. of a red oil. Nuclear maqnetic resonance sprectroscopy 313
showed that the oil was a mixture of hydrazone sulfides of the 314
formula: Cl
Cl--~ NHN=C - C - (S) -C113
Cll 3
Cl
wherein n is 2 or 3. 318
- 10 -
~)s~
The oil was chromatographed on silica qel (hexane 319
eluant) to give a product (3.1 q.~ consisting predominantly of 320
the hyarazone trisulfide (n equal to 3). Sulfur analysis for 322
the product was 19.0~ and chlorine analvsis for the product was 323
38.~.
~_ample_2 326
A solution of 3.3 q. chlorine in 50 ml. carbon 328
tetrachloride was aaded dropwise over a 30-minute period to a 329
cooled (0C) and stirred m ix~ure of 8.0 g. of the bis-2,4,6- 331
trichlorophenylhydrazone of 2,2'-dithiobisisobutyraldehyde in 333
100 ml~ carbon tetrachloride. ~he reaction mixture was 334
filtered to remove a little solid material and then partially 335
evaporated to remove excess chlorine. ~ 2.4 g. sample of 2- 336
methyl-2-propanethiol ~as added and the resultinq solution 337
stirrea for one hour at about 25C. The solvent was then 339
stripped to leave 10.4 g. of a red oil. The oil ~as 340
chromatographed on silica gel (hexane eluant~ to give 2.6 q. 341
the hyarazone trisulfide of the formula:
/ Cl
~ Cl CH3 CH3
Cl ~ N~N=C - C - SSS-C - C~13
CH3 CH3
Cl
Elemental analysis for C~4Hl~Cl4N2S3 showed: %S~ calc. 21.8, 343
found 21.2; %Cl, calc. 30.9, found 31.4. The hydrazone 345
trisulfide was a red oil which solidified on standinq to a low- 346
melting red solid. 347
~xam~le 3 350
___ _ ___ _
A 24 g. sample of chlorine was bubbled into a mixture 352
of 14.5 g. of the bis-phenylhydrazone of 2,2~-dithiobis- 354
isobutyraldehyde over a one-hour period. After stirrinq at 358
about 25C. for three hours, 5 g. of ethanethiol were added and 359
- 11 -
~:3S~2~S
the resultinq solution stirrea overnight. The solvent was then 360
stripped to leave a red oil. ~he oil was chromatographed on 361
silica gel ~benzene eluant) to give 15 g. of a rea oil. 362
Nuclear magnetic resonance spectroscopy and elemental analysis 363
(found 12.6~S, 37.2~Cl~ showed the product to be a mixture of 364
h~drazone sulfides of the formula: 365
Cl
Cl--~HN=C - C - (S) -CH2CH3
Cl CH3
wherein n is 2 or 3. 368
The hydrazone disulfide (n = 2~ was the predominant 369
product. 370
~x_m~ 4 373
A 23-g sample of 2-bromo-2-methylpropionyl bromide 375
was addea dropwise to a cooled (0C.~ slurry of 21.2 g 2,4,6- 378
trichlorophenylhydrazine and 7.9 g pyridine in 500 ml glyme 379
over a 2-hour period. The reaction mixture was stirred l/2 380
hour ana pourea into S00 mI ice water and 20 ml concentrated 381
hydroc~loric acid. ~ solid separated. The solia was filtered, 383
washed with uater and driea to give 27.3 ~ of the bromo- 384
hydrazid~ product (Formula X where ~r is 2,4,6-trichlorophenyl 386
ana ~l and R2 are methyl) as a beige solid, m.p. 10l-lO3C~ 387
; Soaium mercaptide was prepared by bubbling methyl 388
mercaptan into a slurry of 5.~ q sodium hydride (54% in mineral 3B9
oil) in l50 ml dimethylformamide. The sodium mercaptide solu- 391
tion was then cooled in an ice water ba~h while 44.9 g o~ the 393
bromo-hydrazide preparea above in lO0 ml dimethylformamide was 394
added over a one-hour period. After stirring for 15 minutes, 395
150 ml benzene and 300 ml ice water were added. The benzene 397
layer was separated, washed with ~ater~ dried over maqnesium 398
sulfate and evaporated to qive a solid. ~he solid was 399
- 12 -
~al5~z~i
crystallized from lO0 ml boiling hexane to give 38.3 g of the 400
mercapto-hydrazide product (Formula VJI~ where Ar is 2,4,6- 401
trichlorophenyl, ~1, R2 and R~ are methyl and n is l~ as a 402
beige solid, m.p. 85-~9C. 403
~ solution of 22 q of the mercapto-hydrazide prepared 404
above and 14 g phosphorus pentachloride in lO0 ml carbon tetra- 405
chloride was stirred at about 25C. for 2 days and then 406
re1uxed for 30 minutes. The reaction was then cooled (0C.) 408
and 18.9 g phenol was added in one portion. The reaction 410
~ixture was then st;rred at 25C. for 5 days. 25 ml of 411
methanol ~as added to the reaction mixture and the resulting 412
solution was stripped to give an oil. The oil was chromato- 413
qraphed on silica gel (benzene/hexane eluant) to give lO.2 g of 415
an oranqe oil ~hich solidified on standing to an oranqe solid.
Recrystallization from hexane gave 6.4 q of the hydrazone 417
sulfide product, m.p. 5l-52C, of the formula 418
Cl
Cl CH3
Cl - ~ - NHN=C ~ C - S-CH3
Elemental analvsis showed: %S, calc. 9.~, found 9.4; %Cl, 420
calc. 41.0, found 41Ø 421
~__mPl__5 424
A solution of 16.4 ~ 2-methyldithio-2-methylpropionic 427
acid and 25 ml thionyl chloride was stirred and refluxed for l 429
hour. The reaction mixture was then distilled to give 10.5 g 430
of 2-methyldithio-2-methylpropionyl chloride, h.p. 100-122C at 432
55 mm of ~a. 433
The 10.5-q sample of propionyl chloride prepared 434
above was added dropwise over a lO-minute period to 12 g 2,4,6~ 435
trichlorophenylhyarazine and 6 q triethylamine in 250 ml glyme. 436
- 13 -
~S~3Z~5
After stirring for l0 minutes, 200 ml ice water and l0 ml 437
concentrated hydrochloric acid were added. On stirrinq in an 439
ice bath, a solid separated. The solid was filtered, washed 440
with water, dried and recrystallized from hexane to give the 441
hydrazide product ~Formula VIII, where Ar is 2,4,6-trichloro- 442
phenyl, Rt, R~ and R~ are methyl and n is 2~ as a beiqe solid, 443
m.p. 86-a8~c~ 444
By a procedure similar to that of Example 4, the 445
hydrazide product prepared above was chlorinated with 446
phosphorus pentachloride to give the hydrazone disulfide 447
product of the Pormula
/Cl
Cl - ~ NHN=C - C - SS-CH3
CH3
Cl
Elemental analysis for Cl~H~zCl~N252 sho~ed: %S, calc. 17~0, 449
found 17.1; %Cl~ calc. 37.5, found 40.9. 450
Rxam~les 6-13 453
By a procedure similar to that of Examples 1-5, other 455
phenylhydrazone compounds o~ Formula (I~ were prepared. ~hese 458
compounds are tabulated in Table II. 459
Example 14 -- Preparation of the bis- 462
Ph ylhyd--zone--f-2~2~-d-th--kls-so-u-yr~l chlo_lde 463
~ ~ - NHN=C - C - ~
A solution of 14.4 q 2,2'-dithiobisisobutyric acid 467
(Chem. Abs. 64, 6fi35b) and 40 ml thionyl chloride was stirred 468
and refluxed ~or 1 hour. The excess thionyl chloride was 470
removed by evaporation under reduced pressure. The resulting 472
acid chloride product ~as diluted with 30 ml methylene chloride 473
~ 14 -
~)5~5
and added over a 20-minute period to a cooled solution of 13.1 g phenyl-
hydrazine, 13.5 g triethylamine and 150 ml glyme. The reaction was then
diluted with 300 ml water and extracted with methylene chloride. The
methylene chloride extracts were dried over magnesium sulfate and evaporated
to give a dark solid. The solid was recrystallized from hexane-benzene to
give 11.3 g of 2,2'-dithiobisisobutyric acid bis~phenylhydrazide, as a beige
solid, m.p. 144C. Elemental analysis for C20H26N402S2 showed: %S, calc-
15.3; found 13.7.
A solution of 9.4 g 2,2'-dithiobisisobutyric acid bis-hydrazide,
10.0 g phosphorus pentachloride and 100 ml carbon tetrachloride was stirred
and refluxed for 5 hours. The solution was then cooled and added over 20
minutes to a solution of 13.5 g phenol in 100 ml carbon tetrachloride.
Finally, 100 ml ethanol was added to the reaction mixture. The reaction
mixture was then stripped to give 19 g of an oil. The oil was chromato-
graphed on silica gel (benzene eluant) to give 6.0 g of the product, as a
viscous red oil. Elemental analysis for C20H2Llcl2N4s2 gave: %S,
found 13.3; %Cl, calc. 15.5, found 14.8.
The above chlorination reaction with phosphorus pentachloride
is similar to that described in Netherlands Patent Application No. 71.13497
and in United States Patent 3,745,215.
Example 15 - Bis-2,4,6-trichlorophenylhydrazone of
_ 2,2'-dithiobisisobutyryl chloride
Cl
L ~ Cl CH3
CH3
\ Cl
This product was prepared by a procedure similar to that of
Exar~lple 14. m e product is a white solid, m.p. 123-
.. . .
,,, .~.: ,,
~5~LS
124C. Elemental analysis for C20H~BCl~N~S2 gave: ~S, calc. 512
9.7, found 10.1; %cl, calc. 42.8; founa 43.1. 514
Example 16 -- Bis-phenylhydrazone of 517
2 2~-dithi_bis-~ro~___Yl__hl_E_de 518
Cl CH3
I~N=C ~ CH - S
~ ~2
This product was prepared by a procedure similar to 522
that of Example 14. The product is a ~iscous red oil. 524
Elemental analysis for C~8H20Cl~N~S2 gave: %S, calc. 15.0, 525
found 13.6; ~Cl, çalc. 16.6, founa 15.5. 527
Example 17 -- ~is-p-nitrophenylhydrazone 530
of 2 2'-dithiobis~ro~ion~l chloriae 531
_-- --__________ __ ___ __________
(~2N~ lN=C - CH - 5)~
This product was prepared by a procedure similar to 535
that of Example 14. The product is a yellow solid (m.p. ca. 537
80C~ which forms selectively stable complexes with solvents 538
such as benzene and chloroform. 539
Exam~ae_18__-_I__e___C___rol 542
The compounds of Examples 1-16 ~ere tested as juve- 544
nile hormonal mimetic insecticides by the following procedures. 545
Ca__ q__~o_~er_~Tr i-ho~lus-a--iL 548
5 microliters of an acetone solution containing a certain 552
concentration micrograms of the test compound were applied 553
topically to the entire lenqth of the body of a late-fifth- 554
stage cabbage looper larva. Normally lO larvae were treated 555
per test. The treated larvae were then fed until they pupated. 556
The pupae were then incubated until the adult emerged. ~he 55
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3Z~5
mortality of the pupae and adults ~as determined. The 559
compounds t~stea, the concentration (mcg/insect) and the total
pupal and adult mortali~y are tabulated in Table III. 561
Alf_lfa_W_ev~ 3pera_~_st_c3_~yllen_alL 564
~lfala ~eevil larvae were tested by the sa~e 567
proceaure employed for ca~bage looper. The compounas tested, 570
the concentration (mcq/insect~ and the total pupal ana adult 571
; mortality are tabulated in Table IV.
Yellow_~e_lworm_~T_neb_io_m_litorL 574
~bout two-day-old yellow mealworm pupae were tested 578
by the same proceaure employed for cabbage looper. The 580
compounds tested, the concentration (mcg~insect) and the total
pupal and adult mortality are tabulatea in Table V. 581
Kls_inq Bu~-lRh-dnlus-p--llx-u-L 584
~ ate-fifth-staqe kissing bug nymphs ~24 hours after a 588
blood meal~ ~ere tested by the same procedure employed for 590
cabbage looper. ~he compounds tested, the concentration 591
(mcq/insect) ana the total larval, pupal and adult mortality 593
are ~abulated in Table VI.
Example TABL~ II Sulfur Analysis
No Ar Rl R2 R3 nCalc Found
62,4,6-Cl3~ 11 11 C113 l lO.l 9.3
7 " 11 11 -CCl3 213.4 ll.l
8 " 11 11 C113 218.3 16.8
9 " El il i-C3}17 217.0 16.6
~ ~1 C113 C113 217.6 15.3
ll " 11 C113 C113 l9.7 9.4
12 ~ 11 C113 -ccl2ccl2~l 212.4 12.0
13 ~ C~13 C113 4-Cl~ 213.5 17.6
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L5
T~BLE III
Cabbage Looper Control
Compound No.Concentration% Mortali-t~
100
2 0.4 90
3 100 100
4 100 100
100 100
6 0~4 90
7 100 60
8 1.3 90
9 1.2 go
100 100
11 100 100
12 100 10
13 1 90
14 100 100
100 40
16 1 100
TA~LE IV
Alfalfa Weevll Control
Compound No.Concentration% Mortalit~
1 0.3 100
2 0.14 90
3 0.14 90
4 . 0.38 90
0.1~ 90
6 0.3 90
7 5 40
8 1.5.............. 90
9 5 100
0.3 90
11 1.6 90
12 5 10
13 0.46 90
14 1 100
16 1 100
TA~LE V
Yellow Mealworm Control
Compound No. Concentration% M
100
2 10 20
3 10 100
1.6 90
2.1 ~
6 3.7 90
7 10 o
8 4.6 90
9 10 90
11 2.1 90
- 1B -
32~
TABL~ VI
. _
Kissing Bug Control
Compound No.Concentration~ Mortality
2 lO 60
3 lO lO0
4 3.2 90
3.6 90
6 7 90
7 lO lO
8 lO 0
9 10 o
ll 6.5 90
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