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Патент USA US3021368

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United States Patent - O?ice
3,021,358
Patented Feb. 13, 1962
2
1
We are now aware (though this was not known to us
3,021,358
at the outset of our research) that 2,2,2-tri?uoro-l,1-bis
.
INSECTICIDAL BIS-HALOPHENYL DI-FLUORO
'
(p-halophenyl)~ethanes, ethanols and ethyl acetates have
ALIPHATIC COMPOUNDS
been disclosed as synergists for DDT (see Tahori in Jour
nal of Economic Entomology, 1955, vol. 48, pp. 63 8-642,
and Kaluszyner et al. in American Chemical Society Jour
Joseph Bornstein, Brighton, Mass., Murray S. Blum,
Baton Rouge, La., and John J. Pratt, Jr., Wayland,
Mass., assignors to the United States of America as
nal, 1955, vol. 77, pp..4164-4168); however, we have
found surprisingly that our 2,2-di?uoro compounds have
unexpectedly more powerful synergistic insecticidal action
No. 751,579, now Patent No. 2,990,321, dated June
27, 1961. Divided and th'm application Jan. 29, 1960, 10 in combination with DDT than the results obtained by the
Ser. No. 9,154
.
foregoing workers with 2,2,2-tri?uoro compounds would
6 Claims. (Cl. 260-488)
have permitted to expect.
(Granted under Title 35, US. Code (1952), sec. 266)
We will now proceed to illustrate the practice of our
represented by the Secretary of the Army
No Drawing. Original application July 28, 1958, Ser.
inventionby means of several examples, but wish to have
The invention described herein, if patented, may be
manufactured and used by or for the Government for 15 it understood that we do not intend to limit the practice
of our invention to the particular methods therein set
governmental purposes, without the payment to us of any
forth, inasmuch as our novel compounds can be made by
royalty thereon.
other syntheses and may ’be combined with DDT in any
This application is a division of our co-pending appli
desired proportion, as may be most effective under the
cation Serial Number 751,579, ?led July 5, 1958; now
20 circumstances of a particular application.
Patent No. 2,990,321 dated June 27, 1961.
This invention relates to insecticides and more particu
EXAMPLE 1
larly to new bis-(halophenyl)-?uoroaliphatic‘ compounds
2,2-di?uoro-1,I-bis-(p-chlorophenyl) -ethanol
Freshly puri?ed ethyl di?uoroacetate (20.0 g., 0.16
having insecticidal properties.
Compounds of this invention have the general struc
25 mole), diluted with an equal volume of ether, was added
ture:
with stirring in the course of 1 hr. to the ice-cold Grig
H
FCF
nard reagent prepared from 10.7 g. (0.44 g.-atom) of
magnesium turnings and 81 g. (0.44 mole) of l-bromo
4-chlorobenzene in 100 ml. of ether. Stirring and cooling
30 in the ice-bath were maintainedfor 2 hours after comple
wherein Hal and Hal’ are halogen atoms of an atomic
tion of the addition of the ester. The reaction mixture,
after standing at room temperature overnight, was treated,
while stirring and cooling, with saturated ammonium
weight not above 80 -(i.e., ?uorine, chlorine and bro
mine), and wherein Y is hydrogen, hydroxyl or acetoxyl.
Compounds falling under this general formula are 2,2-di 35 chloride, prepared by shaking 40 g. of the salt with ‘100
ml. of water. The yellow suspension was ?ltered with
?uoro-1,1-bis-(p-halophenyl) —ethanes, 2,2-di?uoro-1,1-bis
suction through a sintered-glass funnel, the ?lter cake was
washed with ether, and the combined ethereal extract
washed twice with water before being dried over sodium
?uoro-1,1-bis-(p-halophenyl)-ethanes, which analogs have 40 sulfate. Evaporation of the ether yielded a dark orange
oil which was diluted-with an equal volume of methanol
the general formula:
and refrigerated at —35° for 2 days in order to allow the
(p~halophenyl)-ethanols, and 2,2-di?uoro-l,l-bis-(p-halo
phenyD-ethyl acetates. Also within the purview of our
invention are dehydro?uoro ethene analogs of 2,2-di
'
HG F
traces of biphenyl to crystallize. Filtration of the mix
ture followed by steam distillation of the ?ltrate (2 l. of
distillate was collected and discarded) gave a product
45 which was essentially free of starting material and de
rived products. The oily residue was dissolved inether
The foregoing compounds may be prepared by a Grig
and dried over sodium sulfate. Removal of the solvent
nard type reaction, as will be more fully explained here
and distillation of the residue afforded a 53% yield of
after.
'
Tests have shown that among the foregoing compounds 50 2,2-di?uoro-1,1-bis-(p-chlorophenyl)-ethanol, a liquid
QAQ
the 2,2-di?uoro-1,l-bis-(p-halophenyl)-ethanols are highly
potent insecticides, and are surprisingly and strikingly ef
fective as synergists for DDT; these effects are particu
larly striking when the halogen atoms on the respective
having a RP. of 130—136° C. at 0.20 mm.; index of re
fraction nD2° 1.5780. With concentration H2804 it gave
a cherry-red color. Analysis (c,,H,,c1,F,0)=
phenyl groups are either chlorine or bromine. However, 55
Calculated
the other compounds herein disclosed are likewise valu
able weapons in the arsenal of economic entomology, in- '
0. -
55. 47
Found
55. 63
H
a. 33
3. 47
asmuch as experience has shown that succeeding genera
C1
23. 40
2a. 94
tions of insects quickly acquire immunity to a given type
of insecticide through the breeding of resistant strains. It 60
Upon prolonged standing, t-hick prisms formed, having a
is therefore important to have alternate insecticides and
MP. of 54.5-56.0° C.
1
.
insecticidal. synergists on hand to combat insects which
The m-chlorophenyl and o-chlorophenyl analogs are
have thus acquired immunity against a previously very ef
produced by substituting the same amounts of l-bromo- .
fective insecticide.
'
3
4
3-chlorobenzene or l-bromo-Z-chlorobenzene in lieu of
the l-bromo-4-chlor0benzene of the above example.
‘
ethyl acetate was obtained in liquid form from the 2,2-di
?uoro-1,l-bis-(p-?uorophenyl)-ethanol of Example 3; it
EXAMPLE 2
.
resisted attempts to induce crystallization and isolated as
a very viscous oil at 80° C. and 0.1 mm. pressure; index
'
'
2.2-di?uom-L1-bis-(p-bwmophenyb-erhanol
s of refraction up” 1.5158. Analysis (cmHnFpg:
Example 1 was repeated, but a stoichiometrically equiv
alent amount ( 104 grams; 0.44 mole) of 1,4-dibromo-
‘
benzene was used in lieu of l-bromo-4-chlorobenzene.
Calculated
A 40% yield of 2,2-di?uoro-l,1-bis-(p~bromophenyl)0-ethanol was obtained as a liquid which had a boiling point 10 H
of 153-164‘ C. at 0.17 mm.; index of refraction nun-5
01.53
3- 87,
1.6039._ With concentrated H1804 it gave a red color.
Analys“ (CII‘HMBHF'O):
2,2-di?uor0-1,I-bis-(p-halophenyl)ethane
15
8.0-10.0 grams of 2,2 - di?uoro - 1,1 - bis - (p - chloro
phenyD-ethanol (Ex. 1) were heated under re?ux for ten
days with a mixture of 33 g. of red phosphorus, 1.27 g.
43;‘;
of iodine, so ml. of glacial acetic acid, and 1.0 ml. of
40.6
water. The cooled reaction mixture was ?ltered with
,
20 suction directly into a separator";l1funnel containing 300
.
.‘
.
.
ml. of 2.5% sodium bisul?te.
Upon prolonged ‘magma’ thick m‘ formed’ hams
0‘ 545-56.
'
ate with intermittent shaking and was then extracted with
ether. The ether extract was dried over sodium sulfate
_
25 after being washed with water.
> 2.2-dr?uoro-1.I-bir-(p~?wrophmI)-¢thmwl
In
Removal of the ether
and distillation of the residue in vacuo yielded an oil
Example 1 was repeated, but a stoichiomd?cany equiw
_ alem amount (0 44 mole) of Lb
e only suspension was
neutralized‘ by adding portions of solid sodium bicarbon
EXAMPLE 3
-
61.8
3-9
EXAMPLE 5
‘
Calculated
a
Found
.
which spontaneously crystallized. The crude crystals
I “one
were recrystallized by means of a methanol-water solvent,
and a 90% yield of 2,2-di?uom-1,l-bis-(p-chlorophenyl)
was used in lieu of 1-bromo-4-chlorobenzene. A 43%
. yield
.
.
.
a M.P. of 37.5-38.5’ C. and
of 2,2-d1?uoro-l,l-bis-(p-?uorophenyl)-ethanol
was 30 ethane crystals having
a
- a
obtained in liquid form having a 13.1’. of 99-100‘ 0. at
251°‘. “(é-:11; C91,“; 9'“ mm 1mm” was waned‘
0.05 mm.; index of refraction "1,“ 1.5276. with concentrated H,S04 it gave a red orange color. Analysis
(C14H1oF4o)=
Y”
1
1° ’ = '
'
35
Calculated
58. 56
3. 51
24. 69
4°
Folmd
58.
3.
24.
2,2-di?uoro-l,l-bis-(p- bromophenyl) - ethane crystals
were obtained in a 89% yield from the 2,2-di?uoro-1,l
EXAMPLE 4
bis-(p-bromophenyD-ethanol of Example 2 in the same
2,2-di?uoro-1,1-bis-(p-halophenyl)-ethyl acetate
vent for recrystallization. M.P. 42.0-42.8‘ C. Analysis
way as the chloro analog; methanol was used as the sol
in. 2,2-di?uoro-1,l-bis-(p-chl0rophenyl)-ethan°1 of 4*‘ (cnHmBrsFm
ExamPle 1 was permitted to stand at room temperature
for several hours with a mixture of acetic acid and tri-
“1mm
?uoro acetic anhydride, in accordance with the procedures
generally set forth by Tedder in Chem. Revs. 55, 787 50 g(1955). The resulting product was extracted with petroBr__.
leum ether solvent and recrystallized. A 82% yield of
2,2-di?uoro-l,1-bis-(p-chlorophenyl)-ethyl acetate crys
Calculated
Found
.
Fmmd
‘g-g
4:20
4214s
4215
tained in the form of a viscous oil from the 2,2-di?uoro
55 1,1-bis-(p-?uorophenyD-ethanol of Example 3 in a 90%
yield. It resisted attempts to crystallize; its B.P. is 79
80' C. at 1.5 mm. pressure; index of refraction up“
_1.5179. Analysis (CuHmF?r
55.01
3.60
55.8
as so
Calculated
2,2-di?uoro-1,1 - bis - (p - bromophenyl) - ethyl acetate
66. 14
3. 97
crystals having a M.P. of 80-805‘ C. were obtained in
the same manner in an 86% yield from the 2,2-di?uoro
1,1-bis-(p-hmmophenyD-ethanol of Example 2. Analysis 65
I (CHHuBQFaOaP
Found
66.6
4.0
EXAMPLE 6
Dehydro?uoridatian products-(C??alhQCHF Z-?u
Calculated
Found
70
oro-I ,1 -bis-(p-halophenyl) when:
3.8 grams of 2,2-di?uoro-l,l-bis-(p-bromophenyl)-eth
ane (Ex. 5) were dehydro?uorinated (removal of 1 mole
of hydrogen ?uoride) by heating under re?ux for 2.5
hours with 60 ml. of 2% ethanolic potassium hydroxide.
' The solvent was removed under reduced pressure and the
An 89% yield of 2,2-di?uoro-l,l-bis-(p-?uorophenyl)- 75 residue extracted with several portions of ether. The
3,021,353
6
action of our compounds in combination with DDT,
combined ethereal extract was washed with water and
dried over magnesium sulfate.
Removal of the'ether
‘ when applied to a DDT-resistant strain of adult female
house?ies in the same manner. The ‘ratio of ?uoro com
a?orded a colorless oil which was distilled at diminished
pressure. Upon recrystallization with methanol there was
obtained an 85% yield of 2-?uoro-1,1-bis-(p-bromo '
phenyl)-ethene crystals having a M.P. of 84.2-85.2° C.
5
pounds to DDT was one part of ?uoro compound to 5
parts of DDT.
TABLE I
Analysis (CHI-1.13511‘):
LD»
Calculated
Fotmd
10
C
47. 20
DDT-Sus-
47. 0
H
2. 55
2. 4
Br
44. 86
44. 7
oentible
Flies,
Fluoro
Com-
pound
Crystals of Z-?uoro-1,1-bis-(chlorophenyl)-ethene were 15
Alone
obtained in the same manner from 2,2-di?uoro-1,1-bis
(p-chlorophenyl)-ethane of Example 5, in an 85% yield;
M.P. 78.0-79.5° C. Analysis (Cal-1.01m):
ll‘ound
20
pound,
5 Parts
DDT
2,2-Di?uoro-1,l-bis-(n-chlorophenyD-ethane ____ __
2. 2
0.96
2,2,Drtluoro-1,1-bis-(p-chlorophenyl)-ethanol..___
.2,2-D1?uoro-1,l-bis-(p-chlorophenyl)ethyl ace
3. 8
0. 62
tate_
Calculated
DDT-Re
sistant
Flies,
1 Part
Fluoro
Com
9. 4
1. 6
2-Fluoro-1,1-bls-(n-chlorophen l)-ethene _______ _-
22
11.5
2,2~Ditluoro-l,1-bis-(p-bromop enyl)-ethane_____
2. 1
0.96
4. 9
0. 56
2,2-Di?uoro-1,1-bis-(p-bromphenyD-ethanol ____ __
2,2¢Dl?uoro-1,1-bis-(p-bromophenyD-ethyl ace
62.
3.
26.
fate
35 83
9. 7
1. 7
2-Fluoro-1,l-bis-(p-bromopheuyl)-ethene _______ -.
2,2-Dl?uor0-1,1-b1s-(p-?uorophenyD-ethane ____ ..
21)
5. 1
7. 1
70
25 2,2-Di?uoro-l,l-bis-(p-fluorophenyD-ethanoL.___
2,2-Di?uoro-1,1-bis-(p-?uorophenyD-ethyl ace
7. 2
2. 8
35
8. 5
Liquid Z-?uoro-1,1-bis-(p-?uorophenyl)—ethene was ob
tained from 2,2-di?uoro-L1-bis-(p-?uorophenyD-ethane
tate.
'
2-Fluoro-1,1-bis-(n-?uorophenyD-ethene _______ __
18
28
Control: DDT alone __________________________ __
0.35
1 150
- in a 93% yield; B.P. 81—82° C. at 1 mm. pressure, in
1 (No ?uoro compound, 6 parts DDT.)
den of refraction uni“ 1.5481. Analysis (CHI-19B):
Calculated ‘
Folmd
C
71. 79
71.9
H
3. 87
4. 0
In a further control experiment with the DDT-re
sistant strain of ?ies, a mixture of 1 part of 1,1-bis
(p-chlorophenyl)-ethanol (DMC, a known DDT syner
gist) and 5 parts of DDT was found to have an LD5°
of 3.9, which is less potent thanmost of our new com
pounds.
It appears from the foregoing test results that the com
pounds of the present invention are e?ective as insecti
cides, even when applied alone to insects which have not
house?ies.
- 40 yet bred immunity to DDT, even though the quantity of
The ?rst column of test results indicates the lethal
our ?uoro compounds to achieve the desired insect mor
The following table (Table I) shows the biological
results obtained by testing the foregoing compounds on
effect of our compounds, applied alone to ordinary DDT
susceptible adult female house?ies which were t1'eated
tality is larger than a corresponding quantity of DDT.
to the thorax (1 microliter of the solutions were applied
However, as pointed out, the principal utility of our com
pounds is in the ?eld of DDT synergists where, as shown
in the foregoing table, a most surprising reduction of,
in each instance).
quantity of synergistic mixture (as compared with the
topically by applying acetone solutions of the compounds
Mortality data were taken 24 hours after treatment
quantity of DDT alone) results in e?ective kills of DDT
of the ?ies. One hundred and sixty ?ies were used in
resistant insect strains; (the effectiveness of the compo
each test-4 replicates of 20 ?ies each duplicated from
sitions being in inverse’ratio to their numerical LD5°
2 di?erent ?y populations. The quantity of test com 50 ratings.) This is borne out by a control computation.
pound required to kill 50% of the test ?ies (LD-SO)
on the synergistic effect on a number of the above 2,2
was determined by plotting on a logarithmic scale per
di?uoro compounds, as compared with the synergistic
cent mortality versus dose of test compound.
effect with DDT of the corresponding 2,2,2-tri?uoro com
The second column of test results shows the synergistic
pounds reported by Tahori, supra.
TABLE II
1 Part
1 Part
2,2-Di
Compound
1 Part
2,2,2-tri2.2.2411
Fluoro
Fluoro
Com pound Compound
Fluoro
to 5 Parts
DDT
to 1 Part
DDT
to 10 Parts
DDT
2,2 - Di?uoro - 1,1 - bis - (p-chloro-
171
2,2,2-Tri?uoro - 1,1 -bis - (p-ehloro-
14
0
2,2 - Di?uoro - 1.1 - bis -(p-chloro-
194
2,2,2 - Tri?uoro -1,1-'bis -(p-chloro-
25
15
15
11
phenyD-ethane.
phenyD-ethanol.
2,2 - Di?uoro -1,1 - bis -(p~chloro-
71
2,2,2-Tri?uoro41J-bis-(p-chloro-
125
2,2,2 - tri?uoro -1,1 - bis -(p-bromophenyD-ethane.
2,2.2- Tri?uoro - 1,1 ~bis-(p-bromo-
phenyll-ethyl acetate.
2,2 ‘ Di?uoro -l,1 - bis - (p-bromophenyD-ethane.
2,2 - Di?uoro - 1,1 - bis- (p-bromo-
phenvD-ethanol.
phenyD-ethane.
phenyll-ethanol.
phenyll-ethyl acetate.
169
phenyD-ethanol.
10
0
,
16
12
2,2 - Di?uoro -1,1 - bis - (p-bromo-
71
2,2,2- Tri?uoro -1,1 -bis- (p-bromo-
14
1O
2,2 - Di?uoro -1,1 - bis -(p-?uoro-
42
2,2,2-Tri?uoro -1.1-bls -(p-?uoro-
10
10
phenyll-ethyl acetate.
phenyD-ethanol.
phenyD-ethyl acetate.
phenyD-ethanol.
3,021,358
7
_
8
In the foregoing table, Tahori’s de?nition of syner
gistic activity was used in lieu of an LDm rating, namely
be clear that several modi?cations and changes thereof
may be made without departing from the spirit of our
the factor by which it is possible to reduce the amount
of DDT and still obtain the same mortaility; for exam
invention or from the scope of the subjoined claims. We
thus desire to claim our invention as broadly as the prior
5 art and the essential features of our invention will permit,
pie, with 2,2,2-vtri?uoro-Ll-bise(p-chlorophenyl)-ethanol
and to this end have appended the following claims.
We claim:
1. An insecticidal compound having the formula:
(bis-(p-chlorophenyl)-tri?uoromethyl-carbinol) could be
reduced 15 times (1:15). Thus a high numerical rating
‘ in Table 11 indicates a high degree of synergism.
It
should be noted in this connection that the tests reported
H
FCF
by Tahori, supra, were conducted on a DDT-resistant
strain of Palestinian house?ies (“T” strain) which ap
pear, by reason of Tahori’s comparison ofv that strain
with at “Berkeley” strain, to have less immunity to DDT
a]
than the DDT-resistant house?ies on which our tests were
conducted.
weight not above 80 and wherein Y is a member of the
group consisting of hydrogen, hydroxyl and acetoxyl.
2. The insecticidal compound 2,2-di?uoro-l,l-bis-(p~
chlorophenyl)-ethane.
with DDT, such as carbon black, talc, pyrophyllite, hy 20
_
‘
3. The insecticidal compound 2,2-di?uoro-l,l-bis-(p
chlorophenyl)-ethanol.
4._ The insecticidal compound 2,2-di?uoro-1,1-bis-(p
drocarbon solvent, alcohol, or aqueous emulsion.
The term DDT, as used in the speci?cation and claims,
denotes dichlorodiphenyltrichloroethane (pure or tech
chlorophenyD-ethyl acetate.
5. The insecticidal compound 2,2-di?uoro-1,1-bis-(p
nical grade).
It will thus be seen that we have provided a series of 25
new insecticidal compounds which are particularly e?ec
tive as DDT synergists; they may be arranged as to the
bromophenyD-ethan‘ol.
6. An insecticidal compound being a member of the
group consisting of 2,2-di?uoro-1,l-bis-(p-chlorophenyl)
degree of synergistic ef?ciency in the following general
order:
30
2,2-di?uoro-l,l-bis-(p-halophenyl)-ethyl acetates
2-tluoro-l,1-bis.(p-halophenyl) -ethenes
Bromine and chlorine are generally superior to ?uorine 35
as synergistically e?cient substituents in the phenyl groups
of the above—named compounds; while the para position
I
15 wherein Hal and Hal’ are halogen atoms having an atomic
For economic reasons it is advisable to apply our new
insecticides, when used as the sole active ingredient or in
synergistic combination with DDT, by the use of a proper
solid or liquid diluent, e.g., of the type customarily used
2,2-di?uoro-l,l-bis- (p-halophenyD-ethanols
2,2-di?uoro-l,1-bis- (p-halophenyD-ethanes
l
l
ethane, 2,2-di?uoro-l,l-bis-(p-chlorophenyl)-ethanol, 2,
ZI-di?uoro-1,1-bis-(p-bromophenyl)-ethane, 2,2-di?uoro
l,l-bis-(p-bromophenyl)-ethanol, 2,2-di?uoro-1,1-bis-(p
?uorophenyl)-ethane,_ and 2,2-di?uoro-1,l-bis-(p-?uoro
phenyD-ethanql.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,729,681
Wilson et al. __________ ..- Ian. 3, 1956
is generally preferred, the meta and ortho positions are
2,776,988
Craig et a1. __________ .. Jan. 8, 1957
not excluded from the purview of our invention.
OTHER REFERENCES
Having thus described our invention and several modes 40
by which the same may be carried into practice, it will
“Nature,” vol. 176, Aug. 6, 1955, p. 266 and 267.
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