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Патент USA US2406294

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Patented Aug. 20, 1946 '
12,406,294‘:
oFFics ,
'- UNITED STATES _ PATENT
o
2.40am
‘ '
.
INSECTICIDE
QassiL'Berkeley.
James W. llansen and Carroll 0.
asslgnors to California Spray-Chemical
CaliL,
Corporation, Richmond, Calif" a corporation of
Delaware
No Drawing.‘ Application June 21, 4945,
Serial No. 601,916.
12 Claims. (1167-33)
2
cations, of insecticide, with corresponding wast
This invention relates to compositionswhich
are highly effective in the control'of may insect
pests, and which contain as an active toxic in
gredient a synthetic organic compound which we
have discovered, namely, cyclopropyl-furyl pro- v
penone.
As is well known, substances which possess the
property of paralyzing and killing noxious in
sects when brought into contact with the insect
by various means such as spraying, dusting, etc.,
have very great economic importance, not only
for the protection of crops, but also for their
contribution to the sanitation and comfort of man
and animals. Pyrethrum is an example of a toxic
agent of this kind. The e?lciency of such insec
'
age.
,
These disadvantages are in substantial degree
‘overcome by the use of cyclopropyl furl/‘l prope
none. Due to its relatively high vapor pressure
and the toxicityof its vapors its lethal effective
ness is not limited to'direct contact, but tends to
permeate adjacent cracks, webs, and other shel
tered places, so that when dispersed inthe form
of a spray or a dust it acts both as a contact poi
son and as a fumlgant.
-
Moreover, the toxicity of the vapor of cyclo-'
propyl furyl propenone is‘ such that it may3be
used simply as a fumigant against many insect
pests including'the clothes moth. Evaporation at
room temperature is su?lciently rapid so that no
ticides is measured by two principal factors,v
heating is needed for most fumigations.
,
1
namely, the degree of “knock-down,” and the per
The compound which we have discovered to
cent “kill.” Various knowninsecticides possess ‘ possess these valuable propertieswhich make it
these properties in varying degree. For example, 20 outstanding. for use as a toxic ingredient of in-é '
pyrethrum has the property of producing a high I
secticides is chemically described as "l-cyclopro
degree ‘of knock-down, but many of the insects
pyl, 3(2-furyl), Z-propen-l-one.” It is for con
so‘ immobilized ultimately recover. We have
venience referred to herein as “cyclopropyl furyl
found that cyclopropyl furyl propenone, even
propenone." Its structural formula is as follows: ‘
when used in low concentration, combines to an‘ 25
.
CHI-CH
outstanding degree the properties of high knock
cHr-en-c-cn=cnn
down and high mortality. At the same time this
\
substance can be synthesized without dif?culty;
C
a
/
\ /
0.
and it is free from objectionable odor. Further
One‘ method of preparing this compound is as
more, whenused in amounts adequate to afford so follows: Cyclopropyl methyl ketone and furfural ,
satisfactory pest control, it has noundesirable
in approximately equimolar ratio are agitated in
effect on fabrics or furniture, and produces no
the presence of an aqueous alkaline solution for
irritation or symptoms of toxicity in contact with ,
several hours at normal atmospheric tempera
ture. Following this period of agitation the reac
warm' blooded animals.
‘
7
~
tion mix is allowed to settle. Cyclopropyl furyl
iThe compound of ‘our invention possesses, in
addition to the power to paralyze and kill many
propenone settles readily to the bottom of the
vessel either in the form of yellow crystals or,
insects on directcontact, thepower to kill by
in some cases, possibly due to the absence of seed _
means of the toxicity of its vapor. This surpris
crystals, in the form of an‘ oily liquid.‘ The prod
ing combination of properties adds .to the effec
tiveness of the, insecticidal compositions described
herein containing cyclopropyl furyl propenone.
I I It'is well known that the contact insecticides in
4-0
uct is segregated, by decantation, for example,
and is washed with water or with dilutemi'neral
acid. , It may be further puri?ed by simple steam
common use ‘are effective only insofar as the solid ,
distillation or, if greater purity is required, by
and usually impossible to reach all of the insects
The pure substance, cyclopropyl furyl prope
none, is, at normal atmospheric temperature, a
colorless crystalline solid. The crystals are regs
‘ or liquid phase of the material can be applied to , . vacuum distillationor by recrystallization from a
solvent such as petroleum ether.
\
the body of the insect. It is,extremely dimcult
in an infested area with a'spray or dust. Some of
the insects will be in protected locations such as
crevices, leaf curls, etc., and will escape. .This' ular, 'rhombic, tabular in form, and exhibit par
fact necessitates both heavy and repeated appli 60 allel extinction. " Crystallization does-not take
.4
a minute seed crystal of the substance, and,
therefore, if reasonable precautions are taken,
(identically reared under laboratory conditions)
10 were usedin all tests. All tests werereplicated
a
At 6 mm. kg________________________ --‘________ .- 123.5o
same-mm.
g .................. __
Index of rei‘ractionoi liquid'..-_
several times. The results were obtained by the
as.
.
Hosklns technique in a standard "Hoskins cham
ber” (described in “Chemical Control of Insects," ,
.
Melting point .................... --
38‘38 34° C
......... ._ 1.6076 20,,
Density of liquid at 25° 0--
.
0.8018 speci?c gravity and unsulfonated residue,
This substance has the following properties:
,
'
of 95. The same oil, the same test apparatus and
procedure and the ‘same strain of house?ies
" .‘ straw color and has a distinctive, agreeable odor.‘
V
.
composition used for these tests consisted of ,
tures many degrees below ‘its melting point. In
liquid form, cyclopropyl furyl propenone is a light
‘
'
small percentages of the toxic ingredient in ‘solu
tion in light petroleum (kerosene)' oil of about
~. it may, be preserved as a liquid even at tempera- ‘
Boiling point (pins or minus 0.5° 0.):
'
likewise show for comparison results obtained by
the use .of aspray containing pyrethrum. The
place readily except in the presence of;at least
‘edited by Campbell and Molten, 1943, at page~
102
130),~us_ing 4 ml. of spray solution in each test.
' Solubility in water.----..._
Molecular weight; _______ -_
This substance is‘ soluble in such organic sol
Cone. of .
vents as- acetone, ether, petroleum ether and “ ‘
comp.,
Compound
Mortality
percent in ,,
by
furfural. It is su?lciently' soluble‘ in petroleum
24 hrs.
weight
oil fractions such as kerosene and spray oils to 20
permit its e?ective use as an insecticide in such
carriers.
K"_°°k‘d°wn
percent
Percent Min.
Cyclopropyl iuryl prope—
none ___________________ _.
-
Pyrethrum extract 1.-
‘ Cyclopropyl furyl propenone- is somewhat un- ‘
.Do-l.‘ __________ .-
stable in the pure state even when kept in the
dark and gradually ‘changes from colorless to
slightly yellow. The'technical material as ob
1._o
._-.
1. 37
._-_
1.83
I
25
10
100
10
100
4
97
100
10
4-
5c
48
.
Cyclopropyl' furyl prope-
.
none _________________ ._'_.
‘Do 1 _________________ __
tained without recrystallization will, on standing, <
‘
change in color from light amber to dark yellow
or dark red. -This change reaches equilibrium
60
2. 5
5. 0
_
>
91
100
1 Commercial “20 to 1" extract containing 2.4% pyrethrins.
' The e?icacy of sprays of light oil containing,
after a short time, and a?ects only one to ?ve 30 cyclopropyl furyi propenone against other in‘
per cent of the material. when dissolved in pee - sects is further shown ‘by the'following results
, troleum oil, the stability of cyclopropyl. furyl
. propenone is improved even ing-the presence of
strong sunlight. This slight instability is with
out apparent eifect on the insecticidal value of
the‘ compound. Consequently, it is usually not
.of carefully ccntrolledtests:
35
l’qmnffyc‘l‘l"
propy ury
on de
_
v
'
.~
propenone in light pgsitiger
spray oil
q‘ ‘
Insect‘
'
Percen‘.
mortality
-
necessary to resort to recrystallization‘ or vac
uum distillation when preparing the product for
_
insecticidal compounding.‘
.
1
‘
Cyclopropyl furyl propenone v‘possesses in
secticidal propertiesto a‘ high degree.‘
.
'
MF_
7.5.. _______________ ._
.
‘0 Blank
ODJYL... 7.5 ........... ._
-.
Since it '
3.76 _______________ __
Blank (oilonly).-__
is extremely toxic to house?ies and mosquitoes it
-. 5 ............... _ _
vBlank (oil only)_...
v
1. 2
German cockroach. _ ._..
100
1.2
l. 2
_____d0 ........ n‘ _______ ....
European earwlg.
____
0
100
1. 2
_..-_
_________________ ..
1.2 _._._do ______________ _____
0. 8
25
0
Potato tuber moth larvae
65
0.8 .__.-do ........ "y. ..... ._
i0
is very valuable for use in a ‘_'household” spray,
i. e.,' as an ingredient in compositions adapted to
be used as a space spray.‘ For-thispurpose it is 45 \5 'C'yclopropyl furyl propenone has a distinctive
but pleasant odor, and therefore its use in house
desirable to incorporate it with a light well-re
.hold sprays does not require the addition of a
iined petroleum distillate of the kerosene type
suitable for dispersion by, means of a spray gun. _ - perfume or masking odor, as is the case with ordi
nary ?y sprays. The odor of. cyclopropyl ‘furyl
such use is 2% to 5% by weight of cyclopropyl 50 propenone is sufficiently distinctive and sum‘
'furyl' propenone dissolved in 98% to 95% by . ciently'pleasantso that it masks the odor of the
kerosene.
I
weightv of light ‘petroleum oil. A typical petro
' An example of a suitable sprayable material for.
Cyclopropyl furylvpropenone maybe 'advan- .
~ leum oil suitable for use in such ‘spray solution
tageously used as an aerosol, due to its property
of effective knock-down, as well as its solubility
vis a-re?nedterosene type fraction having the
following qualities:
' -
.
,.
Speci?c gravity___~ ______ _..' ________ __
.
in available oils, alcohols and ethers. This use
0.8018
is brought about by dissolving it in a solvent
Sayboit Universal viscosity____..° PL. 32 to .100 _
Unsulfonated rosidue_l__.._._. _______ ..
ABTM distillation:
,
9'5
‘
'
which is substantially immediately volatile at
average atmospheric conditions, the solution be
60 ing kept in a tight container‘ under su?lcient
Initial -..__.____s-_,__-_.._-__°_ 1L. ‘
840
End point_.._- _______ _-_ _____ .3 r'_.
5.20- ‘
This composition produces highly efiicien-t re.
,sults, i'._ e., rapid knock-down and high mortality,
when atomized into a room without further dilu
' tion. At the same time it does not damage walls,
fabrics or furniture and ‘causes no irritation ‘or
injury to human beings or to pets. A‘quantity
.of undiluted cyclopropyl furyl propenone applied
,
v to the skin ,and'allowed to remain vfor ?fteen l
- _
pressure to maintain the solvent in liquid form
'
until desired for use. 7
- effectively vused in combatting insect pests by
' bringing it into ‘contact with the insects by some
dispersing means such as mechanical spray or
aerosol, we have discovered, as previously ‘stated,
that it- possesses to an important degree'the
property of a fumigant, that is, its vapor is high
jly toxic to many insects. This fumigant prop
minutescaused no discomfort and produced no
erty is accurately shown by the following results
redness or other evidence of irritation or stain.
The e?ectiveness of cyclopropyl 'furyl prope
laboratory conditions. { A quantity. of crystalline
., none when used as a spray in oil against house
-
Although cyclopropyl furyl propenone may be
of tests carried out‘ under carefully controlled ~
‘ cyclopropyl furyl propenone (500 mg.) was placed
'i‘lies is shown by the following test results, which 75 in a loosely woven cloth container which was ,in-.
2,400,294
'serted in the lid of a wide-mouth one-gallon
glass jar and test insects were placed at the bot
tom of the jar. Evaporation under normal at
mospheric conditions was allowed to continue for
two hours, following which the lid was removed,
also for application to animals. An example of’ a
preparation adapted to be used without further
_ dilution for the dusting. of vegetation is as follows: I
.5
the jar aired out and covered with a clean cloth.
The following results were observed:
Per cent kill (24 hours)
' Rose aphid
Bean weevil
_____
_
__e
70
80
_
Clothes moth__
'
Ingredient
Cyclopropyl iuryl propenone. . .4. .......... .1 _______ __
‘r
b
' Pet???» y
2 to 5
Wetting agent _____________________________________ ._
1.0
Inert powdered extender ___________________________ ..
to make 100
10
A similar insecticidal dust for application to an:
100
'imals or to living quarters may be made by the
use of from 3% to 10% of cyclopropyl furyl pro
Confused ?our beetle ____________________ __ 10
penone in the above formula. An example of wet
Due to its effectiveness as a fumigant‘against 15 ting
agent suitable for use in ‘this formula is
various insect pests, and its pleasant odor, cyclo
sodium lauryl sulfate. Examples of suitable ex
Mediterranean flour moth__'_____________ __ 100
propyl furyl propenone is well adapted for the
periodic control of such insects as moths and
?eas in living and storage apartments, for easy
and effective use in greenhouses, and for the 2
fumigation of seed and grain.
ing in powdered form: soapstone, talc, pyro
phyllite and sulfur. The ingredients of these
dust compositions may be ground up together in
the desired proportions. One desirable way of
preparing such dusts is to dissolve the clyclo
-
Another field of use for the'oompound describe
is in horticulture. For such purpose it is desirable
to prepare a base composition which may be
transported to the field in concentrated-form and
there diluted with a dispersing or carrying agent,
such as water. An example of a suitable base
composition or concentrate of this type is as fol
lows:
tenders are any one or combination of the follow
propyl furyl ,propenone in a volatile solvent such
as a low boiling petroleum fraction or alcohol,
' then to spray this solution over the powdered
extender and, after the solvent has been removed '
by evaporation, to regrind the material.
It has been the practice of contact insecticide
>
comp'ounders to» make use of various powdered
30 extenders in addition to those named above.
'
Ingredient
Many of the materials previously used for this
Percent by
weight
purpose have adsorbent properties, for example, Cyclopropyl luryl propenone_
20-30
Vegetable oil ............... _.
8-16
_ __
33
Petroleum spray oil ................................ ._
Emulsiiler _______________ . _
To make 100
fuller’s earth, diatomaceous earth, walnut shell
?our, etc. While cyclopropyl furyl propenone may
u an
be used with such adsorbent materials, we have
fouhd that distinctly better results are obtained
when it is used in conjunction with non-adsorb
ent, relatively nonporous materialssuch as those
The vegetable oil which we prefer to use in the
above composition is cottonseed oil, corn oil, or
previously mentioned. That is, other things be
pine oil. A satisfactory emulsifier for use in this 40 ing equal, greater insecticide efficiency is obtained
composition is a, higher fatty acid ester of a com
when cyclopropyl furyl propenone is compounded
mercial polyethylene glycol of high molecular
with nonporous dusting powder such as talc, than
weight, such as the available glycols ranging in
when it is compounded with adsorbent material
molecular weight from about300-to 600. A pre
such as diatomaceous earth. A preferred form of
ferred ester is one made by esterifying nonvola 45 our invention, therefore, is the use of dusting
tile fatty acids with polyethylene glycol having a
. compositions containing, as the principal toxic in
molecular weight of the order of 400. The fatty
gredient, cyclopropyl vfu'ryl propenone together.
acids suitable for use in this esteriflcation may
be a mixture of higher acids such as is found in‘
the commercial products “tall” oil, marine fatty N)
acids, coconut fatty acids, and “red” oil, or it may
be a relatively re?ned product. A suitable pe
troleum spray oil is the petroleum fraction here
tofore described, having a speci?c gravity of
with relatively nonporous, nonadsorbent, ?nely
divided solids.
The above are examples of the kind of com
positions which we have found to be convenient
and suitable for obtaining practical effective pest
control by the use of cyclopropyl furyl propenone.
~ We have found, however, that the compound is
about 0.8018, or a. similar oil blended with a, lesser 55 compatible chemically, both under storage ‘condi
tions and in field use, with many known insecti
used should preferably have a high unsulfonated
cides and fungicides, including lead arsenate, cal
residue, e. g., 90 or more. This solution is adapted
cium arsenate, thiocyanates, phenothiazine, py
to be used in a 1-400 or 1-800 dilution with water
rethrum, rotenone, wettable' sulfur and copper
with which it readily emulsifies. This diluted 00 compounds, lime-sulfur, and Bordeaux mixture.
proportion of heavier “neutral” oil. _ Any 011 so
composition may be freely applied to leafy crops
and to fruits without danger of phytocidal effect
and provides efficient protection against a large
' number of insect pests.
Since cyclopropyl furyl propenone, while,toxic to
a large number of insects, is ‘not toxic, or not '
markedly toxic, to all insects, it is in some in
stances advantageous to incorporate a small
A vsimpler but highly effective composition, '5 amount of ‘one or more of these additional in
especially for use in making veterinary “dip"
secticides in the compositions containing ‘cyclo
solutions, is one in which the principal ingredi
propyl 'furyl propenone.
ents are cyclopropyl furyl propenone, about 40%
Dust compositions, containing 15%.01' cyclo
by weight, and polyethylene glycol esters of highw
propyl furyl propenone have produced no harm
er fatty acid. about 60% by weight; Such com 70 ful effects on rose foliage. Although used in
position is adapted for use in 1-400 ' to l-800
dilution in water as an animal wash.
concentrations several times those ordinarily ,
needed for adequate pest control, no leaf burning
It is frequently desirable to apply insecticides
or other injury was observed on this type of plant.‘
in the form of dust. This is true not only in the
Likewise, no apparent harm or appreciable stain
case of application to ?eld crops and orchards but 75 ing was caused by the application of composié '
7
8.406.294
.tions containing 'cyc opropyl iuryl propenone in
iuryl propenone in oil solution. and a water
‘
j insecticidal amounts to fabrics, or i'urniture?n-l
' ish. The same freedom from injury ascribable to
1
I
true in the
case of oil sprays and .water sprays
6. An insecticidal spray concentrate compris
ing from 20%‘ to 30% by weight of cyclopropyl
Iuryl propenone, from 5% to 20% by weightoi
emulsifying agent.
the presence of cyclopropyl furyl propenone is
.
I
_
_ ‘
"
4 ' vegetable oil, and the balance consisting oi’ pe
»contain'ing insecticidal amounts oi’ cyclopropyl
furyl propenone.
_
troleum spray oil and a water emulsifying agent.
'I. An insecticidal solution in which the princi
" pal active ingredients are cyclopropyliuryl pro-~
penone and polyethylene glycol esters of higher
fatty acid in weight ratio of about 40:60.
-8'.\ An insecticidal composition containing as
-
We have previously mentioned the compatibil
with various
' ity of cyclopropyl iuryl propenone
special-purpose toxicants and carriers. By the
term "carrier” we intend to include such ma
terials as assist inv the dispersionof the cyclo
active toxic ingredient cyclopropyl furyl prope
propyl ‘furyl propenone as well as those‘ which
none in finely divided form, mixed with a pow
impart- spreading, wetting, conditioning, adher
solid carrier. '
' ing. solvent, or emulsifying action. Examples of 15 dered
9. An insecticidal composition containing-from
vcai'i'ife'i's‘include, in addition‘ to those speci?cally
2 to 5% by weight of cyclopropyl iuryl propenone,
1 ime'ntioned abov , chlorinated solvents,v aligvlated'
about 1% by weight‘ of a wetting agent, and an
_ naphthalenes, esters, vegetable oils, and soaps.
, inert powdered solid carrier.
10. An insecticidal composition comprising as
3 '1. An insecticidal composition containing as’ 20 active toxic ingredient cyclopropyl'iuryl prope-r
" ‘active toxic ingredient cyclopropyl furyl'prope-"
none extended by means of a. volatile solvent over
.noneand a carrier therefor. .
a powdered solid carrier.
2.'~An insecticidal composition containing as
11. An insecticidal composition comprising as‘
-
>
We-claim:
I
‘active toxic ingredient from 1% to 40% by weight
active toxic ingredient cyclopropyl iuryl propel
of cyclopropyl furyl propenone and a carrier 25 none extended by means of a volatile solvent over
solid carrier.
3; An insecticidal composition'containing as ' a nonadsorbent
12. The method of controlling insect pests
therefor.
‘
_
'
.
active ‘toxic ingredient cyclopropyl furyl prope
‘which comprises dispersing over the insect in- ~_
tested area a composition the active toxic ingre
.' none in oil solution'and a. carrier thereion,
4. .An insectitcidal spray-‘composition contain 30 dient of which is cyclopropyl furyl‘ 'propenone'
ing as active toxic ingredient from 1% to 5% by
together with a carrier therefor.
weight of cyclopropyl furyl propenone dissolved
in plant spray petroleum oil.
JAMES w. mans.
5. An insecticidal spray concentrate compris- l
isng from 20% to 30% by weight ‘of cyclopropyl
35
_
CARROLL o. soassm
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