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Патент USA US2107298

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Patented. Feb.“ 8, .1938
_ Lowell Bi Kilgore, Washington, D. 0;, assignor
' to Kllgore Development Corporation, East
_ ‘Falls Church, Va., a corporation of Virginia
No Drawing‘ Application March 27, 1934,
" Serial No. 717,676
11 Claims. (01. 167-22‘)
This invention relates to insecticides and has
' for its general object the provision of a solution
or emulsion which hasthe power of killing in-.
sects and yet is harmless to other animal life.
5 More particularly, this invention concerns an
emulsion or solution which contains one or more
organiccompounds which have ‘as a part'of
one side and is strongly electronegative radical
or group on the _other.side.
A study of the ex
amples which are given below will show exactly
what is included and meant in the above theory
fundamental tothe class of organic compounds 5
which I have discovered to be eihcient insecti-,
The migratory nature of the hydrogen atoms
methylene hydrogen atom, namely, one situated contained in the active methylene grouping to
10 between two keto carbonyl groups. Speci?cally, which I have herein referred and described, is 10
I have discovered a means of killing insects by ' shown by the tendency of these hydrogen atoms
a chemical reaction which reaction is caused by to enter into enol-keto dynamic tautomerism.
This tautomerism is represented as follows:
bringing into contact with an insectv an insecti
their‘ molecular structure a particular tautomeric ' '
cide containing an organic compound having
15 such a tautomeric- methylene hydrogen atom
positioned between two keto-carbonyl groups or
‘between one keto-carbonyl group and an electro
neg'ative ' radical.
The mechanism by which an insect utilizes
20 the oxygen of the air and particularly the chem-.
istry of the transfer of the oxygen to theplaces
of ultimate combustion are‘ different from the
insect must permit
occur the
in red
of molecular
25 oxygen through the walls of the tracheae and
Here the migratory or active hydrogen atom
shifts between the carbonyl and- the methylene
carbon atoms accompanied by a shift in the'dou
ble bond linkage in the opposite direction.‘ When 20
the hydrogen atom is in the “enol’_’. position it is
able to react with theomgen atom of another
molecule of the same onof another compound
provided the oxygen atom. is loosely bound. -
When such an “eno ” compound is brought in 25
during this di?usion or later this molecular oxye contact with the respiratory or combustion'sys
gen must be broken downto atomic form and - tem of an insect, a reaction takes place which
attached to a suitable carrying compound for
paralyzes and subsequently kills the insect,
distribution to the cell- walls.
The tautomeric'group which I have found to,
‘so ’ Myinvention, therefore, consists of an lnsecti- ' -_be
necessary in the molecular structure of those
cide containing an organic chemical compound ‘ "organic
c, mpounds upon which my invention
which appears to be able to compete for the labile :depends' is characterized by the following reac
oxygen involved in the oxygen transfer system of tions which must be considered- together:
an insect thus interfering with themeans of ener-_'
(I) The tautomeric group wherein the “enol"
35 gizing the life sustaining processes. ~
. structure produces adeep red color complex 35
I do not consider thetheory of the action of
this particular tautomeric hydrogencontained in
with ferric chloride.
the compounds which I have discovered to be /_ (2) The methylene hydrogens are replaceable
with an alkyl radical through the interme-'
toxic to insect life, to be essential to my inven
diary of a sodium alkoxide.
' ‘
40 tion, butitis set forth here to illustrate the
broad conception of my invention, and- the scien- _
Theincorporation of such an active methylene
ti?c teachings appurtenant thereto.
radical so positioned between two keto-carbonyl
' I have, discovered that the incorporation into groups which confers upon the organic compound
an organic compound of a methylene group in insecticidal properties is illustrated bysthe beta
45 which the hydrogens vare labile and capable of .di-ketones and substitution products thereof 45
migrating to another position‘ in‘ the molecule, such as is shown below. The fundamental struc
confers upon this organic compound the power to. ture which is operative in the compounds‘ to
kill insects. The hydrogens in thetype of meth
which I refer is represented generically, _'
ylene' group, -CH2—-, to which I refer, are caused
50 to be labile and ‘migratory by the electronic
strain produced by neighboring activating groups’.
wherein R and R’ may or may not be same
This electronic strain or activation is caused by
the presence of a keto carbonyl, C=O, group on
radical or grouping.
' each side of the intervening methylene group or
55 by the presence 'of one keto carbonyl group on
' I have selected the following compounds from
my researches as illustrative of the requisite'
molecular structure which according to my dis- 55
2,107,298 ‘
covery confers insecticidal properties upon an
organic compound. Each one of the following
gamma diketo esters.
The condensation therefore of a vketone with
an organic ester e?ected .by metallic sodium is
the general method of preparation of the beta
diketones referred to in this invention.
compounds has been bio-assayed against insects
and has been found to possess insecticidal prop
>These compounds are often classed as alpha.
Compounds toxic toward insects
The compounds herein listed were biologically '
tested for insecticidal activity using roaches and
(1) Acetyl acetone ____________ __cn,co-cHr-cocm
(2) Dibenzoyl methane__________ __C.HsC0—CHaC_0C~H:
'10 (a) Benzoyl acetone______________ __c.H.cocH,cocH.
’?ies as the test animals. A one percent solution
of each of the compounds in kerosene was used 10
in each instance. The application was made by
dropping one drop of the solution on the abdo
(4) Ethyl acetyl pyruvate__.._CHsCO—CH,—COC00C1Hs
(5) Ethyl benzoyl pyruvate__C.H;C0-—CH,——COCOOC2Hs
men of the ‘roach in‘ accordance with the stand‘
ard test method, ‘(see Gnadinger, C. B. “Pyre
The above compounds were selected to illus
trate the diversity of compounds possible wherein
thrum Flowers”, pp. 88 ii).
15 the essential structure operative in conferring in
secticidal properties upon such a compound is a
In each case a
paralysis of the hind legs developed in about
ten minutes.
This was followed by a complete
methylene group positioned between two keto
paralysis in which state the roach became unable
carbonyl groups as an integral part of its struc- - to move, the legs being drawn up in an irregular
fashion. Although signs of life persisted in some 20
V20 mm.
The following analysis of the structural rela
cases for many hours, there were no recoveries. _
tionships of the‘compounds given in the above
'-The rate ‘of action depended upon the virility
group are pointed _out to indicate the broad scope of the roach and the speci?c compound used.
of the invention and the possibilities which are _ For example, acetyl acetone was found to be
rapid in _its toxic effect while ethyl benzoyl pyru 25
In the first place it will be noted that all of
the above compounds have asja part of their
vate was comparatively‘ slow inaction. Never
theless, it was fatally toxic eventually. The
molecular structure a methylene radical vposi
higher the percentage of the enol tautomer, the
' tioned between two keto-carbonyl groups. Stated
faster the action appears to be.
in another way, all of these compounds are
closely related in that each one contains two
keto-carbonyl- groups separated by a methylene
radical as a characteristic part of their struc
tures, thus:
in a small cage. About 0.3 _cc. of. the spray was
Compound (1) ' illustrates the use of an alkyl
radical for both R and R’ in the generic formula,
In a similar way Compound '(2) shows the use '
of an aryl radical for both R and R’ in the gen
eral formula.
The use of a combination of aryl _
and alkyl radicals as substituents for R and R’
of. the general formula is ‘shown in Compound
The fly tests were conducted _by atomizing a
one percent solution of acetyl acetone in kero
sene into a group of ‘?ve day old ?ies contained
used and after three minutes the ?ies were
transferred to a dry cage for observation. All 35
the ?ies were found to be dead after twenty-four
What I claim is:
1. An insecticide comprising in solution an
organic compound the molecular structure of 40
which has the following tautomeric grouping as
an integral part thereof;
2. An insecticide comprising in solution with
an organic solvent, an organic compound the
molecular structure of which has the following
tautomeric grouping as an integral part thereof;
Compounds (4) and (5) show thatthese sub
' stituents may be other types of groups or radi
cals as in the incident examples, an esteri?ed
carboxyl group wherein
the intermediary of a sprayable vehicle, com
prising‘an organic compound having as part of
a or R"=CO0H(R_")
In Compound (4) an alkyl radical is used for
55 both R’s, while in (5) aryl and alkyl radicals are
used for R and R" respectively in this sub
class of the general formula:
3. An insecticide adapted to be applied through
It'will be noted that Compounds (1), _(2) and
‘(3) are usually prepared by the Claisen con
densation of a ketone and a monobasic ester,
ethyl acetate, according to the general reaction,_
its molecular structure a methylene group posi
tioned between two keto-carbonyl groups wherein 55
a hydrogen atom is labile and migratory.
.4. Insecticide comprising an organic‘ com-_
pound having as part of its molecular structure
a methylene group having a tautomeric ‘hydro
gen atom, and a keto-carbonyl group on each 60
side of said methylene‘ group by the presence'of
which groups the intervening hydrogen atoms
are rendered labile and migratory.
v5. An insecticide adapted to’ be applied
through the intermediary of a- sprayable liquid 65
Such products are often" classed as beta-1
Similarly in the case of Compounds (4). an
(5) the same condensation reaction, namely, by
means of metallic sodium, is used employing a
glilbasic acid ester, ethyl oxalate, and a ketone,
vehicle, comprising an organic compound having
as part of its ‘molecular structure a methylene
radical positioned between two keto-carbonyl
groupsby virtue of which position a hydrogen
atom of said methylene radical becomes labile
and migratory so as to permit the formation of
I the corresponding enol form.
6. An insecticide comprising an alpha, gamma,
diketo ester.
7. An insecticide comprising a beta-diketone.
w 3
8. An insecticide comprising in a sprayable
_ liquid vehicle, an alpha. gamma, diketo ester.
- 9. An insecticide comprising in a sprayable
liquid vehicle a beta-diketone.
compound‘havlng‘as part of its molecular struc
ture, a methylene radical interposed between two
keto carbonyl radicals forming a group which is
subjected to an electronic‘ strain causing the
methylene hydrogen atoms to become labile and 5
10. An insecticide comprising dibenzoyl methane, CsHsCO-CHz-COCsHs.
11. An
‘ .
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