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Патент USA US2126854

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Patented Aug. 16, 1938
2,126,854
UNITED ‘STATES PATENT OFFICE
2,126,854
PROCESS FOR- PREPARING IMPROVED DER
RIS AND CUBE EXTRACTS AND HYDRO
GENATED DERIVATIVES AND PRODUCTS
PRODUCED THEREBY
Robert Wotherspoon, East Orange, N. J., assignor
to Derris, Inc., New York, N. Y., a corporation
of New York
No Drawing. Application April 28, 1934,‘
Serial No. 722,968
.
17 Claims. (Cl. 167-24)
My invention relates to the production of in
Proper removal of all, or part, of these mate
secticides and insect repellent substances and ‘rials results in a product that is readily pulveriz
refers particularly to such products producible able, thereby enhancing its commercial prac
- from derris, cube root and similar sources of sup
5 ply for the products mentioned.
The active principles of Derris (Deguelia) sp.
(tuba root) and Lonchocarpus nicou (cube root)
consist of a mixture of rotenone, deguelin, te
phrosin, toxicarol and several other chemical
10 bodies of lesser insecticidal value. '
Several other plant materials such as the roots
ticability.
There are several ways of accomplishing this,
among which are the following:
Emample 1
The organic solvent solution of these insec
ticidal principles, hydrogenated or not, is placed 10
in a still equipped with steam heating coils or
a steam jacket. The contents are heated to the
of the germs Spatholobus contain one or more
boiling point and the solvent distilled 011. The
of the above mentioned constituents.
These active principles are'soluble in a great a traces of solvent left in the mass is removed by
15 many organic solvents such as ethyl acetate,
benzole, acetone, chloroform, ethylene dichlo
ride, safrol, et cetera.
These solutions of active principles may be
subjecting it to the action of steam introduced 15
through an open steam line placed in the still or
by adding water to the residue and raising it to
the boiling point. The steam carries o? the
ucts of the other principles, which have not as
traces of solvent and by prolonging the opera- '
tion all, or part, of the essential oil of derris is 20
brought over in the same manner. The vapors
are condensed and the essential oil is separated
yet been identi?ed. These hydrogenated prod
from the water.
subjected to the action of hydrogen in the
20 presence of an active catalyst, such as nickel, to
form dihydro-rotenone and hydrogenated prod
ucts are morevstable to light and air than the
25 original material and no doubt will be of great
commercial value.
Concentrated horticultural insecticides con
taining the above mentioned principles are usu
ally prepared from a concentrated organic sol
30 vent solution of derris or cube such as acetone,
ethylene, dichloride, safrol, et cetera, with or
without a spreading agent. and with or Without
other insecticidal principles such as pyrethrum,
et cetera.
35
Other uses have been found for these insec
ticidal principles. They are now being used in
_ preparation 'of
mange
remedies,
insecticidal
soaps, body lice preparations, et cetera.
The need for a dry product containing these
40 principles has developed as a result of these new
outlets. Heretofore the extracts of cube, derris,
et cetera which was obtained- by evaporating off
the solvent used to extract the principles from
the roots were of a viscous nature. This viscous
45 material was di?icult to handle and di?lcult to
remove from the containers in which it was
placed.
1' have found that in the case of derris extract
this viscous property is due to the presence of
50 a small amount of the solvent used for extrac
tion and also to the presence of an hitherto un
_
The oil possesses the following characteris
tics:
Speci?c gravity @ 25° C _________ __
. 998
Optical rotation 100 m. m. tube_____
+5°
Saponiflcation value _____________ __
Saponi?cation value after acetylization __________________________ __
25
24
‘
82. 6
30
Boiling range ‘760 m. m ___________ __ 2l0-250° C.
This oil possesses the characteristic odor of
derris root and is responsible for the insect re
pelling property of derris products while the
35
insecticide remains undistilled.
Valuable insect repellent preparations may be
prepared with this oil. For example, an e?lcient
?y and mosquito repellent can be made by mix
ing 1/; of 1% oil of derris with 99%% of whit
petrolatum.
'
The wet residue ‘left in the still after the re»
moval of the traces of solvent and all, or part,
of the essential oil is removed and broken up into
small lumps. It is placed on trays and dried.
The dried product is then run through a mill and 45
ground to the desired fineness.
Example 2
The organic solvent solution of these insecti
cidal principles, hydrogenated or not, is placed 50
in a vacuum still and the bulk of the solvent is
The ?nal
traces of solvent and some of the essential oil is
discovered constituent of derris root, 1. e. essen- ‘ removed at atmospheric pressures.
tial oil of derris. This essential oil with, or with
out, the traces of solvent left in the extract keeps
the product/in a soft condition.
removed under reduced pressure. The residue,
due to the absence of water is at this point liq- 65
2
2,126,854.
.
ment with the driers is omitted as the distillation
of the solvent will remove the traces of water si
uid, and may be run out in this state through a
draw-o? on the bottom of the still. It solidi?es
upon cooling and may be pulverized.
Example 3
Gil
multaneously.
The preparation of the dried product is carried
The above method is applicable when remov
out as outlined above. The resulting dried ex
tract is light colored, varying from a light amber
ing non-chlorinated solvents. The chlorinated
sélvents such as carbon tetrachloride, ethylene
to a light yellow. This product will find appli
cation in preparing products which necessarily
dichloride, et cetera decompose slightly even un
must be free from color. Commercially it will be
10
more saleable than a product not so treated.
It is understood that these light colored der
ris or cube extracts may also be manufactured
from extracts which have been hydrogenated
either before or after the alkali treatment.
These light colored products may be used in 15
lieu of rotenone as its much lower cost will allow
its use in preparations which now contain only
rotenone. The light colored material obtained
der diminished pressure forming free hydro
chloric acid, the presence of which causes the
destruction of part of the active principles and
yields a dark colored product. The rotenone yield
is lowered to a large extent as a result of this
destructive action.
I have overcome this trouble by adding a small
amount of an anhydrous alkaline earth carbon
ate or alkali metal carbonate to the contents of
the still prior to the distillation. The free acid
‘from hydrogenated extracts is of special value
in moth proofing solutions. Dihydrorotenone or 20
is thus neutralized as fast as it is formed.
Anhydrous sodium carbonate and potassium
hydrogenated derris or cube extracts are of great
er value for this purpose than rotenone because
carbonate are examples of the alkaline carbon
ates and calcium carbonate, and magnesium car
bonate are representative of the type of alkaline
earth carbonates that may be used.
Derris and cube roots contain certain plant
acids and other alkali-soluble material, some, or
of their air and light resisting properties.
By “insecticidal products from derris and sim
ilar insecticidal vegetable sources” as used in my
claims, I mean both the insecticidal products as
actually found in derris and other insecticidal
all, of which are present in extracts obtained by
extracting the roots with volatile solvents. These
vegetable sources and the hydrogenated com- ‘
pounds thereof, among which are rotenone and
30
30 materials cause premature darkening of extracts
dihydrorotenone.
containing them. Derris and cube roots yield
extracts of varying degrees of color. Extracts ob
tained by extracting roots which contain little
coloring matter quickly darken with age or upon
35 exposure to light and air. This is not entirely
due to the decomposition of the active principles
such as rotenone which forms yellow decomposi
tion products. It is mainly due to the plant acids
I do not limit myself to the particular vege
table- sources, times, temperatures or steps of
procedure speci?cally mentioned as these are
given simply as a means for clearly explaining
and alkali soluble material which darkens more
Y
35
What I claim is:
1. In a process for the production of a dry,
friable insecticidal product from derris and simi
lar insecticidal-containing vegetable sources, the
steps which comprise extracting the insecticidal 40
40 quickly and to a deeper shade of color upon ex
posure to light and air than does rotenone. This
darkening action sometimes takes place in the
root itself as a result of prolonged storage or
because of exposure to air.
my invention.
.
‘
principles from the vegetable source by means
of a volatile chlorinated solvent, adding a mem
ber of the group consisting of anhydrous alkali
metal carbonates and anhydrous alkali earth
I have found that these plant acids and other
alkali soluble materials may be removed from
water immiscible extracts containing same, re
gardless of whether or not they have become
metal carbonates to the solvent and removing -
darkened as a result of exposure to air or light
50 before or after extracting them from the orig
friable insecticidal product from derris and simi
lar insecticidal-containing vegetable sources, the
inal roots, by subjecting such extracts to the ac
steps which comprise extracting the insecticidal
45
tion of a weak‘ aqueous solution of an alkali such
as caustic soda, caustic potash, et cetera.
_
The alkali dissolves the plant acids and other
55 alkali soluble material.
The solution of com
bined alkali soluble materials have the disadvan
tage of forming an emulsion with the water im
miscible solvent extract of insecticidal principles
rendering the separation of the latter from the
,
60 aqueous layer somewhat di?lcult.
I have overcome this drawback by adding a
water soluble alkali metal carbonate, such as sodi
um carbonate to the caustic alkali solution. The
mixture separates quickly into two layers. The
85 aqueous solution is withdrawn and is replaced
with an equal amount of water. This mixture is
allowed to settle, the water drawn 011, and the
cloudy solution of insecticide principles is dried
with a water absorbent such as anhydrous sodi
70 um carbonate, calcium sulphate, et cetera and
2. In a process for the production of a dry,
principles from the vegetable source by means of
a water-immiscible solvent, adding an aqueous
solution of an alkali metal hydroxid thereto,
separating the aqueous solution from the water
immiscible solution, and removing practically all
of the solvent and distillable oils from the water
immiscible extract by distillation.
3. In a process for they production of a dry,
friable insecticidal product from derris and simi
lar insecticidal-containing vegetable sources, the
steps which comprise extracting the insecticidal
principles from the vegetable source by means of
a water-immiscible solvent, adding an aqueous
solution of an alkali metal hydroxid and an 65
aqueous solution of an alkaline earth carbonate
thereto, separating the aqueous solution from the
water-immiscible solution, and removing prac
tically all of the solvent and distillable oils from
the water-immiscible extract by distillation.
?ltered. The resulting product is clear and light
4. In a ‘process for the production of a dry,
amber colored retaining the same shade inde?
friable insecticidal product from derris and simi
lar insecticidal-containing vegetable sources, the
steps which comprise extracting the insecticidal
principles from the vegetable source by means of 75
nitely if stored in air tight and light resisting
containers.
75
practically all of the solvent and distillable oils
therefrom by distillation.
If a dry powdered extract is desired the treat
3
3,126,854
a volatile solvent, subjecting the solution to dis
tillation and recovering a distillate oil having a
speci?c gravity at 25° C. of .998, an optical ro
tation 100 m. in. tube of +5°, a saponi?cation
value of 24, a saponi?cation value after acetyliza
tion of 82.6 and a boiling range 760 m. m. of
210°-250° C.
5. In a process for the production of a dry,
lar insecticidal-containing vegetable sources, the
steps which comprise extracting the insecticidal
principles from the vegetable source by means of
a volatile chlorinated solvent, subjecting said
principles to ahydrogenating process, adding a
member of the group consisting of anhydrous
alkali metal carbonates and anhydrous alkali
earth metal carbonates to the solvent and remov
friable insecticidal product from derris and simi
ii) lar insecticidal-containing vegetable sources, the
steps which comprise extracting the insecticidal
principles from the vegetable source by means of
ing practically all of the solvent and'distillable
oils therefrom by distillation.
10
a water-immisciblesolvent, adding an aqueous
solution of an alkali metal hydroxid thereto, re
iii moving the aqueous alkali solution of alkali
lar insecticidal-containing vegetable sources, the
steps which comprise extracting the insecticidal
soluble materials and by distillation recovering
a distillate oil having a speci?c gravity at 25° C.
of .998, an optical rotation 100 m. in. tube of
+5°, a saponi?cation value of 24, a saponi?cation
20 value after acetylization of 82.6 and a boiling
range 760 m. m. of 210°~259° C.
6.121 a process for the production'of a dry,
friable insecticidal product from derris and simi
lar insecticidal-containing vegetable sources, the
steps which comprise extracting the insecticidal
12. In a process for the production of a dry,
friable insecticidal product from derris and simi- <
principles from the vegetable source by means 15
of a water-immiscible solvent, subjecting said
principles to a hydrogenating process, adding an
aqueous solution of an alkali metal hydroxid
thereto, separating the aqueous solution from
the water-immiscible solution, and. removing 20
practically all of the solvent and distillable oils
from the water-immiscible extract by distillation.
13. In a process for the production of adry,
friable insecticidal product from derris and simi
lar insecticidal-containing vegetable sources, the
‘ principles from the vegetable source by means of
steps which comprise extracting the insecticidal
a chlorinated water-immiscible solvent, adding
an anhydrous alkali metal carbonate thereto and
by distillation recovering a distillate oil having
principles from the vegetable source by means of
a speci?c gravity at 25° C. of .998, an optical ro
tation 100 m. m. tube of +5°, a saponi?cation
value of 24, a saponi?cation value after acetyliza
tion of 82.6 and a boiling range 760 m. m. of
21G°-250° C.
'
7. In a process for the production of a dry,
friable insecticidal product from derris and simi
lar insecticidal-containing vegetable sources, the
steps which comprise extracting the insecticidal
principles from the vegetable source by means of
a water-immiscible solvent, adding an aqueous
solution of an alkali metal hydroxid and an
a water-immiscible solvent, subjecting said prin
ciples to a hydrogenating process, adding an
aqueous solution of an alkali 'metal hydroxid
and an aqueous solution of an alkaline earth
carbonate thereto, separating the aqueous solu
tion from the water-immiscible solution, and re
moving practically all of the solvent and distill
able oils from the water-immiscible extract by 35
distillation.
‘
_
14. In a. process for theli’pl‘oduction (if a dry,
friable insecticidal product from derris and simi
lar insecticidal-containing vegetable sources, the
steps which comprise extracting the insecticidal
principles from.- the vegetable source by means
aqueous solution of an alkaline earth carbonate
of a volatile solvent, subjecting said principles to
thereto, removing the aqueous alkali solution of
alkali soluble materials and by distillation re
45 covering a distillate oil having a speci?c gravity
a hydrogenating process, subjecting the solution
to distillation and recovering a distillate oil hav
ing a speci?c gravity at 25° C. of .998, an optical
at 25° C. of .998, an optical rotation 100 m. m.
tube of +5”, a saponi?cation value of 24, a sa
poni?cation value after acetylization of 92.6 and
a boiling range 760 m. m. of 210°-250° C.
3. As a new compound, the oil obtainable from
50
an extract of derris and similar vegetable sources,
the oil having the speci?c gravity at 25° C. of .998,
rotation 100 m. m. tube or" +5", a saponi?cation
value of 24, a saponi?cation value after acetyliza
tion of 82.6 and’ a boiling range of 760 m. m. of
210°-259° C.
15. In a process for-‘the production of a dry, 50
friable insecticidal product from derris and simi
lar insecticidal-containing vegetable sources, the
an optical rotation 109 m. m. of +5", a saponi
steps which comprise extracting the insecticidal
?cation value of 24, a saponi?cation value after
principles from the vegetable source by means of
acetylization of 82.5 and a boiling range 9'60 m. m.
of 210°-250° C.
9. As a new product having insect repelling
properties, a mixture of petroleum hydrocarbons
and the oil obtainable from an extract of derris
and similar vegetable sources, the oil having the
speci?c gravity at 25° C. of .999, an optical
a water-immiscible solvent, subjecting said prin
rotation of 100 in. m. of +5°, a saponiflcation
'value of 24, a saponi?cation value after acetyliza
tion of 82.6 and a boiling range "Z60 in. m. of
65 210°-25ll° C.
10. As a new product having insect repelling
properties, a mixture of petrolatum and the oil
‘obtainable from an extract of derris and similar
vegetable sources, the oil having the speci?c
gravity at 25° C. of .998, an optical rotation 109
in. m. of +5°, a saponi?cation valueoi' 24, a
saponi?cation value after acetylization of 82.6
and a boiling range 760 m. m. of 2l0°-250° C.
ll. In a process for the production of a dry,
friable insecticidal product from derris and simi
55
ciples to a hydrogenating process, adding an
aqueous solution of an alkali metal hydroxid
thereto, removing the aqueous alkali solution of
alkali soluble materials and by distillation re
covering a distillate oil having a speci?c gravity 60
at 25° C. of .998, an optical rotation 100 m. in.
tube of +5°, a saponi?cation value of 24, a
saponi?cation value after acetylization of 82.6
and a boiling range 760 m. m. of 210°-250° C.
316. In a process for the production of a dry, 65
friable insecticidal product from derris and simi
lar insecticidal-containing vegetable sources, the
steps which comprise extracting the insecticidal
principles from the vegetable source by means of
a water-immiscible solvent, subjecting said prin 70
ciples to a hydrogenating process, adding an
anhydrous alkali metal carbonate thereto and
by distillation recovering a distillate oil having a
speci?c gravity at 25° C. oi‘.998, an optical ro
tation 100 m. in. tube of +5°, a saponi?cation
4
2,128,854
value of 24, a saponification value after acetyliza
tion of 82.6 and a boiling range ‘760 m. m. of
210°-250° C.
17. In a process for the production of a dry,
friable insecticidal product from derris and simi
' liar insecticidal-containing vegetable sources, the
steps which comprise extracting the insecticidal
principles from the vegetable source by means of_
,a water-immiscible solvent, subjecting said prin
l0 ciples to a hydrogenating process, adding an
aqueous solution of an alkali metal hydroxid and
an aqueous solution of an alkaline earth carbon
ate thereto, removing the aqueous alkali solu
tion of alkali soluble materials and by distillation
recovering a distillate oil having a specific grav
ity of 25° C. of .998, an optical rotation 100
m. m. tube of +5", a saponi?cation value of 24,
a saponifioation value after acetylization of 82.6
and a boiling range 760 m. m. of 210°-250° C.
ROBERT WOTHERSPOON.
10
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