|Table of Contents|
French patents and German patents
Junior patentees index and assignee index
Insecticidal ingredients, diluents, solvents, stabilizers, etc., used with rotenone products
A list of all patents arranged according to filing dates
STATE PLAN 8OARD
Z- 514 UE October 1940
A3STRACTS OF CENT FOREIGIT AfD D0 STiC P!TE!ITS r EITIZTG TO
DXEPBIS, LOTCEOCAPUS, TENT AD 0 E
(First supplement to E-446)
B R. R oark
In Auguist, 1933, the Bureau of Entcnolog- and Plant c)uarantine
issued mimeographed publication E-446 entitled 1'Abstracts of Foreigna
and Dlomestic Patents Relating to flerris, Lonchiocarr)us, Tephrosia, and
Since that time imany additional patents in th.is field hav been
granted inventors in the United States and abroad, and in order to keep
chemists and entomologists informed of the rapid developments in
rotenone products it seems desirabole to issue a s'!xoleei.t to E-446.
In this supplement, the first of a series to be issued from time to time,
there is included mention of patents jbich refer incidentally to rotenone,
derris, an& cube, and also of patents ,,vhich describe adhesives, wetting
agents, stabilizers, or other adjuvants intended esPecially for use with
rot enone product s.
Readers of this publication vill be intereted in the legal status
of United States reissue patent 18,67 (issued to T. J. Dennis on
N Sovember 22, 1932), which was distracted in -4i.6. On fioveber 6, 1939,
the Supreme Court of the United States refused to revieird the decision of
the United States Circuit Cormt of thppeals for the Seventh Circuit in
Chicago, which had declared this patent to be invalid for lack of origin-
ality on the part of the patptee and for lack of invention over the
ar nMreover, the Peruvian iinstry of Fomento (36) on rebruar 1938,
declared etnis' Peruvian patent 1o. 986 (which was granted hi on
September 15, 1932) null and void because in 1910, namely, 6 years
prior to the granting of the patent, the Goveument of Peru as already
caring on studies with regard to the i-eortance of cube or barbasco
as insecticide or vermifuge, and also the use of this product in powder
form and in the form of extract has been an indust3 freely carried on
in the Republic since remote dates, which clearly established facts show
the absolute lack of originality of the patent in question.
Gol.schmiidt and martinn (18), in British patent 471,153, issued
August 23, 1937, a'lied for February 26, 1936, claim an insecticide
conrising an aromatic isothiocyanate admixed with a pulverulent diluent
or with an insecticide of a different character or with both. '"Mixtures
of aromatic isothiocyanates vith insecticides of a different character,
such as, for exarKle, nicotine, derris extract, or rotenone, have in-
secticieal properties greatly exceeding a mere aggregation; they form
effective liquid insecticides, according to the invention, wthen dissolved
in a solvent or formed into an emulsion, and in this form are *.seful for
s1)ra/ .). The proportion of aromatic isothiocyanate mayr be very small
(cf. Canadian patent 357,959, issued Hlay 19, 1936).
The Lunevale Procucts Ltd. and FitzGibbon (29), in British patent
492,660, issued September 20, 1938, applied for ;arch 20, 1937, claim
the manlfactture of new relatively water-i-asoluble stable complex corapounds
by bringing together in aqueous solution nicotine or a nicotine salt, a
soluble stable copper salt, and a third co-,.ound capable of reacting writh
the cooper salt, the normal e.xpected product of such reaction being
modified by the inclusion of nicotine in a resultant complex body.
The proCucts may be emloyed as such or they may, be made into in-
secticidal and Ligicidal pre-parations by mixing, blending or correci-
itatiing them with or upon or otherwise compounding them ,rith solid
diluents, fillers, or other insecticides and/or fungicides, e.g., lead
arsenate, bordeaux mixture, cuprous oxide, derris preparations, etc.,
or they may instead be mixed with a liquid diluent or dispersing agent
which itself may have insecticidal and/or fungicidal properties.
The I. G. '.arbenindustrie A.-G. (24), in British patent 493,764,
issued October 10, 1933, aPiT,lied for April 9, 1937, in Gerr.any April 11,
1936, claims an insecticide coprising in aexixture a diazoariino com-
pound free from sulphonic acid groups and carbo:xl groups, and a solid
inert substance and/or a vretting agent and/or an ad:iering agent.
i-.in:tures with :no .m contact poisons, for instance derris, may be prepared.
:he Taamlooze e7.nootschap Che~nische Fabrie: Servo and ozenbroek
(32), in Dritish patent 501,801, Iss!.ed 2.e!ru.a- 27, 1939, applied for
Au'.st 25, 1D37, in Holland >- s" 23, 19C3, clai.i a preparation for
co:batinr -lant e-iseases, con-prisin- a sulphonatee. ester derived from
an acid of boron or inos-)horus and a hydroxy compound of high molecular
weight together with an insecticide of the class nicotine, rotenone,
derris, ad like vegetable insecticides.
ort e:ua.ple, castor oil fatty acid, about 30 percent of hich is
converted into the bityl-ether, is esterified ',ith glycol in such a way tLht
one hydroxy group of the gl-col remains unesterified. The free hzrdrox T
group is esterified ith phosphoric acid. and subsequently sulphonated, and.
the reaction product is made into a solution corresponding to 30 percent
of castor oil fatty acid. T.is productt improves the spreading power of
derris or rotenone.
Ripper (37), in British patent 505,853, issued Hay 18, 1939,
applied Xor November 18, 1937, in Austria November 20, 1935, and April 20,
19xn, claims a poison for destroying insects and other invertebrates con-
prising particles of a toxic substance which is injurious to plants when
applied in normal insecticidal quantities or repellent to insects, the
particles being coated with materials insoluble in water but soluble in
the alimentary tract of the vermin and belonging to the classes of pro-
teins or polysaccharides.
For example, a drug containing rotenone is finely ground and
is then introduced into a suspension of 20 percent of casein and 3 percent
of soap solution. The atomizing of the mass occurs in air of 900. The re-
suiting dust is hardened by a treatment with formaldehyde or another alde-
Other materials used as coatings are cellulose, vegetable pro-
teins, and zein.
Saliaris (38), in French pent 829,338, issued June 20, 1938, ap-
plied for February 18, 1937, claims, an insecticide made by absorbing in
an artificially, prepared colloidal gel the active principles of derris,
cube, and analogous plants and evaporating the solvent. Suitable gels
are those of silica, alumina, a mixture of silica and alumina, oxides of
titanium, and those prepared according to German patent 435,671. Suitable
volatile solvents for the active principles of derris and cube are carbon
tetrachlioride, acetone, ether, chloroform, etc. For ea mple, derris extract
(25 percent active constituents) is dissolved in 20 times its weight of
acetone, and colloidal silica is impregnated nith this solution and the
acetone removed by evaporation.
Saliaris (39), in French patent 829,339, issued June 20, 1938,
applied for Tebrua r 18, 1937, claims a method of suspending or
emulsifyiing in water the constituents of d[erris, cube, or analogous
products by the use of a bodZ- with an active cation, that is to sa,
a salt of certain organic bases, having high emulsifying properties.
Suitable products are the chloride of lauryl-trimet rla'mmonium, and
the salts of the products resulting front the action of the chloride
of oleic acid upon dieth:yldiaminoethane. Examples are (1) derris
powder (rotenone 5 percent) is mixed rith 10 to 40 percent of its
weight of a "sa-rmine"; (2) one part of cube extract (rotenone 25 per-
cent) is added to 10 to 50 parts of the chloride of lauryltrinethyl-
ammonium and emulsified in 40 to 200 parts of water.
The 'Lrperial Chemical Industries Linited (25), in German patent
665,075, issued Septenber 16, 1938, applied for October 29, 1935, in
Great Britain October 29, 1934, make eras ntiaIJy the SaMe claims as in
British patent 446,57a, isrmud April 29, 1936.
Neu (33), assignor to the Deutsche ytdrier,-erke Akt.-Ges., in German
patent 635,216, issued September 20, 1938, applied for June 27, 1935,
claims a mixture of cyclic 2:etones and hydrogenated aromatic hydrocarbons
as a solvent for rotenone, derris extract, or prethr extract in the
preparation of solutions in petroleum distillates or emulsions in water.
For example, 0.5 gram pure rotenone is dissolved in a mixture of 10 cc.
cyclochexanone (of 85 percent ketone content) and 25 cc. octoh.rdro-
phenanthrene, or a mixture of 10 cc. tetrahydronaphthalene and 20 cc.
decahydronaphthalene to w hich is added 60 to 80 cc. of light oil (b. p.
150-2500 C.) in order to obtain a clear solution ,Thich is effective
as a fly spray. In another example 0.5 gram rotenone is dissolved in
10 cc. cyclohexanone and 10 cc. decah-dronaphthalene or hexahydroxylol
and added to 30 grams of a 30 percent aqueous solution of the sodium salt
of a sulphated alcohol (with 8 to 10 carbon atoms). A clear solution is
thus obtained which is useful, when diluted ith i-mter, against cattle
grabs and garden insects. Dihydrorotenone and derris extract can be
similarly used. Other cyclic 1cetones mentioned are cyclopentanone and
Schotte and Gornitz (41), assignor to Schering A.-G., Berlin,
in German patent 671,162, issued February 1, 1939, applied for November 14,
1931, claim a mixture of rotenone and veratrin-containing drugs for
combating caterpillars. In addition to the mortality data obtained in
tests upon ep hroclystia absinthiata (Cl.) and given in United States patent
2,024,392 (see p. 34-36 of E-4a16), tests were made upon cabbage worms
(5th-stage larvae) and 4th-stage larvae of ialacosoma neustria i4th Derris
malacensis extract and powidered cube root, with and withoutt sabadilla seed,
showing the mixtures to be more effective.
3ocmixluhl and Gorr (4), in German patent 675,220, issued iLy 3,
1939, applied for !-Lrch 25, 1934 (addition to 674,488), claim an insecti-
cide consisting of derris, pyrethrum, or similar acting drug and an emul-
sifier without an organic solvent.
Examples are, 10 parts of rotenone are dissolved in 100 parts of
ethoxylated (a) castor oil, (b) oleylalcohol, (c) dodec-lphenol, (d) iso-
octylphenol, or (e) oxhenol-camphan.
In another exanmle 100 parts fine derris powder and 50 parts
ethoxyrlated castor oil are warmed w.rith 500 parts ether, and the ether then
3ochInuhl and Gorr (3), assignors to the I. G. Farbenindustrie
A.-G., in German patent 674,488, issued April 17, 1939, applied for 7arch 9,
1934, claim an insecticide consisting of an extract of derris, pyrethrum, or
similar acting drugs in an organic solvent together rith an ether or ester
of a -olyhydric alcohol as an ernlsifving agent. Exwiples are:
Twenty-five parts of derris extract are dissolved in 100 parts
of a mixture of equal parts of toluene and dioxan plus 3 parts ethoxtlated
'ifteen parts of derris extract are dissolved in 100 parts glycol-
monomethyl ether plus 5 parts ethox;rlated castor oil.
T-relve and 'ive-tenths parts der:-s extract are dissolved in 82.5
parts glyColmonomethyl ether plus 5 parts ethoxqlated oleyl alcohol.,
Twelve and five-tenths arts derris extract are dissolved in 82.5
parts glycolmonomethyl ether with 5 parts ethoxylated doceylphenol.
Twelve and five-tenths parts derris extract are dissolved in 82.5
parts glycolmonomethyl ether plus 5 parts ethonylated iso-octylphenol.
Twelve and five-tenths arts derr's extract are dissolved in 82.5
parts glycolmonomethyl ether plus 5 parts ethoxylated oxyphenylcamphan.
Such solutions can be emulsified in water.
The following are mentioned as solvents for derrs extractives:
Alcohol, benzene, carbon tetrachloride, oils, petroleum.
United States Patents:
McConnell'(31), assignor to Tobacco By-Products and Chemical
Corporation, in United States patent 2,071,171, issues February 16, 1937,
applied for June 15, 1935, claims a fumigating package consisting of a
hermetically sealed metallic receptacle having its vertical side wall scored
to provide knock-outs, and a fLimigant within and only partly filling the
.receptacle, the fumigant consist Ing of a combustible material, an oxygen-
supplying material, and a paraslticide material which will evolve a
parasiticidal vapor during fumigation. There are a number of such
parasiticides, such as, for exa.:le, nicotine, anabasine, pyrethrum, daerris,
naphthalene, thiocyanates, and sulfur. A specific mixture contains about
67 percent dry powdered tobacco, 14 percent anhydrous nicotine of 98 per-
cent purity, and 19 percent sodium nitrate.
.ilson (44), assignor to the Standard Oil Company of Indiana, in
United States patent 2,123,457, issued July 12, 1930, applied for January
16, 1931, claims the method of preventing highly refined viscous petroleum
oils from deteriorating and forming acidic bodies, which comprises dissolv-
ing in said oil a small proportion of an alkylJ amino-phenol in mhich the
allqrl group contains from 1 to 4 carbon atoms.
Suitable inhibitors are ortho-aminophenol, para-aminophenol, para-
methylaminophenol, para-benzylaminophenol, dibutylaminophenol, or 1,2-amino-
naphthol. The quantity of inhibitor added to the oil may vary from about
0.002 percent to 0.2 percent. Usually 0.05 percent will be found effective.
A tree spray in the form of an emulsion base may be pre-,ared by
emulsifying two volumes of oil (technical white oil, sa-bolt viscosity 50-100)
in one volume of water containing about 5 to 10 percent of an emulsif.,ing
agent and a preservative. The emulsifying agent may be glue dextrin,
gum tragacanth, or gum ghatti, and the preservative may be cresylic acid,
formaldehyde, or wood creosote. Insecticides may also be incorporated, such
as rotenone, pyrethrum, nicotine, etc. This concentrate mixed -with 50 to
75 times its volume of water makes a spray suitable for sensitive foliage
and which is particularly effective in controlling codling moth, aphis,
fruit tree scale, and other parasites.
Uotherspoon (45), assignor to Derris, Inc., in United States patent
2,126,054, issued August 16, 1938, applied for April 28, 1934, claims
"as a new product having insect repelling properties, a mixture of petroleum
hydrocarbons -td the oil obtainable from an extract of derris and similar
vegetable sources, the oil having the specific gravity at 250 C. of .998,
an optical rotation of 100 m.m. of 450, a saponificrtion value of 24, a
saponification value after acetylization of 82.6 and a boiling range at 760
m. m. of 2100-2500 C."
:o therspoon states:
"I have found that in the case of derris extract this Viscous property
is due to the presence of a small amount of the solvent used for extraction
and also to the presence of an hitherto undiscovered constituent of derris
root, i.e. essential oil of derris. This essential oil with, or without,
the traces of solvent left in the extract keeps the product in a soft con-
"Proper removal of all, or part, of these materials results in a
product that is readily pulverizable, thereby enhancing its commercial
practicability. * This oil possesses the characteristic odor of
derris root and is responsible for the insect repelling property of
derris products while the insecticide remains undistilled.
"Valuable insect repellent preparations may be prepared with this
oil. For example, an efficient fly and mosquito repellent can be made by
mixing 1/4 of 1 percent oil of derris with 99-3/4 percent of white
Solvents mentioned for extracting the active principles of derris
are ethyl acetate, benzol, acetone, chlorofol, ethylene dichloride, and
0'Xane (3r), in United States Patent 2,127,526, issued Augt.st 23,
1938, applied for August 16, 1934, claims a fungicide or insecticide
composition containing a glyceride oil, an oil-soluble insect poison,
a hydrocarbon distillate, the hydrocarbon components of which are of sub-
stantially uniform molecular size, and an oil-soluble emulsifying agent,
the constituents being present in proportions to yield an unstable dis-
persion in water.
0'Kane states: "In addition, the composition may include substances,
either in solution or in suspension in the oil or other contact agent,
which substances serve as a stomach poisonn for insects. Thus an extract
of derris or of cube may be added to serve as such stomach poison."
A specific example of a composition is as follows:
Corn oil 80
Low boiling petroleum derivative 20
Nicotine (98 percent pure) 2
Dispersing agent 2
"The emulsifying agents emplo-ed are desirable oil-soluble emulsifing
agents, particularly when the contact agent is an oil. Such emulsifying
agents include sulphonated castor oil, sulphonated vegetable or animal
oils in general, triethylamine, potassium oleo-abietate, sodium bisulphide,
etc. These materials render the oil or similar contact agent soluble in
the water, or temporarily dispersible therein."
Goodhue (19), in United States patent 2,129,517, issued September
6, 1938, applied for January 10, 1938, claims an adhesive for plant spray
materials which is noninjurious to plant foliage, comprising a substance
remaining in the fractionating column after the removal of solvent and
pine oil in the stem and solvent process for the production of naval store
products from pine wood. This adhesive is suitable for use with powdered
derris root, powdered cube root, powdered pyrethrum flowers, etc. It does
not accelerate the decomposition of the active insecticidal ingredients in
derris and cube and is not injurious to foliage. This adhesive is preferably
employed when emulsified in water with ammonium caseinate containing an
excess of ammonia, the insecticidal mixture being applied as a spray.
Blount (2), assignor to the Union Oil Company of California, in
United States patent 2,132,013, issued October 4, 1938, applied for July 2,
1934, claims an insecticide comprising rotenone oxime, rotenone hydrazone,
or rotenone phenylhydrazone, and aryl, alkyl, and metallic derivatives of
these. These have some insecticidal value, but in contact with moisture,
such as dew, hydrolyze to reform rotenone. Moreover, 'hen the phenyl-
hydrazone derivatives are used the regenerated phenylhydrazine displays
desirable antioxidant properties for the protection of the regenerated
rotenone. This invention may be stated broadly as residing in supplying
to rotenone a stabilizing agent in any of various forms, such as an added
oxidation inhibitor or retarder, or in a combined form -producing toxic
rotenone derivatives, or in combined forms from which regeneration of the
rotenone will taL-e place in use either with or without the regeneration of
an oxidation retarder or other agent capable of protecting the regenerated
rotenone. Apparently all organic agents employed as oxidation inhibitors
or retarders for other purposes, for example as gum inhibitors for gasoline,
may be used as stabilizing agents. This includes monobenzylparaaminophenol,
and also alpha-terpineol, "vanoline" which is paraphenyl-aminophenol,
pyrogallol, hydroquinone, dibenzyl para-aminophenol, and parahydroxyphenyl-
morpholene. Similarly other agents used as gum inhibitors in gasoline may
be employed, such as tributyl-amine and the organic compounds of the non-
gaseous members of the fifth group of the periodic system having a valence
less than five which includes monoaryl alkyl-, diaryl mono alkyl-,
triaryl- and tria]!nyl arsines and corresponding stibines, bismuthines,
phosphines, and vanadines. Also arsine and stibine oxides such as aryl
and alkyl aryl arsine and stibine oxides and substituted phenyl arsine
oxides like paraethoxy phenyl-arsine and dimethyl phenyl arsine oxides
and other arsenic, antimony, and phosphorus compounds like arsenobenzol,
cyclopentyl phenylstibine, phosphobenzol and the like. These organic
agents all serve to retard and inhibit the oxidation of more or less readily
oxidizable organic compounds, and consccuently are useful for the stated
purpose. This applies to all other of the known oxidation inhibitors
included in this definition, and includes amines and other amino compounds
than those heretofore mentioned.
In preparing stable insecticides containi g rotenone per se by
employment of any one or more of these added agents, the agent is supplied
to the derris root or other form of rotenone in whatever physical form the
insecticide is to be prepared, such as a powder or liquid. For example,
the agent may be dissolved in a volatile solvent such as oil of camhor
sassafrassy, pyridine, safrol, pine oil, "cellosolve" (monoethyl ether
of diethylene glycol) and other solvents or in any other solvent having
the required solvent or common solvent properties. This solution may then
be added in desired quantities to powdered derris root, or rotenone may be
dissolved in the solution, either of these admixtures being then distributed
through an inert powdered base if desired. Thus the rotenone material,
before addition to the inert base, will have been intimately co*j'iiingled with
the oxidation retarder and the rotenone-containing particles thereby suf-
ficiently coated or enclosed to protect the rotenone and. insure that the
full action of the retarder will be exerted upon the rotenone material when
subsequently deposited upon foliage to be treated. Similarly, the solution
of oxidation retarder and rotenone may be enmplo-ed as such or may be intro-
duced into water or spray oils, spray oil emulsions, or other oily bases or
the like through the medium of the common solvents, such as above mentioned,
ice., pine oils, oil of camzpoor sassafrassy, cellosolve and the like, the
resultant liquids to be used as sprays or otherwise as may be desired. Thus
in a mineral spray oil base, such as is well known. in the art, paraphenyl-
aminophenol, as a retarder, rotenone, and .ine oil may be used. Here the
pine oil acts as a common solvent for the rotenone, the retarder, and the
spray oil, and the resultant insecticidal oil may be eprtlo,ed as a spray.
If it be desired to prepare an emulsion, any appropriate soap may be intro-
duced. Preferably, neutral or slightly acidic emulsifying agents will be
employed such as triethanolamine oleate and stearate, or other neutral
emulsifier such as calcium caseinate, and lecithint. In water containing
emulsions of this character the retarder will be effective to stabilize
the rotenone before and after use.
The oximes, hydrazones, and related products resulting from the
chemical union with rotenone according to this invention are such as can be
dissolved in certain volatile solvents. While the oximes or hydrazones are
generally insoluble in the ordinary solvents, such as the pjetroleum oils
used for orchard and garden pest control, they are nevertheless soluble in
solvents such as oil of camphor, sassafrassy, safrol, pine oils, pyridine,
Coleman and Zemba (11), assignor to the Dow Chemical Companr, in
United States patent 2,133,972, issued October 25, 1938, applied for Aug.st
10, 1937, claim a substantially water-free insecticidal spray comprising
a noncorrosive organic solvent having dissolved therein as insecticidal
toxicants a product selected from the class consisting of the extracts of
pyrethrin- and rotenone-bearing plants, and a hyrdroxy-alkyl ether of a
phenol. A hydroxy-alkyl ether of 4- tertiary butyl phenol and a petroleum
distillate are specifically mentioned for use with rotenone. An example of
results against flies, according to the Peet-Grady method., with solutions
containing rotenone is as follows:
A solution of 0.1 percent of rotenoue (melting point 1630 C.) was
prepared by dissolving 0.1 gram of rotenone in 12.5 3raims of carbon tetra-
chloride:and Ciluting to 100 milliliters with the usual petroleum distill3,te.
The carbon tetrachloride i-as emnplo:-ed to serve as a mutual solvent, whereby,
in spite of its relative insolubility, the rotenone 'i-as obtained and
maintained in solution in the hydrocarbon oil. This preparation of
0.1 percent rotenone solution was emplcyed as a base solution to p repare
test compositions containing 0.075, 0.05, 0.025, and 0.01 percent rotenone.
Further test solutions vmre prepared in which the h',-Croxyalkl ethers of
phenols were employed as a mutual solvent for both rotenone and petroleum
distillate, in which composition such hydroxyalkyl ethers were found to servo
both as toxicants and as solubilizin- agents. Such solutions vere prepared
by first dissolving the desired amount of rotenone in the h droxyalkyl
ether product and thereafter adding the petroleum distillate thereto. As
the mortality, of flies sprayed with rotenone solutions did not reach a con-
stant value for a period of approximately 72 hours following the spraying
operation, all flies sprayed in this series of experiments were examined
at 24-, 48, and 72-hour periods to deterninie the r.iortality, resulting; from
such treatment. The follovinL results are representative of those obtained
with compositions containing between 0.01 and 0.075 --ercent of rotenone
and from 1 to 3 percent of various hydro:y-alkrl ether compounds.
Average iean mortality in --
Material and concentration in 10 24 48 72
minutes hours hours hours
Percent Percent Percent Percent
0.015o of rotenone 75 7 18 25
0.0255 of rotenone 76 8.6 25.2 37.5
0.0.j of rotenone 8n 11 42.3
0.075% of rotenone 89 --- 41 73.2
0.25% of' rotenone +S of
of 4l-tertiary-butyl-,phenol 93 25 72 79.2
0.05% of rotenone+ 07 of beta-
hydroxy-ethyl ether of -
tertiay-butyl-phenol 97 28 74 88.2
0.075% of rotenone+ 3% of
beta-hydroxy-ethyl ether of
4-tertiary-butyl-phenol 99 34 72.6 92.2
0.0110 of rotenone + 3% of beta-
hydrox-ethyl ether of 2-c;-clo-
hexyl-phenol 81 31.3 52 56.6
PAF~ LANT BOAR
- 10 -
Material and concentration
Nean mortality in --
Percent Percent Percent
0.025% of rotenone + 3% of beta-
hycroxy-ethyl ether of 2 cyclo-
0.05; of rotenone + 3% of beta-
hydroxy-ethyl ether of 2-cyclo-
Simultaneous runs with 3-percent solutions of the beta-hydroxy-ethy1
ethers of 4-tertiary-butyl-phenol and 2-cyclo-hexyl-phenol gave the follow-
iiaterial and concentration
Mean mortality in --
Percent Percent Percent Percent
3% beta-hydroxy-ethyl ether
.3% beta-hydroxy-ethyl ether
Another series of tests showed conclusively that the addition
of the hydroxy-alkJ.l ethers to petroleum distillate solutions of pyrethrin
and rotenone appreciablyr increased their "knockdoim" rate. That is to
say, the combination of materials accomplished a more speedy control of
flies sprayed therewith.
These hydroxy-alkyl ethers of phenols stabilize solutions of
pyrethrins and rotenone against deco. position by light. results with
roteno .e were as follows:
- II -
Average !.ean mortality, in --
.aterial and concentration knockdtwn
in 10 24 48 72
minutes hours hours hours
Percent Percent Pe'cent Percent
Official control insecticide 100 49.7 51 51.6
Official control insecticide
after exposure to sunliht
for 12 cars 93 21 23.6 26.3
0.1% rotenone 92 15.6 48.3 75.6
0.1% rotenone after exposure
to sunlight for 12 days 42 6 8 11.3
0.1% rotenone + 3% beta-hyjdroxy-
ethyl ether of 4-tertiar-butyl-
phenol 98 35.3 93 99.3
0.1% rotenone + 3% beta-hciroxy-
ethyl ether of 4-tertiary-butyl-
lheol after exposure to sunlight 9.3 84.3 93
or 12 days
Schotte and G'rnitz (40), assignors to Schering-X ahlbaum A.-G., Berlin,
in the United States patent 0,133,868, issued Ioveniber 15, 1933, applied for
December 12, 1933, in Germany June 30, 1932, claim as an insecticide a
finely divided mixture, solidified from the molten state, of an insecticidal
vegetable material and a carrier substance, the said carrier substance being
solid at ordinary temperatures, but melting below carbonization temperatures
of said vegetable material aad in its molten state being capable of ex-
tracting the active insecticide from said insecticidal vegetable material.
*or example, derris root is mixed with molten naphthol in the
proportion of 3:5, and the solid mixture is ground with a suitable dilut-
ing agent, such as talc. The product is highly efficient against cater-
pillars and possesses also funmicidal properties.
Comparative tests each ma!C'e with 50 caterpillars of Lii:aris monacha
(5th stage), 20 kgs. being distributed on 2.5 acres, gave the following
A. Mixture of 80 percent of an inert powder and 20 percent
of derris root
Killed Killed Feeding
after after condition
7 dayrs 8 days
Test 1 20 30 Strong
Test 2 22 33 Strong
Test 3 15 30 Strong
- 12 -
B. ilixture of 80 percent of an inert powder and 20 percent
of the derris-root-naphthol mixture
Killed Killed Feeding
after after condition
7 days 8 days
Test 4 32 39 teak
Test 5 33 41 Not feeding
Test 6 29 35 Wfeak
Another example is, equal parts pyrethrum blossoms and derris root
are mixed with molten naphthalene in the proportion of 3:5 and the mixture
ground with alumina. In place of naphthalene or naphthol the following
may be used: Sodium acetate, borax, carbazole, thinnol, isothnymol, and
cxude anthracene. iiolten aliphatic, alicyclic, or cyclic hydrocarbons,
terpenes, and inorganic salts such as crystallized sodium sulphate may be
used. The insecticides such as obtained according to the present inven-
tion may also be combined with other insecticidal substances, such as
arsenic compounds, or with fungicides, such as copper compounds, and w ith
adhesives, such as lime-soaps, or fillers, such as talc, alumina, china
clay, bole, and the like. When using them for spraying purposes it is
useful to add Txrkey red oil or other salts of sulphonic acids.
Sibley (42), assig-nor to the Monsanto Chemical Company, in United
States patent 2,130,516, issued November 29, 1938, applied for October 16,
1936, claims an insecticide having as an active ingredient a material
selected from the class consisting in rotenone and p-rethrum compositions
and a preservative thereof selected from the class consisting in diaryl
arylene diamines, aldehyde derivatives thereof, and the product obtained
by reacting a diarl arylene diamine with an aldehyde and an alcohol.
Specific examples of diaryl ar ,lene diamines ,which may be used
successfully as stabilizers of the toxicity effect of rotenone and pyrethrum
insecticides are diphenyl p-phenylene diamine, di-phenyl m-phenylene diamine,
diphenyl o-phenylene diamine, li-alpha and beta-naphthyl o-, m- and p-
phenylene diamine, ditolyl o-, m- and p-phenylene diamine, di-biphenyl o-,
m- and p-phenylene diamine, diphenyl dixylyl and ditolyl benzidine, and di-,
o-, and p-bipheiyl benzidine.
As examples of derivatives of diaryl arylene dianines, which are
ervlo 0ed according to this invention, aldehydes are reacted therewith, and
the alcLehyde amine products so formed emplo-:red as stabilizers of said
rotenone and pyrethrw containing insecticides. Thus formaldehyde, acetal-
dehyde, butyraldehyde, and heptaldehyde are reacted with the diaryl arylene
diamines defined above, and the resultant products employed as stabilizers
of insecticidal preparations comprising rotenone and pyrethrun.
As a further and more 'referred embodiment of the present invention
the diar'rl arylene diamines of the -resent invention and. as above disclosed
are reacted simultaneouslr with an aliphatic aldehyde and an aloohol to
produce exceptionally efficient stabilizers of insecticides containing,
- 13 -
as an active principle, rotenone and pyrethrum and related compounds. Thus
anry one or more of the diary arylene diamines defined above are reacted
simultaneously with an aliphatic aldehyde, for example, formaldehyde,
acetaldehyde, butyraldehyde, heptaldehydo, and analogous aliphatic aldehydes,
and an alcohol, for example, methrl, ethyl, butyl, propyl, amyl, and
analogous alcohols, also benzyl alcohol and. cyclohexanol.
Varying proportions of the preferred class of stabilizers may be em-
ployed. Preferably, however, the quantity emooyed varies from about
0.5 percent to 10.0 percent, based on the weight of the insecticide.
Faloor (13), assignor to Hxmond Paint and Chemical Coiapany, Inc., in
United States patent 2,144,366, issued January 17, 1939, applied for
October 24, 1933, claims an insecticide comprising an easily oxidizable
organic vegetable toxic material of the group consist inu of prrethrum
and rotenone and a phenol of the group consisting of li.-nocol, giaaiacol,
cresol, thyinol, phenol, eugenol, resorcinol, pyrogallol, anCd hydr6quinone
to stabilize the same.
Other materials that may be used as oxidation inhibitors are p-amino-
phenol, aniline, benzidine, di-beta-naphthylamine, diphenylamine, hexa-ethylene
tetramine, alpha-naphthol, beta-naphtbhol, and phenyl alpha-naphthyrilaine.
Hydroquinone is the best oxidation inhibitor, and guaiacol is second best.
The stabilizing compound is added to the extent of 0.0025 to 1.5
percent by weight of the total insecticide.
Solvents that may be used as a vehicle, such as alcohol, acetone,
carbon tetrachloride, ethylene dichloride, neutral petroleum oil, kerosene,
gasolene, mineral spirits, etc., or mixtures of tro or more of these
solvents, vary in their respective abilities to Cdisperse the inhibitor or
negative catalyst used in any instance so that different proportions of
any particular catalyst are necessary with different vehicles. Acetone,
for example, which may contain some moisture, requires more negative
catalyst to inhibit oxidation than a vehicle of alcohol. Vehicles con-
taining sulphonated oils or moisture require larger proportions of in-
hibitors than those not having these ingredients therein.
Examples of suitable compositions are:
Composition No. 2 Percent by
Derris ....................................... 3.00
Beta naphthol ................................ .003
Ethylene dichloride .......................... 2.00
Alcohol ...................................... 94.97
Composition No. 3. weight
Pyrethr e. 1.2
Rotenone ................................ 1.0
Carbon tetrachloride..................... 1.0
Comnosition No. 5 Percent by
We i ht
Derris ................................. 2.5
Guaiacol ................................ 025
Alcohol ................................ 97.475
Faloon (14), assignor to Tjamniond Paint and Chemical Conpan, Inc in
United States patent 2,144,367, issued January 17, 1939, applied for
October 24, 1933, divided and this publication Eay 14, 1938, claims an in-
secticide comprising a volatile solvent vehicle, an easil- oxidizable
organic vegetable toxic material of the group conisistin.- of pyrethrum
and rotenone dissolved therein, and a naphthol o_' the grou- consisting
of alpha naphthol and beta naphthol to stabilize the same.
The amount of inhibitor added varies from 0.05 to 1.5 percent br
weight of the total combination.
An example is:
Percent by weight
Derris ....................... 3.00
Beta-nanhthol ................ .003
Ethylene dichloride .......... 2.00
Alcohol ...................... 94.97
Faloon (15), assignor to Hammond Paint and Chemical Company, Inc., in
United States patent 2,144,368, issued January 17, 1939, applied for i-la, 14,
1938, claims an insecticide coliprising an easily oxidizable organic vegetable
toxic material of the group consisting of pyrethrum and rotenone and rnhthl-
amine to stabilize the same.
Some of the naphthylamines and derivatives V Aich have been found
satisfactory as oxidation inhibitors or negative catalysts in the present
process are naphthylamine, phenyl alpha-naphthnlamizie, an(! di-beta-
The amount of inhibitor added may vary from 0.05 to 1.5 percent by
weight of the total composition.
Faloon (16), assignor to Hamialond Paint and Chemical CompaTnr, Inc.,
in United States patent 2,144, 369, issued January 17, 1939, ap lied for
May 14, 1938, claims an insecticide comprising an easily ox-idizable organic
- 15 -
vegetable toxic material of the group consisting of pyrethrum and rotenone
and an aromatic amine of the group consisting of dirhenyltmine and
benzidine, Hexamethylenetetramine and para-auinophenol are also suitable.
The solvents used and the amount of oxidation inhibitor added are
the same as described in previous patents by Faloon (United States 7-
Goo hue (21), in United States patent 2,1V6,257, issued ?ebruary 7,
1939, applied for September 23, 1938, claims an adhsive for insecticides
comprising the reaction -products of furfural with aromatic amines of
the group consisting of beta-naphthyl-amine, aniline, and. 9-toluidine.
This adhesive can be used to prevent the removal of spraed or d-ulsted.
insecticides and fungicides from plants by rain, wind, or a combiLation of
these factors. More particularly this invention relates to a grcup of
chemical compounds or mixtures thereof, which, althomh nonadhesive when
applied to plants with the insecticide, become adhesive, resinous, tack,-,
and insoluble in water after exposure to sunlight. This invention can
be used with spray insecticides, but it is especially adapted for use with
insecticides applied in the form of a dust. One advantage of this adhesive
is that any amount of the material may be incorporated without materially
changing the physical properties of the dust. Another advantage is th.at
no dependence need be placed on moisture to cause the material to act as
an adhesive. And still another advantage lies in the stora-e of sich
dusts containing the adhesive, since it is easy to protect the material
from light in inexpensive bags, thus eliminating the difficulties cbae to
caking when adhesives sensitive to moisture are used.
Several methods of incorporation with the insecticide may be used.
For use with dusts simple mixing of the dry powdered light-sensitive
compound with the insecticides gives good results. A better practice,
however, is to grind the insecticide with the adhesive in a ball mill
or other effective grinding machine. A still better but more complicated
method of incorporation is to add. the light-sensitive adhesive to the Cry
insecticide in the form of a solution in water or organic solvents. After
removal of the solvent the adhesive and insecticide mi:--tdre is pulverized
before dusting. An amount of adhesive equal to from 5 to 25 percent of the
weight of the insecticide is recommended.
Xor use with spray insecticides, the light-sensitive co ..position
may be dissolved in the water or added in the form of a suspension, depend-
ing on Ithe solubility of the substance to be used as the adhesive. This
adhesive is effective when used. with powdered derris.
Goodhue (20), in United. States -oatent 2,14.3,253, issued Tebruary 7,
1939, applied for September 26, 1938, claims an adhesive for insecticides
comprising the reaction products of furfural wit',hetones of the group
consisting of acetone, methylethyl-ketone, acetophenone, benzophenone and
2-naphthyl ketone. The properties and uses of this aCJdiesive are similar
to those of the products described in United States patent 2,146,257.
This adhesive is effective when used with powdered derris.
7 6 -r
Kilgore (23), assignor to the Kilgore Development Corporation in
United States patent 2,149,917, issued 14arch 7, 1939, applied for April
24, 1936, claims a process which comprises ithe extraction of rotenone and
other compounds having insecticidal properties front rotenone-bearing plants
by means of an ester belonging to the class of organic compounds known as
delta-epsilon-unsaturated-alpha-gamma-diketo carboxylic esters of the
wherein R, and R2 are the same or different organic radicals or
respectively one organic radical and one hydrogen atom, R4 is an alkqrl
radical or a hydrogen atom, and R3 is any organic radical forming an
ester of the carboxyl group.
Not only do these esters effectively extract rotenone from such
plants but they carry the extracted rotenone into solution in sprayable
vehicles such as hydrocarbon solvents, thus effecting a direct transfer
of the rotenone from the plant to the final insecticide solution.
The following are examples:
One part of a dry, powdered derris root containing 5 percent of
rotenone is intimately admixed wvith four parts by weight of mesityl oxide
oxalate, n-butyl ester,
,C=CH-CO-CH -C0-COOC H
/1 2 4 9
The paste formed by this mixture is then heated at ap:proximately
1000 C. for an hour and the solvent removed. The extract so obtained has
a. red-yellow color and contains approximately 0.8 percent rotenone.
These extractions are suitably made between 300 and 2000 C., the use
of materially higher temperatures causing decomosition of the solvent.
It is frequently advisable to make these extractions in an inert atmosphere,
such as nitrogen or carbon dioxide, especially when a more elevated
temperature is used, in order to prevent excessive coloration.
One part of dry, powdered root of Derris elli-otica containing 5
percent of rotenone is mixed with five Darts of mesityl oxide oxalate,
n-butyl ester. This mixture is then heated to 1500 C. for half an hour in
an atmosphere of nitrogen. The solvent containing the extracted rotenone
is then removed from the mixture.
- 17 -
One part of dry, powdered root of D. elliiptica containing 5 per-
oent of rotenone is mixed with five parts of mesityl oxide oxalate, n-butyl
ester. This mixture is then heated to l5d C. for half an hour in an
atmosphere of carbon dioxide. The solvent containing the extracted rotenone
is then removed from the mixture.
Four parts of powdered root of D. elliptica containing 5 percent
of rotenone are macerated ,,ith five parts by weight of ethyl-3-methyl-3-
n-C M-CH-COCH COOC H
?2 2 5
and treated as in Example I. The resulting extract was of a deep straw-
yellow color which formed an almost colorless solution in kerosene.
A 4 percent solution is then made by diluting 1 part of the extract
with 24 parts by volume of a suitable carrier, as kerosene. This diluted
solution now contains, in addition to the insecticidal properties of the
solvent ester, those of the rotenone, and any other insecticidal sub-
stances so extracted from the plants. This solution is a finished in-
secticide having desirable concomitant physical properties, such as absence
of undesirable odor, little or no color, and good atomization properties.
The examples that follow show the extraction of rotenone from suit-
able plant materials now used commercially as a source of rotenone, and the
consequent production of a new composition having strong insecticidal
The extracts used in the work reported here are made by forming
a paste or heavy dispersion of the powdered plant materials, roots, in the
ester wherein 10 parts of the root are admixed with 25 parts by weight of
the ester. This mixture is then heated at 1000 C. for 1 hour. The extract
is removed by filtration, yielding in most oases extracts having straw%--
yellow to brown-red color. Four-percent solutions of each of the extracts
are then made, using a deodorized kerosene solvent suitable for insecticidal
tests and filtered whenever necessary. The insecticidal effects of these
solutions are then compared with that of similar concentrations of the esters
alone by bio-assays using house flies under identical controlled conditions.
The results of these tests are shown in Table 1. "
The bio-assys were made by using 5-day-old houseflies (i'-usca
domestica). The flies were caged in 5 x 5 inch, cylindrical, all-wire
cages, approximately 100 flies to the cage. Each cage was separately ex-
posed to the same amount of finely atomized spray or fog from wich the
larger droplets had been removed. This was accomplished by using an L-
shaped pipe, 6 inches in diameter and. 1 foot long on each side of the elbow,
- Ids -
mounted with one side of the L in a vertical position. The cage of flies
was then suspended in the top of the upright pipe, and the atomizer was
placed at the other end of the L. Five cubic centimeters of the diluted
ester of the extract was then atomized into the pipe at the bottom end,
producing a highly dispersed, smokelike fog, which was driven evenly
throughout the cage containing flies. The cage of flies so exposed to the
atomized insecticide was then removed and set aside for 24 hours, when the
number of "dead" was determined. "Dead" here included those flies which
were paralyzed and unable to feed after 24 hours. This is a common prac-
tice in rotenone bio-assays.
In addition to the abo,-e bio-assays showing that rotenone is removed
from rotenone-bearing plants by extraction with the esters which are shown
herein, the colorimetric method of Rogers and Calaunari showed strong posi-
tive tests for rotenone in each case, showing that rotenone had been carried
into solution in the finished insecticide.
Biological record showing increase in the kill of f'lies due to insecticidal
material extracted from rotenone-bearing plants b;" the esters.
Esters used as extractants Percent killed by --
Pure Ester and
A. Derris root extractions only rotenone
1 Mesityl oxide oxalate, ethyl ester 9 100
2 1esityl oxide oxalate, n-butyl ester 30 100
3 Ilesityl oxalate, iso-butyl ester 16 100
4 1esityl oxide oxalate, sec.-amyl ester 53 100
5 4iesityl oxide oxalate, cyclohoxyl ester 17 100
6 ljesityl oxide oxalate, tetrahydrofurfurJl ester 4 85
7 Acetalacetone oxalate, n-butyl ester 80 100
8 n-Butyralacetone oxalate, ethyl ester 6 95
9 3-iethyl-3-pentene-2-one-oxalate, ethyl ester 45 85
10 3-iethyl-3-heptene-2-one-oxalate, ethyl ester 2 100
11 Tetrahydroacetophenone oxalate, ethyl ester 4 98
B. Cracca virginiana root extraction
12 i-lesityl oxide oxalate, n-butyl ester 30 67
C. Cube root extraction
13 ivbeityl oxide oxalate, n-butyl ester 30 62
Suitable esters for use in this process are the following* Mesityl
oxide oxalate, ethyl ester; mesityl oxide oxalate, n-butyl ester; mesityl
oxide oxalate, iso-butyl ester; mesityl oxide oxalate, sec.-amyl ester;
mesityl oxide oxalate, cycloheyrl ester; mosityl oxide oxalate, tetrahydro-
furfuryl ester; acetalacetone oxalate, n-butyl ester; n-butyralacetone
oxalate, ethyl ester; 3-mothyl-3-pentono-2-one oxalate, ethyl ester: 3-
methyl-3-heptene-2-one oxalate, ethyl ester; tetrahydroacetophonone oxalate,
- 19 -
Christmann and Jayne (10), assignors to American Cyanamid Company,
in United States patent 2,151,651, issued IMarch 21, 1939, allied for
November 18, 1932, claim rotenone containing a stabilizer selected from a
class consisting of aminophenols, dichloroaniline, salicylic acid, and
The stabilizer material may be incorporated in the rotenono in
substantially any desired or convenient manner. For example, the rotenone
may be dissolved in a solvent, such as acetone, which is also a solvent for
most of the stabilizers, and then the stabilizer may be incorporated therein.
quite satisfactory results are obtained by the use of an acetone solution
containing 0.3 percent of rotenone and 0.1 to 0.3 gram of any of the above
indicated stabilizers per 100 cubic centimeters of solution. Other solvents
or mixtures of these solvents with acetone may likewise bc employed.
Other compounds suitable for stabilizing rotenone, especiall when
it is used for mothproofing fabrics, a e methyl- and ethyl-chloro-anilines,
dichloroaniline, mono- and dichioro-anthranilic acids, pol.yhdroxy phenols
polyamino compounds, and mixed hydroxy-amino, kydroxy-carboxy, and amino-
Nitro substituted phenolic amino compounds may be used. A mixture
of 2.5-dichloro-aniline with oloic acid is pcorticularly satisfactory.
:.iarsico (30), in United States paont 2,150,241, issued !ay 18,
1939, applied for June 18, 1936, claims in an insecticide a rotenone
solution consisting of coniercially pure (90 percent) rotenone dissolved
in chloroform liniment in about the proportions of 1 gram of rotenone to 40
cc. of chloroform liniment, the chloroform liniment being composed of about
30 percent chloroform and about 70 percent camphor soap liniment, and the
comphor soap liniment being composed of hard soap, camphor oil, oil of
Rosbmary, alcohol, and distilled water in the proportions of hard soap 60
gr., cruiphor oil 45 gr., oil of Rosemary 10 cc., alcohol 700 cc., and suf-
ficient distilled water to make 1,000 cc. of the camphor soap liniment. A
pyrethrin solution is similarly prepared (2 ounces of flowers to 400 cc.
of chloroform liniment). Solutions are also made of copper sulphate in
water (2 ounces to 500 cc.) and green soap in water (1 ounce to 200 cc.).
The above described rotenone, pyrethrin copper sulphate, and green soap
solutions are then mixed together and added to pine oil and commercially
pure or 90-percent nicotine, in the proportions of substantially 20
percent of rotenone solution, 20 percent of pyrethrin solution, 10 percent
pine oil, 15 percent green soap solution, 30 percent nicotine, and 5 percent
copper sulphate solution.
WWhile the rotenone solution, pyrethrin solution, nicotine,
and copper sulphate solution are individually very effective
poisons, I have found that they are rendered com.paratively
ineffective when highly diluted in water for sprayring
purposes unless all of them are omlored together and in
substantially the proportions set forth above. At the same
- 20 -
time) the simultaneous use of all of these poisons, or
active ingredients naturally. widens the range of use and,
effectiveness of the insecticide as regact.s the kind of
insects which may be destroyed thereby."
Thompson- (43), assignor to Hercules Po,!der Co., in United States
patent 2,16O4S- issued May 30, 1939, applied for April 28, 1937, claims
an insecticidal composition comprising an additive ether of a.terpene and
an alcohol, a contact insecticide extracted from a plant body, an& a carrier
Claim is alo zde for an insecticidal composition comprising an additive
ether of-a terpene and an alcohol, and a powdered plant insecticidal
material. Suitable toxic materials for addition to the teroene ether are,
for example, the active principles of pyrethrum or of rotenone-bearing
plants; nicotine; nicotine compounds, as nicotine sulfate, etc.; aliphatic
According to Thompson, mixtures of terpene ethers with certain
other insecticidal materials have far greater tomic action on insects than
that of either comp rtof the mixture alone; also certain of the terpene
ethers have a definite action in preventing the deterioration of other
insecticides, such as, for example, the active principles of pyrethrum and of
rotenone-bearing plants, etc., and prolor$ing their useful life.
The terpene ethers used in the compositions in accordance with
this invention are characterized by containing an ether linkage connecting
a terpenic group with another group, and may be prepared in either of two
ways. They may be prepared by the etherification of the hydroxyl group of
a terpene alcohol with another alcohol, or they may be prepared by the
direct addition of an alcohol to a double bond of an unsaturated terpene
compound. The latter type ethers will, for convenience, be termed additivesl
terpene ethers. The alcohol used as the etherifyingagent may, in either
method, be a monohydric alcohol or a poly!hdric alcohol. The monohydric
alcohol may be, for example, methyl alcohol, ethyl alcohol, propyl alcohol,
butylalcnhol-i aryl alcohol, ethylene glycol monethyl ether, ethylene
glycol monobutyl ether, ciethylone glycol monethyl ether, etc. The poly-
hydric alcohol may be, for example, ethylene glycol, diethylene glycol,
The terpene alcohol used to prepare a terpene ether by the
etherification of its hydroxyl group may be any terpene alcohol having a
reactive hydroxyl group, such as, for example, alpha terpineol, b6rneol,
fenchyl alcohol, etc. Crude terpene cuts rich in terpene alcohols may
likewise be etherified. Such ethers may be readily prepared by well-known
The unsaturated terpene compound used to prepare" a terpene ether
by the addition of an alcohol at a double bond may be, for example, alpha
pinene, nopinene, diDentene, te rinene, tex-pinolene, phellandrene)
sylvestrene, alpha~terpineol, beta terpineol, carene, cvniphene, bornylene,
etc. These terpene compounds do not need to be in pure form, but may
be reacted in the form of a crude mixture. Thus, in place of the several
pure terpene compounds, crude natural mixtures, as for example, turpentine,
pine oil, etc., or crude fractions of the -iixtures may be reacted without
the necessity of isolating the resulting ethers in their pure state,
.-. 21 -
for use in the insecticidal compositions in accoreAnce with this invention.
The resulting mixtures of terpene ethers may br, and from the standpoint of
econorr will desirably be, liselt per se in thee insecticidal compositions.
here herein a terpene ether is specified, it will be understood to mean
either a pure conound or a mn.inture preparxd froia a mied terpene fraction.
:Specific compositions comprise the acditivo ether of ethylene
glycol and turpentine, rotenone, and a carrier; also the additive ether
of ethylene glycol and turpentine and powdereI derris root.
A highly active insecticidal d.st may be prepared in accordance
with this invention. Such a dust will comprise a terpene ether in-
corporated into a powdered insecticidal material such as, for example,
ground pyrethrum flowers, powdered derris root, powdered cube, etc.
Faloon (17), assignor to 2Hammond Paint and Chemical Co., Inc., in
United States patent 2,168,064, issued ugast 1, 1939, applied for
June 11, 1935, claims an insecticid a co Dmosition having asprincipal
toxic ingredients powdered organic plant material from a group con-
sisting of derris, cube, or pyrethrum coated with a light-reflecting
pigment in sufficient quantity to inhibit the loss of toxic principles
Of said insecticide when exposed to lig!it, such pigment being selected
from a group consisting of titanium oxide, titanated lithopone, and zinc
The light-reflecting substances particularly applicable as an
ingredient of commercial insecticides are, preferably, titanium-
containing compounds such as titanium oxide, calcium titanox, barium
titanox and titanatad lithopones, antimony oxide, lithopone-zinc sulphide,
zinc oxide, highly calcined gypsum, and barium sulphate.
Typical formulae for the novel inseeticides are the following:
Formula A F-percent rotenone-bearing root (ground), 15 percent; or
pyrethrum powder, 25 percent; titanium oxide base pigment, 12 percent;
kaolin or other inert material, 63 to 73 percent.
Titanium oxide base pigment consist primarily of titanium oxide
in combination with barium sulphate cr a calcium base, and, while the
above percentage of this substance is preferred, the percentage may vary
with reasonable limits. For instance, the titanium oxide base pigment
may be increased to 20 percent, with a proportional reCduction ia the
percentage cf inert carriers. In the place of the titaim oxide base
pigment, tit',nium oxide alone may be employed, or there may be a mixture
of the base pigment and the oxide.
Other formulae substitute 12 percent of antimony oxide, or 15
percent of lihopone zinc sulphide pigment, or 75 to 85 percent of barium
sulphate or calcined gypsum for the 12 percent of titanium oxide base pig-
mont in Formula A.
Faloon states that pyrethrum and rotenone dusts made according to
Formula, A exert a toxic effect on both the cabbage worm and the bean
beetle for a period 65 percent longer than the active life of untreated
A~.ans and Nikitin -(1), assignor to the trustees of the Crop Pro-.
tection Instttute, in.United States patent 2,172,314, issued September
5, 1939, .applied for October 28, 1935, claim adnsting composition com-
prising a-Oppor fugicidal compouid., a zeolite from the group consisting
of alkali and alkaline earth metal zeolites, and an insecticide fro .the
group consisting of pyrethrum and derris, said zeolite acting to stabilize
the dust and, prevent caking thereof. With a composition containing 10
parts sodium zeolite, 10 parts copper sulphate, 7 parts derris, and 75
parts clay, there was more than 90 percent control of the Mexican bean
beetle, with no copper injury to foliage.
Lind (28), assignor to Lin-Tox Corporation, in United States patent
2,173,849, issued September 26, 1939, applied.for September 4, 1937, claims
an insecticide comprising an aqueous solution of a soap of linseed oil,
fatty acids, and a contact poison.
A typical composition has the following formula: Linseed oil soft
potash soar. (dry basis, 2~,.79 percent; total water, 77.93 percent;
rotenone (e.g., from derris root), 0.07 percent; other derris extractives,
0.21 percent; to al, 160 percent.
The rotecone and other extractives may be obtained by extracting
derris root with acetone or other suitable solvent or extracting agent.
For exrp le, the derris extractives may be used in the form of an acetone
solution containing about 5 percent rotenone, 15 percent other extractives,
and 80 percent acetone. 'If such solution is used as such, the above
for mla would contain about 1.12 percent of acetone in lieu of the same
percentage of water.
For a)lication to exterminate the Japanese beetle, it is diluted
by mixing 1 volume ith 9 volumes of water and applying the diluted solu-
tion with any suitable sprayer, e. g., of the atomizer type.
4n:ther. composition which 'is stated to have a rapid lethal effect
on Japanese beetle contains the following, when diluted ready for uses
Linseed oil soft potash soap (dry basis), 1 percent; rotenone, 0.0035
percent; other derris extractivos, 0.010 percent; nicotine, 0.005 percent.
Bousquat (5), assignor to E. I. du Pont de Nemours cnd Company, in
U. S. patent 2,16E;,119, issued July 18, 1939, a.plied for October 3, 1936,
claims an insecAcidal coriposition containing as an essential toxic in-
gredient a butyl anide of 10,11-undocylenic. acid.
The amide is genicrally, though not necessarily, employed in conjunc-
tion with one or more other liquid, semiliquid, or solid insecticidal or
noninsecticidal substances or carriers, such as a substance of the type
commonly used in formulating insecticidal compoitions. A few such sub'
stances or carriers are mentioned as typical: erosone, gasoline, pyrethr j
derris, talc, thiocyanates, phthalates, and pine oil.
Bousquet and Salzberg (6), assignors to E. I. du Pont de Nemours
and Company, in U. S. patent 2,166,118, issued July 18, 1939, applied for
October 3, 1936, claim an insecticidal composition containing a neutral
- 23 -
carboxylic acid amidoe having a heterocyclic radical and an aliphatic hydro-
carbon residue of at least six carbon atoms.
An example is 4-(10,11-undecylenoyl) morpholine. This aide is
generally, though not necessarily, employed in conjrnction with one or
more other liquid or solid insecticidal or noninsocticidal substances,
such as the type of substances commonly used in formulating insecticidal
compositions. Such substances are numerous, and only the following few are
mentioned as typical: Eerosene, gasoline, pyrethrmm, derris, talc, thio-
cyanatos, phthalates, anA pine oil.
Boyce (7),assignor to the GovernmWnt and People of the United States,
in United States patent 2,191,421, issued February 20, 1940, applied for
December 2, 1937, claims an insectici&l dust comprising as a major con-
stitutent walnut-shell flour Qf smaller particle size than 100 screen mesh
and a relatively small amount of an insecticidal toxicant, selected from
the class consisting of the extracts of rotenone- and pyrethrin-bearing
plants, intimately incorporated therewith.
iWalnut-shell flour of 250-400 screen mesh particle sizc was com-
pounded with cube, derris, and other vegetable products of high rotenone
content. Oompositions containing from 0.5 to 1.0 percent by weight of
rotenone were dusted on insect-infeeted plants and deciduous and citrus trees
at 1 pound per tree. All parts of the dusted trees wore found to be covered
by a uniform deposit of the product, and no injury resulted therefrom. In-
sect pests which these compositions were found to control were the citrus
thrips, the greenhouse thrips, the flower thrips, citrus aphids, and the
Other ligno-cellulosic materials may be employed in finely divided
form substantially as described above in the preparation of insecticidal
dustihg compositions, such as the flour prepared from coconut shells,
pecan shells, Brazil nut shells, peach pits, cherry pits, apricot pits,
olive pits, plum pits, cedar wood and bark, birch, and similar ligno-cellu-
Brubaker (8), assignor to M. I. du Pont do Nemours and Company, in
United States patent 2,098,942, issued November 16, 1937, applied for
June 17, 1936, in Germany June 18, 1935, claims a composition of matter suit-
able for protecting materials against parasitic attack comprising a disper-
sion of a parasiticide in a solution of a salt (e.g., the acetate of deace-
tylated chitin) of a polymeric amino-nitrogen containing body substantially
insoluble in water and in 5 percent aqueous ammonia but soluble in at least
the stoichiometrical amount of 2 percent aqueous acetic acid and capable of
forming a coherent film therefrom.
Any dispersable liquid or solid parasiticide compatible with the salts
of the amino polymer may be used in this invention, for exaile, dorris pow-
Carswell (9), assignor to Monsanto Chemical Company, in United States
patent 2,192,894, issued March 12, 1940, applied for November 23, 1936, claims
insecticidal compositions "containing derivatives of cyclohexylamine, a. g.,
N-amyl-N-benzoyl-cyclohexylamine, which is especially valuable for the
- 24 -
control of lcafhoppers on apple trees and grapevines. Suitable concentra-
tions to use for this i'urj-ose are preparations containing about 0.1 percent
of the amylbenzolcyclohexylamine in an emulsion made with the aid of a
sulfon .ted castor oil or a similar wetting or emulsifying agent. In such
uses the compounds of the invention act similarly to materials such as nice-
tine, pyrethrim, derris, rotenone, and proprietary allphatic thiocyanates
but possess t1je 01stinct advantage over such substances in their toxicit.
Coleman and Zemba (12), assignors to the Dow Chemical Company, in
United St tes patent 2,194,924, issued March 26, 1940, applied for July 2,
1938, claim a substantially water-free insecticidal spray comprising a
noncori-osive organic solvent having dissolved therein a toxicant selected
from the class consisting of the extracts of pyrethrin- and rotenone-bearing
plants, and as an added toxicant a compound selected from the group consist-
ing of the b eta-hydroxy-ethyl ethers of 2.4-diethyl phenol and 4a-secondary-
Hydroxy-alkyl ethers may be mixed with rotenone and the toxicant
mixture dissolved in a petroleum distillate to obtain a spray composition
of increased effectiveness, the hiydroxy-aJkyl ether both increasing the
effectiveness of the composition and serving as a mutual solvent for the
rotenono and petroleum distillate, thereby obviating the use of a co-solvent,
such as carbon tetrachloride, in the composition. The proportions of hbdrox.y-
alkyl ether compounds and of the plant extract can be widely varied, to pro-
duce compositions effective for insect control.
Various solvents may be employed as a carrier for the toxicants in
the above-described coLroositions, depending upon the use for which the com-
positions are intended. For example, if an indoor spray is desired, a readily
volatile solvent is most stuittjble. For outdoor work, e. g., in the spray-
ing of cattle, where it is desirable that the spray residue be retained for
a considerable period of time, a heavier and less volatile oil may be employed.
In case the hydroxy-alkyl ether has a limited solubility in a preferred sol-
vent such as kerosene or naphtha, a mixture of such petroleum distillate with,
for example, methyl-ethyl ketone, or carbon tetrachloride may, be employed.e
Other noncorrosive organic solvents such as benzene, ethylene dichloride,
hydrog:enated naphthalene, butyl alcohol, and the like may be used to dissolve
the hydro.-q-alkyl ether or mixtures thereof with plant extracts, provided only
that such solvent be inert with resoect to the toxicants employed and
noiinjurioun to hmans.
Tests on houseflies by the Peet-Grady method are recorded. A 0.1-percent
solution of rotenone (i.P. 1630 C.) was prepared by dissolving 0.1 gram of
rotenone in 12.5 grams of carbon tetrachloride and diluting to 100 milliliters
with the usual petroleum distillate, the carbon tetrachloride being employed
as a i'auuaJl solvent to hold the rotenone in solution. This solution was
employed as a base solution from which to prepare test compositions containing
0.075, 0.05, 0.025, and 0.01 percent of rotenone. Other test solutions were
prepared In which the hydrox -all 1 ethers were employed as a initual solvent
for both roteaone and potroletum. distillate, the hydrox-r-alkyl ethers serving
both as toxicants and as solubilizing agents. Such solutions were prepared
b> first dissolving the desired amount of rotenone in the hydroxy-alkyl ether
and thereafter addling the petroleum distillate to the mixture. As the mor-
tality of flies sprayed with rotenone solutions did not reach a constant
value for a period of aprximtiely 7r hoiir i'ollowing the sprs.ying opera-
tion, all flies sprayed in this serio of e:peritftOhnt8 were eaxtunine ,- at
24-, 48-, and 72-hour periods to determine the mortality resulting, from sutch
treatment. The folowing results are representative of those obtained. with
compositions Containing between 0.01 and 0.075 percent of rotenoiio vid from
1 to 3 percent of the hyxroxy-lkyl ethers:
Material and concentration
Moan mortality1r in-
24 48 7l
hours hours hours
P e r c e n t
0.01 percent rotenone
0.025 percent rotenone
0.05 percent rotenone
0.075 percent rotenone
3 percent of bpta-hydroxy-ethyl
ether of 4-tortiary-butyl-phenol
2 percent of beta-hydroxy-ethvl
ether of 4-secondary-butyl-phenol
0.025 percent rotenone + 3 percent
of beta-hydroxy-ethyl ether of -4-
0.05-percent rotenone + 3 percent
of beta-hydroxy-ethyl ether
0.075 percent rotenone + 3 percent
of beta-hydroxy-ethyL ether
0.05 percent rotenone 6 2percent
of beta-hydroxy-ethyl ether
28 31 33
25 72 79.2
Tests were made to determine the stabilizing effect
droxy-alkyl ethers upon solutions containing rotenone.
exerted by .y-
Material and concentration
0.1 percent rotenone
0.1 percent rotenone 4 3 per-
cent of beta-hydroxy-ethyl
ether of 4-tertiary-butyl-
0.1 percent.rotenone + 3 per-
cent of beta-h*ydroxy-ethyl
ether of 4-tertiary-butyl-
of dtys knockdoim
to light 10 minutes
"-ean mortality in-
24 48 72
hours hoiirs hours
e r c e n
15.6 48.3 75.6
6 8 11.3
35.3 93 99.3
38.3 84.3 93
Other hydroxcy-alkyl ethers of n17lpienols may be used in the compo-
sitions described in the foregoing examples, e.g., beta-hydroxy-ethl ether
of 4-normal-butyl-phenool beta-hydxoxy-ethyl ether of 4-isobutyl henol; beta-
hydroxy-ethyl ether of 4-normal-amyl-phenol; beta-4droxV-ethy1 ether of 2-
ethyl-4-tertiary-aayl phenol; beta-hydroxy-ethyl ether of 2.4-di-isopropyl-
phenol; beta-..bydroxy-ethyl ether of di-isopropyl-phenol; beta-hydrox-ethyl
ether of 2-ethyl-4-isopropyl-phenol; beta-hydroxy-ethyl ether of 4-normal-
hexy! pbanol; beta-hydro --ethyl ether of 4-secondary-hexyl-phenol; beta-
hydroxy-ethyl ether of 4-tertiary-hexyl-phenol; beta-hydroxy-ethyl ether of
4-heptyl-phenol; hydroxy-propyl ether of 2,4-diethyl-phenol; hydroxy-propyl
ether of 2-methyl-4-isopropyl-phenol; hydroxy-propyl ether of 4-secondary-
butyl-phenol; Ipdroxy-butyl ether of 4 secondary-butyl-phenol; hydroxy-butyl
ether of 2.4-diethyl-phenol; etc.
Hill and Ferguson (22), assignors to Gulf Oil Corporation, in United
States-patent 2,192,347, issued March 5, 1940, anplied for February 1, 1937,
claim an insecticidal spray comprising a mineral oil base, minor quantity
of para.teriary,-amyl-phenol, and an organic secondary solvent in amount
sufficient to hold the para-tertiary-amyl-phenol solution in said base.
Para-&tertiary~emyl-phenol may be used either as the sole toxicant
brin conjunction with other materials having insecticidal properties, such
as butyl carbitol thiocyanate and also pyrethrum extracts, rotenone or
derris extracts, deguelin, tephrosin, and the like. Thus, para-tertiary-
ayl"pheol may be used as a substitute for other and higher priced toxi-
icants or to augment other insecticides, such as those of lower kill power,
including the marc or residue of pyrethrum extracts, in preparing insecti-
cidal sprays, The addition of 2 percent of para-tertiary-amyl-_phenol to a
solUtion of pyretbium-rotenone extract in a kerosene base increases the kill
of the-original insecticide mixture from 45 to 65 percent.
"N A spray containing, by weight, 2 percent paratertiary-amylphenol, 4
percent of a 20:1 pyrethrum-rotenone extract, 1.5 percent dibutylphthalate,
and 93S5 percent [sic3 insecticide naphtha, when tested by the Peet-Grady methd
method, caused a knockdown of 98 percent of the houseflies in 10 minutes, a
kill of68 percent in 24 hours, and 70 percent killed and moribund in 72 hours.
Another spray containing, by weight, 2.5 percent paratertiary-amylphefl
S5 Percent dibutylphthalate, 2 percent of 20:1 derris extract (containing
Totenone ,.deguelin and tephrosin) and, 90.5 percent insecticide naphtha, when
tested by the .Peet-.Grndy method, caused a knockdown of 98 percent in 10 min-
utea, aD.kil of ?0 percent in 24. hours, and 72 percent killed And moribund in
Hockenyos (2-3, assignor to Monsanto Chemical C=ajy, '&*ML
'United States patent 2,197,500, issued Aprillf applied for May?, 193
claims a drT insectiaidal composition which is readily dispersible in water
to form a stable dispersion, comprising an organic insecticide of the rotenome
.-. PYr'OhrU7lM=laas3and & water-soluble salt of a hydroxy substituted aromatiO
4honc acid which is soluble in acetone, said product beim& produced by
tissaolvina a mixtttre of the -insecticide -and -dispersing agent in acetone
and eVap rating aVI4 4olution to dryness.
- 27 -
For example, Aresco and an equal weight of derris or cube resin are
dissolved in acetone.
Certain rubber antioxi&-7nts are cffectiv in overcoming the deterio-
rative influence of light on rctenone. Examples are phenyl-beta-nophthylamine,
phenyl-alph--nahthyl.nine, and the homologwaes thereof.
Tests u.on aphids with derris resin at from 1:4,000 to 1:8,000 with
the addition of Aresco, phenyl-beta-naphtylamine, phenyl-bet-naphthlamine
plus lampblack, oleic acid, anJ oleic acid plus lwnpblnck, are recorded,
from which it is concluded that Aresco has a C-istinct inscfzidal value even
when used in very ilute solutions; that Aresco has a preservPt-ve effect on
the active principle and may be employed advwntrtgeously with the phenolic
amine preservatives; and that the addition of lamrnblack has a favorable
effect in combination with the preservatives.
Knight (27), assignor to Shell Development Company, in United States
patent 2,190,173, issued February' 13, 1.40, a -plied for January 18, 1937,
claims the method of increasing the effectiveness in tree sprry oils of oil-
soluble toxics of the class consisting of nicotine and rotenone, which method
comprises incorporating said. toxics in a mineral oil of about 40 to 100
seconds Sayboldt viscosity at 1000 F., adding to said oil about 1 percent to
5 percent of an emulsifier conrising an hydroxy ester of a high molecular
weight or-anic acid (e.g., gl:ycol mono-olev.te, glycero-mono-oleate or glycero-
di-oleate emulsifying said oil in water in the presence of a small amount
of bentonite whereby oil clusters are formed in the wYater, and spraying said
emulsion on trees.
Bentonite insures a satisfactory emulsion and oil deposit when added
toxic materials, such as cryolite, lead aroente, nicotine, rotenone, or
other toxic materials, are incorporated in the enuilsion. Such added ma-
terials may markedly interfere with proper e.-umlsification -.nd oil deposit in
the absence of a conditioner. However, the beritonite comirosition insures
proper emulsification and protects against inversion, and by causing the
substantially complete deposit of oil it makes oil-soluble toxics such as
rotenone and nicotine even more effective.
Neu (34), assignor to Deutsche Hlydrieriverke A.-G., in United States
patent 2,194,446, issued March 19, 1940, a yplied for June 26, 1936, in
Germany June 26, 1935, claims a pest-destroying aqueous emulsion consisting
of a poison of the group consisting of rotenone, di-hydro-rotenone, pyre-
thrins, pyrethrum and derris-root extracts; cyclo-hexanone; h-drcgenatod
naphthalene; with kerosene as a solvent; a fatty alcohol sulfenate having
eight to ten carbon atords in the molecule as an emulsif--ng agent, and water,
the cyclo-hexanone and hydrogenated naphthalene being present in substantial
proportions and sufficient to produce a clear and lasting solution.
In place of cyclohexanone other cyclic ketones can be used, e.g.,
cyclopentanone, methylcyclohexanone, beta-delalinone. Of the hydrogenated
products of naphthalene the tetrahydronaphthalene and the dekahydronaphithalene
have proved particularly suitable, Acetone, chloroform, and benzine are
mentioned as known solvents for rotenone.
- 28 -
The following are examples: In dissolving 0.5 gram of a 100-percent
rotenone (1630 C.) in 10 cc. of cyclohexanone (bearing 85 percent of ketone)
and in adding 90 cc. of kerosene or a mixture of 10 cc. of tetra-hydro- and
10 of deka-hydro-naphthalene, the rotenone will crystallize out after some time
but by the adOition of a solution of 0.5 gram of rotenone in 10 cc. of
cyclohexanone (85 percent), 10 cc. of tetrahydronaphthalene, 20 cc. of deka- -
hwdro-naphthalene, and 60-80 cc. of kerosene, one obtains a liquid which also
after a long standing remains clear and which is very suitable for combating
flies and gnats.
Also in dissolving 0.5 gram of rotenone in 10 cc. of-cyclohexanone
(85 percentS and 10 cc. of dcka-hydro-naphthalene and in adding 30 grams of
an aqueous 30-percent solution of the sodium salts of the sulfuric acid
esters of fatty alcohols with 8-10 C-atoms, one obtains a lasting, clear,
and transparent solution which, when diluted with water, is particularly
fit for corbating gadfly grubs with pasture animals. The dilution made
with water, and iherein the rotenone is finely suspended, has a milky-
turbid aspect and it scarcely precipitates. This diluted solution is also
an excellnt means to combat the horticulture-&maging pests and doesntt
do ay harm to the plants.
Dihydrorotenone, derris extracts, pyrethrins, and pyrethrum extracts
corn be dissolved in quite the same way as rotenone, when the above prescrip-
tions are followed.
- 29 -
1. ADAMS, J. F., and NIITIN, A. A.
1939. Stable parasiticide. U. S. Patent 2,172,314; issued Septn'.Aber
5, 19.9; applied for October 28, 1935; assigned to "*. C.
0MKane and P. Moore, as trustees for the Crop Protection
2. BLOUNT, A. L.
1938. Insecticide. 13. S. Patent 2,132,015; issued 0ctobor 4, 9.
applied for July 2, 1934; assigned to Union Oil Cc pz : of
Z5. BOC1019YL, M., and GORR., 'G.
1939. SchZ@lingsbekmptunGsmittel. German Patent 674.,480; issued
April 17, 1939; akplied for March 9,. 193; assigned to
I. G. Farbonindustria A.-G.
4. -------- and GORR, G.
1939. Schadlingsbecnpfungsmittel. German P.tent 675,220; issued
Ma 3, 1939; applied for ,.trch 25, 1934; assigned to
I. 0. Parbenindustrie A.-G. (addition to 674,488).
5. BOUSQJJUET, E. W'.
1939. Insecticide. U. S. Patent 2,163,119; issued July 18,
1939; applied for October 3, 1936; assigned to E. I.
du Pont de Nemours & Coqpany.
6. --------- and SALZBG, P. L.
1939. Insecticidal compositions contaiining heterocyclic onmides.
U. S. Patent 2,1663,118; issued July 18, 1939;
for October 3, 1936; assigned to B. I. du Pont do Neimours
7. BOYCE, ALFRED I'.
1940. Dusting composition. U. S. Patent 2,191,421; issued
February 20, 1940; applied for December 2, 1937; assigned
to the Government and the People of the United States of
1937. Protection of materials subject to parasitic -ttfck. U. S.
Patent 2,098,942; issued November 13, 1937; aplied for
June 17, 1936; in Germanr June 18, 1935; assigned to-
S. I. du Pont de Nemours & Companr.
- 30 -
9. OARSWELL, T. S.
1940. Insecticide. U. S. Patent 2,192,894; issued March 12, 1940;
applied for November 23, 1936; assigned to iMlonsanto Chem-
10. CHRISTUAMT, L. J., and JANE, D. W., Jr.
1939. Stabilized rotenone compositions. U. S. Patent 2,151,651;
issued M4arch 21, 1939; applied for November 18, 1932; assigned
to American Cyanamid Company.
11. C0LI-.N, Go H., and ZEIMA, J. W.
1938. Household spray. U. S. Patent 2,133,972; issued October 25,
1938; applied August 10, 1937; assigned to the Dow Chemical
12, -------and ZMA, J. 11.
1940. Spray composition. U. S. Patent 2,194,924; issued March 26,
1940; applied for July 2, 1938; assigned to Dow Chemical
13. PALO0N, D. B.
1939. Oxidation inhibitor for insecticides. U. S. Patent 2,144,366;
issued January 17, 1939; applied for October 24, 1933;
assigned to Hammond Paint & Chemical Company, Inc.
1939. Oxidation inhibitor for insecticides. U. S. Patent 2,144,367;
issued January 17, 1939; applied for October 24, 1933;
assigned to Hammond Paint and Chemical Company, Inc.;
divided and this applica, tion May 14, 1938.
1939. Oxidation inhibitor for insecticides. U. S. Patent 2,144.i368
issued January 17, 1939; applied for May 14, 1938; assigned
to Hammond Paint and Chemical Co., Inc.
1939. Oxidation inhibitor for insecticides. U. S. Patent 2,144,369;
issued January 17, 1939; applied for May 14, 1938; assigned
to Hammond Paint and Chemical Co., Inc.
1939. Insecticide. U. S. Patent 2,168 064; issued August 1 1939;
applied for June 11, 1935; assigned to Hammona Paint and
Chemical Company, Inc.
18. GOIDSCHiIDT, S., and MARTIN, K.
1937. Improvements in or relating to toxic agents, more particularly
insecticides. British Patent 471,1%E3; issued August 26,
1937; applied for February 26, 1936.
19. GOODHUE, L. Do
1938. Adhesive for insecticides and a process for making same. U.S.
Patent 2,i29,517; issued September 6, 1938; applied for
January 10, 1930; dedicated to free use of the People of
the United States of America.
20. --- .
1939. Adhesive for insecticides. U. S. Patent 2,146,258; issued
February 7, 1939; applied September 26, 1938; dedicated
to the free use of the People of the United States of
1939. Adhesive for insecticides. U. S. Patent 2,146,257; issued
February 7, 1939; applied for September 23, 1938; dedicated
to the free use of the People of the United States of
22. HILL, M. L., and FERGUSON, B., Jr.
1940, Insecticide. U" S. Patent 2,192,347; issued March 5, 1940;
applied for February 1, 1937; assigned to Gulf Oil Cor-
23, HOCKENYOS, G. L.
1940. Insecticidal composition and method of preparing the same.
U. S. Patent 2,197,500; issued April 16, 1940; applied
for May 7, 1934; assigned to Monsanto Chemical Company.
24. I. G. FAPBENINDUSTRIE Ali7IGESELLSCHAFT
1938. Improvements relating to insecticides. British patent 493,764;
issued October 10, 1938; applied for April 9, 1937, in
Germany April 11, 1936,
25, II,1PERIAL CHEMICAL IISDUSTRIES LIiM1ITED
1938. Verfahren zur Gewinnung von Rotenon und ibm verwondten
Insekticiden. German Patent 665,076; issued September 16,
1938; applied for October 29, 1935; in Great Britain
October 29, 1934.
- 32 -
26. KILGORE, L. B.
1939. Selective extraction of rotenone by certain esters. U. S.
Patent 2,149,917; issued March 7, 1939; applied for April
24, 1936; assigned to Kilgore Development Corporation.
27. KNIGHT, H.
1940. Oil tree spray. U. S. Patent 2,190,173; issued February
13, 1940; applied for January 18, 1937; assigned to
Shell Development Company.
28. LIND, T.
1939. Insecticide. U. S. Patent 2,173,849; issued September 26,
1939; applied for September 4, 1937; assigned to Lin-!Tox
29. LUNEVALE PRODUCTS LIMITED and FitzGIBBON, M.
1938. Improvements in or relating to the manufacture of complex
nicotine products and of insecticidal and fungicidal
preparations comprising the same. British Patent 492,660;
issued September 20, 1938; applied for March 20, 1937.
30. MARIIC0, S. E.
1939. Insecticide and process of making the same. U. S. Patent
2,158,241; issued May 16, 1939; applied for June 18, 1936.
31. McCONNELL, H. K.
1937. Fumigating package. U. S. Patent 2,071,171; issued February
16, 1937; applied for June 15, 1935; assigned to Tobacco
By-Products and Chemical Corporation.
32. NAAL00ZE VENNOOTSCHAP CEIMISCHE FABRIEK SERVO and ROZEFIIBROSK, M. D.
1939. Improvements in or relating to preparations for combating
plant diseases. British Patent 501,801; issued February
27, 1939; applied for August 26, 1937; in Holland August
33. NEU, R.
1938. Verfahren zur Herstellung von zur Insektenbekampfung
geeigneten Lbsungen des Rotenons, seiner Abkbmmlinge,
der Pyrethrine, der Pyrethrum- odor Derriswurzelextrakte.
German Patent 665,216; issued September 20, 1938; applied
for June 27, 1935; assigned to Deutsche Hydrierwerke A.-G.
- 33 -
34. NEU, R.
1940. Pest destroying emulsion. U. S. Patent 2,194,446; issued
March 19, 1940; applied for June 26, 1936; in Germany
June 26, 1935; assigned to Deutsche Hydrierwerke A.-G.
35. O'KANE, W. C.
1938. Active insecticide and fungicide. U. S. Patent 2,127,526;
issued August 23, 1938; applied for August 16, 1934.
36. PERUVIAN MINISTRY OF FOMENTO
1938. Vermifuges and insecticides. Patent of Invention No. 986.
Off. Communication No. 28, February 1, 1938.
37. RIPPER, W. E.
1939. Poison for destroyig insects, animals and the like. Brit-
ish Patent 505,8U; ivaued May 18, 1939; applied for
November 18, 1937; in Austria November 20, 1936, and
April 20, 1937.
38. SALIARIS, Mi. C.
1938. Perfectionnements a la preparation des produits insecticides
et parasiticides. French Patent 829,338; issued June 20,
1938; applied for February 18, 1937.
1938. Perfectionnements a la preparation des produits insecticides
et parasiticides en suspension ou en emulsion. French
Patent 829,339; issued June 20, 1938; applied for February
40. SCHOTTE, H., and GORNITZ, K.
1938. Insecticide and method of making same. U. S. Patent
2,136,86; issued november 15, 1938; applied for December
12, 1933; in Germany June 30, 1932; assigned to Schering-
1939. Raupenbek'mpfungsmittel. German Patent No. 671,162;
issued February 1, 1939; applied for November 14, 1931;
assigned to Schering A.-G., Berlin
42. SIBLEY, R. L.
1938. Insecticidal composition. U. S. Patent 2,138,516; issued
November 29, 1938; applied October 16, 1936; assigned to
Monsanto Ohemical Company.
43. THiPSON, F. M.
1939. Insecticide. U. S. Patent 2,160,579; applied for April
28, 1937; issued hay 30, 1939; assigned to Hercules
44. WILSON, R. E.
1938. Stabilized white oil. U. S. Patent 2,123,457; issued
July 12, 1938; applied for January 16, 1931; renewed
December 6, 1937; assigned to Standard Oil Company of
45. WOTHiERSPOON, R
1938. Process for preparing improved derris and cube extracts
and hydrogenated derivatives and products produced
thereby. U. S. Patent 2,126,854; issued August 16, 1938;
applied for April 28, 1934; assigned to Derris, Inc.
Junior Patentees Index
Ferguson, B., Jr.; see Hill, ii. L.
FitzGibbon, Mz.; see Lunevale Products Limited
Gornitz, K.; see Schotte, H.
Gorr, G.; see Bockmuhl, ixi.
Jayne, D. W., Jr.; see Christmann, L. J.
Martin, K.; see Goldschmidt, S.
Nikitin, A. A.; see Adams, J. F.
Rosenbroek, vi. D.; see Naamlooze Vennootschap Chemische Fabriek Servo
Salzberg, P. L.; see Bousquet, E. W.
Zemba, J. W.; see Coleman, G. H.
American Cyanamid Company; see Christmann, L. J., and Jayne, D. W., Jr.
Derris, Inc.; see Wotherspoon, R.
Deutsche Hydrierwerke A.-G.; see Neu, R.
Dow Chemicnl Company; see Coleman, G. H., and Zemba, J. W.
E. I. du Pont de Nemours and Company; see Bousquet, E. W.; Bousquet, E. V,.
and Salzberg, P. L.; and Brubaker, i. M.
Government and People of the United States of America; see Boyce, A. M.
Gulf Oil Corporation; see Hill, ii. L., and Ferguson, B., Jr.
Hammond Paint and Chemical Company, Inc.; see Faloon, D. B.
Hercules Powder Company; see Thompson, F. ivi.
I. G. Farbenindustrie A.-G.; see Bocluhl, M., and Gorr, G.
- 35 -
Kilgore Development Corporation; see Kilgore, ,L. B.
Lin-Tox Corporation; see Lind, T.
Monsanto Chemical Company; see Carswell, T. S.; Hockenyos, G. L.; and
libley, R. L.
O'Kane, W. C., and Moore, P.; see Adams, J. F., and Nikitin, A. A.
People of the United States of America; see Goodhue, L. D.
Schering-Kahlbaum A.-G. Berlin; see Schotte, H., and Gornitz, K.
Shell Development Company; see Knight, H.
Standard Oil Company of Indiana; see Wilson, R. E.
Tobacco By-Products and Chemical Corporation; see McConnell, H. K.
Union Oil Company of California; see Blount, A. L.
Insecticidal Ingredients, Diluents, Solvents, Stabilizers, etc.,
Used with Rotenone Products
Acetalacetone oxalate n-butyl ester, U; S. 2,149,917
Acetaldehyde diaryl arylene diamine product, U. S. 2,138,516
Acetate of deacetylated chitin, U. S. 2,098,942
Acetone, French 829,338; U. S. 2,126,854; 2,144,366; 2,151,651; 2,173,849;
Acetone-furfural product, U. S. 2,16,258
Acetophenone-furfural product, U. S. 2,146,258
Additive Ether, U. S. 2,160,579
Alcohol, Ger. 674,488; U. S. 2,144,366; 2,144,367
Alcohol, polyhydric, ester of, Ger. 67#,488
Alcohol-diaryl arylene diamine products, U. S. 2,138,516
Alcohol, sulphated, sodium salt, Ger. 665,216
Aldehyde-diaryl arylene diamine products,'U. S. 2,138,b16
Alumina, U. S. 2,136,868
Alumina gel,, French 829,338.
Amino-carboxy compounds, U. S. 2,151,651
Ammonia, U. S. 2,129,517
Ammonium caseinate, U. S. 2,129,517
Amyl alcohol-aldehyde-diaryl arylene diamine product, U. S. 2,138,516
Amyl alcohol-terpene ether, U. S. 2,16U,579
Aniline, U. S. 2,144,366
Aniline, dichloro, U. S. 2,151,651
Aniline, 2,5-dichloro, U. S. 2,151,651
Aniline ethylchloro, U. S. 2,151,651
Aniline-furfural product, U. S. 2,146,257
Aniline methylchloro, U. S. 2,151,651
Anthracene, crude, U. S. 2,136,868
Anthranilic acid, U. S., 2,151,651
Anthranilic acid, chloro, U. S. 2,151,651'
Anthranilic acid, dichloro, U. S. 2,151,651
Antimony oxide, U. S. 2,168,064
Apricot pit flour, U. S. 2,191,421
Aresco, U. S. 2,197,500
Arsenic compounds V. S. 2,136,868
Arsenobenzol, U. S. 2,132,013
Arsine oxide, dimethylphenyl, U.'S."2,132,013
" 36 -
Arsine oxides, U. S. 2,13,013
Arsine, ppraethoxyphenyl, U. S. 2,132,013
Arsines, U. S. 2,132,013
Barium sulphate, U. S. 2,163,064
Barium titanox, U. S. 2,168,064
Bentonite, U. S. 2;190,173
Benzene, Ger. 674,488; U. S. 2,194,j46; Z,194,924
Benidine, U. S. 2,144,366; 2,144,369
Benzidine, di-o-biphenyl, U. S. 2,138,516
Benzidine, di-p-bipbenyl, U. S. 2,138,516
Benzidine, diphenyl, U. S. 2,138,516
Benzidine ditolyl, U. S. 2,138,516
Benzidine, dixylyl, U. S. 2,138,516
Benzol, U. S. 2,126,854
Benzophenone, furfural product, U. S. 2,146,258
Benzyl alcohol-aldehyde-diaryl arylene diamine product, U. S. 2,138,516
Birch flour, U. S. 2,191,421
Bismuthines, U. S. 2,132,013
Bole, U. S. 2,136,868
Borax, U. S. 2,136,863
Boric acid ester, sulphonated, Brit. 501,801
Borneol ethers, U. S. 2,160,579
Bornylene additive ether, U. S. 2,160,579
Brazil nut shell flour, U. S. ,191,421
Butyl alcohol, U. S. 2,194,924
Butyl alcohol-aldehyde-diaryl arylene diamine product, U. S. 2,138,516
Butyl alcohol-terpene ether, U. S. 2,160,579
m-Butyralacetone oxalate ethyl ester, U. S. 2,149,917
Butyraldehyde diaryl arylene diamine product, U. S. 2,138,516
Calcium caseinate, U. S. 2,132,013
Calcium titanox, U. S. 2,168,064
Camphan, oxyphenyl, ethoxylated, Ger. 674,488
Camphene additive ether, U. S. 2,160,579
Camphor sassafrassy oil, U. S. 2,132,013
Carbazole, U. S. 2,136,868
Carbon tetrachloride, French 829,338; Ger. 674,488; U. S. 2,133,972;
Carene additive ether, U. S. 2,160,579
Casein, Brit. 505,853
Castor oil, ethoxylated, Ger. 674,488; 675,220
Castor oil fatty acid Olycol ester, sulphonated phosphoric acid ester of,
Castor oil, sulphonated, U. S. 2,127,526
Cedar bark flour, U. S. 2,191,421
Cedar wood flour, U. S. 2,191,421
Cellosolve, U. S. 2,132,013
Cellulose, Brit. 506,853
Cherry pit flour, U. S. 2,191,421
China cly, U. S. 2,136,868
Chitin, deacetyloted, acetate of, U. S. 2,098,942
Chloroform, French 829,[338; U. S. 2,126,854; 2,194,,4J6
Chloroform liniment, U. S. 2,158,241
S3 7 -
Clay, U. S. 2,172,314
Coconut shell flour, U. S. 2,191,421
Copper compounds, U. d. 2,136,868
Copper-nicotine complex, Brit. 492,660
Copper sulphate, U. S. 2,158,241; r,172,314
Corn oil, U. S. 2,127,526
Creosote wood, U. S. 2,123,457
Cresol, U. S. 2,1,44366
Cresylic acid, U. S. 2,123,457
Cyclohexanol-aldehyde-diaryl arylene diamine product, U. S. 2,138,516
Cyclohexanone, Ger. 665,216; U. S. 2,194,446
Cyclopentanone, Ger. 665,216; U. S. 2,194,446
Dekahydronaphthalene, U. S. 2,194,446
beta-Dekalinone, U. S. 2,194,4.16
Derris oil, U. S. -2,l26,854
Dextrin, U, S. 2,123,457
Diam-tnes, diaryl arylene, U. S. 2,138,516
Diazoamino compound, Brit. 493,764
Di-beta-naphthylamine, U. S. 2,144,366; 2,144,368
fDiethylene glycol, monoethyl ether, U. S. 2,132,013
Diethylene glycol monoethyl ether-terpene ether, U. S. 2,160,579
Diethylene glycol terpene othjr, U. S. 2,160,579
Dihydroroten-ne, Ger. 665,216; U. S. 2,194,446
Dioxan, Ger. 674,488
Dipentene additive other, U. S. 2,160,579
Diphanylamine, U. S. 2,144,366; 2,144,369
uter of a polyh7dric alcohol, Gar. 674,488
EIster, sulphonated, Brit. 501,801
Eaters, unsaturated dliketo carboxylic, U. S. 2,149,917
Ether, French 829,338; Gcr. 674,488
Ethyl acetate, U. S. 2,126,854
Ethyl n.icchol-aldohyde-diaryl arylene diamine product, U. S. 2,138,516
Ethyl alcohol-tepeno ether, U. S. 2,160,579
Ethyl-3-metl,L-3-ieptene-2-1-oz.alate, U. S. 2,149,917
Ethylene dichloride, U. S. 2,126,854; 2,144,366; 2,144,367; 2,194,924
Ethylene- glycol monobutyl ether-terpene ether, U. S. 2,160,579
Ethylene glycol monoethyl either terpene ether, U. S. 2,160,579
Ethylene glycal-terpone ether, U. S. 2,160,579
Ethylene glycol-turpentine ether, U. S. 2,160,579
Extgenl, U. S. 2,144,366
lenihyl aldoholether, U. S. 2,160,579
.oNmaldahyde, U. S. 2l,123,457
Yormaldehyd..-diaryl arylene diamine product, U. S. 2,138,516
?uifural-amine products, U. S. 2,146,257
3l rfral,-ketone products, U. S. 2,146,258
Gasoline, U. S. 2,144,366
Glue, U. S. 2,123,457
Glycero-dI-o1ente, U. S. 2,190,173
Glycero-mono-oleate, U. S. 2,190,173
Glyc-erol-terpene ether, U. S. 2,1(0,579
Gl~yo1-monomsethyl ether, Ger. 674,488
- 38 -
Glycol mono-oleate, U. S. 2,190,173
Green soap, U. S. 2,158,2341.
Guaiacol, U. S. 2,144,366
Gum ghatti, U. S. 2,123,'57
Gum tragacanth, U. S. 2,123,457
Gypsum, calcined, U. S. 2,168,064
Heptaldehyde diaryl arylene diamine product, U. S. 2,138,516
Hexahydroxylol, Ger. 665,216
Hexamethylene tetramine, U. S. 2,144,366; 2,144,369
Hydrocarbon distillate, U. S. 2,127,526
hydrocarbons, alicyclic, U. S. 2,136,868
Hydrocarbons, aliphatic, U. S. 2,136,868
Hydrocarbons, cyclic, U. S. 2,136,868
Hydrocarbons, hydrogenated aromatic, Ger. 665,216."
Hydrocarbons, petroleum, U. S. 2,126,854
Hydroquinone, U. S. 2,132,013; 2,144,366
Hydroxy-amino compounds, U. S. 2,.,151651
Hydroxy-carboxy compounds, U. S. 2,151,651
Hydroxy ethyl ether, U. S. 2,133,972
Isothiocyanate, aromatic, Brit. 471,153
Isothymol, U. S. 2,136,868
Kaolin, U. S. 2,168,064
Kerosene, U. S. 2,144,366; 2,149,917; 2,194,446; 2,194,924
Ketones, cyclic, Ger. 665,216
Lampblack, U. S. 2,197,500
Lauryl trime t hylammonium chloride, French 829,339
Lecithin, U. S. 2,132,C13
Light oil, Cr. 66"i,266
Lignocol, U. S. 2,1--4,366
Lime-soap, U. S. ',1,36,868
Linseed oil-potash soap, U. S. 2,173,849
Lithopone-zinc sulphide, U. S. 2,168,064
Lithopones, titanated, U. S. 2,168,064
Mesityl oxide oxalate cyclohexyl ester, U. S. 2,149,917
Mesityl oxide oxalate ethyl ester, U. S. 2,149,917
Mesityl oxide oxalate isobutyl ester, U. S. 2,149,917
Mesityl oxide oxalate n-butyl ester, U. S. 2,149,917
Mesityl oxide oxalate sec.-amyl ester, U. S. 2,149,917
Mesityl oxide oxalate tetrahydrofurfuryl ester, U. S. 2,149,917
Iviethyl alcohol-aldohyde-diaryl arylene diamine product, U. S. 2,138,516
Methyl alcohol-terpene ether, U. S. 2,160,579
ethyl cyclohexanone, Ger. 665,216; U. S. 2,19,446
Methyl ethyl ketone, U. S. 2,194,924
3-1iethyl-3-heptene-2-one-oxalate ethyl ester, U. S. 2,149,917
3-vethyl-3-pentene-2-one-oxalate ethyl ester, U. S. 2,149,917
t;ethylothylketone-furfural product, U. S. 2,146,258
Mineral oil, U. S. 2,190,173
Mineral spirits, U. S. 2,144,366
K[orpholene, parahydroxyphenyl, U. S. 2,132,013
Morpholine, 4-(10,11-undecylenoyl), U. S. 2,166,118
Naphtha, U. S. 2,199,924
- 39 -
Naphtha, insecticide, U. S. 2,192,347
Naphthalene, U. S. 2,136,868
Naphthalene, decahydro, Ger. 665,216
Naphthalene, hydrogenated, U. S. 2,194,446; 2,194,924
Naphthalene, tetrahydro, Ger. 665,216
Naphthol, U. S. 2,136,868
Naphthol, l,2-amino, U. S. 2,123,457
alpha-Naphthol, U. S. 2,144,366; 2,144,367
beta-Naphthol, U. S. 2,144,366; 2,14-1,367
Naphthylamine, U. S. 2,144,368
alpha-Naphthylamine, phenyl, U. S. 2,144,366; 2,144,368
beta-Naphthylamine-furfural product, U. S. 2,146,257
2-Naphthydetone-furfiiral product, U. S. 2,146,258
Nicotine, U. S. 2,158,241; 2,173,849
Nicotine-copper complex, Brit. 492,660
Nopinene additive ether, U. S. 2,160,579
Oil, glyceride, U. S. 2,127,526
Oil, white, U.' S.- 2,'123,457
Oils, Ger. 674,488
Oils, animal, sulphonated, U. S. 2,127,526
Oils, petroleum, U. S. 2,123,457
Oils, vegetable, sulphonated, U. S. 2,127,526
Oleic acid, U. S. 2,151,651; 2,197,500
Oleyl alcohol, ethoxylated, Ger. 674,488; 675,220
Oleyl chloride-diethyl diaminoethane product, French 829,339
Olive pit flour, U. S. 2,191,421
Organic acid, U. S. 2,190,173
Peach pit flour, U. S. 2,191,421
Pecan shell flour, U. S. 2,191,421
Petrolatum, white, U. S. 2,126,854
Petroleum, Ger. 674,488
Petroleum distillate, Ger. 665,216; U. S. 2,133,9.72
Petroleum oil, U. S. 2,141,366
Phellandrene additive ether, U. S. 2,160,579
Phenanthrene octohydro, Ger. 665,216
Phenol, U. S. 2,144,366
Phenol, alkyl-amino, U. S. 2,123,457
Phenol, 2-cyclohexyl, beta hydroxyethylether, U. S. 2,133,972
Phenol, dibenzyl paraamino, U. S. 2,132,013
Phenol dibutylamino, U. S. 2,123,457
Phenol, 2,4-diethyl, beta-hydroxyethyl ether, U. S. 1,194,924
Phenol, 2,4-diethyl, hydroxy-butyl ether, U. S. 2,194,924
Phenol, 2,4-diethyl, hydroxy-propyl ether, U. S. 2,194,924
Phenol, di-isopropyl, bet,-hydroxyethyl ether, U. S. 2,194,924
Phenol, 2,4-di-isopropyl, beta-hydroxyethyl ether, U. S. 2,194,924
Phenol, dodecyl, ethoxylated, Ger. 674,488; 675,220
Phenol, 2-ethyl-4-isopropyl, beta-hydroxyethyl ether, U. S. 2,194,924
Phenol, 2-ethyl-4-tertiary-amyl, beta-hydroxyethyl ether, U. S. 2,194,924
Phenol, 4-heptyl, beta-hydroxrethyl ether, U. S. 2,194,924
Phenol, hydroxyalkly ether, U. S. 2,133,972
Phenol, 4-isobutyl, beta-hydroxyethyl ether, U. S. 2,194,924
Phenol, iso-octyl, ethoxylated, Ger. 674,448, 675,220
Phenol, 2-methyl-4-isopropyl, hydroxy-propyl ether,. U. S. 2,194,924
Phenol, monobenzylparaamino, U. S. 2,132,013
Phenol, 4-normal-amyl, beta-hydroxyethyl ether, U. S. 2,194,924-
Phenol, 4-normal-butyl, beta-hydroxyethyl ether, U. S. 2,194,924
Phenol, 4-normal-hexyl, beta-htydroxyethyl ether, U. S. 2,194,924
Phenol, ortho-amino, U. S. 2,123,457
Phenol, para-amino, U. S. 2,123,457; 2,144,366; 2,144,369
Phenol, para-benzylamino, U. S. 2,123,457
Phenol, para-methylamino, U. S. 2,123,457
Phenol, ppraphenylamino, U. S. 2,132,013
Phenol, para-tertiary-amyl, U. S. 2,192,347
Phenol, 4-secondary-butyl, beta-hydroxyethyl ether, U. S. 2,194,924
Phenol, 4-secondary-butyl, hydroxybutyl ether, U. S. 2,194,924
Phenol, 4-secondary-butyl, hydroxypropyl ether, U. S. 2,194,924
Phenol, 4-secondary-hexyl, beta-hydroxyethyl ether, U. S. 2,194,924
Phenol, 4-tertiary-butyl, betp-hydroxyethyl ether, U. S. 2,133,972; 2,194,924
Phenol, 4-tertiary-butyl, hydroxyalkyl ether, U. S. 2,133,972
Phenol, 4-tertiary-hexyl, beta-hydroxyethyl ether, U. S. 2,194,924
Phenol-camphan, oxy, ethoxylated, Ger. 675,220
Phenols, amino, U. S. 2,151,651
Phenols, nitro amino, U. S. 2,151,651
Phenols, polyhydroxy, U. S. 2,151,651
Phenyl alpha-naphthylamine, U. S. 2,144,368; 2,197,500
Phenyl beta-naphthylamine, U. S. 2,197,500
m-Phenylenediamine, N-N'-dialphanaphthyl,U. S. 2,138,516
m-Phenylenediamine, W-N'-dibetanaphty, U. S. 2,1 0,516
m-Phenylenediamine, N-IT'-di-biphenyl, U. S. 2,138,516
m-Phenylenediamine, N-Y'-diphenyl, U. S. 2,138,516
m-Phenylenediamine, -N'-ditolyl, U. S. 2,138,516
o-Phenylenediamine, I-N-dialphanaphthyl, U. S. 2t,138,516
o-Phenylenediamine, N-NI-dibetanaphthyl, U. S. 2,138,516
o-Phenylenediamine, R-N'-di-biphenyl, U. S. 2,138,516
o-Phenylenediamine, F-W'-diphenyl, U. S. 2,138,516
o-Phenylenediamine, iY-NI-ditolyl, U. S. 2,138,516
p-Phenylenediamine, N-Nt-dialphanpphthyl, U. S. 2,138,516
p-Phenylenediamine, N-N'-dibetanaphthyl, U. S. 2,138,516
p-Phenylenediamine, N-N'-dibiphenyl, U. S. 2,138,516
p-Phenylenediemine, N-NIdiphenyl, U. S. 2,138,516
p-Phenylenedianine, i-N'-ditolyl, U. S. 2,138,516
Phosphines, U. S. 2,132,013
Phosphobenzol, U. S. 2,132,013
Phosphoric acid ester, sulphoneted, Brit. 501,801
Phthalate, dibutyl, U. S. 2,192,347
Pine oil, U. S. 2,132,013; 2.158,241
Pine oil additive ether, U. S. 2,160,579
Pine oil foots, U. S.'2,129,517
alpha-Pinene additive ether, U. S. 2,160,579
Plum pit flour, U. S. 2,191,421
Polyamino compounds, U. S. 2,151,651
Polysaccharides, Brit. 505,853
Potassium oleo abietate, U. S. 2,127,526
Propyl alcohol-eldehyde-diaryl arylene diamine product, U. S. 2,138,516
Propyl alcohol-terpene ether, U. S. 2,160,579
Proteins, Brit. 505,853
Pyrethrins, U. S. 2,158,241; 2,19'4,4i6
Pyrethrum, U. S. 2,136,868, 2,144 ,366; 2,1 4,46
Pyridine, U. S. 2,132,013
Pyrogallol, U. S. 2,132,013; 2,144,366
Resorcinol, U. S. 2,144,366
Rosin residue, U.. S. 2,129,517
Rotenone hydrazone, U. S. 2,132,013
Rotenone oxime, U. S. 2,132,013
Rotenone phenylhydrazone, U. S. 2,132,013
Sabadilla seed, Ger, 671,162
Safrol, U. S. 2,136,854; 2,132,013
Salicylic acid, U. S. 2,151,651
Sapamine, French 829,339
Silica gel, French 829,338
Soap, U. S. 2,132,013
Soap solution, Brit.' 505,853
Sodium acetbte, U. S. 2,136,868
Sodium bisulphide, U. S. 2,127,526
Sodium nitrate-, U. S. .2,071,171
Sodium sulphate, U., S. 2,.136,868
Sodium zeolite, U. S. 2, 172,314
Stibine, cyc~opentylphenyl, U. S. 2,132,013
Stibine oxides, U. S. 2,132,013
Stibines, U. S. 2,132,013
Sulfonate, fatty alcohol, U. S. 2,194,446
Sulphonated oils,.U. S. 2,144,366
Sulphonic acid, hydroxy substituted aromatic, U. S. 2,197,500
Sylvestrene additive ether, U. S. 2,160,579
Talc, U. S. 2,136,868.
Terpene ethers, U.. S.. 2,160,579
Terpenes, U. S. 2,136,868
Terpinene additive ether, U. S. 2,160,579
alpha-Terpineol, U. S. 2,132,013
alpha-Terpineol additive ether, U. S. 2,160,579
alpha-Terpineol ether, U. S. 2,160,579
beta-Terpineol additive ether, U. S. 2,160,579
Terpinolene additive.ether, U. S. 2,160,579
Tetrahydroacetophenone oxalate ethyl ester, U. S. 2,149,917
Tetrahydronaphthalene, U. S. 2,194,4t6
Thy'mol, U. S. 2,136,868; 2,144,366
Titanium oxide,.U. S. 2,168,064
Titanium oXide gel, French 829,338
Toluene, Ger. 674,488
p-Toluidine-furfural product, U. S. 2,146,257
Tributylamine, U. S. 2,132,013
Triethanolamine oleate, U. S. 2,132,013
Triethanolamine stearate, U. S. 2,132,013
Triethylamine, U. S. 2,127,526
Turkey red oil, U. S. 2,136,868
Turpentine, additive ether, U. S. 2,160,579
10,1l-Undecy'lenic acid, U. S. 2,166,119
Vanadines, U. S. 2,132,013
Vanoline, U. S. 2,132,013
Vegetable proteins, Brit. 505,853
Vertrine, Ger. 671,162
Walnut shell flour, U. S. 2,191,421
Zein, Brit. 505,853
Zinc oxide, U. S. 2,168,064
A List of All Patents Arranged According to Filing Dates
January 16, 1931
November 14, 1931
17ovember 18, 1932
October 2zL, 1933
October 24, 1933
December 12, 1933
i~iarch 9, 1934
March 25, 1934
April 28, 1934
i'iay 7, 1934
July 2, 1934
August 16, 1934
June 11, 1935
June 15, 1935
June 27, 1935
October 28, 1935
October 29, 19Z5
Februar, 26, 1936
April 24, 1936
June 17, 1936
June 18, 1936
June 26, 1936
OCtober 3, 1936
October 3, 1936
October 16, 1936
Nobember 23, 1936
January 18, 1937
February 1, 1937
February 18, 1937
Februrtry 18, 1937
i'arch 20, 1937
April 9, 1937
April 28, 19-7
August 1, 1937
Augtst 26, 1937
September 4, 1937
November 18, 1967
U. S. 2, 123,9457
U. S. 2,151651
U. S. 2,144,366
U. S. 2,144,367
U. S. 2,136,868
U. S. 2,126,854
U. S. 2,197,500
U. S. 2,132,013
U. S. 2,127,526
U. S. 2,168,064
U. S. 2,071,171
U. S. 2,172,314
U. S. 2,149,917
U. S. 2,098,942
U. S. 2,158,241
U. S. 2,194,446
U. S. 2,166,118
U. S. 2,166,119
U. S. 2,138,516
U. S. 2,192,894
U. S. 2,190,173
U. S. 2,192,347
U. S. 2,160,579
U. S. 2,133,972
U. S. 2,173,849
December 2, 1937
January 10, 1938
May 14, 1938
May 14, 1938
July 2, 1938
September 23, 1938
September 26, 1936
U. S. 2,191,421
U. S. 2,129,517
U. S. 2,144,368
U. S. 2,144,369
U. S. 2,194,924
U. S. 2,146,257
U. S. 2,146,258
- 43 -
UNIVERSITY OF FLORIDA
3 1262 09224 7765