April 1942 U E-564
SOME NEW OR LITTLE-USED INSECTICIDES WORTHY OF FURTHER TESTING
Part I. Copper-Arsenic Compoundl/
By R. C. Roark, Division of Insecticide I-estigations
The history of several of our most potont in useu insecticides
reveals that many years frequently elapse bet-,er the first published
account of them and their general adoption. For.e ple, derris was men-
tioned as an insecticide in 1848, and a study of i p bi1ities as
reported in 1919, but it was not used in quantity in the United States
until 1931, Tartar emetic was tested as an insecticide in 1890, but did
not come into large-scale use until about 1936.
The writer believes that the time between the initial discovery of
the insecticidal action of a material and its corner adopLion could be
greatly shortened by proper publicity. When sufficient information on the
insecticidal value of a material is published, its acjercial production
will be eagerly undertaken by the chemical industry eid it will be made
available for public use. The first step in this ola' is to stimulate
interest among entomologists so that -:any tests agi t different insects
will be made. In the present series of papers a, effort is made to bring
to the attention of entomologists m aterials not no used commercially as
insecticides, but which are believed to possess pCssibilities for insect
control that should be further explored.
Compounds Related to Paris Green
Paris green is one of our oldest insectdti,'c and, in spite of
competition from the newer arsonicals such as lead -rsenate, calcium arse-
nate, and zinc arsenite, it is still consumed to the extent of about 2 million
pounds annually. It has the formula 3CuAs O .Cu(C 1-0) 2 and contains
58.55 percent of arsenic trioxide, 33 .39 percent of cupwic oxide (equivalent
to 25.08 percent of copper), and 1O.06 percent of acetic .cid anhydride.
l/ Free use has been made of unpublished data obtained by E. H.
Siegler, of the Division of Fruit Insect Investigation<, ard M. C, Swingle
and associates, of the Division of Control Investigatios. Grateful acknowl-
edgment is made to these Divisions for permission to use their results.
Decrborn 1 21 has prepared compounds analogous to paris green
using such cids of the acetic series as formic, propionic, butyric, mono-,
'and tri>h' re ctc, lauric, paimitic, stearic, and melissic. These
gre are Je h
hot solution of akali-metal salt of the fatty acid (i.e., a soap) and
heating, Unsttrted acids, such as crotonic, oleic, erucic, linoleic, and
linolenic, and lso nixed acids resulting from the saponification of vege-
table or a_:1cos can be similarly used (3, 4, 5, 6, 7). Acids from the
,joi7n oils ha>e aso been emplo ,ed to prepare copper-arsenic compounds:
C--r, coconut, .ottonseed, corn, inuseed, menhaden, palr., peanut, rapeseed,
sesame, soybean, and tung.
The in. eticidal values of these greens have been tested only to a
li[ ~ extent 1 lefing and Baker (12) tested paris green and a number of
its homologues2 n cormparison with lead arsenate for the control of the
au l JZpanese- bct,--l (Ppillia j Nem.). Fotted smartweed plants
.erc sprayed ;itr eah arsenical in several concentrations and then placed
in glass cages u._c.er controlled temperature, relative humidity, and light.
Freshly collected. japanese beetles that had been starved for 6 hours were
distributed in ech cage, and after 48 hours a record was made of beetle
lmorlality and ,,xay injury. Their results for a concentration of 8 pounds
per 100 gallons are as follows:
Coefficient of effectiveness
Injury to foliage
Lead arsenate .....................
faris green .... ................
Paris green, ad four ..........
Paris green sd si: oil ....
Coper lauroars, tto ........
ap s ed-oil g e ............
grflens against th
;ou~ng beetles .in
killed whole-wh eat
Ca pbell (11) tested the effectiveness of some of these
o used flour beetle (Triboliom confusum Duv.) by placing
P ixture of 10 parts of insecticide and 90 parts of finely
.lour for 24 hours, with the following results:
Material Percent mortality
Copper stearoarsenite ................... 83
Soybean-oil green ....... 84
LinseeC-oil green ................................
Fish-oil green ........................... 6
Copper oleoarsenite ........... ............... 7
Lead arsenate ................. 7
Copper crotonoarsenite ............... S8
Copper lauroarsenite ...........
Peanut-oil green .................................. 9i
Copper nonochloroacetoarsenite ........ 64
Copper dichioroacetoarsenite ............ C2
Pa ris green ................................... .. 5
Lead arsenate ................................ ....11
The grcater effs.ctiveness of scme of thcsc ccmi- ounds %,:as attributed in
part to better achesiveness and to a possible difference in particle size.
Several of these greens were tested in the laboratory by J. B. Cahan and A,
M. Phillips, at Sanford, Fla., under the direction of M. C. Swingle, against
fourth instars o' southern armworm (Prodenia Pridsnia (Cram.)) and
'ifth instars of the fall webworm (Ey hantria cuiiea (Drury)) and the melon-
worm (_Diahajji hyalinata (L.)). Cooper oleoarsciute and. greens prepared
from fish oil, tung oil, peanut oil, and linseed oii re effective against
the southern armyworm and the melonworm but were ineffective against the
fall webworm. No significant and consistent differcnccs between these greens
Against la ac of the codling moth (Cazo r. a pmonella L.) the fol-
lowing results w&eo obtained by Dr. Siegler in Iaboratory tests at Belts-
ville, M3. when ho used these greens at the rate o' 4 pounds per 100 gal-
Percen tage of a ple p ls
Material C'rIr .C.....
Fish-oil green .................................... 1.9 0 .0
Peanut-oil green ........... 1.0 5.9
Copper olcoarsenite ......................... 5.7 1.9
Linseed-oil green ......................... 9.6 5.8
Tung-oil green .................................. 14.0 3.2
Copper phenylstearoarsenite ............ 23.6 17.9
nds :ade th ulurized 0: O .aic Acids
,.rated co nc acid, such as oleic, is heated vith
sulur a Paout 2 C., wi th little iine added 1s a catalyst, 1 atom
of lfur a Ihn c. CLupanodonic acid
fro, fish oil h contains 4 oule os Ca heore.ically com'rine
Cith 1, 2, 3, o .oS of sclfur une h c. reamet. The resulting
su Ifurie acis e combined 1'ih cop:1er ono rsenic in the same ,,ay as
he usuifri ed acids (8). Free f its, obtined by saponifying
a xegetable, i or fish oil L Cu a-n sed in this process.
Examples are the c Lacs from peanut, inseed, fish, and tung oils (9, i0).
The sLilfur in thc teens prejaied It suilu.iVed acids ranges from
aiout 4 to 10 percent, the arsic trio\ide from 3$ Lo 39 percent, and the
copper oxide fro att 19 to 21 e'n 2Tese products are of a dirty
Lreen color, V a easy feel re in cluble in water, and require the
addition of a ettn agent.
Sv, ingIe aod ..j'cciates founc that conr r slfoleoaasenite, containing
29,8 percent of rsnic trioxide, 5.0 percent of sulfur, and 17.8 er cent
of cooper, "
balteata Lec.), t cross-strieca av t cr'e'a hnmcsalis (Guen.)),
and the imported ca age ori (Pieis r> L.), c. -as defective against
the melonworm a.a of the Ma ican Lean Veetle (Eoilachna varives
(Muls.)), and th II squash bug (AiasA rti.. (t'e.)), and only partly
effective aF1t (1_ie P -c', (7 l erent mortality in
IS hours at ICO i..) ',hea his materi ,as tes ted by Dr. Siegier
a, rinst codling ioth larvae b the appl plu1 g ethod t a concentration of
4 -ounds pe r ICO gallns, 7.5 j Oet 1 f thc p s vere xory and none w(ere
stung. Lead asnte usua l es o 0 percent of .ormny and sKng
apple plugs at tc soe concentration.
Greens ,_ irio sulfuric tn oil, fish oil, and liieed oil, ,ien
tested agans t mnct, 13 15 7, ici 1 percent of wormy
Iruit and 1., ., d 6.1 e
Effect of Greens on ple Foliae
Dr. 0ies e spod gr cren c icc fo fih Feanut, liseed, anid tunS
oils, and also o htrize fi. 'i.:r d a oils ad op er oeo-
ars.enite and c henylsearore1 uIo o 1n .Sta nan and Gi es
Goldeni apple Iie~ % eltsvil~e 'd. C he cnoe'a iio o1 t hese sprai d\ as
4 oInds jer Ions of a.eo h oliac vws injured in every in-
sance, anid tic .u-oit lrcn. deoi .e L tree "hether this tendency
to cause serious- i;<
has not 3et tee detcrc mined. ,
The aioie roos .nd als o I o; e o~ irom sulfu rized corn, soybean,
and peanuat o~is1. e~ tested in tae 1 uorato ry by 2';injle and associates
against one or more of the following insects Bankd cucumber eee
Colorado potato beetle (Lettinolar a dece'Cie-I. ( ... .o
cabbage worm, imported cabbage larova, eloiwoxi o]oquo larae, soIut in
armnlworm, and southern beet webt'.orrn (P c-zanc'a biit c ais (F z ). T!e
mortality was practically 100 percent or all species except osquito
larvae, which exhibited mortalities of 76 to P4 percent following applica-
tions of 100 p.p.m.
The foregoing results clearly show that these compounds are very toxic
to insect pests. As their physical properties, s uch as wettability, a,,-
hesiveness, etc., vary with the t pe of acid crrplcyed (saturated, unsaturated,
halogenated, etc.), and also with the arsenic and copper content and the
solubility, a series of new insocticidcs possessing a wide range of' physical
and chemical properties is available.
The following uses for these greens are suggested:
(1) The green made from formic acid' contains the most arsenic (60.22
percent As2O3) an- should be superior IL j-t5 s ic in insuring a cu c:'
kill of cotton 1lca hoppers, oll2o;s, 1cll v;.1lo, cotton lcaf 'wor,
Colorado potato beetles, and other insect pests of plants that are resistant
to soluble arsenicals.
(2) The greens made from oleic or stearic acid or from the .atty
acids from peanut, soybean, or other, \egeta >e oils ield but little soluble
arsenic when added to water and are worthy of Csting as suhstitutes for
lead arsenate for combating certain insects. It will Th necessary to add
a little wetting agent to these greens because of the-r greasy charact er
and also a safcner to lessen the effects of' soluble arsenic and soluble
copper upon the foliage of some plants. If the nd cy to injure ap l
foliage can be overcome, these materials would also 1e 'oI, testing a i_1.
the codling moth.
(3) The same greens, because they r i- 1o1aing on water loer,
should prove superior to paris green for h control of surface-feeding
(4) These oil greens are wetted by- petroleum oils. A product iade
by grinding one of these greens in a petrolui.I spray oil and cmulsifyinag,
in water offers possibilities for the control o* insects now combated by
lead arsenate-oil sprays.
(5) All these greens contain a considerable amount of copper (25 79
percent as a maximum in formic green) v hich should display the characteristic
fungicidal action of this metal.
Many cozpcurd3 analogous to parJ
stituting other organic acids for acet
stituted by halogen. or other radiooi
an atom of sul ', dded to eac dolehl
compounds, cal! : ens," have Ieen -
entomologists3 vi th several representat1;Ei-e
greens have sho ,vn te following results.
Shv: been prepared by sub-
> ouc I ac's cmay be sub-
unsturated, they may have
,eicoos of' making these
',, 1eurbog!L. Tests made by
o&ffer;t classes of these
Insect boratc ry ccnditicns
Banded cucumber beetle
Codling moth (larvae)
ColoraCo potato beetle
Confused flour beetle
Cross-striped cabbage worm
Imported cabbage worm
Yexican bean beetle (larvae)
Southern ar.yx orm
Southern beet webworm
Squash bug (adults)
to lead arsenate
to lead arsenate
to lead arsenate
(1) Dearborn, F. E.
19-5. Haologs of paris Ereen. I.
acid series. Jour. Econ.
19 Z. C3 _Joo s of paris p1een.
.id series. Jeur. ZEo.
Vo 1oiogs of paris ei 4':
linolec aciC series. Joui
I-oicogs of paris i, .
a ,i!al and vegetable oih
Loi.er menlers of the acetic
EnL. 23: 710-714.
i i.eubers of the acetic
>. r of the oleic and
ujn. CZ. 70.140-143.
ticides prepared from
ou, EcoE. ant. 70:958-S62.
1937. Ecuble salt of copper arsenite and copper salt of an un-
atu rated fatty acid and process of making the same.
U. S. Patent 2,080,004; issued oay 11.
(8) Dearborn, F. E.
1938. Double salts of copper arsenite and a copper salt of a
higher unsaturated fatty acid. U. S. Patent 2,104,584;
issued January 4.
1938. Insecticide and fungicide. U, S. Patent 2,127,380; issued
1939. Compounds of copper, arsenic, and a sulfmonocarboxylic acid
and process of making them. U. S. Patent 2,159,585;
issued May 23.
1939. Processes of treating glycerides. U. S. Patent 2,169,793;
issued August 15.
1940. Insecticide and fungicide. U. S. Patent 2,201,103; issued
(11) Fassig, W. W., and Campbell, F. L.
19Z7. Re-lative effectiveness of homologs of paris green against
confused flour beetle. (Scientific Note) Jour. Econ.
(12) Fleming, W. E., and Baker, F. E.
1936. Paris green and its homologues as insecticides against the
Japanese beetle. Jour. Agr. Res. 53:187-195.
UNIVERSITY OF FLORIDA
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