LIBRARY _ ... 
 
 Jtarch 1945 state PLANT BOARD «- 646 
 
 United States Department of Agriculture 
 Agricultural Research Administration 
 Bureau of Entomology and Plant Quarantine 
 
 NICOTINE INSECTICIDES. PART I-JSTEW METAL-NICOTINE COMPOUNDS 
 
 By E. L. Mayer and J. B. Gahan, \J Division of Control Investiga- 
 tions, Bureau of Entomology and Plant Quarantine, and C. R. 
 Smith, Eastern Regional Research Laboratory, Bureau of 
 Agricultural and Industrial Chemistry. 
 
 Twenty-five nicotine compounds of a water-resistant type, in 
 which the nicotine is combined usually with a metal to form a com- 
 plex salt, were prepared in 1942 and 1943 at the Eastern Regional 
 Research Laboratory of the Bureau of Agricultural and Industrial 
 Chemistry, for testing against plant-feeding insects by the Bureau 
 of Entomology and Plant Quarantine at its Sanford, Pla., laboratory. 
 Previous work by Hansberry Z/ on a * ew of these materials had shown 
 that as stomach insecticides they were more toxic to newly hatched 
 larvae of the codling moth ( Carpocapsa pomonella (L«)) than 
 were the soluble compounds tested by him. The tests reported here- 
 in were made to determine insect mortality by stomach and contact 
 action, as well as the effect of spray residues and dust deposits 
 left on foliage. The testing methods are somewhat similar to those 
 recently described by Swingle 3/. 
 
 Chemical Nature of Metal-Nicotine Salts 
 
 The direct combination of nicotine with an acid results in the 
 formation of a simple salt. Most, if not all, of these simple salts 
 are very soluble in water. Certain ones, such as the salicylate, 
 benzoate, tartrate, and oxalate, are crystalline solids, stable un- 
 der atmospheric conditions but soluble in water. Many other simple 
 salts are of indefinite composition, and usually hygroscopic. The 
 water-resistant combinations of nicotine with bentonite, tannic acid, 
 or humic acid might be considered as simple salts, but the resemblance 
 is probably superficial. 
 
 1/ Now assistant entomologist, Division of Insects Affecting 
 Man and Animals. 
 
 Z/ Hansberry, R. Toxicity of nicotine compounds to newly 
 hatched codling moth larvae. Jour. Econ. Ent. 35: 915-918. 1942, 
 
 2/ Swingle, M. C. Exploring the insecticidal possibilities 
 of new materials. In. Laboratory procedures in studies of the chem- 
 ical control of insects, edited by P. L. Campbell and P. R. Moulton, 
 Amer. Assoc. Adv. Sci. 20, pp. 82-84. Washington, D. C. 1943. 
 
- 2 - 
 
 A study of the toxicity of the more complex metal-nicotine selte 
 it important in determining whether the toxicity of nicotine ie in- 
 fluenced favorably or otherwise "by its presence in chemical union with 
 the various metals employed. Our knowledge of the effect of molecular 
 structure on toxicity is inadequate. Furthermore, resistance to 
 weathering, including moisture and oxidation effects, would seem to he 
 a desirable property. 
 
 The complex salts of nicotine with a selected metal are of two 
 types, the double salt and the nicotinammino compound. The former re- 
 sults from the combination of the metal and nicotine salts of the same 
 selected acid* The latter Is formed when the nicotine alkaloid reacts 
 with a metal salt of the selected acid. The metals most likely to form 
 these two types of compounds are those that are less electropositive than 
 magnesium, such as iron, cobalt, nickel, copper, cadmium, manganese, zinc, 
 aluminum, and chromium. Of the acids so far tried, the most suitable for 
 forming complex salts that are relatively insoluble in water are benzoic, 
 salicylic, picric, thiocyanic, hydrocyanic, o-benzoylbenzoic, and 
 o-phenoxybenzoic. 
 
 The compounds tested, with their formulas, are listed below. It 
 will be noted that (10), (ll), and (12) contain no metal but are salts 
 of dye acids (13), (14), and (15) are the corresponding metal-nicotine 
 double salts of the dye acids ±/» 
 
 (1) Cupric dinicotine thiocyanate, Cu( CNS) 2# 2 ( C 10 H 14 » 2 .HOTS). 
 
 (2) Cupric dinicotine o-benzoylbenzoate, 
 
 Cu(00C.C 6 H 4 .0C.C 6 H 5 ) 2 .2 (C^H^H^HCOO.CgH^.OC.CgHg) 
 
 (3) Cupric dinicotine benzoate, Cu(00C»CgH g2 .2 (C 10 H 14 H 2 .H00C.CgH 5 ) 
 
 (4) Cupric dinicotine salicylate monohydrate, 
 
 Cu(00C.CgH 4 (0H)) 2 .2 (C 1() H 14 H 2 .H00C.CgH 4 (0H)).H 2 0. 
 
 (5) Zinc mononicotine thiocyanate, Zn(CHS) _.C H, „!! .HCNS. 
 
 2* 10 14 2 
 
 (6) Cupric dinicotine picrate, 
 
 Cu(0.C 6 H 2 (K>3) 3 ) 2 .2 (0 10 H 14 H 2 .HO.C 6 H 2 (H0 2 ) 3 ). 
 
 (7) Zinc dinicotine picrate, 
 
 Zn(O.C 6 H 2 (M, 2 ) 3 ) 2 . 2 (0 10 H 14 H 2 .HO.C 6 H 2 (ir0 2 ) 3 ). 
 
 (8) Zinc dinicotine salicylate, 
 
 Zn( 00C.CgH 4 ( OH) ) .2 ( C 10 H 14 H 2* H0 ' C 6 H 4 ( 0H) * • 
 
 ±/ Compounds (12) to (15), inclusive, were prepared by C. W. 
 Murray, of the Bureau of Agricultural and Industrial Chemistry. 
 
- 3 - 
 
 3) Zinc dinicotine benzoate, Zn(00C.C.H_) o .2 ( C, „H, .H .HC000 H _) . 
 
 o 5 3 10 14 2 6 5 
 
 10) Hicotine chrome orange R, salt of p-nitrobenzeneazosalicylic 
 acid, the dye acid of chrome orange R. 
 
 11) Hicotine paper yellow L (first fraction) , salt of 2, 4-dinitro- 
 1-naphthol. 
 
 12) lieotine paper yellow! (second fraction), similar to (.11) but 
 exact constitution unknown, 
 
 13) Cupric nicotine chrome orange R, double salt with the dye acid 
 of (10). 
 
 14) Cupric nicotine paper yellow L, double salt with the dye acid 
 of ( 11) . 
 
 15) Cupric nicotine stilbene yellow OA, double salt with the acid 
 of a sulfonated nitro stilbene dye* 
 
 16) Cuprous aononicotine thiocyanate, 2 CuCHS.C H H .HCHS. 
 
 17) Cuprous dinicotine thiocyanate, 2 CuCNS.2 (C H H .HOTS). 
 
 18) Cobaltous dinicotine thiocyanate, Co( CNS) _. 2 ( C, _H, ,N .HOTS) . 
 
 2 10 14 2 
 
 19) Hickelous dinicotine thiocyanate, Hi(OTS) 2 (C.-H ,N„.HOTS). 
 
 2 10 14 2 
 
 20) Cuprous nicotine cyanide, 2 CuOT.C H H .HCH. 
 
 21) Nanganous aononicotine salicylate, 
 
 Mn(00C.C H.(OH)) .C in H..H .HOOC.C.H (OH). 
 6 4 2 10 14 2 6 4 
 
 22) Cadmium dinicotine salicylate, 
 Cd( OOC. C 6 H 4 ( OH) ) 2( C^/g.HOOC. C g H 4 ( OH) ) . 
 
 23) Cupric dinicotinamaino benzoate dihydrate, 
 Cu( OOC . OgHj.) 2 . 2C 10 H 14 I 2 . 2H 2 0. 
 
 24) Cupric dinicotinamaino o-benzoylbenzoate dihydrate, 
 
 M ooo.c 6 h 4 ( oo.c 6 h 5 ) ) rtCrfff. » 2 o. 
 
 25) Cuprous dinicotinamaino thiocyanate, (CuOS) ,2 C H I . 
 
 The insecticide used for coaparison in aost of the tests was 
 that usually recoaaended for control of the species. These materials 
 were pyrethrua (pyrethrin I 0.60 percent and pyrethrin II 0.63 per- 
 cent), derris (rotenone 4.8 percent), barium fluo silicate, nicotine 
 sulfate, lead arsenate, sodium fluoride, and dusting sulfur. In some 
 cases they were applied at a greater strength than is recommended for 
 field use. 
 
- 4 - 
 
 The tests were made on representatives of fire orders of insects 
 and a red spider as listed below, with the host plants and form used 
 for each* 
 
 IHSBCT HOST 
 
 Orthoptera (large nymphs)* 
 
 American cockroach - - - - - 
 
 (Periplaneta Mgr.gaRft (L.)) 
 
 Isoptera (adults and large nymphs)! 
 
 A termite ( Eeticulltermes sp.) *- 
 
 Homoptera (wingless agamic form): 
 
 An aphid ( Macro sluhum ambroalae (Thos.)) ftrassleaf wild lettuce 
 
 (kyftfcttfii graiUlfolU) 
 
 Coleoptera (adults): . 
 A blister beetle 
 ( Bplcauta lemniscata ( f. ) ) flgweed ( AmaraflthUB sp.) 
 
 Cowpea weerll ( Calloaobruchua frewa Crowder cowpea 
 
 ■acttlataa (*.)) (Una alfltmala) 
 
 Lepidoptera ( fourth instars) t 
 
 Bean leaf roller (Vrbanuj pro tens (!»•)) »*•* (flftltolui YTUgftlla) 
 
 Cross-striped cabbage worm fmllard ( Braaslca olcr&.cea 
 
 (gyergOBtll rlMQBalU (Qnen.)) »fl«phiil^ 
 
 Greenhouse leaf tier do* 
 
 (Phlzc^ajsala rublgalis (Quen.)) 
 
 Hawaiian beet webworm Pigweed (AmaXAA^bOA «P») 
 
 (HjcmaaiA faiCl&Ug (Cram.)) 
 
 Melon worm ( Piaphania hrallnata (L.)) HmjHs and squash 
 
 <fllTffflrtltn «pp.) 
 
 PirVlnwnrm ( Dl^V^i* n\ t««UH ml Stall A\ Am. 
 
 Southern beet webworm flfveed 
 
 (Pachyzaaclt bipuactalla ( *.)) 
 
 Southern armyworm (Pffldfala ftrjdftnl a Collar*, pigweed 
 
 (Cram.)) 
 
 Acarlna (all stages)! 
 
 Common red spiders ( TeJLu&ZOhuj. «P«) Celery ( Apium grareolens) 
 
- 5 - 
 
 Eleven kinds of plants were used in the tests for phytoxicity — bean, 
 broccoli, collard, lettuce, okra, pea, potato, pumpkin, swiss chard, tomato, 
 and turnip* An attempt was made to use at least fire kinds with each concen- 
 tration of the chemicals, but since the tests were made at different times of 
 the year it was impossible to use the same five for ail the compounds. 
 
 Tests with Dusted Foliage 
 
 The first experiment was to determine the efficiency of the compounds 
 as dusts. The material was applied to both sides of leaf sections in a 
 settling chamber, and the approximate deposit determined from the weight of 
 the dust on a small metal plate placed in the chamber with the leaves. Two 
 dusted leaf sections were used for each species of Insect, each leaf section 
 being placed with 1Q insects in a 9-cm. Petri dish and held at a constant 
 temperature of 80° F. Mortality counts and estimates of the amount of feed- 
 ing were made at the end of 2 and 3 days. The mortality in these closed 
 dishes may have been due to either stomach or contact action. Since these 
 test 8 were only preliminary, no replications were made* 
 
 The compounds of high nicotine content when used as undiluted dusts 
 were very toxic to nearly all the test insects, but the results with only 
 the more practical dilutions are reported here. From the data acquired it 
 appeared that six of the compounds ( table l) were more effective than the 
 others at dilutions containing approximately 5 percent of nicotine. It 
 should be noticed that four of these six materials contained copper as the 
 metal. The blister beetle, the greenhouse leaf tier, and the southern 
 armyworm were shown to be very resistant to all compounds tested. The bean 
 leaf roller and the pickleworm were very susceptible, and the cross-striped 
 cabbage worm, the Hawaiian beet webworm, the melon worm, and the southern 
 beet webworm moderately susceptible. 
 
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- 9 - 
 
 All the compounds listed in table 1 were at least as good as the 
 recommended insecticides except in tests with the southern armyvora and 
 the blister "beetle. Hone of the nicotine dusts had any control effect 
 on the southern armyworm at the concentrations used. 
 
 Cuprous dinicotinaomino thiocyanate repelled the blister beetles 
 but did not kill them, Nicotine paper yellow L (first fraction) had no 
 effect on this insect. 
 
 Cuprous mononicotine thiocyanate was about as effective as derris 
 against t*he cross-striped cabbage worm, but the rotenone content of the 
 derris dust was twice that used in the field* 
 
 Tire of the materials tested on the Hawaiian beet webworm gave higher 
 mortality than the derris dust, which probably was higher in rotenone 
 than the derris used in practical control* 
 
 Against the melon worm cupric dinicotine picrate, zinc dinicotine 
 picrate, cuprous mononicotine thiocyanate, and cupric dinicotine 
 tniocyanate-, in dusts containing 5 percent of nicotine, were more effective 
 than derris at the strength recommended for field use (1.2 percent rotenone): 
 nicotine paper yellow L (first fraction) and cuprous dinicotinammino 
 thiocyanate were as effective as derris at the same respective strength. 
 
 Against the pickleworm all six of the compounds, at both 5 and 2.5 
 percent nicotine, were 100 percent effective, as was also the pyrethrum. 
 Zinc dinicotine picrate and nicotine paper yellow L, however, allowed 
 more feeding than did the pyrethrum. 
 
 Against the southern beet webworm, cupric dinicotine picrate, sine 
 dinicotine picrate, and nicotine paper yellow L (first fraction), at 6 
 percent of nicotine, were approximately as good as derris. 
 
 Phototoxicity rests with Dusts 
 
 A glass cylinder 25 inches high and 11 inches in diameter open at 
 both ends was placed over plants in the garden, and a heavy coating of 
 dust particles was allowed to settle on the leaves. Two applications 
 were made 4 days apart, and the results were recorded 8 days after the 
 first application. From 1 to 12 plants of each kind were used in these 
 tests. The plants were covered only at night and during periods of rain. 
 Since in the tests of insectlcidal effect,- dusts containing 5 percent of 
 nicotine were generally used, it was decided to make the phytotoxicity 
 tests with dusts containing 15 percent of nicotine to provide for a margin 
 of safety. All the compounds at this nicotine concentration were 
 apparently nontoxic to the plants used. 
 
- 10 - 
 
 Tests with Spray Residues 
 
 Tests were next made to determine the effect of the residues from 
 aqueous sprays prepared from the compounds. Plants were sprayed with 
 suspensions containing from 0.05 to 0.14 percent of nicotine, and ex- 
 cised leaf sections were placed in 9-cm. Petri dishes with insects. 
 Of the insects used in these tests — the blister beetle, the southern 
 armyworm, the melon worm, and the pickleworm — only the last two were 
 affected by the compounds. Table 2 gives the data from the results of 
 only those compounds that were effective against either one or both of 
 these two insects. Here again the majority of the most effective com- 
 pounds contain copper. 
 
- 11 - 
 
 
 
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- 12 - 
 
 At the concentrations used all the eompoun-ds listed in table 2 that 
 vere tested against the picklevorm were eq,ual to derris, but in several 
 instances moderate feeding vas evident. The six compounds found to be 
 effective against the melon vera vere alse superior to cerris, vith the 
 possible exception of nicotine paper yallev L (second fraction). 
 
 Phototoxicity Tests vith Spray Residues 
 
 Phytoxicity tests vere Bade on 5 Kinds of plants in the garden plot 
 by thoroughly spraying them vith suspensions of the various nicotine com- 
 pounds containing approximately 0.3 percent of nicotine, 3 times the 
 strength used in the insect tests* It this concentration only 2 of the 
 12 compounds that shoved insecticide! properties vhen applied as sprays 
 had no effect on foliage* They vere cuprous nicotine cyanide and cuprous 
 dlnicotlnammino thiocyanate. Vhem the amount of nicotine vas reduced to 
 tvico that used in the insect tests, only tvo other compounds, cupric 
 nicotine paper yollov L and cuprous mononiootine thiocyanate, vere added 
 to the list of materials safe to use. All the others caused from moderate 
 to severe injury to 2 or more kinds of plants. 
 
 Contact Tests vith Sprays and Busts 
 
 Tests vere made on red spiders fouad on celery in the field by 
 thoroughly dusting them vith a small hand duster and setting the stems of 
 the foliage in flasks of vater in battery jars* By the method used it 
 vas impossible to determine the amount of dust deposited. Of 24 materials 
 tested, only 2 — cupric dlnicotine beasoate (39 percent mortality) and 
 cuprous nicotine cyanide (52 percent mortality) — shoved any toxicity in 
 3 days. In the same period dusting sulfur effected 100 percent mortality. 
 
 Spray tests against the aphid HflgTt mJUassn 1 MJBalasM v * re **•<*■• vith 19 
 of the compounds diluted to 4 pounds per 100 gallons of vater, vhich re- 
 sulted in nicotine concentrations from 0.08 to 0.25 percent, vith 1 percent 
 of saponin added as a vetting agent. The following compounde caused at 
 least 89 percent mortality (percentages of nicotine in parentheses): 
 Cupric diaicotine benzoate (0.185), cupric dinicotine salicylate (0.173), 
 sine diaicotine salicylate (0.173), zinc dinicotine benzoate (0.185), 
 cupric nicotine chrome orange fi (0.088), cupric dlnlcotlnaamine benzoate 
 dihydratt (0.243), cupric dinicotinammino o— oenzoylbenzoate dlhydrate (0.186), 
 and cuprous dinicotinammino thiocyanate (0.250). Nicotine sulfate (40 
 percent nleotlne) diluted to 0.04 percent in vater caused 100 percent 
 mortality. Saponin alone caused 4 percent mortality. The other compounds 
 gave mortalities ranging from to 69 percent. The folloving chemicals were 
 not Included in tfeis teet b+oanse they vere too toxic to the plants at the 
 concentration used: Cupric dinicotine thiocyanate, sine momonicotlne 
 thiocyanate, cobaltous dinicotine thiocyanate, nickelous diniootine thiocy- 
 anate, aaaganese aononicotlne salicylate, and cadmium dinicotine salicylate. 
 
- 13 - 
 
 Another test gave some Indication of the contact action against 
 lepidopterous larvae. Insects in Petri dishes were dusted at the rate of 
 approximately 200 micrograms per square centimeter and fed untreated foliage. 
 By this method it was possible for the insects to pick up and eat particles 
 of Insecticide from the bottom of the dish. At the end of 2 and 3 days 
 mortality counts and estimates of the amount of feeding were made. Against 
 4 the melon worm, with the use of 10 percent dusts (nicotine 1.5 to 5,25 
 * percent) in not one case was the material so efficient as in the dusted- 
 1 foliage test with the same amount of nicotine. Against the southern army- 
 worm, however, when the undiluted material was used the following compounds 
 were at least as effective as in the dusted-foliage tests! Cuprlc dinicotine 
 thiocyanate, cupric dinicotine benzoate, zinc mononicotine thiocyanate, 
 cuprous mononicotine thiocyanate, cuprous dinicotine thiocyanate, cobaltous 
 dinicotine thiocyanate, cuprous nicotine cyanide, and cadmium dinicotine 
 salicylate. 
 
 Miscellaneous Tests Against Roaches, Weevils, and Termites 
 
 All the materials were tested against the American cockroach by 
 sprinkling 0.25 gm. over the bottom of a 6-inch battery jar and then intro- 
 ducing 10 nearly full grown nymphs. A thin film of petrolatum was put on 
 the top inner surface of the jar to prevent the escape of the insects. 
 Cuprous nicotine cyanide was the only effective material, causing 100 percent 
 mortality in 3 days. An equal weight of sodium fluoride, however, killed all 
 the roaches in 1 day. 
 
 In test 8 against the cowpea weevil each compound was thoroughly mixed 
 with Brown Crowder cowpeas, 1 part to 1,000 parts by weight, in a Petri dish. 
 Thirty adult weevils were then introduced, and each dish was placed on its 
 edge. After 4 days mortality counts were made. Hone of the materials caused 
 a mortality greater than 50 percent. The five that killed from 40 to 50 per- 
 cent were cupric dinicotine benzoate (49 percent mortality), cuprous nico- 
 tine cyanide (48 percent), cupric dinicotinammino benzoate dihydrate (44 
 percent), zinc mononicotine thiocyanate (43 percent), and nicotine chrome 
 orange R (42 percent). 
 
 The effectiveness of the materials against termites was determined by 
 the method described by Hockenyos. §J A small piece of crumpled tissue paper 
 and approximately 15 ml. of water were placed in the bottom of a 100-ml. 
 beaker. On top of this a 40- gm. mixture of the compound and sand was intro- 
 duced. After all the sand had become damp, approximately 30 adults or large 
 nymphs were placed in the beaker. Mortality counts were made at the end of 
 4 days. Cupric dinicotine benzoate killed 56 percent of the insects at a 
 dilution of 1 to 1,000 and 22 percent at 1 to 5,000, cuprous nicotine cyanide 
 at 1 to 1,000 repelled the insects and gave a mortality of 15 percent but was 
 ineffective at 1 to 5,000, and cupric dinicotinammino o-benzoylbenzoate 
 dihydrate repelled the insects and killed 54 percent of them at 1 to 1,000, 
 but was ineffective at 1 to 5,000. None of the other compounds caused any 
 mortality. 
 
 5/ Hockenyos, G. L. Laboratory evaluation of soil poisons used in 
 termite control. Jour. Econ. Ent. 32J 147-149. 1939. 
 
- 14 - 
 
 S n mma T* y 
 
 III llll 
 
 3 1262 09238 7082 
 
 Several types of tests were Bade to determine the insecticidal 
 sfficiency of 25 complex salts containing nicotine, usually combined with 
 a metal. 
 
 In feeding tests with dusts diluted to approximately 5 percent nicotine 
 content, at least six of the compounds were as ef fee tire against two to four 
 species as was the recommended insecticide. These compounds, in descending 
 order of effectiveness against from four to six species, were cupric 
 dinicotine picrate, sine dinicotine picrate, cuprous mononicotine thiocyanate, 
 cupric dinicotine thiocyanate, nicotine paper yellow L (first fraction), and 
 cuprous dinicotinammino thiocyanate. When these materials were applied to 
 plants in dusts containing 15 percent of nicotine, little or no injury to the 
 foliage was apparent* 
 
 When tested as sprays, 12 of the compounds were as effective as the 
 recommended insecticides against at least 1 of 4 species of insects on 
 foliage' sprayed with suspensions containing approximately 0.1 percent of 
 nicotine. Of these 12 only 2, cuprous nicotine cyanide and cuprous 
 dinicotinammino thiocyanate, caused no injury to foliage in spray suspensions 
 containing 0.3 percent of nicotine. These are, therefore, the only compounds 
 that can he recommended as safe to use in spray form. 
 
 Most of the compounds that showed appreciable toxicity against 
 lepidoptorous larvae contained copper. Only two materials, cuprous mononico- 
 tine thiocyanate and cuprous dinicotinammino thiocyanate, were 100 percent 
 effective in both dust and spray form. 
 
 When dusted directly in Petri dishes and fed untreated foliage, melon 
 worm larvae were only slightly affected by any of the materials, but the 
 southern armyworm was affected by several where it was possible in each test 
 for the larvae to eat some of the particles. 
 
 Cuprous nicotine cyanide killed all the large nymphs of the American 
 cockroach in 3 days. None of the materials were effective against the 
 cowpea weevil or against termites.