LIBRARY TATE PfeA^rB^ D B-705 United States Department of Agriculture Agricultural Research Administration Bureau of Entomology and Plant Quarantine A REVIEW OP LABORATORY TESTS ON THE TOXICITY OP CERTAIR SEMICARBAZONES TO VARIOUS INSECTS By S. I. Gertler, Division of Insecticide Investigations In the course of its investigations the Division of Insecticide Investi- gations prepared a large number of semicarbazones and submitted them to other Divisions of the Bureau for laboratory tests against a number of insects. Some of these compounds seemed to be promising. Pour patents have been granted on this class of compounds k, % t 6) . It was therefore considered advisable to compile the results of the tests in such a manner as to facilitate the selec- tion of the compounds that were most toxic to any given insect and also those that were toxic to a number of different insects, Semicarbazones may be prepared by condensing aldehydes and ketones with semicarbazide under suitable conditions. Most of them are colorless solids, which crystallize well and have physical properties that easily lend themselves to the preparation of insecticidal mixtures. The insects tested and the Divisions in which they were tested are as follows: Division of Cereal and Porage Insect Investigations: European corn borer ( Pyrausta nubilalis (Hbn. ) ) . Division of Control Investigations: American cockroach ( Perlplaneta ameri cana (L. )) Bean leaf roller ( Urbanus proteus (L.)) Three-striped blister beetle ( Epicauta lemmlscata (P.)) Cabbage looper ( Trlchoplusia ni ( Hbn . ) ) ( = Aut ographa brasslcae (Riley)) Cowpea weevil ( Callosobruchus maculatus (P.)) (=C. chinensis (L.)) Cross-striped cabbageworm ( Evergestis rimosalis TGuen,) ) Hawaiian beet webworm (Hymenia recurvalle (P.)) (=H» fascial is (Cran.)) Imported cabbageworm ( Pieris rapae (L.)) A looper ( Pseudoplusla rugationis (Guen.)) (= sAut ographa oo (Stoll)) Melonworm ( Diaphania hyalinata (L>)) Mexican bean beetle ( Epilachna variv e stl6 Muls.) Okra caterpillar (Anomis erosa Hbn7}~ Rice weevil ( Sltophilus oryza (L.)) Southern armyworm ( Prodenla erldania (Cram.)) Squash bug ( Anasa trlstis (Peg.)) A termite ( Retlculitermes flavipes (I.)) Yellow woollybear ( Diacrisia virginlca (P.)) Division of Pruit Insect Investigations: Codling moth ( Carp o cap aa pomonella (L.)) OCT 2 4 1946 - 2 - Division of Insects Affecting Man and Animals: Furniture carpet beetle ( Anthrenus vorax (Waterh.)) Mosouito (larvae) ( Culex quinouefasciatus Say) Screwworm ( Cochlioniyia americana C. and P.) The methods used for testing are the usual standardized ones which have been used in the past, and so are mentioned only briefly. All the compounds tested against each insect are listed in order of toxicity. Compounds that were tested both as a dust and as a spray are listed twice. All dosages are for dusts. When no figure is given in the dosage column, the material was applied as a spray at a concentration of 8 pounds per 100 gallons unless in- dicated otherwise. American Cockroach (10) Cockroaches that were three- auart ers grown were confined for 2 days in a jar on the bottom of which 0.25 gram of the compound had been dusted. The following compounds were tested: Semicarbazones of benzophenone, pj-chloro- acetophenone, o—chlorobenzaldehyde, cyclohexanone, cyclopentanone, 2,6-di- methyl-k-heptanone, 2,U- dimethyl-Vpentanone, 2-furaldehyde, levulinic acid, 2-methylcyclohexanone, methyl ethyl ketone, piperonal, vanillin, and o-veratr al- dehyde. None of these compounds showed any toxicity to the roaches. Bean Leaf Holler This- test was carried out by feeding dusted bean leaves to fifth instars. The- only compound tested was cyclohexanone serai carbaz one in a dosage of 355 micrograms per souare centimeter. It gave 87 percent kill in 3 days. Three-Striped Blister Beetle The adult beetles were fed either dusted or sprayed Swiss chard leaves. Semicarbazone Dosage Days Percent (micrograms per exposed kill souare centimeter) U-Me t hyl cy cl ohexanone 230 2 100 k 100 Xthyl methyl ketone 250 2 100 6 100 2, U-Dimethyl-3-pentanone 6 9 I 280 2 2-Methylcycl ohexanone 200 2 95 Cyclohexanone 200 2 90 £-Chloroacetophenone 6 87 Cyclopentanone 215 2 85 2-Furaldehyde 8 77 Cyclohexanone 6 76 Benzophenone 285 3 29 "D- Chi oroace t ophenone 280 2 eT-Fur aldehyde 185 2 - 3 - Three-Striped Blister Beetle — cont. Semi carbaz one Do sage Days Percent (micrograms per exposed kill sauare centimeter) 2- Me thyl cy cl ohexanone 6 Salicylaldehyde 150 2 o-Veratral dehyde 260 2 Cahhage Looper Thie test was conducted "by feeding fifth instars dusted collard leaves. The only compound tested was p-chloroacetophenone semi carta zone , which at a dosage of 280 micrograms per scuare centimeter gave h percent kill in 2 days. Codling Moth (£) These tests were conducted on newly hatched larvae, by the apple-plug method, infested shortly after application. Sach compound was sprayed at a concentration of U pounds per 100 gallons. Semi carfcaz one Percent Percent wormy stung p_- Chi or oac e t oph en one 7 21 2-0ctanone 17 2 Cyclopentanone 21 2-Heptanone 30 2-Fur.aldehyde 35 21 U-Methyl cyclohexanone 3« 2-Methylcycl ohexanone U2 Cyclohexanone 50 1 2 , U-Dime thyl-3-pentanone 5 ? Ethyl methyl ketone 56 7 Cinnamal dehyde 66 Methyl propyl ketone 67 3 Sal i cyl aldehyde 7U Benzophenone 76 U-Methyl-2-pentanone 76 o-Veratral dehyde 77 p-Hydroxyacetophenone 78 Acetoacetic acid, ethyl ester 79 3 alpha-Ethyl hutyr aldehyde 79 1 0- Chi orohen zaldehyde *2 p-Methylacetophenone 82 Crotonal dehyde gu p-Aminohenzophenone 86 Benzoin 86 1 Levulinic acid 86 2 , 6-Dimethyl-h-heptanone 87 - U - Codling Moth — cont. C am 4 a A P*\ mm /\ V% A Demi car oaz on© rerceiig wui m jr a ^ >-) rt £T D ItlLIlg Acetophenone 88 Vanillin 88 B en z aldehyde 90 2 Piperonal 91 3 ) U-Dichloroacetophenone 92 2 jcenzix ymono/ Ace tonylace tone (dl) 95 Cowpea Weevil Adult weevils were exposed in a petri dish with peas sprayed with the compound at a concentration of 1:1000. Semi car "baz one Bays exposed Percent kill Methyl ethyl ketone 5 88 Methyl propyl ketone 5 78 Levulinic acid k 77 Cyclopentanone 5 70 2,6-Dimethyl-U-heptanone 5 60 U-Methyl-2-pentanone 5 52 Sal i cylal dehyde 5 Ul Cyclohexanone u 33 Benzoin U 26 2 ,U-Diraethyl-3-P«Btanone U 22 3,U-Dichloroacetophenone U 20 Benzophenone U 19 2-Heptanone u 1H Piperonal u 7 Acetoacetic acid, ethyl ester U h p_-Chloroacetophenone U o- Chi o rohen zal dehyde u u p- An i no h en z ophen one u 3 Benzll (mono) u 3 Acetophenone u 2-Fur aldehyde u Vanillin u Cross-striped Cahbageworm Insects of the fifth instar were fed dusted collard leaves. - 5 - Dosage Days Percent Semi carta zone (micrograms per square centimeter) exposed kill Cycionexanone 310 c "inn Cyclop en tanone cW -5 Ethyl methyl Ketone OCA d. 1UU c— Metnyl cycionexanone J.'+KJ 1. I ion Xw 1UU 4— Metnyl cycionexanone c mn h Cycionexanone Q7 Cy clop ^n tan one O 05 t — j u_r ax o. eny u.o ■z J j 1 2-Heptanone 23 £ j H— i/xine unyi~ 5 — peni/anono 1 "7 A 3 jjovuiimc aciu. 1x20 c 7 f p-Ami noben z ophenone 3 Benzil (mono) 210 3 £- Chi oroben zaldehyde 270 2 3, Ij-Dichloroacet ophenone 185 3 Piperonal 155 2 European Corn Borer (8) Newly hatched larvae were fed sprayed cauliflower leaves, For the sake of comparison all results will he given at a concentration of h pounds per 100 gallons although further tests were made at a concentration as low as 1 pound per 100 gallons. Semicarbazone Days exposed Percent kill Acetophenone 3 99 Benzaldehyde 3 9^ 2,6-Dimethyl-U-heptanone 3 9** p-Chloroacetophenone 2 91 p-Methylacetophenone 3 76 Ethyl methyl ketone 3 11 Benz ophenone 3 ? Cyclopentanone 3 6 U-Methyl-2-pentanone 3 3 Methyl propyl ketone 3 3 Piperonal 2 3 Salicyladehyde 3 3 Acetoacetic acid, ethyl ester 2 2 Acetonylacetone (di) 3 2 pj-Aminobenz ophenone 2 2 £-Chlorobenzaldehyde 2 2 Crotonaldehyde 3 2 3,H-Dichloroacetophenone 2 2 2,U-Dimethyl-3-pentanone 2 2 2-Heptanone 2 2 2-Methylcyclohexanone 2 2 European Corn Borer — cont. - 6 - Semi carbazone Days exposed Percent kill 2-0ctanone 3 2 Vanillin 2 2 pj-Aminobenz ophenone 2 1 Benzll (mono) 2 Cyclohexanone 2 H-Methyl cyclohexanone 2 <£-Ver atral dehyde 2 alpha-Ethylbutyraldehyde 2 Levulinic acid 2 Furniture Carpet Beetle (2) The insects used were half-grown larvae. The results are given in terms of the ratio of the mortality produced by sodium fluosilicate solution to that produced by the compound. Semi car baz one Mortality ratio Semicarbazone Mortality ratio j>-Ami nobenz ophenone l.U Cro tonal dehyde 8.0 j>- Chi or oace t ophenone l.U c_- Chi orobenzaldehyde 10. k Benzophenone 1.5 Ethyl methyl ketone 10.6 Cyclohexanone 2.7 Acetoacetic acid, ethyl Benzil (mono) 3.6 ester 10.7 Acetophenone U.l Piperonal 11.0 3,U-Dichloroacetophenone k.2 Cyclopentanone 12.3 Benzaldehyde U.6 j£-Methylacetophenone 12.7 Methyl propyl ketone 5.0 Vanillin 13.0 lU.O 2-Pur aldehyde 6.5 alpha-Ethylbutyraldehyde 2-Heptanone 7.0 Acetonylacetone (di) 18.2 2 , 6-Dimethyl-h-heptanone 7.3 2-0ctanone 19.1 2 , h_Dimethyl-3-P entanone U-Methyl-2-pentanone 21.5 Sal i cylaldehyde 21.5 Hawaiian Beet Webworm (10) The test insect was the fifth instar, which was fed dusted swiss chard leaves. Dosage Days Percent Semicarbazone (micrograms per exposed kill square centimeter) p-Chloroacetophenone - U 100 Cyclohexanone 2U0 2 100 U 100 Cyclopentanone - 6 100 2-Methyl cyclohexanone - 6 100 U-Methyl cyclohexanone - k 100 Hawaiian Beet Webworm — cont. Semicarbazone Dosage Days Percent (micrograms per exposed kill square centimeter) 385 3 96 325 2 385 2 96 280 2 96 - 6 94 - 4 94 280 3 88 385 2 88 6 82 400 3 77 495 2 -5/' 70 185 2 64 280 2 48 185 2 1+5 340 2 tin 40 \. r 1- 465 2 28 200 2 28 215 2 12 155 2 12 185 2 8 280 3 8 U35 2 8 495 2 8 310 2 4 355 2 4 185 2 u 170 2 185 2 200 2 pj- Ohl r a ce t oph en on e Cyclopentanone Ethyl methyl ketone 2-Heptanone 2,U-Dimethyl-3-pentanone 2-Fur aldehyde 2,4-Dimethyl-3-pentanone 2-Fur aldehyde 2-Heptanone pj-Arainobenzophenone Sal i cylal dehyde 2 , 6-Diraethyl-4-heptanone Methyl propyl ketone Benzil (mono) Benzophenone Acetophenone Cro tonal dehyde Acetoacetic acid, ethyl ester 3,4-Dichloroacetophenone Benzaldehyde alpha-Ethyl Duty ral dehyde p-Hydroxyacetophenone Sal i cylaldehyde Benzoin p-Methylacetophenone 4-Me t hyl -2-pentanone Acetonylacetone (di) Cinnamal dehyde Pi-peronal Imported Cabbageworm (10) Fifth-instar larvae were fed dusted collar d leaves for 2 days. Dosage Percent Semicarbazone (micrograms per kill square centimeter) 2-Fur aldehyde 385 96 Benzophenone 340 72 2, 6-Dimethyl-4-heptanone 185 72 Acetophenone U65 44 Cyclopentanone 325 32 alpha-Ethylbutyral dehyde 280 30 Cinnajnal dehyde 185 23 Benzaldehyde 185 16 Ethyl methyl ketone 385 16 Imported Cabbageworm — cont - 8 - Semicarbazone Dosage (micrograms per square centimeter) Percent kill Sal i cylal dehyde Acetonylacetone (dl) Cro tonal dehyde p-Hydroxyacetophenone 4-Methyl-2-T>entanone p-Chloroacetophenone ■n— Mpthvl ft<*ptoT>herionft Methyl propyl ketone 2-Octanone U95 170 200 >+35 185 280 j j j 280 185 16 12 12 12 12 8 Looper Fourth instars were fed sprayed collard plants. Semicarbazone Days exposed Percent kill 2-Heptanone Ethyl methyl ketone 6 6 67 5U Melonworm (10) Fourth instars were fod dusted or sprayed pumpkin leaves. Semicarbazone Dosage Days (micrograms per exposed sauare centimeter) Percent kill Cyclohexanone . 2 > h-Dimethyl-3-pentanonel/ 355 3 100 k 100 2-Fur aldehyde u 100 Cyclopentanone 2 96 2,U-Dimethyl-3-pentanone 230 3 92 U-Methyl cyclohexanone p_-Chloroacetophenonel/ 356 3 87 7 79 287 3 78 2-Methyl cyclohexanone 6 73 p-Am*nobenzophenone 370 3 72 2-Furaldehyde U35 2 72 Piperonal 230 I 72 U-yethyl cyclohexanone 52 2-Methyl cyclohexanone 385 3 m 2-Heptanone 280 3 3^ Concentration U pounds per 100 gallons. Melonworra — cont - 9 - Semicarbazone do sage i/tiy 3 flTDf) fl fid kill xvi.ll square c©iivj.uie vex / Acetoacetic acid, etnyi ester PI 7 2U Qyclopentanone TOG* p c Ethyl methyl ketone pop p c Levulinic acid c ±0 Sal i cylal deny de P7f\ p 1 p Xcetonylacetone (di) p alpha-Ethyl hutyraldehyde 3 » Crotonaldehyde OAA d li *r 2 ,6-Diraethyl-U-»heptanone 1 OK p li *+ Methyl px-opyl ketone d Ji vanillin