Synergistic insecticidal compositions containing benzyl 2-propynyl ethers
United States Patent [191 Hennessy [451 Apr. 29, 1975 SYNERGISTIC INSECTICIDAL COMPOSITIONS CONTAINING BENZYL 2-PROPYNYL ETHERS [76] Inventor: Douglas J. Hennessy, 47 Grayson Pl., Teaneck, NJ. 07666 [22] Filed: July 5, 1972 [21] Appl. No.: 265,423  
 Related U.S. Application Data [63] Continuation-in-part of Ser. No. 164,41 l, July 20,  
 I971, abandoned.  
 [52] U.S. Cl 424/200; 424/339 [5]] Int. Cl. A0ln 9/36;A01n 9/24 [58] Field of Search 424/200, 339; 260/611 A [56] References Cited UNITED STATES PATENTS 8/l967 Seki et al. 260/6ll A X I/l968 Felia et al. 424/300 X OTHER PUBLICATIONS Pesticide Index, 4th Ed., 1969, p. 188. Hennessy, The Potential of Carbamate Synergists as Pest Control Agents, U.S.-Japan Seminar, (1969).  
 Primary Examiner-Albert T. Meyers Assistant E.taminerLe0nard Schenkman Attorney, Agent, or Firm-Frederick H. Rabin; Philip P. Berestecki [57] ABSTRACT CH 2 O -CH 2 -C CH in which X, Y and 2 represent hydrogen, nitro, halogen other than iodine, or, when X is hydrogen, Y and Z taken together may represent methylenedioxy.  
 14 Claims, No Drawings SYNERGISTIC INSECTICIDAL COMPOSITIONS CONTAINING BENZYL Z-PROPYNYL ETHERS CROSS REFERENCE TO RELATED APPLICATION This is a continuation-in-part of application Ser. No. 5 164,411, filed July 20, 1971, now abandoned.  
  This invention relates to propynyl compounds, to new synergistic insecticidal compositions comprising such compounds, and to their use.  
  It has been discovered that certain propynyl compounds, more fully described below, synergistically enchance the acitivty of insecticides, particularly carbamate, organophosphorus and chrysanthemum monoand di-carboxylic ester insecticides. This synergistic action is, moreover highly selective in that the toxicity of the insecticides to warm-blooded animals is not appreciable increased.  
  The propynyl synergist compounds of the invention operate to protect the envirnoment in which they are used by permitting the use of a lesser dose of insecticide to obtain a percentage insect mortality comparable to that which would result from a larger dose of insecticide alone. This is of particular importance where the insecticide is environmentally persistent or is highly toxic to birds, fish or mammals. Further, in a number of instances, these propynyl synergist compounds broaden the spectrum of activity of the insecticide. They also restore the activity of insecticides against insects which have developed resistance to the insecticide where such resistance is due to metabolism, i.e. enzymic detoxification, of the insecticide. In so restoring activity against resistant insects, it is believed that the propynyl synergist compounds act to inhibit enzymic detoxification.  
  The insecticidal compounds with which the synergist compounds of this invention may be used include the following substances:  
 PHOSPHORIC ACID DERIVATIVES Bis- 0,0-diethylphosphoric acid anhydride (TEPP) 0,0,0,0-Tetrapropyldithiopyrophosphate Dimethyl(2,2,2-trichloro-l-hydroxyethyl)phosphonate (TRICHRORFON) 1.2-Dibromo-l ,2-dichlorethyldimethylphosphate (NA- LED) 2,2-Dichlorovinyldimethylphosphate (DICHLORFOS) 2-Methoxycarbamyll -methylvinyldimethylphosphate (MEVINPHOS) Dimethyll -methyl-2-( methylcarbamoyl )vinylphosphate cis (MONOCROTOPHOS) 50 3-(Dimethoxyphosphinyloxy)-N-methyl-N-methyoxycis-croton-amide I 3-( Dimethoxyphosphinyloxy )-N,N-dimethyl-ciscrotonamide (DICROTOPHOS) 2-Chloro-2-diethylcarbamoyl-l-methylvinyldimethylphosphate (PHOSPI-IAMIDON) 0,0-Diethyl-O-2-(ethylthio)-ethylthiophosphate (DEMETON) 0,0-Diethyl-S-2-(ethylthio)-ethylthiophosphate S-Ethylthioethyl-0,0-dimethyl-dithiophosphate (THI- OMETON) 0,0-Diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE) 0,0-Diethyl-S-2-[(ethylthio)ethylldithiophosphate (DISULFOTON) 0,0-Dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETONMETI-IYL) 2 0,0-Dimethyl-S-( l,2-dicarbethoxyethyl )dithiophosphate (MALATHION) (0,0,0,0-Tetraethyl-S,S-methylene-bis-[dithiophosphate ETHION) O-Ethyl-S,S-dipropyldithiophosphate 0,0-Dimethyl-S-(N-methyl-N- formylcarbamoylmethyl )-dithiophosphate TION) S-N-( l-Cyanol -methylethyl)carbamoylmethyldiethylthiolphosphate (CYANTI-IOAT) S-(2-AcetamidoethyI)-0,0 -dimethyldithiophosphate I-Iexamethylphosphoric acid triamide (I-IEMPA) (FORMO- 0,0-Dimethyl-O-p-nitrophenylthiophosphate (PA- RATHION-METI-IYL) 0,0-Diethyl-O-p-nitrophenylthiophosphate (PARA- THION) O-Ethyl-O-p-nitrophenylthiophosphonate (EPN) 0,0-Dimethyl-0-(4-nitro-m-tolyl)thiophosphate (FEN- TITROTI-IION) 0,0-Dimethyl-O-(2-chloro-4-nitrophenyl)thiophosphate (DICAPTHON) 0,0-Dimethyl-O-p-cyanophenylthiophosphate (CYA- NOX) 0-Ethyl-O-p-cyanophenylphenylthiophosphonate (DI- CI-IROFENTI-IION) -2,4-Dichlorophenyl-O-methylisopropylamidothiophosphate 0.0-Dimethyl-O-2,4,5-trichlorophenylthiophosphate (RONNEL) O-Ethyl-O-Z,4,5-trichlorophenylethylthiophosphonate (TRICHLORONAT) 0,0-Dimethyl-O-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS) 0,0-Diethyl-O-2.5-dichloro-4-bromophenylthiophosphate (BROMOPHOS-ETHYL) 4-tert. Butyl-Z-chlorophenyl-N-methyl-O- methylamidophosphate (CRUFOMAT) Dimethyl-p-( methylthio )phenylphosphat&#39;e 0.0-Diemthyl-O-(3-methyl-4- methylmercaptophenyl)thiophosphate (FENTHION) Isopropylamino-O-ethyl-O-(4-Methylmercapto-3- methylphenyl)-phosphate 0,0-Diethyl-O-p[(methylsulphinyl)phenyl]- thiophosphate (FENSULFOTHION) 0,0-DiemthyI-O-p-sulphamidophenylthiophosphate O-[p-( Dimethylsulphamido )phenyl]0,0-dimethylthiophosphate (FAMPI-IUR) 0,0,0,O&#39;-Tetramethyl-0,0-thiodi-p-phenylenethiophosphate O-(p-(p-Chlorophenylazophenyl)0,0-dimethylthiophosphate (AZOTHOAT) O-Ethyl-S-phenyl-ethyldithiophosphonate O-Ethyl-S-4-chlorophenyl-ethyldithiophosphonate O-Isobutyl-S-p-chlorophenyl-ethyldithiphosphonate 0,0-Dimethyl-S-p-chlorophenylthiophosphate 0,0-Diemthyl-S-(p-chlorophenylthiomethyl)- dithiophosphate 0,0-Diethyl-p-chlorophenylmercaptomethyldithiophosphate (CARBOPHENOTI-IION) 0,0-Diethyl-S-p-chlorophenylthiomethylthiophosphate 0,0-Diemthyl.-S-( carbethoxy-phenylmethyl )dithiophosphate (PHENOTHOAT) 0,0-Diethyl-S-(carbofluoroethoxy-phenylmethyl)- dithiophosphate pyrazolyl 7 2-Fluorethyl(4-bisphenyl)acetate 2-Fluoro-N-methyl-N( l-naphthyl )-acetamide Pentachlorophenol and salts 2,2,2-Trichloro-N-( pentachlorophenyl )-acetimidoyl chloride N&#39;-(4-Chloro-2-methylphenyl)-N,N-dimethylformamidine (Chlorphenamidine) 4-Chlorobenzyl-4fluorophenyl-sulphide side) 5,6-Dichloro-l-phenoxycarbanyl-2-trifluoromethylbenzimidazole (Fensoflor) Trieyclohexyl-stannic-hydroxide 2-Thiocyanatoethyl-lauric acid ester B-Butoxy-B-thiocyanatodiethyl-ether lsobornyl-thiocyanatoacetate p-Chlorophenyl-p-chlorobenzenesulphonate (Ovex) 2,4-Dichlorophenyl-benzenesulphonate p-Chlorophenyl-benzenesulphonate (Fenson) p-Chlorophenyl-2,4,5-trichlorophenylsulphone radifon) p-Chlorophenyl-2,4,S-trichlorophenylsulphide (Tetrasul) Methyl bromide p-Chlorophenyl-phenylsulphone p-Chlorobenzyl-p-chlorophenylsulphide side) 4-Chlorophenyl-2,4,5-trichlorophenylazosulphide 2(p-tert.-Butylphenoxy)-l-methylethyl-2-chloroethylsulphite 2(p-tert.-Butylphenoxy)cyclohexyl-2-propinyl-sulphite 4,4&#39;-Dichloro-N-methylbenzenesulphonanilide N-( 2-Fluoro-l l ,2,2-tetrachloroethylthio methanesulphonanilide 2-Thio-I ,3-dithiolo-(4,5-6)quinoxaline (Thioquinox) Chloromethyl-p-chlorophenylsulphone l 3,6,8- Tetranitrocarbazole and Prop-2-ynyl-(4-t-butylphenoxy)-cyclohexylsulphite (Propargil).  
 Chrysanthemum monoand di-carboxylic esters 3-(2,4-pentadienyl)-4-oxo-2-cyclopenten-l-yl chrysanthemumate (Fluoroben- (Tet- (Chloroben- 3-( 2-( 2-butenyl )-4-oxo-2-cyclopentenl -yl chrysanthemumate 3-allyl-2-methyl-4-oxo-2-cyclopentenl -yl chrysanthemumate 6-chloropiperonyl chrysanthemumate 2,4-dimethylbenzyl chrysanthemumate 2,3,4,5-tetrahydro-phthalimidomethyl chrysanthemumate (benzyl-3-furyl) methyl chrysanthemumate methyl 3(2,4-pentadienyl)-4-oxo-2-cyclopenten-l-yl chrysanthemumdicarboxylate methyl 3(Z-butenyl)-4-oxo-2-cyclopenten-l-yl chrysanthemumdicarboxylate Preferred insecticides are the carbamate compounds, particularly l-naphthyl methylcarbamate (carbaryl), 4-benzo(b)-thienyl-N-methylcarbamate (Mobam), 3- methyl- 1 -phenyl-5-pyrazolyl-N-methyl-carbamate (pyrolan), l-(dimethylcarbamoyl)-5-methyl-3- dimethylcarbamate (Dimetilan oisopropoxyphenyl methylcarbamate (Baygon), 8-(2- methylquinolyl)-N-methylcarbamate (GS 13 98), and 3,5-diisopropylphenyl methylcarbamate (HRS 1422). Also preferred are the phosphoric acid derivatives, particularly 0,0-dimethyl-S-[ Z-methoxyl ,3,4-thiadiazol- 5-(4H)-onyl-(4)-methyl]-dithiophosphate (GS 13005 0,0-diethyl-O-( 2-isopropyl-4-methyl-6-pyrimidyl CH 0-CH -CECH [I] wherein X, Y and Z are all halogen other than iodine. Preferred are those compounds in which X, Y and Z are all chlorine atoms, particularly those with 2,3,4 2,3,6 and 2,4,5 configurations.  
  The lethality of insecticidal compounds, particularly carbamates has been found to be enhanced synergisitically by benzyl 2-propynyl ethers represented by the formula wherein X, Y and Z represent hydrogen, nitro, halogen other than iodine, or, when X is hydrogen, Y and Z taken together may represent methylenedioxy, and provided that, when both X and Y are hydrogen, Z is other than nitro.  
  Examples of these benzyl 2-propynyl ethers are given in Table ll and their synergistic activity with insecticidal carbamates is illustrated in Example 2.  
  It has been found that the lethality of insecticidal organophosphorus compouds and of the aforesaid cyclopropanecarboxylic acid esters is synergistically enhanced by benzyl 2-propynyl ethers represented by the formula R-CH O-CH C 5 CH wherein R represents an aromatic hydrocarbon selected from the class consisting of naphthyl and groups having the structural formula wherein X, Y and Z represent hydrogen, nitro or halogen other than iodine.  
  Examples of these benzyl 2-propynyl ethers are compounds ll-A through ll-F and 11-1-1 thorugh 11-0, inclusive, and the compounds of Table 11a.  
  The following example illustrates the preparation of these compounds.  
 EXAMPLE 1 Compounds ll-A through ll-F were prepared by following the general procedures of Guermont (1) and of Marszak, Diament and Guermont (2). To a stirred solution of 0.23 g (0.10 mol) of sodium metal dissolved in 90 ml of propynyl alcohol was added 0.01 mol of the appropriate benzyl halide. The reaction mixture was stirred at room temperature for three hours and then refluxed for one hour to insure completion of the reaction. The reaction mixture was poured into 100 ml of water, and the oily layer was extracted into ether. The ether layer was separated, washed with water, percent sodium hydroxide solution. saturated sodium chloride solution, dried (Na SO and concentrated in vacuo. Compounds ll-A, 11-3 and ll-C were distilled at reduced pressure. and compounds ll-D and Il-E and ll-F were crystallized from 95 percent ethanol. Compound ll-H may be similarly prepared using the appropriate benzyl halide.  
 1. .I. P. Guermont. Mcm. scr. chim. etat (Paris). 147 (1955). 2. l. Mars-Zak. G. Diamcnt and J. P. Guermont. Mcm. scr. chim. etat (Paris) 35. 67 (1950).  
 Compound ll-R was similarly prepared but was chromatographed on silica gel with benzene as the eluant.  
  Compounds ll-P and &#34;-0 were prepared in the following manner. A mixture of 1.38 g (0.01 mol) of anhydrous potassium carbonate, 0.01 mol of the appropriate benzyl halide and 1.38 g of propynyl alcohol dissolved in 100 ml of acetone was refluxed with stirring for twenty-four hours. The reaction mixture was poured into 100 ml of water, and the oily layer was ex-&#39; tracted with ether. The ether layer was separated, washed with water, 10% sodium hydroxide solution, saturated sodium chloride solution, dried (Na SO and concentrated in vacuo. Compound ll-P was distilled at reduced pressure; &#34;-0 was crystallized from 95% ethanol.  
  Compound ll-G was prepared by a modification of the procedure employed in preparing compounds ll-P and 11-0. 3,4-Methylenedioxybenzyl alcohol was substituted for propynyl alcohol, and propynyl bromide was substituted for the benzyl halide. The crude oil of ll-G was dissolved hot in hexane, and upon cooling, the starting material, methylenedioxybenzyl alcohol precipitated. The solution was filtered, and the filtrate was concentrated in vacuo. The residue was chromatographed on an alumina column and eluted with benzene.  
  The 2-propynyl chloronitrobenzyl ethers, compounds Il-I through ll-O inclusive, were prepared as follows. A solution of 5 percent (w/v) sodium propynylate in propynyl alcohol was prepared by reacting sodium metal or sodium hydride with anhydrous propynyl alcohol. To 170 ml ofthe sodium propynylate/propynyl alcohol there was added 0.1 mol of the chloronitrobenzyl bromide or chloronitrobenzyl chloride and the mixture was stirred at room temperature for five hours and then refluxed until essentially free of benzyl halide (1-2 hrs). The major portion of the propynyl alcohol was removed by distillation under reduced pressure and the residue was treated with 100 ml of water and extracted with ether or benzene. The organic layer was separated, washed with saturated sodium chloride, dried (Na SO and fractionally distilled in vacuo to collect th respective chloronitrobenzyl 2-propynyl ether which was identified by infrared and nuclear magnetic resonance spectra.  
  The yields, melting or boiling points, analyses and spectral data are given in Tables Ill and 1V.  
 TABLE III Com- Yield Bp. (mm) or Analyses 7c 1r, cm Nmr data, 8 ppm. pound No. 71. mp, C Calcd. Found (assignment) (assignment) ll-A 63-5 (0.05) 3322 (C E CH) 6.96 (s,4,Ar-H) 2381 (C E C) 4.33 (s,2.ArCH  
  3.86 (d.2,J=2Hz,CH -C E CH) 2.19 (t,i,J=2Hz,C E CH) 11-8 90 7681 (0.05) C 55.84 55.92 3279 (C E CH) 7.11 (m,3,Ar-H) H 3.75 3.83 2114 (C C) 4.40 (s,2,Ar-CH,)  
  4.08 (d,2,.1=2Hz,CH C E CH) 2.38 (t,1,J=2Hz,C E CH) ll-C 79-81 (0.07) C-55.84 55.71 3322 (C E CH) 7.20 (m 3,ArH)  
 H 3.75 3.83 2123 (C E C) 4.48 (s,2,Ar-CH 4.12 (d,2,.I=2Hz,CH C CH) 2.35 (t,1,J=2Hz,C E CH) &#34;D 57 C 48.14 48.11 3222 (C E CH) 7.31 (s,2,Ar-H) H 2.83 2.75 2171 (C E C) 4.58 (s,2,Ar-CH 4.19 (d,2,J=2Hz,Ch C E C-H) 2.28 (t,1J=2Hz,C E CH) ll-E 29 C 48.14 48.24 3311 (C E CH) 7.49 (d.1.J=8Hz,ArH) H 2.83 2.85 2228 (C E C) 7.26 (d,1,.l=8Hz,ArH)  
  4.86 (s,2.ArCH 4.23 (d,2.J=2Hz,O-CH 2.44 (t.1 ,.I=2H1.,C E CH) ll-F 50 35 C 48.14 48.02 3279 (C CH) 7.50 (s.1,Ar-H) H 2.83 2.97 2279 (C E C) 7.35 (s,l.Ar-H) 4.53 (s,2,ArCH 4.23 (d,2,J=2Hz.CH -C E CH) 2.36 (t.1,J=2Hz,C CH) [LG 20 C 69.46 69.68 3268 (CE CH) 6.87 (m, ,Ar-H) H, 5.30 5.53 2123 (C C) 6.03 (s,2,O-CH O) 4.53 (s,2,ArCH 4.14 (d,2,J=2H7.,OCH  
 TABLE IV Com- Analyses, percent pound Yield, Bl. (mm) Ir, cmr NMR data, 6, ppm. No. Compound, name and formula percent rM.1., C. Calcd. Found (assignment) (assignment) l2-nitrobenzy1Z-propynyl ether 1 C 82 6277 3379 (CEC EI (m1 Ar }l) ---1 1 s0 95 0. 05 H 4. 74 4. 31 2,281 020 4. 73 (s, 2, Ar-ogp N 7. 33 7. 37 1,650,1,333(NO2) 4. 08 (d, 2, J =2Hz, CEZCEOH) 2. 23 (t, 1, J :2Hz, e o-g) etheh H] o 62. 82 62.89 3,279 (o=cg) 7. 64 1, 2,l=8Hz, m-g) -Q----i I 57 H 4.74 4. 74 2,119 (050 7.00 (d, 2,L:8Hz, Ar-g N 7. 33 7. 31 1,522, 1,351 (N0 4. 21 (S, 2, Al -C2 3. 71 (d, 2, zra, CH C CH) 1. 97 (t,1, .T =2Hz, CEO-g) ILR {a-naphthylmethyl 2-pr0pynyletl1er l {C 85.68 85. 93 3,250 (C CE) 8.06 (In, 1, perili) a-C1 H1CH OCH C CH- j H H 6.16 6. 24 2,265 (C O) 7.55 (m, 7, AT-ili) 4. 95 (d, 2, ArCl12) 4.07 (d, 2, EZHZ, OOH2) 2. 34 (t, 1 J =2Hz, C C11 TABLE V The following are additional NMR spectral data for Some Substituted Benzyl Propynyl Ethers PROTON ASSIGNMENTS Structure Cpd. No. Aromatic Bcnzylic Propynylic Acetylemc unsubst. 7.27, s, 5H 4.52, s, 2H 4.05, d, 2H 2.32, t, 1H 2CL 7.02-7.55, m 4H 4.66, s, 2H 4.18, d, 2H 2.42, t, 1H 3-Cl 7.20-7.34, m, 4H 4.50, s, 2H 4.13, d, 2H 2.43, t, 1H 4Cl ll-A 7.23, s, 4H 4.48, s, 2H 4.18, d, 2H 2.42, t, 1H 3--NO 7.40-8.18, m, 4H 4.67, s, 2H 4.25, d, 2H 2.52, t, 1H 2,3--Cl 6.98-7.48, m 3H 4.66, s, 2H 4.24, d, 2H 2.42, t, 1H 2,4-Cl ll-B 7.05-7.47, m 3H 4.58, s, 2H 4.22, d, 2H 2.48, t. 1H 2,5-Cl 7.17-7.47, m, 3H 4.59, s, 2H 4.25, d, 2H 2.43, t, 1H 2,6-Cl, ll-N 7.25, s, 3H 4.83, s, 2H 4.23, d, 2H 2.52, t, 1H 3,4-Cl ll-C 6 95-7 40, m, 3H 4.45, s, 2H 4.17, d, 2H 2.57, t, 1H 3,5-Cl 7.23, s, 3H 4.52, s, 2H 4.14, d, 2H 2.37, t, 1H 2,4,5Cl,-, ll-F 7.47,7.62,ss, 2H 4.62, s, 2H 4.27, d, 2H 2.42, t, 1H 2Cl,3-NO ll-L 7.30-7.90, m, 3H 4.73, s, 2H 4.38. d, 2H 2.74, t, 1H 2Cl,4NO ll-N 7.63-8.22, m 3H 4.73, s, 2H 4.33, d, 2H 2.49, t, 1H 2-Cl,5-NO 7.39-8.35, m, 3H 4.68, s, 2H 4.33, d, 2H 2.51, t, 1H 2Cl,6-NO ll-K 7.24-7.76, m, 3H 4.92, s, 2H 4.18. d, 2H 2.65, t, 1H 3CI,4NO 11-0 7.30-7.95, m, 3H 4.67, s, 2H 4.26, d, 2H 2.47, t, 1H 2NO 3Cl 11-1 7.48, s, 3H 4.67, s, 2H 4.22, d, 2H 2.66, t, 1H 2NO 4Cl ll-J 7.61-8.02, m, 3H 4.82, s, 2H 4.19, d, 2H 2.30, t, 1H 2NO ,4Cl 7.40-8.30, m, 3H 4.67, s, 2H 4.33, d, 2H 2.51, t, 1H 3-NO ,4Cl ll-M 7.54,7.92,ds, 3H 4.67, s, 2H 4.33, d, 2H 2.76, t, 1H  
  1n the foregoing example, melting points were determined on a Fisher-Johns apparatus. Melting points and boiling points were uncorrected. Infrared spectra were obtained on a Perkin-Elmer 137 Grating Spectrophotometer. Nuclear magnetic resonance spectra were determined on Varian A-60 and A-6OA NMR Spectrophotometers, probe temperature 38, with signals reported relative to internal tetramethylsilane. Nuclear magnetic resonance spectra and infrared spectra were taken in carbon tetrachloride. Thin layer chromatograms were carried out on Silica Gel G coated glass slides. Column chromatography was performed using Alumina Woelm, Neutral, activity 1. Yields were based upon isolated product and no developmental work was performed to improve yields.  
  The effectiveness of the synergists disclosed herein is believed to be largely due to their ability to interfere with or inhibit the action of mixed function oxygenase (MFO), an entity present in insects, and which, in many cases at least, serves to metabolize insecticides to relatively innocuous products and hence to render them non-lethal. It follows that the synergistic effectiveness of any particular synergist with any particular insecticide depends not only on the efficacy of the synergist in inhibiting MFO metabolism, but the degree to which the particular insecticide is susceptible to detoxification by MFO metabolism.  
  Thus, for example, the insecticide carbaryl has a relatively low lethality to the common house fly by virtue of the ease with which it undergoes MFO metabolism to innocuous products in that insect. Synergists according to the invention are therefore very effective in terms of raising the lethality of carbaryl. On the other hand the insecticide Dimetilan is relatively lethal to house flies and while it can still be synergized to a significant extent by compounds according to the invention, the increase in lethality is less (and hence the degree of synergism is less) than with carbaryl.  
  In general, carbamate insecticides are synergized by compounds according to the invention to the extent that a combination of carbamate and insecticide will have the same lethality as a significantly greater dose of insecticide alone. This is generally true also of the insecticidal esters of Chrysanthemum monoand dicarboxylic acids.  
  The effect of synergist candidates administered jointly with organophosphorus (OP) insecticides in many cases brings about increased lethality. However, in some instances unchanged lethality or even decreased lethality is observed. According to the present state of knowledge, the observed decrease in lethality can be attributed, especially with some phosphorothioate or -dithioate insecticides, to the fact that at least some MFO metabolites of those insectides are more lethal than the original compounds and the effectiveness of the original compounds as insecticides depends on MP metabolism producing those lethal derivatives. By inhibiting or interfering with the MFO metabolism, it is postulated. the putative synergist may give a net effect in which inhibition of metabolic potentiation is of greater import than is inhibition of metabolic detoxification.  
  Where a net synergism is observed with OP insecticide. metabolic potentiation is either unimportant or is of less importance than metabolic detoxification. The lack of any effect by a synergist candidate can be explained either as a balancing of potentiation and detoxification, or as no significant inhibition of either type.  
  The following examples illustrate the enhanced lethality of insecticidal Carbamates, insecticidal organophosphorus compounds and pyrethrum when utilized in conjunction with the above-described propynyl synergist compounds.  
  In the insecticidal compositions of the present invention comprising one of the aforementioned insecticidal compounds and one of the propynyl synergist compounds, from about 0.1 to about parts by weight of the synergist compound may be employed per one part by weight of the insecticide compound. Preferably, there should be at least about 0.5 part by weight of synergist per one part by weight of insecticide.  
  The insecticidal compositions according to the invention may be used in a variety of ways and may be mixed with other materials such as vehicles, carriers and adjuvants whose nature will depend on the mode of application. Thus, for example, the active ingredients, insecticide and synergist, may be applied in a powder or dust in which case they may be mixed with a solid carrier such as a clay, for example, Fullers earth, bentonite, talc, kieselguhr or diatomaceous earth. Non-clay carriers such as by-product lignin, wood, and walnut shell flour may also be used.  
  For liquid spray application the active ingredients may be dispersed or dissolved in a liquid carrier. Various carriers known to the art may be employed including water, hydrocarbon solvents of various descriptions, lower ketones, alcohols and mixtures of such materials, provided that they are substantially inert to the active ingredients.  
  In some cases emulsions or dispersions of the active ingredients in the liquid carrier may be desirable and such may be prepared by agitation of the active ingredients with the carrier. Surface active emulsifying or dispersing agents may be employed to aid in the procedure, and in this connection there may be mentioned fatty alcohol sufates, for example, sulfonated castor oil or alkyl benzene sulfonates, soaps, such as sodium oleate and non-ionic surfactants such as high molecular weight alkyl polyglycol ethers. Such emulsifying and dispersing agents commonly possess wetting agent properties.  
  Compositions according to the invention may also contain adjuvants such as wetting agents and humectants.  
  In general, use compositions according to the invention (including the carrier and various adjuvants) may be formulated according to known techniques, and, in accordance with conventional practice, may contain from about 2 percent to about 20 percent by weight active ingredients (synergist and insecticide), though, of course, concentrates containing say 10-80 percent active ingredients may be prepared for sale with subsequent dilution by the user. It is contemplated that formulations according to the invention may be employed in aerosol dispensers, in which case the above proportions do not include the aerosol propellant. ln aerosol uses the proportion of propellant to total charge will be that normally employed, for example. 25-95 percent of the total charge.  
 EXAMPLE 2&#39; Synergism of Insecticidal Carbamates By Benzyl 2- Propynyl Ethers.  
  The synergistic effect with carbaryl and pyrolan of the synergist compounds Il-A through ll-l-l was determined by the jar-film assay technique using unsexed, susceptible, three to 5-day old, Wilson strain house flies that had not been subjected to selection by treatment with insecticide. The required solutions of the insecticide and of the synergist compound were prepared in acetone at a concentration of one milligram per milliliter. One-pint wide mouth glass jars were coated with the appropriate insecticide-synergist combination by rolling the jars containing aliquots of the appropriate solutions diluted to three milliliters with acetone to deposit, by evaporation, a film of the test materials. The flies were transferred under carbon dioxide anesthesia and held in the jar at room temperature. Perforated aluminum foil was used to cover the jars and to hold cotton saturated with 10% sugar solution. Counts were made at intervals, but the recorded mortality was based on 24-hour kill, rather than knockdown. All prostrate nonmoving flies were considered dead. A determination was then made of the contact synergistic ratio [SR], which is the ratio of the LC of insecticide alone to the LC of the insecticide when applied together with the synergist. The LC of the insecticide was estimated from a log-probit plot of percent kill versus dosage. The LC of carbaryl alone for the Wilson strain fly is 1.0 mg/ jar, by the jarfilm assay technique; for pyrolan alone, the LC is 0.15 mg/jar. The LC of the combination of insecticide and synergist was determined at a synergist to insecticide parts by weight ratio of five to one. The results are shown in Table VI.  
  The effect of compounds Il-C, Il-D and [LB with Dimetilan and GS 13798 was determined from tests on polyvalent resistant (CH strain) houseflies that had been chilled and to the dorsal region of which was applied an acetone solution of synergist and insecticide at a ratio of two to one. Duplicate tests were performed using ten four to five-day old female houseflies per test. After dosage, the flies were put in a plastic petri dish with cotton soaked in a sugar-water solution. The percent kills after 24 hours for the two tests were averaged and are shown in Table Vll. These doses of insecticide used without synergist caused 10-40 percent mortality.  
 II-F.  
  In Table VII, and in the tables following it, the doses TABLE X of topically applied insecticides and of synergists unless otherwise noted are expressed as micrograms per fly Synergist] Insecticide 0.5/1 l/l 2/I 5/1 Insecticide alone (fig/ y ratio:  
 TABLE VII 5 Insecticide Dimetilan as 137% Insccticidc dose: 0 2 I V 1.0 73 97 I00 I00 I00 synergist dose. 4 2 050 33 57 100 97 00 0.25 3 synergist Compound No. lo (H3 i II-C 0 I00 92 &#34;-0 o 100 100 II-E I o 100 100 The synergistic effect of benzyl Z-propynyl eth ers with mobam was determined from topical appllcation tests on IN/WHO and Rutgers A strain houseflies. The synergist and insecticide were dissolved in ACS Grade TABLE X] acetone in such quantities that a 1.0 ,u liter volume applied to the thorax of 3-to-5 day old CO -anesthetized synergisl Insecticide 05H m female adult house flies contained the desired dosage. Insecticide akme After being treated, the flies were confined, 10 to a ratio: plaster petri dish, with 3-5 dishes/treatment, and held mccticidc for 24-hr. observation of mortality. Reconstituted skim Do w v&#39; d r&#39; mllk on cot ten dental wicks as pro lded u mg the 25 L0 93 100 I00 00 m0 holding period. The percent kills after 24 hours are 050 83 97 97 93 m0 shown in Table VIII for the IN/WHO strain and Table .25 27 53 Z 3 6 IX for the Rutgers A strain. 30  
 TABLE VIII Mobam dose: 0.20 0.20 0.l0 0.10 0.05 0.05 Synergist dose: L0 0 1.0 0 0.50 0 0.25  
 Synergist Compound No. lI-C 2 99 0 27 0 4 II-D 0 2 I00 0 0 l0 II-E 0 2 I00 0 33 0 5 II-H I0 25 I00 II-I 7 25 97 &#34;-1 I3 25 I00 Il-K IO 25 I00 II-L 3 25 89 Il-M I0 25 9O II-N I2 97 &#34;-0 I0 25 TABLE IX Mobam dose: 0 0 0.60 040 0.60 0.40 0.30 0.30 0 15 0.15 Synergist dose 7.5 5.0 0 0 3.0 2.0 1.5 0 0.75  
 synergist Compound No.  
 Il-C 0 4 67 0 20 Il-D 0 4 92 II-E 0 4 99 0 0 I7 lI-H 7 7 I00 II-I 3 7 37 II-] 0 7 70 II-K 0 7 97 II-L 0 7 52 The effects of varying the insecticide dose and the TABLE XII ra&#39; are further illustrated, with synerglst msecnclde no 60 Synergist/ Insecticide 0.5/1 Ill 2/] 5/1 synergist compounds II-D, Il-E, II-F and Mobam msec- Insecticide alum ticide, in Tables X, XI and XII. Table X shows percent ratio: mortality of the subject IN/WHO houseflies 24 hours I nsccticldc after topical application of Mobam. both with and without synergist compoundll-D&#39;, Table XI shows the mor- 65 L0 93 100 93 93 m0 tahty data using synergist compound II-E; and Table 0&#39;50 83 7O 83 97 XII shows the mortality data using synergist compound 0.25 27 3; 2(7) The data in Table X illustrate that a dose of insectibles 11 and 11a was determined by topical application cide 1.0 #g/fly) which ould nOI be Considered to gi e tests on lN/WHO strain, and Rutgers A strain and polyadequaie comm] (LDt-a) does g Such Control 91) valent, resistant, CH strain houseflies usingthe proce- When 9 with I of Synergist- Furthermore when dures of Example 2. The percent kills after 24 hours of the appl1ed dose consists of equal parts of Mobam and IN/WHO strain fli are shown in Table of E3 the dose of Mobam need only be to ach&#39;eve gers A strain flies, in Table XVll; and of CH strain flies,  
 &#34; in Table XVlll. The doses of insecticide alone to the The synergistic effect of lN/WHO flies of synergist CH strain flies caused -40 percent mortality.  
 TABLE XVI Diazinon GS 13005 lnsecticide dose: 0 0.03 0.03 0 0.10 0.10 0.10 0.10 0.05 0.05 Synergist dose: 1 0 0.15 l 0 0.50 0.25 0.125 0 0.25  
 Synergist Compound No.  
 we 0 5 2s &#34;D 0 5 40 ll-E 0 5 45 ll-H I0 19 I00 11-1 7 19 99 ll-J 13 19 99 ll-K 10 19 100 ll-L 3 19 97 ll-M 10 19 79 ll-N 7 84 11-0 10 19 90 ll-P 0 0 30 0 16 96 85 69 O 10 ll-Q 0 16 90 67 43 0 ll-R 0 0 22 0 12 68 65 49 compound ll-K with Dimetilan, pyrolan, Baygon and TABLE XVll HRS 1422 is illustrated by the 24 hour percent mortalitydata in Tables XII, XIV and XV. GS 13005 dose: 0 1.0 1.0 Synergist dose: 5.0 0 5.0 TABLE Xlll Synergist Compound Dimetilan Dimetilan With 7 Dimctilan Dose Alone Five Parts ll-K n 2 &#34;-1 0 13 100 ll-K 0 13 100 0.13 43 100 0 l3 8} &#39;3 ll-M 0 13 63 ll-N 2 11-0 3 13 47 ll-P 0 3 92 11-0 0 3 100 TABLE XIV ll-R 0 2 55 Pyrolan Pyrolan With 45 Pyrolan Dose alone Fivc Parts ll-K TABLE XVI 5.0 43 15 Diazinon GS 1300s 6&#39;2 8 Insecticide dose: 0 5 l 7 0.25 8O 0 Syncrg1stdose. 10 10 4%) syplcrgist Compound Y ll-C 0 95 &#34;-0 0 6O TABLE XV ll-E 10 65 lnsec- Baygon Baygon With HRS HRS 1422 With ticide alone Five Parts 1422 Five Parts 11-K The synerg1st effect on lN/WHO fl1es of synerglst compound ll-K with Gardona and Bidrin is illustrated 0125 0 83 0 77 by the 24 hour percent mortal1ty data 1n Tables XlX 60 and XX.  
 TABLE XlX EXAMPLE 3 Gardona G ardonu With Synergism of Insecticidal Organophosphorus Com- 6; Gmkm pounds By Benzyl 2-Propynyl Ethers. (H35 100 The synergistic effect with Diazinon and GS 13005 of 22 various of the benzyl 2-propynyl ethers identified in Ta- 19 20 TABLE XX ergist compounds was determined by topical application tests on polyvalent, resistant CH strain houseflies Bidrin Bidri w following the procedure of Example 2. The percent Bidri&#34; D080 Alum Five Part5 kills after 24 hours are reported in Table XXlll. Applion 57 cation of the insecticide alone caused -40 percent 0.063 0 0 mortality.  
  EXAMPLE 4 TABLE xxm Synergism of Mobam and GS 13005 In German Male 10 Cockroaches. Pyrethrum dose: 0 2 The synergistic effect with mobam of synergist comsync&#39;gm 10 4 pounds ll-H and ll-K is further illustrated by the 24 svnergistcmnpound hour mortality data on German male cockroaches (Bla- No. tella Germanicus) shown in Table XXI. The synergists 0 50 and insecticide were diluted in acetone and applied in I? 8 3; small droplets to the thorax of the insect. These doses of synergist alone gave zero percent insect mortality..  
  TABLE XXI The average percent knockdown of CH strain flies, as a function of time, resulting from spray application Mobam dose: 012 012 of pyrethrum, alone and with synergist, are given in synergist dose; 0 0.60m) Table XXIV. Duplicate tests were performed using 50 CH strain houseflies per test. Test solutions of 100 mg synergistNgompound and 200 mg of pyrethrum per cc of acetone, 200 mg of 10 9Q synergist per cc of acetone, and a mixture of 100 mg of 10 I00 pyrethrum and 100 mg of synergist per cc of acetone I were prepared. The fifty CH strain houseflies were put in a liter spray chamber and 1 cc of the test solution (a) Pretreated with synergist two hours before applying insecticide. was sprayed Into the test chamber a spray pistol. time of treatment with synergist and also at time of 30 The synergist alone at g/ caused no knock (cl Untreated. down.  
 TABLE XXIV Synergist Dose (Mg/cc) Minutes No. Pyrethrum Synergist 5 IO 15 20 25 3O 4O 50 60 100 0 3 6 14 25 32 37 58 62 62 200 0 3 27 44 e0 60 64 82 86 87 ll-E 100 I00 5 9 17 44 55 59 77 93 95 The synergistic effect with GS 13,005 of compounds The selectivity of the synergist compounds of this inlI-I-l, Il-K, II-P, Il-Q and II-R is illustrated by the 24 vention is illustrated by the results of sleeping-time exhour mortality of German male cockroaches shown in tension tests and of acute toxicity tests on Swiss albino Table XXII. These doses of synergist alone caused zero white male mice. percent insect mortality.  
  TABLE XXII EXAMPLE 6 681x00; d Extension of Sleeping Time of Barbiturate and Nons ncr isrdn zf 8 2:8 8.28m Balrbiturate Depressant Drugs by synerglsts.  
  he effect of various synergist compounds on sleepsynergist Compound ing time of sodium Secobarbital [Secobarbital] and of I 3,3-diethyl-5-methyl-2,4-dioxypiperidine [Noludar] H2 I :88 was determined by administering the drug, with and 11-1 23 90 without synergist, to approximately 38-day old male :3 5 mice weighing from 25 to 30 grams. Synergists were administered in each of two doses, 74.0 mg/kg (dilution Control (b) 0 l0 0 being 2.0 mg/0.l ml corn oil), and 110.0 mg/kg (dilucmtml (c) 0 0 5 60 tion 3.0 mg/0.1 ml oil). Secobarbital was administered (a) Prctreated with synergist two hours before applying insecticide. at a dose Of (dilution ml water). (bl Treated with acetone at time of treatment ith nergist and also at time of N l d was d i i d at a d f l treatment \uth insecticide. w lmrented. lutlon 3.0 mg/0.1 ml water). The synergist was administered one hour prior to administration of the Secobarbital or Noludar. Secobarbital and Noludar sleeping EXAMPLE 5 Synergism of Pyrethrum The synergistic effect with pyrethrum of various syntimes were obtained for both the control (drug only) and the treated (synergist plus drug) mice by noting the time lapse between the administration of the drug and the recovery of the righting reflex, i.e. when the animal regains conciousness and can walk up an inclined wooden tray with coordination. The relative sleeping time (R.S.) was noted. The R.S. is the extended sleeping time in the treated mice (synergist plus drug) divided by the sleeping time in the control mice (drug only). The mean sleeping time for the treated mice and the R.S. are shown on Table XXV for various synergist compounds.  
 TABLE XXV Secobarbital (37 mg/K) Synergist 1 l mg/K) Synergist (74 mg/K) Noludar (110 mg/K) Synergist 1 l0 mg/K) Synergist Mean Relative Mean Relative Mean Relative Com ound Sleeping Sleeping Sleeping Sleeping Sleeping Sleeping 0. Time (Min.) Time Time (Min.) Time Time (Min.) Time ll-C 33 1.0 50 1.3 ll-D 60 1.2 46 1.0 11-15 44 1.4 45 1.1 ll-F 46 1.0 38 1.3 ll-H 51 2.1 44 1.4 68 2.2 11-1 32 1.3 3| 1.2 56 1.8 11-1 30 1.4 27 1.0 70 2.2 ll-K 44 2 48 1.5 75 2.4 ll-L 42 1.8 31 1.0 56 1.8 ll-M 47 2 29 1.0 47 2.1 ll-N 39 1.7 1.0 58 1.9 11-0 26 1.1 52 2.4 [LP 46 1.0 44 1.5 11-0 73 1.6 30 1.1 41 2.1 ll-R 96 1.6 1.2 49 1.7 Sesoxane 8.3 6.1 3.1  
 EXAMPLE 7 cide. Eight mice were treated, per dosage, with each Synergism of Acute Toxicity of Dimetilan, GS 13005, Secobarbital and Methadone.  
  To determine the acute toxicity of dimetilan alone, eight dosage levels of Dimetilan, ranging from 4 to 32 mg per kg were applied to eight, Swiss. albino, white, male mice per dosage level. The mice weighed approximately 23 to 27 grams and were 5 to 6 weeks old. The number of mice dead 48 hours after administration of the Dimetilan (lethality) are shown in Table XXVI. The Dimetilan was administered intraperitoneally in 0.1 ml of corn oil one hour after the administration of the same dose of corn oil alone.  
 TABLE XXVI Dimetilan Dose 1 M g/ kg Lethality synergist. The mice were watched for a minimum of 6 hours while held in a glass jar with bedding individually after intraperitoneal injection of the test solutions. Lethality was noted, the animals were weighed and transferred in cages, and food and water were supplied. Control mice were given 0.1 ml of corn oil at the time of administration of the synergist to the test mice and 0.1 ml corn oil plus Dimetilan at the time of administration of the insecticide to the test mice. The number of mice dead at the end of 48 hours is reported in Table XXVll.  
 TABLE XXVIl Dimetilan dose (Mg/kg): 0 Synergist dose (Mg/kg): 1000 240 Synergist Compound No.  
  Sesoxanc Control (0.1 ml oil) By the same procedure, the synergism of acute toxicity of GS 13,005, Secobarbital and o-dimethylamino- 4,4-diphenyl-3-heptanone [Methadone] was determined. The mice lethality data are shown in Table XXVlll (a) OS U005 (71 mg/kg) in (Ll ml corn oil. (h) Sccoharhilal (90 mg/kg) in ().l ml corn oil. Methadone (32 mg/kg) in (Ll ml corn oil.  
 I claim:  
  1. An insecticidal composition comprising 0,0- dimethyl-S-[ 2-methoxy-l ,3,4-thiadiazo1-5(4H )-onyl- (4)-methyl]-dithiophosphate and, per part of said dithiophosphate, from 2 to 5 parts by weight of a benzyl propynyl ether of the formula wherein each of X, Y and Z represents hydrogen, notro, or chlorine.  
 2. The insecticidal composition of claim 1 in which the benzyl propynyl ether is 3,4-dichlorobenzyl 2- propynyl ether.  
  3. The insecticidal composition of claim 1 in wich the benzyl propynyl ether is 2,3.4-trichlorobenzyl 2 propynyl ether.  
  4. The insecticidal composition of claim 1 in which the benzyl propynyl ether is 2,3,6-trichlorobenzyl 2- propynyl ether.  
  5. The insecticidal composition of claim 1 in wich the benzyl propynyl ether is 2,6-dichlorobenzyl 2-propynyl ether.  
  6. The insecticidal composition of claim 1 in which the benzyl propynyl ether is 2-nitro-3-chlorobenzyl 2- propynyl ether.  
  7. The insecticidal composition of claim 1 in which the benzyl propynyl ether is 2-nitro-4-chlorobenzyl 2- propynyl ether.  
  8. The insecticidal composition of claim 1 in which the benzyl propynyl ether is 2-nitro-6-chlorobenzyl 2- propynyl ether.  
  9. The insecticidal composition of claim 1 in which the benzyl propynyl ether is 2-chloro-3-nitrobenzyl 2 propynyl ether.  
  10. The insecticidal composition of claim 1 in which the benzyl propynyl ether is 3-nitro-4-chlorobenzyl 2- propynyl ether.  
  11. The insecticidal composition of claim 1 in which the benzyl propynyl ether is 2-chloro-4-nitrobenzyl 2- propynyl ether.  
  12. The insecticidal composition of claim 1 in which the benzyl propynyl ether is 3-chloro-4-nitrobenzyl 2- propynyl ether.  
  13. The insecticidal composition of claim 1 in which the benzyl propynyl ether is 2-nitrobenzyl Z-propynyl ether.  
  14. The insecticidal composition of claim 1 in which the benzyl propynyl ether is 4-nitrobenzyl 2propynyl