Patent Abstract:
Compounds of the formula ##STR1## wherein the symbols have assigned meanings, and their use as insecticides and/or miticides.

Full Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This is a continuation-in-part of copending application bearing U.S. Ser. No. 848,596 filed on Apr. 7, 1986. 
    
    
     DESCRIPTION OF THE INVENTION 
     It has been found that insecticidal and acaricidal activity is possessed by compounds of the formula ##STR2## wherein X is oxygen or sulfur; 
     R is alkyl or alkenyl of up to twenty carbon atoms, phenyl, or phenalkyl of up to ten carbon atoms; 
     R 1  is alkyl, or alkenyl of up to six carbon atoms, or phenalkyl of up to ten carbon atoms; 
     R 2  is alkyl, alkenyl, alkynyl, haloalkyl or alkylthioalkyl of up to ten carbon atoms; napthyl, pyridyl, or thienyl; phenyl, or phenalkyl or phenalkenyl of up to ten carbon atoms, which may be substituted on the ring by from one to three substitutents selected from halogen, methyl, methoxy, nitro, amino, mono- and dialkylamino, and mono- and dialkylaminocarbonyl wherein each alkyl moiety contains from one to four carbon atoms; 
     R 3  is 
     (a) one of the moieties represented by R 2  or is ##STR3## wherein R 4  is alkyl of one to four carbon atoms, phenyl, or phenalkyl of up to ten carbon atoms, R 5  is hydrogen or one of the moieties represented by R 4 , or R 4  and R 5  together with the interjacent nitrogen atom represent 1-piperidino, 2-(ethoxycarbonyl)-1-piperidino, or 4-morpholino. 
     In these compounds, each alkyl, alkenyl, alkylene and alkenylene (as in phenalkyl and phenalkenyl) moiety may be straight-chain or branched-chain. 
     Compounds of Formula I can be prepared by treating a phosphonothioic or phosphonodithioic chloride of the formula: ##STR4## with an alkali metal salt of a sulfonamide of the formula ##STR5## 
     The treatment of the chloride (II) with a salt of the sulfonamide (III) is effected by adding the chloride at a controlled rate to a solution of the salt in an inert solvent, at a low temperature--for example, 0° C.-5° C.--moisture being excluded, then warming the mixture to room temperature, or somewhat above. Preferably, the chloride is added as a solution in the same solvent in which the salt is dissolved. Suitable as the solvent are organic materials such as ether and tetrahydrofuran, or acetonitrile. The product is isolated and purified by conventional procedures, as shown in the examples, hereinafter. 
     As is shown in U.S. Pat. No. 4,390,929, and in U.S. Pat. No. 4,190,652, the phosphonodithioic chloride precursor (II, X is sulfur) can be prepared by treating a phosphonothioic dichloride of the formula ##STR6## with an appropriate thiol, R 1  -SH, in the presence of a solvent and an amine base, as hydrogen halide acceptor. Aromatic hydrocarbons, such as toluene, are suitable as the solvent. Any tertiary amine base is suitable, but the trialkylamines appear to be most suitable. Water should be excluded from the reaction mixture--as by using anhydrous reagents and conducting the treatment under nitrogen. Isolation of the product is effected by conventional techniques. 
     The phosphonothioic chloride precursor (II, X is oxygen) can be prepared by a method analogous to that described in U.S. Pat. No. 4,190,652 for preparing the corresponding phosphonodithioic chloride--i.e., by treating a phosphonic dichloride of the formula ##STR7## with an appropriate thiol, R 1  -SH, in the presence of an inert solvent and an amine base as hydrogen chloride acceptor. Aromatic hydrocarbons, such as toluene, are suitable as the solvent. Any tertiary amine base is suitable, but the trialkylamines appear to be most suitable. Water should be excluded from the reaction mixture--as by using anhydrous reagents and conducting the treatment under nitrogen. Isolation of the product is effected by conventional techniques. 
     The phosphonothioic chloride (II, X is oxygen) also can be prepared by the method described by A. A. Neimysheva, et al., Journal of General Chemistry, U.S.S.R. (English), 1966, volume 36, pages 520-525--i.e., by slowly adding an appropriate sulfenyl chloride 
     
         R.sup.1 --S--Cl                                            (VI) 
    
     to a stirred solution of the appropriate phosphonous dichloride of the formula ##STR8## in sulfur dioxide at a low temperature--e.g., -15° C. to -60° C.--then warming the resulting mixture to room temperature, stripping it of volatiles and vacuum distilling the residue to give the product. 
     Those phosphonothioic chlorides (II, X is oxygen) wherein R 1  is alkyl also can be prepared by treating a S,S--di--R 1  R-phosphonodithioate of the formula ##STR9## wherein both of R 1  are the same, with a chlorinating agent selected from sulfuryl chloride and chlorine. Suitably, the treatment is conducted by adding the chlorinating agent to a stirred solution of the dithioate in an inert solvent, at a temperature of about 0°-10° C. Suitable solvents are the haloalkanes, such as methylene dichloride and carbon tetrachloride. Water should be excluded from the reaction mixture--as by using anhydrous reagents and conducting the treatment under nitrogen--i.e., in a nitrogen atmosphere. Preferably a slight stoichiometric excess--up to about 10% excess--of the chlorinating agent is used, relative to the dithioate. Isolation and purification of the product is accomplished by conventional techniques. In many cases, the by-product R 1  -sulfenyl chloride is a low-boiling material that is easily removed by evaporation techniques. 
     The dithioate precursors (formula VIII) can be prepared by known methods. Conveniently, they can be prepared by treating the appropriate alkylphosphonous dichloride (VII) in an inert solvent, with two equivalents of the appropriate thiol, R 1  -SH, either in the form of its alkyl metal salt, or in the presence of two equivalents of a hydrogen chloride acceptor. 
     The sulfonamide precursors (III) as a class are known compounds, and the alkali metal salts thereof are prepared by conventional methods and techniques, as is demonstrated in the Examples, hereinafter. Those of the class that are novel are readily prepared by conventional methods, as by treating the appropriate sulfonyl halide, R 3  --SO 2  --halogen, with the appropriate amine, R 2  NH 2 . Compounds of Formula III wherein R 3  =-NR 4  R 5  are prepared; a method for their preparation is described by G. Weisz and G. Schulze, Annalen Der Chemic, volume 729, pages 40-51 (1969). 
     The preparation and isolation of particular individual species of the genus of Formula I are described in the Examples, hereinafter. Other typical individual species are the following, each identified in terms of the symbols in Formula I, in all cases X being oxygen: 
     
         ______________________________________Species R       R.sup.1  R.sup.2 R.sup.3______________________________________A     methyl  propyl   methyl  1-piperidinoB     ethyl   1-methyl-                  methyl  1-piperidino         propylC     ethyl   propyl   methyl  4-morpholinoD     methyl  1-methyl-                  methyl  4-morpholino         propylE     methyl  propyl   methyl  di-(n-butyl)aminoF     ethyl   1-methyl-                  methyl  di-(n-butyl)amino         propylG     ethyl   propyl   methyl  (methyl)(phenyl)aminoH     methyl  1-methyl-                  methyl  (methyl)(phenyl)amino         propylI     ethyl   propyl   propargyl                          methylJ     methyl  1-methyl-                  propargyl                          methyl         propylK     methyl  propyl   propargyl                          dimethylaminoL     ethyl   1-methyl-                  propargyl                          dimethylamino         propylM     methyl  propyl   methyl  2-(ethoxycarbonyl)-1-                          piperidinoN     ethyl   1-methyl-                  methyl  2-(ethoxycarbonyl)-1-         propyl           piperidino______________________________________ 
    
     The preparation, isolation and testing of individual species of the genus of Formula I, in particular instances, are described in the following examples. In each case, the identity of each of the products, and each of the precursors, was confirmed as necessary by appropriate chemical and spectral analyses. 
    
    
     EXAMPLE 1 
     S-(1-methylpropyl) P-ethyl N-methyl-N-(methylsulfonyl)-phosphonamidothioate (1) 
     Under nitrogen, 30.7 ml of triethylamine was added over 10 minutes to a stirred mixture of 14.7 g of ethylphosphonic dichloride, 23.9 ml of 2-butanethiol and 125 ml of dry toluene at 5°-10° C. The resulting mixture was stirred at 5° C. for 2 hours, then at room temperature for 15 hours, diluted with ether and filtered. The filtrate was washed with water, dried (Na 2  SO 4 ) and stripped of solvent. Hexane was added to the residue, and the mixture was washed with dilute aqueous bicarbonate solution, then with water, dried (Na 2  SO 4 ) and stripped of solvent. The residue was distilled in a Kugelrohr apparatus to give S,S-bis(1-methylpropyl)ethylphosphonodithioate (1A). 
     Under nitrogen, a solution of 1.64 ml of sulfuryl chloride in 10 ml of carbon tetrachloride was added drop-by-drop over 36 minutes to a stirred solution of 5.09 g of 1A in 40 ml of carbon tetrachloride at 0° C. The resulting mixture was stirred at 0° C. for 7 minutes, for 1.5 hours at 5° C., then stripped of solvent under very low pressure, and the residue was distilled in a Kugelrohr apparatus to give S-(1-methylpropyl)ethylphosphonochloridothioate (1B), as a colorless liquid, b.p.: 70° C., 0.005 Torr. 
     7.55 g of methylamine was added over one hour to a stirred mixture of 11.4 g of methanesulfonyl chloride and 50 ml of ether at 5° C. The resulting mixture was stirred at 5° C. for one hour, for 15 hours at room temperature, then filtered. The filtrate was dried (MgSO 4 ) and stripped of solvent, to give N-methyl methanesulfonamide (1C), as a yellow liquid. 
     0.12 g of sodium hydride was added to a stirred mixture of 0.54 g of 1C and 10 ml of ether, at 5° C. under nitrogen. The resulting mixture was stirred at room temperature for one hour, cooled to 5° C. and a solution of 1 g of 1B in 3 ml of ether was added drop-by-drop, at 5°-10° C. The mixture was stirred for 2.5 hours at 5° C., at room temperature for 24 hours, then 3 ml of tetrahydrofuran was added and the mixture was stirred for 16 hours. Then the mixture was diluted with methylene chloride, and washed with water, and the organic phase was dried (Na 2  SO 4 ) and the solvent was evaporated. The residue was vacuum-chromatographed over silica gel, using ether as eluent, to give 1, as an amber liquid. 
     EXAMPLE 2 
     S-propyl P-ethyl N-(ethylsulfonyl)-N-methylphosphonamidothioate (2) 
     41.0 g of sulfuryl chloride was added drop-by-drop to 25.5 ml of 1-propanethiol, with stirring, at 0° C., under nitrogen. After 15 minutes, the mixture was added drop-by-drop (over 45 minutes) to 40.62 g of ethylphosphonous dichloride and 60 ml of sulfur dioxide at -70° C. under nitrogen. After 20 minutes the mixture was allowed to warm to room temperature and the solvent was evaporated. The residue was distilled in a Kugelrohr apparatus to give S-propyl ethylphosphonochloridothioate (2A) as a colorless liquid, b.p.: 95° C., 0.30 Torr. 
     2 was prepared as a yellow liquid, by treating 2A with N-methyl ethanesulfonamide (prepared from ethylsulfonyl chloride and methylamine, according to the procedure described for preparing 1C from methylsulfonyl chloride and methylamine), according to the procedure described in Example 1 for preparing 1 from 1B and 1C. 
     EXAMPLES 3 TO 138 
     The following additional individual species of the genus of Formula I, each identified in terms of the symbols used in Formula I, in all cases X being oxygen, were prepared from the appropriate reagents by the procedures described in Examples 1 and 2. 
     
                                           TABLE I__________________________________________________________________________ExampleCompoundNo.  No.   R   R.sup.1   R.sup.2                           R.sup.3   Physical State__________________________________________________________________________3    3     ethyl          propyl    methyl methyl    Amber liquid4    4     ethyl          1-methylpropyl                    methyl phenyl    Yellow liquid5    5     ethyl          propyl    methyl phenyl    Yellow liquid6    6     ethyl          1-methylpropyl                    methyl 4-methylphenyl                                     Amber liquid7    7     ethyl          propyl    methyl 4-methylphenyl                                     Amber liquid8    8     ethyl          1-methylpropyl                    methyl phenyl    Amber liquid9    9     ethyl          1-methylpropyl                    methyl 4-chlorophenyl                                     Amber liquid10   10    ethyl          1-methylpropyl                    1-methyl-                           phenyl    Amber liquid                    ethyl11   11    ethyl          1-methylpropyl                    benzyl phenyl    Yellow liquid12   12    ethyl          1-methylpropyl                    methyl styryl    Yellow liquid13   13    ethyl          1-methylpropyl                    methyl 2,4,6-trimethyl-                                     Amber liquid                           phenyl14   14    ethyl          1-methylpropyl                    methyl 2,5-dichloro-                                     White solid, m.p.:                           phenyl    90-96° C.15   15    ethyl          1-methylpropyl                    methyl 4-bromophenyl                                     Yellow liquid16   16    ethyl          1-methylpropyl                    methyl 2-nitrophenyl                                     Amber liquid17   17    ethyl          1-methylpropyl                    methyl 1-methylethyl                                     Pale yellow liquid18   18    ethyl          propyl    methyl chloromethyl                                     Yellow liquid19   19    ethyl          propyl    methyl butyl     Pale yellow liquid20   20    ethyl          propyl    methyl 3-chloropropyl                                     Yellow liquid21   21    ethyl          propyl    methyl 1-methylethyl                                     Yellow liquid22   22    ethyl          1-methylpropyl                    phenyl phenyl    Yellow liquid23   23    ethyl          1-methylpropyl                    methyl 1-naphthyl                                     Yellow liquid24   24    ethyl          1-methylpropyl                    methyl 2,4,5-tri-                                     Amber liquid                           chlorophenyl25   25    ethyl          1-methylpropyl                    methyl 4-nitrophenyl                                     Amber liquid26   26    ethyl          1-methylpropyl                    methyl 4-methoxyphenyl                                     Yellow liquid27   27    ethyl          propyl    methyl 2-naphthyl                                     Yellow liquid28   28    ethyl          propyl    methyl 2,4,6-trimethyl-                                     Yellow liquid                           phenyl29   29    ethyl          propyl    methyl 1-naphthyl                                     Yellow liquid30   30    ethyl          propyl    methyl 2,4,5-tri-                                     Yellow liquid                           chlorophenyl31   31    ethyl          propyl    methyl 2,5-dichloro                                     White solid                           phenyl    m.p.: 81.5-85.532   32    ethyl          propyl    methyl 2-nitrophenyl                                     Yellow liquid33   33    ethyl          propyl    methyl 4-bromophenyl                                     Yellow liquid34   34    ethyl          propyl    methyl 4-nitrophenyl                                     Yellow liquid35   35    ethyl          propyl    methyl 4-methoxyphenyl                                     Yellow liquid36   36    ethyl          1-methylpropyl                    methyl chloromethyl                                     Yellow liquid37   37    ethyl          1-methylpropyl                    methyl 3-chloropropyl                                     Yellow liquid38   38    ethyl          1-methylpropyl                    methyl butyl     Pale yellow liquid49   39    ethyl          1-methylpropyl                    methyl ethyl     Yellow liquid40   40    ethyl          1-methylpropyl                    methyl 4-chlorophenyl                                     Yellow liquid41   41    ethyl          propyl    methyl benzyl    Yellow liquid42   42    ethyl          propyl    methyl styryl    Yellow liquid43   43    ethyl          butyl     methyl 1-methylethyl                                     Colorless liquid44   44    methyl          propyl    methyl 1-methylethyl                                     Yellow liquid45   45    methyl          1-methylpropyl                    methyl 2-naphthyl                                     Yellow liquid46   46    ethyl          propyl    methyl phenyl    Yellow liquid47   47    ethyl          2-methylpropyl                    methyl 1-methylethyl                                     Pale yellow liquid48   48    ethyl          2-methylpropyl                    methyl 3-chlorophenyl                                     Pale yellow liquid49   49    ethyl          2-methylpropyl                    methyl ethyl     Pale yellow liquid50   50    ethyl          hexyl     methyl 1-methylethyl                                     Colorless liquid51   51    ethyl          2-methylpropyl                    methyl butyl     Pale yellow liquid52   52    ethyl          2-methylpropyl                    methyl 2-chlorophenyl                                     Colorless liquid53   53    ethyl          1,1-dimethylethyl                    methyl ethyl     Pale yellow liquid54   54    ethyl          1,1-dimethylethyl                    methyl 3-chloropropyl                                     Pale yellow liquid55   55    ethyl          1,1-dimethylethyl                    methyl 1-methylethyl                                     Yellow liquid56   56    ethyl          1,1-dimethylethyl                    methyl chloromethyl                                     Colorless liquid57   57    ethyl          propyl    methyl dichloromethyl                                     Yellow liquid58   58    ethyl          1-methylpropyl                    methyl dichloromethyl                                     Yellow liquid59    59   ethyl          propyl    methyl propyl    Pale yellow liquid60   60    ethyl          propyl    1-methylethyl                           phenyl    Yellow liquid61   61    ethyl          propyl    methyl phenyl    Yellow liquid62   62    ethyl          1-methylpropyl                    methyl 4-fluorophenyl                                     Amber liquid63   63    ethyl          1-methylpropyl                    methyl 4-iodophenyl                                     Amber liquid64   64    ethyl          1-methylpropyl                    methyl 3-nitrophenyl                                     Amber liquid65   65    ethyl          1-methylpropyl                    methyl 2-aminophenyl                                     Amber liquid66   66    ethyl          1,1-dimethylpropyl                    methyl methyl    Pale yellow liquid67   67    ethyl          1,1-dimethylpropyl                    methyl 1-methylethyl                                     Pale yellow liquid68   68    ethyl          propyl    methyl octyl     Pale yellow liquid69   69    methyl          propyl    methyl ethyl     Pale yellow liquid70   70    methyl          1-methylpropyl                    methyl ethyl     Pale yellow liquid71   71    ethyl          1-methylpropyl                    methyl 2-thienyl Amber liquid72   72    methyl          propyl    methyl propyl    Pale yellow liquid73   73    methyl          propyl    methyl octyl     Pale yellow liquid74   74    methyl          1-methylpropyl                    methyl octyl     Pale yellow liquid75   75    methyl          propyl    methyl chloromethyl                                     Pale yellow liquid76   76    methyl          1-methylpropyl                    methyl propyl    Yellow liquid77   77    methyl          propyl    methyl 3-chloropropyl                                     Pale yellow liquid78   78    methyl          1-methylpropyl                    methyl 3-chloropropyl                                     Yellow liquid79   79    methyl          1-methylpropyl                    methyl chloromethyl                                     Pale yellow liquid80   80    ethyl          1-methylpropyl                    methyl 2,4-dinitrophenyl                                     Amber liquid81   81    ethyl          1-methylpropyl                    methyl 4-(methylamino)                                     Yellow liquid                           3-nitrophenyl82   82    ethyl          1-methylpropyl                    methyl 2,4,6-trimethyl                                     Yellow liquid                           phenyl83   83    ethyl          1-methylpropyl                    methyl 3-(methylamino-                                     Yellow gel                           carbonyl)phenyl84   84    ethyl          propyl    methyl 4-iodophenyl                                     Yellow liquid85   85    ethyl          propyl    methyl 4-fluorophenyl                                     Yellow liquid86   86    methyl          propyl    methyl butyl     Yellow liquid87   87    methyl          1-methylpropyl                    methyl butyl     Pale yellow liquid88   88    methyl          1-methylpropyl                    methyl 1-methylethyl                                     Yellow liquid89   89    methyl          propyl    methyl methyl    Pale yellow liquid90   90    methyl          1-methylpropyl                    methyl methyl    Pale yellow liquid91   91    ethyl          1-methylpropyl                    methyl propyl    Pale yellow liquid92   92    ethyl          1,1-dimethylethyl                    methyl methyl    Pale yellow liquid93   93    ethyl          propyl    methyl 2,4-dinitro-                                     Yellow liquid                           phenyl94   94    ethyl          propyl    methyl 4-(methylamino)-2-                                     Yellow liquid                           nitrophenyl95   95    ethyl          propyl    methyl 2-aminophenyl                                     Amber liquid96   96    ethyl          propyl    methyl 2-thienyl Yellow liquid97   97    ethyl          1,1-dimethylethyl                    methyl propyl    Pale yellow liquid98   98    ethyl          1-methylpropyl                    methyl propyl    Pale yellow liquid99   99    ethyl          propyl    methyl 4-fluorophenyl                                     Yellow liquid100  100   ethyl          propyl    methyl 2,4,6-trimethyl-                                     Yellow liquid                           phenyl101  101   ethyl          2-methylpropyl                    methyl methyl    Very pale yellow                                     liquid102  102   ethyl          2-methylpropyl                    methyl octyl     Pale yellow liquid103  103   methyl          propyl    methyl 2-methyl-2-                                     Very pale yellow                           propenyl  liquid104  104   methyl          1-methylpropyl                    methyl 2-methyl-2-                                     Very pale yellow                           propenyl  liquid105  105   ethyl          1-methylpropyl                    methyl 2-methyl-2-                                     Pale yellow liquid                           propenyl106  106   ethyl          propyl    methyl 3-(methylamino-                                     Colorless liquid                           carbonyl)phenyl107  107   ethyl          1-methylpropyl                    methyl 3-pyridyl Amber liquid108  108   ethyl          propyl    methyl 3-pyridyl Amber liquid109  109   methyl          propyl    methyl phenyl    Amber liquid110  110   methyl          1-methylpropyl                    methyl phenyl    Yellow liquid111  111   methyl          propyl    methyl 4-bromophenyl                                     Yellow liquid112  112   methyl          1-methylpropyl                    methyl 4-bromophenyl                                     Yellow liquid113  113   methyl          propyl    ethyl  methyl    Pale yellow liquid114  114   methyl          1-methylpropyl                    ethyl  ethyl     Yellow liquid115  115   methyl          propyl    ethyl  ethyl     Very pale yellow                                     liquid116  116   methyl          1-methylpropyl                    ethyl  methyl    Pale yellow liquid117  117   methyl          1-methylpropyl                    methyl methyl    Pale yellow liquid118  118   methyl          1,1-dimethylethyl                    methyl 3-chloropropyl                                     Pale yellow liquid119  119   methyl          1,1-dimethylethyl                    methyl methyl    Yellow liquid120  120   methyl          1,1-dimethylethyl                    methyl propyl    Pale yellow liquid121  121   methyl          1-methylpropyl                    ethyl  1-methylethyl                                     Yellow liquid122  122   methyl          1-methylpropyl                    propyl 1-methylethyl                                     Yellow liquid123  123   methyl          1-methylpropyl                    propyl ethyl     Pale yellow liquid124  124   ethyl          propyl    methyl 2-methyl-2-                                     Pale yellow liquid                           propenyl125  125   methyl          1,1-dimethylpropyl                    methyl 1-methylethyl                                     Yellow liquid126  126   methyl          propyl    propyl methyl    Yellow liquid127  127   methyl          propyl    propyl ethyl     Yellow liquid128  128   methyl          2-methylpropyl                    methyl methyl    Yellow liquid129  129   methyl          2-methylpropyl                    methyl propyl    Yellow liquid130  130   ethyl          1,1-dimethylethyl                    methyl butyl     Pale yellow liquid131  131   methyl          propyl    ethyl  1-methylethyl                                     Yellow liquid132  132   methyl          2-methylpropyl                    methyl 1-methylethyl                                     Yellow liquid133  133   methyl          1-methylpropyl                    methyl octyl     Pale yellow liquid134  134   methyl          propyl    methyl 3-(ethylthio)-                                     Yellow liquid                           propyl135  135   methyl          1-methylpropyl                    methyl 3-(ethylthio)                                     Pale yellow liquid                           propyl136  136   methyl          1-methylpropyl                    ethyl  3-chloropropyl                                     Yellow liquid137  137   ethyl          propyl    methyl 3-(ethylthio)                                     Yellow liquid                           propyl138  138   ethyl          1-methylpropyl                    methyl 3-(ethylthio)                                     Yellow liquid                           propyl__________________________________________________________________________ 
    
     EXAMPLE 139 
     S-1,1-dimethylpropyl N,P-dimethyl-N-((1-methylethyl)sulfonyl)phosphonamidodithioate (139) 
     At about 0° C., 17.05 g of 40% methylamine in water was added drop-by-drop to a solution of 14.25 g of 1-methylethanesulfonyl chloride in 30 ml of methylene chloride. Then the mixture was allowed to warm to room temperature, held for 2 hours, and diluted with water. The organic phase was separated, dried (Na 2  SO 4 ) and stripped of solvent to give N,1-dimethylethanesulfonamide (139A), as an amber liquid. 
     26.85 g of methylphosphonothioic dichloride and 18.5 ml of 1,1-dimethylpropanethiol were mixed with 25 ml of dry toluene under nitrogen. Then 15.15 g of triethylamine was added drop-by-drop to the mixture over 45 minutes, the temperature of the mixture being allowed to rise to 38° C. The mixture was filtered, and the solvent was stripped from the filtrate. The residue was slurried in ether, the slurry was filtered, and the filtrate was stripped of solvent. The residue was distilled under reduced pressure in a Kugelrohr apparatus to give 1,1-dimethylpropyl methylphosphonochloridodithioate (139B), b.p.: 70° C. at 0.03 Torr. 
     A solution of 0.95 g of 139A in 1 ml of dry THF was added drop-by-drop to a suspension of 0.37 g of sodium hydride in 4 ml of dry THF, under nitrogen, at 0° C. The mixture was allowed to warm to room temperature, then after 30 minutes was cooled to 0° C. and a solution of 1.5 g of 139B in 2 ml of dry THF was added drop-by-drop. The mixture was allowed to warm to room temperature and after 3 hours and 40 minutes was filtered. The solvent was stripped from the filtrate. The residue was flash chromatographed over silica gel using a 1.5:8.5 v:v mixture of ethyl acetate and a hexane as eluent, to give 139, as a yellow liquid. 
     EXAMPLE 140 
     S-1-methylpropyl P-ethyl-N-methyl-N-(phenylsulfonyl)phosphonamidodithioate (140) 
     With stirring at 5° C., 6.8 g of 40% methylamine in water was added over 45 minutes to 17.7 g of a mixture of benzenesulfonyl chloride and 50 ml of dry THF. Then the mixture was stirred at room temperature for 5.5 hours, diluted with methylene chloride and filtered. The filtrate was washed with water, dried (Na 2  SO 4 ) and stripped of solvent. The residue was dissolved in methylene chloride, the solution was washed with water, dried and stripped of solvent to give N-methyl-benzenesulfonamide (140A), as a yellow liquid. 
     At 5° C., under nitrogen, 34.8 ml of triethylamine was added drop-by-drop over 10 minutes to a stirred mixture of 40.75 g of ethylphosphonothioic dichloride and 22.5 g of 2-butanethiol. The resulting mixture was stirred at room temperature for 21 hours, diluted with ether, filtered, and the solvent was stripped from the filtrate. The residue was distilled in a Kugelrohr apparatus to give 1-methylpropyl ethylphosphonochloridodithioate (140B), as a yellow liquid, b.p.: 90° C., 0.003 Torr. 
     At 5° C., under nitrogen, 1.2 g of potassium tertiary-butoxide was added to a stirred solution of 1.7 g of 140A in 30 ml of acetonitrile. The mixture was stirred at room temperature for one hour, a solution of 2.25 g of 140B in 6 ml of acetonitrile was added drop-by-drop, the mixture was stirred for 3 hours and then refluxed for 4 days. The mixture was diluted with methylene chloride, washed with water, dried (Na 2  SO 4 ) was stripped of solvent. The residue was vacuum-chromatographed on silica gel, using a 9:1 v:v mixture of methylene chloride and ether as eluent. The entire product was rechromatographed over silica gel using a 1:1 v:v mixture of methylene chloride and hexane, to give 140, as a yellow liquid. 
     EXAMPLES 141 TO 144 
     The following additional individual species of the genus of Formula I, each identified in terms of the symbols used in Formula I, X being sulfur in all cases, were prepared from the appropriate reagents by the procedures described in Examples 139 and 140. 
     
                       TABLE II______________________________________Ex-am-  Com-ple  pound                                PhysicalNo.  No.      R       R.sup.1                        R.sup.2                              R.sup.3                                     State______________________________________141  141      methyl  1-methyl-                        methyl                              1-methyl-                                     colorless                 propyl       ethyl  liquid142  142      ethyl   1-methyl-                        methyl                              1-methyl-                                     colorless                 propyl       ethyl  liquid143  143      ethyl   propyl methyl                              1-methyl-                                     colorless                              ethyl  liquid______________________________________ 
    
     EXAMPLE 144 
     S-(1-methylpropyl) P-ethyl-N-(dimethylaminosulfonyl)-N-methylphosphonamidothioate (144) 
     At 5° C., 6.8 g of a 40% solution of methylamine in water was added over 12 minutes to a stirred mixture of 14.3 g of dimethylsulfamoyl chloride and 50 ml of methylene chloride, and the mixture was stirred at room temperature for 24 hours. The organic phase was separated, washed with water, dried (MgSO 4 ) and stripped of solvent, to give trimethylsulfamide (144A), as a colorless liquid. 
     At 5° C., under nitrogen, 0.24 g of sodium hydride was added to a stirred solution of 0.69 g of 144A in 15 ml of THF, then a solution of 1.1 g of 1B in 3 ml of THF was added drop-by-drop over 2 minutes. The mixture was stirred a room temperature for 5 days, diluted with methylene chloride, washed with water, dried (Na 2  SO 4 ) and stripped of solvent. The residue was vacuum chromatographed over silica gel, using a 9:1 v:v mixture of methylene chloride and ether as eluent, to give 144, as a yellow liquid. 
     EXAMPLES 145-147 
     The following additional individual species of the genus of Formula I, each identified in terms of the symbols used in Formula I, X being oxygen and R 3  being dimethylamino, in all cases, were prepared from the appropriate reagents by the procedures described in Example 141. 
     
                       TABLE III______________________________________Example Compound                       PhysicalNo.     No.       R       R.sup.1                            R.sup.2                                  State______________________________________145     145       ethyl   propyl methyl                                  yellow                                  liquid146     146       methyl  propyl methyl                                  amber                                  liquid147     147       methyl  1-methyl-                            methyl                                  amber                     propyl       liquid______________________________________ 
    
     Compounds of the invention have been found to be toxic with respect to invertebrate pests, by which is meant insects of the class Insecta and related classes of arthropods, such as the acarids (e.g., mites), ticks, spiders, wood lice and the like. In particular, they have been found to be highly toxic to mites. Further, it has been found that compounds of the invention act systemically--that is, when applied to the plant, a compound of the invention penetrates into the cells and vascular system of the plant and is translocated therein and thereby disseminated throughout the plant without injury to the plant, yet effectively kills insects that chew upon tissues of the plant or suck juices from the plant. Some of the compounds act upon the insects very rapidly--i.e., they are &#34;quick-knockdown agents&#34;, even though they may not be very toxic to the insects. 
     For application, a compound of the invention ordinarily is applied most effectively by formulating it with a suitable inert carrier or surface-active agent, or both. The invention, therefore, also includes compositions suitable for combatting pests, such compositions comprising an inert carrier or surface-active agent, or both, and as active ingredient at least one compound of the invention. The invention also provides a method of combatting pests at a locus, which comprises applying to that locus a compound of the invention or a pesticidal composition according to the invention. 
     The term &#34;carrier&#34; as used herein means an inert solid or liquid material, which may be inorganic or organic and of synthetic or natural origin, with which the active compound is mixed or formulated to facilitate its application to the plant, seed, soil or other object to be treated, or its storage, transport and/or handling. Any of the materials customarily employed in formulating pesticides--i.e., horticulturally acceptable adjuvants--are suitable. 
     Suitable solid carriers are natural and synthetic clays and silicates, for example, natural silicas such as diatomaceous earths; magnesium silicates, for example, talcs; magnesium aluminum silicates, for example, attapulgites are vermiculites; aluminum silicates, for example, kaolinites, montmorillonites and micas; calcium carbonate; calcium sulfate; synthetic hydrated silicon oxides and synthetic calcium or aluminum silicates; elements such as, for example, carbon and sulfur; natural and synthetic resins such as, for example, coumarone resins, polyvinyl chloride and styrene polymers and copolymers; bitumen; waxes such as, for example, beeswax, paraffin wax, and chlorinated mineral waxes; solid fertilizers, for example, superphosphates; and ground, naturally-occurring, fibrous materials, such as ground corncobs. 
     Examples of suitable liquid carriers are water, alcohols such as isopropyl alcohol and glycols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as cellosolves; aromatic hydrocarbons such as benzene, toluene and xylene; petroleum fractions such as kerosene, light mineral oils; chlorinated hydrocarbons such as carbon tetrachloride, perchloroethylene and trichloromethane. Also suitable are liquefied, normally vaporous and gaseous compounds. Mixtures of different liquids are often suitable. 
     The surface-active agent may be an emulsifying agent or a dispersing agent or a wetting agent; it may be nonionic or ionic. Any of the surface-active agents usually applied in formulating herbicides or insecticides may be used. Examples of suitable surface-active agents are the sodium and calcium salts of polyacrylic acids and lignin sulfonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitan, sucrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohols or alkyl phenols, for example, p-octylphenol or p-octylcresol, with ethylene oxide and/or propylene oxide; sulfates or sulfonates of these condensation products, alkali or alkaline earth metal salts, preferably sodium salts, of sulfuric or sulfonic acid esters containing at least 10 carbon atoms in the molecule, for example, sodium lauryl sulfate, sodium secondary alkyl sulfates, sodium salts of sulfonated castor oil, and sodium alkylaryl sulfonates such as sodium dodecylbenzene sulfonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxides. 
     The compositions of the invention may be prepared as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders are usually compounded to contain 25-75% by weight of active compound and usually contain, in addition to the solid carrier, 3-10% by weight of a dispersing agent, 2-15% of a surface-active agent and, where necessary, 0-10% by weight of stabilizer(s) and/or other additives such as penetrants or stickers. Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant or surface-active agent, and are diluted in the field with further solid carrier to give a composition usually containing 0.5-10% by weight of the active compound. Granules are usually prepared to have a size between 10 and 100 BS mesh (1.676-0.152 mm), and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 0.5-25% by weight of the active compound, 0-1% by weight of additives such as stabilizers, slow release modifiers and binding agents. Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, cosolvent, 10-50% weight per volume of the active compound, 2-20% weight per volume emulsifiers and 0-20% weight per volume of appropriate additives such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are compounded so as to obtain a stable, non-sedimenting, flowable product and usually contain 10-75% weight of the active compound, 0.5-5% weight of dispersing agents, 1-5% of surface-active agent, 0.1-10% weight of suspending agents, such as defoamers, corrosion inhibitors, stabilizers, penetrants and stickers, and as carrier, water or an organic liquid in which the active compound is substantially insoluble; certain organic solids or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or as antifreeze agents for water. 
     Of particular interest in current practice are the water-dispersible granular formulations. These are in the form of dry, hard granules that are essentially dust-free, and are resistant to attrition on handling, thus minimizing the formation of dust. On contact with water, the granules readily disintegrate to form stable suspensions of the particles of active material. Such formulations contain 90% or more by weight of finely divided active material, 3-7% by weight of a blend of surfactants, which act as wetting, dispersing, suspending and binding agents, and 1-3% by weight of a finely divided carrier, which acts as a resuspending agent. 
     Aqueous dispersions and emulsions, for example, compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the present invention. The said emulsions may be of the water-in-oil or of the oil-in-water type, and may have thick, mayonnaise-like consistency. 
     It is evident from the foregoing that this invention contemplates compositions containing as little as about 0.0001% by weight to as much as about 95% by weight of a compound of the invention as the active ingredient. 
     The compositions of the invention may also contain other ingredients, for example, other compounds possessing pesticidal, especially insecticidal, acaricidal or fungicidal properties, as are appropriate to the intended purpose. 
     The method of applying a compound of the invention to control pests comprises applying the compound, ordinarily in a composition of one of the aforementioned types, to a locus or area to be protected from the insects, such as the foliage and/or the fruit of plants. The compound, of course, is applied in an amount sufficient to effect the desired action. This dosage is dependent upon many factors, including the carrier employed, the method and conditions of the application, whether the formulation is present at the locus in the form of an aerosol, or as a film, or as discrete particles, the thickness of film or size of particles, and the like. Proper consideration and resolution of these factors to provide the necessary dosage of the active compound at the locus to be protected are within the skill of those versed in the art. In general, however, the effective dosage of the compound of the invention at the locus to be protected--i.e., the dosage which the insect contacts--is of the order of 0.001 to 0.5% based on the total weight of the formulation, though under some circumstances the effective concentration will be as little as 0.0001% or as much as 2%, on the same basis. 
     Activity of compounds of the invention with respect to insect and acarine pests was determined by using standardized test methods to measure the toxicity of the compounds as follows: 
     I. Houseflies (Musca domestica (Linne)) were tested by placing 50 4- to 5-day old adult houseflies into a spray cage and spraying with 0.6 ml of a solution of test compound. After spraying, the flies were observed to ascertain any knockdown effect, and then were anesthetized with CO 2  and transferred to a recovery cage containing a milk pad for food. The cages were held for 18-20 hours after which mortality counts were made. Both dead and moribund flies were counted. The tests were conducted employing several different dosage rates for each test compound. 
     II. Pea aphids (Acyrthosiphon pisum (Harris)) were tested by placing about 100 adult aphids on broad bean plants. The plants were sprayed with dilutions of an acetone solution of the test compound in water containing an emulsifier and held under laboratory conditions for 18 to 20 hours, at which time the living aphids on the plants were counted. The tests were conducted employing several different dosage rates for each test compound. 
     III. Adult female two-spotted spider mites (Tetranychus urticae (Koch)) were tested by placing 50-75 mites on the bottom side of leaves of pinto bean plants. The leaves were sprayed with dilutions of an acetone solution of the test compound in water containing an emulsifier and kept under laboratory conditions for about 20 hours, at which time mortality counts were made. The tests were conducted employing several different dosage rates for each compound. 
     IV. Third instar corn earworm larvae (Heliothis zea (Boddie)) were tested by spraying broad bean plants with dilutions of an acetone solution of the test compound in water containing an emulsifier. Immediately after spraying, 5 larvae were transferred to the plant and held for 44-46 hours, at which time the dead and moribund larvae were counted. The tests were conducted employing several different dosage rates for each test compound. 
     In each set of tests, identical tests were conducted using parathion as a standard for comparison. 
     In each instance, the toxicity of the test compound was compared to that of a standard pesticide, parathion, the relative toxicity of the test compound then being expressed in terms of the relationship between the amount of the test compound and the amount of the standard pesticide required to produce the same percentage (50%) of mortality in the test insects. By assigning the standard pesticide an arbitrary rating of 100, the toxicity of the test compound was expressed in terms of the Toxicity Index, which compares the toxicity of the test compound of the invention with that of the standard pesticide. That is to say, a test compound having a Toxicity Index of 50 would be half as active, while one having a Toxicity Index of 200 would be twice as active, as the standard pesticide. The results are set forth in Table IV. 
     
                       TABLE IV______________________________________    Toxicity IndexCompound             Pea      Corn    SpiderNumber     Housefly  Aphid    Earworm Mite______________________________________1          30K.sup.(a)                30K      30.sup. 21002          25K.sup.  20K      60.sup. 23003          40K.sup.  10K      35.sup. 24004          30K.sup.  25K      10.sup. 120005          10K.sup.  10.sup.  55.sup. 32006          10 .sup.  20K      0.sup.  5207          0 .sup.   10K      0.sup.  3708          30K.sup.  100.sup. 15.sup. 38009          30K.sup.  70.sup.  45.sup. 260010         25K.sup.  30K      20.sup. 150011         30K.sup.  150K     10.sup. 85012         15K.sup.  50K      20.sup. 100013         10K.sup.  35K      10.sup. 47014         15K.sup.  25K      10.sup. 230015         15K.sup.  25K      10.sup. 1750016         30K.sup.  25K      10.sup. 65017         25K.sup.  30.sup.  40.sup. 140018         30K.sup.  25K      15.sup. 350019         20K.sup.  10K      5.sup.  410020         20K.sup.  15.sup.  10.sup. 500021         15K.sup.  10.sup.  15.sup. 700022         10K.sup.  15K      10.sup. 100023         &lt;5K.sup.  15K      5.sup.  110024         &lt;5K.sup.  15K      10.sup. 50025         5K.sup.   5K       5.sup.  75026         10K.sup.  35K      0.sup.  75027         0 .sup.   5.sup.   0.sup.  44028         0 .sup.   5.sup.   0.sup.  5029         0 .sup.   5.sup.   0.sup.  46030         &lt;5 .sup.  5.sup.   0.sup.  80031         &lt;5K.sup.  5.sup.   0.sup.  510032         10K.sup.  &lt;5K      0.sup.  54033         &lt;5 .sup.  5K       10.sup. 240034         &lt; 5 .sup. &lt;5.sup.  0.sup.  65535         &lt;5 .sup.  5.sup.   0.sup.  42536         20K.sup.  15K      5.sup.  220037         15K.sup.  25K      5.sup.  220038         20K.sup.  60.sup.  5.sup.  320039         20K.sup.  60.sup.  10.sup. 220040         15K.sup.  20K      5.sup.  290041         10K.sup.  20.sup.  15.sup. 290042         5K.sup.   10K      5.sup.  120043         0 .sup.   5K       0.sup.  34044         10K.sup.  10K      280.sup.                                 420045         &lt;5K.sup.  10K      10.sup. 90046         &lt;5K.sup.  5K       5.sup.  85047         5K.sup.   10K      0.sup.  90048         5 .sup.   120K     0.sup.  100049         5K.sup.   60K      30.sup. 43050         0 .sup.   &lt;5.sup.  0.sup.  4551         5K.sup.   30K      0.sup.  100052         15K.sup.  30K      5.sup.  490053         15K.sup.  45K      95.sup. 80054         5K.sup.   30K      15.sup. 250055         10K.sup.  45K      35.sup. 100056         15K.sup.  40K      35.sup. 300057         5K.sup.   10.sup.  5.sup.  320058         15K.sup.  20.sup.  0.sup.  460059         10K.sup.  15.sup.  65.sup. 510060         0 .sup.   5.sup.   0.sup.  150061         &lt;5 .sup.  5.sup.   10.sup. 35062         15K.sup.  40.sup.  10.sup. 480063         5K.sup.   30.sup.  20.sup. 280064         10K.sup.  10.sup.  15.sup. 510065         10K.sup.  10.sup.  0.sup.  29066         30K.sup.  90.sup.  15K     120067         25K.sup.  120.sup. 15.sup. 170068         0 .sup.   0.sup.   0.sup.  510069         10K.sup.  20.sup.  160.sup.                                 450070         15K.sup.  10.sup.  160K    230071         10K.sup.  50.sup.  0.sup.  240072         10K.sup.  35.sup.  115K    240073         0 .sup.   &lt;5.sup.  0.sup.  50074         &lt;5K.sup.  45.sup.  30.sup. 65075         10K.sup.  25.sup.  35K     240076         20K.sup.  85.sup.  35.sup. 380077         10K.sup.  10.sup.  20.sup. 550078         10K.sup.  35.sup.  70.sup. 550079         20K.sup.  130K     20.sup. 180080         &lt;5 .sup.  0.sup.   0.sup.  26081         &lt;5 .sup.  &lt;5.sup.  &lt;5.sup. 65082         &lt;5 .sup.  &lt;5.sup.  0.sup.  65083         &lt;5 .sup.  5.sup.   0.sup.  45084         &lt;5K.sup.  5.sup.   10.sup. 170085         &lt;5K.sup.  0.sup.   10.sup. 130086         &lt;5K.sup.  5.sup.   30.sup. 160087         10K.sup.  20K      20.sup. 430088         15K.sup.  20K      40.sup. 830089         15K.sup.  15K      110.sup.                                 120090         20K.sup.  20K      130.sup.                                 230091         5K.sup.   15K      0.sup.  280092         15K.sup.  30K      75.sup. 160093         &lt;5 .sup.  0.sup.   0.sup.  8594         0 .sup.   0.sup.   5.sup.  46095         0 .sup.   0.sup.   0.sup.  6096         5 .sup.   10.sup.  0.sup.  530097         5K.sup.   10.sup.  25.sup. 480098         10K.sup.  20.sup.  15.sup. 790099         &lt;5 .sup.  5.sup.   30.sup. 4800100        0 .sup.   5.sup.   0.sup.  2300101        10K.sup.  25.sup.  0.sup.  3200102        &lt; 5K.sup. 10.sup.  0.sup.  2700103        &lt;5K.sup.  5.sup.   10.sup. 2000104        5K.sup.   20.sup.  10.sup. 1700105        10K.sup.  40.sup.  0.sup.  4100106        &lt;5K.sup.  &lt;5.sup.  0.sup.  475107        5K.sup.   20.sup.  0.sup.  3000108        5K.sup.   10.sup.  10.sup. 2000109        5K.sup.   30.sup.  55.sup. 3300110        5 .sup.   75.sup.  25.sup. 4300111        75 .sup.  5.sup.   20.sup. 1100112        5 .sup.   20.sup.  20.sup. 1800113        10 .sup.  20.sup.  120.sup.                                 1700114        10 .sup.  30.sup.  70.sup. 1800115        5 .sup.   15.sup.  90.sup. 2400116        10 .sup.  120.sup. 35.sup. 750117        10 .sup.  25.sup.  20.sup. 1000118        5 .sup.   60.sup.  15.sup. 1600119        10 .sup.  30.sup.  20.sup. 600120        15 .sup.  120.sup. 10.sup. 100121        10 .sup.  40.sup.  30.sup. 750122        20K.sup.  85K      30K     2600123        20K.sup.  65K      20K     5300124        10K.sup.  25K      &lt;5.sup. 3300125        20K.sup.  95K      30.sup. 3500126        20K.sup.  25.sup.  35.sup. 1900127        20K.sup.  40K      35K     6200128        25K.sup.  70K      100K    3500129        20K.sup.  70K      70K     2400130        5K.sup.   30.sup.  5K      800131        10K.sup.  45.sup.  25K     1100132        20K.sup.  50.sup.  35.sup. 500133        5K.sup.   25.sup.  0.sup.  1700134        5K.sup.   30.sup.  25.sup. 800135        20K.sup.  60.sup.  40.sup. 1100139        10K.sup.  30K      20.sup. 240140        &lt;5 .sup.  10.sup.  0.sup.  280141        10K.sup.  15K      30.sup. 240142        5K.sup.   60K      5.sup.  45143        5 .sup.   15.sup.  10.sup. 430144        20K.sup.  100.sup. 20.sup. 2800145        5K.sup.   20.sup.  25.sup. 1200146        15 .sup.  60.sup.  20.sup. 1100147        15 .sup.  40.sup.  80.sup. 1900______________________________________ .sup.(a) K indicates &#34;rapid knockdown 
    
     Additional compounds of this invention are those of Formula I wherein R, R 1 , R 2  and R 3  are as defined in Table V. 
     
                       TABLE V______________________________________Com-                                     Phys-pound                                    ical*No.    R      R.sup.1   R.sup.2                         R.sup.3    State______________________________________148    CH.sub.3         n-C.sub.3 H.sub.7                   C.sub.2 H.sub.5                         CH.sub.3   P Y L149    CH.sub.3         sec-C.sub.4 H.sub.9                   C.sub.2 H.sub.5                         C.sub.2 H.sub.5                                    Y L150    CH.sub.3         n-C.sub.3 H.sub.7                   C.sub.2 H.sub.5                         C.sub.2 H.sub.5                                    P Y L151    CH.sub.3         sec-C.sub.4 H.sub.9                   C.sub.2 H.sub.5                         CH.sub.3   P Y L152    CH.sub.3         sec-C.sub.4 H.sub.9                   n-C.sub.3 H.sub.7                         CH.sub.3   P Y L153    CH.sub.3         tert-C.sub.5 H.sub.11                   CH.sub.3                         3-chloro-propyl                                    Y L154    CH.sub.3         tert-C.sub.5 H.sub.11                   CH.sub.3                         CH.sub.3   Y L155    CH.sub.3         tert-C.sub.5 H.sub.11                   CH.sub.3                         n-C.sub.3 H.sub.7                                    P Y L156    CH.sub.3         sec-C.sub.4 H.sub.9                   C.sub.2 H.sub.5                         iso-C.sub.3 H.sub.7                                    Y L157    CH.sub.3         sec-C.sub.4 H.sub.9                   n-C.sub.3 H.sub.7                         iso-C.sub.3 H.sub.7                                    Y L158    CH.sub.3         sec-C.sub.4 H.sub.9                   n-C.sub.3 H.sub.7                         C.sub.2 H.sub.5                                    P Y L159    C.sub.2 H.sub.5         n-C.sub.3 H.sub.7                   CH.sub.3                         2-methyl-1-                                    P Y L                         propene160    CH.sub.3         tert-C.sub.5 H.sub.11                   CH.sub.3                         iso-C.sub.3 H.sub.7                                    Y L161    CH.sub.3         C.sub.3 H.sub.7                   n-C.sub.3 H.sub.7                         CH.sub.3   Y L162    CH.sub.3         C.sub.3 H.sub.7                   n-C.sub.3 H.sub.7                         C.sub.2 H.sub.5                                    Y L163    CH.sub.3         iso-C.sub.4 H.sub.9                   CH.sub.3                         CH.sub.3   Y L164    CH.sub.3         iso-C.sub.4 H.sub.9                   CH.sub.3                         C.sub.3 H.sub.7                                    Y L165    C.sub.2 H.sub.5         tert-C.sub.4 H.sub.9                   CH.sub.3                         n-C.sub.4 H.sub.9                                    P Y L166    CH.sub.3         n-C.sub.3 H.sub.7                   C.sub.2 H.sub.5                         iso-C.sub.3 H.sub.7                                    Y L167    CH.sub.3         iso-C.sub.4 H.sub.9                   CH.sub.3                         iso-C.sub.3 H.sub.7                                    Y L168    C.sub.2 H.sub.5         sec-C.sub.4 H.sub.9                   CH.sub.3                         n-C.sub.8 H.sub.17                                    P Y L169    CH.sub.3         n-C.sub.3 H.sub.7                   CH.sub.3                         3-ethylthio-propyl                                    Y L170    CH.sub.3         sec-C.sub.4 H.sub.9                   CH.sub.3                         3-ethylthio-propyl                                    P Y L171    C.sub.2 H.sub.5         tert-C.sub.4 H.sub.9                   CH.sub.3                         phenyl     Y L172    CH.sub.3         tert-C.sub.4 H.sub.9                   CH.sub.3                         phenyl     Solid                                    mp 95°                                    to                                    101° C.173    CH.sub.3         sec-C.sub.4 H.sub.9                   CH.sub.3                         3-chloropropyl                                    Y L174    C.sub.2 H.sub.5         n-C.sub.3 H.sub.7                   CH.sub.3                         3-ethylthiopropyl                                    Y L175    C.sub.2 H.sub.5         sec-C.sub.4 H.sub.9                   CH.sub.3                         3-ethylthiopropyl                                    Y L176    C.sub.2 H.sub.5         iso-C.sub.4 H.sub.9                   CH.sub.3                         dimethylamino                                    Y L177    CH.sub.3         tert-C.sub.4 H.sub.9                   CH.sub.3                         dimethylamino                                    Y L178    CH.sub.3         iso-C.sub.4 H.sub.9                   CH.sub.3                         dimethylamino                                    Y L179    C.sub.2 H.sub.5         tert-C.sub.4 H.sub.9                   CH.sub.3                         dimethylamino                                    Y L180    C.sub.2 H.sub.5         n-C.sub.3 H.sub.7                   C.sub.2 H.sub.5                         dimethylamino                                    Y L181    C.sub.2 H.sub.5         tert-C.sub.4 H.sub.9                   C.sub.2 H.sub.5                         dimethylamino                                    Y L182    C.sub.2 H.sub.5         sec-C.sub.4 H.sub.9                   C.sub.2 H.sub.5                         dimethylamino                                    Y L183    C.sub.2 H.sub.5         sec-C.sub.4 H.sub.9                   CH.sub.3                         4-morpholino                                    B L184    C.sub.2 H.sub.5         sec-C.sub.4 H.sub.9                   CH.sub.3                         piperidino B L185    CH.sub.3         tert-C.sub.4 H.sub.9                   C.sub.2 H.sub.5                         dimethylamino                                    Y L186    CH.sub.3         n-C.sub.3 H.sub.7                   C.sub.2 H.sub.5                         dimethylamino                                    Y L187    C.sub.2 H.sub.5         tert-C.sub.4 H.sub.9                   CH.sub.3                         4-morpholino                                    Y L188    CH.sub.3         tert-C.sub.4 H.sub.9                   CH.sub.3                         4-morpholino                                    Y L189    CH.sub.3         iso-C.sub.4 H.sub.9                   CH.sub.3                         4-morpholino                                    Y L190    CH.sub.3         tert-C.sub.4 H.sub.9                   CH.sub.3                         piperidino Y L191    CH.sub.3         iso-C.sub.4 H.sub.9                   CH.sub.3                         piperidino Y L192    CH.sub.3         tert-C.sub.5 H.sub.11                   CH.sub.3                         4-morpholino                                    Y L193    CH.sub.3         tert-C.sub.5 H.sub.11                   CH.sub.3                         piperidino Y L194    CH.sub.3         tert-C.sub.5 H.sub.11                   CH.sub.3                         dimethylamino                                    Y L195    C.sub.2 H.sub.5         tert-C.sub.5 H.sub.11                   C.sub.2 H.sub.5                         dimethylamino                                    Y L196    C.sub.2 H.sub.5         tert-C.sub.5 H.sub.11                   CH.sub.3                         dimethylamino                                    Y L______________________________________ *P Y L = Pale Yellow Liquid Y L = Yellow Liquid B L = Brown Liquid 
    
     Systemic Activity Tests 
     Systemic activity of compounds of Formula I was determined as follows: 
     Mite Tests 
     The roots of pinto bean plants (Phaseolus vulgaris) in the primary leaf stage were placed in a flask containing water plus the test chemical. The stem of the plant was wrapped with non-absorbent cotton fitted snugly into the neck of the flask, to prevent possible fumigant action by the test chemical. Then the plant was infested with 50-100 adult female two-spotted spider mites, held for 48 hours at 85° F., and 50% relative humidity when mortality in the mites was determined visually. A series of different dosages of the test compound in the water were used, and the LC 50  dosage (the dosage in parts per million by weight of the test chemical in the water required to effect fifty percent kill of the mites) was determined. 
     Compounds Nos. 1, 2, 3, 5, 17, 18, 19, 21, 26, 36, 37, 39, 44, 48, 51-59, 62, 64, 66, 67, 69-72, 75-79, 86-92, 96-99, 101, 103-105, 107-110, 120, 122-129, 131, 135 and 144-147 were found to have significant activity. 
     Aphid Tests 
     Broad bean plants in the 6 to 8 leaf stage were removed from pots and their roots were washed free of soil. Each was placed in a flask containing 100 ml of a water solution of the test compound. The plant stems were wrapped with non-absorbent cotton fitted snugly into the neck of the flask to prevent possible fumigant action by the test compound. The flask was positioned under a wooden stage with the stem of the plant extending up through a slot in the stage. A 6&#34;×6&#34; square of paper was placed flat on the stage around the stem of the plant. A plastic ring 5 inches in diameter and 2 inches high, coated on the inside with petroleum jelly, was placed around the plant to prevent the aphids from escaping. 50 to 100 aphids were placed within each ring. Then the plant was held for 48 hours at 85° F., and 50% relative humidity when mortality in the mites was determined visually. A series of different dosages of the test compound in the water were used, and the LC 50  dosage (the dosage in parts per million by weight of the test chemical in the water required to effect fifty percent kill of the aphids) was determined. 
     Compounds Nos. 1, 3, 17, 18, 21, 39, 44, 48, 52, 55, 56, 59, 66, 69, 71, 72, 75-79, 86-92, 97, 98, 101, 105, 107, 110, 114, 116, 122-129, 131, 133-135, 144 and 147 were found to have significant activity.

Technology Classification (CPC): 2