Patent Publication Number: US-4649148-A

Title: Insecticidal uses of diaminoguanidine hydrazone compounds

Description:
This application is a division of Ser. No. 704,974, filed Feb. 25, 1985, U.S. Pat. No. 4,575,560, issued on Mar. 11, 1986. 
    
    
     The invention is diaminoguanidine hydrazone compounds of the formula (I) ##STR1## wherein R 1  &#39; and R 2  &#39; are H, and R 1  and R 2  are individually selected from fluoro, chloro, bromo, trifluoromethyl, CF 3  CH 2  O, CHF 2  X, CF 3  X, CHY 2  CF 2  X, or CHFYCF 2  X, where X is O or S and Y is F of Cl; or R 1  and R 1  &#39; or R 2  and R 2  &#39; are --OCF 2  O--, --OCF 2  CHFO--, --OC(CH 3 ) 2  --O-- or --OCF 2  CF 2  O--; 
     R is H, ##STR2## where R 3  is C 1  -C 2  alkyl, or C 1  -C 2  haloalkyl, R 4  is hydrogen or C 1  -C 2   alkyl; or R 3  and R 4  when taken together may form a ring represented by CH 2  (CH 2 ) n  -- where n is 3 or 4; R 5  is C 1  -C 4  alkyl optionally substituted with one to three halogens or C 3  -C 4  alkenyl, with the proviso that when R is ##STR3## R 1  and R 2  are CF 3  CH 2  O, CHF 2  X, CF 3  X, CHY 2  CF 2  X, or CHFYCF 2  S, where X is O or S and Y is F or Cl; R 1  and R 1  &#39; or R 2  and R 2  &#39; are --OCF 2  O--, --OC(CH 3 ) 2  --O--, --OCF 2  CHFO-- or --OCF 2  CF 2  O--. 
     While the use of diaminoguanidine compounds as antiprotozoal agents and especially as anticoccidial agents is known in the art as described in U.S. Pat. No. 3,992,446 and Belgian Pat. No. 824,811, there is no suggestion in the literature that diaminoguanidine hydrazone compounds are effective insecticidal agents or further that some of these compounds exhibit antifeeding activity when applied to plants. 
     The diaminoguanidine hydrazone compounds of the invention as well as other diaminoguanidine hydrazone compounds are effective in controlling lepidopterous insects and are useful for protecting agronomic crops, trees, shrubs, and ornamentals from attack by these insects. Many of these compounds also exhibit antifeeding activity thus providing additional protection to treated plants. 
     Novel formula (Ia) diaminoguanidine dialkyl ureas of the invention wherein R is ##STR4## in formula (I) may be readily prepared by the reaction of an appropriately substituted diaminoguanidine of formula (Ib) wherein R is H in formula (I) with from 1 to 2 molar equivalents of N,N-disubstituted carbamoyl chlorides of formula (III) in a solvent such as acetonitrile in the presence of a tertiary amine such as triethylamine or diisopropylethylamine as illustrated in Flow Diagram I below. ##STR5## wherein R 1 , R 1  &#39;, R 2 , R 2  &#39;, R 3  and R 4  are as described above. 
     Formula (Ia) diaminoguanidine monosubstituted ureas may be prepared by the reaction of the appropriately substituted formula (Ib) diaminoguanidine with from 1 to 1.5 molar equivalents of a formula (IV) isocyanate in an inert solvent such as ether as illustrated in Flow Diagram II below. ##STR6## wherein R 1 , R 1  &#39;, R 2 , R 2  &#39; and R 4  are as described above. 
     When R 1  and R 2  and R 1 , R 1  &#39; and R 2 , R 2  &#39; are not the same, both of the above reaction sequences give rise to isomeric mixtures of the formula (Ia) products as indicated below. ##STR7## wherein R 1 , R 1  &#39;, R 2 , R 2  &#39;, R 3 , and R 4  are as described above. 
     Diaminoguanidine hydrazones of formula (Ib) may be prepared by the reaction of two molar equivalents of an appropriately substituted aldehyde of formula (Va) dissolved in an organic solvent with an alcoholic or aqueous alcoholic solution of a diaminoguanidine salt of the formula ##STR8## as illustrated in Flow Diagram III(a) below. 
     Uniquely, unsymetrical diaminoguanidines where R 1  ≠R 2  and R 1 , R 1  &#39;≠R 2 , R 2  &#39; may then be obtained cleanly by the novel reaction of a symetrical diaminoguanidine with a minimum of one molar equivalent of hydroxylamine hydrochloride followed by reaction of the thus-formed monosubstituted guanidine with an appropriately substituted aldehyde of formula (Vb) as illustrated in Flow Diagram III(b) below. ##STR9## 
     The Formula (Ib) insecticidal diaminoguanidines may also be converted to insecticidal Formula (Ic) diaminoguanidines by reaction of with 1.0 to 1.25 molar equivalents of an appropriately substituted chloroformate of formula (VI) in an organic solvent such as acetonitrile, ether, toluene, methylene chloride and the like, in the presence of a tertiary amine such as triethylamine or diisopropylethylamine as illustrated in Flow Diagram (IV) below. ##STR10## wherein R 1 , R 1  &#39;, R 2 , R 2  &#39; and R 5  are as described above. 
    
    
     The present invention is further illustrated by the following non-limiting examples. 
     EXAMPLE 1 
     Preparation of p-(2,2,2-trifluoroethoxy)benzaldehyde ##STR11## 
     Potassium hydroxide pellets (85%, 13.2 g, 0.2 mol) are added to 4-hydroxybenzaldehyde (24.4 g, 0.2 mol) and 18-crown-6 (2.6 g, 5% mol) in diglyme (150 mL). The red reaction mixture is stirred for 16 hours at room temperature and then a solution of 2,2,2-trifluoroethyl-p-toluenesulfonate (50.8 g, 0.2 mol) in diglyme (100 mL) is added over 30 minutes, after which the mixture is allowed to stir at room temperature for 45 minutes. The resulting suspension is then heated at reflux for 24 hours. The mixture is cooled to 10° C. and poured into ice water (1300 mL). The organic materials are extracted with ether (4×200 mL), and the extracts washed with 5% sodium hydroxide (2×100 mL), water (2×100 mL) and saturated sodium chloride (1×100 mL), and dried over MgSO 4 . Evaporation of the ether gives an amber oil which is purified by high performance liquid chromatography using silica gel on a Waters 500 unit and 50:50 hexane and methylene chloride as eluant to give 12.3 g of the title product with R f  0.25. Anal. Calcd for C 9  H 7  F 3  O 2  (204.15) C, 52.94; H, 3.43. Found C, 52.04; H, 3.59. 
     EXAMPLE 2 
     Preparation of 1,3-bis{[p-(tetrafluoroethoxy)benzylidene]-amino}guanidine ##STR12## 
     A solution of p-tetrafluoroethoxybenzaldehyde (35.07 g, 0.158 mol) in 2B alcohol (20 mL) is added over 70 minutes to a stirred slurry of diaminoguanidine hydrochloride (9.91 g, 0.079 mol) in 2B alcohol (60 mL) and water (15 mL) at 45° C. The resulting solution is refluxed for one hour, cooled to 5° C. and the hydrochloride salt collected by filtration and washed with cold alcohol and ether to give a white solid (40.5 g, 2 crops, 96%):mp 262°-264° C. 
     The hydrochloride salt (40.53 g, 0.076 mol) is stirred with ethyl acetate (250 mL) and neutralized with aqueous potassium carbonate (3.62 mol, 50 mL). The organic layer is washed with water, dried over Na 2  SO 4 , filtered and evaporated to a yellow solid. Crystallization from benzene-hexane gives the product as a yellow powder (37.4 g, 99%) with mp 125°-130° C. 
     EXAMPLE 3 
     Preparation of 1-amino-3-{[p-(trifluoromethyl)benzylidene]amino}-guanidine, hydrochloride and p-tolualdehyde,α,α,α,-trifluoro-, oxime, (E)- ##STR13## 
     A mixture of 1,3-bis{[p-(trifluoromethyl)benzylidene]amino}guanidine (15.0 g, 0.0374 mol), hydroxylamine hydrochloride (2.76 g, 0.0393 mol) and ethanol (95%, 100 mL) is refluxed for one hour and 30 minutes. After stirring at room temperature for 16 hours, the reaction mixture is cooled in a freezer and the white solid is filtered (7.25 g). The filtrate is evaporated to approximately 30 mL and then cooled. The resulting purple solid (4.4 g) is collected by filtration and reslurried in hot chloroform (75 mL). Filtration gave the title hydrochloride as a white solid with mp 236°-249° C. (dec). 
     The filtrate is evaporated to approximately 10 mL and then cooled. The title oxime is collected by filtration as white powder (1.72 g) mp 98°-102.5° C. 
     Using a similar procedure, 1-amino-3-p{[p-(1,1,2,2-tetrafluoroethoxy)benzylidene]amino}guanidine hydrochloride (white solid, mp 205°-212° C.); 1-amino-3-{p-(trifluoroethoxy)benzylidene]amino}guanidine hydrochloride (white powder; mp 235°-238° C.); and 1-amino-3-(p-chlorobenzylideneamino)guanidine hydrochloride may be prepared. The second products of the reactions, p-(1,1,2,2-tetrafluoroethoxy)benzaldehyde oxime (pinkish white solid, mp 47°-53.5° C.); α,α,α-trifluoro-p-anilaldehyde oxime (off-white solid, mp 46°-49.5° C.) and p-chlorbenzaldehyde oxime may also be isolated from the reactions. 
     EXAMPLE 4 
     Preparation of 1-{[p-(1,1,2,2-tetrafluoroethoxy)benzylidene]amino}-3-{[p-(trifluoromethyl)benzylidene]amino}guanidine ##STR14## 
     p-Tetrafluoroethoxybenzaldehyde (1.7 g) in 4 mL of ethanol is added over three minutes to a stirred and warm mixture of 2.0 g of 1-amino-3-{[p-(trifluoromethyl)benzylidene]amino}guanidine hydrochloride in 9 mL of 8:1 ethanol/water. After heating at reflux for one hour, the mixture is concentrated in vacuo to give 3.6 of a white solid. The solids are dissolved in 150 mL of chloroform and treated with 10 mL of 3.6M potassium carbonate and 50 mL of water containing 5% sodium hydroxide. The product is extracted into ethyl acetate 300 mL and the organic layer washed with salt solution, dried over sodium sulfate and concentrated in vacuo to give 3.3 g of yellow solid. Crystallization from hexanechloroform afforded 2.6 g of the title product as a yellow solid with mp 132°-137° C. 
     Utilizing the procedures of Examples 2 and 4 and substituting the appropriate aldehyde and guanidine yields compounds illustrated below. ##STR15## wherein unless specified R 1  &#39; and R 2  &#39; are H. 
     
         ______________________________________                                    
Symmetrical diaminoguanidine hydrazones                                   
             Free base Physical                                           
R.sub.1 =R.sub.2                                                          
             or Salt   appearance  mp ° C.                         
______________________________________                                    
4-CF.sub.3   Free base Yellow solid                                       
                                   181-182                                
4-F          Free base Pale yellow 166-167                                
                       solid                                              
4-F          HCl salt  White solid 289.5-290                              
4-HCF.sub.2 CF.sub.2 O                                                    
             Free base Pale yellow   127-130.5                            
                       powder                                             
4-CF.sub.3 O Free base Yellow solid                                       
                                   118-120                                
4-HCF.sub.2 O                                                             
             Free base Yellow solid                                       
                                   132-135                                
4-HCF.sub.2 O                                                             
             HCl salt  White solid   235-235.5                            
4-HCCl.sub.2 CF.sub.2 O                                                   
             Free base Yellow solid                                       
                                     90-92.5                              
4-HCCl.sub.2 CF.sub.2 O                                                   
             HCl salt  White solid 243-245                                
 ##STR16##   Free base Yellow solid                                       
                                   86-91                                  
 ##STR17##   HCl salt  White solid 241-247                                
4-HCF.sub.2 CF.sub.2 S                                                    
             Free base Yellow solid                                       
                                   135-139                                
4-HCF.sub.2 CF.sub.2 S                                                    
             HCl salt  Yellow white                                       
                                   273-278                                
                       fluffy solid                                       
                                   (dec)                                  
4-CF.sub.3 CH.sub.2 O                                                     
             Free base Light yellow                                       
                                   160-162                                
                       powder                                             
4-CF.sub.3 CH.sub.2 O                                                     
             HCl salt  Beige crystal-                                     
                                   230-236                                
                       line solid                                         
4-HCF.sub.2 S                                                             
             Free base Yellow solid                                       
                                   141.5-143                              
4-HCF.sub.2 S                                                             
             HCl Salt  White solid 253-254                                
                                   (dec)                                  
R.sub.1 R.sub.1 &#39;/R.sub.2 R.sub.2 &#39;                                       
 ##STR18##   HCl salt  White powder                                       
                                   243-247                                
 ##STR19##   HCl salt  White powder                                       
                                   301-305                                
 ##STR20##   Free base Pale yellow solid                                  
                                   132-135                                
 ##STR21##   HCl salt  White solid 216-244                                
______________________________________                                    
 ##STR22##                                                                
Unsymmetrical diaminoguanidine hydrazones                                 
R.sub.1                                                                   
      R.sub.2                                                             
______________________________________                                    
CF.sub.3                                                                  
      Cl         Free base Yellow solid                                   
                                     184-186                              
CF.sub.3                                                                  
      Br         Free base Yellow solid                                   
                                     187.5-188                            
CF.sub.3                                                                  
      Br         HI salt   Yellow solid                                   
                                     243-244                              
CF.sub.3                                                                  
      HCF.sub.2 CF.sub.2 O                                                
                 Free base Yellow powder                                  
                                     132-137                              
Br    HCF.sub.2 CF.sub.2 O                                                
                 Free base Yellow powder                                  
                                     149-158                              
Cl    HCF.sub.2 CF.sub.2 O                                                
                 Free base Yellow solid                                   
                                     177-180                              
Cl    HCF.sub.2 CF.sub.2 O                                                
                 HCl salt  White solid                                    
                                     251-259                              
CF.sub.3 O                                                                
      HCF.sub.2 CF.sub.2 O                                                
                 Free base Yellow powder                                  
                                     106-109                              
CF.sub.3 O                                                                
      HCF.sub.2 CF.sub.2 O                                                
                 HCl salt  White solid                                    
                                       261-263.5                          
                                     (dec)                                
______________________________________                                    
 
    
     EXAMPLE 5 
     Preparation of 4,4-dimethyl-2-{[p-(1,1,2,2-tetrafluoroethoxy)benzylidene]amino}-allophanimidic acid [p-(1,1,2,2-tetrafluoroethoxy)benzylidene]hydrazide ##STR23## 
     A solution of 1,3-bis{[p-(1,1,2,2-tetrafluoroethoxy)benzylidene]amino}guanidine (29.84 g, 0.06 mol), diisopropylethylamine (15.51 g, 0.12 mol) and dimethylcarbamoyl chloride (129.2 g, 0.12 mol) in acetonitrile (200 mL) is stirred at reflux for 22 hours. The reaction mixture is cooled, and the acetonitrile is evaporated under reduced pressure. The residue is dissolved in ethyl acetate (250 mL), and the organic solution is washed with water, saturated NaCl and dried over Na 2  SO 4 . The solvent is evaporated under reduced pressure, and the residue is crystallized from benzene-hexanes to give the desired product as a yellow solid, mp 141.5°-143.5° C. in 92.9% yield. 
     Utilizing the above procedure and substituting the appropriate dialkylcarbamoyl chloride and diaminoguanidine hydrazone compound, yields the compounds illustrated below. 
     
         ______________________________________                                    
 ##STR24##                                                                
R.sub.3   R.sub.4     R.sub.3 R.sub.4                                     
                                    mp °C.                         
______________________________________                                    
CF.sub.3  CF.sub.3    CH.sub.3                                            
                              CH.sub.3                                    
                                    124-126                               
Cl        Cl          CH.sub.3                                            
                              CH.sub.3                                    
                                    169-161                               
Br        Br          CH.sub.3                                            
                              CH.sub.3                                    
                                    172-178                               
CF.sub.3 O                                                                
          CF.sub.3 O  CH.sub.3                                            
                              CH.sub.3                                    
                                    113-115                               
HCF.sub.2 O                                                               
          HCF.sub.2 O CH.sub.3                                            
                              CH.sub.3                                    
                                    83.5-85.5                             
HCCl.sub.2 CF.sub.2 O                                                     
          HCCl.sub.2 CF.sub.2 O                                           
                      CH.sub.3                                            
                              CH.sub.3                                    
                                    153-154                               
HCFClCF.sub.2 O                                                           
          HCFClCF.sub.2 O                                                 
                      CH.sub.3                                            
                              CH.sub.3                                    
                                    142-144                               
HCF.sub.2 CF.sub.2 S                                                      
          HCF.sub.2 CF.sub.2 S                                            
                      CH.sub.3                                            
                              CH.sub.3                                    
                                    143-146                               
F         F           CH.sub.3                                            
                              CH.sub.3                                    
                                    186-187                               
HCF.sub.2 S                                                               
          HCF.sub.2 S CH.sub.3                                            
                              CH.sub.3                                    
                                    130-133                               
{HCF.sub.2 CF.sub.2 O                                                     
          {Br and     CH.sub.3                                            
                              CH.sub.3                                    
                                     60-65                                
and Br}   HCF.sub.2 CF.sub.2 O}                                           
                      --      --                                          
{CF.sub.3 and                                                             
          {Br and     CH.sub.3                                            
                              CH.sub.3                                    
                                    129-130                               
Br}       CF.sub.3 }  --      --                                          
{CF.sub.3 and                                                             
          {Cl and     CH.sub.3                                            
                              CH.sub.3                                    
                                    149-151                               
Cl}       CF.sub.3 }                                                      
{CF.sub.3 O and                                                           
          {HCF.sub.2 CF.sub.2 O                                           
                      CH.sub.3                                            
                              CH.sub.3                                    
                                    102-120                               
HCF.sub.2 CF.sub.2 O}                                                     
          and CF.sub.3 O}                                                 
                      --      --                                          
CF.sub.3  CF.sub.3    C.sub.2 H.sub.5                                     
                              C.sub.2 H.sub.5                             
                                    150-151                               
HCF.sub.2 CF.sub.2 O                                                      
          HCF.sub.2 CF.sub.2 O                                            
                      C.sub.2 H.sub.5                                     
                              C.sub.2 H.sub.5                             
                                     99-100                               
CF.sub.3 O                                                                
          CF.sub.3 O  C.sub.2 H.sub.5                                     
                              C.sub.2 H.sub.5                             
                                     67-70                                
CF.sub.3  CF.sub.3    (CH.sub.2).sub.4                                    
                                  120-123                                 
HCF.sub.2 CF.sub.2 O                                                      
          HCF.sub.2 CF.sub.2 O                                            
                      (CH.sub.2).sub.4                                    
                                  136-137                                 
______________________________________                                    
 
    
     EXAMPLE 6 
     Preparation of allophanimidic acid, 4-(2-chloroethyl)-2-{[p-(trifluoromethyl)benzylidene]amino}-allophanimidic acid [p-(trifluoromethyl)benzylidene]hydrazide ##STR25## 
     A solution of 2-chloroethylisocyanate (2.9 g, 0.0275 mol) in ether (8 mL) is slowly added to a slightly turbid mixture of 1,3-bis{[p-(trifluoromethyl)benzylidene]amino}guanidine (10.03 g, 0.025 mol) in ether (200 mL). After stirring for two hours at room temperature, the product is collected by filtration, washed with ether, and dried in a vacuum oven at 50°-60° C. to give 11.78 g of the above product with a mp 133° C. 
     Utilizing the above procedure and substituting the appropriate substituted or unsubstituted isocyanate and diaminoguanidine hydrazone compound yields the compounds illustrated below. 
     
         ______________________________________                                    
 ##STR26##                                                                
R.sub.1   R.sub.2     R.sub.3    mp °C.                            
______________________________________                                    
CF.sub.3  CF.sub.3    CH.sub.3   146.5-147                                
Cl        Cl          CH.sub.3   Decomposes                               
                                 on heating                               
HCF.sub.2 O                                                               
          HCF.sub.2 O CH.sub.3   113.0-114                                
HCF.sub.2 CF.sub.2 O                                                      
          HCF.sub.2 CF.sub.2 O                                            
                      CH.sub.3   139.5-142.5                              
CF.sub.3  CF.sub.3    C.sub.2 H.sub.5                                     
                                 180                                      
HCF.sub.2 CF.sub.2 O                                                      
          HCF.sub.2 CF.sub.2 O                                            
                      C.sub.2 H.sub.5                                     
                                 119.0-120.5                              
HCF.sub.2 CF.sub.2 O                                                      
          HCF.sub.2 CF.sub.2 O                                            
                      ClCH.sub.2 CH.sub.2                                 
                                 116.0-118                                
______________________________________                                    
 
    
     EXAMPLE 7 
     Preparation of 3-{p-(trifluoromethyl)benzylidene]-2-{{[p-(trifluoromethyl)benzylidene]amino}amidino}carbazate ##STR27## 
     Ethyl chloroformate (2.98 g, 0.0275 mol) is added dropwise to a refluxing solution of 1,3-bis{[p-trifluoromethyl)benzylidene]amino}guanidine (10.03 g, 0.025 mol) and diisopropylethylamine &#34;DIPEA&#34; (3.55 g, 0.0275 mol) in acetonitrile (130 mL). After refluxing for one hour the mixture is cooled and acetonitrile (50 mL) is added. The resulting white solids collected by filtration, are washed with acetonitrile and dried in a vacuum oven at 50°-60° C. to give 6.9 g. The solid is slurried in hot isopropanol and filtered to give the product as white fluffy needles (6.0 g), mp 202° C. 
     EXAMPLE 8 
     Preparation of 2,2,2-trichloroethyl 3-[p-(trifluoromethyl)benzylidene]-2-{{[p-trifluoromethyl)benzylidene]amino}amidino}carbazate ##STR28## 
     A solution of 2,2,2-trichloroethyl chlorformate (2.33 g, 0.011 mol) in ether (10 mL) is added dropwise to a solution of 1,3-bis{[p-(trifluoromethyl)benzylidene]amino}guanidine (4.01 g, 0.01 mol) and triethylamine (1.13 g, 0.011 mol) in ether (80 mL). The resulting mixture is stirred for one hour and then allowed to stand overnight. Additional 2,2,2-trichloroethyl chlorformate (2.33 g, 0.011 mol) and triethylamine 11.13 g, 0.011 mol) are added and stirring continued for four hours. The reaction mixture is filtered and the filtrate evaporated to dryness. The residue is dissolved in ethyl acetate, and the mixture is washed with water, dried over Na 2  SO 4 , filtered, and evaporated to a pale yellow solid. Successive crystallizations from toluene and isopropanol gave the title product (0.54 g) with mp 150.5°-151° C. 
     EXAMPLE 9 
     Preparation of 3-[p-(trifluoromethyl)benzylidene]-2-{{[p-(trifluoromethyl)benzylidene]amino}amidino}carbazate ester ##STR29## 
     A solution of 2-chloroethyl chloroformate (235.9 g, 1.65 mol) in acetonitrile (250 mL) is added in a steady stream to a solution of 1,3-bis-{[p-(trifluoromethyl)benzylidene]amino}guanidine (602.0 g, 1.5 mol) and diisopropylethylamine (213.3 g, 1.65 mol) in acetonitrile (7500 mL) while the temperature is maintained below 35° C. Additional acetonitrile (1000 mL) is added and the reaction mixture stirred for one hour. The fluffy white solids are collected by filtration, washed with acetonitrile (2000 mL) and dried to give 610 g of the product with mp 188° C. 
     Utilizing the procedures of examples 7, 8, and 9 and substituting the appropriate hydrazone and chloroformate gives the compounds illustrated below. ##STR30## wherein unless specified R 1  &#39; and R 2  &#39; are H. 
     
         __________________________________________________________________________
                                     Physical                             
R.sub.1      R.sub.2      R.sub.5    appearance                           
                                            mp °C.                 
__________________________________________________________________________
CF.sub.3     CF.sub.3     CH.sub.3   White solid                          
                                              174-174.5                   
HCF.sub.2 CF.sub.2 O                                                      
             HCF.sub.2 CF.sub.2 O                                         
                          CH.sub.3   White solid                          
                                            181-183                       
Cl           Cl           CH.sub.3   White solid                          
                                            189.5-190                     
CF.sub.3     CF.sub.3     C.sub.2 H.sub.5                                 
                                     White needles                        
                                            202                           
Cl           Cl           C.sub.2 H.sub.5                                 
                                     White solid                          
                                            154-185                       
HCF.sub.2 O  HCF.sub.2 O  C.sub.2 H.sub.5                                 
                                     Pale yellow                          
                                            154-155                       
                                     solid                                
HCF.sub.2 CF.sub.2 O                                                      
             HCF.sub.2 CF.sub.2 O                                         
                          C.sub.2 H.sub.5                                 
                                     White solid                          
                                            152.5-155                     
CF.sub.3 O   CF.sub.3 O   C.sub.2 H.sub.5                                 
                                     Cream color                          
                                            169-170                       
                                     solid                                
CF.sub.3 and Cl                                                           
             Br and CF.sub.3                                              
                          C.sub.2 H.sub.5                                 
                                     White solid                          
                                              189-189.5                   
HCF.sub.2 S  HCF.sub.2 S  C.sub.2 H.sub.5                                 
                                     Pale yellow                          
                                            152-153                       
                                     solid                                
HCF.sub.2 O  HCF.sub.2 O  C.sub.2 H.sub.5                                 
                                     Pale yellow                          
                                            134-135                       
                                     solid                                
CF.sub.3     CF.sub.3      -n-C.sub.3 H.sub.7                             
                                     White solid                          
                                            181-182                       
CF.sub.3     CF.sub.3      .sub.-i-C.sub.3 H.sub.7                        
                                     White solid                          
                                              178-178.5                   
HCF.sub.2 CF.sub.2 O                                                      
             HCF.sub.2 CF.sub.2 O                                         
                           .sub.-i-C.sub.3 H.sub.7                        
                                     White solid                          
                                              129-131.5                   
HCCl.sub.2 CF.sub.2 O                                                     
             HCCl.sub.2 CF.sub.2 O                                        
                           .sub.-i-C.sub.3 H.sub.7                        
                                     White solid                          
                                            131-133                       
CF.sub.3 O   CF.sub.3 O    .sub.-i-C.sub.3 H.sub.7                        
                                     White solid                          
                                            142-144                       
 ##STR31##                                                                
              ##STR32##    .sub.-i-C.sub.3 H.sub.7                        
                                     White powder                         
                                            127.5-130                     
HCF.sub.2 CF.sub.2 S                                                      
             HCF.sub.2 CF.sub.2 S                                         
                           .sub.-i-C.sub.3 H.sub.7                        
                                     Pale yellow                          
                                            120-124                       
                                     fluffy solid                         
CF.sub.3     CF.sub.3      -n-C.sub.4 H.sub.9                             
                                     White needles                        
                                            185                           
CF.sub.3     CF.sub.3      .sub.-i-C.sub.4 H.sub.9                        
                                     White solid                          
                                              184- 184.5                  
CF.sub.3     CF.sub.3      .sub.----sec-C.sub.4 H.sub.9                   
                                     White solid                          
                                            153.5-154                     
CF.sub.3 O   CF.sub.3 O    .sub.----sec-C.sub.4 H.sub.9                   
                                     White solid                          
                                              126-128.5                   
Cl           Cl            .sub.----sec-C.sub.4 H.sub.9                   
                                     White solid                          
                                            149-150                       
CF.sub.3     CF.sub.3     CH.sub.2 CH.sub.2 Cl                            
                                     White solid                          
                                            188                           
CF.sub.3 O   CF.sub.3 O   CH.sub.2 CH.sub.2 Cl                            
                                     Fluffy white                         
                                            166-167                       
                                     solid                                
HCF.sub.2 CF.sub.2 O                                                      
             HCF.sub.2 CF.sub.2 O                                         
                          CH.sub.2 CH.sub.2 Cl                            
                                     Pale orange-                         
                                            128-135                       
                                     white solid,                         
                                     and remelt at                        
                                            170-182                       
{HCF.sub.2 CF.sub.2 O and Cl}                                             
             {Cl and HCF.sub.2 CF.sub.2 O}                                
                          CH.sub.2 CH.sub.2 Cl                            
                                     Light brown                          
                                            117-119                       
 ##STR33##                                                                
              ##STR34##   CH.sub.2 CH.sub.2 Cl                            
                                     Off-white powder                     
                                            110-137                       
{HCF.sub.3 CF.sub.2 O and CF.sub.3 O}                                     
             {CF.sub.3 O and HCF.sub.2 CF.sub.2 O}                        
                          CH.sub.2 CH.sub.2 Cl                            
                                     Off-white                            
                                            120-180                       
                                     powder                               
HCF.sub.2 S  HCF.sub.2 S  CH.sub.2 CH.sub.2 Cl                            
                                     White solid                          
                                            138-139                       
CF.sub.3     CF.sub.3     CH.sub.2 CH.sub.2 Cl                            
                                     Light beige                          
                                            155-160                       
                                     powder                               
CF.sub.3     CF.sub.3     CH.sub.2 CH.sub.2 Br                            
                                     White solid                          
                                            184-185                       
CF.sub.3     CF.sub.3     CH.sub.2 CCl.sub.3                              
                                     Pale yellow                          
                                            150.5-151                     
                                     solid                                
CF.sub.3 O   CF.sub.3 O   CH.sub.2 CCl.sub.3                              
                                     Cream color                          
                                            137.5-140                     
                                     solid                                
CF.sub.3     CF.sub.3     C(CH.sub.3).sub.2CCl.sub.3                      
                                     Fluffy white                         
                                            162-164                       
                                     solid                                
CF.sub.3     CF.sub.3     CH.sub.2CHCH.sub.2                              
                                     White solid                          
                                            190                           
HCCl.sub.2CF.sub.2 O                                                      
             HCCl.sub.2CF.sub.2 O                                         
                          CH.sub.2CH White solid                          
                                            165-166                       
CF.sub.3 O   CF.sub.3 O   CH.sub.2 CH.sub.2CH.sub.2                       
                                     White solid                          
                                            176.5-177                     
CF.sub.3     CF.sub.3                                                     
                           ##STR35## White solid                          
                                            146.5-147.5                   
CF.sub.3     CF.sub.3     oleyl      White solid                          
                                            137-140                       
CF.sub.3     CF.sub.3                                                     
                           ##STR36## White solid                          
                                            168-169                       
__________________________________________________________________________
R.sub.1 R.sub.1 &#39;/R.sub.2 R.sub.2 &#39;                                       
 ##STR37##                 .sub.-i-C.sub.3 H.sub.7                        
                                     White solid                          
                                            125-132                       
__________________________________________________________________________
 
    
     EXAMPLE 10 
     The insecticidal activity of the compounds of this invention is demonstrated by the following tests wherein compounds are evaluated against test insect species at rates of from 10 to 1000 ppm. Test formulations and procedures used for evaluation are as follows: 
     Test Formulations 
     A. 100 mg of the test material is weighed, placed in a funnel over a 113 g narrow-mouth bottle, rinsed into the bottle with a 35 mL scoop of acetone, followed by a 35 mL scoop of water and another 35 mL scoop of acetone to yield 1000 ppm in 65% acetone. If the material is not soluble, it is broken up with a glass rod and used as a suspension. 
     B. This stock solution (&#34;A&#34;) is used to make 300 ppm solutions or suspensions by pipetting 30 mL of &#34;A&#34; into a bottle containing 70 mL of 50% acetone to yield 300 ppm. Further dilutions in 50% acetone are made as required. 
     C. Tests requiring 10 ppm acetone solutions: 1 mL of &#34;A&#34; is pipetted into 99 mL of acetone to yield 10 ppm. Additional dilutions are made using 50% acetone as required. 
     Initial Tests 
     Tobacco Budworm-Heliothis virescens (Fabricus). 
     A cotton plant with two true leaves expanded is dipped for three seconds with agitation in 300 ppm solution. A 1.27 to 1.91 cm square of cheesecloth with about 50 to 100 budworm eggs 0-24 hours old is also dipped in the test solution and placed on a leaf of the cotton platn, all being placed in the hood to dry. The leaf with the treated budworm eggs is removed from the plant and placed in a 226 g Dixie cup with a wet 5 cm piece of dental wick and covered with a lid. The other leaf is placed in a similar cup with a wick and a piece of cheesecloth infested with 50-100 newly hatched larvae is added before covering the cup with a lid. After three days at 80° F., 50% relative humidity, observations of egg hatch are made, as well as kill of newly hatched larvae, any inhibition of feeding, or interference of any sort with normal development. 
     Southern Armyworm-Spodoptera eridania (Cramer). 
     A Sieva lima bean plant with just the primary leaves expanded to 1.91 cm is dipped for three seconds with agitation in the &#34;A&#34; solution of 1000 ppm and set in the hood to dry. Following this, one leaf is placed in a 9 cm petri dish which has a moist filter paper in the bottom and 10 third-instar armyworm larvae about 1 cm long. This dish is covered and held at 80° F., and 50% r.h. After two days, mortality counts and estimates of the amount of feeding are made. Compounds showing partial kill and/or inhibition of feeding are held for an extra day for further observations. Those materials which produce greater than 75% mortality, or which show only trace feeding damage are further tested. 
     All compounds showing activity as defined above are retested, using the second leaf on the bean plant, after an interval of seven days from original treatment, as an assay of residual activity. 
     Secondary Tests 
     Tobacco Budworm-Heliothis virescens (Fabricus) 
     Third Instar 
     Three cotton plants with just expanded cotyledons are dipped in 1000 ppm solution and placed in the hood to dry. When dry, each cotyledon is cut in half, and 10 are each placed in a 28 g plastic medicine cup containing a 1.25 cm dental wick saturated with water, and one third-instar budworm larva is added. The cup is capped and held for three days at 80° F., 50% relative humidity, after which mortality counts are made. Compounds killing more than 75% of the larvae are further tested. 
     
         ______________________________________                                    
Rating System                                                             
______________________________________                                    
        0   No effect                                                     
        1   11-25%                                                        
        2   26-35%                                                        
        3   36-45%                                                        
        4   46-55%                                                        
        5   56-65%                                                        
        6   66-75%                                                        
        7   76-85%                                                        
        8   86-99%                                                        
        9   100%                                                          
______________________________________                                    
 
    
     Data obtained are reported in Table IA, IB and IC below. 
     
                                           TABLE IA                                
__________________________________________________________________________
Evaluation of Diaminoguanidine Hydrazone Urea Compounds as Insecticides   
 ##STR38##                                                                
                                            LC.sub.50 /                   
                                                *FD.sub.50 /              
                                            ppm ppm       *FD.sub.50 /    
                    Mortality Rating        South-                        
                                                South-    ppm             
                    Southern                                              
                            Tobacco Budworm ern ern LC.sub.50 /ppm        
                                                          Tobacco         
Compound            Armyworm                                              
                            1st Instar                                    
                                    3rd Instar                            
                                            Army-                         
                                                Army-                     
                                                    Tobacco               
                                                          Bud-            
R.sub.1                                                                   
       R.sub.2                                                            
              R.sub.3                                                     
                 R.sub.4                                                  
                    1000                                                  
                       100                                                
                          10                                              
                            300                                           
                               100                                        
                                  10                                      
                                    1000                                  
                                       100                                
                                          10                              
                                            worm                          
                                                worm                      
                                                    Budworm               
                                                          worm            
__________________________________________________________________________
CF.sub.3                                                                  
       CF.sub.3                                                           
              CH.sub.3                                                    
                 CH.sub.3                                                 
                    9  9  8 8  6  0 9  9  0 15  12   96     3             
HCF.sub.2 CF.sub.2 O                                                      
       HCF.sub. 2 CF.sub.2 O                                              
              CH.sub.3                                                    
                 CH.sub.3                                                 
                    9  9  0 9  5  --                                      
                                    8  2    7, 7                          
                                                8, 6                      
                                                    491   2, 5            
Cl     Cl     CH.sub.3                                                    
                 CH.sub.3                                                 
                    9  0  --                                              
                            0  -- --                                      
                                    0  0  --                              
                                            --  --  --    --              
Br     Br     CH.sub.3                                                    
                 CH.sub.3                                                 
                    9  9  0 0  -- --                                      
                                    2  0  --                              
                                            --  --  --    --              
CF.sub.3 O                                                                
       CF.sub.3 O                                                         
              CH.sub.3                                                    
                 CH.sub.3                                                 
                    9  9  9 -- -- --                                      
                                    9  3  --                              
                                            10, 23                        
                                                 8, 30                    
                                                    77,                   
                                                          1, 4            
HCF.sub.2 O                                                               
       HCF.sub.2 O                                                        
              CH.sub.3                                                    
                 CH.sub.3                                                 
                    9  9  0 0  -- --                                      
                                    0  -- --                              
                                            75  46  --    --              
HCCl.sub.2 CF.sub.2 O                                                     
       HCCl.sub.2 CF.sub.2 O                                              
              CH.sub.3                                                    
                 CH.sub.3                                                 
                    9  9  --                                              
                            -- -- --                                      
                                    0  2  --                              
                                            26  28  140   &lt;30             
 ##STR39##                                                                
        ##STR40##                                                         
              CH.sub.3                                                    
                 CH.sub.3                                                 
                    9  9  9 -- -- --                                      
                                    9  4  0 --  --  201    10             
HCF.sub.2 CF.sub.2 S                                                      
       HCF.sub.2 CF.sub.2 S                                               
              CH.sub.3                                                    
                 CH.sub.3                                                 
                    9  9  3 -- -- --                                      
                                    6  6  0 --  --  --    --              
F      F      CH.sub.3                                                    
                 CH.sub.3                                                 
                    8  0  --                                              
                            -- -- --                                      
                                    0  -- --                              
                                            --  --  --    --              
HCF.sub.2 S                                                               
       HCF.sub.2 S                                                        
              CH.sub.3                                                    
                 CH.sub.3                                                 
                    9  9  0 -- -- --                                      
                                    0  -- --                              
                                            --  --  --    --              
HCF.sub.2 CF.sub.2 O                                                      
       Br and                                                             
and BR HCF.sub.2 CF.sub.2 O                                               
              CH.sub.3                                                    
                 CH.sub.3                                                 
                    9  9  9 -- -- --                                      
                                    6  0  --                              
                                            --  --  --    --              
CF.sub.3 and                                                              
       Br and                                                             
Br     CF.sub.3                                                           
              CH.sub.3                                                    
                 CH.sub.3                                                 
                    0  9  0 -- -- --                                      
                                    6  0  --                              
                                            --  --  --    --              
CF.sub.3 and                                                              
       Cl and                                                             
Cl     CF.sub.3                                                           
              CH.sub.3                                                    
                 CH.sub.3                                                 
                    9  9  5 -- -- --                                      
                                    0  0  --                              
                                            --  --  --    --              
CF.sub.3 O and                                                            
       HCF.sub.2 CF.sub.2 O                                               
HCF.sub.2 CF.sub.2 O                                                      
       and CF.sub.3 O                                                     
              CH.sub.3                                                    
                 CH.sub.3                                                 
                    9  9  --                                              
                            -- -- --                                      
                                    7  3  --                              
                                            --  --  --    --              
CF.sub.3                                                                  
       CF.sub.3                                                           
              CH.sub.3                                                    
                 H  9  9  1 8  0  --                                      
                                    6  -- --                              
                                             5   5  --    --              
HCF.sub.2 O                                                               
       HCF.sub.2 O                                                        
              CH.sub.3                                                    
                 H  9  0  --                                              
                            7  -- --                                      
                                    0  -- --                              
                                            --  --  --    --              
HCF.sub.2 CF.sub.2 O                                                      
       HCF.sub.2 CF.sub.2 O                                               
              CH.sub.3                                                    
                 H  9  9  0 -- -- --                                      
                                    4  -- --                              
                                            16, 34                        
                                                12, 19                    
                                                    --    --              
CF.sub.3                                                                  
       CF.sub.3                                                           
              C.sub.2 H.sub.5                                             
                 C.sub.2 H.sub.5                                          
                    9  9  7 0  -- --                                      
                                    4  -- --                              
                                             8, 12                        
                                                 8, 11                    
                                                    --    --              
HCF.sub.2 CF.sub.2 O                                                      
       HCF.sub.2 CF.sub. 2 O                                              
              C.sub.2 H.sub.5                                             
                 C.sub.2 H.sub.5                                          
                    9  9  1 -- -- --                                      
                                    5  0  0 --  --  --    --              
CF.sub.3 O                                                                
       CF.sub.3 O                                                         
              C.sub.2 H.sub.5                                             
                 C.sub.2 H.sub.5                                          
                    9  9  0 -- -- --                                      
                                    8  -- --                              
                                            --  --  --    --              
CF.sub.3                                                                  
       CF.sub.3                                                           
              C.sub.2 H.sub.5                                             
                 H  9  0  --                                              
                            0  -- --                                      
                                    0  -- --                              
                                            --  --  --    --              
HCF.sub.2 CF.sub.2 O                                                      
       HCF.sub.2 CF.sub.2 O                                               
              C.sub.2 H.sub.5                                             
                 H  9  9  0 -- -- --                                      
                                    4  -- --                              
                                            34  12  --    --              
__________________________________________________________________________
 FD.sub.50 = The concentration of insecticide required to reduce insect   
 feeding by 50%.                                                          
 
    
     
                                           TABLE IB                                
__________________________________________________________________________
Diaminoguanidine hydrazones as insecticides                               
 ##STR41##                                                                
wherein unless specified R.sub.1 &#39; and R.sub.2 &#39; are H                    
               Mortality Rating                                           
          Free Southern                                                   
                       Tobacco Budworm                                    
Compound  Base, B                                                         
               Armyworm                                                   
                       1st Instar                                         
                               3rd Instar                                 
R.sub.1                                                                   
   R.sub.2                                                                
          or salt, S                                                      
               1000                                                       
                  100                                                     
                     10                                                   
                       300                                                
                          100                                             
                             10                                           
                               1000                                       
                                  100                                     
                                     10                                   
__________________________________________________________________________
CF.sub.3  B    9  9  0 6  0  --                                           
                               8  0  --                                   
                     9                                                    
F         B    9/R*                                                       
                  2  --                                                   
                       0  0  --                                           
                               3  -- --                                   
F         S    9  2  --                                                   
                       -- -- --                                           
                               -- -- --                                   
HCF.sub.2 CF.sub.2 O                                                      
          B    9  9  0 9  0/R                                             
                             --                                           
                               9  0  --                                   
CF.sub.3 O                                                                
          B    9  9  4 -- -- --                                           
                               7  -- --                                   
HCF.sub.2 O                                                               
          B    9  6  0 0  -- --                                           
                               0  -- --                                   
HCF.sub.2 O                                                               
          S    9  8  0 0  -- --                                           
                               0  -- --                                   
HCCl.sub.2 CF.sub.2 O                                                     
          B    9  0  0 -- -- --                                           
                               4/R                                        
                                  -- --                                   
HCCl.sub.2 CF.sub.2 O                                                     
          S    9  9  7 -- -- --                                           
                               5  0/R                                     
                                     --                                   
 ##STR42##                                                                
          B    9  9  7 0                                                  
                       -- -- --                                           
                               9  0  0                                    
 ##STR43##                                                                
          S    9  9  6 -- -- --                                           
                               9/R                                        
                                  0/R                                     
                                     0/R                                  
HCF.sub.2 CF.sub.2 S                                                      
          B    9  9  --                                                   
                       -- -- --                                           
                               0/R                                        
                                  -- --                                   
HCF.sub.2 CF.sub.2 S                                                      
          S    9  9  6 -- -- --                                           
                               0/R                                        
                                  -- --                                   
CF.sub.3 CH.sub.2 O                                                       
          B    4  0  --                                                   
                       -- -- --                                           
                               0/R                                        
                                  0  --                                   
CF.sub.3 CH.sub.2                                                         
          S    9  8  6 -- -- --                                           
                               0/R                                        
                                  0  --                                   
HCF.sub.2 S                                                               
          B    8  9  --                                                   
                       -- -- --                                           
                               0/R                                        
                                  0/R                                     
                                     0                                    
HCF.sub.2 S                                                               
          S    9  9  --                                                   
                       -- -- --                                           
                               0/R                                        
                                  -- --                                   
CF.sub.3                                                                  
   Cl     B    9  9  --                                                   
                       -- -- --                                           
                               4/R                                        
                                  0/R                                     
                                     0                                    
CF.sub.3                                                                  
   Br     B    9  9  9 -- -- --                                           
                               0/R                                        
                                  -- --                                   
CF.sub.3                                                                  
   Br     S    9  8  0 -- -- --                                           
                               0/R                                        
                                  0/R                                     
                                     --                                   
                  9                                                       
CF.sub.3                                                                  
   HCF.sub.2 CF.sub.2 O                                                   
          B    9  9  9 -- -- --                                           
                               3  -- --                                   
                     0                                                    
Br HCF.sub.2 CF.sub.2 O                                                   
          B    9  9  --                                                   
                       -- -- --                                           
                               0/R                                        
                                  -- --                                   
Cl HCF.sub.2 CF.sub.2 O                                                   
          B    9  9  0 -- -- --                                           
                               0/R                                        
                                  0  --                                   
Cl HCF.sub.2 CF.sub.2 O                                                   
          S    9  9  --                                                   
                       -- -- --                                           
                               0/R                                        
                                  -- --                                   
               0  0                                                       
R.sub.1 R.sub.1 &#39;/R.sub.2 R.sub.2 &#39;                                       
 ##STR44##                                                                
          S    9  8 9                                                     
                     6 -- -- --                                           
                               0/R                                        
                                  0  --                                   
 ##STR45##                                                                
          S    9  0  4 -- -- --                                           
                               0/R                                        
                                  0/R                                     
                                     --                                   
 ##STR46##                                                                
          B    9  9 0                                                     
                     0 -- -- --                                           
                               0/R                                        
                                  0/R                                     
                                     --                                   
 ##STR47##                                                                
          S    9  0  --                                                   
                       -- -- --                                           
                               0/R                                        
                                  -- --                                   
Cl        HNO.sub.3                                                       
               9  0  --                                                   
                       -- -- --                                           
                               0  -- --                                   
Br        HNO.sub.3                                                       
               9  5  --                                                   
                       0  -- --                                           
                               -- -- --                                   
CF.sub.3  HCl  9  9  0 9  0/R                                             
                             0 5  0/R                                     
                                     --                                   
Cl        HCl  8  0/R                                                     
                     0 -- -- --                                           
                               0  -- --                                   
               9/R                                                        
Cl        Base 9  0  0 5  -- --                                           
                               0  -- --                                   
CF.sub.3 O                                                                
          HCl  9  9  0 9  -- --                                           
                               -- -- --                                   
Cl Br     HCl  9  2/R                                                     
                     --                                                   
                       0  -- --                                           
                               0  -- --                                   
CF.sub.3                                                                  
   Br     HCl  9  -- --                                                   
                       9  0/R                                             
                             0 0/R                                        
                                  0/R                                     
                                     0                                    
__________________________________________________________________________
 R*  Indicates reduced feeding is observed                                
 
    
     
                                           TABLE IC                                
__________________________________________________________________________
Evaluation of diaminoguanidine hydrazones as insecticides                 
 ##STR48##                                                                
wherein unless specified R.sub.1 &#39; and R.sub.2 &#39; are H                    
                           Mortality Rating                               
                           Southern Tobacco Budworm                       
Compound                   Armyworm 1st Instar                            
                                          3rd Instar                      
R.sub.1 R.sub.2 R.sub.5    1000                                           
                              100                                         
                                 10 300                                   
                                       100                                
                                          10 1000                         
                                                100                       
                                                   10                     
__________________________________________________________________________
CF.sub.3                                                                  
        CF.sub.3                                                          
                CH.sub.3   9  9  3  -- -- -- 6/R*                         
                                                -- --                     
HCF.sub.2 CF.sub.2 O                                                      
        HCF.sub.2 CF.sub.2 O                                              
                CH.sub.3   9  9  -- -- -- -- -- -- --                     
                              9                                           
CF.sub.3                                                                  
        CF.sub.3                                                          
                C.sub.2 H.sub.5                                           
                           9  7  9  -- -- -- -- -- --                     
Cl      Cl      C.sub.2 H.sub.5                                           
                           8  9  -- -- -- -- -- -- --                     
HCF.sub.2 O                                                               
        HCF.sub.2 O                                                       
                C.sub.2 H.sub.5                                           
                           9  9  0  -- -- -- 2  -- --                     
CF.sub.3 O                                                                
        CF.sub.3 O                                                        
                C.sub.2 H.sub.5                                           
                           9  9  6  -- -- -- 7/R                          
                                                2  --                     
CF.sub.3 and                                                              
        Br and  C.sub.2 H.sub.5                                           
                           9  9  0  -- -- -- 0/R                          
                                                -- --                     
Br      CF.sub.3                                                          
CF.sub.3 and                                                              
        Cl and  C.sub.2 H.sub.5                                           
                           9  9  0  -- -- -- 8  0/R                       
                                                   --                     
Cl      CF.sub.3                                                          
HCF.sub.2 S                                                               
        HCF.sub.2 S                                                       
                C.sub.2 H.sub.5                                           
                           9  0  -- -- -- -- 0/R                          
                                                -- --                     
HCF.sub.2 S                                                               
        HCF.sub.2 O                                                       
                 -n-C.sub.3 H.sub.7                                       
                           9  0  -- -- -- -- 0  -- --                     
CF.sub.3                                                                  
        CF.sub.3                                                          
                 -n-C.sub.3 H.sub.7                                       
                           9  9  4  -- -- -- 0  -- --                     
CF.sub.3                                                                  
        CF.sub.3                                                          
                 .sub.-i-C.sub.3 H.sub.7                                  
                           9  9  9  0  -- -- 3/R                          
                                                0/R                       
                                                   --                     
HCF.sub.2 CF.sub.2 O                                                      
        HCF.sub.2 CF.sub.2 O                                              
                 .sub.-i-C.sub.3 H.sub.7                                  
                           9  9  0  -- -- -- 5  0  --                     
HCCl.sub.2 CF.sub.2 O                                                     
        HCCl.sub.2 CF.sub.2 O                                             
                 .sub.-i-C.sub.3 H.sub.7                                  
                           7  0  -- -- -- -- 0/R                          
                                                0/R                       
                                                   --                     
CF.sub.3 O                                                                
        CF.sub.3 O                                                        
                 .sub.-i-C.sub.3 H.sub.7                                  
                           9  9  7  -- -- -- 5  5/R                       
                                                   --                     
                                             9                            
 ##STR49##                                                                
         ##STR50##                                                        
                 .sub.-i-C.sub.3 H.sub.7                                  
                           9  9  0  -- -- -- 0/R                          
                                                -- --                     
HCF.sub.2 CF.sub.2 S                                                      
        HCF.sub.2 CF.sub.2 S                                              
                 .sub.-i-C.sub.3 H.sub.7                                  
                           9  9  -- -- -- -- 5/R                          
                                                0  --                     
R.sub.1 R.sub.1 &#39;/R.sub.2 R.sub.2 &#39;                                       
 ##STR51##                                                                
         ##STR52##                                                        
                 .sub.-i-C.sub.3 H.sub.7                                  
                           8  5  0  -- -- -- 0/R                          
                                                0  --                     
CF.sub.3                                                                  
        CF.sub.3                                                          
                 -n-C.sub.4 H.sub.9                                       
                           9  0  -- -- -- -- 0  -- --                     
CF.sub.3                                                                  
        CF.sub.3                                                          
                 .sub.-i-C.sub.4 H.sub.9                                  
                           9  0  -- 0  -- -- 0  -- --                     
CF.sub.3                                                                  
        CF.sub.3                                                          
                 ##STR53## 9  9  6  -- -- -- 6/R                          
                                                0/R                       
                                                   --                     
CF.sub.3 O                                                                
        CF.sub.3 O                                                        
                 ##STR54## 9  9  0  -- -- -- 8  0/R                       
                                                   --                     
Cl      Cl                                                                
                 ##STR55## 9  0  -- -- -- -- 0/R                          
                                                0  --                     
CF.sub.3                                                                  
        CF.sub.3                                                          
                ClCH.sub.2 CH.sub.2                                       
                           9  9  8  -- -- -- 2/R                          
                                                0  --                     
CF.sub.3 O                                                                
        CF.sub.3 O                                                        
                ClCH.sub.2 CH.sub.2                                       
                           9  9  5  -- -- -- 8/R                          
                                                0/R                       
                                                   0/R                    
HCF.sub.2 CF.sub.2 O                                                      
        Cl and  ClCH.sub.2 CH.sub.2                                       
                           9  9  -- -- -- -- 0/R                          
                                                -- --                     
and Cl  HCF.sub.3 CF.sub.2 O                                              
 ##STR56##                                                                
         ##STR57##                                                        
                ClCH.sub.2 CH.sub.2                                       
                           9  9  -- -- -- -- 0/R                          
                                                -- --                     
HCF.sub.2 CF.sub.2 O                                                      
        CF.sub.3 O and                                                    
                ClCH.sub. 2CH.sub.2                                       
                           9  9  -- -- -- -- 0/R                          
                                                -- --                     
and CF.sub.3 O                                                            
        HCF.sub.2 CF.sub.2 O                                              
HCF.sub.2 S                                                               
        HCF.sub.2 S                                                       
                ClCH.sub.2 CH.sub.2                                       
                           9  0  -- -- -- -- 0/R                          
                                                -- --                     
CF.sub.3                                                                  
        CF.sub.3                                                          
                BrCH.sub.2 CH.sub.2                                       
                           9  0  0  -- -- -- 0  -- --                     
CF.sub.3                                                                  
        CF.sub.3                                                          
                Cl.sub.3 CCH.sub.2                                        
                           9  9  8  -- -- -- 8  0/R                       
                                                   0                      
CF.sub.3 O                                                                
        CF.sub.3 O                                                        
                Cl.sub.3 CCH.sub.2                                        
                           9  9  9  -- -- -- 0/R                          
                                                1/R                       
                                                   --                     
CF.sub.3                                                                  
        CF.sub.3                                                          
                Cl.sub.3 CC(CH.sub.3).sub.2                               
                           9  9  0  -- -- -- 9  0/R                       
                                                   0                      
CF.sub.3                                                                  
        CF.sub.3                                                          
                CH.sub.2CHCH.sub.2                                        
                           9  9  0  -- -- -- 0/R                          
                                                0  --                     
CF.sub.3 O                                                                
        CF.sub.3 O                                                        
                CH.sub.2CHCH.sub.2                                        
                           9  8  6  -- -- -- 0/R                          
                                                -- --                     
CF.sub.3                                                                  
        CF.sub.3                                                          
                 ##STR58## 9  0  -- 0  -- -- 0  -- --                     
__________________________________________________________________________
 R* -- indicates reduced feeding is observed