Abstract:
There are provided substituted acid amide, arylhydrazone compounds (amidrazones) of formula I ##STR1## the use thereof for the control of insect and acarid pests and methods and compositions for the protection of crops from the damage and loss caused by said pests.

Description:
BACKGROUND OF THE INVENTION 
     Certain insect and acarid pests are harmful and cause enormous losses annually in agricultural crops, stored products and human and animal health. It is an object of this invention to provide substituted acid amide, N-arylhydrazone compounds (amidrazones) which are effective agents for the control of pestiferous insects and acarina. 
     It is another object of this invention to provide a method for the protection of important agronomic crops from the harmful and damaging effects caused by insect and acarid pests. 
     It is a further object of this invention to provide insecticidal and acaricidal compositions. 
     SUMMARY OF THE INVENTION 
     The present invention provides a method for the control of insects or acarina which comprises contacting said insects or acarina or their food supply, breeding ground or habitat with an insecticidally effective amount of an amidrazone compound of formula I ##STR2## wherein 
     A is C--R 4  or N; 
     B is C--R 5  or N; 
     W is C--R 6  or N with the proviso that one of A, B or W must be other than N; 
     Y is hydrogen, halogen, CN, NO 2 , C 1  -C 6  alkyl, C 1  -C 6  haloalkyl, C 1  -C 6  alkoxy or C 1  -C 6  haloalkoxy; 
     n is an integer of 0, 1 or 2; 
     R is hydrogen, C 1  -C 10  alkyl optionally substituted with one or more halogens, C 3  -C 6  cycloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, (C 1  -C 4  alkyl)SO x , (C 1  -C 4  haloalkyl)SO x , phenyl optionally substituted with one to three halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, (C 1  -C 4  alkyl)SO x , (C 1  -C 4  haloalkyl)SO x , NO 2  or CN groups, or phenoxy optionally substituted with one to three halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, (C 1  -C 4  alkyl)SO x , (C 1  -C 4  haloalkyl)SO x , NO 2  or CN groups, 
     C 3  -C 12  cycloalkyl optionally substituted with one or more halogens, C 1  -C 6  alkyl, C 1  -C 6  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, (C 1  -C 4  alkyl)SO x , (C 1  -C 4  haloalkyl)SO x , phenyl optionally substituted with one to three halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, NO 2  or CN groups, or pbenoxy optionally substituted with one to three halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, NO 2  or CN groups, or 
     phenyl optionally substituted with one or more halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, NO 2  or CN groups; 
     R 1  is hydrogen or C 1  -C 4  alkyl; 
     R 2  and R 3  are each independently hydrogen, 
     C 1  -C 10  alkyl optionally substituted with one or more halogen, hydroxy, C 1  -C 4  alkoxy, (C 1  -C 4  alkyl)SO x , CONR 7  R 8 , CO 2  R 9 , R 10 , R 11 , C 3  -C 6  cycloalkyl optionally substituted with one to three halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, NO 2  or CN groups, phenyl optionally substituted with one or more halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, CO 2  or CN groups, or pyridyl optionally substituted with one or more halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, NO 2  or CN groups, 
     C 3  -C 10  alkenyl optionally substituted with one or more halogen, hydroxy, C 1  -C 4  alkoxy, (C 1  -C 4  alkyl)SO x , CONR 7  R 8 , CO 2  R 9 , R 10 , R 11 , C 3  -C 6  cycloalkyl optionally substituted with one to three halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkyl, NO 2  or CN groups, phenyl optionally substituted with one or more halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, CO 2  or CN groups, or pyridyl optionally substituted with one or more halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, NO 2  or CN groups, 
     C 3  -C 10  alkynyl optionally substituted with one or more halogen, hydroxy, C 1  -C 4  alkoxy, (C 1  -C 4  alkyl)SO x , CONR 7  R 8 , CO 2  R 9 , R 10 , R 11 , C 3  -C 6  cycloalkyl optionally substituted with one to three halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, NO 2  or CN groups, phenyl optionally substituted with one or more halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, CO 2  or CN groups, or pyridyl optionally substituted with one or more halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, NO 2  or CN groups, 
     C 3  -C 12  cycloalkyl optionally substituted with one or more halogen, hydroxy, C 1  -C 4  alkoxy, (C 1  -C 4  alkyl)SO x , CONR 7  R 8 , CO 2  R 9 , R 10 , R 11 , C 3  -C 6  cycloalkyl optionally substituted with one to three halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, NO 2  or CN groups, phenyl optionally substituted with one or more halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, CO 2  or CN groups, or pyridyl optionally substituted with one or more halogen, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy, NO 2  or CN groups or 
     R 2  and R 3  may be taken together to form a ring represented by the structure ##STR3## 
     R 4 , R 5  and R 6  are each independently hydrogen, halogen, CN, NO 2 , (C 1  -C 4  alkyl)SO x , (C 1  -C 4  haloalkyl)SO x , C 1  -C 6  alkyl, C 1  -C 6  haloalkyl, C 1  -C 6  alkoxy or C 1  -C 6  haloalkoxy; 
     R 7 , R 8  and R 9  are each independently hydrogen or C 1  -C 4  alkyl; 
     R 10  is NR 12  R 13 , ##STR4## 
     R 11  is ##STR5## 
     R 12 , R 13 , R 14  and R 15  are each independently hydrogen or C 1  -C 4  alkyl; 
     X is O, S or NR 14  ; 
     r is an integer of 0 or 1; 
     p and m are each independently an integer of 0, 1, 2 or 3 with the provisos that only one of p, m or r can be 0 and that the sum of p+m+r must be 4, 5 or 6; 
     x is an integer of 0, 1 or 2; or 
     the acid addition salts thereof. 
     The present invention further provides N-arylamidrazone compounds of formula I wherein A, B, W, Y, n, R, R 1 , R 2 , and R 3  are as described hereinabove with the proviso that when all of A, B and W are other than N, then R and one of R 2  or R 3  must be other than hydrogen and with the further proviso that when one of A, B or W is N, then Y, R 4 , R 5  or R 6  must be other than C 1  -C 10  alkyl. 
     Compositions and methods for the protection of growing plants from attack and infestation by insects and acarina are also provided. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     A variety of insects and acarina cause great economic loss by damaging or destroying agricultural crops and other valuable plants; by aiding in the spread and development of bacteria, fungi and viruses that produce diseases of plants; and by destroying or lowering the value of stored foods, other products and possessions. Insects and acarina present some of the farmers&#39; greatest problems the world over. The need for alternative and effective insect and acarid control is a global concern. 
     It has now been found that the substituted acid amide, N-arylhydrazone compounds of formula I are especially efficacious insecticidal and acaricidal agents, particularly against Coleoptera, Lepidoptera and Acarina. 
     The formula I amidrazone compounds of the present invention have the structural formula ##STR6## wherein A, B, W, Y, n, R, R 1 , R 2  and R 3  are described hereinabove. The term halogen as used in the specification and claims designates chlorine, fluorine, bromine or iodine. The term acid addition salts designates those salts formed by acids commonly known in the art such as hydrogen chloride, hydrogen bromide, hydrogen bisulfate, hemi-hydrogen sulfate and the like. In the above definition when n is 0 then Y is hydrogen. 
     Preferred compounds of the invention are those wherein R, R 2  and R 3  are each independently hydrogen or C 1  -C 6  alkyl, A is C--R 4 , B is C--R 5 , W is C--R 6 , Y is halogen and n is 1. Particularly preferred compounds are those wherein R 1  is hydrogen, R 4  is halogen, R 5  is hydrogen and/or R 6  is C 1  -C 6  alkyl substituted with one or more halogens, preferably trifluoromethyl. 
     Other preferred compounds of the invention are compounds having the structure ##STR7## wherein 
     R is C 1  -C 10  alkyl; 
     R 1  is hydrogen or C 1  -C 4  alkyl; 
     R 2  is C 1  -C 10  alkyl; 
     R 3  is hydrogen or C 1  -C 10  alkyl; and 
     R 4 , R 6  and Y are each independently hydrogen, halogen, CN, NO 2 , C 1  -C 6  alkyl, C 1  -C 6  haloalkyl, C 1  -C 6  alkoxy, or C 1  -C 6  haloalkoxy. 
     The N-arylamidrazones of formula I may be prepared by reacting an acid chloride, hydrazone (hydrazinoyl chloride) of formula II with an amine compound, HNR 2  R 3 , as shown in flow diagram I. ##STR8## 
     Compounds of formula II may be prepared by reacting a suitable arylhydrazine of formula III with the appropriate acid chloride, RCOCl, to obtain an N-arylhydrazide of formula IV and reacting the formula IV hydrazide with a chlorinating agent such as thionyl chloride to give the desired formula II N-arylhydrozinoyl chloride product. The reaction is illustrated in flow diagram II. ##STR9## 
     The substituted N-arylamidrazone compounds of the present invention are effective for controlling insect and acarid pests. Said compounds are also effective for protecting growing or harvested crops from attack and infestation by such pests. 
     In practice, generally about 10 ppm to 10,000 ppm, preferably about 100 to 5,000 ppm of the formula I compound dispersed in a liquid carrier, when applied to the plants or the soil or water in which they are growing, is effective to protect the plants from insect and acarina attack and infestation. Soil application of the formula I compounds is particularly effective for the control of the post-embryonic development stages of Coleoptera and Diptera. Applications, such as spray applications, of compositions of the invention are generally effective at rates which provide about 0.125 kg/ha to about 250 kg/ha, preferably about 10 kg/ha to 100 kg/ha. Of course, it is contemplated that higher or lower rates of application of the N-arylamidrazone compounds may be used dependent upon the prevailing environmental circumstances such as population density, degree of infestation, stage of plant growth, soil conditions, weather conditions and the like. 
     Advantageously, the compounds of the invention may be used in conjunction with, or in combination with other biological and chemical control agents including other insecticides, nematicides, acaricides, molluscicides, fungicides and bactericides such as nuclear polyhedrosis viruses, pyrroles, arylpyrroles, halobenzoylureas, pyrethroids, carbamates, phosphates, and the like. 
     Typical formulations suitable for the formula I compounds of the invention are granular compositions, flowable compositions, wettable powders, dusts, microemulsions, emulsifiable concentrates and the like. All compositions which lend themselves to soil, water and foliage application and provide effective plant protection are suitable. Compositions of the invention include the formula I N-arylamidrazone amide compound admixed with an inert solid or liquid carrier. 
     Where compositions of the invention are to be employed in combination treatments with other biological or chemical agents, the composition may be applied as an admixture of the components or may be applied sequentially. 
     For a more clear understanding of the invention, specific examples thereof are set forth below. These examples are merely illustrative, and are not to be understood as limiting the scope and underlying principles of the invention in any way. 
     EXAMPLE 1 
     Preparation of 2,2-Dimethylpropionic acid,2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazide ##STR10## 
     A solution of 2,6-dichloro-4-(trifluoromethyl)phenylhydrazine (50.0 g, 0.20 mol) in methylene chloride is treated dropwise with trimethylacetyl chloride (30.6 g, 0.254 mol), stirred for 30 minutes; treated with 10% aqueous NaOH and stirred for 3 hours. The phases are separated; the organic phase is washed with water, dried over MgSO 4  and concentrated in vacuo to give an off-white solid residue. The solid is recrystallized from 1,2-dichloroethane to give the title product as a white solid, 55 g (82% yield), mp 140°-141°, identified by  1  HNMR,  13  CNMR and IR spectral analyses. 
     EXAMPLES 2-42 
     Preparation of substituted N-arylhydrazide derivatives ##STR11## 
     Using essentially the same procedure described above for Example 1 and substituting the appropriate arylhydrazine and acid chloride, the compounds shown in Table I are prepared and identified by  1  HNMR,  13  NMR and IR spectral analyses. 
     
                                           TABLE I__________________________________________________________________________ ##STR12##ExampleNumber A     B     W     Yn    R               mp °C.__________________________________________________________________________ 2    CCl   CH    CCF.sub.3                   6-Cl  (CH.sub.3).sub.2 CHCH.sub.2                                         135-136 3    CCl   CH    CCl   6-Cl  (CH.sub.3).sub.3 C                                           124-125.5 4    CCl   CH    CH    6-Cl  (CH.sub.3).sub.3 C                                         114-115 5    CBr   CH    CCF.sub.3                   6-Br  (CH.sub.3).sub.3 C                                         118-120 6    CBr   CH    CCF.sub.3                   6-Br  CH.sub.3        173-175 7    CBr   CH    CCF.sub.3                   6-Br  C.sub.6 H.sub.5 181-184__________________________________________________________________________ ##STR13## 8    CCH.sub.3       CH    CCl   H     (CH.sub.3).sub.3 C                                         103-106 9    CCl   CH    CCF.sub.3                   6-Cl  (CH.sub.3).sub.3 CCH.sub.2                                         125-12710    CCl   CH    CCl   6-Cl   -pClC.sub.6 H.sub.5                                         188-19011    CCl   CH    CCF.sub.3                   6-Cl  (CH.sub.3).sub.2 CH                                         158-15912    CCl   CH    CCl   6-Cl  cyclopropyl     186-18813    CCl   CH    CCF.sub.3                   6-Cl  CH.sub.3 CH.sub.2 C(CH.sub.3).sub.2                                         121-12314    CH    CH    CCF.sub.3                   H     (CH.sub.3).sub.3 C                                         136-13915    CCl   CH    CCF.sub.3                   H     (CH.sub.3).sub.3 C                                         143-14516    CCl   CH    CCF.sub.3                   6-Cl                          ##STR14##      125-12717    CCl   CCl   CCl   5,6-diCl                         (CH.sub.3).sub.3 C18    N     CH    CCF.sub.3                   6-Cl  (CH.sub.3).sub.3 C                                           151-151.519    CCl   CH    CCl   6-Cl                          ##STR15##      138-14020    CCl   CH    CCF.sub.3                   6-Cl   -pClC.sub.6 H.sub.5 OC(CH.sub.3).sub.2                                         137-13921    CCF.sub.3       CH    CH    H     (CH.sub.3).sub.3 C                                          98-10022    CCl   CH    CCF.sub.3                   6-Cl                          ##STR16##      101-10323    CCl   CH    CCl   6-Cl  cyclohexyl      188-18924    CCl   CH    CCF.sub.3                   6-Cl  C.sub.6 H.sub.5 C(CH.sub.3).sub.2                                         104-10525    CCl   CH    CCl   6-Cl  CF.sub.3 CF.sub.2                                         131-13226    CCl   CH    CCl   6-Cl  (CH.sub.3).sub.2 CH                                         164-16527    CCl   CH    CCF.sub.3                   6-Cl  cyclopropyl     172-17428    CCl   CH    CCl   6-Cl  CH.sub.3 CH.sub.2 C(CH.sub.3).sub.2                                         132-13429    CCl   CH    CCF.sub.3                   6-Cl                          ##STR17##      160-16230    CBr   CH    CCF.sub.3                   6-Br  (CH.sub.3).sub.3 C                                         140-14131    CCl   CH    CCl   6-Cl  CH.sub.3 (CH.sub.2).sub.5 C(CH.sub.3).sub.232    N     N     CCl   H     (CH.sub.3).sub.3 C                                         178-18233    CCl   CH    CCF.sub.3                   6-Cl                          ##STR18##      121-12334    CCl   CH    CCF.sub.3                   6-Cl   -pClC.sub.6 H.sub.5 C(CH.sub.3).sub.2                                         105-10735    CCl   CH    CCF.sub.3                   6-Cl  ClCH.sub.2 C(CH.sub.3).sub.2                                         119-12036    CCl   CH    CCF.sub.3                   6-Cl                          ##STR19##      174-17537    CCl   CH    CCl   6-Cl  ClCH.sub.2 C(CH.sub.3).sub.2                                         124-12538    CCl   CH    CH    5-CF.sub.3                         (CH.sub.3).sub.3 C                                           170-177.539    CCl   CH    CCF.sub.3                   6-Cl  1-methylcyclohexyl                                         105-10740    CH    CCF.sub.3             CH    H     (CH.sub.3).sub. 3 C                                         158-16041    CF    CF    CF    5,6-diF                         (CH.sub.3).sub.3 C                                         154-15742    CBr   CH    F     6-Br  (CH.sub.3).sub.3 C                                         118-120__________________________________________________________________________ 
    
     EXAMPLE 43 
     Preparation of 1-chloro-2,2-dimethylpropionaldehyde, 2-(2,6-Dichloro-α,α,α-trifluoro-p-tolyl)hydrazone ##STR20## 
     A mixture of 2,2-dimethyl-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazide propionic acid (50.0 g, 0.152 mol) and thionyl chloride (53.8 g, 0.452 mol) in toluene is heated at reflux temperature for 8 hours, cooled to room temperature and concentrated in vacuo to give an oil residue. The oil is dissolved in hexanes and passed through a silica gel filtercake. The filtercake is washed with several portions of hexanes. The filtrates are combined and concentrated in vacuo to give the title product as a yellow oil, 47.2 g (90% yield), identified by  1  HNMR,  13  CNMR and IR spectral analyses. 
     EXAMPLES 44-84 
     Preparation of substituted N-arylhydrazinoyl chlorides ##STR21## 
     Using essentially the same procedure as described above in Example 43 and substituting the appropriate hydrazide substrate, the compounds shown in Table II are prepared and identified by  1  HMR,  13  CNMR and IR spectral analyses. 
     
                                           TABLE II__________________________________________________________________________ ##STR22##ExampleNumber A     B     W     Yn    R               mp °C.__________________________________________________________________________44    CCl   CH    CCF.sub.3                   6-Cl  (CH.sub.3).sub.2 CHCH.sub.245    CCl   CH    CCl   6-Cl  (CH.sub.3).sub.3 C                                         44.5-45.546    CCl   CH    CH    6-Cl  (CH.sub.3).sub.3 C47    CBr   CH    CF    6-Br  (CH.sub.3).sub.3 C48    CBr   CH    CCF.sub.3                   6-Br  CH.sub.349    CBr   CH    CCF.sub.3                   6-Br  C.sub.6 H.sub.550    CCH.sub.3       CH    CCl   H     (CH.sub.3).sub.3 C51    CCl   CH    CCF.sub.3                   6-Cl  (CH.sub.3).sub.3 CCH.sub.252    CCl   CH    CCl   6-Cl   -pClC.sub.6 H.sub.5                                         12053    CCl   CH    CCF.sub.3                   6-Cl  (CH.sub.3).sub.2 CH54    CCl   CH    CCl   6-Cl  cyclopropyl55    CCl   CH    CCF.sub.3                   6-Cl  CH.sub.3 CH.sub.2 C(CH.sub.3).sub.256    CH    CH    CCF.sub.3                   H     (CH.sub.3).sub.3 C57    CCl   CH    CCF.sub.3                   H     (CH.sub.3).sub.3 C58    CCl   CH    CCF.sub.3                   6-Cl                          ##STR23##59    CCl   CCl   CCl   5,6-diCl                         (CH.sub.3).sub.3 C60    N     CH    CCF.sub.3                   6-Cl  (CH.sub.3).sub.3 C61    CCl   CH    CCl   6-Cl                          ##STR24##62    CCl   CH    CCF.sub.3                   6-Cl   -pClC.sub.6 H.sub.5 OC(CH.sub.3).sub.263    CCF.sub.3       CH    CH    H     (CH.sub.3).sub.3 C64    CCl   CH    CCF.sub.3                   6-Cl                          ##STR25##65    CCl   CCH   CCl   6-Cl  cyclohexyl66    CCl   CCH   CCF.sub.3                   6-Cl  C.sub.6 H.sub.5 C(CH.sub.3).sub.267    CCl   CH    CCl   6-Cl  CF.sub.3 CF.sub.268    CCl   CH    CCl   6-Cl  (CH.sub.3).sub.2 CH69    CCl   CH    CCF.sub.3                   6-Cl  cyclopropyl70    CCl   CH    CCl   6-Cl  CH.sub.3 CH.sub.2 C(CH.sub.3).sub.271    CCl   CH    CCF.sub.3                   6-Cl                          ##STR26##      110-11172    CBr   CH    CCF.sub.3                   6-Br  (CH.sub.3).sub.3 C73    CCl   CH    CCl   6-Cl  CH.sub.3 (CH.sub.2).sub.5 C(CH.sub.3).sub.274    N     N     CCl   H     (CH.sub.3).sub.3 C75    CCl   CH    CCF.sub.3                   6-Cl                          ##STR27##76    CCl   CH    CCF.sub.3                   6-Cl   -pClC.sub.6 H.sub.5 C(CH.sub.3).sub.2                                         85-8877    CCl   CH    CCF.sub.3                   6-Cl  ClCH.sub.2 C(CH.sub.3).sub.278    CCl   CH    CCF.sub.3                   6-Cl                          ##STR28##      71-7379    CCl   CH    CCl   6-Cl  ClCH.sub.2 C(CH.sub.3).sub.280    CCl   CH    CH    5-CF.sub.3                         (CH.sub.3).sub.3 C81    CCl   CH    CCF.sub.3                   6-Cl  1-methylcyclohexyl82    CH    CCF.sub.3             CH    H     (CH.sub.3).sub.3 C83    CH    CH    CH    5-F   (CH.sub.3).sub.3 C84    CBr   CH    F     6-Br  (CH.sub.3).sub.3 C__________________________________________________________________________ 
    
     EXAMPLE 85 
     Preparation of N-Ethyl-2,2-dimethylpropionamide, 2-(2,6-Dichloro-α,α,α-trifluoro-p-tolylhydrazone ##STR29## 
     A solution of (2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazone 1-chloro-2,2-dimethylpropionaldehyde (20.0 g, 0.0575 mol) in tetrahydrofuran is treated dropwise with 70% aqueous ethylamine (28.0 g, 0.144 mol) at room temperature, stirred for 1 hour and concentrated in vacuo to give a semi-solid residue. The semi-solid is dispersed in ether and water. The phases are separated; the organic phase is washed with water, dried over MgSO 4  and concentrated in vacuo to give the title product as a yellow oil, 19.8 g (97% yield), identified by  1  HNMR,  13  CNMR and IR spectral analyses. 
     EXAMPLES 86-169 
     Preparation of substituted N-arylamidrazones ##STR30## 
     Using essentially the same procedure described above in Example 85 and substituting the appropriate hydrazinoylchloride and a suitable amine, the compounds shown in Table III are prepared and identified by  1  HNMR,  13  CNMR and IR spectral analyses. 
     Hydrochloride salts of the invention may be prepared in accordance with the procedure outlined below. 
     EXAMPLE 146 
     Preparation of N-Ethyl-2,2-dimethylproprionamide,2-(2,6-dichloro-α,α,α-trifluoro-p-tolylhydrazone hydrochloride ##STR31## 
     A stirred mixture of N-ethyl-2,2-dimethylpropionamide, 2-(2,6-dichloro-α,α,α-trifluoro-p-tolylhydrazone (0.1 g, 2.8 mmol) and hexane is bubbled through with HCl gas for a 30 minute period. The resultant reaction mixture is filtered to give the title compound as a white solid, 1.13 g, mp 202°-202.5° C. 
     
                                           TABLE III__________________________________________________________________________ ##STR32##ExampleNumberA    B  W    Yn  R         R2           R3   mp °C.__________________________________________________________________________ 86  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           pClC.sub.6 H.sub.5                                        H 87  CCl  CH CCl  6-Cl                 (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2 CH.sub.2                                        H 88  CCl  CH CCl  6-Cl                 (CH.sub.3).sub.2 CH                           CH.sub.3 CH.sub.2 CH.sub.2                                        H    48-50 89  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 CCH.sub.2                           CH.sub.3 CH.sub.2 CH.sub.2                                        H 90  CCl  CH CCl  6-Cl                 (CH.sub.3).sub.2 CH                           cyclopropyl  H 91  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3 ).sub.3 CCH.sub.2                           CH.sub.3 CH.sub.2                                        H 92  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.2 CH                           CH.sub.3 CH.sub.2                                        H    62-64 93  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           CF.sub.3 CH.sub.2                                        H 94  CBr  CH CCF.sub.3             6-Br                 (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2                                        H 95  CBr  CH CCF.sub.3             6-Br                 (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2 CH.sub.2                                        H 96  CBr  CH CCF.sub.3             6-Br                 (CH.sub.3).sub.3 C                           C.sub.6 H.sub.5 CH.sub.2                                        H 97  CBr  CH CCF.sub.3             6-Br                 (CH.sub.3).sub.3 C                           furfuryl     H 98  CBr  CH CCF.sub.3             6-Br                 CH.sub.3  CH.sub.3 CH.sub.2                                        H 99  CBr  CH CCF.sub.3             6-Br                 C.sub.6 H.sub.5                           CH.sub.3 CH.sub.2                                        H100  CCl  CH CCl  6-Cl                 (CH.sub.3).sub.3 C                           H            H    131-135101  CCl  CH CCl  6-Cl                 (CH.sub.3).sub.3 C                           CH.sub.3     CH.sub.3                                             61-63102  CCl  CH CCl  6-Cl                 (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2                                        H103  CCl  CH CCF.sub.3             H   (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2 CH.sub.2                                        H104  CCl  CH CH   6-Cl                 (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2 CH.sub.2                                        H105  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           H            H      100-102.5106  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           CH.sub.3     H      78-79.5107  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           CH.sub.3     CH.sub.3108  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           CH.sub..sub.3 CH.sub.2 CH.sub.2                                        H109  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           (CH.sub.3).sub.3 C                                        H    67.5-68.5110  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           (CH.sub.3).sub.2 CHCH.sub.2                                        H111  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2112  CCl  CH CCl  6-Cl                 cyclopropyl                           CH.sub..sub.3 CH.sub.2                                        H    65-67113  CCl  CH CCF.sub.3             6-Cl                 CH.sub.3 CH.sub.2 C(CH.sub.3).sub.2                           CH.sub.3 CH.sub.2                                        H114  CBr  CH CCF.sub.3             6-Br                 (CH.sub.3).sub.3 C                           (CH.sub.3).sub.2 CH                                        H115  CCl  CH CCF.sub.3             H   (CH.sub.3).sub.3 C                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2116  CCl  CH CCF.sub.3             6-Cl                 CH.sub.3 CH.sub.2 C(CH.sub.3).sub.2                           CH.sub.3 CH.sub.2                                        CH.sub.3 CH.sub.2117  CCl  CH CCF.sub.3             H   (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2                                        H118  CCl  CH CCl  6-Cl                 CH.sub.3 CH.sub.2 C(CH.sub.3).sub.2                           CH.sub.3 CH.sub.2                                        H119  CCl  CH CCF.sub.3             6-Cl                 C.sub.6 H.sub.5 C(CH.sub.3).sub.2                           CH.sub.3 CH.sub.2                                        H120  CCl  CH CCF.sub.3             H   (CH.sub.3).sub.3 C                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                           CH.sub.2121  CH   CH CCF.sub.3             H   (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2                                        H122  CH   CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.2 CHCH.sub.2                           CH.sub.3 CH.sub.2                                        H    86.5-88.5123  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                           CH.sub.2124  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           cyclohexyl   H125  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                        H126  CBr  CH CF   6-Br                 (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2                                        H127  CCl  CCl        CCl  5,6-diCl                 (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2                                        H    63-65128  CCl  CH CCl  6-Cl                 CH.sub.3 (CH.sub.2).sub.5 C(CH.sub.3).sub.2                           CH.sub.3 CH.sub.2                                        H129  CCl  CH CCF.sub.3             6-Cl                  ##STR33##                           CH.sub.3 CH.sub.2                                        H130  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           CH.sub.3 (CH.sub.2).sub.2 CH.sub.2                                        H131  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           (CH.sub.3).sub.2 CH                                        H132  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                            ##STR34##   H133  CCl  CH CCl  6-Cl                 pClC.sub.6 H.sub.5                           (CH.sub.3).sub.2 CH                                        H    124-127134  CCl  CH CCl  6-Cl                 pClC.sub.6 H.sub.5                           CH.sub.3 CH.sub.2                                        H    127-132135  CCl  CH CCF.sub.3             6-Cl                 C.sub.6 H.sub.5 C(CH.sub.3).sub.2                           C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                        H136  CCl  CH CCF.sub.3             6-Cl                  ##STR35##                           CH.sub.3 CH.sub.2                                        H    74-75137  CCF.sub.3     CH CH   H   (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2                                        H138  CCl  CH CCF.sub.3             H   (CH.sub.3).sub.3 C                           C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                        H139  CCl  CH CCF.sub.3             H   (CH.sub.3).sub.3 C                            ##STR36##   H140  CH   CH CCF.sub.3             H   (CH.sub.3).sub.3 C                            ##STR37##   H141  CCl  CH CCF.sub.3             6-Cl                 pClC.sub.6 H.sub.5 C(CH.sub.3).sub.2                           CH.sub.3 CH.sub.2                                        H142  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           C.sub.6 H.sub.5 CH(CH.sub.3)                                        H143  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           (CH.sub.3).sub.2 NCH.sub.2 CH.sub.2                                        H144  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2 C(CH.sub.3).sub.2                                        H145  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                            ##STR38##   H    100.5-101.5 146*CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2                                        H      202-202.5147  CBr  CH CCF.sub.3             6-Br                 (CH.sub.3).sub.3 C                            ##STR39##   H148  CCl  CH CCF.sub.3             6-Cl                  ##STR40##                           CH.sub..sub.3 CH.sub.2                                        H149  CCl  CH CCF.sub.3             6-Cl                  ##STR41##                           CH.sub..sub.3 CH.sub.2                                        H150  CCl  CH CCF.sub.3             6-Cl                 CH.sub.3 CH.sub.2 C(CH.sub.3).sub.2                           C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                        H151  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           C.sub.6 H.sub.5 CH.sub.2                                        H152  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           CH.sub..sub.3 CH.sub.2                                        CH.sub..sub.3 CH.sub.2153  CCl  CH CCF.sub.3             6-Cl                  ##STR42##                           CH.sub.3 CH.sub.2                                        H154  CCl  CH CCF.sub.3             6-Cl                  ##STR43##                           (CH.sub.3).sub.2 CH                                        H155  CCl  CH CCF.sub.3             6-Cl                 ClCH.sub.2 C(CH.sub.3).sub.2                            -pCF.sub.3 OC.sub.6 H.sub.5                                        H    203-205156  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           neopentyl    H157  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           H.sub.2 NCOCCH(CH.sub.3).sub.2                                        H    160-162158  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                            ##STR44##   H159  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                            -pClC.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                        H160  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                            ##STR45##   H161  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                            ##STR46##   H162  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           CH.sub.3 (CH.sub.2).sub.4 CH(CH.sub.3)                                        H163  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           (C.sub.2 H.sub.5).sub.2 N(CH.sub.2).sub.3                           CH(CH.sub.3) H164  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                           CH.sub.2 CHCH.sub.2                                        H165  CCl  CH CCF.sub.3             6-Cl                 1-methylcyclohexyl                           CH.sub.3 CH.sub.2                                        H166  CCl  CH CH   5-CF.sub.3                 (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2                                        H167  CF   CF CF   5,6-diF                 (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2                                        H168  CBr  CH CF   6-Br                 (CH.sub.3).sub.3 C                           CH.sub.3 CH.sub.2                                        H169  CCl  CH CCF.sub.3             6-Cl                 (CH.sub.3).sub.3 C                            ##STR47##   H__________________________________________________________________________ *Hydrochloride salt 
    
     EXAMPLE 170 
     Insecticidal and Acaricidal Evaluation of N-arylamidrazone compounds 
     Test solutions are prepared by dissolving the test compound in a 35% acetone in water mixture to give a concentration of 10,000 ppm. Subsequent dilutions are made with water as needed. 
     Spodoptera eridaniia, 3rd instar larvae, southern armyworm 
     A Sieva limabean leaf expanded to 7-8 cm in length is dipped in the test solution with agitation for 3 seconds and allowed to dry in a hood. The leaf is then placed in a 100×10 mm petri dish containing a damp filterpaper on the bottom and ten 3rd instar caterpillars. At 3 and 5 days, observations are made of mortality, reduced feeding, or any interference with normal molting. 
     Tetranychus urticae(OP-resistant strain), 2-spotted spider mite 
     Sieva limabean plants with primary leaves expanded to 7-8 cm are selected and cut back to one plant per pot. A small piece is cut from an infested leaf taken from the main colony and placed on each leaf of the test plants. This is done about 2 hours before treatment to allow the mites to move over to the test plant to lay eggs. The size of the cut, infested leaf is varied to obtain about 100 mites per leaf. At the time of test treatment, the piece of leaf used to transfer the mites is removed and discarded. The newly mite-infested plants are dipped in the test solution for 3 seconds with agitation and set in the hood to dry. After 2 days, one leaf is removed and mortality counts are made. After 5 days, another leaf is removed and observations are made of mortality of the eggs and/or newly emerged nymphs. 
     Diabrotic undecimpunctata howardi, 3rd instar southern corn rootworm 
     One cc of fine talc is placed in a 30 ml wide-mouth screw-top glass jar. One mL of the appropriate acetone test solution is pipetted onto the talc so as to provide 1.25 mg of active ingredient per jar. The jars are set under a gentle air flow until the acetone is evaporated. The dried talc is loosened, 1 cc of millet seed is added to serve as food for the insects and 25 mL of moist soil is added to each jar. The jar is capped and the contents thoroughly mixed on a Vortex Mixer. Following this, ten 3rd instar rootworms are added to each jar and the jars are loosely capped to allow air exchange for the larvae. The treatments are held for 6 days when mortality counts are made. Missing larvae are presumed dead, since they decompose rapidly and can not be found. The concentrations used in this test correspond approximately to 50 kg/ha. 
     The data obtained are shown in Table IV. 
     
                       TABLE IV______________________________________Insecticidal and Acaricidal Evaluation of N-Arylamidrazones  % MortalityCompound Armyworm.sup.1               2-Spotted Mite.sup.2                           Corn Rootworm.sup.3(Ex. No.)    (300 ppm)  (300 ppm)   (50 kg/ha)______________________________________ 85       0          0          100 86      100         0           80 87       40         90         100 88      --         --          -- 89       0          0          100 90       0          0           20 91       0          80         100 92       0          0          100 93       0          0          100 94      --          80         100 95       80         0          100 96      100         40          80 97       0          0          100 98       40         0           40100       0          40          0101       0          0           60102       0          60         100103       40         0          100104       0          90          50105       20         0           90106       40         0          100107      --         --          100108       90         50         100109       0          0           50110       0          0          100111      100         40          90112       40        100          20113       20        100         100114       40        100         100115       0          0          100116       20         50         100117       20         0          100118       50         70         100119      100         50          90120      --          30          20121       80         40         100122       0          0           40123       0          0           60124       50         80         100125       0          30         100126       0          80          90128       0          0           30129      100         40          0130       80         80         100131       70         0          100132      --          40         100133      --          0           0134       0          30          0135       0          0           0136       0          70         100137       0          0          100138       0          0          100139       0          70         100140       0          0            50141      100         0           0142       0          0          100143       0          0          100144       0          0          100145       0          0          100146       0          0          100147       0          0          100148       50         0          100149      100         80          80150       0          60         100152       80         0          100153      100         0          100156      --          0          100157       0          0          100158       40         0          100159       0          0          100160       0          0          100161       0          0          --162       0         100         100163       0          0          100164       0          0          100167       0          0          100168       0          80          90169       0          0          100______________________________________ .sup.1 Armyworm is 3rd instar larvae, southern armyworm .sup.2 2-Spotted Mite is 2spotted spider mite (0Presistant) .sup.3 Corn Rootworm is 3rd instar southern corn rootworm