AU599124B2 - Insecticidal N-(optionally substituted) -N'- substituted-N, N'-disubstituted hydrazines - Google Patents

Description

599124

AUSTRALIA

COMMONWEALTH OF PATENT ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE CLASS INT. CLASS Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority: '4 4 eq

C

C

4 4 4 4 C Related Art: This document contains aie amendments made under Section 49 and is correct for printing.

NAME OF APPLICANT: ROHM AND HAAS COMPANY ADDRESS OF APPLICANT: Independence Mall West, Philadelphia, Pennsylvania 19105.

United States of America.

NAME(S) OF INVENTOR(S) Adam CHI-TUNG HSU, Donald Wesley HAMP ADDRESS FOR SERVICE: DAVIES COLLISON, Patent Attorneys 1 Little Collins Street, Melbourne, 3000.

cce COMPLETE SPECIFICATION FOR THE INVENTION ENTITLED: "INSECTICIDAL N-(OPTIONALLY SUBSTITUTED)-N'-

SUBSTITUTED-N,N'-DISUBSTITUTEDHYDRAZINES"

The following statement is a full description of this including the best method of performing it known to invention, us

-I-

IA-

INSECTICIDAL N-(OPTIONALLY SUBSTITUTED)-

N'-SUBSTITUTED-N,N'-DISUBSTITUTEDHYDRAZINES

This invention is concerned with novel N-(optionally substituted)-N'-substituted-N,N'-disubstitutedhydrazines, which are useful as insecticides, compositions containing those compounds and methods of their use. The disclosed hydrazines are new compounds.

The search for compounds which have a combination of excellent insecticidal activity and low undesirable toxicity is a continuing one because of factors such as the desire for compounds exhibiting 0 *f greater activity, better selectivity, low undesirable environmental impact, low production cost and 1 effectiveness against insects resistant to many known insecticides.

Compounds of the present invention are particularly suitable for controlling plant-destructive insects in crops of cultivated plants, ornamentals and 0b forestry.

Certain hydrazine derivatives have been disclosed in the literature.

In 25 Aust. J. Chem., 523-529 (1972), several N,N'-dibenzoylhydrazine derivatives are disclosed 25 including N'-i-propyl-; N'-n-propyl-; N'-(2-methyl- 9 propyl)-; N'-(3-methylbutyl)-; N'-benzyl- and N'-phenyl- N,N'-dibenzoylhydrazine in which one or both nitrogen atoms are alkylated or phenylated.

SIn 61 Helv. Chim. Acta, 1477-1510 (1978), several N,N'-dibenzoylhydrazine and hydrazide derivatives including N'-t-butyl-N-benzoyl-N'-(4-nitrobenzoyl)-hydrazine are disclosed.

In 44 2556-2567 (1922), isopropyli hydrazine (CH 3

CH-NH-NH

2 symmetrical diisopropyl- -2hydrazine, dibenzoylisopropylhydrazine and certain derivatives are disclosed.

In 44 J.A.C.S.f 1557-1564 (1972) isopropyl, menthyl and bornyl semicarbazides are disclosed.

In 48 1030-1035 (1926), symmetrical di-methyiphenylinethyihydrazine and certain related compounds including 1 ,2-bis-methylphenylmethyl-4phenyl-semicarbazide are disclosed.

In 27 Bull. Chem. Soc. Japan, 624-627 (1954), certain hydrazine derivatives including alpha-betadibenzoylphenylhydrazine are disclosed.

In J. Chemn. Soc. 1531-1536 (1966), N,N'dibenzoylphenylhydrazine and N-acetyl-N'-benzoyl-pnitrophenyihydrazine are disclosed.

In 56B Chem. Berichte, 954-962 (1923), symmetrical di-isopropyihydrazines, symmetrical diisobutyl- and certain derivatives including N,N'diisobutyldibenzoylhydrazine are disclosed.

In 590 Annalen der Chemie, 1-36 (1954) certain N,N'-dibenzoylhydrazine derivatives are disclosed including N'-methyl- and N'-(2-phenyl)-isopropyl-N,N'dibenzoylhydrazine.

Iii J. Chem. Soc., 4191-4198 (1952) N,N'-di-npropylhydrazine, N,N' -dibenzoylhydrazine and dinitrobenzoyl are disclosed.

In 32 Zhur. Obs. Khim. 2806-2809 (1962) N'- 2,4-methyl-2,4-pentadiene-N,N' -dibenzoylhydrazine is disclosed.

In 17 Acta. Chim. Scand. 95-102 (1963), 2-benzoyl-thiobenzhydrazide (C H 5

-CS-NHNH-CO-C

65 H and certain hydrazone and hydrazine derivatives are disclosed including 1 2dibenzoyl-benzylhydrazine.

In 25 Zhur. Obs. Khim, 1719-1723 (1955) N,N'bis-cyclohexylhydrazine and N,N' -dibenzoylcyclohexylhydrazine are disclosed.

Y

3 0 99 o ao ooo o 9 o 25 In J. Chem. Soc., 4793-4800 (1964), certain dibenzoylhydrazine derivatives are disclosed including tribenzoylhydrazine and N,N'-dibenzoylcyclohexylhydrazine.

In 36 J. Prakt. Chem., 197-201 (1967), certain dibenzoylhydrazine derivatives inzluding N'-ethyl-; N'-.-propyl-; N'-isobutyl-; N'-neopentyl-; N'-nheptyl-; and N'-cyclohexylmethyl-N,N'-dibenzoylhydrazines are disclosed.

In 26 4336-4340 (1961) N'-t-butyl-N,N'di-(t-butoxycarbonyl)hydrazide is disclosed.

In 41 3763-3765 (1976), N'-t-butyl-N- (phenylmethoxycarbonyl)-N'-(chlorocarbonyl)hydrazide is disclosed.

In 94 7406-7416 (1972) N'-T-butyl- N,N'-dimethoxycarbonylhydrazide is disclosed.

In 43 808-815 (1978), N'-t-butyl-Nethoxycarbonyl-N'-phenylaminocarbonylhydrazide and N't-butyl-N-ethoxycarbonyl-N'-methylaminocarbonylhydrazide are disclosed.

None of the above references discloses any biological activity for the specified compounds.

In 39 J. Econ. Ent., 416-417 (1946), certain N-phenyl-N'-acylhydrazines are disclosed and evaluated for their toxicity against codling moth larvae.

The N-(optionally substituted)-N'-substituted- N,N'-disubstitutedhydrazines of the present invention differ from known compounds primarily by their N and N' substituents.

Compounds of the present invention are also distinguished by their excellent insecticidal activity, particularly against insects of the orders Lepidoptera and Coleoptera, and most particularly against insects of the order Lepidoptera, without material adverse impact on beneficial insects.

1 I)i:i psi -4.

The presen-1 invention provides insecticidal.

compounds which are substituted hydrazines of the formula: 4_1 _2 R -C-R 1 3

R

10 0 0 a0 *00 0 0 2 0 wherein X and XI are the same or different 0, S or NR; R is hydrogen; (C 1

-C

6 )alkyl; (C 1

-C

6 )alkoxy- (C 1 -C )alkyl having independently the stated number of carbon atoms in each alkyl group; (C 1 -C 6 )alkyl-thio-(C 1 -c 6 )alkyl.

having independently the stated number of carbon atoms in each alkyl group; (C 2 -C 6 alkenyl; (C 2 -C 6 )alkynyl; or phen-(C 1 -C 4 alkyl where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C 1

C

4 )alkyl, halo-(C 1 -C 4 alkyl (C 1

C

4 )alkoxy, halo-(C 1

-C

4 )alkoxy, carboxy, (C 1

-C

4 )alkoxy-carbonyl, (C 1

-C

4 alkanoyloxy or NZZ'; R 2and R3are the same or different hydrogen or 4 (C 1 -C 4 )alkyl; R is (CI- C 4 )alkyl substituted with 1 to 4 fluoro; straight chain (C 2 -C 4 )alkenyl; carboxyl; (C 1 -C 3 )alkoxy-carbonyl; cyano; cyano substituted (C 1 -C 4 )alkyl; tri(C I- C 2 alkylsilyl having independently the stated number of carbon atoms in each alkyl group; or tri (C 1 -C 2 )alkylsilylmethyl having 0009 0000 0 4 ~1

V

independently the stated number of carbon atoms in each alkyl group; provided thatR and R 3 are both alkyl when R 4is carboxyl or alkoxycarbonyl; and and B are the same or different unsubstituted or substituted naphthyl where the substituents can be from one to three of the same or different halo; nitro; (C 1 -C 4 )alkoxy; (C 1

-C

4 )alkyl or NZZ'; unsubstituted or substituted phenyl where the substituents can be from one to five of 9 the same or different halo; nitroso; nitro; *cyano; hydroxy; (C 1

C

6 )alkyl; halo- (C 1 -C 6 alkyl; cyano-(C -C )alkyl; hydroxy-(C C 6 9.,alkyl; (C C )alkoxy; halo- (C -C alkoxy; (C 1 -C 6 )alkoxy- (C 1 -C 6 alkyl having Poo independently the stated number of carbon atoms in each alkyl group; (C 1 -C 6 )alkoxy- 20. (C -C )alkoxy having independently the to 1 6 0 09 stated number of carbon atoms in each alkyl go ORSRI g rop OO2 Rgroup; -OCO 2H Va00 group; (C -C alkanoyloxy- (C _C alkyl having independently the stated number of carbon atoms in each alkyl group; (C 2 -C 6 )alkenyl optionally substituted with 9@ *00 ';alo, cyano, (C C )alkyl, halo-(C -C 4 a4 9 alkoxy, (C 1 -C 4 )alkylthio or (C 1 -C 4 alkoxy; (C 1 -C 4 alkadienyl; (C 2 -C 6 )alkenyloxy; (C 2 -C 6 )alkenyl-carbonyl; (C 2 -C 6 alkenyloxy-carbonyloxy; (C 2 -C )alkynyl optionally substituted with halo, cyano, nitro, hydroxy, (C 1 -C 4 )alkoxy, halo- (C 1 -C 4 alkyl, (C 1 -C 4 )alkylthio or (C -C )alkyl; carboxy; -RCO RI group; -COR 1 0 -6group; -COil group; halo- (C -C alkyl-carbonyl; -CO R group; (C 1 c haloalkoxy-carbony.; -OCOR group; -OIWO 2 R' group; amino amino substituted with hydroxy, (CI- C 4 )alkoxy or (C 1 -C 4 )alkylthio; -CONZZ' group;(C2 6) alkenyl-carbonylamino; hydroxy- (C 1 -C 6 )alkylaminocarbonyl; -OCONZZ' group; -NZCOZ' group;

-NZCO

2 Zo group; thiocyanato; isothiocyanato; thiocyanato- (C 1 -C 6 alkyl; (Cl-C 6 )alkylthio; halo-(C 1

-C

6 alkylthio; -S(O)Z group; -SO 2

Z

:0 group; -OSO 2 R group; -OS0 2 H group; -SO 2NZZ' group; -CSR group; -CSH- group; alkylcarbonylthio 9, -SCQR group; -SCOH group; -NZCSZ' group; unsubstituted or substituted phenyl having one 0 *1,5 to three of the same or different halo, cyano, nitro, hydroxy, (C -C )alkyl, halo-(C C 4 *alkyl, (C 1

C

4 )alkoxy, carboxy, (C 1

C

4 alkoxy-carbonyl, (C 1 -C 4 )alkanoyloxy, amino, -C alkylamino or di (C -C alkylamino 4* .2 0 having independently the stated number of to carbon atoms in each alkyl group; phenoxy 0 where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, alkoxy, carboxy, (C 1 -C 4 )alkyl-carbonyl, 8(C 1 -C 4 )alkanoyloxy, amino, (C 1 -C 4 alkylamino or di(C 1 -C 4 )alkylamino having independently the stated number of carbon atoms in each alkyl group; benzoyl where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C 1 -C 4 )alkyl, halo-(C 1

C

4 )alkyl, (C 1 -c 4 ~ft I t -7alkoxy, carboxy, (C -C alkoxy-carbonyl, (C 1 -C 4 1-)alkanoyloxy, amino, (C-C alkylamino or di(C 1 -C 4 )alkylamino having independently the stated number of carbon atoms in each alkyl group; benzoyloxy-

(C

1 -c 6 )alkyl.; phenylthio- (C 1 -C 6 alkyl where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C 1

-C

4 )alkyl, halo- (C 1 -C 4 alkyl, (C 1

-C

4 alkoxy, carboxy, (C 1 -C 4 )alkoxy-carbonyl, (C 1 -C 4 )alkanoyloxy, amino, (C i- C 4 )alkylamino or di(C 1

C

4 )alkylamino having independently the stated number of carbon atoms in each alkyl. group; group where is hydroxy, (C 1 -C 4 )dlkyl, (C -C )alkoxy, amino phenylamino, 4t -COR, -COHl or benzoyl; (C 2

C

6 )oxiranyl; acetyithiosemicarbazone; pyrrolyl; oxazolyl, unsubstituted or subs'dtuted with one or two methyl groups; or when two adjacent positions on the phenyl ring are 'ft substituted with alkoxy groups, these groups may be joined to form, together with the carbon atoms to which they are attached, a 5 or 6 membered dioxolano or dioxano heterocyclic ring; unsubstituted or substituted (C -C 10 )alkyl having one to four of the same or different :1halo, cyano, nitro, hydroxy, (C 1 -C 4 )alkoxy, halo-(C -C )alkoxy, carboxy, (C -C 4 alkoxy-carbonyl, (C 1

-C

4 )alkanoyloxy, phenyl or -NZZ'; i4 -8unsubstituted or substituted (C 3 -C )cycloalkyl or unsubstituted or substituted.

(C -C )cycloalkyl(C -C )lkyl having one to four of the same or different halo, cyano, hydroxy, (C 1 -C )alkyl, halo-(C -C 4 alkyl, (C 1 -C )alkoxy, halo-(C 1 -C )alkoxy, carboxy, (C -C alkanoyl, (C alkoxy-carbonyl, (C-C alkanoyloxy or

-NZZ';

unsubstituted or substituted (C C )alkenyl or unsubstituted or substituted (C -C 8 alkadienyl having as substituent(s) a o furyl, thienyl or pyridyl or one to four of :the same or different halo, cyano, nitro, ~hydroxy, (C 1 -C 4 )alkyl, (C 3

C

6 )cycloalkyl, halo-(C -C )alkyl, (C -C )alkoxy, halo- (C C )alkoxy, carboxy, (C C 4 alkoxy-carbonyl, (C 1 -C 4 )alkanoyloxy or

NZZ';

00 a020 unsubstituted or substituted (C 3

C

8 )cycloalkenyl or unsubstituted or substituted (C 3 -C 8 )cycloalkadienyl having as substituent(s) one to four of the same or a different halo, cyano, nitro, hydroxy, :0"2(C 1 -C )alkyl, halo-(C 1 -C )alkyl, (C 1

-C

4 alkoxy, halo- (C 1 -C 4 )alkoxy, carboxy,

(C

1 -C 4 )alkoxy-carbonyl, (C 1 c 4 )alkanoyloxy or -NZZ'; unsubstituted or substituted (C -C 8 alkynyl having as substituent(s) one to four of the same or different halo, cyano, nitro, hydroxy, (C 1 -C 4 alkyl, halo-(C 1 -C 4 n I'll I- I I 4, 4 o *44 44 4 .4 44 4 08 44 4* 1.5 4444 0*

S

.4.

9 alky', (C 1 -C 4 alkoxy, halo-(C 1

C

4 )alkoxy, carboxy, (C 1 -0 4 alkoxy-carbonyl, (C 1 -C 4 aJlkanoyloxy, phenyl or -NZZ'; phenalkyl having one to four carbon atoms in the alkyl group and wherein the alkyl group is unsubstituted or substituted with one to three of the same or different halo, cyano, hydroxy, (C 1 -C 4 )alkoxy, (C 1 -C 4 alkoxy-carbonyl or -NZZ', and the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C 1 -C 4 )alkyl, halo- (C 1 -C 4 alkyl, cyano- (C 1 -C 4 alkyl, (C I- C 4 )alkoxy, halo- (C 1

C

4 alkoxy, carboxy, (C 1 -C 4 )alkoxy-carbonyl, (C 1

-C

4 )alkanoyloxy, (C 2

C

6 )alkenyl, halo- (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl or -NZZ'; phenalkenyl having two to six carbon atoms in the alkenyl group and the alkenyl group is un:3ubstituted or substituted with one to three of the same or different halo; cyano, hydroxy, (C 1

-C

4 )alkyl, halo- (C 3 -C 4 alkyl, (C 1

-C

4 )alkoxy, halo- (C 1 -C 4 )alkoxy, (C 1 -C 4 alkoxy-carbonyl or -NZZ', and the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C 1 -C 4 )alkyl, halo- (C 1 -C 4 alkyl, (C 1

-C

4 )alkoxy, halo- (C 1

-C

4 alkoxy, carboxy, (C 1

C

4 )alkoxy-carbonyl, (C 1 -C 4 )alkanoyloxy or -NZZ'; 4.

44 4 4 44 4.

.4 $44 4440 4 4 44 o4,~ 4444 4 L4J O 4 1 w fv 2 10 unsubstituted or substituted five-memberod heterocycle selected from furyl, thienyl, triazolyl, pyrroly., isopyrrolyl, pyrazolyl, isoimidazolyl, thiazolyl, isothiazolyl, oxazolyl and isooxazolyl where the substituents can be from one to three of the same or different halo; nitro; hydroxy; (C -C )alkyl;- (C C )alkoxy; carboxy; (C 1

C

6 )alkoxy-carbonyl; -RCO 2

H

goup;-RCO2 ROgroup; -CONZZ' group; amino -NZCOZ' group; (C 1

C

6 )alkylthio; or unsubstituted or substituted phenyl U" having one to three of the same or *different halo, nitro, (C 1 -C 6 )alkyl, halo- *"is(C C )alkyl, (C -C )alkoxy, halo-(C C 6 alkoxy, carboxy, -C )alkoxy-carbonyl or 4~ 4unsubstituted or substituted six-membered heterocycle having one, two, three or four -420 nitrogen atoms and two to five nuclear carbon atoms where the substituents can be from one to three of the same or different halo; nitro; hydroxy; I-C 6 )alkyl;

(C

1 -C )alkoxy; carboxy; (C 1

-C

6 "2.5alkoxy-carbonyl; -RCO H group; -RCO RI group; -CONZZ' group; amino NZCOZ' group; (C 1 -C 6 )alkylthio; or unsubstituted or substituted phenyl having one to three of the same or different halo, nitro, (C 1 -C 6 alky, halo- (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, halo-(C 1 -C 6 )alkoxy, carboxy,

(C

1 -C )alkoxy-carbonyl or amino rr 1 II -1L~1 11 49 1 4 2 2 5 30 4, 4.

r644 4i 9 where R, R' and R" are (C -C 6 )alkyl; Z and Z' are hydrogen or (C 1

-C

4 )alkyl; "amino" means NZZ' or agronomically acceptable salts thereof.

Insecticidal compositions of the invention comprise one or more of the above compounds together with agronomically acceptable diluent or carrier. The invention also extends to the use of said compounds and compositions as insecticides. The compositions usually contain from about 0.0001% to about 99% by weight of the compound.

The term "halo" should be understood as including chloro, fluoro, bromo and iodo. The term "alkyl" by itself or as a part of another substituent, unless otherwise stated, includes straight or branched chain groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, neopentyl and the like and where indicated higher homologues and isomers such as i-octyl, isooctyl and the like. The term "haloalkyl" by itself or as part of another substituent is an alkyl group of the stated number of carbon atoms having one or more halo atoms bonded thereto such as chloromethyl, 1- or 2-bromoethyl, trifluoromethyl and the like. Analogously, "cyanoalkyl" by itself or as part of another group is an alkyl group of the stated number of carbon atoms having one or more cyano groups bonded thereto; "haloalkoxy" by itself or as part of another group is an alkoxy group of the stated number of carbon atoms having one or more halo atoms bonded thereto such as difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2,2,2-trifluoroethoxy and the like. "Alkenyl" and "alkynyl" by themselves or as part of another substituent comprise straight and branched chain groups of the stated number of carbon atoms. "Alkadienyl" is

I

;ai i fT: ,I 1 1 1- 111~ 11-~ 12 a straight or branched chain alkenyl group comprising two carbon-carbon double bonds that can be conjugated such as 1,3-butadienyl, cumulated such as 1,2propadienyl or isolated such as 1,4-pentadienyl.

Representative examples of five-membered heterocycles includes 2-furyl; 3-furyl; 2-thienyl; 3-thienyl; 4-(1,2,3-triazolyl); 3-(1,2,4-triazolyl); 5-(1,2,4-triazolyl); 2-pyrrolyl; 2-oxazolyl; and the like.

Because of their anticipated good insecticidal activity, compounds of the present invention for use in the insecticidal compositions and formulations include those wherein any one or combination of two or more of the substituents conform to the following definitions: 415 X and X' are 0 or S; R is hydrogen; (C -C )alkyl; (C 1

-C

4 )alkoxy-

(C

1

-C

4 )alkyl having independently the stated number of carbon atoms in each alkyl group; methylthiomethyl; (C 2

-C

5 )alkenyl;

(C

2

-C

5 )-alkynyl; or phen-(C 1

-C

2 )alkyl where the phenyl ring is unsubstituted or ~substituted with one or two halo, nitro,

S(C

1

-C

4 )alkyl or (C 1

-C

4 )alkoxy; s R 2 and R are the same or different hydrogen or (C -C 3 )alkyl; 4 3 R4 R is (C 1

-C

3 )alkyl substituted with one to four I fluoro; straight chain (C 2

-C

4 )alkenyl; S* carboxyl; (C 1

-C

2 )alkoxy-carbonyl; cyano; cyano substituted (C 1

-C

3 )alkyl; tri- (C -C 2 )alkylsilyl having independently the stated number of carbon atoms in each alkyl group; or tri(C 1

-C

2 )alkylsilylmethyl having independently the stated number of carbon atoms in each alkyl group; provided that R 2 and R are both alkyl when R is carboxyl or alkoxycarbonyl; and 13 A and B are the same or different unsubstituted naphthyl; @4 4.

I *44 .4 4 4 44 4. 1 4 4,

I

I 44 44 4 4414 34 4 4 4e* unsubstituted or substituted phenyl where the substituents can be from one to three of the same or different halo; nitro; cyano; (C 1 -C 4 alkyl; halo- (C 1 -C 4 )alkyl;cyano-(C 1 -C 4 )alkyl; (C 1 -C 4 )alkoxy; (C 1 l-C 4 alkoxy- (C 1 -C 4 alkyl having independently the stated number of carbon atoms in each alkyl group; -COZ; carboxy; (C 1 -C 4 alkoxy-carbonyl; (C 1 -C 4 )alkanoyloxy; (C 2 -C 6 )alkenyl; (C 2 -C 6 )alkynyl; amino thiocyanato; (CI- C 4 )alkylthio; -CSR group; -CSH; unsubstituted or substituted phenyl having one to two of the same or different halo, nitro, (C 1

-C

4 alkyl, (C 1

C

4 )alkoxy, carboxy, -NZZ'; phenoxy where the phenyl ring is unsubstituted or substituted with one or two of the same or different halo, nitro, (C 1

-C

4 )alkyl, (C 1

C

4 )alkoxy, carboxy, -NZZ'; or when two adjacent positions on the phenyl ring are substituted with alkoxy groups, these groups may be joined to form together with the carbon atoms to which they are attached a 5- or 6-m"embered dioxolano or dioxano, heterocyclic ring; unsubstituted or substituted (C 1 -C 8 )alkyl having one to three of the same or different halo, cyano, (C 1 -C 4 )alkoxy, phenyl, (C 1 -C 4 )alkoxy-carbonyl or halo- (C 1

-C

4 )alkoxy; 0 4 4 69 14 t a1 6 6.1 unsubstituted or substituted (C 3 -C 6 )cycloalkyl or unsubstituted or substituted (C 3 -C 6 )cycloalkyl(C 1 -C 4 )alkyl having one or two of the same or different halo, (C 1 -C 4 alkyl, halo-(C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1

C

4 )alkanoy. or halo- (C 1 -C 4 )alkoxy; unsubstituted or substituted (C 2

C

6 )alkenyl having as substituent(s) a furyl or one to three of the same or different alkyl, halo-(C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy or halo- (C 1

C

4 )alkoxy; unsubstituted or substituted (C 3

-C

6 )cycloalkenyl having as substituent(s) one or two of the same or different halo, (C 1

C

4 alkyl, halo-(C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy or halo- (C 1 -C 4 )alkoxy; unsubstituted or phenyl substituted alkynyl; phenalkyl having one or two carbon atoms in the alkyl group and the alkyl group is unsubstituted or substituted with one or two of the same or different halo, (C 1 -C 4 )alkyl, halo-(C 1 -C 4 )alkyl, (C 1

C

4 alkoxy or halo- (C 1

C

4 )alkoxy and the phenyl ring is unsubstituted or substituted with one or two of the same or different halo, cyano, (C 1 -C 4 )alkyl, halo-(C 1 -C 4 )alkyl, (C 1 -C 4 )alkox.y or halo- (C 1 -C 4 )alkoxy; phenalkenyl having two or three carbon atoms in the alkenyl group and the alkenyl group is unsubstituted or substituted with halo, (C 1 -C 4 )alkyl, halo-(C 1 -C 4 alkyl,

C

i 15

(C

1

-C

4 )alkoxy or halo-(C 1

-C

4 )alkoxy and the phenyl ring is unsubstituted or substituted with one or two of the same or different halo, cyano, (C 1

-C

4 )alkyl, halo-(C 1

-C

4 alkyl, (C 1

-C

4 )alkoxy or halo-(C 1

-C

4 )alkoxy; unsubstituted or substituted five-membered heterocycle selected from furyl, thienyl, triazolyl, pyrrolyl, and oxazolyl where the substituents can be one or two of the same or different halo; nitro; (C 1

-C

4 )alkyl;

(C

1

-C

4 )alkoxy; -NZZ'; or unsubstituted or substituted phenyl having one or two of the same or different halo, nitro, (C -C 4 *1 4 6 alkyl, halo-(C 1

-C

4 )alkyl, (C 1 -C4)alkoxy, halo-(C 1

-C

4 )alkoxy, carboxy or -NZZ'; or unsubstituted or substituted six-membered heterocycle having one or two nitrogen 4, atoms and 4 to 5 nuclear carbon atoms where I 464 the substituents can be one or two of the same or different halo; nitro;

(C

1

-C

4 )alkyl; (C 1

-C

4 )alkoxy; thio-(C 1

-C

4 S"'alkoxy; -NZZ'; or unsubstituted or substituted phenyl having one or two of the Oak, same or different halo, nitro, (C -C 4 0"025 alkyl, halo-(C 1

-C

4 )alkyl, (C 1

-C

4 )alkoxy, halo-(C -C 4 )alkoxy, carboxy or -NZZ'; y where Z and Z' are hydrogen or 4 1(CI-C 4 )alkyl; and agronomically acceptable salts.

Insecticidal compounds of the present invention believed to have very good activity for use in the irt*-* *n 1 1 1 '1 i 16 10 0 9* *0 0 0 "0 0 *0 15 0 00 0 00 *o o* 25 insecticidal compositions and formulations of the present invention include those where any one or combination of two or more of the substituents conform to the following definitions: X and X' are 0 or S;

R

1 is hydrogen; (C1-C 4 )alkyl; (C 1

-C

4 )alkoxy-

(C

1

-C

4 )alkyl having independently the stated number of carbon atoms in each alkyl group; (C 2

-C

5 )alkenyl; (C 2

-C

5 )alkynyl; or benzyl where the phenyl ring is unsubstituted or substituted with one halo, nitro, (C 1 -C4)alkyl or (C 1

-C

4 )alkoxy; 2 3 R and R are the same or different hydrogen or (C -C2)alkyl; 4 R is (C 1

-C

3 )alkyl substituted with 1 to 4 fluoro; straight chain (C 2

-C

4 )alkenyl; methoxycarbonyl; cyano; cyano substituted

(C

1

-C

2 )alkyl; tri(C 1

-C

2 )alkylsilyl having independently the stated number of carbon atoms in each alkyl group; or tri(C 1 -C2)alkylsilylmethyl having independently the stated number of carbon atoms in each alkyl group; provided that R 2 and R are both alkyl when R 4 is methoxycarbonyl; and A and B are the same or different unsubstituted naphthyl; I~ rts unsubstituted or substituted phenyl having one to three of the same or different halo; nitro; cyano; (C 1

-C

4 )alkyl; halo-

(C

1

-C

4 )alkyl; cyano-(C 1

-C

4 )alkyl; (C 1

-C

4 alkoxy; (C 1

-C

4 )alkoxy-(C 1

-C

4 )alkyl having independently the stated number of carbon atoms in each alkyl group; -COZ; (CI-C4)alkoxy-carbonyl; (C 1

-C

4 )alkanoyloxy; ~t ;1 -i i

I

"1 i b k 0 11 1 IIIA -1 I 0 17 thiocyanato; -NZZ'; (Ci- C 4 )alkylthio; -CSZ; -CS 2 Z; unsubstitu-ed or substituted phenyl having one or two of the same or different halo, nitro, (C 1

C

4 )alkyl, (C 1

C

4 )alkoxy, carboxy, -NZZ'; or phenoxy where the phenyl.

ring is unsubstituted or substituted with one or two of the same or different halo, nitro, (C -C alkyl, (C 1 -C)alkoxy, carboxy, -NZZ'; or when two adjacent positions on the phenyl ring are off substituted with alkoxy groups, these groups may be joined to form together with *4the carbon atoms to which they are attached a 5- or 6-membered dioxolano or dioxano heterocyclic ring; unsubstituted or substituted (C -C alkyl having one to three of the same or t I tatdifferent halo, cyano, nitro, carboxy,

(C

1 -C )alkoxy, phenyl, (C-C) ItC *alkoxy-carbonyl or halo-(C -C )alkoxy; unsubstituted or substituted (C 3 -C 6 )cyclo- 444 aikyl or unsubstituted or substituted to*. (C -C cycloalkyl (C -C alkyl, where the 3 6 substituent is halo, (C 1 -C 4 )alkyl, (C 1 -C 4 alkanoyl, (C 1

C

4 )alkoxy or halo-(C 1

C

4 alkoxy; unsubstituted or substituted (C alkenyl having one or two of the same or different halo, (C -C )alkyl, (C -C 4 JA 30 alkoxy or halo-(C -C )alkoxy; 1 i.~ 18 unsubstituted or substituted (C 4

-C

6 )cycloalkenyl where the substituent is halo (Cl-C 4 )alkyl, (C -C 4 )alkoxy or halo-

(C

1

-C

4 )alkoxy; unsubstituted or phenyl substituted alkynyl; benzyl where the phenyl ring is EI, unsubstituted or substituted with one or 0 two of the same or different halo, methyl "or ethyl; unsubstituted or substituted five-membered heterocycle selected from furyl, thienyl, pyrrolyl and oxazolyl where the substituents can be one or two of the same or different halo, nitro, (CI-C4)alkyl or (C -C )alkoxy; or .1 4 unsubstituted or substituted six-membered heterocycle having one or two nitrogen atoms and four to five nuclear carbon atoms where the substituents can be one or two of the same or different halo, nitro, (C alkyl, (C 1

-C

4 )alkoxy or thio-(C 1

-C

4 )alkoxy; where Z and Z' are hydrogen or

(C

1

-C

4 )alkyl; including agronomically acceptable salts thereof.

Because of their anticipated excellent insecticidal activity, preferred compounds of the present invention for use in the insecticidal 30 compositions and formulations of the present invention include those where any one or combination of two or a \u 19 more of the substituents conforms to the following definitions: X and X' are 0;

R

1 is hydrogen; methyl; ethyl; (C 1 -C2)alkoxy-

(C

1

-C

2 )alkyl having independently the stated number of carbon atoms in each alkyl group (C 2

-C

5 )alkenyl; (C 2

-C

5 )alkynyl; or benzyl where the phenyl ring is unsubstituted or substituted with halo; R and R 3 are the same or different hydrogen or

(C

1

-C

2 )alkyl; 4 R is (C 1

-C

2 )alkyl substituted with 1 to 4 fluoro; straight chain (C 2

-C

4 )alkenyl; cyano; cyano substituted (C -C 2 )alkyl; 15 tri(C 1

-C

2 )alkylsilyl having independently the stated number of carbon atoms in each alkyl group; or tri(C 1

-C

2 )alkylsilylmethyl having independently the stated number of carbon atoms in each alkyl group; and o A and B are the same or different phenyl or substituted phenyl where the substituents can be from one to three of the same or different halo, nitro, (C 1

-C

4 )alkyl,

(C

1

-C

4 )alkoxy or halo-(C 1

-C

4 )alkyl; unsubstituted or substituted (C 1

-C

6 )alkyl having one to two of the same or different halo, phenyl or cyano; unsubstituted (C 4

-C

6 )cycloalkyl; unsubstituted or substituted (C 2

-C

6 )alkenyl having one to three of the same or different halo or (C 1

-C

4 )alkyl; i i I I I 20 unsubstituted (C 4

-C

6 )cycloalkenyl;

IS

1 2 i 11 1~ 4, I I i t

ILI

5 ft 4 *4

I

0 0 phenalkyl having one or two carbon atoms in the alkyl group and the phenyl ring is unsubstituted or substituted with one or two of the same or different halo,

(C

1

-C

4 )alkyl or (C 1

-C

4 )alkoxy; unsubstituted or substituted pyridyl or 2,5-pyrazinyl where the substituent can be halo, nitro, (C 1

-C

4 )alkyl, (C 1

-C

4 )alkoxy or

(C

1

-C

4 )thioalkoxy; or unsubstituted furyl or thienyl or an unsubstituted or substituted pyrrolyl where the substituent can be (C 1

-C

4 )alkyl; including agronomically acceptable salts thereof.

Because of their anticipated outstanding insecticidal activity, more preferred compounds of the present invention for use in the insecticidal compositions and formulations of the present invention include those where any one or combination of two or more of the substituents conforms to the following definitions: X and X' are 0; R is hydrogen; methyl; methoxymethyl; (C 2

-C

4 alkenyl; (C 2

-C

5 )alkynyl; benzyl; or 4halobenzyl; 2 3 R and R are the same or different hydrogen, methyl or ethyl; R is trifluoromethyl; 2,2,2-trifluoroethyl; straight chain (C 2

-C

4 )alkenyl; cyano; cyanomethyl; tri(C 1

-C

2 )alkylsilyl having independently the stated number of carbon X. pbt. i *I i Es i i I; a rr.r L I:C -ii.-l i ll~--r~ 21 atoms in each alkyl group; or trimethylsilylmethyl; and A and B are the same or different phenyl or substituted phenyl where the substituents can be one, two or three of the same or different chloro, fluoro, bromo, iodo, nitro, methyl, ethyl, methoxy or trifluoromethyl; (C 2

-C

3 substituted alkenyl having one to three of the same or different chloro, bromo, methyl or ethyl; \cyclohexenyl; Sbenzyl; Ir

S"

t unsubstituted or substituted pyridyl or where the substituent can be 15 halo, methyl, ethyl or methoxy; or It t o t unsubstituted furyl or thienyl or an C, unsubstituted or substituted pyrrolyl where the substituent can be ethyl or methyl; including agronomically acceptable salts thereof.

Because of their relatively low insecticidal activity at low application rates, less preferred compounds are those wherein R is CF 3 and A and B are unsubstituted phenyl or R is trimethylsilyl and A and B are 4-chlorophenyl or A is 4-ethylphenyl and B is Those N'-substituted,N,N'-diacylhydrazines of Formula I which possess acidic or basic functional groups may be further reacted to form novel salts with appropriate bases or acids. These salts also exhibit pesticidal activity. Typical salts are the ;t lT.' 22 agronomically acceptable metal salts, ammonium salts and acid addition salts. Among the metal salts are those in which the metal cation is an alkali metal cation such as sodium, potassium, lithium or the like; alkaline earth metal cation such as calcium, magnesium, barium, strontium or the like; or heavy metal cation such as zinc, manganese, cupric, cuprous, ferric, ferrous, titanium, aluminum or the like. The ammonium salts include those in which the ammonium cation has the formula NRR6R7R 8 wherein each of R 5 R R and R are independently hydrogen, hydroxy, (C 1

-C

4 )alkoxy,

(C

1

-C

2 0 )alkyl, (C 3

-C

8 )alkenyl, (C 3

-C

8 )alkynyl,

(C

2

-C

8 )hydroxyalkyl, (C 2

-C

8 )alkoxyalkyl, (C2-C aminoalkyl, (C 2

-C

6 )haloalkyl, amino, (C 1

-C

4 )alkyl- or 15 (C 1

-C

4 )dialkylamino, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, having up to four carbon atoms in the alkyl moiety, or a5 6 7 8 C any two of R R R or R can be taken together to form with the nitrogen atom a 5- or 6-membered heterocyclic ring, optionally having up to one r' additional hetero atom oxygen, nitrogen, or sulfur) in the ring, and preferably saturated, such as piperidino, morpholino, pyrrolidino, piperazino or the like, or any three of R R R or R can be taken together to form with the nitrogen atom a 5- or •6-membered aromatic heterocyclic ring, such as piperazole or pyridine. When R R R or R substituent in the ammonium group is a substituted phenyl or substituted phenylalkyl, the substituents on 30 the phenyl and phenalkyl will generally be selected from halo, (C 1 -C)alkyl, (C 1

-C

4 )alkoxy, hydroxy, nitro, trifluoromethyl, cyano, amino, (Cl-C 4 )alkylthio and the like. Such substituted phenyl groups preferably have up to two such substituents. Represenative ammonium L 35 cations include ammonium, dimethylammonium, 2-ethylr hi 1 1

E;

'ir rt- irl i 23 hexylammonium, bis(2-hydroxyethyl)ammonium, tris(2hydroxyethyl)ammonium, dicyclohexylammonium, t-octylammonium, 2-hydroxyethylammonium, morpholinium, piperidinium, 2-phenethylammonium, 2-methylbenzylammonium, n-hexylammonium, triethylammonium, trimethylammonium, tri(n-butyl)-ammonium, methoxyethylammonium, diisopropylammonium, pyridinium, dialkylammonium, pyrazolium, propargylammonium, dimethylhydrazinium, octadecylammonium, 4-dichlorophenylammonium, 4-nitrobenzylammonium, benzyltrimethylammonium, 2-hydroxyethyldimethyloctadecylammonium, 2-hydroxyethyldiethyloctylammonium, decyltrimethylammonium, hexyltriethylammonium, 4-methylbenzyltrimethylammonium, and the like. Among the acid addition salts are those in which 5 the anion is an agronomically acceptable anion such as hydrochloride, hydrobromide, sulfate, nitrate, perchlorate, acetate, oxalate and the like.

The above-identified preferred embodiments are based on the 34 examples which were made, tested and '20 disclosed infra and the disclosure in the following six related European applications: U.S. Application No. EPC Application No. Local No.

911 177 86308068.5 64289/86 789 797 858 482 87303092.8 71471/87 821 187 87300534.2 67894/87 835 073 873017305 69266/87 S005 82073 87301730.5 69266/87 005 824 012 380 87303090.2 71473/87 885 508 911 928 87303091.0 71472/87 rfc i 31 1 1 1 1 t 1 I- 24 15

I

*I

0 4s 4 tr 15 va o o2 o 30 4* 0 o' 625 These related applications disclose nearly 1,000 active compounds in which the presently disclosed R 2

R

3 and 4 R are methyl and A and B are various unsubstituted and substituted moieties including alkyl, phenyl and 5- and 6-membered heterocyclic rings.

The present inventors have determined that a critical feature of the structure which leads to activity is not the t-butyl substituent of the related applications (R2=R3=R =methyl) but that one of the nitrogens be substituted with a bulky substituent.

This bulky substituent is preferably a trisubstituted alpha carbon or a trisubstituted beta carbon. However, the bulky substituent may also be a trisubstituted gamma carbon or a disubstituted alpha carbon.

Compounds of the present invention which were made and used in insecticidal compositions and formulations include those where, independently, X and X' are 0; R is hydrogen;

R

2 and R are hydrogen, methyl or ethyl; 4 R is trifluoromethyl, cyano, allyl, methoxycarbonyl, or trimethylsilyl; and A and B are the same or different unsubstituted or substituted phenyl having one or two of the same or different chloro, fluoro, nitro, methyl or ethyl; or unsubstituted thienyl.

Since one of ordinary skill in the art would anticipate homologues to be active, the present invention also includes compounds for use in insecticidal compositions and formulations where any one or combination of two or more of the substituents conforms to the following definitions: X and X' are 0; i ii^. 1 i- i Wrt^- 25 R is hydrogen or methyl;

R

2 and R 3 are hydrogen or (C 1

-C

3 )alkyl; R is trifluoromethyl, 2,2,2-trifluoroethyl, cyano, cyanomethyl, straight chain (C2-C4)alkenyl, carboxyl, methoxycarbonyl, tri-

(C

1

-C

2 )alkylsilyl having independently the stated number of carbon atoms in each alkyl group or tri(C 1

-C

2 )alkylsilylmethyl having independently the stated number of carbon 0 atoms in each alkyl group; and A and B are the same or different thienyl or unsubstituted phenyl or substituted phenyl where the substituents can be one to three of the same or different chloro, fluoro, nitro, methyl, ethyl or propyl; including S. agronomically acceptable salts thereof.

The compounds of this invention or their it precursors can be prepared according to the following processes. Process A can be used when preparing '0 compounds according to Formula I where X and X' are both oxygen and A and B are the same (for example, both A and B are phenyl or 4-chlorophenyl) or different (for example, A is 4-methylphenyl and B is 4-chlorophenyl).

Process

A:

5 Step 1 0

R

2

R

2 S1 l3 Base 1 3 A- -C1 NHR NHC-R A-C-NR -NHC-R 14 4So l vent 14 4

R

II III IV i i L:r: 26 Step 2 0o 11 1 1 1 A-C-NR -NHC-R B-C-Cl 14

R

IV V 0 0 9-ovet"A-C-NR

-N--C-B

4, t 9 9,.

9$ 9 9 99 9 6e 9,

S

9*

I.

4.9 49 S 9.

4, 9 96* where R 1, R 2, R 3, R 4, A and B are as defined above for Formula I and X and X1 are oxygen.

When R 4is cyano the intermediate IV may be made as follows: Step la 0

R

2

-C-R

3 0 1 M-CN A-C-NR NH 2 Solvent VII a 0R 2 A-C-NR NHC-R

UN

&S4

S

949 .9 99 9. 9

S

IVa where M Na Process B can be used when preparing compounds according to Formula I where X and X' are oxygen, and R 1, R 3, R 4, A and B are as defined above for Formula I.

27 Process B: Method 1 Step 1 0 11 1 A-C-NR NH 2

VI

0 R Catalyst (optional) Solvent A-C-NR N=C 14

R

VII VIII 4, 4 0 4 A,.

to 4 0 4 *0

S

0 64 0 I S 464

£S~

I'

4 44 0 4 0*

A,

S

0? Step 2 03 11 A-C-NR N=C Reducing~ Agen~t_ Solvent Catalyst (optional) 0 R A-ct-NR1 NHCH* \R4 VIII Ix (IV) Step 3 0R3 A-C-NR NECH >1 4 0

+I

R3 R4 Base A-'NNIC- Solvent Ix (IV) X I) 0 B 44.h 40

S

I 9 As can be seen above, the intermediate product of Step 2, the compounds of Formula IX, corresponds to the compounds of Formula IV. In addition, the compound of Formula X corresponds to the compounds of Formula I where X and X1 are oxygen.

X

44 28 Method 2

A-C-W

Ri1 2 1 4 R -C-R Base Solvent

XII

it 14 I 49 49 I. a 9 8~ 44 &4 9 94

I.

9* ~O 9w 4.

9 4' t I 1~4.

91 99 4 It I I 4449 4 &£9 94 I9 4. '1'0 0 0 A-C-N N-C-B R 2 C I

R

1 2 3 4 where R R R R A and B are as defined above for Formula I and W is a good leaving group such as halo, for example, chloro; an alkoxy, for example, ethoxy; methyl sulfonate (-OSO 2 CH 3 or an ester, for example, acetate (-OC(0)CH 3 Process C can be used when preparing compounds according to Formula I where A, B and R 1 are as defined for Formula I and one or both X and V' are sulfur.

Process C: Step 1:

X

11

A-C-Y

1-3

NHNHC-R

11~ 1~4 Base Solvent'

XR

A-N-NH

412 R XIII III XIV '1 4 ^*.iwmMwMf'aWwiKVMwww^'^w-w^v^^u^ witWWW-tSfWW* 29 Step 2:

X

11 R' A-C-A NH 4 2 R -C-R 13

R

XIV

X'

-C-Y

B-C-Y Base Solvent X

X'

11 R N -B 4 2 R 00 0 0r 0 00 0 o 0.

*0 0 0 00 9.

00a ,0 1 2 3 4 where R R R R A and B are as defined above for Formula I and one or both X and X' are sulfur, and Y is a good leaving group such as carboxyalkylthio (for example, carboxymethylthio, -SCH 2

CO

2 alkylthio (for example, methylthio); or halo (for example, chloro).

Process D can be used when preparing compounds according to Formula I where X and X' are oxygen and R A and B are as defined above for Formula I.

*0 o 0 00 S*10 0 0 0 0 Process D: Step 1:

R

2 1- 3 NHNHC-R R R

III

2 Base Solvent O R~ Z-0-c-NR'NH 4

-R

3 4

R

XVI XVII Step 2 2 RO R0 0 O 1I 3 II I 1 Z-O-C-NR NHC-R B-C-C1 Base Z-O-C-NR N-C-B I Solvent 4 1 2 R R -C-R 13

R

XVII

XVIII

-1

%I

j s' i i 30 Step 3 O O Z-O-C-NR N- C-B 4 2 R -C-R 13

R

Acid Solvent

O

i II

NHN--C-B

4 2 R -C-R 13

R

XIX

XVIII

t fr I o S* 00 00 0 0 O 0 0 0 00 t 0 5 I I I 0 0 Step 4

O

II

A-C-C1

II

1

NHN--C-B

4 2 R -R

R

XIX

0 0 II R 1

II

Base A-C-N-N--C-B Solvent 4 2

R

wherein R R R R A and B are as defined above for Formula I and Z is t-butyl; ethyl; phenyl; or benzyl.

The starting materials for each process are generally commercially available, or can be prepared by generally customary and known methods.

In Process A, a compound of Formula II is reacted with a monosubstituted hydrazine of Formula III or a corresponding acid addition salt such as the hydrochloride salt or the like in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford an intermediate product of Formula IV which can be isolated or further reacted with a compound of Formula V in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford the desired product of Formula I.

When A and B are the same, for example, both A and B are 4-chloropinyl, two equivalents of a compound

I~

J:a~ -tjM( 4L ~~II1 i ~l-----.ra~-rr;E-rucru~r p i CDI LCI~ 31 1 r e t 99 9 9 r* 9 #9*"15 0 o 9 6 of Formula II or V are reacted with a monosubstituted hydrazine of Formula III in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford the desired product of Formula I.

Examples of the compounds of Formula II and/or Formula V which can be used in the above processes include benzoyl chloride, 4-chlorobenzoyl chloride, 4-methylbenzoyl chloride, 3,5-dichlorobenzoyl chloride, 2-bromobenzoyl chloride, 3-cyanobenzoyl chloride, 3-toluoyl chloride, 4-toluoyl chloride, 4-ethylbenzoyl chloride, 2-nitrobenzoyl chloride, 2,3-dimethylbenzoyl chloride, 2-nitro-5-toluoyl chloride and the like. The compounds of Formula II and/or Formula V are generally commercially available or can be prepared by known procedures.

Examples of the compounds of Formula III which can be used in the above processes include 1,1-dimethyl-3-butenylhydrazine, (trimethylsilylmethyl)hydrazine, (1,1,l-trifluoro-2-propyl)hydrazine, (2,2,2-trifluoroethyl)hydrazine, (l-cyano-l-methyl)ethylhydrazine and the like. The compounds of Formula III are generally commercially available or can be prepared by known procedures. For example, the Grignard reagent addition product of acetone azine in diethyl ether is hydrolyzed by the addition of an acid (such as oxalic acid), in a suitable solvent or mixture of solvents (such as ethanol and diethyl ether, 1:1) to afford the monosubstituted hydrazine of Formula III.

Suitable solvents for use in the above processes include water; alcohols such as methanol, ethanol, isopropanol and the like; hydrocarbons such as toluene, xylene, hexane, heptane and the like, glyme; tetrahydrofuran; acetonitrile; pyridine; or haloalkanes such as methylene chloride or mixtures of these solvents.

32 Preferred solvents are water, toluene, methylene chloride or a mixture of these solvents.

Examples of bases for use in the above processes include tertiary amines such as triethylamine; pyridine; potassium carbonate; sodium carbonate; sodium bicarbonate; sodium hydroxide; or potassium hydroxide.

Preferred bases are sodium hydroxide, potassium hydroxide or triethylamine.

In Process B, Method 1, a compound of Formula VI is reacted with a ketone or aldehyde of Formula VII in an inert or substantially inert solvent or mixture of solvents and optionally in the presence of a catalyst c ce to afford an intermediate product of Formula VIII. The intermediate product of Formula VIII is then further t 15 reacted with a reducing agent in an inert or *t N' substantially inert solvent or mixture of solvents to afford a second intermediate product of Formula IX (IV) which can be isolated or further reacted with a compound of Formula V in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford the desired product of Formula X Examples of the compounds of Formula VI which Oe can be used in the above Process B, Method 1, include 2i benzoylhydrazine, 4-chlorobenzoylhydrazine, 2-methylbenzoylhydrazine, 4-methylbenzoylhydrazine, and the like. The compounds of Formula VI are generally commercially available or can be prepared by known procedures.

Examples of the compounds of Formula VII which can be used in the above Process B, Method 1, include trifluoroacetone, methacrolein, ethyl pyruvate and the like. The compounds of Formula VII are generally commercially available or can be prepared by known procedures.

33 Optionally, a catalyst may be used in Step 1, Method 1 of Process B. Suitable catalysts generally include organic acids such as acetic acid, trifluoroacetic acid, oxalic acid and the like; mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and the like; arylsulfonic acids such as toluenesulfonic acid; or pyridinium toluenesulfonate.

Preferred catalysts are organic acids or arylsulfonic acids. Most preferred catalysts are acetic acid or trifluoroacetic acid.

Suitable solvents for use in the above Process B, Method 1, Step 1, include alcohols such as methanol, «r t ethanol, isopropanol and the like; hydrocarbons such as S" toluene, benzene; ethers such as tetrahydrofuran (THF), 15 glyme and the like; or dimethylformamide. Preferred solvents are alcohols and hydrocarbons. Most preferred solvents are alcohols such as methanol or ethanol.

Examples of suitable reducing agents for use in the above Process B, Method 1, Step 2, include hydrides **20 such as sodium borohydride and derivatives thereof such as sodium cyanoborohydride, lithium aluminum hydride and derivatives thereof and the like; or diborane.

Preferred reducing agents are sodium borohydride and derivatives thereof or lithium aluminum hydride and "0'25 derivatives thereof. Most preferred as reducing agents a are borane and diborane.

Optionally, in Process B, Method 1, Step 2, a catalyst may be included. Examples of suitable Scatalysts include organic acids such as acetic acid, trifluoroacetic acid; or mineral acids such as hydrochloric acid, sulfuric acid and the like.

Preferred catalysts are organic acids or hydrochlor:' acid. Most preferred catalysts are acetic acid, trifluoroacetic acid or hydrochloric acid.

Suitable solvents for use in the above Process i 34 B, Method 1, Step 2, include alcohols such as methanol, ethanol, isopropanol and the like; ethers such as tetrahydrofuran (THF), diethylether, glyme and the like; or halohydrocarbons such as methylene chloride, chloroform and the like. Preferred solvents are alcohols and most preferred are methanol or ethanol.

Step 3 of Process B, Method 1 corresponds to Step 2 of Process A. Consequently, those bases and solvents suitable for use in Step 2 of Process A are suitable for use in Step 3, Method 1 of Process B including the preferred bases and solvents described S, above.

In Process B, Method 2, and N'-substituted-N'benzoylhydrazine of Formula XII is reacted with a compound of Formula XI in the presence of a base in an *I inert or substantially inert solvent or mixture of solvents to afford the desired product of Formula I.

The compounds of Formula XI are generally commercially available or can be prepared from commercially available compounds by procedures well known to those skilled in the art as described below.

Examples of the compounds of Formula XII which can be used in the above Process B, Method 2, include N'-(l,1-dimethyl-3-butenyl)-N'-benzoylhydrazine, .'25 N'-(trimethylsilylmethyl) -N'-(4-methylbenzoyl) hydrazine, N'-(1,1,l-trifluoro-2-propyl)-N'-(2,4dichlorobenzoyl)hydrazine, N'-(l-cyano-l-methyl)ethyl- N'-(2-methylbenzoyl)hydrazine and the like.

Suitable solvents for use in the above Process o 30 B, Method 2, include water; hydrocarbons such as toluene, xylene, hexane, heptane and the like; alcohols such as methanol, ethanol, isopropanol, and the like; glyme; tetrahydrofuran; acetonitrile; pyridine; or haloalkcnes such as methylene chloride; or mixtures of these solvents. Preferred solvents are water, toluene, i 35 methylene chloride or a mixture of these solvents.

Examples of bases suitable for use in the above Process C includes tertiary amines such as triethylamine; pyridine; potassium carbonate; sodium carbonate; sodium bicarbonate; sodium hydroxide; or potassium hydroxide. Preferred bases are sodium hydroxide, or triethylamine.

The compounds of Formula XI are commercially available, such as nicotinoyl chloride hydrochloride, isonicotinoyl chloride hydrochloride and ethyl picolinate or can be prepared from commercially available materials by procedures known to those skilled in the art.

The compounds of Formula XII can be prepared by procedures known to those skilled in the art from commercially available reactants. By way of example, a suitably substituted hydrazine (such as (1,1,1trifluoro-2-propyl)hydrazine) is reacted with an aldehyde or ketone (such as acetone) in the presence of a base (such as triethylamine) to'afford a hydrazone which is then reacted with a benzoyl chloride in an inert or substantially inert solvent or mixture of solvents in the presence of a base (such as sodium hydroxide) to afford an N'-substituted-N'-benzoyl- 25 hydrazone which is then reacted with an acid (such as hydrochloric acid) to afford the compound of Formula XII. Alternatively, a suitable substituted hydrazine (such as (trimethylsilylmethyl)hydrazine) is reacted with di-tert-butyldicarbonate in an inert or 30 substantially inert solvent or mixture of solvents (such as toluene/water) to afford an N'-(trimethylsilylmethyl)-N-t-butoxycarbonylhydrazine which is then reacted with a benzoylchloride in an inert or ;substantially inert solvent or mixture of solvents to afford an N'-(trimethylsilylmethyl)-N'-benzoyl-N-tr 7 1 36 butoxycarbonylhydrazine which is then reacted with an acid to afford the desired compound of Formula XII.

In Process C, a compound of Formula XIII is reacted with a monosubstituted hydrazine of Formula III or a corresponding acid addition salt such as the hydrochloride salt or the like in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford an intermediate compound of Formula XIV which can be isolated or further reacted with a compound of Formula XV in the presence of a base in an inert or substantially inert solvent or mixture r of solvents to afford the desired product of Formula I.

ru In Process D, a monosubstituted hydrazine of t Formula III or a corresponding acid addition salt, such as the hydrochloride salt or the like, is reacted with a compound of Formula XVI in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford an intermediate product of Formula XVII. The intermediate product of Formula XVII is then further reacted with a compound of Formula V in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford a second intermediate product of Formula XVIII. The second intermediate product of Formula XVIII is then further reacted with an acid in an inert or substantially inert 1* o* Ssolvent or mixture of solvents to afford a third intermediate product of Formula XIX. The third intermediate product of Formula XIX is then further reacted with a compound of Formula II in the presence 30 of a base in an inert or substantially inert solvent or mixture of solvents to afford the desired product of Formula I.

SExamples of the compounds of Formula XVI which can be used in the above Process D include di-t-butylcarbonate, diethylcarbonate, diphenylcarbonate, i^ 1 I *U;ai;-j _ffl-jmW'..-aaI^^. 37 dibenzylcarbonate and the like. The compounds of Formula XVI are generally commercially available or can be prepared by known procedures.

Suitable solvents for use in the above Process D, Steps 1, 2 and 4 include water; tetrahydrofuran; dioxane; toluene; alcohols such as methanol, ethanol and isopropanol; hexane; acetonitrile; pyridine; and haloalkanes such as methylene chloride; or mixtures of these solvents.

Preferred solvents are dioxane; toluene; tetrahydrofuran; pyridine; methylene chloride or water.

Most preferred solvents are dioxane; water or toluene.

t SExamples of the bases for use in the above 4, Process D, Steps 1, 2 and 4 include tertiary amines such as triethylamine; pyridine; potassium carbonate, sodium carbonate; sodium bicarbonate; sodium hydroxide; and potassium hydroxide.

Preferred bases are sodium hydroxide; potassium hydroxide; pyridine or triethylamine.

Suitable solvents for use in the above Process D, Step 3 include alcohols such as methanol, ethanol and isopropanol; water; tetrahydrofuran; dioxane; and acetonitrile.

Preferred solvents are methanol or ethanol.

I Examples of acids for use in the above Process D, Step 3 include concentrated hydrochloric acid or concentrated sulfuric acid.

When A and B are the same, for example, both A and B are unsubstituted phenyl, two equivalents of a J compound Formula XIII or XV are reacted with a monosubstituted hydrazine of Formula III in the presence of a base in an inert or substantially inert solvent or mixture of solvents to afford the desired product of Formula I.

Af 38 Examples of the compounds of Formula XIII and/or Formula XV which can be used in the above Process C include 3-methyl-methylthio-thiobenzoate, 4-chloromethylthio-thiobenzoate, 4-methyl-methylthio-thiobenzoate, carboxymethylthio-thiobenzoate and the like.

The compounds of Formula XIII and/or Formula XIV are generally commercially available or can be prepared by known procedures.

Suitable solvents for use in the above Process C are generally polar high-boiling solvents such as dimethylformamide (DMF); glyme; tetrahydrofuran (THF); r, and pyridine. The preferred solvent is pyridine.

Suitable bases for use in the above Process C include tertiary amines such as triethylamine; and pyridine. The preferred base is pyridine.

r The above Processes A and B, Method 1, can be carried out at temperatures between about -20 0 C and about 100 0 C. Preferably, these reactions are carried out between about -5 0 C and about 50 0

C.

The above Process B, Method 2, can be carried out at temperatures between about -50 0 C and about 150 0 C. Preferably when W is a halo radical, the reaction is carried out between about 0°C and about 0 C. When W is alkoxy, the reaction is preferably 640#25 carried out between about 100 0 C and about 150 0 C. When 1 f W is methyl sulfonate, the reaction is preferably carried out between about -20 0 C to about 20 0 C. When W is an ester, the reaction is preferably carried out S- between about 0 C and about 50 0

C.

30 Process C can be carried out at temperatures between about 10°C and 200 0 C. Preferably, this reaction is carried out between about 70 0 C and about S1000C.

Process D can be carried out at temperatures between about 0°C and 100 0 C. Preferably, these

V

~Ui ;-ii 39 reactions are carried out between about 0 0 C and about 0

C.

Preparation of the compounds of the present invention by Processes A, B, C and D are preferably carried out at about atmospheric pressure, although higher or lower pressures can be used if desired.

Substantially equimolar amounts of reactants are preferably used in Processes A, B and C, although higher or lower amounts can be used if desired.

Generally, about one equivalent of base is used Sper equivalent of starting material of Formula II, V, XI and/or XIII. Where the acid addition salt of the monosubstituted hydrazine of Formula III is used, one Sadditional equivalent of base is used. For example, in Process A, when substituents A and B are the same and a monosubstituted hydrazine is used, about two equivalents of base are used since about two equivalents of a suitably substituted benzoyl chloride of Formula II or V are employed. In Process A, when ,.2o0 substituents A and B are different and an acid addition salt of the monosubstituted hydrazines of Formula III 00 is used, about two equivalents of base are used in Step 1 and about one equivalent of base is used in Step 2.

Modifications to the above processes may be necessary to accommodate reactive functionalities of particular A and/or B substituents. Such modifications would be apparent and known to those skilled in the art.

-It will be appreciated by those skilled in the art that electronic forces may give rise to more than one isomer of the compounds of Formula I such as enantiomers, conformers and the like. There may be a difference in properties such as physical characteristics and degree of biological activity between such isomers. Separation of a specific isomer 40 can be accomplished by standard techniques well known to those skilled in the art such as silica gel chromatography.

The agronomically acceptable salts embraced by the invention can be prepared by reacting a metal hydroxide, a metal hydride or an amine or ammonium salt, such as a halide, hydroxide or alkoxide with a compound of Formula I having one or more hydroxy or carboxy groups or reacting a quaternary ammonium salt, such as chloride, bromide, nitrate or the like with a metal salt of a compound of Formula I in a suitable Ssolvent. When metal hydroxides are used as reagents, useful solvents include water; ethers such as glyme and the like; dioxane; tetrahydrofuran; alcohols such as ,4'*1l5 methanol, ethanol, isopropanol and the like. When metal hydrides are used as reagents, useful solvents include nonhydroxylic solvents, for example, ethers such as dioxane, glyme, diethylether and the like; tetrahydrofuran; hydrocarbons such as toluene, xylene, O0 hexane, pentane, heptane, octane and the like; dimethylformamide, and the like. When amines are used as reagents, useful solvents include alcohols, such as methanol or ethanol; hydrocarbons, such as toluene, xylene, hexane and the like; tetrahydrofuran; glyme; dioxane; or water. When ammonium salts are used as I reagents, useful solvents include water; alcohols, such as methanol or ethanol; glyme; tetrahydrofuran; or the like. When the ammonium salt is other than a hydroxide or alkoxide, an additional base, such as potassium or sodium hydroxide, hydride, or alkoxide is generally j used. The particular choice of solvent will depend on Sthe relative solubilities of the starting materials and the resultant salts, and slurries rather than solutions of certain reagents may be used to obtain the salts.

Generally, equivalent amounts of the starting reagents 3' i 3 C i i -j i ill 41 are used and the salt-forming reaction is carried out at about 0°C to about 100 0 C, preferably at about room temperature.

The acid addition salts of the present invention can be prepared by reacting hydrochloric, hydrobromic, sulfuric, nitric, phosphoric, acetic, propionic, benzoic or other suitable acid with a compound of Formula I having a basic functional group in a suitable solvent. Useful solvents include water, alcohols, ethers, esters, ketones, haloalkanes and the like. The particular choice of solvent will depend on the relative solubilities of the starting materials and the resulting salts and slurries rather than solutions of certain reagents may be used to obtain the salts.

Generally, equivalent molar amounts of starting materials are used and the salt-forming reaction is carried out at from about -10°C to about 100°C, preferably at about room temperature.

cr, tThe following examples will further illustrate ,20 this invention but are not intended to limit it in any way. In Table I, some N'-substituted-N,N'-diacyl hydrazines of the present invention that have been made are listed. The structure of these compounds was confirmed by NMR and in some cases by IR and/or elemental analysis. Specific illustrative preparation of the compounds of Examples 8, 15 and 28 are described after Table I.

I

42 TABLE I 2CB

LI

I I S See I C C 1 CC It C C 4* C Cl C I C 14CC

I,

I C I CCC Sr t I ICr I S

(IC

.2 0

C

Cat II 4* I C C I C Ex No.

1 2 3 4 5 6 7 8 9 11 12 13 14 15 16 R 2

H

H

H

H

H

H

H

Me Me Me Me Me Me Me Me Me R 3 Me me Me Me

H

H

H

Me Me Me Me Me Me Me Me Et R4 CF 3 CF 3 CF 3 CF 3 CF 3 CF 3

CF

3

CM

CM

CM

CN

CN

CM

CM

A c6 H 3 Me 2 -2,3 c6 H 3 Me 2 2,3 c6 H 3 C1 2 -3,4 C6 H 4C1-4 c64H C C6 H 4 -Me c6 C 6 H 3 C1 2 4 C 6 H 3 Me 2 C6 H 3NO 2Me-2,5 6 H3 Cl2 C H 6 C 6

H

3 C1 2 C6 H C1F-4 17 Me Me CM

S

C6 H 4me-3 C6 H 4Et-4 c6 H 4 Me-2 C H 4C1-4 c6 H 3 F 2 2,6 C6 H 4Me-2 C6 N 4NO 2-2

C

6 H 3 Me 2 C 6 H 3 Me 2 C6 H Me-3 C6 H 4Cl-4 C 6

H

4 Me-3 ii 43

CN

CO 2 Me CH 2 CH=CHi 2 m 2 CH=CH 2 CH 2 CH=C-1 2 Si~e 3 Sime 3 Sime 3 Sime 3 Si~e 3 Si~e 3 c6 H c6 HNe5 c 6 H 4 Et-4 C6 H 4Cl-4 c6 H 4 Me-2 C6 H 4NO 2-2 c6 H 4 Et4

C

6 H 4 Me-3 C6 H 4me-4 C6 H 4Me-3 c6 4l C6 H NOD0 C6 H 4Cl-4 C6 H 4 ve-2 C6 H 10 2-2 c6 H 2

C

6 H 3 Me 2 -3 44 I I I t.

4, 4 4 t~ 44 4 4 I 4 *4 4 .4 44 4 444* 44 S S 4I4 4' I S

III

C 41 S I C It d, t 4*49 0 44*0 54 9* I 4 0 S 4 /1 '71

'I

4 44 EXAMPLE No. 8 Preparation of N'-(l-cyano-l-methyl)ethyl-N,N'-dibenzoylhydrazine To a suspension of benzoylhydrazine (13.6 g, 0.1 mole) in deionized water (50 ml) at 5 0 C with stirring was dropwise added concentrated hydrogen chloride (9.8 g, 0.1 mole). To the resulting clear solution was added sodium cyanide (5.2 g, 0.1 mole) and acetone g, 0.11 mole). A white and thick precipitate appeared.

The cooling bath was removed and the reaction flask was stoppered tightly. The reaction mixture was stirred for 18 hours. The precipitate was collected by suction-filtration and was washed with a small amount of water to give 17.5 g (86.2% yielded) of desired intermediate, N'-(1-cyano-l-methyl)ethyl-N-benzoic acid 15 hydrazide, as the starting material for the next step.

82-92 0

C).

To the solution of N'-(1-cyano-l-methyl)ethyl-Nbenzoic acid hydrazide (2 g, 0.01 mole) in dry methylene chloride (25 ml) under nitrogen at room temperature with stirring was added benzoyl chloride S(2.02 g, 0.014 mole). To the above mixture was dropwise added triethylamine (1.31 g, 0.013 mole). The reaction mixture was stirred at room temperature for t4"* hours. The reaction mixture was diluted with 6"2,5 methylene chloride (50 ml), washed with water and brine. The organic layer was dried over MgSO 4 and the solvent was evaporated at reduced pressure to give a residue. The residue was treated with ethyl acetate/hexane mixture affording a crude solid- 30 formed product which was collected by suction- 'i filtration (1 g, 33% yield). An analytical sample was m.p. 202-204 0 C. NMR and IR spectra showed the desired product.

1 i 1 1 -r 1-' 'II 45 Elemental Analysis C H 70.34 5.58 70.20 5.67 Calc. Found

N

13.67 13.40 I Ir 1.0 r I It It t It I rt~

I

30 I I (II I If 1r 0 Ii I 1 9 EXAMPLE No. 15 Preparation of N'-(1-cyano-l-methyl)ethyl-N,N'-di-4-toluoylhydrazine To the suspension of 4-toluic acid hydrazide (15.0 g, 0.1 mole) in water (150 ml) and ethanol ml) at 5 0 C with stirring was dropwise added concentrated hydrogen chloride (10 g, 0.1 mole). To the above still suspension was carefully added sodium cyanide (5.3 g, 0.1 mole) and acetone (6.6 g, 0.11 mole). The reaction flask was stoppered tightly and the cooling bath was removed. The resulting viscous reaction mixture was stirred at room temperature for more than 24 hours. The precipitate was collected by suction-filtration and was washed with a small amount of diluted hydrogen chloride and water affording 14.6 g. of N'-(1-cyano-l-methyl)ethyl 4-toluic acid hydrazide as the starting material for the next step.

Analytical sample was obtained by crystallization from ethyl acetate/hexane m.p. 146-148 0

C.

To the solution of N'-(1-cyano-l-methyl)ethyl 4toluic acid hydrazide (2.17 g, 0.01 mole) in dry methylene chloride (65 ml) under nitrogen with magnetic stirring was added 4-dimethylaminopyridine catalyst (1.34 g, 0.011 mole) followed by 4-methylbenzoyl chloride (2.52 g, 0.017 mole). To the above mixture was dropwise added triethylamine (1.1 g, 0.011 mole).

The reaction mixture was slightly exothermic. After stirring at room temperature for 40 minutes the reaction mixture was diluted with methylene chloride ml), washed with diluted HCI solution (2X50 ml), dil NaOH (50 ml), 1120 (50 ml) and brine. The organic C~ -i ii i l 46 10 Ct t Ir

'I

C it i

C

ae Ct layer was dried over MgSO 4 and the solvent was evaporated under reduced pressure to give a residue.

The residue was treated with ethyl acetate/hexane mixture and the resulting solid was collected by suction-filtration and affording 2.75 g (82% yield) of almost pure product. 192-198 0 C) NMR and IR spectra showed the desired product.

By following substantially the procedures in Example 8 (without catalyst) or 15 (with catalyst) and using the reactants shown below in Table II, the products of Examples 8 to 24 were prepared.

TABLE II Ex. Compound of Compound of Compound of No. Formula VI Formula VIIa Formula V 8 benzoylhydrazine acetone benzoyl chloride 9 benzoylhydrazine acetone 4-chlorobenzoyl chloride 4-toluoylhydrazine acetone 3-methylbenzoyl chloride 11 benzoylhydrazine acetone 3-methylbenzoyl chloride 12 4-chlorobenzoyl- acetone 4-chlorobenzoyl chloride hydrazine 13 4-toluoylhydrazine 14 4-toluoylhydrazine 4-toluoylhydrazine 16 benzoylhydrazine 17 thienoy1hydrazine 18 4-ethylbenzoylhydrazine 19 2-toluoyhydrazine 4-chlorobenzoylhydrazine acetone acetone acetone methylethylketone acetone acetone acetone acetone 3, 5-dimethylbenzoyl chloride 4-fluorobenzoyl chloride 4-methylbenzoyl chloride benzoyl chloride 3-methylbenzoyl chloride 3, 5-dimethylbenzoyl chloride 3,5-dirmthylbenzoyl chloride 3-methylbenzoyl chloride 4 ct~ 1 47 Ex. Compound of Compound of Compound of No. Formula VI Formula VIIa Formula V 21 2,4-difluorobenzoyl- acetone 4-chlorobenzoyl chloride hydrazine 22 2-toluoylhydrazine acetone 3-methylbenzoyl chloride 23 2-nitrobenzoyl- acetone 3-methylbenzoyl chloride hydrazine 24 2-chlorobenzoyl- acetone 3-methylbenzoyl chloride hydrazine ft EXAMPLE NO. 28 Preparation of N'-(l,l-dimethyl-3- Sbutenyl)-N,N'-dibenzoylhydrazine To a gently refluxing solution of allyl magnesium bromide (380 ml of 1 M solution) was added acetone azine (20 g) dissolved in diethyl ether (200 ml). The solution was refluxed for three days. Upon cooling, a saturated solution of ammonium chloride ml) was added. The aqueous layer was separated and washed twice with diethyl ether (200 ml). The combined j ether extracts were dried over anhydrous magnesium S'0 sulfate, filtered and the ether removed at reduced pressure. The product was distilled through a vigreux column at 3.1 torr and collected in a dry ice/acetone I "o cooled receiving flask. The boiling point was 60-650C.

I 15 g of product was collected.

Oxalic acid (16.7 g) was dissolved in a solution of ethanol:diethyl ether (150 ml) and water (3.3 g) was added. To this acid solution was added the hydrazone (13 g) dissolved in diethyl ether (75 ml).

The solution was stirred for 24 hours then filtered.

The solid is washed once with diethyl ether. The filtrate was concentrated and combined with the solid ito afford a 71% yield (17.2 g) of the hydrazine oxalate.

ia, i -i f 48 The 1,l-dimethyl-3-butenylhydrazine oxalate (2 g) was dissolved in toluene and neutralized with aqueous sodium hydroxide. To this solution was added benzoyl chloride (2.8 g) and sodium hydroxide (50% Aq.

solution) (3.2 g) at 25 0 C. The reaction mixture was ,'armed to room temperature and stirred. The mixture was diluted with hexane and filtered to afford an oily product which solidified upon standing. (m.p.

105-112 0

C).

Examples 26 and 27 were made generally in accordance with the procedures for Example 29 above.

The (trimethylsilylmethyl)hydrazine, trifluoroalkyl hydrazine and (2-carbmethoxy-2-propyl)hydrazine were made generally in accordance with the procedures from Noll, Sprier, Daubert, JACS 73, 3867, 1951; Hung, Le; Breton, JOC 46, 5413, 1981; and Organic Synthesis Vol 5, pg. 43, respectively. From these starting materials Examples S* 1-7, 25 and 29-34 were made generally in accordance with the procedure for Example 28 above.

t" 4The reactants shown below in Table III were used to prepare Examples 1-7 and 25-.34.

S*4 TABLE III Ia SEx. Compound of Compound of Compound of No. Formula II Formula III Formula V 1 2,3-dimethyl (1-methyl-2,2,2- 2,4-dichloro benzoylchloride trifluoroethyl) benzoylchloride hydrazine 2 2,3-dimethyl (1-methyl-2,2,2- benzoylchloride trifluoroethyl) benzoylchloride hydrazine 3 2,3-dimethyl (1-methyl-2,2,2- benzoylchloride trifluoroethyl) toluoylchloride hydrazine a '.7 1 1 1 H, Ex. Compound of No. Formula II 4 benzoylchloride 1 0 t t t tl 5 6 4 3 0 3, 4-dichloro benzoylchloride 4-chlorobenzoyl chloride benzoylchloride benzoylchloride 4-toluoylchloride 3-toluoylchloride benzoylchloride 4-ethylbenzoyl chloride 4 -chlorobenzoyl chloride 2-toluoyl chloride 2-nitrobenzoyl chloride benzoyl chloride 4-ethylbenzoyl chloride 49 Compound of Formula III trifluoroethyl) hydrazine 2-trifluoroethyl) hydrazine 2-trifluoroetEhyl) hydrazine 2-trifluoroethyl) hydrazine (1-carbnethoxy-lmethylethyl) hydraz ine l-dirrethyl-3butenyl) hydrazine butenyl) ehydrazin butenyl) hydrazine huyazine in hyrieyslleh) hydrazine hyrineyslllehl hydrazine Compound of Formula V benzoylchloride 3, 4-dichloro benzoylchloride 4- chlorobenzoyl chloride benzoylchloride benzoylchloride 4 -toluoylchloride 3-toluoylchloride benzoylchloride chloride 4 -chlorobenzoyl chloride 2 -toluoyl chloride 2-nitrobenzoyl chloride henzoyl chloride 3, benzoylchloride 4 Ja 50 It will be appreciated by those skilled in the art that compounds of Formula I can be used as precursors for preparing other compounds of Formula I by procedures well known to those skilled in the art.

For example, a suitable compound of Formula I can be reduced, alkylated, substituted, esterified, hydrolyzed or the like.

As previously noted, the compounds of the present invention exhibit excellent insecticidal 1 0 activity and are most active against insects of the S, orders Lepidoptera and Coleoptera.

In general, for the control of insects in S, "agriculture, horticulture and forestry, the compounds S" of the present invention may be used at a dosage corresponding to from about 10 grams to about kilograms of the active substance per hectare and from about 100 grams to about 5 kilograms per hectare of the tit active substance is preferred. The exact amount of V;r: dosage for a given situation can be routinely determined and depends on a variety of factors, for example, the substance used, the kind of insect, the formulation used, the state of the crop infested with the insect and the prevailing weather conditions. The term "insecticidal" as employed in the specification 5 and claims of this application is to be construed as any means which adversely affects the existence or growth of the target insects at any stage in their life cycle. Such means can comprise a complete killing action, eradication, arresting in growth, inhibition, 30 reducing in number, reproductive inhibition (such as ovicidal or chemisterilant) or any combination thereof.

The term "control" or "combat" as employed in the Sspecification and claims of this application is to be construed as meaning "insecticidal" activity or protection of plants from insect damage. By ~lq ~"r 51 t 4 4.

t I 3 4 a o "insecticidally effective amount" is meant that dosage of active substance sufficient to exert insect "control".

The compounds of the present invention, for practical applications, can be utilized in the form of compositions or formulations. Examples of the preparation of compositions and formulations can be found in the American Chemical Society publication "Pesticidal Formulation Research", (1969), Advances in Chemistry Series No. 86, written by Wade Van Valkenburg; and the Marcel Dekker, Inc. publication "Pesticide Formulations", (1973), edited by Wade Van Valkenburg. In these compositions and formulations, the active substance or substances are mixed with conventional inert agronomically acceptable plant compatible and/or pesticidally inert) diluents or extenders such as solid carrier material or liquid carrier material, of the type usable in conventional compositions or formulations. By agronomically acceptable carrier is meant any substance which can be used to dissolve, disperse or diffuse the active ingredient in the composition without impairing the active ingredient's effectiveness and which by itself has no significant detrimetnal effect on the soil, equipment, desirable plants or agronomic environment.

If desired, conventional adjuvants such as surfactant, stabilizers, antifoam agents and antidrift agents may also be added.

Examples of compositions and formulations according to the invention are aqueous solutions and dispersions, oily solutions and oil dispersions, pastes, dusting powders, wettable powders, emulsifiable concentrates, flowables, granules, baits, invert emulsions, aerosol compositions and fumigating candles.

Wettable powders, pastes, flowables and 52 I I

I

ti r I iI Itt I i I 4 4o I 00 440 emulsifiable concentrates are concentrated preparations which are diluted with water before or during use.

Baits are preparations generally comprising a food or other substance attractive to the target pest, that includes at least one lethal or non-lethal toxicant. Lethal toxicants kill the pest upon ingesting the bait while non-lethal toxicants change the behavior, feeding habits and physiology of the pest for the purpose of control.

The invert emulsions are mainly used for air application, where large areas are treated with a comparatively small amount of preparation. The invert emulsion may be prepared in the spraying apparatus shortly before, or even during, the spraying operation by emulsifying water in an oil solution or an oil dispersion of the active substance.

Compositions and formulations are prepared in a known manner, for instance by extending the active compounds with conventional dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g., conventional surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as halogenated hydrocarbons, dichlorodifluoromethane and trifluorochloromethane, as well as butane, propane, nitrogen and carbon dioxide; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, r "2V i 53 especially chlorinated, aromatic hydrocarbons chlorobenzenes, etc.), cycloalkanes cyclohexane, etc.), paraffins petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons methylene chloride, chloroethylenes, etc.), vegetable oils soybean oil, cottonseed oil, corn oil, etc.), alcohols methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof glycol monomethyl ether, etc.), amines ethanolamine, etc.), amides dimethyl formamide, etc.), sulfoxides dimethyl sulfoxide, etc.), acetonitrile, ketones acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, I" isophorone, etc.), and/or water; solid carriers including ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, i( montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates; solid carriers for granules include crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material o i such as sawdust, coconut shells, corn cobs and tobacco stalks. The following may be chiefly considered for use as conventional carrier vehicle assistants: emulsifying agents, such as cationic and/or nonionic and/or anionic emulsifying agents polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolysates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

54 Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

If desired, it is possible to use colorants in compositions and formulations containing compounds of the present invention such as inorganic pigments, for example, iron oxide, titanium oxide and Prussian Blue, 10 and organic dyestuffs, such as alizarin dyestuffs, azo t I dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The active compounds of the present invention S,.1 may be employed alone or in the form of mixtures with one another and/or with such solid/or liquid dispersible carrier vehicles and/or with other known r, Ucompatible active agents, especially plant protection agents, such as other insecticides, arthropodicides, nematicides, fungicides, bactericides, rodenticides, herbicides, fertilizers, growth-regulating agents, synergists, etc., if desired, or in the form of particular dosage preparations for specific application P made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate mixtures in which the active compound is present in an amount substantially between about 0.1% and 99% by weight, and preferably between about 1% and 75% by weight, of the mixture.

Mixtures suitable for direct application or field application generally contemplate those in which the active compound is used in an amount substantially between about 0.0001% and preferably between about A b-s~lt~UI~-i--i- 55 t C StL 115

LI

*I Cr

II

20 252° 0.001% and by weight of the mixture. Thus the present invention contemplates overall formulations and compositions which comprise mixtures of a conventional dispersible carrier such as a dispersible inert finely divided carrier solid, and/or a dispersible carrier liquid such as an inert organic solvent and/or water, preferably including a surface-active effective amount of a carrier vehicle assistant a surface-active agent, such as an emulsifying agent and/or a dispersing agent), and an amount of the active compound generally, between about 0.0001% and about 99% by weight of the composition, preferably between about 0.001% and about 90% by weight of the composition, and more preferably between about 0.01% and about 75% by weight of the composition, which is effective for the purpose in question.

The active compounds can be applied as sprays by methods commonly employed, such as conventional highgallonage hydraulic sprays, low gallonage sprays, ultra-low-volume sprays, airblast spray, aerial sprays, and dusts. If low volume applications are desired, a solution of the compound is usually used. In ultralow-volume applications, a liquid composition containing the active compound is usually applied as a spray mist) by means of atomizing equipment in finely divided form (average particle size of from about 50 to about 100 microns or less) using airplane crop spraying techniques. Typically only a few liters per hectare are needed and often amounts up to about to 1000 g/hectare, preferably about 40 to 600 g/hectare are sufficient. With ultra-low-volume, it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about to about 95% by weight of the active compound.

Furthermore, the present invention contemplates :r "IIICI"CI. 1I__I jl 4"-t~Brui*silU~~lr-L9*r 56 methods of combatting or controlling insects, which comprises contacting insects with an insecticidally effective amount of at least one active compound of the invention alone or together with a diluent or carrier vehicle, in a composition or formulation) as noted above. The term "contacting" as employed in the specification and claims of this application is to be construed as applying to at least one of such insects and the corresponding habitat thereof Ad 0 the locus to be protected, for example, to a growing crop or to an area where a crop is to be grown) the active compound of this invention alone or as a constituent of a composition or formulation. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, dry dressing, moist dressing, wet dressing, slurry dressing, encrusting and the like.

20 It will be realized, of course, that the rrr concentration of the particular active compound utilized in admixture with the carrier vehicle will oc depend upon such factors as the type of equipment aaa, ao.. employed, method of application, area to be treated, types of pests to be controlled and degree of infestation. Therefore, in special cas 3 it is possible to go above or below the aforementioned i concentration ranges.

preparations are produced for example, by taking up the active substance in a solvent and by using the resulting solution, as the case may be in the presence of a binder, to impregnate a granular carrier material, such as porous granules (for example, pumice and attaclay), or chopped tobacco stems or the like.

A granular preparation (frequently termed a

I

IILP LII--~17-i ll~sY 57 "pellet") may alternatively be produced by compressing the active substance together with powdered minerals in the presence of lubricants and binders and by disintegrating and straining the composite to the desired grain size.

Dusts are obtainable by intimately mixing the active substance with an inert solid carrier material in a concentration of from about 1 to about 50% by weight. Examples of suitable solid carrier materials 1,110 are talc, kaolin, pipe clay, diatomaceous earth, 0 dolomite, gypsum, chalk, bentonite, attapulgite and colloidal SiO or mixtures of these and similar substances. Alternatively organic carrier materials such as, for example, ground walnut shells may be used.

Wettable powders and flowables are produced by mixing from about 10 to about 99 parts by weight of a 1, solid inert carrier such, for example, as the tr aforementioned carrier materials with from about 1 to t about 80 parts by weight of the active substance 20 optionally dissolved in a volatile solvent such as too acetone, from about 1 to about 5 parts by weight of a dispersing agent such, for example, as the lignosulfonates or alkylnaphthalene sulfonates known "o for this purpose and preferably also from about 0.5 to about 5 parts by weight of a wetting agent, such as fatty alcohol sulfates, or alkylarylsulfonates of fatty acid condensation products. In the case of flowables, a liquid inert carrier such as water is also included.

To produce emulsifiable concentrates the active compound is dissolved or finely divided in a suitable solvent which preferably is poorly miscible with water, an emulsifier being added to the resulting solution.

Examples of suitable solvents are xylene, toluene, high-boiling aromatic petroleum distillates, for example solvent naphtha, distilled tar oil and mixtures 58 of these liquids. Examples of suitable emulsifiers are alkylphenoxypolyglycol ethers, polyoxyethylene sorbitan esters of fatty acids or polyoxyethylene sorbitol esters of fatty acids. The concentration of the active compound in these emulsifiable concentrates is not restricted within narrow limits and may vary between about 2% and about 50% by weight depending upon toxicant solubility. A suitable liquid highly concentrated primary composition other than an emulsifiable concentrate is a solution of the active substance in a liquid which is readily miscible with water, for example, acetone, to which solution a dispersant and, as the case may be, a wetting agent are added. When such a primary composition is diluted with water shortly before or during the spraying operation an aqueous dispersion of the active substance is I obtained.

i An aerosol preparation according to the invention is obtained in the usual manner by 20 incorporating the active substance or a solution woo *0 thereof in a suitable solvent in a volatile liquid suitable for use as a propellant such, for example, as o° a mixture of chlorine and fluorine derivatives of *ofl methane and ethane.

Fumigating candles or fumigating powders, i.e., preparations which when burning are capable of emitting a pesticidal smoke, are obtained by taking up the active substance in a combustible mixture which may, for example, comprise a sugar or a wood, preferably in 30 the ground form, as a fuel, a substance to sustain combustion such, for example, as ammonium nitrate or potassium chlorate, and furthermore a substance for retarding combustion, for example kaolin, bentonite and/or colloidal silicic acid.

A bait preparation comprises a food or other 59 substance attractive to pests, a carrier, the toxicant and may optionally include other substances commonly used in preparations of this kind, such as, a preservative to inhibit bacterial and fungal growth, a waterproofing agent to prevent disintegration under wet conditions and dyes or colorants as described above.

In addition to the aforementioned ingredients, the preparations according to the invention may also contain other substances commonly used in preparations of this kind.

For example, a lubricant, such as calcium stearate or magnesium stearate, may be added to a wettable powder or to a mixture to be granulated.

Furthermore, there may, for example, be added "adhesives" such as polyvinylalcohol cellulose derivatives or other colloidal materials, such as casein, to improve the adherence of this pesticide to 4U S, the surface to be protected.

4 4 Representative preparation of compositions and 20 formulations including the compounds of the present invention are set forth below as Examples A through I by way of illustration but not limitation.

o Example A 6 Granular Ingredient %/wt.

Toxicant and toxicant impurities 0.25 Trite-. X-305 (binder) 0.25 oxide ethanol) Agsorb 24/48 (diluent) 99.50 (Montmorillonite clay) Preparation: The toxicant and Triton X-305 are Sdissolved into methylene chloride and the mixture is C rr rr ill 60 added to the Agsorb with continuous mixing. The methylene chloride is then allowed to evaporate.

Example B Dust Ingredient %/wt.

Toxicant and toxicant impurities Talc 99.0 t Preparation: Toxicant is dissolved in excess acetone and the mixture is impregnated onto the talc.

t0 The acetone is then permitted to evaporate.

Example C Wettable Powder Ingredient %/wt.

Toxicant and toxicant impurities 31.3 ,15 Duponal WA Dry (wetter) (Sodium lauryl sulfate) Reax 45A (dispersant) (Sodium lignin sulfonate) Barden clay (diluent) 31.7 HiSil 233 (diluent) 30.0 (Sodium silica) S* Preparation: The toxicant, optionally dissolved in a volatile solvent, is absorbed onto the Barden clay and HiSil carriers. The Duponal and Reax are then added and the entire dry mixture blended until homogeneous. The composition is then micronized to a fine particle size.

1- 61

I

St If 4 t 20 1 4 t 4 4 4 I I Example D Emulsifiable Concentrate Ingredient %/wt.

Toxicant and toxicant impurities 15.0 Sponto 232T (emulsifier) (Anionic and nonionic blend of the following surfactants: calcium dodecyl benzene sulfonate; and ethoxylated alkylphenol) Sponto 234T (emulsifier) (Anionic and nonionic blend of the following surfactants: calcium dodecyl benzene sulfonate; and ethoxylated alkylphenol) Cyclohexanone (solvent) 22.5 Tenneco 500-100 (solvent) 52.5 (Aromatic solvent mixture principally comprising xylene, cumene and ethyle benzene having a boiling point range of 143-174°C (290-345 0

F)

Preparation: All ingredients are mixed together with continuous agitation until a homogeneous clear solution is obtained.

Example E Aerosol Ingredient Toxicant and toxicant impurities Freon 12 %/wt.

99.5 Preparation: The components are mixed and packaged under pressure in a suitable container equipped with a release spray valve.

7, 62 Example F.

Fumigating Candle or Fumigating Powder Ingredient %/wt.

Toxicant and toxicant impurities Wood dust 96.0 Starch Preparation: Toxicant, wood dust, and starch are blended together and then molded into a candle o, using a small amount of water to activate the starch.

to Example G Bait Method A Ingredient %/wt.

Toxicant and toxicant impurities 1.00 heat Bran (carrier and attractant) 89.95 Corn Syrup (attractant) 7.00 Corn Oil (attractant) 2.00 Kathon 4200 (preservative) 0.05 too "(2-n-octyl-4-isothiazolin-3-one) Preparation: The corn oil and corn syrup are added to the wheat bran with adequate mixing. The 'toxicant and Kathon are premixed with excess acetone and this solution is added to the wheat bran base with continued mixing. The acetone is then permitted to evaporate.

Method B Ingredient %/wt.

Toxicant and toxicant impurities 0.06 Granulated Sugar (carrier and attractant) 99.94

A

i i r II rr 63 Example H Pellet Same as Example G, Method A, with this addition: the bait composition is formed into 0.64 cm diameter by 0.95 cm long pellets using a suitable die and press apparatus.

Example I Flowable Ingredient %/wt.

Toxicant and toxicant impurities 31.3 Duponal WA Dry (wetter) (Sodium lauryl sulfate) Reax 45A (dispersant) I (Sodium lignin sulfonate) HiSil 233 (diluent) 30.0 (Sodium silica) Kelzan (thickener) (Xanthan gum) Water 31.2 too Preparation: The toxicant is absorbed onto the HiSil carrier. The Duponal and Reax are then added and 1, 9* the entire dry mixture blended until homogeneous. The composition is then micronized to a fine particle size.

The resulting powder is suspended in water and the Kelzan added.

Compositions and formulations according to the present invention may also include known pesticidal compounds. This expands the spectrum of activity of the preparations and may give rise to synergism.

The following known insecticidal, fungicidal and acaricidal compounds are suitable for use in such a combined preparation.

H t i 7. 64 A 40 *2 5 Insecticides such as: Chlorinated hydrocarbons, for example, 2,2-bis(pchiorophonyl) -1,1,1-trichioroethano and hexachloroepoxyoctahydrodimothanonapht.ha lone; Carbamates, for example, N-mothyl-1-naphthylcarbamatos; Dinitrophenols, for example, 2-mothyl-4 ,6-dinitrophenol and 2- (2-butyl) 6-dinitrophienyl-3 ,3-dimethylacrylate; organic phosphorus compounds, such as dimethyl-2methoxy-3-carbonyl-1-methylvinyl phosphate, 0, O-diethiyl-o-p-nitrophenylphosphorothioate; N-monomethylamide of O,O-dimethyldithiophosphorylacetic acid; Diphenylsulfides, for example, p-chlorobenzyl or p-chlorophenyl sulfide and 2,4,4' diphenylsulfide; Diphenylsulfonates, for exml, p-chlorophenylbenzenesulfonate; Methylcarbinols, for example, 4 ,4-dichloro-1-trichloromethylbenzhydrol; Quinoxaline compounds, such as methylquinoxaline dithiocarbonate; Axnidines such as N'-(4-chloro-2-methylphenyl) N,Ndime thylformamidine; Pyrethroids such as Allethrin; Biologicals such as Bacillus thuringiensis preparations; organic tin compounds such as tricyclohexyltin hydroxide; Synergists such as piperonyl butoxide; insect growth regulators such as N-benzoyl-phenyl ureas, for example, diflubenzuron.

Fungicides such as: organic mercury compounds, for example, phenylmercuryacetate and methylmercurycyanoguanide;

A

r I ~rrr~ t .0 40(P15 ff t

SI

A i

"I

v 65 Organic tin compounds, for example, triphenyltin hydroxide and triphenyltin acetate; Alkylenebisdithiocarbamates, for example, zinc ethylenebisthiocarbamate and managanese ethylenebisdithiocarbamate; and 2,4-dinitro-6-(2-octyl-phenylcrotonate), 1-bis(dimethylamino)phosphoryl-3-phenyl-5-amino- 1,2,4-triazole, 6-methylquinoxaline-2,3-dithiocarbonate, 1,4-dithioanthraquinone-2,3-dicarbonitrile, N-trichloromethylthiophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, N-dichlorofluoromethylthio-Nphenyl-N'-dimethylsulfonyldiamide and tetrachloroisophthalonitrile.

Biological Activity It has been found by biological evaluation that compounds according to the present invention have pesticidal activity and are capable of controlling larvae and adult forms of pests, especially insects from the orders Lepidoptera and Coleoptera and most especially insects from the order Lepidoptera. One skilled in the art will know how to determine the activity of a given compound against a given insect and the dosage required to obtain general or selective insecticidal effects. The compounds of the present invention in part affect the normal development of insects, particularly insects from the order Lepidoptera, by directly and/or indirectly influencing the moulting process.

As previously noted, the compounds of the present invention are particularly suitable for controlling plant destructive insects in crops of cultivated plants, such as, but not limited to, cotton,

-I

iii; i i r 66 t l t ~tt I *4 I 94 Ia vegetables, corn and other cereals and the like; forestry, such as, but not limited to, birch, spruce, pine, fir and the like; and ornamental plants, flowers and trees. Compounds of the present invention are also particularly suitable for controlling insects destructive to stored commodities such as seeds and the like; fruit crops, such as, but not limited to fruit and/or citrus trees, raspberry bushes and the like; and turf, such as, but not limited to, lawns, sod and the like.

In evaluating the pesticidal activity of the compounds of this invention, the following test procedures were employed.

A test solution containing 600 parts per million (ppm) was made by dissolving the test compound in a solvent (acetone:methanol, adding water to give an acetone:methanol:water system of 5:5:90 and then a surfactant. A 1:1 mixture of an alkylarylpolyetheralcohol (sold under the trademark Triton X-155) and a modified phthalic glycerol alkyl resin (sold under the trademark Triton B-1956) was utilized at the equivalent of 1 ounce per 100 gal. of test solution as a surfactant.

Initial evaluations were made on one or more of the following pests: Code Symbol Common Name Latin Name SAW Southern Armyworm Spodoptera eridania MBB Mexican Bean Beetle Epilachna varivestis For the foliar oean beetle and armyworm tests, individual bean (Phaseolus limensis var. Woods' Prolific) leaves are placed on moistened pieces of filter paper in Petri dishes. The leaves are then sprayed with the test solution using a rotating 1 I I- i;r 67 c 16 I 66 It

II

SII

t 4 4* turntable and allowed to dry. The dishes are infested with 10 third instar larvae of Southern armyworm or Mexican bean beetle. The dishes are then covered.

The percent mortality for the bean beetle and armyworm evaluations are determined 96 hours after treatment. Evaluations are based on a scale of 0-100 percent in which 0 equals no activity and 100 equals total kill.

The rotating turntable consists of a fixed, continuously operating spray nozzle under which targets are rotated at a fixed speed and distance. If the target is a Petri dish (such as for the armyworm), the distance from the nozzle is 38.1 cm (15 inches).

If the target is a Mason jar, the distance between the ,15 screened lid and the nozzle is 15.24 cm (6 inches) (25.4 cm (10 inches) from the base of the jar to the nozzle). The nozzle is located 8 inches from the rotating shaft. The targets on individual platforms revolve around the shaft at 1 revolution per 20 seconds 20 but only a brief portion of this time occurs in the spray path. Targets pass only once under the nozzle and then are removed to drying hoods.

0 The nozzle used is a 1/4 JCO Spraying Systems (Wheaton, Illinois) air atomizing nozzle equipped with a No. 2850 fluid cap and No. 70 air cap. At the guage pressure of 68.5 x 103 N/m 2 (10 psig) air pressure used and with liquid siphon feed 1.9 1/hr (0.5 gallons per hour) are delivered in a round spray pattern with a 21° spray angle. Targets are misted with spray droplets to 30 the point that the droplets coalesce to form a uniform thin film insufficient to drown test organisms.

All treatments are maintained at 23.9-26,7°C (75-80 0 F) under continuous fluorescent light in a well-ventilated room.

The results of the initial insecticidal evaluations are given in Table IV.

16 904 0 4 0 .9 0 f b-*"^vI~g '-*sI e nncc~*i,-r

L

1 68 TABLE IV Initial Biological Evaluations Foliar Application Test Species

I,

a 4 t 4a4 4, 4 '1'0 *0 4 *4 *4 I 44 4 4

I.

i 4 444 15 00 404 44 4 0 04 *0 4 440 o 0 4 0444 40 44 4 4 Example No.

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 21

SAW

100 100 100 100 0 100 100 100 100 100 100 100 100 100 50 100 100 100 100

MB

0 0 0 0 0 0 1' 4 69 TABLE IV (contd.) Initial Biological Evaluations Foliar Application -Test Species 1 2* 49 Example No.

22 23 24 26 27 28 29 30 31 32 33 34

SAW

100 100 100 100 100 100 0 100 100 0

MBB

.4 444 4444 4 0444 44 04 .4 0 4 The following words are trademarks which may be registered: Triton, Agsorb, Duponal, Reax, HiSil, Sponto, Tenneco, Kathon and KeJlzan.

S t tI 0 0 a 0

Claims (14)

1. An insecticidally active compound which is a substituted hydrazine having the formula: 10 LI iLL I Ii L It Ii I I I I (4 IL LI I ('II II. I. I IIS @4 @0 0 *0 20 *4I wherein X and X' are the same or different 0, S or NR; R is hydrogen; (C 1 -C 6 )alkyl; (C 1 -C 6 )alkoxy- (C 1 -C 6 alkyl having independently the stated number of carbon atoms in each alkyl group; (C 1 -C 6 )alkylthio- (C 1 -C 6 )alkyl having independently the stated number of carbon atoms in each alkyl group; (C 2 -C 6 )alkenyl; (C 2 -C 6 )alkynyl; or phen-(C 1 -C 4 )alkyl where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C 1 -C 4 alkyl, halo- (C 1 C 4 )alkyl (C 1 -C 4 alkoxy, halo- (C 1 -C 4 )alkoxy, carboxy, (C 1 -C 4 )alkoxy-carbonyl, (C 1 -C 4 )aikanoyloxy or NZZ'; Rand R 3are the same or different hydrogen or i(C 1 -C 4 )alkyl; R s(C 1 -C 4 )alkyl substituted with 1 to 4 fluoro; straight chain (C 2 -C 4 )alkenyl; carboxyl; (C 1 -C 3 )alkoxy-carbonyl; cyano; cyano substituted (C 1 -C 4 )alkyl, tri(C 1 -C 4 alkylsilyl having independently the stated number of carbon atoms in each alkyl group; or tri (C 1 -C 2 )alkylsilylmethyl having .bat, S .bat. I. 4 I 72 independently the stated number of carbon atoms in each alkyl group; provided that R2 3 4 and R are both alkyl when R is carboxyl or alkoxycarbonyl; and A and B are the same or different unsubstituted or substituted naphthyl where the substituents can be from one to three of the same or different halo; nitro; (C 1 -C 4 alkoxy; (C1-C 4 )alkyl or NZZ'; unsubstituted or substituted phenyl where the substituents can be from one to five of the same or different halo; nitroso; nitro; cyano; hydroxy; (Cl -C 6 )alkyl; halo-(C 1 -C 6 alkyl; cyano-(C 1 -C 6 )alkyl; hydroxy-(C 1 -C 6 I. t1 61 6 alkyl; (C 1 -C 6 )alkoxy; halo-(C 1 -C 6 )alkoxy; alkyl; (C 1 -C )alkoxy-(C 1 -C 6 )alkyl having independently the stated number of carbon atoms in evch alkyl group; (C 1 -C 6 )alkoxy- (C1-C6)alkoxy having independently the ,ao0 stated number of carbon atoms in each alkyl group; -ORSR' group; -OCO2R group; 2CO2H group; (C 1 -C 6 )alkanoyloxy-(C 1 -C 6 )alkyl ~having independently the stated number of carbon atoms in each alkyl group; (C 2 -C 6 )alkenyl optionally substituted with halo, cyano, (C 1 -C 4 )alkyl, halo-(C 1 -C 4 alkoxy, (C 1 -C 4 )alkylthio or (C 1 -C 4 )alkoxy; (C 1 -C 4 alkadienyl; (C 2 -C 6 )alkenyloxy; (C 2 -C 6 )alkenyl-carbonyl; (C 2 -C 6 alkenyloxy-carbonyloxy; (C 2 -C 6 )alkynyl optionally substituted with halo, cyano, nitro, hydroxy, (C 1 -C 4 )alkoxy, halo- (C 1 -C 4 )alkyl, (C 1 -C 4 )alkylthio or (C1-C alkyl; carboxy; -RCO 2 R' group; -COR; -COH; 'I -73 hal- 1 C) alkyl-carbonyl; -CO fl group; (C 1 -C 6 )haloalkoxy-carbonyl; -OCOR group; -ORCQ 2 RI group; amino amino substituted with hydroxy, (C -C )alkoxy or (C 1 -C 4 )alkylthio; -CONZZ' group; (C 2 C 6 alkenyl-carbonylamino; hydroxy- (C 1 -C 6 alkylamino-carbonyl; -OCONZZ' group; -NZCOZ' group; NZCO Zgroup; th'ocga~a isothiocyanato; (G 4 b4iA,,GA (C 1 -C 6 )alkylthio; halo-(C 1 -C 6 )alkylthio; -S(O)Z group; -SO 2 Z group; -OSO 2 R group; -OS 2H rou; SO2 NZIgroup; -CSR group; -CSII group; -SCOR group; -SCOH group; -NSCSZ' group; unsubstituted or substituted phenyl having one to three of the same or different halo, cyano, nitro, hydroxy, (Ci- C 4 )alkyl, halo-(C 1 -C 4 )alkyl, (C 1 -C 4 alkoxy, carboxy, (C -C alkoxy-carbonyl, (C-C alkanoyloxy, amino, (C 1 alkylamino or di(C 1 -C )alkylamino having independently the stated number of carbon atoms in each alkyl group; phenoxy where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, 419tt (C 1 -C 4 alkyl, halo- (C 1 -C 4 alkyl, (C 1 -C 4 ttotit alkoxy, carboxy, (C 1 -C 4 )alkyl-carbonyl, (C -C alkanoyloxy, amino, (C alkylamino or di(C l-C 4 )alkylamino having independently the stated number of carbon atoms in each alkyl group; benzoyl where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C -C )alkyl, halo-(C -C )alkyl, (C -C 4 kr0 -74 alkoxy, carboxy, (C 1 -C 4 )alkoxy-carbonyl, (C I- C 4 a2kanoyloxy, amino, (C 1 -C 4 alkyl- amino or di(C 1 -C 4 )alkyJlamino having independently the stated number of carbon atoms in each alkyl group; benzoyloxy- (C 1 -C 6 alkyl; phenylthio-(CI- c 6 alkyl where the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C C )alkyl, halo- (C -C )alkyl, (C C 4 alkoxy, carboxy, (C C )alkoxy-carbonyl, (C 1 -C 4 )-alkanoyloxy, amino, (C 1 c 4 )alkyl- independently the stated number of carbon amn ord( 1 C)2kyaiohvn atoms in each alkyl group; group where is hydroxy, (C -C )alkyl, I1t (C 1 -C )alkoxy, amino phenylamino, -COR, -COH or benzoyl; (C 2 -C 6 )oxiranyl; acetyithiosemi- carbazone; pyrrolyl; oxazolyl, unsubstituted or substituted with one or two methyl groups; or when two adjacent positions on the phenyl ring are substituted with alkoxy groups, these 6 0 groups may be joined to form, together with the carbon atoms to which they are attached, a 5 or 6 membered dioxolano or iC44 dioxano heterocyclic ring; unsubstituted or substituted (C 1 -C 10 )alkyl having one to four of the same or different '130 halo, cyano, nitro, hydroxy, (C 1 -C 4 )alkoxy, halo-(C -C )alkoxy, carboxy, (C -C 4 alkoxy-carbonyl, (C 1 -C 4 )alkanoyloxy, phenyl or -NZZ'; 75 unsubstitutod or substituted (C 3 -Co )cyclo- alkyl or unsubstituted or substituted (C 3 -C 8 )cyclo(C 1 -C 4 )alkyl having one to four of the same or different halo, cyano, nitro, hydroxy, (C 1 -C 4 )alkyl, halo-(C 1 -C 4 alkyl, (C 1 -C 4 )alkoxy, halo-(C 1 -C 4 )alkoxy, carboxy, (C 1 -C 4 )alkanoyl, (C 1 -C 4 alkoxy-carbonyl, (C0 1 -C 4 )alktanoyloxy or -NZZ'; unsubstituted or substituted (C 2 -C 8 )alkenyl or unsubstituted or substituted(C2 8) alkadienyl having as substituent(s) a furyl, thienyl or pyridyl or one to four of the same or different halo, cyano, nitro, hydroxy, (C 1 C 4 )alkyl, (C 3 C 6 )cycloalkyl, halo- (C 1 -C 4 )alkyl, (C 1 C 4 )alkoxy, halo- (C 1 -C 4 )alkoxy, carboxy, (C 1 -C 4 alkoxy-carbonyl, (C 1 -C 4 )alkanoyloxy or -NZZI' unsubstituted or substituted (C 3 C 8 )CYClo- alkenyl or unsubstituted or substituted (C 3 -C 8 )cycloalkadienyl having as substituent(s) one to four of the same or different halo, cyano, nitro, hydroxy, (C 1 -C 4 )alkyl, halo-(C 1 -C 4 )alkyl, (C 1 C 4 alkoxy, halo- (C 1 -C 4 )akoxy, carboxy, (C 1 -C 4 )alkoxy-carbonyl, (C 1 -C 4 )alkanoyloxy or -NZZ'; unsubstituted or substituted (C 2 -C 8 )alkynyl having as substituent(s) one to four of the same or different halo, cyano, nitro, hydroxy, (C 1 -c 4 )alkyl, halo-(C 1 -c 4 )alkyl, C 84* 4 44 20 4 4* SI 4 4 4 444 *4*4 '4 44 *4 4 4 4 L. j -76- (C 1 -C 4 )alkoxy, halo- (C 1 -C 4 alkoxy, carboxy, (C -C alkoxy-carbonyl, (C-C alkanoyloxy, phenyl. or -NZZ'; phenalky. having one to four carbon atoms in the alkyl. group and wherein the alkyl. group is unsubstituted or substituted with one to three of the same or different halo, cyano, hydroxy, (C 1 -C 4 )alkoxy, (C 1 C 4 alkoxy-carbonyl or -NZZ', and the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C C )alkyl, halo- (C C )alkyl, cyano-(C -C )alkyl, (C C 4 alkoxy, halo-( 1 -C 4 )alkoxy, carboxy, (C C )alkoxy-carbonyl, (C C )alkanoyloxy, (C -C alkenyl, halo- (C -C )alkenyl, (C -C )alkynyl or -NZZ'; phenalkenyl having two to six carbon atoms 9 titin the alkenyl group and the alkenyl group t '110is unsubstituted or substituted with one to three of the same or different halo, cyano, I off hydroxy, (C 1 '_C 4 )alkyl, halo-(C 1 -C 4 )alkyl, (C 1 C 4 )alkoxy, halo- (Cl-C 4 alkoxy, (Cl-C 4 alkoxy-carbony! or -NZZ', and the phenyl ring is unsubstituted or substituted with one to three of the same or different halo, cyano, nitro, hydroxy, (C 1 -C )alkyl, halo- (C 1 -C 4 )alkyl, (C 1 -C 4 alkoxy, halo-(C 1 -C 4 alkoxy, carboxy, (C -C alkoxy-carbonyl, (C 1 -C )alkanoyloxy or -NZZ'; unsubstituted or substituted five-membered heterocycle selected from furyl, thienyl, triazolyl, pyrrolyl, isopyrrolyl, 77 pyrazolyl, isoimidazolyl, thiazolyl, isothiazolyl, oxazolyl and isooxazolyl where the subatituents can be from one to three of the same or different halo; nitro; hydroxy; (C 1 -C 6 alkyl; (C 1 -C 6 )alkoxy; carboxy; (C 1 -C 6 Yalkoxy-carbonyl; -RCO 2 11 group; RCO 2 RI group; -CONZZ' group; amino -NZCOZI group; (C 1 -C 6 )alkylthio; or unsubstituted or substituted phenyl having one to three of the same or different halo, nitro, (C 1 -C 6 )alkyl, halo- (C 1 -C 6 alkyl, (C 1 -C 6 alkoxy, halo- (C 1 -C 6 alkoxy, carboxy, (C -C )alkoxy-carbonyl or amino (-NZZI) or t t unsubstituted or substituted six-membered heterocycle having one, two, three or four nitrogen atoms and two to five nuclear carbon atoms where the substituents can be from one to three of the same or different nitro; hydroxy; (C 1 -C 6 )ak (C -C )alkoxy; carboxy; (C -C 6 alkoxy-carbonyl; -RC 2 H- group; -RCO 2 RI group; -CONZZ' group; amino -NZCOZ' group; (C 1 -C 6 )alkylthio; or unsubstituted or substituted phenyl having t a one to three of the same or different halo, nitro, (C -C )alkyl, halo- (C _C )alkyl, (C 1 -C 6 )alkoxy, halo- (C 1 -C 6 alkoxy, carboxy, (C -C )alkoxy-carbonyl or amino (-NZZ jwhere R and R' are (C 1 -C 6 )alkyl; Z and Zare hydrogen or (C 1 -C 4 )alkyl; "amino", means NZZ'; or an agronomically acceptable salt thereof. -78-

2. A compound according to claim 1 wherein X and X' are 0 or S; Ris hydrogen; (C -C )alkyl.; (C -C )alkoxy- (C 1 -C 4 )alkyl having independently the stated number of carbon atoms in each alkyl group; methyithiomethyl; (C 2 alkenyl; (C 2 alkynyl; or phen-(C 1 -C 2 )alkyl where the phenyl ring is unsubstitutei or substituted with one or two halo, nitro, (C -C 4 )alkyl or (C 1-C 4 )alkoxy; Rand R 3 are the same or different hydrogen or 4 (C 1 -C 3 alkyl; R i (C-C3)alylsubstituted with one to four fluoro; straight chain (C -C )alkenyl; carboxyl; (C 1 -C 2 alkoxy-carbonyl; cyano; *cyano substituted (C 1 -C 3 )alkyl; tri(C 1 -C29- alkylsilyl having independently the stated number of carbon atoms in each alkyl group; or tri (C 1 -C 2 alkylsilylmethyl having independently the stated number of carbon he atoms in each alkyl group; and V 9 A and B are the same or different unsubstituted naphthyl; unsubstituted or substituted phenyl where the substituents can be from one to three It4 'A *0 of the same or different halo; nitro; a cyano; (C 1 -C 4 )alkyl; halo-(C 1 -C 4 )alkyl; cyano- (C -C alkyl; (C -C alkoxy; (C alkoxy-(C -C )alkyl having independently the stated number of carbon atoms in each- alkyl group; -COZ; carboxy; (C 1 -C 4 alkoxy-carbonyl; (C 1 -C 4 )alkanoyloxy; (C 2 -C 6 )alkenyl; (C 2 -C 6 )alkynyl; amino thiocyanato; (C 1 -C 4 )alkylthio; -79- -CSR; -CSH; unsubstituted or substituted phenyl having one to two of the same or different halo, nitro, (C 1 -C 4 )alkyl, (CI- C 4 alkoxy, carboxy, -NZZ'; phenoxy where the phenyl ring is unsubstituted or substituted with one or two of the same or different halo, nitro, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, carboxy, -NZZ'; or when two adjacent positions on the phenyl ring are substituted with alkoxy groups, these groups may be joined to form, together with the carbon atoms to which they are attached, a 5- or 6-membered dioxolano or dioxano heterocyclic ring; unsubstituted or substituted (C 1 -C 8 al _C )aky 'a having one to three of the same or different halo, cyano, (C C alkoxy, t~ 44 phenyl, (C 1 -C 4 )alkoxy-carbonyl or halo- (C 1 -C 4 )alkoxy; unsubstituted or substituted (C C )cyclo- 3 6d alkyl or unsubstituted or substituted I (C 3 C 6 )cycloalkyl(C -c 4 )alkyl 'having one or two of the same or different halo, (C 1 -C 4 alkyl, halo-(C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, "4425 (C 1 -C )alkanoyl or halo- (C-C alkoxy; 1- 4 unsubstituted or substituted (C 2 -C )alkenyl having as substituent(s) a furyl or one to three of the same or different(C_ halo-(C -C )alkyl, (C -C )alkoxy or halo-(C -C )alkoxy; 301 80 unsubstituted or substituted (C 3 -C 6 )cyclo- alkeny. having as substituents one or two of the same or different halo, (C 1 C 4 alkyl, halo-(C 1 -C 4 )alkyl, (CI- C 4 )alkoxy or halo-(C 1 C 4 )alkoxy; unsubstituted or phenyl substituted alkynyl; phenalkyl having one or two carbon atoms in the alkyl group and the alkyl group is *0 0 10 unsubstituted or substituted with one or *9two of the same or different halo, (C c 4 alkyl, halo-(C -C )alkyl, (C C )alkoxy or 0 0 hal-(i-c4 alkxyand the phenyl ring is unsubstituted or substituted with one or two of the same or different halo, cyano, 9:8: (C 1 -C 4 )alkyl, halo- (C 1 -C 4 alkyl, (C 1 -C 4 000 alkoxy or halo-(C 1 -C 4 )alkoxy; 0 0*0phenalkenyl having two or three carbon atoms in the alkenyl group and the alkenyl group is unsubstituted or substituted with 00*0halo, (C -C )alkyl, halo-(C C )alkyl, th 0 4 1 -C 4 )alkoxy or halo-(C 1 -C 4 )alkoxyanth phenyl ring is unsubstituted or substituted with one or two of the same or different halo, cyano, (C 1 -C 4 )alkyl, halo-(C 1 -C 4 alkyl, (C -C )alkoxy or halo-(C -C )alkoxy; unsubstituted or substituted five-membered heterocycle selected from furyl, thienyl, triazolyl, pyrrolyl, and oxazolyl where the substituents can be one or two of the same or different halo; nitro; (C -C )alkyl; 71 4 81 (C 1 C 4 )alkoxy; -NZZ t or unsubstituted or substituted phenyl having one or two of the same or different halo, nitro, (C 1 -C 4 alkyl, halo-(CI- C 4 )alkyl, (C 1 -C 4 )alkoxy, halo-(C 1 -C 4 alkoxy, carboxy or -NZZI; or unsubstituted or substituted six-membered heterocycle having one or two nitrogen atoms and 4 to 5 nuclear carbon atoms where q to the substituents can be one or two of the 1 C to same or different halo; nitro; (C-C) alkyl; (C C )alkoxy; thio-(C 1 -C )alkoxy; -NZZ'; or unsubstituted or substituted rV, phenyl having one or two of the same or different halo, nitro, (C 1 C 4 )alkyl, halo- i(C -C alkyl, (C -C alkoxy, halo- (C C)- alkoxy, carboxy or -NZZ'; t where R and R' are (C -C )alkyl; Z and Z' are hydrogen or (C -C )alkyl.

3. A compound according to claim 2 wherein X and X' are 0or S; oR is hydrogen; (C 1 -C 4 )alkyl; (C 1 -C 4 )alkoxy- (C 1 -C 4 )alkyl having independently the stated number of carbon atoms in each alkyl group; (C 2 -C 5 )alkenyl; (C 2 -C 5 )alkynyl; or benzyl where the phenyl ring is unsubstituted or substituted with one halo, nitro, (C 1 -C 4 )alkyl or (C 1 -C 4 )alkoxy; 2 3 R and R are the same or diffe~rent hydrogen or is(C -C )alkyl; R 4 is(C 1 -C 3 )alkyl substituted with 1 to 4 fluoro; straight chain (C -C )alkenyl; methoxycarbonyl; cyano; cyano substituted I 82 (C -C 2 )alkyl; tri(C 1 -C 2 )alkylsilyl having independently the stated number of carbon atoms in each alkyl group; or tri(C 1 -C2)- alkylsilylmethyl having independently the stated number of carbon atoms in each alkyl group; provided that R 2 and R 3 are both alkyl when R 4 is methoxycarbonyl; and 0. A and B are the same or different 'o unsubstituted naphthyl; 't unsubstituted or substituted phenyl having 4t one to three of the same or different halo; nitro; cyano; (C 1 -C 4 )alkyl; halo-(C 1 -C 4 alkyl; cyano-(C 1 -C 4 )alkyl; (C -C 4 )alkoxy; (C 1 -C 4 )alkoxy-(C 1 -C 4 )alkyl having •1 ,5 independently the stated number of carbon atoms in each alkyl group; -COZ; (C -C 4 alkoxy-carbonyl; (C 1 -C 4 )alkanoyloxy; I* thiocyanato; -NZZ'; (C 1 -C 4 )alkylthio; -CSZ; -CS 2 Z; unsubstituted or substituted phenyl having one or two of the same or o different halo, nitro, (C 1 -C )alkyl, (C -C 4 )alkoxy, carboxy, -NZZ'; or phenoxy where the phenyl ring is unsubstituted or substituted with one or two of the same or different halo, nitro, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, carboxy, -NZZ' or when two adjacent positions on the phenyl ring are substituted with alkoxy groups, these Sgroups may be joined to form, together with the carbon atoms to which they are attached, a 5- or 6-membered dioxolano or dioxano heterocyclic ring; i, *--erA 83 '4 r t 4, 'tlU C t 4 C t 1 unsubstituted or substituted (C 1 -C 6 alkyl havinq one to three of the same or different halo, cyano, nitro, carboxy, (C 1 -C 4 )alkoxy, phenyl, (C 1 C 4 alkoxy-carbonyl or halo- (C1-C 4 )alkoxy; unsubstituted or substituted (C 3 C 6 )cyclo- alkyl or unsubstituted or substituted (C 3 C 6 )cycloalkyl (C 1 -C 4 alkyl, where the substituent is halo, (C 1 C 4 )alkyl, (C 1 -C 4 )alkanoyl, (C 1 -C 4 )alkoxy or halo- (C 1 -C 4 )alkoxy; unsubstituted or substituted (C 2 -C 6 alkenyl having one or two of the same or different halo, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy or halo- (C 1 -C 4 )alkoxy; unsubstituted or substituted (C 4 -C 6 )cyclo- alkenyl where the substituent is halo (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy or halo- (C 1 C 4 )alkoxy; unsubstituted or phenyl substituted alkynyl; benzyl where the phenyl ring is unsubstituted or substituted with one or two of the same or di -'ent halo, methyl or ethyl; unsubstituted or substituted five-membered heterocycle selected from furyl, thienyl, pyrrolyl and oxazolyl where the substituents can be one or two of the same or different halo, nitro, (C 1 -C 4 )alkyl or 4* 4 4*64 tt **nr, 4 1< 'I I i 84 (C 1 -C 4 )alkoxy; or unsubstituted or substituted six-membered heterocycle having one or two nitrogen atoms and four to five nuclear carbon atoms where the substituents can be one or two of the same or different halo, nitro, (CI-C 4 alkyl, (C 1 -C 4 )alkoxy or thio-(C 1 -C 4 )alkoxy; where Z and Z' are hydrogen or S- (C 1 -C 4 )alkyl.

4. A compound according to claim 3 wherein X and X' are 0; R is hydrogen; methyl; ethyl; (C 1 -C2)alkoxy- (C 1 -C 2 )alkyl having independently the stated number of carbon atoms in each alkyl group (C 2 -C 5 )alkenyl; (C 2 -C 5 )alkynyl; or benzyl where the phenyl ring is unsubstituted or substituted with halo; 3 R and R are the same or different hydrogen or (C 1 -C 2 )alkyl; R £0 R is (C -C 2 )alkyl substituted with 1 to 4 *OOO* fluoro; straight chain (C 2 -C 4 )alkenyl; cyano; cyano substituted (C 1 -C2)alkyl; tri(C 1 -C 2 )alkylsilyl having independently the stated number of carbon atoms in each alkyl group; or tri(C 1 -C 2 alkylbilylmethyl S. having independently the stated number of carbon atoms in each alkyl group; and A and B are the same or different phenyl or substituted phenyl where the substituents can be from one to three of the same or Si different halo, nitro, (C 1 -C 4 alkyl, (C 1 -C 4 )alkoxy or halo-(C 1 -C 4 )alkyl; :A ^ift l 85 unsubstituted or substituted (C 1 -C 6 )alkyl having as substituent(s) one to two of the same or different halo, phenyl or cyano; unsubstituted (C 4 -C 6 )cycloalky; unsubstituted or substituted (C 2 -C 6 )alkenyl having as substituent(s) one to ithree of the same or different halo or (C 1 -C 4 )alkyl; 00 unsubstituted (C 4 cycloalkenyl; I phenalkyl having one or two carbon atoms in 10 the alkyl group and the phenyl ring is unsubstituted or substituted with one or two of the same or different halo, (C 1 -C 4 a alkyl or (C 1 -C )alkoxy; 001 4 unsubstituted or substituted pyridyl or 2,5-pyrazinyl where the substituent can be halo, nitro, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy or (C 1 -C 4 )thioalkoxy; or 0L*0 00 unsubstituted furyl or thienyl or an unsubstituted or substituted pyrrolyl where the substituent can be (C 1 -C 4 )alkyl. A compound according to claim 4 wherein X and X' are 0; 1 R is hydrogen; methyl; methoxymethyl; (C 2 -C 4 alkenyl; (C 2 -C 5 )alkynyl; benzyl; or 4- halobenzyl; 2 3 R and R are the same or different hydrogen, methyl or ethyl; i 86 R 4 is trifluoromethyl; 2,2,2-trifluoroethyl; straight chain (C 2 -C 4 )alkenyl; cyano; cyanomethyl; tri(C 1 -C 2 )alkylsilyl having independently the stated number of carbon atoms in each alkyl group; or trimethyl- silylmethyl; and A and B are the same or different phenyl or substituted phenyl where the substituents can be one, two or three of the same or S"o different chloro, fluoro, bromo, iodo, nitro, methyl, ethyl, methoxy or trifluoro- methyl; (C 2 -C 3 substituted alkenyl having one to three of the same or different chloro, bromo, methyl or ethyl; cyclohexenyl; r t benzyl; unsubstituted or substituted pyridyl or 2,5-pyrazinyl where the substituent can be .0 halo, methyl, ethyl or methoxy; or unsubstituted furyl or thienyl or an unsubstituted or substituted pyrrolyl where the substituent can be ethyl or methyl.

6. A compound according to claim 2 wherein 25 X and X' are 0; R is hydrogen or methyl; R 2 and R 3 are hydrogen or (C 1 -C 3 )alkyl; R 4 is trifluoromethyl, 2,2,2-trifluoroethyl, cyano, cyanomethyl, straight chain (C 2 -C 4 sI 87 alkenyl, carboxyl, methoxycarbonyl, tri(C 1 -C 2 )alkylsilyl having independently the stated number of carbon atoms in each alkyl group or tri(C1-C 2 )alkylsilylmethyl having independently the stated number of carbon atoms ir each alkyl group; and A and B are the same or different thienyl or unsubstituted phenyl or substituted phenyl where the substituents can be one to three of the same or different chloro, fluoro, Snitro, methyl, ethyl or propyl.

7. A compound according to claim 6 wherein X and X' are 0; R is hydrogen; 2 3 R and R are hydrogen, methyl or ethyl; 4 R is trifluoromethyl, cyano, allyl, methoxycarbonyl, or trimethylsilyl; and A and B are the same or different unsubstituted or substituted phenyl having one or two of the same or different chloro, fluoro, nitro, methyl and ethyl; or unsubstituted thienyl. 4

8. A compound according to claim 7 where X and X' are 0; R is hydrogen; and 2 3 4 R is hydrogen, R is methyl, R is trifluoro- methyl, and A and B are the same or different unsubstituted or substituted phenyl where the substituents can be one or two of the same or different chloro, methyl or nitro; or i 3 2 R and R are the same or different methyl or 4 ethyl, R is cyano, and A and B are the

11. v t t I Ij r Ir-; 88 same or different unssbstituted or substituted phenyl where the substituents can be one or two of the same or different chloro, fluoro, methyl, ethyl or nitro; or R 2 and R 3 are methyl, R 4 is allyl, and A and B are the same or different unsubstituted or methyl substituted phenyl; or 2 3 4 R and R are hydrogen, R is trimethylsilyl, and A and B are the same or different substituted phenyl where the substituents S" can be one or two of the same or different methyl, ethyl or nitro. 9. A compound according to claim 8 wherein X and X' are 0; R is hydrogen; and R 2 is hydrogen, R is methyl, R 4 is trifluoro- methyl, and A and B are unsubstituted phenyl, or A is 2,3-dimethylphenyl and B is 2,4-dichlorophenyl, 3,5-dimethylphenyl or 2-nitro-5-methylphenyl; or 2 3 4 R and R are methyl, R is allyl, and A and B are both unsubstituted phenyl or 3-methyl- phenyl; or 2 3 4 R and R are hydrogen, R is trimethylsilyl, and A is 4-ethylphenyl and B is methylphenyl, or A and B are both 2-methyl- phenyl or 2-nitrophenyl. S 1 0. A compound according to claim 8 wherein X and X' are 0; R is hydrogen; 2 3 R and R are methyl; 4 R is cyano; and 1 i F- I: 89 A and B are the same or different unsubstituted or substituted phenyl where the substituents can be one or two of the same or different chloro, fluoro, methyl, ethyl or nitro. 11. An insecticidal composition comprising an agronomically acceptable diluent or carrier and an t ,insecticidal compound according to any one of the preceding claims. t q

12. A composition according to claim 11 containing said insecticidal compound in an amount of from 0.0001 to 99% by weight of the composition.

13. A composition according to claim 12 wherein the amount of said insecticidal compound is from 0.01 to 99% by weight of the composition. So 14. A method of controlling insects which comprises contacting said insects with an insecticidally effective amount of a compound according to any one of claims 1 to 10 optionally in a composition according to a, a 20 any one of claims 11 to 13. A method according to claim 14 wherein said compound or composition is applied to insects or to growing plants or an area in which plants are to be grown at from 10 grams to 10 kilograms per hectare of 4~ 25 the compound.

16. A method according to claim 15 wherein the application rate is from 100 grams to 5 kilograms per hectare of the compound. ;a I 90

17. A method according to any of claims 14 to 16 wherein said insects are from the order of Lepidoptera or Coleoptera.

18. A compound according to claim 1, an insecticidal composition comprising a said compound, in a method of use thereof, substantially as hereinbefore described .a with reference to the Examples.

19. The steps, featurcz, eempesitiens and eempe referred to or indicated in the specifi on and/or claims of this applicatio- i vidually or s collectivel any and all combinations of any two a ro rcf caid ctopc or foaturoe. r Dated this 30th day of July 1987 ROHM AND HAAS COMPANY By its Patent Attorneys DAVIES COLLISON oLAa a 4"