ZA200301173B - Disubstituted benzenes as insecticides. - Google Patents

Description

1,4-DISUBSTITUTED BENZENES AS INSECTICIDES

This is a nonprovisional of Application Numbers 60/229,701 and ‘ 60/277,203 filed on September 1, 2000 and March 20,2001, respectively.

FIELD OF THE INVENTION

The present invention relates to methods for controlling insects. In particular, it relates to control by the application of certain novel substituted benzenes.

BACKGROUND OF THE INVENTION

The present invention relates to methods for controlling insects. In particular, it relates to control by the application of certain novel substituted benzenes. More particularly, it pertains to 1,4-disubstituted benzene compounds and compositions containing the same which are useful for controlling insects in agricultural crops. Even more particularly, this invention relates 1,4-disubstituted benzene compounds and compositions and their uses as insecticides against a variety of insects, including larvae, such as tobacco budworm.

SUMMARY OF THE INVENTION

It has now been found that certain substituted benzenes, particularly 1,4- disubstituted benzenes, and their agriculturally acceptable salts, are effective as insecticides. These benzenes may be represented by the following formula I: 3 2B

Wa 5p8 :

I in which:

A is hydrogen; aryl; alkylheterocyclyl; alkenylaminopolycyclyl; . alkenylaminoheterocyclyl; alkylaminopolycyclyl; carbonylaminopolycyclyl; and

Formula II, where Formula III is

Cs ~(CH,),-U-R? mx where nisOorl;

U is -CH,-, -O-CH,-, oxygen, sulfur, sulfonyl, alkyl, oxyalkyloxy, alkenylamino, cabonylamino and -NR?®, where R’ is hydrogen, hydroxy, alkyl, haloalkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

R? is aryl; alkylpolycyclyl; heterocyclyl; polycyclyl; 1-R?; 1-R*; and 2-R®, where:

R%is ; : (J .

Rr where J, L, and W are independently hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, aminoalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, aryloxy, and heterocyclyl;

R'is 8 1 X : . 7 = NZ 6 NP 5Y 4 rR?

where X, Y, and Z are independently hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, aryloxy, and heterocyclyl;

B and D are independently hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyaminoalkyl, 2-(Formula XII), 3-(Formula III), 5-(Formula ITI), and 6-(Formula III), where Formula IIL n, U, R%, R’, R*, R%, J,L, W, X,Y, and Z are as defined above;

R is -T-(CH,)-R’, NR®(R") or heterocyclyl;

T is -CH,-, carbonyl, oxygen, nitrogen, and sulfur; mis 0,1,2,3,o0r4;

R'is -NR®)(R’); alkyl; aryl; -C(O)N(R")(R"); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; -N(O)R)R'); -P(O)R“HR"); PORDHR®); alkylamino, where the cyclohexyl, aryl and heterocyclyl moieties may be optionally substituted with halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, alkylamino; where

RS R7, R%, R%, RZ, R®, R! and R' are independently hydrogen, alkyl, alkoxy, alkylthio, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and -(CH,),-NR'®)(R"), where pislor2; and

RS and RY are independently hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl.

The present invention is also directed to a composition containing an insecticidally effective amount of a compound of Formula I in admixture with at least one agriculturally acceptable extender or adjuvant, wherein A,B,D,and R are as defined above.

In addition, the present invention relates to a method of controlling insects that comprises applying to locus on crops, such as cotton, vegetables, fruits, where control is desired an insecticidally effective amount of a the above composition.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect of the present invention, certain substituted benzenes, particularly 1,4-disubstituted benzenes, and the agriculturally acceptable salts thereof, have now been found to be effective as insecticides. These benzenes may be represented by the following formula I: 3,_28B 5 D 6

I : in which;

A is selected from the group consisting of hydrogen; aryl; alkylheterocyclyl,; alkenylaminopolycyclyl; alkenylaminoheterocyclyl; alkylaminopolycyclyl; carbonylaminopolycyclyl; where the aryl, heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and Formula III, where Formula III is -(CH,),-U-R?

Ii wherein nisOorl;

U is selected from the group consisting of -CH,-, -O-CH,~, oxygen, sulfur, : sulfonyl, alkyl, oxyalkyloxy, alkenylamino, cabonylamino and -NR’, where

R’ is selected from the group consisting of hydrogen, hydroxy, alkyl, haloalkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

R? is selected from aryl; alkylpolycyclyl; heterocyclyl; polycyclyl; where the aryl, heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, y haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; 1-R®; 1-R*; and 2-R?, wherein: } R}is 5

J

(J

L

R® where J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, aminoalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, aryloxy, and heterocyclyl, where the aryl and heterocyclyl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;

R'is 8 1X

NG) z 6 3 5Y 4

R where X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, ] carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, - alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, aryloxy, and heterocyclyl, where the phenyl, aryl, and heterocyclyl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;

B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, . alkoxy, haloalkoxy, alkoxyaminoalkyl, 2-(Formula III), 3-(Formula III), 5- (Formula III), and 6-(Formula III), wherein Formula IIL, n, U, R2, R®, RY, R%, J, L, ) W, X,Y, and Z are as defined above;

Ris-T-(CH,),-R’, -NR*(R") or heterocyclyl, where the heterocyclyl moiety may be optionally substituted with halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, alkylaza, arylcarbonyl, benzyl, allyl, propargyl, alkylamino; where the aryl moiety may be optionally substituted with halogen, hydroxy, alkyl, 10 . haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl

T is selected from the group consisting of -CH,-, carbonyl, oxygen, nitrogen, and sulfur; mis0,1,2,3,or4;

R! is selected from the group consisting of -N(R®*)(R®); alkyl; aryl; -

C(O)NR®)(R™); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; -

NO)R™MR"); POYRYR™); -P(SHR™)R™); alkylamino, where the cycloalkyl, aryl and heterocyclyl moieties may be optionally substituted with halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, alkylamino; where "20 RR’, R%, R%, RZ, RY”, R" and RY are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkylthio, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and - (CH), NR')R"), where pisior2;

R'¢ and R" are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl.

Agriculturally acceptable salts of the 1,4-disubstituted benzenes include, - but are not limited to, for example, the salts of hydrochloric acid, sulfonic acid, ethanesulfonic acid, trifluoroacetic acid, methylbenzenesulfonic acid, phosphoric acid, gluconic, acid, and pamoic acid.

Some preferred compounds are those in which

A is selected from the group consisting of hydrogen; alkylaminopolycyclyl; carbonylaminopolycyclyl; where the polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and Formula ITI, where Formula III is -(CH,),-U-R?

II : wherein nisOorl;

U is selected from the group consisting of -CH,-, oxygen, and -NR®, where R® is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

R? is selected from aryl, alkylpolycyclyl; heterocyclyl; polycyclyl; where the aryl, heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and 1-R?, wherein R? is:

J

(re

L

R® where J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, and aryloxy, where the aryl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;

B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyaminoalkyl;

Ris-T-(CHy,-R!, where

T is selected from the group consisting of -CH,-, oxygen, nitrogen, and sulfur; mis1,2,3,or4;

R! is -NRHR®), where

R® and R® are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and -(CH,),-NR)(R""), where pislor2;

R!'¢ and RY are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and the corresponding agriculturally acceptable salts thereof.

Some particularly preferred compounds are those in which

A is hydrogen or Formula III, where Formula III is -(CH,),-U-R?

I wherein nisOor 1;

U is selected from the group consisting of -CH,-, oxygen, and -NR?, where R’ is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

R? is selected from heterocyclyl; polycyclyl; where the heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy,

haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and 1-R?, wherein R® is:

J

(>

L

Rr? where J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, and aryloxy, where the aryl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;

B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyaminoalky];

T is oxygen or nitrogen mis 2, 3, or 4,

R'is -NR*(R’), where

R® and R? are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and ~(CH,),-N(R'*)(R"), where pislor2;

R'% and RY are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl.

Some more particularly preferred compounds are those in which A is

Formula III, where Formula III is -(CH,),-U-R? 0x wherein nis 1; . U is oxygen or -NR’, where R® is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl; : R? is 1-R?, wherein R® is:

J

(J

L

RS where J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, and aryloxy, where the aryl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;

B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyaminoalkyl;

T is oxygen or nitrogen : mis 2;

R'is -NR*(R®), where

R? and R® are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and -(CH,),-N(R')(R""), where : pislor?2;

R' and RY are independently selected from the group : consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; ] Some yet even more particularly preferred compounds are those in which

U is oxygen or -NR’, where R’ is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

R?is 1-R?, wherein R? is: . J (3

L

R3 where J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, and aryloxy, where the aryl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;

B and D are independently selected from hydrogen, halogen, and alkoxy;

T is oxygen;

R! is -N(R*(R®); where

R’and R’ are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and -(CH,),-N(R'*)(R"), where pisior2;

R'* and R" are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalky]l;

Some still yet even more particularly preferred compounds are those in which U is oxygen or -NR’, where R’ is hydrogen; R? is 1-R®, wherein R? is: :

J . (SD

L

R® where J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy,

: nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyi, . alkoxycarbonyl, haloalkoxycarbonyl, aryl, and aryloxy, where the aryl moieties may be optionally substituted with ’ halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;

B and D are hydrogen;

R'is -NR®)(R®); where R®and R” are alkyl.

In another aspect, the present invention is directed to certain novel 1,4- "disubstituted benzenes per se and agriculturally acceptable salts thereof falling within the scope of formula I above. These compounds include, for example, the following novel 1,4-disubstituted benzenes: 3 2B ) 5p 6

I in which:

A is Formula III, where Formula III is -(CH,),-U-R?

II wherein nis 1; :

U is oxygen;

R? is 1-R®; wherein:

R®is ; J : [Jw

L

R’

where J is 2-chloro or 2-fluoro, L is 3-chloro or 5-fluoro, and W is : hydrogen or 4-chloro.

B and D are hydrogen;

R is -T-(CH,),-R', where

T is oxygen; mis 2;

R'is -N(R®*)(R®), where R® and R® are ethyl.

Additional preferred compounds are those in which

A is selected from the group consisting of hydrogen; alkylaminopolycyclyl; and carbonylaminopolycyclyl; where the polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and Formula III, where Formula III is -(CH,),-U-R?

II wherein nisQorl;

U is selected from the group consisting of -CH,-, oxygen, alkyl, oxyalkyloxy, alkenylamino, cabonylamino and -NR’, where R’ is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

R? is selected from aryl; alkylpolycyclyl; heterocyclyl; polycyclyl; where the aryl, heterocyclyl and polycyclyl moieties are optionally substituted with ) one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, - alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and 1-R*, wherein R* is

8 1 X

NG) z 6 3 5Y 4 rR! where X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy:;

Band D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, and alkoxyaminoalkyl;

R is -T-(CH,),-R" or heterocyclyl; where the heterocyclyl moiety may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl, propargyl;

T is selected from the group consisting of -CH,-, oxygen, nitrogen, and sulfur; mis, 2,3, or4;

R' is selected from the group consisting of NRYR); alkyl; aryl; -

C(ONR®)R™); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; and -

N(O)R)R"), where the aryl and heterocyclyl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl; where

R%, R’, RZ R®, RM and RY are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and - (CH,),-NR*)R'"), where pislor2;

R'® and R' are independently selected from the group consisting of . hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and the corresponding agriculturally acceptable salts thereof.

Additional particularly preferred compounds are those in which Aishydrogen or Formula III, where Formula XII is ~(CH,),-U-R? 101 wherein nisOorl;

U is selected from the group consisting of -CH,-, oxygen, and -NR®, where R’ is selected from the group consisting of hydrogen, hydroxy, alkyl, : sulfonylalkyl, cabonylamino, and carbonylalkyl;

R? is selected from alkylpolycyclyl; heterocyclyl; polycyelyl; where the . 15 heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, : haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and 1-R*, wherein R* is 8 1 X z 6X 3 5Y 4 rR where X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;

B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, . alkoxy, haloalkoxy, and alkoxyaminoalkyl;

R is -T-(CH,),-R! or heterocyclyl; where ) the heterocyclyl moiety may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl, propargyl;

T is selected from the group consisting of oxygen, nitrogen, and sulfur; . mis1,2,3,or4;

R'is sclectcd from the group consisting of -N(R®)(R?); alkyl; aryl; -

C(O)NR'»(R"); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; and -

N(O)R™)R"), where the aryl and heterocyclyl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl; where

R%, BR’, R', R®, R™ and R* are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and - (CH,), NR )(R"), where pislor2;

R'® and R" are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and the corresponding agriculturally acceptable salts thereof.

Additional more particularly preferred compounds are those in which

A is Formula III, where Formula ITI is oo -(CH,),-U-R? mn

Co wherein nisl;

U is oxygen or -NR’, where R’ is selected from the group consisting of . hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

R?is 1-R*, wherein R? is 8 1 X

LL z 6 3 5Y 4 rR? where X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;

B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, and alkoxyaminoalkyl,

R is -T-(CH,),-R' or heterocyclyl; where the heterocyclyl moiety may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl, propargyl;

T is oxygen or nitrogen; mis1,2,3,or4;

R! is selected from the group consisting of -N(R®)(R®); alkyl; aryl; -

C(ONR'*)(R"); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; and -

N(O)R™)}(R"), where the ary! and heterocyclyl moieties may be optionally ] 25 substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl; where

R’, R’, R™ R® R" and R” are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl,

alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and - : (CH), NR)R'), where pislor2; : R' and RY are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and the corresponding agriculturally acceptable salts thereof.

Additional yet even more particularly preferred compounds are those in which

A is Formula III, where Formula III is -(CH,),-U-R? mI wherein

U is oxygen or -NR’, where R’ is hydrogen;

R?is 1-R®, wherein R* is 8 1X

LL

Zz 6 3 5Y 4 : rR? where X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, ’ alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted : with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;

B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, and alkoxyaminoalkyl,

R is -T-(CH,),-R" or heterocyclyl; where . the heterocyclyl moiety may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl, propargyl;

T is oxygen or nitrogen; mis 2;

R! is -NR¥(R’) or N(O)YR"YR), where R®, R®, R*, and R¥ are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and - (CH,),-NR*)R"), where : pislor2;

R'® and R" are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and the corresponding agriculturally acceptable salts thereof.

Additional still yet even more particularly preferred compounds are those in which

A is Formula III, where Formula III is -(CH,),-U-R? 111 wherein

U is O or -NR’, where R’ is hydrogen;

R? is selected from 1-R%, wherein R* is . 8 1 X

LL

Z

. 6 3 5Y 4

R*

where X, Y, and Z are independently selected from the group . consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, ) alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;

B and D are hydrogen; the heterocyclyl is a piperazinyl moiety, where the the piperazinyl moiety may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl, propargyl;

T is oxygen;

R'is -NRHR?) or -N(O)R™)(R'), where R%, R®, R, and R* are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, and carbonylamino; and the corresponding agriculturally acceptable salts thereof.

Further preferred compounds are those in which

A is Formula III, where Formula ITI is -(CH,),-U-R? mm wherein

Uis 0;

R? is selected from 1-R*, wherein R* is 8 1 X . RY

NX 3 5Y 4

R*

where X,Y, and Z are independently selected from the group , consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, ] alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted : with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;

R'is -NRY)R?) or -N(O)R™)(R'®), where R®, R®, R and R* are alkyl; and the corresponding agriculturally acceptable saits thereof.

In addition to those compounds set forth above, the present invention is also directed to certain novel 1,4-disubstituted benzenes per se and agriculturally acceptable salts thereof falling within the scope of formula I above. These compounds include, for example, the following novel 1,4-disubstituted benzenes: 3 2B {5 5p 6 :

I in which:

A is Formula III, where Formula III is -(CH,),-U-R? 11} wherein nisl;

U is oxygen; ’ R? is 1-R*; wherein:

R'is

8 1 X

LL, z 6 3 . 5Y 4

Rr? where X is 4-chloro or 5-chloro, Y is 6-chloro or 6-bromo, and Z is hydrogen;

Band D are hydrogen;

R is -T-(CH,),-R' or a piperazinyl moiety; where the piperazinyl moiety is substituted with 4-ethyl;

T is oxygen; mis 2;

R'is -NRYHR’) or -N(O)R")(R"), where R®, R%, R" and R" are ethyl; and the agriculturally acceptable salts thereof, preferably the hydrochloride salts.

In another aspect, the present invention is directed to a composition containing an insecticidally effective amount of a compound of Formula I, including, without limitation, those compounds disclosed above as being preferred, particularly preferred, and per se novel, in admixture with at least one agriculturally acceptable extender or adjuvant, wherein A, B, D, and R are as defined above.

In another aspect, the present invention relates to a method of controlling insects that comprises applying to locus on crops, such as cotton, vegetables, fruits, where control is desired an insecticidally effective amount of the above compositions.

Certain intermediates or the present invention are novel. These include compounds of formula XII: 3,2 5 6

XII wherein:

X Ais -(CH,),-U-R? wherein : .nisQorl;

U is -C(0)-, -CH,-, oxygen, or -NR’, where R® is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

R? is selected from hydrogen, halo, hydroxy, and 1-R*, wherein:

R'is 8 1 X

LL, z 6 3 5Y 4

Rr? where X,Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;

Ris -T-(CH,),-R!, where

T is selected from the group consisting of oxygen, nitrogen, and sulfur; mis 0, 1,2,3,0r4;

R' is hydrogen, halo, alkyl, or -N(R®)(R®); where R® and R® are ] independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and - (CH) -NR®R™), where pislor2;

R'® and R" are independently selected from the group . consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl. ; Some preferred intermediates are those in which nis 1; U is oxygen; R? is 1-R* wherein:

R'is 8 1 X

LL

4 6 3 5Y 4

R* where X,Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;

T is oxygen or sulfur; mis 2; and

R' is halo. 20 . Some particularly preferred intermediates are those in which nis 1; U is -

CH,-; R? is 1-R*, wherein:

R*is ) 8 1 X

LL

. Zz 6 3 5Y 4

R'

where X, Y, and Z are independently selected from the group . consisting of hydrogen, halogen, cyano, nitro, amino, azido, © carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, baloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;

T is oxygen; m is 0; and

R! is hydrogen or alkyl.

Additional preferred intermediates are those in which n is 0; U is -C(O) or -

CH,-; R? is hydrogen, halo or hydroxy; T is oxygen; m is 2; and R} is NERY)RY), where R® and R’ are alkyl.

Additional novel intermediates are compounds of formula UU:

B

D

E3cE

Y uu where X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy; T is selected from the group consisting of oxygen, nitrogen, and sulfur; and R" is alkyl.

For the purposes of this invention, as regards to the above substituents, the following definitions apply:

The terms “alkyl”and “alkoxy”, alone or as part of a larger moiety, include , chains of 1 to 14 carbon atoms, preferably straight or branched alkyls of 1 to 6 carbon atoms; while “halogen” or “halo”, alone or as part of a larger moiety, : includes chlorine, bromine, fluorine, and iodine atoms. The terms “alkenyl” or “alkynyl”, used alone or as part of a larger moiety, includes straight or branched chains of at least two carbon atoms containing at least one carbon-carbon double or triple bond, preferably upto 12 carbon atoms, more preferably, up to ten carbon atoms, most preferably up to seven c carbon atoms. The term “cycloalkyl” includes rings of three to twelve carbon atoms, preferably rings of three to six carbon atoms. The terms “haloalkyl” and “haloalkoxy”, alone or as part of a larger moiety, include straight or branched chain alkyls of 1 to 14 carbon atoms, preferably lower straight or branched chain alkyls of 1 to 6 carbon atoms, wherein one or more hydrogen atoms have been replaced with halogen atoms, as, for example, trifluoromethyl or 2,2,2-trifluoroethoxy, respectively. “Aryl” referstoan aromatic ring structure, including fused rings, having 5 to 10 carbon atoms. “Heterocyclyl” refers to an aromatic ring structure, including fused rings, having at least one nitrogen, sulfur or oxygen atom. “Amino” refers to compounds of nitrogen that may be considered derived from ammonia and includes primary, secondary and tertiary amines wherein one or more of the hydrogen atoms is : replaced with alkyl groups. “THF” refers to tetrahydrofuran, “DMF” refers to

N,N-dimethylformamide, “DPAD” refers to 1,1'-(azodicarbonyl)dipiperidine, and "A.T." refers to ambient temperature.

The compounds of the present invention were prepared by methods generally known to those skilled in the art. Many of the compounds of the present invention in which R' is naphthyl were prepared in the manner shown in Schema 1.

In Schema 1, a 4-hydroxy-benzaldehyde (SM1) was reacted with the appropriately substituted alkyl chloride hydrochloride salt (SM2) in a solvent, for example, DMF : or THF, at 0°C to ambient temperature in the presence of a base, for example, potassium carbonate, to yield the appropriately substituted alkoxy benzaldehyde (BB). The appropriately substituted benzaldehyde (BB) was then reduced in a solvent, for example methanol, with a reducing agent, for example, lithium . aluminum hydride, sodium borohydride, or triacetoxyborohydride, to yield the appropriately substituted phenyl alkoxy alcohol (CC). The appropriately : substituted phenyl alkoxy alcohol (CC) can also be prepared by reacting the appropriately substituted alkyl chloride hydrochloride salt (SM2) with either the appropriately substituted acid (SM3) or phenyl alcohol (SM4) in a solvent in the presence of a reducing agent as set forth above. The appropriately substituted phenyl alkoxy alcohol (CC) can then be reacted with either p-toluene sulfonyl chloride (SM5) and a base, for example triethylamine, in a solvent to form the appropriately substituted phenyl alkylthio- or alkoxysulfonyl toluene (DD) or sulfonyl chloride in a solvent to form the appropriately substituted phenylalkylthio or phenylalkoxy chloride hydrochloride (EE).

If necessary, the naphthyl ring can be prepared at this time. In general, the naphthyl ring was prepared via the formation of the appropriate naphthol. The preparation of the naphthol begins by reacting: 1) the appropriately substituted benzaldehyde (SM6) with either sodium hydride and 3- : (triphenylphosphino)propanoate hydrochloride in THF and N-N-dimethylsulfoxide (DMF) or with succinic acid, disodium salt and acetic anhydride to form the appropriately substituted phenylbutenoic acid (FF); 2) the appropriately substituted phenyl iodide (SM7) with but-3-ynol, a base, for example, triethylamine, copper iodide and a palladium phosphine complex to yield the appropriately substituted phenylbutynol (GG); 3) the appropriately substituted phenylcarbonylpropanoic acid (SMS) with zinc and mercury (II) chloride in water to form the appropriately substituted phenylbutanoic acid (HH), which can also be preprepared by hydrogenating the appropriately substituted phenylbutenoic acid (FF) or } phenylbutynol (GG) in alcohol with palladium on carbon followed by treatment with chromium oxide and sulfuric acid; 4) the appropriately substituted 2- . (diethylaminocarbonyl)benzene (SM9) with n-butyllithium followed by prop-2- enylbromide and a dimethylthio-copper chloride complex to yield the appropriately substituted 2-(diethylaminocarbonyl)-3-prop-2-enylbenzene (JJ); or 5) the appropriately substituted benzene (SM10) with oxolan-2-one and aluminium : chloride at elevated temperature to form the appropriately substituted trihydronaphthalen-1-one (KK). The trihydronaphthalen-1-one (KK) can also be : prepared by reacting the appropriately substituted phenylbutanoic acid (HH) with an acid, for example polyphosphoric acid, or reacting the appropriately substituted 2-(diethylaminocarbonyl)-3-prop-2-enylbenzene (JJ) with methyllithium. The appropriately substituted trihydronaphthalen-1-one (KK) is then reacted with bromine in a solvent, for example methylene chloride, to form the the appropriately substituted 2-bromo-trihydronaphthalen-1-one (LL). The appropriately substituted 2-bromo-trihydronaphthalen-1-one (LL) is then reduced with a reducing agent and lithtumbromide in a solvent, for example, DMF, in the manner described above to form the appropriately substituted naphthol (MM), which is commercially availabe when (MM) is 4-chloronaphthol. The appropriately substiuted naphthol (MM) was then reacted with either the appropriately substituted benzaldehyde (BB), alcohol (CC), toluene (DD), or hydrochloride (EE) to form the targeted 1- substitutedalkylthio or alkoxy-4-((substituted naphth-1-yl)oxyalkyl)benzene (I), for example, (2-(4-(((4-chloronaphthyl)methoxy)methyl)phenoxy)ethyl)diethylamine.

Additional substituents can be added to the naphthol ring by reacting a 6- aminonaphth-1-ol (SM11) with toluene sulfonyl chloride in the manner disclosed above to yield the 6-amino-1-(methylphenylsulfonyloxy)naphthalene (NN). The 6- amino-1-(methylphenylsulfonyloxy)naphthalene (NN) was then reacted with t- butyl nitrite in a solvent, for example at 0 °C followed by a copper (II) halide, for example, copper (II) chloride, to yield the appropriate 6-halo-1- (methylphenylsulfonyloxy)naphthalene (PP). The 6-amino-1- (methylphenylsulfonyloxy)naphthalene (NN) was also reacted with an excess of a copper (II) halide, for example, copper (II) chloride, in a solvent followed by t- butylnitrite in the manner disclosed above to form the appropriate 5,6-dihalo-1- : (methylphenylsulfonyloxy)naphthalene (QQ). The appropriately substituted naphthalene (QQ) or (PP) can then reacted with a base, for example, potassium hydroxide, and an alcohol, for example, ethanol, in a mixture of a solvent, for example, THF, and water to yield the appropriately substituted naphthol (RR), for . example 5,6-dichloronaphthol. When the naphthol was a 5,6-dihalonaphthol (RR) it was reacted with either the appropriately substituted benzaldehyde (BB), alcohol ) (CC), toluene (DD), or hydrochloride (EE) and a borane-pyridine complex under acidic conditions, or a base, for example, sodium hydride or triethylamine, in a solvent, for example DMF, or a phosphine complex, for example n- butylphosphine, and DPAD in a solvent, for example, THF, to form the targeted 1- substitutedalkylthio or alkoxy-4-((5,6-substituted naphth-1-yl)oxyalkyl)benzene (Ia), for example, (2-(4-((5,6- dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine.

A halo substituent, for example chloro, can be added to the 4-postion of naphthol ring at this time by reacting the appropriately substituted naphthol (MM) or (RR) with a sulfuryl halide, for example, sulfuryl chloride, in a solvent to yield the appropriately substituted 4-halonaphthol (SS). The appropriately substituted 4- halonaphthol (SS) can be reacted either the appropriately substituted benzaldehyde (BB), alcohol (CC), toluene (DD), or hydrochloride (EE) in the manner described above to form the targeted 1-substitutedalkylthio or alkoxy-4-((5,6-substituted naphth-1-yl)oxyalkyl)benzene (Ib), for example, (2-(4-((4,6- dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine.

As depicted in Schema 2, compounds of the present invention wherein U is nitrogen and n is 1 were prepared by reacting the appropriately substituted benzaldehyde (BB) with the appropriately substituted 1-aminonaphthalene (SM12), for example, 1-amino-4-chloronaphthalene, under acidic conditions to form the appropriately substituted 1-aza-1-naphthyl-2-phenylethene (TT), which was then reduced with a reducing agent in the manner disclosed above to yield the targeted targeted 1-substituted -4-((substituted naphth-1-yl)aminoalkyl)benzene (IV), for example, (2-(4-(((4-chloronaphthyl)amino)methyl)phenoxy)- ethyl)diethylamine.

As depicted in Schema 3, compounds of the present invention wherein U is 3 -CH,- and n is 1 were prepared by reacting the appropriately substituted 1- aminonaphthalene (SM12) with the appropriately substituted 4-methylthio-, 4- : methoxy-, or 4-methylamino-1-vinylbenzene (SM13) with t-butylnitrite, in a solvent, for example, acetonitrile, in the presence of palladium acetate to form the appropriately substituted 2-(4-methylthio-, 4-methoxy-, or 4- methylaminophenyl)vinylnaphthalene (UU). The vinylnaphthalene was then hydrogenated in a solvent, for example, ethanol, with a palladium on carbon to form the appropriately substituted 2-(4-methylthio-, 4-methoxy-, or 4- methylaminophenyl)ethylnaphthalene (WW). The ethylnaphthalene (WW) was then reacted in solvent, for example methylene chloride, with boron tribromide to form the appropriately substituted 2-(4-thio-, 4-hydroxy-, or 4- aminophenyl)ethylnaphthalene (XX). The ethylnaphthalene (XX) was in turn reacted with the appropriately substituted alkyl chloride hydrochloride salt (SM2) and an excess of a base, for example, potassium carbonate, in solvent, for example,

DMF, to form the targeted 1-substituted -4-((substituted naphth-1-yl)ethyl)benzene (V), for example, (2-(4-(((4-chloronaphthyl)amino)methyl)phenoxy)- : ethyl)diethylamine. :

Schema 4 depicts another route in which the compounds of the present invention may be prepared. In Schema 4, the appropriately substituted benzaldehyde (SM3) is reacted with a haloalkylbromide, for example, 1-bromo-2- chloromoethane, to yield the appropriately substituted 4-haloalkoxybenzaldehdye (YY), which in turn is reduced with a reducing agent in an alcohol, for example methanol, in the manner described above to form the appropriately substituted 4- haloalkoxyphenylmethan-1-ol (ZZ). The phenylmethan-1-ol (ZZ) was then : reacted at 0 °C to ambient temperature with the appropriately substituted naphthol or phenol (SM14), a phosphine complex , and DPAD in a solvent in the manner described above to yield the corresponding halo-1-(4-substituted naphthyl- or 4- substituted phenyl)oxy)methyl)phenoxy)alkane (AAA), for example, 2-chloro-1- (4-((4-chloronaphthyloxy)methyl)phenoxy)ethane. The alkane (AAA) was then reacted with the appropriate substituent, for example, cis-2,6-dimethylpiperidine, . and a base in acetonitrile to form the corresponding, 1-(subtituted alkoxy)-4-((4- substituted naphthyl or phenyl)oxy)methyl)benzene (VI), for example 1-(2~(2,6- dimethylpiperidyl)ethoxy)-4-((4-chloronaphthyloxy)methyl)benzene. At this point, the benzene (VI) can optionally be reacted with 3-chloroperoxybenzoic acid in chloroform at 0 C to form the corresponding 2-(4-substituted naphthyl or phenyl)oxy)methyl)phenoxy)alkyl)alkanone (VII), for example, amino(2-(4-((5,6- dichloronaphthyloxy)methyl)phenoxy)ethyl)diethyl-1-one

Schema 5 illustrates yet another route for preparing the compounds of the present invention wherein R' is a disubstituted amino. In schema 5, the appropriately substituted (4-hydroxyphenyl)methan-1-ol (SM4) was reacted with a bromomethylisocyanate and a reducing agent, for example potassium carbonate, in a solvent, for example, DMF, in the manner disclosed above to form the corresponding (4-(cyanomethoxy)phenyl)methan-1-ol (BBB). The methan-1-ol (BBB) was then reacted with sulfinyl chloride in a solvent, for example, chloroform, at 0 °C to form the corresponding 4-(cyanomethoxy)-1- (chloromethyl)benzene (CCC), which was in turn reacted with the appropriately substituted naphthol or phenol (SM14) and a reducing agent, for example, potassium carbonate, in a solvent, for example DMF, in the manner described above to yield the corresponding 1-(((4-substituted naphthyl- or 4-substituted phenylJoxy)methyl)-4-(cyanomethoxy)benzene (DDD). The 4- (cyanomethoxy)benzene (DDD) was reacted with borane in a solvent, for example,

THF, at 0 °C to form the appropriately substituted 1-(((4-substituted naphthyl- or 4-substituted phenyl)oxy)methyl)-4-(aminomethoxy)benzene (EEE). The 4- (aminomethoxy)benzene (EEE) was in turn reacted with the appropriate oxoalkyl chloride, for example, acetyl chloride, in a solvent, for example, pyridine or THF, at 0 °C to yield the corresponding 1-(((4-substituted naphthyl- or 4-substituted phenyDoxy)methyl)-4-(oxoalkylaminomethoxy)benzene (FFF). The 4- (oxoalkylaminomethoxy)benzene (FFF) was then reacted with borane in a solvent in the manner described above to yield the targeted 1-(((4-substituted naphthyl- or

4-substituted phenyl)oxy)methyl)-4-(atkylaminomethoxy)benzene (VIII). At this . point, additional moieties can be optionally added to the amino group by reacting the 4-(alkylaminomethoxy)benzene (VIII) with the appropriate substituted alkyl, ’ alkoxy, or alkoxyalkyl halide and a base, for example, triethylamine, to yield the target 1-(((4-substituted naphthyl- or 4-substituted phenyl)oxy)methyl)-4- (disubstituted amino)methoxy)benzene (IX).

Schema 1

B where TisO B 1.(CH,),-Cl ase

HT cHo + RECH) Cl — er RI(CH),-T CHO 0 Hydrochloride 0°C - AT.

D SM2 D sM1 BB

B flhere T ig S B :

H-T COH 1 gy, ReducingAgent pi cpy (CH,),-U-H - Solvent n

D D

SM3 CC where T isOorS

B where T and U are O and Uis O

Reducing Agent

HT — CH), -U-H + Mememtam (CH). SMm2 Solvent

D

SM4

Reducing Agent

BB Solvent 0°C- AT.

B

0 fn 1. - E cc + Cl—S Base RI-(CH,),~T (CH), Y fl Solvent 0=8=0 0] D

SM5 DD Q

B

SOC, R'-(CH,),T (CH,),-U-CI

Solvent

D

Hydrochloride

EE

Schema 1 (continued) } o

INaH + mr NA : En DMSO/THF _ - SUNT -_— x — or 0 0 0 Na FF $Mé6 ONa Ac,0 0 = / oH = OH

AL = bs _————————

Cul/PdCl,(PPh,), X sM7 Base GG

[0] ° SL ECL xX 0 fo) HH

SMS Pd/C/Alcohol/H. or

FF or GG 1) PIC / Alcohol / H, 2)Cr,0y/Acid

Q Q x ISHS 1) nBuLi 8 NC _—

NS 2) BrCH,CH=CH, \

CuCl-SMe,

SM9 ==

JJ

0 0 + fo) AlCl, ¥2 JENN ¢ JE SN

SM10 wm KK sis} 3 MeLi fo) . Br

Br,

KK —— MM = xf

Solvent

LL

. OH

Reducing Agent also commercially available

LL — TEE a x 20 where X is 4-Cl

LiBr . Solvent

MM

Schema 1 (continued)

Borane-pyridine/Acid : or B

Base/Solvent/ 0 °C i. . R

BB,CC,DD,orEE + MM — > RACH » Cty UisO

Phospine complex/DPAD D where

Solvent 0°C-AT. X ) 0

S oH o) of SC + 4 B = Z NH, 0 Solvent x ZF “NH,

SM11 NN

Q

1. t-BuONO/Solvent/0°C S 2. CuX,/5-7°C 00

Yo

X

PP

[0]

FiY , 1. 6Cu(X)Y/Solvent/A.T. 5 2. +-BuONO/0°C 0 where X=Y = Halo C,

Y

QQ

OH

1 .

PP or QQ Base, Alcoho CI) where Y is H or Halo

Solvent, H,0 X

Y

RR

Schema 1 (continued) where X = Y = halo . Borane-pyridine/Acid or B

Base/Solvent/ 0 °C

BB,CC,DD,orEE + RR — fr —— > r=) —eny wh

Phospine Complex/DPAD D

Solvent 0°C-A.T.

X

Y

OH Ia where Y is H in RR

S0,Z, oe x where X can be attac

MMorRR —(—7 ——.— > the 6-positon

Solvent where Z is halo Zz

SS

Borane-pyridine/Acid or B

Base/Solvent/ 0 °C 1 _

BB,CC,DD,orEE + 88 — = RACH 1 cu

Phospine Comlex/DPAD D

Solvent xX 0°C-A.T.

Ib z 5 .

Schema 2

B z NH, Acid 1.(CH,) <)—~

Cl R hat H, nT

BB + Bex Alcohol g oN

D

Y ” xX i SM12

Y

TT

B

TT Reducing Agent RI-(CH,)T— — N

D AN 4 z PN

Y

: Iv

Schema 3

B

8 AT PS

Vy. Pd(OAc), D

SM12 + nS +BuONO 2 > 4

D Solvent

SM13 Y

UU

B am ~T /

Pd/C D

UU — Alcohol ~~ z X

Y ww

B a a

BBr, D x

Solvent z

Y

XX

} B

J Base RICH)

Solvent

D

9G

Y

Vv

Schema 4 where T is O and B

Q is Halo

SM3 + Q-(CH,) -Br __ Reducing Agent _ Q-(CH,),-T CHO

SM13 Solvent 0°C-A.T. D

YY

B

Reducing Agent Q-(CH,)_-T ——— 2/m

YY Alcohol OH 0°C- AT. D

YA A

B

RZ-OH + zz Fhospine Complex/DPAD _ Q-(CH,),-T olvent O-R?

SM14 0°C- AT. B where R? is substituted or AAA unsubstituted naphthyl or phenyl

B

Base R-(CH,).T

I —_—— m

AAA + RAH een : OR?

A D

VI

B

CHCI O=R!-(CH,) + CICH,COH ———a (CH,).F

VI 613 0°C NR?

D

A211

Schema 5 where T and U are O andmandn are 1 B

Reducing Agent CN(CH,) A

SM4 + NC—(CH,)—Br Soly ont (CH) T (CHp),-U-

AT. o

BBB

B

SOCl1

BBB — >» CN-(CH)),-T (CHy),-Cl

Sglvent

D

CCC

B

Reducing Agent sMi4 + CCC inion bi ab ave, )—emon

D

DDD

B

Borane pode ,. HH. N-(CH,) - _O-R2

DDD 5 glvent N-(CH,),, +). OK

D

EEE

B where R8 is alkyl

EEE O=R8-Cl hi —(CHy),T (CH,),-O-R2 —_——

Solvent O=R? 5

FFF

B erp Borane (cy, x (CHy), OR?

T Solvent © fs 0°C D vila x )

N—~ (CH) T CH,),-O-R?

G66 + RQ — RY ’ Re where Q is halo and R?® D is alkyl alkoxy, or IX alkoxyalkyl

The present invention is now described in more detail by reference to the following examples, but it should be understood that the invention is not construed as being limited thereto.

EXAMPLE 1

This example illustrates one protocol for the preparation of (2-(4-((5,6- ’ dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine (Compound 223).

Step A (6-aminonapthyl)((4-methylphenyl)sulfonyl)oxy

A stirred solution of 5.0 grams (0.031 mole) of 6-amino-1-naphthol {available from TCI America, Portland, OR) and 6.1 grams (0.032 mole) of p- toluenesulfonyl chloride (available from Aldrich Chemical Company, Milwaukee,

WI) in 225 mL of methylene chloride (available from J. T. Baker Inc.,

Phillipsburg, NJ) was cooled in an ice bath, and 5.3 grams (0.038 mole) of triethylamine was added dropwise. The reaction mixture was then allowed to warm to ambient temperature where it stirred for about 18 hours. After this time, the reaction mixture was washed with three 75 mL portions of water, dried with sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 9.1 grams of title compound. The NMR spectrum was consistent with the proposed structure.

StepB (5,6-dichloronapthyl)((4-methylphenyl)sulfonyl)oxy

Under a nitrogen atmosphere, 2.0 grams (0.0064 mole) of (6- aminonapthyl)((4-methylphenyl)sulfonyl)oxy was taken up in 6 mL of acetonitrile (available from EM Sciences, Gibbstown, NJ). The mixture was stirred at ambient temperature for ten minutes and then 5.1 grams (0.038 mole) of copper (II) chloride was added. The resulting mixture was stirred at ambient temperature for ten minutes. At the conclusion of this period, the mixture was cooled in an ice bath : and 0.85 mL (0.0064 mole) of t-butyl nitrite was added dropwise during a ten minute period. Upon completion of addition, the reaction mixture was stirred at 7- 8 °C for 1.25 hours. At the conclusion of this period, the reaction mixture was poured into an ice-cold aqueous 10% hydrochloric acid solution and extracted with ethyl acetate. The extract was washed with one 25 mL portion of an aqueous solution saturated with sodium chloride, dried with sodium sulfate and filtered.

The filtrate was concentrated under reduced pressure, yielding about 2.0 grams of crude product. The crude product was purified by column chromatography on silica gel, yielding 1.0 grams of title compound; mp 104-109 °C. The NMR spectrum was consistent with the proposed structure.

Step C 5,6-dichioronaphthol

To a mixture of 0.85 gram (0.0023 mole) of (5,6-dichloronapthyl)((4- methylphenyl)sulfonyl)oxy in 40 mL of ethanol (available from J. T. Baker Inc.) was added 5 ml. of tetrahydrofuran (THF, available from Aldrich Chemical

Company). The resulting mixture was stirred to effect dissolution and then a solution of 1.3 grams (0.023 mole) of potassium hydroxide (available from VWR

Scientific Products, Bridgeport, NJ) in 40 mL of water was added. Upon completion of addition, the reaction mixture was under reflux for one hour. After this time, most of the solvent was removed under reduced pressure to yield a residue. The residue was extracted with one 20 mL portion of diethyl ether. The extract was acidified to a pH of 5-6 with ice-cold aqueous 5% hydrochloric acid and then extracted with ethyl acetate. The ethyl acetate extract was washed with an aqueous solution saturated with sodium chloride, dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, yielding 0.33 gram of title compound. The NMR spectrum was consistent with the proposed structure. , StepD (4-(2-diethylamino)ethoxy)phenyl)methan-1-ol : A solution of 37.2 grams (0.22 mole) of 2-(diethylamino)ethyl chloride hydrochloride (available from Aldrich Chemical Company), 26.8 grams (0.22 mole) of 4-hydroxybenzyl alcohol (available from Aldrich Chemical Company)

and 89 grams (0.65 moles) of potassium carbonate (available from VWR Scientific

Products) in 1200 mL of N,N-dimethylformamide (DMF, available from EM

Sciences) was stirred at ambient temperature for about 18 hours. After this time, the solvent was remove under reduced pressure, yielding a residue. The residue was taken up in water and then extracted with ethyl acetate. The extract was washed with one portion of an aqueous 10% sodium hydroxide solution followed by one portion of water and then one portion of an aqueous solution saturated with sodium chloride, dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, vielding 2.38 grams of title compound. The

NMR spectrum was consistent with the proposed structure.

Step E Compound 223

A stirred solution of 0.33 gram gram (0.0016 mole) of 5,6-dichloronapthol and 0.35 gram (0.0016 mole) of (4-(2-diethylamino)ethoxy)phenyl)methan-1-ol in 15 mL of THF was cooled in an ice bath, and 0.24 mL (0.0017 mole) of tributylphosphine (available from Aldrich Chemical Company) followed by 0.42 gram (0.0017 mole) of 1-1'-(azadicarbomyl)dipiperidine (available from Aldrich

Chemical Company) were added. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it stirred for 72 hours.

After this time, the reaction mixture was diluted with ethyl acetate, and an aqueous solution saturated with sodium chloride was added. The organic layer was separated, dried with magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding about 0.45 gram of crude product.

The crude product was purified by column chromatography on silica gel, yielding 0.13 gram of Compound 223, The NMR spectrum was consistent with the proposed structure.

EXAMPLE 2

This example illustrates one protocol for the preparation of the ] hydrochloride salt of (2-(4~((5,6- dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine (Compound 224).

Compound 225 (prepared in the manner of Example 1), 0.07 gram (0.00017 mole), was taken up in 1 mL of methylene chloride (available from EM Sciences) and 1 mL of one molar hydrochloric acid in diethyl ether (available from Aldrich

Chemical Company) was added. The solvent was removed under reduced pressure to yield a solid. The solid was taken up in heptane. The resulting precipitate was collected by vacuum filtration, yielding 0.07 gram of Compound 226; mp 204-206 °C. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 3

This example illustrates one protocol for the preparation of (2-(4-((6- quinolylamino)methyl)phenoxy)ethyl)diethylamine (Compound 15).

Step A 4-(2-(diethylamino)ethoxy)benzaldehyde

A solution of 5.0 grams (0.041 mole) of 4-hydroxybenzaldehdye (available from Aldrich Chemical Company), 8.5 grams (0.049 mole) of 2-diethylaminoethyl chloride hydrochloride (available from Aldrich Chemical Company), and 13.5 grams (0.098 mole) of potassium carbonate (available from J. T. Baker Inc.) in 100 mL of DMF was stirred at ambient temperature for 72 hours. At the conclusion of this period, the reaction mixture was poured into 100 mL of water and extracted with three 50 mL portions of diethyl ether. The combined extracts were washed with one 25 mL portion of water, dried with sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 5.1 grams of title . compound. The NMR spectrum was consistent with the proposed structure.

StepB Compound 15

To a stirred solution of 1.0 gram (0.0045 mole) of 4-(2- (diethylamino)ethoxy)benzaldehyde and 0.65 gram (0.0045 mole) of 6- aminoquinoline (available from Aldrich Chemical Company) in 25 mL of 1,2- dichloroethane (DCE, available from Aldrich Chemical Company)was added 0.3 mL (0.0045 mole) of glacial acetic acid (available from J. T. Baker Inc.) followed by 1.4 grams (0.0068 mole) of sodium triacetoxyborohydride (available from

Aldrich Chemical Company). Upon completion of addition, the reaction mixture was stirred at ambicnt temperature for three hours. At the conclusion of this period, 50 mL of 10% aqueous sodium hydroxide was added dropwise. The resulting solution was extracted with three 25 mL portions of diethyl ether. The extracts were combined, washed with one 25 mL portion of an aqueous solution saturated with sodium chloride, dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, yielding 1.25 grams of a dark brown paste. The dark brown paste was purified by column chromatography on silica gel, yielding 0.13 gram of Compound 15. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 4

This example illustrates one protocol for the preparation of (2-(4-(((4- chloronaphthyl)amino)methyl)-2-methoxyphenoxy)ethyl)diethylamine (Compound 263).

Step A 4-(2-(diethylamino)ethoxy)-2-methoxybenzaldehyde

This compound was prepared in the manner of Step A, Example 3, using 2.5 grams (0.016 mole) of 4-hydroxy-2-methoxybenzaldehdye (available from

Lancaster Synthesis Inc., Windham, NH), 3.4 grams (0.02 mole) of 2- diethylaminoethyl chloride hydrochloride, and 5.5 grams (0.04 mole) of potassium carbonate in 75 mL of DMF. The yield of the title compound was 2.6 grams. The

NMR spectrum was consistent with the proposed structure.

Step B Compound 263

This compound was prepared in the manner of Step B, Example 3, using 1.0 gram (0.004 mole) of 4-(2-(diethylamino)ethoxy)-2-methoxybenzaldehyde, 0.71 gram (0.004 mole) of 1-amino-4-chloronaphthalene (available from Aldrich

Chemical Company), 0.25 ml (0.004 mole) of glacial acetic acid, 1.3 grams (0.006 mole) of sodium triacetoxyborohydride and 50 mL of 1,2-dichloroethane (DCE).

The yield of Compound 263 was 0.52 gram. The NMR spectrum was consistent with the proposed structure.

EXAMPLE §

This example illustrates one protocol for the preparation of (2-(4-(((4- chloronaphthyl)methoxy)methyl)phenoxy)ethyl)diethylamine (Compound 8).

Step A (4-(2-diethylamino)ethoxy)phenyl)methan-1-ol

A solution of 4.0 grams (0.08 mole) of 4-(2- (diethylamino)ethoxy)benzaldehyde (prepared in the manner of Step A, Example 3) and 2.7 grams (0.08 mole) of sodium borohydride (available from Aldrich

Chemical Company) in 40 mL of methanol (available from J. T. Baker Inc,) was stirred at ambient temperature for about 18 hours. After this time, the reaction : mixture was quenched with water and extracted with several portions of methylene chloride. The organic extracts were combined, dried with magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 4.1 grams : of title compound.

StepB 4-chloronaphthalenecarbaldehye

To a stirred solution of 6.7 grams (0.026 mole) of a 1.0M solution of tin(iv) chloride in dichloromethane (available from Aldrich Chemical Company) in 10 mL of methylene chloride was added 3.0 grams (0.026 mole) of 3,3-dichloromethyl methyl ether (available from Aldrich Chemical Company). The resulting solution was stirred for one hour at ambient temperature. After this time, a solution of 2.8 mL (0.021 mole) of 4-chloronaphthalene was added. Upon completion of addition, the reaction mixture was stirred at ambient temperature for about 18 hours. At the conclusion of this period, the reaction mixture was quenched with water, washed with water followed by an aqueous solution saturated with sodium chloride, dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, yielding about 2.1 grams of title compound.

Step C (4-chloronaphthyl)methan-1-ol

This compound was prepared in the manner of Step C, Example 1, using 2.1 grams (0.011 mole) of 4-chloronaphthalenecarbaldehye, 70 mL of methanol, 20 mL of THF, and 2 grams (0.054 mole) of sodium borohydride. This preparation differs in that sodium borohydride was used rather than a solution of potassium hydroxide in water. The yield of the title compound was 1.9 grams.

Step D Compound 8

This compound was prepared I the manner of Step E, Example 1, using 0.5 gram (0.0026 mole) of (4-chloronaphthyl)methan-1-ol, 0.6 gram of (4-(2- diethylamino)ethoxy)phenyl)methan-1-ol, 70 mL of THF, 0.79 mL (0.0031 mole) of tributylphosphine, and 0.73 gram (0.0029 mole) of 1-1'- (azadicarbomyl)dipiperidine. The yield of Compound 8 was 0.3 gram.

EXAMPLE 6

This example illustrates one protocol for the preparation of 1-(2-(2,6- dimethylpiperidyl)ethoxy)-4-((4-chloronaphthyloxy)methyl)benzene (Compound 106).

StepA Mixture of 4-(2-bromoethoxy)benzaldehyde and 4-(2- chloroethoxy)benzaldehyde

Sodium hydride (60% dispersion in mineral oil, available from Aldrich

Chemical Company),4.4 grams {0.11 mole), was washed with three portion of hexane (available from J. T. Baker Inc.) and 200 mL of DMF was added. The resulting mixture was cooled to 0 C and 50 mL (0.6 mole) of 1-bromo-2- chloromoethane (available from Aldrich Chemical Company) followed by 12.2 grams (0.1 mole) 4-hydroxybenzaldehyde were added. Upon completion of addition, the reaction mixture was heated to 40 °C where it stirred for about 72 hours. After this time, the reaction mixture was extracted with several portions of ethyl acetate. The organic extracts were combined, dried with magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 7.4 grams of title mixture. The NMR spectrum was consistent with the proposed : structure. :

This compound was prepared several times in the manner described above.

Step B Mixture of (4-(2-bromoethoxy)phenyl)methan-1-ol and (4-(2- chloroethoxy)phenyl)methan-1-ol

This compound was prepared in the manner of Step C, Example 1, using 8.7 grams (0.047 mole) of the mixture of 4-(2-bromoethoxy)benzaldehyde and (4- (2-chloroethoxy)phenyl)methan-1-ol, 400 mL of methanol, and 3.5 grams (0.094 - mole) of sodium borohydride. This preparation differs in that no THF was used and sodium borohydride was used rather than a solution of potassium carbonate in water. The yield of the title mixture was 8.4 grams. The NMR spectrum was consistent with the proposed structure.

Step C. 2-chloro-1-(4-((4-chloronaphthyloxy)methyl)phenoxy)ethane 5 .

A stirred solution of 8.4 grams (0.045 mole) of the mixture of (4-(2- bromoethoxy)phenyl)methan-1-ol and (4-(2-chloroethoxy)phenyl)methan-1-ol, 8.1 grams (0.045 mole) of 4-chloronaphthol, and 13.7 mL (0.054 mole) of tributylphosphine in 500 mL of TIIT was cooled in an icc bath and 12.6 grams (0.049 mole) of 1-1'-(azodicarbomyl)dipiperidine was added. Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it stirred for 24 hours. After this time, the solvent was reduced under reduce pressure, yielding a solid. The solid was purified by column chromatography on silica gel, yielding 15 grams of crude product. The crude product was further purified by column chromatography on silca gel, yielding 6.7 grams of title compound.

Step D Compound 106

A stirred mixture of 0.4 grams (0.001 mole) of 2-chloro-1-(4-((4- chloronaphthyloxy)methyl)phenoxy)ethane and 5 mL (0.037 mole) of cis-2,6- dimethylpiperidine was heated to just below reflux for about 72 hours. After this time, the reaction mixture was analyzed by thin layer chromatography (TLC), which indicated the reaction was incomplete. The reaction mixture was concentrated under reduced pressure and subject to column chromatography on silica gel, yielding 0.2 gram of compound 106. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 7

This example illustrates one protocol for the preparation of amino(2-(4- ((5,6-dichloronaphthyloxy)methyl)phenoxy)ethyldiethyl-1-one (Compound 183). (2~(4-((5,6-Dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine (prepared in the manner of Example 1), 0.1 gram (0.0003 mole), was taken up in mL of chloroform (available from EM Sciences). The resulting solution was cooled to 0 °C in an ice bath and 0.09 gram (0.0004 mole) of 3- chloroperoxybenzoic acid (available from Aldrich Chemical Company) was added.

Upon completion of addition, the resuliing mixture was stirred for ten minutcs and 10 then the ice bath was removed. The reaction mixture was allowed to warm to ambient temperature where it stirred for 35 minutes. At the conclusion of this period, the reaction mixture was poured into a solution of 25 mL of chloroform and 10 mL of aqueous 5% sodium hydroxide. The organic layer was separated, dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, yielding 0.15 gram of compound 183; mp 81-87 °C. The NMR spectrum was consistent with the proposed structure. :

EXAMPLE 8

This example illustrates one protocol for the preparation of (2-(4-((4,6- - dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine (Compound 216).

Step A 4,6-dichloronaphthol

This compound was prepared in the manner of Step B, Example 1, using 5.0 grams (0.029 mole) of 6-aminonaphthol, 200 mL of acetonitrile, 4 grams (0.03 mole) of copper (IT) chloride, and 3.3 grams (0.032 mole) of t-butyl nitrite. The yield of the title compound was 1.4 grams.

StepB Compound 216

: This compound was prepared in the manner of Step E, Example 1, using 0.4 gram (0.0022 mole) of 4,6-dichloronaphthol, 0.49 gram (0.0022 mole) of (4-(2- ) diethylamino)ethoxy)phenyl)methan-1-ol, 80 mL of THF, 0.5 gram (0.0025 mole) of tributylphosphine, and 0.55 gram (0.0022 mole) of 1-1'- (azodicarbomyl)dipiperidine. The yield of Compound 216 was 0.3 gram.

EXAMPLE 9

This cxample illustrates one protocol for the preparation of (2-(4~(((4- chloronaphthyl)amino)methyl)phenoxy)ethyl)diethylamine (Compound 84).

A stirred solution of 0.2 gram (0.0001 mole) of 4-(2- (diethylamino)ethoxy)benzaldehyde (prepared in the manner of Step A, Example 3), 0.22 gram (0.0001 mole) of 1-amino-4-chloronaphthalene (available from

Aldrich Chemical Company), and one drop of p-toluenesulfonic acid monohydrate (available from Aldrich Chemical Company) in 5 mL of toluene was heated at reflux for ten hours. At the conclusion of this period, the reaction mixture was concentrated under reduced pressure, yielding a residue. The residue was taken up in 5 mL of methanol and about 0.2 grams (0.004 mole) of sodium borohydride was added. The resulting mixture was stirred at ambient temperature for about 18 hours. After this time, the mixture was quenched with water and extracted with several portions of diethyl ether. The extracts were combined, dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, yielding 0.8 gram of Compound 84. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 10

This example illustrates one protocol for the preparation of (2-(4-(((4- chloronaphthyl)amino)methyl)phenylthio)ethyl)diethylamine (Compound 71).

Step A (4-(2-diethylamino)ethylthio)phenyl)methan-1-ol

Under a nitrogen atmosphere, 0.6 gram (0.017 mole) of lithium aluminum hydride (available from Aldrich Chemical Company) was taken up in 20 mL of

THF. The resulting mixture was stirred to effect dissolution and a solution of one gram (0.007 mole) of 2-mercaptobenzoic acid (available from Aldrich Chemical

Company) 10 mL of THF was added. The resulting was stirred for 70 minutes. At the conclusion of this period, the solution was cooled in an ice bath und 10 mL of ethyl acetate was carefully added during a 30 minute period. Upon completion of addition, 5 mL of water followed by 1.3 grams (0.008 mole) of 2- (diethylamino)ethyl chloride hydrochloride was added . Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it stirred for about 18 hours. After this time, about 10 mL of aqueous 10% sodium hydroxide followed by an addition 10 mL of ethyl acetate was added. The resulting mixture was filtered. The organic layer of the filtrate was separated from the aqueous layer, washed with an aqueous solution saturated with sodium chloride, dried with sodium sulfate and filtered, yielding 3.32 grams of a yellow liquid. The yellow liquid was purified by column chromatography on silica gel, yielding 0.5 gram of title compound. The NMR spectrum was consistent with the proposed structure.

Step B 4-(2-(diethylamino)ethylthio)benzaldehyde

Under a nitrogen atmosphere, a stirred solution of 0.2 mL (0.003 mole) of dimethyl sulfoxide (DMSO, available from Aldrich Chemical Company) in 10 mL of methylene chloride of was cooled to -60 °C and 0.2 mL (0.002 mole) of oxalyl chloride (available from Aldrich Chemical Company) was added. The resulting solution was stirred at -60 °C for 15 minutes. At the conclusion of this period, a solution of 0.5 gram (0.002 mole) of (4-(2-diethylamino)ethylthio)phenyl)methan-

1-o0l in about 20 mL of methylene chloride was added. The mixture was stirred at - 60 °C to -40 °C of 30 minutes and 1.5 mL (0.011 mole) of triethylamine was added. Upon completion of addition, the reaction mixture was stirred at -40 °C for ) 1.5 hours. At the conclusion of this period, the reaction mixture was filtered through a silica gel plug. The filter cake was washed with one 150 mL portion of ethyl acetate. The filtrate was concentrated under reduced pressure, yielding 0.2 gram of title compound. The NMR spectrum was consistent with the proposed structure.

StepC Mixture of (2-(4-(2-aza-2-(4- chloronaphthyl)vinyl)phenylthio)ethyldiethylamine and Compound 71

A solution of 0.2 (0.001 mole) of 4-(2- (diethylamino)ethylthio)benzaldehyde, 0.2 gram 6-amino-4-chloronaphthalene, 0.4 gram (0.002 mole) of sodium triacetoxyborohydride and 10 drops of glacial acetic acid in 10 mL of DCE was stirred at ambient temperature for about 18 hours. At the conclusion of this period, 50 mL of 10% aqueous sodium hydroxide followed by 75 mL of ethyl acetate was added. The organic layer was separated from the aqueous layer and filtered through phase separated filter paper, yielding 0.4 gram of crude product. This crude product was combined with 0.1 gram of crude product prepared in a similar experiment to yield a total of 0.5 gram of crude product. The 0.5 gram of crude product was purified by column chromatography on silica gel, yielding 0.1 gram of mixture of (2-(4-(2-aza-2-(4- chloronaphthyl)vinyl)phenylthio)ethyl)diethylamine and Compound 71. The NMR } spectrum was consistent with the proposed structure.

Step D Compound 71

A stirred solution of 0.1 gram (0.0008 mole) of borane-dimethylamine : complex (available from Aldrich Chemical Company) and 0.1 gram (0.0003 mole) of the mixture of (2-(4-(2-aza-2-(4~ chloronaphthyl)vinyl)phenylthio)ethyl)diethylamine and Compound 71 in 2 mL of glacial acetic acid was heated at 60 °C for three hours. After this time, the reaction mixture was allowed to cool to ambient temperature and 5 ml of ethyl acetate was : added. The resulting mixture was washed with an aqueous 10% sodium hydroxide solution. The organic layer was separated from the aqueous layer and filtered through phasc separation filter paper, yielding 0.1 gram of an oil. The oil was purified by column chromatography on silica gel, yielding 0.1 gram of product.

The 0.1 gram of product was combined with 0.1 gram of product from a previous experiment to yield 0.2 gram of Compound 71. The NMR spectrum was consistent with the proposed structure. 1s EXAMPLE 11

This example illustrates one protocol for the preparation of diethyl(2-(4- ((2,3,4-trichlorophenoxy)methyl)phenoxy)ethyl)amine (Compound 308).

Step A (2-(4-chloromethyl)phenoxy)ethyl)diethylamine hydrochloride

Under a nitrogen atmosphere, 2 mL (0.027 mole) of thionyl chloride (available from J. T. Baker Inc.) was added dropwise to a stirred solution of 58 grams (0.026 mole) of 4-(2-(diethylamino)ethoxy)benzaldehyde (prepared in the manner of Step A, Example 3) in 150 mL of methylene chloride. Upon completion of addition, the reaction mixture was stirred at ambient temperature for about 2.5 } hours. After this time, the reaction mixture was heated to 50 °C and the solvent was removed under reduced pressure, yielding 7.2 grams of title compound. The

NMR spectrum was consistent with the proposed structure.

StepB Compound 308

A stirred solution of 0.3 gram (0.001 mole) of (2-(4- chloromethyl)phenoxy)ethyl)diethylamine hydrochloride, 0.2 gram (0.0009 mole) ) of 2,3 ,4-trichlorophenol (available from Aldrich Chemical Company), 0.9 gram (0.003 mole) of cesium carbonate (available from Aldrich Chemical Company) and a catalytic amount of sodium jodide (available from Aldrich Chemical Company) in 10 mL of acetone (available from J. T. Baker Inc.) was heated to 60 C for about 18 hours. After this time, the solvent was removed under reduced pressure and about 10 mL of methylene chloride was added. The resulting solution was filtered, and the filtrate was filtered through a silica gel pad, yielding 0.2 gram of

Compound 308. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 12

This example illustrates one protocol for the preparation of diethyl(2-(4- ((2,5-difluorophenoxy)methyl)phenoxy)ethyl)amine (Compound 346).

This compound was prepared in the manner of Step B, Example 11, using 0.3 gram (0.001 mole) of (2-(4-chloromethyl)phenoxy)ethyl)diethylamine hydrochloride, 0.1 gram (0.0009 mole) of 2,5-difluorophenol (available from

Aldrich Chemical Company), 0.9 gram (0.003 mole) of cesium carbonate and a catalytic amount of sodium iodide in 10 mL of acetone. The yield of Compound 346 was 0.2 gram. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 13 i This example illustrates one protocol for the preparation of 1,2-dichloro-5- {[4-(4-ethylpiperazinyl)phenylJmethoxy } naphthalene (Compound 355).

Step A 4-piperazinylbenzonitrile

Under a nitrogen atmosphere, a stirred miture of 10.0 grams (0.055 mole) . of 4-bromobenzonitrile (available from Aldritch Chemical Company) and 23.7 grams (0.28 mole) of piperazine (available from Aldrithc Chemical Company was : heated at 120 °C for about 45 hours. After this time, the reaction mixture was taken up in 150 ml of aqueous 10% sodium hydroxide. The resulting solution was extracted with three 50 mL portions of methylene chloride. The combined extracts were washed with one 50 mL portion of an aqueous saturated sodium chloride solution, dried with sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 8.6 grams of a green paste. The green paste was purified by column chromatography on silica gel, yielding 3.8 grams of a paste.

The paste was taken up in 50 mL of diethyl ether. The resulting solution was warmed on a rotovap and decanted away from the insoluble paste. The decantate was concentrated, yielding 3.2 grams of the title comound. The NMR spectrum was consistent with the proposed structure.

Step B 4-(4-ethyl)piperazinylbenzonitrile

Under a nitrogen atmosphere, a stirred solution of 3.16 grams (0.017 mole) of 4-piperazinylbenzonitrile , 2.0 mL (0.025 mole) of iodoethane (available from

Aldritch Chemical Company), and 7.1 mL (0.051 mole) of triethylamine in 50 mL of THF was heated at reflux for about three hours. At the conclusion of this period, the reaction mixture was allowed to cool to ambient temperature and 100 mL of water was added. The resulting solution was extracted with two 50 mL portions of diethyl ether. The combined extracts were washed with 100 mL portion of water, dried with sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 3,2 grams of crude product. The crude product was purified by column chromatography on silica gel, yielding 2.9 grams of tilte compound. The NMR spectrum was consistent with the proposed structure.

Step C [4-(4-ethylpiperazinyl)benzaldehyde

Under a nitrogen atmosphere, a stirred solution of 2.8 grams (0.013 mole) ) of 4-(4-ethyl)piperazinylbenzonitrile in 35 mL of anhydrous toluene (available from Aldrich Chemical Company) was cooled to —70 °C and 12 mL (0.02 mole) of diisobutylaluminum hydride (1.5M in toluene, available from Aldritch Chemical

Company) was added dropwise at a rate to maintain the temperature below —60 °C during about a 15 minute period. Upon completion of addition, the reaction mixture was stirred at —60 °C for two hours. At the conclusion of this period, 10 mL of methanol was added dropwise followed by 10 mL of water. The resulting solution was allowed to warm to ambient temperature. Once at the prescribed temperature, 10 mL of methylene chloride was added. The resulting mixture was filtered and the filtrate was transferred to a separatory funnel. The organic layer was separated from the aqueous layer, dried with sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 1.6 grams of an orange paste. The orange pasted was was filtered through a silica gel plug. The filter cake was washed with one 75 mL portion of methylene chloride followed by one 50 mL portion of a 5% methanol/95% methylene chloride solution. The filtrate was concentrated under reduced pressure, yielding 0.5 gram of title compound. The

NMR spectrum was consistent with the proposed structure.

Step D [4-(4-ethylpiperazinyl)phenyljmethan-1-ol

This compound was prepared in the manner of Step A, Example 5, using 0.4 gram (0.019 mole) of [4-(4-ethylpiperazinyl)benzaldehyde and 0.4 gram } (0.01 mole) of sodium borohydride in 40 mL of absolute ethanol (available from J.

T. Baker Inc.) The yield of the title compound was 0.3 gram. The NMR Spectrum was consistend with the proposed structure.

StepE © Compound 355

This compound was prepared in the manner of Step E, Example 1, using 0.23 gram gram (0.0011 mole) of 5,6-dichloronapthol, 0.25 gram (0.0011 mole) of [4-(4-ethylpiperazinyl)phenyl]methan-1-ol, 0.36 mL (0.0014 mole) of tributylphosphine, and 0.35 gram (0.0014 mole) of 1-1'- (azadicarbomyl)dipiperidine in 15 mL of THF. The yield of compound 355 was 0.04 gram. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 14

This example illustrates one protocol for the preparation of 5-{[4-(8-aza- 1,4-dioxaspiro[4.5]dec-8-y)phenyl methoxy} -1,2-dichloronaphthalene (Compound 362).

StepA 5-[(4-bromophenyl)methoxy]-1,2-dichloronaphthalene

A stirred mixture of 4.0 grams (0.019 mole) of 5,6-dichloronapthol in 60 mL of THF was cooled in an ice bath and 1.1 grams (0.023 mole) of Sodium hydride (60% dispersion in mineral oil) was added during a ten minute period.

Upon completion of addition, the mixture was stirred for twenty minutes. After this time, a solution of 5.8 grams (0.023 mole) of 4-bromobenzyl bromide (available from Aldrich Chemical Company) in 40 mL of THF was added dropwise. Upon completion of addition, the reaction mixture was allowed towarm to ambient temperature where it stirred for seven days. After this time, the reaction mixture was taken up in 100 ml of water. The resulting solution was extracted } with two 200 mL portions of diethyl ether. The combined extracts were washed with one 75 mL portion of a 10% aqueous lithium chloride solution, dried with sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding the crude product. The crude product was triturated with a mixture of diethyl ether and petroleum ether. The resulting solid was collected by filtration,

yielding 5.3 grams of the title comound. The NMR spectrum was consistent with

N the proposed structure. ‘ Step B Compound 362

To a 100 mL roundbottom flask was added 0.02 gram (0.00002 mole) of tris(dibenzylideneacetone)dipalladium (0) (available from Strem Chemical,

Newburyport, MA), 0.04 gram (0.00006 mole) of racemic 2,2'- bis(diphenylphosphino)-1,1’-binaphthy! (available from Strem Chemical), and 35 mL of toluene. The resulting mixture was evacuated and then backfilled with nitrogen. This evacuation and backfill procedure was repeated two more times.

The resulting mixture was strirred at ambient temperature for 30 minutes. After this time, 0.75 gram (0.002 mole) of 5-[(4-bromophenyl)methoxy]-1,2- dichloronaphthalene, 0.52 gram (0.004 mole) of 4-piperidone ethylene ketal (available from Lancaster Synthesis Inc.), and 0.38 gram (0.004 mole) of sodium t- butoxide (available from Aldrich Chemical Company) were added to the 100 mL round bottom flask. Upon completion of addition, the above set forth evacuation and backfill procedure was repeated three times. The reaction mixture was heated to 80-85 °C were it stirred for 4 to 4.5 hours. After this time, the heating was discontinued and the reaction mixture was stirred for about 18 hours. After this time, the reaction mixture was filtered through a celite pad and rinsed with toluene. "The filtrate was concentrated under reduced pressure yielding the crude product.

The crude product was purified by column chromatography on neutral alumina (deactivated with 6% water), yielding 0.7 gram of title compound. The NMR spectrum was consistent with the proposed structure.

It is well known to one of ordinary skill in the art that the compounds of ‘ formula I of the present invention can contain optically-active and racemic forms.

It is also well known in the art that the compounds of formula I may contain stercoisomeric forms and/or exhibit polymorphism. It is to be understood that the present invention encompasses any racemic, optically-active, polymorphic or . stereoisomeric form, or mixtures thereof. It should be noted that it is well known in the art how to prepare optically-active forms, for example by resolution of a ‘ racemic mixture or by synthesis from optically-active starting materials.

Representative compounds prepared by the methods exemplified above are listed in Table 1. Characterizing properties are given in Table 2.

Biological Data

Candidate insecticides are evaluated for activity against the tobacco budworm (Heliothis virescens [Fabricius]) in a surface-treated diet test.

In this test one mL of molten (65-70°C) wheat germ-based artificial diet is pipetted into each well of a four by six (24 well) multi-well plate (ID# 430345-15.5 mm dia. x 17.6 mm deep; Corning Costar Corp., One Alewife Center, Cambridge,

MA 02140). The diet is allowed to cool to ambient temperature before treatment with candidate insecticide.

For a determination of insecticidal activity, solutions of the candidate insecticides are prepared for testing using a Packard 204DT Multiprobe® Robotic

System (Packard Instrument Company, 800 Research Parkway, Meriden, CT 06450), in which the robot first dilutes a standard 50 millimolar DMSO solution of candidate insecticide with a 1:1 water/acetone solution (V/V) in a ratio of 1:7 stock solution to water/acetone. The robot subsequently pipettes 40 microliters of the so- prepared solution onto the surface of the diet in each of three wells in the 24 multi- well plate. The process is repeated with solutions of seven other candidate insecticides. Once treated, the contents of the multi-well plate are allowed to dry, } leaving 0.25 millimoles of candidate insecticide on the surface of the diet, or a concentration of 0.25 millimolar. Appropriate untreated controls containing only , DMSO on the diet surface are also included in this test.

For evaluations of the insecticidal activity of a candidate insecticide at varying rates of application, the test is established as described above using sub-

multiples of the standard 50 millimolar DMSO solution of candidate insecticide. . For example, the standard 50 millimolar solution is diluted by the robot with

DMSO to give 5, 0.5, 0.05, 0.005, 0.0005 millimolar, or more dilute solutions of : the candidate insecticide. In these evaluations there are six replicates of each rate of application placed on the surface of the diet in the 24 multi-well plate, for a total of four rates of application of candidate insecticide in each plate.

In each well of the test plate is placed one second instar tobacco budworm larvea, each weighing approximately five milligrams. After the larvae are placed in each well, the plate is sealed with clear polyfilm adhesive taupe. The tape over each well is perforated to ensure an adequate air supply. The plates are then held in a growth chamber at 25 °C and 60% relative humidity for five days (light 14 hours/day).

After the five-day exposure period insecticidal activity for each rate of application of candidate insecticide is assessed as percent inhibition of insect weight relative to the weight of insects from untreated controls, and percent mortality when compared to the total number of insects infested.

The compounds of the present invention were active in the diet test against the tobacco budworm. Over fifteen of the compounds listed in Table 1 exhibited precent growth inhibition values of 70% or greater. Compounds 224, 353, 354, 355,357,364, 366,367, 368369, 372, and 373-379 exhibited percent growth inhibition values of 80% or greater. Table 3 gives the insecticidal activity data for compounds tested in the diet test.

For insecticidal application, the active compounds are formulated into insecticidal compositions by admixture in insecticidally effective amount with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the . material in a given application. Thus, for agricultural use the present insecticidal compounds may be formulated as granules of relatively large particle size, as water-soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other . known types of formulations, depending on the desired mode of application.

These insecticidal compositions may be applied either as water-diluted ’ sprays, or dusts, or granules to the areas in which insect control is desired. These formulations may contain as little as 0.1%, 0.2% or 0.5% to as much as 95% or more by weight of active ingredient.

Dusts are free flowing admixtures of the active ingredients with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed flours, and othcr organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful herein is one containing 1.0 part or less of the insecticidal compound and 99.0 parts of talc.

Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersant. The wettable powder is ultimately applied to the locus where insect control is desired either as a dry dust or as an emulsion in water or other liquid. Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet, inorganic diluents.

Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing, or emulsifying agent to facilitate dispersion.

For example, a useful wettable powder formulation contains 80.8 parts of the insecticidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. By way of illustration, compound 223 was formulated as a 25% wettable powder (25%

WP) as follows:

) ~~ COMPONENT AMOUNT (wtwt%)

Compound 223 901% pure) 275% , Diluent 5.0%

Wetting Agent 1.0%

Dispersing Agent 16.0%

UV Stabilizer 0.5%

Carrier/Diluent 50.0%

Other useful formulations for insecticidal applications are emulsifiable concentrates (ECs) which are homogeneous liquid compositions dispersible in water or other dispersant, and may consist entirely of the insecticidal compound and a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as

Xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvent.

For insecticidal application these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the insecticidal composition.

Flowable formulations are similar to ECs except that the active ingredient is suspended in a liquid carrier, generally water. Flowables, like ECs, may include a small amount of a surfactant, and contain active ingredient in the range of 0.5 to 95%, frequently from 10 to 50%, by weight of the composition. For application, flowables may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated. ] Typical wetting, dispersing, or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and - sulfates and their sodium salts; alkylaryl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of long-chain mercaptans . and ethylene oxide. Many other types of useful surface-active agents are available in commerce. The surface-active agents, when used, normally comprise from 1 to 0 15% by weight of the composition.

Other useful formulations include suspensions of the active ingredient in a relatively non-volatile solvent such as water, com oil, kerosene, propylene glycol, or other suitable solvents.

Still other useful formulations for insecticidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the toxicant is carried on : relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as carbon dioxide, propane, or butane, may also be used. Water-soluble or water-dispersible granules are also useful formulations for insecticidal application of the present compounds. Such granular formulations are free-flowing, non-dusty, and readily water-soluble or - water-miscible. The soluble or dispersible granular formulations described in U.S.

Pat. No. 3,920,442 are useful herein with the present insecticidal compounds. In use by the farmer on the field, the granular formulations, emulsifiable concentrates, flowable concentrates, solutions, etc., may be diluted with water to give a concentration of active ingredient in the range of say 0. 1% or 0.2% to 1.5% or 2%.

The active insecticidal compounds of this invention may be formulated and/or applied with other insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals. In using an active compound of this invention, whether formulated alone or with other agricultural chemicals, to - control insects, an effective amount and concentration of the active compound is applied to the locus where control is desired. The locus may be, e.g., the insects themselves, plants upon which the insects feed, or the insect habitat. When the locus is the soil, e.g., soil in which agricultural crops have been or will be planted, . the composition of the active compound may be applied to and optionally incorporated into the soil. For most applications the effective amount may be as ’ low as, e.g. about 10 to 500 g/ha, preferably about 100 to 250 g/ha.

In a further embodiment of the present invention, several of the compounds disclosed above have themselves been found to be novel and useful intermediates in the preparation of the 1,4-disubstituted benzene insecticides disclosed and claimed herein.

Included among these intermediates are those compounds having the formula XII: 3 2

RQ) 5 6

XII wherein:

Ais -(CH,),-U-R* wherein nisOorl;

U is -C(0)-, -CH,-, oxygen, or -NR’, where R’ is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

R? is selected from hydrogen, halo, hydroxy, and 1-R*, wherein:

R'is 8 1 X

LL

. z 6 3 5Y 4 : . i. where X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido,

carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, . alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, ‘ where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy:;

Ris -T-(CH,)_-R!, where

T is selected from the group consisting of oxygen, nitrogen, and sulfur; mis0,1,2, 3, or4;

R' is hydrogen, halo, alkyl, or -NR®)®R®); where R® und R® are independently selected from the group consisting of hydrogen, alkyl, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and -(CH,),-

NR)R"), where pislor2;

R'® and R" are independently selected from the group consisting of hydrogen, alkyl, alkoxyalkyl, and aminoalkyl.

Some preferred intermediates of formula XII are those in which: nis 1; U is oxygen; R? is 1-R?, wherein:

R*is 8 1 X

Zz 6 3 5Y 4 rR! where X, Y, and Z are independently selected from the group : consisting of hydrogen, halogen, cyano, nitro, amino, azido, ’ carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and ary] moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;

T is oxygen or sulfur; ‘ mis 2; and

R! is halo; ’ Additional preferred intermediates of formula XII are those in which nis 1;

Uis-CH,-; R*is 1-R*, wherein:

R*is 8 1 X

T= Nz N2

LL

BN 3 5Y 4

R* where X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;

T is oxygen; m 1s 0; and

R' is hydrogen or alkyl.

Preferred intermediates of formula XII also include those compounds in which n is 0; U is -C(O); R* is hydrogen; T is oxygen; m is 2; and R' is -N(R®(R), where R® and R’ are alkyl as well as those in which n is 0; U is -CH,-; R? is halo or hydroxy; T is oxygen; m is 2; and R' is -N(R*)(R®); where R® and R® are alkyl. ] In addition to the compounds set forth above, compounds of formula UU, ) 25 described generally in Schema 3 above and in greater detail below, have also been found to be novel and useful intermediates in the preparation of the 1,4- disubstituted benzene insecticides disclosed and claimed herein:

B

D

0

Y

[018 where X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy; T is selected from the group consisting of oxygen, nitrogen, and sulfur; and R' is alkyl.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Table 1 ) Insecticidal Optionally Substituted Benzenes ‘ 3 2B 0)

D 6 5 Formula I (FI) : -T-(CH,),-R -(CH,),-U-R?

Formula II (FIT) Formula III (FIIT)

J 8 1 X 7 2

W z 6 3

L 5Y 4

R? R*

Formula I

A and D are H; R is FII; T is O; m is 2; R' is N(C,H,),

CmpndNo. B no U FR’ X Y Z 1 2FlII 1 N 1-R* 4C1 H H 2 3-FlI 1 N 1-R' 4Cl H H

Formula I

Band D are H; Ris FII; T is O; m is 2; R' is N(C,H,),

Cmpnd No. A 3 Wi a Nos 4 —

Cl 5 \, > J ° qa

Table 1 (continued) - Formula I

B and D are H; Ris FII; T is O; m is 2; R' is N(C,H,),

Cmpnd No. A 6

BY

7 0} iN

N

0

XNNF he

Formula I

Ais FIII: B and D are H; R is FII; T is O: mis 2; R! is N( CH,):nis 1

CmpndNo. U Rr?

EE

= Re

So cl 9 0) oe

Nn .

N . 0) z

Sn

CF, il 0

Na ; I J) cl 12 0)

Na

ZZ

F

ER 6 ¢

SN

Table 1 (continued)

Formulal :

AisFIII; B and D are H; Ris FII; Tis O; mis 2: Rl is N(C,Hs): n is 1

CmpndNo. U Rr?

Sy 16 N

NZ

" 17 N

XO)

Cl 18 N cd } 0

Cl 19 N

Sox cg ©

N

Cl 9 22 0

Sy 23 O

N ‘d

Sa cl 24 0

Ny Cl 0)

Cl

Table 1 (continued) )

Formula I

Ais FIII; B and D are H; R is FII; T is O: mis 2: R! is N{ CH): n is 1

CmpndNo. U R? 26 0) 4 [¢] cl 27 0) 0 50

Ci 28 @)

Ny cl 29 0)

Cl 0 7 cl cl 31 0 0 oo

XT

32 0) ~

Sn cl cl 33 O cl 34 0 20. : cl 0 . OC, ci

Table 1 (continued)

Formula I

Ais FIII: B and D are H; R is FII; Tis O; m is 2; R' is N{( CHy)inis 1

CmpndNo. U Rr? 36 0

C2, cl 37 8)

N

CCL cl cl 38 N

N

WL ci cl 38 0) os = Cl

Formula I

Ais FIII;B and D are H; nis 1; Uis N: R?*is 1-R*; X is 4-Cl: Yand Z are H

Cmpnd No. R 39 -N(C,H,), 40 o ps

A jy 41 NY [o] oO

Jug ye A

A

4 A \.

Table 1 (continued)

Formula I

Ais FIlI; B and D are H; Ris FII; T is O; nis 0; R?is 1-R*; Yand Z are H

CmpndNo. m R' u X 43 0 CH, CH, 4-Br 44 0 CH, 1 4-Cl 45 1 1-CH, -OC,H,0- 4-Cl 46 1 0 J -CH=N- 4-Cl

Se \— 47 2 N(C,H,), -OC,H,0- 4-Cl 48 2 N(CH), Ji 4-Cl 49 2 N(C,H,), -NHC,H,- 4-Cl 50 2 N(C,H,), OCH, 4-Cl 51 N(C,Hy), 0) 4-Cl 52 N(C,Hy), CH, 4-Cl 53 N(C,H,), SO, 4-Cl 54 N(C,H,), CO 4-Cl 55 N(C,Hy), CF, 4-Cl 56 N(C,Hy), -CH(OH) 4-Cl 57 N(CH), -CH,S- 4-Cl 58 N(C,Hy), CH,SO 4-Cl 59 N(C,Hy), CH,SO, 4-Cl 60 2 -OC,H;, -CH,NH- 4-Cl

Formula 1

Ais FIII: Band D are H: Ris FI; Tis O; mis 1; nis 1; R?is 1-R*: X is 4-Cl: Y and

ZareH

Cmpnd No. u R! 61 0] -CH,=C(Cl), 62 N -C(0)O

Se \—

Formula I

AisFII; Band D are H; Ris FII; nis 1; R* is 1-R%;

Cmpnd No. m T u R X Y Z 64 1 0) N -CH, 4-Cl H H 65 1 0 N -CH,F 4-Cl H H

Table 1 (continued)

Formula I

Ais FIII; B and D are H; Ris FII; nis 1; R? is 1-R%; . EE T 75 =e A E--J

Cmpnd No. m T U R! X Y Z 66 1 8) 0 ~N 4-C1 H H

ST

67 1 0) 0 ~N 4-Cl H H

Hydrochloride Salt N Ne 68 1 0] 0 vy’ 4-Cl H H

Ss —T

N

N\ - N ~ cH , 69 1 0) 0 \ 4-Cl H H nN ON

Nd

Mc, 70 1 0 0 ™ 4-Cl H H

NO

71 2 8S N N(G,H,), 4-Cl H H 72 2 0 CH, -N(C,H,), 4-Br H H 73 2 0] CH, -N(C,H,), 4-Cl H H 74 2 0 N -N(CH,), H H H 75 2 (0) N -N(C,H), H H H 76 2 0) N % H H H : \_/ ’ 77 2 0) N -N(CH,), 4-Br H H 78 2 0) N -N(C,Hy), 4-Br H H 79 2 0 N -N(isopropyl)2 4-Br H H 80 2 6) N NY 4-Br H H \_/ 81 2 0 N J 4-Br H H 82 2 0) N -NH(C,H,) 4-Cl H "H 83 2 0 N -N(CH,), 4-Cl H H 84 2 0) N -N(C,H,), 4-Cl H H 85 2 0) N -N(C,Hs), 4-Cl H H

Chloride Salt 86 2 0 N -N(C,H,), 8-Cl H H : 87 2 0) N -N(isopropyl)2 4-Cl H H 88 2 0] N -N(C,H,), 4-Cl H H 89 2 0 N % 4-Cl H H \__7/

Table 1 (continued)

Formula I

Ais FIII; B and D are H; R is FI; nis 1; R? is 1-R%;

Cmpnd No. m T u R X Y Z 90 2 0 N J 4-Cl H H 91 2 0) N Oo 4-Cl H H ~N ~« \ 92 2 0) N 0 4-Cl H H

NN «

Joo - H 93 2 0 N _ {OD 4-Cl H 94 3 0) N -N(CH,), 4-Cl H H 95 3 0) N -N(C,Hy), 4-Cl H H 96 3 0) N /\ 4-Cl H H

NP

97 4 0 N -N(C,H,), 4-Cl H H 98 2 0 0) —) 4-Cl H H 99 2 0] (0) 4-Cl H H 0 100 2 0) 0) 4-Cl H H 2 101 2 0 0] 4-Cl H H =) 102 2 0) 0) O 4-Cl H H 103 2 0 0 -Q 4-Cl H H 0) - H 4 2 O ~~) 4-Cl H 105 2 0) 0) 4-Cl H H —N

Table 1 (continued)

Formula I

Ais FIII; Band Dare H; Ris FII; nis 1; R%is 1-R%; ’ Cmpnd No. m T 8] R X Y Z 106 2 0 0 4-Cl H H . —N ) 107 2 0) 0 4-Cl 6-Cl H —N 108 2 0 Oo 0 4-Cl H H “(Oo 109 2 0) 6) <0) 4-Cl H H 110 2 0 0 0 4-Cl H H “OG 111 2 0] 0) 0) a 4-Cl H H 112 2 0 0 O) 4-Cl H H

N— 113 2 0 0 NN 4-Cl H H

AN

114 2 10) 0 0 4-Cl H H —N NHo~ /

O —~ 115 2 0 —) 0 4-Ci H H 116 2 8) Oo — 0 4-Cl1 H H —N - © a 117 2 0 0 20s 4-Cl H H =

Table 1 (continued)

Formulal

Ais FIII; B and D are H; Ris FII; nis 1; R*is 1-R%; « —_— gu 7

Cmpnd No. m T u R X Y Z 118 2 0 © VN 4-Cl H H . \_/ 119 2 0 © : 4-Cl H H /—\ —N © 120 2 0) O / 4-Cl H H —N © 121 2 0 O 4-Cl H H

N

Ra 122 2 0 O AAA 4-Cl H H 123 2.0 0 AAAg 4-Cl H H 124 2 0 © 208 4-Cl H H 125 2 0 0 MN, w AC H H 126 2 0) O “0 4-Cl H H 127 2 6) O /\ 4-Cl H H «<0 128 2 0) 0 CY 4-Cl H H 129 2 0] 0 \ 4-Cl H H

OC

130 2 0 0) 4-Cl H H

Sa oc,

Is

Table 1 (continued)

Formula I

Ais FIIL; B and D are H; R is FII; n is 1; R? is 1-R%; _— =; 7

Cmpnd No. m T u Rr X Y Z , 131 2 0 0 CH, 4-Cl H H no—L _

CH

132 2 O O CH; _ 4-Cl H H aes 133 2 0 © ~ 4-Cl H H 134 2 0) 0) OMe 4-Cl H H

De

MeO 135 2 0 © oh 4-Cl H OH “Or

HC

136 2 0 0 4-Cl H H

N a 137 2 O oO \, 4-Cl H H 2, 138 2 0 © | 4-Cl H H 0 139 2 0) 0 ve 4-Cl H H —N 140 2 O O ho * 4-Cl H H =O -Cl 141 2 0 © 0 4 H H 142 2 6) O —] 5-Cl 6-Cl H 143 2 0 O CHg <> 4-Cl H H —N

Table 1 (continued)

Formula I

Ais FIII; B and D are H; Ris FI; nis 1; R? is 1-R%;

Cmpnd No. m T u R! X Y Z 144 2 0 © 7s 4-C1 H H : \ 145 2 0 O ( 4-Cl H H —N 146 2 O 0 Nath 4-Cl H H 147 2 0 0 NTN 4-Cl H H 148 2 O 0 4-Cl H H {) 149 2 0 @) \ NL 4-Cl H H 4 150 2 (0) 0 J Cl H H 151 2 0 © . 4-Cl H H . N

Co

N

152 2 Oo O \ 4-Cl H H

N ow

N . 153 2 O 0 MeO 4-Cl H H /\ 5 —N N \v4 154 2 O 0) 4-Cl H H ; — ) 155 2 0 0 CFs 4-Cl H H

I \ CS —N N —/

Table 1 (continued)

Formula I

Ais FIII; B and D are H; Ris FII; nis 1; R? is 1-R*;

CmpndNo. m TI U R X Y Z " H 156 2 0 © reYer 4-Cl H 157 2 0 0 = 0) & 4-Cl H H [eo] 158 2 O 0 Cl 4-Cl1 H H i. £

BNA ) 159 2 0 0 o 4-Cl H H 8 /~CH,

N (e] 160 2 0 0 4-Cl H H oY.

N

Fo A 161 2 0 0 LO 4-Cl H H

J

NN

0 162 2 Oo 0] \ N= 4-Cl H H ~~ 163 2 0] 0 HG 4-Cl H H 4 Nay 164 2 O 0) 4-Cl H H rs : 165 2 0) Oo \ 4-Cl H H

N N—CH,

HC < 166 2 6) 0 Ny Wa otk 4-Cl H H ( ; CH, 2 4- 167 0) (0) {0 Cl H H 168 2 0 0 4-Cl1 H H

Table 1 (continued)

Formula I

Ais FIII; B and D are H; Ris FII; nis 1; R% is 1-R%;

Cmpnd No. m T uU R X Y Z 169 2 0 0 4-Cl H H . —N (Fa N N 2 170 2 Oo 0 HG 4-Cl H H

A) 171 2 0 0 NN 4-Cl H H 172 2 0) 0 aN 4-Cl H H

A

0O—N 173 2 9) 0 \ 4-Cl H H %

N—N 174 2 0) 0) ~ 4-Cl H H

A

S—N 175 2 0 0 N OCE, 4-Cl H H 176 2 (0) 0) 3 4-Cl H H 7/7

Rass 177 2 0) 0 -OC,H, 4-Cl H H . 178 2 0) 0 -N(C,H;)(OCH,) 4-Cl H H 179 2 0) 0) -N(C,H;),(OCH,) 4-Cl H H 180 2 0) 0) -NHCH; 4-Cl H H 181 2 0) 0 Nee 4-Cl 6-Cl H (a 182 2 0 0) r= 4-Cl 6-Cl H

Hydrochloride Salt —N:=0 183 2 0] 0) No 5-Cl 6-Cl1 H

Oo 184 2 0 0 -NH(C,Hs) 4-Cl H H 185 2 0 0 -NH(C,H,) 4-Cl H H

Hydrochloride Salt

Table 1 (continued)

Formula I

Ais FIII; B and D are H; Ris FII; nis 1; R? is 1-R%;

CmpndNo. m TI U R! X Y Z 186 2 O 0 -N(C,H,), 2-Cl H H . 187 2 0 0 -N(C,Hy,), 3-Cl H H 188 2 0) 0) -N(C,H,), 4-Cl H H 189 2 O 0] -N(C,H,), 4-Cl H H

Chloride Salt 190 2 0 0 -N(C,Hs)(CH,), 4.Cl H H

Iodide Salt 191 2 O 0 -N(CH,CN(C,Hy) 4-Cl H H 192 2 0) 6) -N(CoH5)(CH3) 4-Cl H H 193 2 0 0 -N(CoH5)(CH3) 4.C1 H H

Hydrochloride Salt } 194 2 0 0) -NHtBu 4-Cl H H 195 2 0 0 -N(C;H(OC,Hy) 4-Cl H H 196 2 0 0) -N(CH,CH=CH,), 4-Cl1 H H 197 2 0 0) -NCH,C(OCH,), 4-Cl H H 198 2 0 0 -NC;H,OCH;, 4-Cl H H 199 2 O 0) -NC,H, 4-Cl H H 200 2 O 0 -N(CH,)C,H,CN 4-Cl1 H H 201 2 0 0 -N(C,IL)C I, 4-Cl H H 202 2 Oo C -N(C,H,), 4-Cl H H 203 2 0 0 -N(isopropyl), 4-Cl1 H H 204 2 0 0) -N(CcH,5), 4-Cl H H 205 2 0 6) -N(CH,)C,,H,; 4-Cl H H 206 2 0) O -N(C,H,), 5-Cl H H 207 2 0 Oo -N(C,H,), 6-Cl H H 208 2 0 0 -N(C,Hy), 7-Cl H H 209 2 0 0] -N(C,H,), 8-Cl H H 210 2 0 0) -N(C,H,), 2-Cl 4-Cl H 211 2 Oo O -N(C,Hs,), 2-Cl 5-Cl H 212 2 0 0 -N(C,H,), 2-Cl 6-Cl H 213 2 0 0 -N(C,H,), 2-Cl 8-Cl H 214 2 0 0 -N(C,H,), 4-Cl 5-Cl 6-Cl 215 2 0 0 -N(C,Hy), 4-Cl 5-Cl H 216 2 0 O -N(C,H,), 4-Cl 6-Cl H 217 2 O 0 -N(C,H,), 4-Cl 6-Cl H . Chloride Salt 218 2 0 0 -N(C,H,), 4-Cl 6-Cl H

Sulfonic Salt : 219 2 0 0) -N(C,Hy,), 4-Cl 6-Cl H

Trifluoroacetic Salt 220 2 0 0 -N(C, Hs), 4-Cl 6-Cl H

Methylbenzenesulfonic

Salt 221 2 0) 0) -N(C,Hy), 4-Cl1 7-Cl H

Table 1 (continued)

Formula I

Ais FIII; B and D are H; Ris FII; nis 1; R*is 1-R%

Cmpnd No. m I U R X Y Z 22 °° 2 0 © N(CH), 4-Cl Cl H 223 2 0 © N(CH), 5-Cl 6CI H 224 2 0 O N(CH), 5-Cl 6CIl H

Chloride salt 225 2 0 oO N(CH), 5-Cl 6Cl H

Phosphoric salt 226 2 0) 0 -NHtBu 5-Cl 6-Cl H 227 2 0 O N(CH), 6-Cl Cl H 228 2 0 © N(CH), 4-Br H H 225 2 O O -N{C,Hs), 6-Br H H 230 2 0 © N(CH), 5-Br H H 231 2 0 © N(CH), 4-F H H 232 2 0 © N(CH), A-CF, H H 233 2 0 O 2N(C,H,), 6-CF, H H 234 2 0 © N(CH), 4-N, H H 235 2 0 © N(CH), 4-OCH3 H H 236 2 0 O N(CH), 4-OCH3 H H

Chloride Salt 237 2 0 © N(CH), 5-OCH3 H H 238 2 0 O N(CH), 4-NO, H H 239 2 0 O N(CH), 4-CN H H 240 2 0 O “N(C,H,), 2-CHj3 H H 241 2 0 O©O N(CH), 6-CHj H H 242 2 0 O©O N(C,H,), ® _ H H 243 2 0 O NCH), Oe H H 244 2 0 O N(CH), 5-Cl 6-CF, H 245 2 0 © 2N(C,H,), 5-Cl 6Br H 246 2 0 © N(C,H,), 5-Cl 6-1 H 247 2 0 © 2N(C,H,), 5.1 6-Cl H 248 2 0) O -N(C,H,), 5-Cl 6-OCF, H 249 2 0 O N(CH), 5-Cl 6CN H 250 2 0 0) -N(C,Hs), 5-Cl 6-NO, H oo 251 2 0 O N(CH), 5-CF, 6CI H 252 2 0 © N(C,H,), 5.0CH, 6Cl H } 253 2 0 0 -N(C,H,), 4-CF, 6-Cl H 254 2 0 0 o 5-Cl 6-Cl H —N

Table 1 (continued)

Formula I

Ais FIII; B and D are H; Ris FII; nis 1; R? is 1-R%;

CmpndNo. m TI U X' X YZ 255 2 0 CH 5-Cl 6-Cl H —N ) 256 ~Cl - H 2 0 oO 0) 5-C 6-Cl 257 2 0 8 N(C,H,), 5-Cl 6Cl H 258 2 0 SO, N(C,H,), 5-Cl 6CL H 259 3 0 O N(C,H.), 4-Cl H H 260 4 0 © N(C,H,), 4-Ci H H

Please note that Compound No. 261 is a mixture of Compound 212 and (2-(4- ((2.4,6-trichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine.

Formulal

Ais FIII; Ris FIL; T is O; mis 2; R' is -N(C,H,),; R*is 1-R%; X is 4-CL; Y and Z are H

Cmpnd No. B D n U 262 2-F H 1 N 263 2-OCH, H 1 N 264 3-OCH, H 1 N 265 3-OCH, 5-OCH;, 1 N 266 5-(0OC,H,N(C,Hs),) H 1 N 267 2-Cl H 1 N 268 3-Cl1 H 1 N 269 2-Cl 3-Cl 1 N 270 2-Cl 6-Cl 1 N 271 3-Cl 5-Cl 1 N - - Q 272 3-Cl 5-Cl 0 Yen P

Formulal

A and D are H; Ris FII; T is O; m is 2; R! is N(C,Hj), : CmpndNo. B n U FE J L wv 273 5FIT 1 N 1-R 4-Cl H H ) 274 6FI 1 N 1R 4Cl H H

Formula I

AisFIII; Band Dare H; Ris FII; Tis O; mis 2; nis 1; Uis O

Table 1 (continued)

Cmpnd No. R! R? } 275 — ~~) 276 0

Olh O 277 N(CH), )

Formula I

Ais FIII; B and D are H; Ris FII; mis 2; T is O; R' is -N(C,H,),; nis 1; R?is 1-R3; ~~ mpdN. © I L w 278 N H H ‘H 279 N 2-OCF, H H : 280 N 4-OCF, H H 281 N 2-0C,H, H H 282 N 3-0CH, H H 283 N 2-Cl H H 284 N 4-Cl H H 285 N 2-Cl 3-Cl1 H 286 N 2-Cl 3-Cl 4-Cl 287 N 2-Cl 4-Cl H 288 N 2-Cl 4-Cl 5-Cl 289 N 3-Cl 4-Cl H 290 N 3-Cl 5-Cl H 291 N 2-CH, H H 292 N 2-CH, 4-Cl H 293 N 3-CH, 4-Cl H 294 N 2-F 3-F H 295 N 2-F 3-F 4-F 296 N 2-F 4-F H 297 N 2-F 4-F 5-F 298 N 2-CH, 3-CH, H 299 N 2-CH, 4-CH, H 300 N 2-OCH,4 4-OCH, H 301 N 2-OCH, 5-0OCH, H . 302 N 3-OCH, 5-OCH, H 303 Oo 3-OCH, 5-OCH, H 304 0) H H H ’ 305 O 2-Cl H H 306 0 4-Cl H H 307 Oo 2-Cl 3-Cl H 308 Oo 2-Cl 3-Cl 4-Cl 309 Oo 2-Cl 4-Cl H

Table 1 (continued)

Formula I

A is FIII; B and D are H; R is FII; m is 2; T is O; R is -N(C,H,),; nis 1; R*is 1-R’; _mpnd No. U J L w 310 0 2-Cl 4-Cl1 5-Cl : 311 oO 2-Cl 5-Cl1 H 312 0] 2-Cl 6-Cl H 313 Oo 3-Cl 4-Cl H 314 Oo 3-Cl 5-Cl H 315 0 2-Cl 4-Br H 316 oO 2-Cl 6-Br H 317 0 2-Cl 5-CH, H 318 0 2-C(CH,), H H 31% O 3-C(CH,), H H 320 0) 4-C(CH,), H H 321 0 2-isopropyl H H 322 (0) 4-C,H, H H 323 0) 4-OCH, H H 324 0) 4-OCF, H H 325 0 2-CN H H 326 0) 5-CN H H 327 0] 2-NC(0O)CH, H H 328 0) 2-C(O)OC,H; H H 329 0) 4-C(O)CH, H H 330 0 2-C(O)CH, 3-OCH, H 331 0 2-C(O)CH, 4-OCH, H 332 0 2-CH, 4-Cl H 333 0 3-CH, 4-Cl1 H 334 0 2-NO, 4-Cl H 335 0) 4-Cl1 H 1-0] 336 0 4-Cl1 5-CH, 1-0) 337 0) 2-CH, 4-CH, H 338 0 2-CH, 3-CH, 5-CH, 339 0) 2-CH, 3-CH; 6-CH; 340 oO 2-OCH, 4-CH, H 341 Oo 2-Br 4-Br H } 342 Oo 2-Br 6-Br H 343 6) 2-Br 4-CH, H 344 0) 2-Br 4-CH,4 6-Br 345 0) 2-F 3-F H 346 0] 2-F 5-F H

Table 1 (continued)

Formula I

Ais FIII; B and D are H; R is FII; mis 2; T is O; R! is -N(C,H,),; nis 1; R*is 1-R; ’ mpnd No. U hj L WwW 347 6] 2-F 6-F H 348 0 3-F 5-F H 349 0) 4-F 6-F H 350 0 3-F 4-F 6-F 351 Oo 3-CF, H H 352 0 2-CF, 5-CF, H

Formula I

A isFIII; B and D are H; nis 1; Uis O; R*is 1-R* : Cimpnd R X Y Z

No. 353 —~ W-cron, 4-Cl H H 354 Wen 4-Cl1 6-Cl H 355 ~~ eon, 5-Cl 6-Cl H 356 It 5-C1 6-Cl H

Oe 357 Worn 5-Cl1 6-Br H 358 ~~ ) 5-C1 6-Cl H 359 "STs 5-C1 6-Cl H 360 A or 5-C 6-Cl H 361 ¢ 5-Cl 6-Cl H

NS

Tf 362 ~X 5-C1 6-Cl H 363 ~~ 4-Cl 6-Cl H —N_N-CH,CH, . 364 M\ 5-Cl1 6-Cl H —N_ N-CH,CH(CH,),

Table 1 (continued)

Cmpnd R X Y Z ] No. 365 Vat 5-Cl 6-C! H / ) cl 366 a 5-Cl 6-Cl H a 367 \ 5-Cl 6-Cl H —N N-CH, \_/ 368 ~N V-ongngn, 5-Cl 6-Cl H \_/ 6 -Cl 6-C1 u 369 —N_ -cHicHy, >-Cl oT 0

UNS PC ES H

_/ 371 \ 5-Cl1 6-Cl H ~~

Formula I

AisFIII; Band Dare H; Ris FII; Tis O; nis 1; R*is 1-R%; Z is H

Cmpnd No. m n Rf X Y u 372 0 1 BE 5Cl 6-Cl 0 373 0 1 2 5-Cl 6-Cl 10)

Y

374 0 1 4-Cl H 0

N-CH, 375 0 1 4-Cl- H 0)

N-CH,CH, 376 1 1 5-Cl 6-Cl 0]

HC-N ) 377 1 1 5-Cl 6-Cl 0 : CHCH—N ) 378 1 1 {Hs 5-Cl 6-Cl O <7” 379 2 0 N(C,Hy), 4Cl H -CHOCH,

a0

Table 2

Characterizing Data

Cmpd No Empirical Formula Melting Point/Physical State 1 C,H,,CIN,O OIL 2 CyH,,CIN,O OIL 3 C,.H;;N;0, OIL 4 C,3H,CIN,O OIL

C,,H;,CIN,O, OIL 0 C,H,,CIN,O OIL 7 C,;H,;CIN,O, SOLID 8 C,,H,sCINO, SOLID 9 C,,H,:N,0, SOLID

C,;H,F;N,0, SOLID 11 C,,H,;CIN,O, OIL 12 C,H,FN,0, OIL 13 C,;H;,N,O OIL 14 C,,H,,N,;0 LIQUID

C,H; N,O LIQUID 16 C,H,,N,0 SOLID 17 C,H, CIN,0, OIL 18 C,sH,,CIN;O LIQUID 19 C,.H;,CIN,O, 93-95 °C

C,;H,,CIN,O OIL 21 C,;H,,NO, SOLID 22 C, H,:N,0, OIL 23 C,H,,CIN,0, OIL 24 CHF .NO,S 39 C,H,;;CIN, OIL 40 C,sH;,CIN,O OIL 41 C,sH3,CIN,O, FOAM 43 C,,H,,BrO OIL 44 C,sH,5CIN,O, 220 °C > 45 C,H,,Cl0, 106-107 °C 46 C,3H,,CIN,C, OIL : 47 C,,H,;CING, OIL 48 C,3HyCIN,O, 210°C > ) 49 C,sH;,CIN,O OIL 60 C,;H,,CINO, OIL : 61 C,H;;Cl,0, SOLID 62 C,sH,(CINO, 90-92 °C 63 C,sH,CIN,O, 123-125 °C

Table 2 (continued)

Cmpd No Empirical Formula Melting Point/Physical State ’ 64 C,H ;;CINO 92-93 °C 65 C,H,,CIFNO SOLID 66 C,H,;,CIN,O, 122-124 °C 67 C,cH,,CIN,C,.C1 SOLID 68 C,oH;.CIN,O, 159-161 °C 69 C,H,,CIN,O, 104-106 °C 70 C,H,,CIN,O, SOLID 71 C,;H,,CIN,S OIL 72 C,HBINO OIL 73 C,H,;CINO OIL 74 C,H N,O LIQUID 75 C3 HyeN,0 OIL 76 C,sHy6N,0, SOLID 77 C,H;:BrN,O LIQUID 78 C,;H,,BtN,O SOLID 79 C,H; BiN,O SOLID : 80 C,;H,;BiN,0, SOLID 81 C,;H,sBiN,O SOLID 82 C,H,:CIN,O 184-187 °C 83 C,,H,;CIN,O LIQUID 84 C,:H,,CIN,O OIL 85 C,:H,,CIN,0.CIH 86 C,H,,CIN,O PASTE 87 C,sH;, CIN,O SOLID 88 C,H;,CIN,O LIQUID 89 C,;H,,CIN,O, SOLID 90 C,;H,;CIN,O SOLID 91 C,.H,;CIN,O, 102-104 °C 92 C,,H,,CIN,O, OIL 93 C,H,,CIN,O SOLID 94 C,,H,,CIN,O SOLID 95 C,sH3,CIN,O LIQUID 96 C,,H,,CIN,O, LIQUID 97 C,H;,CIN,O LIQUID 98 C,H,,CIO, LIQUID 99 C,H,:CINO, SOLID . 100 C,sH,6CINO, SOLID 101 C,H,,CINO, 89-90 °C 102 C,s:H,sCINO, OIL 103 C,:H,;CINO, OIL 104 C,:H,;CING, OIL 105 C,H;CINO, 60-65 °C 106 C,H; CINO, OIL

Table 2 (continued)

Cmpd No Empirical Formula Melting Point/Physical State 107 CyH,,CLNO, OIL 108 C,;H;,CINO, 85-87 °C } 109 C;,H,,CINO, 89-91 °C 110 Cy, H,,CINO, 112-115 °C 111 C;H;,CINO, 88-91 °C 112 C,sH,,CINO, SOLID 113 C,H,,CIN,0, OIL 114 C,H,,CIN,0, OIL 115 CyoH,,CIN, 0, OIL 116 C,oH,,CIN, 0, OIL 117 CoH, CIN,O, 71-73 °C 118 C,H,,CINO,S OIL 119 C,sH,:CINO, OIL 120 C,sH,,CINO, OIL 121 C,sH,,CINO, LIQUID 122 C,H,CINO, 88-90 °C 123 C,elL,,CINO, OIL 124 C,eH,,CINO, OIL 125 C,6H;,CINO, OIL 126 C,,H,.CINO, SEMI SOLID 127 CyoH,,CIN,0, 91-92 °C 128 C,sH,CINO, SYRUP 129 C,.H,,CIN,0, SYRUP 130 C,;H,;CIF;NO, SYRUP 131 C,H, CING, 58-59 °C 132 C,;H,,CINO, OIL 133 C,sH,,CIN,O, OIL 134 C,:H,;CING, 96-98 °C 135 C,H, CINO, OIL 136 C,H,CINO, 95-96 °C 137 C,cH,,CLLNO, 87-88 °C 138 C;H;,CIN,0O, OIL : 139 C,;H,CINO, OIL 140 C,eH;,CINO, OIL 141 C,:H,,CINO, 75-77 °C 142 C,H,;CI,NO, 152-154 °C : 143 C,,H,,CINO, OIL 144 C,,H,,CINO,S 83-86 °C } 145 C,sH;,CINO, OIL 146 C,sH;,CINO, OIL 147 C,6H;,CINO, OIL 148 C,6H;,CINO, OIL 149 C;0H,,CIN,0, 131-135 °C

Table 2 (continued)

Cmpd No Empirical Formula Melting Point/Physical State 150 C,:H,,CINO, OIL 151 C,,H,,CIN;0, OIL 152 C,,H,,CIN,0, 133-136 °C 153 C,,H,,CIN,0, OIL 154 C,,H,,CINO, 90-91 °C 155 C,,H,CIF:N,0, 80-82 °C 156 C,,H,;,CIFN,0, 120-121 °C 157 C,H,,CIN,0, OIL 158 C,H, CLN,O, OIL 159 C,,H,,CINO, OIL 160 CoH, CIN, O, OIL 161 C,,H,,CINO, 123-125 °C 162 C,H,,CIN,O, OIL 163 C,,H,,CIN,0O, OIL 164 C,,H,;CIN,O, 164-166 °C 165 C,H, CIN,0, 83-89 °C 166 C,,H,,CIN,0, OIL 167 C,,H,:CIN,0, 135-140 °C 168 C,H,,CINO, OIL 169 C,,H,,CIN,0, OIL 170 C,H,,CINO, OIL 181 C,,H,.CLNO, OIL 183 C,;H,.CLNO, 81-87 °C 184 C,;H,,CINO, LIQUID 185 C,H,,CINO,.Cl 201-203 °C 186 C,;H,.CINO, LIQUID 187 C,,H,.CINO, OIL 188 C,;H,.CINO, OIL 189 C,,H,CINO,.CIH SOLID 190 C,,H,,CINO, I LIQUID 191 C,;H,;,CIN,O, LIQUID 192 C,,H,,CINO, SOLID 193 C,,H,,CINO,.Cl SOLID 194 C,;H,,CINO, 84-85 °C 195 C,H,,CINO, SYRUP 196 C,.1,CINO, OIL : 197 C,,H,CINO, OIL 198 C,H, CINO, SEMI-SOLID 199 C,,H,CINO, 138-145 °C 200 C,,H,,CIN,0, OIL 201 C,sH,,CINO, OIL 202 C,,H,,CINO, OIL 203 C,.H,,CINO, OIL

Table 2 (continued)

Cmpd No Empirical Formula Melting Point/Physical State ‘ 204 C,,H,,CINO, OIL 205 C;sH;,CINO, 63-64 °C 206 C,;H,,CINO, LIQUID 207 C,;H,,CINO, LIQUID 208 C,;H,.CINO, OIL 209 C,;H,,CINO, LIQUID 210 C,:H,,CLLNO, OIL 211 C,sH,:CLNO, OIL 213 C,;H,,CI,NO, LIQUID 214 C,:H,,CLLNO, SOLID 215 C,.H,.CLNO, LIQUID 216 C,.H,:CLNO, OIL 217 C,:H,:CLNO,.CIH 200 °C > 218 Cy,H,sCLNO,.CH, 0,8 SOLID 219 C,:H,;CL,NO,.C,HF,0, SOLID 220 C,,H,;CLNO,.C,H,0,S SOLID 21 C,,H,,CLLNO, PASTE 222 C,H,;CLNO, PASTE 223 C,;H,,CLLNO, OIL 224 C,;H,.CLLNO,.Cl 204-206 °C 225 C,H,,CLNO,.H,0,P SOLID 226 C,;H,,CI,LNO, 215-217 °C 227 C,,H,,CLNO, OIL 228 C,H,,BrNO, OIL 229 C,;H,BrNO, SOLID 230 C,;H,;BrNO, SOLID 231 C,H, ,FNO, SOLID 232 C,,H,F;NO, OIL 233 C,.H,F.NO, COLORLESS OIL 234 C,:H,;N,0, OIL 235 C,,H,,NO, OIL 236 . C,Hy,NO,.CIH SOLID 237 C,H,.NO, OIL 238 C,,H,N,0, OIL 239 C,H, N,0, OIL 240 C,,H,,NO, "OIL . C241 C,H, NO, SOLID 242 C,H; ,FNO, 67-71 °C ) 243 C,H,,CINO, OIL 259 C,H,,CINO, LIQUID 260 C,sH,,CINO, LIQUID 261 C,:H,sCLNO,.C,,H,,C1,NO, LIQUID 262 C;H,CIFN,O LIQUID

Table 2 (continued) :

Cmpd No Empirical Formula Melting Point/Physical State 263 Cy H,,CIN,0, LIQUID 264 C,,H,,CIN,O, SOLID 265 C,sH;,CIN,O, LIQUID 266 C,.H,,CIN,O, LIQUID 267 Cs H,,CLN,O LIQUID 268 C,;H,.CLLN,O LIQUID 269 C,;H,,CI;N,0 SOLID 270 C,sH,,CLN,O SOLID 271 C,:H,:CLN,0 SOLID 272 C,H,,CLN,0, SOLID 273 C.H,CIN,O LIQUID 274 C,oH,CIN,O LIQUID 275 C,oH,,CIN,O, OIL 276 C,,H;,CIN,O, OIL 277 CHL CINO, OIL 278 CH, N,0 OIL 279 CoH, sF,N,O, OIL 280 C,oH,sF,N,0, OIL 281 C,H, N,O, OIL 282 C,sH,,N,0, OIL 283 C,.H,;CIN,O OIL 284 C,,H,,CIN,O OIL 285 CysH,,CLN,O OIL 286 C,sH;CLN,O OIL 287 C,,H,,CLLN,O OIL 288 C,sH,;CLLN,0O OIL 289 C,.H,,CLLN,O OIL 290 C,sH,,CLN,O OIL 291 C,;H,N,O LIQUID 292 C,sH,,CIN,O LIQUID 293 C,;H,,CIN,O LIQUID 294 C,H, F,N,O OIL 295 CoH, F.N,O OIL 296 CH, F.N,O OIL 297 CoH, F3N,O OIL 298 C, H;,)N,O OIL . 299 C,H, ,N,O OIL 300 Cy H,,N,O, OIL ] 301 C, H;N,O, OIL 302 C,H; N,0, OIL 303 C,;H,,NO, LIQUID 304 C,H; NO, SOLID 305 CH,,CINO, SOLID

Table 2 (continued)

Cmpd No Empirical Formula Melting Point/Physical State 306 CsH,CINO, SOLID 307 C,,;H,,CLLNO, LIQUID 308 C,H,,CLLNO, SOLID 309 C,,H,;CLNO, LIQUID 310 C,,H,,CLNO, LIQUID 311 C,,H,,CLLNO, LIQUID 312 C,,H,;,CLNO, LIQUID 313 C,,H,;CLLNO, SOLID 314 C,,H,;CLNO, SEMI-SOLID 315 C,,H,;BrCINO, SOLID 316 C,H,.BrCING, LIQUID 317 C,,H,CINO, LIQUID 318 C,;H;;NO, LIQUID 319 C,,H;NO, SOLID 320 C,,H3;NO, LIQUID 321 C,H; NO, LIQUID 322 C,H; NO, SOLID 323 C,,H,,NO, SOLID 324 C,H, F;NO, SOLID 325 C,.H,N,O, LIQUID 326 C,.H,.N,0, LIQUID 327 C,;H,N, 0,4 SOLID 328 C,H,,NO, SOLID 329 C,H,,NO, LIQUID 330 C,H,,NO, LIQUID 331 C,,H,,NO, SOLID 332 C,H,:CINO, LIQUID 333 C,,H,CINO, SOLID 334 C,sH,,CIN,O, LIQUID 335 C,H,;CIN,0O, LIQUID 336 C,:H,,CIN,O, LIQUID 337 C, H,,)NO, LIQUID 338 C,H; NO, SOLID 339 C,H; NO, SOLID 340 C, H,)NO, LIQUID 341 C,sH,;Br,NG, SOLID : 342 CsH,3Br,NO, LIQUID 343 C,H,6BrNO, LIQUID ) 344 C,H,sBr,NO, SOLID 345 CH, F,NO, SOLID 346 C,,H,,F,NO, LIQUID 347 C,sH,;F,NO, LIQUID 348 CoH,,F,NO, LIQUID

Table 2 (continued)

Cmpd No Empirical Formula Melting Point/Physical State 349 C,,H,,F,NO, LIQUID 350 C,H,F;NO, LIQUID . 351 C, H,,F;NO, LIQUID 352 C, H,;F NO, LIQUID 353 C,,H,,CIN,O SOLID 354 C,;H,,CLLN,O SOLID 355 C,;H,,CLN,O SOLID 356 C,sHxsCLN, 0, SOLID 357 C,;H,,BrCIN,O 150-151 °C 358 C,,H,,CLLN,O 142-145 °C 355 C,Hy5CLN, OG 131-133 °C 360 C,;H,,CLLN,O 135-137 °C 361 C,sH,:CLN,O SOLID 363 C,.H,,CLN,O SOLID 364 C,;H,;CLLN,O SOLID 365 C,sH,:CLN,O SOLID 366 C,,H,,CLN,O SOLID 267 C,,H,,CLN,O SOLID 368 C,,H,CL,N,O SOLID 369 C,,H,,CLN,O SOLID 370 C,;H,,CLFN,O SOLID 371 C,H,,CLN,O SOLID 372 C,,H,,CLLNO, OIL 373 C,,H;,CLLNO, OIL 374 C,;H,,CINQ, SEMI-SOLID 375 C,,H,,CING, OIL 376 C,H,;CLLNO, OIL 377 C,sH,,CLNO, OIL 378 C,;H,,CI,NO, SOLID 379 C,H, CING, SOLID

Table 3

Insecticidal Activity of 1,4-Disubstituted Benzenes

Incorporated into the Diet (SRTD) of Tobacco Budworm

Rate of Percent Growth Percent

CmpdNo. Application] Inhibition? Mortality3 8 4.6 11 — 4.6 35 -— 5.6 12 -— 21 5.6 20 -— 47 4.6 23 — 49 4.6 16 -— 66 4.6 9 -— 68 5.6 16 -— 72 5.6 23 — 73 5.6 24 -- 5.6 20 — 77 5.6 17 -— 78 5.6 12 — 5.6 0 -— 79 6.6 -4 -— 80 5.6 12 -- 82 5.6 12 -—- 84 6.6 -20 -— 6.6 34 — 5.6 11 — 85 6.6 20 me 5.6 15 -— 87 6.6 -2 — 88 5.6 1 -— 89 5.6 12 — 93 6.6 3 — 94 4.6 18 -— 99 6.6 6 — 100 6.6 6 -— 101 6.6 14 — 102 6.6 7 — 103 5.6 25 — } 104 5.6 21 — 105 4.6 24 — 106 6.6 35 — . 107 6.6 17 — 111 5.6 1 — 112 5.6 26 Jo 113 5.6 ~3 — 114 5.6 0 — 117 5.6 10 —

Table 3 (continued)

Rate of Percent Growth Percent

CmpdNo. Application! Inhibition2 Mortality3 118 4.6 6 -—- 121 4.6 12 -— 122 5.6 23 —— 123 5.6 30 ~—- 124 5.6 20 ——- 125 5.6 18 — 126 6.6 14 ~—- 130 6.6 17 —— 131 6.6 25 ——- 132 5.6 27 oo 133 4.6 28 —- 134 4.6 12 — 135 5.6 24 — 136 4.6 33 ——— 137 4.6 28 —— 138 4.6 27 — 139 4.6 26 -— 140 5.6 32 -— 141 6.6 24 ——— 142 6.6 32 ——- 143 4.6 22 -— : 144 4.6 20 -— 145 5.6 29 o—— 146 5.6 25 — . 147 5.6 33 — 148 5.6 4 -— 149 5.6 22 -— 150 5.6 12 — 151 5.6 5 — 152 4.6 16 — 153 4.6 19 — 154 6.6 27 ——— : 161 5.6 23 — 163 5.6 24 ——- i166 5.6 24 — 181 6.6 43 — 183 6.6 28 ~— 6.6 18 — 184 5.6 43 — 187 4.6 14 — 188 6.6 1 —— . 6.6 19 —— 6.6 -1 — 190 5.6 4 -—- 191 6.6 6 — 192 6.6 2 — 193 6.6 4 —

Table 3 (continued)

Rate of Percent Growth Percent

CmpdNo. Application! Inhibition Mortality3 194 6.6 19 — 195 5.6 30 — : 196 5.6 20 —- 197 4.6 43 — 198 5.6 21 — 199 5.6 9 —- 200 5.6 19 —- 1201 5.6 13 —- 202 5.6 20 —-- 203 6.6 14 — 206 6.6 12 — ) 207 6.6 20 — 209 6.6 17 — 213 4.6 3 — 214 6.6 18 —-- 215 6.6 8 — 216 6.6 2 — 6.6 1 — 6.6 1 —- 6.6 14 —- 217 6.6 26 — 6.6 34 — 218 6.6 28 — 219 6.6 16 — 220 6.6 28 — 221 6.6 13 -— 222 6.6 24 -—- 223 6.6 63 — 7.6 3 — 7.6 17 —- 224 6.6 81 — 6.6 20 — 6.6 32 — 226 6.6 59 — 227 4.6 7 — 228 6.6 17 -- 6.6 5 —- 6.6 0 —- 229 6.6 14 — 230 6.6 12 — 231 5.6 3 — . 232 6.6 25 — 6.6 1 — 233 6.6 17 —- 234 5.6 -3 —- 236 4.6 14 — 237 5.6 12 —-

Table 3 (continued)

Rate of Percent Growth Percent

CmpdNo. Application! Inhibition? Mortality3 238 6.6 22 — 239 5.6 5 - ) 241 5.6 8 — 242 6.6 11 —— 243 6.6 10 ——- 262 4.6 7 ——— 263 5.6 26 ——— 264 6.6 19 —— 267 4.6 7 —- 273 5.6 5 — 290 5.6 1 -— 306 4.6 -2 —_— 308 5.6 18 -— 313 4.6 37 -— 350 4.6 21 — 353 3.6 100 100 4.6 100 67 5.6 45 — 6.6 21 — . 354 3.6 100 100 4.6 100 100 5.6 96 17 6.6 -2 — 355 3.6 100 100 4.6 100 100 5.6 96 17 6.6 -2 -— 356 3.6 2 — 4.6 -4 — 357 3.6 100 100 4.6 50 99 5.6 — 15 360 3.6 73 — 4.6 11 — 364 4.6 83 —— 5.6 -1 wn 365 3.6 28 —— 4.6 18 — 366 36 82 — 4.6 47 -— 5.6 3 — \ 367 3.6 100 100 4.6 100 100 5.6 98 33 6.6 25 — 368 3.6 100 100 4.6 100 100

Table 3 (continued)

Rate of Percent Growth Percent

CmpdNo. Application! Inhibition? Mortality3 56 102 50 6.6 36 —- 369 3.6 100 100 4.6 100 100 5.6 100 83 6.6 28 — 372 3.6 100 100 4.6 100 100 5.6 100 100 6.6 42 —- 373 3.6 100 100 4.6 97 17 5.6 37 -- ‘ 6.6 -1 — 374 3.6 100 100 4.6 98 50 5.6 41 -—- : 6.6 -1 --- 375 3.6 101 100 4.6 85 17 5.6 23 — : 376 3.6 100 100 4.6 100 100 5.6 89 -—- 6.6 22 —— 371 3.6 100 100 4.6 99 67 5.6 59 — 6.6 4 -— 378 3.6 100 100 4.6 100 100 5.6 101 83 6.6 48 — 379 3.6 86 33 4.6 11 _—

FOOTNOTES

1 The rate of application is expressed as the negative log of the molar concentration of the test compound in the diet. 2 percent growth inhibition is derived from the total weight of the insects (IW) at each rate of application in the test relative to the total weight of insects in an untreated control, . % Gr. Inh. = [IW (control) - I (test)/IW (control)] x 100. 3 Percent mortality is derived from the number of dead insects (TD) relative to the total number of insects (TI) used in the test, % Mortality = TD/TI x 100

Claims (4)

WE CLAIM:

1. A compound of formula I: : 3 2B 9S S 556 I wherein: A is selected from the group consisting of hydrogen; aryl; alkylheterocyclyl; alkenylaminopolycyclyl; alkenylaminoheterocyclyl; alkylaminopolycyclyl; carbonylaminopolycyclyl; where the aryl, heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and Formula III, where Formula III is -(CH,),-U-R? ux wherein nisOor 1; U is selected from the group consisting of -CH,~, -O-CH,-, oxygen, sulfur, sulfonyl, alkyl, oxyalkyloxy, alkenylamino, cabonylamino and -NR®, where R’ is selected from the group consisting of hydrogen, hydroxy, alkyl, haloalkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl; R? is selected from aryl; alkylpolycyclyl; heterocyclyl; polycyclyl; where the : 25 aryl, heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl,

haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, : alkoxycarbonyl, haloalkoxycarbonyl, or aryl; 1-R?; 1-R*; and 2-R*, wherein: R%is J (J L Rr where J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, aminoalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, aryloxy, and heterocyclyl, where the aryl and heterocyclyl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy; R'is

8 1X LL z 6 3 5Y 4 R* where X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, aryloxy, and . heterocyclyl, where the phenyl, aryl, and heterocyclyl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;

B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, . alkoxy, haloalkoxy, alkoxyaminoalkyl, 2-(Formula III), 3-(Formula IIT), 5- (Formula III), and 6-(Formula III), wherein Formula ITI, n, U, RL, R>, RL. RS, J, L, : W, X,Y, and Z are as defined above; Ris-T-(CH,),-R!, -NR®HR) or heterocyclyl, where the heterocyclyl moiety may be optionally substituted with halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, alkylaza, arylcarbonyl, benzyl, allyl, propargyl, alkylamino; where the aryl moiety may be optionally substituted with halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl; T is selected from the group consisting of -CH,-, carbonyl, oxygen, nitrogen, and sulfur; misO0,1,2,3,or4; R'is selected from the group consisting of -N(R*)(R®); alkyl; aryl; - C(O)N(R™®)(R™); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; - NOYR™R"); -PO)RHR™); -P(SYR)R'); alkylamino, where the aryl and heterocyclyl moieties may be optionally substituted with halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl; where RR’, R% R%, RR”, R™ and RY are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkylthio, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and - (CH,),-NR')[R'"), where pislor2; R'® and RY are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and the corresponding agriculturally acceptable salts thereof.

:

2. A compound of claim 1 wherein A is selected from the group consisting of hydrogen; alkylaminopolycyclyl; carbonylaminopolycyclyl; where the polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and Formula III, where Formula III is

' -(CH,),-U-R? Im wherein nisQorl;

U is selected from the group consisting of -CH,-, oxygen, and -NR®, where R® is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

R? is selected from aryl, alkylpolycyclyl; heterocyclyl; polycyclyl; where the aryl, heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and 1-R’, wherein R® is:

J

[J L R® where J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, : haloalkoxycarbonyl, aryl, and aryloxy, where the aryl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy; B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyaminoalkyl;

R is -T-(CH,),-R!, where , T is selected from the group consisting of -CH,-, oxygen, nitrogen, and sulfur; ‘ mis1,2,3, or4, R! is -NR®*)(R®); where R? and R’ are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and -(CH,),-N(R'*)(R""), where pislor2; R'® and R" are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and the corresponding agriculturally acceptable salts thereof.

3. A compound of claim 1 wherein Ais selected from the group consisting of hydrogen; alkylaminopolycyclyl; and carbonylaminopolycyclyl; where the polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and Formula XII, where Formula III is -(CH,),-U-R? IM wherein nisQorl; U is selected from the group consisting of -CH,-, oxygen, alkyl, oxyalkyloxy, alkenylamino, cabonylamino and -NR’, where R® is selected from the group - consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

R? is selected from aryl; alkylpolycyclyl; heterocyclyl; polycyclyl; where the : aryl, heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, ‘ haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and 1-R*, wherein R* is 8 1 X RY” LX BNC3 5Y 4 R* : where X,Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy; B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, and alkoxyaminoalky]; R is -T-(CH,),-R' or heterocyclyl, where the heterocyclyl moiety may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl, propargyl; T is selected from the group consisting of -CH,-, oxygen, nitrogen, and sulfur; ’ mis 1, 2,3, or4; R' is selected from the group consisting of -N(R®)(R®); alkyl; aryl; - C(ONR™)(R™); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; and - N(O)YR")R"), where the aryl and heterocyclyl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl; where R%, R%, R'2, R®, R" and R" are independently selected from the ’ group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and - (CH),"NR')[R"), where pislor2; R'® and RY are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and the corresponding agriculturally acceptable salts thereof.

4, A compound of claim 3 wherein A is hydrogen or Formula III, where Formula III is -(CH,),-U-R? © 15 ny wherein nis 0 or 1; U is selected from the group consisting of -CH,-, oxygen, and -NR®, where R® is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl; R? is selected from alkylpolycyclyl; heterocyclyl; polycyclyl; where the heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, baloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and 1-R*, wherein R* is 8 17 X z 6 3 5Y 4 rR?