EP0506709A1

EP0506709A1 - Arthropodicidal pyrazolines

Info

Publication number: EP0506709A1
Application number: EP19910900580
Authority: EP
Inventors: Rafael Shapiro
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1989-11-27
Filing date: 1990-11-20
Publication date: 1992-10-07
Also published as: WO1991008207A1; JPH05501708A; AU7897391A

Abstract

Pyrazolines arthropodicides présentant la formule (I) dans laquelle X, O ou S et Q représentent la formule (II) dans laquelle F complète un anneau benzène, pyridine ou thiopène fusionné, et la formule (III) dans laquelle A représente SO2, C(O) ou CRaRb, n'=0 ou 1.Arthropodicidal pyrazolines having the formula (I) in which X, O or S and Q represent the formula (II) in which F completes a fused benzene, pyridine or thiopene ring, and the formula (III) in which A represents SO2, C ( O) or CRaRb, n '= 0 or 1.

Description

TITLE

ARTHROPODICIDAL PYRAZOLINES

Background of the Invention

Field of the Invention

Disclosed are arthropodicidal pyrazolines, compositions containing them and their use.

State of the Art

WO88/302995 discloses arthropodicidal

pyrazolines of the formula:

wherein:

Q is and

A is 1, 2 or 3-atom bridge having 0 to 3 carbon atoms and 0 to 1 oxygen atom, NR₆ group, or

S(O)_q group, wherein each carbon individually can be substituted with 1 to 2 substituents selected from 1 to 2 halogen, C₁ to C₆ alkyl, C₂ to C₄ alkoxycarbonyl or phenyl optionally substituted with 1 to 3 substituents selected from W and one of the carbon atoms can be C(O) or C(S).

Summary of the Invention

This invention pertains to compounds of

Formula I including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and use of these compounds as arthropodicides. The compounds are:

wherein:

Q is selected from the group

Q-1 Q-2

and

A is selected from the group SO₂, C(O) and

CR_aR_a;

B is selected from the group H, C₁-C₆ alkyl, C₃-C₆ cycloalkyl optionally substituted with 1 to 2 halogens or 1 to 2 CH₃, C₄-C₆ cyclo- alkylalkyl, C₁-C₆ haloalkyl, OR₇, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₆ alkoxyalkyl, C₂-C₆ cyanoalkyl, C₃-C₈ alkoxycarbonylalkyl, CO₂R₃, C(O)R₃, C(O)NR₃R₄, C(S)NR₃R₄, C(S)R₃, C(S)SR₃, phenyl, phenyl substituted with (R₅)_p, benzyl, and benzyl substituted with 1 to 3 substituents independently selected from W;

W is selected from the group halogen, CN, NO₂, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy, C₁-C₂ alkylthio, C₁-C₂ haloalkylthio, C₁-C₂ alkylsulfonyl, and C₁-C₂ haloalkylsulfonyl;

R₁, R₂ and R₅ are independently selected from the group R₃, halogen, CN, N₃, SCN, NO₂,

OR₃, SR₃, SOR₃, SO₂R₃, OC(O)R₃, OSO₂R₃, CO₂R₃, C(O)R₃, C(O)NR₃R₄, SO₂NR₃R₄, NR₃R₄, NR₄C(O)R₃, OC(O)NHR₃, NR₄C(O)NHR₃, and

NR₄SO₂R₃, or when m is 2, (R₁)2 when

attached to adjacent carbon atoms can be taken together as -OCH₂O-, -OCH₂CH₂O- or -CH₂CH₂O- to form a 5- or 6-membered fused ring or when n is 2, (R₂)₂ when attached to adjacent carbon atoms can be taken together as -OCH₂O-, -OCH₂CH₂O- or -CH₂CH₂O- to form a 5- or 6-membered fused ring or when p is 2, (R₅)₂ when attached to adjacent carbon atoms can be taken together as -OCH₂O-, -OCH₂CH₂O- or -CH₂CH₂O-, each of which can be substituted, independently, by 1 to 4 halogen atoms or 1 to 2 methyl groups;

R₃ is selected from the group H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ halo- alkenyl, C₂-C₆ alkynyl, C₂-C₆ haloalkynyl, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylthioalkyl. C₁-C₂ nitroalkyl, C₂-C₆ cyanoalkyl, C₃-C₈ alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, phenyl, benzyl, and phenyl or benzyl substituted with 1 to 3

substituents independently selected from W; R₄ is selected from the group H and C₁-C₄ alkyl or R₃ and R₄ when attached to the same atom can be taken together as (CH₂)₄, (CH₂)₅ or

(CH₂CH₂OCH₂CH₂);

R₆ is selected from the group SR₃, SOR₃, SO₂R₃, C(O)R₃, CO₂R₃, C(O)NR₃R₇, C(S)NR₃R₇, C(S)R₃, C(S)OR₃, P(O)(OR₃)₂, P(S)(OR₃)₂, P(O)(R₃)OR₃ and P(O) (R₃) (SR₇); provided that when R₆ is other than COR₃, C(O)NR₃R₇ or C(S)NR₃R₇ then R₃ is other than H;

R₇ is selected from the group H, C₁-C₄ alkyl, C₂-C₄ alkenyl, and C₂-C₄ alkynyl;

R_a and R_b are independently selected from the group H and C₁-C₃ alkyl;

X is O or S;

n is 1 to 2;

m is 1 to 3;

p is 1 to 3;

Y is selected from the group H, C₁-C₂₂ alkyl, C₂-C₂₂ alkoxyalkyl, CHO, C₂-C₂₂ alkyl- carbonyl, C₂-C₂₂ alkoxycarbonyl, C₂-C₂₂ haloalkylcarbonyl, C₁-C₂₂ alkylthio, C₁-C₂₂ haloalkylthio, phenylthio, phenylthio substituted with 1 to 3 substituents independently selected from W and S-J; J is selected from the group

NR₈CR₉, NR₈S(O)_tR₉, N '

^X

J ₁ J ₂ J₃ J ₄

NR₈R₁₂ an d SR₁₀ ;

J₅ J₆ J₇ J₈ R₈ and R₁₂ are independently selected from the group C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₄-C₇ cycloalkylalkyl, phenyl optionally substituted with 1 to 2 substituents selected from W, benzyl optionally substituted with 1 to 2 substituents selected from W, phenethyl optionally substituted with 1 to 2 substituents selected from W, C₂-C₆ cyanoalkyl, C₂-C₆ alkoxyalkyl, C₃-C₈ alkoxycarbonylalkyl and C₄-C₈ dialkylamino- carbonylalkyl, or R₈ and R₁₂ can be taken together as (CH₂)₄, (CH₂)₅ or (CH₂)₂O(CH₂)₂; R₉ is selected from the group F, C₁-C₂₂ alkyl, C₁-C₆ haloalkyl, C₁-C₂₂ alkoxy, C₂-C₈ dialkyl- amino, piperidinyl, pyrolidinyl, morpholino, C₁-C₄ haloalkoxy, C₁-C₄ alkoxy substituted with cyano, nitro, C₂-C₄ alkoxy, C₄-C₈

alkoxyalkoxy, C₁-C₂ alkylthio, C₂-C₃ alkoxy- carbonyl, C₃-C₅ alkylaminocarbonyl and

phenyl, or R₉ is phenyl optionally substituted with 1 to 2 substituents selected from W, or phenoxy optionally substituted with 1 to 2 substituents selected from W;

R₁₀ and R₁₁ are independently selected from the group C₁-C₄ alkyl, C₂-C₄ haloalkyl and phenyl optionally substituted with 1 to 2 substituents selected from W, or R₁₀ and R₁₁ can be taken together as (CH₂)₂, (CH₂)₃ or

CH₂C(CH₃)₂CH₂;

R₁₃ is selected from the group H, F, Cl and CF₃; R₁₄ is selected from the group H and F;

R₁₅ is selected from the group C₁-C₄ alkyl,

CO₂CH₃, C₃-C₆ cycloalkyl, C₄-C₇ cyclo- alkylalkyl, phenyl optionally substituted with F or Cl in the para-position, and benzyl optionally substituted with F or Cl in the para-position;

R₁₆ is selected from the group H, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ halo- alkenyl, phenyl optionally substituted with F, Cl, Br, CF₃, CH₃, OCF₃, and benzyl optionally substituted with F, Cl, Br, CH₃, CF₃ or OCF₃;

t is O to 2; and

Y₁ is O or S;

characterized further in that, when Q is Q-11,

(i) R₁ is in the para position and m is 1; (ii) R₁₃ is other than Cl when R₁₅ is

n-propyl and R₁ is Cl;

(iii) R₁₆ is other than CH₃ or allyl when R₁₃ is Cl, R₁₅ is CO₂CH₃ and R₁ is CF₃; (iv) R₁₆ is other than benzyl when R₁₃ is Cl,

R₁₅ is CO₂CH₃ and R₁ is OCF₃;

(v) Y is selected from the group H, CH₃,

C(O)CH₃, and CO₂CH₃; (vi) Y is selected from the group H and

CO₂CH₃ when R₁₃ is F or Cl, R₁ is CF₃ and R₁₆ is CH₃;

(vii) R₁₃ and R₁₄ are not simultaneously H;

and

(viii) R₁ is selected from the group CF₃, OCF₃

Cl and Br.

In the above definitions, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl", denotes straight chain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the different butyl, pentyl, hexyl isomers.

Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy or

hexyloxy isomers.

Alkenyl denotes straight chain or branched alkenes, e.g., vinyl, 1-propenyl, 2-propenyl,

3-propenyl and the different butenyl, pentenyl and hexenyl isomers.

Alkynyl denotes straight chain or branched alkynes, e.g, ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl and hexynyl isomers.

Alkylthio denotes methylthio, ethylthio and the different propylthio, butylthio, pentylthio and

hexylthio isomers.

Alkylsulfinyl, alkylsulfonyl, alkylamino, etc., are defined analogously to the above examples.

Cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term "halogen", either alone or in compound words such as "haloalkyl", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of haloalkyl include CH₂CH₂F, CF₂CF₂H and CH₂CHFCl. The terms "halocyclo- alkyl", "haloalkenyl" and "haloalkynyl" are defined analogously to the term "haloalkyl".

The total number of carbon atoms in a substituent group is indicated by the "C_i to C_j" prefix where i and j are numbers from 1 to 22. For example, C₁ to C₃ alkylsulfonyl would designate methylsulfonyl through propylsulfonyl; C₂ alkoxyalkoxy would designate OCH₂OCH₃; C₄ alkoxyalkoxy would designate the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including OCH₂OCH₂CH₂CH₃ and

OCH₂CH₂OCH₂CH₃; C₂ cyanoalkyl would designate CH₂CN and C₃ cyanoalkyl would designate CH₂CH₂CN and

CH(CN)CH₃; C₂ alkylcarbonyl would designate C(O)CH₃ and C₄ alkylcarbonyl would include C(O)CH₂CH₂CH₃ and C(O)CH(CH₃)₂; and as a final example, C₃ alkoxy- carbonylalkyl would designate CH₂CO₂CH₃ and C₄ alkoxy- carbonylalkyl would include CH₂CH₂CO₂CH₃ , CH₂CO₂CH₂CH₃ and CH(CH₃)CO₂CH₃.

Preferred Compound A are those of Formula I wherein:

R_a is H;

R_b is H;

B is selected from the group H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₆ alkoxyalkyl, C₃-C₈ alkoxy- carbonylalkyl, CO₂R₃, C(O)R₃, C(O)NR₃R₄, C(S)NR₃R₄, C(S)R₃, C(S)SR₃, phenyl, and phenyl substituted by (R₅)_p;

R₂ is selected from the group R₃, halogen, CN,

SCN, NO₂, OR₃, and SR₃; R₃ is selected from the group H, C₁-C₄ alkyl, C₁-C₂ haloalkyl, C₃-C₄ alkenyl, C₃-C₄ haloalkenyl, propargyl, phenyl, and benzyl, or phenyl or benzyl substituted with one of F, Cl, Br, CF₃, OCF₃, OCF₂H or NO₂;

p is 1 or 2;

m is 1 or 2;

X is O;

Y is selected from the group H, C₁-C₄ alkyl, SCH₃, SCCl₃, SO₂CH₃, SC₆H₅, 2-NO₂-C₆H₄S, C(O)CH₃, C(O)CH₂CH₃, C(O)CF₃; CO₂CH₃, CO₂CH₂CH₃, and S-J;

J is J₁, J₂, J₃, J₄ or J₅;

R₈ and R₁₂ are independently selected from the group C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₅-C₆ cycloalkyl, C₃-C₈ alkoxycarbonylalkyl, phenyl, benzyl, and phenethyl, each

phenyl, benzyl and phenethyl optionally substituted with W, or, R₈ and R₁₂ can be taken together as (CH₂)₄, (CH₂)₅ or

(CH₂)₂O(CH₂)₂;

R₁₀ and R₁₁ are independently selected from the group C₁-C₃ alkyl and phenyl;

t is 2; and

W is selected from the group Cl, F, Br, CN, C F₃, C₁-C₂ alkyl, C₁-C₂ alkoxy, OCF₂H,

OCF₃, and NO₂.

Preferred Compounds B are Compounds A wherein:

B is selected from the group H, C₁-C₄ alkyl, C₃-C₄ alkoxycarbonylalkyl, CO₂R₃, C(O)R₃, phenyl and phenyl substituted with (R₅)_p; R₁ is selected from the group halogen, CN, SCN, NO₂, OR₃, SR₃, SO₂R₃, CO₂R₃, C(O)R₃, and R₃, with one substituent in the

4-position;

R₁ can be taken together as -CH₂C(CH₃)₂O-,

OCH₂CH₂O-, OCF₂CF₂O- or -CF₂CF₂O- to form a 5- or 6-membered fused ring;

R₅ is selected from the group H, R₃, halogen,

CN, SCN, NO₂, OR₃, SR₃, SO₂R₃, C(O)R₃, OSO₂R₃, CO₂R₃, C(O)R₃, C(O)NR₃R₄,

SO₂NR₃R₄, and NR₃R₄;

R₃ is selected from the group H, C₁-C₄ alkyl, C₁-C₂ haloalkyl, C₃-C₄ alkenyl, and

propargyl;

R₄ is selected from the group H and CH₃;

m and p are independently 1 or 2 and one

substituent is in the para-position;

Y is is selected from the group H, CH₃, COCH₃,

CO₂CH₃, and S-J;

J is J₁ or J₂; .

R₈ is selected from the group C₁-C₄ alkyl and phenyl optionally substituted with Cl or CH₃; and

R₉ is selected from the group C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₁-C₆ haloalkyl, dimethyl- amino, phenyl optionally substituted with Cl and CH₃, or, R₉ is C₁-C₄ alkoxy

substituted with C₂-C₄ alkoxy or 1 to 6 halogens.

Preferred Compounds C are Compounds B wherein:

R₁ is selected from the group Cl, F, Br, CF₃, CN, OCF₃, OCF₂H, OCF₂CF₂H, and SCF₂H; R₂ and R₅ are independently selected from the group H, Cl, F, Br, CN, CF₃, CH₃, OCF₂H, OCF₃, SCH₃, SCF₂H, NO₂, and OCH₂CF₃;

B is selected from the group H, CH₃, CH₂CH₃, CO₂CH₃, CO₂CH₂CH₃, CO₂(CH)(CH₃)₂, phenyl and phenyl substituted with (R₅)_p, and; R₆ is selected from the group SO₂R₃, CO₂R₃ COR₃, and CONHR₃.

Preferred Compounds D are Compounds C wherein Q is Q-1. Preferred Compounds E are Compounds C wherein Q is Q-2.

Preferred Compounds F are Compounds C wherein

Q is Q-3.

Preferred Compounds G are Compounds C wherein

Q is Q-4.

Preferred Compounds H are Compounds C wherein Q is Q-5.

Preferred Compounds I are Compounds C wherein Q is Q-6. Preferred Compounds J are Compounds C wherein Q is Q-7.

Preferred Compounds K are Compounds C wherein Q is Q-8. Preferred Compounds L are Compounds C wherein

Q is Q-9.

Preferred Compounds M are Compounds C wherein

Q is Q-10.

Preferred Compounds N are Compounds C wherein Q is Q-11.

Specifically preferred Compounds are:

(O) Methyl-3,3a,4,5-tetrahydro-5-(methyl- sulfonyl)-7-(trifluoromethyl)-2-[[[4- (trifluoromethyl)phenyl]amino]carbonyl]-

2H-pyrazolo[4,3-c] quinoline-3a- carboxylate (Q-1);

(P) 7-Chloro-3,3a,4,5-tetrahydro-3a-methyl-5- (methylsulfonyl)-N-[4-(trifluoromethyl)- phenyl]-2H-pyrazolo[4, 3-C]quinoline- 2-carboxamide (Q-1); and

(Q) 7-Chloro-3,3a,4,5-tetrahydro-3a,5-dimethyl-N- 4-(trifluoromethyl)phenyl]-2H-pyrazolo-

[4,3-c]-quinoline-2-carboxamide (Q-11).

Details of the Invention

For descriptive purposes, Q-1, where R_a and R_b are H, is used as a representative value of Q in the discussion that follows and is referred to by the following numbering system:

Compounds of Formula I can be prepared by the reaction of aryl isocyanates of Formula II and substituted 3,3a,4,5-tetrahydro-2H-pyrazolo- [4,3-c]quinolines of Formula III as shown in Scheme I. Typical reactions involve the combination of equimolar amounts of II and III in aprotic organic solvents including ether, ethyl acetate,

tetrahydrofuran, or dichloromethane. The temperature at which the reaction is run can be between -20°C and 80°C, with preferred temperatures being in the range of about -10°C to 40°C.

Scheme 1

II III

Z=R₆ or R₁₆ Tetrahydropyrazoloquinolines of Formula III can be prepared by acid hydrolysis of their

phosphorylated derivatives of Formula IV, as shown in Scheme 2.

Scheme 2

1

IV: Z = R₆ or R₁₆

R₁₇= Me or Et

The reaction of Scheme 2 is generally carried out by contacting the substrate with one to three equivalents of a strong acid such as HCl or p-toluene sulfonic acid, optionally containing some water, in a solvent such as ethanol or dioxane for 1 to 72 hours at 50°C to 100°C. The initial product of the

reaction is a salt of III which can either be

neutralized and extracted into an organic solvent for use in the reaction of Scheme 1, or used in that reaction directly in the presence of one to two equivalents of a suitable organic or inorganic base.

An alternate method for preparing compounds of Formula IV which are not suited to the reaction conditions described above is to exchange one bridgehead N-substituent for another, as outlined in Scheme 3.

Scheme 3

C R

IV: Z=protecting group IV: Z= H

IV Z = R₆ or R_{1 6} In reaction (A) of Scheme 3, a compound of Formula IV wherein the Z substituent is a suitable protecting group, such as i-butyloxycarbonyl, benzyl, or trifluoroacetyl, can be deprotected by reaction conditions suited to the particular protecting group, such as acidic, hydrogenolytic, or basic conditions, respectively. Such protecting groups and methods for their removal are well-known to one skilled in the art.

In reaction (B) of Scheme 3, the deprotected compound of Formula IV is typically combined with one equivalent of an alkylating agent corresponding to the desired Z substituent in an inert solvent such as dimethylformamide or tetrahydrofuran in the presence of one equivalent of a strong base such as sodium hydride at a temperature of between 0°C and 80°C for 0.1 to 24 hours. The product can be isolated by concentration, dilution with water, extraction into an organic solvent such as ether, and concentration. The product can be purified by crystallization or chromatography on silica gel, or it may be carried along as such to the following reaction.

The compounds of Formula IV are produced by the cyclization reaction of an olefinic phosphoryl- hydrazone of Formula V induced by the combination of a mild base such as triethylamine and a mild

halogenating agent such as N-bromosuccinimide, as shown in Scheme 4. Scheme 4

Z=R₆ or R_{1 6}

R_{1 7}=Me or Et

In the reaction of Scheme 4, the hydrazone of Formula V is typically dissolved in an inert,

anhydrous solvent in the presence of one of the base/haloimide components at -20 to 50° and the other component is added gradually. The product can be isolated by washing the reaction mixture with water, evaporating the solvent, and either recrystallizing or chromatographing to remove by-products.

The synthesis of compounds of Formula V can be accomplished by condensing an aldehyde of Formula VI with diethyl or dimethyl phosphorohydrazidate VII, as shown in Scheme 5. Scheme 5

VI VII

Z=R₆ or R₁₆ R₁₇ = Me or Et

The reaction of Scheme 5 can be conducted by contacting aldehyde VI and compound VII in an inert solvent such as dichloromethane for 0.1 to 16 hours, optionally in the presence of a catalytic (0.1 to 10%) amount of an acid such as acetic or p-toluene sulfonic, and optionally in the presence of an inorganic drying agent such as anhydrous magnesium sulfate. The product can be isolated by washing out excess VII with water and concentrating the dried solution. It can be purified, if desired, by

recrystallization or chromatography.

Compounds of Formula VI can be prepared by reacting, for example, an N-sulfonyl or N-benzyl anthranilic aldehyde of Formula VIII with alkylating agents of Formula IX, wherein L is a suitable

leaving-group, such as Cl, Br, I, OSO₂CH₃, or OSO₂Ar, as shown in Scheme 6. Scheme 6

VIII IX

Z = R₆ or R_{1 6} L = halo, OSO₂Me, etc.

The reaction of Scheme 6 is typically carried out by combining equimolar quantities of VIII and IX in a suitable solvent for alkylation reactions, such as dimethylformamide (DMF) in the presence of

slightly more than one equivalent of a suitable base, such as anhydrous potassium carbonate, and stirring vigorously at a temperature between 0° and 100°C.

The product is generally isolated by diluting the mixture with water and filtering the precipitated product or extracting into a solvent such as ether. Recrystallization or chromatography affords the pure product. Compounds of Formula VIII are recognized by those skilled in the art as being obtainable from substituted anilines or heterocyclic amines by known methods. Compounds of Formula IX are either known or are readily available from olefins or allylic

alcohols by known methods. In those cases where an R₆ or R₁₆ substituent would not be compatible with the reaction conditions prescribed in Schemes 2, 3, 4, 5, or 6, a strategy outlined in Scheme 7 can be employed.

Scheme 7

I I

( PG = protecting group) ( R_{1 6} is H)

( B) I ( R_{1 6} is H) I ( neit her R₆ nor

R_{1 6} is H)

In reaction A of Scheme 7, a compound of Formula I wherein the R₆ or R₁₆ substituent is replaced by a suitable protecting group, such as benzyloxycarbonyl, benzyl, trichloroethoxycarbonyl, trichloroacetyl, and the like, can be deprotected by conditions suited to that protecting group. Such protecting groups and methods for their removal are well known to one skilled in the art.

In reaction B of Scheme 7, the deprotected compound of Formula I is typically combined with an electrophilic species (E) corresponding to the desired R₆ or R₁₆ substituent (acyl halide or anhydride, alkyl chloroformate, carbamoyl halide, chlorophosphate, etc.) optionally in the presence of an acid-binding agent in an inert solvent such as dichloromethane, and the product of Formula I is isolated by washing with water, concentration, and crystallization or chromatography.

Using the methods described for Q=Q-1, the compounds of Formula I for which Q=Q-2 to Q-11 can also be prepared. Methods for preparing

intermediates for Q-9 and Q-10 can be found in the following references: J. Am. Chem. Soc., 100, 7600 (1978), J. Org. Chem., 50, 2066 (1985), and

J. Het. Chem., 23 , 1645 (1986).

The following Examples further illustrate the invention. EXAMPLE 1

Methyl 3,3a,4,5-tetrahydro-5(methylsulfonyl)-7- (trifluoromethyl)-2([4-(trifluoromethyl)phenyl- amino]carbonyl)2H-pyrazolo[4,3-c]quinoline-3a- carboxylate

Step A: Methyl 2-(methylsulfonylamino)-4-(trifluoro- methyl)benzoate

To a solution of 5.2 g of methyl 4-(trifluoro- methyl) anthranilate in 15 mL of pyridine was added 3.5 mL of methanesulfonyl chloride. After allowing the mixture to stand overnight, it was diluted with ice-water and acidified with aqueous HCl. The

resulting crystalline product was filtered, washed with water, suction-dried, and chromatographed to provide 4.4 g of product.

¹H NMR (CDCl₃) 8 3.1 (s, 3H), 4.0 (s, 3H), 7.4 (m, 1H), 8.0 (d, 1H), 8.2 (d, 1H), 10.6 (br s, 1H). Step B: 2-(methylsulfonylamino)-4-(trifluoro- methyl)benzaldehyde

The product (4.4 g) from Step A was dissolved in 50 mL of tetrahydrofuran at (THF) 0°C and 20 mL of 1 M LiAlH₄ in THF was added dropwise. After being stirred at 25°C for 0.5 hours, 30 mL of IN HCl was added dropwise. After extraction with ethyl acetate, drying with MgSO₄, and removal of solvent under vacuum, the product was dissolved in a 100 mL of dichloromethane and stirred with 15 g of activated manganese dioxide at 40°C for 2.5 hours. The MnO₂ was filtered off using Celite® and the filtrate was concentrated and triturated with hexanes to provide 2.1 g of a white solid.

1H NMR (CDCI₃) δ 3.16 (s, 3H), 7.5 (d, 1H), 7.87

(d, 1H), 8.0 (s, 1H), 10.0 (s, 1H), 10.7 (br s, 1H).

Step C: Methyl 2-(N-[2-formyl-5(trifluoromethyl)- phenyl]-N-(methylsulfonyl)aminomethyl)- 2-propenoate

To a solution of the product from Step B in 10 mL of dimethylformamide (DMF) was added 1.2 g of potassium carbonate and 1.6 g of methyl 2-brom ethyl- acrylate. After being stirred vigorously for hours at 25°C, the mixture was diluted with aqueous HCl and the resulting product was filtered, washed with water, and suction-dried to provide 2.5 g of a solid; mp 110°C to 112°C.

1H NMR (CDCl₃) δ 3.09 (S, 3H), 3.70 (s, 3H), 4.59 (s, 2H), 5.75 (s, 1H), 6.30 (s, 1H), 7.58 (s, 1H), 7.72 (d, 1H), 8.05 (d, 1H), 10.25 (s, 1H). Step D: Methyl 3,3a,4,5-tetrahydro-5-(methylsulfonyl)-7-trifluoromethyl)-2-([4-trifluoromethyl)phenylamino]carbonyl)2H- pyrazolo[4,3-c]quinoline-3a-carboxylate A mixture of 2.4 g of the product from Step C, 1.2 g of diethylphosphonohydrazidate, and 1 g of anhydrous magnesium sulfate in 50 mL of

dichloromethane was stirred for 2 hours at 25°C.

After filtration of the drying agent, washing the solution with water, drying with MgSO₄, filtration, and removal of solvent under vacuum, 3.8 g of an oil was obtained. This was dissolved in 150 mL of ether containing 2 mL of triethylamine, cooled to 0°C, and 2.2 g of N-bromosuccinimide was added over a period of 20 minutes. The mixture was allowed to warm to

25°C, and was then washed with water and brine, dried with MgSO₄, and concentrated under vacuum. After chromatographing the residue on silica gel eluting with a gradient of ethyl acetate in hexanes, the purified cyclization product was heated in 100 mL of methanol containing 2.2 g of p-toluenesulfonic acid monohydrate at 65°C for 16 hours. The methanol was removed under vacuum, the residue was stirred with a mixture of ether and aqueous NaHCO₃, the ether extract was washed with brine and dried with MgSO₄. To the dried extract was added 1.3 g of 4-trifluoromethylphenyl isocyanate and the ether was removed under vacuum. The residue was triturated with a small volume of ether to provide 0.6 g of the final product; mp 221°C to 223°C.

¹H NMR (CDCl₃) δ 3.15 (s, 3H), 3.62 (d, 1H), 3.79 (s, 3H), 3.85 (d, 1H), 4.65 (d, 1H), 5.21 (d, 1H), 7.41 (d, 1H), 7.61 (ABq, 4H), 8.05 (m, 3H).

EXAMPLE 2

7-Chloro-3,3a,4,5-tetrahydro-3a,5-dimethyl-N[4- (trifluoromethyl)phenyl]-2H-pyrazolo-[4,3-c]- quinoline-2-carboxamide

Step A: 4-Chloro-2-([(1,1-dimethylethoxy)carbonyl] amino)benzoic acid

A mixture of 110 ml of 1N NaOH, 17.2 g of

2-amino-4-chlorobenzoic acid, and 75 ml of t-butyl alcohol was stirred at room temperature, and 24.0 g of di-t-butyldicarbonate was added dropwise. This mixture was stirred for 16 hours and then the mixture was extracted twice with 25 ml of hexanes. The organic extract was washed with three 20-ml portions of saturated aqueous NaHCO₃. The aqueous extracts were combined with the reaction mixture and cooled to 0-5°C. This mixture was acidified with 1N KHSO₄ solution to pH 2 and extracted with three 300 ml portions of ether.

The ether extracts were washed with IN NaOH, dried over MgSO₄, and concentrated. The resultant solid was dried under vacuum to provide 20.1 g of a creamy white solid.

IR (mineral oil): 1740, 1675 cm^-1.

¹H NMR (acetone-d₆) : δ 1.54 (s, 9H), 7.08 (m, 1H),

8.10 (d, 1H), 8.58 (d, 1H) (NH and CO₂H offscale).

Step B: 1,1-Dimethylethyl[5-chloro-2(hydroxymethyl)- phenyl]carbamate

The title compound from Step A, 14.65 g, was suspended in 400 ml of CH₂Cl₂. Diisobutylaluminum hydride (18 ml of a IN solution in hexanes) was then slowly added to this suspension, producing a clear yellow solution. This solution was cooled to 0-5°C, and an additional 208 ml of the aluminum reagent was added dropwise. The reaction mixture was then stirred for 16 hours at room temperature, quenched with 10 ml of methyl alcohol, and diluted with 600 ml of CH₂Cl₂. This solution was washed twice with 500 ml of IN aqueous KHSO₄, three times with 500 ml of H₂O, and once with brine. The cloudy organic layer was dried over MgSO₄, filtered through Celite, and concentrated to 5 g of a yellow oil. Chromatography on silica gel afforded 3.26 g of the title product as a yellow oil.

1H NMR (CDCl₃): δ 1.50 (s, 9H), 2.82 (t, OH),

4.57 (d, 2H), 6.89-7.02 (m, 2H), 7.83 (s, 1H), 7.96 (s, 1H).

Step C: 1,1-Dimethylethyl (5-chloro-2-formylphenyl)- carbamate

The title compound of Step B, 3.26 g, was dissolved in 120 ml of CH₂Cl₂ and treated with 8.20 g of MnO₂. This mixture was heated at reflux for 4 hours, cooled to room temperature, and filtered through Celite. The organic solution was

concentrated under vacuum to provide the title product as an oil, 2.72 g. ¹H NMR (CDCl₃): δ 1.56 (s, 9H), 7.10 (dd, 1H),

7.55 (d, 1H), 8.56 (d, 1H), 9.90 (s, 1H), 10.52 (br s, 1H).

Step D: 1,1-Dimethylethyl (5-chloro-2-formylphenyl)

(2-methyl-2-propenyl)carbamate

A solution of 1.36 g of the title compound of Step C in 10 ml DMF was treated with 0.24 g NaH (60% dispersion in mineral oil) in small portions. To this solution was added 1.01 g of 1-bromo-2-methyl-2- propene. After 2 hours at room temperature , the reaction mixture was poured over ice, and the

resultant mixture was extracted with ether. The ether extract was washed twice with water and with brine, dried over MgSO₄, and concentrated.

Chromatography on silica provided the title product as an oil, 0.88 g.

¹H NMR (CDCl₃): δ 1.40 (s, 9H), 1.77 (s, 3H),

4.21 (S, 2H), 4.80 (s, 1H), 4.90 (s, 1H), 7.24-7.46 (m, 2H),

7.85 (d, 1H), 10.03 (s, 1H). Step E: 1,1-Dimethylethyl 7-chloro-2-(diethoxyphos- phinyl)-3,3a,4,5-tetrahydro-3a-methyl-2H- pyrazolo[4,3-c]quinoline-5-carboxylate

To a solution of 0.57 g of diethyl

phosphorohydrazidate and 3 drops of glacial acetic acid in 10 ml of ether was added a solution of 0.88 g of the title compound of Step D in 10 ml of ether. This solution was stirred at 0-5°C for 30 minutes and diluted with 20 ml of ether. This solution was washed with saturated aqueous NaHCO₃, water, and brine. The ether extract was then dried over MgSO₄ and concentrated under vacuum to afford 1.15 g of the intermediate hydrazone as a yellow oil. This

material and 0.18 g of triethylamine in 20 ml of ether was stirred at 0°C, and 0.23 g of

N-bromosuccinimide was added in portions. This mixture was diluted with 30 ml of ether after 20 minutes and washed with saturated aqueous NaHCO₃, water, and brine. The ether extract was dried over MgSO₄ and concentrated. Chromatography on silica provided 0.39 g of the title compound as yellow oil, 1H NMR (CDCl₃): δ 1.25 (s, 3H), 1.33 (t, 6H),

1.52 (s, 9H), 3.3 (d, 1H), 3.5 (d, 1H), 3.8 (d, 1H)

4.2 (m, 4H), 4.6 (d, 1H),

7.2-7.5 (m, 2H), 7.85 (d, 1H).

Step F: Diethyl (7-chloro-3,3a,4,5-tetrahydro-3a- methyl-2H-pyrazolo[4,3-c]quinolin-2-yl)- phosphonate

A mixture of 0.81 g of the title compound of

Step E and 3.5 g of trifluoroacetic acid in 20 ml of CH₂Cl₂ was stirred at room temperature for three hours. This mixture was poured over ice, and saturated aqueous NaHCO₃ was added to obtain a pH of 9-10. The layers were separated, and the organic phase was washed with water and brine. The organic layer was dried over MgSO₄ and concentrated.

Chromatography on silica provided 0.51 g of the title compound as a brown foam.

¹H NMR (CDCl₃): δ 1.30 (s, 3H), 1.33 (m, 6H),

3.3-3.4 (m, 2H), 3.5 (d, 1H), 3.7 (d, 1H), 4.2 (m, 5H),

6.55-6.70 (m, 2H), 7.65 (d, 1H).

Step G: Diethyl (7-chloro-3,3a,4,5-tetrahydro-3a,5- dimethyl-2H-pyrazolo[4,3-c]quinolin-2-yl)- phosphonate

To a solution of 0.51 g of the title compound of Step F in 10 ml of DMF was added 0.09 g of NaH (60% dispersion) in mineral oil. After 1 hour, this mixture was cooled to 0°C, and 0.43 g of iodomethane was added. The mixture was then stirred at room temperature for 1 hour and poured over ice. This mixture was extracted with ether, and the ether extracts were washed with water four times and once with brine. The organic phase was dried over MgSO₄ and concentrated. Chromatography on silica provided 0.33 g of the title compound as yellow crystals. 1H NMR (CDCl₃): δ 1.32 (s, 3H), 1.35 (m, 6H),

2.96 (s, 3H), 3.25 (d, 1H), 3.5 (m, 2H), 3.76 (d, 1H), 4.2 (m, 4H), 6.58-6.70 (m, 2H), 7.68 (d, 1H).

Step H: 7-Chloro-3,3a,4,5-tetrahydro-3a,5-dimethyl- N-[4-(trifluoromethyl)phenyl)-2H-pyrazolo- [4,3-c]quinoline-2-carboxamide

A solution of 0.33 g of the title compound of Step G in 15 ml of ethanol and 0.77 ml of

concentrated HCl was heated at reflux for 2 hours. This mixture was concentrated, and the residue was triturated with ether and hexane. Filtration provided 0.24 g of a solid which was then suspended in 8 ml of CH₂Cl₂ and treated with 1.3 ml of saturated aqueous NaHCO₃ and 0.15 g of

p-(trifluoromethyl)phenylisocyanate. This mixture was stirred for 16 hours, diluted with CH₂Cl₂, and washed with H₂O and brine.

The organic phase was dried over MgSO₄ and concentrated to give a solid. Trituration with ether/hexane and filtration afforded 0.36 g of a compound of this invention as a light yellow powder, mp 149°C to 153°C.

1H NMR (DMSO): δ 1.24 (s, 3H), 2.97 (s, 3H),

3.44 (d, 1H), 3.54 (d, 1H), 3.63 (d, 1H), 3.90 (d, 1H), 6.81 (s, 1H), 7.62-7.67 (m, 3H),

7.8 (d, 1H), 7.89 (d, 2H), 9.32 (s, 1H).

EXAMPLE 3

7-Chloro-3,3a,4,5-tetrahydro-5-benzyl-3a-methyl- N-[4-(trifluoromethyl)phenyl]-2H-pyrazolo- [4,3-clquinoline-2-carboxamide

Step A: 2- (Benzyl) amino-4-chlorobenzoic acid

A mixture of 8.25 g of 2-amino-4-chlorobenzoic acid, 24 mL of benzaldehyde, 7.38 g of sodium acetate and 38 mL of acetic acid in 300 mL of a 70:30

ethanol/water solution was stirred rapidly at 0-5°C. Sodium borohydride, 5.0 g, was added in small

portions, maintaining the temperature below 5°C.

This mixture was neutralized with about 300 mL of saturated aqueous NaHCO₃, and this mixture was extracted with two 500 mL portions of ethyl acetate. The combined organic extracts were washed with water and brine, dried over MgSO₄ and concentrated. The resultant solid was triturated with hexanes and filtered, washing with hexanes. The light yellow powder, dried in air, weighed 8.23 g (mp 167-170°C). ¹H NMR (CDCl₃): δ 4.45 (s, 2H), 6.56-6.65 (m, 2H),

7.28-7.45 (m, 6H), 7.91 (d, 1H),

8.10 (br s, 1H). Step B : N-[5-Chloro-2-(hydroxymethyl)phenyl]

benzylamine

The title compound from Step A, 3.00 g, was stirred in 120 mL of dry tetrahydrofuran at 0°C, and a 1.0 mL ether solution of lithium aluminum hydride was added dropwise. This mixture was stirred at 0°C for 30 minutes and at room temperature for 15

minutes. A few drops of methanol were added to quench excess hydride, then this mixture was diluted with ether. The ether solution was washed with water and brine, dried over MgSO₄, and concentrated under vacuum to afford 2.74 g of a yellow oil.

¹H NMR (CDCl₃): 8 1.64 (br S, 1H), 4.34 (s, 2H),

4.64 (s, 2H), 5.30 (br s, 1H), 6.61 (m, 2H), 6.97 (d, 1H), 7.20-7.40 (m, 5H). Step C: 2-[N-(Benzyl)amino]-4-chlorobenzaldehyde

The title compound of Step B, 2.98 g, was submitted to the reaction conditions of Example 2, Step C to provide 2.81 g of a yellow oil.

Purification by silica gel chromatography provided the title compound as an oil, 2.40 g.

1H NMR (CDCl₃): δ 4.43 (d, 2H), 6.60-6.70 (m, 2H),

7.20-7.45 (m, 6H), 8.84 (br s, 1H), 9.80 (s, 1H).

Step D: 2-(N-[Benzyl]-N-[2-methyl-2-propenyl]amino)- 4-chlorobenzaldehyde

The title compound of Step C, 2.74 g, was submitted to the reaction conditions of Example 2, Step D. Silica gel chromatography afforded 1.01 g of the title compound as an oil.

1H NMR (CDCl₃): 8 1.72 (s, 3H), 3.68 (s, 2H),

4.35 (s, 2H), 4.94 (br s, 2H), 6.76-7.46 (m, 7H), 7.73 (d, 1H), 10.36 (s, 1H).

Step E: 5-Benzyl-7-chloro-3,3a,4,5-tetrahydro-3a- methyl-N-[4-(trifluoromethyl)phenyl]-2H- pyrazolo[4,3-c]quinoline-2-carboxamide

The title compound of Step D, 1.01 g, was submitted to the reaction conditions of Example 2, Step E. Silica gel chromatography afforded the purified cyclization intermediate, which was then submitted to the reaction conditions of Example 2, Step H. A compound of this invention was thus obtained as 1.52 g of a tan powder, mp 190.5-193°C. ¹H NMR (CDCl₃): δ 1.38 (s, 3H), 3.40 (d, 1H),

3.58-3.66 (overlapping d, 2H), 4.02 (d, 1H), 4.54 (s, 2H), 6.73

(m, 2H), 7.20-7.40 (m, 5H), 7.56 (d, 2H), 7.66 (d, 2H), 7.72 (d, 1H), 8.17 (s, 1H). EXAMPLE 4

7-Chloro-3,3a,4,5-tetrahydro-3a-methyl-N-[4-(trifluoromethyl)phenyl]-2H-pyrazolo[4,3-c]quinoline- 2-carboxamide

The title compound of Example 3, Step E, 1.11g, was dissolved in a mixture of 25 mL of

dimethoxyethane, 25 mL of methanol and 2 mL of formic acid. This solution was added, dropwise, to a stirred suspension of 1.0 g of 10% palladium on carbon in 25 mL of 4.4% methanolic formic acid.

After 1 hour, an additional 25 mL of 4.4% methanolic formic acid was added dropwise over 20 minutes. This mixture was filtered through Celite® and washed with ethyl acetate, and the filtrate was concentrated.

The residue was dissolved in ethyl acetate and washed with saturated aqueous NaHCO₃, IN NaOH, water, and brine. The organic phase was dried over MgSO₄ and concentrated under vacuum. Silica gel chromatography of the residue afforded 0.57 g of a compound of this invention as a light yellow solid, mp 86.5-90°C.

1H NMR (CDCl₃): δ 1.38 (s, 3H), 3.36-3.52 (m, 2H),

3.65 (d, 1H), 4.04 (d, 1H), 4.35 (br s, 1H), 6.63 (m, 1H), 6.72 (m, 1H), 7.52-7.70 (m, 5H), 8.19

(s, 1H).

Using the procedures described above, the following compounds can be prepared as exemplified in Tables 1 to 14 in which X=O, Y=H and R_a=R_b=H unless otherwise noted.

J

I

1 l

1 1

Formulation and Use

The compounds of this invention will generally be used in formulation with an agriculturally

suitable carrier comprising a liquid or solid diluent or an organic solvent. Useful formulations of the compounds of Formula I can be prepared in

conventional ways. They include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry

flowables and the like. Many of these can be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from

about one to several hundred liters per hectare.

High strength compositions are primarily used as

intermediates for further formulation. The

formulations, broadly, contain from less than about 1% to 99% by weight of active ingredient(s) and at least one of a) about 0.1% to 20% surfactant(s) and b) about 5% to 99% solid or liquid diluent(s). More specifically, they will contain effective amounts of these ingredients in the following approximate

proportions:

Percent by weight

Active

Ingredient Diluent(s) Surfactant(s)

Wettable Powders 25-90 0-74 1-10

Oil Suspensions, 5-50 40-95 0-15

Emulsions, Solutions,

(including Emulsifiable

Concentrates)

Dusts 1-25 70-99 0-5

Granules, Baits 0.01-95 5-99 0-15

and Pellets

High Strength 90-99 0-10 0-2

Compositions Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New

Jersey. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C.

"McCutcheon's Detergents and Emulsifiers Annual", Allured Publ. Corp., Ridgewόod, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active

Agents", Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, U.S. 3,060,084). Granules and pellets can be made by spraying the active

material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning,

"Agglomeration", Chemical Engineering. December 4, 1967, pages 147 and following, and "Perry's Chemical Engineer's Handbook", 4th Ed., McGraw-Hill, New York, 1963, pages 8 to 59 and following.

Example A

Emulsifiable Concentrate

methyl-3,3a,4,5-tetrahydro-5-(methylsulfonyl)- 7-(trifluoromethyl)-2-[[[4-(trifluoromethyl)- phenyl]amino]carbonyl]-2H-pyrazolo[4,3-c]- quinoline-3a-carboxylate 20%

blend of oil soluble sulfonates

and polyoxyethylene ethers 10% isophorone 70%

The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product.

Example B

Wettable Powder

methyl-3,3a,4,5-tetrahydro-5-(methylsulfonyl)- 7-(trifluoromethyl)-2-[[[4-(trifluoromethyl)- phenyl]amino]carbonyl]-2H-pyrazolo[4,3-c]- quinoline-3a-carboxylate 30%

sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 63%

The active ingredient is mixed with the inert materials in a blender. After grinding in a hammer- mill, the material is re-blended and sifted through a 50 mesh screen. Example C

Dust

Wettable powder of Example B 10%

pyrophyllite (powder) 90%

The wettable powder and the pyrophyllite diluent are thoroughly blended and then packaged. The product is suitable for use as a dust.

Example D

Granule

methyl-3,3a,4,5-tetrahydro-5-(methylsulfonyl)- 7-(trifluoromethyl)-2-[[[4-(trifluoromethyl)- phenyl]amino]carbonyl]-2H-pyrazolo[4,3-c]- quinoline-3a-carboxylate 10%

attapulgite granules (low volative

matter, 0.71/0.30 mm; U.S.S. No.

25-50 sieves) 90% The active ingredient is dissolved in a volatile solvent such as acetone and sprayed upon dedusted and pre-warmed attapulgite granules in a double cone blender. The acetone is then driven off by heating. The granules are then allowed to cool and are packaged.

Example E

Granule

Wettable powder of Example B 15%

gypsum 69%

potassium sulfate 16%

The ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 0.1 to 0.42 mm (U.S.S. No. 18 to 40 sieves), the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. These granules contain 4.5% active ingredient.

Example F

Solution

methyl-3,3a,4,5-tetrahydro-5-(methylsulfonyl)- 7-(trifluoromethyl)-2-[[[4-(trifluoromethyl)- phenyl]amino]carbonyl]-2H-pyrazolo[4,3-c]- quinoline-3a-carboxylate 25%

N-methyl-pyrrolidone 75%

The ingredients are combined and stirred to produce a solution suitable for direct, low volume application.

Example G

Aqueous Suspension

methyl-3,3a,4,5-tetrahydro-5-(methylsulfonyl)- 7-(trifluoromethyl)-2-[[[4-(trifluoromethyl)- phenyl]amino]carbonyl]-2H-pyrazolo[4,3-c]- quinoline-3a-carboxylate 40%

polyacrylic acid thickener 0.3% dodecyclophenol polyethylene glycol

ether 0.5% disodium phosphate 1.0% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7% The ingredients are blended and ground together in a sand mill to produce particles substantially all under 5 microns in size. Example H

Oil Suspension

7-chloro-3,3a,4,5-tetrahydro-3a-methyl-5- (methylsulfonyl)-N-[4-(trifluoromethyl)- phenyl]-2H-pyrazolo[4,3-c]quinoline-2-carboxamide 35%

blend of polyalcohol carboxylic 6.0% esters and oil soluble petroleum

sulfonates

xylene range solvent 59.0%

The ingredients are combined and ground together in a sand mill to produce particles substantially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.

Example I

Bait Granules

methyl-3,3a,4,5-tetrahydro-5-(methylsulfonyl)- 7-(trifluoromethyl)-2-[[[4-(trifluoromethyl)- phenyl]amino]carbonyl]-2H-pyrazolo[4,3-c]- quinoline-3a-carboxylate 3.0% blend of polyethoxylated nonyl- 9.0% phenols and sodium dodecyl- benzene sulfonates

ground up corn cobs 88.0%

The active ingredient and surfactant blend are dissolved in a suitable solvent such as acetone and sprayed onto the ground corn cobs. The granules are then dried and packaged.

Compounds of Formula I can also be mixed with one or more other arthropodicides, fungicides, nematocides, bactericides, acaricides, or other biologically active compounds to form a

multi-component pesticide giving an even broader spectrum of effective agricultural protection.

Examples of other agricultural protectants with which compounds of this invention can be formulated are:

Arthropodicides:

3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester (monocrotophos)

methylcarbamic acid, ester with 2,3-dihydro-2,2- dimethyl-7-benzofuranol (carbofuran)

O-[2,4,5-trichloro-α-(chloromethyl)benzyl]phosρhoric acid, O',O'-dimethyl ester (tetrachlorvinphos)

2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion) phosphorothioic acid, O,O-dimethyl, O-p-nitrophenyl ester (methyl parathion)

methylcarbamic acid, ester with α-naphthol (carbaryl) methyl O-(methylcarbamoyl)thiolacetohydroxamate

(methomyl)

N'-(4-chloro-o-tolyl)-N,N-dimethylformamidine

(chlordimeform)

O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidylphos- phorothioate (diazinon)

octachlorocamphene (toxaphene)

O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN) (S)-α-cyano-m-phenoxybenzyl(1R,3R)-3-(2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate (deltamethrin) Methyl-N',N'-dimethyl-N-[(methylcarbamoyl)oxy]-1- thioox amimidate (oxamyl)

cyano(3-phenoxyphenyl)-methyl-4-chloro-a-(1-methyl- ethyl)benzeneacetate (fenvalerate)

(3-phenoxyphenyl)methyl(±)-cis,trans-3-(2,2-dichloro ethenyl)-2,2-dimethylcyclopropanecarboxylate (permethrin) α-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropane carboxylate (cypermethrin)

O-ethyl-S-(p-chlorophenyl)ethylphosphonodithioate

(profenofos)

phosphorothiolothionic acid,

O-ethyl-O-[4-(methylthio)-phenyl]-S-n-propyl ester

(sulprofos).

Additional arthropodicides are listed hereafter by their common names: triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fonophos, isofenphos, methidathion, methamidiphos, monocrotphos, phosmet, phosphamidon, phosalone, pirimicarb, phorate,

terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, metal- dehyde and

rotenone.

Fungicides:

methyl 2-benzimidazolecarbamate (carbendazim)

tetramethylthiuram disulfide (thiuram)

n-dodecylguanidine acetate (dodine)

manganese ethylenebisdithiocarbamate (maneb)

1,4-dichloro-2,5-dimethoxybenzene (chloroneb)

methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate

(benomyl)

1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2- ylmethyl]-1H-1,2,4-triazole (propiconazole)

2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide

(cymoxanil)

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1- yl)-2-butanone (triadimefon) N-(trichloromethylthio)tetrahydrophthalimide (captan) N-(trichloromethylthio)phthalimide (folpet)

1-[[[bis(4-fluorophenyl)][methyl]silyl]methyl]-1H- 1,2,4-triazole.

Nematocides:

S-methyl 1-(dimethyIcarbamoyl)-N-(methyIcarbamoyloxy)- thioformimidate

S-methyl 1-carbamoyl-N-(methylcarbamoyloxy) thioformimidate

N-isopropylphosphoramidic acid, O-ethyl

O'-[4-(methylthio)-m-tolyl]diester (fenamiphos)

Bactericides:

tribasic copper sulfate

streptomycin sulfate Acaricides:

senecioic acid, ester with 2-sec-butyl-4,6-dinitro- phenol (binapacryl)

6-methyl-1,3-cithiolo[4,5-ß]quinoxalin-2-one

(oxythioquinox)

ethyl 4,4'-dichlorobenzilate (chlorobenzilate)

1,1-bis(p-chlorophenyl)-2,2,2-trichloroethanol

(dicofol)

bis(pentachloro-2,4-cyclopentadien-1-yl) (dienochlor) tricyclohexyltin hydroxide (cyhexatin)

trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxo- thiazolidine-3-carboxamide (hexythiazox)

amitraz

propargite

fenbutatin-oxide Biological

Bacillus thuringiensis

Avermectin B.

Utility

The compounds of this invention exhibit activity against a wide spectrum of foliar and soil inhabiting arthropods which are pests of growing and stored agronomic crops, forestry, greenhouse crops,

ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will recognize that not all compounds are equally effective against all pests but the compounds of this invention display activity against economically important agronomic, forestry, greenhouse, ornamental food and fiber

product, stored product, domestic structure, and nursery pests, such as: larvae of the order Lepidoptera including fall and beet armyworm and other Spodoptera spp., tobacco budworm, corn earworm and other Heliothis spp., European corn borer, navel orangeworm, stalk/stem borers and other pyralids, cabbage and soybean loopers and other loopers, codling moth, grape berry moth and other tortricids, black cutworm, spotted cutworm, other cutworms and other noctuids, diamondback moth, green cloverworm, velvetbean caterpillar, green cloverworm, pink bollworm, gypsy moth, and spruce budworm; foliar feeding larvae and adults of the order

Coleoptera including Colorado potato beetle, Mexican bean beetle, flea beetle, Japanese beetles, and other leaf beetles, boll weevil, rice water weevil, granary weevil, rice weevil and other weevil pests, and soil inhabiting arthropods such as Western corn rootworm and other Diabrotica spp., Japanese beetle, European chafer and other coleopteran grubs, and wireworms; adults and larvae of the orders Hemiptera and Homoptera including tarnished plant bug and other plant bugs (miridae), aster leafhopper and other leafhoppers (cicadellidae), rice planthopper, brown planthopper, and other planthoppers (fulgoroidea), psylids,

whiteflies (aleurodidae), aphids (aphidae), scales (coccidae and diaspididae), lace bugs (tingidae), stink bugs (pentatomidae), cinch bugs and other seed bugs (lygaeidae), cicadas (cicadidae), spittlebugs (cercopids), squash bugs (coreidae), red bugs and cotton stainers (pyrrhpcoridae); adults and larvae of the order acari (mites) including European red mite, two spotted spider mite, rust mites, McDaniel mite, and foliar feeding mites; adults and immatures of the order Orthoptera including grasshoppers; adults and immatures of the order Diptera including leafminers, midges, fruit flies

(tephritidae), and soil maggots; adults and immatures of the order

Thysanoptera including onion thrips and other foliar feeding thrips.

The compounds are also active against

economically important livestock, household, public and animal health pests such as: arthropod pests of the order Hymenoptera including carpenter ants, bees, hornets, and wasps; arthropod pests of the order Diptera including house flies, stable flies, face flies, horn flies, blow flies, and other muscoid fly pests, horse flies, deer flies and other Brachycera, mosquitoes, black flies, biting midges, sand flies, sciarids, and other Nematocera: arthropod pests of the order Orthoptera including cockroaches and crickets; arthropod pests of the order Isoptera

including the Eastern subterranean termite and other termites; arthropod pests of the order Mallophaga and

Anoplura including the head louse, body louse, chicken head louse and other sucking and chewing parasitic lice that attack man and animals; arthropod pests of the order Siphonoptera including the cat flea, dog flea and other fleas.

The specific species for which control is exemplified are: fall armyworm, Spodoptera

fruigiperda: tobacco budworm, Heliothis virescens: boll weevil, Anthonomus grandis; aster leafhopper, Macrosteles fascifrons: black bean aphid, (Aphis Fabae); southern corn rootworm, Diabrotica

undecimpunctata. The pest control protection afforded by the compounds of the present invention is not limited, however, to these species. The compounds of this invention may also be utilized as rodenticides.

Application

Arthropod pests are controlled and protection of agronomic crops, animal and human health is achieved by applying one or more of the Formula I compounds of this invention, in an effective amount, to the

environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Because of the diversity of habitat and behavior of these arthropod pest species, many

different methods of application are employed. A preferred method of application is by spraying with equipment that distributes the compound in the

environment of the pests, on the foliage, animal, person, or premise, in the soil or animal, to the plant part that is infested or needs to be protected. Alternatively, granular formulations of these toxicant compounds can be applied to or incorporated into the soil. Other methods of application can also be employed including direct and residual sprays, aerial sprays, baits, eartags, boluses, foggers, aerosols, and many others. The compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like which entice them to ingest or otherwise contact the compounds.

The compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of

application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, and

synergists such as piperonyl butoxide often enhance the efficacy of the compounds of Formula I.

The rate of application of the Formula I

compounds required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, etc. In general, application rates of 0.01 to 2 kg of active ingredient per hectare are sufficient to provide large-scale effective control of pests in agronomic ecosystems under normal

circumstances, but as little as 0.001 kg/hectare or as much as 8 kg hectare may be required. For

nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as about 0.1 mg/square meter or as much as 150 mg/square meter may be required.

The following tests demonstrate the control efficacy of compounds of Formula I on specific pests; see Index Table A for compound descriptions.

TEST A

Fall Armyworm

Test units, each consisting of an 8-ounce plastic cup containing a layer of wheat germ diet, approximately 0.5 cm thick, were prepared. Ten third-instar larvae of fall armyworm (Spodoptera frugiperda) were placed into each cup. Solutions of each of the test compounds (acetone/distilled water 75/25 solvent) were sprayed onto the cups, a single solution per set of three cups. Spraying was

accomplished by passing the cups, on a conveyer belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds of active ingredient per acre (about 0.55 kg/ha) at 30 p.s.i. The cups were then covered and held at 27°C and 50% relative humidity for 72 hours, after which time readings were taken. Of the compounds tested, the following resulted in greater than or equal to 80% mortality: 1, 3, 4, 6, 7, 8, 10, 11, 12, 13, 14, 15, 16 and 17.

TEST B

Tobacco Budworm

The test procedure of Test A was repeated for efficacy against third-instar larvae of the tobacco budworm (Heliothis virescens) except that mortality was assessed at 48 hours. Of the compounds tested, the following resulted in greater than or equal to 80% mortality: 1, 3, 4, 6, 7, 8, 10, 11, 12, 13, 14, 15 and 17. TEST C

Southern Corn Rootworm

Test units, each consisting of an 8-ounce plastic cup containing 1 sprouted corn seed, were prepared. Sets of three test units were sprayed as described in Test A with individual solutions of the test compounds. After the spray on the cups had dried, five third-instar larvae of the southern corn rootworm (Diabrotica undecimounctata howardi) were placed into each cup. A moistened dental wick was inserted into each cup to prevent drying and the cups were then covered. The cups were then held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following resulted in greater than or equal to 80% mortality: 1, 3, 4, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 17.

TEST D

Boll Weevil

Five adult boll weevils (Anthonomus grandis) were placed into each of a series of 9-ounce cups. The test procedure employed was then otherwise the same as in Test A. Mortality readings were taken 48 hours after treatment. Of the compounds tested, the following resulted in greater than or equal to 80% mortality: 1, 3, 4, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 and 17.

TEST E

Aster Leafhopper

Test units were prepared from a series of 12-ounce cups, each containing oat (Avena sativa) seedlings in a 1-inch layer of sterilized soil. The test units were sprayed as described in Test A with individual solutions of the below-listed compounds. After the oats had dried from the spraying, between 10 and 15 adult aster leafhoppers (Mascrosteles

fascifrons) were aspirated into each of the covered cups. The cups were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested on aster leafhopper, the following resulted in greater than or equal to 80% mortality: 1, 6, 7, 9, 12, 13, 15 and 17.

TEST F

Two-Spotted Spider Mite

Test units, each consisting of one-inch square sections of kidney bean leaves, were infested with 20 to 30 adult two-spotted spider mites (Tetranychus urticae) and sprayed as described in Test A with individual solutions of the below-listed compounds.

Three test units were sprayed per solution. Sprayed leaf sections were then placed on a layer of moistened cotton in a Petri dish «and held at 27°C and 50%

relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, none resulted in greater than or equal to 80% mortality.

Claims

CLAIMS What is claimed is :

1. A compound of the formula

wherein:

Q is selected from the group

A is selected from the group SO₂, C(O) and

CR_aR_a;

B is selected from the group H, C₁-C₆ alkyl, C₃-C₆ cycloalkyl optionally substituted with 1 to 2 halogens or 1 to 2 CH₃, C₄-C₆ cyclo- alkylalkyl, C₁-C₆ haloalkyl, OR₇, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₆ alkoxyalkyl, C₂-C₆ cyanoalkyl, C₃-C₈ alkoxycarbonylalkyl, CO₂R₃, C(O)R₃, C(O)NR₃R₄, C(S)NR₃R₄, C(S)R₃, C(S)SR₃, phenyl, phenyl substituted with

(R₅)_p, benzyl, and benzyl substituted with 1 to 3 substituents independently selected from W;

W is selected from the group halogen, CN, NO₂, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy,

C₁-C₂ haloalkoxy, C₁-C₂ alkylthio, C₁-C₂ haloalkylthio, C₁-C₂ alkylsulfonyl, and C₁-C₂ haloalkylsulfonyl;

NR₄SO₂R₃, or when m is 2, (R₁)₂ when

R₃ is selected from the group H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ halo- alkenyl, C₂-C₆ alkynyl, C₂-C₆ haloalkynyl, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylthioalkyl,

C₁-C₆ nitroalkyl, C₂-C₆ cyanoalkyl, C₃-C₈ alkoxycarbonylalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, phenyl, benzyl, and phenyl or benzyl substituted with 1 to 3

substituents independently selected from W;

R₄ is selected from the group H and C₁-C₄ alkyl or R₃ and R₄ when attached to the same atom can be taken together as (CH₂)₄, (CH₂)₅ or (CH₂CH₂OCH₂CH₂);

R₆ is selected from the group SR₃, SOR₃, SO₂R₃, C(O)R₃, CO₂R₃, C(O)NR₃R₇, C(S)NR₃R₇, C(S)R₃, C(S)OR₃, P(O)(OR₃)_2, P(S)(OR₃)₂, P(O)(R₃)OR₃ and P(O) (R₃) (SR₇); provided that when R₆ is other than COR₃, C(O)NR₃R₇ or C(S)NR₃R₇ then

R₃ is other than H;

R_a and R_b are independently selected from the group H and C₁-C₃ alkyl;

X is O or S;

n is 1 to 2;

m is 1 to 3;

p is 1 to 3;

Y is selected from the group H, C₁-C₂₂ alkyl, C₂-C₂₂ alkoxyalkyl, CHO, C₂-C₂₂ alkylcarbonyl, C₂-C₂₂ alkoxycarbonyl, C₂-C₂₂ haloalkylcarbonyl, C₁-C₂₂ alkylthio, C₁-C₂₂ haloalkylthio, phenylthio, phenylthio substituted with 1 to 3 substituents independently selected from W and S-J;

J is selected from the group

NR₈CR₉ NR₈S(O)_tR₉,

J₁ J₂ J₃ J₄ NR₈R₁₂ and SR₁₀;

J₅ J₆ J₇ J₈ R₈ and R₁₂ are independently selected from the group C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₄-C₇ cycloalkylalkyl, phenyl optionally substituted with 1 to 2 substituents selected from W, benzyl optionally substituted with 1 to 2 substituents selected from W, phenethyl optionally substituted with 1 to 2 substituents selected from W, C₂-C₆ cyanoalkyl, C₂-C₆ alkoxyalkyl, C₃-C₈ alkoxycarbonylalkyl and C₄-C₈ dialkylamino- carbonylalkyl, or R₈ and R₁₂ can be taken together as (CH₂)₄, (CH₂)₅ or (CH₂)₂O(CH₂)₂; R₉ is selected from the group F, C₁-C₂₂ alkyl, C₁-C₆ haloalkyl, C₁-C₂₂ alkoxy, C₂-C₈ dialkylamino, piperidinyl, pyrolidinyl, morpholino, C₁-C₄ haloalkoxy, C₁-C₄ alkoxy substituted with cyano, nitro, C₂-C₄ alkoxy, C₄-C₈

alkoxyalkoxy, C₁-C₂ alkylthio, C₂-C₃ alkoxycarbonyl, C₃-C₅ alkylaminocarbonyl and

CH₂C(CH₃)₂CH₂;

R₁₅ is selected from the group C₁-C₄ alkyl,

R₁₆ is selected from the group H, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ halo- alkenyl, phenyl optionally substituted with

F, Cl, Br, CF₃, CH₃, OCF₃, and benzyl optionally substituted with F, C1, Br, CH₃, CF₃ or OCF₃;

t is O to 2; and

Y₁ is O or S;

characterized further in that, when Q is Q-11,

n-propyl and R₁ is Cl;

(iii) R₁₆ is other than CH₃ or allyl when R₁₃ is Cl, R₁₅ is CO₂CH₃ and R₁ is CF₃; (iv) R₁₆ is other than benzyl when R₁₃ is C1,

R₁₅ is CO₂CH₃ and R₁ is OCF₃;

(v) Y is selected from the group H, CH₃,

C(O)CH₃, and CO₂CH₃;

(vi) Y is selected from the group H and

CO₂CH₃ when R₁₃ is F or Cl, R₁ is CF3 and R₁₆ is CH₃;

(vii) R₁₃ and R₁₄ are not simultaneously H;

and

(viii) R₁ is selected from the group CF₃, OCF₃

Cl and Br.

2. A compound according to CLaim 1 wherein: R_a is H;

R_b is H;

B is selected from the group H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₈ alkenyl, C₂-C₆ alkynyl, C₂-C₆ alkoxyalkyl, C₃-C₈ alkoxycarbonylalkyl, CO₂R₃, C(O)R₃, C(O)NR₃R₄, C(S)NR₃R₄, C(S)R₃, C(S)SR₃, phenyl, and phenyl substituted by (R₅)_p;

R₂ is selected from the group R₃, halogen, CN,

SCN, NO₂, OR₃, and SR₃;

R₃ is selected from the group H, C₁-C₄ alkyl, C₁-C₂ haloalkyl, C₃-C₄ alkenyl, C₃-C₄ haloalkenyl, propargyl, phenyl, and

benzyl, or phenyl or benzyl substituted with one of F, Cl, Br, CF₃, OCF₃, OCF₂H or NO₂;

p is 1 or 2;

m is 1 or 2;

X is O;

Y is selected from the group H, C₁-C₄ alkyl, SCH₃, SCCI₃, SO₂CH₃, SC₆H₅, 2-NO₂-C₆H₄S, C(O)CH₃, C(O)CH₂CH₃, C(O)CF₃; CO₂CH₃,

CO₂CH₂CH₃, and S-J;

J is J₁, J₂, J₃, J₄ or J₅;

(CH₂)₂O(CH₂)₂; R₁₀ and R₁₁ are independently selected from the group C₁-C₃ alkyl and phenyl;

t is 2; and

OCF₃, and NO₂.

3. A compound according to Claim 2 wherein:

B is selected from the group H, C₁-C₄ alkyl,

C₃-C₄ alkoxycarbonylalkyl, CO₂R₃, C(O)R₃, phenyl and phenyl substituted with (R₅)_p;

R₁ is selected from the group halogen, CN,

SCN, NO₂, OR₃, SR₃, SO₂R₃, CO₂R₃, C(O)R₃, and R₃, with one substituent in the

4-position;

R₁ can be taken together as -CH₂C(CH₃)₂O-,

R₅ is selected from the group H, R₃, halogen, CN, SCN, NO₂, OR₃, SR₃, SO₂R₃, C(O)R₃, OSO₂R₃, CO₂R₃, C(O)R₃, C(O)NR₃R₄,

SO₂NR₃R₄, and NR₃R₄;

R₃ is selected from the group H, C₁-C₄ alkyl,

C₁-C₂ haloalkyl, C₃-C₄ alkenyl, and

propargyl;

R₄ is selected from the group H and CH₃;

m and p are independently 1 or 2 and one

substituent is in the para-position;

Y is is selected from the group H, CH₃, COCH₃,

CO₂CH₃, and S-J;

J is J₁ or J₂;

R₈ is selected from the group C₁-C₄ alkyl and phenyl optionally substituted with Cl or

CH₃; and R₉ is selected from the group C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₁-C₆ haloalkyl, dimethyl- amino, phenyl optionally substituted with

Cl and CH₃, or, R₉ is C₁-C₄ alkoxy

substituted with C₂-C₄ alkoxy or 1 to 6 halogens. 4. A compound according to Claim 3 wherein:

R₁ is selected from the group Cl, F, Br, CF₃,

CN, OCF₃, OCF₂H, OCF₂CF₂H, and SCF₂H;

R₂ and R₅ are independently selected from the group H, Cl, F, Br, CN, CF₃, CH₃, OCF₂H, OCF₃, SCH₃, SCF₂H, NO₂, and OCH₂CF₃;

B is selected from the group H, CH₃, CH₂CH₃, CO₂CH₃, CO₂CH₂CH₃, CO₂(CH)(CH₃)₂, phenyl and phenyl substituted with (R₅)p, and; R₆ is selected from the group SO2R₃, CO₂R₃ COR₃, and CONHR₃.

5. A compound according to Claim 4 wherein Q is Q-1.

6. A compound according to Claim 4 wherein

Q is Q-2.

7. A compound according to Claim 4 wherein Q is Q-3.

8. A compound according to Claim 4 wherein Q is Q-4.

9. A compound according to Claim 4 wherein Q is Q-5.

10. A compound according to Claim 4 wherein Q is Q-6.

11. A compound according to Claim 4 wherein

Q is Q-7.

12. A compound according to Claim 4 wherein

Q is Q-8.

13. A compound according to Claim 4 wherein

Q is Q-9.

14. A compound according to Claim 4 wherein

Q is Q-10.

15. A compound according to Claim 4 wherein

Q is Q-11.

16. A compound according to Claim 4:

methyl-3,3a,4,5-tetrahydro-5-(methy1- sulfonyl)-7-(trifluoromethyl)-2-[[[4- (trifluoromethyl)ρhenyl]amino]carbonyl]- 2H-pyrazolo[4,3-c] quinoline-3a- carboxylate (Q-l);

17. A compound according to Claim 4:

7-chloro-3, 3a,4,5-tetrahydro-3a-methyl-5- (methylsulfonyl)-N-[4-(trifluoromethyl)- phenyl]-2H-pyrazolo[4, 3-C]quinoline- 2-carboxamide (Q-1); and

18. A compound according to Claim 4:

7-chloro-3,3a,4,5-tetrahydro-3a,5-dimethyl-

N-4-(trifluoromethyl)phenyl]-2H-pyrazolo- [4,3-c]-quinoline-2-carboxamide (Q-11).

19. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound according to any one of Claims 1 to 18 and a carrier therefor.

20. A method for controlling arthropods comprising applying to the arthropods or to their environment an arthropodicidally effective amount of a compound according to any one of Claims 1 to 18.