CA1244415A - Heteroaryl-substituted 1, 3-cycloalkanediones and derivatives thereof - Google Patents

Abstract

HETEROARYL-SUBSTITUTED 1,3 - CYCLO-ALKANEDIONES AND DERIVATIVES THEREOF

ABSTRACT OF THE DISCLOSURE

Novel aromatic heteromonocyclic-substituted 1,3-cycloalkanediones, enol ester derivatives and salts thereof, exhibit herbicidal activity against a variety of broadleaf and grassy weeds. Certain 2-(2-pyrazinyl) 1,3-cycloalkanediones and their enol esters were also found to be active as mite adulticides and ovicides.

SPECIFICATION

Description

129~ 15 13,032 FIELD OF THE INVENTION
This invention relates in general to novel heteroaryl-substituted 1,3~cycloalkanediones and deriva-tives thereof. In one aspect, this invention relates ~o novel compositions which exhibit herbicidal activity against a variety of broadleaf and grassy weeds. In a further aspect, this invention relates to certain derivatives of the com~ositions which also are active as mite adulticides and ovicides.
.

DESCRIPTION OF THE PRIOR ART
Prior to the present invention certain hetero-cycl c alkanediones had been investigated for their antihypertensive properties. For example, T. Tsujikawa et al., in Heterocycles 6 (3) 261-266 (1977) reported certain tetrahydropyridinyl 1,3-cyclohexanediones and related hydrogenated 5-, 6- and 7-ring compounds. These and other related compounds were invariably described in the literature as having an exocyclic double bond join-ing the two ring systems:

~ ~ C33 and hence are non-aromatic heterocyclic compounds.
Other compounds which have been reported in the literature are the isomeric 2-pyridinyl 1,3-indanediones or pyrophthalones, such as .

2 ~ 5 13,032 See for example, the works of J. Ploquin, et al., Eur. J. Med. Chem. - Chim. Ther. 9 (5), 519-525;
526-533 (1974), J G. Lombardino, J. Org. Chem. 32, 1988-19~2 (1967), J. Kacens, et al., C.A. 78, 57523 n (1973) and K. Buggle and M. Nangle, Chem. & Ind. (1976) 111-112.
Japanese patent 73/11,097 which issued April 10, 1973 to Sankyo describes certain herbicidal thiazolidines including compounds such as:

O H
while K. Hirai, et al., Chem. Pharm. Bull. 20, 1711-1715 (1972), discloses compounds such as O
C~x3 wherein X is S or O.
Pyridinium betaines such as CH3 ~ ~ ~

have been disclosed by B. Karele, O. Neilands, Chem.
Abs. 85 20763; (1976).
References are also made in the literature to bicyclic 1,3-cycloalkanediones, such as _ 3 _ 12~4~L5 13,032 reported by J. E. Douglass and H. D. Fortner, J. Het. Chem.
0, 115-116 (1973).
Few of the aforementioned literature references discloses aromatic, heteromonocyclic-substituted 1,3-cyclo-alkanediones, much less make any mention of herbicidal or miticidal activity. Moreover, six-membered monocyclic aromatic nitrogen heterocycles joined by a carbon atom to the dione ring at the 2-position were not known prior to this invention.

DESCRIPIION OF THE INVENTION

In its broad aspect, this invention is directed to novel compositions, processes for their preparation, her-bicidal and miticidal compositions and uses thereof. The novel compositions of this invention can be conveniently represented by the following formula:
O

HET ~ X
C
YO
wherein X is a 2 or 3 member alkylene chain which may be substituted wi~h one or more alkyl or alkenyl, wherein the permissible substituents are one or more alkyl, cyano, ~Z~4~5 13,032 halogen, nitro, alkoxy, alkylthio, alkylsulfinyl, alkyl-sulfonyl, dialkylamino, acylamido or acyl substituents, or any two substituents together may form an alkylene or alkenylene chain having from 2 to 6 carbon atoms com-pleting a 3,4,5,6 or 7- membered ring structure, with the proviso that when X is a 2-membered alkylene chain substituents thereon when taken with X do not form an aromatic ring;
Y is hydrogen, any salt forming cation (Na~, NH46~, Ca ~, etc), and -C-Z where Z is hydrogen, halogen, o alkyl, alkoxy, alkylthio, amino, alkylamino, dialkylamino, alkenyl, alkynyl, bicycloalkyl, bicycloalkenyl, cycloalkyl, cycloalkenyl, phenyl, phenylalkyl, naphthyl or naphthylalkyl all of which except hydrogen and halogen may be substituted with one or more alkyl, carboxy, cyano, nitro, alkoxy, alkoxy-carbonyl, halogen, haloalkyl, alkoxyalkyl, alkylthio, alkyl-sulfinyl, alkylsulfonyl, alkylsulfinylalkyl, alkylsulfonyl-alkyl, alkylthioalkyl or dialkylamino substituent, or Z is HET
__o~O
X
wherein X is as above and;

.

13,032 HET is selected from the group of:
Rl~_~H

(I) whereiR Rl is H, alkyl (Cl-C5), alkoxy (Cl-C4), alkylthio (Cl-C4), alkylsulfinyl (Cl-C4), alkylsulfonyl ~Cl-C4), alkenyl (C2-C5), alkylamino (Cl-C4), dialkylamino (C2-C5), amino, hydroxy, alkoxyalkyl (C2-C4), alkylthioalkyl (C2-C4), alkylsulfinylalkyl (C2-C4), alkylsulfonylalkyl (C2-C4), trifluoromethoxy, halogen, haloalkyl or poly-haloalkyl, with the longest straight chain of atoms being 3 or less in number;
R2 is H or alkyl (Cl-C2)i R3 is H, CH3, alkoxy (Cl-C2), or alkylthio (Cl-C2), with the longest straight chain of atoms being 3 or less in number; R5 R4 (II) R6 wherein R4, R5 and R6, individually, are H, haloalkyl, halogen, alkyl (Cl-C5) polyhaloalkyl, alkoxy (Cl-C4), alkylthio (Cl-C~), hydroxy, amido, amino, alkylsulfonyl (Cl-C4), alkylamino, dialkylamino, or alkylsulfinyl (Cl-C4).
R7 = alkyl ~Cl-C3), halogen, haloalkyl or poly-haloalkyl;

~ 2 ~ 13,032 (III) ~ N
Rlo wherein ~ is H, alkyl (Cl-C4), halogen, alkoxyl (Cl-C3), alkylthio (Cl-C3), haloalkyl, polyhaloalkyl, alkoxyaLkyl (C2-C4), alkylthioalkyl (C2-C4), alkylsulfinylalkyl (C2-C4) or alkylsulfonylalkyl (C2-C4);
R9 is H, alkyl (Cl-C4), alkenyl (C2-C4), haloalkyl, halogen, polyhaloalkyl, alkoxy (Cl-C3), or alkylthio (Cl-C3), with the longest straight chain of atoms being 4 or less in number;
Rlo is H, methyl, ethyl, alkoxy (Cl-C3) or alkylthio (Cl-C3); -R

(IV) R12 ~ `~
~ N

wherein Rll and R13 are the same as Rl and R12 is thesame as R9 with the proviso that the total number of carbon atoms for Rll, R12 and R13 is no greater than 8;

(V) N
~ -N

wherein R14 is the same as R8; R~5 is the same as Rl and R16 is the same as Rg, with the proviso that the ~otal ~ 4~ 13,032 number of carbon atoms for R14, R15 and R,6 lS no greater than 8;

(VI) R22 N -N

wherein R20 is the same as R8; R21 is the same as Rl, and R22 is hydrogen or methyl, wQth the proviso that at least one of R2d, R~l and R22 is other than hydrogen;

5VII) wherein R23 and R24 are the same as ~ , and R25 is the same as Rl, with the proviso that the total number of carbon atoms for R23, R24 and R25 is no greater than 8; and at of R23, R24 and R25 is other than hydrogen lZ~41~ 13.032 (VIII) N ~ N

wherein R26 and R27 are H, alkyl (Cl-C5), alkoxy (Cl-C4), alkylthio (Cl-C4), alkenyl ~C2-C5), alkylamino (Cl-C4), dialkylamino (C2-C5), amino, hydroxy, alkoxyalkyl (C2-C4), alkylthioalkyl (C2-C4), alkylsulfinylalkyl (C2 C~), alkyl-sulfonylalkyl (C2-C4), trifluoromethoxy or haloalkyl with the longest straight chain of atoms being 3 or less in number and a maximum of 5 carbon atoms for all carbon-containing substituents.

~ N~
(IX) wherein R29 and R28 are the same as R~6 and R27;

R3~

(X) N N
~, wherein R30 is the same as R26 and R31 is the same as R8;
and 13,032 ~ R33 (XI) R32 N N
wherein R32 is the same as Rg and R33 is the same as R8;

It should be noted that when Y in the generic for-mula above is hydrogen, the ring to which Y O is attached can exist in its tautomeric 1,3-cyclodione form:
o e ~ X _ ~C X

YO
wherein X is as indica.ted above.

/

_ . . _ 2 ~ 5 13jO32 Illustrative compositions which can be prepared in accordance with the teachings of this invention include, among others:
5~ Methylethyl)-2-(4-methylthio-2-pyridinyl)-1,3-cyclo-hexanedione, 2-(4-Dimethylamino-2-pyridinyl)-5-(1-methylethyl)-1,3-cyclohexanedione, 2-(4-Meehoxy-6-methyl-2-pyridinyl)-5~ methylethy~ 3 cyclohexanedione, S-Ethyl-2-~4-methoxy-2-pyridinyl)-5-me~hyl-3-pentanoyloxy-2-cyclohexen-l-one, 5-Methyl-5~1-methylethyl)-2-(4-methyl-2-pyridinyl)-1,3-cyclohexanedione;

3-Butanoyloxy-5-methyl-5-(1-methylethyl)-2-(4-methyl-2-pyridinyl)-2-cyclohexen-1-one, 2-(4-Methoxy-?-pyridinyl)-5-methyl-5~ methylethyl)-1,3-cyclohexanedione, 2-(4-Methoxy-2-pyridinyl)-5-(2-propenyl)-1,3-cyclohexanedione, 5- Methyl-2-(4-methyl-2-pyridinyl)-1,3-cyclohexanedione, 5-(1-Methylpropyl)-2-(3-pyridinyl)-1,3-cyclohexanedione, 5-Ethyl-3-hexanoyloxy-5-methyl-2-(4-methyl-3-pyridinyl)-2-cyclohexen-l-one,

4-Methyl-2-(2-pyridinyl)-1,3-cyclopentanedione, 2-(4-~thoxy-2-pyridinyl)-4,4,5,5-tetramethyl-1,3-cycl~-pentanedione, 2-(3-E~yl-2-pyrazinyl)-S-(l-methylethyl)-1,3-cyclohexane-dione, ~!

5-Methyl-5-(1-methylethyl)~3-pentanoyloxy-2-(2-pyraæinyl)-2-cyclohexene-l-one 2-(5-Methoxy-3-methyl-2-pyrazinyl)-5-methyl-5-(1-methyl-ethyl)-1,3-cyclohexanedione, 2-(5,6-Dimethyl-4-pyrimidinyl)-5-(1-methylethyl)-1,3 cyclo-hexanedione, 2-(6-Methoxy-S-methyl-4-pyrimidinyl)-5-methyl-5-methoxy-methyl-3-propanoyloxy-2-cyclohexen-1-one, 2-(4,6-Dimethyl-5-pyrimidinyl)-L,3 cyclopentanedione;
2-~4,5-Dimethyl-3-pyridazinyl)-5-~2-ethylthiopropyl)-1,3-cyclohexanedione;

5,5-Dimethyl-2-(3,5-dimethyl-4-pyridazinyl)-3-octanoyloxy-2-cyclohexen-l-one, 5,5-Diethyl-2-(2-pyrimidinyl)-1,3-cyclohexanedione, 13,032 8-~2-(1,3,5-triazinyl)]-spiro14.5]decane-7,9-dione, 2-[5-Ethyl-3-(1,2,4-triazinyl)]-5-(1-methylethyl)-1,3-cyclohexanedione, 2-[6-Methyl-5-(1,2,4-triazinyl)]-5-(1-methylethyl)-1,3-cyclohexanedione, and 2-[5-Ethyl-6-(1,2,4-triazinyl]-3-hexanoyloxy-5-(tri-fluoromethyl~-2-cyclohexen-1-one Preferred compositions which are encompassed by the generic fo~mula, include:
5,5-Dimethyl-2-(2-pyridinyl)-1,3-cyclohexanedione, 5,5-Dimethyl-2-(2-Pyridinyl)-1,3-cyclohexanedione sodium salt, 5,5-Dimethyl-2-(4-methyl-2-pyridinyl)-1,3-cyclohexane-dione, 5-(1-Methylethyl)-2-(2-pyridinyl)-1,3-cyclohexanedione, 5-(1-Methylethyl)-2-(4-methyl-2-pyridinyl)-1,3-cyclohexane-dione, 2-(4-Ethyl-2-pyridinyl)-5-(1-methylethyl)-1,3-cyclohexane-dione, 2-(4-Methoxy-2-pyridinyl)~5-~1-methylethyl)-1,3-cyclohexane-dione, 8-(2-pyridinyl)-spiro[4.5]decane-7,9-dione, 5-Ethyl-5-methyl-2-(2-pyridinyl)-1,3-cyclohexanedione, 5-(1-Methylpropyl)-2-(2-pyridinyl)-1,3-cyclohexanedione, 5-(1,1-Dimethylethyl)-2-(2-pyridinyl)-1,3-c;clol~xanedione, 5-(1-Ethylpropyl)-2-(2-pyridinyl)-1,3-cyclohexanedione, 5,5-Dime~hyl-2-(3,5,6-trimethyl-2-pyrazinyl)-1,3-cyclohexane-dione, 5,5-Dimethyl-3-hexanoyloxy-2-(3,5,~-trimethyl-2-pyrazinyl)-2-cyclohexene-l-one, 5-(1-Methylethyl)-2-(3,5,6-trimethyl-2-pyrazinyl)-1,3-cyclollexanedione, 3-Hexanoyloxy-5-(1-methylethyl)-2-(3,5,6-trimethyl-2-pyrazinyl)-2-cyclohexen-1-one, 5,5-Dimethyl-3-(2-methylpropanoyloxy)-2-(3-methyl-2-pyrazinyl)-2-cyclohexene-1-one, and 8-(3,5,6-Trimethyl-2-pyrazinyl)-spiro[~.5]decane-7,9-dione 1;244 'LlS
13,032 In practice, the novel dione compositions of this invention can be p~epared by the reactions of hetero-cyclic lithium derivatives in accordance with the procedure of Edwards and Teague, JACS 71, 3548 (1949):

~1 2 (1) ~ + (i-Pr)2N-Li 1 ~ ~ + (i-Pr)2NH

3 3 R3 CH~Li 1 "O Rl o R2 ~ f O-alkyl (l)THF/ 80 C ~ ~C ~
2) 1 ll ~ (2)H0/H~o ~N ~ H2 X
~ N ~ C-O-alkyl ~ R3 J
R3 ~ CH2Li O alkyl-0-C
dicarboxylic ester keto ester O
reactant in~ermediate Rl o )~C ~ NaOC2H5 ) R2 ~
3 ) in C2H50H N C~ X
alkyl~~-C~ R3 \ ~ ~
keto ester 0 ..
~ntermediate O
substituted 2-(2-pyridinyl) -1,3-cycloalkanidione The lithium diisopropylamide (LDA) of step (1) is prepared by reaction of n-butyllithium (or other alkyllithium) with diisopropylamine and the 2-methylpyridine is then added to the mixture giving the 2-pyridylmethyllithi~l.
The resulting solution in tetrahydrofuran (THF is then fed, with care to exclude air and moisture, to a 200 2~ 5 13,032 percent excess of the dicarboxylic ester (such as diethyl 3,3-dimethylglutarate) at about -80C. (Use of excess ester minimizes double addition of the organolithium reagent). The keto ester is worked up by neutralization of its basic solution and finally purified by vacuum distillation in a short-path apparatus. In the final step (3), cyclization of the keto ester to dion~ is conducted by refluxing with 1 mol of sodium ethoxide in ethanol. In addition to 2-methylpyridines, me~hyl and methylene groups at the pyridine 4-position are also highly activa~ed and react rapidly with organolithium reagents to form lithium salts analogous to the above.
Such lithium derivatives of 4-methyl groups, or the ethyl methylene groups in either the 2- or 4-position, however, do not lead to the desired compounds. If a 2-methyl-pyridine bears an additional methyl or ethyl group a~
position 4, ~i.e., R is -CH3 or -CH2CH3) one must employ an alkylli~hium (C4H ~i, etc.) or phenyllithium reagent R - ClH2Li CHLi ~D ~ ~ or ~ ~
~N ~ ~ C4HgLi CH3 CH3 CH ~ or (Lead to unwanted 3 \ ~Li Products) \ CH3 IH3 or (Lead to desired products) 1249L41$
13,032 in place of LDA to achieve lithiation at 2-methyl rather than upon the 4-alkyl substituent. The alternate use of alkyl-and phenyllithium reagents to achieve this selective lithiation has been described by Kaiser, et al, J. Org.
Chem. 38 71 (1973) and by Arens et al., Rec. Trav. Chim.
69, 287,(1950).
When pyridines bear methyl groups at positions both alpha and beta to the ring nitrogen then organo-lithium (and o~her organometallic) reactions occur preferentially at the activated alpha- attached group as indicated.

CH3 CH3 CH3 CH2Li CH3 CH2Li When no activated methyl group is present, as with 3-picoline the metallation procedure still occurs but it is less facile and the intermediate formed is a much more reactive species.
The enol esters of the diones are conveniently prepared by treatment of the dry potassium salts of the diones with an equivalent of acid chloride and a small amount of dicyclohexyl-18-crown-6, as a stirred slurry in dry THF. Following the reaction the stripped residue is extracted with ether and the latter solution washed quickly with 0.2N NaOH at 0-5C to remove unreacted dîone.
(Fil~ration through silica gel or extraction with 7% aqueous TEA will remove any unreacted acid chloride indicated by the IR spectrum). The ether solutions are then dried over MgSO~, filtered and stripped to give the desired esters.

--- ~\
s 13,032 In ~eneral, the process conditions and reaction ~arîable u3ed in the synthesis of the compositions of this invention, will depend, in part, upon the particular re-agents emI)loyed. For example, in the keto ester formation from 2,4 timethylpiperidines, alkyllithi~s and phenyl-lithiums.are the reagents em?loyed. For all ~the~ methyl heterocycles in addition to LDA, alkyl-, and phenyl-lithiums, sodium Amide, potassium amide and co~binaticns of hese amides with sodium and potassium tert-butoxide m2',' 10, be feasible for the deprotonation step. .
The overall mole ratio of methyl heterocycle to or~anometallic reatent to dicarboxylic ester is from about 1:0.1:1 to from 1:2:10 and more prefera~ly about 3, Although a variety of solvents can be e~ploye~
in the keto ester formation step, such as ethyl ether, isopropyl ether, dioxane, ethyle~e glycol din~thyl ether ~nd benzene, tetrahydrofuran is preferseG
Tem~eratures for the ~eaction of heterocycle and organometallic base can range frDm about -80C to about +10C. a~d preferably from about -10C to about -20C. Reaction tem~eratures for the dicarboxylic ester condensation are from about -100C. to about -50~C aFld pr~ferably about -80C. The subsequent holding temperature is from aboue -10C. to about ~10C. are preferably about O~C. for a period of from about 0.5 to about 36 hours and prefesably from about 4 to 16 hours.
.The preferred neutsalization agent is carbon dioxide, although hydrochloric, sulfuric or phosphoric acids can ~e empLoyed as well as amnoni~T chloride.

,A, 4~5 13,032 For ~yclization of the keto ester to the dione sodium ethoxide is the preferred base although other alkali alkoxides such as potassium ethoxide may be used. The reaction is conducted in a mole ratio of base to keto ester of from about 0.1:1 to about 5:1 and preferably 1:1 and at a tempe-rature of from about room tem~erature to about 150C, preferably about 80C. The reaction time can vary from about 1 minute to about 24 hours and preferably is from about 1.5 hours to about 3 hours. The choice of reaction solvent is not ~ecessarily critical and any solvent not decomposed by the cycliza~ion base can be employed. For example, ethylene glycol and its mono and diethers can be used with ethanol, propanol or isopropyl alcohol being preferred. For extraction ethyl ether or dichloromethane are the preferred solvent, although any solvent with limited water ~iscibility can be utilized. In many cases, however, the product crystallizes out and needs no extraction~
Extraction is usually carried out at a pH of from about 3.5 to about 10 and more preferably between 5 and 8. It should be noted ~hat the basic diones may also be recovered as mineral acid salts.
For the preparation of the enol esters, the parent dione, preferably the sodium or potassium salt there-of, is reacted with an acid anhydride or more preferably an acid chloride in a mole ratio of dione to acylating a~ent of from about 1:2 to about 2:1 and preferably 1:1. The reaction is conducted within the temperature range of from about 0C to about 50C, more preerably from about 25 to about 35C and in a solvent such as tetrahydrofuran. Other solvents, such as dioxane, ethylene gLycol dimethyl ether and the like can also be employed.

S

13,032 In the examples, certain of the starting materials were prepared in accordance with methods dis-closed in the literature. For example, 2,3-dimethyl-pyrazine was prepared from 2,3-dimethyl~5,6-dihydro-pyrazine by the method of G. P. Rizzi, J. Org. Chem. 33, 1333 (1968) which itself was prepared by the procedure of T. Ishiguro and M. Matsumura, Yak. Zass. 78, 229, (1958).
4-Ethyl-2-methylpyridine was prepared by the procedure of Kaiser et al., J. Org. Chem. 38, 71, (1973). 4-Methoxy-2-picoline-n-oxide was prepared by reacting 4-nitro-2-picoline-n-oxid~ with methanolic potassium carbonate solution accord-ing to the general procedure of E. Profft et al., Germany (East) 69, 126; 10/5/69; Chem. Abs. 72, 90309w (1970). The crude product was not purified but was reacted directly with phosphorous trichloride in chloroform solution to give the known 4-methoxy-2-picoline starting material, based upon the general method of Herz and Tsai, J. Am. Chem. Soc. 76, 4184 (1954).
As indicated in the following exar.ples, the aromatic heteromonocyclic-substituted 1,3-cycloalkanediones of this invention show significant toxici~y to a variety of broadleaf and grassy weeds, under conditions of pre-emergent and/or postemergent application, and have potential utility as selective and non-selective herblcides.
Moreover, certain of the substituted 2-(2-pyrazinyl) 1,3-cycloalkanediones and their enol esters display toxicity to both adult mites and mite eggs as hereinafter indicated in the examples.

~ 5 ~13,032 The following examples illustrate the best mode presently conteu2lated for the practice of this invention:

ETHYL 3,3-DIMETHYL-5-KETO-6-(2-PYRIDINYL)HEXANOATE
All glassware was dried overnight at 130C and - assembled under dry nitrogen. All liquid transfers were conducted through a stainless steel cannula with nitrogen pressure.
A solution of n-butyllithium (0.6 mol~ in hexane was fed to a stirred solution of dry diisopropyl~mine (60.7 g., 0.6 mol) in 600 ml of dry THF with cooling to -lO to -20~. 2-Picoline (55.9 g, 0.6 mol), dried over .
3A molecular sieves, was then added, with stirring9 to the original mixture over an ll-min. period holding the temperature at -lO to -20. A 167 ml portion (O.l mol) of the resulting solution of 2-picolyllithium in THF was ~hen added to a solution of diethyl 3,3-dimethylglutarate (64.9 g, 0.3 mol) over a 2 hour period with stirring and cooling to -78. The resulting mixture was allowed to warm to 0 and then held at this temperature for approximately 16 hours. Water (50 ml) was then added, with stirring, to the mixture, cooled to 9-5, and gaseous C2 then fed into the stirred mixture for approximately 85 minutes until the pH of the solution was 7-7.5. THF
was then evaporated from the neutralized mixture under reduced pressure and the residue diluted with ether, filtering the ether solution to remove insoluble materials.
The ether filtrate was extracted 4 times with 6N HCl and ~he combined acid extracts washed with one portion o ~ 2 ~ 5 13,032 ether. The pH of the aqueous layer was adjusted to 11 with aqueous 6N NaOH causing an oil to precipitate.
This was extracted with ether and the ether extract washed with brine, dried (MgS04) and evaporated to give 12.55 g of crude oily keto ester. Flash distillation through-a Kugelrohr apparatus gave 7.9 g of ester (30.0% yield), bp 130-148/0.1 mm; ir (K~r) 1725 cm 1 (ester C=O). A 2.65 g fraction, bp 120-125/0.05 mm, from a redistillation gave the following nmr spectrum (CDC13) ~ 1.0-1.5 (m, 9, ethyl CH3 and CH3-C-CH3), 2.3-2.9 (m, 4, CH2-C-CH2), 3.8-4.4 (q plus s, 4, ethyl CH2 plus pyridyl CH2), 6.7-8.7 (m, 4, pyridine ring).

5,5-DIMETHYL-2-(2-PYRIDINYL)-1,3-CYCLOHEXANEDIONE
To a refluxing solution of 0.34 g (0.0147 mol) of sodium in 50 ml dry ethanol (distilled from Mg) was added 3.87 g (0.0147 g) of ethyl 3,3-dimethyl-5-keto-6-(2-pyridinyl) hexanoate over a 4 minute period. The mixture was then refluxed for 1.5 hour af~er which it 20 was evaporated to dryness and the residue dissolved in water and extracted twice with ether, discarding the latter extracts. The pH of the aqueous layer was ad-justed to 10 with HCl causing the prod~ct to separate as a white solid. It was recovered by extracting 3 times with CH2C12, readjusting the pH of the aqueous layer from 11 to 10 and again extracting 3 times with 5H2C12. The combined, dried (MgSO4) CH2C12 extracts were filtered and evaporated to give 2.48 g (77.6%) of a white solid, mp 161.5-165. Recrystallization from e~hyl acetate gave ~ 5 13,032 2.04 g (63.9% yield) of white fibrous crystals, m~ 163-165.5; ir (KBr) 2500-300 cm l (H-bonded N or 0), 1638 cm 1 (conj C=O), 1553 cm 1; nmr (CDC13) ~ 1.1 (s, 6, CH3), 2.45 (s, 4, CH2), 7.0-8.2 (m, 3, pyridinyl protons at C-4,5 and 6), 9.3-9.6 (m, l, pyridinyl C-3 proton).
- Analysis Calcd. for C13H15N02: C, 71.86; H, 6.96, N, 6.45 Found: C, 71.71; H, 7.00; N, 6.64 105,5-DIMETHYL-3-OCTANOYLOXY-2- (2-PYRAZINYL) CYCLOHEX-EN-l-ONE
~ ~ Octanyl chloride (6.41 g, 0.039 mol) was fed at room temperature and over a 5 minute interval, to a stirred slurry of 5,5-dimethyl-2-(2-pyrazinyl)-1,3-cyclo-hexanedione potassium salt (10.0 g, 0.039 mol) and 1 drop of dicyclohexyl-18-crown-6 in 150 ml of THF tdried over 3A molecular sie~es). The temperatl~e increased from 24. 5 to 31.5 and partial solution of solids was apparent after 12 minu~es following completion of the feed. Stirring 20 was continued for approximately 23 hours at which time the mixture was evaporated to dryness under vacuum. The residue was stirred with ether, the ether slurry filtered and the filtrate washed quickly, and in succession, with ice cold 0.25N NaOH (t~ice), 7% aqueous triethylamine and saturated aqueous NaCl. The ether layer was dried (MgS04), filtered and vacuum stripped to dryness giving 11.2 g (83.2%) of orange oily product; ir (KBr) 1755 cm 1 (ester C=O), 1640-1665 ~conj C=O, C=C), 1135 cm 1, 1090 cm 1;
nmr (CDC13) ~ 0.7~1.4 (m, 19, 3 x CH3 plus 5 x CH2), 2~1-2.7 (m, 6, C~ adj to C=O), 8.45-8.7 (m, 3, aromatic).

12~4415 13,032 Analysis Calcd. for C20H28N203: C, 69.74; H, 8.19;
N, 8.13 Found: C, 69.71; H, 8.33; N9 7,64 5-tl-METHYLETHYL) 2-(2-PYRIDINYL)-1, 3-CYCLOHEXANEDIONE
The subject compound was prepared from ethyl 3~ methylethyl)-6-(2-pyridinyl)-5-oxohexanoate and a sodi~m ethoxide solution according to the general procedure of Example 2, but em~loying a 2.83 hour reflux period following completion of the feed. Cn working up the reaction the ether-extracted aqueous phase was adjusted to pH 6 causing the product to separate as a tan solid -which was extracted with ether, recovered by evaporation and recrystallized twice from cyclohexene to give a solid, mp 110-112C, The confirmatory elemental analysis is shown in Table II.

5-~1-METHYLETHYL)-2-(4-METHYL-2-PYRIDINYL~-1,3-CYCLOHEXANEDIONE
The procedure of Example 2 was used to prepare the title compound from ethyl 3-(1-methylethyl)-6-~4-methyl-2-pyridinyl)-5-oxohexanoate and sodium ethoxide - using a 2 hour reflux period in ethanol. The product was liberated as an oil from the aqueous phase by adjusting the pH to about 5 and recovered by ether extraction. The ether extract was worked up giving a semi-solid which was recrystallized successively from ethyl acetate and isopropyl ether giving the product,as a solid, mp 104.5-~2~4 ~15 13,032 106.5C. The confirmatory elemental analysis is shown in Table II.

2-(4-METHOXY-2-PYRIDINYL)-5-(1-METHYLETHYL)-1,3-CYCLOHEXANEDIONE
The title compound was prepared from ethyl 6-(4-methoxy-2-pyridinyl)-3-(1-methylethyl)-5-oxohexanoate and ethanolic sodium ethoxide, refluxing for 2 hours according to the procedure of Exam~le 2. The product separated from the aqueous phase as a yellow solid upon adjusting the pH to about 6 and was recovered by extraction with dichloromethane. Evaporation of the dried extract and recrystallization from acetonitrilP
gave the product as a white solid, mp 152-154.5C. The confirmatory elemental analysis is shown in Table II.

ETHYL 3,3-DIMETHYL-6-(4-METHYL-2-PYRIDINYL)-5-OXOHEXANOATE
A 1.9 molar solu~ion of phenyllithium in benzene-ethyl ether (95 ml, 0.18 mol) was added, with stirring, to 180 ml of dry tetrahydrofuran (THF~ in a dry, argon-blanketed system (Example 1) cooled to -10 to -20C.
Continuing the stirring and cooling to -15C, a 27.7 ml portion (0.18 mol) of dry 2,4-lutidine was added over a 7 minute period and the black solution stirred at -15 to -20C for 30 minutes. This solution was then fed, with stirring, to a solution of diethyl 3,3-dimethylglutarate (116.8 g, 0.54 mol) in 230 ml of dry THF, with cooling to -78C. The resulting mixture was allowed to warm to 0C
and then held at this temperature for approximately 16 .

~ 4~ 5 13,032 hours. Water (60 ml) was then added, with stirring, to the mixture, at 0 5C, and gaseous CO2 then fed in until the pH reached about 6 to 8 and a white solid had precipitated.
The mixture was then worked up according to the general procedure of Example 1, flash distilling the~crude product to give the yellow, oily es~er over the approximate range of 120~-210C/0.2mm (Kugelrohr air temperature); ir (KBr) 1730 cm~l (ester C=O).

. .
5-(1-METHYLETHYL)-2-(3,5,6-TRIMETHYL-2-PYRAZIN~L)-1,3-CYCLOHEXANEDIONE POTASSIUM SALT
5-(1-Methylethyl~-2-(3,5,6-trimethyl-2-pyrazinyl)-1,3-cyclohexanedione (18.13 g, 0.062 mol) was~
dissol~ed in a solution of 4.1 g (0.062 mol) potassium hydroxide in 100 ml of water. The solution was filtered and the yellow filtrate stripped to dryness on a rotary evaporator and finally dried to constant weight in a vacuum oven. The weight of potassium salt was 20.28 g (99.0~/O of theory).

EXAMPLE g . .
3-HEXANOYLOXY-5-(1-METHYLETHYL~-2-(3,5,6-TRIMETXYL-2-PYRAZINYL)-2-CYCLOHEXENE-l-ONE
The subject compound was prepared by reaction of 5-(1-methylethyl)-2-(3,5,6-trimethyl-2-pyrazinyl)-1,3-cyclohexanedione potassium salt (Example 8) with hexanoyl chloride employing the general procedure described in Example 3, but allowing the reaction mixture to stir at room temperature over the weekend. Following the reaction, the ether ~olution of crude prodact was extracted ~2~ 5 13,032 quickly with ice-cold 0.25 n NaOH, dried (MgSO4), filtered and evaporated to give a residue product show-ing some acid chloride contamination by IR examination.
Dry-column chromatography using 1:1 ethyl acetate/hexane gave analytically pure material as shown by thP elemental analysis of Table II.
In a manner sim~lar to that employed in the above examples other l,3-diones and derivatives were prepared from the appropriate keto ester precursors.
Tab~es I, II, III and IV below, set forth the structures and identification of the precursors and dione derivatives, and Table V below indicates physical properties and elemental analysis of the l,3-diones.

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13, 032 ~ C~
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13,032 TABLE II
PYRlDINYL 1,3-DIONES

COMPOUND Rl ~ R3 D E G J R L Y

2 H H H H H CH3 CH3 H ~ Na 3 CH3 H H H H C~13 CH3 H H H
4 H H H H H CH(CH3~ H H H H
CH3 H H H H CH(CH3!2 H H H H
6 C2H5 H H H H CH(C~3~ H H H H

7 CH30 H H HH CH(CH3~ H H H H
B H H H HH -(CH2)4- H H H H

lD H H H Ht H H H H

11 H H H HH C(CH3)3 H H H H
12 H H H HH CH(C2H5)2 H H H H
19 H H H H H H H H H H~HCl 22 H H CH3 H H CH3 CH3 ~I H K
23 H H CH3 H H CH3 CH3 H H COCH(CH3)2 24 ~C2H5 H H H CH3 CH3 H H H
HC2H5 H H H CH3 CH3 ~ H COCH3 26 HC2H5 H H H CH3 CH3 H H ~C5 ~7 H H Cl H H C~3 CH3, H H H
28 H CH3 H H H C(CH3)2 H , H H H

~;~4~5 13, 032 TABLE II (Continued) PYRIDINYL 1, 3-DIONES

R~,_ o~E

COMPOU~ R3 D X G J ~C L Y

36 . H H CH3 H H C~13 CH3 H H COC7H15 37 ~H 3 .HCL
. . o O

~2~ 5 X ~ ~ ~ ~ ~ O

b t~ X T ~ X 3 1~ ~Q~ x ~ . 1 X ~ 5 I ~
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~Z~415 13,032 Selected heteroaryl-substituted 1,3-cyclo-alkanedione com~oun ~ and derivatives representative of those useful in accordance with this invention were tested with respect to their miticidal, mite ovicida~ and pre-emergent and post-emergent herbicidal activity.
-Suspensions of ~he test compounds were prepared by dissolving one gram of compound in 50 milliliters of acetone in which had been dissolved 0.1 gram (10 percent of the weight of compound) of an alkylphenoxy-ethanol surfactant, as an emulsifying or dispersing agent. The resulting solution was mixed into 160 milliliters of water to give roughly 200 milliliters of a suspension containing the compound in finely divided form. The thus prepared stoc~ suspension contained 0.5 percent by weight of compound.
The test concentrations employed in ~he ~ests described hereinbelow werP obtained by diluting the stock suspension with water. The test procedures were as follows:

Mite Folia~e SpraY Test Adults and nymphal stages of the two-spotted mi~e (~etranychus ur~icae (Roch)), reared on Tendergreen -bean plants at 80 + 5~F. and 50 + ~ percent relative humidity, were the test organisms. Infested leaves from a stock culture were placed on the primary leaves of ~wo bean planes six to eigh~ inches in height, growing in a two-and-a-half inch clay pot. 150-200 Mites, a sufficient number for testing, trans~erred from the excised leaves to the fresh plants in a period of twenty-four hours.
Following the twenty-four hour transfer period, ~he excised leaves were removed from the infested plants.

~ 2 ~ 5 13,032 The test compounds were formulated by dilutin~ the stock ~uspension with water to provide 6uspensions containing ~he desired amount of test compound per million parts of final ormulation. The potted plants (one pot per compoundj were placed on a revolvin~ turntable an~ ~prayed with l~o-110 milliliters of test compound formulation by use of a DeVilbis spray gun set at 40 psig. sir pressure. ~l~s application, which lasted 30 seconds, was sufficient to we~ the plants to run-off. As a control, 100-110 milliliters of a water solution containing acetone and emulsifier in the ~ame concentrations as the test compound formulation, but containing no test compound, were also sprayed on infested plants. The sprayed plunts were held at 80 + 5F. and 50 ~ 5 percent rel.tive humidity for four days, after which, a ~ortality c.ount of motile forms was made on ~he leaves of the test pl~nts, A~ly individual which was capable of locomotion upon prodding was considered living.

i-e ~l.~e .~e The test organism was the egg of the ~wo-spotted mite (Tetranychus urticae (Koch)), as ob~ained from adults reared on Tendergreen bean pla~ts under controlled conditions of 80 ~ 5F. and 50 + 5 percent relative humidi~y. Heavily infested leaves from a stock culture were placed on the primary leaves of two bean plants six to eight inches in height, growing in a two-and-a-half inch clay pot. Females were allowed to oviposit for a period of 48 hours and then the leaves of the infested plants were dipped in a solution containing 800 parts of tetraethyl pyrophosphate per million parts of water in order to destroy the reproductory L49~5 13,032 for~s and thus prevent further egg laying. This solution of tetraethyl pyrophosphate does not affect ~he viability of the eggs. The plants were allowed to dry thoroughly.
~e test compounds were formulated by diluting the sto~k suspension with water to give a suspension containing varying amounts of test compound per million parts of final formulation. The potted plants (one pot per compound) were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbis ~pray gun set at 40 psig. air pressure. This application which lasted 30 seconds, was sufficient to wet the plants to run-off. As a control, 100-110 milliliters of a water solution containing acetone and emulsifier in the same concentrations as the test compound formulation, but containing no test compound, were also sprayed on plants infested with eggs. The sprayed plan~s were held at 80 ~ 5F.
and 50 + 5 percent relative humidity for four days, after which a microscopic examination was made of unhatched (dead) and hatched (living) eggs.
The results obtained are set forth in Table VI
below:

2 ~ 5 13,032 T~L~ VI
M~TICIDAL ACTIVITY (c) OF 2_(2-PYRAZI~L) 1,3-DIO~S
ACTIYITY O~
PUUND STRUCTURE MITE ADULT MITE EGG

CH3(40 ~H3 ~ CH3 14 CH3 ~ N ~ CH3 (7) (500) C) CC5Hll CH3 o X~ ~ ~10) (500) CH3 N ~ CH(CH3)2 CH O
CH3~y~N ~/ 3ll 16 CH3 ~ N ~ ~ CH(CH3)2 (70) (92) OCOC5Hll (c) i = inactive. Numbers in perenthe~es are LD values. The latter refers to that concentration of test 50 solution resulting in 50% kill when sprayed to drip-off on plant leaves.

~2~4'~L~ILS

13, 032 TABLE VI (CONTINUED) MITICIDAL ACTIVITY (c) ûF 2- (2-PYRAZINYL) 1, 3 -DIONES

ACTIVITY QN
~;uMPOUNO STRUCTURE MITE ADULT MITE EGG

CH3 o 17 ~ ~CH3 (5 Q COCH (CH3) 2 18CH3`~N ~ ~ (3~ (270) CH3' N
O

29~ N~L ~\/ CH3 N '\\ /~ CH3 O ' .

C~13 N ~CH3 0 COCH (CH3) 2 ~2~4 ~S ~-13, 032 TA~L~; VI (CONTINIJED) MITICIDAL ACTIVII'Y (C) o~ 2-(2-PYRAZINYL~ 1,3-DIO~~tES

ACTI VI TY ON
COMPOUND STRUCTURE _ MITE ADULT MITE EGG

31 ~ CH3 CH
3 \" N ~ \\
32 l N ~ ~ <CH3 ~ CH3 CH/~N ~3L~ i i -- ~4 --.

13,032 The compounds of th-s invention possess activity both as pre-emergence and post-emergence herbicides and, accordingly, one aspect of this invention comprises the application o~ the operative materials to undesired vegetation by any means whereby said materials are brought into contact with living plants (which include seeds and germinating seedlings), e.g., by application to the soil before any plants emerge or by direct application to foliage.
The compounds are effective for both grassy weeds such as crabgrass, wild oats, barnyard grass, yellow fox~ail, green foxtail, quackgrass, and rye grass, and broadleaf weeds such as mustard, pigweed, lambsquarters, and sheep sorrel are readily controlled while a broad spectrum of crops is unaffected.

The new toxicants may be applied conveniently in the form of a spray containing the acti~e ingredient in a concentration within the range of 0.01-20.0% by weight, and preferably from 1 to 10.0% by weight.
T,horough coverage of the foliage is effected for contact killing. For pre-emergence control of plants amounts within the range of 1/16 to 100 pounds per acre are generally used.
~ le compounds may be dispersed directly in water or a solut`ion in an organic solvent, such as acetone, dimethylformamlde, and dimethylsulfoxide emulsified in aqueous medium by the aid of a dispersing ~Z~4:1 5 13,032 agent. As dispersing and wetting agents there may be employed soft or hard sodium or potassium soaps, alkylated aromatic sodium sulfonates such as sodium dodecylbenzenesulfona~e, an amine salt as for example dibutylammonium dodecylbenzenesulfonate, alkali metal salts of sulfated fatty alcohols, ethylene oxide condensation products of alkyl phenols, or tall oil or higher mercaptans and other dispersing and wetting agents. Formulation of dry compositions is accomplished by mixing with finely divided solid carriers. Suitable carriers comprise talc, clay, pyrophyllite, silica and fuller's earth. Usually the toxicant will be only a minor proportion. The dry formulation may be used as a dust or dispersed in aqueous medium before application. If the latter it is convenient to incorporate a wetting or dispersing aid into the formulation.
Both the solid and the liquid formulations above described are useful in the application of herbicides because they facilitate uniform distribution and aid in the destruction of undesirable plants by maintaining the active ingredient in a form which enables prompt assimilation by the plant and efficient utilization of its weed destroying properties. The described conditioning agen~s enable the proper use by an unskilled operator without elaborate equipment to achieve the desired herbicidal effects.

~24~ 5 13,032 The effectiveness of compounds representative of this invention as terrestrial herbicides were evaluated as pre-emergence herbicides and post-emergence herbicides. The test plants were mustard, teaweed, crabgrass and giant foxtail. For the pre-emergence test, seeds of the type of plan~s as shown in Table VII were sown in fresh soil. In the pre-emergence test, the soil was sprayed with a solution of the test compound immediately after the seeds were planted. The solution was about a 1% by weight solution of the test compound in acetone. The compounds were applied at the rate of 8 lbs/acre of soil surface, except where otherwise indicated in Table ~'II.
Approxima~ely three weeks after spray applica-tions, the herbicidal activity of the compound was deter-mined by visual observation of the treated areas in com-parison with untreated controls. These observations are reported in Table~7II as percent control of plant growth.
In the post-emergence test the soil and developing plants were sprayed about two weeks after the seeds were sown. Except where indicated otherwise in Tab~e VII,the compounds were applied at the rate of 8 lbs/
acre from about a 1% by weight solution of the test com-pound in acetone. The post-emergence herbicidal activity was measured in the same way as the pre-emergence activity at three weeks following treatment.
The results are indicated in Table VII below:

13,032 TABLE VII
_ .
HERBI CI DAL ACTIVITY ( d) % Control of Test Plant Indicated Mustard Teaweed cral~gras s Giant Foxtai Compound Post Pre Post Pre Post Pre Post Pre 2 lO0 100 100 80 100 100 100 100 3 lO0 100 100 lOC 100 100 100 100 4 100 100 100 100 100 90 100 lO0 100 100 65 50 100 lO0 100 100 7 100 100 100 100 lO0 100 100 100

8 10~ 95 100 100 100 80 100 ~0

9 100 100 lO0 100 lO0 50 45 90 lO 100 100 lO0 100 lO0 60 100 80 11 lO0 100 100 100 100 6C 100 80 13 0 85 30 60 100 100 95 lO0 30 100 100 ~00 100 16 70 0 20 20 100 100 ~00 100 21 g9 100 80 100 45 50 20 50 23 100 100 lO0 90 ~0 50 60 --0 0 50 0 5~ 0 0 0 13,032 TABLE VII (Continued) HERBICID~L ACTIVITY~J
% Control of Test Plant Indicated Mustard Teaweed Crabgrass Giant Fox~ail Compound Post Pre Post Pre Post Pre Post Pre 0 lO0 0100 0 31 lO0 0 lO0 0 lO0 0100 0 33 ~0 0 0 0 80 030 0 34(e) 0 50 0 60 0 0 0 0 37(f)3~ 0 30 0 0 Q 0 0 38 90 0 80 ~0 lO0 4040 50 39 50 ~ 0 0 0 40 0 0 0 -~

__ _ __ _ (d) Rate of application = 8 lbs. per acre.
(e) Activity on yellow nutsedge: Preemergence control = 100%.
(f) Activity on morningglory: Pos~emergence control = 100%

.

.

13,032 TABLE VII(Continued) HEHBICIDAL ACTIVITY(d) .

% Control of Test Plant Indicated Mustard Teaweed _rab~rass Giant Foxtail Kno~n Post Pre Post Pre Post Pre Post Pre o CH
~< -- O O O O O O O

CH ~ 0 0 0 0 0 0 0 0 ~ 4 ~ 5 13,032 I~ will be understood that the plant species employed in the above tests are merely representative of a wide variety of plants that can be controlled by the use of the compounds of this inventionO The compounds contemplated in this invention may be applied as mite ovicides, ~iticides and herbicides according to methods known to those skilled in the art. Compositions containing the compounds as the active toxicant will usually comprise a carrier and/or diluent, either liquid or solid.
Suitable liquid diluents or carriers include uater, petroleum distillates, or other liquid carriers with or without surface active agents. Liquid concen~rates may be prepared by dissolving one of these compounds with a nonphytotoxic solvent such as acetone, xylene, or nitrobenzene and dispersing the toxicants in water with the aid of suitable surface active emulsifying and dispersing agents.
~ le choice of dispersing and emulsifying agents and the amount employed is dictated by the nature of the cornposition and the ability of the agent to facilitate the dispersion of the toxicant. Generally, it is desirable to use as little of the agent as is possible, consistent with the desired dispersion of the toxicant in the spray so that rain does not re-emulsify the toxicant after it is applied to the plant and wash it off the plant. Nonionic, anionic, amphoteric or cationic dispersing and emulsifying agents 13,032 may be employed; for example, the condensation products of alkylene oxides with phenol and organic acids, alkyl aryl sulfonates, complex ether alcohols, quaternary a~onium compounds, and the like.
In the preparation of wettable powder or dust or granulated composi~ions, the active ingredient is dispersed in and on an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fullers earth, and the like. In the formulation of the wetta~le powders the aforementioned dispersing agents as well as lignosulfonates can be included.
The required amount of the toxicants cont~m-plated herein may be applied per acre treated in from 1 to 200 gallons or more of liquid carrier and/or diluent or in from about 5 to 500 pounds of inert solid carrier and/or diluent. The concentration in the liquid concen-trate will usually vary from a~out 10 to 95 per cent by weight and in the solid formulations from about 0.5 to about ~0 per cent by weight. Satisfactory sprays, dusts, or granules for general use contain from about 1/4 to 15 pounds of active toxicant per acre.
The pesticides contemplated herein prevent attack by insects and mites upon plants or other material to which the pesticides are applied, and ~hey have rela-tively high residual toxicity. With respect to plants, they have a high margin of safety in that when used in sufficient amount to kill or repel the insects, they do --~4~L415 13,032 not burn or injure the plant, and they resist weathering which includes wash-off caused by rain, decomposition by ultraviolet light, oxidation, or hydrolysis in the presence of moisture or, at least such decomposition, oxidation, and hydrolysis as would materially decrease the desirable pesticidal characteristic of the toxicants or il~part undesirable characteristic for instance, phytotoxicity, to the toxicants. The toxicants are so chemically inert that they are compatible with substantially any other constituents of the spray schedule, and they may be used in the soil, upon the seeds, or the roots of plants without injuring either the seeds or roots of plants.
They may also be used in combination with other pesticidally active compounds. ~len used as miticides they will normally be applied to the foliage of the plants to be treated.
It will be appreciated that the compounds of this inven~ion can also be used in combination with other biologically active compounds.

Although the invention has been illustrated by the preceding examples it is not to be construed as being limited to ~he materi~ls employed therein, but rather, the invention is directed to the generic area as herein-befor~ disclosed. Various modifications and embodiments thereof can be made without departing from the spirit and scope thereof.
-

Claims (47)

WHAT IS CLAIMED IS:

1. A compound of the formula:

wherein:
X is a 2 or 3 member alkylene chain which may be substituted with one or more alkyl or alkenyl having up to five carbon atoms, wherein said alkyl or alkenyl may be substituted with one or more cyano, halogen, nitro, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, dialkylamino, acylamido or acyl substituents none of which contain more than four carbon atoms, or any two substituents together may form an alkylene or alkenylene chain having from 2 to 6 carbon atoms completing a 3, 4, 5, 6 or 7- membered ring structure, with the proviso that when X is a 2-membered alkylene chain, substituents thereon when taken with X do not form an aromatic ring;
Y is hydrogen, a salt forming cation or where Z is:

hydrogen, halogen, alkyl, alkoxy, alkylthio, amino, alkylamino, dialkylamino, alkenyl, alkynyl, bicycloalkyl, bicycloslkenyl, cycloalkyl, cycloalkenyl, phenyl, phenylalkyl, naphthyl or naphthylalkyl all of which except hydrogen and halogen may be substituted with one or more alkyl, carboxy, cyano, nitro, alkoxy, alkoxycarbonyl, halogen, haloalkyl, alkoxyalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkylthioalkyl or dialkylamino substituent provided that Z may not contain more than seven aliphatic carbon atoms, or Z is wherein X is as defined above and;
HET is selected from the group of:

(I) wherein R1 is H, alkyl (C1-C5), alkoxy (C1-C4), alkylthio (C1-C4), alkylsulfinyl (C1-C4), alkylsulfonyl (C1-C4), alkenyl (C2-C5), alkylamino (C1-C4), dialkylamino (C2-C5), amino, hydroxy, alkoxyalkyl (C2-C4), alkylthioalkyl (C2-C4), alkylsulfinylalkyl (C2-C4), alkylsulfonylalkyl (C2-C4), trifluoromethoxy, halogen, haloalkyl or polyhaloalkyl, with the longest straight chain of atoms being 3 or less in number;
R2 is H or alkyl (C1-C2);
R3 is H, CH3, alkoxy (C1-C2), or alkylthio (C1-C2), with the longest straight chain of atoms being 3 or less in number;

(II) wherein R4, R5 and R6, individually, are H, haloalkyl, halogen, alkyl (C1-C5), polyhaloalkyl, alkoxy (C1-C4), alkylthio (C1-C4), hydroxy, amido, amino, alkylsulfonyl (C1-C4), alkylamino, dialkylamino, or alkylsulfinyl (C1-C4);

R7 = alkyl (C1-C3), halogen, haloalkyl or polyhaloalkyl;

(III) wherein R8 is H, alkyl (C1-C4), halogen, alkoxyl (C1-C3), alkylthio (C1-C3), haloalkyl, polyhaloalkyl, alkoxyalkyl (C2-C4), alkylthioalkyl (C2-C4), alkylsulfinylalkyl (C2-C4) or alkylsulfonylalkyl (C2-C4); R9 is H, alkyl (C1-C4), alkenyl (C2-C4), haloalkyl, halogen, polyhaloalkyl, alkoxy (C1-C3), or alkylthio (C1-C3), with the longest straight chain of atoms being 4 or less in number; R10 is H, methyl, ethyl, alkoxy (C1-C3), or alkylthio (C1-C3);

(IV) wherein R11 and R13 are the same as R1 and R12 is the same as R9 with the proviso that the total number of carbon atoms for R1, R12 and R13 is no greater than 8;

(V) wherein R14 is the same as R8; R15 is the same as R1 and R16 is the same as R9, with the proviso that the total number of carbon atoms for R14, R15 and R16 is no greater than 8;

(VI) wherein R20 is the same as R8; R21 is the same as R1, and R22 is hydrogen or methyl, with the proviso that at least one of R20, R21, and R22 is other than hydrogen;

(VII) wherein R23 and R24 are the same as R8, and R25 is the same as R1, with the proviso that the total number of carbon atoms for R23, R24 and R25 is no greater than 8; and at least one of R23, R24 and R25 is other than hydrogen;

(VIII) wherein R26 and R27 are H, alkyl (C1-C5), alkoxy (C1-C4), alkylthio (C1-C4), alkenyl (C2-C5), alkylamino (C1-C4), dialkylamino (C2-C5), amino, hydroxy, alkoxyalkyl (C2-C4), alkylthioalkyl (C2-C4), alkylsulfinylalkyl (C2-C4), alkylsulfonylalkyl (C2-C4), trifluoromethoxy, haloalkyl with the longest straight chain of atoms being 3 or less in number and a maximum of 5 carbon atoms for all carbon-containing substituents;

(IX) wherein R29 and R28 are the same as R26 and R27;

(X) wherein R30 is the same as R26 and R31 is the same as R8; and (XI) wherein R32 is the same as R9 and R33 is the same as R8.

2. A compound according to claim 1 wherein X is a 2 member alkylene chain.

3. A compound according to claim 1 wherein X is a 3 member alkylene chain.

4. A compound according to claim 1 wherein Y is hydrogen.

5. A compound according to claim 1 wherein Y is a salt forming cation.

6. A compound according to claim 1 wherein HET is:

wherein R1 is H, alkyl (C1-C5), alkoxy (C1-C4), alkylthio (C1-C4), alkylsulfinyl (C1-C4), alkylsulfonyl (C1-C4), alkenyl (C2-C5), alkylamino (C1-C4), dialkylamino (C2-C5), amino, hydroxy, alkoxyalkyl (C2-C4), alkylthioalkyl (C2-C4), alkylsulfinylalkyl (C2-C4), alkylsulfonyalkyl (C2-C4), trifluoromethoxy, halogen, haloalkyl or polyhaloalkyl, with the longest straight chain of atoms being 3 or less in number;
R2 is H or alkyl (C1-C2);

R3 is H, CH3, alkoxy (C1-C2), or alkylthio (C1-C2), with the longest straight chain of atoms being 3 or less in number.

7. A compound according to claim 6 wherein R1, R2 and R3 are hydrogen, and X is a 3 member alkylene chain.

8. A compound according to claim 6 wherein R1 is alkyl, R2 and R3 are hydrogen, and X is a 3 member alkylene chain.

9. A compound according to claim 6 wherein R1 is alkoxy, R2 and R3 are hydrogen, and X is a 3 member alkylene chain.

10. 5,5-Dimethyl-2-(2-pyridinyl)-1,3 -cyclohexanedione.

11. 5,5-Dimethyl-2-(2-pyridinyl)-1,3 -cyclohexanedione sodium salt.

12. 5,5-Dimethyl-2-(4-methyl-2-pyridinyl) -1,3-cyclohexanedione.

13. 5-(1-Methylethyl)-2-(2-pyridinyl)-1, 3-cyclohexanedione.

14. 5-(1-Methylethyl)-2-(4-methyl-2-pyridinyl)-1,3-cyclohexanedione.

15. 2-(4-Ethyl-2-pyridinyl)-5-(1-methylethyl)-1,3-cyclohexanedione.

16. 2-(4-Methoxy-2-pyridinyl)-5-(l-methylethyl)-1,3-cyclohexanedione.

17. 8-(2-pyridinyl)-spiro[4.5]decane-7,9-dione.

18. 5-Ethyl-5-methyl-2-(2-pyridinyl) -1,3-cyclohexanedione.

19. 5-(1-Methylpropyl)-2-(2-pyridinyl) -1,3-cyclohexanedione.

20. 5-(1,1-Dimethylethyl)-2-(2-pyridinyl) -1,3-cyclohexanedione.

21. 5-(1-Ethylpropyl)-2-(2-pyridinyl) -1,3-cyclohexanedione.

22. A compound according to claim 1 wherein HET is:
wherein R4, R5 and R6, individually, are H, haloalkyl, halogen, alkyl (C1-C5), polyhaloalkyl, alkoxy (C1-C4), alkylthio (C1-C4), hydroxy, amido, amino, alkylsulfonyl (C1-C4), alkylamino, dialkylamino, or alkylsulfinyl (C1-C4), and R7 is alkyl (C1-C3), halogen, haloalkyl or polyhaloalkyl.

23. A compound according to claim 22 wherein R4, R5, R6 and R7 are hydrogen and X
is a 3 member alkylene chain.

24. A compound according to claim 22 wherein at least one of R4, R5, R6 and R7 is alkyl and X is a 3 member alkylene chain.

25. 5-(1-Methylpropyl)-2-(3-pyridinyl) -1,3-cyclohexanedione.

26. 5-Ethyl-3-hexanoyloxy-5-methyl-2-(4-methyl-3-pyridinyl)-2-cyclohexan-1-one.

27. A compound according to claim 1 wherein HET is:

wherein R8 is H, alkyl (C1-C4), halogen, alkoxyl (C1-C3), alkylthio (C1-C3), haloalkyl, polyhaloalkyl, alkoxyalkyl (C2-C4), alkylthioalkyl (C2-C4), alkylsulfinylalkyl (C2-C4), or alkylsulfonylalkyl (C2-C4);
R9 is H, alkyl (C1-C4), alkenyl (C2-C4), haloalkyl, halogen, polyhaloalkyl, alkoxy (C1-C3), or alkylthio (C1-C3), with the longest straight chain of atoms being 4 or less in number; and R10 is H, methyl, ethyl, alkoxy (C1-C3), or alkylthio (C1-C3).

28. A compound according to claim 27 wherein R8, R9 and R10 are alkyl and X is a 3 member alkylene chain.

29. A compound according to claim 27 wherein R8, R9 and R10 are alkyl, X is a 3 member alkylene chain and Y is .

30. 5,5-Dimethyl-2 (3,5,6-trimethyl -2-pyrazinyl)-1,3-cyclohexanedione.

31. 5,5-Dimethyl-3-hexanoyloxy-2-(3,5,6-trimethyl-2-pyrazinyl)-2-cyclohexene-1-one.

32. 5-(1-Methylethyl)-2-(3,5,6-trimethyl-2-pyrazinyl)-1,3-cyclohexanedione.

33. 3-Hexanoyloxy-5-(1-methylethyl)-2-(3,5,6-trimethyl-2-pyrazinyl)-2-cyclohexen-1-one.

34. 5,5-Dimethyl-3-(2-methylpropanoyloxy)-2-(3-methyl-2-pyrazinyl)-2-cyclohexene-1-one.

35. 8-(3,5,6-Trimethyl-2-pyrazinyl)-spiro [4.5] decane-7,9-dione.

36. A method of controlling undesired plant growth which comprises subjecting said plant to a herbicidally effective amount of the compound of claim 1.

37. A method of controlling undesired plant growth which comprises subjecting said plant to a herbicidally effective amount of the compound of claim 6.

38. A method of controlling undesired plant growth which comprises subjecting said plant to a herbicidally effective amount of 5,5-dimethyl-2-(2-pyridinyl)-1,3-cyclohexanedione..

39. A method of controlling undesired plant growth which comprises subjecting said plant to & herbicidally effective amount of the compound of claim 22.

40. A method of controlling undesired plant growth which comprises subjecting said plant to a herbicidally effective amount of the compound of claim 27.

41. A method of controlling adult mites and mite eggs which comprises subjecting said adult mites and mite eggs to a miticidally effective amount of 5,5-dimethyl-3-(2-methylpropanoyloxy) -2-(3-methyl-2-pyrazinyl)-2-cyclohexene-1-one.

42. A method of controlling adult mites and mite eggs which comprises subjecting said adult mites and mite eggs to a miticidally effective amount of 5,5-dimethyl-2-(3,5,6-trimethyl -2-pyrazinyl)-1,3-cyclohexanedione.

43. A method of controlling adult mites and mite eggs which comprises subjecting said adult mites and mite eggs to a miticidally effective amount of 5,5-dimethyl-3-hexanoyloxy-2-(3,5,6, -trimethyl-2-pyrazinyl)-2-cyclohexene-1-one.

44. A method of controlling adult mites and mite eggs which comprises subjecting said adult mites and mite eggs to a miticidally effective amount of 5-(1-methylethyl)-2-(3,5,6,-trimethyl -2-pyrazinyl)-1,3-cyclohexanedione.

45. A method of controlling adult mites and mite eggs which comprises subjecting said adult mites and mite eggs to a miticidally effective amount of 3-hexanoyloxy-5-(1-methylethyl)-2-(3,5,6,-dimethyl-2-pyrazinyl)-2-cyclohexene-1-one.

46. A method of controlling adult mites and mite eggs which comprises subjecting said adult mites and mite eggs to a miticidally effective amount of 8-(3,5,6,-trimethyl-2-pyrazinyl)-spiro [4.5]decane-7,9-dione.

47. A method of preparing a 1,3-cycloalkanedione compound of the formula:
wherein R1 is H, alkyl (C1-C5), alkoxy (C1-C4), alkylthio (C1-C4), alkylsulfinyl (C1-C4), alkylsulfonyl (C1-C4), alkenyl (C2-C5), alkylamino (C1-C4), dialkylamino (C2-C5), amino, hydroxy, alkoxyalkyl (C2-C4), alkylthioalkyl (C2-C4), alkylsulfinylalkyl (C2-C4), alkylsulfonylalkyl (C2-C4), trifluoromethoxy, halogen, haloalkyl or polyhaloalkyl, with the longest straight chain of atoms being 3 or less in number;
R2 is H or alkyl (C1-C2);
R3 is H, CH3, alkoxy (C1-C2), or alkylthio (C1-C2), with the longest straight chain of atoms being 3 or less in number.
wherein X is a 2 or 3 member alkylene chain which may be substituted with one or more alkyl or alkenyl, wherein said alkyl or alkenyl may be substituted with one or more alkyl, cyano, halogen, nitro, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, dialkylamino, acylamido or acyl substituents, or any two substituents together may form an alkylene or alkenylene chain having from 2 to 6 carbon atoms completing a 3,4,5,6 or 7-membered ring structure, with the proviso that when X is a 2-membered alkylene chain substituents thereon when taken with X do not form an aromatic ring; which comprises reacting a 1-pyridylmethyllithium:

with an excess of a dicarboxylic acid ester wherein R1, R2 and R3 are as above, with an excess of a dicarboxylic acid ester at a temperature of from about -100°C to about -50°C to form a keto ester, and cyclization of the keto ester to said 1,3-cycloalkanedione in the presence of an alkali alkoxide, in a mole ratio of from 1:0.1 to 5:1 (of keto ester to base), at a temperature of from room temperature to about 150°C.