United States Patent [191 Bereznak et al.

US005747497A

5,747,497 May 5, 1998

[11] Patent Number:

[45] Date of Patent:

[54] FUNGICIDAL FUSED BICYCLIC PYRIMIDINONES

[75] Inventors: James Francis Bereznak. Aston. Pa.; Zen-Yu Chang. Hockessin. Del.; Thomas Paul Selby; Charlene Gross Stemberg. both of Wilmington. Del.

[73] Assignee: E. L du Pont de Nemours and Company. Wilmington. Del.

[21] Appl. No.: 545,827

[22] PCT Filed: May 10, 1994

[86] PCT No.: PCT/US94/04965

§ 371 Date: Nov. 8, 1995

§ 102(e) Date: Nov. 8, 1995

[87] PCT Pub. No.: WO94/26722

PCI‘ Pub. Date: Nov. 24, 1994

[51] Int. Cl.6 .................... .. A61K 31/505; A61K 31/495; C07D 239/86; C07D 239/95

[52] US. Cl. ........................ .. 514/259; 514/260; 544/283; 544/284; 544/285; 544/286; 544/287; 544/288; 544/289; 544/290; 5441291; 544/292; 544/293

[58] Field 01' Search ................................... .. 544/283-293; 514/259-260

[56] References Cited

U.S. PATENT DOCUMENTS

3,560,619 2/1971 Harrisonetal. ...................... .. 544/285

3,692,527 9/1972 Kiinig et a1 .... .. 96/109 3,714,354 1/1973 Stam .......... .. 424/251

3,755,582 8/1973 Bullock et al 424/251 3,784,693 1/1974 Habeck etal 424/250 3,867,384 2/1975 Bullock et a1 . 260/2564 4,276,295 6/1981 Ishikawa et a1. 424/251 4,521,420 6/1985 Manner et al. 514/259 4,833,144 5/1989 Takahashi et al. 514/259 4,861,780 8/1989 Takahashi et a]. 514/259 5,008,266 4/1991 Takahashi eta]. 514/259 5,276,038 1/1994 Takasugi et al. 514/259 5,304,530 4/1994 Cli?'et al. 504/266 5,354,755 10/1994 Takasugi et al. ..................... .. 514/259

FOREIGN PATENT DOCUMENTS

O 276 825 8/1988 European Pat. O?". C07D 239/95 2218301 10/1973 Germany . 210 452 6/1984 Germany ................... .. CO7D 239/95

253 622 l/l988 Germany ................... .. C07D 401/04

OTHER PUBLICATIONS

P.N. Bhargava and S.N.Singh. Synthesis of Some New 6. S-Diiodo-S-Substimted-Z-Thio-3-Aryl (or Alkyl)—4(3)-Quinazolones. The Journal of Scienti?c

Research Banaras Hindu University. )QCI (1&2). 27-32. 1969-1970.

P.N. Bhargava and M.R.Chaurasia. 4(3H)Quinazolones:Synthesis 6.8-Disubstituted-S-Substituted—2—Thio-3-Aryl(or Alkyl)4(3H)Quinazoloncs. J. Indian Chem. Soc.. L111. 46-49. Jan. 1976.

Ram Lakhan and Babban J. Rai. Synthesis and Antibacterial Activity of 2—[[W—(Dialkylamino)alkyl]thio|-3-aryl(or a1kyl)-6.8—disubstituted—4(3H)-quinazo1inones. J.Che m.Eng. Data. 32. NO. 3. 384—386. 1987.

P.N.Bhargava and Radhey Shyarn. Synthesis and Spectral Studies on Some Typical 4(3H)Quinazolones as Possible Antimalarials. Egypt.J.Chem.. 18. No. 3. 393-401. 1975.

Grout et al. J. Chem. Soc. 3551-3557. Sep. 1960.

Hedayatullah et al. J. Heteracyclic Chem. 1033-1037. Sep. 1978. Suesse. M. et al. Chemical Abstracts. 115(7). Abstract No. 71634p (1991). Bhargava. P. et al. Chemical Abstracts. 89(19). p. 573. Abstract No. 1635302 (1978). Bhargava. P. et al. Chemical Abstracts. 89(13). p. 908. Abstract No. 109345e (1978). Bhargava. P. et al. Chemical Abstract. 85(1). p. 450.Abstract No. 5582f (1976). Lakhan. R. et al. Chemical Abstracts. 107(5). p.396. Abstract No. 36462u (1987). Abstract: US 4.605.657 (Aug. 12. 1986). Abstract: JP 5-9044365-A (Mar. 12. 1984). Abstract: DE 3 220 898-A (Dec. 8. 1983).

Abstract: DD 210 452-A (Jun. 13. 1984).

Abstract: DD 253 622-A (Jan. 27. 1988).

Abstract: EP 0 276 826-A (Aug. 3. 1988).

Abstract: EP 0 316 657-A (May 24. 1989).

Abstract: EP 0 393 999-A (Oct. 24. 1990).

Abstract: DD 278 788-A (May 16. 1990).

Abstract: DD 287 033-A (Feb. 14. 1991). Abstract: DD 287 034-A (Feb. 14. 1991).

Studies on of

15(6).

Primary Examiner—Matthew V. Crumbling

[57] ABSTRACT

This invention pertains to compounds of Formulae I. II and III. as de?ned in the disclosure and claims. including all geometric and stereoisomers. N-oxides. agriculturally suit able salts thereof. agn‘cultural compositions containing them and their use as fungicides.

19 Claims, No Drawings

5 .747.497 3

phenyl optionally substituted with R13. R15. and R“; or phenyl optionally substituted with R13. R15. and R16; or

R5 and R6 are taken together to form —-CH2(CH2),,, CH.,—;

R7 is C3-C1O alkyl: C3—C7 cycloalkyl; C4-C7 alkenyl; propynyl; C5—Cl0 alkynyl; (jg-C!0 haloalkyl', C3-C1O haloalkenyl: C3-Clo haloalkynyl; C2-Cl0 alkoxyalkyl; Cz-C10 alkylthioalkyl; C2-C10 alkylsul?nylalkyl; C2~C1o alkylsulfonylalkyl; C4—C 10 alkenyloxyalkyl; (IA-C1o alkynyloxyalkyl; CFC1O (cycloalkyl)oxyalkyl; CFC1o alkenylthioalkyl; CFC10 alkynylthioalkyl; cé-c 10 (cycloalkyl)thioalkyl; cz-c1o haloalkoxyalkyl; C,,—1Cl0 haloalkenyloxyalkyl; C4-C1o haloalkynyloxy alkyl; C4—C10 alkoxyalkenyl; CFC10 alkoxyalkynyl; CFC1o alkylthioalkenyl; C4-Cl0 alkylthioalkynyl; CFC10 triakylsilylalkyl; C 1-C lo alkyl substituted with NRUR12 or nitro; C2—C1o alkyl substituted with cyano; Cl-C10 alkoxy; Cl-C10 haloalkoxy; Cl-C10 alkylthio; C l-C10 haloalkylthio; NRmR"; or phenyl. pyridyl. furanyl. thienyl. naphthyl. benzofuranyl. benzothienyl. or quinolinyl each optionally substituted with R“. R”. and R16;

R9 is hydrogen; C2-Cl0 alkyl; (Is-C7 cycloalkyl; C3—C10 alkenyl; C3—C10 alkynyl; C3--C10 haloalkyl; C3—C10 haloalkenyl', C3—C 1O haloalkynyl; C3—Cl0 alkoxyalkyl other than butoxyethyl; C2—Cl0 alkylthioalkyl; C2-C1o alkylsul?nylalkyl; C2-C10 alkylsulfonylalkyl; CFC10 cycloalkylalkyl; C4—C 1O alkenyloxyalkyl; CFC10 alkynyloxyalkyl; CFC m (cycloalkyhoxyalkyl; C 4-C m alkenylthioalkyl; CFC1o alkynylthioalkyl; Cf-Cl0 (cycloalkyl)thioalkyl; C2—C 1O haloalkoxyalkyl', C4—C 10 haloalkenyloxyalkyl. CA-C1o haloalkynyloxyalkyl; CFC“, alkoxyalkenyl; CFC10 alkoxyalkynyl; C4—C1O alkylthioalkenyl; C4-C1o alkylthioalkynyl; CFC1O tri alkylsilylalkyl; cl-cl0 alkyl substituted with NR1‘R12; CFCl0 cyanoalkyl; C -Cl0 nitroalkyl; C1 --C8 alkyl substituted with CO2R 1; pyridyl. furanyl. thienyl. or naphthyl each optionally substituted with R14. R15. and R16; _N=cR“R“; —NR12R"; —OR“’'; or —NC (=Q)N'R“R‘2; or R3 and R“ are both iodine and R9 is phenyl optionally substituted with R14. R15. and R16; or

R7 and R9 are taken together to form —CH2(CH2),,, CH2—;

R10 is hydrogen; C1—C4 alkyl; Cl-C4 alkoxy; or NRI‘RH; R11 is independently hydrogen; CFC,‘ alkyl; or phenyl

optionally substituted with at least one R13; R12 is independently hydrogen; C1--C8 alkyl; or phenyl

optionally substituted with at least one R“; or R1 1 and RI2 are taken together to form

—CH2CH2CH2CH2—. —CH2(CH2)3CH2—. —CH2CH20CH2CH2-—. ——CH2CH(Me)CH2CH(Me) car. or —CH2CH(Me)OCH(Me)CI-I2-—;

R13 is independently halogen; C1-C4 alkyl; C1—C4 alkoxy; CFC‘, haloalkyl; nitro; or cyano;

R14 is independently C1-C6 alkyl; C1-C6 alkoxy; C1-C6 haloalkyl; halogen; C2-C8 alkynyl; C1-C6 thioalkyl; phenyl or phenoxy each optionally substituted with at least one R13; cyano; nitro; C 1-C6 haloalkoxy; C 1—C6 haloalkylthio; C2-C6 alkenyl; C2-C6 haloalkenyl; acetyl; CO2Me; or N(Cl-C2 alkyl)2;

R15 is independently methyl; ethyl; methoxy; methylthio; halogen; or tri?uoromethyl;

R16 is independently halogen; and R17 is independently C1-C8 alkyl; or phenyl optionally

substituted with at least one R13.

20

35

45

55

65

4 DETAILED DESCRIPTION OF THE

INVENTION

In the above recitations. the term “alkyl”. used either alone or in compound Words such as “alkylthio.” “haloalkyl.” or “alkylthioalkyl” denotes straight-chain or branched alkyl; e.g.. methyl. ethyl. n-propyl. i-propyl. or the different butyl. pentyl. hexyl. etc. isomers. “CycloalkyP’ denotes cyclopropyl. cyclobutyl.

cyclopentyl. and cyclohexyl. The term “cycloalkyloxyalky ” denotes the cycloalkyl groups linked through an oxygen atom to an alkyl chain. Examples include cyclopentyloxym ethyl and cyclohexyloxybutyl. The term “cycloalkylthio alkyl” are the cycloalkyl groups linked through a sulfur atom to an alkyl chain; e.g.. cyclopropylthiopentyl. “Cycloalky lalkyl" denotes a cycloalkyl ring attached to a branched or straight-chain alkyl; e.g. cyclopropylmethyl and cyclohexy lbutyl. '

“AlkenyP’ denotes straight chain or branched alkenes; e.g.. l-propenyl. 2-propenyl. 3-propeny1 and the diiferent butenyl. pentenyl. hexenyl. etc. isomers. Alkenyl also denotes polyenes such as 1.3-hexadiene and 2.4.6 heptatriene.

“AlkynyP’ denotes straight chain or branched alkynes; e.g.. cthynyl. l-propynyl. 3-propynyl and the di?erent butynyl. pentynyl. hexynyl. etc. isomers. “AlkynyP‘ can also denote moieties comprised of multiple triple bonds; e.g.. 2.7-octadiyne and 2.5.8-decatriyne. .

“Alkoxy" denotes methoxy. ethoxy. n-propyloxy. isopro pyloxy and the dilferent butoxy. pentoxy. hexyloxy. etc. isomers. “Alkoxyalkenyl" and “alkoxyalkynyl” denoted groups in which the alkoxy group is bonded through the oxygen atom to an alkenyl or alkynyl group. respectively. Examples include CH3OCH2CH=CH and (CH3)2 CHOCH2CECCH2. The corresponding sulfur derivatives are denoted “alkylthioalkenyl and “alkylthioalkynyl.” Examples of the former include CH3SCH2CH=CH and CH3CH2SCH2(CH3)CH=CHCH2. and an example of the latter is CH3CH2CH2CH2SCH2CEC.

“Alkenyloxy” denotes straight chain or branched alkeny loxy moieties. Examples of alkenyloxy include H2C=CHCH2O. (CH3)2C=CHCH2O. (CH3) CH=CHCH2O. (CH3)CH=C(CH3)CH2O and CH2——-CHCH2CH2O. “Alkenylthio” denotes the similar groups wherein the oxygen atom is replaced with a sulfur atom; e.g.. H2C=CHCH2S and (CH3)CH=C(CH3)CH2S. The term “alkenyloxyalkyl” denotes groups in which the alkenyloxy moiety is attached to an alkyl group. Examples include H2C=CHCH2OCH2CH2. H2C=CHCH2OCH (CH3)CH2. etc. “Alkenylthioalkyl" denotes the alkenylthio moieties bonded to an alkyl group. Examples include H2C=CHCH2SCH(CH3)CH(CH3) and (CH3)CH=C(CH3) CH2SCH2.

“Alkynyloxy" denotes straight or branched alkynyloxy moieties. Examples include HCECCH2O. CH3CCCH2O and CH3CECCH2CH2O. “Alkynyloxyalkyl" denotes alky nyloxy moieties bonded to alkyl groups; e.g.. CH3C=_=CCH2OCH2CH2 and HCECCH2OCH(CH3)CH2. “Alkynylthioalkyl" denotes alkynylthio moieties bonded to alkyl groups. Example include CHaéCC?zSCHzC?2 and CH3C-=-CCH2CH2SCH(CH3)CH2.

“Alkylthio” denotes methylthio. ethylthio. and the di?’er ent propylthio. butylthio. pentylthio and hexylthio isomers. “Alkylthioalkyf’ denotes alkylthio groups attached to an alkyl chain; e.g.. CH3CH2SCH2CH(CH3) and (CH3)2 CHSCH2.

5.747.497 5

“Alkylsul?ny " denotes both enantiomers of an alkylsul? nyl group. For example. CH3S(O). CH3CH2S(O). CH3CH2CH2S(O). (CH3)2CHS(O) and the different butylsul?nyl. pentylsul?nyl and hexylsu?nyl isomers. “Alkylsu1?nylalkyl" denotes alkylsul?nyl groups attached to an alkyl chain; e.g.. CH3CH2S(O)CH2CH(CH3) and (CH3)2CHS(O)CH2. Examples of “alkylsulfonyl” include CH3S(O)2.

CH3CH2S(O)2CH3CH2CH2S(O)2. (CH3)2CHS(O)2 and the different butylsulfonyl. pentylsulfonyl and hexylsulfonyl isomers. “Alkylsulfonylalkyl” denotes alkylsulfonyl groups attached to an alkyl chain; e.g.. CH3CH2S(O)2CH2CH(CH3) and (CH3)2CHS(O)2CH2. The term “halogen”. either alone or in compound words

such as “haloalkyl”. denotes ?uorine. 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 di?’erent. Examples of “haloalky ” include F3C. ClCH2. CF3CI-I2 and CF3CF2. Examples of “haloalkenyl” include (Cl)2 C=CHCH2 and CF3CH2CH=CHCH2. “Haloalkenyloxy alkyl” denotes haloalkenyl groups bonded to oxygen and in turn bonded to alkyl groups. Examples include CF3CH2CH=CHCH2OCH2 and (Cl)2C=CHCH2OCH2. Examples of “haloalkynyl” include HCECCHCL CF3CEC. CChkC and FCHZCECCHZ. “Haloalkyny loxyalkyl" denotes haloalkynyl groups bonded through an oxygen atom to an alkyl moiety. Examples include CF3CECCH2CH2. C1CH2CECCH2CH2OCH(CH3). etc. Examples of “haloalkoxy” include CF30. CCI3CH2O. CF2HCH2CH2O and CF3CH2O. “Haloalkoxyalkyl” denotes haloalkoxy groups bonded to straight-chain or branched alkyl groups; e.g.. CF2HCH2CH2OCH2CH2. CCl3CH2OCH (CH3) and CF3OCH2.

‘Trialkylsilyl” designates a group with three alkyl groups bonded to silicon; e.g.. (CH3)3Si and t-Bu(CH3)2Si. ‘Tri alkylsilylalkyl” denotes tn'alkylsilyl groups bonded to another straight-chain or branched alkyl group. Examples include (CH3)3SiCH2 and t-Bu(CH3)2SiCH2CH(CH3)CH2. The total number of carbon atoms in a substituent group

is indicated by the “Cr-Ci” pre?x where i and j are numbers from 1 to 10. For example. C 1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C2 alkoxyalkoxy designates CH3OCH2O; C3 alkoxyalkoxy designates. for example. CH3OCH2CH2O or CH3CH2OCH2O; and C4 alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms. examples including CH3CH2CH2OCH2O. and CH3CH2OCH20. Examples of “alkoxyalkyP’ include CH3OCH2. CH3OCH2CH2. CH3CH2OCH2. CH3CH2CH2OCH2 and CH3CH2OCH2.

Preferred for reasons of ease of synthesis or greater fungicidal activity are: Preferred l The compounds of Formula I as de?ned above wherein: Q is O; R1 is C3-C8 alkyl; C4—C8 alkenyl; C4—C8 alkynyl; C1—CS

haloalkyl; C3-C8 haloalkenyl; C2-C8 alkoxyalkyl; C2—C8 alkylthioalkyl; C5-C8 cycloalkylalkyl; C2—C8 alkyl substituted with cyano; C1—CB alkoxy; C1—C8 haloalkoxy; C1-C8 alkylthio; or C4-C8 alkenyloxy alkyl; or pyridyl. furanyl. or thienyl each optionally substituted with RM and R15;

R2 is C3--CB alkyl; C3—C8 alkenyl; C3-C8 alkynyl; Cl-Ca haloalkyl; C3—C8 haloalkenyl; C3—C8 alkoxyalkyl; CZ-Cs alkylthioalkyl; C4—C8 cycloalkylalkyl; C3-C3

25

35

50

65

6 cyanoalkyl; C4-C8 alkenyloxyalkyl: or phenyl option ally substituted with R“;

R3 is halogen; C1—C8 alkyl; C2—Cs alkynyl; C3—Ca cycloalkyl; C1-C8 haloalkyl: CFC8 alkoxy; Cr-C8 haloalkoxy; C1—C8 alkylthio; C1—C8 alkylsulfonyl: C2~C8 alkoxyalkyl; C2—C8 alkylthioalkyl; C4—C8 cycloalkylalkyl; or C5—C8 trialkylsilylalkynyl; and

R14 is methyl; ethyl; methoxy; ethoxy; Cl-C2 haloalkyl; halogen; acetylenyl; propargyl; methylthio; ethylthio: cyano; nitro; CFC; haloalkoxy: vinyl: allyl; acetyl; CO2Me; or N(C1—C2 alkyl)2.

Preferred 2 The compounds of Formula 11 as de?ned above wherein:

Q is O; n is O;

R3 is halogen; CFC8 alkyl; C2-C8 alkynyl; C3—CB cycloalkyl; C1-C8 haloalkyl; C1-C8 alkoxy: (II-CB haloalkoxy; C1-C8 alkylthio: CFCS alkylsulfonyl: C2-C8 alkoxyalkyl; C2-Ca alkylthioalkyl; CFCB cycloalkylalkyl; or C5-C8 trialkylsilylalkynyl:

R5 is C3-C5 alkyl; crc7 alkenyl; cs-c5 alkynyl; c,-cB haloalkyl; C5-C8 haloalkenyl; C2-C8 alkoxyalkyl other than methoxypropyl; C2-C8 alkylthioalkyl; Cit-Cs cycloalkylalkyl; C2-C8 alkyl substituted with cyano; C l-C8 alkoxy; C1-C18 haloalkoxy; CFC8 alkylthio; or C4-C8 alkenyloxyalkyl; or phenyl. furanyl. or thienyl each optionally substituted with R14 and R”;

R" is cs-ca alkyl; ca-c7 alkenyl; C3-C8 alkynyl; C1-C8 haloalkyl; C3-C8 haloalkenyl; C3—C8 alkoxyalkyl other than propoxymethyl; C2—CB alkylthioalkyl; CFC8 cycloalkylalkyl: C5—C8 cyanoalkyl; CFC8 alkenyloxy alkyl; phenyl optionally substituted with R“; or C3--Cs alkyl substituted with phenyl optionally substituted with R13 and R15; and

R14 is methyl; ethyl; methoxy; ethoxy; C PC: haloalkyl; halogen; aoetylenyl; propargyl; methylthio; ethylthio: cyano; nitro; C l-C2 haloalkoxy; vinyl; allyl; acetyl; COzMe; or N(Cl—C2 alkyl)2.

Prefmed 3 The compounds of Formula 111 as de?ned above wherein:

Q is O; R3 is halogen; C1-C8 alkyl; C2—C8 alkynyl; C3-C8

cycloalkyl; CFC8 haloalkyl; Cl-C8 alkoxy; CFC8 haloalkoxy; C1-C8 alkylthio; C1-C8 alkylsulfonyl; C2—C8 alkoxyalkyl; CFC8 alkylthioalkyl; CVC8 cycloalkylalkyl; or C5—C,s trialkylsilylalkynyl.

R7 is C3—C8 alkyl; CFC? alkenyl; propynyl; C2—C8 haloalkyl; C3-C8 haloalkenyl; C2-Ca alkoxyalkyl; C2—C8 alkylthioalkyl; C2-C8 alkyl substituted with cyano; Cl-C8 alkoxy; C1-C8 haloalkoxy; C1—C8 alky lthio; or C4—C8 alkenyloxyalkyl; or phenyl. pyridyl. furanyl. or thienyl each optionally substituted with R“ and R15;

R9 is C3-C8 alkyl; C3-C‘3 alkenyl; C3-C8 alkynyl: C3-C,3 haloalkyl; C3-C8 haloalkenyl; C3-C8 alkoxyalkyl; C2—C8 alkylthioalkyl; C4-Ca cycloalkylalkyl; CFCg cyanoalkyl; C4418 alkenyloxyalkyl; —NR12RU; or R and R‘ are both iodine and R9 is phenyl optionally substituted with R“ and R15; and

R14 is methyl; ethyl; methoxy; ethoxy; Cl-C2 haloalkyl; halogen; aoetylenyl; propargyl; methylthio; ethylthio; cyano; nitro; Cl-C2 haloalkoxy; vinyl; allyl', acetyl; CO2Me; or N(C1-C2 alkyl)2.

Preferred 4 The compounds of Preferreds 1.2. and 3 wherein:

5 .747,497 7

R1 is C3-C8 alkyl: C4-C8 alkenyl; C4-C8 alkynyl; C3—C8 haloalkyl: C3-C8 haloalkenyl; C3--C8 alkoxyalkyl; or thienyl optionally substituted with at least one of R14 and R15;

R2 is C3—C8 alkyl; C3—C8 alkenyl; C3-C8 alkynyl: CFC8 haloalkyl; C3-C8 haloalkenyl; C3—C8 alltoxyalkyl; or phenyl optionally substituted with R13;

R3 is halogen; C1-C4 alkyl: C1-C4 haloalkyl: C1-C4 alkoxy; C1-C4 haloalkoxy; acetylenyl; or trimethylsi lylacetylenyl;

R5 is C3—C5 alkyl; C4—C7 alkenyl; C3-C5 alkynyl; C3-C3 haloalkyl: Cs-C8 haloalkenyl'. C3—CB alkoxyalkyl; or phenyl or thienyl each optionally substituted with R14 and R15;

R6 is C3—C1B alkyl', C3-C7 alkenyl'. C3—C8 alkynyl; C3—Cs haloalkyl; C3-C8 haloalkenyl; Cir-C8 alkoxyalkyl; or phenyl optionally substituted with R13;

R7 is C3—CB alkyl; C4-C7 alkenyl; propynyl; C3-C8 haloalkyl; C3-C8 haloalkenyl; C3,—C(.l alkoxy; C3-C8 alkoxyalkyl; or phenyl or thienyl each optionally sub stituted with R14 and R15;

R‘3 is C3-C8 alkyl; C3-C8 alkenyl; C3-C8 alkynyl; C3—C8 haloalkyl; C3haloalkenyl; C3-C8 alkoxyalkyl; —NR12R"; or R3 and R4 are both iodine and R9 is phenyl optionally substituted with RM and R“; and

R1“ is methyl; ethyl; methoxy; methylthio; halogen; trif luoromethyl'; or N(C1—C2 alky1)2.

Preferred 5 The compounds of Preferred 4 wherein: R1 is C3—C8 alkyl; C4-C33 alkenyl; CFC8 alkynyl; C3-C8

haloalkyl; or C3-C8 haloalkenyl; R2 is C3—C8 :i1].lcyl;C3--C8 alkenyl; C3—C,3 alkynyl: C3—C8

haloalkyl; C3-C8 haloalkenyl; or phenyl optionally substituted with R13;

R3 is halogen; R4 is hydrogen or halogen; ‘ R5 is C3-C5 alkyl; C4-C7 alkenyl; C3-C5 alkynyl; C3~C8

haloalkyl; or C5—C8 haloalkenyl; or phenyl optionally sub stituted with R1‘ and R15; R6 is ca-c8 alkyl; 03-0, alkenyl; ca-c8 alkynyl; cs-c8

haloalkyl; C3-C8 haloalkenyl; or phenyl optionally substituted with R13;

R7 is C3-C8 alkyl; Cir-C7 alkenyl; propynyl; C3—C8 haloalkyl; or C3-C8 haloalkenyl; or phenyl optionally substituted with R‘4 and R1’; and

R9 is C3-C8 alkyl; C3-C8 alkenyl; C3—Cg akynyl; C3—C8 haloalkyl; ca-c8 haloalkenyl; _NR1 R"; or R3 and R4 are both iodine and R9 is phenyl optionally substi tuted with R“ and R15.

Preferred 6 The compounds of Preferred 5 wherein said compounds

are selected from the group:

6-bromo-3-propyl-2-propyloxy-4(3H)-quinazolinone; 6.8-diiodo-3-propyl-2-propyloxy-4(3H)-quinazolinone; 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone; and 6.8-odo-3-propyl-2-(pheuylamino)-4(3H)-quinazolinone. It is recognized that some reagents and reaction condi

tions described below for preparing compounds of Formulae I. II. and HI may not be compatible with some functionalities claimed for R1-R17. n. m. and Q. In these cases. the incorporation of protection/deprotection sequences into the synthesis may be necessary in order to obtain the desired products. The cases in which protecting groups are necessary. and which protecting group to use. will be appar

3O

35

50

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65

8 ent to one skilled in chemical synthesis. See Greene. T. W. and Wuts. P. G. M.; Protective Groups in Organic Synthesis, 2nd Ed.; John Wiley & Sons. Inc; New York. (1980) for suitable protecting groups.

In the following description of the preparation of com pounds of Formulae I. H. and III. compounds of Formulae Ia and lb. Ila-He. and IlIa-IIIe are various subsets of the compounds of Formulae I. II. and III. All substituents in compounds of Formulae Ia and lb. lIa-IIc. and lIIa-Ille and 2-7 are as de?ned above for Formulae I. H. and [[I. Compounds of this invention can exist as one or more

stereoisomers. The various stereoisomers include enantiomers. diastereomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active than the others and how to separate said stereoisomers. Accordingly. the present invention comprises mixtures. individual stereoisomers. and optically active mix tures of compounds of Formulae I. II. and III as well as agriculturally suitable salts thereof. The compounds of Formulae I. II. and III can be prepared

as described below in Schemes l-9 and Examples l-3.

Synthesis of Compounds of Formula I

Compounds of Formula Ia. compounds of Formula I wherein Q is O. can be made by the method illustrated in Scheme 1.

An anthranilic acid (Z-aminobenzoic acid) of Formula 2 is condensed with an isothiocyanate of Formula Rl-NCS to form the 2-thioquinazo1inedione of Formula 3. This con densation is preferably performed in the presence of a base such as tn'ethylarnine. S-Methylation of this compound affords the 2-methylthio-4(3H)-quinazolinone of Formula 4.

For the introduction of the R20 group. the Z-methylthio 4(3H)-quinazolinone of Formula 4 is treated with a mixture of a base. for example sodium hydride. in RZOH solvent. The reaction mixture is stirred at a temperature from about 0° C. to 120° C. for 1-120 hours. The desired 2-R2O-4(3H) -quinazolinone can be isolated from the reaction mixture by extraction into a water-immiscible solvent. and puri?ed by chromatography or recrystallization. Similar synthetic pro cedures are described in US. Pat. No. 3.755.582. incorpo rated herein by reference.

Scherne 1

R3 0 ll 0 \ OH iU-NCS ;

EtOH, heat

NH,

R

2

R3 o l

N/R 1% A u-PrOH

N S NaOH

R H

5.747.497

-continued Scheme 1

R3 o

I l N/ R

NaH E k R2—OH. heat

N SMe

R

R3 0

R! N /

/ R’ N an. R

Ia

Anthranilic acids of Formula 2 are known or can be prepared by known methods. For example see. March. J. Advanced Organic Chemistry; 3rd ed. John Wiley: New York. (1985). p 983. The isothiocyanates of Formula R‘-NCS can be prepared from the corresponding amine by treatment with thiophosgene as known in the art. For example. see J. Heterocycl. Chem. (1990). 27. 407.

Alternatively. 2-thioquinazolinediones of Formula 3 can be prepared by treatment of the (C1-C4 alkyl) anthranilic acid ester of Formula 5 with thiophosgene to form the isothiocyanate ester. followed by treatment with an amine of formula R1NH2 (Scheme 2).

Scheme 2

R3 0 II C\ 0(C1-C4 alkyl) LCIZCZS

_____> 2. I'lIgN'R1 NH;

R

5

R3 O

Rt N/

N AS R H

The anthranilic acid ester of Formula 5 is treated with thiophosgene at a temperature from about —20° C. to 100° C. for l to 48 hours optionally in an inert solvent. Often this reaction is performed in a biphasic mixture in the presence of a base. such as calcium carbonate. and an acid. such as aqueous hydrochloric acid. The resulting isothiocyanate may be isolated by extraction into a water-immiscible solvent. such as methylene chloride. followed by drying of the organic extracts and evaporation under reduced pressure. Alternatively. the isothiocyanate can be combined in situ with the amine of Formula HZNR1 and stirred at about —20° C. to 50° C. for 0.1 to 24 hours. The desired 2-thioquinazolinediones of Formula 3 can be isolated from the reaction mixture by aqueous extraction. and puri?ed by chromatography or recrystallization. Similar synthetic pro cedures are described in J. Hetemcycl. Chem. (1990). 27. 407.

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10 Compounds of Formula Ib. compounds of Formula I

wherein Q is S. can be prepared as illustrated in Scheme 3.

M

R3 0

R1 /

N P185 or

R2 Lawesson’s E N ¢I\()/ reagent

R

R3 S

l Rt

N

R4 lb

Treatment of the quinazolinone of Formula Ia with phos phorous pentasul?de or Lawesson’s reagent [2.4-bis(4 methoxyphenyl)- 1.3 -dithia-2.4dipho sphetane-2.4-disul? de] in an inert solvent such as dioxane at a temperature from 0° C. to the re?ux temperature of the solvent for 0.1 to 72 hours a?ords the quinazolinethione of Formula lb. This procedure is desm‘ibed in the literature. for example see US. Pat. No. 3.755.582. Synthesis of Compounds of Formula II

4(3H)-Quinazolinones of Formula 11a. compounds of Formula 11 wherein n is 0 and Q is O. can be prepared by a modi?cation of the synthesis illustrated in Scheme 1. As illustrated in Scheme 4. the Z-thioquinazolinedione of For mula 6 is alkylated with R's-X wherein X is a typical leaving group such as Br. I. CHBSO3 (OMs). or (4-CH3-Ph)SO3 (Ul‘s) to alford the 2-R6S-4(3H)-quinazolinone of Formula Ila. One or more equivalents of a base can be used to accelerate the process. Bases such as sodium hydroxide and sodium hydride are suitable.

Scheme 4

R3 0 base

R5 ___9 N/ R6—X

N A S R H

6 X = Br. I. OMs. OTs

R3 0

R5 N/

A N SR‘5

R

Typically. the Z-thioquinazolinedione is dissolved or dis persed in an inert solvent such as dimethylformamide and treated with a base at a temperature from about —20° C. to 60° C. with a base. The reaction mixture may then be heated to just above ambient temperature to the re?ux temperature of the solvent for 0.1 to 24 horas to effect deprotonation. After cooling. the reacn'on mixture is cooled and treated with R°-—-X and stirred for 0.1-24 hours at a temperature from

5.747.497 11

about 20° C. to the re?ux temperature of the solvent. The quinazolinone of Formula Ila can be isolated by extraction into a water-immiscible solvent. and puri?ed by chromatog raphy or recrystallization.

2-Thioquinazolinediones of Formula 6 are prepared as described above in Schemes 1 and 2 for 2-thioquinazolinediones of Formula 3.

4(3H)-Quinazolinones of Formula lIb. compounds of Formula 11 wherein Q is O and n is 1 or 2. can be prepared by oxidation of the corresponding —SR6 compound of Formula Ia using well~known procedures for oxidation of sulfur (Scheme 5). For example. see March. J. Advanced Organic Chemistry; 3rd ed.. John Wiley: New York. (1985). p 1089.

Scheme 5

R3 0 5 oxidation 3

N/R / N )\ SR.

R

11a

R3 0

RS N/

A N S(O)»R6

R

n = l or 2

11b

4(3H)-Quinazolinethiones of Formula IIc. compounds of Formula [I wherein Q is S. can be prepared by treatment of the corresponding quinazolinone with phosphorous penta sul?de or Lawesson’s reagent as described in US. Pat. No. 3.755.582 and above for compounds of Formula Ib (Scheme 6).

Scheme 6

R3 O

R. _m_> / Lawesson‘s N reagent

A N S(0)..R°

R

R3 S

Rs N /

A N S(0)»R6

R

Synthesis of Compounds of Formula [II 4(3l-I)-Quinazo1inones of Formula 111a. compounds of

Formula m wherein Q is O. can be prepared by the method illustrated in Scheme 7. This method is described in detail in US. Pat. No. 3.867.384 and incorporated herein by refer ence.

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12

Scheme 7

R3 | 7 HNR$R° E

N /R heat

7‘\ N Z

R

Z = SMe or Cl

7

R3 O

l R1 N/

A N NR‘R9

R

One method of preparation of compounds of Formula 111a is by treatment of a 2-methylthio4-(3H)-quinazolinone of Formula 7 (Z=SMe) with an excess of an amine of Formula HNRBR9 at about 150° C. to 175° C. A second method is to contact a 2-chloro4(3H)-quinazolinone of Formula 7 (Z-——C1) with one equivalent of HNRSRQ and one equivalent of an acid scavenger. for example triethylaamine. or with two equivalents of HNR8R9. at a temperature between 60° C. and 120° C. optionally in the presence of a solvent. The preparation of compounds of Formula 7 wherein Z is

SMe is described above and in US Pat. No. 3.755.582. The synthesis of compounds of Formula 7 wherein Z is Cl is described in US. Pat. No. 3.867.384. Amines of Formula HNR3Rg are commercially available or can be prepared by well-known methods (March. J. Advanced Organic Chem istry; 3rd ed.. John Wiley: New York. (1985). p 1153).

In addition to the methods described above. compounds of Formula Ia and [la can be prepared by displacement of the 2-ch1orine in the appropriate 4(3H)-quinazolinone. rather than by displacement of the 2-SCH3 group (Scheme 1) or S-alkylation of the thiocarbonyl (Scheme 4). As described above for compounds of Formula Ib and He.

quinazolinethiones of Formula IIIb can be prepared by treatment of the corresponding quinazolinone with P255 or Lawesson’s reagent (Scheme 8).

Scheme 8

R3 0

R7 /

N P155 0|’

J\ Lawessm‘s ; N NRBR9 reagent

R

R3 S

R7 N/

)\ N NR‘R9

R

IlIb

Alternatively. 4(3H)-quinazolinones and quinazolineth iones of Formulae [Ed and me. compounds of Formula 111

5,747,497 13

wherein R8=—C(=O)R12. can be prepared by acylation of the corresponding quinazolinones or quinazolinethione wherein R8=H (Formula 1110) as illustrated in Scheme 9.

R3

R3

The quinazolinones of Formula llIc can be treated with an acylating agent of Formula R1°C(=O)L wherein L is an appropriate leaving group such as chlorine or OC(=O)(H or C1-C4 alkyl). In a similar fashion. compounds of Formula [[I wherein R8 is ---C(=O)NHR12 (Formula me) can be prepared by condensing quinazolinones of Formula 111C with isocyanates of Formula RMN=C=O using well known procedures.

Salts of compounds of Formulae I. 11. and 111 can be formed by treating the free base of the corresponding compound with strong acids such as hydrochloric or sulfuric acid. Salts can also be prepared by alkylation of a tertiary amine group in the molecule to form. for example. the ttialkylammonium salt. N-Oxides of compounds of Formu lae I. H. and III can be made by oxidizing the corresponding reduced nitrogen compound with a strong oxidizing agent such as meta-chloroperoxybenzoic acid.

EXAMPLE 1

Synthesis of 6-Bromo-3-propyl-2-propyloxy-4(3H) quinazolinone

All reactions were conducted under a nitrogen atmry sphere. Step A To a solution of 200 mL of ethanol containing 37 g of

Z-arnino-S-bromobenzoic acid was added dropwise 17.72 mL of n-propyl isothiocyanate with stirring. The mixture was heated at re?ux for 8 h. allowed to cool to room temperature and stirred for approximately 60 h. The mixture was then cooled to approximately 5° C. and ?ltered to obtain 15.42 g of an o?-white solid. Step B To a solution containing 15.4 g of the product of Step A

dissolved in 100 mL of 10% propanolic sodium hydroxide was added 3.2 mL of iodomethane with stirring. The mixture

14 was stirred at room temperature for 10 min. then heated at re?ux for 1.5 h. and then allowed to cool to room tempera ture and stirred overnight. The reaction mixture was ?ltered

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65

to obtain 11.47 g of a white solid. The white solid was puri?ed by column chromatography on silica gel eluting with hexane and then 9:1 hexanezethyl acetate. Collection and evaporation of those fractions containing the least polar component (according to thin layer chromatography. 6:1 hexane/ethyl acetate mixture as the development solvent) yielded 6.55 g of a white solid. mp. 97°—99° C. Step C To 150 mL of propanol cooled to approximately —60° C.

was added 0.83 g of NaH (60% active in oil) with stirring. To this mixture at —60° C. was added 6.5 g of the puri?ed product'obtained in Step B. The mixture was allowed to warm to room temperature and stirred for approximately 48 h to yield a clear solution. The reaction solution was poured into water and extracted twice with diethyl ether. The ether extracts were washed twice with water. dried over magne sium sulfate. ?ltered and the ?ltrate was then evaporated to yield 10.3 g of an oil. Thin layer chromatography indicated starting material and desired product were both present. Step D To propanol cooled to —50° C. was added 0.60 g of NaH

(60% active in oil) with stirring. To this mixture at —40° C. was added the product of Step C and the mixture was allowed to warm to room temperature and stirred for approximately 72 h. The mixture was then heated at re?ux for 30 min. cooled to room temperature. poured into water and extracted twice with diethyl ether. The combined ether extracts were washed three times with water. dried over magnesium sulfate. ?ltered and the ?ltrate was evaporated to yield an oil. The oil was puri?ed by column chromatography on silica gel eluting with hexane followed by 9:1 hexane! ethyl acetate. Collection and evaporation of the fractions containing only the least polar component (according to thin layer chromatography on silica gel. 9:1 hexane/ethyl acetate mixture as the development solvent) yielded 4.46 g of the title compound as a white solid. mp. 57°-59° C.: 1H NMR

5.747.497 15

(400 MHZ. CDCl_.) 5 8.3 (s.1H). 7.7 (n1.lH). 7.3 (m.lH). 4.43 (t.2H). 4.05 (t.2H). 1.85 (l'rLZH). 1.7 (m.2H). 1.06 (L3H). 0.97 (L3H).

EXAMPLE 2

Synthesis of 6-Brom0-3-n-butyl-2-n-propylamino-4 (3H)-quinazolinone

Step A To a solution of 200 mL of ethanol containing 15.15 g of

2-amino-5-bromobenzoic acid was added dropwise 9.3 rnL of n-butyl isothiocyanate with stirring. To this reaction solution was added 9.77 mL of triethylamine. The reaction solution was heated at re?ux for 4 h during which time a solid precipitated. The reaction mixture was cooled to 0° C. and ?ltered to obtain 19.89 g of an oif-white solid. mp. 246°~248° C. Step B To a solution containing 7 g of the product of Step A

suspended in 50 rnL of chloroform was added 1.97 mL of sulfuryl chloride with stirring. The solution was heated at re?ux for 5 h. then cooled to room temperature. The reaction solution was poured into water and extracted twice with methylene chloride. The organic extracts were dried over magnesium sulfate. ?ltered and the ?ltrate was then evapo rated to a yellow solid The solid was puri?ed by column chromatography on silica gel eluting with 6:1 hexane/ethyl acetate. Collection and evaporation of the fractions contain ing only the second-least polar component (according to thin layer chromatography on silica gel. 4:1 hexane/ethyl acetate mixture as the development solvent) yielded 3.2 g of white solid. mp. 56°-58° C. Step C To a solution containing 1.02 g of the puri?ed product

obtained in Step B dissolved in 25 mL of tetrahydrofuran was added 0.5 mL of n-propylamine. The reaction mixture was stirred for approximately 24 h at room temperature. The reaction was then ?ltered and the ?ltrate was evaporated to obtain an oil. The oil was dissolved in diethyl ether and

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16 EXAMPLE 3

Synthesis of 6-Bromo-3-n~propyl—2-n-propylthio4 (3H )-quinazolinone

Step A To a solution of 150 ml. isopropanol containing 29.7 g of

2-amino-5-bromobenzoic acid was added dropwise 15.64 rnL of n-propyl isothiocyanate with stirring. The reaction mixture was then heated at re?ux for 15 h. The reaction mixture was cooled to 0° C. and ?ltered to obtain 9.12 g of an off-white solid. Step B To a solution containing 0.34 g of the product of Step A

suspended in 20 rnL of 10% propanolic sodium hydroxide was added 0.22 rnL of iodopropane with stirring. The reaction mixture was stirred 1.5 h at room temperature. The reaction was poured into water and extracted twice with methylene chloride. The methylene chloride extractions were washed twice with water. dried over magnesium sulfate. ?ltered. and the ?ltrate was then evaporated to yield a white solid. The solid was puri?ed by column chromatog raphy on silica gel eluting with 8:1 hexane/ethyl acetate. Collections and evaporation of the fractions containing only the least-polar component (according to thin layer chroma tography on silica gel. 6:1 hexane/ethyl acetate mixture as the development solvent) yielded 0.27 g of the title com pound as a white solid. mp. 65°-67° C.: 1H NMR (400 MHz. CDCla): 5 0.99-1.10 (m.6H). 1.80 (m.4H). 3.25 (t.2H). 4.10 (t.2H). 7.41 (d.lH). 7.78 (d.lH). 8.30 (SJH).

Using the procedures outlined in Schemes 1-9 and Examples l-3. the compounds of Tables l-12 hereinafter can be prepared. The compounds referred to in the Tables which follow are illustrated below: The following abbreviations are used in the Tables which

follow. All alkyl groups are the normal isomers unless indicated otherwise. See structures in Index Tables A-C hereinafter for ring system numbering.

washed twice with water and once W1th brine. The ether 40 5:566:53“ pr=pmpyl y solution was dried over magnesium sulfate. ?ltered and the n = normal CN = cyano

?ltrate was then evaporated to yield 0.74 g of the title 15° th 1 ifsqlcb th km compound as a white solid. mp. 71°-73° C.: 1H NMR (400 3:13;! y B: =13‘; y 0 MHz. CDCl,) 0.97-1.04 (m.6H). 1.45 (111.211). 1.70 (m.4H). PH ‘2 phcnyl 3.50 (111.2H). 4.00 (t.2H). 4.50 (s.1H). 7.24 (d.lH). 7.60 (d.lH). 8.20 (5.111).

TABLE 1

Oompounds of Formula I wherein: Q = O. R2 = n-Pr. R3 = 6-1, R‘ = H, and

5.747.497 29

Formulation/Utility Compounds of this invention will generally be used in

formulation with an agriculturally suitable composition. The fungicidal compositions of the present invention comprise an e?iective amount of at least one compound of Formula I. II. or 111 as de?ned above and at least one of (a) a surfactant. (b) an organic solvent. and (c) at least one solid or liquid diluent. Useful formulations can be prepared in conventional ways. They include dusts. granules. pellets. solutions. suspensions. emulsions. wettable powders. emulsi?able concentrates. dry ?owables and the like. Sprayable formu lations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hect are. High strength compositions are primarily used as inter mediates for further formulation. The formulations will typically contain elfective amounts of active ingredient. diluent and surfactant within the following approximate ranges which add up 100 weight percent.

Weight Percent

Active Ingredient Diluent Surfactant

Wertable Powders 5-90 0-74 1-10 Oil Suspensions, Emulsions. 5-50 40-95 0-15 Solutions, (including Emulsi?able Concentrates) D1515 1-25 70-99 0-5 Granules, Baits and Pellets 0.01-99 5-99.99 0-15 High Strength Compositions 90-99 0-10 0-2

Typical solid diluents are described in Watkins. et al.. Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed.. Dorland Books. Caldwell. N .J . Typical liquid diluents and solvents are described in Marsden. Solvents Guide, 2nd Ed.. Interscience. New York. (1950). McCutcheon’s Deter gents and Emulsi?ers Annual. Allured Publ. Corp.. Ridgewood. N.J.. 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. and the like. Methods for formulating such compositions are well

known. Solutions are prepared by simply mixing the ingre dients. Fine solid compositions are made by blending and. usually. grinding as in a hammer mill or ?uid energy mill. Water-dispersible granules can be produced by agglomerat ing a ?ne powder composition; see for example. Cross et a1.. Pesticide Formulations. Washington. D.C.. (1988). pp 251-259. Suspensions are prepared by wet-milling; see. for example. U.S. Pat. No. 3.060.084. Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning. “Agglomeration”. Chemical Engineering. Dec. 4. 1967. pp 147-148, Perry's Chemical Engineer’s Handbook. 4th Ed.. McGraw-Hill. New York. (1963). pp 8-57 and following. and WO 91/13546. Pellets can be prepared as described in U.S. Pat. No. 4.172.714. Waterd ispersible and water-soluble granules can be prepared as taught in DE 3.246.496. For further information regarding the art of formulation.

see U.S. Pat. No. 3.235.361. Col. 6. line 16 through Col. 7. line 19 and Examples 10 through 41; U.S. Pat. No. 3.309. 192. Col. 5. line 43 through Col. 7. line 62 and Examples 8.

‘12. 15. 39. 41. 52. 53. 58. 132.138-140. 162-164. 166. 167 and 169-182; U.S. Pat. No. 2.891.855. Col. 3. line 66 through Col. 5. line 17 and Examples 1-4; Klingman. Weed Control as a Science. John Wiley and Sons. Inc.. New York.

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65

30 (1961). pp 81-96; and Hance et al.. Weed Control Handbook, 8th Ed.. Blackwell Scienti?c Publications. Oxford. (1989).

In the following Examples. all percentages are by weight and all formulations are prepared in conventional ways. Compound 1 refers to the compound described in Index Table A hereinafter.

Example A Wettable Powder

Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.

Example B Granule

Compound 37 10.0% attapulgite granules (low volative 90.0%. matter, 0.711030 mm; U.S.S. No. 25-50 sieves)

Example C Extruded Pellet

Compound 25 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.

Example D Emulsi?able Concentrate

Compound 37 20.0% blend of oil soluble sulfonates 10.0% and polyoxyethylene ethers isophorone 70.0%.

The compounds of this invention are useful as plant disease control agents. especially for the control of cereal powdery mildews (e.g.. Erysiphe graminis f. sp. tritici. the causal agent of wheat powdery mildew). The present inven tion therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected. or to the plant seed or seedling to be protected. an effective amount of a compound of Formula I. 11. or III or a fungicidal composition containing said compound. The compounds and compositions of this invention provide control of dis eases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete. Ascomycete. Oomycete and Deutero mycete classes. They are etfective in controlling a broad spectrum of plant diseases. particularly foliar pathogens of ornamental. vegetable. ?eld. cereal. and fruit crops. These pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermarum, Alternan'a brassicae, Septoria nodorum, Cercosporidium personatum, Cer cospora arachidicola. Pseudocercosporella

5 .747.497 31

herpotrichoides, Ccrcospora beticola, Botrytis cinerea, Monilim'a fructicola, Pyricularia oryzae, Podasphaera leucotricha, Venturia inaequalis, Erysiphe gramim's, Uncinula necatm; Puccinia recondita, Puccim'a graminis, Hemileia vasratrix, Puccinia srriiformis, Puccim'a arachidis, Rhizoclonia solani, Sphaerotheca fuliginea, Fusarium oxysporum, Verlicillium dahliae, Pythium aphanidermatum, Phytophthora megaspemta and other generea and species closely related to these pathogens. Compounds of this invention can also be mixed with one

or more other insecticides. fungicides. nematocides. bactericides. acaricides. serniochemicals. repellants. attractants. pheromones. feeding stimulants or other biologi cally active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Examples of other agricultural protectants with which com pounds of this invention can be formulated are: insecticides such as acephate. avermectin B. azinphosmethyl. bifenthrin. biphenate. buprofezin. carbofuran. chlordimeform. chlorpyrifos. cy?uthrin. deltamethrin. diazinon. di?ubenzuron. dimethoate. esfenvalerate. fenpropathrin. fenvalerate. ?pronil. ?ucythrinate. ?ufenprox. fluvalinate. fonophos. isofenphos. malathion. metaldehyde. metha midophos. methidathion. methomyl. methoprene. methoxychlor. monocrotophos. oxamyl. parathion-methyl. permethrin. phorate. phosalone. phosmet. phosphamidon. pirimicarb. profenofos. rotenone. sulprofos. terbufos. tetrachlorvinphos. thiodicarb. tralomethrin. trichlorfon and triilumuron; fungicides such as benomyl. blasticidin S. bromuconazole. captafol. captan. carbendazim. chloroneb. chlorothalonil. copper oxychloride. copper salts. cyrnoxanil. cyproconazole. cyrodinil. dichloran. diclobutrazol. diclomezine. difenoconazole. diniconazole. dodine. edifenphos. epoxyconazole fenarimol. fenbuconazole. fenpropidine. fenpropimorph. ?uquinconazole. ?usilazol. ?utolanil. ?utriafol. folpet. furalaxyl. hexaconazole. ipconazole. iprobenfos. iprodione. isoprothiolane. kasugamycin. mancozeb. maneb. mepronil. metalaxyl. metconazole. myclobutanil. neo-asozin. oxadixyl. penconazole. pencycuron. phosethyl-Al. probenazole. prochloraz. propiconazole. pyrifenox. pyrimethanil. pyroquilon. sulftir. tebuconazole. tetraconazole. thiabendazole. thiophanate-methyl. thiuram. triadimefon. triadimenol. tricyclazole. ttiticonazole. uniconzole. valida mycin and vinclozolin; nematocides such as aldoxycarb. fenamiphos and fosthietan; bactericides such as oxytetracyline. streptomycin and tribasic copper sulfate; acaricides such as amitraz. binapacryl. chlorobenzilate. cyhexatin. dicofol. dienochlor. fenbutatin oxide. hexythiazox. oxythioquinox. propargite and tebufenpyrad; and biological agents such as Bacillus thuringiensis and baculovirus.

In certain instances. combinations with other fungicides having a similiar spectrum of control but a different mode of action will be particularly advantageous for resistance man agement. Preferred combinations comprise a compound of Formula I. II. or III. and a fungicide selected from the group ?usilazole. cyproconazole. tetraconazole. fenpropimorph. fenpropidine. cymoxanil. benomyl. caibendazim. manco zeb. and maneb.

Plant disease control is ordinarily accomplished by apply ing an effective amount of a compound of this invention either pre- or post-infection. to the portion of the plant to be protected such as the roots. stems. foliage. fruit. seeds. tubers or bulbs. or to the media (soil or sand) in which the plants to be protected are growing. The compounds can also be applied to the seed to protect the seed and seedling.

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32 Rates of application for these compounds can be in?u

enced by many factors of the environment and should be determined under actual use conditions. Foliage can nor mally be protected when treated at a rate of from less than 1 g/ha to 5.000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed. The following TESTS demonstrate the control e?icat'y of

compounds of this invention on speci?c pathogens. The pathogen control protection afforded by the compounds is not limited. however. to these species. See Index Tables A. B. and C for compound descriptions.

Test compounds were ?rst dissolved in acetone in an amount equal to 3% of the ?nal volume and then suspended at a concentration of 200 ppm in puri?ed water containing 250 ppm of the surfactant Trern® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in the following tests.

TEST A

The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Erysiphe graminis f. sp. tritici. (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20° C. for 7 days. after which disease ratings were made.

TESTB

The test suspension was sprayed to the point of run-01f on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20° C. for 24 h. and then moved to a growth chamber at 20° C. for 6 days. after which disease ratings were made.

TESTC

The test suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20° C. for 24 h. and then moved to a growth chamber at 20° C. for 5 days. after which disease ratings were made.

TEST D

The test suspension was sprayed to the point of run-off on grape seedlings. The following day the seedlings were inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20° C. for 24 h. moved to a growth chamber at 20° C. for 6 days. and then incubated in a saturated atmosphere at 20° C. for 24 h. after which disease ratings were made.

TESTE

The test suspension was sprayed to the point of run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension of Botryris cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20° C. for 48 h. and moved to a growth chamber at 20° C. for 5 days. after which disease ratings were made.

In the Tables below. “=‘H NMR data for oils are listed in Index Table D