This invention relates to derivatives of propenoic acid useful as fungicides, to processes for preparing them, to compositions containing them, and to methods of using them to combat fungi, especially fungal infections of plants.

There are described in EP-A-0 370 629 fungicidal derivatives of propenoic acid which have the general formula (I) wherein A is hydrogen, halo, hydroxy, C. , alkyl, C. , alkoxy, C, , haloalkyl, C, , haloalkoxy, C- , alkylcarbony1, C- , alkoxycarbonyl, phenoxy, nitro or cyano; R and R , which may be the same or different, are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted heterocyclylalkyl, optionally substituted cycloalkylalkyl, optionally substituted aralkyl, optionally substituted heteroarylalkyl, optionally substituted aryloxyalkyl, optionally substituted heteroaryloxyalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted aryl, optionally 3 optionally C0 ₂ R ,

-C0 R ³ R ⁴ , - erein m is 0 or 1, ring system; and R an R , w c may e the same or erent, are hy rogen, optionally substituted alkyl, optionally substituted aralkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl or optionally substituted heteroaryl. The compounds contain at least one carbon-carbon double bond and one carbon-nitrogen double bond and exist in the form of geometric isomers. The isomers which result from the unsymmetrically substituted double bonds of the propenoate group and the oxime ether are identified by the commonly used terms, "E" and "Z".

The present invention provides a compound of formula (I) wherein A is halogen, hydroxy, C. , alkyl, C. , haloalkyl, C. , alkoxy, C- , haloalkoxy or cyano, but is preferably hydrogen; and one of R and R is methyl and the other is pyridyl or pyrimidinyl substituted by one or more substituents independently selected from halogen, hydroxy, C- , alkyl (itself optionally substituted by C- , alkoxy), C- , haloalkyl, C._, alkoxy (optionally substituted by halogen, R ³ R ^A N, cyano, R ³ C(0), R ³ 0C(0), R ³ R ⁴ NC(0), R ³ SC(0),

H ₂ N.NHC(0), R ³ S(0) _m wherein m is 0, 1 or 2, C ₃ _ ₆ cycloalkyl [itself optionally substituted by C._, alkyl] or a 5- or 6-membered heterocyclic

ring containing one or two oxygen atoms, optionally being in the form of a lactone, the heterocyclic ring being optionally fused to a benzene ring and

3 optionally substituted by C. . alkyl), R S(0) wherein n is 0, 1 or 2, C ₂ _ ₆ alkenyl, C _{2 6} alkynyl, C ₂ _, alkenyloxy, C„_ ₆ alkynyloxy, nitro, cyano,

C0 ₂ R ³ , NR ³ R ⁴ , NR ³ R ⁴ C(0), NR ³ R C(S), R ³ R ⁴ C:N0, C ₃ _ ₆ cycloalkyl, C ₃ _ _fi cycloalkyloxy (itself optionally substituted by C. , alkyl), C- ₆ alkoxy(C. ,)alkoxy, an aromatic 5-membered ring containing 1, 2 or 3 nitrogen atoms (itself optionally substituted by C- , alkyl), C-_ ₆ alkoxy(C- ₆ )haloalkoxy, phenoxy(C., ,)alkoxy, phenyl(C., ,)alkoxy(C.,_ ₆ )- alkoxy, C- , alkoxy(C ₁ _ ₆ )alkoxy(C._ ₆ )alkoxy, di(C. .alkoxy)(C-_ ₆ )alkoxy,

C« _fi alkenyloxy(C._ ₆ )alkoxy, C« ₆ alkenyloxy(C., ₆ )haloalkoxy, a 5- or

6-merabered heterocyclic ring containing one or two heteromoieties independently selected from N, S, S(0), S(0) ₂ or 0 and optionally being fused to a benzene ring, the heterocyclic ring being optionally substituted by C- , alkyl and when it contains an oxygen atom it may be in the form of a lactone, the heterocyclic ring is linked directly to the pyridine or pyrimidine ring or is linked through an 0, 0CH ₂ or CH ₂ 0 moiety, phenyl, phenoxy or phenyl(C-_,)alkoxy; wherein any of the foregoing phenyl moieties is optionally substituted by halogen, C- . alkyl, C- . haloalkyl, C- , alkoxy, C-_, haloalkoxy, nitro or cyano, or the other of R and R is a pyridine or pyrimidine ring optionally substituted with any of the moieties already listed as substituents for pyridine and pyrimidine rings above and fused to an aromatic 5-membered ring containing one or two heteroatoms

3 4 independently selected from nitrogen, oxygen and sulphur; and R and R are independently hydrogen or C. _fi alkyl (itself optionally substituted by

1 2 halogen or cyano); provided that when A is hydrogen and one of R and R is methyl then the other is not: pyrid-2-yl monosubstituted with chloro, cyano, fluoro, bromo, methyl or 5-ethyl, or substituted with 3-5-difluro or

3,4,5,6-tetrafluro; pyrid-3-yl substituted with 6-methyl, 4-cyano, 5-cyano,

6-cyano or 2,6-dichloro; pyrid-4-yl monosubstituted with cyano; pyrimidin-2-yl substituted with 4-methyl, 4,6-dimethyl or 4,6-dimethoxy; pyrimidin-4-yl substituted with 2-chloro, 2-methoxy, 2-methyl, 2-cyano,

6-methyl, 6-chloro, 6-methoxy, 6-phenyl or 2,6-dimethyl; or pyrimidin-5-yl substituted with 2-methyl, 4-methyl or 2,4-dimethyl.

The compounds of the invention contain at least one carbon-nitrogen double bond and at least one carbon-carbon double bond, and are sometimes obtained in the form of mixtures of geometric isomers. However these

mixtures can be separated into individual isomers, and this invention embraces .such isomers, and mixtures thereof in all proportions.

The individual isomers which result from the unsymmetrically substituted double bond of the propenoate group and the oxime are identified by the commonly used terms "E" and "Z". These terms are defined according to the Cahn-Ingold-Prelog system which is fully described in the literature (see, for example, J March, "Advanced Organic Chemistry", 3rd edition, Wiley-Interscience, page 109 et seq).

For the carbon-carbon double bond of the propenoate group, usually one isomer is more active fungicidally than the other, the more active isomer usually being the one wherein the group -C0 ₂ CH ₃ and -0CH, are on opposite sides of the olefinic bond of the propenoate group (the (E)-isomer). These (E)-isomers form a preferred embodiment of this invention.

Halogen includes fluorine, chlorine, bromine, and iodine.

Alkyl and the alkyl moieties of alkoxy, haloalkyl and haloalkoxy can be in the form of straight or branched chains and, unless otherwise stated, suitably contain from 1 to 6 carbon atoms. Examples are methyl, ethyl, iso-propyl and tert-butyl.

Examples of haloalkyl and the -haloalkyl moiety of haloalkoxy are difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoroprop-1-yl, 2,2,3,3,3-pentafluoroprop-l-yl, l,l,l-trifluoroprop-2-yl and 4-fluorobut-1-yl.

Cycloalkyl is, unless otherwise stated, C~_ ₆ cycloalkyl. Examples are cyclopropyl and cyclohexyl.

Alkoxy optionally substituted by C- , cycloaklyl is, for example, cyclopropylmethoxy.

Alkenyl and alkynyl moieties of alkenyloxy and alkynyloxy suitably contain from 2 to 6 carbon atoms, typically 2 to 4 carbon atoms, in the form of straight or branched chains. Examples are ethenyl, allyl and propargyl.

The 5- or 6-membered heterocyclic ring containing one or two oxygen atoms is, for example a furan, tetrahydrofuran or tertahydropyran ring.

The aromatic 5-membered ring containing 1, 2 or 3 nitrogen atoms which is optionally substituted by C. , alkyl is, for example, imidazole, N-methylimidazole, pyrazole, 1,2,4-triazole or 1,2,3-triazole.

The 5- or 6-membered heterocyclic ring containing one or two heteromoieties independently selected from N, S, S(0), S(0) ₂ or 0 is, for

_ 4 _ example, a pyridine, morpholine, piperidine, furan, tetrahydrofuran, dioxolane or tetrahydropyran ring.

The pyridine or pyrimidine ring fused to an aromatic 5-membered ring containing one or two heteroatoms independently selected from nitrogen, oxygen and sulphur is, for example, a thienopyrimidine.

In one aspect the present invention provides a compound of formula (I)

1 2 wherein one of R and R is methyl and the other is pyridine substituted by one or more moieties independently selected from C-_, alkoxy, , ₆ haloalkyl, C- g haloalkoxy, C- . alkoxy(C- _t g)alkyl, C« , alkoxy(C ₁ _ ₆ )alkoxy, nitro, H ₂ C0, NH-.CS, C0 ₂ R , phenyl (itself optionally subsituted by halogen, C. , alkyl, C. , haloalkyl, cyano, C. , alkoxy or

C. , haloalkoxy) or imidazole (itself optionally substituted by C-_, alkyl); and R is C. , alkyl. It is preferred that the pyridine is a pyrid-2-yl moiety substituted by one or more moieties selected from C. , alkoxy, C., , haloalkyl, C.. , haloalkoxy, C-_, alkoxy(C, g)alkyl or C. , alkoxy(C. ₆ )alkoxy«

In another aspect the present invention provides a compound of formula

1 2 (I) wherein one of R and R is methyl and the other is pyrimidine substituted by one or more moieties independently selected from C _{2 g} alkyl,

C. ₆ haloalkyl, C- g alkoxy, C. , haloalkoxy, C. _g alkylthio, C- ₆ alkylsulphinyl, chloro, fluoro, C« , alkynyloxy, C ₂ , alkenyloxy, di(C. , alkyl)amino, C ₁ _, alkoxy(C, ₆ )alkyl, C-_ _ή alkoxy(C._ ₆ )alkoxy, C0 ₂ R , phenoxy or phenyl(C. ,)alkoxy; wherein the phenyl moieties of any of the foregoing are optionally substituted by halogen, C-_, alkyl, C. . haloalkyl, cyano, C, , alkoxy or C- , haloalkoxy; and R is C. , alkyl; and when the pyrimidine is substituted by at least one of the foregoing it may additionally be substituted by methyl; provided that when the pyrimidine is a pyrimidin-4-yl it is not substituted by 2-methoxy, 2-chloro, 6-chloro or

6-methoxy, and that when the pyrimidine is a pyrimidin-2-yl it is not substituted by 4,6-dimethoxy.

In a further aspect the present invention provides a compound of formula (IA) wherein Y is C ₂ _ ₆ alkyl, C- , haloalkyl, C ₁ _, alkoxy, C._ ₆ alkylthio, C. ₆ alkylsulphinyl, C ₁ _ _g haloalkoxy, C ₁ _, alkoxy(C ₁ _ ₆ )alkyl,

C, ₆ alkoxy(C- ₆ )alkoxy, C._ ₄ alkoxy(C ₁ _g)alkoxy(C ₁ _,)alkoxy, di(C ₁ _,alkox )(C ₁ _g)alkoxy or C- g alkynyloxy; and Z is hydrogen, fluorine, chlorine or C, _g alkyl; and when Z is fluorine, chlorine or C. ₆ alkyl Y may also be methyl. It is preferred that Y is C ₂ _ ₆ alkyl, C., ₆ haloalkyl, C- g alkoxy, C. g alkylthio, C ₁ _g alkylsulphinyl, C.._g

haloalkoxy or C, , alkynyloxy; and Z is hydrogen, fluorine, chlorine or

1 1

C. , alkyl; and when Z is fluorine, chlorine or C, , alkyl Y may also be methyl. Further it is preferred that Y is C. , alkoxy or C.. _ft haloalkoxy; and that Z is hydrogen, fluorine, chlorine or methyl.

In another aspect the present invention provides a compound of formula 2 (IB) wherein Y is C _{2 6} alkyl, C- , haloalkyl, C. ₆ alkoxy, C. ₆ alkylthio,

C., g alkylsulphinyl, C. g haloalkoxy or C ₂ . alkynyloxy; and Z is hydrogen, fluorine, chlorine or C, , alkyl; and when Z is fluorine,

2 2 chlorine or C _n , alkyl Y may also be methyl. It is preferred that Y is

2 C. g alkoxy or C-. g haloalkoxy; and that Z is hydrogen, fluorine, chlorine or methyl.

According to the present invention there are provided the individual

Compounds Nos 236 to 693 having the general formula (I) and the values of

1 2 R , R and A given in Table I. All of the compounds in Table I are

(E)-propenoates.

idin-2-yl

336 4-iso-propyloxy- CH. 7.58 75-77 pyrimidin-2-yl

337 6-CH ₃ S-pyrazin-2-yl CH, 338 3-CF ₃ -5-F-C ₆ H ₃ CH, 339 CgH ₅ -S CH, 340 4-C0NH ₂ -pyrid-2-yl CH-

TABLE I (continued)

TABLE I (continued)

Compound R A Olefinic Melting No. Point °C

418 2-sec-butyloxy-pyrimidin-4-yl CH- 419 4-C ₂ Hr0-6-CH ₃ 0-pyrimidin-2-yl CH, 420 4-sec-butyloxy-pyrimidin-2-yl CH, 421 4-CH ₃ -6-CF ₃ -pyrimidin-2yl CH, 422 5-(3,5-di-Cl-C ₆ H ₃ )-furan-2-yl CH- H 7.60 Gum ³ 423 CH ₃ 4-C ₂ H ₅ 0-

-pyrimidin-2-yl H 7.53 108.8-110.8

424 5-CgH ₅ -thiophen-2-yl CH, H 7.60 90-93 425 4-CH ₃ 0C ₂ H ₄ 0-pyrid-2-yl CH, H 7.60 Gum 426 6-iso-propyloxy-pyrazin-2-yl CH, H 7.61 Gum 427 3-iso-propyloxy-pyrazin-2-yl CH, H 7.58 Gum 428 4-CH ₃ 0-5-CH ₃ -pyrimidin-2-yl CH, H 7.79 105-106 429 5-CF ₃ -pyrid-2-yl CH, H 7.60 Gum 430 2-(CgH ₅ -0-CH ₂ )-thiazol-4-yl CH, H 7.58 Gum 431 2-iso-propyloxy-pyrimidin-5-yl CH, H 7.60 Oil 432 4-iso-propyloxy-5-CH ₃ -pyrimidin-

-2-yl CH, H 7.58 Gum

433 4-CF ₃ CH ₂ 0-5-CH ₃ -pyrimidin-2-yl CH- H 7.59 130-131 434 6-C ₂ Hr0-pyrid-2-yl CH, H 7.60 64.4-65.6 435 4-C ₂ HrO-5-F-pyrimidin-2-yl CH, H 7.58 100-102 436 4-CH ₃ 0-5-F-pyrimidin-2-yl CH, H 7.58 79-81 437 2-C ₂ Hc0-pyrimidin-5-yl CH, H 7.59 84-85 438 4,5-di-CH ₃ 0-pyrimidin-2-yl CH, H 7.58 118-120 439 6-(2-Cl-CgH ₄ )-pyrid-2-yl CH, H 7.61 Gum 440 6-(N-CH ₃ -imidazol-2-yl)-pyrid-2-yl C*-.H_.-., H 7.62 Gum 441 6-CF ₃ CH ₂ 0-pyrimidin-4-yl CH- H 7.61 Gum 442 4-CF ₃ -6-CF ₃ CH ₂ 0-pyrid-2-yl CH, H 7.61 84.1-85.1 443 4-CF ₃ CH ₂ 0-5-F-pyrimidin-2-yl CH, H 7.58 88-89 444 ,6-di-iso-propyloxy-l,3,5- CH, H 7.57 Gum triazin-2-yl

445 4-iso-propyloxy-5-F-pyrimidin-2-yl CH- H 7.58 89-91 446 4-CF ₃ -6-C ₂ H ₅ 0-pyrid-2-yl CH, H 7.60 Gum 447 5-(2,4-di-F-CgH ₃ )-thiophen-2-yl CH- H 7.59 125-126

TABLE I (continued)

Compound R ^J A Olefinic Melting No. Point °C

475 2-tert-butyloxy-pyrimidin-4-yl CH, 476 4-tert-butyloxy-pyrimidin-2-yl CH, 477 6-C ₂ H ₅ 0-pyrid-3-yl CH. 478 CHP, 5-iso-propyl- -pyrimidin-4-yl

479 4-C ₂ H ₅ 0-5-Cl-pyrimidin-2-yl CH ₃ 480 4-(morpholin-4-yl)-pyrimidin-2-yl CH, 481 6-CH ₃ 0-pyrid-3-yl CH, 482 2-CH--5-iso-propyl-pyrimidin-4-yl CH- 483 4-allyloxy-pyrimidin-2-yl CH- 484 4-iso-propyloxy-5-Cl-pyrimidin-2-yl CH- 485 4-CF ₃ CH ₂ 0-5-Cl-pyrimidin-2-yl CH, 486 5-Cl-pyrimidin-2-yl CH, 487 4-0H-pyrimidin-2-yl CH- 488 4-cyclopropylCH ₂ 0-pyrimidin-2-yl CH- 489 4-(tetrahydropyran-2-yl)CH ₂ 0-

-pyrimidin-2-yl CH-

490 4-(tetrahydrofur-3-yl)CH ₂ 0-

-pyrimidin-2-yl CH- H 7.57 Gum

491 CH 2-CH,-5-iso-propyl- pyrimidin-4-yl H 7.53 Gum

492 2-CH ₃ 0-pyrid-3-yl CH,, H 7.58 Oil

493 2-CF ₃ CF ₂ CH ₂ 0-pyrimidin-4-yl CH, H 7.60 Gum

494 4-CF ₃ CF ₂ CH ₂ 0-pyrimidin-2-yl CH, H 7.59 108-110

495* C ₆ H ₅ S0 ₂ CH ₂ CH- H 7.52 Gum

496 4-(tetrahydrofur-2-yl)CH ₂ 0-

-pyrimidin-2-yl CH- H 7.58 Gum

497 4-(tetrahydropyran-4-yloxy)

-pyrimidin-2-yl CH- H 7.60 Gum

498 4-(2-methylprop-2-enyl)oxy-

-pyrimidin-2-yl CH, H 7.58 Gum

TABLE I ( continued)

1 2

Compound R R

No .

522 4-(fur-2-yl)-CH ₂ 0-pyrimidin-2-yl

523 4-(l-methylcyclopropyl)-CH ₂ 0-pyrimidin-2-yl

524 4-(2-methylcyclopropyl)-CH ₂ 0-pyrimidin-2-yl

525 4-cyclopropylCH(CH ₃ )0-pyrimidin-2-yl

526 4-phenoxy-pyrimidin-2-yl

527 4-(l-methylcyclopropyloxy)pyrimidin-2-yl 528 ^" 4-cyclopentyloxy-pyrimidin-2-yl

529 4-cyclohexyloxy-pyrimidin-2-yl

530 4-CH ₃ (CH ₂ ) ₄ 0-pyrimidin-2-yl

532 4-cyclobutyloxy-pyrimidin-2-yl

533 4-CH ₃ (CH ₂ ) ₂ CH(CH ₃ )0-pyrimidin-2-yl

534 2-C ₂ H ₅ 0-thiazol-5-yl

535 2-iso-propyloxy-thiazol-5-yl

536 3-methyl-isoxazol-5-yl

537 3-C ₂ H ₅ 0-isoxazol-4-yl

538 3-iso-propyloxy-isoxazol-4-yl

539 3-C ₂ H ₅ 0-isoxazol-5-yl

540 3-iso-propyloxy-isoxazol-5-yl

541 5-iso-propyl-6-F-pyrimidin-4-yl

542 5-iso-propyl-6-Cr,Hr0-pyrimidin-4-yl

543 5-iso-propyl-6-CF-,CH ₂ 0-pyrimidin-4-yl

544 2-CH,-5-iso-propyl-pyrimidin-4-yl

545 2-CH--5-iso-propyl-6-CH-0-pyrimidin-4-yl

546 2-CH.--5-iso-propyl-6-F-pyrimidin-4-yl

547 6-(CF ₃ ) ₂ CH0-pyrimidin-4-yl

548 6-CHF ₂ CH ₂ 0-pyrimidin-4-yl

549 6-CH ₂ FCH ₂ CH ₂ 0-pyrimidin-4-yl

550 6-CH ₂ FCH ₂ CH ₂ CH ₂ 0-pyrimidin-4-yl 551" 6-CF ₃ CH ₂ CH ₂ CH ₂ 0-pyrimidin-4-yl

552 6-CF ₃ CF ₂ CH(CH ₃ )0-pyrimidin-4-yl

553 6-CHF ₂ CF ₂ CH(CH ₃ )0-pyrimidin-4-yl

554 6-CF ₃ CHFCF ₂ CH ₂ 0-pyrimidin-4-yl

TABLE I (continued)

Compound R R A

No.

555 6-CF ₃ CF ₂ CF ₂ CH ₂ 0-pyrimidin-4-yl

556 5-F-6-CF ₃ CH ₂ 0-pyrimidin-4-yl

557 5-Cl-6-CF ₃ CH ₂ 0-pyrimidin-4-yl

558 5-CH ₃ -6-CF ₃ CH ₂ 0-pyrimidin-4-yl

559 5-CH ₃ CH ₂ -6-CF ₃ CH ₂ 0-pyrimidin-4-yl

560 5-CH ₃ CH ₂ CH ₂ -6-CF ₃ CH ₂ -pyrimidin-4-yl

561 5-CN-6-CF ₃ CH ₂ 0-pyrimidin-4-yl

562 3-CH ₃ 0-4-CF ₃ -pyrid-2-yl

563 3-CH ₃ CH ₂ 0-4-CF ₃ -pyrid-2-yl

564 2-CH ₃ CH ₂ 0-pyrid-3-yl

565 2-CH ₃ 0-pyrid-4-yl

566 2-CH ₃ CH ₂ 0-pyrid-4-yl

567 3-CH ₃ 0-pyrid-4-yl

568 3-CH ₃ CH ₂ 0-pyrid-4-yl

569 4-CH ₃ 0-pyrid-3-yl

570 4-CH ₃ CH ₂ 0-pyrid-3-yl

571 5-CH ₃ CH ₂ 0-pyrid-2-yl

572 0

573 4-CH ₃ CH ₂ 0CH ₂ CH ₂ CH ₂ 0-pyrimidin-2-yl

574 4-CH ₃ 0CH ₂ CH ₂ CH ₂ 0-pyrimidin-2-yl

575 4-phenoxyCH ₂ CH ₂ CH ₂ 0-pyrimidin-2-yl

576 4-CH ₃ CH ₂ 0CH ₂ CH ₂ CH(CH ₃ CH ₂ )-0-pyrimidin-2-yl

577 4-CH ₃ 0CH ₂ CH ₂ CH ₂ 0CH ₂ CH ₂ CH ₂ 0-pyrimidin-2-yl

578 4-phenylCH ₂ 0CH ₂ CH ₂ CH ₂ 0-pyrimidin-2-yl

579 0

580 0

581 0

582 4-CH ₃ 0CH(CH ₃ )CH ₂ 0-pyrimidin-2-yl

583 0

584 4-iso-propyloxyCH ₂ CH-(CH ₂ Cl)0-pyrimidin-2-yl

585 4-CH ₃ 0CH ₂ CH(CH ₂ Cl)0-pyrimidin-2-yl

586 4-CH ₃ CH ₂ 0CH ₂ CH(CH ₂ 0CH ₂ CH ₃ )-0-pyrimidin-2-yl

TABLE I (continued)

_ Compound R R A

No.

587 0

588 0

589 4-CH ₃ 0CH ₂ CH(CH ₃ )0-pyrimidin-2-yl

590 4-allyloxyCH ₂ CH(CH ₂ Cl)0-pyrimidin-2-yl

591 4-CH ₃ (CH ₂ ) ₃ OCH ₂ CH(CH ₃ )0-pyrimidin-2-yl

592 4-CH ₃ 0CH ₂ CH(CH ₂ CH ₃ )0-pyrimidin-2-yl

593 4-CH ₃ -CO-CH ₂ CH(CH ₃ )0-pyrimidin-2-yl

594 4-(CH ₃ ) ₃ COCH ₂ CH(CH ₃ )0-pyrimidin-2-yl

595 4-CH ₃ CH ₂ 0CH ₂ CH(CH ₃ )0-pyrimidin-2-yl

596 4-CH ₃ OCH ₂ 0-pyrimidin-2-yl

597 4-CH ₃ CH ₂ 0CH ₂ 0-pyrimidin-2-yl

598 4-CH ₃ CH ₂ 0CH(CH ₃ )0-pyrimidin-2-yl

599 4-(fur-3-yl)-CH ₂ 0-pyrimidin-2-yl

600 4-cyclopropylCH ₂ 0-5-CH ₃ -pyrimidin-2-yl

601 4-cyclopropylCH ₂ 0-5-F-pyrimidin-2-yl

602 4-(tetrahydropyran-4-yl)0-5-CH--pyrimidin-2-yl

603 4-(tetrahydropyran-4-yl)0-5-F-pyrimidin-2-yl

604 4-(fur-2-yl)CH ₂ 0-5-CH ₃ -pyrimidin-2-yl

605 4-(fur-2-yl)CH ₂ 0-5-F-pyrimidin-2-yl

606 4-(fur-3-yl)CH ₂ 0-5-CH ₃ -pyrimidin-2-yl

607 4-(fur-3-yl)CH ₂ 0-5-F-pyrimidin-2-yl

608 4-(tetrahydropyran-2-yl)CH ₂ 0-5-CH ₃ -pyrimidin-2-yl

609 4-(tetrahydropyran-2-yl)CH ₂ 0-5-F-pyrimidin-2-yl

610 4-(tetrahydrofur-2-yl)CH ₂ 0-5-CH ₃ -pyrimidin-2-yl

611 4-(tetrahydrofur-2-yl)CH ₂ 0-5-F-pyrimidin-2-yl

612 4-(tetrahydrofur-3-yl)CH ₂ 0-5-CH ₃ -pyrimidin-2-yl

613 4-(tetrahydrofur-3-yl)CH ₂ 0-5-F-pyrimidin-2-yl

614 4-CF ₃ CH ₂ 0-pyrimidin-2-yl

615 4-CF ₃ CH ₂ 0-pyrimidin-2-yl

616 2-CH ₃ OCgH ₄ CH ₂ CH ₂

617 4-[(CH ₃ ) ₂ C:N0]-pyrimidin-2-yl

618 4-(NHCH ₂ CF ₃ )-pyrimidin-2-yl

TABLE I (continued)

- -

Compound R R A

No.

619 4-(l,2,4-triazol-l-yl)-pyrimidin-2-yl

620 4-ethynyl-pyrimidin-2-yl

621 4-prop-2-ynyl-pyrimidin-2-yl

623 4-allyl-pyrimidin-2-yl

624 4-cyclopropyl-pyrimidin-2-yl

625 4-CH ₃ 0-5,6-di-CH ₃ ~pyrimidin-2-yl

626 4-(NHCH ₃ )-pyrimidin-2-yl

627 4-CH ₃ 0-5-N0 ₂ -pyrimidin-2-yl

628 4-C ₂ H ₅ 0-5-N0 ₂ -pyrimidin-2-yl

629 4-iso-propyloxy-5-N0 ₂ -pyrimidin-2-yl

630 4-CF ₃ CH ₂ 0-5-N0 ₂ -pyrimidin-2-yl

631 4-C ₂ H ₅ 0-5-CH ₃ 0-pyrimidin-2-y1

632 4-iso-propyloxy-5-CH-0-pyrimidin-2-yl

633 4-CF ₃ CH ₂ 0-5-CH ₃ 0-pyrimidin-2-yl

634 4-C ₂ H ₅ 0-5-CF ₃ -pyrimidin-2-yl

635 4-C ₂ H ₅ 0-5-C ₂ H ₅ 0CH ₂ -pyrimidin-2-yl

636 4-N-(C ₂ H ₅ ,CH ₃ )-pyrimidin-2-yl

637 4-C ₂ Hr-pyrimidin-2-yl

638 5-C ₂ H ₅ -pyrimidin-2-yl

639 4-allyloxy-5-CH ₃ -pyrimidin-2-yl

640 4,5-di-CH ₃ -pyrimidin-2-yl

641 4-(3-butenyloxy)-pyrimidin-2-yl

642 4-(2-methyl-2-propenyloxy)-pyrimidin-2-yl

643 4-(2-butynyloxy)-pyrimidin-2-yl

644 4-(3-butynyloxy)-pyrimidin-2-y1 645" 4-(3-buten-2- loxy)-pyrimidin-2-yl 646" 4-(2-butenyloxy)-pyrimidin-2-yl

647 4-C ₂ H ₅ 0-5-CN-pyrimidin-2-yl

648 4-iso-propyloxy-5-CN-pyrimidin-2-yl

649 4-CF ₃ CH ₂ 0-5-CN-pyrimidin-2-yl

650 4-CH ₃ 0-5-CN-pyrimidin-2-yl

651 5-CF ₃ CH ₂ 0-pyrimidin-2-yl

TABLE I (continued)

_ _

Compound R R A

No.

652 4-CH ₃ C0CH ₂ 0-pyrimidin-2-yl

653 4-CH ₃ 0C0CH ₂ 0-pyrimidin-2-yl

654 4-CH ₃ CH ₂ OCOCH ₂ 0-pyrimidin-2-yl

655 4-H ₂ NC0CH ₂ 0-pyrimidin-2-yl

656 4-CH ₃ SC0CH ₂ 0-pyrimidin-2-yl

657 4-CH ₃ CH ₂ C0CH ₂ 0-pyrimidin-2-yl

658 4-H ₂ NC0CH(CH ₃ )0-pyrimidin-2-yl

659 4-H ₂ N.NHC0CH(CH ₃ )0-pyrimidin-2-yl

660 4-CH ₃ 0C0CH(CH ₃ )0-pyrimidin-2-yl

661 4-CH ₃ CH ₂ 0C0CH(CH ₃ )0-pyrimidin-2-yl

662 4-CH ₃ C0CH(CH ₃ )0-pyrrimidin-2-yl

663 4-CH ₃ C0CH ₂ CH ₂ 0-pyrimidin-2-yl

664 4-H ₂ NC0CH ₂ CH ₂ 0-pyrimidin-2-yl

665 4-CH ₃ CH ₂ CH ₂ 0C0CH ₂ CH ₂ 0-pyrimidin-2-yl

666 4-CH ₃ CH ₂ 0C0CH ₂ CH(CH ₃ )0-pyrimidin-2-yl

667 4-CH ₃ 0COCH ₂ CH(CH ₃ )O-pyrimidin-2-yl

668 4-CH ₃ C0CH(CH ₃ )0-pyrimidin-2-yl

669 4-CH ₃ COCH(CH ₃ )CH ₂ 0-pyrimidin-2-yl

670 4-CH ₃ OCOCH(CH ₃ )CH ₂ 0-pyrimidin-2-yl

671 4-(CH ₃ ) ₂ CHSCH ₂ CH ₂ 0-pyrimidin-2-yl

672 4-CH ₃ S0 ₂ CH ₂ CH ₂ 0-pyrimidin-2-yl

673 ø

674 4-CH ₃ SCH ₂ CH ₂ 0-pyrimidin-2-yl

675 4-NCCH ₂ CH ₂ SCH ₂ CH ₂ 0-pyrimidin-2-yl 676" 4-(butyn-3-yloxy)-pyrimidin-2-yl

677 4-F ₂ CH0-pyrimidin-2-yl

678 6-F ₂ CH0-pyrimidin-4-yl

679 4-CF,0-pyrimidin-2-yl

680 6-CF ₃ 0-pyrimidin-4-yl

681 4-CHF ₂ CF ₂ 0-pyrimidin-2-yl

682 6-CHF ₂ CF ₂ 0-pyrimidin-4-yl

683 4-CCl ₃ 0-pyrimidin-2-yl

TABLE I (continued)

No.

684 6-CCl ₃ 0-pyrimidin-4-yl CH _q H

685 5-CF,-pyrimidin-2-yl CH., H

686 4-CH ₃ 0-5-CF ₃ -pyrimidin-2-yl CH ₃ H

687 4-C ₂ H ₅ 0-5-CF ₃ -pyrimidin-2-yl CH ₃ H

688 4-iso-propyloxy-5-CF,-pyrimidin-2-yl CH ₃ H

689 4-C ₂ H _c 0-5-CH ₃ 0CH ₂ -pyrimidin-2-yl CH ₃ H

690 4-(pyrid-3-yl-CH ₂ 0)-pyrimidin-2-yl CH ₃ H

691 4-(pyrid-2-yl-CH ₂ 0)-pyrimidin-2-yl CH ₃ H

692" 2, -di-Cl ₂ -CgH ₃ -0CH ₂ CH H

693" CH, CH- H

Chemical shift of singlet from olefinic proton on β-methoxypropenoate group of major oxime ether isomer (ppm from tetramethylsilane).

¹ 3:1 mixture of (E:Z) isomers about the oxime ether C=N.

² 1:1 mixture of (E:Z) isomers about the oxime ether C=N.

³ 7:1 mixture of (E:Z) isomers about the oxime ether C=N. * 3:2 mixture of (E:Z) isomers about the oxime ether C=N.

In the form of a gum, NMR data given in Table II. ø Structure given later under ^■ 'Chemical Formulae"

The compounds of the invention are characterized by the melting points given in Table I and/or by the NMR data given in Table II.

TABLE II : SELECTED PROTON NMR DATA

Table II shows selected proton NMR data for certain compounds described in Table I. Chemical shifts are measured in ppm from tetramethylsilaπe, and deuterochloroform was used as solvent throughout. The operating frequency of the NMR spectrometer was 270 MHz except in the case of compound No 285 where it was 400 MHz. The following abbreviations are used: s = singlet sept = septet d = doublet m = multiplet dd = double doublet br = broad t = triplet ppm = parts per million q = quartet

Compound

Proton NMR Data (δ) No.

236 1.33(3H,t • 2 20(3H,s); 3.60(3H,s); 3.73(3H,s); 4.35(2H,q);

5.14(2H,s .' 7 0-7.5(4H,m); 7.50(lH,s); 7.95-8.10(2H,m) ppm. 237 2.23(3H,s ' 3.68(3H,s); 3.80(3H,s); 5.20(2H,s); 7.10-7.20(lH,m);

7.25-7.403H,m); 7.50-7.60(2H,m) _; 7.59(lH,s); 7.67-7.80(lH,m);

8.64-8.74 lH,m) ppm.

240 2.12(3H,s , 2.22(3H,s); 2.38(3H,s); 3.67(3H,s); 3.81(3H,s);

5.08(2H,s • 7.1-7.5(4H,m); 7.58(lH,s) ppm. 241 3.67(3H,s ' 3.80(3H,s); 4.08(3H,s); 5.10(2H,s); 7.10-7.20(11..■),

7.24-7.40 3H,m); 7.50-7.60(lH,m); 7.59(lH,s); 7.63-7.80(2H,m);

8.60-8.70 lH,m) ppm.

243 3.64(3H,s ; 3.73(3H,s); 5.16(2H,s) ₅ 6.95-7.30(10H,m); 7.54(lH.s)j

7.60-7.80 2H,m); 8.55-8.70(lH,m) ppm. 244 3.65( i,s . 3 75<3H,sV 5.15(2H,s); 5.42(2H,s); 7.10-7.40(9H,m);

7.45-7.56 _,m); 7.57,.H,s); 7.58-7.70(2H,m); 8.60-8.70(lH,m) ppm.

246 3.69(3H,s , 3.80(3H,s); 5.06(2H,s); 5.58(2H,s); 7.10-7.40(4H,m);

7.50-7.60 lH,m); 7.59(lH,s); 7.60-7.70(lH,m); 7.90-8.00(lH,m);

8.45-8.55 lH,m) ppm.

247 2.38(3H,s • 3.62(3H,s); 3.76(3H,s); 5.11(2H,s), 7.10-7.50(5H,m);

7.56(lH,s . 7.65-7.75(lH,m); 7.95-8.05(lH,m); 8.60-8.70(lH,m) ppm.

248 2.22(3H,d i 3.68(3H,s); 3.80(3H,s); 5.13(2H,s); 6.7-7.5(7H,m);

7.58(lH,s ppm.

252 2.13(3H,s • 3.67(3H,s); 3.80(3H,s); 5.20(2H,s); 7.10-7.40(4H,m);

7.50-7.55 «,»); 7.60(lH,s); 7.70-7.80(lH,m); 8.60-8.75(2H,m) ppm.

253 3.68(3H,s • 3.83(3H,s); 4.09(3H,s); 5.04(2H,s); 7.10-7.40(4H,m);

7.45-7.55 IH.m); 7.61(lH,s); 7.90-8.00(lH,m); 8.55-8.65(lH,m);

8.85-8.95 lH,m) ppm.

.54 2.34(3H,s . 3.69(3H,s) ₅ 3.82(3H,s); 5.19(2H,s); 7.10-7.60(5H,m);

7.60(lH,s . 7 79(lH,t); 8.08(lH,d) ppm.

255 2.22(3H,s ' 3.65(3H,s); 3.80(3H,s); 5.15(2H,s); 7.15(2H,m);

7.35(2H,m _; 7.50(lH,m); 7.60(lH,s)s 7.80(lH,m); 7.90(lH,m) _PP m.

TABLE II (continued)

^CompoUnd Proton NMR Data (δ)

No.

257 2.18(3H,s); 3.68(3H,s); 3.92(3H,s); 5.13(2H,s); 6.70-7.50(7H,m); 7.60(lH,s) ppm.

261 2.40(3H,s); 3.70(3H,s); 3.83(3H,s); 5.18(2H,s); 7.10-7.60(8H,m); 7.59(lH,s); 7.98(2H,m) ppm.

262 2.25(3H,s); 3.62(3H,s); 3.80(3H,s); 5.15(2H,s); 5.65(lH,brs); 6.65(lH,brs); 7.17(lH,m); 7.33(2H,m); 7.40-7.50(2H,m); 7.59(lH,s); 7.72(lH,d); 7.85(lH,d); 8.09(lH,s) ppm.

263 2.40(3H,s); 3.68(3H,s); 3.82(3H,s); 5.35(2H,s); 7.18(lH,m); 7.35(2H,m); 7.54(lH,m); 7.58(lH,s); 7.60(lH,d); 9.07(lH,d) ppm.

266 1.05(3H,t); 1.80(2H,q); 2.21(3H,s); 3.68(3H,s); 3.82(3H,s);

3.95(2H,t); 5.15(2H,s); 6.89(lH,d); 7.20(4H,m); 7.35(2H,m);

7.52(lH,m); 7.59(lH,s) ppm.

270 2.30(3H,s); 3.68(3H,s); 3.83(3H,s); 5.25(2H,s); 7.18(lH,m); 7.35(2H,m); 7.48(lH,m); 7.61(lH,s); 8.22(lH,s); 9.33(lH,s) ppm.

271 2.22(3H,s); 3.68(3H,s); 3.81(3H,s); 5.16(2H,s); 7.18(2H,m); 7.35(3H,m); 7.50(3H,m); 7.60(lH,s) ppm.

278 2.22(3H,s); 3.68(3H,s); 3.82(3H,s); 4.56(2H,d); 5.15(2H,s);

5.28(lH,d); 5.42(lH,d); 6.05(lH,m); 6.90(lH,d); 7.15-7.40(6H,m); 7.52(lH,m); 7.59(lH,s) ppm.

280 2.35(3H,s); 3.68(3H,s); 3.82(3H,s); 4.03(3H,s); 5.30(2H,s); 6.68(lH,d); 7.18(lH,m); 7.34(2H,m); 7.54(lH,s); 7.58(lH,s); 8.50(lH,d) ppm.

281 2.09(3H,s); 3.67(3H,s); 3.81(3H,s); 5.20(2H,s); 7.10-7.20(lH,m); 7.25-7.45(2H,m); 7.50-7.60(2H,m); 7.59(lH,s); 7.61-7.80(3H,m) ppm.

282 3.63(3H,s); 3.76(3H,s); 5.20(2H,s); 7.10-7.80(8H,m); 7.56(lH,s) ppm.

283 1.15(3H,t); 2.78(2H,q); 3.68(3H,s); 3.82(3H,s); 5.15(2H,s); 7.18(lH,m); 7.33(2H,m); 7.50(2H,m); 7.58(lH,m); 7.60(lH,s); 7.80(lH,d); 7.90(lH,s) ppm.

285 3.66(3H,s); 3.79(3H,s); 5.20(2H,s); 7.10-7.60(8H,m); 7.58(lH,s); 7.73(lH,d); 7.78(lH,s); 7.88(lH,s) ppm.

TABLE II (continued)

Compound Proton NMR Data (δ)

No.

286 2.66(6H,s ; 3,63(3H,s); 3.75(3H,s); 4.82(2H,s); 7.00-7.70(8H,m);

7.52(lH,s ppm. 287 2.68(3H,d ; 3.70(3H,s); 3.81(3H,s); 4.99(2H,s); 5.33(lH,brd),

7.10-7.60 5H,m); 7.58(lH,s); 7.68(2H,d); 7.75(lH,s) ppm. 288 1.31(6H,t ; 2.02(3H,d); 3.69(3H,s); 3.83(lH,s); 4.12(4H,q);

5.18(2H,s ; 7.11-7.20(lH,m); 7.27-7.36(2H,m); 7.37-7.45(lH,m);

7.56(lH,s ppm.

289 1.24(6H,t ; 3.62(3H,s); 3.74(3H,s); 4.03-4.19(4H,m); 5.20(2H,s);

7.10-7.17 lH,m); 7.25-7.43(6H,m); 7.53(lH,s); 7.56-7.64(2H,m) ppm.

290 2.38(3H,s 3.68(3H,s); 3.82(3H,s); 4.00(3H,s); 4.09(3H,s);

5.32(2H,s 7.10-7.60(4H,m); 7.40(lH,s); 7.59(lH,s) ppm. 291 2.13(3H,s 3.69(3H,s); 3.81(3H,s); 5.03(2H,s); 6.17(lH,m);

6.37(lH,m 6.78(lH,m); 7.15(lH,m); 7.31(2H,m); 7.47(lH,m);

7.58(lH,s 9.06(lH,brs) ppm.

292 2.19(3H,s 3.60(3H,s); 3.74(3H,s); 5.08(2H,s); 6.20(lH,m);

6.48(lH,m 6.88(lH,m); 7.20(lH,m); 7.37(2H,m); 7.51(lH,m);

7.56(lH,s 10.30(lH,brs) ppm.

294 2.52(3H,s 3.69(3H,s); 3.82(3H,s); 5.00(2H,s); 6.95(lH,d);

7.08(lH,t 7.18(lH,m); 7.24-7.40(5H,m); 7.54(lH,m); 7.59(lH,s);

8.65(2H,d ppm.

295 2.23(3H,s ; 2.52(lH,m); 3.69(3H,s); 3.82(3H,s); 4.71(2H,d);

5.15(2H,s ; 6.98(lH,m); 7.18(lH,m); 7.25-7.40(5H,m); 7.51(lH,m);

7.60(lH,s ppm.

296 1.84(3H,d ; 3.67(3H,s); 3.80(3H,s); 4.96(2H,s); 7.10-7.50(5H,m);

7.56(lH,s ppm. 299 1.24(3H,t 1.91(3H,s); 3.66(3H,s); 3.79(3H,s); 3.99(2H,q);

4.82(2H,s 7.10-7.50(4H,m); 7.56(lH,s) ppm.

301 2.35(3H,s 2.51(lH,m); 3.68(3H,s); 3.82(3H,s); 5.05(2H,d);

5.32(2H,s 6.76(lH,d); 7.18(lH,m); 7.34(2H,m); 7.55(lH,m);

7.58(lH,s 8.58(lH,d) ppm.

TABLE II (continued)

^CompOUnd Proton NMR Data (δ)

No.

303 1.21(3H,t); 2.22(3H,s); 2.65(2H,q); 3.68(3H,s); 3.82(3H,s); 5.14(2H,s); 7.18(3H,m); 7.32(2H,m); 7.55(2H,m); 7.57(lH,m); 7.59(lH,s) ppm.

305 2.12(3H,s); 2.33(3H,s); 3.67(3H,s); 3.82(3H,s); 5.03(2H,s); 7.10-7.14(lH,m); 7.24-7.37(2H,m); 7.46-7.53(lH,m); 7.57(lH,s) ppm.

306 2.20(3H,s); 3.07(3H,s); 3.70(2H,s); 3.84(3H,s); 5.15(2H,s); 7.14-7.22(lH,m); 7.31-7.40(2H,m); 7.43-7.50(lH,m); 7.60(lH,s) ppm.

307 3.63(3H,s); 3.75(3H,s); 3.78(3H,s); 5.44(2H,s); 6.70-7.60(7H,m); 7.60(lH,s); 8.59(lH,brs) ppm.

308 1.03(3H,t); 1.81(2H,m); 2.35(3H,s); 3.68(3H,s); 3.82(3H,s); 4.36(2H,t); 5.31(2H,s); 6.65(lH,d); 7.18(lH,m); 7.35(2H,m); 7.55(lH,d); 7.58(lH,s); 8.50(lH,d) ppm.

309 0.90(3H,t); 1.32(4H,m); 1.46(2H,m); 1.78(2H,m); 2.22(3H,s); 3.68(3H,s); 3.82(3H,s); 3.98(2H,t); 5.15(2H,s); 6.89(lH,d); 7.15-7.38(6H,m); 7.52(lH,m); 7.59(lH,s) ppm.

310 0.99(3H,t); 1.48(2H,m); 1.78(2H,m); 2.35(3H,s); 3.68(3H,s); 3.82(3H,s); 4.41(2H,t); 5.31(2H,s); 6.65(lH,d); 7.18(lH,m); 7.32(2H,m); 7.55(lH,d); 7.58(lH,s); 8.49(lH,d) ppm.

312 1.75(3H,s); 1.80(3H,s); 2.22(3H,s); 3.68(3H,s); 3.82(3H,s);

4.52(2H,d); 5.15(2H,s); 5.48(lH,t); 6.90(lH,d); 7.15-7.35(6H,m); 7.51(lH,m); 7.58(lH,s) ppm.

316 2.22(3H,s); 2.96(6H,s); 3.68(3H,s); 3.82(3H,s); 5.15(2H,s); 6.72(lH,dd); 6.94(lH,d); 7.00(lH,s); 7.15-7.38(4H,m); 7.52(lH,m); 7.58(lH,s) ppm.

317 3.69(3H,s); 3.83(3H,s); 5.26(2H,s); 7.1-7.6(6H,m); 7.61(lH,s); 8.00(lH,d); 8.07(lH,s) ppm.

318 2.05-1.70(12H,m); 2.54(lH,m); 3.55(lH,m); 3.68(3H,s); 3.82(3H,s); 4_98(2H,s); 7.13(lH,m); 7.30(2H,m); 7.47(lH,m); 7.57(lH,s) ppm.

319 2.25(3H,s); 3.68(3H,s); 3.80(3H,s); 5.24(2H,s); 6.96(lH,s); 7.47-7.15(5H,m); 7.58(lH,s); 7.59-7.51(3H,m) ppm.

TABLE II (continued)

^Compound Proton NMR Data (δ)

No.

320 2.23(3H,s); 3.30(3H,s); 3.62(3H,s); 3.78(3Hs); 5.18(2H,s);

7.12(lH,m); 7.28(2H,m); 7.38(lH,m); 7.53(lH,s); 8.00(lH,d); 8.72(lH,d) ppm.

323 2.22(3H,s); 3.38(3H,s); 3.56(2H,m); 3.69(3H,s); 3.82(3H,s); 3.83(2H,m); 5.14(2H,s); 5.28(2H,s); 7.05(lH,m); 7.17(lH,m); 7.25-7.40(5H,m); 7.52(lH,m); 7.60(lH,s) ppm.

324 2.22(3H,s); 3.68(3H,s); 3.82(3H,s); 4.80(2H,s); 5.16(2H,s); 6.98(lH,m); 7.18(lH,m); 7.32(5H,m); 7.50(lH,m); 7.59(lH,s) ppm.

326 2.22(3H,s); 3.68(3H,s); 3.82(3H,s); 5.15(2H,s);

6.26,6.52,6.81(lH,t); 7.10(lH,d); 7.18(lH,m); 7.3-7.4(3H,m); 7.41-7.55(3H,m); 7.60(lH,s) ppm.

328 2.14(3H,s); 2.37(3H,s); 3.68(3H,s); 3.83(3H,s); 5.18(2H,s); 6.04(lH,d); 6.50(lH,d); 7.12-7.18(lH,m); 7.27-7.39(2H,m); 7.50-7.57(lH,m); 7.58(lH,s) ppm.

329 2.16(3H,s); 3.62(3H,s); 3.65(3H,s); 3.78(3H,s); 5.11(2H,s); 6.42-6.44(lH,m); 6.53-6.56(lH,m); 7.12-7.19(lH,m); 7.25-7.33(2H,m); 7.48(lH,m); 7.52-7.57(lH,m); 7.58(lH,s) ppm.

330 2.29(3H,s); 3.68(3H,s); 3.80(3H,s); 5.14(2H,s); 7.16(lH,m); 7.28-7.43(3H,m); 7.51(lH,m); 7.59(lH,s); 8.02(lH,d); 8.77(lH,d) ppm.

331 2.22(3H,s); 3.68(3H,s); 3.81(3H,s); 5.15(2H,s);

6.24, 6.51, 6.79(lH,t); 7.0-7.7(8H,m); 7.58(lH,s) ppm.

339 1.73(3H,s); 3.70(3H,s); 3.83(3H,s); 5.11(2H,s); 7.13-7.20(lH,m) ; 7.25-7.46(5H,m); 7.52-7.59(3H,m); 7.61(lH,s) ppm.

340 2.33(3H,s); 3.61(3H,s); 3.80(3H,s); 5.18(2H,s); 5.70(lH,brs); 7.17(lH,m); 7.30(lH,br,s); 7.35(2H,m); 7.51(lH,m); 7.60(lH,s); 7.75(lH,dd); 8.13(lH,brs); 8.70(lH,d) ppm.

341 2.20(3H,s); 3.69(3H,s); 3.82(3H,s); 5.14(2H,s); 7.06-7.20(2H,m) ; 7.28-7.40(3H,m); 7.44-7.56(2H,m); 7.60(lH,s) ppm.

342 1.43(3H,t); 2.32(3H,s); 3.69(3H,s); 3.80(3H,s); 4.10(2H,q); 5.19(2H,s); 6.75(lH,m); 7.16(lH,m); 7.29-7.39(3H,m); 7.52(lH,m); 7.59(lH,s); 8.38(lH,d) ppm.

TABLE II (continued)

^Compound Proton NMR Data (δ)

No.

344 2.08(3H,s); 3.69(3H,s); 3.82(3H,s); 5.16(2H,s); 7.10(lH,t);

7.20(lH,m); 7.35(4H,m); 7.45(lH,m); 7.60(lH,s); 7.62(2H,d);

8.60(lH,brs) ppm. 352 2.28(3H,s); 2.48(lH,m); 3.68(3H,s); 3.82(3H,s); 5.03(2H,d);

5.22(2H,s); 7.18(lH,m); 7.35(2H,m); 7.55(lH,m); 7.59(lH,s);

8.10(lH,d); 8.22(lH,d) ppm.

357 2.10(3H,s); 2.22(3H,s); 2.33(3H,s); 3.67(3H,s); 3.81(3H,s); 5.06(2H,s); 6.01(lH,s); 7.12-7.16(lH,m) ; 7.27-7.33(2H,m); 7.46-7.51(lH,m); 7.58(lH,s) ppm.

358 2.15(3H,s); 2.39(6H,s); 3.68(3H,s); 3.81(3H,s); 5.09(2H,s); 6.65(lH,s); 7.12-7.18(lH,m) ; 7.27-7.36(2H,m) ; 7.46-7.52(lH,m) ; 7.58(lH,s) ppm.

359 2.22(3H,s); 3.68(3H,s); 3.82(3H,s); 5.10(2H,s); 6.93(lH,s); 7.13-7.19(lH _t m); 7.29-7.38(2H,m); 7.45-7.51(lH,m); 7.59(lH,s) ppm.

360 2.24(3H,s); 2.30(3H,s); 3.53(3H,s); 3.75(3H,s); 4.35(lH,s); 4.96(2H,s); 7.00-7.06(lH,m) ; 7.18-7.28(2H,m) ; 7.33-7.39(lH,m) ; 7.55-7.70(4H,m); 7.60(lH,m) ppm.

362 2.31(3H,s); 3.69(3H,s); 3.82(3H,s); 5.21(2H,s); 7.19(lH,m); 7.34(2H,m); 7.49(lH,m); 7.60(lH,s); 7.87(lH,dd); 8.03(lH,d); 8.82(lH,d) ppm.

363 3.69(3H,s); 3.79(3H,s); 3.82(3H,s); 5.14(2H,s); 6.86(2H,d); 7.20(lH,m); 7.37(2H,m); 7.47(lH,s); 7.47(lH,m); 7.55(2H,d); 7.61(lH,s); 8.29(lH,s) ppm.

367 2.18(3H,s); 3.70(3H,s); 3.83(3H,s); 4.26(2H,s); 5.11(2H,s);

7.15-7.22(lH,m); 7.30-7.40(6H,m) ; 7.42-7.49(lH,m) ; 7.60(lH,s);

7.62(lH,s) ppm. 372 1.48(3H,t); 2.28(3H,s); 3.69(3H,s); 3.81(3H,s); 4.17(2H,q);

5.18(2H,s); 7.10-7.21(2H,m) ; 7.21-7.37(5H,m) ; 7.57-7.62(lH,m) ;

7.60(lH,s); 8.25(lH,d) ppm.

TABLE II (continued)

Compound

Proton N.p . Data (δ) No.

373 Major Isomer: 3.61(3H,s); 3.76(3H,s); 5.37(2H,s); 7.13(lH,t);

7.13-7.20(lH,m); 7.32-7.39(2H,m); 7.55-7.62(I.H,m) ; 7.59(lH,s) ppm.

Minor Isomer: 3.69(3H,s); 3.82(3H,s); 5.23(2H,s); 7.05(lH,t);

7.13-7.20(lH,m); 7.32-7.39(4H,m) ; 7.55-7.62(lH,m); 7.59(lH,s) ppm.

374 2.27(3H,s); 2.55(3H,s ; 3.66(3H,s); 3.80(3H,s); 5.20(2H,s); 6.97(lH,d); 7.12-7.19 ;iH,m); 7.26(lH,d); 7.26-7.38(2H,m) ; 7.54-7.59(lH,m); 7.59 ;iH,s) ppm.

375 2.18(3H,s); 2.51(3H,s ; 3.68(3H,s); 3.82(3H,s); 5.10(2H,s); 6.90(lH,d); 7.02(lH,d ; 7.12-7.17(lH,m); 7.28-7.38(2H,m); 7.47-7.52(lH,m); 7.59 lH,s) ppm.

376 2.33(3H,s); 3.21(3H,s ; 3.63(3H,s); 3.83(3H,s); 5.27(2H,s); 7.12-7.19(lH,m); 7.30-7.39(2H,m); 7.37(lH,d); 7.47-7.53(lH,m); 7.60(lH,s); 7.77<lH,d] ; ppm.

377 2.22(3H,s); 3.18(3H, _S ; ; 3.69(3H,s); 3.85(3H,s); 5.13(2H,s); 7.15(lH,d); 7.15-7.19( lH,m); 7.30-7.37(2H,m); 7.58(lH,d);

7.61(lH,s) ppm.

378 2.26(3H,s); 2.54(3H,s ; 3.69(3H,s); 3.83(3H,s); 5.12(2H,s); 7.04-7.09(lH,m); 7.15 7.20(lH,m); 7.31-7.40(3H,m) ; 7.45-7.53(2H,m); 7.59 lH,s) ppm.

379 2.31(3H,s); 2.53(3H,s ; 3.65(3H,s); 3.88(3H,s); 5.13(2H,s);

7.04-7.09(lH,m); 7.12-7.18(lH,m); 7.29-7.36(2H,m); 7.39(lH,d);

7.43-7.52(2H,m); 7.58 lH,s) ppm.

; 3.71(3H,s); 3.85(3H,s); 4.63(2H,q); lH,m); 7.29-7.41(2H,m); 7.41-7.52(lH,m); ppm.

; 5.38(2H,s); 7.1-8.1(8H,m) ; 7.65(lH,s)ppm. ; 3.69(3H,s); 3.84(3H,s); 4.19(2H,q); lH,m); 7.29-7.40(2H,m); 7.40-7.50(lH,m) ; ppm.

TABLE II (continued)

^Compound Proton NMR Data (δ)

No.

390 1.31(3H,t); 2.28(3H,s); 2.90(2H,q); 3.67(3H,s); 3.80(3H,s);

5.20(2H,s); 7.04(lH,d); 7.11-7.18(lH,m); 7.27-7.38(3H,m) ;

7.52-7.60(lH,m); 7.59(lH,s) ppm. 396 2.27(3H,s); 3.69(3H,s); 3.83(3H,s); 3.99(3H,s); 5.19(2H,s);

7.1-7.5(5H,m); 7.60(lH,s); 8.78(lH,s) ppm.

398 2.32(3H,s); 3.64(3H,s); 3.78(3H,s); 5.25(2H,s); 7.13-7.20(lH,m); 7.28-7.38(3H,m); 7.42(lH,d); 7.56-7.64(lH,m) ; 7.60(lH,s); 7.64(2H,d); 7.75(2H,d) ppm.

399 2.27(3H,s); 3.70(3H,s); 3.84(3H,s); 5.15(2H.s); 7.13-7.20(lH,m) ; 7.18(lH,d); 7.28-7.38(3H,m) ; 7.50-7.56(lH,m) ; 7.61(lH,s); 7.62(2H,d); 7.71(2H,d) ppm.

400 1.35(3H,t); 2.22(3H,s); 3.20(2H,q); 3.70(3H,s); 3.84(3H,s); 5.13(2H,s); 7.14-7.19(2H,m); 7.30-7.37(2H,m) ; 7.45-7.50(lH,m); 7.56(lH,d); 7.60(lH,s) ppm.

405 1.36(6H,d); 2.32(3H,s); 3.69(3H,s); 3.82(3H,s); 4.69(lH,m);

5.18(2H,s); 6.73(lH,dd); 7.17(lH,m); 7.28-7.37(3H,m) ; 7.52(lH,m); 7.60(lH,s); 8.38(lH,d) ppm.

408 2.42(3H,s); 3.66(3H,s); 3.80(3H,s); 5.27(2H,s); 7.1-7.4(3H,m) ; 7.47(lH,d); 7.51(lH,m); 7.61(lH,s); 7.76(lH,d); 9.07(lH,s) ppm.

409 2.28(3H,s); 2.57(3H,s); 3.48(3H,s); 3.69(3H,s); 3.83(3H,s); 4.48(2H,s); 5.21(2H,s); 7.1-7.7(4H,m) ; 7.60(lH,s) ppm.

410 1.35(6H,d); 2.26(3H,s); 3.69(3H,s); 3.82(3H,s); 5.18(2H,s); 5.37(lH,m); 7.11(lH,s); 7.1-7.5(4H,m); 7.59(lH,s); 8.73(lH,s) ppm.

411 2.38(3H,s); 3.68(3H,s); 3.82(3H,s); 5.32(2H,s); 5.48(2H,s); 6.71(lH,d); 7.18(lH,m); 7.30-7.50(7H,m) ; 7.55(lH,m); 7.58(lH,s); 8.52(lH,d) ppm.

414 2.15(3H,s); 2.25(3H,s); 3.25-3.30(8H,m); 3.65(3H,s); 3.70(3H,s); 3.82(3H,s); 3.84(3H,s); 3.89-3.94(8H,m) ; 5.09(2H,s); 5.18(2H,s); 7.13-7.19(2H,m); 7.25-7.38(4H,m); 7.44-7.52(2H,m); 7.55(lH,s); 7.60(2H,s); 7.75(lH,s) ppm.

TABLE II (continued)

Compound

Proton NMR Data (δ) No.

416 2.35(3H,s ; 3.70(3H,s); 3.84(3H,s); 5.23(2H,s); 7.17-7.21(lH,m);

7.32-7.39 2H,m); 7.47-7.53(lH,m); 7.62(lH,s); 8.11(lH,d);

8.40(1H,dd); 9.38(lH,d) ppm.

418 1.00(3H,t 1.36(3H,d) 1.70(lH,m) 1.82(lH,m); 2.28(3H,s);

3.68(3H,s 3.82(3H,s) 5.13(lH,m) 5.20(2H,s); 7.18(lH,m);

7.35(2H,m 7.41(lH,d) 7.48(lH,m) 7.60(lH,s); 8.40(lH,d) ppm.

420 0.98(3H,t 1.36(3H,d) 1.72(2H,m) 2.32(3H,s); 3.68(3H,s);

3.82(3H,s 5.28(lH,m) 5.32(2H,s) 6.61(lH,d); 7.18(lH,m);

7.35(2H,m 7.55(lH,m) 7.59(lH,s) 8.49(lH,d) ppm.

422 2.11(3H,s 3.70(3H,s) 3.85(3H,s) 5.19(2H,s); 6.72(lH,d);

6.74(lH,d 7.13-7.40(4H,m); 7.50-7.58(3H,m); 7.60(lH,s) ppm.

425 2.32(3H,s 3.45(3H,s); 3.69(3H,s); 3.76(2H,t); 3.82(3H,s);

4.20(2H,t 5.18(2H,s); 6.81(lH,dd); 7.17(lH,m); 7.29-7.37(2H,m);

7.42(lH,d 7.51(lH,m); 7.60(lH,s); 8.39(lH,d) ppm.

426 1.38(6H,d 2.25(3H,s); 3.68(3H,s); 3.82(3H,s); 5.19(2H,s);

5.30(lH,m 7.18(lH,m); 7.32(2H,m); 7.51(lH,m); 7.61(lH,s);

8.08(lH,s 8.61(lH,s) ppm.

427 1.38(6H,d 2.25(3H,s); 3.68(3H,s); 3.82(3H,s); 5.20(2H,s);

5.32(lH,m 7.18(lH,m); 7.34(2H,m); 7.54(lH,m); 7.58(lH,s);

8.08(lH,d 8.13(lH,d) ppm.

429 2.33(3H,s 3.70(3H,s); 3.83(3H,s); 5.21(2H,s); 7.18(lH,t);

7.34(2H,t 7.50(lH,t); 7.60(lH,s); 7.85(lH,dd); 8.02(lH,d);

8.82(lH,s ppm.

430 2.32(3H,s ; 3.68(3H,s); 3.82(3H,s); 5.20(2H,s); 5.39(2H,s);

6.96-7.04 3H,m); 7.13-7.19(lH,m); 7.24-7.38(4H,m);

7.47-7.58 3H,m) ppm.

431 1.40(6H,d 2.20(3H,s); 3.69(3H,s); 3.84(3H,s); 5.14(2H,s);

5.29(lH,m 7.1-7.5(4H,m); 7.60(lH,s); 8.71(2H,s) ppm.

432 1.38(6H,d 2.12(3H,s); 2.34(3H,s); 3.68(3H,s); 3.82(3H,s);

5.29(2H,s 5.47(lH,m); 7.18(lH,m); 7.34(2H,m); 7.55(lH,m);

7.58(lH,s 8.30(lH,s) ppm.

T.ABLE II (continued)

^Compound Proton NMR Data (δ)

No.

439 2.38(3H,s); 3.70(3H,s); 3.83(3H,s); 5.20(2H,s); 7.17(lH,m); 7.35(4H,m); 7.50(2H,m); 7.61(lH,s); 7.65(2H,m); 7.72(lH,t); 7.88(lH,d) ppm.

440 2.35(3H,s); 3.70(3H,s); 3.84(3H,s); 4.15(3H,s); 5.20(2H,s); 6.99(lH,s); 7.14(lH,s); 7.18(lH,m); 7.35(2H,m); 7.54(lH,m); 7.62(lH,s); 7.72(lH,t); 7.85(lH,d); 8.16(lH,d) ppm.

441 2.27(3H,s); 3.70(3H,s); 3.85(3H,s); 4.81(2H,q); 5.19(2H,s); 7.18(lH,m); 7.34(3H,m); 7.48(lH,m); 7.61(lH,s); 8.86(lH,s) ppm.

444 1.42(12H,d); 2.27(3H,s); 3.68(3H,s); 3.82(3H,s); 5.31(2H,s);

5.39(2H,sept); 7.13-7.19(lH,m) ; 7.29-7.38(2H,m) ; 7.47-7.56(lH,m) ;

7.57(lH,s) ppm. 446 1.40(3H,t); 2.28(3H,s); 3.69(3H,s); 3.84(3H,s); 4.42(2H,q);

5.19(2H,s); 6.87(lH,s); 7.16(lH,m); 7.34(2H,m); 7.51(lH,m);

7.60(lH,s); 7.67(lH,s) ppm.

448 2.32(3H,s); 3.63(3H,s); 3.76(3H,s); 5.23(2H,s); 6.85-6.95(2H,m); 7.12-7.19(lH,m); 7.28-7.38(3H,m); 7.42(lH,d); 7.55-7.64(2H,m); 7.60(lH,s) ppm.

449 1.16(3H,s); 2.22(3H,s); 3.68(3H,s); 3.80(3H,s); 4.21(2H,q); 5.10(2H,s); 6.90(lH,d); 7.12(lH,d); 7.12-7.18(lH,m) ; 7.27-7.51(6H,m); 7.59(lH,s); 7.73(lH,d) ppm.

450 1.14(3H,t); 2.32(lH,s); 3.63(3H,s); 3.77(3H,s); 4.18(2H,q); 5.21(2H,s); 7.00(lH,d); 7.11-7.16(lH,m); 7.29-7.52(5H,m) ; 7.39(lH,d); 7.58-7.63(lH,m) ; 7.59(lH,s); 7.73-7.78(lH,m) ppm.

454 1.18(6H,d); 2.21(3H,s); 3.19(lH,sept) ; 3.67(3H,s); 3.81(3H,s); 3.99(3H,s); 5.10(2H,s); 7.16(lH,m); 7.33(2H,m); 7.48(lH,m); 7.57(lH,s); 8.59(lH,s) ppm.

455 1.15(6H,d); 2.27(3H,s); 3.38(lH,sept) ; 3.66(3H,s); 3.80(3H,s); 5.14(2H,s); 7.16(lH,m); 7.33(2H,m); 7.45(lH,m); 7.58(lH,s); 8.68(lH,s); 9.02(lH,s) ppm.

460 2.20(3H,s); 2.68(3H,s); 3.68(3H,s); 3.82(3H,s); 5.08(2H,s);

7.12-7.18(lH,m); 7.29-7.37(2H,m) ; 7.44-7.50(lH,m) ; 7.59(lH,s); 7.66(lH,s) ppm.

TABLE II (continued)

Compound

"roton NMR Data (δ) No.

461 1.87(3H,s); 2.42-2.50 2H,m); 2.78-2.87(2H,m) ; 3.68(3H,s); 3.80(3H,s); 4.99(2H,s ; 7.12-7.36(8H,m); 7.41-7.48(lH,m); 7.57(lH,s) ppm.

462 1.80(3H,s); 2.61-2.68 2H,m); 2.79-2.86(2H,m); 3.67(3H,s); 3.80(3H,s); 4.99(2H,s ; 7.13-7.35(8H,m); 7.44-7.49(lH,m); 7.57(lH,s) ppm.

463 2.24(3H,s); 3.69(3H,s ; 3.84(3H,s); 5.14(2H,s); 7.11-7.39(7H,m); 7.41-7.45(lH,m); 7.50 7.55(2H,m); 7.60(lH,s) ppm.

464 2.32(3H,s); 3.63(3H,s ; 3.78(3H,s); 5.24(2H,s); 7.12-7.19(2H,m) ; 7.29-7.48(6H,m); 7.55 •7.64(2H,m); 7.59(lH,s) ppm.

465 1.17(3H,t); 1.94(3H,s ; 2.37(2H,q); 3.15(2H,s); 3.68(3H,s); 3.81(3H,s); 4.99(2H,s ; 7.11-7.15(lH,m); 7.27-7.34(2H,m); 7.42-7.46(lH,m); 7.57 lH,s) ppm.

466 1.44(3H,t); 2.23(3H,s ; 3.69(3H,s); 3.81(3H,s); 4.10(2H,q); 5.17(2H,s); 7.13-7.20 lH,m); 7.30-7.37(2H,m); 7.48(lH,t); 7.51(lH,m); 7.60(lH,s ; 8.27(lH,s); 8.42(lH,s) ppm.

469 1.21(6H,dd); 2.13(3H, ); 2.80(lH,sept); 3.63(3H,s); 3.76(3H,s); 4.00(3H,s); 4.99(2H,q ; 7.08(lH,m); 7.26(3H,m); 7.54(lH,s); 8.64(lH,s) ppm.

471 1.00(3H,t); 2.29(3H,s ; 2.91(2H,q); 3.67(3H,s); 3.82(3H,s); 5.16(2H,s); 7.17(lH,m ; 7.34(2H,m); 7.45(lH,m); 7.54(lH,s); 9.15(lH,s) ppm.

472 1.15(3H,t); 2.25(3H,s 2.76(2H,q); 3.65(3H,s); 3.78(3H,s); 4.99(2H,s); 7.10(lH,m 7.25(3H,m); 7.53(lH,s); 9.70(lH,s) ppm.

473 2.24(3H,s); 3.69(3H,s , 3.82(3H,s); 3.89(3H,s); 5.17(2H,s); 7.14-7.20(lH,m); 7.29 7.39(2H,m); 7.49(lH,d); 7.51(lH,m); 7.60(lH,s); 8.30(lH,s 8.46(lH,s) ppm.

474 1.41(6H,d); 1.45(3H,t 2.27(3H,s); 3.68(3H,s); 3.81(3H,s): 4.50(2H,q); 5.31(2H,s 5.40(lH,sept); 7.ll-7.21(lH,m); 7.26-7.41(2H,m); 7.457.59(lH,m); 7.57(lH,s) ppm.

- 34 - TABLE II (continued)

^{Com OUnd} Proton NMR Data (δ)

No.

475 1.63(9H,s); 2.25(3H,s); 3.68(3H,s); 3.82(3H,s); 5.19(2H _f s); 7.18(lH,m); 7.34(2H,m); 7.40(lH,d); 7.50(lH,m); 7.60(lH,s); 8.39(lH,d) ppm.

476 1.61(9H,s); 2.30(3H,s); 3.68(3H,s); 3.82(3H,s); 5.30(2H,s); 6.55(lH,d); 7.18(lH,m); 7.34(2H,m); 7.55(lH,m); 7.58(lH,s); 8.45(lH,d) ppm.

478 1.20(6H,d); 2.19(3H,s); 2.86(lH,sept); 3.63(3H,s); 3.76(3H,s); 4.98(2H,s); 7.09(lH,m); 7.25(3H,m); 7.53(lH,s); 8.70(lH,s); 9.09(lH,s) ppm.

480 2.32(3H,s); 3.66(4H,m); 3.68(3H,s); 3.79(4H,m); 3.82(3H,s); 5.30(2H,s); 6.43(lH,d); 7.1-7.5(4H,m) ; 7.57(lH,s); 8.35(lH,d) ppm.

481 2.20(3H,s); 3.68(3H,s); 3.80(3H,s); 3.94(3H,s); 5.12(2H,s); 6.70(lH,d); 7.13-7.20(lH,m); 7.29-7.37(2H,m) ; 7.47-7.52(lH,m) ; 7.59(lH,s); 7.92(lH,dd); 8.34(lH,d) ppm.

482 1.14(6H,d); 2.25(3H,s); 2.68(3H,s); 3.27(lH,sept) ; 3.67(3H,s); 3.80(3H,s); 5.12(2H,s); 7.16(lH,m); 7.31(2H,m); 7.46(lH,m); 7.58(lH,s); 8.57(lH,s) ppm.

483 2.35(3H,s); 3.69(3H,s); 3.81(3H,s); 4.92(2H,d); 5.2-5.5(lH,m) ; 5.31(2H,s); 6.0-6.2(lH,m); 6.70(lH,d); 7.1-7.6(4H,m) ; 7.57(lH,s); 8.53(lH,d) ppm.

487 2.18(3H,s); 3.68(3H,s); 3.82(3H,s); 5.19(2H,s); 6.40(lH,d); 7.18(lH,m); 7.33(2H,m); 7.42(lH,m); 7.61(lH,s); 7.91(lH,d); 10.15(lH,s) ppm.

488 0.4(2H,m); 0.65(2H,m); 1.3(lH,m); 2.35(3H,s); 3.65(3H,s); 3.80(3H,s); 4.25(2H,d); 5.30(2H,s); 6.70(lH,d); 7.1-7.6(4H,m) ; 7.60(lH,s); 8.50(lH,d) ppm.

489 1.38-1.68(5H,m); 1.87-1.95(lH,m) ; 2.33(3H,s); 3.44-3.54(lH,m) ; 3.67(3H,s); 3.67-3.78(lH,m) ; 3.81(3H,s); 4.02-4.09(lH,m) ; 4.32-4.46(2H,m); 5.30(2H,s); 6.73-6.75(lH,d) ; 7.15-7.20(lH,m) ; 7.30-7.40(2H,m); 7.53-7.57(lH,m) ; 7.58(lH,s); 8.50-8.52(lH,d) ppm.

TABLE II (continued)

Compound

Proton NMR Data (δ) No.

490 1.69-1.81(lH,m); 2.04-2.18(lH,m) ; 2.33(3H,s); 2.69-2.84(lH,m) ; 3.65-3.73(lH,m); 3.68(3H,s); 3.75-3.84(lH,m); 3.81(3H,s); 3.88-3.96(2H,m); 4.28-4.45(2H,m); 5.30(2H,s); 6.66-6.68(lH,d); 7.15-7.20(lH,m); 7.30-7.38(2H,m); 7.53-7.56(lH,m); 7.57(lH,s); 8.50-8.52(lH,d) ppm.

491 1.19(6H,d); 2.17(3H,s); 2.27(3H,s); 2.83(lH,sept) ; 3.63(3H,s); 3.76(3H,s); 4.98(2H,d); 7.09(lH,m); 7.25(3H,m); 7.53(lH,s); 8.57(lH,s) ppm.

492 2.20(3H,s); 3.67(3H,s); 3.80(3H,s); 3.96(3H,s); 5.13(2H,s); 6.88(lH,dd); 7.14-7.20(lH,m) ; 7.29-7.38(2H,m) ; 7.50-7.55(lH,m) ; 7.58(lH,s); 7.60(lH,dd); 8.15(lH,dd) ppm.

493 2.24(3H,s); 3.69(3H,s); 3.82(3H,s); 4.89(2H,t); 5.21(2H,s); 7.18(lH,m); 7.33(2H,m); 7.48(lH,m); 7.58(lH,d); 7.60(lH,s); 8.47(lH,d) ppm.

495 major isomer 2.03(3H,s); 3.67(3H,s); 3.80(3H,s); 3.92(2H,s); 4.84(2H,s); 7.09-7.87(9H,m); 7.54(lH,s) ppm.

496 1.70(lH,m); 2.00(3H,m); 2.35(3H,s); 3.65(3H,s); 3.80(3H,s); 3.90(2H,m); 4.2-4.6(3H,m) ^• 6.70(lH,d); 7.1-7.6(4H,m) ; 7.60(lH,s); 8.50(lH,d) ppm.

497 1.80(2H,m); 2.10(2H,m); 3.60(2H,m); 3.65(3H,s); 3.80(3H,s); 4.00(2H,m); 5.30(2H,s); 5.40(lH,m); 6.65(lH,d); 7.l-7.6(4H,m); 7.60(lH,s); 8.50(lH,d) ppm.

498 1.83(3H,s); 2.35(3H,s); 3.69(3H,s); 3.82(3H,s); 4.86(2H,s); 5.00(lH,s); 5.10(lH,s); 5.31(2H,s); 6.72(lH,d); 7.1-7.6(4H,m); 7.58(lH,s); 8.54(lH,d) ppm.

499 2.33(3H,s); 3.15(6H,brs) ; 3.69(3H,s); 3.81(3H,s); 5.31(2H,s); 6.35(lH,d); 7.1-7.6(4H,m); 7.57(lH,s); 8.29(lH,d); ppm.

501 1.86(3H,s); 2.40-2.47(2H,m); 2.72-2.79(2H,m); 3.66(3H,s);

3.79(3H,s); 3.80(3H,s); 4.98(2H,s); 6.81(2H,d); 7.09(2H,d); 7.11-7.16(lH,m); 7.27-7.32(2H,m); 7.40-7.45(lH,m); 7.57 (lH,s) ppm.

TABLE II (continued)

Compound

Proton NMR Data (δ) No.

503 2.07(3H,s); 3.67(3H,s); 3.80(3H,s); 5.08(2H,s); 6.97-7.04(2H,m); 7.15-7.19(2H,m); 7.27-7.37(4H,m); 7.47-7.52(lH,m); 7.58(lH,s) ppm.

504 1.50(3H,d); 2.27(3H,s); 3.71(3H,s); 3.85(3H,s); 5.19(2H,s);

5.83(lH,sept); 7.09(lH,m); 7.28(lH,s); 7.35(2H,m); 7.49(lH,m);

7.62(lH,s); 8.76(lH,s) ppm.

518 1.24(3H,t); 2.34(3H,s); 3.60(2H,q); 3.68(3H,s); 3.81(2H,m);

3.83(3H,s); 4.58(2H,m); 5.32(2H,s); 6.74(lH,d); 7.1-7.6(4H,m);

7.57(lH,s); 8.53(lH,d) ppm.

528 2.35(3H,s); 3.68(3H,s); 3.81(3H,s); 5.31(2H,s); 5.47-5.54(lH,m);

6.61(lH,d); 7.15-7.19(lH,m); 7.29-7.39(2H,m); 7.55-7.59(lH,m);

7.58(lH,s); 8.49(lH,d) ppm.

551 2.06(2H,m); 2.27(3H,s); 2.27(2H,m); 3.70(3H,s); 3.84(3H,s);

4.43(2H,t); 5.20(2H,s); 7.18(lH,m); 7.20(lH,s); 7.35(2H,m);

7.49(lH,m); 7.61(lH,s); 8.75(lH,s) ppm.

645 1.45(3H,d); 2.32(3H,s); 3.68(3H,s); 3.82(3H,s); 5.18(lH,d);

5.32(lH,d); 5.31(2H,s); 5.78(lH,m); 5.92(lH,m); 6.62(lH,d);

7.17(lH,m); 7.33(2H,m); 7.55(lH,m); 7.58(lH,s); 8.50(lH,d) ppm.

646 1.77(3H,d); 2.34(3H,s); 3.68(3H,s); 3.82(3H,s); 4.86(2H,d);

5.31(2H,s); 5.67-5.99(2H,m); 6.67(lH,d); 7.15(lH,m); 7.34(2H,m);

7.54(lH,m); 7.58(lH,s); 8.50(lH,d) ppm.

676 1.66(3H,d); 2.36(3H,s); 2.47(lH,d); 3.68(3H,s); 3.81(3H,s);

5.31(2H,s); 5.87(lH,m); 6.71(lH,d); 7.1-7.6(4H,m); 7.57(lH,d);

8.56(lH,d) ppm.

692 2.00(3H,s); 3.66(3H,s); 3.80(3H,s); 4.86(2H,s); 5.03(2H,s);

6.75(lH,d); 7.10-7.20(2H,m); 7.30-7.38(3H,m); 7.40-7.45(lH,m);

7.58(lH,s) ppm.

693 1.88(6H,s); 3.68(3H,s); 3.81(3H,s); 4.98(2H,s); 7.11-7.15(lH,m);

7.28-7.35(2H,m); 7.45-7.49(lH,m); 7.57(lH,s) ppm.

The compounds of the invention of formula (I) may be prepared by the

1 2 * steps shown in Scheme 1. The terms A, R and R are as defined above, R

1 2 is either R or R and X is a leaving group (such as halogen (chlorine, bromine or iodine) or OSOp-CF,).

The compounds of formula (I) may be prepared by treating oximes of general formula (III) with a suitable base (such as sodium hydride or sodium methoxide), in a suitable solvent (such as N,N-dimethylformamide or tetrahydrofuran), to form the anion and then adding a compound of formula

(II).

Oximes of the general formula (III) are known in the chemical literature. The compound of general formula (II) where X is bromine and the propenoate group has the (E)-configuration is described in EP-A-0203606.

Oximes of formula (III) can be prepared by reacting a compound of formula (XI) with hydroxylamine in a suitable solvent (for example a mixture of a primary alcohol (such as methanol or ethanol) with water) optionally in the presence of a buffer (such as a salt of an organic acid (for example sodium acetate)).

Compounds of formula (XI) can be prepared by treating a compound of

* 1 2 formula (XII) (R is either R or R but is not methyl) with an acid, preferably a strong mineral acid such as hydrochloric acid of suitable concentration, in a suitable solvent, for example acetone. Compounds of formula (XII) can be prepared by treating a compound of formula (XIII)

(wherein X is typically chlorine, bromine or 0S0 ₂ CF-) with an alkoxyvinyl tin (for example (l-ethoxyvinyl)tri-n-butyltin) in the presence of a suitable catalyst (such as bis(triphenylphosphine)palladium(II) chloride) in a suitable solvent (for example N,N-dimethylformamide).

Alternatively, compounds of formula (XI) can be prepared by reacting a compound of formula (XIV) with a methyl magnesium halide in a suitable solvent (for example diethyl ether or tetrahydrofuran). Compounds of formula (XIV) can be prepared by reacting a compound of formula (XIII) with a trialkylamine (such as trimethylamine) which is preferably in aqueous solution, and in the presence of a suitable organic solvent (for example diethyl ether), and then introducing a source of cyanide anions (for example potassium or sodium cyanide).

Alternatively, compounds of formulae (XI), (XII), (XIII) and (XIV) can be prepared by methods known in the literature.

Alternatively, compounds of formula (I) can be prepared by treating the substituted hydroxylamine (XV) (or a salt thereof, for example its hydrochloride salt) with a compound of formula (XI). The substituted

- lo - hydroxylamine (XV) wherein A is hydrogen may be prepared as described in EP 0463488.

Alternatively compounds of the invention of formula (I) may be

1 2 prepared by the steps shown in Scheme 2. The terms A, R , R and X are as defined above, R is hydrogen or a metal (such as sodium or potassium), and

R is an alkyl group. Each transformation is performed at a suitable temperature and usually, though not always, in a suitable solvent.

The compounds of the invention of formula (I) can be prepared from phenylacetates of formula (VI) or the ketoesters of formula (X) by the steps shown in Scheme 2.

Thus compounds of formula (I) can be prepared by treatment of phenylacetates of formula (VI) with a base (such as sodium hydride or sodium methoxide) and methyl formate. If a species of formula CH,L, wherein L is a leaving group such as a halide (chlorine, bromine or iodine), or a CH,S0 ₄ anion, is then added to the reaction mixture, compounds of formula (I) may be obtained. If a protic acid is added to the reaction mixture, compounds of formula (IX) wherein R is hydrogen, are obtained. Alternatively the species of formula (IX) wherein R is a metal (such as sodium), may themselves be isolated from the reaction mixture.

Compounds of formula (IX) wherein R is a metal can be converted into compounds of formula (I) by treatment with a species CH-L, wherein L is as

5 defined above. Compounds of formula (IX) wherein R is hydrogen can be converted into compounds of formula (I) by successive treatment with a base

(such as potassium carbonate) and a species of general formula CH,L.

Alternatively, compounds of formula (I) can be prepared from acetals of formula (IV) by elimination of methanol under either acidic or basic conditions. Examples of reagents or reagent mixtures which can be used for this transformation are lithium di-isopropylamide; potassium hydrogen sulphate (see, for example, T Yamada, H Hagiwara and H Uda, J. Chem. Soc. Chemical Communications, 1980, 838, and references therein); and triethylamine, often in the presence of a Lewis acid such as titanium tetrachloride (see, for example, K Nsunda and L Heresi, J. Chem. Soc. Chemical Communications, 1985, 1000).

Acetals of formula (IV) can be prepared by treatment of methyl silyl ketene acetals of formula (V) with trimethyl orthoformate in the presence of a Lewis acid such as titanium tetrachloride (see, for example, K Saigo, M Osaki and T Mukaiyama, Chemistry Letters, 1976, 769).

Methyl silyl ketene acetals of formula (V) can be prepared from phenylacetates of formula (VI) by treatment with a base and trialkylsilyl halide of formula R,SiCl or R,SiBr, such as trimethylsilyl chloride, or a base (such as triethylamine) and a trialkylsilyl triflate of formula R,Si-OS0 ₂ CF, (see, for example, C Ainsworth, F Chen and Y Kuo, J. Organometallic Chemistry, 1972, 46, 59).

It is not always necessary to isolate the intermediates (IV) and (V); under appropriate conditions compounds of formula (I) may be prepared from phenylacetates of formula (VI) in "one pot" by the successive addition of suitable reagents listed above.

Phenylacetates of formula (VI) may be prepared from phenylacetates of formula (VII). Thus, if an oxime of general formula (III) is treated with a suitable base (such as sodium hydride or sodium methoxide) and the phenyl acetates of formula (VII) are added, phenylacetates of formula (VI) are obtained.

Phenylacetates of formula (VII) can be obtained from isochromanones of formula (VIII) by treatment with HX, wherein X is a halogen (such as bromine), in methanol. This transformation may also be accomplished in 2 steps if the isochromanone (VIII) is treated with HX in a non-alcoholic solvent, and the resulting phenylacetic acid is then esterified using standard procedures (see, for example, I Matsumoto and J Yoshizawa, Jpn. Kokai (Tokkyo Koho) 79 138 536, 27.10.1979, Chem. Abs., 1980, 92, 180829h; and G M F Lim, Y G Perron and R D Droghini, Res. Disci., 1979, 188, 672, Chem. Abs., 1980, 92, 128526t). Isochromanones of formula (VIII) are well known in the chemical literature.

Alternatively, compounds of formula (I) can be prepared by treatment of ketoesters of formula (XI) with •methoxymethylenation reagents such as methoxymethylenetriphenylphosphorane (see, for example, W Steglich, G Schramm, T Anke and F Oberwinkler, EP 0044 448, 4.7.1980).

Ketoesters of formula (XI) may be prepared from ketoesters of formula (X), by treatment with the anion of oximes of general formula (III) as described above. Ketoesters of formula (X) are described in EP 0331 061.

Therefore, to summarise, Schemes 1 and 2 illustrate certain methods by which the oxime ether and the 3-methoxypropenoate moieties, respectively, may be constructed in the final stages of the synthesis of the compounds of the invention of formula (I). An alternative final stage or stages in the synthesis of the compounds of the invention of formula (I) is a

1 2 modification to one of the groups R or R or to the substituent A. Thus,

1 2 for example, if A, or a substituent on one of the groups R and R when that group is a pyridine or pyrimidine ring, is a suitably positioned amino group, it may be converted in the final stages of the reaction sequence through diazotisation into a halogen atom.

In a further aspect the present invention provides a process for the preparation of a compound of formula (I).

In other aspects the present invention provides the intermediate compounds 2-acetyl-4-(2,2,2-trifluoroethoxy)pyrimidine, 2-acetylpyrimidin- -4-one and 2-acetyl-4-chloropyrimidine.

The compounds of the invention are active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae on rice.

Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts e.g. coffee, pears, apples, peanuts, vegetables and ornamental plants. Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildews on various hosts such as Sphaerotheca macularis on hops, Sphaerotheca fuliginea on cucurbits (e.g. cucumber), Podosphaera leucotricha on apple and Uncinula necator on vines.

Helminthosporium spp., Rhynchosporium spp., Septoria spp., Pyrenophora spp., Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals.

Cercospora arachidicola and Cercosporidium personata on peanuts and other

Cercospora species on other hosts, for example, sugar beet, bananas, soya beans and rice.

Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts.

Alternaria spp. on vegetables (e.g. cucumber), oil-seed rape, apples, tomatoes and other hosts.

Venturia inaequalis (scab) on apples.

Plasmopara viticola on vines.

Other downy mildews such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on cucurbits.

Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoa

and other hosts.

Thanatephorus cucumeris on rice and other Rhizoctonia species on various hosts such as wheat and barley, vegetables, cotton and turf.

Some of the compounds show a broad range of activities against fungi in vitro. They may also have activity against various post-harvest diseases of fruit (e.g. Penicillium digitatum and italicum and Trichoderma viride on oranges, Gloeosporium musarum on bananas and Botrytis cinerea on grapes).

Further, some of the compounds may be active as seed dressings against Fusarium spp., Septoria spp., Tilletia spp., (bunt, a seed-borne disease of wheat), Ustilago spp. and Helminthosporium spp. on cereals, Rhizoctonia solani on cotton and Pyricularia oryzae on rice.

The compounds may have systemic movement in plants. Moreover, the compounds may be volatile enough to be active in the vapour phase against fungi on the plant.

The invention therefore provides a method of combating fungi which comprises applying to a plant, to a seed of a plant or to the locus of the plant or seed a fungicidally effective amount of a compound as hereinbefore defined, or a composition containing the same.

The compounds may be used directly for agricultural purposes but are more conveniently formulated into compositions using a carrier or diluent. The invention thus provides fungicidal, insecticidal and miticidal compositions comprising a compound as hereinbefore defined and an acceptable carrier or diluent therefor.

The compounds can be applied in a number of ways. For example, they can be applied, formulated or unformulated, directly to the foliage of a plant, to seeds or to other medium in which plants are growing or are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation, or they can be applied as a vapour or as slow release granules.

Application can be to any part of the plant including the foliage, stems, branches or roots, or to soil surrou ⁿ ding the roots, or to the seed before it is planted, or to the soil genera_.ly, to ddy water or to hydroponic culture systems. The invention compount..; may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods.

The term "plant" as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes preventative, protectant, prophylactic and eradicant treatments.

The compounds are preferably used for agricultural and horticultural purposes in the form of a composition. The type of composition used in any instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dustable powders or granules comprising the active ingredient (invention compound) and a solid diluent or carrier, for example, fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fuller's earth, gypsum, diatomaceous earth and china clay. Such granules can be preformed granules suitable for application to the soil without further treatment. These granules can be made either by impregnating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler.

Compositions for dressing seed may include an agent (for example, a mineral oil) for assisting the adhesion of the composition to the seed; alternatively the active ingredient can be formulated for seed dressing purposes using an organic solvent (for example, N-methylpyrrolidone, propylene glycol or dimethylformamide). The compositions may also be in the form of wettable powders or water dispersible granules comprising wetting or dispersing agents to facilitate the dispersion in liquids. The powders and granules may also contain fillers and suspending agents.

Emulsifiable concentrates or emulsions may be prepared by dissolving the active ingredient in an organic solvent optionally containing a wetting or emulsifying agent and then adding the mixture to water which may also contain a wetting or emulsifying agent. Suitable organic solvents are aromatic solvents such as alkylbenzenes and alkylnaphthalenes, ketones such as isophorone, cyclohexanone, and methylcyclohexanone, chlorinated hydrocarbons such as chlorobenzene and trichlorethane, and alcohols such as benzyl alcohol, furfuryl alcohol, butanol and glycol ethers.

Suspension concentrates of largely insoluble solids may be prepared by ball or bead milling with a dispersing agent with a suspending agent included to stop the solid settling.

Compositions to be used as sprays may be in the form of aerosols wherein the formulation is held in a container under pressure of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.

The invention compounds can be mixed in the dry state with a pyrotechnic mixture to forr a composition suitable for generating in enclosed sp. :_es a smoke co fining the compounds.

Alternatively, the compounds may be used in micro-encapsulated form. They may also be formulated in biodegradable polymeric formulations to obtain a slow, controxled release of the active substance.

By including suitable additives, for example additives for improving the distribution, adhesive power and resistance to rain on treated surfaces, the different compositions can be better adapted for various utilities.

The invention compounds can be used as mixtures with fertilisers (e.g. nitrogen-, potassium- or phosphorus-containing fertilisers). Compositions comprising only granules of fertiliser incorporating, for example coated with, the compound are preferred. Such granules suitably contain up to 25% by weight of the compound. The invention therefore also provides a fertiliser composition comprising a fertiliser and the compound of general formula (I) or a salt or metal complex thereof.

Vettable powders, emulsifiable concentrates and suspension concentrates will normally contain surfactants, e.g. a wetting agent, dispersing agent, emulsifying agent or suspending agent. These agents can be cationic, anionic or non-ionic agents.

Suitable cationic agents are quaternary ammonium compounds, for example, cetyltrimethylammonium bromide. Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example, sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example, sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropylnaphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl- or nonylphenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins. Suitable suspending agents are hydrophilic colloids (for example, polyvinylpyrrolidone and sodium carbox methylcellulose), and swelling clays such as bentonite or attapulgite.

Compositions for use as aqueous dispersions or emulsions are generally supplied.in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being diluted with water before use. These concentrates should preferably be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain up to 95%, suitably 10-85%, for example 25-60%, by weight of the active ingredient. After dilution to form aqueous preparations, such preparations may contain varying amounts of the active ingredient depending upon the intended purpose, but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight of active ingredient may be used.

The compositions of this invention may contain other compounds having biological activity, e.g. compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal or insecticidal activity.

A fungicidal compound which may be present in the composition of the invention may be one which is capable of combating ear diseases of cereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporium spp., seed and soil-borne diseases and downy and powdery mildews on grapes and powdery mildew and scab on apple, etc. By including another fungicide, the composition can have a broader spectrum of activity than the compound of general formula (I) alone. Further the other fungicide can have a synergistic effect on the fungicidal activity of the compound of general formula (I). Examples of fungicidal compounds which may be included in the composition of the invention are (+)-2-(2,4-dichlorophenyl)-3-(lH-l,2,4- -triazol-1-yl)propyl 1,1,2,2-tetrafluoroethyl ether, (RS)-l- -aminopropylphosphonic acid, (RS)-4-(4-chlorophenyl)-2-phenyl-2-(IH-1,2,4- -triazol-l-ylmethyl)butyronitrile, (RS)-chloro-N-(cyano(ethoxy)methyl)- -benzamide, (Z)-N-but-2-enyloxymethyl-2-chloro-2' ,6'-diethylacetanilide, l-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea, 1-[2RS,4RS;2RS,4RS)- -4-bromo-2-(2,4-dichlorophenyl)tetrahydrofurfuryl]-1H-1,2,4- triazole, 3-(2,4-dichlorophenyl)-2-(lH-l,2,4-triazol-l-yl)quinazolin-4 (3H)-one, 3-chloro-4-[4-methyl-2-(lH-l,2,4-triazol-l-methyl)-l,3-dioxo lan- -2-yl]phen 1-4-chlorophenyl ether, 4-bromo-2-cyano-N,N-di- methyl-6-trifluoromethylbenzimidazole-l-sulphonamide, 4-chlorobenzyl N- -(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)thioacetamida te, 5-ethyl-

-5,8-dihydro-8-oxo(1,3)-dioxolo( ,5-g)quinoline-7-carboxylic acid, α-[N-(3- -chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone, anilazine, BAS 454, benalaxyl, benomyl, biloxazol, binapacryl, bitertanol, blasticidin S, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, chlorbenz- thiazone, chloroneb, chlorothalonil, chlorozolinate, copper containing compounds such as copper oxychloride, copper sulphate and Bordeaux mixture, cycloheximide, cymoxanil, cyproconazole, cyprofuram, di-2-pyridyl disulphide l,l'-dioxide, dichlofluanid, dichlone, diclobutrazol, diclomezine, dicloran, dimethamorph, dimethirimol, diniconazole, dinocap, ditalimfos, dithianon, dodemorph, dodine, edifenphos, etaconazole, ethirimol, ethyl (Z)-N-benzyl-N-([methy(methylthioethylideneamino- -oxycarbonyl)amino]thio)-β-alaninate, etridazole, fenapanil, fenarimol, fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, flutolanil, flutriafol, fluzilazole, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, imazalil, iprobeπfos, iprodione, isoprothiolane, kasugamycin, mancozeb, maneb, mepronil, metalaxyl, methfuroxam, metsulfovax, myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxycarboxin, penconazole, pencycuron, pent-4-enyl N-furfuryl-N-imidazol- -1-ylcarbonyl-DL-homoalaninate, phenazin oxide, phthalide, polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, prothiocarb, pyrazophos, p ^* -ifenox, pyroquilon, pyroxyfur, pyrrolnitrin, quinomethionate, quintozene, streptomycin, sulphur, techlofthalam, tecnazene, tebuconazole, thiabendazole, thiophanate-methyl, thiram, tolclofos-methyl, triacetate salt of l,l'-iminodi(octamethylene)di- guanidine, triadimefon, triadimenol, triazbutyl, tricyclazole, tridemorph, triforine, validamycin A, vinclozolin and zineb. The compounds of general formula (I) can be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases. '

Suitable insecticides which may be incorporated in the composition of the invention include buprofezin, carbaryl, carbofuran, carbosulfan, chlorpyrifos, cycloprothrin, demeton-s-methyl, diazinon, dimethoate, ethofenprox, fenitrothion, fenobucarb, fenthion, formothion, isoprocarb, isoxathion, monocrotophos, phenthoate, pirimicarb, propaphos and XMC.

Plant growth regulating compounds are compounds which control weeds or seedhead, formation, or selectively control the growth of less desirable

plants (e.g. grasses). Examples of suitable plant growth regulating compounds for use with the invention compounds are 3,6-dichloropicolinic acid, l-(4-chlorophen l-4,6-dimethyl-2-oxo-l,2-dihydropyridine-3- -carboxylic acid, methyl-3,6-dichloroanisate, abscisic acid, asulam, benzoylprop-ethyl, carbetamide, daminozide, difenzoquat, dikegulac, ethephon, fenpentezol, fluoridamid, glyphosate, glyphosine, hydroxybenzonitriles (e.g. bromoxynil), inabenfide, isopyrimol, long chain fatty alcohols and acids, maleic hydrazide, mefluidide, morphactins (e.g. chlorfluoroecol), paclobutrazol, phenoxyacetic acids (e.g. 2,4-D or MCPA), substituted benzoic acid (e.g. triiodobenzoic acid), substituted quaternary ammonium and phosphonium compounds (e.g. chloromequat, chlorphonium or mepiquatchloride), tecnazene, the auxins (e.g. indoleacetic acid, indolebutyric acid, naphthylacetic acid or naphthoxyacetic acid), the cytokinins (e.g. benzimidazole, benzyladenine, benzylaminopurine, diphenylurea or kinetin), the gibberellins (e.g. GA,, GA ₄ or GA-,) and triapenthenol.

The following Examples illustrate the invention. Throughout the Examples, the term 'ether' refers to diethyl ether, magnesium sulphate was used to dry solutions, and solutions were concentrated under reduced pressure. Reactions involving air ,or water sensitive intermediates were performed under an atmosphere of nitrogen and solvents were dried before use, where appropriate. Unless otherwise stated, chromatography was performed on a column of silica gel as the stationary phase. Where shown, infrared and NMR data are selective; no attempt is made to list every absorption in all cases. H NMR spectra were recorded using CDCl,-solutions unless otherwise stated. The following abbreviations are used throughout:

DMF = N,N-dimethylformamide m.p. = melting point t = triplet NMR = nuclear magnetic resonance ppm = parts per million q = quartet IR = infrared s = singlet m = multiplet b.p. = boiling point d = doublet br = broad

* EXAMPLE 1

This Example describes the preparation of the stereoisomer of methyl 2-[2-(2-pyridyl[meth lsulphonyl]oximinomethyl)phenyl]-3-methoxypropenoate in which the propenoate and oximino groups have the (E)- and (Z)-configurations respectively (Compound No. 238 of Table I).

A solution of 2-[2-(2-pyridyl[methylthio]oximinomethyl)phenyl]-3- -methypropenoate (3.1g, prepared from the α-chloro-oxime of 2-formyl-

pyridine in two steps as described in Example 5 of EP-A-O 370 629 for the parallel, reactions with α-chlorobenzaldehyde oxime) in dichloromethane (100ml) was stirred and cooled in an ice bath. meta-Chloroperbenzoic acid (2.6g of 55% pure material) was added in portions over 5 minutes. After 15 minutes, analysis by thin-layer chromatography indicated partial reaction and a second batch of meta-chloroperbenzoic acid (2.6g) was added and the reaction mixture was allowed to stir at room temperature. After 30 minutes, the reaction mixture was washed with aqueous sodium bicarbonate, dried, concentrated and chromatographed using ethyl acetate as eluant to give the title compound (2.1g, 62% yield) as a cream-coloured solid. The product from a subsequent preparation had m.p. 150-154°C.

The configuration of the title compound was established by single-crystal X-ray analysis. It follows that the starting material has the same (E,Z)-configuration.

EXAMPLE 2

This Example describes the preparation of (E,E)-methyl 2-[2-(2- -pyridyl[methylsulphonyljoximinomethyl)phenyl]-3-methoxyprop enoate (Compound No. 251 of Table I) by stereomutation of the isomer in which the oximino-group has the (Z)-configuration.

A mixture of (E,Z)-methyl 2-[2-(2-pyridyl[methylsulphonyl]- oximinomethyl)phenyl]-3-methoxypropenoate (200mg, prepared as described in Example 1) and potassium thiocyanate (48mg) in DMF (10ml) was heated at 100°C for 4 hours. Analysis by thin-layer chromatography indicated that no reaction had occurred. Further potassium thiocyanate (50mg) was added and the mixture was heated until the DMF boiled under reflux. After a further 4 hours, thin-layer chromatography (ethyl acetate) indicated that although a little starting material remained, the major component was a new and faster-running compound. After cooling the reaction mixture was diluted with water. Material extracted into an organic solvent was chromatographed using ethyl acetate to give the title (E,E)-isomer (50mg) as a cream- coloured solid; m.p. 122-127°C (plus a further 75mg of slightly impure material: combined yield about 50%).

Like potassium thiocyanate in the reaction described above, potassium bromide in refluxing DMF also effects (Z) to (E)-isomerisation of the oximino double bond.

EXAMPLE 3 This Example describes the preparation of (E,E)-methyl 2-[2-(2- -pyridyl[methylthio]oximinomethyl)phenyl]-3-methoxypropenoat e (Compound No. 247 of Table I).

A mixture of (E,E)-methyl 2-[2-(2-pyridyl[methyl-sulphonyl]oximino- methyl)phenyl]-3-methoxypropenoate (80mg, prepared as described in Example 2) and sodium methanethiolate (18mg) in DMF was heated at 80-100°C for 6 hours. After cooling, the reaction mixture was diluted with water and extracted with ethyl acetate. The extracts were dried, concentrated and chromatographed using a mixture of ethyl acetate and hexane (1:1) as eluant to give the title compound (35mg, 48% yield) as a pale yellow gum; IR maximum (film): 1707cm ^"1 ; -*H NMR: See Table II.

EXAMPLE 4 This Example describes the preparation of the stereoisomer of methyl 2-[2-(2-pyridyl[amino]oximinomethyl)phenyl-3-methoxypropenoa te in which the propenoate and oximino groups have the (E)- and (Z)-configurations respectively (Compound No. 246 of Table I).

A mixture of (E,Z)-methyl 2-[2-(2-pyridyl[methylsulphonyl]- oximinomethyl)phenyl]-3-methoxypropenoate (lOOmg, prepared as described in Example 1), and concentrated aqueous ammonia (2 drops) in DMF (5ml) was stirred at room temperature for 3 hours and then at 80-100°C for 4hours. After cooling, the reaction mixture was diluted with water and extracted with ethyl acetate. The extracts were dried, concentrated and then chromatographed using ethyl acetate and hexane (1:1) as eluant to give the title compound (60mg, 71% yield) as a yellow gum; IR maxima (film): 3500, 3384 and 1704 cm ^-1 ; -*H NMR : See Table II.

It was found that other nucleophilic reagents such as alkoxides, phenoxides and thiolates also reacted with the same starting material by displacement of methylsulphinate.

EXAMPLE 5 This Example illustrates the preparation of (E),(E)-methyl 2-[2-(4- -trifluoromethylpyrid-2-yl-acetoximinomethyl)phenyl]-3-metho xypropenoate (Compound No. 260 of Table I).

A solution of 2-chloro-4-trifluoromethylpyridine (3.33g), (1-ethoxy- vinyl)tri-n-butyltin (5.95g) and bis(triphenylphosphine)palladium (II) chloride (0.4g) in DMF (40ml) was heated at 70°C for 16 hours. The reaction mixture was cooled to room temperature, potassium fluoride (60ml of a 10% aqueous solution) was added and the resulting mixture was stirred

for 1 hour then filtered through Hyflo supercel filter aid which was rinsed through with ether. The filtrate was extracted with ether (x2) and the combined extracts were washed with brine, then dried, concentrated and chromatographed using ether:hexane 1:4 as the eluant to give l-ethoxy-l-(4- -trifluoromethylpyrid-2-yl)-ethylene (1.4g, 35% yield) as a pale yellow liquid; -H NMR (270MHz): δ 1.45(3H,t), 4.00(2H,q), 4.42(lH,d), 5.50(lH,d), 7.40(lH,d), 7.88(lH,s), 8.72(lH,d) ppm.

A solution of l-ethoxy-l-(4-trifluoromethylpyrid-2-yl)-ethylene (1.4g) in acetone (15ml) was treated with hydrochloric acid (5ml of a 2M solution). The reaction mixture was allowed to stand for 16 hours then concentrated, diluted with water and neutralised with sodium bicarbonate. The aqueous phase was extracted with ether (x2) and the combined extracts were washed with brine, dried and concentrated to give 2-acetyl-4- -trifluoromethylpyridine (1.2g, 99% yield) as a pale yellow liquid. IR maximum (film): 1705cm ^~ .

A solution of 2-acetyl-4-trifluoromethylpyridine (1.2g), hydroxylamine (0.495g) and sodium acetate (2.2g) in a mixture of ethanol:water (20:10 ml) was heated under reflux for 2 hours. The reaction mixture was poured into water and extracted with ethyl acetate (x2). The combined extracts were washed with water, dried and concentrated to give a solid which was washed with hexane to give (E)-2-acetyl-4-trifluoromethylpyridine oxime (l.Og, 77% yield) as a pale pink solid; ^J H NMR (270MHz): δ 2.39(3H,s), 7.47(lH,d), 7.89(lH,brs), 8.12(lH,s), 8.12(lH,s), 8.78(lH,d); ppm.

A solution of 2-acetyl-4-trifluoromethylpyridine oxime (0.66g) in DMF (10ml) was added dropwise to a stirred suspension of sodium hydride (0.078g) in DMF (20ml). An hour later, the reaction mixture was cooled to 0°C and a solution of (E)-methyl-2-[2-(bromomethyl)phenyl]-3-methoxyprop- enoate (0.92g) in DMF (10ml) was added dropwise. After a further 2 hours, the reaction mixture was poured into water and extracted with ether (x3). The organic extracts were washed with brine, dried, concentrated and chromatographed using ethyl acetate:hexane 3:7 as the eluant to give the title compound (0.844g, 64% yield) as a colourless oil; IR maxima (film): 1708, 1633 cm ^"1 ; ¹ H NMR (270MHz): δ 2.33(3H,s), 3.69(3H,s), 3.82(3H,s), 5.20(2H,s), 7.18(lH,m), 7.35(2H,m), 7.45(lH,d), 7.50(lH,m), 7.61(lH,s), 8.14(lH,s), 8.75(lH,d) ppm.

EXAMPLE 6 This Example illustrates the preparation of (E), (E)-methyl 2-[2-(4- -ethoxypyrimidin-2-yl-acetoximino-methyl)phenyl]-3-methoxypr openoate (Compound No. 269 of Table I).

A solution of 2-chloro-4-ethoxypyrimidine (6.34g), (1-ethoxyvinyl)- -tri-n-butyltin (14.4g) and bis(triphenylphosphine)palladium (II) chloride (lg) in DMF (60ml) was heated at 90°C for 60 hours. The reaction mixture was cooled to room temperature and potassium fluoride (100ml of a 10% aqueous solution) was added. The resulting mixture was stirred for 1 hour then filtered through Hyflo supercel filter aid which was rinsed through with ether. The filtrate was extracted with ether (x2) and the combined extracts were washed with brine, then dried, concentrated and chromato¬ graphed using ethyl acetate:hexane 1:4 as the eluant to give 1-ethoxy-l- -(4-ethoxypyrimidin-2-yl)-ethylene (2.7g, 35% yield) as an orange oil; IR maximum (film): 1550cm ^"1 ; ^l H NMR (270MHz): δ 1.40(3H,t), 1.50(3H,t), 4.02(2H,q), 4.45(2H,q), 4.58(lH,d), 5.65(lH,d), 6.60(lH,d), 8.48(lH,d) ppm.

A solution of l-ethoxy-l-(4-ethoxypyrimidin-2-yl)-ethylene (2.7g) in acetone (20ml) was treated with hydrochloric acid (6ml of a 2M solution). The reaction mixture was allowed to stand for 16 hours, then warmed at 40°C for l-i. hours, and concentrated. The residue was diluted with water and neutralised with sodium bicarbonate. The aqueous phase was extracted with ethyl acetate (x2) and the combined extracts were washed with brine, dried and concentrated to give 2-acetyl-4-ethoxypyrimidine (1.8g, 78% yield) as a colourless oil which partially solidified on standing, and was used without further purification; IR maximum (film): 1717cm ; **H NMR (270MHz): δ 1.45(3H,t), 2.74(3H,s), 4.53(2H,q), 6.85(lH,d), 8.60(lH,d) ppm.

A solution of 2-acetyl-4-ethoxypyrimidine (1.8g), hydroxylamine hydrochloride (0.83g) and sodium acetate (2.2g) in a mixture of ethanol:water (30:10 ml) was heated under reflux for 3 hours. The reaction mixture was then poured into water and extracted with ethyl acetate (x3). the combined extracts were washed with brine, dried and concentrated to give a solid which was washed with hexane to give (E)-2-acetyl-4-ethoxy- pyrimidine oxime as an off-white solid (1.15g, 60% yield); -H NMR (270MHz): δ 1.44(3H,t), 2.38(3H,s), 4.50(2H,q), 6.68(lH,d), 8.48(lH,d), 9.80(lH,brs) ppm.

A solution of 2-acetyl-4-ethoxy-pyrimidine oxime (0.8g) in DMF (15ml) was added dropwise to a stirred suspension of sodium hydride (O.lOg) in DMF (10ml). .An hour later, the reaction mixture was cooled to 0°C and a

solution of (E)-methyl 2-[2-(bromomethyl)phenyl]-3-methoxypropenoate (1.22g) in DMF (15ml) was added dropwise. After a further 2 hours the mixture was poured into water and extracted with ether (x3). The organic extracts were washed with brine, dried, concentrated and chromatographed using ethyl acetate:hexane 3:2 as the eluant to give the title compound (0.84g, 51% yield) as a white solid, m.p. 87-89°C; IR maxima (nujol mull): 1698, 1623cm ^"1 ; -H NMR (270MHz): δ 1.42(3H,t), 2.33(3H,s), 3.68(3H,s), 3.82(3H,s), 4.46(2H,q), 5.30(2H,s), 6.65(lH,d), 7.18(lH,m), 7.34(2H,m), 7.55(lH,d), 7.58(lH,s), 8.50(lH,d) ppm.

The 2-acetyl-4-ethoxypyrimidine used in this example has also been prepared as follows.

A solution of 2-chloro-4-ethoxy pyrimidine (20g from the reaction of 1 equivalent of sodium ethoxide with 2,4-dichloropyrimidine at 0-5°C) in ether (50ml) was added to ice cooled trimethylamine (50ml of a 30% aqueous solution). After stirring the mixture for 2 hours a solution of potassium cyanide (9.0g) in water (50ml) was added and the resulting mixture was stirred vigorously at room temperature. After 16 hours the reaction mixture was extracted with ether (3x50ml) and the combined extracts were washed with brine, dried and concentrated to give 2-cyano-4-ethoxy- pyrimidine (14.6g, 77% yield) as a pale yellow liquid which gradually crystallised (m.p. 35°C); -H NMR (270MHz): δ 1.42(3H,t), 4.49(2H,q), 6.89(lH,d), 8.49(lH,d) ppm.

Methyl magnesium bromide (4.4ml of a 3M solution in ether) was added to a solution of 2-cyano-4-ethoxypyrimidine in THF (20ml) at -50°C. After 1 hour the reaction mixture was quenched by adding hydrochloric acid (10ml of a 2M solution) followed by sodium bicarbonate to produce a neutral solution. This mixture was extracted with ether (x3) and the combined extracts were washed with water, dried and concentrated to give a dark gum, bulb to bulb distillation of this gum gave 2-acetyl-4-ethoxypyrimidine (1.35g, 64% yield) as a white low melting solid (b.p. 70-80°C at O.lmmHg).

EXAMPLE 7

This Example describes the preparation of a single stereoisomer of methyl 2-[2-(3-trifluoromethylphenyl[amino]oximinomethyl)phenyl]-3- -r„_;thoxy-(E)propenoate (Compound No. 284 of Table I).

Potassium hydroxide (10.5g) and, 15 minutes later, 3-trifluoro- methylbenzonitrile (15.Og) were added to a stirred solution of hydroxylamine hydrochloride (12.8g) in ethanol (300ml) and the resulting mixture was heated under reflux overnight. After cooling, the reaction

mixture was poured into water and extracted with ether. The ether extracts were dried and concentrated under reduced pressure to give an oil (15.4g) which turned into a waxy solid on standing. This material, containing 3-trifluoromethylbenzamide oxime (stereochemistry uncertain), was used for the next stage without purification.

A solution of part of the crude benzamide oxime (5.0g) in DMF (40ml) was added dropwise to a stirred suspension of sodium hydride (600mg) in DMF (20ml) (effervescence). After 15 minutes, a solution of (E)-methyl 2-[2-(bromomethyl)phenyl]-3-methoxypropenoate (7.0g) in DMF (40ml) was added in portions to the resulting bright yellow reaction mixture. Three hours later the reaction mixture was poured into water and extracted with ether. The extracts were washed with water, dried and chromatographed twice using first ethyl acetate:hexane (1:1) and then acetone:dichloro- methane (1:19) as eluant to give the title compound (1.9g, 16% yield over both stages) as a yellow gum; IR maxima (film): 3481, 3371, 1701 cm ^" .

In a subsequent preparation of the title compound it solidified on standing to give a pale yellow solid, m.p. 96-98°C.

EXAMPLE 8 This Example describes the preparation of a single stereoisomer of methyl 2-[2-(3-trifluoromethylphenyl[chloro)oximinomethyl)-phenyl]- 3- -methoxy-(E)-propenoate (Compound No. 317 of Table I).

A solution of a single stereoisomer of methyl 2-[2-(3-trifluoro- methylphenyl[amino]oximinomethyl)phenyl]-3-methoxypropenoate (0.50g, prepared as described in Example 7) in concentrated hydrochloric acid (10ml) was cooled to about 5°C. Water (10ml) was added, whereupon a white gummy precipitate appeared. A solution of sodium nitrite (0.50g) in water (2ml) was then added dropwise with stirring at such a rate as to keep the temperature below 10°C; the mixture became yellow and brown fumes were observed. After 15 minutes, a solution of copper(I) chloride (0.75g) in water was added to the mixture (which became blue) and it was then warmed at 50°C for 1.5 hours (whereupon it turned bright green). After cooling, the reaction mixture was diluted with water and extracted with dichloromethane. The extracts were washed with a 1:1 mixture of water and concentrated hydrochloric acid and then with water, then dried, concentrated and chromatographed using ethyl acetate:hexane (1:4) as eluant to give the title compound (85mg, 16% yield) as a colourless gum; IR maximum (film): 1708 cm ^"1 ; ^l E NMR : See Table II.

EXAMPLE 9

This Example illustrates the preparation of a single stereoisomer of methyl 2-[2-(3-trifluoromethylphenyl-[N-methylamino]-oximinomethyl) - phenyl]-3-methoxy-(E)-propenoate (Compound No. 287 of Table I).

A solution of 3-trifluoromethylbenzaldoxime (13.Og) in DMF (40ml) was treated portionwise with N-chlorosuccinimide (10.Og in lg portions) whilst maintaining a reaction temperature of 35°C. The reaction was stirred for 3 hours and then poured into water and extracted with ether. The combined extracts were washed with brine, dried and concentrated to give α-chloro- -3-trifluoromethylbenzaldoxime (12.0g, 78% yield) as a white crystalline solid m.p. 30°C; IR maxima (film): 3411, 1616 cm ^"1 ; -H NMR (270MHz): δ 7.56(lH,t), 7.71(lH,d), 8.04(lH,d), 8.12(lH,s), 8.28(lH,s) ppm.

A solution of α-chloro-3-trifluoromethylbenzaldoxime (2.0g) in ether at 0°C was treated with monomethylamine gas until there was an excess of the monomethylamine. The reaction mixture was poured into water and extracted with ether. The combined ether extracts were dried and concentrated to give an orange gum. Trituration with hexane gave α-N- methylamino-3-trifluoromethylbenzaldoxime (0.5g, 25% yield) as a white solid m.p. 76.6 ^β C; IR maxima (mull): 3393, 3220, 1654 cm ^"1 ; -H NMR (270MHz): δ 2.73(3H,d), 5.33(lH,brs), 7.5-7.8(4H,m) ppm.

A solution α-N-methylamino-3-trifluoromethylbenzaldoxime (0.3g) in DMF (5ml) was added dropwise to a stirred suspension of sodium hydride (0.068g) in DMF (10ml). 2*ι_ Hours later the reaction mixture was cooled to 0°C and a solution of (E)-methyl 2-[2-(bromomethyl)phenyl]-3-methoxypropenoate (0.4g) in DMF (5ml) was added. After 16 hours the mixture was poured into water and extracted with ether. The organic extracts were washed with brine, dried, concentrated and chromatographed using ether:hexane 1:1 as the eluant to give the title compound (0.105g, 18% yield) as pale brown oil.

IR maxima (nujol mull): 3400, 17 70077,, 11662288 ccnm ^"1 ; ^* *H NMR given in Table II. EXAMPLE 10

This Example illustrates the preparation of a single stereoisomer of methyl 2-[2-(diethylphosphono-acetoximinomethyl)phenyl]-3-methoxy-( E)- -propenoate (Compound No 288 of Table I).

Acetyl chloride (17.8 ml) was added to triethyl phosphite keeping the temperature below 30°C. After the addition, stirring was continued for 24 hours and then the reaction mixture was distilled to give acetyl diethylphosphonate (31.3g, 70% yield) as a colourless oil bp 72°C at 0.3

mmHg; IR maximum (film): 1797 cm ^"1 ; ^X H NMR (270 MHz): δ 1.37(6H,t), 2.48(3H,d), 4.23(4H,q) ppm.

Acetyl diethylphosphonate (14g) was added to a solution of hydroxylamine hydrochloride (7.31g) and pyridine (8.8ml) in ethanol keeping the temperature below 30°C. The reaction was stirred for 48 hours and then concentrated, the residue was partitioned between dichlorome hane (250ml) and hydrochloric acid (250ml of a 2M solution). The organic phase was washed successively with hydrochloric acid (5x100ml of a 2M solution), sodium bicarbonate (5x100ml of a 10% solution) and water (100ml), then dried and concentrated to give acetyl diethylphosphonate oxime (3.9g, 27% yield) as a colourless oil; IR maxima (film): 3185, 1445, 1235 cm ~ ; ^X H NMR (270 MHz): δ 1.38(6H,t), 2.08(3H,d), 4.13-4.29(4H,m), 11.32(lH,brs) ppm.

A solution of acetyl diethylphosphonate oxime (l.Og) in DMF (13ml) was added dropwise to a sitrred suspension of sodium hydride (0.12g) in DMF (5ml). An hour later, a solution of (E)-methyl 2-[2-(bromomethyl)phenyl]- -3-methoxypropenoate (1.46g) in DMF (7ml) was added dropwise. After 24 hours the mixture was poured into water (70ml) and extracted with ether (3x70ml). The organic extracts were washed successively with brine, sodium hydroxide (2x70ml of a 2M solution) and water, then dried, concentrated and chromatographed using ethyl acetate:hexane 4:1 as the eluant to give the title compound (0.45g; 22% yield) as a pale yellow oil; IR maxima (film) : 1707, 1633 cm ^-1 ; *-H NMR given in Table II.

EXAMPLE 11 This Example illustrates the preparation of (E), (E)-methyl 2-[2-(4-[2,2,2-trifluoroethoxy]-pyrimidin-2-y1-acetoximino-m ethyl)phenyl]- -3-methox propenoate (Compound No 417 of Table I).

2,2,2-Trifluoroethanol (51.3ml) in DMF (135ml) was added to a suspension of sodium hydride (29.5g) in DMF (335ml) keeping the temperature below 10°C. After 1 hour the resulting mixture was added to a solution of 2,4-dichloropyrimidine (lOOg) in DMF (330ml) keeping the temperature between -5 and -10°C. 1 Hour later the resulting reaction mixture was poured into water (11) and extracted with ethyl acetate (3x400ml). The combined extracts were washed with brine, dried and concentrated to give 70% pure 2-chloro-4-(2,2,2-trifluoroethoxy)-pyrimidine (142g) as a pale orange oil; --H NMR (270 MHz): δ 4.78(2H,q), 6.83(lH,d), 8.42(lH,d) ppm.

The 2-chloro-4-(2,2,2-trifluoroethoxy)-pyrimidine (142g) in toluene (330ml) was added to trimethylamine (140ml of a 45% aqueous solution) at

0°C. After stirring for 16 hours the organic phase was separated off. The aqueous phase was added to toluene (330 ml) then _ ^* solution potassium cyanide (44g in 170ml water) was added at 0°C. The reaction mixture was stirred for a further 16 hours and then the organic phase was separated, the aqueous was extracted with ether (2x200ml) and the combined organic extracts were dried and concentrated to give 2-cyano-4-(2,2,2-trifluoro- ethoxy)-pyrimidine (73.5g, 77% yield) as a yellow oil; -*H NMR (270MHz): δ 4.85(2H,q), 7.10(lH,d), 8.64(lH,d) ppm.

Methyl magnesium bromide (115ml of a 3.0 M solution in ether) was added to 2-cyano-4-(2,2,2-trifluoroethoxy)-pyrimidine (70.Og) in THF (300ml) at -40°C. After the addition it was stirred for Vk hours at -40°C then treated with water (50ml), followed by enough 2M hydrochloric acid to make the reaction mixture just acid, this was stirred for Vk hours and then neutralised with sodium bicarbonate, and extracted with ether (3x300ml). The combined ether extracts were dried and concentrated to give 2-acetal-4- -(2,2,2-trifluoroethoxy)-pyrimidine (66.8g, 88% yield) as a brown oil; IR maxima (film): 1718 cm ^"1 ; ^l NMR (270 MHz): δ 2.74(3H,s), 4.92(2H,q), 7.05(lH,d), 8.74(lH,d) ppm.

2-Acetal-4-(2,2,2-trifluoroethoxy)-pyrimidine (0.47g) was dissolved in a mixture of ethanol (10ml) and water (5ml) and heated to 40°C for 1 hour with hydroxylamine hydrochloride (0.16g) and sodium acetate (0.43g). The reaction mixture was poured into water and extracted with ethyl acetate (3x50ml). The combined extracts were dried and concentrated. The residue was washed with hexane to give 2-acetal-4-(2,2,2-trifluoroethoxy)- pyrimidine oxime (0.35g, 70% yield) as a white solid, m.p. 179-181°C; ^* H NMR (270 MHz): δ 2.39(3H,s), 4.87(2H,q), 6.88(lH,d), 8.60(lH,d) ppm.

A solution of 2-acetal-4-(2,2,2-trifluoroethoxy)-pyrimidine oxime (0.347g) in DMF (5ml) was added dropwise to a stirred suspension of sodium hydride (0.035g) in DMF (5ml). 1% Hours later, the reaction mixture was cooled to 0°C and a solution of (E)-methyl 2-[2-(bromomethyl)phenyl]-3- -methoxypropenoate (0.4g) in DMF (5ml) was added dropwise. After 24 hours the mixture was poured in water and extracted with ethyl acetate (x3). The organic extracts were washed with brine, dried, concentrated and chromatographed using ethyl acetate:hexane 4:1 as the eluant to give the title compound (0.3g, 49% yield) as a white solid, m.p. 90-92°C; IR maxima (nujol mull): 1696, 1636 cm ^"1 ; -H NMR (270 MHz): δ 2.35(3H,s), 3.68(3H,s), 3.82(3H,s), 4.85(2H,q), 5.31(2H,s), 6.82(lH,d), 7.18(lH,m), 7.34(2H,m), 7.55(lH,m), 7.59(lH,s), 8.64(lH,d) ppm.

EXAMPLE 12 This Example illustrates the preparation of (E),(E)-methyl 2-[2-(4-N-dimethylpyrimidin-2-yl-acetoximino-methyl)phenyl]- 3-methoxypropen oate (Compound No 499 of Table I).

2-Acetyl-4-(2,2,2-trifluoroethoxy)-pyrimidine (1.48g, prepared as in Example 11) was heated to reflux in acetone (20ml) containing 2M hydrochloric acid (4ml) for 30 minutes. Qn cooling a white crystalline product, 2-acetyl-pyrimidin-4-one (0.49g, 53% yield), was filtered off and dried m.p. 199°C; IR maxima (nujol mull); 2925, 1705, 1653 cm ; ^l R NMR (270 MHz): 2.68(3H,s), 6.66(lH,d), 8.04(lH,d), 10.6(lH,brs) ppm.

2-Acetyl-pyrimidin-4-one (3.6g) was heated to reflux with phosphoryl chloride (50ml) for 20 minutes. After cooling, the reaction mixture was concentrated and the residue treated with iced water, which was neutralized with sodium bicarbonate, and extracted with ether. The combined ether extracts were dried and concentrated to give 2-acetyl-4- -chloropyri idine (2.2g, 54% yield) as a pale brown solid m.p. 65-67°C; IR maxima (nujol mull): 1714 cm ^"1 ; ^l E NMR (270 MHz): δ 2.79(3H,s); 7.53(lH,d), 8.81(lH,d) ppm.

A solution of 2-acetyl-4-chloropyrimidine (l.Og) in ether was cooled to 0°C whilst dimethylamine gas was bubbled through. After the solution had been saturated with dimethylamine it was left for 16 hours, then poured into water and extracted with ethyl acetate. The combined extracts were dried and concentrated to give a brown gum which was chromatographed using ethyl acetate as the eluant to give 2-acetyl-4-N-dimeth lamino pyrimidine (0.47g, 44% yield) as a white solid m.p. 80°C; ^l H NMR (270 MHz): δ 2.70(3H,s), 3.18(6H,brs), 6.49(lH,d), 8.35(lH,d) ppm.

A solution of 2-acetyl-4-N-dime h lamino pyrimidine (0.47g), hydroxylamine (0.75g) and sodium acetate (l.Og) in methanol (70ml) was heated to reflux for Vk hours. The reaction mixture was concentrated, treated with water, and extracted with ethyl acetate. The combined extracts were dried and concentrated to give 2-acetyl-4-N-dimethylamino pyrimidine oxime (0.38g, 74%) as a pale brown solid m.p. 206°C; --H NMR (270 MHz): δ 2.36(3H,s), 3.14(6H,brs), 6.38(lH,d), 8.25(lH,d) ppm.

A solution of 2-acetyl-4-N-dimethylamino pyrimidine oxime (0.38g) in DMF (5ml) was added dropwise to a stirred suspension of sodium hydride (O.lg) in DMF (10ml). 2-_* Hours later the reaction mixture was cooled to 0°C and a solution of (E)-methyl 2-[2-(bromomethyl)-phenyl]-3-methoxy propenoate (0.6g) in DMF (10ml) was added dropwise. After a further 2-ι-

hours the mixture was poured into water and extracted with ethyl acetate. The organic extracts were washed with brine, dried, concentrated and chromatographed using ethyl acetate as the eluant to give the title compound (0.36g, 44% yield) as a clear oil; -H NMR see Table II.

EXAMPLE 13

This Example illustrates the preparation of (E), (E)-methyl 2-[2-(2,4- -dichlorophenoxymethyl-acetoximinomethyl)phenyl]-3-methoxypr openoate (Compound No. 692 of Table I).

(E)-Methyl 2-[phthalimidooxymethyl phenyl]-3-methoxypropenoate (1.57g) (prepared as described in Example 4 of EP 0463488) was dissolved in methanol (50ml) at room temperature, hydrazine hydrate (0.214g,) added and the resulting solution stirred for 2 hours. The white precipitate which formed was filtered off and the solvent removed to give a white semi-solid. This was diluted with ether, the white solid filtered off and the filtrate evaporated to give (E)-methyl 2-[2-aminooxymethylphenyl]-3-methoxy- propenoate (0.94g, 93%) as a yellow oil which was used immediately in the next stage without further purification.

A mixture of (E)-methyl 2-[2-aminooxymethylphenyl]-3-methoxypropenoate

(0.94g), 2,4 dichlorophenoxyacetone (0.87g) and pyridine (0.8ml) in methanol (10ml) and water (2ml) was stirred at room temperature for 24 hours. The solution was poured into water (300ml) and extracted with diethyl ether (3x200ml). The etheral extracts were washed with 2N HCl and

NaHCO-, dried and the solvent removed to give a yellow gum. This was purified by flash column chromoatography eluted with n-hexane:diethyl ether

2:1 to give the title compound (0.157g, 9% yield) as a yellow gum; H NMR see Table II.

A fraction (0.629g, 36% yield) was also obtained which was a mixture

1 (6:7) of the title compound and the corresponding (Z), (E) isomer; H NMR

(270 MHz): δ 1.97(3H,s); 3.66(3H,s); 3.80(3H,s); 4.58(2H,s); 5.04(2H,s);

6.85(lH,d); 7.05-7.20(2H,m); 7.30-7.46(4H,m); 7.57(lH,s) ppm.

EXAMPLE 14

The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (No. 1 or 2) in 4 cm diameter minipots. The test compounds were formulated either by bead milling with aqueous Dispersol T or as a solution in acetone or acetone/ethanol which was diluted to the required concentration immediately before use. For the foliage diseases, the formulations (100 ppm active

ingredient) were sprayed onto the foliage and applied to the roots of the plants in the soil. The sprays were applied to maximum retention and the root drenches to a final concentration equivalent to approximately 40 ppm a.i. in dry soil. Tween 20, to give a final concentration of 0.05%, was added when the sprays were applied to cereals.

For most of the tests the compound was applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant was inoculated with the disease. Exception to this were the test on Erysiphe graminis in which the plants were inoculated 24 hours before treatment, and in the test against Puccinia recondita for compounds Nos. 310, 329 and 398-506, the plants were inoculated with the disease 48 hours before treatment. Foliar pathogens were applied by spray as spore suspensions onto the leaves of test plants. After inoculation, the plants were put into an appropriate environment to allow infection to proceed and then incubated until the disease was ready for assessment. The period between inoculation and assessment varied from four to fourteen days according to the disease and environment.

The disease control was recorded by the following grading :

4 = no disease

3 __ trace-5% of disease on untreated plants

2 = 6-25% of disease on untreated plants

1 __ 26-59% of disease on untreated plants

0 = 60-100% of disease on untreated plants

The results are shown in Table III.

TABLE III

Compound Table Pr Egh Egt Sn Po Tc Vi Ca Pv Pil No No

TABLE III (continued)

Compound Table Pr Egh Egt Sn Po Tc Vi Ca Pv Pil No No

TABLE III (Continued)

Compound Table Pr Egh Egt Sn Po Tc Vi Ca Pv Pil No No

TABLE III (Continued)

Compound Table Pr Egh Egt Sn Po Tc Vi Ca Pv Pil No No

TABLE III (Continued )

Compound Table Pr Egh Egt Sn Po Tc Vi Ca Pv Pil No No

st st

St St

CM CM st st

TABLE III (Continued)

Compound Table Pr Egh Egt Sn Po Tc Vi Ca Pv Pil

No No

TABLE III (Continued)

Compound Table Pr Egh Egt Sn Po Tc Vi Ca Pv Pil No No

a = 10 ppm foliar spray only b _. _= _1._2. ppppmm ccoommbbiinneedd ffoolliiaarr ssp.r.a-.y., .a_.n.d root drench c = 100 ppm foliar application only

Key to Diseases

Pr Puccinia recondita Tc Thanetophorus cucumeris

Egh Erysiphe graminis hordei Vi Venturia inaequalis

Egt Erysiphe graminis tritici Ca Cercospora arachidicola

Sn Septoria nodorum Pv Plasmopara viticola

Po Pyricularia oryzae Pil Phytophthora infestans lycopersici

CHEMICAL FORMULAE (as in description)

,

CHEMICAL FORMULAE FOR COMPOUNDS IN TABLE I

Compound 307 is

Compound 325

Compound 379

Compound 385 is

Compound 408

Compound

Compound 581 is

Compound 583 is

Compound

Compound 588 is

Compound 673 is

Scheme 1.

(XIII) X — R - CN (XIV)

- 74 -