TW200302051A - Fungicides - Google Patents

Abstract

The use as a plant fungicide of a compound of the general formula (I): wherein R is H, halo, C1-8 alkyl or cyano; X and Y are independently halo, C1-8 alkoxy, C1-8 alkylthio, aryloxy, arylthio, heteroaryloxy, heteroarylthio, aryl(C1-4)-alkoxy, heteroaryl(C1-4)alkoxy, aryl(C1-4)alkylthio, heteroaryl(C1-4)alkylthio, C1-8 alkylamino, C2-8 alkenylamino, C2-8 alkynylamino, di(C1-8)alkylamino, d(C2-8)-alkenylamino, di(C2-8)alkynylamino, C2-8 alkiinyl(C2-8)alkynylamino C2-8 alkenyl-(C1-8)alkylamino or C2-8 alkenyl(C1-8)alkylarnino arylamino, aryl(C1-8 alkyl)amino, heteroarylamino, heteroaryl(C1-8 alkyl)amino, aryl(C1-4)alkylamino, aryl(C1-4)alkyl-(C1-8 alkyl)amino, heteroaryl(C1-4)alkylamino, heteroaryl(C1-4)alkyl (C1-8 alkyl)amino, morpholino or pipendino, or Y is hydroxy. Provided that when X is C1-8 alkoxy, aryloxy, morpholino or piperidino, R and Y are not both halo; any of the foregoing alkyl, alkenyl, alkynyl, aryl, heteroaryl, morpholino or piperidino groups or moieties being optionally substituted. Also included are plant fungicidal compositions containing these compounds and many of the compounds themselves.

Description

(1) 200302051, description of the invention (the description of the invention should state: the technical field, the prior art, the content, the embodiments, and the drawings of the invention are described briefly) The present invention relates to certain substitutions used as plant fungicides ^ 1,2,4-triazolo [1,5 -a] pyrimidine compounds. The invention also relates to plant fungicidal compositions containing these compounds and to various compounds themselves.

It is known from patent references that a variety of substituted s-1,2,4-triazolo [1,5-a] pyrimidines can be used to control phytopathogenic fungi. Examples of related patent publications include EP-A-0071792, EP-A-0550113, US 5593996, EP-A-

08345 13, WO 94/20501, WO 98/46607, WO 98/46608, WO 99/48893, EP-A-0945453, WO 99/41255, US 5985 883, US 5986135, US 6242451, and US 625 53 09. Other substituted sl, 2,4-triazolo [l, 5-a] pyrimidines are described in GB-A-1 148629 and by G. Makisumi in Chemical and Pharmaceutical Gazette (Tokyo), ΐ961, 9,80 1-808 & 808- 814. These other triazolopyrimidines have been reported for use in animals with a coronary vessel relaxation effect (GB-A-1 148629) or as a potent anticancer agent (Υ. Makisuma). The present invention relates to the provision of additional substituted sl, 2,4-triazolo [l, 5-a] pyrimidines are used as plant fungicides. According to the present invention, a compound of general formula (1) is provided as a plant fungicide: β Υ

Wherein R is fluorene, halogen atom, Ci8 alkyl group or cyano group; X and γ are halogen atom, alkoxy group, Ci8 alkylthio group, aryloxy group, arylthio group, heteroaryloxy group 200302051 _ (2) Invention Description Continued, heteroarylthio, aryl (CV4) alkoxy, heteroaryl (ualkoxy, aryl ((: 丨 _4) alkthio, heteroaryl (Ci.4) alkthio Group, cv8 alkylamino group, c2.8 alkenylamino group, C2.8 alkynylamino group, di (Cu) alkylamino group, di (c2_8) alkenylamino group, di (c2.8) alkynyl group Amine, c2.8 alkenyl (c2.8) alkynylamino, c2.8 alkynyl (Cl.8) alkylamino or c2_8 alkenyl (c ^) alkylaminoarylaryl, aryl (Ci.salkyl) amino, heteroarylamino, heteroaryl (c ^ alkyl) amino, aryl (c ^) alkylamino, aryl (cv4) alkyl (Ci. 8alkyl) amino, heteroaryl (C1-4) alkylamino, heteroaryl (Cy) alkyl (CV8alkyl) amino, morpholinyl or piperidinyl or Y is hydroxyl, but when When X is (^ _8 alkoxy, aryloxy, morpholinyl or piperidinyl, R and Y may not both be halogen atoms; the aforementioned alkyl, alkenyl, alkynyl, aryl, heteroaryl, morpholine Or piperidinyl One or a part thereof may be substituted as necessary. One aspect of the present invention provides a compound of general formula (I) for use as a plant fungicide, wherein R is hydrogen, a halogen atom, a Cm alkyl group or a cyano group; X and Y are respectively Halogen, Ci.8 alkoxy, Ci.8 alkylthio, aryloxy, arylthio, heteroaryloxy, heteroarylthio, aryl (CV4) alkoxy, heteroaryl (CV4 ) Alkoxy, aryl (CV4) alkylthio, heteroaryl (CV4) alkylthio, Ci_8 alkylamino, C2_8 dilute amino, C2.8 fast amino, di (Ci-8) Alkylamino, arylamino, aryl (Ci-8 alkyl) amino, heteroarylamino, heteroaryl (c ^ alkyl) amino, aryl (CV4) alkylamino, Aryl (CV4) alkyl (c8 alkyl) amino, heteroaryl (Cm) alkylamino or heteroaryl (Ci_4) alkyl ((: 8 alkyl) amino or Y is hydroxyl , Morpholinyl, or piperidinyl, but when X is not a halogen atom, R and Y may not both be functional atoms; the aforementioned alkyl, alkenyl, alkynyl, aryl, heteroaryl, morpholinyl, or piperidine Either or part of the base may be 200302051 (3) Description of the invention Continuation pages are replaced as necessary. Don't provide compounds of general formula (I) used as plant fungicides, where R is H, halogen atom, CV8 alkyl or cyano; X is halogen atom, C ^ 8 alkylthio, arylthio, heteroaryloxy Group, heteroarylthio group, aryl ((^. 4) alkylthio group, heteroaryl (Ci.4) alkenylthio group, Cualkenylamino group, 02.8 dilute amino group, c2_8 alkynylamine Base, di (Ci.8) alkylamino, arylamino, aryl (Ci-8alkyl) amino, heteroarylamino, heteroaryl (c! -8alkyl) amino, Aryl (CV4) alkylamino, aryl (cv4) alkyl (CV8 alkyl) amino, heteroaryl (Ci.4) alkylamino or heteroaryl (Ci-4) alkyl (Ci -8 alkyl) amine group; and Y is a halogen atom, a hydroxyl group, a Ci-8 alkoxy group, a Ci.8 alkylthio group, an aryloxy group, an arylthio group, a heteroaryloxy group, a heteroarylthio group, an aryl group (Cm ) Alkoxy, heteroaryl (〇V4) alkoxy, aryl (CV4) alkylthio, heteroaryl (Ci-4) alkylthio, Ci-8 alkylamino, C2-8 alkenylamine , C2_8 alkynylamino, di (Cn) alkylamino, arylamino, aryl (Ci.8alkyl) amino, heteroarylamine, heteroaryl (C! -8 alkyl) Amine, aromatic (CV4) alkylamino, aryl ((ν4) alkyl (CV8alkyl) amino, heteroaryl (Ci.4) alkylamino or heteroaryl (〇v4) alkyl (Cn alkyl ) Amino, morpholinyl, or piperidinyl; any of the aforementioned alkyl, alkenyl, alkynyl, aryl, heteroaryl, morpholinyl, or piperidinyl, or a portion thereof, may be substituted as necessary. " The compounds of the present invention contain one or more asymmetric carbon atoms and may exist as enantiomers (or as diastereomeric pairs) or as a mixture thereof. However, these mixtures can be separated into individual isomers or pairs of isomers, and the present invention encompasses such isomers and mixtures thereof in various proportions. It is expected that for any given compound, the fungicidal activity of one isomer will be higher than the other. -10- 200302051 _, 4, I Description of the invention Continuation page Unless stated otherwise, the alkyl and alkyl portions of alkoxy, alkylamino, etc. are suitable to contain 1 to 6 typically 1 to 4 carbon atoms in a straight chain Or branched chain form. Examples include methyl, ethyl, n- and iso-propyl, n-, second-, iso- and third-butyl n-pentyl and n-hexyl. Appropriate substituents of the alkyl group and the alkyl portion include, for example, a halogen atom, a hydroxyl group, a Ci_4alkoxy group, and a Ci_4alkoxy (C ^ 4) alkoxy group. When the substituent is a halogen atom as necessary, the haloalkyl group or a part thereof is typically a trichloromethyl group or a trifluoromethyl group. Alkenyl and alkynyl moieties also suitably contain 1 to 6 typically 1 to 4 carbon atoms in the form of a straight or branched chain. Examples are propenyl, 2-methacryl and propynyl. Optionally, the substituent includes a halogen atom typically a fluorine such as 2,2,2-trifluoro-1-methylethyl. Halogen atoms include fluorine, chlorine, bromine and iodine. The most common are fluorine, chlorine or bromine. Aryl is usually phenyl, but also includes naphthyl, anthracenyl, and phenanthryl. Heteroaryl is typically a 5- or 6-membered aromatic ring containing one or more 0, N or S heteroatoms, which may be fused to one or more other aromatic or heteroaromatic rings such as a benzene ring. For example, thienyl, sulfanyl, oh 17 groups, heterophilic sigma group, sigma sigma group, sultan sigma group, oh sigma group. Rice sigma group, trisigma group, isothiosigma group, tetrasalyl group, thiadiazolyl group, pyridyl group, pyrimidinyl group, pyridoyl group, datalyl group, triphenyl group, benzofuranyl group, benzo Thienyl, dibenzofuranyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, indolyl, quinolinyl, quinolinyl and, if appropriate, N oxides thereof. Either aryl or heteroaryl is optionally substituted with one or more of such substituents typically present in a pesticide composition. Existing substituents include one or more of the following: _atomic, meridian, sho-11-200302051 I Description of the invention Sequelyl, alkyl (especially methyl and ethyl), c2_6 alkenyl (especially propenyl), C2-6 alkynyl (especially propynyl), Cu alkoxy (especially methoxy), c2_6 alkenyl (especially propyleneoxy), c3_6 alkynyl (especially propynyloxy), halogen (c ^ ) Alkyl (especially trifluoromethyl), halo (Ci-6) alkoxy (especially trifluoromethoxy), <: alkanylthio (especially methylthio), hydroxy ((: 1- 6) Alkyl, € 1-4 alkoxy ((: 1-4) alkyl, CV4 alkoxy (Ci-4) alkoxy, C3-6 cycloalkyl, C3_6 cycloalkoxy (C 丨 · 4) alkyl, Optionally substituted aryl (especially substituted phenyl if necessary), optionally substituted heteroaryl (especially substituted pyridyl or pyrimidinyl if necessary), optionally substituted aryloxy (especially Optionally substituted phenoxy), optionally substituted heteroaryloxy (especially substituted pyridyloxy or pyrimidinyloxy), optionally substituted arylthio (especially optionally Instead of phenylthio), optionally substituted heteroarylthio (especially substituted pyridinethio or pyrimidinylthio), optionally substituted aryl (ChJ alkyl (especially substituted if necessary) Benzyl, optionally substituted phenethyl and optionally substituted phenyl-n-propyl), optionally substituted heteroarylalkyl (especially substituted arodinyl- or pyrimidinyl (( ^ · 4) Alkyl), optionally substituted aryl (C2-4) alkenyl (especially substituted styryl if necessary), optionally substituted heteroaryl (C2_4) alkenyl (especially selected Requires substituted pyridyl vinyl or pyrimidinyl vinyl), optionally substituted aryl (Ci.4) alkoxy (especially substituted benzyloxy and phenethyloxy), and optionally Substituted heteroaryl (Ci-4) alkoxy (especially substituted pyridyl- or pyrimidinyl (C! _4) alkoxy if necessary), optionally substituted aryloxy (ChJ alkyl (specially Phenoxymethyl), optionally substituted heteroaryloxy (Ci-4) alkyl (especially substituted pyridineoxy-12-200302051发明 I Invention Description Continued

-Or pyrimidinyloxy (C14) alkyl), optionally substituted aryl (C ^ 4) alkylthio (especially substituted benzylthio and phenylethylthio), if necessary Substituted heteroaryl (C i _4) alkylthio (especially substituted pyridyl- or pyrimidinyl (Cl _4) alkylthio), substituted arylthio (C 1-4) alkyl if necessary (Specific phenylthio-methyl), optionally substituted heteroarylthio (Ci_4) alkyl (specifically substituted pyridinethio- or pyrimidinylthio (Ci.4) alkyl), 醯Oxygen, including C i _4 alkoxyl (especially ethoxyl) and benzyloxy, cyano, isocyano, thiocyanate, isothiocyanate, nitro, -NR, R ", -NHCOR ', -NHCONR'R", -CONR'R ", -COOR', -C02R ', -0S02R ,, -COR', -CR, = NR, or -N = CR, R ,, Where R, and R "are hydrogen, C4 alkyl, halo (CV4) alkyl, CV4 alkoxy, halo ((^ _4) alkoxy, CV4 alkylthio, 0: 3-6 cycloalkyl, C3.6 cycloalkyl (CV4) alkyl, phenyl or benzyl, phenyl and benzyl can be optionally substituted with halogen atom, Ci_4 Or (: Bu 4 alkoxy substituted.

Substituents which may be present in the aryl ring or heteroaryl ring of any of the aforementioned substituents include one or more of the following: halogen atom, mesityl group, M group, Ci_4 alkyl group, 02.4 diaryl group, (32_4 Alkynyl, (1; 1.4 alkenyloxy, €: 2.4 alkenyloxy, €; 3-4 alkynyloxy, halo- (Cm) alkenyl, halo- (Ci_4) alkenyloxy, Cb4 thiol, halo (Cm) alkylthio, hydroxy (CV4) alkyl, CV4 alkoxy (CV4) alkyl, C3.6 cycloalkyl, C3-6 cycloalkyl (CV4) alkyl, alkoxy, phenoxy, Benzyloxy, benzamyloxy, cyano, isocyano, thiocyanate, isothiocyanate, nitro, NR, R ,,, -NHCOR ,, -NHCONR'R ", -CONR ' R ,,, -COOR ,, -C02R ,, -0S02R ,, -COR ,, -CR, = NR, or -N = CR, R "where R 'and R" are as defined above. -13-200302051 _ m I Description of the Invention Continued R is typically H, a halogen atom or an h alkyl group. Usually it is a fluorenyl group or a gas. When one of X or Y is an aryloxy group, an arylthio group, a heteroaryloxy group, or a heteroarylthio group , Aryl (Ci_4) alkoxy, heteroaryl (Ci_4) alkoxy, aryl (CV4) alkylthio, heteroaryl ((^-4) alkylthio, Amino, aryl (Ci-8 alkyl) amino, heteroaryl amino, heteroaryl (Ci-8 alkyl) amino, aryl alkyl amino, aryl (CV4) alkyl ( When Ci-8 alkyl) amino, heteroaryl (Cm) alkylamino or heteroaryl (C4) alkyl (C ^ alkyl) amine, the other is suitable for halogen atom, cv8 An oxy group, a Ci-8 alkylthio group, a Cn alkylamino group, a di (Cn) alkylamino group, or an example of Y is a hydroxyl group.

Another aspect of the present invention provides a compound of general formula (I) for use as a plant fungicide, wherein R is H, halogen atom, Ci-8 alkyl group or cyano group; X is halogen atom, Cu alkoxy group, CV8 alkylthio group, Ci .8 alkylamino or di (Cn) alkylamino and Y is aryloxy, arylthio, heteroaryloxy, heteroarylthio, aryl (CV4) alkoxy, heteroaryl (Cm ) Alkoxy, aryl (CV4) alkylthio, heteroaryl (Cm) alkylthio, Ci.8 alkylamino, C2-8 alkenylamino, C2.8 alkynylamino, di (C ^ ) Alkylamino, arylamino, aryl (Ci.8alkyl) amino, heteroarylamino, heteroaryl (Cmalkyl) amino, aryl (Cm) alkylamino, Aryl (cv4) alkyl (CV8alkyl) amino, heteroaryl (Ci_4) alkylamino, heteroaryl (Ci.4) alkyl (C ^ alkyl) amino, morpholinyl or piperazine Pyridyl; any of the aforementioned alkyl moieties may be optionally substituted with an atom, and any of the aforementioned aryl or heteroaryl radicals may be optionally substituted with an i atom, a Ci_4 alkyl group, a cv4 alkoxy group, and a halogen (cv4) Alkyl, halo (Ci-4) alkoxy, cyano, nitro, amine, CV4 alkylamino, or di (cv4) A substituted amino group. In this regard, R is typically a halogen atom or a Ci_4 alkyl group and X 200302051_, I. Description of the Invention Continued Typical is a halogen atom (particularly bromine), a C! _4 alkoxy group or a Ci_4 alkylthio group. Aryl is usually phenyl and heteroaryl is, for example, pyridyl, pyrimidinyl, thienyl or imidazolyl. Typical γ is CV4 alkylamino, halo (cv4) alkylamino, c2_4 alkylamino, halo (C2_4) alkylamino, C2_4 alkylamino, _ (C2-4) alkylamino, Benzyloxy, benzylamino, heteroaryl (CV3) alkylamino, where the heteroaryl moiety is, for example, pyridyl, thienyl or imidazolyl, and the phenyl and heteroaryl moieties of the T group are as required Substituted with a halogen atom, ci_4 alkyl group, C i_4 alkoxy group, halo (cv4) alkyl group, ^ (Cn) alkoxy group, cyano group, or nitro group. Yet another aspect of the present invention provides a compound of general formula (I) for use as a plant fungicide, wherein R is H, halogen atom, OV8 alkyl or cyano; X is aryloxy, arylthio, heteroaryl Oxy, heteroarylthio, aryl (Ci.4) alkoxy, heteroaryl (CV4) alkoxy, aryl (Cy) alkylthio, heteroaryl ((: 1-4) alkylthio Group, C ^ .8 alkylamino group, C2.8 dilute amino group, C2_8 alkynylamino group, di (Ci_8) alkylamino group, arylamino group, aryl (Ci-8 alkyl) amino group , Heteroarylamino, heteroaryl (cv8 alkyl) amino, aryl (CV4) alkylamino, aryl (Ci-4) alkyl (Ci_8 alkyl) amino, heteroaryl (Ci -4) alkylamino or heteroaryl (Ci · 4) alkyl (cv8alkyl) amino; and Y is a halogen atom, hydroxyl, cv8alkoxy, Ci.8alkylthio, alkylamino Or di (Ci.8) alkylamino groups; any of the aforementioned alkyl moieties may be optionally substituted with halogen atoms, and any of the aforementioned aryl or heteroaryl groups may optionally be substituted with halogen atoms, Cr4 alkyl Radical, c4alkoxy, halo (Cl_4) alkyl, halo (Cm) alkoxy, cyano, nitro, amino, Ci_4 alkyl Or a di (CN4) alkylamino group. In this regard, R is typically a halogen atom or a CN4 alkyl group and Y is typically a halogen atom (especially chlorine), a hydroxyl group, a Ci-4 alkylamino group, or a halogen (Ci-4) alkylamino. Aromatic 200302051 ㈧ 发明, I Description of the invention The continuation group is usually phenyl, and the heteroaryl group is, for example, pyridyl, pyrimidinyl, thienyl, or imidazolyl. Typical X is phenylthio Or heteroarylthio, where the heteroaryl moiety is, for example, pyridyl, thienyl, or imidazolyl, and the phenyl and heteroaryl moieties are optionally substituted with a halogen atom, Ci_4 alkyl group, Ci_4 alkoxy group, halogen ( Cm) alkyl, i (C 丨 _4) alkoxy, cyano, or nitro substitution. In another aspect, the present invention provides compounds of general formula (I) for use as plant fungicides, where R is an _ atom ( (Eg gas); X is phenoxy, phenylthio, heteroaryloxy (such as pyridyloxy and pyrimidinyloxy), heteroarylthio (such as pyridylthio and pyrimidinylthio), morpholinyl, or piperidine And Y is C i .8 alkylamino, c2_8 alkenylamino, 02.8 alkynylamino, di (cv8) alkylamino, di (C2_8) alkenylamino, di (C2_8) alkynylamino, c2.8alkenyl (c2_8) alkynylamino c2.8alkynyl ((ν8) alkylamino or c2.8alkenyl (Cn) alkylamino); Any one, or part of, alkenyl, alkynyl, benzyl, heteroaryl, morpholinyl, or piperidinyl, or a part thereof may be substituted as necessary. Atoms, especially fluorine, are typically substituted by alkyl, alkenyl, and alkynyl Groups; and halogen atoms (such as gas and fluorine), Ci-4 alkyl, halogen (Ci-4) alkyl (such as trifluoromethyl), Ci-4 alkoxy, and halogen (Ci-4) alkoxy (Such as trifluorofluorenyloxy) and nitro are typically phenyl and heteroaryl substituents. Y is, for example, 2,2,2-trifluoro-1-methylethylamino and N-ethyl-2-methacrylamino. 'In yet another aspect, the present invention provides compounds of general formula (I) for use as plant fungicides, wherein R is a halogen atom (eg, gas); X is phenylthio, heteroaryloxy (eg, pyridyloxy and Pyrimidinyloxy) or heteroarylthio (such as pyridylthio and pyrimidinylthio); and Y is a halogen atom (such as gas); any of the aforementioned phenyl or heteroaryl moieties may be substituted, such as by the above paragraph The substituent is -16-200302051 description of the invention (Continued). The invention also includes such novel compounds of general formula (I). As such in yet another aspect, the present invention provides a compound of general formula (I) in which R is hydrogen, halogen atom, (V8 alkyl or cyano group; X and y are halogen atom, Cu alkoxy group, and Ci_8 thio group respectively. , Aryloxy, arylthio, heteroaryloxy, heteroarylthio, aryl (Cm) alkoxy, heteroaryl (CV4) alkoxy, aryl (Cl_4) alkylthio, heteroaryl ((V4) alkylthio, CV8 alkylamino, C2.8 alkenylamino, C2_8 alkynylamino, di (c ^) alkylamino, arylamino, aryl ((^ _ 8 Alkyl) amino, heteroarylamino, heteroaryl (CV8 alkyl) amino, aryl (CV4) alkylamino, aryl (〇v4) alkyl (CV8 alkyl) amino, hetero Aryl (CV4) alkylamino or heteroaryl (C14) alkyl (C1-8 alkyl) amino or Y is hydroxyl, morpholinyl or piperidinyl, but when X is not a halogen atom , R and Y may not both be a halogen atom, and any one or a part of the aforementioned alkyl, alkenyl, alkynyl, aryl, heteroaryl, morpholinyl, or piperidinyl may be substituted as necessary; when When X is bromine and R is fluorenyl, Y is not diethylamino or 3- (diethylamino) -propylamino; when X is chlorine and R When it is methyl, Y is not benzylamino; and when X is bromine or chlorine and R is fluorene or fluorenyl, Y is not chlorine or hydroxyl. More particularly, the invention includes a compound of formula (I), wherein R Is fluorene, halogen atom, Ci-8 alkyl group or cyano group; X is halogen atom, Ci.8 alkylthio group, arylthio group, heteroaryloxy group, heteroarylthio group, aryl group 4) alkylthio group, heteroaryl group (Ci_4) alkylthio, alkylamino, C2.8 alkenylamino, C2.8 alkynylamino, di (C "8) alkylamino, arylamino, aryl (( ^ · 8 alkyl) amino, heteroarylamino, heteroarylalkyl) amino, aryl (C! -4) alkylamino, aryl (CV4) alkyl ((: b 8 alkyl Alkyl) amino, heteroaryl (Cm) alkylamino or hetero200302051 (Π) Description of the invention continued on aryl (Ci-4) alkyl (cv8alkyl) amino; and γ is a halogen atom, a hydroxyl group, (^ _8 alkoxy, CV8 alkylthio, aryloxy, arylthio, heteroaryloxy, heteroarylthio, aryl ((^-4) alkoxy, heteroaryl (Cl_4) alkane Oxy, aryl (Cm) alkylthio, heteroaryl (Ci_4) alkylthio, (8 alkylamino, C2-8 alkenylamino, c2.8 alkynylamino, di (c ^) Alkylamino, arylamino, aryl (Ci-8alkyl) amino, heteroarylamino, heteroaryl (Ci.8alkyl) amino, aryl (Ci_4) alkyl Amine, aryl (CV4) alkyl (Ci-8alkyl) amino, heteroaryl (Ci-4) alkylamino or heteroaryl (Ci-4) alkyl (CV8alkyl) amino , Morpholinyl, or piperidinyl; any of the foregoing alkyl, alkenyl, alkynyl, aryl, heteroaryl, morpholinyl, or piperidinyl groups or a portion thereof may be optionally substituted; but when X is When bromine and R are methyl, Y is not diethylamino or 3- (diethylamino) -propylamino; when X is gas and R is methyl, Y is not benzylamino; and when X is When it is bromine or chlorine and R is fluorene or methyl, Y is not gas or hydroxyl. The present invention also includes a compound of general formula (I), wherein R is a halogen atom (such as chlorine); X is a phenoxy group, a phenylthio group, a heteroaryloxy group (for example, 'such as pyridyloxy and pyrimidinyloxy), Arylthio (such as pyridylthio and pyrimidinylthio), morpholinyl, or piperidinyl; and fluorene is CV8 alkylamino, C2.8 alkenylamino, C2_8 alkynylamino, di (Cy) alkane Diamino, di (C2.8) alkenylamino, di (C2_8) alkynylamino, C2.8 alkenyl (C2.8) alkynylamino C2_8alkynyl (CV8) alkylamino or C2_8 Alkenyl (C ^) alkylamino; any one of the aforementioned alkyl, alkenyl, alkynyl, benzyl, heteroaryl, morpholinyl, or piperidinyl or part thereof may be substituted as necessary. Li atom, especially fluorine, is a typical substituent of alkyl, alkenyl and alkynyl; halogen atom (such as chlorine and fluorine), CV4 alkyl, halogen (Cm) alkyl (such as trifluoromethyl " Ci-4 alkoxy And halogen (Ci-4) alkoxy (such as trifluoromethoxy) -18-200302051 Description of the invention Continued (12) and nitro is a typical substituent of benzyl and heteroaryl. Y is for example 2, 2,2-trifluoro-1-methylethylamino and N-ethyl-2-methylpropylamino. The invention further includes a compound of general formula (I), wherein R is a halogen atom (e.g. Chloro); X is phenylthio, heteroaryloxy (such as pyridyloxy and pyrimidinyloxy) or heteroarylthio (such as pyridylthio and pyrimidinylthio); and Y is a halogen atom (such as chlorine); the foregoing Either of the phenyl or heteroaryl moieties may be substituted as desired, for example with the substituents described in the previous paragraph.

Further definitions of the aforementioned compounds of general formula (I) with regard to their use as fungicides (including the stated ordinary, typical, appropriate and exemplary values) are equally applicable to the compounds of the present invention. The compounds forming part of the invention are exemplified in Table 1 below. The compounds have the general formula (I), and the values of R and X and Y are listed in the table.

Table 1 Compound RXY melting point mass ion number (° C) (Μ7Μ + Γ) 1 ch3 Br NHCH (CH3) 2 270 2 ch3 Br nhch2cf3 310 3 ch3 S-4-F-phenylCl 295 4 ch3 S-5- CHr Imidin-2-yl OH 328 5 ch3 sch3 NHCH2CF3 278 6 ch3 S-4-F-phenylNHCH (CH3) 2 oil 318 7 ch3 I OH 277 8 Cl Br Cl 267 9 ch3 Br OCHr2,4,6- Fr Phenyl 202-4 374 -19- 200302051 I Description of Invention Continued

10 ch3 Br NHCH2-4-F-phenyl 338 11 ch3 Br Morinyl 299 12 ch3 Br pyridyl 297 13 ch3 Br OCHr3-CF3-phenyl 388 14 ch3 Br OCHrF5-phenyl410 15 ch3 Br OCHr4-CN- Phenyl 345 16 ch3 Br 0CHr3-N02-phenyl 365 17 ch3 Br NH (CH2) 3-imidazol-1-yl 338 18 ch3 Br NHCH2-pyridin-2-yl 321 19 ch3 Br NHCH2CeCH 268 20 ch3 Br NHCHr thiophene- 3-yl 326 21 Cl S-4-F-phenyl C1 22 Cl D than fluorenyl (S) -NHCHCH3CF3 127 23 Cl pyridyl n (c2h5) (ch2c (ch3) = ch2) 133 24 Cl S-5- CHr Amidin-2-yl Cl 25 Cl Morinyl (S) -NHCHCH3CF3 Amorphous 351 26 Cl Morpholine n (c2h5) (ch2c (ch3) = ch2) Amorphous 337 27 Cl S-3-N02-benzene Cl 28 Cl 04-F-phenyl (S) -NHCHCH3CF3 156 29 Cl 0-4-F-phenyl N (C2H5) (CH2C (CH3) = CH2) 90 30 Cl S-3,4,5-F3 -Benzyl Cl 218 31 Cl 0-3,4,5-F3-phenyl (R) -NHCHCH3CF3 128 32 Cl 0-3,4,5-F3-phenyl n (c2h5) (ch2c (ch3) = ch2 ) 169 33 Cl S-2-N02-phenyl Cl -20- 200302051 Description of the invention continued 34 Cl 0-2-N02-phenyl (S) -NHCHCH3CF3 amorphous 403 35 Cl 0-2-N02-phenyl N (C2H5) (CH2C (CH3) = CH2) Amorphous 489 36 Cl S-4-MeO-phenyl Cl 37 Cl O-4-MeO-phenyl (S) -NHCHCH3CF3 388 38 Cl O-4-MeO-phenyl N (C2H5) (CH2C (CH3) = CH2) 374 39 Cl 0-2-pyridyl Cl 282 40 Cl 0-2-D than ydoyl (s) -nhchch3cf3 359 41 Cl 02-pyridyl N (C2H5) (CH2C (CH3) = CH2) 345 42 Cl S-2- F-phenylCl 43 Cl 0-2-F-phenyl (S) -NHCHCH3CF3 376 44 Cl 0-2-F-phenyl n (c2h5) (ch2c (ch3) = ch2) 362 45 Cl S-2- CH3-phenylCl 46 Cl 0-2-CH3-phenyl (S) -NHCHCH3CF3 372 47 Cl 0-2-CH3-phenylN (C2H5) (CH2C (CH3) = CH2) 358 48 Cl S-2, 6-Fr phenyl Cl 49 Cl 0-2,6-F2-phenyl (S) -NHCHCH3CF3 394 50 Cl 0-2,6-F2-phenyl N (C2H5) (CH2C (CH3) = CH2) 380 51 Cl 0-2,4,6-F3-phenyl (s) -nhchch3cf3 185 52 Cl 0-2,4,6-Fr phenyl N (C2H5) (CH2C (CH3) = CH2) 203 53 Cl 0-1 -Czeki (s) -nhchch3cf3 408 54 Cl 0-1-Czeki N (C2H5) (CH2C (CH3) = CH2) 394 55 Cl O2-Me0-5-Br-phenyl (S) -NHCHCH3CF3 466 56 Cl 0-2-Me0-5-Br-phenyl N (C2H5) (CH2C (CH3) = CH2) 452 57 Cl S-2-MeO-phenyl (S) -NHCHCH3CF3 123

-21-200302051 _ I Description of Invention Continued

58 Cl S-2-MeO-benzyl N (C2H5) (CH2C (CH3) = CH2) 101 59 Cl S-phenyl (S) -NHCHCH3CF3 374 60 Cl S-phenyl N (C2H5) (CH2C (CH3) = CH2) 360 61 Cl 〇-2-CF3-phenyl (S) -NHCHCH3CF3 442 62 Cl 0-2-CF3-phenylN (C2H5) (CH2C (CH3) = CH2) 101 63 Me Morinyl (S ) -NHCHCH3CF3 64 Me Morpholinyl N (C2H5) (CH2C (CH3) = CH2) 65 Me S-3-N02-phenyl Cl 66 Me 0-4-F-phenyl (S) -NHCHCH3CF3 67 Me 0- 4-F · phenyl N (C2H5) (CH2C (CH3) = CH2) 68 Me S-3,4,5-F3-phenyl Cl 69 Me 0-3,4,5-Fr phenyl (R)- NHCHCH3CF3 70 Me 0-3,4,5-F3-phenyl N (C2H5) (CH2C (CH3) = CH2) 71 Me S-2-N02-phenyl Cl 72 Me 0-2-N02-phenyl (S ) -NHCHCH3CF3 73 Me 0-2-N02-phenyl N (C2H5) (CH2C (CH3) = CH2) 74 Me S-4-MeO-phenyl Cl 75 Me O-4-MeO-phenyl (S)- NHCHCH3CF3 76 Me O-4-MeO-phenyl N (C2H5) (CH2C (CH3) = CH2) 77 Me 0-2-¾ ° ¾ Cl 78 Me 0-2-Homosigma (S) -NHCHCH3CF3 79 Me 0-2-sigma stilbyl N (C2H5) (CH2C (CH3) = CH2) 80 Me S-2-F-phenyl Cl 81 Me 0-2-F-phenyl (S) -NHCHCH3CF3 -22- 200302051 Invention Description Continued 82 Me 0-2-F-phenyl N (C2H5) (CH2C (CH 3) = CH2) 83 Me S-2-CH3-phenyl Cl 84 Me 0-2-CH3-phenyl (S) -NHCHCH3CF3 85 Me 0-2-CH3-phenyl N (C2H5) (CH2C (CH3) = CH2) 86 Me S-2,6-F2-phenyl Cl 87 Me 0-2,6-F2-phenyl (s) -nhchch3cf3 88 Me 0-2,6-F2-phenyl N (C2H5) ( CH2C (CH3) = CH2) 89 Me 0-2,4,6-F3-phenyl (S) -NHCHCH3CF3 90 Me 0-2,4,6-Fr phenyl n (c2h5) (ch2c (ch3) = ch2 ) 91 Cl pyridyl (S) -NHCHCH3CF3 92 Cl pyridyl N (C2H5) (CH2C (CH3) = CH2) 93 Cl O-2-MeO-phenyl (S) -NHCHCH3CF3 94 Cl O-2-MeO-benzene N (C2H5) (CH2C (CH3) = CH2) 95 Cl 0-2,4,5-F3-phenyl (S) -NHCHCH3CF3 96 Cl 0-2,4,5-F3-phenylN (C2H5) (CH2C (CH3) = CH2) 97 Cl S-2,4,5-F3-phenyl (S) -NHCHCH3CF3 98 Cl S-2,4,5-F3-phenyl N (C2H5) (CH2C (CH3) = CH2) 99 Cl S-2,4,6-F3-phenyl (S) -NHCHCH3CF3 100 Cl S-2,4,6-F3-phenyl n (c2h5) (ch2c (ch3) = ch2) 101 Cl 0-2,6-F2-phenylNHCH (CH3) 2 102 Cl 〇2,4,6-F3-phenylNHCH (CH3) 2 103 Cl 〇_2-CzechylNHCH (CH3) 2 104 Cl 0- 2-Me0-5-Br-phenylNHCH (CH3) 2 105 Cl S-2-MeO-phenylNHCH (CH3) 2

-23-200302051 _ (17) I Description of invention 106 C1 S-phenylNHCH (CH3) 2 107 C1 0-2-CF3-phenylNHCH (CH3) 2 108 C1 Morinyl NHCH (CH3) 2 109 C1 S-3-N02-phenylNHCH (CH3) 2 110 C1 0-4-F-phenylNHCH (CH3) 2 111 C1 S-3,4,5-Fr PhenylNHCH (CH3) 2 112 C1 0- 3,4,5-F3-phenylNHCH (CH3) 2 113 C1 S-2-NCV phenylNHCH (CH3) 2 114 C1 〇-2-N02-phenylNHCH (CH3) 2 115 C1 S-4- MeO-phenylNHCH (CH3) 2 116 C1 O4-Me0-phenylNHCH (CH3) 2 Compounds of formula (I) can be prepared as shown in the following reaction schemes 1 to 6, where R is as defined above and L is a leaving group. For example, a halogen atom. γ is shown as ORrNHRpNHR ^, NR2R3, or NR3R4; and χ is shown as ORl, SR1, SR2, or NR1R2. The values of R1, Han2, R3, and 114 are derived from the definitions of X and γ listed above. Hanning's base is N, N-

As shown in Reaction Figure 1, the compound where Y is an amine linkage substituent (Π) where R is a fluorenyl group can be prepared via a compound of the general formula (III) and a suitable first-order amine RiNHz or second-order HNH, which is convenient It is prepared by reacting in a solvent such as Dimethyfene 'at about 0 ° C in the presence of Hanning base. The compound of the general formula (III) can be prepared by treating the compound of the general formula (IV) with a phosphine gas under reflux conditions. Compounds of formula (IV) can be prepared by treating compounds of formula (V) with liquid bromine at room temperature, e.g., glacial acetic acid. Compounds of general formula (V) where R is methyl are commercially available. -24- 200302051 Description of the invention continued (18) Compound (VI) where Y is a 0-linked substituent can be prepared by reacting a compound of formula RrL with a compound of general formula (IV) in the presence of a suitable base as shown in Reaction Figure 2. Compound (VII) in which X is an S-bonded substituent and Y is an amine-bonded substituent, as shown in Reaction Figure 3, can be treated by, for example, filling a compound of general formula (VIII) with chloroform, followed by treatment with an amine R2NH2. preparation. The compound of the general formula (VIII) can be prepared by reacting the compound of the general formula (IV) with a thiol of the general formula RJH.

The compound (IX) in which X is an S-linked substituent and Y is an amine-linked substituent, as shown in Reaction Figure 4, can also be prepared by reacting a compound of the general formula (II) with a formula R2SH thiol. Compound (XI) in which X is a bridging substituent and Y is an amine-bonded substituent, as shown in Reaction Figure 5, can be obtained by vaporizing a compound of general formula (X) using, for example, phosphine gas, followed by the use of an amine R2R3NH in DMF. Prepared by processing. Compounds of general formula (X) can be prepared by reacting a compound of general formula (IV) with a phenol of formula RiOH in the presence of a suitable base such as KF4K2C03.

The compound (XIII) in which X is an N-bridged substituent and Y is an amine-linked substituent, as shown in Reaction Scheme 6, can be chlorinated by using a compound of general formula (XII), for example, phosphonium chloride, followed by amine R3R4NH in DMF Prepared by processing. The compound of the general formula (XII) can be prepared by reacting the compound of the general formula (IV) with an amine of the formula R3R4NH in DMF. -25-200302051 (19) Description of the invention Continuation page Reaction diagram N,

N (V)

OH

巳 2

OH

N CI (IV)

Br R ί ^ ΝΗ2 NHR,

1,/

Scheme 2 OH

Br

Ri-L, alkali

R

Br

OH

OH

R 2 \ NH

(VII)

Br

R2SH

R 1, NH

-26- (IX) (20) 200302051 Reaction Figure 5

OH

Br R ^ H

Reaction Diagram OH

Br Invention Description Continued OH R2, N, R3

9H

R. ^ NH

Ν ο, (XI

R 1 / RIN R

R 1 / RIN R Other compounds of the general formula (I) can be prepared from marketed 5-methyl-iso-triazolo [l, 5-a] pyrimidin-7-ol (compounds here R Is methyl) or prepared using compounds (II), (III), (IV), (VI) or (VIII) as intermediates. In addition, a reference method can be prepared from the intermediate described by Y. Makisumi in Chemical Pharmacopoeia (Tokyo), 9,801-808 & 808-814. The compound of formula (I) is an active fungicide that can be used to control one or more of the following pathogens: rice and wheat Pyricularia oryzae (Magnap (mhe grisea) and other Pyricularia genera of other hosts; wheat Puccinia tdticina ( Or recondita)], Puccinia striifoirmis and other rust fungi, Barley Puccinia hordei, Puccinia hordei and other rust fungi, and other hosts (such as turf, rye, Rust fungi in coffee, pear, apple, peanut, beet, vegetables, and ornamental plants; Erysiphe cichoracearum in gourds (such as melon); barley, wheat, rye, and Trichoderma graminearum

-27- 200302051 (21) I Description of Invention Continued

[Blumeria (or Erysiphe) graminis] and other hosts of various powder molds such as hops (Sphaerotheca macularis), gourds (such as cucumber) [Sphaerotheca fusca (Sphaerotheca fuliginea)], Tomato, eggplant and green pepper Leveillula taurica, Apple's Podsphaera leucotricha and Grape's Uncinula necator; cereals (eg wheat, barley, rye), turf Cochliobolusspp., Helminthosporium spp., Drechslera spp. (Pyrenophora spp.), Rhynchosporium spp., And other hosts [Mycosphaerella graminicola (Septoria tritici)] and small dark bulb shell [Phaeosphaeria nodorum (Stagonospora nodorum or Septoria nodorum)], Pseudocercosporella herpotrichoides and Gaeumannomyces graminis; cocoa sporara Cercosporidium personatum and other hosts such as sugar beet, banana, soybean and rice Cercospora; tomato, strawberry, vegetable, grape and other host Botrytis cinerea (Gray mold) and other suitable and other Botrytis; vegetables (such as carrots), oilseed rape, apples, tomatoes, Nicotiana, tadpoles (such as wheat) and other hosts of Alternaria; apple, pear, stone fruit, woody stone fruit and other hosts of Venuria spp. (Including Venturia inaequalis ) (Spot disease)); certain hosts include cereals such as wheat and tomato Cladosporiumspp .; stone fruits, woody stone fruits and other hosts' Monilinia spp .; tomatoes, turf, wheat , Meng Lu and other hosts of Didymella spp .; Oil-28- 200302051 (22) Description of the invention continued page

Seed rape, turf, rice, potato, wheat and other hosts Phoma spp .; wheat, wood and other hosts Aspergillus spp. And Aureobasidium spp. ; Ascochyta spp .; Wandou, wheat, barley, and other hosts; Apple, pear, onion, and other hosts [Stemphylium spp. (Pleospora spp ·); summer diseases of apples and pears [For example, bitter rot (Glomerella cingulata), black rot or insect eye disease, leaf spot Botryosphaeria obtusa, brook spot disease (Mycosphaerella pomi), western Apple rust (Gymnosporangium juniperi-virginianae), black spot disease (Gloeodes pomigena), small spot disease (Schizothyrium pomi), and white record disease (Vitis vinifera) Botryosphaeria dothidea))]; Plasmopara viticola of grapes; other downy mildews such as Bremia lactucae of lettuce, soybean, Peronospora and other hosts spp.) Pseudoperonospora humuli (Pseudoperonospora humuli) and Pseudoperonospora cubensis (Pythium spp.) Of turf and other hosts (including Pythium ultimum); potatoes and plants % Of Phytophthora infestans and Phytophthora infestans in vegetables, grasses, pears, peppers, ornamentals, tobacco, cocoa and other hosts; rice and turf Thanatephorus cucumeris and others Hosts (eg wheat and barley, peanuts, vegetables, cotton and turf) other Rhizoctonia spp .; turf, peanuts, potato, oilseed rape and other host Sclerotinia spp. ·); Turf, Peanut-29- 200302051 (23) Description of Inventions Continued

Sclerotium spp. And other hosts; Gibberella fujikuroi of rice; hosts in a certain range include turf, coffee and vegetables Colletotrichum spp .; Laetisaria fuciformis of turf ; Mycosphaerella spp .; Banana, peanut, citrus, American walnut, papaya, and other hosts; citrus, soybean, melon, pear, lupin, and other hosts; Diaporthe spp .; citrus , Elsinoe spp., Grape, Coriandrum, American walnut, Rose, and other hosts; Verticillium spp., A range of hosts including flax seeds, potatoes, and tomatoes; oil Seed rape and other hosts of Pyrenopeziza spp .; Oncobasidium theobromae, the cocoa that causes the vascular bundle to wither; and various hosts but special wheat,

Fusarium spp ·, Typhula spp ·, Microdochium nivale, Ustilago spp., Urocystis spp., Tilletia spp ·, and Ergot ( Claviceps purpurea); Beet, barley, and other hosts, Ramularia spp .; diseases of special fruits after harvesting [such as Penicillium digitatum, Penicillium italicum ) And Trichoderma viride (Colletotrichum musae and Gloeosporium musarum) and Botrytis cinerea]; other pathogens of grapes are worthy of note: Eutypa lata, grapes Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, Pseudopeziza tracheiphila, and Stereum hirsutum; other pathogens of trees -30- 200302051 Description of the invention Continued (24) Bacteria (such as Lophodermium seditiosum) or other pathogenic bacteria of wood worth mentioning is Cephaloascus fragrans Long. Ceratocystisspp., Ophiostomapiceae, Penicillium, Trichoderma pseudokoningii, Trichoderma viride, Trichoderma harzianum 'Aspergillus niger, Leptographium lindbergi, and Aureobasidium pullulans; and fungal vectors of viral diseases [e.g. cereals

Polymyxa graminis is used as a vector for barley yellow mosaic virus (bymv) and sugar beet polymyxa betae is used as a vector for rhizomania]. The compounds of formula (I) can be active on one or more fungi by moving to the apex, to the base, or locally on the plant tissue. In addition, the compound of formula (1) may be sufficiently volatile to be effective against one or more plant fungi.

The present invention therefore provides a method for combating or controlling phytopathogenic fungi, comprising applying a fungicidal effective amount of a compound of formula (I) or a composition containing a compound of formula ⑴ to a plant, to a plant seed, to a plant or seed location, Or to earthworm or any other plant growth medium such as a nutrient solution. The term "plant" is used here to include seedlings, shrubs and trees. In addition, the fungicidal method of the present invention includes treatment with a protective agent, a cure, a system, an eradication agent, and an anti-germination agent. The compound of formula (I) is preferably used in the form of a composition for agronomic, horticultural and turf uses. In order to apply a compound of formula (I) to a plant, to a plant seed, to a plant or -31-200302051 (25) Description of the Invention The position of the seed of the continuation sheet, or to the soil or any plant growth medium thereof, the compound of formula (I) is usually Formulated into a composition which, in addition to the compound of formula (I), includes a suitable inert diluent or carrier and optionally a surfactant (SFA). Surfactants are chemistries that can modify interfacial properties (such as liquid / solid, liquid / air, or liquid / liquid interface) by reducing interfacial tension, thereby causing changes in other properties (such as dispersibility, emulsification, and / yanth). Product. More preferably all the compositions (both solid and liquid formulations) comprise, by weight, 0 · 0 0 0 1 to 9 5%, more preferably 1 to 8 5% such as 5 to 60% of the compound of formula (I). When the composition is generally used for fungal control, the use rate of the compound of formula (1) is 0.1 g to 10 kg / ha, preferably 1 g to 6 kg / ha and more preferably 1 g to i kg / ha. When used for treating seeds, the use rate of the compound of formula (1) is from 0.0001 g to 10 g (for example, 0.001 g or 0.05 g), preferably 0.005 g to 10 g, and more preferably 0.005 per kg of seed. Grams to 4 grams. In another aspect, the present invention provides a fungicidal composition comprising a fungicidal effective amount of a compound of formula (I) and a suitable carrier or diluent. In yet another aspect, the present invention provides a method for combating and controlling fungi at a location, comprising treating the location of the fungus or fungus with a fungicidal effective amount of a composition comprising a compound. The composition can be selected from a variety of formulations including dispensable powders (DP), soluble powders (SP), water-soluble granules (SG), water-dispersible granules (WG), wettable powders (WP), granules ( Gr) (slow or fast release), soluble thickener (SL), oil-miscible liquid (0L), ultra-low volume liquid (UL), emulsifiable thickener (EC), dispersible thickener (DC), emulsion Agents (including oil-in-water (EW) and 200302051 (26) Description of the invention continued on water-in-oil (EO) emulsions), microemulsions (ME), suspension concentrates (SC), aerosols, smoke formulations, Capsule suspension (CS) and seed treatment formulation. The formulation formulation to be selected in any case will depend on the particular purpose and the physical, chemical and biological properties of the compound of formula (I).

Dispersable powder (DP) is prepared by mixing a compound of formula (I) with one or more solid diluents (such as natural clay, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, American activated clay, chalk, Diatomaceous earth, calcium phosphate, calcium carbonate and magnesium carbonate, sulfur, lime, flour, talc and other organic and inorganic solid carriers), mechanically grind the mixture into fine powder to prepare 0 soluble powder (SP). Mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate, or sulphate) or one or more water-soluble organic solids (such as polysaccharides) and optionally one or more wetting agents, one Or a mixture of dispersants or additives to improve water dispersibility / solubility. The mixture is then ground to a fine powder to prepare it. Similar components can also be granulated to form water-soluble granules (s G). φ Wettable powder (WP) is prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and preferably one or more dispersants and optionally one or more suspending agents.俾 Auxiliary dispersion in liquid. The mixture is then ground to a fine powder to prepare it. Similar compositions can be granulated to form water-dispersible granules (W G). Granules (GR) are manufactured by granulating a mixture of a compound of formula (I) and one or more powdery solid diluents or carriers, or by making a preform billet granule. Add the compound of formula (I) (or its suitable to -33-200302051) Description of the invention continued (27)

When the solution of the additive is adsorbed on a porous granular material (such as pumice, activated clay, fuller's earth, American activated white clay, diatomaceous earth, or ground corn cob); or by compound (I) ( Or its solution in an appropriate additive) is adsorbed on a hard core material (such as sand, silicate, inorganic carbonate, sulfate or phosphate) and is prepared by drying if necessary. Additives commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones, and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, pastes) Refined, sugars and vegetable oils). Granules also contain one or more other additives (such as emulsifiers, wetting agents or dispersants). Dispersible concentrates (DC) can be prepared by dissolving a compound of formula (I) in water or an organic solvent (such as a ketone, alcohol or glycol ether). The solution may contain a surfactant (for example, to improve water dilution or prevent crystallization in a spray tank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) can be prepared by dissolving a compound of formula (I) in an organic solvent (containing one or more wetting agents, one or more emulsifiers, or a mixture thereof, as needed) . Organic solvents suitable for emulsifiable concentrates include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes), such as SOLVESSO 100, SOVIS 150, and SOVIS 200; Is a registered trademark), ketones (such as cyclohexanone or methylcyclohexanone), alcohols (such as benzyl alcohol, furfuryl alcohol, or butanol), N-methylpyrrolidone (such as N-methylpyrrolidone) Or N-octylpyrrolidone), diamidamines of fatty acids (such as C 8-C! G fatty acid dimethylamine), and chlorinated hydrocarbons. Emulsifiable concentrates are made by emulsifying spontaneously when water is added, and are made with sufficient stability to allow spray application to emulsifiers with appropriate equipment. The preparation of oil-in-water emulsifiers involves -34- 200302051 (28) Description of the invention Continuing to obtain the compound of formula (I), the compound of formula (I) or liquid (if it is not liquid at room temperature, it can be typical at a reasonable temperature) Melt below 70 ° C) or as a solution (by dissolving the compound of formula (I) in a suitable solvent) and then emulsifying the resulting liquid or solution to water containing one or more surfactants under high shear to make an emulsion Agent. Suitable solvents for oil-in-water emulsions include vegetable oils, gasified hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkyls), and other suitable organic solvents with low solubility in water.

Microemulsions (ME) are produced by mixing a mixture of water with one or more solvents and one or more surfactants to spontaneously produce a thermodynamically stable isotropic liquid formulation. The compound of formula (I) is initially present in water or in a solvent / surfactant complex. Suitable solvents for microemulsions include those previously described for emulsifiable concentrates or oil-in-water emulsions. Microemulsions can be oil-in-water or water-in-oil systems (the systems that exist can be determined by conductivity measurements) and are also suitable for mixing water- and oil-soluble pesticides in the same formulation. Microemulsions are suitable for dilution in water and can maintain the microemulsion form or form conventional oil-in-water emulsions. Suspension concentrates (SC) comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). Suspension concentrates can be prepared by ball-milling or bead-milling a solid compound of formula (I) in a suitable medium and optionally containing one or more dispersants to produce a fine-particle suspension of the compound. The composition may include one or more humectants, and may include suspending agents to reduce the rate of particle settling. In addition, the compound of formula (I) may be dry-milled and added to water containing the aforementioned additives to produce a predetermined end product. Aerosol formulations include a compound of formula (I) and a suitable propellant (e.g. n-butane-35-200302051 description of the invention continued (29) alkanes). The compound of formula (I) can also be dissolved or dispersed in a suitable medium (e.g., water or a water-miscible liquid such as n-propanol) to obtain a composition for a non-pressurized manual spray pump. The compound of formula (I) can be mixed with a high-temperature technical mixture in a dry state to form a composition suitable for producing a compound-containing smoke in an enclosed space.

The capsule suspension (c S) can be prepared in a similar manner to the EW formulation, but with an additional polymerization stage, an aqueous dispersion of oil droplets is obtained, where each oil droplet is encapsulated by a polymer shell and contains the formula (I) The compound and, if necessary, a carrier or diluent. The polymer shell can be prepared via an interfacial polycondensation reaction or via a fusion procedure. The composition can be used to release the compound of formula (I) in a controlled manner and can be used for seed treatment. Compounds of formula (I) can also be formulated in biodegradable polymer matrices, providing a slow and controlled release of the compounds.

The composition includes one or more additives to improve the biological effectiveness of the composition (e.g., by improving the wettability, retention, or dispersibility of the surface; treating the surface to form raindrop resistance; or the absorption or mobility of the compound of formula (I)). These additives include surfactants, oil-based spray additives such as certain mineral oils or natural vegetable oils (such as soybean oil and rapeseed oil), and these additives and other biological property enhancing adjuvants (which can assist or modify formulas) (I) Compounds that act as compounds). The compounds of formula (I) can also be formulated for seed treatment, for example in the form of a powder composition including dry seed treatment powder (DS), water-soluble powder (SS) or slurry dispersible water dispersible powder (WS); or in a liquid composition including Flowable concentrate (FS), solution (LS) or capsule suspension (CS). DS, SS, WS, -36- 200302051 (30) Description of the Invention Continued The preparation of the F S and L S compositions is very similar to the preparation of the D P, SP, WP, SC, and DC compositions described above, respectively. Compositions for treating seeds include agents (e.g., mineral oil or film-forming barriers) that help the composition adhere to the seeds. Wetting agents, dispersants and emulsifiers can be used as cationic, anionic, zwitterionic or nonionic surfactants.

Suitable cationic surfactants include quaternary ammonium compounds (such as cetyltrimethylammonium bromide), imidazophos, and amine salts.

Suitable anionic surfactants include alkali metal salts of fatty acids, fatty acid monoester salts of sulfuric acid (such as sodium lauryl sulfate), salts of sulfonated aromatic compounds (such as sodium dodecyl benzoate, dodecyl) Phenylbenzoic acid, butylnaphthalene sulfonate and diisopropyl- and triisopropyl-naphthalenesulfonate mixtures), ether sulfates, alcohol ether sulfates (eg, lauryl-3-sodium sulfate ), Ether carboxylates (such as sodium lauryl ester 3-carboxylate), phosphate esters [one or more fatty alcohols and phosphoric acid (mainly monoesters) or with phosphorus pentoxide (mainly diesters) Reaction products, such as the reaction products of lauryl alcohol and tetraphosphoric acid; in addition, these products can be ethoxylated)], sulfosuccinates, paraffins or olefin sulfonates, taurates and lutein Esters. Suitable zwitterionic surfactants include theophylline, propionate, and glycine esters. Suitable nonionic surfactants include alkylene oxides (such as ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof) and fatty alcohols (such as oleyl or cetyl alcohol), or with alkylphenols Products (such as octyl phenol, nonyl phenol or octyl cresol); partial esters derived from long-chain fatty acids or hexitol anhydrides; Ministry-37- 200302051 Description of the Invention Continued (31) Esters and epoxy Condensation products of ethane; intercalation polymers (including ethylene oxide and propylene oxide); alkanolamines; simple esters (such as fatty acid domain ethylene glycol esters); amine oxides (such as lauryl Dimethylamine oxide) and lecithin. Suitable suspending agents include hydrocolloids (e.g. polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (e.g. bentonite or activated clay).

The compound of formula (I) can be applied by any of the known methods for applying fungicidal compounds. For example, compounds of formula (I) can be applied to any part of a plant (including leaves, stems, branches or roots), with or without formulation, to seeds before sowing, or to a medium on which the plant will grow or will be planted (such as root Surrounding loquat, generally loquat, paddy field or water-japonica cultivation system), direct application or spraying, spreading, immersion application as cream or paste formulation, vapor application or via distribution or 搀The mixed composition (such as a granular composition or a composition packaged in a water-soluble tape) is applied in a soil or an aqueous environment.

Compounds of formula (I) can also be injected into plants or sprayed on vegetative bodies using electric spraying techniques or other low volume methods, or applied by soil or air irrigation systems. The composition used as an aqueous preparation (aqueous solution or dispersion) is usually supplied as a concentrate containing a high proportion of the active ingredient, and the concentrate is added to water before use. Concentrates include DC s, SC s, EC s, EW s, M E s, SGs, SPs, WPs, WGs, and CSs, and are required to tolerate long-term storage, and added to water to form an aqueous formulation after storage can be maintained The homogenization is sufficient for a period of time for which it can be applied by conventional spray equipment. Such water-based -38-200302051 description of the invention continued (32) The preparation depends on the purpose of use, and contains unequal amounts of the compound of formula (I) (for example, 0 · 0 0 0 1 to 10% by weight). Compounds of formula (I) can be used in combination with fertilizers, such as nitrogenous, sour or fertilisers. Suitable formulations include fertilizer granules. The mixture suitably contains up to 25% by weight of a compound of formula (I). The invention therefore also provides a fertilizer composition comprising a fertilizer and a compound of formula (I).

The composition of the present invention contains other biologically active compounds, such as micronutrients, or compounds having similar or complementary fungicidal activity, or compounds having plant growth regulating activity, bactericidal, insecticidal, nematicidal, or cytotoxic activity. By including another fungicide, the resulting composition has a broader range of activity or a higher degree of specific activity than the compound of formula (I) alone. In addition, other fungicides can have synergistic synergistic effects on fungicides of compounds of formula (I).

The compound of formula (I) may be the sole active ingredient of the composition, or the compound of formula (I) may be mixed with one or more other active ingredients such as pesticides, fungicides, synergists, herbicides or plant growth regulators (Whichever is appropriate). Other active ingredients can: provide a composition with a broader range of activity or higher persistence in the location; synergistic or complementary activities of the compound of formula (I) (such as by increasing the rate of effect or overcoming exclusion) And complementary); or overcome or prevent distribution of individual components to exhibit resistance. The specific other active ingredients will be determined depending on the intended use of the composition.

Fungicidal compounds that can be included in the composition of the present invention are, for example, AC-39-200302051_ (33) Description of the invention continued on page 382042 (N- (l-cyano-1,2-dimethylpropyl) -2- (2,4-Diphenoxypropramine), acibenzolar-S-methyl, alanycarb, aldimorph, anilazine, Azaconazole, azafenidin, azoxystrobin, benalaxyl, benomyl, biloxazol , Bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan Carbendazim chloride hydrate, carboxin, carpropamid, carvone, CGA 4 1396, CGA 41397, chinomethionate, Chlorbenzthiazone, chlorothalonil, chlorozolinate, clozyl acon), copper-containing compounds such as copper chloride, copper quinolinate, copper sulfate, copper taurate and Bordeaux, cyamidazosulfamid, cyflufenamid, cyflufenamid, Cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-carboxidine disulfide 1,1 dioxide, di Dichlofluanid, diclocymet, diclomezine, dicloran, didecyl dimethyl gasification money, desophencarb (Diethofencarb), difenoconazole, difenzoquat, diflumetorim, thiolinoleic acid 0,0-di-iso-propyl-S-〒S , Dimefluazole, dimetconazole, dimeconazole 200302051 (34) Description of the Invention Continued

(dimethirimol), dimethomorph, dimoxystrobin, diniconazole, dinocap, dithianon, dodecyl Dimethylammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, Isabzan (Ethaboxam), ethirimol, (Z) -N-fluorenyl-N ([fluorenyl (methyl-thioethyleneaminooxycarbonyl) amino] sulfur)-/ 5-alanine Ethoxylate, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, Fenhexamid, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, fenben (Ferbam), ferimzone, fluazinam, fludioxonil, flumetover, and fomov lumorph), fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, and fortorani (flutolanil), flutriafol, folpet, fosetyl-ming, fuberidazole, furalaxyl, furametpyr , Guazatine, hexaconazole, mesosa, hymexazole, imazalil, imibenconazole, imicon Iminoctadine, iminoctadine triacetate, ipconazole, ippenfo-41-200302051 description of the invention continued (35)

(iprobenfos), iprodione, iprovalicarb, isopropyl butyl carbamate, isoprothiolane, kasugamycin, Kresoxim-methyl, LY 1 86054, LY2 1 1 79 5, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim ), Mepronil, metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin, beauty Metrafenone, MON65500 (N-propenyl-4,5-dimethyl-2-trimethylsilylthiophene-3-carboxamide), myclobutanil, NTN03 0 1 , Neoasozin, dimethyldithiocarbamate, nicobifen, niothale-isopropyl, nuarimol, ofurace ), Organic mercury compounds, oxadixyl, oxasulfuron, oxolinic acid, oxpo conazole), oxycarboxin, pefurazoate, penconazole, pencycuron, phenazinoxide, phenazinoxide, Europe, Picoxystrobin, polyoxin D, polyram, bobenazole, prochloraz, pomethidon ( pfocymidone), propamocarb, popamocarb hydrochloride, propiconazole, propineb, propionic acid, prothioconazole, Paracoro Zuobing (pyraci0str〇bin), -42- 200302051 Description of the invention continued (36)

Pyrazophos, Pyrifenox, Pirimethanil, Pyroquilon, Pyroxyfur, Pyrrolnitrin, Tetraammonium compound, quinomethionate, quinoxyfen, quintozene, sipconazole, sodium pentaqipanate, spirossami ( spiroxamine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, sebendazol (Thiabendazole), thifluzamide, 2- (thiocyanomethylthio) -benzothiazal, thienyl-methyl, thiram, tiadinil, timiben Timibenconazole, tolclofos-methyl, tollfluanid, triadimefon, triadimenol, triazbutil , Triazoxide, tricyclazole, tridemorph ), Trifloxystrobin, triflumizole, triforine, triticonazole, validamycin A, vapam ), Vinclozolin, XRD-563, zineb, ziram, zoxamide and compounds of the formula:

Compounds of formula (I) can be mixed with earthworm, peat, or other rooting media to protect -43-200302051 Description of the Invention Continued (37) Protect plants against fungal diseases carried in seeds, soil or leaves.

Several mixtures may contain active ingredients with significantly different physical, chemical or biological properties, and therefore it is not easy to adopt the same conventional formulation form. In this case, other formulation forms can be prepared. For example, if one active ingredient is a water-insoluble solid and the other active ingredient is a water-insoluble liquid, though, each active ingredient can be dispersed in the same continuous aqueous phase in a way that the solid active ingredient is dispersed as a suspension ( Use a formulation similar to SC), but disperse the liquid active ingredient into an emulsion (using a method similar to EW). As a result, the obtained composition was a suspension emulsion (SE) formulation. The present invention is illustrated by the following examples, in which the following abbreviations are used: ml: ml nmr = nuclear magnetic resonance g = gram DMSO = dimethyl sulfoxide ppm = parts per million parts DMF = N, N-dimethyl formic acid Amine M + = Mass ion Η PLC = High performance liquid chromatography

Example 1 This example exemplifies 5-methyl-6- > odor-7-digasethylamino-me-1,2,4-triazolo [l, 5-a] pyrimidine (compound No. 2, Table 1) Preparation stage 1 A solution of bromine (4.1 ml) in glacial acetic acid (20 ml) was added dropwise to 5-methyl-iso-triazolo [l, 5-a] pyrimidin-7-ol. (10.0 g) in glacial acetic acid (80 ml) with stirring at room temperature. After the addition was complete, the solution was stirred at room temperature for 3 hours. The solid was isolated by filtration, washed with ethanol and air-dried to obtain 5-methyl-6-bromo-h-triazolo [l, 5-a] pyrimidin-7-ol (14.8 g, 98% yield) as ash-44. -200302051 Description of Invention Continued (38) Yellow solid. β nmr5 2.40 (3H, s), 3.80 (lH, bs), 8.20 (lH, s) ppm. Phase 2

Phosphonium chloride (2.5 ml) was carefully added dropwise to 5-methyl-6-bromo-me-triazolo [1,5-a] pyrimidin-7-ol (5.0 g). After the addition is complete, the mixture is refluxed for 24 hours, cooled to room temperature and carefully poured onto crushed ice with stirring. The resulting red solution was extracted with aerosol, washed with water, dehydrated, and the solvent was removed to obtain 5-methyl-6-bromo-7-chloro-me-triazolo [l, 5-a] pyrimidine (3.60 g, 70% yield Rate) was a yellow solid. 4 nmr5 2.90 (3H, s), 8.50 (lH, s) ppm. Phase 3

2,2,2-trifluoroethylamine (3.2 mL) was added dropwise to 5-methyl-6-bromo-7-chloro · h-triazolo [l, 5-a] pyrimidine ( 2.5 g) and Haning base (2.6 ml) in anhydrous DM SO (25 ml). The reaction was stirred at room temperature for 3 days, poured into ice-cold water and extracted with ether. The ether extract was washed with water and dehydrated with anhydrous magnesium sulfate, and the ether was removed to obtain the title compound (1.35 g, 43% yield) as a yellow solid (M + = 3 10). 4 nmr (5 2.80 (3H, s), 5.00 (2H, m), 6.00 (lH, m), 8.30 (lH, s) ppm. Example 2 This example illustrates 5-methyl-6-bromo- 7-Isopropylamino-Homo · 1,2,4-trito [1,5-a] ° dense bite (Compound No. 1, Table 0 Preparation of Isopropylamine (0.7 5 ml) at 0 t Added dropwise to 5-methyl-6-mo ... 7-gas-homo-triazolo [l, 5-a] pyrimidine (1.0 g) (prepared as described in step 2 of Example 1) and Hanning base ( 1.0 ml) in anhydrous DMSO (10 ml). Reacted at -45- 200302051 Description of the invention continued (39) Stir for 2.5 hours at room temperature, pour into ice-cold water and extract with ether. Wash the ether extract with water and dry with water Dehydration of magnesium sulfate and removal of ether gave the title compound (0.7 g, 65% yield) as a yellow powder (M + = 270). IH nmr5 1.4 (6H, d), 2.7 (3H, s), 5.3 (lH, m ), 5.7 (lH, d), 8.2 (1 H, s) ppm o Example 3

This example illustrates 5-methyl-6- (4-fluoro-phenylthio) -7-isopropylamino-me-1,2,4-triazolo [l, 5-a] pyrimidine (Compound No. 6, Table 1)

5-methyl-6- > odor-7-isopropylamino-me-1,2,4-disialo [l, 5-a] pyridine (0.230 g) (as in Example 2) (Prepared as described above), a mixture of 4-fluorothiophenol (0.128 g) and anhydrous potassium carbonate (0.138 g) in ethylene glycol (6 ml) was stirred at 150 ° C. under a nitrogen atmosphere for 3 hours. The reaction mixture was cooled to room temperature, poured into ice water and extracted with ethyl acetate. The ether extract was washed with water, dehydrated with anhydrous magnesium sulfate, and the solvent was removed to obtain a yellow oil. The oil was purified by bond elution chromatography and eluted with ethyl acetate / hexane 1: 3 to obtain the title compound (0.0 3 2 G, 11% yield) as a yellow oil (M + = 318). lU nmr5 1.3 (6H? d)? 2.7 (3H, s), 5.4 (lH, m), 6.4 (lH? d)? 7.0 (4H, m), 8.3 (lH, s) ppmo Example 4 This example Illustrate 5-methyl-6- (4-fluoro-phenylthio) -7-chloro-me-1,2,4-triazolo [l, 5-a] pyrimidine (Compound No. 3, Table 1 ) In the preparation stage 15-methyl-6-bromo-h-triazolo [1,5-a] pyrimidin-7-ol (0.700 g), 4-fluorothiophenol (0.390 g) and anhydrous potassium carbonate ( 0.415 g) in ethylene glycol (5 ml) -46- 20030205j (4 °) Description of the invention Continued on page / ¾ J./D. Stir for 5 hours at 140-150 ° C under nitrogen atmosphere. The reaction mixture was cold-bathed 卩 ▽ P to room temperature, acidified to pH 1, and the solid was filtered to obtain 5-methyl-6 " * (4 -extreme thiosulfanyl) -homo-1,2,4-trisigma The hydrazine, 5-a] σ dense -7-ol, was white solid " 'The product was used in the next step without further purification. Stage 2 Poetry from the crude product of stage 1 5-methyl-6- (4-fluoro-benzylthiobenzyl_ 丨, 2,4-diazolo [l, 5-a] pyrimidine_7-ol (0 · 39g) and phosgene gas (5ml) refluxed for 23 hours and allowed to cool to room temperature. The resulting red solution was carefully poured onto crushed ice, extracted with lice-like solution, washed with water, and dehydrated with anhydrous magnesium sulfate. Removed The solvent was recovered with a red residue, which was subjected to column chromatography (silica gel, eluted with ethyl acetate / hexane 1: 1) and Η p L c (eluted with ethyl acetate / hexane 2: 5) The title compound (0.036 g) was obtained as a white solid (M + = 295). Nmr5 2.8 (3H5s), 7.〇 (2H? T), 7.2 (2H5m)? 8.5 (1H? S) ppm 〇 Example 5 The description of this example (Compound No. 22, Table 丨) in the preparation stage 1 _ bromine (4.1 liters); a solution of glacial acetic acid (6 ml) was added dropwise to Π sentence D, 2, at room temperature, 4] Triazolo U, 5-a]. A solution of amidin-5 (1H) -one (18.0 c g) in ice I (»0 ml). After the addition is complete, the solution is stirred at room temperature for 3 hours to borrow The solid was separated by filtration, washed with ethanol, and air-dried to obtain p-methyl-homo-triol, n, 5. _a] Bite · 7 • ol (192 g, 7% yield) Off-white solid: M + 1236; MP > 256t. Stage 2 6 ,; odor 1 Although all _ [1, 2, 4] Sansa And [15_ 小 密 Lake_5 (1h Bu Shio 0-47 · (41) (41) 200302051 Description of the invention continued on gram), piperidine (7 ml), potassium carbonate (5 g) in DMF (80 milligrams) On) The mixture was stirred overnight at 100 ° C. The yellow thick suspension was cooled to ambient temperature and evaporated to dryness under reduced pressure. The residue was resuspended in ethanol at 60 ° C for about 1 hour. · After filtration, the mother liquor Evaporate to dryness to obtain 6-N-pyridyl-7-hydroxy-iso- [1,2,4] trisialo [l, 5-a] pyrimido-5 (1H) -one (4.9 g, 80 〇 / 〇) as a gray-yellow solid: M "299; MP 255 ° C; nmr (D2〇) 5 7.78 (lH, s) ppm. Stage 3 Phosphonium chloride (35 ml) was carefully added dropwise to 6-N- Pyridyl-7-hydroxy-homo- · [1,2,4] triazolo [l, 5-a] pyrimidin-5 (1H) -one (3.5 g). After the addition was complete, the mixture was refluxed for 2 hours and cooled At room temperature, carefully pour onto crushed ice with stirring. The resulting red solution was extracted with ether, washed with water, dehydrated and the solvent was removed to obtain 5,7-dichloro-6pyridyl-homo -Triazolo [1,5-a] pyrimidine (3.60 g, 70% yield) as a yellow oil. M + 272; 1H nmr (CDCl3 δ 1.48-1.75 (6H, m)? 3.02-3.14 (4H? M ) 5 8.48 (lH, s) ppm 0 Stage 4 φ (S) -2,2,2-trifluoro-1-methyl-ethylamine (830 mg) was added dropwise to 70 ° C to 5,7- Bath of 2-gas-6-N-pyridyl-me-trisialo [1,5_a] pyrimidine (500 mg) in anhydrous DMF (30 mmol). The reaction was stirred for 12 hours, poured into ice-cold water and extracted with ether. The extract was washed with water, dehydrated with anhydrous sulfuric acid and magnesium, and the ether was removed to protect the title compound (448 mg, 70% yield). It was a gray-yellow solid: M + 349; M.P. 127t ° Example 6 This Preparation of Examples (Compound No. 28, Table 1)

200302051 (42) Phase 1 γΤ \ Xitong (5 6 -bromo-7 -hydroxy-iso- [1,2,4] triazolo [1,5-a] pyrimidine-5 (1 with '... I, y Zhaniheke), 4-fluoro-phenol (2g), potassium carbonate (2.5g) in DMF (50mKi), and stirred overnight at 100 ° C. The yellow thick suspension was cooled to ambient temperature 'And evaporated to dryness under reduced pressure. The residue was resuspended in ethanol at 60 ° C for about 1 hour. After filtration, the mother liquor was evaporated to dryness to obtain 6- (4-fluorophenoxy) -7-hydroxy-iso- [1 , 2,4] triazolo [l, 5-a] pyrimidin-5 (1H) -one (2.25 g, 48%) was a gray-yellow solid: M-i26, M + 1263; MP> 256 ° C; nmr (D20) (5 7.18-7.24 (4H, m), 7.85 (lH, s) ppm 〇Phase 2 Phosphonium chloride (20 ml) was carefully added dropwise to 6- (4-fluorophenoxy) -7-hydroxyl -Homo- [1,2,4] triazolo [l, 5-a] pyrimidin-5 (1H) -one (2 g). After the addition is complete, the mixture is refluxed for 3 hours, cooled to room temperature, carefully with stirring Pour onto crushed ice. The resulting red solution is extracted with diethyl ether, washed with water, dehydrated and the solvent is removed to obtain 5,7-digas-6- (4-fluorophenoxy) -h-triazolo [l, 5-a ] Pyrimidine (1.32 g, 57% yield) Yellow solid: MP 130 ° C; lH nmr (CDCl3) 5 6.74-6.78 (2H, m) * 6.94-7.04 (2H, m), 8.52 (lH, s) ppm. Stage 3 (S) -2,2, 2-trifluoro-p-methyl-ethylamine (385 g) was added dropwise to 5,7-dichloro-6- (4-fluorophenoxy) _h-triazolo [1,5-a] pyrimidine (255 mg) in anhydrous DMF (30 ml). The reaction was stirred for 12 hours, poured into ice-cold water and extracted with ether. The ether extract was washed with water and dehydrated with anhydrous magnesium sulfate. -49- 200302051 (43) Invention Description Continued

Water and ether were removed to give the title compound (286 mg, 89% yield) as a beige solid .; M, P, 156 ° C. Example 7 This example shows the fungicidal properties of the compound of formula (I). The compounds are tested on fungal diseases of various plant leaves. Adopt technology as follows. Plants are grown in John Innes Potting Compost (No. 1 or No. 2) in mini-bottles of 4 cm in diameter and 3.5 cm in depth, or in artificial cellulose-based growth media. The test compounds were prepared as acetone solutions or acetone / ethanol (1: 1 volume ratio) solutions, and the solutions were diluted to 75 or 100 ppm with reverse osmosis water just before use (in other words, 0.75 mg or 1 g of compound in a final volume of 10 ml). ) 'S concentration. Leaf spray was applied to monocotyledon crops with TWEEN 20 (0.05% volume ratio). Thun is a registered trademark. Each compound of formula (I) is applied as a leaf (Folr) (the chemical solution is applied to the leaves of the test plant by spraying the plant to the maximum droplet holding capacity); the system is applied (Syst) (10 ml of the chemical solution is rooted) Wet treatment) or stem application (chemical solution is applied to the stem of the test plant by spraying the plant until it will flow out). The test was performed on the following species: grape uniaxial mold (PLASVI) and grape hook shell (UNCINE); tomato pathogenic Phytophthora (PHYTIN) and gray grape clover (BOTRCI); apple verticillium (VENTIN ); Blumeria graminis f.sp. tritici (ERYSGT), Stagonospora nodorum (LEPTNO) and PUCCRT of wheat; and Pyricularia oryzae (PYRIOR) and Rhizoctonia 200302051 of rice (44) Description of the invention (cont. Solani) (RHIZS). Each treatment was repeated application of two or more plants to uniaxial grape, Phytophthora infestans, Phytophthora infestans, Grape vine, and Verticillium, and cellulose growth medium was used in all experiments. The test of B1 umeria graminis f.sp. tritici, crustaceans, Puccinia sclerotiorum, Rhizoctonia solani, and Pyricularia oryzae was repeated in two views, each containing 6 to 10 plants for each treatment . The plants were inoculated with a calibrated fungal spore suspension 1 or 2 days before the chemical application (E r d) or 6 hours, 1 or 2 days after the chemical application (Pr 0t). After chemical application and inoculation, the plants are cultivated in a high-humidity environment and then placed in an appropriate environment for infection until the disease is ready to be evaluated. Blumeda graminis f.sp. tdtici plants were inoculated using the "shake" inoculation technique. Grape cockleshell plants are inoculated using the "blowing" inoculation technique. As for the V. grapevine plant, it was cultured under high humidity conditions for another 24 hours before evaluation. The time between the application of the chemical and the evaluation can vary from 5 to 14 days depending on the disease and environment. However, individual compounds are evaluated for all compounds after an equal period of time. The evaluation was performed on uniaxial grape and Verticillium spp., And the evaluation was performed on a single leaf of two plants that were repeated, and each repeated plant line of Phytophthora infestans and Botrytis cinerea was performed on two leaves. Three repetitive plants of Gracilaria cuspidatum were evaluated, while cr lines were individually evaluated for a single leaf. What about Biuineria graminis f.sp. tritici a? For Dictyostelium edulis and Pyricularia oryzae, the evaluation was performed on all plants in each replicate or each of the cellulose growth media. For Rhizoctonia solani, the number of individual infected plants in two replicates was assessed. -51- 200302051 (45) Description of the invention Continued The degree of disease (in other words, the percentage of leaf area covered by active budding disease) or the percentage of infected plants per bottle is evaluated visually. For each treatment, the estimates obtained from all the repeated experiments were averaged to obtain the average disease value. Untreated control plant lines were evaluated in the same way. The following are examples of compounds showing plant fungicidal activity against one or more diseases: Table 1 Compounds 1, 2, 3, 6, 21-25, 27, 28, 30, 3 1, 33-35 °

Example 8 This example shows the fungicidal properties of the compound of formula (I). Here, the compound is tested on leaf circle fungal analysis on a variety of plants. The method is as follows. The test compound was dissolved in DMSO and diluted to 200 ppm in water.

Erysiphe graminis f.sp. hordei (Erysiphe graminis): Barley leaf segments are placed on agar in a 24-well plate and the test compound solution is sprayed. After allowing it to completely dry for 12 to 24 hours, the leaf discs were inoculated with a fungal spore suspension. After proper culture, the activity of the compound on the 4th day after inoculation was evaluated as a prophylactic fungicidal activity. Powdery mildew f.sp. tritici (Triticum aestivum): Wheat leaf segments were placed on agar in 24-well plates and the test compound solution was sprayed. After allowing it to completely dry for 12 to 24 hours, the leaf discs were inoculated with a fungal spore suspension. After proper culture, the activity of the compound on the 4th day after inoculation was evaluated as a prophylactic fungicidal activity.

Pyricularia oryzae: Rice leaf segments are placed on agar in a 24-well plate and the test compound solution is sprayed. After allowing it to completely dry for 12 to 24 hours, the leaf discs were inoculated with a fungal spore suspension. After appropriate cultivation, the activity of the compound on the 4th day after inoculation was evaluated as a prophylactic fungicidal activity. -52- 200302051 (46) Description of the invention Continued tile Botrytis cinerea (Botrytis cinerea): Round ingots of pea leaves are placed on agar in a 24-well plate and the test compound solution is sprayed. After allowing it to completely dry for 12 to 24 hours, the leaf discs were inoculated with a fungal spore suspension. After appropriate cultivation, the activity of the compound at 4 days after inoculation was evaluated as a prophylactic fungicidal activity.

Phytophthora infestans (late blight of potatoes or tomatoes): Round ingots of tomato leaves were placed on agar in a 24-well plate and sprayed with the test compound solution. After allowing it to completely dry for 1 to 2 to 4 hours, the leaf discs were inoculated with a fungal spore suspension. After proper culture, the activity of the compound on the 4th day after inoculation was evaluated as a prophylactic fungicidal activity. Uniaxial grape vine (Dampus botrytis): The grape leaves are roundly placed on agar in a 24-well plate and the test compound solution is sprayed. After allowing it to completely dry for 12 to 24 hours, the leaf discs were inoculated with a fungal spore suspension. After appropriate cultivation, the activity of the compound 7 days after the inoculation was evaluated as a prophylactic fungicidal activity.

The compounds in the following table 1 have a disease control rate higher than 60%: Trichoderma barley, compounds 22, 25, 31, 34; Trichoderma wheat, compounds 22, 25, 34, 37, 49; Rice sprouts, compounds 22, 25, 28, 29, 34, 38, 49, 57, 59; Botrytis cinerea, 26, 49, 52, 59; Botrytis cinerea, compounds 29, 35, 38, 49, 54, 55, 56, 57; Late blight , Compound 2 8; Ultimate Pythium, Compound 5 2. -53-

Claims (1)

200302051 Scope of application and patent application 1. The use of a formula (IM compound as a plant fungicide: Where R is H, halogen atom, Ci_8 alkyl group or cyano group; X and Y are halogen atom, Cm alkoxy group, Cm alkylthio group, aryloxy group, arylthio group, heteroaryloxy group, heteroarylthio group respectively , Aryl (Ci β4) alkoxy, heteroaryl (Cm) alkoxy, aryl (C1-4) alkylthio, heteroaryl (Cm) alkylthio, (: 8 alkynylamino , C2.8 dilute amino group, C2.8 alkynylamino group, di (Ci.8) alkenylamino group, di (c2.8) alkenylamino group, di (c2.8) alkynylamino group, c2_8 alkenyl (c2.8) alkynylamino, C2e8 alkynyl (Cn) alkylamino or C2_8 alkenyl (C ^) alkylaminoarylarylamine, aryl (C ^ alkyl) amine , Heteroarylamino, heteroaryl (C1-8 alkyl) amino, aryl (Ci-4) alkylamino, aryl (Cle4) alkyl ((: 8 alkyl) amino, Heteroaryl (CV4) alkylamino, heteroaryl (Ci.4) alkyl (Cmalkyl) amino, morpholinyl or piperidinyl, or Y is hydroxyl, but when X is alkoxy, In the case of aryloxy, morpholinyl, or piperidinyl, R and Y may not both be halogen atoms; any of the aforementioned alkyl, alkenyl, alkynyl, aryl, heteroaryl, morpholinyl, or piperidinyl Or part of it To be substituted 2. The use of a compound of general formula (I) as a plant fungicide as described in claim 1 in the scope of patent application, wherein R is hydrogen, halogen atom, C ^ 8 alkyl or cyano; X and Y respectively Is a halogen atom, Ci_8 alkoxy group, CV8 alkylthio group, aryloxy group, -54- 200302051 _ application for patents continued on arylthio group, heteroaryloxy group, heteroarylthio group, aryl group (CrJ alkoxy group, Heteroaryl (CVJ alkoxy, aryl (Ci_4) alkylthio, heteroaryl (C 丨 · 4) alkylthio, carbamoylamino, dilute amino, hydrazone 2-8 fastylamino, di ( C1-8) alkylamino, arylamino, aryl (C1-8alkyl) amino, heteroarylamino, heteroaryl (C1-8alkyl) amino, aryl (C! _4) alkylamino, aryl (CV4) alkyl (<: 8 alkyl) amino, heteroaryl (Ci.4) alkylamino or heteroaryl (Ci ^) alkyl (Ci .8 alkyl) amine or Y is hydroxyl, morpholinyl or piperidinyl, but when X is not a halogen atom, R and Y may not be both halogen atoms; the aforementioned alkyl, alkenyl, alkynyl, aryl Any one of, or a heteroaryl group, a morpholinyl group, or a piperidinyl group or a part thereof may be optionally substituted. 3 For example, the use of the compound of the general formula (I) as a plant fungicide in the first patent application range, wherein R is a halogen atom, a halogen atom, an alkyl group or a cyano group; X is a halogen atom, and a sulfur atom of Cu. , Arylthio, heteroaryloxy, heteroarylthio, aryl (Ci-4) alkylthio, heteroaryl (Ci-4) alkylthio, (: thioalkylamino, C2 .8 Alkylamino, Fastylamino, Di (Ci_8) alkylamino, arylamino, aryl (Ci_8alkyl) amino, heteroarylamino, heteroaryl (CV8 alkyl) Amine, aryl (Cm) alkylamino, aryl (c4) alkyl (cv8 alkyl) amino, heteroaryl (Ci-4) alkylamino or heteroaryl (C〗- *) Alkyl (Ci-8 alkyl) amino group; and Y is halogen atom, hydroxyl group, alkoxy group, Ci.8 alkylthio group, aryloxy group, arylthio group, heteroaryloxy group, heteroarylthio group , Aryl (Ci.4) alkoxy, heteroaryl (Cl_4) alkoxy, aryl (<: 丨 4) alkylthio, heteroaryl ((: 1.4) alkylthio, Alkylamino, c2_8alkenylamino, c2_8alkynylamino, di (CV8) alkylamino, arylamino, aryl (Ci-8alkyl) amino, heteroarylamine Group, heteroaryl group (Ch 200302051 _ patent application scope continued page # alkyl) amino group, aryl (Ci_4) alkyl amino group, aryl (Cy) alkyl (C ^ 8 alkyl) amino group, heteroaryl (Ί ^ _4) alkylamino or heteroaryl (ChJ alkyl (〇 ^ _8alkyl) amino, morpholinyl, or piperidinyl; the aforementioned alkyl, alkenyl, alkynyl, aryl, hetero Any of aryl, morpholinyl, or piperidinyl or a part thereof may be substituted as necessary. 4. The use of a compound of the general formula (I) as a plant fungicide as claimed in claim 1, 2 or 3, wherein R is fluorene, a halogen atom or a C ^ 4 alkyl group. 5. The use of a compound of general formula (I) as a plant fungicide, such as in the scope of application for patents 1, 2, or 3, wherein when one of X or Y is an aryloxy group, an arylthio group, a heteroaryloxy group, Heteroarylthio, arylalkoxy, heteroaryl (Ci_4) alkoxy, aryl ((: 丨 -4) alkylthio, heteroaryl ((: 丨 -4) alkylthio, aryl Amine, aryl (Ci.8 alkyl) amine, heteroaryl amine, heteroaryl (< 8 alkyl) amine, aryl (CV4) alkyl amine, aryl (Cm ) Alkyl (CV8 alkyl) amino, heteroaryl (Cm) alkylamino or heteroaryl (Ci_4) alkyl (Cn alkyl) amine, the other is preferably a halogen atom, c1-8 Benzyloxy, cv8 alkylthio, (: alkyl alkylamino, di (Ci_8) alkylamino, or hydroxyl in the example of Y. 6 · General formula (I) as in item 1 of the scope of patent application The compound is used as a plant fungicide, wherein R is H, halogen atom, Ci.8 alkyl group or cyano group; X is halogen atom, Cu alkoxy group, CV8 alkylthio group, Cu alkylamino group or di ( C ^) alkylamino and Y are aryloxy, arylthio, heteroaryloxy, heteroarylthio, aryl ((: 丨 -4) alkane Group, heteroaryl (Ci-4) alkoxy, aryl (Cm) alkylthio, heteroaryl (Ci_4) alkylthio, C ^ 8 alkylamino, C2_8 alkenylamino, C2_8 alkynyl Amine, di (CV8) alkylamino, aryl-56- 200302051 _ Application for patents continued on amine, aryl (Cu alkyl), heteroarylamine, heteroaryl (cv8 alkyl) ) Amino, aryl (Cm) alkylamino, aryl (CV4) alkyl ((V8 alkyl) amino, heteroaryl (Ci-4) alkylamino, heteroaryl) alkyl ( Ci_8 alkyl) amine, morphinyl, or 暧 σ; any one of the aforementioned radicals may be substituted with a halogen atom as needed, and any of the aforementioned aryl or heteroaryl may be optionally substituted with a halogen atom, Ci.4 alkyl, Ci_4 alkoxy, halo (Cm) alkyl, halo (CV4) alkoxy, cyano, nitro, amine, (4) alkyl amine or di (ChJ alkyl amine) 7. The use of the compound of the general formula (I) as a plant fungicide as described in claim 1 in the scope of the patent application, wherein R is fluorene, a halogen atom, (^ _8 alkyl or cyano; X is aryloxy , Arylthio, heteroaryloxy, heteroarylthio, aryl (Ci_4) Oxy, heteroaryl ((: 丨 _4) alkoxy, aryl ((^ -4) alkylthio, heteroaryl (c ^ .4) thiothio, cv8 thioamino, c2. 8 dilute amino groups, (1: 2-8 fast amino groups, bis (Ci-8) alkyl groups, aryl amino groups, aryl alkyl groups) amino groups, heteroaryl amino groups, heteroaryl groups (1_8 Alkyl) amine, aryl (CbJ alkyl amine, aryl (Ci-4) alkyl (Ci-8 alkyl) amine, heteroaryl ((V4) alkyl amine or heteroaryl ( (^ · 4) alkyl (Ci-8 alkyl) amino groups; and γ is a halogen atom, hydroxyl, cle8 alkoxy, (v8 alkylthio, cv8 alkylamino, or di (Ci.8) alkyl Amine group; any of the aforementioned alkyl moieties may be optionally substituted with || atom, and any of the aforementioned aryl or heteroaryl group may be optionally substituted with halogen atom, Cm alkyl, C1-4 alkyl , Halo (Ci_4) alkyl, halo (Ci.4) alkoxy, cyano, nitro, amine, c ^ 4 alkylamino or di (Ci-4) alkylamino. 8 · If the compound of general formula (I) in item 1 of the scope of patent application is used as a fungicide for plant killing 200302051 patent application, where R is a halogen atom; X is phenoxy, phenylthio, heteroaryloxy Group, heteroarylthio group, morpholinyl group or piperidinyl group; and Y is C if alkylamino group, [2-8 alkylamino group, [2-8 alkylamino group, di ([1.8) alkylamino group, Di (C2_8) diluted amino, di (fluorene 2-8) quickamino, C2-8 di (c2_8) alkynylamino C2_8alkynyl (Ci-8) alkylamino or C2_8 alkenyl ( Ci-8) an alkylamino group; any one of the aforementioned alkyl, alkenyl, alkynyl, phenyl, heteroaryl, morpholinyl, or piperidinyl groups or a part thereof may be substituted as necessary. 9. Use of a compound of general formula (I) as a plant fungicide, wherein R is a halogen atom; X is phenylthio, heteroaryloxy or heteroarylthio; and Y is a halogen atom; the aforementioned phenyl or Any of the heteroaryl moieties may be substituted as necessary. 10 · —Compounds of general formula (I): Where R is hydrogen, halogen atom, Ci.8 alkyl or cyano; X and Y are halogen atom, 1-8 alkoxy, CV8 alkylthio, aryloxy, arylthio, heteroaryloxy, heteroaryl Thio, aryl (Cl_4) alkoxy, heteroaryl (Cl-4), alkoxy, aryl (Ci-4) alkylthio, heteroaryl (Cm) alkylthio, CV8 Cylamino, C2.8 alkylamino, C2.8 alkylamino, bis (Cl.8) alkylamino, arylamino, aryl (Ci-8 alkyl) amino, heteroaryl Aminoamine, heteroaryl (Ci_8 alkyl) amino, aryl (Cm) alkyl amino, aryl (C! -4) alkyl (Cu alkyl) amino, heteroaryl (Ci.4 ) Alkylamino or heteroaryl (ChJ alkyl (Ci-8 alkyl) amino or Y is hydroxyl, morpholinyl or piperidine-58- 200302051 application patent continuation page; the aforementioned alkyl, alkenyl Any of alkynyl, aryl, heteroaryl, morpholinyl, or piperidinyl or a portion thereof may be optionally substituted; but when X is not a halogen atom, R and Y may not both be halogen atoms When X is bromine and R is methyl, Y is not diethylamino or 3- (diethylamino) -propylamino; when X is gas and R is methyl, Y is not Benzylamino; and when X is bromine or chlorine and R is fluorene or fluorenyl, Y is not chlorine or hydroxyl. 11. A compound of formula (I) wherein R is fluorene, a halogen atom, a CV8 alkyl group, or Cyano; X is a halogen atom, (: ^ 8 alkylthio, arylthio, heteroaryloxy, heteroarylthio, aryl ((^ · 4) alkylthio, heteroaryl (Ci-4 ) Alkylthio, C8 alkylamino, C2-8 alkenylamine, C2-8 alkynylamine, di (cv8) alkylamino, arylamino, aryl (Ci-8 alkyl ) Amine, heteroarylamino, heteroaryl (C ^ alkyl) amino, aryl (Ci-4) alkylamino, aryl (CV4) alkyl (C ^ 8alkyl) amino , Heteroaryl ((: 丨 _4) alkylamino or heteroaryl (Ci-Oalkyl (<: alkyl) amino); and Y is a halogen atom, a hydroxyl group, a Ci_8 alkoxy group, Ci.8 Alkylthio, aryloxy, arylthio, heteroaryloxy, heteroarylthio, aryl (Ci-4) alkoxy, heteroaryl (Cl-4) alkoxy, aryl (Cm) alkylthio, heteroaryl (Cm) alkylthio, Cy alkylamino, c2_8 alkenylamino, c2_8 alkynylamino, di ((ν8) alkylamino, arylamino, Aryl (C ^ s alkyl Amino group, heteroarylamino group, heteroaryl (C ^ alkyl) amino group, aryl ((: 丨 _4) alkylamino group, aryl (Ci_4) alkyl (CV8 alkyl) amino group, Heteroaryl (Ci.J alkylamino or heteroaryl (C ^) alkylalkyl) amino, morpholinyl or piperidinyl; the aforementioned alkyl, alkenyl, alkynyl, aryl, heteroaryl Any one or a part of the amino group, morpholinyl group, or piperidinyl group may be substituted as required; but when X is bromine and R is methyl, Y is not 200302051 -(Diethylamino) -propylamino; when X is gas and R is methyl, Y is not benzylamino; and when X is bromine or gas and R is fluorene or methyl, fluorene is Chlorine or hydroxyl. 12. Compounds of general formula (I) as defined in item 1 of the scope of patent application, wherein R is a halogen atom; X is phenoxy, phenylthio, heteroaryloxy, heteroarylthio, morpholinyl or piperazine Pyridyl; and hydrazone is (^ .8 alkylamino, C2.8 alkenylamino, (: 2.8 alkynylamino, di (Cn) alkylamino, di (C2.8) alkenylamino) , Di (C2.8) alkynylamino, C2.8 alkenyl (C2-8) alkynylamino C2.8alkynyl (Cn) alkylamino or C2.8alkenyl (Cn) alkylamine; Any of the foregoing alkyl, alkenyl, alkynyl, phenyl, heteroaryl, morpholinyl, or piperidinyl groups or a part thereof may be substituted as necessary. 13. General formula as defined in item 1 of the scope of patent application (I) a compound in which R is a halogen atom; X is a phenylthio group, a heteroaryloxy group, or a heteroarylthio group; and Y is a halogen atom; any of the foregoing phenyl or heteroaryl moieties may be selected as necessary A plant fungicidal composition comprising a fungicidal effective amount of a compound as defined in claim 1 of the scope of patent application and a suitable carrier or diluent thereof. 15. A method for combating or controlling phytopathogenic fungi, comprising: To plant < , Plant seeds, plant or seed location, or soil or any other plant growth medium, apply a fungicidal effective amount of a compound as defined in the scope of patent application item 1 or a composition as defined in the scope of patent application item 14 -60- 200302051 Lu, (1), the designated representative figure in this case is ... Figure _ (2), the component representative symbols of this representative figure are simply explained: 柒 'If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: