DESCRIPTION

AN AGRICULTURAL AND HORTICULTURAL DISEASE CONTROLLER AND A METHOD FOR CONTROLLING THE DISEASES

Technical Field

The present invention relates to an agricul¬ tural and horticultural disease controller containing as an active ingredient a 1,2,3-thiadiazole derivative represented by the general formula (1), or a salt thereof:

wherein Rl is Φ a hydrogen atom, © a (C1-C12)alkyl group, 0> a halo(C1-C12)alkyl group, <£> a (C2-C12)- alkenyl group, © a halo(C2~Ci2)alkenyl group, © a (C2~Ci2)alkynyl group, ® a halo(C2~Ci2)alkynyl group, © a (C3-Ce)cycloalkyl group, © an unsubstituted phenyl group, © a substituted phenyl group having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (Ci-CβJalkyl groups, halo(Cι-C6)alkyl groups, (Ci-CβJalkoxy groups, halo(Ci-Cβ)alkoxy groups, (Ci-Cβ)alkylthio groups, halo(Cι-C6)alkylthio groups, (C2-Ce)alkenyl groups and (C2~C6)alkynyl groups, © a group represented by the formula:

R3 O

I II

-(C)„,-COR5

R4

(wherein R3 and R<, which may be the same or different, are hydrogen atoms, (C ₁ -C ₁₂ )alkyl groups or halo- (Cι-Ci ₂ )alkyl groups, m is zero or an integer of 1 to 6, and R5 is a hydrogen atom; a (Cι-Ci ₂ )alkyl group; a halo(C ₁ -C ₁₂ )alkyl group; a (C ₂ -Ci ₂ )alkenyl group; a

(C ₂ -Ci ₂ )alkynyl group; an unsubstituted phenyl group; a substituted phenyl group having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (Cι-C ₆ )alkyl groups, halo(Cι-Ce)alkyl groups, (Ci-Cβ)alkoxy groups, halo(Ci-Cβ)alkoxy groups, (Ci-CβJalkylthio groups, halo(Cχ-C ₆ )alkylthio groups, (C ₂ -C ₆ )alkenyl groups and (C ₂ ~C ₆ )alkynyl groups; an unsubstituted phenyl(Ci-Cβ)alkyl group; or a substituted phenyl(Ci-Cβ)alkyl group having on the ring one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (Cι~C ₆ )alkyl groups, halo(Ci-Cβ)alkyl groups, (Ci-Cβ)alkoxy groups, halo(C ₁ -C ₆ )alkoxy groups, (Ci-CβJalkylthio groups, halo(Cι-C ₆ )alkylthio groups, (C ₂ ~C ₆ )alkenyl groups and (C ₂ ~C ₆ )alkynyl groups), © a .group represented by the formula:

I II

- ( C ) _m -CN (R6 )R7

I

R4

(wherein R3, R4 and m are as defined above, and R6 and R7, which may be the same or different, are hydrogen atoms; (C1-C12)alkyl groups; halo(C ₁ -C ₁₂ )alkyl groups; (C ₂ -Ci ₂ )alkenyl groups; (C ₂ -Ci ₂ )alkynyl groups; (Cι-Ci ₂ )alkoxy(Cι-C ₆ )alkyl groups; (Cι-Cι )alkylthio- (Ci-Cβ)alkyl groups; cyano(C ₁ -C ₁₂ )alkyl groups; unsubstituted phenyl groups; substituted phenyl groups having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (Ci-CβJalkyl groups, halo(Cι-C6)alkyl groups, (Ci-Cβjalkoxy groups, halo(Ci-Cβ)alkoxy groups, (Ci-Cβ)alkylthio groups, halo(Cι~C ₆ )alkylthio groups, (C ₂ ~C ₆ )alkenyl groups and (C ₂ -Cβ)alkynyl groups; unsubstituted phenyl(Ci-Cβ)alkyl groups; or substituted phenyl(Ci-Cβ)alkyl groups having on the ring one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (Cι~C ₆ )alkyl groups, halo(Cι-C ₆ )alkyl groups, (Cι~C ₆ )alkoxy groups, halo(Ci-Ce)alkoxy groups,

(Cι-Cβ)alkylthio groups, halo(Cι-C ₆ )alkylthio groups, (C ₂ -Cβ)alkenyl groups and (C ₂ ~C ₆ )alkynyl groups; R ^β and R7 being able to be taken together to represent a (C-j-CβJalkylene group which may contain an oxygen atom

between adjacent carbon atoms of the carbon chain), <8 group represented by the formula: R3

-(C) _n -ON=C(R6)R7

I R4

(wherein R3, R4, R6 and ^~ , and n is an integer of 1 to 6), or © a group represented by the formula:

[wherein R3, R4 and n are as defined above, A is

-0-

O

II

-OC¬

RS 0

I II

-OCH-CO-

(wherein R ⁹ is a hydrogen atom, a (Cι~Ci ₂ )alkyl group or a halo(C ₁ -C ₁₂ )alkyl group),

-S- ,

-SO- ,

-SO2-

R90 -OC IH-CII ₍ NRlO)-

{wherein R9 is as defined above, and Rio is a hydrogen atom, a (Cι-Ci ₂ )alkyl group or a halo(Cι-Ci ₂ )alkyl group, R9 and Rio being able to be taken together to represent a (C4-C6)alkylene group which may contain, between adjacent carbon atoms of the carbon chain, an oxygen atom, a sulfur atom or

N-Rii

(wherein RU is a hydrogen atom, a (Cι-Ci ₂ )alkyl group or a halo(C ₁ -C ₁₂ )alkyl group)}, or

-N(Riθ)

(wherein io is as defined above), and ^β is a hydrogen atom; a (Cι-Cχ ₂ )alkyl group; a halo(C ₁ -C ₁ 2)alkyl group; a (C ₂ ~Ci ₂ )alkenyl group; a (C2~Ci ₂ )alkynyl group; a (C ₁ -C ₁₂ )alkoxy(C ₁ -C ₁₂ )alkyl group; a (Cι~Ci ₂ )alkylthio- (Cι-Ci2)alkyl group; a cyano(C1-C ₁ 2)alkyl group; an unsubstituted phenyl group; a substituted phenyl group having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (Ci-CβJalkyl groups, halo(Ci-Cβ)alkyl groups, (Ci-Cβ)alkoxy groups, halo(Ci-Cβ)alkoxy groups, (Ci-CβJalkylthio groups, halo(C ₁ -C ₆ )alkylthio groups, (C ₂ -Cβ)alkenyl groups and (C ₂ ~C ₆ )alkynyl groups; an unsubstituted phenyl(Ci-Cβ)- alkyl group; a substituted phenyl(Cι-Cβ)alkyl group having on the ring one or more substituents which may be the same or different and are selected from the group

consisting of halogen atoms, nitro group, cyano group,

(Ci-Cβ)alkyl groups, halo(Ci-Cβ)alkyl groups, (Ci-Cβ)- alkoxy groups, halo(Ci-Cβ)alkoxy groups, (Cι~C ₆ )alkyl- thio groups, halo(Cι-C6)alkylthio groups, (C ₂ ~C ₆ )alkenyl groups and (C2-C ₆ )alkynyl groups; an unsubstituted 5- or

6-membered heterocyclic ring having one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom; or a substituted 5- or 6-membered heterocyclic ring having one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom, said substituted hetero¬ cyclic ring having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (Ci-Cβ)alkyl groups, halo(Ci-Cβ)alkyl groups, (Ci-Cβ)- alkoxy groups, halo(Ci-Cβ)alkoxy groups, (Ci-Cβjalkyl- thio groups, halo(Cι-C ₆ )alkylthio groups, (C ₂ ~C ₆ )alkenyl groups and (C ₂ ~C ₆ )alkynyl groups], and R2 is (i) a group represented by the formula:

-X-R12

[wherein X is an oxygen atom or a sulfur atom, and i is CD a hydrogen atom, © a (Cι~Ci ₂ )alkyl group, © a halo(Cι-Ci ₂ )alkyl group, Φ a (C ₂ -Ci ₂ )alkenyl group, © a halo(C ₂ ~Ci ₂ )alkenyl group, © a (C ₂ ~Ci ₂ )alkynyl group, Φ a halo(C ₂ ~Ci ₂ )alkynyl group, © a hydroxy(Ci-Cβ)alkyl

group, © a (C ₁ -C ₁₂ )alkoxy(C ₁ -C ₁₂ )alkyl group, © a

(Cι-Ci2)alkylthio(Cι-Cι ₂ )alkyl group, © a (C ₃ -C ₆ )cyclo- alkyl group, © a (C3-C6)cycloalkyl(Cι-Ci ₂ )alkyl group,

© an unsubstituted phenyl group, ® a substituted phenyl group having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group,

(Ci-Cβ)alkyl groups, halo(Ci-Cβ)alkyl groups, (Ci-Cβ)- alkoxy groups, halo(Ci-Cβ)alkoxy groups, (Cι-Ce)alkyl- thio groups, halo(Cι-Cβ)alkylthio groups, (C ₂ ~C ₆ )alkenyl groups, (C ₂ -C ₆ )al ynyl groups, and (Cτ _. -C ₆ )alkoxycarbonyl (Ci-CβJalkyloxy groups, © an unsubstituted phenyl(Ci-Cβ)alkyl group, © a substituted phenyl- (Ci-Cβ)alkyl group having on the ring one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (Ci-CβJalkyl groups, halo(Ci-Ce)alkyl groups, (Ci-Cβ)alkoxy groups, halo (Cι-Cs )alkoxy groups, (Cι-Ce)alkylthio groups, halo(Ci-Ce)alkylthio groups, (C ₂ ~C ₆ )alkenyl groups and (C2~Cβ)alkynyl groups, © a diphenyl(Cι-Ce)alkyl group, © a phenoxyfCi-Cβ)alkyl group, © a group represented by the formula:

-B-N ₍ R13)R14

{wherein B is a (Ci-Ce)alkylene group which may be substituted by a (Ci-Ce)alkyl group or a phenyl group, and 1 and *4, which may be the same or different, are hydrogen atoms; formyl groups; (C ₁ -C ₁₂ )alkyl groups;

— o —

(C ₂ ~Ci ₂ )alkenyl groups; (C ₂ ~Ci ₂ )alkynyl groups;

(Cι-C ₆ )alkylcarbonyl groups; unsubstituted phenyl groups; substituted phenyl groups having one or more substituents which may be the same or different and are selected from the group consisting of hydrogen atom, halogen atoms, nitro group, cyano group, (Cι-Cβ)alkyl groups, halo(Ci-Cβ)alkyl groups, (Cι-Cβ)alkoxy groups, halo(Ci-Cβ)alkoxy groups, (Cι-C ₆ )alkylthio groups, halo(Ci-Cβ)alkylthio groups, (C ₂ ~C ₆ )alkenyl groups and (C ₂ -C ₆ al ynyl groups; phenylcarbonyl groups; unsub¬ stituted l,2,3-thiadiazol-5-yl-carbonyl groups; or substituted l,2,3-thiadiazol-5-yl-carbonyl groups having a halogen atom or a (Ci-Cβ alkyl group as the substituent; R ¹³ and R ¹⁴ being able to be taken together to represent a (C ₄ -C ₅ )alkylene group which may contain, between adjacent carbon atoms of the carbon chain, an oxygen atom, a sulfur atom or

N-Ri

(wherein RU is as defined above)}, ® a group represented by the formula:

-C(R15)=C(R16)-R17

(wherein R" is a hydrogen atom or a (Cι-C ₆ )alkyl group, Ri6 is a hydrogen atom, a halogen atom or a (Cι-Ce)alkyl group, and R* ⁷ is a nitro group, a cyano group, a (Cι-Cβ)alkylcarbonyl group, a (Ci-Cεϊalkoxycarbonyl group, a phenylcarbonyl group, or a substituted amino-

carbonyl group having one or more substituents which may be the same or different and are selected from the group consisting of hydrogen atom, (C ₁ -C ₁₂ )alkyl groups, unsubstituted phenyl group, and substituted phenyl groups having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group,

(Cι-C ₆ )alkyl groups and (Cι-Ce)alkoxy groups, Ris and RI being able to be taken together to represent a (C ₃ - CβJalkylene group which may be substituted by one or more (Ci-CβJalkyl group and/or an oxo group), © a group represented by the formula:

(wherein two Ri ^β 's, which may be the same or different, are hydrogen atoms, (Ci-CβJalkylcarbonyl groups, phenylcarbonyl groups, unsubstituted l,2,3-thiadiazol-5- yl-carbonyl groups, or substituted l,2,3-thiadiazol-5- yl-carbonyl groups having a halogen atom or a (Ci-Cβ)- a kyl group as the substituent, and £ is zero or an integer of 1 to 12), © a 5- or 6-membered hetero- cyclic (Cι-Ce)alkyl group having one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom, © tri(Cι-C ₆ )alkylsilyl(Cι-C ₆ )alkyl groups, or ® l,2,3-thiadiazol-5-yl-carbonyloxy- (C ₁ -C ₁₂ )alkyl groups having on the ring a halogen atom or (Ci-CβJalkyl group as the substituent], (ii) a group

represented by the formula: -O-N=C(Ri9)R20

[wherein Ris and R20. which may be the same or different, are Φ hydrogen atoms, © halogen atoms, © nitro groups, ® cyano groups, © (C ₁ -C ₁₂ )alkyl groups, © halo(C ₁ -C ₁₂ )alkyl groups, φ (C ₃ -C ₆ )cycloalkyl groups, © (C ₂ -Ci ₂ )alkenyl groups, © (C ₂ ~Ci ₂ )alkynyl groups, © (Cι-Ci ₂ )alkoxy(Cι-Ci ₂ )alkyl groups, © (Cι-Ci ₂ )alkoxycarbonyl groups, © unsubstituted phenyl groups, © substituted phenyl groups having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (Cι-Cβ)alkyl groups, halo(Ci-Cβ)alkyl groups, (Ci-Cβ)alkoxy groups, halo(Ci-Cβ)alkoxy groups, (Cι~C ₆ )alkylthio groups, halo(Cι-C ₆ )alkylthio groups, (C ₂ ~C ₆ )alkenyl groups and (C ₂ -C ₆ )alkynyl groups, ® unsubstituted 5- or 6-membered heterocyclic rings having one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom, © substituted 5- or 6-membered hetero¬ cyclic rings having one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom, said substituted heterocyclic ring having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms.

nitro group, cyano group, (Cι-Cβ)alkyl groups, halo(Ci-Cβ)alkyl groups, (C ₁ -C ₆ )alkoxy groups, halo(C ₁ -C6)alkoxy groups, (Ci-Cβjalkylthio groups, halo(Cι-C6)alkylthio groups, (C ₂ ~C ₆ )alkenyl groups and (C ₂ ~C6)alkynyl groups, © groups represented by the formula;

-SR5

(wherein R ⁵ is as defined above), or © groups represented by the formula:

-N(R6)R7

(wherein R6 and R ⁷ are as defined above), i9 and R20 being able to be taken together to represent © a (C ₃ -Cβ)cycloalkane ring or ® a 5- or 6-membered heterocyclic ring containing, between adjacent carbon atoms of the carbon chain, one or more hetero atoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom], (iii) a group represented by the formula:

-N(R21 ₎ R22

[wherein R2i and R22, which may be the same or different, are φ hydrogen atoms, © (C ₁ -C ₁₂ )alkyl groups, © unsubstituted halo(C ₁ -C ₁₂ )alkyl groups, φ

substituted halo(C ₁ -C ₁₂ )alkyl groups having a hydroxyl group or a (Ci-Cβ)alkoxy group as the substituent, © (C ₂ ~Ci ₂ )alkenyl groups, © (C ₂ ~Ci ₂ )alkynyl groups, ® (C ₁ -C ₁₂ )alkoxy(Ci-Cβ)alkyl groups, © (Cι-Cχ ₂ )alkylthio- (Ci-Cβ)alkyl groups, ® cyano(C ₁ -C ₁₂ )alkyl groups, © substituted cyano(Ci-Cβ)alkyl groups having on the alkyl chain a substituent selected from the group consisting of (Ci-Cβ)alkoxy groups, (C ₂ ~C ₆ )alkenyloxy groups, (C ₂ -Cβ)alkynyloxy groups, (Cι-C ₆ )alkylthio groups, (Cι-C ₆ )alkoxycarbonyl(Cι-Cβ)alkoxy groups, (Ci-Cβ)- alkoxycarbonyl(Cι-C ₆ )alkylthio groups, phenoxy group, phenylthio group and pyrazol-1-yl group, © unsub¬ stituted carbamoyl(Cι-C ₆ )alkyl groups, © substituted carbamoyl(Cι-Cβ)alkyl groups having on the alkyl chain a substituent selected from the group consisting of (C ₁ -C ₆ )alkoxy groups, (C ₂ ~C ₆ )alkenyloxy groups, (C ₂ ~C ₆ )alkynyloxy groups, (Ci-Cβ)alkylthio groups, (Cι-C ₆ )alkoxycarbonyl(Cι-Cβ) lkoxy groups, (Ci-Cβ)- alkoxycarbonyl(Cι-C ₆ )alkylthio groups, phenoxy group, phenylthio group and pyrazol-1-yl group, © hydroxy- (Cι-Cβ)alkyl groups, ® di(Cι-C ₆ )alkoxy(Cι-Cβ)alkyl groups in which the (Ci-Cβ)alkoxy groups may be the same or different, © unsubstituted (Ci-CβJalkoxycarbonyl- (Cι-Cβ)alkyl groups, Φ substituted (Ci-CβJalkoxy- carbonyl(Cι-Cβ)alkyl groups having on the alkyl chain a substituent selected from the group consisting of (Cι-Cβ)alkyl groups, (Cι-Ce)alkoxy groups, (C ₂ -C ₆ )- alkenyloxy groups, (C ₂ -C ₆ )alkynyloxy groups, (Ci-Cβ)-

alkylthio groups, (Cι-C6)alkoxycarbonyl(Cι-C6)alkoxy groups, (Cι-C ₆ )alkoxycarbonyl(Cι-C ₆ )alkylthio groups, phenyl group, phenyl(Ci-Cβ)alkyl group, phenoxy group, phenylthio group and pyrazol-1-yl group, © unsub- stituted phenyl groups, © substituted phenyl groups having one or more substituents which may be the same or different and are selected from the group consisting of l) halogen atoms, 2) nitro group, 3) cyano group, 4) (Ci-Cβ)alkyl groups, ⁵⁾ halo(Ci-Cβ)alkyl groups, ⁶ > (Cι-C6)alkoxy groups, ⁷⁾ halo(Ci-Cg)alkoxy groups, 8 ⁾ (Cι-C ₆ )alkylthio groups, 9) halo(Cι-C ₆ )alkylthio groups, 10 ⁾ (C ₂ -C ₆ )alkenyl groups, H) (C ₂ -C ₆ )alkynyl groups, 12) (Ci-CβJalkylcarbonyl groups, 13) carboxyl group, 14) (Cι-Ci ₂ )alkoxycarbonyl groups, 15) methylenedioxy group, 16 ⁾ phenyl group, 1 ⁷⁾ groups represented by the formula:

O

II

-C-N(R23)(R24 ₎

(wherein R23 and R24, which may be the same or differ¬ ent, are hydrogen atoms; (C ₁ -C ₁₂ )alkyl groups; halo- (Cι-Ci ₂ )alkyl groups; (C ₂ ~Ci ₂ )alkenyl groups; (C ₂ -C ₁₂ )- alkynyl groups; unsubstituted phenyl groups; substituted phenyl groups having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, cyano group, nitro group, (Ci-Cβjalkyl groups and (Ci-Cε)alkoxy groups; or 5- or 6-membered heterocyclic rings containing, between adjacent carbon atoms of the carbon chain, one or more

hetero atoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom) , 18) groups represented by the formula:

-S0 -R25

(wherein R25 is a hydrogen atom, hydroxyl group, a (Cχ-Ci ₂ )alkyl group, a halo(Cι~C ₆ )alkyl group, an unsubstituted phenyl group, a substituted phenyl group having as the substituent(s) one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, (Cι-C ₆ )alkyl groups and (Ci-Cβ)alkoxy groups, unsubstituted 1,2,3- thiadiazol-5-yl group, or substituted 1,2,3-thiadiazol- 5-yl groups having halogen atom, (Ci-Cβ)alkyl group or (C ₁ -C ₆ )alkoxy group as the substituent), 19 ⁾ groups represented by the formula:

O

II

-NH-C-R25

(wherein R25 is as defined above), 20) groups represented by the formula:

O

II -NH-C-0-R26

(wherein R26 i _{s a} (Cι~C ₆ )alkyl group, a phenyl group or a phenyl(Cι-C ₆ )alkyl group), 21) groups represented by the formula:

-NH-S0 -R25

(wherein R25 is as defined above), 22) groups represented by the formula:

0

(wherein R25 i _s as defined above), and 23) groups represented by the formula:

0

(wherein R26 _s as defined above), © unsubstituted phenyl(C1-C6)alkyl groups, Φ substituted phenyl(Ci-Cβ)- alkyl groups having on the ring one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (Cι-Ce)alkyl groups, halo(Ci-Cβ)alkyl groups, (Ci-Cβ)alkoxy groups, halo(Ci-Cβ)alkoxy groups, (Ci-Cβ)alkylthio groups, halo(Cι-Ce)alkylthio groups, (C2-C6)alkenyl groups and (C2-C ₆ )alkynyl groups, © naphthyl groups, © groups represented by the formula:

-(CH ₂ ) _P NHR18

(wherein Ri ^β is as defined above, and p is an integer of 1 to 12), or © 5- or 6-membered heterocyclic rings having one or more hetero atoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom, R21 and R 2 being able to be taken together to represent © a

(C ₄ -C ₆ )alkylene group which may contain an oxygen atom between adjacent carbon atoms of the carbon chain, or Φ a diaminomethylene group], (iv) a group represented by the formula:

-N(R6)NHR27

[wherein R6 is as defined above, and R ⁷ is Φ a hydrogen atom, © a (C3.-C ₁₂ )alkyl group, © a halo- (Cι-Ci ₂ )alkyl group, Φ a (C ₂ -Ci ₂ )alkenyl group, © a (C ₂ -C ₁₂ )alkynyl group, © a (C ₁ -C ₁₂ )alkoxy(Ci-Cβ)alkyl group, Φ a (Cι-Ci ₂ )alkylthio(Cι-C ₆ )alkyl group, © a cyano(C ₁ -C ₁₂ )alkyl group, © an unsubstituted phenyl group, © a substituted phenyl group having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (Cι-Cβ)alkyl groups, halo(Cι~C ₆ )alkyl groups, (Cι-Cβ)alkoxy groups, halo(Cι~C ₆ )alkoxy groups, (Ci-Cβialkylthio groups, halo(Cι-C ₆ )alkylthio groups, (C ₂ ~C ₆ )alkenyl groups and (C ₂ -C ₆ )alkynyl groups, © an unsubstituted phenyl- (Cι-Cβ)alkyl group, © a substituted phenyl(Ci-Cβ)alkyl group having on the ring one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (Cι-Cβ)alkyl groups, halo(Cι~C ₆ )alkyl groups, (Ci-CβJalkoxy groups, halo(Ci-Cε)alkoxy groups, (Ci-Cβ)- alkylthio groups, halo(Cι-C6)alkylthio groups, (C2-C6)-

alkenyl groups and (C ₂ -C6)alkynyl groups, © a group represented by the formula:

O

II

-C-R6

(wherein R ⁶ is as defined above), ® a group represented by the formula:

0

II -C-OR6

(wherein R6 is as defined above), © a group represented by the formula:

O

(wherein R ^β and R ⁷ are as defined above), or Φ a group represented by the formula:

-SO2-R ⁶

(wherein 6 is as defined above)], (v) a group represented by the formula:

-NHN(R6)R2 ⁷

[wherein R6 and are as defined above, R6 and 2 being able to be taken together to represent

=C ₍ R28 ₎ R29

(wherein R28 and R29, which may be the same or different, are hydrogen atoms; (Ci-Cε)alkyl groups; halo(Ci-Cβ) lkyl groups; (C ₃ -C ₆ )cycloalkyl groups; unsubstituted phenyl groups; substituted phenyl groups having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, (Ci-Cβ)alkyl groups and (Cj-Cβ)alkoxy groups; or 5- or 6-membered heterocyclic rings containing, between adjacent carbon atoms of the carbon chain, one or more hetero atoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom; R28 and R29 being able to be taken together to represent a (C ₃ -C ₆ )- cycloalkane ring or a 5- or 6-membered heterocyclic ring containing one or more sulfur atoms between adjacent carbon atoms of the carbon chain), or R ^β and R ²⁷ being able to be taken together with the nitrogen atom to which they are bonded, to represent a 5- or 6-membered heterocyclic ring which may contain, between adjacent carbon atoms of the carbon chain, one or more hetero atoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom], or (vi) a group represented by the formula:

-N ₍ Rβ ₎ -OR30

(wherein R ^β is as defined above, and R30 is a hydrogen atom, a (Cι~Ci ₂ )alkyl group, a halo(C ₁ -C ₁₂ )alkyl group, a (C ₃ -C ₆ )cycloalkyl group, a (C ₂ -Ci ₂ )alkenyl group, a (C ₂ -C ₁₂ )alkynyl group, an unsubstituted phenyl(Ci-C _δ )- alkyl group, or a substituted phenyl(Ci-Cβ)alkyl group having on the ring one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (Cι-C ₆ )alkyl groups, halo(Cι-C ₆ )alkyl groups, (Ci-Cβ)- alkoxy groups, halo(Cι-C ₆ )alkoxy groups, (C _∑ -CβJalkenyl groups and (C ₂ -C ₆ )alkynyl groups).

Background Art

Japanese Patent Unexamined Publication No. 54- 9272 discloses l,2,3-thiadiazole-5-carboxylic acid derivatives, a process for production thereof and an agent containing the derivative and having herbicidal and growth-regulating effects.

Disclosure of Invention

The present inventors earnestly investigated for developing a novel agricultural and horticultural disease controller and consequently found that 1,2,3- thiadiazole derivatives or salts thereof, which include some of the compounds disclosed in USP 4177054, are useful for herbicide and growth segulater, whereby the present invention has been accomplished.

Best Mode for Carrying Out the Invention

In the definition of the substituents of the 1,2,3-thiadiazole derivative of the general formula (I) used as the active ingredient of the agricultural and horticultural disease controller of the present invention, the halogen atom includes chlorine atom, bromine atom, iodine atom and fluorine atom. The term "(Cι~Ci ₂ )alkyl group" means a linear or branched alkyl group of 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl or the like. The term "halo- (C ₁ -C ₁₂ )alkyl group" means a substituted and linear or branched alkyl group of 1 to 12 carbon atoms having as the substituent(s) one or more halogen atoms which may be the same or different. The term "(C ₂ -C ₆ )alkenyl group" means a linear or branched alkenyl group of 2 to 6 carbon atoms having a double bond. The term "halo- (C ₂ -C ₆ )alkenyl group" means a substituted and linear or branched alkenyl group of 2 to 6 carbon atoms having as the substituent(s) one or more halogen atoms which may be the same or different. The term "(C _∑ -Cβ)alkynyl group" means a linear or branched alkynyl group of 2 to 6 carbon atoms having a triple bond. The term "halo- (C ₂ -C ₆ )alkynyl group" means a substituted and linear or branched alkynyl group of 2 to 6 carbon atoms having as the substituent(s) one or more halogen atoms which may be the same or different.

The term "5- or 6-membered heterocyclic ring having one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom" means any heterocyclic ring derived from furan, thiophene, pyrrole, oxazole, thiazole, isothiazole, pyrazole, imidazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5- thiadiazole, 1,3,4-thiadiazole, 1,2,4-triazole, pyri¬ dine, pyridazine, pyrimidine, pyrazine, pynolidine, piperidine, morpholine, thiamorpholine, dithiolane, di- thian, piperazine, dioxelan, imidazolizine and the like. Preferable examples of the substituents of the 1,2,3-thiadiazole derivative of the general formula (I) used in the present invention are as follows. There is preferably used a compound in which R is a (C ₁ -C ₁₂ )- alkyl group, halo(C ₁ -C ₁₂ )alkyl group, (C ₃ ~C ₆ )cycloalkyl group, (C ₂ ~Ci ₂ )alkenyl group, halo(C ₂ ~Ci ₂ )alkenyl group, (C ₂ -C ₁₂ )alkynyl group, halo(C ₂ -Ci ₂ )alkynyl group, unsubstituted phenyl group or substituted phenyl group, and R2 is -X-R12. There is more preferably used a compound in which Ri is a (Ci-Cβ)alkyl group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl or n-hexyl, and R2 is a hydroxyl group, its salt, a thiol group, its salt, an amide group, or an anilide group.

There is most preferably used a compound in which Rl is a methyl group and R ² is a hydroxyl group, its salt, a thiol group, its salt, an amide group, or an

anilide group.

As the salt of the 1,2,3-thiadiazole derivative of the general formula (I), there can be exemplified salts with alkali metals such as sodium, potassium, etc.; salts with alkaline earth metals such as calcium, magnesium, etc.; unsubstituted ammonium salt; substituted ammonium salts having one or more substituents which may be the same or different and are selected from the group consisting of (Cι-Ci ₂ )alkyl groups, unsubstituted phenyl group, substituted phenyl groups, unsubstituted benzyl group and substituted benzyl groups; and guanidium salt.

The 1,2,3-thiadiazole derivative of the general formula (I) or salt thereof used as the active ingredient of the agricultural and horticultural disease controller of the present invention can be produced, for example, by any of the processes exemplified below:

NHCOR"

Rl ¹

Hydrolysis

⁽ IX ⁾ (VIII)

wherein R is as defined above, R' is a (Ci-CεJalkyl group, R" is an amino group or a (Ci-Cβjalkyl group, and

Hal is a halogen atom.

A compound of the general formula (XII) is reacted with a compound of the general formula (XI) to obtain a compound of the general formula (X). The compound (X) is cyclized after or without isolation to obtain a 1,2,3-thiadiazole derivative of the general formula (1-1). The derivative (1-1) is hydrolyzed after or without isolation to obtain a compound of the general formula (IX). The compound (IX) is halogenated after or without isolation, whereby the acid halide of the general formula (VIII) can be produced.

The compound of the general formula (XII) can be produced by the process described in J. Org. Chem., 43, 2087 (1978), Formation of C-C bonds. Vol. 3, p. 259, 1979 (Georg Thime Publishers, Stuttgart), etc.

From the acid halide of the general formula (VIII) produced by the above process, the 1,2,3- thiadiazole derivative of the general formula (I) or salt thereof used as the active ingredient of the agricultural and horticultural disease controller of the present invention can be produced, for example, by any of the processes illustrated below.

Production process 1 ,

(VIII) d-2)

H _N (R21)R22 (ID

H _N (R21 ₎ R22 (ID

₎ R22 (1-3)

wherein Ri, R ¹² , R2i, R22 and Hal are as defined above.

The acid halide of the general formula (VIII) is reacted with an alcohol of the general formula (III) to obtain a 1,2,3-thiadiazole derivative of the general formula (1-2). The compound (1-2) is reacted with an amine of the general formula (II) after or without isolation of the compound (1-2), whereby a 1,2,3- thiadiazole derivative of the general formula (1-3) can be produced.

The 1,2,3-thiadiazole derivative of the general formula (1-3) can be.produced also by reacting the acid halide of the general formula (VIII) with an amine of the general formula (II).

Production process 2.

( VIII ) ( 1-4 )

wherein Ri9, R20 and Hal are as defined above.

A 1,2,3-thiadiazole derivative of the general formula (1-4) can be produced by reacting the acid halide of the general formula (VIII) with a compound of the general formula (IV).

Production process 3.

(

(1-6)

wherein R ^β , R27 and Hal are as defined above.

A 1,2,3-thiadiazole derivative of the general formula (1-5) can be produced by reacting the acid halide of the general formula (VIII) with a compound of the general formula (V). Similarly, a 1,2,3-thiadiazole

derivative of the general formula (1-6) can be produced by reacting the acid halide of the general formula (VIII) with a compound of the general formula (VI).

Production process 4.

OR30 (VIII) (1-7)

wherein R ^β , R30 and Hal are as defined above.

A 1,2,3-thiadiazole derivative of the general formula (1-7) can be produced by reacting the acid halide of the general formula (VIII) with a compound of the general formula (VII). Typical compounds as the 1,2,3-thiadiazole derivative of the general formula (I) or a salt thereof are listed in Table 1 but they are not intended in any way to limit the scope of the present invention.

The abbreviations in the R column and R ² column in Table 1 stand for the following compounds:

Ph:

Q2: Q3: > Q4:

General formula (I):

Table 1

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

Note: "cyclo" means a cyclic CβHn group. - Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 1 (Cont'd)

- Cont'd -

Table 2 shows 1H-NMR data of the 1,2,3- thiadiazole derivatives having a physical property expressed by the word "oil", "paste" or "NMR" in Table 1.

Table 2

- Cont'd -

Table 2 (Cont'd)

- Cont'd -

Table 2 (Cont'd)

No 1H-NMR [CDCI ₃ /TMS, δ value (ppm)

265 4.001 (s, 3H), 6.104 (s, 2H), 7.934 (s, IH) , 8.378 (s, IH).

267 7.3-7.5 (m, 3H), 8.12 (q, 2H) 273 7.1-7.5 (m, 4H) 282 1.41 (t, 3H), 2.27 (s, 3H), 4.44 (q, 2H) , 5.88 (s, 2H), 7.2-7.6 (m, 4H) .

296 0.939 (t, 3H), 1.45 (m, 2H), 1.65 (m, 2H) , 2.970 (s, 3H), 3.82 (m, 2H) , 5.75 (d, IH) , 6.48 (d, IH). 343 1.38 (t, 3H), 2.96 (s, 3H) , 4.32 (dd, 2H), 7.47 (t, IH), 7.85 (d, IH), 8.00-8.05 (br, 2H) , 8.21 (br, IH). 355 0.86 (t, 3H), 1.46 (m, 2H) , 2.87 (s, 3H) , 3.07 (dd, 2H), 6.43 (m, IH) , 7.39 (d, 2H) , 7.97 (br, IH), 8.10 (m, IH), 9.75 (br, IH) . 360 0.92 (t, 3H), 1.36 (m, 2H), 1.51 (m, 2H) , 3.21 (dd, 2H), 6.21 (br, IH) , 7.44 (d, 2H) , 7.98 (s, IH), 8.08 (br, IH), 9.19 (br, IH) . 362 1.36 (s, 9H), 2.84 (s, 3H) , 6.05 (s, IH) , 7.34 (m, 2H), 7.81 (s, IH), 7.90 (m, IH) , 9.41 (br, IH). 369 1.03-1.21 (m, 6H), 3.19 (dd, 2H) , 3.41 (dd, 2H) , 6.87 (d, IH), 7.24 (m, 2H) , 7.73 (d, IH), 10.21 (br, IH). 371 0.89 (t, 3H), 1.20-1.70 (m, 8H), 3.24 (dd, 2H) , 6.21 (br, IH), 7.40-7.50 (m, IH) , 7.99 (s, IH) , 8.05 (br, IH), 9.01 (br, IH) . 372 2.95 (s, 3H), 7.25-7.95 (m, 7H) , 8.06-8.14 (br, 2H), 8.56 (br, IH) .

373 2.89 (s, 3H), 3.4-3.8 (br, 8H) , 7.02 (d, IH) , 7.35 (t, IH), 7.47 (br, IH), 7.87 (d, IH) , 9.53 (br, IH).

- Cont'd -

Table 2 ( Cont ' d)

The 1,2,3-thiadiazole derivatives of the general formula (I) or salts thereof according to the present invention are useful for agricultural and horti¬ cultural disease control. For example, the compounds listed in Table 1 are very effective in controlling various diseases, for instance, rice blast (Pyricularia oryzae) , rice sheath blight (Rhizoctonia solani) , rice helminthosporium leaf spot (Cochliobolus miyabeanus) , powdery mildew of various host plants, such as powdery mildew of barley and wheat (Erysiphe qraminis) , oats crown rust (Puccinia coronata) , rust of other plants, tomato late blight (Phytophthora infestans) , late blight or Phytophthora rots of other plants, downy mildew of various plants, such as cucumber downy mildew (Pseudoperonospora cubensis) and grape downy mildew

(Plasmopara viticola), apple scab (Venturia inaequalis) , apple alternaria leaf spot (Alternaria ali) , pear black

spot (Alternaria kikuchiana) , citrus melanose (Diaporthe citri) , cucumber bacterial blight (Pseudomonas syrinqae pv. lachrvmans) , tomato bacterial wilt (Pseudomonas solanacearum) , cabbage black rot (Xanthomonas campestris) , citrus canker (Xanthomonas citri (Hasse) Dowson), rice bacterial leaf blight (Xanthomonas oryzae) , cabbage bacterial soft rot (Erwinia carotovora) , and tobacco mosaic (Tobacco mosaic virus). The agricultural and horticultural disease controller of the present invention is markedly effective in controlling the above-exemplified diseases which damage paddy field crops, upland crops, fruit trees, vegetables, other crops, flowers and ornamental plants, and the like. Therefore, the desired effects of the agricultural and horticultural disease controller of the present invention can be obtained by applying the disease controller to the paddy field water, stalks and leaves of fruit trees, vegetables, other crops, flowers and ornamental plants, soil, etc., at a season at which the diseases are expected to occur, before their occurrence or at the time when their occurrence is confirmed.

In general, the agricultural and horticultural disease controller of the present invention is used after being prepared into a conveniently usable form according to an ordinary manner for preparation of agrochemicals.

That is, the 1,2,3-thiadiazole derivative of

the general formula (I) or salt thereof according to the present invention and, optionally, an adjuvant are blended with a suitable inert carrier in a proper proportion and prepared into a suitable preparation form such as a suspension, emulsifiable concentrate, soluble concentrate, wettable powder, granules, dust or tablets through dissolution, dispersion, suspension, mixing, impregnation, adsorption or sticking.

The inert carrier used in the present invention may be either solid or liquid. As the solid carrier, there can be exemplified soybean flour, cereal flour, wood flour, bark flour, saw dust, powdered tobacco stalks, powdered walnut shells, bran, powdered cellulose, extraction residue of vegetables, powdered synthetic polymers or resins, clays (e.g. kaolin, bentonite, and acid clay), talcs (e.g. talc and pyrophyllite) , silica powders or flakes (e.g. diatomaceous earth, silica sand, mica and white carbon, i.e. synthetic, high-dispersion silicic acid, also called finely divided hydrated silica or hydrated silicic acid, some of commercially available products contain calcium silicate as the major component), activated carbon, powdered sulfur, powdered pumice, calcined diatomaceous earth, ground brick, fly ash, sand, calcium carbonate powder, calcium phosphate powder and other inorganic or mineral powders, chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride), and

compost. These carriers may be used alone or as a mixture thereof.

The liquid carrier is that which itself has solubility or which is without such solubility but is capable of dispersing an active ingredient with the aid of an adjuvant. The following are typical examples of the liquid carrier and can be used alone or as a mixture thereof. Water; alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone; ethers such as ethyl ether, dioxane, Cellosolve, dipropyl ether and tetrahydrofuran; aliphatic hydrocarbons such as kerosene and mineral oils; aromatic hydrocarbons such as benzene, toluene, xylene, solvent naphtha and alkylnaphthalenes; halogenated hydrocarbons such as dichloroethane, chloro¬ form, carbon tetrachloride and chlorobenzene; esters such as ethyl acetate, diisopropyl phthalate, dibutyl phthalate and dioctyl phthalate; amides such as di- methylformamide, diethylformamide and dimethylacetamide; nitriles such as acetonitrile; and dimethyl sulfoxide.

The following are typical examples of the adjuvant, which are used depending upon purposes and used alone or in combination in some cases, or need not to be used at all.

To emulsify, disperse, dissolve and/or wet an active ingredient, a surfactant is used. As the surfactant, there can be exemplified polyoxyethylene

alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene higher fatty acid esters, polyoxy¬ ethylene resinates, polyoxyethylene sorbitan mono- laurate, polyoxyethylene sorbitan monooleate, alkyl- arylsulfonates, naphthalenesulfonic acid condensation products, ligninsulfonates and higher alcohol sulfate esters.

Further, to stabilize the dispersion of an active ingredient, tackify it and/or bind it, there may be used adjuvants such as casein, gelatin, starch, methyl cellulose, carboxymethyl cellulose, gum arabic, polyvinyl alcohols, turpentine, bran oil, bentonite and ligninsulfonates.

To improve the flowability of a solid product, there may be used adjuvants such as waxes, stearates and alkyl phosphates.

Adjuvants such as naphthalenesulfonic acid condensation products and polycondensates of phosphates may be used as a peptizer for dispersible products. Adjuvants such as silicon oils may also be used as a defoaming agent.

The content of the active ingredient may be varied as required. In dusts or granules, the suitable content thereof is from 0.01 to 50% by weight. In emulsifiable concentrates or flowable wettable powders, it is also from 0.01 to 50% by weight.

The present inventive agricultural and horticultural disease controller containing the 1,2,3-

thiadiazole derivative of the general formula (I) or a salt thereof as an active ingredient is used to control various diseases in the following manner. That is, it is applied to a crop on which the diseases are expected to occur, or a site where the occurrence of the diseases is undesirable, as it is or after being properly diluted with or suspended in water or the like, in an amount effective for control of the diseases. For example, to control the diseases of paddy rice, said disease controller can be used by a method such as submerged application to a regular paddy field, application to a rice nursery bed, dressing of seeds for direct sowing on flooded paddy field, or seed disinfection.

The applying dosage of the present inventive agricultural and horticultural disease controller containing the 1,2,3-thiadiazole derivative of the general formula (I) or a salt thereof as an active ingredient is varied depending upon various factors such as a purpose, diseases to be controlled, a growth state of a plant, tendency of disease occurrence, weather, environmental conditions, a preparation form, an application method, an application site and application time. It may be properly chosen in the range of 0.1 g to 10 kg (in terms of the active ingredient) per 10 ares depending upon purposes.

The present inventive agricultural and horticultural disease controller containing the 1,2,3- thiadiazole derivative of the general formula (I) or a

salt thereof as an active ingredient may be used in admixture with other agricultural and horticultural disease controllers in order to expand both spectrum of controllable diseases and the period of time when effective applications are possible or to reduce the dosage.

Typical examples and test examples of the present invention are described below but they should not be construed as limiting the scope of the invention. In the examples, parts are all by weight.

Example 1

Each compound listed in Table 1 50 parts Xylene 40 parts

Mixture of polyoxyethylene 10 parts nonylphenyl ether and calcium alkylbenzenesulfonate

An emulsifiable concentrate was prepared by mixing uniformly the above ingredients to effect dissolution.

Example 2

Each compound listed in Table 1 3 parts Clay powder 82 parts

Diatomaceous earth powder 15 parts

A dust was prepared by mixing uniformly and grinding the above ingredients.

Example 3

Each compound listed in Table 1 5 parts Mixed powder of bentonite and clay 90 parts Calcium lignin sulfonate 5 parts Granules were prepared by mixing the above ingredients uniformly, and kneading the resulting mixture together with a suitable amount of water, followed by granulation and drying.

Example 4 Each compound listed in Table 1 20 parts Mixture of kaolin and synthetic, 75 parts high-dispersion silicic acid Mixture of polyoxyethylene 5 parts nonylphenyl ether and calcium alkylbenzenesulfonate

A wettable powder was prepared by mixing uniformly and grinding the above ingredients.

Test Example 1

Controlling effect on rice blast by submerged application

Rice plants at the 5 to 6 leaf stage culti¬ vated in a 1/10000-are pot were subjected to submerged application of a chemical containing each compound listed in Table 1 as an active ingredient, in a dosage of 200 g/10 a in terms of the active ingredient. After standing in a greenhouse for 1 week, the plants were

inoculated with a suspension of spores of blast fungus

(Pyricularia oryzae) by spraying.

After the inoculation, the plants were allowed to stand in a moist chamber for 1 day and then a greenhouse for 6 days to cause the disease sufficiently.

Then, lesions in each leaf were counted and then compared with those on the untreated plot, and the controlling degree was calculated, whereby the effect was judged according to the following criterion.

Effect Controlling degree (%)

A 100 - 95

B 94 - 85

C 84 - 60

D 59 - 0 As a result of the above test, the compounds listed in Table 1 were found to have a marked blast- controlling activity. Of these compounds, the following were rated C or higher: compound Nos. 1 to 42, 44 to 61, 62 to 89, 92 to 95, 97 to 100, 103 to 131, 133 to 136, 138 to 140, 142, 144 to 166, 168 to 192, 194 to 196, 198 to 200, 202 to 222, 224, 225, 227 to 233, 237, 240 253 to 255, 268, 269, 272, 273, 276, 278, 287 to 296, 342 to 346, 348, 351, 354 to 357, 361, 362, 366, 369, 372, 374 and 375. In particular, the following were rated A, namely, the following had an excellent blast- controlling activity: compound Nos. 1, 3, 5 to 19, 21, 24 to 26, 28, 29, 32, 33, 37 to 40, 52, 54, 55, 57 to

59, 64 to 68, 70 to 74, 77 to 80, 84, 92, 93, 99, 103, 104 to 121, 123 to 125, 128, 130, 131, 138, 145, 146, 149, 152, 153, 156, 157, 159, 160, 169, 172 to 174, 175 to 192, 194, 198, 199, 202, 208 to 210, 213, 215 to 221, 224, 225, 227 to 229, 233, 237, 253, 278, 288 to 290, 294, 343, 344, 346, 355, 356, 362, 372, 374 and 375.

Test Example 2

Controlling effect on barley powdery mildew

Barley plants at the 3.5 leaf stage cultivated in a pot were applied with a spray mix containing each compound listed in Table 1 as an active ingredient at the concentration of 200 ppm. After standing thus treated plants in a greenhouse for 1 week, the plants were inoculated with spores of powdery mildew fungus (Erysiphe qraminis f. sp. hordei)

After the inoculation, the plants were allowed to stand in a greenhouse for 1 week to cause the disease sufficiently. Then, lesions in each leaf were counted and then compared with those on the untreated plot, and the controlling degree was calculated, whereby the effect was judged according to the following criterion.

As a result of the above test, the compounds

listed in Table 1 were found to have a marked powdery mildew-controlling activity. Of these compounds, the following were rated B or higher: compound Nos. 7 to 9, 15, 16, 33, 40, 66, 72, 84, 104 to 107, 111 to 113, 115 to 117, 122 to 124, 128, 130, 139, 145, 180, 193, 194, 215, 217, 218 and 224. In particular, the following were rated A: compound Nos. 7 to 9, 15, 16, 33, 40, 66, 72, 84, 104 to 107, 111 to 113, 115 to 117, 122 to 124, 128, 130, 139, 145, 180, 193, 215, 217, 218 and 224.

Referential Production Example 1

Production of sodium 4-ethyl-l,2,3- thiadiazole-5-carboxylate (compound No. 8)

To a solution of 0.13 g of sodium hydroxide in 3 ml of ethanol was added 0.5 g of 4-ethyl-l,2,3- thiadiazole-5-carboxylic acid, and the reaction was carried out at room temperature for 24 hours.

After completion of the reaction, the solvent was distilled off under reduced pressure and the crude product thus obtained was recrystallized from ethanol to obtain 0.44 g of the desired- compound.

Physical property: m.p. 250 ^β C (decomp.). Yield: 77%.

Referential Production Example 2

Production of t-butylammonium 4-ethyl-l,2,3- thiadiazole-5-carboxylate (compound No. 185)

In 3 ml of ethanol was dissolved 0.4 g of 4- ethyl-l,2,3-thiadiazole-5-carboxylic acid, after which 0.19 g of t-butylamine was added to the solution and the reaction was carried out at room temperature for 24 hours.

After completion of the reaction, the crystals precipitated in the reaction solution were collected by filtration and washed with n-hexane to obtain 0.54 g of the desired compound. Physical property: m.p. 105 - 107°C. Yield: 93%.

Referential Production Example 3

Production of N-isopropyl-5-(N'-isopropyl- carbamoyl)-l,2,3-thiadiazol-4-ylacetamide (compound No. 252)

o

II

N- -CH ₂ COCH ₃ N- -CH ₂ CNHC ₃ H ₇ -i

N II -COCH ₃ N II -CNHC ₃ H ₇ -i

II 0 II 0

In dimethyl sulfoxide was suspended 0.1 g of sodium hydride, after which 1 g of isopropylamine was added to the suspension, followed by ice-cooling. Then, 0.5 g of methyl 5-methoxycarbonyl-l,2,3-thiadiazol-4- ylacetate was added and the resulting mixture was stirred at room temperature and allowed to stand for 24 hours.

After completion of the reaction, the reaction mixture was poured into ice water and the desired compound was extracted with ethyl acetate. The extracted solution was washed with water, dried over anhydrous sodium sulfate, and then distilled under reduced pressure to remove the solvent. The crude product thus obtained was purified by a column chromatography to obtain 0.23 g of the desired compound. Physical property: m.p. 146 - 156 ^β C. Yield: 37%.

Referential Production Example 4

Production of ethyl 4-(2-methylphenoxymethyl)- l,2,3-thiadiazole-5-carboxylate (compound No. 281)

In 20 ml of dimethylformamide was suspended

0.5 g of sodium hydride, after which 1.57 g of 2-

methylphenol was added to the suspension and the resulting mixture was stirred at room temperature for 5 minutes. The reaction mixture was cooled with ice, followed by adding thereto 3 g of ethyl 4-chloromethyl- 1,2,3-thiadiazolecarboxylate, and the resulting mixture was stirred at room temperature and allowed to stand for

24 hours.

After completion of the reaction, the reaction mixture was poured into ice water and the desired compound was extracted three times with ethyl acetate. The extracted solution was washed with water, dried over anhydrous sodium sulfate, and then distilled under reduced pressure to remove the solvent, whereby 1.33 ς of the desired compound was obtained. Physical property: nD 1.5579 (20.1 ^β C). Yield: 33%.

Referential Production Example 5

Production of isopropyl 4-methyl-l,2,3- thiadiazole-5-carboxylate (compound No. 18)

To 1.0 g (6.9 mmoles) of 4-methyl-l,2,3- thiadiazole-5-carboxylic acid were added 40 ml of thionyl chloride and 2 drops of dimethylformamide at room temperature, and the resulting mixture was refluxed

with heating for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the excess thionyl chloride was distilled off and 7.0 ml of tetrahydrofuran was added to the residue. Then, 2.1 g (21 mmoles) of triethylamine and 0.83 g (13.8 mmoles) of isopropanol were added and the resulting mixture was stirred at room temperature for 18 hours, after which a saturated aqueous sodium chloride solution was added. The desired compound was extracted with ethyl acetate and the organic layer was washed successively with diluted hydrochloric acid, a saturated aqueous sodium hydrogencarbonate solution and a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The resulting residue was purified by a silica gel column chromatography (n-hexane : ethyl acetate = 10 : 1) to obtain 1.0 g of the desired compound.

Physical property: nD 1.4400 (14.3 ^β C). Yield: 79%.