AU610553B2 - Microbicidal compositions - Google Patents

Microbicidal compositions Download PDF

Info

Publication number
AU610553B2
AU610553B2 AU10974/88A AU1097488A AU610553B2 AU 610553 B2 AU610553 B2 AU 610553B2 AU 10974/88 A AU10974/88 A AU 10974/88A AU 1097488 A AU1097488 A AU 1097488A AU 610553 B2 AU610553 B2 AU 610553B2
Authority
AU
Australia
Prior art keywords
alkyl
substituted
group
unsubstituted
halogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
AU10974/88A
Other versions
AU1097488A (en
Inventor
Werner Fory
Robert Nyfeler
Werner Topfl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of AU1097488A publication Critical patent/AU1097488A/en
Application granted granted Critical
Publication of AU610553B2 publication Critical patent/AU610553B2/en
Assigned to NOVARTIS AG reassignment NOVARTIS AG Alteration of Name(s) in Register under S187 Assignors: CIBA-GEIGY AG
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
    • C07F9/6539—Five-membered rings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Agronomy & Crop Science (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Cosmetics (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

It contains, as active substance, a 2-chloro-4-trifluoromethyl-thiazole-5-carboxylic acid derivative of the formula I <IMAGE> in which R represents an organic radical which has not more than 40 carbon atoms and which can, if appropriate, also contain nitrogen, oxygen or sulphur, and which can be converted by hydrolysis and/or oxidation into a carboyl group which is bonded to the thiazole ring. These compounds are distinguished by a good microbicidal action and are used for controlling or preventing infection of plants with phytopathogenic microorganisms. Some of these compounds are known, many are new. The novel 2-chloro-4-trifluoromethyl-thiazole-5-carboxylic acid derivatives and their preparation are also a subject of this invention.

Description

:i i 9 t S F Ref: 48542 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE: Class Int Class a Complete Specification Lodged: S. Accepted: Published: Priority: =2 Related Art: Name and Address of Applicant: Ciba-Geigy AG Klybeckstrasse 141 4002 Basle
SWITZERLAND
Spruson Ferguton, Patent Attorneys Level 33 St Martins Tower, 31 Markat Street Sydney, New South Wales, 2000, Australia Address for Service: Complete Specification for the inventlon entitled: Microbicidal Compositions The following statement is a full description of this invention, including the best method of performing it known to ms/us r 5845/3 Microbi-ci-dal Compositionf- The pre sent i nventi on relIate s to rf ungi c idal and mi crobi c idal compos iti ons which contain as active Ingredient a 2-chloro-4-trifluoromethyl-thiazol-5carbo-ic acid derivative of formula I, to the preparation of these derivatives and to compositions containing them, as well as to methods for con-trolling or preventing infestation of plants by phytopathogenous microorganisms.
According to a broad form of the present invention there is provided a method for controlling and preventing infestation of plants by phytopathogenous microorganisms, which comprises treating the plants or parts thereof with an effective amount of a 2-chloro-4-trifluoromethylacid derivative of formula I 4 0404 00 4 0 000 g 0 00 604 064 4400 0 V F 3 C R
A
I)
064- 9640 0 04 wherein R is a radical selected from among cyano, -COXR 1 -CONR R 4 or is34 -15 -COD, X is oxygen or sulfur, Ris hydrogen, CG 1 -C 18 alkyl or C 3 -C 18 cycloalkyl, which is unsubstituted or substituted by halogen, a group -YR 2 A, nitro,
-N(R
3 )COA, -EN(R 3 m G(A)=NC 1
-G
4 alkyl, -EN(R 3 C(A)=NH or O in which groups one of the indices m must be zero, further C 1
-C
1 alkyl or C 3 -C 18 cycloalKyl can be substituted by cyano, a group mCX MX10' *-XCXR 10 -(X)CXN(R 3 NMR 3
)R
4 CHA-C0R 1 7 -C0 7 0 8 9 5
)R
6 j C 3 -C cycloalkyl or C 5 8 cycloa.lkenyl R1further represents C 3 -C 8 alkenyl or 0 G- C 1 cycloa1kenyl, which is unsubstituted or substituted by halogen, C 1 0 1 -C 4 alkoxy, C 1 4 alkylthio, C 1 -G haloalKoxy, C IC 4haoalylor grup-COO)m -R10' -CQA, -CQN(A)R 3 or -PO(R 5 )R 6 R, further represents C 3 -C 8 alkynyl which is unsubstltuted or substituted by mU or MQ R 2 is C 1
C
8 alkyl or C 3 -C 8 cycloalkyl, which is unsubstituted or substituted by a group selected from C 1 -C 8 alkoxy, C 1 -C alkylthio,
C
2 C alkoxyalkyl halogen, cyano, a group -CX(X) mRio, -(X)m-*CXA$ -2m CXRio0, -N(R 3
)COA,
-CN(R 3 [N(R 3 I-M-C(A)=NC -C 4 alkyl, A. -X-U or XQ; Rfurther represents C 3 -C alkenyl or C 3 -C cycloalkenyl unsubstituted or substituted by halogen; or R 2 represents a radical -()mUor Q m is zero or one; Y is oxygen, sulfur, -SO- or -SO 2 A is a radical -N(R 3 )R 4 D is a radical -N(R 3 )MR 4 mR 3 one of R 3 and R4is hydrogen or C 1 -C 8 alkyl, the other or both independently represent C -C alkyl or C -C cycloalkyl which is unsubstituted or C 1
-C
8 alkyl or C 3 cycloalkyl which is substituted by a group selected from C 1 -C~alKoxy, C 2 -C~alkoxyalkoxy, *qb C 1 -C~alkylthio, cyano, a group -G00R 10
C
1 -C 4 alkylcarbamoy), 4,015 di-CG 1 -Calkylcarbamoyl piperidinocarbonyl pyrrolidinocarbonyl, piperidino or pyrrolidino; R 3 and Rfurther represent CC aleiyl or C -C cycloalkenyl which is unsubstituted or substituted by a group 900 selected from halogen, C -C alkoxy, C -C rycloalkyl, cyano,
-COOR
1 0, C 1 -C 4 alkylcarbamoyl or piperidinocarbamoyl; R 3 and R 0 S represent f urther G 3
-C
6 al kynyl whi ch i s unsubsti tuted or substi tuted by U; or R 3 and R 4 represent a radical or 3 4m mI Rand R 4 together with the nitrogen atom, to which they are bound form a saturated or unsaturated heterocycle with 5 to 9 ring members 010cI may S include once or several times -NH1-, -N-C 1
-C
4 alkyl, -GO- or H22 -C(0R )OR 8 and whic'it mAy be substituted by halogen, cyano, '0900. C 1 -C~alkoxy, amino, C 1 -c 4 alkylamino dl-C 1 -C 4 alkylamino or a *coo group -C00R 10 and R 6 are Irdependently of each other hydrogen, C 1
-C
4 a~kyl or C -C alkoxy, ~O Rand Rare independently of each other C -C alkyl or 7 1 R7 and R8form together an alkylene chain of 2 to 4 chain-llr*,s, kand Rio are independently of each other hyOrogen, C 1 -C~alkyl, C -C cycioalkyl, 3 alkenyl C 2 -Galkoxyalkyl,
C
3 -C alkoxyalkoxyalky'll Lo Chaloalkyl (C 1
-C
3 alkylene)mLJ, -(,cakln)mQ C -C 4 haloalkoxy; U is phenyl or naphthyl, which is unsubstituted or substituted once or 'LWVT 1949 3 several times by halogen, C 1 -C 4 alkyl, -Y-C I-C 4 alkyl, C C 4 haloalkyl,
C
1 -C 4 haloalkoxy, cyano, nitro, carboxyl, -CQOR 7 -CONH 2 -CONHR 7
-CON(R.
7 -so 2 NHR 7 so 2 N(R 7 2 pyrrolidino, piperidino, pyrrolidinocarbonyl or piperidiriocarbonyl; E is a C C 8 alkylene orC 2 -C 8 alkenylenechiwchs unsubstituted or substituted by halogen, C 1 -C 4 alkoxy,
C
1
-C
4 alkylthio, C 1 -C 4 haloalkoxy or by a group -CO(O) mR 1 0 A, -(GO)M and which may be interrupted by -GO- or Q is a heterocyclic radical selected from among furan, tetrahydrofuran, pyran, pentahydropyran, dioXan, dioxalan, thiophen, thiazole, thienyl, pyrrolidino, pipa~ridino, morpholino, azepino which are unsubstituted or substituted by methyl; 00 or a composition comprising the compound of formula I together with a 15 microbicidally acceptable carrier, adjuvant and/or diluent.
00 0 Novel 2-chloro-4-trifluoromethiyl-thiazolyl-5-carbonic acid derivatives 0 00 correspond to the formula Ia 00 0 0000 00 0 0 0 0 000 G 0 00 G000~ 000 0000 a 0 0 F 3 C- (Ia) Ra is a radical selected from among cyano, -COXRi,* -G0R, I-CONR IR I or -COD, in which 000 X is oxygen or sulfur, 0000 000 Rl is C 11 -C 18 alkyl or CG 3 -C ,cycloalkyl which are unsubstituted or 000 C 1 -C alkyl or C -C 18 cycloalkyl substituted by a halogen, a group A, nitro, -N(R )COA, -EN(R C alkyl, -EN(R 3 fm C(A).NH or -EN(R 3 ))jj*CONI2(CO m)R 3
]-N(R
3 .0:00 4
N(R
3 )Jm CONO 103 C~R4 in which groups one 00 of the indices m must be zero, C 1 -C 18 alKyl or C 3 -C 18 cycloalkyl are ~00 further substituted by cyano, a group -CMX mXRi 0 W -XGXR 10 -(X)jMCXN(R 3 )N(R 3 )R 4 1 -CHA-C00R 10 -C(0R 7 )(OR 8
)R
9 -PO(R OR 6
C
3
-C
8 cyc loalkyl or C 5
-C
8 cycloallkenyl; with the proviso that -XR 1 Is not C 1 -C 10 haloalkoxy,
C
2 -C 10 alkoxyalkoxy, phenylthlo or benzyloxy if these groups are unsubstutited or phenoxy substituted; M0CW949y1 w Rl further is C 3 -C l 8 cycloalkenyl which is unsubstituted or C 3 -C alkenyl or C 3
-C
1 cycloalketyl substituted by halogen, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkoxy, G 1 -C 4 haloalkyl or a group -CO(O) R 10 -_COA, -CON(A)R 3 or -PO(R 5 )R 6 if X is sulfur, RIis also a group or -E-Q R 2 Is C 1 -C 3 alkyl or C 3 -C 8 cycloalkyl, which is unsubstituted or substituted by CI- C 8 alkoxy, C]_C 8 alkylthio, C 3
C
8 alkoxyaikoxy, halogen, cyano, or a group -CX(X) mRio$ M_-CX-A, m CXR 10 -N(R 3 )COA, 3 3
T(C(A)-NC
1
C
4 alkyl, A, -XU or -XQ; R2further is C 3
C
8 alkenyl or C 3
C
8 cycloaikyl which is unsubstituted or halosubstituted; or R2is a group mU or -CE) MQ m is zero or 1; Y is oxygen, sulfur, -SO- or -SO 2 A is a group -N(R 3 )R 4 1 D is a group -N(R MNR 4
)(CO)
01
R,
wherein one of R 3 and R4is hydroclien or unsubstituted C 1 -C 8 alkyl; Sthe other or both independently represent C 3
C
18 cycloalkyl which is Sunsubstituted or substituted by C 1 8 alkoxy, C 2 -C 8 alkoxyalkoxy, cyano, a group -G00R 10 C 1
C
4 alkylcarbamoyl, di-C 1 -Calkylcarbamoyl, C 1 -C alkylamino, di-C 1
-C-
alkylamirro, piperidinocarbonyl, pyrrolidinocarbonyl, piperidino or pyrrolidino; R3and R4further represent C 3 C Faikeny1 or CG 3
-GC
8 cycloalkenyl, Swhich is unsubstituted or substituted by halogen, C 1
C
8 alkoxy, C 3
C
8 cycloalkenyl, cyano, a group -C00R 10
C
1 -C alkylcarbamoyl, di-C 1 -C alkylcarbamoyl U, pyrrolidinocarbonyl or piperidinocarbonyl
R
3 and R4further are a group or with the proviso Sthat only one of Rand Ris hydrogen or C 1 -C alkyi; Rand R 4 together with the nitrogen atom, to which they are bound also Srepresent an unsaturated or saturated heterocycle with 5 to 9 ring-members wihich is Interrupted once or several times by oxygen, sulfur', nitrogen, imino,
C
1 -C alkylimino, or -C(OR.,)OR 8 and which may be substituted by halogen, cyano, CI- C 8 alkoxy, amino, C I-C 4 alklaino, di-C -C alkylamino or -COOR 10 R 5 and R 6 are independently of each o-har hydroxyl, C 1 -C 4 alkyl or C Calkoxy;
R
7 and Rare Independently of each other C 1 -Calkyl or Rand Rform together a 2 to 4 membered alkylene chain,
R
9 and R are independently of each other hydrogen, C 1 -C alkyl,
C
3 -C cycloalkyl C 3 -C 8 cycloalkenyl, C 3 -C 8 alkenyl ,C2alkoxyalkyl C 4 -C alkoxyalkoxyalkyl C 1 -~aoly,-C- 3 alkyl 'jM-UI 1 -C 3 alkyl IT-Q C 1
-G
4 haloalkoxy, C 1 -C 4 haloalkoxy-C 1
C
4 alkyl; U i s a phenyl or naphthyl whi ch i s unsubsti tuted or substi tuted once or several times by halogen, C,-C 4 alkyl, -Y-C 1
C
4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, cyano, nitro, -COOI, -COQR 7
-CONFI
2 -CONHR 7 -CON(R 7 2 so 2 NHR 7 so 2 N(R 7 2 pyrrolidino, piperidino, pyrrolidinocarbonyl or piperidinocarbonyl; E is a CG 1
-C
8 alkylene or C 2
-C
8 alKenylene chain, which Is unsubstituted or substituted by halogen, C 1 C 4 alkoxy, C 1
-~C
4 alkylthio, 044015 C 1 -C 4 haloalkoxy or a, group -CO(0) MRIO -(GO)-mA or Q and/or is Interrupted by a chain-member -CO- or C(0R )OR 8 a Q is a heterocyclic radical selected from among furan, tetrahydrofuran, pyran, pentahydropyran, dioxan, dioxalan, thiophen, thiAzole, thienyl, pyrrolidino, piperidino, morpholino, azepino which are unsubstituted or 0*Y~o substituted by methyl.
acid derivatives Are known from the literaturei 64O 2 ,4-Dimethyl thi azol-5-carboxami des are disclosed as fungicides In US patent 4 It 3,725,427; 2-chloro-4-trifluoromethylthiazol-5-carbonic acid derivatives are disclosed as antidotes (safeners) to reduce the phytotoxic action of strong herbicides on cultivated plants in US patents 4,199,506, 4,251,261, in the published European patent applications 27,Ql8 44,201 and 63,353, It has been found that the 2-chloro-4- acid derivatives of formula I have extraordinary good microbicidal activity S and are able to cure or prevent cultivated pLj~from Infestation of phytopathological microbes and fungi.
The compounds of formula I are stable at room temperature, They can be used in the agricultural and In related fields for controlling pests, especially for controlling and preventing phytopathogenic microorganisms.
The derivatives of formula 1 are characterised by excellent fungicidal LMMbltiWi$949Y
'.AJ
MPMW_
-6activity over a wide application range and unproblematic handling. These derivatives further possess nematicidal properties which make them suitable for controlling nemnatodes, especially phytopathogenic nematodes.
Because of their pronounced microbicidal activity the derivatives of formula I are preferred, wherein the group R contains a maximum of carbon atoms, among them the derivatives falling under the formula I F wherein R Is a radical selected from among cyano, -COXP -CONR 3 R 4 or
-COD,
X Is oxygen or sulfur, R1is hydrogen, C 1 -C 18 alkyl or C 3
-C
18 cycloalkyl, Which is *4s~t--t~or- substituted by halogen, a group -YR 2 A, nitro, -N(DR )OA, -4N(R C(A'=NC alkyl C(A)=NH or IN(R CON[(CO) R J-NR -M(R CONE(CO)m R1-N (R3)]m (CO)mR 4 00005 in which groups one of the Indices m must be zero, further C 1 -C 1
KY
or C 3
-C
18 cycloalkyl can be substituted by cyano, a group **C(Xm XRlop -XCXR 10 _MXm CXA, -(XCXN(R 3
)N(R
3
)R
4 -CFIA-C00R 10 -C(OR 7 OR 8
)R
9
-PO(R
5
)R
6 C 3
C
8 cycloalkyl or C 5 -C 8 cycloalKenyl R 1 further represents C 3 -C 8 alkenyl or 00*20 C 3 -C 18 cycloalkenyl, which is unsubstituted or substituted by halogen, C alkoxy, C 4 alkylthio, C 1 -C 4 haloalkoxy,
C
1 -C 4 haloalkyl or a group m Rl 0 -COA, -CON(A)R3 or _PO(R )R R 1 further represents C 3 -C alkynyl which Is S unsubstituted or substituted by mU or Q V ,a1 R is C 1 I-C 8 alkyl or C 3
-C
8 cycloalkyl, which is unsubstituted or 00 substituted by C1 1 -C 8 alkoxy, C 1 -C 8 akylthto, C 2 -C 8 alkoxyalkyl S halogen, cyano, or a group -CX(X)mRlos -(X)mCXROp
-N(R
3 )COA, -(N(3)3m C(A)-NH, 111 3 Mm C()lCI4a ly A, or XQ; R 2 further represents C 3
-C
8 a lkenyl or C 3 -C~cycloalkenyl, which is unsubstituted or substituted by halogen; or R 2 represents a radical mU or Q mn Is zero or one; Y is oxygen, sulfur, -SO- or SO 2 A is a radical -N(R 3
)R
4 LM /949Y -7- D is a radical -N(R 3 )MR 4 mR 3 one of R 3 nd R 4 is hydrogen and the other or botrh independently represent C 5 -C 8 alkyl or C 3
-C
8 cycloalkyl, which is unsubstituted or C 1
C
8 alkyl or C 3 -C 8 cycloalkyl which is substituted by a group selected from C 1 -C 8 alkoxy, C 2 -C 8 alkoxyalkoxy, C-C 8 alkylthio, cyano, a group -C00R 10 C 1
-C
4 alkylcarbamoyl, di-C 1 -C 4 alkylcarbamoyl piperidinocarbonyl, pyrrolidinocarbonyl piperidino or pyrrolidino; R 3 and R 4 further represent C 3 -C 4 alkenyl or C3C8 cycloalkenyl which is unsubstituted or substituted by halogen, CI- C 8 alkoxy, C 3
C
8 cycloalkyl or cyano, -C00R 10 C I-C 4 alkylcarbamoyl or pippridinocarbamoyl; R 3 and R 4 represent further C 3
C
8 alkynyl, which is unsubstituted or substituted by U, or R 3 and R 4 represent a radical or R 3 and R 4 together with the nitrogen atom, to which they are bound form a saturated or unsaturated heterocycle with 5 to 9 ring members which may 0 11 Include once or several times -N-C 1 -C alkyl, -GO- or CO 0 4 OR 8 and which may be substituted by halogen, cyano, 0 -C alkoxy, 00*00 amino, C.
1 -C 4 alkylamlno di -Cl-C 4 alkylamino or a group -C00RI 0 009 R, and R 6 are Independently of each other hydrogen, C 1 -C 4 a kyl or "g C CCalkoxy; Rand R a are independently of each other C F C 4 alkyl or Rand R 8 form together an alkylene chain of 2 to 4 chain-links, Rand R 1 4re independently of each other hydrogen, Q -C alkylo c 3-c 8 eycloalkylo C 3 -C alkenyl, C 2 -Calkoxyalkyl 2 5 C 3
C
8 alkoxyalkoxyalkyl C 1 -C 4 haloalkyl, I-C 3 alkylene)m Ut 000 (C -C alkylene) Q, C -G haloalkoxy; S U is phenyl or naphthyl, which Is unsubstituted or substituted once or 0Z~ several times by halogen, C 1 -Calkyl. -Y-CC~a l C 1 Chaloalkyl, C 1
-C
4 haloalkoxy, cyano, nitro, carboxyl, -COOR 7 -CON11 2 1 0*0 -CQNHR -CON(R -So NHR 7
-SOZN(R
7 ),proiio ~:piperidino, pyrrolidino, carbonyl or piperidinocarbonyl; E Is a C I-C 8 alkylene or C 2
-C
8 alkenylene chain, which Is unsubstituted or substituted by halogen, C,-C 4 alkoxy, C 1 -C 4 alkylthio, Cl-C 4 haloalkoxy or by a group -OO 0 -(CO)MA, (CO) mQ and which may be interrupted by _CO- or -C(0R )OR; Q Is a, heterocyclic radical selected from among furan, tetrahydrof!.tran, r imj /99 7a pyran, pentahydropyran, dioxan, dioxalan, thiophen, thienyl thiazole, pyrrolidino, piperidino, morpholino, azepino which are unsubstituted or substituted by methyl.
Good microbicidal activity show especially the derivatives of the formula lb 0 1 "0 000 '*0 k; 0
F
3 wherein Rlhas the meaning given Pbove.
(1b) Also good activity is shown by the derivatives of the formula IC
(IC)
wherein R2has the meaning given above, as well as the compounds of the formula, Id where In R8 and R 4 have the meaning given above, (1d) 0000 0 a Some of the 2-chloro-4-trifluoromethyl-thiazol--carbolic acid derivatives are new, those correspondin~g to the formula Ia 00 0aad a0 0 00 4 0 0 wherei n al Ra Is a radical selected from among cyano, -COXR,, -COR 1 -CNR R 4 or -COD, in which D and X have the meaning given above, 0O R, is C 11 -Cel 8 alkyl or C, .C 18 cycloalkyl which are unsubstituted or Cl-C 18 alkyl or C 3 -Ct 8 cyc]oalkyl substituted by halogen, a group
-YR
2 A, nitro, -N(R 3 COA, -N(R 3 4 alky1,
-(NR
3 )1-C(A).WN or N(C0,)R 3 3-N(R 3 )t -[(31-0(C)mR3-C~ 4 In which groups one of~ the Indices m must be zerot C I-cl~alkyl or C 3
-C
18 cycloalkyl are further substituted by cyano, a group C(X)'-XRl 0 0 -XCXR 10 oXYCA LMMATCNH49Y 7b
(R
3
)N(R
3
)R
4 -CHA-C00R 10 -C(0k 7 )(0R 8
)R
9 *-P0(R 5
)R
6
C
3
-C
8 cycloalkyl c C 5
-C
8 cycloalkenyl; with the proviso that is not C 1
-C
10 haioalkoxy, C 2
-C
10 alkoxyau4oxy, phenylthlo or benzyloxy if these groups are unsubstituted or phenoxy substituted; further is C 3
-C
18 cycloalkenyl, which is unsubstituted or
C~--C
8 aIkeny1 or C~~C 18 cy:1oalkenyl substituted by halogen,
C
1
-C
4 aikoxy, C 1
C
4 alkylthio, C 1
-C
4 haloalkoxy,
C
1
-C
4 haloalkyl -CO(0) R COA or a group rn 10' -CON(A)R 3 or
-XJ(R
5
)R
6 if X is sulfur, Ri is also a group or m
R
2 is 3 alky1 or C 3
-C
8 cycloalkyl, which is unsubstituted or substituted by C~.C 8 alkoxY~ C 1
-C
8 alkylthio, C 3
-C
8 alkoxyalkoxy, halogen, cyano c~r a group ~CX(X)mRi 0
-(X),~CXR
10
N(R
3 )COA, -EN(R 3
-~N(R
3 1
-C
4 alkyl, A, -XU or -XQ; further is C 3
-C
8 alkenyl or C 3
-C'
8 cycloalkyl which is unsubstituted or halosubstituted; or is a group ~(E)mU or ~K2iY niis* zero or 1; Y Is oxygen sulfur, -SO- or A is a group -N(R 3
)R
4 0 Is a group ~N(R 3
)N(R
4 )(CO)mR~~ wherein on~ of and R 4 is hydrogen or unsubstituted
C
1
-C
18 alkyl the other or both independently represent C 3
C
18 cycloalkyl which B unsubstituted or substituted by C 1
-C
8 alkoxy, C 2
-C
8 a1~oxyalkoxy, cyano, a group -C00R 10
C
1
-C
4 alKylcarbamoyl, dl-C 1
C
4 a1ky1carbamoy1~ C 1
-C
4 alkylamino, di-.C 1
-C
4 alkyi~m1no, piperidinocarbonyl, pyrrolidinocarbonyl, piperidino or pyrrolidino;
R
3 and R 4 further represent C 3
-C
8 &lKenyl or C 3
-C
8 cycloalkenyl, which Is un~ubstituted or substituted by halogen, C 1
-C
8 alkoxy, t~ C 3
-C
8 cyc1o~lkeny1, cyano~ a group -C00R 10
C
1
-C
4 alkylcarbamoyl, d'i-C 1
-C
4 alkylcarbamoyl U~ pyrrolidinocarbamoyl or piperidiriocarbamoyl
H
3 and R 4 further are a group or with the proviso that in m only one of R 3 ano H 4 is hydrogen or C 1
-C
4 aIkyl; and R 4 together with the nl~rogen atom, to which they are bound also present an unsaturated or saturated heterocycle with S to 9 ring-memuors 0 KX~ Z17y -7c which is interrupted once or several times by oxygen, sulfur, nitrogen, imino, C 1 C alkylimino, or -C(0R )OR- and which may be substituted by halogen, cyano, C 1 -C 8 alkoxyamino, C 1 -C 4 alkylamino, di-C 1 -C 4 alkylamino or -C00R 10 5 and R6are independently or each other hydroxyl, CI- C 4 alkyl or C 2 -C 4 al koxy; Rand R8are independently of each otner C 1 -C 4 alkyl or Rand R 8 form toqeLl'ier a 2 to 4 memberpd alkylene chain, R 9 and Roare independently of each other hydrogen, C 3
-C
8 cycloalkyl C 3 -C 8 cycloalkenyl, C 3 C 8 alkenyl, C 2 -C 8 alkoxyalky'l, C 4 -C 8 ako-,,yalIkoxy alIkylI, C 1 -C 4 haloalkyl 1 -C 3 alkyl I 'TU, 1
-C
3 alIkyI)> Q, C 1
-G
4 haloalkoxy, Cl-C 4 haloalkoxy-C 1 -C 4 alkyl; U is a phenyl or naphthyl, which Is unsubstitutec or substituted once or several times by halogen, C 1 -C 4 alkyl, -Y-C 1 -C 4 alkyl, C 1 -C 4 haloto alkyl, C -C haloalkoxy, cyano, nitro, -COQH, -COOR 7
-CM
2 0 ~oo -OH 7
C(
7
-S
2
NH
7 1 -so 2 7 2 1 pyrrolidino, piperidino, pyrrolidinocarbonyl or piperidinocarbonyl; E is a C I-C 8 alkylene or C I-C 8 alkenylene chain, which is un substituted or substituted by halogen, C Q 4 alkoxy,
C
1 -C alkylthlo,1 4C -C 4 haloalkoxy or a group -CO(O)M Rl _(COOor -(CO)mQ and/or is interrupted by a chain-member -GO- or 404 C(OR 7
)R
8 9Is a heterocyclic radical selected from among furan, tetrahydroaol'2 furan, pyran, pentahydropyran, dioxan, dioxalan, thiophen, thiazole, thienyl pyrrolidino, piperidino, morpholino, azepino which are %o~o'unsubstituted or substituted by methyl, 000 New are also the Z-chlorrQ-4-trifluloromethylthiazol derivatives formula lb F 3 LOo 0* (Ib) wherein Ris C 0
C
18 alkyl or C 3 -C cycloalkyl un~substituted or substituted by halogen or C 1 7C 5 alkyl or RIIs C 1 -C 18 alkyl or C 3
C
18 cycloalkyl substituted by a group -XR 2 A, nitro, -N(R 3
)CQA,
-tN(R 3 4[N(R 3 -EN(R 3 1-m-CON[(CO) m R 3 )-NR V E R) .0 OR (O MR 4 in which LM:'4,TCW/949y 7d groups one of the indices must be zero, C,-C 18 alkyl or C3-C 18 cyc alkyl are further substituted by cyano, a group -C(X>-m-Xlio, -(X>-MCXA, -(X)CXN(R 3 )R 4 -CHA-COOR 10, -C(OR 7 XOR 8)R9P )R 61 C3-C 8 cycloalkyl or CVC 8 cycloalkenyl a* 0 0000 0 0 0 06 0 6400 0 0000 0 000000 0 0 0 0 0 6060 0 6 0 00 0 C' 0 4 V 4 94, iAA I", M/ 7<10 549Y -8- R' further is C 3
-C
8 alkenyl or C 3 -C 18 cycloalkenyl which is substituted by halogen, C 1
C
4 alkoxy, C 1
-C
4 alkylthio, C I-C 4 haloalkoxy, C 1
C
4 haloalkyl or by a group -CO(O)mR-1 0 1 -COA, -CONi(A)R 3 or -PO(R 5 )R 6 R"is also a group U or with the proviso, that is not unsubstitLut~d benzyl or substituted or unsubstituted phenyl and mi, X, Y, A, D, R 3 1 R 4 R~5 R 6 1 R 7 1 R 8
R
9 1 R 10 U, E and Q have the meaning given above under formula Ia.
Especially good activity showed those 2-chloro-4-trifuloromethylthlazol-E,carbonic acid derivatives of the formula Ib, wherein R1is
C
1
-C
18 alkyl which is substituted by ha.logen, cyano, C 1 -C alkylthio, C -C alkoxycarbonyl, C 1 -C alkylsulfonyl, C 8 cycloal'kyl or 00 0C- C cycloalKenyl or a gru U or-(E)-Q and E, m, Q and U 06 have the meaning given above under formula Ia, most active were those, 0 ?S wherein R 1 corresponded to a radical tetrahydropyran-2-yl1-me thylI 0'2 ,2-dlmethyl-l ,3-dioxolan--4-ylmethyl I 2-dihydrobenz-1l4-dioxan-2ylmethyl thlophen-2-yl-3, 4-methyl enedioxybenzyl 5-methyl thi azol-2- 6 ylethyl para-toolylether-1-,yl bomyl norbomyl fenchyl menthyl, 0000 cyanoethyl phenoxyethyl methyl sul fonyl ethyl phenylthloethyl ethoxycarbonylmetaethoxycarbonyleth-l-yl 5,5-dlmethyl-tetrahydrofuran-2on-3-yl 2-oxopyrrol i di nomethyl cx-methoxycarbonyl benzyl, ca-cyanobenzy1 o,-benzoyl benzyl cx-me thoxycar bonylI cX-phenyl benzyl or morphollnomiethyl.
Good activity showed also the derivatives of the formula 1b, where'in a o Is C 1
-C
1 alkyl, substituted by -(X)F-CXA and, wherein A, m and X have the meaning given above, uii,.Aer formula lb.
0 006 New are further the 2-chloro-4-trifluoromethylthiazol-5-thiocarbonic acid Sderivatives of the formula Ic v Y't KXW:1217y -9-
F
3 C (Ic) wherein R 2 has the meaning given above under formula Ia.
New are also the 2.-chloro-4-trifluoromethylthiazol-5-carboxamides of the formula Id F k ~(Id) wherein R 3 and R4. independently of each other are hydrogen, Cj-C8atoo or0-Ccycloalkyl which is unsubstituted or substituted by Ci-Csalkoxy, Ci-Caalkoxyalkoxy, C 1 -Coallcylthio, cyano, a ycov~a -COORIa, CI-Ci4alkylcarbamoyl, di-Ci-Cisalkylcarbamoyl, Ci-Ct~alkylot~bamino, di-CI-C01akylamino, piperidinocarbonyl, pyrrolidinocarbonyl, piperidino or pyrrolidino;
R
3 and R4. further represent C 3 -Csalkenyl or C3,-Cacycloalkenyl which to is unsu'bSLituted or substituted by halogen, Ci-Caalkoxy, 03-COCYCloalkyl o a vaw cyano, -COORia, Ci-C~alkylcarbamoyl or piperidino- 0 carbamoyl; R 3 and R4. represent further C3-'0salkynyl, which is unsubstituted or substituted. by U, or R, 3 and R4 represent a radical or R 3 and R4, tcgetlher with the nitrogen atom, to which they are bound form a saturated or unsaturated heterocycle 4444 with 5 to 9 ring members which may include once or several times -N-0 1 -C~alkyl, -00- or -C(0R 7 )0Ra and which may be substituted 6 by halogen, cyano, C1-0oalkoxy, amino, CI-Ci4alkylamirio, di,-C 1
-C
4 alkylamino or aV *e6. -000RIo and wherein E, mn, Q, Rio and U have the meaning given above under formula lb.
Of these amides, those wherein -N(R 3 )'l44 corresponds to a tcouf defined below, have especially good activity.
-N-dichlorobenzyl-N--methylcarbamoyl, S-N-b~enzyl-N-i sopropylcarbamoyl, r 10 -N-cyclohexyl-N-methoxycarbamoylethylcarbamoyl, -1N-2 ,6-dime thylphenyl-N-me thoxycarbamoyle th- -yl or 1-cyclupent-1-yl)-N-metI, -lcarbamoyl.
New are further the 2-chloro-4-trifluoromethyl-tbiazol-5-carbohydrazides of the formula Ie
F
3 1 13' (Ie) wherein m, teich R 3 independently of the other and R 4 have the meaning given above under formula Ia. Among those, the hydrazides of the formula If show'd especially good activity 444.
U
4444 44 4, 4444 44 .4 8 4444 4 4 9444 4 444444 4 4 44 44 6 4 *4 4 44 44 4 4 44 4 4944-4.
4 4 444~Q 4444 844 F C =j-CO- q CO) 3 (if) wherein RV: and R9~ independently of each other represent hydrogen, Cl-Coealkyl, C 3 -Cacycloalkyl, phenyl or benzyl whereby phenyl and benzyl are unsubstituted or substituted by halogen,
C
1 -Ci~alkYl, CI-C~haloalkyl, CI-Ci~alkoxy, Cl-C4haloalkoxy, nitro, carboxyl, C-1-C~alkoxycarbonyl, carbamoxy or methylcarbamoyl, R'3' and RI: together represent also a 4 5 membered alkylene chain, whi~ch may be interrupted by oxygen, sulfur, a imino or CI-O4alkylimlino and which may be substituted once or several times by Ci-Cz~lkyl., In these definitions, the alcleswhere not otherwise specified, are undlerstooO, to have 1 to 18 carbon atoms. They can be straight-chained ot branched. The most usual v4"\are e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.butyl, tert.butyl, n-pentyl, isopentyl, n-hexyl and n-octyl. The alkenyl and alkynyl v~eg kcan also be straight-chained or branched and contain 3 to 18 carbon atoms. The most used x.s6t are e.g. allyl, methallyl, butene, butadiene, propynyl, methylpropynyl, 1-butynyl
SI
A
and 2-butynyl. Cycloalkyl or cycloalkenyl Eve.& have preferably 3 to 13 carbon atoms and can also be benizannellated. Typical representatives are e.g. cyclopropyl, cyclopentyl, cyclohe,,yl, cyclohexeny., indan, tetrahydronaphtlia.in, decalin. Halogen stands for fluorine, chlorine, bromine and iodine atoms, especially fluorine and bcoues chlorine. H-aloalkyl arid haloalkenyl ~-iare mono- or polysubstituted with halogen atoms.
The above-mentioned rzes ~k can be unsubstituted or substituted, typical substituents of such rests are halogen or alkyl, alkenyl, alkynyl, cycloalkyl, aryl. or aralkyl -ee- wh1oh are bound via rOQP oxygen, sulfur or an imino group. The aryl r.2 a be substituted in turn. These rests can also be bound via a sulfinyl-, sulfonyl-, 9C .9 carbonyl-, carbonyloxy-, carbamoyl-, sulfamoyl- or an amino-oxy- 9' ~roup #4 bridge to the alicyclic hydrocarbon-e 'St.
949 ,11 The substituent Q, as well as the -este .4R3 and R 4 with the nitrogen *atom, to which they are bound can represent unsaturated or saturated heterocycles with 5 to 12 ring members, which may include one two or three additional heteroatoma or a sulfinyl- or sulfonyl group. They can further contain one or two carbonyl groups and be benzannellated :9 unsubstituted or substituted.
.944 9:Possible heteroatoms are in this context one, two or three additional nitrogen atoms, up to two oxygen or sulfur atoms, whereby two oxygen atoms cannot be in vicinal position.
Examples for such heterocycles are listed below: pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazolime, pyrazolidime, isazoline, isazolidine, oxazoline, oXazolidime, jisothiazolidine, thiazoline, thiazolidine, diatbiazolidine, oxadiazolidine, piperidine, piperazipe, tetrahydropyrimidine and pyrazine, morpholine, thiomorpholine, thiazine, hexahydrotriazine, tetrahydropyrazine, oxadiazime, oXatriazine, hjxahydroazepine, hexahydrodiazepine, diazepine, hexahydrodiaze,,pine, azacyclooctan, Indolime, iseindoline, benzimidazoline, benzindazoline, benzroxa- -12zoline, benzthiazolins, benzisococazoline, benzthiazole, tetrahydrochinoline, te trahydro is ochino line, tatrahydrochinazo line, tetroahydirochinoxaline, tetrahydropbthalazine, benzomorpholine, berizothiomorpholine, tetrahydrobeni~azepine, tetrahydrobenzdiazepine, tetrahydrobenzoxazepine, 1 ,5-diab~cycloi4. 3.O1nonane, dihydrobenzoxazepine, 1,6-diabicyclo[5.3.O]decane, l,4-dirabicyclo[j3.3.OJoctane, 1,5-diazabicyclotj4.4.O]decane.
The above heterocycles can also be substituents. Further examples of heterocyclic systems which may occur as substituents are e.g.
pyrrole, inddazole, pyrazole, isoxazule, thiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole, thiatiazole, furan, tetrahydrofui n, dioxole, dioxolane, oxathiole, oxathiojlane, thiophen, tetrahydrothilopheni, dithiolan, dithiazole, pyridine, 4of pyran, thiopyran, pyridazine, pyrimidine, pyrazine, tetrahydropyrarl, tetrahydrotbiopyran, dioxin, dioxan, dithiin, dithian, is.,oxazine, thiazine, oxathiine, uziathiane, triazine, oxadiazine, 4thiadiazine, oxathiazine, dioxazine, azejpine, oxepin, thiepin, diazepine, oxazepine, indole, benzofuran, benzothiophen, indazole, benzimidazole, benzdioxol, benzdithiol, benzisoxazole, benz- "q thiazole, benzoxazole, benzoxathiole, benztriazole, bensoxadiazole, benzofurazane, benzothiadiazole, quinolin, isoquinolin, chromene, 'p chromane, isochromene!, isoc~hromanp, thiochromene, isothiochromene, thiochromane, isotblochromane, cinnoline, chinazoline, chinoxalino, phtalazine, benzdloxin, benzdithiin, benzoxazine, benzdioxan, benzoxathiane, benzotriazine, benzazepine, benzdilazepint?, benzoxazepine, purine, pteridine, phenoxazirie, phenothiazine.
jroup-s The heterocyclic *.-ool-okcan be substituted as mentioned above.
Some derivatives of the formula I are known from tho. literature and can be produced by known methods.
0 V.
The thiazol derivatives of formula I are produced e.g. according to US patent 4,199,506, by condensing an acrylic acid ester of the formula Il with chlorocarbonyl-sulfonylchloride of the formula III, according to the reaction scheme P3 NI-R'+ (III) 3C'==-L The 2-oxo-4-trifluoromethyl-thiazol-5-carbonic acid derivative otained is heated with phosphoroxycbloride whereby according to the reaction conditions and the amount of phoshoroxychloride used, a 2-chloro-4-trifluoromethyl-thiazol-5-carbonic acid derivative of the formula Ia or 2-chloro-4-trifluoromethyl-thiazol-carbichloride of the formula Ila (1a) (Ila) 4Acrylic acid derivatives of tlh. formula III can be prepared according to J. Het. Chem. 9 (1972) S13 by condensing an acetoacetic 0 iliaester with trifluoromethylnitril in a boiling solvent in the presence of sodium acetate, according to the reaction scheme
F
3 C-CN CH3-CH-9IR'
F
3 G-0--OH-9QR' Staring rom2-chloro-4-trif],uoronethyl-thiazol-5-carbochloride of formula Ila, the ollowing active derivatives of formula I can be preparod according to known methodst -14 R1-X
XR
1 1i (Ila) 1.
(Ib) amine HA(D) F 3 (Id) amine HA (D) 09*~ .9 9 9 099 9>999 *9 0 0099 0 000* 0 *9*990 0 0 00 00 0 99 4 *9 00 0 0 0* 0 *00*90 *000 0 00 *0 0 0* 9 0 00 0 #0 4 2c (Ila)
R
1
-G
(1c) In these formulae A and RI have the meaning given above under formula Ia and G is an instable nucleofuge rest, such as a halogen atom or a lower-alkyl sulfoxy rest.
In these reactions there are used inert solvents and diluents are used to it the particular reaction conditions. There may be mentioned as examples; halohydrocarbons, especially ohiorohydrocarbops su~ch as tetrachloroethylene, tetrachioroethane, dichioropropane, methylene chloride, dichlorobutape, chloroform, chloronaphthalene, dichloronaphthalene, carbon tetrachloride$ triohloroet'hane, trichioroethylene, pentachioroethane, difluorobenzene, 1 ,2-dichlovothane, 1 ,l-diohloroethane, I ,2-cis-dichloroethylene, ohlorobenzene, fluorobenzene, bromobenzene, lodobenzene, dichlorobenzene, dibizomobenzene, chlorotoluene and. trichlorobenzene; ethers, such as ethyl propyl ether, methyl tert.-buty. ether, n-butyl ethyl ether, di-n-butyl ether, diisobutyl ether, diisoamy! ether, diisopropyl ether, anisole, phenetole, cyclohexyl methyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxan, thioanisole and dichiorodiethyl ether; nitrohydrocarbons, such as nitromethane, nitroethane, nitrobenzene, chloronitrobenzene and o-nitrotoluene; nitriles, such as acetonitrile, butyronitrile, isobutyronitrile, benzonitrile and m-chlorobenzonitrile; aliphatic or cycloaliphatic hydrocarbons, such as heptane, pinane, nonane, cymol, petroleum fractions within a boiling range of from 700 to 19000, cyclohexane, methylcyclohexane, Decalin, petroleum ether, hexane, ligroin, trimethylpentane, 2,3,3-trimethylpentane and octane; esters, such as ethyl acetate, ethyl acetoacetate and isobutyl acetate; amides, for example formamide, methylformatide and dime thylf ormamide.
Surprisingly, it has been found that the compounds of formula I of this invention have, for practical field application purposes, a very advantageous microicidal spectrum against phytopathogeaic fungi and bacteria. Compounds of formula I have very advantageous curative, systemic and, in particular, preventive properties 1 and 0 can be used for protecting numerous cultivated plants. With the compounds of formula I it Is possible to inhibit or destroy the microorganisms Which occur irn plants or, in parts of plants (fruit, blossoms, leaves, stems, tuberes, toots) in different crops of useful plants, While at the same time the parts of plants which grow later U are also protected from attack by such microorganismso .4:00* The compounds of formula I are effective against the phytopathogotnic, fungi belonging to the following classes; Fungi imperfet~ki (e.g.
Botrytis, lielmlnthosporium, Fusarlum, Septoria, Cercospora, Pyricularia, Alternaria); fasidiomyqetes the geneta 1Iemileia, Rbizocotonia, Puccinia);4 and, in particular, against the class of the Agcomycetes (eqr. Venturia, Podoophaera, IErysiphe, M1onilinia, Uncinul In addition, the compoun-s of formula I have a systemic action. They can also be used as dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings aginat fungus infections as well as against phytopathopenic fungi which Occur in the soil.
i i 16 9 9*r Sr 9 t1 Apart from their microbicidal activity, the compounds of formula I have nematocidal properties which make them especially suitable for controlling plant nematodes. For this utility, the compositions of the invention can be used curatively, preventively or systemically.
They exhibit a broad range of activity against the various species of nematode and therefore satisfy the requirements of practice.
In the rates of application indicated below, the compounds of the invention, are especially well tolerated by plants.
Accordingly, the invention also relates to microbicidal compositions (i as well as to the use of the compounds of formula I for controlling phytopathogenic microorganisms, in particular phytopathogenic fungi, or for protecting plants from attack by said microorganisms.
S The invention further embraces the preparation of agrochemical 4, compositions, which comprises homogeneously mixing the active ingredient with one or more compounds or groups of compounds .9 described herein. The invention furthermore relates to a method of treating plants, which comprises applying thereto the compounds of formula I or the novel compositions.
Target crops to be protected within the scope of the present invention comprise e.g, the following species of plants: cereals (wheat, barley, rye, oats, rice, sorghum and related crops), beet (sugar beet and fodder beet), pomea, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, ,aspberries and blackberries), leguminous plants (beans lentils, peas, soybeans), oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts), cuumber plants (cucumber, marrows, melons), fibre plants (cotton, flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit, mandarins), vegetables (spinach, lettuce, asparagus, cabbages, a carrota, onions, tomatoes, potatoes, paprika), lauraceae (avocados, cinnamon, camphor), or plants such as maize, tobacco, nuts, coffee, .9.99.9 .9 .9 .9.
.99 .9 .9 17 sugar cane, tea, vines, hops, bananas and natural rubber plants, as well ais ornamentals (flowers, shrubs, deciduous trees and conifers).
This recitation constitutes no limitation.
The compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds.
These compounds can be both fertilisers or micronutrienL donors or other preparations that influence plant growth. They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, mollusicides or mixtures of several of these preparations, if desired together with further carriers, su~rfactants or 0application promoting adjuvants customarily employed in the art of o00 formulation.
0 4 Suiitable carriers and adjuvants can be solid or liquid and Porrespond to the substances ordinarily employed. in formolation technology, eig. natural or regenerated mineral substances, solvents, dispersats, wetting agents, taqkifiors, thickeners, binders or fertilisers.
0 A preferred method of applying a compound of formula I, or an agrooheinical composition which contains at least one of sai compounds, is foliar application. The number of applications and the rate of application depend on the risk of infestation by the corresponding pathogen, (speci.es of fungus9). H4,oVer, the compound of formnula I can also penetrate the plant throtvgh the roots via the Ssol! (Systemic action) by impregnating the locua of the plant with a liquid formulation, or by applying the compounds in solid form~ to the doilt e~g. In granular formt (soil application) 4 The compounds of formula I may also be applied to seeds (ctoatinlg) by impregnating the seeds either with a liquid formulation Oontaining a compound of formula 1) or coating them With a solid formulation. In Opecioal cases, further typos of applicatio. are also poasible, eigt 00100tivo treatment of the plant stems or buds.
1 8 The compounds of formula I are used in un d*fiOt .i preferably, together with the adjuvants conventionally pri~ In Je art of formulation, and are therefore formulated in kawni rro, to emulsifiable concentrates, coatable pastes, diraWcty oryablo or dilutable solutions, dilute emulsions, wettable poWdars. toluble powders, dusts, granulates, and also encapsulations .lo eg polymer substances# As with the riature of the cotnpositionol tho methods of application, such as spraying, 4tonmisinig, dusting, 4atrin4, Qoatirig or pouring, are chosen in accordance with time, intendod IC obJectivee and the prevailing circumstances- Advantageous -rates of applic4tion are normally from 50 g to 5 kg of active ingredient per heqtare, preferably from 100 g to 2 kg a,i,/ha, most prpferably from 200 g to 600 g a.i./ha.
090 *0 0 000 The formulationa, i.e* the composition$, preparation$ Or mixcture$ oe 0o containing the compound (active Ingrediet of ormula I and) where 00000: appropriate, a solid or liquid4 adjuvant, are prepared in %nown maniner, e~g. by hqmogeneously Tnixng and/or grinding the active i ngtedients with extenders, eigs PolVeptst solid carriers and, where Apprcpriate, 4urfaae-aciVe compounds (surfactants), *0 0 S00 0 4. Suitable solvents avr oromatic hydrocarbons, preferably the 0 0 0 00 fractions containing 8 to 12 carbon atoms, Pogo Xylerio mixtures or substituted naphithaleties, phthalates such as dibotyl, phthialote or diootyl phtbalate, aJ1iphatiq hydrocarbons such nEI cyclofiexane or paraffins, alcohols and glycols and thwir ethers and esterso ouch as G 0 aethanol,, ethylene glycol, ethylene glycol monomethyl or monoethyl etheor, ketones such as cylhxnnstrongly polar solvents such ~s rotyL--pyr~idoedimethyl sulfogi.o or dimothylformamide, as well as vegetable oils or epoxidised vegetable oils such a&s epoxdised coconut oil, OutnEloWe Oil or soybean oil;~ or watert SThe solid carriers used for dusts and dispersible powders, aro normally natural mineral fillers such as Calcite, talcum, kaoliti) rnntmrillonite or attapulgite. In order to improve the physical proporties iLt is also possible, to add hiighly diapersed silicia acid -19 or h 8hly dispersed absorblmnt polymers. Suitable granulated adsorptive carriers are porous types, for ex~ample pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great numbez of pregranulated materials of inorganic, nr organic nature can be used, e.g. especially dolomite or pulverised plant residues. Particularly advantageous application pr'omfi-ting adjuvants which are able to reduce subetantially the rate r application are also natural (an~imal or vegetable) or synthetic phospholipids of the series of the cephalims and lecithins, which can be obtained Q~g. from animal or plant ce~lls, in particular from soybeans, Examples of useful physical forms are phosphatidyl qholine mixtures, Examples of synthetic phospholipids are dioctanoylphospbatidyl choline and dipglmitpylphosphatidyl choline, o Depending on the nature of the compound of 'formula I to be formulda- 4499 ted, suitable surface-octive compounds are non-ionic, cationic and/or anionic surfactanto havit~g good emulsifying, dispersing and wetting properties, The; torm, "surf actants" will also be understood as comprising mixtures of sorfaotants, 6 q Suitable anionic stirfactants can be both water-soluble soaps and water-sqoiuble synthetic sorface-active oompoonds.
Suitable, soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (Cio-Go2), the sodium or potassium salts of oleic or 0 V 4 teairic acid, or of natural fatty Qcid mixtures which can be obtained e.g. from coconut Qil ot; tallow oil,, Mention may also be made of fa~ty acid meLlhyllaurin salts, More frequently, however, so-called synthetic surfactants are u~ed, especially fatty sulfonates, fatty sulfates, solfonated bmnzimidazole derivatives or alkylaulfonates.
20 The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a Ce-C 2 2 alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethyleine oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are corresp.'ading phosphates, e.g. salts of the phosphoric ra i acid ester of an adduct of p-nonylphenol with 4 to 14 moles of O* m ethylene oxide.
Non-ioi.c surfactants are preferably polyglycol ethdr derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) .q hydrocarbon moiety and 6 to 18 carbon atom in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts oi polyethylene oxide with polypropylene glycol. ethylenediaminopropylene glycol and alkylpolypropylene glycol containing 1 to 0, 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
S Representative examples of non-ionic surfactants are nonylphenolpolypthyXethanols, castor oil polyglycol ethers, polypropylene/ polyethylene oxide adducts, tributylphenoxypolyethyleneethanol, i 21 0 9 Q 0 4 0 4 9 09 polyethylene glycol anid octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cs-C 2 zalkyl radical and, as further substituents, unsubstituted or halogenated alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The agrochemical compositions usually contain 0.1 to 99 by weight, preferably 0.1 to 95 by weight, of a compound of formula I, 99.9 to 1 by weight, preferably 99.8 to 5 by weight, of a solid or liquid adjuvant, and 0 to 25 by weight, preferably 0.1 to 25 by weight, of a surfactant.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also contain further auxiliaries such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for obtaining special effects.
Such agrochemical compositions constitute an object of the present invention.
The following non-limitative Examples serve to illustrate the invention in more detail. Temperatures are given in Centigrades in the following examples and tables, pressures are given in millibar (mbar), percentages and parts are by weight.
9444 9r4 a r 9 04 44, 22 4444 44 4 ~9 4 499 4,44 44 49 4.94 4444 4 49 44 44 4 0 9 44 04 4 o 4~ 44 44 9 4 44 Example 1.1: Preparation of 2-chloro-5-(2-phenoxyethoxycarbonyl)-4trifluoromethyl-thiazole
CF
3 00CH 2 CHZO-* 6.3 g (0.045 mol) of 2-phenoxyethanol are added slowly while stirring to a solution of 11 g (0.44 mol) of carbonyl-4-trifluoromethyl-thiazole in 100 ml of absolute toluene.
The solution is then cooled to 0 5' and 3.6 g (0.045 mol) of triethylamine are added dropwise while stirring. Triethylaminehydrochloride precipitates from the reaction mixture, After everything is added, the suspension is stirred for 20 hours at room temperature and then poured onto ice-water. The organic phase is separated, dried over sodium sulfate and concentrated in a rotatory evaporator. The residue cristallizes. In order to purify it, the crystals are suspended in petrol-ether, filtered and dried. In this manner 8.7 g (57 Z) of the title compound are obtained, m.p. 70-72*.
Example 1 Preparation of 4- trifluorome thyl-thiazole A H(CHA) A solution of 2.8 g (0.027 mol) of triethylamine and 4.1 g (0.027 mol) of N-isopiropylbenzylamine in 50 ml of ethylacetate are added dropwise at Q0 to 50 into a stirred solution of 6.5 g (0.025 mol) of 2-chloro-3-chlorocarbonyl-4-trifluoromethyl-thiazole.
After the addition is complete, the reaction mixture, which has turned into a yellow solution is stirred for 15 hours at room temperature and then 'sored onto ice-water. The organic plba~e is separated$ dried over sodium sulfate, purified with -%cttve charcoal, filtered and concentrated on a rotatory evaporator. The residue, a red-brown Gil is purified by chromatography in ethyl acetata/hexan 444' 44 4 4 4 4 4 44 -23over a silica-gel column. After evaporation of the eluaitt, there remains 6.5 g (73 of a colourless oil with correct chemical analysis.
Example 1.3: Preparation of 2-chloro-5-(1-methoxycarbonyl-eth-lyloxy-carbonyl) -4-trifluoromethyl-thiazole Y3
CF
3 -*==*-COOCHCOCH3 A mixture consisting of 6.94 g of 2-chloro-5-carboxyl-4-trifluorqmethyl-thiazole, 5 g of 2-bromopropionic acid-ivethyl ester and 4.5 g 06*4 of potassium carbonate, suspended in, 50 ml of an'hydrous dimethylat Iormamide is stirred under nitrogen atmosphere at room temperature owff during 3 hours. The reaction-mixture is then filtered and the filtrate is poured into Itce-water/ethyl-acetate 1:1. The organic phase is separated, washed 3 times with ice-water, dried and concentrated in a rotatory evaporator. The residue, a colourless oil is distilled for purification. One obtains 8.5 g (75 of title product as colourless oil b.p. 75-8O*/0.015 mbar.
A '1 9 24 In analogy to these examples the following compounds are prepared: CF 3-j=---COR1 Table 1 Dbvs. constant No. nhvs. constant 94$ 409 1.001 1.002 1.003 1.004 1 .005 1 .006 1.007 1,008 1.009 1.010 1.011 1.012 1.013 1.014 1,.015 1.016 1.017 1 .018 1.019 1.020 I.021 1.022 1 .023 1.024 1 .025 1.026 1.027 1,028 1 .029 1 .030 1,.031 1.032 1.033 1.034 1 .035 1 .036 1 .037 .1.038 1.039 1,.040 1 .x41 1-.042 1 .043 1 -dodecyl 1-octadecyl cyclopropylmethyl cyclopen tylmethyl cyclonexylinethyl cyclohexyle thyl tetrahydrofuran- 2-yl-me thyl pentahydropyran-2-yl-methyl 2, 2-dimethyl-1 ,3-dioxolan-4-yl-rnethyl 1 ,2-dihydrobenz-1 ,4-dioxan-2-ylinethyl furan-2-ylmethyl thiophen-2-ylme thyl 3, 4-methylendioxybenzyl thiophen-2-ethyl pheny le thyl para tolyl-eth-1-yl 3, geranyl 2-hexen-l -yl 1-hexen-6-yl 1 -hexen-3-yl 2-chloro-2-propen-1 -yl 3-chloro-2-propen-1 -yl 3-phenyl-2-propen-1 -yl cyclopentyl cyclohexyl 2-methyl-cyclohexyl 3-me thyl-cyclohexyl 4-methyl-cyclohexyl cyol ododecyl 2,3-dime thyl-cyclohexyl 2,4-dime thyJ-cyclohexyl 2, 6-cUmethyl-cyclohexyl 3, 5-dime thyl-cycloexy].
4 -tert .butyl-cyclohexyi.
b ornyi.
norbornyl fenchy].
menthyl 2 ,2-dichlor-cyclopropylimethyl -OH2 -ON -CI1Z-CHZ-CN M. P.
oil resin oil M. P.
60 630 96 980 m. p. 64 67' oil M, P.
oil oil oil 65 670 25 No. Rl phys. constant
IC
9*99 9 99* 9 999 9.9.
o Q 99 '.99 9 *9,9 99#999 9 99 9 99 9 9 9 o o 9o 9 9 ~o9 9 9 99 09 9 9* 9 9 1.044 1.045 1.046 1.047 1.048 1.049 1.050 1 .051 1 .052 1 .053 1 .054 1 .055 1 .056 1.057 1.058 1.059 1.060 1.061 1.062 1.063 1.064 1 .065 1 .066 1 .067 1,.068 1.069 1 .070 1.071 1.072 1.073 1.074 1.075 1.076 1.077 1 .0OA 1,079 1 .080 1.081 1.082 1.083 1 .084 1 .085 1 .086 1.087 1 .088 1 .089 1 .090 1.091 -CHz-PO(0C 2
H
5 2 2-nitro-.ethyl 2-allyloxy-ethyl 2-benzyloxy-e thyl para-chilorbenzyloxye thyl ortho-ch:1orbenzyloxyethyl cyclopropyloxye thyl cyclohexyloxyethyl 2-phenoxyethyl para-chlo rphenoxyethyl
-CH
2
-CH
2
-SCH
3
-CH
2
-CH
2
-SO-CH
3
-CH
2
-CH
2 -S0 2
-CH
3
-CHR-CH
2 -CHg-SCH3
-CH
2 CH2-CHZ--S-CfI 3
-CH
2
-CHR-CH
2 -S0 2
-CH
3
-CHZ-CH
2
-S-C.H
9
-CH
2
-CH
2
-S-CH
2
-CH=CH
2 cyclohexylthioe thyl benzylthioethyl para-chltorbenzyl thiuethyl phenylthioethyl phenylsulfonyle thyl para-tolylthioethyl para-chlorpheuylthioethyl phenylthiopropyl 5-naphthylthioe thyl 2-phenylthio-1 -methyl-ethyl 2-phienylthio-1 -chioromethyl-ethyl
-CH
2
-CH
2
-S-CH
2 -C00C2Hs -CfjCHSCH(CH 3
)COOC
2
H
.CH
2
-C
2 S-Q0-N(OHa) 2 piperidinoylthioethyl -CH2-CHi 2 -S-CS-N( OH 3 2 piperidinothiocarbonylthioe thyl
-CH
2
-COOCH
3 -CfHa-0000 2
HS
-CH9-C0O04 9 (n)
-CH(CH
3
)COOCH
3 -C(Oii 3 RC00C2H5
-CH
2 -0H 2 -C0C11 5, 5-dimethyl-tetrahydrofuran-2-Qn-3-yl -cH-CO-N(O 2 40)2 -CHzCON[CH( OH 3 )212
-CH
2 00N[CH 2 (C1 3
)O
2 Hsj 2 -C1I 2
CO(CHZCH-CHZ
2 2-methyipiperidinoylmethy3.
azepinoylmethyl m. p. 70 72' m. p. 86 88' m. p. 47 -49' b.p, 80 0.025 mnbar b.p. 25 -800/ 0.015 mbar m.p. 100 1020 oil 26 No. Riphys. constant 000 4 .4 Q 0 00 0400 0 00 0000 *090 09 CCI 0 0 04 4 0~.
0 00 04 o o~ 444404 0 40*4 ~0 4£ 0* 0 09 0 04 0 #4 1 .092 1 .093 1 .094 1.095 1.096 1 .097 1 .098 1 .099 ID 1.100 -1.101 1,102 1.103 1.104 1.105 1.106 1.107 1,108 1.109 1.110 1411 1.112 1.113 0 1.114 1.115 0 1.116 1,117 1,118 1.119 1.120 1.121 1.122 .1 .123 1.i124 1.125 1.126 1.127 1.128 10 1.129 1 .130 1,131 1.132 1 13 5"1 1,134 1.135 ai-dome thy 1 N-me thyl-ariilidometnyl 2,6-dime thylplhenyl)-N-(methoxycarbonyl-eth-1-yl)-carbamoylinethyI.
-CH
2 -CH2-NH-CO-CH 3 cyclopropancarbamoyl-e thyl
-CHZ-CH
2 -NH-C0CHC2 benzamoyl-ethyl thienyl-2-carbarnoylethyl.
furylcarbamoyle thyl
-CH
2 -CU 2-NH-CO-NH-CH 3 S(OH3 3) 3 phenylureylene-ethy.
-CHICH
2
N(CH
3
)COCH
3 -CHaCHaN(CH 3 )CoCHClR
-CH
2
CH
2 N(0H 3
)CONHCH
3 CH2CU N( CH 2 SO2CH N-methyl--phenyl sulfamoyl-ethy1
-CH
2
CH
2 N( C 3
H
7 COCHcJ, 2
-CHZCH
2
N(CH
2 CH=0HZ)CONHCl 2 2-oxo-pyrrolidino-e tbyl dicyclohexylme thyl ca-phenylbenzyl ca-methylbenzyl ao-caboxylbenzyl ca-carboxyl-para--chlorbenzyl a.-metoxycatbony1'-benzyl ca-e thoxycatbonyl-benzyl ca-cyanobenzy.
v-benzoyl-berizyl.
ca-methoxycarbonyl-ca-phenyJlbenzyI -0H 2 -CfI 2 -N(C11 3 pyrrolidinoethyl pipe ridinoe thyl inorpholinoethyl anilinoethy.
pata (1-methoxycairbonyl)etbhoXyphienyI para( 3-methyl-i ,3-oxazolldin-2--,yl)pbienyJ.
para(N -(dime thyl-ireylene)-pheny.
meta(N' -diTP.thyl-mreylene)plienyI 0-cyano-0-methnoxycarbony1-o tyry.1-4-yl 13, -di(methoxyo~arbonyl) -styryl-4-y.
5,-dicyano--styryl-4-yl m.p. 95 970 m. p. 62 660 m. p. 58 62* oil h.p. 62 64* 11. p.
Mb.
M. P, 78 105 106 810 109' 1100 s.p, 185 1870 (bydrochloride) 27 Nr. Rlphys. constant 1.136 1.137 1.138 1.139 1.140 1.141 1 .142 4 0044 0104 P4 4
I
0 #44 00*144 0 4 44 a 0 0* 0 0$ 0 4 04 1 .143 144 1,145 1.146 1.147 1.148 1.149 1 .150 1.151 1.152 1.153 1 .154 1 .1 5 1 .156 Table 2 Ni:.
-0000p~
-COOH
-COO benzy! -000(4, 4-dimethyl-tetrahydro-fur-3yl-2-on) -000( 4-metbyl-thiazol-5-ylethyl) -COO(2, 3,5,6-diepoxy-cyclohexan-1-yl) syn. isomer -000(2,3,5, 6-diepoxy-cyclohexan-1-yl) anti isomer cU-(4-qhlorphenyl)benzyl ce-( 2-chiorphenyl) benzyl a-0(-chlorphenyl) -4-chlorbenzyl Q,-(2-.chlorphenyl) -2Z-chlorbenzyl 2-chlorphenyl) -4-ablorbenzy! ci-(4-fluorphenyl) -benzy1 2-f luorphenyl)-benzyl c4-( 4-fluorphenyl) -4-flu~rbenzyl ci-( 2-fluorphenyi.) -2-f luorbenzyl c4-( 2-f 1uorpbenyj) -4-fluorbenzyl c-(4-anisyl)-benzyl c-(4-nlethoxyphenyl) -benzyl ci-( 3-trif2,vorphenyl) -bepzyl in.p. 100 1020 M.p. 64 670 m.p. 144 1750 ni.P. 144 1200
M.IP.
M.P.
Mn.P.
600 1250 580 C F 3 ==-00C-S-R' phys. con~stant *004 04 00 4 *a 4 a.
0 2.001 2.002 2.03 2.004 2.005 2.006 2.007 2.008 2.009 2.010 2.011 2.012 2.013 -Cfl2-C00CHa -Coa1-cooc -CII(0H3 C0H -CH2-CHZ-C00H pipe ridinamoylme thyl azepinamoylme thyl anilidome thyl Para chioranilidmethyl 2-carboxyiphenylme thyl ben zyl p. 0-62 M.P. 60 62' 28 Table 3 Nr. R 3
F
3 CON /R3 (Id) phys. constant 3.001 3.0Q02 3.00Q3 3.004 3.005 3.006 3.007 3.008 3.009 44 4 4 444* 44 44 444 4,4, ~*44 4 4 0444 4444*4 4 4 4 *4 44 4 4 44 4 44 44 4 4 44
~C)
4 4 4 44~~ 4 0 04 44 4 44 4 4 04 0 4* 3,.010Q 3.011 3,012 3.013 3.014 3.015 3.016 3.017 3.018 3,019 3.020 3.021 3.02 2 3,023 3.02 4 3.025 3.026 3.027 3.028 3.029 3.030 3.031 3.032 3. 03 3.034 3.035 3.036 3.037 3, Q38 3.039 3.040 3.041 3.042 3.043 3.,044 allyl al2lyl allyl 2-me thyl-2-propen- 1 -yl 2 -me thyl-2-propen-1 -yl 2-chlor-2-propen-I -y 1 2-chloz'-2-propen-1 -yl 2-cblor-2-propen-1 -yl 2-chlor-2-pi-opep-1-yl 3-chlor-2-propen-1 -yl propyl methyl methyl methyl isopiopy! isopropyl
H
H
methyl methyl ethyl ethyl
H
methyl isopropyl cyclopropyl ethyl ally.
cyc lohexcyl phenyl phenyl cyclohexyl 2, 6-cdiethyl-pheny.
phenyl phenyl 4-chlor-phenyl 2, 4-dirchlor-pheny1 3, 4-diohlor-phenyl 3-trifluormethyl-phenyl methyl
H
H
H
methyl allyl 2-me thexy-e thy) isopropyl isopropyl cyclohexyl 2-me thoxy-ethyl isopropyl cyclohexyl 2-chlor-2-propenl-yl propyl 2-me thoxy-ethyl cpyclohexyl benzyl 2,6-clichlor-benzyl m.p. 118 benzy, ot 4-chlip,-benzyl benzy] phenyl, phenyl.
4-chlor-phenyl 2-chlor-4-brom-phenyl 3-trifluormethyl-phenyl -CH 2 -C00C 2 1 -OH2~-COOCH 3 -0HR-C-NH-C3fi 7
IW
-Cfi2I-CQ-N(C~fHs) 2 -OH a-C 11 a-ON -CfH 2 -CUH2CN 'C~z'CfH 2
.CN
-OH2-CH2-CN -OH 2
-CH
2
-COH
-CHZ-CHa-C000H[3 m~p, 116 1200 -CH(C~i3)COOCH 3 mip. 120 123" -OI12-C00U -CH2-CN -CHz--CN -CH2-cN CII 2-ON
-CH
2
-ON
l-cyanocyclopent-l-yl m.p. 130 1336 3-trfluoromethyl-cyclohoxyl -NfI -N(Cfl 3 a
-NH-OII
29 Nr. R.
3 phys. constant 3.045 3.046 3.047 3.048 3.049 3.050 3,051 3.052 3.053 3,054 3,055 3.056 3.057 3.058 3.059 3.060 3.061 3,062 3.0Q63 3.064 3.065 3.066 3.067 3,068 3.069 3.070 3.071 3.072 3,073 H anilino .P H 2-benzoyl-hydrazo H 2-plhenylsulfonyl-hydrazo pyrrolidino piperidipo 2-me thylpiperidino 2 -e thylpiperidino hexahydroazepino morpholino 2,2,5,5-tetraiethyl 1 ,3-oxazolidin-3-yl 5, 5-dimethylL-2, 2-tetra-me thylen-1 3-oxazolidin-3-yl 5, 5-dimo~thy1-2 -penitamnethyleni-1 ,3-oxa~olidin-3-yl 2-phpnyl-1 3-oxa~o2lLdin-3-y1 2, 2-tetramethylen-benzthiazol-3-y1 2-oxo-pyrrol-idino hexahydro-2-oxNo-azepino 3-oxo-thiomorplio]inQ 2-oxo-1 ,3-oxazolin-3-yl 2-trichloromethyl-1 3-oxazolidin-3-yl H 2-chlorbenzyl Hf 2-hexylbenzyl
CZH
5
C
2
H
5 allyl H Mp 137 1380 40 410 56 580 88 890 89 910 115 1160 100 1010 1,5491 72 740 1,5027 ti 4 *444 4, 644# 4 4 #4 4 4 I 4, #44414 4 .4 4 4.
4 44 phenyle thy),
C
2 H5 2-chlo :obenzyl al ly'A
C
4
H
9 -n 2 ,6-d.Lqhlorbenzyl Hi ally 1 2,6-d:LqhloIberizyl ethoxycroton-2-yl 2-Olhora2lly1 #444 4 44 4* 4 #4 4 4 4 4 44 3.074 CH(Clb) 2 3,075 4-.clor-2-fluor-6-isopropQ~cypheny).
3.076 cyano-dime thylmrethyl 3.077 chlorphenyl 3i078 cayano-dimty1.-methyl 3#079 2, 2-dJimpthylindanyl 3.080 ,henyX 3.081 dlphenylmiethyl 3.082 2, 6-difluorophenlyl 3.083 th iazol- 2-yI 3.084 2-carboy- 4-chlorphony1.
3.085 3-trifluormethyleyclohoexy1 3.086 2,4, 6-trichloruiitnp 3.08" Vinfuryt 3. 0V 3, 4-methylendioxybenzyl 3,089 4-anidosul~onylphenyl 3.090 1,,2-diphepyleth-l-yl
H
H
H
m~p.
A20 lmp, n 20
D
m.pv nOV4p lMP* eMPO 10, p 123 130 125 78& 174- 125 177- 160 12$0 1320 1 280 800 1750 1270 1790 1610 nmp, 136 1,38' M.P. 132 1340 MOpO mo~p.
Mi p mjpo 1091, 1 860 102 1310 1890 1480 NE. R3 phys. constant 3.091 ca-methylbenzyl 3.092 benzoylamido 3.093 4-fluorbepzyl 3,094 2, 2-diphenyleth-1-yl 3.095 1-cyano-cyc2opent-l-yl 3.096 l-cyano-cyclohex-1l-yl 3.097 2-methoxycarbonyl-4chlorphenyl 3.098 2-me thylaminocarbonyl- 4-chiorphenyl 3.099 2 -dime thy lanvno 3.100 anilino 3.101 2-chlorarutlino 3.102 4-chloranilino 3.103 1-Qyanocytc1opent-1-y1
H
ff
H
Hf methoxycarbonylne Chyl If m. p. 131 m. p. 192 m. p, 128 m: p 127 m p, 145 m, p. 145 1330 194" 1300 1 290 1470 1470 09 4994 .9 49 9 004 4 6 44 4~ 4 4 9 .444 949940 9 9 *4 44 9 9 40 49 94 4 9 44 444644 6 4 4904 4 44 2. Formulation Examples for active ingredients of the formula I N, per cent by weight) 2,1 W4ettable powders active ingredient from the Tables 1-3 sodium lignosuiphonate sodium 1aury, su],pEte sodium diisobuitylnaphthalene-, suiphona t Qctylphenolpolyethylene glycol ether (7-8 mol ethylene o~ido) highly dispersed Pilicic acid kaolin
C)
6 6% 10 10 04 The active Ingredient is mi~ced well with the adjuvants and ground %0~C well in a suitablIe mill. Wettable powders are obtained that can be diluted with water to give suspension$ of Any desired concentration, 2.2 Emulsifiable concentrate active ingredient from the Tables 1-3 otc~yphenolpolyethylone glycol ether tool ethylene oxide) U~ 3 43 'CONHR* -CON(R7 2 t -SOa2flR7 _S$OZNt 7 24 Pyrrol tdinot 010~lrto, ovrrolldinotarbonvI or DertdtnocarboflVI 31 calcium dodecylbenzenesulphonate 3 castor oil polyglycol ether mol of ethylene oxide) 4 cyclohexanone 30 xylene mixture 50 Emulsions of any desired concentration can be prepared from this concentrate by dilution with water, 2,3 Dusts a) b) active ingredient from the Tables 1-3 5 8 0 talcum 95 kaolin 92 Dusts that are ready for use are obtained by mixing the active ingredient with the carriers and grinding in a suitable mill.
2.4 Extruder granulate active ingredient from the Tables 1-3 10 sodium lignosulphonate 2 carboxymethylcellulose 1% kaolin 87 et 4 4 The active ingredient is mixed with the adjuvants, ground and moistenec 1 ?0 with water, This mixture is extruded and then dried in a stream of air, Coated granulate o active ingredient from the Tables 1-3 3 a% polyethylene glycol (MW 200) 3 kaolin 94 (HW molecular weight) The finely ground active ingredient is uniformly applied in a mixer to the kaolin moistened with polyethylene glycol. A duat-ftee coated granulate is obtained in this manner.
e L 32 2.6 Suspension concentrate active ingredient from the Tables 1-3 40 ethylene glycol 10 nonylphenolpolyethylene glycol ether (15 mol of ethylene oxide) 6 sodium lignosulphcnate 10 carboxymethycellulose 1 37 aqueous formaldehyde solution 0.2 IC silicone oil in the form of a 75 aqueous emultsion 0,8 water 32 The finely ground active ingredient is intimately mixed with the adjuvants. In this manner, a suspension concentrate is obtained from which suspensions of any desired concentration can be prepared by *9 Cdilution with water.
9* *99* 3. Biological Examples; Example 3.1: Action against Puccinia gamini on wheat 00a) Residual protective action Wheat plants are treated 6 days after sowing with a spray mixture (0,06 active ingredient) prepared from a wettable powder formulation of the test compound. After 24 hours the treated plants are infected on* with a uredopore auswiponsion of the fungus, The infected plants are incubated for 48 ovurs at 95-100 relative humidity and about 200C and erthen stood in a greenhouse at about 220C. Evaluation of rust pustule development is made 14, days after infection.
b) Systemic action Wheat plants are treated days after sowing with a Opray mixture (0,02 4ctive ingrodiontf based on the volume of the ooit) prepared SO from a wattable powder formulation of the test compound, After 48 hours the treated plants are infected with a uredosportse suspension of the II 1 33 fungus. The plants are then incubated for 48 hours at 95-100 relative humidity and about 20 0 C and then stood in a greenhouse at about 220C.
Evaluation or rust pustule development is made 12 days after infection.
Compounds of the Tables 1-3, especally 3.040 exhibit good activity against Puccinia fungi. The Puccinia attack was irhibited almost completely. Puccinia attack is 100 on untreated and infected control plants.
Example 3.2: Action against Cercospora arachidicola on groundnut plants IC> Residual protective action S°o Groundnut plants 10-15 cm in height are sprayed, with a spray mixture (0.02 of active ingredient) prepared from a wettable powder formulation of the test compound, and infected 48 hours later with a Sconidia suspension of the fungus. The infected plants are incubated for 72 hours at about 21 0 C and high humidity and then stood in a greenhouse until the typical leaf specks occur. Evaluation of the fungicidal action is made 12 days after infection and is based on the number and si; of the specks.
4 Compared with untreated and infected control plants (number and size of the specks I00%), Cercospora attack on groundnut plants treated with cormpounds of the tables 1-3 is substantially reduced. Thus compound 1.009 inhibits the occurenco of specks almost completoly (0 to SExample 3.3: Action against Erysiphe graminis on barley a) Residoal protective action Barley plants about 8 cm in hei:ht are sprayed with a spray mixture (0.006 active lgredient) prepared from a wettable powder formulation of the test compound,. The treated plants are dusted with conidia
T
4 i -34 of the fungus after 3 to 4 hours. The infected barley plants are stood in a greenhouse at about 22 0 C. The fungus attack is evaluated after days.
Compounds of the Tables 1-3 exhibit good activity against Erysiphe fungi. For example, the compounds 1.009, 1.012, 1.065, 1.115, 1.127, 1.137, 3.077, 3.084 and 3.086 inhibited Erysiphe attack almost completely (attack 0-10 On the other hand, Er'siphe attack is 100 on untreated and infected control plants.
Example 3.4: Residual proteutive action against Venturia inaequalis on tL apple shoots Residual protective action rr, Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture prepared from a wettable powder formulation of the test coinpouid. The plants are infected 24 hours later with a conidia suspension of the fungus. The plants are then incubated for days at 90-100 relative humidity and stood in a greenhouse for a further 10 days a 20°-24 0 C. Scab infestation is evaluated 15 days Safter infection.
ln Compounds from the Tables 1-3 exhibit good activity against Venturia.
S0Attack is 100 on untreated and infected shoots.
Example 3.5: Action against Botrytia cinerea on beans Residual protective action Bean plants about 10 cm in height are sprayed with a 'pray mixture (0.02 prepared from the test compound formulated as vettable powder.
0 After 48 hours, the treated plants are infected with a conidia suspension of the fungus. The infected plants are incubated for 3 days at 95-100 relative humidity and 21 0 C, and evaluation of the fungus attack is then made. Many compounds of tables 1 3 very strongly inhibit fungus attack. At a concentration of 0.02 compounds 1.004, mm- hI 47 DATED this TENTH day of JANUARY 1991 c-i a0e 0O0 00 9 b 4049 9., 0 0 9ca '0 40 35 1.012, 1.065, 1.115, 1.127, 1.137, 3.077, 3.084 and 3.086 are fully effective (attack 0 to 5 Botrytis attack on untreated and infect bean plants is 100 Example 3.6: Action against Pyricularia oryzae on rice-plants a) Residual protective actiun Two week old rice plants are sprayed with a spraying mixture containi.;3 0.006 of active substance, that was prepared from a wettable powder of the substance to be tested. After 48 hours the plants were infested with a suspension containing conidia of the fungus. The infected plants are kept at 24' and 95-100 relative humidity for 5 days before the fungus infestation is evaluated.
b) Systemic action Two week old rice plants in flower pots are sprayed with a spraying mixture containing 0.006 of active substance, that was prepared by diluting a wettable powder of the substance to be tested with the required amount of water. The flower pots are then added wirb water so that the stems of the rice plants stand in water. After 48 hours the plants are infectea with a suspension containing conidia of the fungus.
The fungus-infectation is evaluated after an incubation period of days during which the rice plants were kept at about 24' and 95-100 rolativ humidity.
The compounds of tables 1 to 3 are very effective against Pyricularia orizae. The Pyricularia infection is 100 on infected but not treated control plants. The tested compounds, especially 1.115 and 3.040 inhibited fungus attack on rice plants to 0-5 0040o 0; 0 0I 0x4 0 a I 0 Examplg 3.7: Action against Tilletia caries on wheat Winter barley of the type Probus is infected with spores of Tilletia caries, to the rate of 3 g of dry fungus-spore per kg of barley seed.
The infected seeds are dried and then macerated in a rolling-mixer with an aqueous solution of the compound to be tested, so that 60 ppm of active substance per weight of seed gets applied. The seeds are then r, 36 dried. The infected and treated barley is sown in October in a field by means of a sowing machine. Lots of 2 m length containing 3 rows are arranged in triple repetition.
The test is evaluated when the spicules are ripe by evaluating the percentage of spicules infested with Tilletia caries.
The compounds of tables 1 to 3 are very effective against Tilletia caries. While plants from infected but not treated seed showed a 100 Tilletia-infestation, the tested compounds reduced the infection to 0 5 00. 0 oo,: 0O Example _38: Action against Helminthosporium gramineum on barley Winter barley of the type "Cl" which is naturally infected with Helminthosporium gamineum is treated in a rolling-mixer with a solution o, of the compound to be tested, so that 60 ppm per weight of seed get applied.
000aol The infected and treated barley is sown in October in a field by means Seo of a sowing machine, so that lots of 2 m containing 3 rows of plants a *0 0 :0 are arranged in triple repetition.
The test is evaluated when the spicules develop and the percentage of stalks which are infected with Helminthosporium gramineum are counted.
0O The compounds of tables 1 3 are very effective against a oo a Helminthosporium gramineum. While plants from infected but not treated 0 seed showed a 100 Helminthosporium-infection, the tested compounds reduced the infection to 0 to 5 Example 3.9: Action against Phytophtora on tomato plants a) Residual-protective action Three week old tomato-plants are sprayed with a spray-solution containing 0.006 of active substance, which has been prepared from a wettable powder of the substance to be tested. The treated plants are infected with a suspension of sporangia of t-'n fungus. The plants are
I
S37 then kept at 200 and 90 100 relative humidity. The test is evaluated after a 5 day incubation period by evaluation the degree of Phytophthora-infection.
b) Residual-curative action Three week old tomato-plants are infected with a suspension of sporangia of Phytophthora. After an incubation period of 22 hours in a humid chamber at 200 and 90 100 relative humidity, the infected plants are dried and sprayed wich a spray-solution containing 0.006 of active substance.
lO The tested compounds of tables 1-3 showed in these test remarkable activity against Phytophtora.
o Example 3.10: Action against Rhizoctonia solani (soil fungus) on orice plants a) Soil application, local protective action 12 days old rice-plants are watered with a spray-solution, made by dilution of a formulation, containing 0.006 of active substance, in So such a manner that none of the plant-parts above ground are S6 contamined. In order to infect the treated plants, a suspension of mycelium and sclerotia of Rhizoctonia solani is poured onto the soil c around the plant. After 6 days incubation period at 27° temperature (day) and 23° (night) at 100 relative humidity in a humid-box in the clima-room, the fungus infection on the sheath, the leaves and the stem is estimated.
o b) Leaf application, local protective action 12 days old rice plants are sprayed with a spray-solution, which has been prepared by diluting a formulation with water. After one day the plants are infected by spraying them with a suspension of mycelium and sclerotia of Rhizoctonia solani. After an incubation period of 6 days at a temperature of 27' (day) and 23' (night) at 100 relative humidity in a humid box in the clima-room, the fungus infection on the sheath, the leaves and the stem is evaluated.
i 38 The tested compounds of tables 1, 2 and 3 showed in this test good activity against Rhizoctoria solanii. Best protection was achieved with compound 3.040.
Example 3.11: Action against Xanthomonas oryzae on rice (Oryza sativa) a) Residual protective action 3 week old rice plants of the type "Calora" or "S6" are sprayed in the green-house with a spray-solution containing 0.02 of active substance. After one day when the coating from the spray has dried, the plants are put into a clima chamber of 24° temperature and 75 85 S relative humidity, where the are infected. Infection is carried out by cutting the points of the leaves with a scissors, which had been dipped into a suspension of Xanthomonas oryzae. After 10 days incubation period, the best is evaluated. Infected leaves will curl up and become necrotic. The extent of the pathologic symptoms serves to determine the o a c, extent of the residual activity of the substance tested.
b) Systemic action 3 week old rice plants of the type "Calora" or "S6" are sprayed in the goo green-house with a spray-solution containing 0.006 of active 0 substance. Three days later the plants are put into a clima-chamber of ?0 24° temperature and 75 85 relative humidity and infected. Infection is carried out by cutting the points of the leaves with a scissors that has been dipped into a suspension of Xanthomonas oryzae. After 10 days incubation period, the test is evaluated. Infected leaves will curl up o, and become necrotic. The extent of the pathologic symptoms serves to determine the degree of the systemic activity of the substance to be tested.
The tested compounds of tables 1, 2 and 3 showed good activity against Xanthonomas oryzae, The compounds 1.127 and 1.137 reduced the fungiesinfection to 0 20 while infected not treated control plants were S3Q 100 1 infected.

Claims (9)

1. A method for controlling and preventing infestation of plants by phytopathogenous microorganisms, which comprises treating the plants or parts thereof with an effective amount of a 2-chloro-4-trifluoromethyl- acid derivative of formula I F 3 wherein R is a radical selected from among cyano, -COXR 1 -CONR 3 R 4 or -COD, X Is oxygen or sulfur, RIs hydrogen, C 1 C 18 alkyl or C 3 C 18 cycloalKyl, which is unsubstituted or substituted by halogen, a group -YR 2 1 A, nitro, -N(R 3 )COA, -EN(R 3 ))j-M-C(A)NC 1 C 4 alkyl, -[N(R 3 )1iTG(A)=NH or MNR 3 )]ij-CO-'NE(CO) mR 3 -NR 3 1 -EN(R 3 JCON (CO'R 3 3 1-0.CO)mR 4 In which groups one of the indices m must be zero, further C 1 -C 1 alkyl .0.0 or C -C 18 cycloalkyl can be substituted by cyano, a group 004 'D M XR 10 s -XCXRlo, -(X>j-MCXA, -(X)CXN(R3)N(R 3 )R 4 1 a00a -CHA-C00R 10 -C(OR 7 )=(OR 8 )R 9, -PO(R 5 )R 6 C 3 -C 8 cycloalkyl or C 5 -C cycloalKenyl,, R I further represents C 3 -C 8 alkenyl or C 3 -C 18 cycloalkenyl, which is unsubstituted or substituted by halogen, C -C aflsoXY, alkylthio, C -Chaloalkoxy, C 1 -C 4 haloalkyl or a group -CO(O)--RICOiCN()3o 0 0 -PO(R )R R 1 further represents C 3 -C alkynyl which is unsubstituted or substituted by U or Q RIs C 1 -C 8 alKyl or C 3 -C 8 cyc&Ioalkyl, which is unsubstituted or substituted by a group selected from C,-C alkoxy, C 1 -C alKylthio, o C 2 -C 8 alkoxyalkyl halogen, cyanci, a group -CX(X) mRio, m*CXA, 0 mCXR CA m 10 3 )CA, akl A, -X-U or XQ; R2 further represents C 3 _C 8 alkenyl or CG 3 -Ccycloalkenyl, which is unsubstituted or substituted by halogen; or R 2 represents a radical -EMUor mQ; m is zero or one; Y is oxygen, sulfur, -SO- or -SO 2 A is a radical NR3R4 11'Oi a radical -NN(R(RetcOmR 3 9y ;I- Plr 00 0 994 409k 0o 0 0 0 4 0 E0 0 0 0 0 0 0 uQ 0, 99 0c 0. 0 V 9 40 one of R3 and R4 is hydrogen or C 1 -C 8 alkyl, the other or both independently represent C 5 -Cgalkyl or C 3 -C8cycloalkyl unsubstituted or C 1 -Cgalkyl or C 3 -C 8 cycloalkyl which is substituted by a group selected from C 1 -C 8 alkoxy, C 2 -C 8 alkoxyalkoxy, C 1 -c 8 alkylthio, cyano, a group -COOR 10 C 1 -C 4 alkylcarbamoyl, di-C 1 -C 4 alkyl1carbamoyl, piperidinocarbonyl, pyrrolidinocarbonyl, piperidino or pyrrolidino; R 3 and R4 further represent C 3 -C 4 alkenyl or C 3 -C 8 cycloalkenyl which is unsubstituted or substituted by a group selected from halogen, C 1 -CG 8 alkoxy, C 3 -C 8 cycloalkyl, cyano, -COOR 1 O, C 1 4alkylcarbamoyl or piperidinocarbamoyl; R 3 and R4 represent further C 3 -C 6 alkynyl, which is unsubstituted or substituted by U; or R 3 and R 4 represent a radical or (E-Q R3 and R 4 together with the nitrogen atom, to which they are bound form a saturated or unsaturated heterocycle with 5 to 9 ring members which may include once or several times -N-C 1 -C 4 alkyl, -CO- or -C(0R 7 )0R 8 and which may be substituted by halogen, cyano, C 1 -C 8 alkoxy, am' C 1 -c 4 alkylamino di-C 1 -C 4 alkylamino or a group -COOR 10 5 and R 6 are independently of each other hydrogen, C 1 -C 4 alkyl or C 2 -C 4 alkoxy; R7 and R are independently of each other C 1 -C 4 alkyl or R7 and R8 form together an alkylene chain of 2 to 4 chain-links, R9 and R 10 are independently of each other hydrogen, C -C 8 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 alkenyl, C 2 -C 8 alkoxyalkyl, C 3 -CG 8 alkoxyalkoxyalkyl, C -C 4 haloalkyl, -C 3 alkylene)mU, -(C 1 -C 3 alkylene) Q, C 1 -C 4 haloalkoxy; U is phenyl or naphthyl, which is unsubstituted or substituted once or several times by halogen, C 1 -C 4 alkyl, -Y-C 1 -C alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, cyano, nitro, carboxyl, -COOR 7 -CONH 2 -CONHR 7 -CON(R 7 -S0 2 NHR 7 -S0 2 N(R 7 pyrrolidino, piperidino, pyrrolidinocarbonyl or piperidinocarbonyl; E is aC I-C 8 alkylene or C 2 -CG 8 alkenylene chain, which is unsubstituted or substituted by halogen, C 1 -C 4 alkoxy, SC 4 alkylthio, C 1 -C 4 haloalkoxy or by a group -O(O)m Ri0' A, mQ and which may be interrupted by -CO- or -C(0R 7 )0R 8 IV qK A*' pyra~penahydopyrn~dix41 Qis a heterocyclic radical selected from among furan, tetrahydrofuran, pyrn, enthydopyandioandioxalan, thiophen, thiazole; thienyl, pyrrl~dnopipridnomorpholino, azepino which are unsubstituted or or copostio copriingthecompound of formula I together with a microbicidally acceptable carrier, adjuvant and/or diluent.
2. 2-chloro-4-trifluoromethyl-thliazolyl-5-carbonic acid derivatives of the formula Ia F 3 C- -R Ra I s a radi cal selected from among cyano, -COXR 1 -CORI, -CONR3R4 or -COD, in which X is oxygen or sulfur, R. is C 1 C 18 alKyl or C 3 -C 1 cycloalkyl which are unsubstituted or 04 C 1 -C 1 alkyl or C-18 3 -C 18 cycloalkyl substituted by a halogen, a group 0 -YR 2 A, nitro,, -N(R 3 )COA, -1N(R 3 )J1-C(A)=NC 1 -C 4 alkyl, 0 -EN(R or -(N(R 3 )~-OKCmR1NR) 04 3 MCEC) R (Q mR4 In which groups one of the indices m must be zero, C I- C 1 alkyl or C 3 C ,cycloalkyl are Sfurther substituted by cyano, a group -C(X)mXRiO, -XCXR 10 -(X)-CXN(R 3 )N(R 3 )R 4 -CHA-C00R 10 -C(0R 7 )(0R 8 )R 9 -PO(R 5 )R 6 C 3 -C~cycloalkyl or C 5 -C 8 cyclo- alkenyl; with the proviso that -XR 1 is not C 1 -C 10 haloalKoxy, C 2 -C 1 alkoxyalkoxy, phenylthio or benzyloxy if these groups are unsubstutited or phenoxy substituted; Rfurther is C 1 cycloalkenyl, which is unsubstituted or C 3 -C 8 alkenyl or C 3 -C 18 cycloalkenyl substituted by halogen., C 1 C 4 al koxy, C 1 -C alkYl thlo, C 1 Chaoloy C 1 Cqhaloalkyl or a group -00(0) MR lQ -COA, -GON(A)R 3 or SIf X is sulfur, Ris also a group or R 2 is CI'Clalkyl or C 3 -Ccycioalkyl, which is unsubstituted or substituted by C 1 -C 8 alkoxy, Cl-C~alkylthio, C 3 -C~alkoxyalkoxy, halogen, cyano, or a group -CX(X)mRi 0 -(XYCX-A, -(X)MCXRioI _N(R )COA, -CN(R )3jr(C(A) =NC,-C alkyl, A, 3
10-42- -XU or -XQ; Rfurther is C 3 C 8 alkenyl or C 3 -C 8 cycloalkyl which is unsubstituted or halosubstituted; or R2is a group U or (,Q m is zero or 1; Y Is oxygen, sulfur, -SO- or -SO 2 A is a group -N(R 3 )R 4 D is a group -N(R)N(R 4 (CO) inR 3 1 wherein one of R 3 and R4is hydrogen or unsubstituted C,-C 18 alkyl, the other or both independently represent C 3 C 18 cycloalkyl which is unsubstituted or substituted by C 1 -C 8 alkoxy, C 2 'C 8 alKoxyalkoxy, cyano, a group -COOR 10 C I-C 4 alkyI- carbamoyl di-CI- C 4 alkylcarbarioyl C 1 C 4 alkylamino, di-C 1 C 4 alkylamino, piperidinocarbanyl, pyrrolidinocarbonyl, piperidino or pyrrolidino; R 3 and R4further represent C 3 -C 8 alKenyl or C 3 -C 8 cycloalkenyl, which is unsubstltuted or substituted by halogen, C 1 -C alkoxy, C 3 -C cycloalkenyl, cyano, a group -G00R 1 ,CCalyabaol di-C 1 -C alkylcarbamoyl, U, pyrrolidinocarbonyl or piperidinocarbonyl; Rand Rfurther are a group or with the proviso that only one of Rand Ris hydrogen or rC C lkyl; R 3 and R 4 together with the nitrogen atom, to which they are Sbound also represent an unsaturated or saturated heterocycle with 5 to 9 ring-members which is interrupted once or several times by oxygen, sulfur, nitrogen, imino, C 1 -C alkylimino, or -C(0R )OR and which may be substituted by halogen, cyano, C -Calkoxy, amino, C 1 -C alkylamino, di-C 1 Cakamn orC0R; C 2 alylamao orxy;O and4 R 6 aeidpndnl0fec;ohrhdoy, Caklo Rand Rare Independently of each other hydroxlyl, or lklo Rand R 8 form together a 2 to 4 membered alkylene chain, R 9 and R 0are independently of each other hydrogen, C 1 -C 3 alkyl, C 3 -c 8 cycloalkyl, Q3- 8 cycl oalkenyl, C 3 -CYaikenyl, C2.-C 8 akx~kl 4 -C 8 alkoxyaikoxyalkyl,, C 1 -C 4 haloalkyl, I-c 3 alkyl)j--J, -C 3 alkyl)FQ, C 1 -C 4 ha loalkoxy, Cl-C 4 halo. alkoxy-C alkyl; U Is a phnyl or naphthyl, wich Is unsubstituted or substituted once or several times by halogen, CI- C 4 alkyl, -Y-C I-C 4 alkyl, C 1 -C 4 halo- aikyl, CI- C 4 haloalkoxy, cyano, nttro, -COON, -COOR 7 -CONH 2 43 -CONHR 7 -CON(R 7 2 so 2 NHR 7 so 2 N(R 7 2 pyrrolidino, p Iperi di no, pyrrol idi nocarbonyl or pi peri di nocarbonyl E is a C 1 -C aalkylene or C 2 C 8 alkenylene chain, which is unsubstituted or substituted by halogen, CI- C 4 alkoxy, C 1 -G 4 alkylthio, C 1 -C 4 haloalkoxy or a group -CO(O) mR1 0 -(CO)T-A or -(CO)mQ and/or is interrupted by a chain-member -CO- or C(QR 7 )0R 8 Q Is a heterocyclic radical selected from among furan, tetrahydrofuran, pyran, pentahydropyran, dioxan, dioxalan, thiophen, thiazole, thienyl, pyrrolidino, piperidino, morpholino, azepino which are unsubstituted or substituted by methyl. 3. 2-chloro-4-trifluoromethyl-thlazol-5-carbonic acid derivatives of the formula lb F s F b (Ib) I I tI~ I I wherein Rlis C 10 -C 18 alkyl or C 3 -CCcycloalkyl unsubstituted or substiluted by halogen or C, -C 5 alKyl or R'is alkyl orC QycloalKyl substituted by a group "XR 2 ,A niro 3 CW -(N(R 3 )1T-C(A)-NC,-C 4 alkyl, WNR 3 )IM-C(A)=N14i 1NR)mCN(O MR31N3, N(R 3 )1,-OrN(CO) m R 3 N(R 3 >j-CO)MR 4 In which groups one of the Indices must be zero, Q -CQ 18 alkyl or C 3 -C 18 cyclolkyl are further substituted by cyano, a group -C(X)F-XRlol -(X)CXN(R 3 )R 4 -CHA-C00R 1 ,t -C(OR 7 )(OR 8 )R 9 -PQ(R )R 6 o C 3 C,,cycloalKyl or C 3 -C~Cycloalkenyl, Rfurther is C _C 18 cycloalkenyl which is unsubstituted or G 3 -C alkenyl or C 3 C 18 cycloalkenyl substituted by halogent C 1 -CYlkoxy, G 1 -Cilalkylthio, Cl-c 4 haloalKoxy, C 1 -C haloalkyl or by A. group -CO(O) 1 R 1 -COAi -CQN(A)R, or -PO(R )R 6 Ais also a group or with the proviso, that Is not unsubstitutod benzyl or iubrstituted' or unsub~tituted phenyl and m, X, Y, A, 0, RV, R 4 RS, R 6 RV, AV Rq, R 10 U, and 0 have the meani ng gi ven I n clIai m I 4, 2-chloro-4-trilfluoromethyt-thiizol-carbonic acid-derivatives of~ the formula lb according to claim 3, wherein RIIs C 1 -C 18 alkyl which I 'C- I KXW: 12 17y l V. 44- is substituted by halogen, cyano, C 1 -C 4 alkylthio, C -C 4 alkoxy- carbonyl, C 1 Caksufnl C-Ccycloalkyl or C-Cclo alkenyl or a group or and E, m, Q and U have tho meaning given in claim 1. 2-ch oro-4-tri fluoromethyl -th Iazol -carbon ic acid derivatives of the formula lb according to claim 3, wherein Ris a group tetrahydro- pyran-2-yl-methyl 2,2-dimethyl-l ,3-dioxolan--4-ylmethyl 1 ,3-dihydro- benz-i ,4-dioxan-2-ylrnethyl thiophen-2-ylmethyl, 3,4-methylenedioxybenzy], thi azol-2-yl ethyl, para toolyl-l-yl, bomyl, norbomyl, fenchyl, methyl, cyanoethyl, phenoxyethyl methyl sulfonylmethyl, phenylthioethyl, ethoxycarbonylmethyl ethioxycarbonyleth-l-yl, furan-2-.on-3-yl, 2-oxopyrrol idinomethyl cx-methoxycarbonylbenzyl, (x-qyanobenzyl, c-benzoylbenzyl c4-methoxycarbonyl cx-phenylbenzyl or morphol I nomethyl 6, 2-chloro-4-trifluoromethyl-thiazl.-carbonic acid derivatives of the formula lb accordIing to claim 3, wherein Ris C -C 12 alkyl, substituted by -(X)-CXA and wherein A, m and X have the meaning given In m o claim 1, i2X 7, 2-chloro-4-trifluooimethyl-thiazol-carbonic acid derivatives according to claim 6 wherein m 1i3 zero, X oxygen and A has the meaning given In claim 1, 8. 2-chloro-4-trifluoromethyl-thiazol carbonic acid derivative according, to claim 6 wherein RlIs azepinomethyl N-(,G,-dimethyl- phenyl)-M-(methoxycarbonyleth-I-.yl)-carbamoylmethyl or 2-plperidinoeth-l4 yl. 9, Z.,chloro-4.tri fl1uoroniethyl th Iazol -carbon Ic acid derivatives of the formula( ?cF wherein R.has the meani ng givon I n cl aim 1I 1A, 2-chloro-4-trfuoromethyl-,5-carbonic acid amides of the formula Id (1d) wherein one of R3and R4Is hydrogen or unsubstItuted C 1 -C 8 alkyl, the other or both Independently represent (YXWd217y *44y4eFC 3 -C~cycloalkyl which is unsubstituted or substituted by C -C 8 alkoxy, CG 1 C 8 alKoxyalkoxy, G 1 -C 8 alkylthio, cyano, a group -C00RJO, C 1 -C 4 alkylcarbamoyl, di-C 1 -C 4 alkylcarbamoyl C I- C 4 alkylamino, di-C I- C 4 alkylamino, piperidinocarbonyl, pyrrol.dinotcarbonyl, piperidino or pyrrolidino; R 3 and R4further represent C 3 -C 8 alkenyl or C 3 -C cycloalkenyl which is unsubstituted or substituted by halogen, C 1 -C 8 alkoxy, C 3 C 8 cycloalkyl or a group cyano, -C00R 10 C 1 -C 4 alkylcarbamoyl or piper idinocarbamoyl;, R 3 and R 4 represent further C 3 "C 8 alkynyl, which is unsubstituted or S substituted by U, or Rand R 4 represent a radical E or S R 3 and R 4 together w' 4 th the nitrogen atom, to which they are bound form a saturated or unsaturated, heterocycle with 5 to 9 ring members which may Sinclude once or several times -N-C 1 C 4 alkyl, -CO- or S OR 8 and which may be substituted, by halogen, cyano, C alkoxy, amino, C- C 4 alkylamino, di"C 1 -C 4 alkylaminQ or a group -COQR 10 and Wherein E, m, Q, RIO and U have the meaning gi~ven above under formula I In claim 1. III Z-chloro-6-trifluoromethyl-4-thiazol-carbonic acid amides of the formula Id according to claim 10, wherein -N(R )R 4 Is a group -2-,44-di j chlorobenzyl-N-methylcarbamoyl N-benzyl-N-.isopropylcarbamoyl, -cyclo- hexy1.-N-methoxycarbamoylethylcarbanoy1, IN-2, 6-d Imethy phony IN-methoxy- S carbamoylIeth-l -yl -carbamoylI, or (lI-canope nt-I-y I) -N-me thy 1carbamQy I
12. 2-chloro-5-trlfluoromethyl-.thiazol-.carbohydrazides of the S formula le -(R4 wherein each R 3 Independently of the other and R 4 have the meaning given in claim 1.
13. 2-chloro-4-trifluoromethyl-thiazo1-a-carbonic acid hydrazide of formula (if) wherein, R 3 R 4 ad 5 i depndntly of each other represent hydrogen, NOjNi/~ /949Y -46 C I-C 8 alkyl C 3 -C 8 cycloalkyl phenyl or benzyl whereby phenyl and benzy! are unsubstituted or substituted by halogen, C-C 4 alkyl, C 1 -C 4 haloalkyi C 1 C 4 alkoxy, C 1 -C 4 haloalkoxy, nitro, carboxyl, C -C alkoxycarbonyl, carbamoxy or methylcarbiamoyl, R 3 and R 4 together represent also a 4 5-membered alkylene chain, which may be Interrupted by oxygen, sulfur, imino or C 1 -C 4 alkylimino and which may be substituted once or se.eral times by C 1 -C 4 alkyl. 14, A method according to claim 1wherein the microorganisis are phytopathogenic fuogi. A miethod according to claim 1 wherein the microorganisms are soil borne phytopathogenic bacteries.
16. A method according to claim 1, 14 or 15 which comprises treating seeds.
17. A method according to claim 1, 14 or 15 which comprises treating rice plants,
18. A microbicidal and fungicidal composition for controlling and preventing infestation of plants by phytopathogenous microorganisms, S substanti ally as hereinbefore described with reference to any one of E: xamples 2.1 but, excluding any formu~lation therein containing any one of compounds 1,019 to 1,022 or 3.066.
19. 2-chloro-4-.trifluoromethiyl-thiazolyl-i-carbonic acid derivatives, substantially as hereinibefore descy ,ed with reference to any one of the Examples 1,1 to 1.3 or any one of Compounds 1,001 to 1,018, 1.023 to 1,156, 2,001 to 2.013, 3.001 to 3.065, or 3,067 to 3.103, A method for controlling and preventing Infestation of plants by phytopathogenous microorganisms, which comprises treating the plants or parts thereof with an effective amount of a compound qccording to claim 19 or a com~position according -to claim 18. 21, A method for controlling and preventing infestations of piants by phytopathogenous microorganisms, which cnprise treating the plants or Da. parts thereof with an effective mount of' a 2 -chloro-4-trifluoromiethyl-fiazolyl-5-caribonilc acid derivative, which derivative Its substantially i. herein described with roferenre to any one or' compounds 1,018 to 1.022 oi 3A66,. or a composition comprising said derivative togetlher with a mi~r'ibicidally accoptable cairier, adjuvant and/or di iaint. KXW'.lal7y 47 DATED this TENTH day of JANUARY '1991 Ciba-Geigy AG Patent Attorneys for the AP.Iicant SPRUSON FERGUSON o0~ 0$ 00 0 0 o 00 00$ 0 0 o 0$' 0000 0 0 0 ~1 0 0 0 (0 0 000 00 0 040000 0 0
AU10974/88A 1987-01-30 1988-01-29 Microbicidal compositions Ceased AU610553B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH35187 1987-01-30
CH351/87 1987-01-30

Publications (2)

Publication Number Publication Date
AU1097488A AU1097488A (en) 1988-08-04
AU610553B2 true AU610553B2 (en) 1991-05-23

Family

ID=4185044

Family Applications (1)

Application Number Title Priority Date Filing Date
AU10974/88A Ceased AU610553B2 (en) 1987-01-30 1988-01-29 Microbicidal compositions

Country Status (11)

Country Link
EP (1) EP0279239B1 (en)
JP (1) JP2764265B2 (en)
KR (1) KR950009517B1 (en)
AT (1) ATE82275T1 (en)
AU (1) AU610553B2 (en)
BR (1) BR8800374A (en)
CA (1) CA1338418C (en)
DE (1) DE3875750D1 (en)
ES (1) ES2052612T3 (en)
IL (1) IL85236A (en)
ZA (1) ZA88635B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU616579B2 (en) * 1988-11-29 1991-10-31 Dow Agrosciences Llc Substituted thiazoles and their use as fungicides

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IE59962B1 (en) * 1986-09-26 1994-05-04 Rohm & Haas Five-membered heterocyclic derivatives of n'-substituted-n, n'-diacylhydrazines
US4837242A (en) * 1987-01-20 1989-06-06 Sumitomo Chemical Company, Limited Thiazoles and pyrazoles as fungicides
US5135927A (en) * 1987-01-30 1992-08-04 Ciba-Geigy Corporation Microbicidal composition
JP2788458B2 (en) * 1987-10-23 1998-08-20 三井化学株式会社 Novel amide derivative, method for producing the same, and agricultural / horticultural fungicide containing them
EP0335831A1 (en) * 1988-03-15 1989-10-04 Ciba-Geigy Ag Thiazole-5-carboxylic acid amides for protecting cultivated plants against the phytotoxic activity of highly active herbicides
US5136042A (en) * 1988-06-03 1992-08-04 Mitsui Toatsu Chemicals, Inc. Process for the preparation of thiazolecarboxylic acid chlorides
AU6049590A (en) * 1989-07-25 1991-02-22 Monsanto Company Substituted carboxanilidothiazoles and their use as fungicides
CA2081935C (en) * 1991-11-22 2004-05-25 Karl Eicken Anilide derivatives and their use for combating botrytis
DE4301356A1 (en) * 1993-01-20 1994-07-21 Basf Ag Process for the preparation of 2-alkyl-4-fluoromethyl-thiazolecarboxylic acid alkyl esters
JPH0812653A (en) * 1994-04-26 1996-01-16 Nissan Chem Ind Ltd Carboxylic oxime ester derivative and microbicidal agent for agricultural and horticultural purposes
JP3726306B2 (en) * 1994-04-27 2005-12-14 日産化学工業株式会社 Pyrazolecarboxylic acid derivatives and plant disease control agents
GB9424379D0 (en) * 1994-12-02 1995-01-18 Agrevo Uk Ltd Fungicides
WO2001030757A1 (en) * 1999-10-28 2001-05-03 Microcide Pharmaceuticals, Inc. Drug discharge pump inhibitors
US7056917B2 (en) * 2001-04-26 2006-06-06 Daiichi Pharmaceutical Co., Ltd. Drug efflux pump inhibitor
JP2004269515A (en) * 2003-02-18 2004-09-30 Nippon Nohyaku Co Ltd Substituted heterocyclic amide derivative, its intermediate, agricultural and horticultural agent and method for using them
EP1548007A1 (en) 2003-12-19 2005-06-29 Bayer CropScience S.A. 2-Pyridinylethylcarboxamide derivatives and their use as fungicides
UY29723A1 (en) * 2005-08-05 2007-02-28 Basf Ag USE OF ARILANILIDS FOR SEED TREATMENT
EP1787981A1 (en) 2005-11-22 2007-05-23 Bayer CropScience S.A. New N-phenethylcarboxamide derivatives
JP4848306B2 (en) * 2007-04-12 2011-12-28 不二サッシ株式会社 Opening restriction stopper device in casement window
AR066162A1 (en) * 2007-07-31 2009-07-29 Bayer Cropscience Sa FUNGICIDE DERIVATIVES OF N- CICLOALQUIL -N- CARBOXAMIDA- BICICLICA
CN110483449B (en) * 2019-08-30 2023-03-03 新乡学院 Preparation method of gamma-lactone derivative

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4308391A (en) * 1979-10-01 1981-12-29 Monsanto Company 2-Amino-4-substituted-thiazolecarboxylic acids and their derivatives
US4640702A (en) * 1980-07-14 1987-02-03 Monsanto Company 2-chloro-4-trifluoromethyl-thiazolecarbothioic acids useful as herbicidal safeners

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3725427A (en) * 1966-12-07 1973-04-03 Uniroyal Ltd Certain 2,4-dimethyl-5-carboxamido-thiazoles
US4199506A (en) * 1978-05-15 1980-04-22 Monsanto Company 2,4-Disubstituted-5-thiazolecarboxylic acids and derivatives
RO84370B (en) * 1981-04-22 1984-09-30 Monsanto Co Herbicidal composition with antidote

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4308391A (en) * 1979-10-01 1981-12-29 Monsanto Company 2-Amino-4-substituted-thiazolecarboxylic acids and their derivatives
US4640702A (en) * 1980-07-14 1987-02-03 Monsanto Company 2-chloro-4-trifluoromethyl-thiazolecarbothioic acids useful as herbicidal safeners

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU616579B2 (en) * 1988-11-29 1991-10-31 Dow Agrosciences Llc Substituted thiazoles and their use as fungicides

Also Published As

Publication number Publication date
KR880008749A (en) 1988-09-13
CA1338418C (en) 1996-06-25
ES2052612T3 (en) 1994-07-16
JPS63201178A (en) 1988-08-19
BR8800374A (en) 1988-09-20
AU1097488A (en) 1988-08-04
IL85236A0 (en) 1988-07-31
JP2764265B2 (en) 1998-06-11
IL85236A (en) 1992-12-01
ATE82275T1 (en) 1992-11-15
EP0279239B1 (en) 1992-11-11
KR950009517B1 (en) 1995-08-23
ZA88635B (en) 1990-07-25
EP0279239A1 (en) 1988-08-24
DE3875750D1 (en) 1992-12-17

Similar Documents

Publication Publication Date Title
AU610553B2 (en) Microbicidal compositions
KR100482919B1 (en) Pyrimidine-4-one derivatives as insecticides
RU2058983C1 (en) Triazine derivative, process for preparation thereof, and herbicidal composition based thereon
FI95376C (en) Microbicidal 2-anilino-pyrimidine derivatives
PL97786B1 (en) PEST KILLER AND PLANT GROWTH REGULATING AGENT
JPH0672131B2 (en) Oxime ether, method for producing the same, composition for protecting cultivated plant containing the compound, and method for protecting cultivated plant
JP2018524341A (en) Phenoxyhalogen phenylamidines and their use as fungicides
AU615658B2 (en) Thiazole derivatives
CA1278695C (en) Herbicidal composition
JPH09502421A (en) Azoxycyanobenzene derivative
JPH03190853A (en) Microbial insecticide
US5135927A (en) Microbicidal composition
PL132245B1 (en) Agent for controlling and/or protection against paralysis by harmfuk microorganisms and method of manufacture of novel derivatives of arylamines
KR850001547B1 (en) Process for the preparation of homoserine derivatives
AU612573B2 (en) Benzothiazinone derivatives
US4992434A (en) Microbicidal composition
HU198008B (en) Process for producing n-/3-chloro-4-isopropyl-phenyl/-carboxamide derivatives and herbicide compositions containing them as active components
CA1206160A (en) Microbicidal compositions
CS201517B2 (en) Fungicide means
JPH04283572A (en) Substituted-2,3-dihydro-2-oxo- 1,5-benzodiazepines and use thereof as fungicide
KR940011459B1 (en) Process for preparing thiazinone derivatives
EP0240047B1 (en) Fungicides
CA1126751A (en) Fungicidal alkoxyalkoxyacetyl acylalanines
RU2070197C1 (en) Thiazolyl-5-carbonamide derivatives, fungicidal agent for controlling fungal diseases of plants, and process for controlling fungal diseases of plants
GB2127820A (en) Microbicidal imidazolidine-2,4- dione derivatives