AU685957B2 - Carbamoyl carboxylic acid hydrazides and their use against fungi - Google Patents
Carbamoyl carboxylic acid hydrazides and their use against fungi Download PDFInfo
- Publication number
- AU685957B2 AU685957B2 AU27353/95A AU2735395A AU685957B2 AU 685957 B2 AU685957 B2 AU 685957B2 AU 27353/95 A AU27353/95 A AU 27353/95A AU 2735395 A AU2735395 A AU 2735395A AU 685957 B2 AU685957 B2 AU 685957B2
- Authority
- AU
- Australia
- Prior art keywords
- alkyl
- aryl
- alkoxy
- cyano
- carry
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
- C07C271/42—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/54—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/22—O-Aryl or S-Aryl esters thereof
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
- C07C243/26—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C243/34—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a carbon skeleton further substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/22—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/60—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups having oxygen atoms of carbamate groups bound to nitrogen atoms
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
0050/44896 Carbamoylcarbohydrazides The present invention relates to carbamnoylcarbohydrazides of the general formula I
X
2
R
2
R
3
X
3
R
5
R
6 R-X- C-NC-C-N-N -R 7
I
and their salts, where the radicals have the following meanings:
R
1 is Cl-C 8 -alkyl, C 2
-C
8 alkenyl or C 2
-C
8 -alkynyl, it being possible for these radicals to be partly or completely halogenated and/or to carry one to three of the following groups: cyano, C 1
-C
4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 alkylthio, Cl-C 4 -alkoxycarbonyl, C 3
C
7 CYCloalkyl, C 3
-C
7 -CYCloalkenyl, aryl, aryloxy and heteroaryl, it being possible for the cyclic radicals in turn to carry one to three of the following substituents: halogen, cyano, Cl-C 4 -alkyl, Cl-C 4 alkoxyalkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy,
C
1
C
4 -alkylthio, C 1
C
4 -alkoxycarbonyl, aryl, aryloxy and heteroaryl,
C
3
-C
7 CYCloalkyvl or C 3
-C
7 -CYCloalkenyl, it being possible for these radicals to be partly or completely halogenated and/or to carry one to three of the following groups: cyano, Cl-C 4 alkyl, C 1
-C
4 -alkoxyalkyl, Cl-C 4 -haloalkyl, Cl-.C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 alkylthio, Cl-C 4 -alkoxycarbonyl, aryl, aryloxy and aryl-(Cl-.C 4 )-alkyl, it being possible for the cyclic groups to carry one to three of the following substituents: halogen, cyano, C 1
-C
4 -alkyl, Cl-C 4 -alkoxyalkyl, Cl-C 4 -haloalkyl, C 1
-C
4 -alkoxy, C 1
-C
4 -haloalkoxy, Cl-C 4 -alkylthio, C 1 -0 4 -alkoxycarbonyl, aryl and aryloxy, a non-aromatic 4- to 8-membered ring, which, as ring members, in addition to carbon can also contain one or two of the heteroatoms oxygen, sulfur and nitrogen, it being possible for the carbon atots in the ring to carry one or two of the following groups: halogen, cyano, Cl-C 4 alkyl, Cl-C 4 -alkoxy- 45 alkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl 1
-C
4 alkylthio, Cl-C 4 -alkoxycarbonyl, aryl and aryloxy and R0A
'V
I
0050/44896 2 the second and each further nitrogen atom as a heteroatom in the ring carrying hydrogen or a C 1
-C
4 -alkyl group, aryl or heteroaryl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano,
C
1 -0 4 -alkyl, C 1
-C
4 -alkoxyalkyl, C 1
-C
4 -haloalkyl, C 1 -C4-alkoxy,
C
1
-C
4 -haloalkoxy, C-C 4 alkylthio, C-C 4 -alkoxycarbonyl, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following substituents: halogen, cyano, C 1
-C
4 -alkyl, C 1
-C
4 -alkoxyalkyl, C 1
-C
4 -haloalkyl, C 1
-C
4 -alkoxy, C 1
-C
4 -haloalkoxy, C 1
-C
4 -alkylthio and
C
1 -0 4 -alkoxycarbonyl or
W
1
W
2 where
W
1 is C 1
-C
8 -alkyl which can be partly or completely halogenated and/or can carry one to three of the following groups: cyano, C-C 4 -alkoxy, C 1 -0 4 -haloalkoxy,
C
1
-C
4 -alkylthio, aryl, aryloxy and heteroaryl, it being possible for the cyclic groups in turn to carry one to three of the following substituents: halogen, cyano,
C
1
-C
4 -alkyl, C 1
-C
4 -alkoxyalkyl, C 1
-C
4 -haloalkyl,
C
1
-C
4 -alkoxy, C 1
-C
4 -haloalkoxy, C-C 4 -alkylthio,
C
1
-C
4 -alkoxycarbonyl,..aryl and aryloxy,
C
2
-C
8 -alkenyl or C 2
-C
8 -alkynyl, it being possible for these radicals to be partly or completely halogenated and/or to carry one to three of the following groups: cyano, C 1
-C
4 -alkoxy, C 1
-C
4 -haloalkoxy, C 1
-C
4 -alkylthio,
C
1
-C
4 -alkoxycarbonyl, aryl and aryloxy, it being possible for the cyclic groups in turn to carry one to three of the following substituents: halogen, cyano, C 1
-C
4 -alkoxy,
C
1 -C4-haloalkoxy, C-C4--alkylthio, C 1
-C
4 -alkoxycarbonyl, aryl and aryloxy,
C
3
-C
7 -cycloalkyl or C 3
-C
7 -cycloalkenyl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano, C 1
-C
4 -alkyl, C 1
-C
4 -alkoxyalkyl,
C
1
-C
4 -haloalkyl, C 1
-C
4 -alkoxy, Cl-C 4 -haloalkoxy,
C
1
-C
4 -alkylthio, Cl-C 4 -alkoxycarbonyl, aryl and aryl-(C 1 -CO)-alkyl, it being possible for the groups which contain aryl to carry one to three of the following substituents: halogen, cyano, C,-C 4 -alkyl, Cj-C4-alkoxyalkyl, Cl-C 4 -haloalkyl, C 1
-C
4 -alkoxy, C 1
-C
4 -haloalkoxy,
C
1
-C
4 -alkylthio, C 1
-C
4 -alkoxycarbonyl, aryl and aryloxy or
C.)
0050/44896 3 aryl or heteroaryl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano, C 1
-C
4 -alkyl, Cl-C 4 -alkoxyalkyl, C-C 4 -haloalkyl,
C
1
-C
4 -alkoxy, Cl-C 4 -haloalkoxy, C 1
-C
4 -alkylthio,
C-C
4 -alkoxycarbonyl, aryl and aryloxy and
W
2 is hydrogen or one of the groups W 1
R
2 is hydrogen or C 1
-C
8 -alkyl or C 3
-C
7 -cycloalkyl, which can be partly or completely halogenated
R
3 is C-C 8 -alkyl, it being possible for this radical to carry one to three of the following groups: halogen, cyano,
C
1
-C
4 -alkoxy, C 1
-C
4 -haloalkoxy, C 1
-C
4 -alkylthio and
C
1
-C
4 -alkoxycarbonyl,
C
3
-C
7 -cycloalkyl or phenyl-(C 1
-C
4 )-alkyl, it being possible for the rings of these radicals to carry one to three of the following groups: halogen, cyano, C 1
-C
4 -alkyl, C 1
-C
4 -alkoxyalkyl, C 1
-C
4 -haloalkyl, C 1
-C
4 -alkoxy, C 1
-C
4 -haloalkoxy,
C
1
-C
4 -alkylthio, C-C 4 -alkoxycarbonyl, aryl and aryloxy;
R
4 is hydrogen or one of the radicals R 3 or
R
3 and R 4 together with the C atom to which they are bonded, are a 4- to 8-membered ring which, as ring members, in addition to carbon can also contain one or two of the heteroatoms oxygen, sulfur and nitrogen, it being possible for the carbon atoms in the ring to carry one or two of the following groups: halogen, cyano, C 1 -C4-alkyl, C 1
-C
4 -alkoxyalkyl, C 1
-C
4 -haloalkyl, C-C 4 -alkoxy, C 1
-C
4 -haloalkoxy, Cl-C 4 -alkylthio, C -C 4 -alkoxycarbonyl, aryl and aryloxy and nitrogen as a heteroatom carrying hydrogen or a C 1 -C4-alkyl group;
R
5 is one of the radicals R 2
R
6 is C-C-alkyl, C 2
-C
8 -alkenyl or C 2
-C
8 -alkynyl, it being possible for these radials to be partly or completely halogenated and/or to carry one to three of the following groups: cyano, C 1
-C
4 -alkoxy, C 1
-C
4 haloalkoxy, C 1
-C
4 -alkylthio,
C
3
-C
7 -cycloalkyl, C 3
-C
7 -cycloalkenyl, aryl, aryloxy and heteroaryl, it being possible for the cyclic radicals in turn to carry one to three of the following substituents: halogen, cyano, C 1
-C
4 -alkyl, C 1
-C
4 -alkoxyalkyl, C 1
-C
4 -haloalkyl, cj/ AT 0050/44856 4
C
1
-C
4 -alkoxy, C 1
-C
4 -haloalkoxy, Ci-C 4 -alkylthio, aryl, aryloxy and heteroaryl,
C
3
-C
7 -cycloalkyl or C 3 -C7-cycloalkenyl, it being possible for these radicals to be partly or completely halogenated and/or to carry one to three of the following groups: cyano,
C
1
-C
4 -alkyl, Cl-C 4 -alkoxyalkyl, C-C 4 -haloalkyl, C-C 4 -alkoxy,
C
1
-C
4 -haloalkoxy, Cl-C 4 -alkylthio, aryl, aryloxy and aryl-(Cl-C 4 )-alkyl, it being possible for the cyclic groups to carry one to three of the following substituents: halogen, cyano, C 1
-C
4 -alkyl, CL-C 4 -alkoxyalkyl, C 1
-C
4 -haloalkyl, Ci-C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 -alkylthio, aryl and aryloxy, a non-aromatic 4- to 8-membered ring, which, as ring members, in addition to carbon can also contain one or two of the heteroatoms oxygen, sulfur and nitrogen, it being possible for the carbon atoms in the ring to carry one or two of the following groups: halogen, cyano, Ci-C 4 -alkyl, C 1
-C
4 -alkoxyalkyl, C 1
-C
4 -haloalkyl, C 1
-C
4 -alkoxy, C 1
-C
4 -haloalkoxy, Ci-C 4 -alkylthio, aryl and aryloxy and the second and each further nitrogen atom as a heteroatom in the ring carrying hydrogen or a Ci-C 4 -alkyl group, aryl or heteroaryl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano,
C
1
-C
4 -alkyl, C 1
-C
4 -alkoxyalkyl, Cl-C 4 -haloalkyl, Ci-C 4 -alkoxy,
C
1
-C
4 -haloalkoxy, C 1
-C
4 -alkylthio, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following substituents: halogen, cyano, Ci-C 4 -alkyl, Ci-C 4 -alkoxyalkyl, Cl-C 4 -haloalkyl, C 1
-C
4 -alkoxy,
C
1
-C
4 -haloalkoxy and C 1
-C
4 -alkylthio or if R 3 is isopropyl, hydrogen;
R
7 is one of the radicals R 6 excluding hydrogen;
X
1 is oxygen or sulfur,
X
2 is oxygen or sulfur,
X
3 is oxygen or sulfur; excluding the compounds according to the following definition of the radicals: Ia-d (R 1 Ph-CH 2
R
2 H; R 3
CH
3
(CH
2 2
CH
3
CH(CH
3 2 or Ph-CH 2
R
4
,R
5 H; R 6
,R
7
CH
2
CH
2 Cl), 0050/44896 Ie-h (R 1
C(CH
3
R
2
R
3 =0H3, CH(CH 3 2
CH(CH
3
)CH
2 CH3,
CH
2
CH(CH
3 )2 or Ph-OH 2
R
4
,R
5 H; R 6
,R
7
=CH
2
CH
2 Br), Ii (RI Ph-OH 2
R
2
R
3
OH
3
R
4 ,RS H; R 6
CH
3
R
7 Ph), Ij-k (R 1 Ph-OH 2
R
2 H; R 3
CH(CH
3 2 or CH 2
CH(CH
3
R
4
,R
H; R 6
,R
7 Ph), Il
(R
1
C(CH
3 3
R
2
R
3
=CH(CH
3 2 R4,R 5
,R
6 H; R 7 Ph), Im (R 1 Ph-OH 2
R
2
R
3 Ph-OH 2
R
4
R
5
R
6
,R
7
CH
2
CH
3 In-o (R1 Ph-OH 2
R
2
R
3 C H 2
SOH
3 or CH 2
OH
2
SCH
3
R
4
,R
H; R 6
,R
7
CH
2
CH
2 Cl).
The invention additionally relates to processes for preparing the compounds I and their salts, compositions containing these substances, and a method for controlling harmful fungi and the use of these substances therefor.
In addition, the present invention relates to amino acid hydrazide intermediates of the general formula IV
R
3
X
3
R
5
R
6 2 -0-N N -R 7
IV
where X 3 is oxygen and R 3 is a group CH(CH 3 2
CH
2
OH(CH
3 )2 or CH(0H 3
)C
2
H
5 and R 4
R
5
R
6 and R 7 have the meaning given in claim 1, excluding the compounds according to the following definition of the radicals: IVa-b (R 3
CH(CH
3 2 or (CH 2 2
CH
3
R
4
,R
5 H; R 6
,R
7
CH
2
CH
2 Cl), IVc-e (R 3
OH(CH
3 2
OH(CH
3
)CH
2
OH
3 or OH 2
OH(CH
3
R
4
,R
5
H;
R
6
,R
7
CH
2
CH
2 Br), IVf (R 3
OH(CH
3 2
R
4
,R
5
,R
6
R
7 =Ph), IVg (R 3 CH (CHD) 2
R
4
R
5 H; R 6
R
7 Ph) compositions are known from DE-B 1 199 540 which contain alkylcarbohydrazides, eg. the compound of the following formula
%L
0050/44896 6 0
II
H
3
C-CH
2
-H-CHCCH
2
-CH--NH-NH
and which have an action against powdery mildew fungi.
JP-A 69/27 997 additionally describes the use of 4-methoxycarbonylterephthalic hydrazide or terephthalic bishydrazide for controlling rice blast.
However, these agents are still not satisfactory as fungicides.
Further carbohydrazides are additionally known from the literature; nothing has been reported, however, of a fungicidal action of these compounds (cf. Pharmazie 44, (1988) page 608 to page 611; Pharmazie 44, (1989) page 316 to page 317; J. Org. Chem. 36, (1971) page 1580 to page 1584; Farm. Pol. 28, (1972) page 615; EP-A 361 977; Collect. Czech. Commun. 49, (1989) page 2551 to page 2561).
It is an object of the present invention to provide novel carbamoylcarbohydrazides having improved action against harmful fungi.
We have found that this object is achieved by the compounds I and their salts described at the outset.
Furthermore, we have found important intermediates of the general formula IV for preparing these substances.
We have additionally found compositions containing them, processes for preparing the compounds I and their salts and the compositions containing them and in addition a process for controlling harmful fungi and the use of the compounds I and their salts therefor.
The compounds I and their salts can be prepared starting from the corresponding carbamoylcarboxylic acids II. Preferably, they are obtained by the processes A, B and C described in the following (the Houben-Weyl references relate to: Houben-Weyl, Methoden der Organischen Chemie (Methods of Organic Chemistry), 4th edition, Thieme Verlag, Stuttgart).
A Sr 0050/44896 7 Process A carbamoylcarbohydrazides I are obtained by reacting the carbamoylcarboxylic acids II with the hydrazines III.
X
2
R
2
R
3
X
3
R
5
R
6 ii I 1 I I I I
R
1
-X
1 C C -C-OH N R 7
I
R
4 II III
X
2
R
2
R
3
X
3
R
5
R
6 II I I II I I R1-X 1 C N-R 7
I
R
4 The carbamoylcarboxylic acids II are known or obtainable by known methods, especially starting from the amino acids on which they are based for example, Houben-Weyl "Methoden der organischen Chemie" [Methods of Organic Chemistry], Volume 15/1, 4th Edition, Thieme Verlag Stuttgart 1977; JP 53148530; JP 52151146; J. Org. Chem. 43 [1978], 2930-2932; J. Chem. Soc., Perkin Trans.
1, 1972, 1983-1985; Chem. Ber. 104 (1971], 3156-3167; J. Or, Chem. 36 [1971], 49-59; Helv. Chim. Acta 52 [1969], 282-291; Tetrahedron 34 [1978], 2763-2766; Chem. Pharm. Bull. 19 (1971], 912-929; J. Chem. Soc. 1952, 2076-2079).
The hydrazines III are likewise known or easily obtainable .jf.
Houben-Weyl, volume 10/2, page 1 to page 71 and page 169 to page 409, especially page 396 to page 399 and page 402 to page 405).
This process A is preferably carried out by first converting the carbamoylcarboxylic acids II to carboxyl-activated derivatives, especially to acyl cyanides or anhydrides (cf. Pharmazie 44, (1989) page 316 to page 317 and page 608 to page 611; Tetrahedron Letters, volume 18, (1973) page 1595 to page 1598 and Houben- Weyl, volume 15/1, page 28 to page 32). These derivatives are then reacted with the hydrazines III in the presence of bases.
i0 o V 0050/44896 8 A suitable reaction for preparing the carboxyl-activated acylcyanides is eg. the reaction of the carb:rcylcarboxylic acids II with diethyl cyanophosphonate, especial- sn an inert solvent such as tetrahydrofuran, toluene or dichloromethane.
To prepare the carboxyl-activated anhydrides, the reaction of the carbamoylcarboxylic acids II with carbonyl chlorides such as isobutyl chloroformate in the presence of bases and in the presence or absence of an inert solvent such as toluene or tetrahydrofuran is preferred.
The reaction of the hydrazines III with the carboxyl-activated carbamoylcarboxylic acids II is preferably carried out in a solvent such as dichloromethane, tetrahydrofuran or toluene.
In particular, the bases used can be the hydrazines III themselves, the bases customarily being recovered from the crude product.
In a preferred embodiment of this stage of the process, the carbamoylcarboxylic acid II, the hydrazine III, the reagent suitable for generating the carboxyl-activated derivative of the carbamoylcarboxylic acid II and the base are reacted in a one-pot process, if appropriate in an.inert solvent, and the crude product is then worked up to the carbamoylcarbohydrazide I in a manner known per se.
Process B The carbamoylcarbohydrazides I, in which R 1 is a group -W 1
W
2
C=N-,
are also obtained by converting the carbamoylcarbohydrazides I, in which X 1
X
2 and X 3 are in each case oxygen, and the group RI-Xl-(CO) is a protective group which can be removed in a manner known per se, to carbohydrazides IV and reacting these with chloroformyl oximes V in the presence of bases.
Stage Ba: Preparation of the carbohydrazides IV 0050/44896
X
2
R
2
R
3
X
3
R
R1-X1-C-N-C N-R 7 R2 I N
R
3
X
3
R
5
R
6 I II I 1 C N N -R 7
I
R4
IV
The removal of the group R-Xl-(CO) from the carbamoylcarbohydrazides I can be carried out in a manner known per se (cf. Houben- Weyl, volume 15/1, page 46 to page 305, especially page 126 to page 129; Pharmazie 44, (1989) page 316 to page 317).
Suitable removable groups especially contain the tert-butyl group and additionally the benzyl group as a radical R 1 If R 1 tert-butyl, for example, removal customarily takes place by reaction with an acid, in particular a protic acid such as hydrochloric acid, hydrobromic acid or trifluoroacetic acid (loc.
cit.).
The carbamoylcarbohydrazides I suitable as starting substances are obtainable by known processes (cf. Pharmazie 44, (1989) page 316 to page 317 and page 608 to page 611; Houben-Weyl, volume 15/1, page 28 to page 32) or in particular by process A according to the invention.
Stage Bb: Preparation of the carbamoylcarbohydrazides I
RAI
Ui ~k V'e 0050/44896 W1 0 R 2
R
3 X3 R 5
R
6 II=N-- I II I N R C=N-O--C--Cl H N C- N- N
I
W
2
W
1 i C=N- 0- C=N-
O-
0 R 2
R
3
X
3
R
5
R
6 II I I II I I C-N--C N-R 7
I
I
The carbohydrazides IV resulting from the synthesis stage (Ba) are reacted with the chloroformyl oximes V in the presence of bases.
The chloroformyl oximes V are known or obtainable by known processes, eg. by phosgenation of oximes (cf. Z. Chem. 9, (1967) page 344 to page 345).
The reaction is preferably carried out in an organic solvent, especially in toluene, methylene chloride, tetrahydrofuran or mixtures of these.
Suitable bases are equally inorganic and organic bases, organic bases and, among these in turn, tertiary amines such as triethylamine, pyridine and N-methylpiperidine being preferred.
As a rule, the reaction is carried out at from -40 to 50°C, preferably from -10 to The carrying-out of this reaction is otherwise familiar to the person skilled in the art, so no further explanations are needed (cf. Houben-Weyl, volume 15/1, page 117 to page 125; Dev.
Endocrinol. 13 (Neurohypophyseal Pept. Horm. Other Biol. Act.
Pept.), (1981) page 37 to page 47).
Process C The carbamoylcarbohydrazides of the general formula I according to claim 1, in which R 6 is Ci-Cs-alkyl, C 4
-C
7 -cycloalkyl or aryl-(C 1
-C
4 )-alkyl, are also obtainable by reacting carbamoylcarbohydrazides of the general formula I according to claim 1, in which R 6 is hydrogen, with a compound of the general formula R 6
-X
/T C 0050/44896 11 in which R 6 is C 1 -Cs-alkyl, C 4
-C
7 -cycloalkyl or aryl-(Cl-C 4 )-alkyl and X is a negative leaving group, with additional use of a base.
The carbanoylcarbohydrazides of the general formula I, in which R 6 is hydrogen, are obtainable in a manner known per se (cf.
DE-A 1 089 390; Zh. Org. Khim. 14 (1978), page 1086), or in particular by process A according to the invention.
A suitable negative leaving group X is the methylsulfonyl or the 4-methylphenylsulfonyl anion and preferably halide anions such as iodide and in particular chloride and bromide.
The bases used are especially alkali metal carbonates and alkoxides such as sodium carbonate, sodium methoxide and sodium ethoxide, in addition alkaline earth metal carbonates such as calcium carbonate, alkali metal or alkaline earth metal hydroxides, eg. sodium hydroxide and calcium hydroxide, hydrides, eg. sodium hydride, hydrogencarbonates, eg. sodium hydrogencarbonate, alkanes, eg. n-butyllithium, or tertiary amines such as triethylamine.
The reaction can be carried out without solvent or in a solvent which is inert under the reaction conditions, such as dimethylformamide, tetrahydrofuran, dichloromethane or alkanols such as methanol or ethanol.
As a rule, the reaction is carried out at from 10 to 60 0 C and under atmospheric pressure.
Otherwise, the process is carried out in a manner known per se (cf. Houben-Weyl, volume 10/2, page 402 to page 404).
The reaction mixtures obtained by processes A, B and C are customarily worked up to the compounds I in the customary manner, eg. by mixing with water, separating the phases and, if necessary, purifying the crude products by chromatography. The intermediates and final products are obtained in some cases in the form of colorless or slightly brownish, viscous oils which can be freed from the volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and final products are obtained as solids, they can also be purified, for example, by recrystallizing or digesting.
0/ 0050/44896 12 Depending on the nature of the substituents, the compounds of the formula I can, if appropriate, be present as geometrical and/or optical isomers or isomer mixtures. Both the pure isomers and the mixtures of the isomers have fungicidal action.
The salts are also part of the invention, in particular of the acid-stable compounds I which contain basic centers, especially basic nitrogen atoms, ie. in particular the salts with mineral acids such as sulfuric acid and phosphoric acid or Lewis acids such as zinc chloride. Customarily, the nature of the salts does not matter. In the context of the invention, those salts are preferred which do not damage the plants, surfaces, materials or spaces to be kept free of harmful fungi and do not adversely affect the action of the compounds I.
The salts of the compounds I are accessible in a manner known per se, especially by reacting the corresponding carbamoylcarbohydrazides I with said acids in water or an inert organic solvent at from -80 to 120 0 C, preferably from 0 to In the preparation of the carbamoylcarbohydrazides I according to process B, there are also obtained novel intermediates of the general formula IV
R
3
X
3
R
5
R
6 I II I I H2 C C--N N R 7
IV
R4 where X 3 is oxygen and R 4
R
5
R
6 and R 7 have the meanings given in claim 1 and R 3 is a group CH(CH3) 2
CH
2
CH(CH
3 2 or CH(CH 3
)C
2
H
5 the compounds according to the following definition of the radicals already being known: IVa-b (R 3
CH(CH
3 2 or (CH 2 2
CH
3
R
4
,R
5 H; R 6
,R
7 CH2CH 2 Cl), IVc-e (R 3
CH(CH
3 2
CH(CH
3
)CH
2
CH
3 or CH 2
CH(CH
3 2
R
4
,R
5
H;
R
6
,R
7
CH
2
CH
2 Br), IVf (R 3
CH(CH
3 2
R
4
,R
5
,R
6 H; R 7 Ph), IVg (R 3
CH(CH
3 2
R
4
,R
5 H; R 6
,R
7 Ph) 0050/44896 13 (cf. Pharmazie, 44, (1989) page 608 to page 611; Pharmazie, 44, (1989) page 316 to page 317; EP-A 0 361 977; Int. J. Pept.
Protein Res. 21 (1983) page 406; Farm. Pol. 28, (1972) page 615 to page 619).
Among the novel amino acid hydrazides IV, those are preferred in which R 3 is a group CH(CH 3 2
R
4 and R 5 have the meanings given in claim 1,
R
6 is C 1
C
8 -alkyl, it being possible for this radical to be partly or completely halogenated and/or to carry one to three of the following groups: cyano, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy, C 1
-C
4 alkylthio, C 3
-C
7 -cycloalkyl, C 3
-C
7 cycloalkenyl, aryl, aryloxy and heteroaryl, it being possible for the cyclic radicals in turn to carry one to three of the following substituents: halogen, cyano, Cl-C 4 -alkyl, Cl-C 4 -alkoxyalkyl, Cj-C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy and C 1
-C
4 -alkylthio, aryl, aryloxy and heteroaryl and
R
7 is aryl, it being possible for this radical to carry one to three of the following groups: halogen, cyano, Cl-C 4 -alkyl, Cl-C 4 alkoxyalkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 -alkylthio, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following substituents: halogen, cyano, Cl-C 4 -alkyl, Cl-C 4 -alkoxyalkyl, Cl-C 4 -haloalkyl, C 1
-C
4 alkoxy, C 1
-C
4 -haloalkoxy and Cl-C 4 -alkylthio.
With respect to their use for preparing carbainoylcarbohydrazides I, the compounds IV compiled in the following tables are particularly preferred.
Table 1.
3 C CH 3 H CH 0 R 5
R
6 I 1 1I 1 1 H-N-C N -R 7
H
No. R5 R6 R 2 iH CH 3 4-Cl--C 6
H
4 3 1H 11R 3 4-CH 3
C
6
H
4 0050/44896 No. R5R 6
R
4 H CH 3 4-OCH 3
-C
6
H
4 H CH 3 3,4-(OCH 3 2
-C
6
H
3 6 CH 3
CH
3 4-Cl-0 6
H
4 8 H CH 3 4-Cl.-C 6
H
4 9 H CH 3 4-CH 3
-C
6
H
4 H CH(CH 3 2
CH
2 -(4-Cl-C6H4) 11 H
CH(CH
3 2 4-C).
12 H CH (CH 3 2
CH(C
6 5 )(4-C1-COO4 13 H CH(CH 3 2 4-C1--C 6
H
4 14 CH 3 CH (CH 3 2 4-CH 3 -0 6
H
4 H CH(CH 3 2 4-OCH 3 -0 6 H4 16 H CH(CH 3 2 3,4-(OCH 3 2
-C
6
H
3 17 H CH 2
CH
3
CH
2 (4-Cl-C6H4) 18 H CH 2
CH
3
CHCH
3 (4-Cl--C6H4) 19 H CH 2
CH
3
CH(C
6
H
5 )(4-C1-CSH4)
CH
3
CH
2
CH
3 4-C1-C 6
H
4 21 H CH 2
CH
3 4-CH 3
-C
6
H
4 22 FH CH 2
CH
3 4-OCH 3
-C
6 H4 23 H CH 2
CH
3 3,4-(OCH 3 2
-C
6
H
3 24 H cycl--CSH9 CH 2 (4-Cl--C 6
H
4 H cyclo-c 5
H
9 CH (CH 3 (4-C--C 6
H
4 26 H CYClo-C5Hg CH(C 6
H
5 (4-C1-C 6
H
4 27 H cyclo-CsHg 4-C1-C 6
H
4 28 H cyclo-C 5 H9 4-CH 3
-C
6
H
4 29 H cyclo-C 5 H9 4-OCH 3 6
H
4 H cyclo- 5
H
9 3, 4-(OCH 3 2
-C
6
H
3 31 H CYClo-C 6 Hlj CH 2 (4-C1-C 6
H
4 32 H CYClo-C6Hjj CH(CH 3 )(4-C1-C6H4) 33 H CYClo- 6 Hjj CH(C 6 5 (4-C1-COH 4 34 H CYClo-C6H11 4-C1--C 6
H
4 H CYClo-C6H1jj 4-CH 3
-C
6
H
4 36 H CYClo-C6H11 4-OCH 3
-C
6
H
4 37 H CYC1-C6Hjj 3, 4-(OCH3) 2
-C
6 H3 38
CH
3
CH
3
COS
39 CH 3
CH
3 4-Cl1-C 6
H
4
CH
3
CH
3 4-CH3-C6H4 41 CH 3
CH
3 4-OCH 3
-C
6
H
4 42 CH 3
CH
3 3,4-(OCH 3 2 -0 6
H
3
ATO
0050/44896 In the definition of the compounds I given at the outset, collective terms were used which are representative of the following substituents: halogen: fluorine, chlorine, bromine and iodine; alkyl: straight-chain or branched alkyl groups having 1 to 8 carbon atoms, eg. C-C 6 -alkyl such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-i-methylpropyl and 1-ethyl-2-methylpropyl; haloalkyl or partly or completely halogenated alkyl: straightchain or branched alkyl groups having 1 to 4 or 8 carbon atoms (as mentioned above), it being possible in these groups for the hydrogen atoms to be partly or completely replaced by halogen atoms (as mentioned above), eg. C 1
-C
2 -haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl; alkoxy: straight-chain or branched alkoxy groups having 1 to 4 carbon atoms, eg. C 1
-C
3 -alkoxy such as methoxy, ethoxy, propoxy and 1-methylethoxy; alkoxyalkyl: straight-chain or branched alkyl groups having 1 to 8 carbon atoms (as mentioned above), which in any desired position carry a straight-chain or branched alkoxy group (as mentioned above) having, in the case of C 1
-C
4 -alkoxy, 1 to 4 carbon atoms, such as methoxymethyl, ethoxymethyl, n-propoxymethyl, n-butoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1-ethoxyethyl, 2-ethoxyethyl, 2-n-prpoxyethyl and 2-butoxyethyl; haloalkoxy: straight-chain or branched alkoxy groups having 1 to 4 carbon atoms (as mentioned above), it being possible in these groups for the hydrogen atoms to be partly or completely replaced by halogen atoms (as mentioned above), eg. C 1
-C
2 -haloalkoxy such as chloromethoxy, dichloromethoxy, trichloromethox>, fluoro- ~c -1
I
I/ 0 0050/44896 16 methoxy, difluoromethoxy, trifluoromethoxy, chiorofluoromethoxy, dichiorofluoromethoxy, chiorodifluoromethoxy, 1-fluoroethoxy, 2-f luoroethoxy, 2, 2-difluoroethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro3-2, 2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy and pentafluoroethoxy; alkylthio: straight-chain or branched alkyl groups having 1 to 4 carbon atoms (as mentioned above), which are bonded to the structure via a sulfur atom eg. Cl-C 4 -alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, n-butylthio and tert-butylthio; alkoxycarbonyl: straight-chain or branched alkoxy groups having 1 to 4 C atoms (as mentioned above), which are bonded to the structure via a carbonyl group alkenyl: straight-chain or branched alkenyl groups having 2 to 8 carbon atoms and a double bond in any desired position, eg.
C
2
-C
6 -alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-l-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1.-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyle 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-zethyl-1-pentenyl,.
2-methyl- 1-pentenyl, 3-methyl- 1-pentenyl, 4-methyl- 1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-rethyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1-dimethyl-2-butenyl, 1, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenylt 1, 3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 2, 2-dimethyl-3-butenyl, 2,3-dimethyl-l-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl--3-butenyl, 3, 3-dimethyl-l-butenyl., 3, 3-dimethyl-2-butenyl, 2-ethyl- 1-butenyl, 2-tethyl-2-butenyl, 2--ethyl-3-butenyl, 1,1, 2-trimethyl-2-propenyl, 1-ethyl-l-mnethyl-2-propenyl, 1-ethyl-2-methyl- 1-propenyl and 1-ethyl-2-methyl-2-propenyl; 0050/44896 17 alkynyl: straight-chain or branched alkynyl groups having 2 to 8 carbon atoms and a triple bond in any desired position, eg.
C
2
-C
6 -alkyny. such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-inethyJ-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butyiiyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1--pentynyl, 4-methyl-2-pentynyl, 1, 1-dimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1, 2-dimethyl-3-butynyl, 2, 2-dimethyl-3-butynyl, 3, 3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl--3-butynyl and 1-ethyl-1-methyl-2-propynyl; cycloalkyl: monocyclic alkyl groups having 3 to 7 carbon ring members, eg. C.'-C 7 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl; cycloalkenyl: monocyclic alkyl groups having 5 to 7 carbon ring members which contain one or more double bonds, eg.
C
5 -0 7 -CYCloalkenyl such as cyclopentenyl, cyclohexenyl and cycloheptenyl; non-arimatic 4- to 8-membered rings, which, as ring members, in addition to carbon also contain one or two oxygen, sulfur or nitrogen atoms, such as saturated 5- or 6-membered rings having1 ox 2 nitrogen and/or oxygen atoms such as 3-tetrahydrofuranyl, 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-morpholinyl and 3-morpholinyl; aryl: monocyclic or polycyclic ar:omatic groups having 6 to carbon atoms, such as phenyl and~ naphthyl; arylalkyl: aryl groups (as mentioned above), whic~h in the case of aryl-(Ci--C 4 )-alkyl are bonded to the structure via alkyl groups having 1 to 4 carbon atoms (as mentioned above), eg.
phenyl-(C 1
-C
4 )-alkyl such as benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 1-phenylethyl, 1-phenylpropyl and 1-phenylbutyl; aryloxy: aryl groups (as mentioned above), which are bonded to the structure via an oxygen atom such as phenoxy, 1-naphthoxy and 2-naphthoxy; 0050/44896 18 heteroaryl: aromatic mono- or polycyclic radicals, which in addition to carbcn ring members can additionally contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and an oxygen or a sulfur atom or an oxygen or a sulfur atom, eg.: 5-membered heteroaryl, containing 1 to 3 nitrogen atoms: ring-heteroaryl groups, which in addition to carbon atoms can contain 1 to 3 nitrogen atoms as ring members, eg. 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-triazol-3-yl and 1,3,4-triazol-2-yl; 5-membered heteroaryl, containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur atom or oxygen atom or 1 oxygen or 1 sulfur atom: 5-membered ring heteroaryl groups, which in addition to carbon atoms can contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom or 1 oxygen or sulfur atom as ring members, eg. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2 ,.4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl; benzo-fused 5-membered heteroaryl, containing 1 to 3 nitrogen atoms or 1 nitrogen atom and/or an oxygen or sulfur atom: ring heteroaryl groups which in addition to carbon atoms can contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom or 1 oxygen or one sulfur atom as ring members, and in which 2 adjacent carbon ring members or 1 nitrogen and 1 adjacent carbon ring member can be bridged by a buta-1,3-diene-1,4-diyl group; 5-membered heteroaryl bonded via nitrogen, containing 1 to 4 nitrogen atoms, or benzo-fused 5-membered heteroaryl bonded via nitrogen, containing 1 to 3 nitrogen atoms: ring heteroaryl groups which, in addition to carbon atoms, can contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms as ring members, and in which 2 adjacent carbon ring me..oers or one nitrogen and one adjacent carbon ring member can be bridged by a buta-1,3-diene-1,4-diyl group, these rings being bonded to the structure via one of the nitrogen .ring members;
_IV
S -1 -k.
-I
0050/44896 19 6-membered heteroaryl, containing 1 to 3 or 1 to 4 nitrogen atoms: 6-membered ring heteroaryl groups which, in addition to carbon atoms, can contain 1 to 3 or 1 to 4 nitrogen atoms as ring members, eg. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, 1,3,5--triazin-2-yl, 1,2,4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl; benzo-fused 6-membered heteroaryl, containing 1 to 4 nitrogen atoms: 6-membered ring heteroaryl groups, in which 2 adjacent carbon ring members can be bridged by a buta-1,3-diene-1,4-diyl group, eg. quinoline, isoquinoline, quinazoline and quinoxaline.
The statement partly or completely halogenated is intended to express that in the groups characterized in this way the hydrogen atoms can be partly or completely replaced by identical or different halogen atoms, as mentioned above.
With respect to their biological action against harmful fungi, compounds I are preferred in which
R
7 is C 3
-C
7 -cycloalkyl or C 3
-C
7 -cycloalkenyl, it being possible for these radicals to be partly or completely halogenated and/or to carry one to three of the following groups: cyano, Cl-C 4 -alkyl, C 1
-C
4 -alkoxyalkyl, C 1
-C
4 -haloalkyl, C 1
-C
4 -alkoxy,
C
1
-C
4 -haloalkoxy, C 1
-C
4 -alkylthio, aryi, aryloxy and aryl-(C 1
C
4 )-alkyl, it being possible for the cyclic groups to carry one to three of the following substituents: halogen, cyano, C 1
-C
4 alkyl, C-C 4 -alkoxyalkyl, C 1
-C
4 -haloalkyl,
C
1
-C
4 -alkoxy, C-0 4 -haloalkoxy, C 1
-C
4 -alkylthio, aryl and aryloxy or
R
7 is a non-aromatic 4- to 8-membered ring which, as ring members, in addition to carbon can also contain one or two of the heteroatoms oxygen, sulfur and nitrogen, it being possible for the carbon atoms in the ring to carry one or two of the following groups: halogen, cyano, C 1
-C
4 -alkyl,
C
1
-C
4 -alkoxyalkyl, C 1
-C
4 -haloalkyl, C 1
-C
4 -alkoxy, C 1
-C
4 -haloalkoxy, C-C 4 -alkylthio, aryl and aryloxy and the second and each further nitrogen atom as a heteroatom in the ring carrying hydrogen or a C 1
-C
4 -alkyl group or
R
7 is aryl or heteroaryl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano, C 1
-C
4 -alkyl, C 1
-C
4 -alkoxyalkyl, C 1
-C
4 -haloalkyl,
C
1
-C
4 -alkoxy, C 1
-C
4 -haloalkoxy, C 1
-C
4 -alkylthio, aryl, aryloxy T C 0050/44896 and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following substituents: halogen, cyano, C 1
-C
4 -alkyl, Ci-C 4 -alkoxyalkyl, C 1
-C
4 -haloalkyl, Ci-C 4 -alkoxy, Cl-C 4 -haloalkoxy and Cl-C 4 -alkylthio.
Particularly preferred compounds I are those in which the radicals have the following meanings, namely per se or in combination:
R
1 is Cl-C6-alkyl, it being possible for this radical to carry one to three of the following groups: halogen, C 1
-C
4 -alkoxy, phenyl and phenoxy, especially Cl-C 4 -alkyl and benzyl,
R
1 is C 3
-C
7 -cycloalkyl, it being possible for this radical to carry one to three of the following groups: halogen,
C
1
-C
4 -alkoxyalkyl, phenyl and phenoxy and especially cyclopropyl, cyclopentyl and cyclohexyl,
R
1 is aryl, it being possible for this radical to carry one to three of the following groups: halogen, Cl-C 4 -alkyl and Ci-C 4 -alkoxy, especially phenyl and naphthyl, which can be unsubstituted and/or in turn can carry one to three of the following groups: fluorine, chlorine, bromine, Cl-C 4 -alkyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy and tert-butoxy, and in particular unsubstituted phenyl, 1-naphthyl and 2-naphthyl,
R
2 is hydrogen,
R
3 is Ci-C 6 -alkyl, especially Ci-C 4 -alkyl,
R
3 is C 3 -C6-cycloalkyl, especially cyclopropyl, cyclopenty' or cyclohexyl,
R
4 is hydrogen,
R
4 is C 1 -Cs-alkyl, especially Ci-C4-alkyl,
R
4 is C 3
-C
6 -cycloalkyl, especially cyclopropyl, cyclopentyl or cyclohexyl,
R
4 is hydrogen,
R
3 is C 1
-C
6 -alkyl and R 4 is hydrogen,
R
5 is hydrogen, n1 0050/44896 21
R
3 is C 3
-C
6 -cycloalkyl and R 4 is hydrogen,
R
5 is C-C 4 alkyl, especially methyl or ethyl,
R
5 is C 3 -C--cycloalkyl, especially cyclopropyl,
R
6 is C 1
-C
6 -alkyl, especially methyl, ethyl, n-propyl or isopropyl,
R
6 is C 3
-C
7 -cycloalkyl,
R
6 is aryl, it being possible for this radical to be unsubstituted or to carry one to three of the following groups: fluorine, chlorine, bromine, cyano, Ci-C 4 -alkyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, trifluoromethoxy, phenyl and phenoxy,
R
7 is phenyl, it being possible for this radical to be unsubstituted or to carry one to three of the following groups: fluorine, chlorine, bromine, cyano, C 1
-C
4 -alkyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, trifluoromethoxy, phenyl and phenoxy,
R
7 is naphthyl, it being possible for this radical to be unsubstituted or to carry one to three of the following groups: fluorine, chlorine, bromine, cyano, C 1
-C
4 -alkyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, trifluoromethoxy, phenyl and phenoxy,
R
7 is C 3 -Cy-cycloalkyl, it being possible for this radical to be unsubstituted or to carry one to three of the following groups: halogen, C 1
-C
4 -alkyl and Cl-C 4 -alkoxy, especially substituted C 5
-C
7 and in particular C 6 -cycloalkyl of this type.
With regard to the meaning of X 1
X
2 and X 3 compounds I are particularly preferred where X 1
X
2 and X 3 are oxygen. If one or more of X 1
X
2 and X 3 are sulfur, those compounds I are particularly preferred where X 1 and X 2 are sulfur, especially those where only
X
1 is sulfur. However, those compounds I can also be preferred where only X 2 is sulfur.
The compounds I conip.led in the following tables are very particularly preferreuawith respect to their use.
'I
0050/44896 Table 2 0 H R 3 0 R 5
R
6 C-N-CC- N N-R 7
H
X
1 is oxygen or sulfur.
No. RI
R
3
R
5
R
6
R
7 1 C (C! 3 3 CH (CH3) 2 CF! 3
CF!
3
C
6
F!
2 C(CF! 3 3
CH(CH
3 )C2H5 H CF! 3
C
6 3 C (CH 3
CH
2 CH(CH3)2 H CF! 3
C
6
H
4 C(CH 3 3 CH(CH3)2 H CF! 3 4-Cl-C 6 H4 C(CH3).3 CH(CH3)2 H CF! 3 4-CH 3
-C
6 H4 6 C(CH 3 )3 CH(CH3)2 H CF! 3 4-OCH 3 -C6H4 7 C(CH3)3
CH(CF!
3 )2 H CH3 3,4-(OCF! 3 2
-C
6 H3 8 CH(CH) cYclo-C 3 H5 H CF! 3 4-Cl--C 6
H
4 9 CF!(CH 3 )2 CYClo-C 4 H7 H CF! 3 4--Cl-C 6 H4 CH(CH3)2 cyclo-C5H9 H CH 3 4-Cl--C 6
H
4 11 CH (CH3) 2 cyclo-C 6 H11 H CF! 3 4-C1-C 6 H4 12 CF!(CF!3)2
CH
2
C
6
H
5 H CF! 3
C
6
H
13 CF!(CH3)2
CF!(CF!
3 )C2H5 H CH3 C 6
H
14 CH(CH3)2
CH
2 CH(CH3)2 H CF! 3
C
6
H
CH(CF!3)2
CH(CH
3 )2 CH3 CF! 3 4-C1.-C 6
H
4 16 CF!(CH3)2
CF!
2
C
6
H
5 H CF! 3 4-CH 3 6
H
4 17 CF!(CH 3 )2 CH(CF!3)2 H CF! 3 4-OCF! 3 -C6!4 18 CH(CH) CH( CH3)2 F! CF!3 3,4-(CH 3 )2-C6H3 19 C 6 Hs
CH(CH
3 2 H CF! 3
C
6
H
20 C 6
F!
5
CH(CF!
3
)C
2 H5 H CF! 3
C
6 21 C 6 Hs
CF!
2 CF(CH3)2 H CF! 3
C
6
H
22 C 6
H
5
CF!(CF!
3 2
CF!
3
CF!
3 4-Cl--C 6
H
4 23 C 6
F!
5
CH
2
C
6
H
5 H CF! 3 4-CH 3
-C
6
H
4 24 C 6
H
5
CH(CF!
3 )2 H CF! 3 4-OCH 3 -C6H4 25 C 6
H
5 CH(CF!3) 2 H! CF! 3 3, 4-(OC! 3 2 -C6H3 26 CH(CH3)2
CF!(CF!
3 2 H CH(CF! 3 )2 C 2 (4-Cl-C6H4) 27 CH(CF! 3 )2 CH(CH 3 2 H Ct* CH 3 2
CH(CH
3 )(4-Cl-C6H4) 28 CF!(CH,3) 2 CH(CF!3)2 F! CH (CHzj)2 CH(C 6 F!S)(4-C1-CGH4) 29 CH(CH3)2
CF!(CH
3 2 H CH(CH3)2 4-Cl-C 6 H4 CF!(CH3)2
CH(CF!
3 2 CH3 CF!(CF! 3 )2 4-CH 3
-C
6 H4 31 CH(CH3)2
CF!(CH
3 2 iH CH(CH 3 )2 4-OCF! 3
-CGF!
4 0050/44896 No. Rl
R
3
R
5
R
6
R
7 32 CH(CH3)2
CH(CH
3 )2 H CH (CH 3 2 3,4-(OCH 3 2 -C6H3 33 CH(CH)
CH(CH
3 2 H CH 2 CH3 CH 2 (4-C1--C6H4) 34 CH(CH 3 )2 CH(CH3)2 H CH 2
CH
3
CH(CH
3 )(4-C--C6H4) CH(CH3)2 CH(CH3)2 H JCH 2
CH
3
CH(C
6
H
5 fl4-C-06H4) 36 CH(CH 3 )2 CH(CH 3 )2 CH 3
CH
2
CH
3 4-CH 3 -C6H4 37 CH(CH 3 2
CH(CH
3 )2 H CH 2
CH
3 C11 2 (4-CH 2 38 CH(CH3)2
CH(CH
3 2 H CH 2
CH
3 4-OCH 3
-C
6
H
4 39 CH(CH)
CH(CH
3 )2 H CH 2
CH
3 3, 4-(OCH 3 2
-C
6 H3
CH(CH
3 )2 CH(CH 3 )2 H cyclo-C5H9 CH 2 (4-Cl-C6H4) 41 CH(CH3)2 CH(CH3)2 H cyclo-CsH9 CH(CH 3 )(4-Cl-06H4) 412 CH(CH 3 )2 CH(CHa)2 H CYClo-5Hq CH (C 6 H) (4-C1-C6H4) 43 CH(CH 3 )2 CH (CH 3 2 H cyclo-CsH9 4-Cl-C 6
H
4 44 CH(CH 3 )2 CH(CH 3 )2 H cyclo-C 5 H9 4-CH3-C6H4
CH(CH
3 )2 CH(CH 3 )2 H1 CYC1o-C5H9 4-OCH 3
-C
6 H4 46 CH(CH 3 )2 CH(CH3)2 H cyclo-C5H9 3,4-(OCH 3 2 -C6H3 47 CH (CH 3 2 CHICH 3 )2 H CYC10-C6Hu. CH 2 (4-Cl-CSN4) 48 CH(CH 3 )2 CH(CH 3 )2 H cyclo-C6Hul CH(CH 3 )(4-C1-C6H4) 49 CH(CH 3 )2 CH(CH 3 )2 H CYClO-C6Hji CH(C 6 H5)(4-Cl-C6H4)
CH(CH
3 )2 CH(CH 3 2 H CYC1-C6Hjj 4-Cl-C 6
H
4 C(H)C(C) 2 H cloCH1 4H-CH 52 CH(CH 3 )2 CH(CH 3 )2 H CYC10-C6Hi1 4-CH 3
-C
6 H4 52 CH(CH)
CH(CH
3 )2 H CYClO-C6HII 34-OCH 3 C6H 54 CH(CH 3 )2 CH(CH3) 2 H CH 3 1-C H1 34- 6
H
5
CH)-C
CH(CH
3 )2 CH(CH 3 2 H H CH 3 4-C 6
H
5
-C
6 H4 56 CH(CH 3 )2 CH(CH 3 )2 H CH 3 4-C 6
H
5
-C
6 H4 57 CH(CH3)2
CCH(CH
3 2 H CH 3 4-CF 3
-C
6 H4 58 CH(CH3)2
CH(CH
3 2 H CH 3 4-CN3-C 6
H
4 59 CH(CH3)2 CH(CH3)2 H CH 3 4-0CN-C6H4 CH(CH3)2
CH(CH
3 )2 H CH 3 4-0C2H 5
-C
6 H4 61 CH(CH 3 2
CH(CH
3 2 H CH 3 4-F-C 6 H5-4 62 CH(CH3)2
CH(CH
3 )2 H CH3 4-Br-C6H4 63 CH(CH3)2
CH(CH
3 )2 H CH 3 4-C(C)-C6H4 64 CH (CH3) 2 CH(CH3)2 H CH 3 4--C (H-C 6 H4 CH(CH3)2 CH(CH3)2 H CH 3 3-C1--C 6 H4 66 CH(CH3)2
CH(CH
3 )2 H CH3 3-C1-C 6
H
67 CH(CH3)2
CH(CH
3 )2 H Cfl3 2,4-Cl 2
-C
6 H3 68 CH (CH3) 2 CH(CH 3 2 H CH3 2,6-C 2
-C
6
H
3 69 CH(CH 3 2
CH(CH
3 )2 H CH 3 2,-0H 3 C64 CH(CH3)2
CH(CH
3 2 H CH 3 3--CH 3
-C
6 4 71 CH(CH 3 2
CH(CH
3 )2 H CH 3 23-CH 3 2
-CH
72 CH(CH 3 )2 CH(CH 3 )2 IH CH 3 2,3-(CH 3 2 -C6H3 H-Al
T
0050/44896 No. RI
R
3
R
5
R
73 CH (CH) CH (CH3) 2 H CH 3 3,5-(CH 3 2 -C6H 3 74 CH (CH 3 2
CH(CH
3 )2 H CH 3 2,6-(CH3) 2
-C
6 H3 CH (CH 3 2 CH (CH 3 2 H CH 3 2-OCH 3
-C
6
H
4 76 CH(CH3)2 CH(CH3)2 H CH 3 3-OCH 3
-C
6
H
4 77 CH (CH 3 2 CH(CH 3 )2 H CH 3 4-0C 2
H
5
-C
6 H4 78 CH (CH3) 2 CH(CH 3 )2 H CH 3 3-0C 2
H
5
-C
6 H4 79 CH (CH 3 2 CH (CH3) 2 H CH 3 2-0C 2
H
5 -C6H4 CH (CH3) 2 CH (013) 2 H CH 3 3,4-(OC 2 H5) 2 -C6H3 81 CH (CH 3 2
CH(CH
3 )2 H CH 3 2-F-C 6
H
4 82 CH (CH 3 2 CH(CH 3 )2 H CH 3 3-F-C 6 H4 83 CH (CH3) 2
CH(CH
3 )2 H CH 3 3-CH(CIH3)2 8 CHC)2CH
(CH
3 2 H CH 3 4-CH(CH 3 2 CH (CH3) 2CHC) 2 H C 3
-C-
6 4 86 CH (CH3) 2 CH(CH3)2 H CH3 3--CF 3 -0 6
H
4 87 CH (CH 3 2 CH(CH 3 )2 H CH 3 3CF3-6H 88 CH (CH 3 2
CH(CH
3 )C2H CH 3
CH
3
C
6
H
89 CH (CH 3 2 CH 2 (CH3 )2 CH 3
CH
3
C
6
H
89 CH (CH 3 2 CHCH(CH 3 )2 CH 3
CH
3 4--C 6
H
91 CH (CH 3 2 CH(CH 3 2
CH
3
CH
3 4-0H 3 -0 6 H4 92 CH (CH 3 2 CH(CH3)2
CH
3
CH
3 4-OCH 3 C6H4 93 CH(H 3 CHCH) C 3 4-OCH 3 -06H 94 CH (CH 3 )2H CH (CH3) 2 CH CH 3 -1CH CH (CH 3 )C2H CH(CH 3
)C
2 H H3 CH 3 34-CH3)-CH 96 CH (CH 3 C2H5 CCH(CH 3 )2 H CH 3 4-Cl-C 6 H4 97 CH (CH 3
C
2 H5 CH (CH3) 2H H CH 3 4-C1 3
-C
6 H4 98 CH (CH 3
C
2 H5 CH2C(CH 3 )2 H CH 3 4-OCH--6H4 99 CH (CH 3
C
2 H5 CH(CH 3 )2 CH CH 3 34-(CH 3 )Z-C6H 100 CH(CH 3 )C2Hs CH (CH 3 2 H ,CH 3 4-CH3-C6H4) 101 CH(CH 3 )C2H5 CH(CH 3 2 H CH 3 3,4(CH)2-C193H4 102 CH(CH 3 )C2H5 CH(CH 3
)C
2 H H CH 3 C4-C-H 4 103 CH (CH)CH CH (CH3) 2 H CH 3 4C C 6 H) 4 -C-64 104
CH
2 -H5CH(CH 3 2 H CH 3 4-Cl-C 6 H4 1052 CH 2
(CH
3 O06H4) CH(CH 3 2 H H CH 3 4-Cl-C 6
H
4 106 CH 2 C(H) H -1CH 107 CH 2 -CH4 CH(CH3) 2 CH CH 3 4-10H 108 C-C 6 H CHCH 3 H H 3 -Cl1-C 6
H
4 109 CH4-CH 3
-C
6 H 4) CH(CH 3 )2 H CH 3 4--CH 106 4CH-(-CH6H4) CH (CH 3 2 H CH 3 4-C1-C 6 H4 107 4CH4-C 6 H4) CH(CH3)2 H CH3 4-CJ.-C 6 H4 11 2 cyclo-C5H9 CH (CH3) 2 H CH 3 4-C1-C 6
H
4 113 CYC1-C6HU. CH(CH3)2 H C 3 4-Cl-C 6 H4 H/11 now 0050/44896 No. Rl
R
3
R
5
R
6
R
7 114 C 2 HS CH (CH 3 2 H CH 3 4-Cl--C 6
H
4 115 CH 2
CH
2 CH3 CH (CH 3 2 H CH 3 4-Cl-0 6
H
4 116 CH 2
CH
2
CH
2
CH
3 CH (CH 3 2 H CH3 4-CI-C 6
H
4 117 CH 2 CH(CH3)2 CH(CH3)2 H CH 3 4-C1--C 6
H
4 118 (CH 2 4 CH3 CH (CH 3 2 H CH 3 4-C1--C 6
H
4 119 (CH 2 5
CH
3 CH (CH 3 2 H CU 3 4--Cl-C 6
H
4 120 C1CH 2 CH2 CH (CH 3 2 H CU 3 4-C1--C 6
H
4 121 C1 3
CCH
2 CH (CH3) 2 H CH 3 4-C1--C 6
H
4 122 CH 3
OCH
2
CH
2 CH (CH 3 2 H CU 3 4-C1--C 6
H
4 123 CH 2 =CH CH (CH 3 2 H CU 3 4-CI--C 6
H
4 124 CH 3
OCH
2 CH(CH3) CH (CH 3 2 H CH 3 4-C1--C6H 4 125 Cl(CH 3 )CH CH (CH 3 2 H CH 3 4-C1--C 6
H
4 12 C 6
H
5
OCH
2
CH
2 CH (CH 3 2 H CH 3 4-C1C 6
H
4 127 CH 2 =C(CH3) CH (CH 3 2 H CU 3 4--C1-C 6
H
4 128 CHU(CH 3 2 CH (CH3) 2 H C 6
H
5
CU
2 (4-Cl-CGH4) 129 CH (CH 3 2 CH(CH 3 )2 H C 6
H
5 jCH(CU 3 (4-Cl-C 6
H
4 130 CH (CH 3 2 CH (CH 3 2 H COS CH(C 6 HS) (4---C-6H4) 131 CH(CH 3 2 CH (CH 3 2 H C 6
H
5 4-C1--C 6
H
4 132 CH(CH 3 2 CH (CH 3 2 H C 6 HS 4-CH 3 -C6H4 133 CH (CH 3 2 CH(CH 3 )2 H C 6 Hs 4-OCH 3 -CrH4 134 CH (CH 3 2 cyclO-C3Hg H C 6
H
5 4-C1--C 6
H
4 135 CH (CH 3 2 cyclO-C 4
H
7 H C 6
H
5 4-C1--C6H 4 136 CH(CH 3 )2 cyclo-CsHg H C 6
H
5 4-Cl-C 6
F
4 137 CH (CH 3 2 CYC10o-C6Hll H C6H 5 4-C1--C 6
H
4 138 CH(CH 3
)C
2
H
5 CH (CH 3 2 H CH (CH 3 2 4-Cl-C 6
H
4 139 CH (CH 3
C
2
H
5 CH (CH 3
C
2
H
5 H CH(CH 3 )2 4-Cl-C 6
H
4 140 CH(CH 3 )C2HB CH 2
CH(CH
3 2 H CH(CH 3 )2 4-C1-C 6
H
4 141 CH (CH 3
C
2 HS CH (CH 3 2 H CH(CH 3 )2 4-Cl-C 6
H
4 142 CH(CH 3 )C2H5 CH (CH 3 2 H CH(CH 3 )2 4-C1-C6H4 143 CH (CH 3
C
2 H5 CH(CH 3 )2 H CH (CH 3 2 4-Cl-C 6
H
4 35144 CH(CH 3
)C
2
H
5 CH (CH 3 2 H CH(CH 3 )2 4-Cl-C 6
H
4 145 CH (CH 3 C2H5 CH(CH 3 )2 H CH(CH 3 )2 4-C1--C 6
H
4 146 CH (CH 3
C
2 H5 CH(CH 3 )C2H5 H CH(CH 3 )2 4-C2.-C6H 4 147 CH 2
-C
6
H
5
CH
2
CH(CH
3 )2 H CH(CH 3 )2 4-Cl-C 6
H
4 148 CH 2
-C
6
H
5 CH (CH 3 2 H CH(CH 3 )2 4-Cl-C 6
H
4 149 CH 2 -(4-CH 3 O--C6H4) CH (CH 3 2 H CH(CH 3 )2 4-Cl-C 6
H
4 150 CH 2 -(4-CH 3 -C6H4) CH (CH 3 2 H CH(CH 3 )2 4-Cl-C 6
H
4 151 CH 2 -(4-Cl-C 6 H4) CH (CH 3 2 H CH(CH 3 )2 4-C1--C 6 H4 152 4-Cl1-C 6 H4 CH(CH 3 )2 H CH(CH3)2 4-Cl-C 6
H
4 45153 4-CH 3
-C
6 H4 CH (CH 3 2 H CH(CH 3 )2 4-Cl-C 6
H
4 154 4C 3 -H CH (CH 3 2 H CH(CH 3 )2 4-Cl-' 6
H
4 R,4 7 0050/44896 No. IRI
R
3
R
5
IR
6
R
135 4-C 6 HS-C6H4 CH(CH3)2 H CH(CH 3 2 4-C1-C 6
H
4 156 cyClo-C5H9
CH(CH
3 )2 H CH(CHj)2 4-Cl-C6H4 157 cyclo-C6Hi1 CH(CH3)2 H CH(CH 3 2 4-Cl-C61 4 158 C 2 HS
CH(CH
3 )2 H CH(CH 3 )2 4-Cl-C 6
H
4 159 CH 2
CH
2
CH
3
CH(CH
3 )2 H CH(CH 3 2 4--Cl-C 6
H
4 160 CH 2
CH
2
CH
2
CH
3 CH(CH3)2 H CH(CH 3 2 4-C1--C 6
H
4 1i61 CH 2 CH(CH 3 )2 CH(CH3)2 H CH (CH 3 2 4-C1-C 6
H
4 162 (CH 2 4 CH3 CH(CH3)2 H CH(CH3)2 4-C1--C 6 H4 163 (CH 2 5
CH
3 CH(CH3)2 H CH(CH 3 2 4-Cl-C6H4 164 C1CH 2
CH
2
CH(CH
3 )2 H CH(CH 3 2 4-Cl-C 6
H
4 165 C1 3
CCH
2 CH(CH3)2 H CH(CH 3 )2 4-C1-C 6
H
4 166 CH 3
OCH
2 CH2 CH(CH 3 )2 H CH(CH3)2 4-Cl-0 6
H
4 167 CH 2 =CH CH(CH3)2 H -CH(CH3)2 4-Cl-C 6 H4 168 CH 3
OCH
2 CH(CH3) CH(CH 3 )2 H CH(CH3)2 4-Cl-C 6
H
4 169 Cl(CH 3 )CH CH(CH 3 )2 H CH(CH 3 2 4-Cl-C 6
H
4 170 C 6
HSOCH
2 CH2 CH(CH3)2 H CH(CH 3 2 4-Cl-C 6
H
4 171 CH 2
=C(CH
3 CH(CH3)2 H CH(CH 3 2 4-Cl-C 6
H
4 172 C 6 HS
CH(CH
3 2 H CYClo-C3H5 C 6
HS
173 C 6
H
5 CH(CH3)2 H CYC1o-3H5 4--Cl-6H 4 174 C 6
H
5
CH(CH
3 )2 H CYClo-C 3 H5 4-CH 3
-C
6
H
4 175 C 6
H
5
CH(CH
3 )2 H CYClo- 3 H5 4-OCH 3
-C
6
H
4 76 C 6 H5 CH(CH3)2 H cyclo-3H5 3,4-(OCH 3 2 -C6H3 172 CH(CH 3 2 CH(CH3)2 H CYC3.o-C 3 H5 C 6
H
173 CH(CH 3 )2 CH(CH 3 )2 H CYC1o-C3H5 4-C1-C 6
H
4 174 CH(CH 3 )2 CH(CH 3 )2 H CYClo-C3H5 4-CHa--C6H4 175 CH(CH 3 )2 CH(CH 3 )2 H CYC1o-C3H5 4-OCH 3
C
6
H
4 176 CH(CH 3 )2 CH(CH 3 2 H CYClO-C 3 H5 3, 4-(OCH 3 2 -C6H3 177 CH(CH 3 2 CH(CH3)2 H CH 2 CH(CH3)2 4-Cl-C 6
H
4 178 CH(CH 3 2
CH(CH
3 )2 H CH 3
CH
2 CH2 4-CH 3 -0 6 H4 179 CH(CH 3 2 CH(CH3)2 H CH 3
(CH
2 )3 4-C1-C 6
H
4 180 CH(CH 3 2 CH(CH3)2 H CH(CH 2 CH3)2 14--0H 3
-C
6 H4 181 C(CH 3 )3 CH(CH3)2 H CH 3
C
6 182 CH(CH3)2
CH(CH
3 )2 H CH 3
C
6
H
183 C 6 H5 CH (C113)2 H CH 3
C
6
H
184 CH(CH 3 2 CH(CH3)2 H CH 3 4-CH 3
-C
6
H
4 185 C 6 Hs CH(CH3)2 H CH 3 4-CH 3
-C
6
H
4 186 CH(CH 3 )C2H5 CH(CH 3 )2 H CH 3 4-CH 3
-C
6 H4 186 CH 2 CH(CH3)2 CH(CH3)2 H CH 3 4-CH 3
-C
6 H4 188 CH 2 C6H5 CH(CH 3 2 H CH 3 4--0H 3
-C
6 H4 189 CH(CH 3 )2 CH(CH 3 2 H CH 3 4-Cl-C 6 H4 ~190 I CH- ICH (CH3) 2 0050/44896 rT No.
191 192 193 194 195 196 197 198 199 200 l 201 202 203 204 205 206 207 208 209 210 211 212 213 214
CH
2 C6H5 C(CH3) 3 CH(CH3)2
R
3 CH(CH3)2 H T CH 3 t4Cl-C6H4 ICH(CH3)2 CH (CH3) 2 H C 2
H
H C2H I 1* 4-C H 3 C6 H 4-CH 3
-C
6
H
4 4-CH 3
-C
6 H4 4-C-C 6
H
4
CH(CH
3
)C
2 H5
C(CH
3 )3
I
CH(CH3)2 CH (CH3) 2
IH
H
C
2 H5
C
2
H
5 CH(CH3)2
CH(CH
3
)C
2
HS
CH (CH 3 2
CH(CH
3
)C
2
HS
C (CH 3 ~3 C(CH3)3
C(CH
3 3 C (CH 3 3 C (CH 3 3
C(CH
3 )3 CH(CH~V, C 2
H
5 'i-Cl-C6H~4 42
CH(CH
3 )2 CH (CH3) 2
CH(CH
3 )2 CH (CH 3 2
C
2 H5 4-Cl-C 6
H
I
H
H
H
CH(CH
3 )2
CH(CH
3 )2
H
H
4-CH 3
C
6
H
4-CH 3
-C
6 H4 4-Cl-C 6
H
4 4-CH 3
-C
6 H4 t
CH(CH
2
CH
3 2 4-CH 3
-C
6 H4
CH(CH
3 2 CH (CH 3 2
H
H
(CH
2 3
CH
3 CYC10-C5H9 4-CH 3
-C
6 H4 4-CH 3
-C
6 H4 I 7 I i
CH(CH
3 )2 (CH 2 3
CH
3 I I
C(CH
3 3
C(CH
3 )2
C(CH
3 2
C(CH
3 2 C (CH 3 )2
I
CH(CH
3 2
CH(CH
3 2
H
H
cyclo-C 5 H9 n-C 5 Hll 4-Cl-C 6
H
4 4-C l-C 6
H
4 4-CH 3
-C
6
H
4
CH(CH
3 2 CH (CH 3 2
CH(CH
3 )2
H
H
n-C6Hj 4-C H 3 -C 6 H4 4-CH 3
-C
6
H
4 H n-C 4 i
C(CH
3 )2 C (CH 3 2 C (CH 3 2
CH(CH
3 2
CH(CH
3 )2
IH
IH
CH
2 -C(CH3) 3
C(CH
3 2 C2H5 4-CH 3
-C
6 H4 4-CH 3
-C
6 H4 4-CH 3
-C
6 H4 I i 1 4 CH (CH 3 2 CH (CH 3 2
H
H
CH(CH
3 )C3H7 n-C 5 Hll 4-CH 3
C
6 H4 4-C1-C 6
H
4 4-C 1-C 6
H
4 C (CH~)
CH(CH
3 2 'l 6 1 26C(CH 3 2 CH (CH 3 2 HI-71 4-Cl-C 6
H
4 217 C C(CH 3 2 CH (CH 3 2 H nC8H17 14-Cl--C 6
H
4 218 219 C (CH 3 2
C(CH
3 2
CH(CH
3 2
CH(CH
3 2
H
H
CH
2 -C(CH3) 3 C (CH 3 2
C
2 Hs 4-Cl-C614 4-C1-C 6H 4 4--C -C 6
H
4
I
220 IC(CH3)2 CH (CH 3 2 CH(C3 Ct3H~7 J 0050/44896 Table 3 0 H R 3 0 R 11 1 R1X1C-N-C N X -4
Z
1 4 oxygen or sulfur.
R1R 3
R
5
R
6 X z
C(CH
3 )3 CH (CH3) 2 H
CH
3 -4-Cl C (CH 3 3 CH (CH3) 2 H
OH
3 -4.-CH 3 H CH 3 -4-OCH 3
C(CH
3 )3 CH(H3)2 H H 3 -3,4-(00H3)2 O(CH3)3 CH(H3)2. H OH 3 H ,~(C3 CH(C 3 CH(CH3)2 H CH 3 -4-CH CH(CH3)2 CH (,H 3 2 H OCH3 OH 6 H 4-Cl3 CH(CH3)2 CH(CH 3 )2 H CHH3 4-Cl CH(CH3)2
H(CH
3 )2 H ClOC5 CH(CH3)2 CH (CH 3 )2 H CH3 4-O(CH3)2 CH3) CH(CH3)2 H CH3 l- CH(0) CH(CH32
H
3 CH3-4CH CH(C3) CH(CH3)2 H 3 -0 3 CH(C) CH(CH3)2 H 3 IH3 3,4 (OCH3)2 0C 6 H5 CH(CH3)2 IH ICH3- 4-Cl Cy(Clo H3)2 H(CH 3 )2 H L1H3 -H 6 4-Cl OCH(H3)2 CH(CH3)2 H CHH3 4-Cl 0050/44896 7 No. R 1
R
3 Fs R 6 x z CH (CH 3 2
CH(CH
3 2 H C 6
H
5 -4-Cl1 31 CH (CH 3 2 CH (CH 3 2 H C 6
H
5 -4-CH3 32 1 CH(CH 3 2 CH (CH 3 2 ,H __C 6
H
5 -4-OCH 3 Table 4 W1 0 H R 3 0 RS R 6 C=N0---C-N -CC N-N -R 7
W
2
H
No. W1 WJ 2 R3R 5
R
6
R
1 OH 3
OH
3 CH (CH 3 2 H CH 3 0OHR 3
-O
6
H
4 2 CU 3
CH
3
CH(CH
3 2 H CH 3 3,4-(OH 3 2 -0 6
H
3 3 OH 3
C
6
H
5
CH(CH
3 2 H OH 3
C
6
H
4 CH 3
C
6
H.
5
CH(CH
3 2 H OH 3 4-Cl-C 6
H
4
CH
3
C
6
H.
5 CH(0H 3 2 H OH 3 4-CH 3 -0 6
H
4 6 CU 3 0 6
H
5 CH (OH 3 H ICH 3 4-OCH 3
-C
6 H4 7 OH 3 0 6
H
5
CH(C
3 2
OH
3 3,4-(OCH 3 2
-C
6
H
3 7 OH 3 4CH 3 H CH(0H 3 )2 H OH 3
CH
9 OH 3 4-0H 3 -0 6
H
4 CH (CH 3 2 H OH 3 4.O- 6
H
4
OH
3 4-0H 3
-C
6
H
4
CH(OH
3 2 H OH 3 4-0H-C 6
H
4
OH
3 4-CH 3
-C
6 H4 OH(0H 3 2 H O H 3 4-00H 3
-C
6
H
4 11 OH 3 4-0H 3 -0 6 H4 OH(0H 3 )2 H OH 3 34-(0H 3 6 H 3 13 OH 3 4-0H 3
-C
6
H
4 OH(0H 3 2 H CH(0 3 0H 2 4-Cl3-0 6
H
14 OH 3 4-CH 3
-C
6
H
4 OH(0H 3 2 H OH(0H 3 2 4-C1-C 6
H
4
OH
3 4-0H 3 -0 6 H4 OH(CH 3 2 H 0H 2 0H 3 OH(0H 3 (4-Cl-C 6
H
4 1i6 CH 3 4-0H] 3 -0 6
H
4 OH(0H 3 2 H 0H 2 0H 3 CH(0 6
H
5 (4-l-0 6
H
4 17 OH 3 I4-Cl-C 6
H
4 OH(0H 3 2 H OH 3
C
6
H
18 OH 3 4-Cl-0 6
H
4 OH(0H 3 2 H OH 3 4-Cl-C 6
H
4 19 OH 3 4-Cl-C 6
H
4 OH(0H 3 2 H OH 3 4-CH 3
-C
6
H
4 20 OH 3 4-Cl-C 6
H
4 OH(0H 3 2 H OH 3 4-OCH 3
-C
6 H4 21 OH 3 4-Cl- 6
H
4 OH(0H 3 2 H CH 3 3, 4--(0OH 3 2
-C
6
H
3 22 OH 3 4-Ol- 6
H
4 OH(0H 3 2 H OH(0H 3 2
CH
2 (4-Cl-06H4) 23 OH 3 4-Cl-C 6
H
4 OH(0H 3 2 H OH(CH 3 )2 4-Cl-C 6
H
4 24 OH 3 4-Ol-C 6
H
4 OH(0H 3 2 H 0H 2 0H 3 OH(0H 3 (4-l--0 6 H4)
OH
3 4-Ol-C 6
H
4
CH(CH
3 2 H 0H 2 0H 3 OH(0 6
H
5 (4-l--0 6
H
4 0050/44896 No. W1 W 2
R
3 jR5 R 6 IV7 26 CH 3
CH
3
CH(CH
3 2 _JH CH 3 4--Cl-0 6
H
4 27 CH 3
CH
3
CH(CH
3 2 H CH 3 4-CH 3
-C
6
H
4 Table s H (CH 3 2CH H Rf 1_1 I i -0 R
R
1 N C C N N
H
No. RI
R
6
R
8 1 CH(CH 3 2
CH
3
CH
3 2 CH(CH 3 2
CH
3 Cl 3 CH(CH 3
)C
2 HS
CH
3
CH
3 4 CH(CH 3
)C
2 HS
CH
3 Cl
CH
2
C
6
H
5
CH
3
CH
3 6 CH 2
C
6
H
5
CH
3
C).
7 CH(CH 3 2
C
2
H
5
CH
3 8 CH(CH 3 )2
C
2
H
5
C].
9 CH(CH 3 )2
CH(CH
3 2
CH
3
CH(CH
3 2
CH(CH
3 )2 Cl 11 CH(CH 3 )2 n-C 4 H9
CH
3 12 CH(CH 3 2
CH
2
CH(CH
3 )2 Cl 13 CH(CH 3 )2 n-C 4
H
9
CH
3 14 CH(CH 3 2
CH
2
CH(CH
3 )2 Cl
CH(CH
3 j2
CH(C
2 HS)2
CH
3 16 CH(CH 3 2
CH(C
2
H
5 )2 Cl 17 CH(CH 3 )2
CH
2
-C
6
H
5
CH
3 18 CH(CH 3 2
CH
2
-C
6
H
5 Cl 19 C(CH 3 3 CYClo-C5Hg
CH
3
CH(CH
3 2 CYClo-C5H9
CH
3 21 CH(CH 3 )C2H5 CYC1o-C5H9
CH
3 22 C(CH 3 3 CYC1o-C 5 H9 Cl
CH(CH
3 )2 cyclo-C5H9 Cl 24 CH(CH 3
)C
2 HS cyclo-CSH9 cl
C(CH
3 3 CYCl0-C 6 Hji
CH
3 26 CH(CH 3 2 CYCl0-C 6 Hjj
CH
3 27 CH(CH 3
)C
2
H
5 ICYClo-C 6 Hji 1H 3 0050/44896 No. R 1 6R 28 C (CH 3 3 CYClo-C 6 Hjj 0].
29 CH (CH 3 2 CYCl0-C6Hi1 02.
530 CH(CH 3 )QH5 CYCl0-C6H1. 02 31 CH (0H 3 2
C
6
H
5 CH3 32 CH (CH 3 2
CH(CH
3
)C
2
H
5 01 33 CH(CH 3 2
C
6
H
5
CH
3 10134 ICH(CH 3 2 OHCH)0H Table 6 s H (CH 3 )2CH 0 H R 6 1 1 11 1 1 0 -R
R
1 O- N- C C N- N
H
No. RR6R 8 1 CH(CH 3 )2 CH 3
OH
3 2
CH(CH
3 2
CH
3 01
CH(CH
3
)C
2 H5 OH 3
OH
3 4
CH(CH
3
)C
2 Hs OH 3 01
CH
2
C
6
H
5
CH
3
CH
3 6
CH
2
C
6
H
5
OH
3 cl 7 CH(CH 3 2
C
2 HS
CH
3 8 CH (CH 3 2
C
2
H
5 01 9
CH(CH
3 2
CH(CH
3 )2
CH-
3 CH (CH 3 2
CH(CH
3 )2 Cl 11
CH(CH
3 2 n-C 4 H9
OH
3 12 CH (CH 3 2 n-C 4
H
9 Cl 13
CH(CH
3 2
CH
2
CH(CH
3 2
OH
3 14
CH(CH
3 2
CH
2
CH(CH
3 2 01
CH(CH
3 2
CH(C
2
H
5 )2
OH
3 16
CH(OH
3 )2 CH (O 2 HS) 2 02.
17 CH(CH 3 2
CH
2
-C
6
H
5
OH
3 18 CH )2 CH 2
-C
6
H
5 Cl 19
O(H
3 3 cyclo-C5H9
CH
3 20 CH(0H 3 )2 cyclo-CsH9
OH
3 21
CH(CH
3
)C
2 HS cyclo-C5H9
OH
3 22
(CH
3 3 cyclo-CsHg 01 0050/44896 32 No. R1 R 6
R
8 23 CH(CH 3 2 cyclo-C5H 9 Cl 24 CH(CH 3
)C
2
H
5 cyclo-C 5 H9 C1 25 C(CH 3 3 Cyclo-C 6
H
1 1 CH3 26 CH(CH 3 2 Cyclo-C 6
H
1 1 eCl 27 CH(CH 3
)C
2
H
5 Cyclo-C6H1 1 CH3 28 C(CH 3 3 Cyclo-C6H1 1 Cl 29 CH(CH 3 2 Cyclo-C 6
H
1 1
"C
CH(CH3)C 2
H
5 Cyclo-CSH 1 u Cl 31 CH(CH 3 2
C
6
H
5
CH
3 32 CH(CH 3 2 C6H 5 el 33 CH(CH 3 2
CH(CH
3 )C2H 5 CH3 34 CH(CH 3 2
CH(CH
3
)C
2
H
5 Cl The novel compounds of the formula I are suitable as fungicides.
The novel compounds, or the compositions containing them, can be applied for example by spraying, atomizing, dusting, scattering or watering in the form of directly sprayable solutions, powders, suspensions, even high-percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusting compositions, scattering compositions or granules. The application forms depend on the intended uses; in each case they should if possible ensure the finest dispersion of the active compounds according to the invention.
Normally, the plants are sprayed or dusted with the active compounds or the seeds of the plants are treated with the active compounds.
The formulations are prepared in a known manner, eg. by extending the active compound with solvents and/or carriers, if desired using emulsifiers and dispersants, where if water is used as a diluent other organic solvents can also be used as auxiliary solvents. Suitable auxiliaries for this purpose are mainly: solvents such as aromatics (eg. xylene), chlorinated aromatics (eg.
chlorobenzenes), paraffins (eg. petroleum fractions), alcohols (eg. methanol, butanol), ketones (eg. cyclohexanone), amines (eg.
ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (eg. kaolins, aluminas, talc, chalk) and ground synthetic minerals (eg. highly disperse silica, silicates), emulsifiers such as nonionic and anionic emulsifiers (eg. polyoxyethylene fatty alcohol ethers, alkanesulfonates and 0050/44896 33 arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.
Suitable surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, eg.
lignosulfonic, phenolsulfonic, naphthalenesulfonic and dibutylnaphthalenesulfonic acid, and also of fatty acids, alkyl- and alkylarylsulfonstes, alkyl-, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol- or tributylphenylpolyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene [sic], lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
Powder, scattering and dusting compositions can be prepared by mixing or joint grinding of the active substances with a solid carrier.
Granules, eg. coated, impregnated and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
Solid carriers are mineral earths such as silica gel, silicic acids, silica gels [sic], silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, tree bark meal, wood meal and nutshell meal, cellulose powder or other solid carriers.
Examples of such preparations are: I. a solution of 90 parts by weight of a compound I according to the invention and 10 parts by weight of N-mnethyl-2-pyrrolidone, which is suitable for application in the form of very small drops; II. a mixture of 10 parts by weight of a ccmpound I according to the invention, 70 parts by weight of xylene,, 10 parts by weight of the addition product of from 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-monoethanolamide, 0050/44896 34 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 5 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil; a dispersion is obtained by finely dispersing the solution in water.
III. an aqueous dispersion of 10 parts by weight of a compound I according to the invention, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil; IV. an aqueous dispersion of 10 parts by weight of a compound I according to the invention, 25 parts by weight of cyclohexanol, 55 parts by weight of a petroleum fraction of boiling point from 210 to 280 0 C, and 10 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil; V. a mixture, ground in a hammer mill, of 80 parts by weight, preferably of a solid compound I according to the invention, 3 parts by weight of the sodium salt of diisobutylnaphthalene-2-sulfonic acid, 10 parts by weight of the sodium salt of a.lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel; a spray liquor is obtained by finely dispersing the mixture in water; VI. an intimate mixture of 3 parts by weight of a compound I according to the invention and 97 parts by weight of finely divided kaolin; this dusting composition contains 3% by weight of active compound; VII. an intimate mixture of 30 parts by weight of a compound I according to the invention, 62 parts by weight of powdered silica gel and 8 parts by weight of liquid paraffin which has been sprayed onto the surface of this silica gel; this preparation gives the active compound good adhesion; VIII. a stable aqueous dispersion of 40 parts by weight of a compound I according to the invention, 10 parts by weight of the sodium salt of a phenolsulfonic acid/urea/formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water, which can be further diluted; 0050/44896 IX. a stable oily dispersion of 20 parts by weight of a compound I according to the invention, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid/urea/ formaldehyde condensate and 50 parts by weight of a paraffinic mineral oil.
The novel comp:unds are distinguished by an outstanding activity against a ,pectrum of phytopathogenic fungi, in particular from the cl~~a of Deuteromycetes, Ascomycetes, Phycomycetes and Basidiomycetes. They are systemically active in some cases and can be employed as foliar and soil fungicides.
They are of particular importance for the control of a multiplicity of fungi on various crop plants such as wheat, rye, barley, oats, rice, corn, lawns [sic], cotton, soybeans, coffee, sugar cane, grapes, fruit and decorative plants and vegetable plants such as cucumbers, beans and cucurbits, and on the seeds of these plants.
The compounds are applied by treating the fungi or the seeds, plants, materials or the soil to be protected from fungal attack with a fungicidally effective.amount of the active compounds.
They are applied before or after the infection of the materials, plants or seeds by the fungi.
The novel compounds are specifically suitable for the control of the following plant diseases: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoctonia species on cotton and lawns [sic], Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries, vines, decorative plants and vegetables, Cercospora arachidicola on groundnuts, Pseudocercosporella herpotrichoides on wheat, barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Fusarium and Verticillium species .on various plants, Plasmopara viticola on vines, Alternaria species on vegetables and fruit.
0050/44896 36 The novel compounds can also be employed in the protection of materials (preservation of wood), eg. against Paecilomyces variotii.
The fungicidal compositions in general contain from 0.1 to preferably from 0.5 to 90, by weight of active compound.
Depending on the type of effect desired, the application rates are from 0.025 to 2, preferably from 0.1 to 1, kg of active compound per ha.
In seed treatment, amounts of active compound of from 0.001 to g, preferably 0.01 to 10 g, per kilogram of seed are in general needed.
The compositions according to the invention can also be present as fungicides together with other active compounds in the application form, eg. with herbicides, insecticides, growth regulators, fungicides or alternatively with fertilizers.
On mixing with fungicides, in many cases an increase in the fungicidal spectrum of action is obtained here.
The following list of fungicides with which the compounds according to the invention can be applied together is intended to illustrate the combination possibilities, but not restrict them: sulfur, dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediamine bisdithiocarbamate, tetramethylthiuram disulfide, ammonia complex of zinc N,N-ethylenebisdithiocarbamate, ammonia complex of zinc N,N'-propylenebisdithiocarbamate, zinc N,N'-propylenebisdithiocarbamate, N,N'-polypropylenebis(thiocarbamoyl) disulfide; nitro derivatives, such as dinitro(l-methylheptyl)phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-secbutyl-4,6-dinitrophenyl isopropyl carbonate, diisopropyl heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate,- 2,4-dichloLo-6-(o-chloroanilino)-s-triazine, 0,0-diethyl phthalimidophosphonothioate, phinyl]-3-phenyl-l,2,4-triazole, 2,3-dicyano-l,4-dithioanthraquinone, 2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl l-(butylcarbamoyl)-2-benzimidazolecarbamate, 2-methoxycarbonylaminoi.; 0050/44896 37 benzimidazole, fur-2-yl)benzimidazole, thiazolyl-4-yl)benzimidazolee 1,1,2, 2-tetrachioroethylthio) tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, N-dichlorofluoromethylthio-N' I '-diinethyl-N-phenylsulfanide, 5-ethoxy-3-trichloromethyl-1, 2, 3-thiadiazole, 2-thiocyanatorethylthiobenzothiazole, 1, 4-dichloro-2, 2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, 2-thiopyridine-i--oxide, 8-hydroxyquinoline or its copper salt, 2, 3-dihydro-5--carboxanilido-6-4methyl-1, 4-oxathiin, 2, 3-dihydro-5-carboxanilido-6-methyl-1, 4-oxathiin-4 ,4-dioxide, 2-xethyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-.carboxanilide, 2, 5-dimethylfuran-3-carboxanilide, 2,4, 5-trimethylfuran-3-carboxanilide, fu ran-3--carboxamide, N--cyc lohexyl-N--methoxy-2, furan-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine-2 2-trichloroethyl acetal, piperazine-1, 4-diylbis 2,2, 2-trichioroethyl) )formainide, 3, 4-dichloroanilino)-1-formylamino-2, 2, 2-trichioroethane, 2,6-dirnethyl-N-tridecylmorpholine or its salts, 2,6-dixnethyl-Ncyclododecylmorpholine or its salts, N-f 3-(p-tert-butylphenyl)-2-methylpropyl ]-cis-2, 6-dimethylmorpho line, N-f 3-(p-tert-butylphenyl)-2--methylpropyl]-piperidine, 1-f 2, 4-dichlorophenyl)-4--ethyl-1, 3-dioxolan-2-ylethyl]-1H-1, 2, 4-triazole, 4-dichlorophenyl )-4-n-propyl-1, 3-dioxolan-2-ylethyl 4-triazole, n-propyl)-N-( 2,4, 6-trichlorophenoxyethyl)-N '-imidazolylurea, 4-chlorophenoxy) 3-dimethyl-1-( 1H-1 4-triazol-1-yl) -2-butanone, (2-chiorophenyl 4-chlorophenyl dinemethanol [sic], 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis (p-chlorophenyl )-3-pyridinemethanol, 1, 2-bis (3ethoxycarbonyl-2-thioureido )benzene, 1, 2-bis (3-methoxycarbonyl- 2-thioureido)benzene, f2-( 4-chiorophenyl) ethyl]-( 1, -dimethylethyl 2, 4-triazole-1-ethanol (sic], 1-f 2-chlorophenyl)- 4-f luorophenyl )oxiran-2-ylmethyl]-1H-1, 2, 4-triazole, and various fungicides, such as dodecylguanidine acetate, 3-f 3, 5-dimethyl-2--oxycyclohexyl )-2-hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N-( 2, 6-diniethylphenyl )-N-2-furoy.
alaninate, 2, 6-dimethylphenyl 2 -methoxyacetyl )alanine methyl ester, 2, 6-dimethylphenyl )-N-chloroacetyl-D, L-2-aminobutyrolactone, DL-N-( 2, 6-dixnethylphenyl )-N-(phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3-(3 phenyl) 4-dioxo-1, 3-oxazolidine, 3-f 3, 5-dichlorophenyl-( 3-oxazolidine-2, 4-dione, 3-(3 phenyl isopropylcarbamoylhydantoin, 3, 0050/44896 38 phenyl 2-dimethylcyclopropane-1, 2-dicarboximide, 2-cyano-fN-ethylaminocarbonyl-2-methoximino ]acetamide, 2, 4-dichlorophenyl)pentyl 2, 4-triazole, 2, 4-difluoroct-( 1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol, 3-chloro-2, 6-dinitro-4--trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2--aminopyridine, (bis (4-f luorophenyl )methylsilyl)methyl)-1H-1, 2, 4-triazole, strobilurins such as methyl E-methoximino~a-(o-tolyloxy) -o-tolyl ]acetate, methyl 2-f 2-cyanophenoxy) pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate, methyl E-methoximino fa-(2, 5-dimethoxy)-o-tolyl ]acetaxnide.
Anilinopyrimidines such as 4, 6-dimethylpyrimidin-2-yl) aniline, N-f 4-mnethyl-6-( 1-propynyl )pyrimidin-2-yl ]aniline, 4-iethyl-6-cyclopropylpyrimidin-2-yl) aniline.
Phenylpyrroles such as 2, 2-difluoro-l,3-benzodioxol-4-yl )pyrrole-3--carbonitrile.
Cinnamamides such as 4-chlorophenyl 3, 4-dimethoxyphenyl)acrylic acid morpholide.
Synthesis examples The procedures given in the synthesis examples below can be used with modification of the starting compounds to obtain further representatives of the compounds IV and I. The physical data of the correspondingly prepared products are given in the tables attached in each case.
Example 1 L-Valine (2-methyl-2-( 4-methylphenylhydrazide) [sic] ml of trifluoroacetic acid were added with cooling to 1 g (3 mmol) of Nak-(tert-butoxycarbonyl)-L-valine (2-methyl- 2-(4--methylphenyl)hydrazide sic] and the mixture was subsequently stirred at 000 for one hour. It was then warmed to 20 0
C,
the trifluoroacetic acid was largely removed by distillation and the residue was taken up in dichloromethane. The organic phase was washed in each case with 40 ml of 10% strength by weight sodium hydroxide solution and water and dried. The sol.ent was then removed. 0.7 g of L-.valine 2-methyl-2-(4-methylphenylhydrazide) [sic] remained, which was used in the following stage without purification.
0050/44896 39 The intermediates IV of the type [sic] listed in the following table were prepared in a similar manner.
Table 7
H
3 C CH 3 H CH 0 R 5
R
6 H-N-C N-R 7
H
No. R 5
R
6
R
7 M.p. (cmnr-1) 1 H CH 3 4-C1-C 6
H
4 oil 2 H CH 3 4-CH 3
-C
6
H
4 oil 3 H C 2
H
5 4-Cl--C 6
H
4 3245,2964,2934,2872,1669,1493 4 H CH(C8 3 2 4-CH 3
-C
6
H
4 3250,2963,2931,2871,1673,1512 Example 2 Na-(sec-Butoxycarbonyl)-L-valine 2-methyl-2-(4-methylphenyl)hydrazide 0.39 g (2.9 mmol) of sec-butyl chloroformate was added dropwise at 0 0 C to 0.7 g (3 mmol) of L-valine 2-methyl-2-(4--methylphenyl)hydrazide and 0.32 g (3.2 mmol) of triethylamine in 10 ml of toluene. After 15 hours at 20 0 C, the organic phase was washed in each case with 20 ml of 10% strength by weight hydrochloric acid, sodium hydrogencarbonate solution and water. The organic phase was dried and the solvent was then removed. 0.6 g of the title compound remained as an oil (compound 6 in Table 6).
Example 3 Na'-(tert-Butoxycarbonyl)-L-valine 2-methyl-2-(4-chlorophenyl)hydrazide g (0.05 mol) of triethylamine were added dropwise at -15*C to 10.9 g (0.05 mol) of tert-butoxycarbonyl-L-valine in 200 ml of dimethylformamide and the whole was subsequently stirred for minutes. 6.8 g (0.05 mol) of isobutyl chlorocarbonate were then added and the mixture was left for 10 minutes at -15 0 C. 7.8 g (0.05 mol) of N-methyl-N-(4-chlorophenyl)hydrazine in 50 ml of dimethylformamide were then added to this solution. It was subse- 0050/44896 quently stirred at -15°C for 1 hour and the reaction mixture was left at 20 0 C for a further 2 hours. The solvent was then removed by distillation, the residue was taken up in ethyl acetate and the organic phase was washed in succession in each case with 10 ml of 5% strength by weight citric acid, 5% strength by weight sodium hydrogencarbonate solution and water. The organic phase was dried and concentrated, and the residue which remained was chromatographed on silica gel (methyl tert-butyl ether:n-hexane 5.5 g of the title compound were obtained as an orange-red resin (compound 27 in Table 6).
Example 4 Na-(tert-Butoxycarbonyl)-L-valine 2-methyl-2-(4-methylphenyl)hydrazide 5.1 g (0.051 mol) of triethylamine and then, at 0°C, 8.31 g (0.051 mol) of diethyl cyanophosphonate were added to a solution of 10.85 g (0.05 mol) of N-tert-butoxycarbonyl-L-valine and 5.95 g (0.05 mol) of 4-methylphenylhydrazine in 100 ml of tetrahydrofuran. The mixture was stirred at 0OC for one hour and at 0 C for a further 15 hours, and after removing the solvent the residue was taken up with ethyl acetate. The organic phase was washed in each case with 40 ml of 10% strength by weight sodium hydroxide solution, 10% strength by weight hydrochloric acid, saturated sodium hydrogencarbonate solution and water. The organic phase was dried and the solvent was then removed. 9.8 g of Na-(tert-butoxycarbonyl)-L-valine 2-(4-methylphenyl)hydrazide remain 163-164 0 C, compound 21 in Table 6).
0.48 g (3.4 mmol) of methyl iodide and 0.47 g (3.4 mmol) of potassium carbonate were added at 20 0 C to 1 g (3.1 mmol) of this compound in 10 ml of dimethylformamide. The mixture was left at this temperature until starting compound was no longer detectable and the solvent was then removed by distillation. The residue was taken up in ethyl acetate. The organic phase was washed with water, dried and concentrated. The oil which remained was chromatographed on silica gel (cyclohexane:ethyl acetate 2:1) and 0.3 g of the title compound was obtained as a yellow oil (compound 28 in Table 6).
"0 0050/44896 Table 8 0 H 11 Rl 1 0- C- N-
R
3 0 R I I
H
N -R 7 No. R 1
R
3
R
5
R
6
R
7 M.P. IR (cm-1) 1 C (CHI) 3 CH (CH 3 2 H OH 3
C
6
H
5 108 2 CH (CH 3 2 CH (CH 3 2 H CH 3 065 115 3 C 6
H
5 CH (CH3) 2 H CH 3
C
6
H
5 138-140 4 CH (CH 3 2 CH (CH 3 2 H OH 3 4-CH 3
-C
6 H4 118-120
C
6
H
5 CH (CH 3 2 H CH 3 4-CH 3
-C
6
H
4 154 6 CH(CH 3
)C
2
H
5 CH (CH 3 2 H OH 3 4-CH 3
-C
6 H4 1) 7 CH 2 CH (CH 3 2 CH (CH 3 2 H OH 3 4--CH 3
-C
6
H
4 Oil 8 CH 2
C
6
H
5
CH(CH
3 )2 H CH 3 4-CH 3
-C
6
H
4 163 9 CH(CH 3 2
CH(CH
3 )2 H CH 3 4-C--C 6
H
4 154
C
6
H
5
CH(CH
3 )2 H CH 3 4-C1-C 6
H
4 178-180 11 CH 2
C
6
H
5
CH(CH
3 2 H OH 3 4-C2.-C 6
H
4 161 12 C(CH 3 3 CH (CH 3 2 H C 2 HS 4-CH 3
-C
6
H
4 84-86 13 CH(C H 3 2
CH(CH
3 2 H C 2
H
5 4-CH 3
-C
6
H
4 137-139 14 CH(CH 3
)C
2
H
5
CH(CH
3 2 H 2 5 4-CH 3
-C
6
H
4 118-120
C(CH
3 )h CH(CH3) 2 H C 2
H
5 4-Cl-C 6
H
4 156 16 CH(CH 3 2
CH(CH
3 2 H C 2
H
5 g 4-Cl-C 6
H
4 163-165 17 CH(CH 3 )C2H5 CH(CH 3 2 H C 2
H
5 4-C1--C 6
H
4 168 18 CH(CH 3 2
CH(CH
3 2 H CH (CH, 3 2 4-CH 3
-C
6
H
4 118-120 19 CH(CH 3
)C
2
H
5
CH(CH
3 2 H CH(OH 3 2 4-CH 3
-C
6
H
4 124-126
C(CH
3 3
CH(CH
3 2 H H 4--C1-C 6
H
4 162 21 C(CH 3 3
CH(CH
3 2 H H 4-CH 3
-C
6
H
4 163-164 22 CH 2 CH(CH3)3
CH(CH
3 2 H OH 3 4-Cl-C 6
H
4 133 23 C(CH 3 3
CH(CH
3 2 H H 4-OH 3 0-C 6 H4 171 24 C(CH 3 3
CH(CH
3 2 H CH 2
CH(CH
3 )2 4-C1-C 6
H
4 171
C(CH
3 3
CH(CH
3 )2 H CH 2
CH(CH
3 )2 4-CH 3
-C
6
H
4 184-185 26 C(0113)3 C. '(CH 3 2 H 0C6H15 06115 189-193 27 C(CH 3 3
CH(CH
3 2 H OH 3 4-C1-C 6
H
4 2) 28 C(CH 3 3
CH(CH
3 )2 H OH 3 4-0113-614 3) 29 O(OH 3 3
OH(OH
3 2 H CH (OH 2 CH3) 2 4-CH 3
-C
6 H4 1130 0050/44896 No. -R 1
R
3 Rs R 6
R
7 M.P. (0C) IR (cm-1) C (CH 3 3
CH(CH
3 2 H (CH2) 3
CH
3 4-CH 3
-C
6
H
4 137-139 31 C(CH 3 3 CH (CH 3 2 H CYclo-C 5
H
9 4-CH 3
-C
6
H
4 141-142 32 C (CH 3 3 CH (CH 3 2 H (CH 2 3
CH
3 4-Cl-C 6
H
4 160-161 33 C(CH 3 3 CH (CH3) 2 H cyclo-C 5
H
9 4--Cl-C 6 H4 164-166 34 C(CH 3 3 CH (CH 3 2 H CH 2
C
6
H
5 4-Cl--C 6
H
4 168-172
CH(CH
3 )2 CH(CH 3 2 H CH 2
-C
6
H
5 4-Cl-C 6
H
4 171-173 36 CH(CH 3
)C
2
H
5
CH(CH
3 )2 H CH 2
-C
6
H
5 4-Cl-C 6
H
4 161-171 37 CH(CH 3 2
CH(CH
3 2 H ICYClo-C 5
H
9 4-Cl-C 6
H
4 221-223 38 CH(CH 3 2
CH(CH
3 )2 H (CH 2 3
CH
3 4-Cl-C 6
H
4 193-194 39 CH(CH 3
)C
2 H5 CH(CH 3 2 H (CH 2 3
CH
3 4-Cl-C 6
H
4 166-168 40 C(CH 3 2 CH(CH3)2 H C(CH 3 2 4-Cl-C 6
H
4 152 41 CH(CH 3 2 CH (CH 3 2 H CH(CH 3 )C2H 5 4-Cl- 6
H
4 162 42 CH(CH 3
)C
2 H5 CH(CH3)2 H CH(CH 3
)C
2
H
5 4-Cl--C 6
H
4 136 43 CH(CH 3 )2 CH(CH 3 )2 H ICYClo-C 6 Hjj. 4-CH 3
-C
6
H
4 193-195 44 CH(CH 3 2
CH(CH
3 )2 H (CH 2 3
CH
3 4-CH 3
-C
6 H4 176-177
CH(CH
3 )02H5 CH(CH 3 )2 H (CH 2 3
CH
3 4-CH 3
-C
6
H
4 1.42 46 C(CH 3 3
CH(CH
3 )2 TH CH(CH 3 2 4-CH 3 -0 6
H
4 139 47 CH(CH 3 2
CH(CH
3 )2 H CyClo- 5 H9 4-CH 3
-C
6
H
4 188 48 CH(CH 3
)C
2 H5 CH(CH 3 )2 H -~cyclo-C 5
H
9 4-CH 3 -0 6
H
4 160
CH(CH
3 )2 CH(CH 3 2 'H CH 2
-C
6
H
5 4-CH 3
-C
6
H
4 146-148
CH(CH
3 2
CH(CH
3 2 H CYCl0-C 6 Hji 4-0CH 3
-C
6
H
4 216 51 C(CH 3 3
CH(CH
3 2 H I(CH 2 3
CH
3 4-CH 3
O-C
6
H
4 Oil 52 C(CH3)3 CH(0H 3 )2 H Icyclo-CsH9 4-CH 3
O-C
6
H
4 130-13 -2 53 CH(CH 3 2
CH(CH
3 2 H cyclo- 5 H9 4-CH 3
O-C
6
H
4 172-175 54 CH(CH 3 2
CH(CH
3 2 H (CH 2 3
CH
3 4-CH 3
O-C
6 H4 158-160
CH(CH
3
)C
2 H5 CH(CH 3 2 H CYC1o- 5
H
9 4-CH 3
O-C
6
H
4 161 56 jCH(CH 3
)C
2
H
5 CH (CH 3 2 H (CH 2 3
CH
3 4-CH 3
O-C
6
H
4 128-130 355 H(H)
CH(CH
3 2 H CH(CH 3 2 4-0H 3
-C
6
H
4 160 58 CH (CH 3
_)C
2 H,5 CH (CH 3 H CH 2
-C
6
H
5 4-CH 3
-C
6
H
4 139 59 CH(CH 3 2 EH (CH 3 2 H CH(C 2
H
5 2 4-CH 3
-C
6
H
4 oil
CH(CH
3 2
CH(CH
3 2 H C 2
H
5 CYClo-C6Hlj 173-175 1) IR (cnr- 1 3280, 2969, 2935, 1674, 1515, 1243 2) 1H-NMR (CDCl 3 0.98 (dd,2H); 1.4 2.12 3.8 3.95 5.35 (d,1H, 6.8 7.18 (d,2H) 3) 1H-NMR (OD1 3 1.98 (dd,6H); 1.45 2.13 2.25 3.12 3.87 5.2 (d,lH,NH); 6.74 (d,2H); 7.00 8.13 (s,1H,NH)
'-I
0050/44896 43 Table 9 1 0 H R 3 0 R 5
R
6 S\ I I I II 1 1 C C-N N -R 7 W- H No. W 1 W2 R3 R 5
R
6
R
7 M.p.(oC) 1 CH 3
CH
3
CH(CH
3 2 H CH3 4-C1-C 6
H
4 104 2 CH 3 CH3 CH(CH 3 2 H CH 3 4-CH 3 -C6H 4 84 Use examples It was possible to show the fungicidal action of the compounds of the general formula I by the following tests: The active compounds were prepared as a 20% strength by weight emulsion in a mixture of 70% by weight of cyclohexanol, 20% by weight of Nekanil® LN (Lutensol® AP6, wetting agent with emulsifier and dispersant action based on ethoxylated alkylphenols) and by weight of Emulphor® EL"(Emulan® EL, emulsifier based on ethoxylated fatty alcohols) and diluted with water according to the desired concentration.
Plasmopara viticola Leaves of potted vines of the variety MUller-Thurgau were sprayed with aqueous spray liquor which contained 80% by weight of active compound and 20% by weight of emulsifier in the dry substance. In order to assess the duration of action of the active compounds, the plants were placed in a greenhouse for 8 days after the spray coating had dried on. Only then were the leaves infected with a zospore suspension of Plasmopara viticola (vine Peronospora). The vines were first placed for 48 hours in a chamber containing water vapor-saturated air at 24°C and then for 5 days in a greenhouse at from 20 to 30°C. After this time, the plants were placed in the moist chamber again for 16 hours to accelerate escape from the sporangiophore. The extent of fungal outbreak on the bottoms of the leaves was then assessed visually.
0050/44896 44 In this test, the plants treated with an aqueous preparation containing 250 ppm of the compounds 4, 6, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20 and 22 from Table 6 in each case showed a maximum attack of 15%, while untreated plants were attacked to
Claims (9)
1. A carbamoylcarbohydrazide of the general formula I X 2 R 2 R 3 X 3 R 5 R 6 II I I II I R1-Xl-C-N-C N -R7I R4 or its salts, where the radicals have the following meanings: R 1 is C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl or C 2 -C 8 -alkynyl, it being possible for these radicals to be partly or completely halogenated and/or to carry one to three of the following groups: cyano, C-C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C-C 4 -alkoxycarbonyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 cycloalkenyl, aryl, aryloxy and heteroaryl, it being possible for the cyclic radicals in turn to carry one to three of the following substituents: halogen, cyano, C-C 4 -alkyl, C 1 -c 4 -alkoxyalkyl, Cl-C4--haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -c 4 -alkoxycarbonyl, aryl, aryloxy and heteroaryl, C 3 -C 7 -cycloalkyl or C 3 -C 7 cycloalkenyl, it being possible for these radicals to be partly or completely halogenated and/or to carry one to three of the following groups: cyano, C 1 -0 4 -alkyl, C 1 -C 4 -alkoxyalkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkoxycarbonyl, aryl, aryloxy and aryl-(C 1 -CO)-alkyl, it being possible for the cyclic groups to carry one to three of the following sub- stituents: halogen, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxyalkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 alkoxy, CI-C 4 haloalkoxy, C 1 -C 4 -alkylthio, C-C 4 -alkoxycarbonyl, aryl and aryloxy, a non-aromatic 4- to 8-membered ring, which, as ring members, in addition to carbon can also contain one or two of the heteroatoms oxygen, sulfur and nitrogen, it being possible for the carbon atoms in the ring to carry one or two of the following groups: halogen, cyano, C 1 -C 4 alkyl, C-C 4 -alkoxyalkyl, C 1 -C4-haloalkyl, C 1 -C 4 alkoxy, C.-C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkoxycarbonyl, aryl and aryloxy and the second and N., 0050/44896 46 each further nitrogen atom as a heteroatom in the ring carrying hydrogen or a Cl-C 4 -alkyl group, aryl or heteroaryl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano, Cl-C 4 -alkyl, Cl-C 4 -alkoxyalkyl, Cl 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C-0 4 -haloalkoxy, Cl-C 4 -alkylthio, Cl-C 4 -alkoxycarbonyl, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following substituents: halogen, cyano, Cl-C 4 -alkyl, Cl-C 4 -alkoxyalkyl, Cl-C 4 -haloalkyl, C 1 C 4 -alkoxy, Cl-C 4 -haloalkoxy, C-C 4 -alkylthio and Cl-C 4 -alkoxycarbonyl or WlW 2 where W 1 is Cl-C 8 alkyl which can be partly or completely halogenated and/or can carry one to three of the following groups: cyano, C 1 -C 4 alkoxy, CI-C 4 -halo- alkoxy, Cl-C 4 -alkylthio, aryl, aryloxy and hetero- aryl, it being possible for the cyclic groups in turn to carry one to three of the following substituents: halogen, cyano, Cl-C 4 -alkyl, Cl-C 4 -alkoxyalkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, C 1 -C 4 -haloalkoxy, Cl-0C 4 -alkylthio, Cl-C 4 -alkoxycarbonyl, aryl and aryloxy, C 2 -0 8 alkenyl or C 2 -0 8 -alkynyl, it being possible for these radicals to be partly or completely halogenated and/or to car::y one to three of the following groups: cyano, C 1 -C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 -alkyl- thio, Cl-0 4 -alkoxycarbonyl, aryl and aryloxy, it being possible for the cyclic groups in turn to carry one to three of the following substituents: halogen, cyano, Cr-C4-alkoxy, Cl-C 4 -haloalkoxy, Cl 1 -C 4 alkyl- thio, Cl 1 -C 4 -alkoxycarbonyl, aryl and aryloxy, C 3 -C 7 cycloalkyl or C 3 -C 7 cycloalkenyl, it being pos- sible for these radicals to carry one to three of the following groups: halogen, cyano, Cl-C 4 alkyl, Cl-C 4 -alkoxyalkyl, Cl-C 4 -haloalkyl, Cl-C 4 alkoxy, C 1 -C haloalkoxy, C 1 -C 4 alkylthio, Cl-C 4 -alkoxy- carbcoayl, aryl and aryl-(C 1 C 4 )-alkyl, it being pos- sible for the groups which contain aryl to carry one to three of the following substituents: halogen, cyano, Cl-C 4 alkyl, Cl-C 4 alkoxyalkyl, CI-C 4 -halo- 0050/44896 47 alkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-0 4 -alkyl- thio, Cl-C 4 -alkoxycarbonyl, aryl and aryloxy or aryl or heteroaryl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano, Cl-C 4 -alkyl, CI-.C 4 -alkoxy- alkyl, Cl-C 4 haloalkyl, Cl-C 4 alkoxy, Cl-C 4 -halo- alkoxy, Cl-C 4 -alkylthio, Cl-C 4 -alkoxycarbonyl, aryl and aryloxy and W 2 is hydrogen or one of the groups WI; R 2 is hydrogen or Cl-C 8 -alkyl or C 3 -C 7 -cycloalkyl, which can be partly or completely halogenated; is R 3 is Cl-.C 8 -alkyl, it being possible for this radical to carry one to three of the following groups: halogen, cyano, Cl-.C 4 -alkoxy, Cl-0 4 -haloalkoxy, Cl-C 4 -alkylthio and C 1 -C 4 -alkoxycarbonyl, C 3 C 7 -CYCloalkyl or phenyl-(Cl-0 4 )-alkyl, it being pos- sible for the rings of these radicals to carry one to three of the following groups: halogen, cyano, Cl-C 4 alkyl, Cl-C 4 -alkoxyalkyl, Cl-0 4 -haloalkyl, Cl-0 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 -alkylthio, Cl-C 4 -alkoxycarbonyl, aryl and aryloxy; R 4 is hydrogen or one of the radicals R 3 or R 3 and R 4 together with the C atom to which they are bonded, are a 4- to 8-mnembered ring which, as ring members, in addition to carbon can also contain one or two of the heteroatoms oxygen, sulfur and nitrogen, it being possible for the carbon atoms in the ring to carry one or two of the following groups: halogen, cyano, Cl-C 4 -alkyl, Cl-C 4 -alkoxyalkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 -alkylthio, Cl-C 4 alkoxycarbonyl, aryl and aryloxy and nitrogen as a heteroatom carrying hydrogen or a Clr-C4-alkyl group; R 5 is one of the radicals R 2 R 6 -is Cl-0C 8 alkyl, C 2 -C 8 -alken~ or C 2 -C 8 -alkynyl, it being possible for these rad ials to be partly or completely halogenated and/or to carry one to three of the following groups: cyano, Cl-0 4 alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 alkylthio, C 3 -C 7 CYCloalkyl, C 3 -C 7 -CYCloalkenyl, 0050/44896 48 aryl, aryloxy and heteroaryl, it being possible for the cyclic radicals in turn to carry one to three of the following substituents: halogen, cyano, Cl-C 4 -alkyl, Cl-C 4 alkoxyalkyl, Cl-C 4 -haloalkyl, C 1 -C 4 alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 -alkylthio, aryl, aryloxy and heteroaryl, C 3 C 7 cycloalkyl or C 3 -C 7 CYCloalkenyl, it being possible for these radicals to be partly or completely halogenated and/or to carry one to three of the following groups: cyano, Cl-C 4 alkyl, Cl 1 -C 4 -alkoxyalkyl, Cl-C 4 -haloalkyl, Cl 1 -C 4 alkoxy, Cl-C 4 -haloalkoxy, Cl-C 4 -alkylthio, aryl1, aryloxy and aryl-(Cl-C 4 )-alkyl, it being possible for the cyclic groups to carry one to three of the following sub- stituents: halogen, cyano, Cl-C 4 -alkyl, Cl-0 4 -alkoxyalkyl, Cl-C 4 -haloalkyl, Cl-0 4 alkoxy, C 1 -0 4 -haloalkoxy, Cl-C 4 -alkylthio, aryl and aryloxy, a non-aromatic 4- to 8-mnembered ring, which, as ring members, in addition to carbon can also contain one or two of the heteroatoms oxygen, sulfur and nitrogen, it being possible for the carbon atoms in the ring to carry one or two of the following groups: halogen, cyano, Cl-C 4 alkyl, Cl-C 4 -alkoxyalkyl, Cl-C 4 -haloalkyl, Cl-C 4 -alkoxyr Cl-C 4 -haldcilkoxy, Cl-C 4 -aJlkylthio, aryl and aryloxy and the second and each further nitrogen atom as a heteroatom in the ring carrying hydrogen or a Cl-C 4 -alkyl group, aryl or heteroaryl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano, C 1 -C 4 -alkyl, Cl-C 4 -alkoxyalkyl, Cl-C 4 -haloalkyl, Cl-C 4 alkoxy, Cl-C 4 -haloalkoxy, C 1 -C 4 -alkylthio, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following sub- stituents: halogen, cyano, Cl-C 4 -alkyl, Cl-0C 4 -alkoxy- alkyl, C-C 4 -haloalkyl, Cl 1 -C 4 -alkoxy, Cl-C 4 -haloalkoxy and CI-C 4 -alkylthio or if R 3 is isopropyl, hydrogen; R 7 is one of the radicals R 6 excluding hydrogen; X 1 is oxygen or sulfur, X 2 is oxygen or sulfur, X 3 is oxygen or sulfur; 0050/44896 49 excluding the compounds according to the following definition of the radicals: I a-d Ie-h Ii I j-k 11 Im In-o (RI Ph-OH 2 R 2 R 3 CU 3 (CH 2 2 CH 3 CH(CH 3 )2 or Ph-OH 2 R 4 ,R 5 R 6 ,R 7 CH 2 CH 2 Cl), (RI C(CH 3 3 R 2 H; R 3 =CU 3 CH(CH3)2, CH(CH 3 )CH 2 CH3, CH 2 CH(CH 3 2 or Ph-OH 2 R 4 ,R 5 H; R 6 pR 7 =CH 2 CH 2 Br), (RI Ph-CH 2 R 2 R 3 CH 3 R 4 fR 5 H; R 6 =CU 3 R 7 Ph), (R 1 Ph-CH 2 R 2 H; R 3 CH(CH 3 )2 or CH 2 CH(CH3)2; R 4 ,RS H; R 6 ,R 7 =Ph), (R 1 C(CH 3 3 R 2 R 3 =CH(CH3) 2 R 4 R 5 R 6 H; R 7 Ph) (R 1 Ph-CH 2 R 2 H; R 3 =Ph-OH 2 R 4 R 5 H; R 6 ,R 7 CH 2 CH 3 (RI Ph-OH 2 R 2 H; R 3 =CH 2 SCH 3 or CH 2 CH 2 SCH3; RS= H; R 6 ,R 7 CH 2 CH 2 Cl).
2. A process for preparing carbamoylcarbohydrazides of the general formula I or their salts as claimed in claim 1, which comprises reacting a carbamoylcarbohydrazide of the general formula II X 2 R 2 R~z X 3 Rl- X1-CNC -C-OH with a hydrazine of the general formula III R 5 R 6 I I H-N- N R 7 III and if desired converting the compound I thus obtained to one of its salts in a manner known per se.
3. A process for preparing carbamoylcarbohydrazides of the general f ormula I in which R 1 is a group WIW 2 or their saltts as claimed in claim 1, which comprises converting a carbamoylcarbohYdrazide of the general formula I 0050/44896 X 2 R 2 R 3 X 3 R 5 R 6 II I II I 1 R 1 -X C N-C N -R 7 I R4 where X 1 X 2 and X 3 are in each case oxygen, and the group Rl-Xl-(CO) represents a protective group which can be removed in a manner known per se, to an amino acid hydrazide IV R 2 R 3 X 3 R 5 R 6 15 I II 1 1 H--N-C -C-N N R 7 IV R4 reacting the amino acid hydrazide IV thus obtained with a chloroformyl oxime of the general formula V W 1 0 II V W 2 in the presence of a base and if desired converting the com- pound I thus obtained to one of its salts in a manner known per se.
4. A process for preparing carbamoylcarbohydrazides of the gen- eral formula I or their salts as claimed in claim 1, in which R 6 is C 1 -C 8 -alkyl, C 4 -C 7 -cycloalkyl or aryl-(C-C 4 )-alkyl, which comprises reacting a carbamoylcarbohydrazide of the general formula I as claimed in claim 1, in which R 6 is hydrogen, with a compound of the general formula R 6 in which R 6 is Ci-C 8 -alkyl, C 4 -C 7 -cycloalkyl or aryl-(C 1 -C 4 )-alkyl and X is a negative leaving group, with additional use of a base and if desired converting the compound I thus obtained to one of its salts in a manner known per se.
S'ff 0050/44896 51 A composition suitable for controlling harmful fungi, con- taining customary additives and an effective amount of a com- pound of the general formula I or one of its salts as claimed in claim 1, excluding the compounds la to Io.
6. A process for controlling harmful fungi, which comprises treating the harmful fungi, their environment or the plants, surfaces, materials or spaces to be kept free from them with an effective amount of a compound of the general formula I or one of its salts as claimed in claim 1, including the com- pounds la to Io, or a composition containing I as claimed in claim
7. The use of the compounds of the general formula I or of one of their salts as claimed in claim 1, including the compounds Ia to Io, for controlling harmful fungi.
8. An amino acid hydrazide of the general formula IV R 3 X 3 R 5 R 6 I 1 i I I lH 2 N C C- N N -R 7 R4 where X 3 is oxygen and R 3 is a group CH(CH 3 2 CH 2 CH(CH 3 2 or CH(CH 3 )C 2 H 5 and R 4 R 5 R 6 and R 7 have the meaning given in claim 1, excluding the compounds according to the following definition of the radicals: IVa-b IVc-e IVf IVg (R 3 CH(CH 3 2 or (CH 2 2 CH 3 R 4 ,R 5 H; R 6 ,R 7 CH 2 CH 2 Cl), (R 3 CH(CH 3 2 CH(CH 3 )CH 2 CH 3 or CH 2 CH(CH 3 2 R 4 ,R 5 H; R 6 ,R 7 CH 2 CH 2 Br) (R 3 CH(CH 3 2 R 4 ,R 5 ,R 6 H; R 7 Ph), (R 3 CH(CH 3 2 R 4 ,R 5 H; R 6 ,R 7 Ph).
9. An amino acid hydrazide of the general formula IV as claimed in claim 8, in which R 3 is a group CH(CH 3 2 R 4 and R 5 have the meaning given in claim 1, i vi R 6 is C 1 -C 8 -alkyl, it being possible for this radical to be partly or completely halogenated and/or to carry one to three of the following groups: cyano, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 3 -C 7 -cycloalkyl, 0050/44896 52 0 3 -C 7 CYCloalkenyl, aryl, aryloxy and heteroaryl, it being possible for the cyclic radicals in turn to carry one to three of the following substituents: halogen, cyano, CI-C 4 -alkyl, Cl-0 4 alkoxyalkyl, Cl-0 4 -haloalkyl, C 1 -C 4 alkoxy, Cl-C4-haloalkoxy, Cl-C 4 -alkylthio, aryl, aryloxy and heteroaryl and R 7 is aryl, it being possible for this radical to carry one to three of the following groups: halogen, cyano, Cl-C 4 -alkyl, Cl-C 4 -alkoxyalkyl, C 1 -C 4 -haloalkyl, Cl-C 4 -alkoxy, Cl-C 4 -haloalkoxy, Cl-.C 4 -alkylthio, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following sub- stituents: halogen, cyano, CI-C 4 -alkyl, Cl-C 4 -alkoxy- alkyl, Cl-0C 4 -haloalkyl, Cl-C 4 alkoxy, Cl-C 4 -haloalkoxy and Cl-C 4 -alkylthio. 0050/44896 Carbamoylcarbohydrazides Abstract Carbamoylcarbohydrazides I R 1 X-- X 2 R 2 R 3 X 3 R 5 R 6 II I I II I C-N-C N -R 7 R4 and their salts, where the radicals have the meanings: R 1 is unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heteroaryl or an unsubsti- tuted or substituted non-aromatic carbo- or heterocycle, W 1 W 2 C=N-, where W 1 is an unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heteroaryl and W 2 is hydrogen or W 1 R 2 is hydrogen or unhalogenated or halogenated alkyl or cyclo- alkyl; R 3 is unsubstituted or substituted alkyl, cycloalkyl or phenyl- alkyl; R 4 is hydrogen or one of the radicals R 3 or R 3 and R 4 together with the C atom to which they are bonded, are an unsubstituted or substituted, saturated carbo- or heterocycle; R 5 is one of the radicals R 2 I.. 0050/44896 54 R 6 is unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heteroaryl, an unsubsti- tuted or substituted non-aromatic carbo- or heterocycle or, if R 3 isopropyl, hydrogen; R 7 is one of the radicals R 6 excluding hydrogen, X 1 ,X 2 ,X 3 [sic] are in each case oxygen or sulfur and processes for their preparation, compositions containing them, their use and also intermediates IV R 3 X5 R 5 R 6 H2N C C N R 7 I where X 3 is oxygen and R 3 is a group CH(CH 3 2 CH 2 CH(CH 3 2 or CH(CH 3 )C 2 H 5 are described. (A ''1 INTERNATIONAL SEARCH REPORT Intern: aliApplication No IPCT/EP 95/01924 CL.ASSIF:ICATION 01: SUMICT'MA'lI'IR IPC 6 C07C271/22 C07C271/54 C07C271/34 C07C333/04 C07C271/60 C07C333/20 C07C243/38 A01N47/12 A0IN47/14 A01N47/18 A0IN47/22 A01N47/24 According to International [latent Classification (IFPQ or to both national classification and IPC FIELD S SEA RCIIlED Minimum documentation searched (classification systm followed by classification rymbols) IPC 6 C07C Documentation scarchcd other than minimum documentation to thc extent that such documents arc included in the fields searched Electronic data basec onsulted during the intcrnation~al search (name of data base and, whcre practical, search terms used) C. DOCUMENTS CONSIDE D~r BO E Category Citation of document, with indication, whcrc appropniate, of the relevant passages Relevant to claim No. X PHARMAZIE, 1,2 vol.44, no.8, 1989, BERLIN DD pages 542 544 S. ZAKHARIEV ET AL. 'Synthese und geschwulsthemniende Wirkung von N,N-Di(2-chlorethyl)-hydrazinen der .alpha.-Aminocarbons~ureantimetabol ite' see page 543, examples 1,3,5 X PHARMAZIE, 1,2 vol.44, no.9, 1989, BERLIN DD pages 608 611 S. ZAKHARIEV ET AL. 'Synthese und geschwulsthemmende Wirkung in vivo von N,N,-Oi (2-chloroethyl)hydraziden natUri icher .alpha.Aminocarbons~uren' cited in the application see page 610,example 46 J-v] Further documents are listed in the continuation of box C. J] Patent famiuly members are listed in annex, Special categories of eited documents later document published after the International filing date docuentdefningthegenralstat oftheart hic isnotor prionity date and not in confliet with the application but ocuentdefiingthegeneal tat of he rt hichis ot ited to understand the pnireiple or theory underlying the considered to be of particular relevance invention earlier document but published on or aftcr the international XW document of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on prionity claim(s) or involve an inventive step when the document is taken alone which is cited to establish the publication date of another document of particular relevance; the claimed invcntion citation or other special reason (as speciflied) cannot be considered to involve an Inventive step when thc 0.document refemrng to an oral disclosure, use, exhibition or documnentIS combined with tine or more other such doeu- other meant ments, such combination being obvious to a person skilled document published pnior to the international filing date but in the art. later than the pniority date claimed W document member of the same patent family Date of the actual completion of the international seareh Date of mailing of the Intemnational search report October 1995 07.11.95 Name and mailing address of the ISA Authorized officer European P'atentOffice, 11.11, 5181 IPatentlaan 2 2281 IV Itilswilk ide. 1' 31.70) 340-2040, Tx. 31 651 cpo nI, S uet Pax: 1 31.70) 340.3016 Sue t Foin PCT'ISA 210 (iecond iheet) (Jiiiy 1992) page 1 of 3 JN1'TERNATIONAL SEARCH REPORT Internt &I Application No PCT/EP 95/01924 C.(Continuation) DOCUMEI~NS CONSII)IULID TO BE[ RlIXLIVANT Category Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No, X PHARMAZIE, 1,2 vol .44, no.5, 1989, BERLIN DD pages 316 317 S. ZAKHARIEV ET AL. 'Synthese von N,N-Di(2-brometyhl)hydraziden einiger natiirl icher .alpha.-Aminocarbons~uren' cited in the application see page 316, example 7 X JOURNAL OF MEDICINAL CHEMISTRY,1 vol .25, no.11, 1982, WASHINGTON US pages 1317 1321 E. ESCHER ET AL. 'Structure-activity studies on the C-terminal anmide of substance P' see page 1319, right column, line 20 line 33 X CHEMICAL AND PHARMACEUTICAL BULLETIN.,1 vol .29, no.12, 1981, TOKYO JP pages 3630 3638 S. SHINAGAWA ET AL. 'Synthetic studies on enkephalin analogs. I. Potent analgesic activity of H-Tyr-D-Ala-Gly-Phe-NHNH-CO-R lower alkyl)' see table I, examples 19, 11 X CHEMICAL ABSTRACTS, vol. 94, no. 9,1 2 March 1981, Columbus, Ohio, US; abstract no. 58093, S. ZAKHARIEV ET AL. page siehe RN 75016-97-6, L-Phenylalanine, N-[(phenylmethoxy)carbonyl]-, 2,2-bis(2- i odoethyl )hydrazide siehe RN 7FO27-32-6, DL-Phenylalanine, 4-chl oro-N-[(phenylmethoxy)carbonyl 2, 2-bi s(2-chl oroethyl )hydrazide NEOPLASMA, vol .27, no.2, 1980 pages 137 142 X CHEMICAL ABSTRACTS, vol. 77, no. 13,1 September 1972, Columbus, Ohio, US; abstract no. 88819, K. RADECKI ET AL. page 496; cited in the application siehe RN 37637-46-0, L-Glutamic acid, N-[(phenylmethoxy)carbonyl]-, ester, 1-(2,2-diphenylhydrazide) FARM. POL., vol .28, no.6, 1972 pages 615 619 rorm PCT'lS&12iii (oinuation ofiecond sheet) (July 1992) page 2 of 3 INTERNATIONAL SEARCH REPORT tntcm: al Application No PCT/EP 95/01924 C(Continuation) D~OCUME~NTS CX)NSIDERBI) TO BEf, RIILFWANT Category 'ICitation of documnent, with indicatUon, where appropriate, or thc relevant passages Relevant to claim No. CHEMICAL ABSTRACTS, vol. 65, no. 5, 29 August 1966, Columbus, Ohio, US; abstract no. 7269h, BOZENNA BATOR ET AL siehe RN 6715-75-9, Valine, N-carboxy-, N-benzyl ester, 2-phenyihydrazide, L- ROCZNIKI CHEM., no.5, 1966 pages 761 766 DE,B,11 99 540 (SCHERING AG) 26 August 1965 cited in the application see claim; examples 1 1,5-7 Pom, PCT ISA.2i0 (continuation of seand shett) (JuY 1992) page 3 of 3 INTERNATIONAL SEARCH REPORT ia~ormnatof on patent tfmllJy members lntenv il Application No PCT/EP 95/01924 Patent document I Publication Patent family I Publication cited in search report daemember(s) Idate DE-B- 1199540 CH-A- 450058 FR-A- 1418676 11-02-66 NL-A- 6501398 05-08-66 US-A- 3214334 26-10-65 L Form PCTISA1D1 (patent family annex) (July 1992)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4419516A DE4419516A1 (en) | 1994-06-03 | 1994-06-03 | Carbamoyl carboxylic acid hydrazide derivs. |
| DE4419516 | 1994-06-03 | ||
| DE1995104423 DE19504423A1 (en) | 1995-02-10 | 1995-02-10 | New carbamoyl carboxylic acid hydrazide derivs. |
| DE9504423 | 1995-02-10 | ||
| PCT/EP1995/001924 WO1995033710A1 (en) | 1994-06-03 | 1995-05-20 | Carbamoyl carboxylic acid hydrazides and their use against fungi |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2735395A AU2735395A (en) | 1996-01-04 |
| AU685957B2 true AU685957B2 (en) | 1998-01-29 |
Family
ID=25937165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU27353/95A Expired - Fee Related AU685957B2 (en) | 1994-06-03 | 1995-05-20 | Carbamoyl carboxylic acid hydrazides and their use against fungi |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0763014A1 (en) |
| JP (1) | JPH10501215A (en) |
| KR (1) | KR970703306A (en) |
| AU (1) | AU685957B2 (en) |
| BR (1) | BR9507914A (en) |
| CA (1) | CA2191999A1 (en) |
| IL (1) | IL113916A0 (en) |
| WO (1) | WO1995033710A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI332943B (en) | 2001-07-10 | 2010-11-11 | Synta Pharmaceuticals Corp | Taxol enhancer compounds |
| TWI297335B (en) | 2001-07-10 | 2008-06-01 | Synta Pharmaceuticals Corp | Taxol enhancer compounds |
| TWI252847B (en) | 2001-07-10 | 2006-04-11 | Synta Pharmaceuticals Corp | Synthesis of taxol enhancers |
| TWI330079B (en) * | 2003-01-15 | 2010-09-11 | Synta Pharmaceuticals Corp | Treatment for cancers |
| DK1781604T3 (en) | 2004-06-23 | 2013-09-16 | Synta Pharmaceuticals Corp | BIS (THIO-HYDRAZIDE-AMID) SALTS FOR TREATMENT OF CANCERS |
| EP1877048A1 (en) | 2005-04-15 | 2008-01-16 | Synta Pharmaceuticals Corporation | Combination cancer therapy with bis(thiohydrazide) amide compounds |
| JP2010501562A (en) | 2006-08-21 | 2010-01-21 | シンタ ファーマシューティカルズ コーポレーション | Compounds for treating proliferative disorders |
| JP2010502616A (en) | 2006-08-31 | 2010-01-28 | シンタ ファーマシューティカルズ コーポレーション | Combination of bis (thiohydrazide amide) to treat cancer |
| WO2008033494A2 (en) | 2006-09-15 | 2008-03-20 | Synta Pharmaceuticals Corp. | Purification of bis(thiohydrazide amides) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1199540B (en) * | 1963-12-27 | 1965-08-26 | Schering Ag | Means effective against powdery mildew |
-
1995
- 1995-05-20 BR BR9507914A patent/BR9507914A/en not_active Application Discontinuation
- 1995-05-20 JP JP8500247A patent/JPH10501215A/en active Pending
- 1995-05-20 CA CA002191999A patent/CA2191999A1/en not_active Abandoned
- 1995-05-20 WO PCT/EP1995/001924 patent/WO1995033710A1/en not_active Application Discontinuation
- 1995-05-20 EP EP95922467A patent/EP0763014A1/en not_active Withdrawn
- 1995-05-20 AU AU27353/95A patent/AU685957B2/en not_active Expired - Fee Related
- 1995-05-20 KR KR1019960706896A patent/KR970703306A/en not_active Application Discontinuation
- 1995-05-30 IL IL11391695A patent/IL113916A0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA2191999A1 (en) | 1995-12-14 |
| JPH10501215A (en) | 1998-02-03 |
| EP0763014A1 (en) | 1997-03-19 |
| IL113916A0 (en) | 1995-08-31 |
| WO1995033710A1 (en) | 1995-12-14 |
| BR9507914A (en) | 1997-09-23 |
| KR970703306A (en) | 1997-07-03 |
| AU2735395A (en) | 1996-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU685957B2 (en) | Carbamoyl carboxylic acid hydrazides and their use against fungi | |
| US5847194A (en) | Carbamoylcarboxamides | |
| AU728829B2 (en) | Carbamoylcarboxamides | |
| JP2002517413A (en) | Use of 2- (N-phenylamino) pyridine as fungicide and novel 2- (N-phenylamino) pyrimidine | |
| US6124345A (en) | Carbamoyl carboxylic acid amide oximes | |
| US5955473A (en) | Fungicidal quinolines | |
| KR20000004916A (en) | Fungicidally active carboxylic acid amides | |
| KR100342145B1 (en) | p-hydroxyaniline derivatives, preparation methods thereof and uses thereof | |
| EP0672654B1 (en) | Fungicidal carbamoyloxime carbonic acid amides | |
| WO1995023786A1 (en) | Carbamoyl carboxylic acid amides, process for producing them and their use as fungicides | |
| MXPA98001273A (en) | Carbamoilcarboxami | |
| WO1995023785A1 (en) | Carbamoyl carboxylic acid amides, process for producing them and their use as fungicides | |
| JP2003206252A (en) | Benzhydryl derivative | |
| DE4419516A1 (en) | Carbamoyl carboxylic acid hydrazide derivs. | |
| DE4407023A1 (en) | Carbamoyl carboxylic acid amide derivs | |
| DE19504423A1 (en) | New carbamoyl carboxylic acid hydrazide derivs. | |
| DE4438738A1 (en) | New carbamoyl carboxylic acid amide derivs. | |
| DE4446458A1 (en) | Carbamoyl carboxylic acid amide derivs. | |
| DE4434462A1 (en) | Carbamoyl carboxylic acid amide derivs. | |
| DE4407022A1 (en) | Carbamoyl carboxylic acid amide derivs. |