US 2010/0168175 A1Published application

Atpenins

AssigneeBayer CropScience AG

InventorsIsabelle ADELT, Robert VELTEN, Welf Burkhard WIESE, Ulrike WACHENDORFF-NEUMANN, Karl-Heinz KUCK, Peter DAHMEN, Arnd VOERSTE, Ronald EBBERT, Franz von NUSSBAUM

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Abstract

The present invention relates to processes for preparing certain 2-pyridones and 2-pyridinols, to novel compounds of these two types and to their use as biologically active compounds, in particular for controlling harmful microorganisms in crop protection, in the medicinal field and in the protection of materials.

Claims6

Dependent claims

Process for preparing 2-pyridones of the formula (I)

in which
X represents hydrogen, —C(═O)OR5, —C(═O)NR6R7, —C(═O)CR8R9R10, or represents —C(═O)aryl or —(C═O)hetaryl, each of which is optionally substituted in the aryl or heteraryl moiety,
R1 represents hydrogen or alkyl, alkenyl, alkynyl, cycloalkyl, aryl, hetaryl, optionally mono- or polysubstituted by identical or different substituents,
R2 represents hydrogen, methyl or ethyl,
R3 represents hydrogen,
R5 represents hydrogen or alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, bicycloalkyl, aryl, hetaryl, optionally mono- or polysubstituted by identical or different substituents,
R6 represents hydrogen, C1-C8-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C3-C8-cycloalkyl;
C2-C6-haloalkyl, halo-C2-C4-alkoxy-C1-C4-alkyl, C3-C8-halocycloalkyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms;
(C1-C3-alkyl)carbonyl-C1-C3-alkyl, (C1-C3-alkoxy)carbonyl-C1-C3-alkyl;
halo-(C1-C3-alkyl)carbonyl-C1-C3-alkyl, halo-(C2-C3-alkoxy)carbonyl-C1-C3-alkyl having in each case 1 to 13 fluorine, chlorine and/or bromine atoms;
represents —CH2—C≡C—R11 or —CH2—CH═CH—R11,
R7 represents hydrogen or represents alkyl, alkenyl, alkynyl, cycloalkylalkyl, cycloalkenylalkyl, each of which is optionally mono- or polysubstituted by identical or different substituents, or represents -M-Q-Z,
R8 represents hydrogen, alkyl or haloalkyl,
R9 represents hydrogen, halogen or represents alkyl, alkenyl, alkynyl, alkoxy, alkylthio, cycloalkyl, cycloalkenyl, or bicycloalkyl, each of which is optionally mono- or polysubstituted by identical or different substituents,
R10 represents hydrogen or represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, bicycloalkyl, bicycloalkylalkyl, aryl, arylalkyl, hetaryl or hetarylalkyl, each of which is optionally mono- or polysubstituted by identical or different substituents,
R9 and R10 furthermore together with the carbon atom to which they are attached form a carbocycle or heterocycle which may be saturated or unsaturated and which may be fused with a further carbocycle and which may furthermore optionally be substituted,
R11 represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C7-cycloalkyl, (C1-C4-alkoxy)carbonyl, (C3-C6-alkenyloxy)carbonyl, (C3-C6-alkynyloxy)carbonyl or cyano,
M represents in each case optionally substituted cycloalkylene, cycloalkenylene, bicycloalkylene, arylene or hetarylene,
Q represents a direct bond, C1-C4-alkylene, C2-C4-alkenylene, C1-C4-alkylenoxy, oxy-C1-C4-alkylene, O, S, SO, SO2 or NR12,
Z represents hydrogen or represents Z1, Z2, Z3, Z4, Z5 or Z6, where Q does not represent O, S, SO, SO2, NR12 if Z represents hydrogen,
Z1 represents phenyl which is optionally mono- to pentasubstituted by identical or different substituents,
Z2 represents pyridinyl which is optionally mono- to trisubstituted by identical or different substituents,
Z3 represents cycloalkyl or bicycloalkyl, each of which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen, alkyl, cycloalkyl and/or —(CR13R14)mSiR15R16R17,
Z4 represents unsubstituted C1-C20-alkyl or represents C1-Cm-alkyl which is mono- or polysubstituted by identical or different substituents from the group consisting of halogen, alkylthio, alkylsulphynyl, alkylsulphonyl, alkoxy, alkylamino, dialkylamino, haloalkylthio, haloalkylsulphynyl, haloalkylsulphonyl, haloalkoxy, haloalkylamino, halodialkylamino, —SiR15R16R17 and C3-C6-cycloalkyl, where the cycloalkyl moiety for its part may optionally be mono- or polysubstituted by identical or different substituents from the group consisting of halogen and C1-C4-alkyl,
Z5 represents C2-C20-alkenyl or C2-C20-alkynyl, each of which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen, alkylthio, alkylsulphynyl, alkylsulphonyl, alkoxy, alkylamino, dialkylamino, haloalkylthio, haloalkylsulphynyl, haloalkylsulphonyl, haloalkoxy, haloalkylamino, halodialkylamino, —SiR15R16‘R17 and/or C3-C6-cycloalkyl, where the cycloalkyl moiety for its part may optionally be mono- or polysubstituted by identical or different substituents from the group consisting of halogen and C1-C4-alkyl,
Z6 represents a saturated or unsaturated 3- to 7-membered ring which is optionally mono- or polysubstituted and which contains a silicon atom as ring member, in which Q represents a direct bond or C1-C4-alkylene,
or
M-Q-Z together represent 1H-2,3-dihydroinden-4-yl, 1,3-dihydro-2-benzofuran-4-yl or 1,3-dihydro-2-benzothien-4-yl, each of which is optionally mono- to trisubstituted by methyl, or represent 1,2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalen-5-yl,
R12 represents hydrogen, C1-C8-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C2-C6-haloalkyl, C3-C6-haloalkenyl, C3-C6-halo-alkynyl or C3-C6-cycloalkyl,
R13 represents hydrogen or C1-C4-alkyl,
R14 represents hydrogen or C1-C4-alkyl,
m represents 0, 1, 2 or 3,
R15 and R16 independently of one another represent hydrogen, C1-C8-alkyl, C1-C8-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl or C1-C6-haloalkyl,
R17 represents hydrogen, C1-C8-alkyl, C1-C8-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C3-C6-cycloalkyl, or represents in each case optionally substituted phenyl or phenylalkyl,
characterized in that
according to process (1)
(a) oxymalonic acid derivatives of the formula (III)
in which
Y represents halogen, hydroxyl or —O-AM in which
AM represents an alkali metal selected from the group consisting of lithium, sodium, potassium and caesium,
are reacted with amides of the formula (IV)
in which
R1a represents alkyl, alkenyl, alkynyl, cycloalkyl, aryl, hetaryl, optionally mono- or polysubstituted by identical or different substituents,
Xa represents —C(═O)OR5a, —C(═O)CR8R9R10 or represents —C(═O)aryl or —(C═O)hetaryl which is optionally substituted in the aryl or heteraryl moiety, and
R5a represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, bicycloalkyl, aryl, hetaryl, optionally mono- or polysubstituted by identical or different substituents, and
R8, R9 and R10 have the meanings given above,
if appropriate in the presence of a diluent,
thus giving 2-pyridones of the formula (I-b)
in which Xa, X1a and R3 have the meanings given above
which are subsequently
(b) if appropriate reacted with an alkylating agent, if appropriate in the presence of a base, a Lewis acid or a molecular sieve and, if appropriate, in the presence of a diluent,
giving 2-pyridones of the formula (I-c)
in which
Xa, R1a and R3 have the meanings given above, and
R2a represents methyl or ethyl,
after which
(c) if appropriate the 2-pyridones of the formula (I-b) or the formula (I-c) are hydrogenated in the presence of a transition metal catalyst or in the presence of Lewis or Brønsted acids, thus giving 2-pyridones of the formula (I-d)
in which R2, R3 and Xa have the meanings given above,
and
(d) if appropriate, the 2-pyridones of the formula (I-b) or the formula (I-c) or the formula (I-d), in which Xa represents —C(═O)OR5a are cleaved, thus giving the 2-pyridones of the formula (I-e)
in which R1, R2 and R3 have the meanings given above;
or according to process (2)
(e) 2-pyridones of the formula (I-f)
in which
R1, R2 and R3 have the meanings given above and
Xb represents —C(═O)OH or —C(═O)OR5b in which
R5b represents C1-C4-alkyl,
are reacted with amines of the formula (VIII)
in which R6 and R7 have the meanings given above,
if appropriate in the presence of diluents and if appropriate in the presence of reaction auxiliaries, thus giving the 2-pyridones of the formula (I-g)
in which
R1, R2 and R3 have the meanings given above and
Xc represents —C(═O)NR6R7;
or
according to process (3)
(f) 2-pyridones of the formula (I-e)
in which R1, R2 and R3 have the meanings given above
are reacted, if appropriate in the presence of diluents and if appropriate in the presence of basic reaction auxiliaries, thus giving the 2-pyridones of the formula (I-h)
in which R1, R2 and R3 have the meanings given above;
and that 2-pyridinols of the formula (II)
in which
X and R2a have the meanings given above, and
R3a and R4 each represent acetyl
are obtained by reacting,
according to process (4),
(g) 2-pyridones of the formula (I-i)
in which R2a, R3 and X have the meanings given above
with an acetylating agent, if appropriate in the presence of a diluent and if appropriate in the presence of a basic reaction auxiliary.

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Dependencies are inferred from the claim text.

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Abstract

Process for preparing 2-pyridones of the formula (I)

in which
X represents hydrogen, —C(═O)OR5, —C(═O)NR6R7, —C(═O)CR8R9R10, or represents —C(═O)aryl or —(C═O)hetaryl, each of which is optionally substituted in the aryl or heteraryl moiety,
R1 represents hydrogen or alkyl, alkenyl, alkynyl, cycloalkyl, aryl, hetaryl, optionally mono- or polysubstituted by identical or different substituents,
R2 represents hydrogen, methyl or ethyl,
R3 represents hydrogen,
R5 represents hydrogen or alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, bicycloalkyl, aryl, hetaryl, optionally mono- or polysubstituted by identical or different substituents,
R6 represents hydrogen, C1-C8-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C3-C8-cycloalkyl;
C2-C6-haloalkyl, halo-C2-C4-alkoxy-C1-C4-alkyl, C3-C8-halocycloalkyl having in each case 1 to 9 fluorine, chlorine and/or bromine atoms;
(C1-C3-alkyl)carbonyl-C1-C3-alkyl, (C1-C3-alkoxy)carbonyl-C1-C3-alkyl;
halo-(C1-C3-alkyl)carbonyl-C1-C3-alkyl, halo-(C2-C3-alkoxy)carbonyl-C1-C3-alkyl having in each case 1 to 13 fluorine, chlorine and/or bromine atoms;
represents —CH2—C≡C—R11 or —CH2—CH═CH—R11,
R7 represents hydrogen or represents alkyl, alkenyl, alkynyl, cycloalkylalkyl, cycloalkenylalkyl, each of which is optionally mono- or polysubstituted by identical or different substituents, or represents -M-Q-Z,
R8 represents hydrogen, alkyl or haloalkyl,
R9 represents hydrogen, halogen or represents alkyl, alkenyl, alkynyl, alkoxy, alkylthio, cycloalkyl, cycloalkenyl, or bicycloalkyl, each of which is optionally mono- or polysubstituted by identical or different substituents,
R10 represents hydrogen or represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkenylalkyl, bicycloalkyl, bicycloalkylalkyl, aryl, arylalkyl, hetaryl or hetarylalkyl, each of which is optionally mono- or polysubstituted by identical or different substituents,
R9 and R10 furthermore together with the carbon atom to which they are attached form a carbocycle or heterocycle which may be saturated or unsaturated and which may be fused with a further carbocycle and which may furthermore optionally be substituted,
R11 represents hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C7-cycloalkyl, (C1-C4-alkoxy)carbonyl, (C3-C6-alkenyloxy)carbonyl, (C3-C6-alkynyloxy)carbonyl or cyano,
M represents in each case optionally substituted cycloalkylene, cycloalkenylene, bicycloalkylene, arylene or hetarylene,
Q represents a direct bond, C1-C4-alkylene, C2-C4-alkenylene, C1-C4-alkylenoxy, oxy-C1-C4-alkylene, O, S, SO, SO2 or NR12,
Z represents hydrogen or represents Z1, Z2, Z3, Z4, Z5 or Z6, where Q does not represent O, S, SO, SO2, NR12 if Z represents hydrogen,
Z1 represents phenyl which is optionally mono- to pentasubstituted by identical or different substituents,
Z2 represents pyridinyl which is optionally mono- to trisubstituted by identical or different substituents,
Z3 represents cycloalkyl or bicycloalkyl, each of which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen, alkyl, cycloalkyl and/or —(CR13R14)mSiR15R16R17,
Z4 represents unsubstituted C1-C20-alkyl or represents C1-Cm-alkyl which is mono- or polysubstituted by identical or different substituents from the group consisting of halogen, alkylthio, alkylsulphynyl, alkylsulphonyl, alkoxy, alkylamino, dialkylamino, haloalkylthio, haloalkylsulphynyl, haloalkylsulphonyl, haloalkoxy, haloalkylamino, halodialkylamino, —SiR15R16R17 and C3-C6-cycloalkyl, where the cycloalkyl moiety for its part may optionally be mono- or polysubstituted by identical or different substituents from the group consisting of halogen and C1-C4-alkyl,
Z5 represents C2-C20-alkenyl or C2-C20-alkynyl, each of which is optionally mono- or polysubstituted by identical or different substituents from the group consisting of halogen, alkylthio, alkylsulphynyl, alkylsulphonyl, alkoxy, alkylamino, dialkylamino, haloalkylthio, haloalkylsulphynyl, haloalkylsulphonyl, haloalkoxy, haloalkylamino, halodialkylamino, —SiR15R16‘R17 and/or C3-C6-cycloalkyl, where the cycloalkyl moiety for its part may optionally be mono- or polysubstituted by identical or different substituents from the group consisting of halogen and C1-C4-alkyl,
Z6 represents a saturated or unsaturated 3- to 7-membered ring which is optionally mono- or polysubstituted and which contains a silicon atom as ring member, in which Q represents a direct bond or C1-C4-alkylene,
or
M-Q-Z together represent 1H-2,3-dihydroinden-4-yl, 1,3-dihydro-2-benzofuran-4-yl or 1,3-dihydro-2-benzothien-4-yl, each of which is optionally mono- to trisubstituted by methyl, or represent 1,2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalen-5-yl,
R12 represents hydrogen, C1-C8-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C2-C6-haloalkyl, C3-C6-haloalkenyl, C3-C6-halo-alkynyl or C3-C6-cycloalkyl,
R13 represents hydrogen or C1-C4-alkyl,
R14 represents hydrogen or C1-C4-alkyl,
m represents 0, 1, 2 or 3,
R15 and R16 independently of one another represent hydrogen, C1-C8-alkyl, C1-C8-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl or C1-C6-haloalkyl,
R17 represents hydrogen, C1-C8-alkyl, C1-C8-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, C3-C6-cycloalkyl, or represents in each case optionally substituted phenyl or phenylalkyl,
characterized in that
according to process (1)
(a) oxymalonic acid derivatives of the formula (III)
in which
Y represents halogen, hydroxyl or —O-AM in which
AM represents an alkali metal selected from the group consisting of lithium, sodium, potassium and caesium,
are reacted with amides of the formula (IV)
in which
R1a represents alkyl, alkenyl, alkynyl, cycloalkyl, aryl, hetaryl, optionally mono- or polysubstituted by identical or different substituents,
Xa represents —C(═O)OR5a, —C(═O)CR8R9R10 or represents —C(═O)aryl or —(C═O)hetaryl which is optionally substituted in the aryl or heteraryl moiety, and
R5a represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, bicycloalkyl, aryl, hetaryl, optionally mono- or polysubstituted by identical or different substituents, and
R8, R9 and R10 have the meanings given above,
if appropriate in the presence of a diluent,
thus giving 2-pyridones of the formula (I-b)
in which Xa, X1a and R3 have the meanings given above
which are subsequently
(b) if appropriate reacted with an alkylating agent, if appropriate in the presence of a base, a Lewis acid or a molecular sieve and, if appropriate, in the presence of a diluent,
giving 2-pyridones of the formula (I-c)
in which
Xa, R1a and R3 have the meanings given above, and
R2a represents methyl or ethyl,
after which
(c) if appropriate the 2-pyridones of the formula (I-b) or the formula (I-c) are hydrogenated in the presence of a transition metal catalyst or in the presence of Lewis or Brønsted acids, thus giving 2-pyridones of the formula (I-d)
in which R2, R3 and Xa have the meanings given above,
and
(d) if appropriate, the 2-pyridones of the formula (I-b) or the formula (I-c) or the formula (I-d), in which Xa represents —C(═O)OR5a are cleaved, thus giving the 2-pyridones of the formula (I-e)
in which R1, R2 and R3 have the meanings given above;
or according to process (2)
(e) 2-pyridones of the formula (I-f)
in which
R1, R2 and R3 have the meanings given above and
Xb represents —C(═O)OH or —C(═O)OR5b in which
R5b represents C1-C4-alkyl,
are reacted with amines of the formula (VIII)
in which R6 and R7 have the meanings given above,
if appropriate in the presence of diluents and if appropriate in the presence of reaction auxiliaries, thus giving the 2-pyridones of the formula (I-g)
in which
R1, R2 and R3 have the meanings given above and
Xc represents —C(═O)NR6R7;
or
according to process (3)
(f) 2-pyridones of the formula (I-e)
in which R1, R2 and R3 have the meanings given above
are reacted, if appropriate in the presence of diluents and if appropriate in the presence of basic reaction auxiliaries, thus giving the 2-pyridones of the formula (I-h)
in which R1, R2 and R3 have the meanings given above;
and that 2-pyridinols of the formula (II)
in which
X and R2a have the meanings given above, and
R3a and R4 each represent acetyl
are obtained by reacting,
according to process (4),
(g) 2-pyridones of the formula (I-i)
in which R2a, R3 and X have the meanings given above
with an acetylating agent, if appropriate in the presence of a diluent and if appropriate in the presence of a basic reaction auxiliary.

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