Organic compounds -- part of the class 532-570 series – Organic compounds – Nitriles
Reexamination Certificate
2000-09-14
2001-07-17
Ramsuer, Robert W. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Nitriles
Reexamination Certificate
active
06262291
ABSTRACT:
The invention relates to a novel process for preparing substituted cyanophenyluracils, said compounds being known as herbicidally active compounds, to novel substituted N-(cyanophenyl)aminoalkenamides as intermediates therefor and to an inventive process for their preparation.
It is known that certain substituted cyanophenyluracils can be prepared by reaction of appropriate aminoalkenoic esters with appropriate cyanophenyl isocyanates or with cyanophenylurethanes in the presence of reaction auxiliaries, such as, for example, sodium hydride (cf. EP 648749). However, with this procedure, yield and quality of the resulting products are not always entirely satisfactory, and the reaction components required are not very suitable for industrial purposes.
Furthermore, it is known that certain substituted phenyluracils can be prepared by reaction of appropriate substituted N-(phenyl)aminoalkenamides with suitable carbonic acid derivatives (cf. WO 95/32952). However, the synthetic croup described in this publication includes many steps and is complicated.
The present invention, accordingly, provides
(a) a process for preparing substituted cyanophenyluracils of the general formula (1)
in which
R
1
represents optionally substituted alkyl,
R
2
represents hydrogen, halogen or alkyl,
R
3
represents hydrogen or halogen and
R
4
represents amino, halogen or the grouping —N(R
5
)SO
2
R
6
,
in which
R
5
represents hydrogen or represents respectively optionally substituted alkyl, alkylcarbonyl, alkylsulphonyl, cycloalkylcarbonyl, cycloalkylsulphonyl, arylcarbonyl or arylsulphonyl and
R
6
represents respectively optionally substituted alkyl, cycloalkyl or aryl,
characterized in that substituted N-(cyanophenyl)aminoalkenamides of the general formula (II)
in which
R
1
, R
2
, R
3
and R
4
are each as defined above,
are reacted with carbonic acid derivatives of the general formula (III)
Z
1
—CO—Z
2
(III),
in which
Z
1
and Z
2
are identical or different and each represents halogen, alkoxy, aryloxy, imidazolyl or triazolyl,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent at temperatures between −20° C. and +150° C.,
(b) novel substituted N-(cyanophenyl)aminoalkenamides of the general formula (II)
in which,
R
1
represents optionally substituted alkyl,
R
2
represents hydrogen, halogen or alkyl,
R
3
represents hydrogen or halogen and
R
4
represents amino, halogen or the grouping —N(R
5
)SO
2
R
6
,
in which
R
5
represents hydrogen or represents respectively optionally substituted alkyl, alkylcarbonyl, alkylsulphonyl, cycloalkylcarbonyl, cycloalkylsulphonyl, arylcarbonyl or arylsulphonyl and
R6 represents respectively optionally substituted alkyl, cycloalkyl or aryl, and
(c) a process for preparing substituted N-(cyanophenyl)aminoalkenamides of the general formula (II), characterized in that cyanophenylpyrimidinones of the general formula (IV)
in which
R
1
, R
2
, R
3
and R
4
are each as defined above
are reacted with basic compounds in the presence of a diluent at temperatures between −20° C. and +100° C.
The present invention also provides a novel preparative route to substituted cyanophenyluracils of the general formula (I), which combines the steps described above in a general manner under (c) and (a).
It is surprising that this novel route gives substituted cyanophenyluracils of the general formula (I) in a much more simple way and also in higher yields and improved quality. Especially the smooth ring-opening reaction of cyanophenylpyrimidinones of the formula (IV) to give substituted N-(cyanophenyl)aminoalkenamides of the formula (II) constitutes a very surprising new way of preparing substituted N-(aryl)-&bgr;-aminoalkenamides.
The invention preferably relates to the preparation of compounds of the formula (I) and also of novel compounds of the formula (II), in which in each case
R
1
represents optionally fluorine- and/or chlorine-substituted alkyl having 1 to 4 carbon atoms,
R
2
represents hydrogen, fluorine, chlorine, bromine or alkyl having 1 to 4 carbon atoms,
R
3
represents hydrogen, fluorine, chlorine or bromine and
R
4
represents amino, fluorine, chlorine or the grouping —N(R
5
)SO
2
R
6
in which
R
5
represents hydrogen or represents respectively optionally fluorine- and/or chlorine-substituted alkyl, alkylcarbonyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, represents respectively optionally fluorine- and/or chlorine-substituted cycloalkylcarbonyl or cycloalkylsulphonyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups, or represents respectively optionally fluorine- and/or chlorine-substituted phenylcarbonyl or phenylsulphonyl, and
R
6
represents optionally fluorine- and/or chlorine-substituted alkyl having 1 to 6 carbon atoms, represents optionally fluorine- and/or chlorine-substituted cycloalkyl having 3 to 6 carbon atoms, or represents respectively optionally fluorine- and/or chlorine-substituted phenyl.
The invention relates in particular to the preparation of compounds of the formula (I) and to novel compounds of the formula (II) in which in each case
R
1
represents respectively optionally fluorine- and/or chlorine-substituted methyl or ethyl,
R
2
represents hydrogen, fluorine, chlorine, bromine, methyl or ethyl,
R
3
represents hydrogen, fluorine or chlorine and
R
4
represents fluorine, chlorine or the grouping —N(R
5
)SO
2
R
6
in which,
R
5
represents hydrogen or represents respectively optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, acetyl, propionyl, methylsulphonyl or ethylsulphonyl, represents respectively optionally fluorine- and/or chlorine-substituted cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cyclopropylsulphonyl, cyclobutylsulphonyl, cyclopentylsulphonyl or cyclohexylsulphonyl, or represents respectively optionally fluorine- and/or chlorine-substituted phenylcarbonyl or phenylsulphonyl, and
R
6
represents respectively optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectively optionally fluorine- and/or chlorine-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or represents respectively optionally fluorine- and/or chlorine-substituted phenyl.
If, for example, in the process step described above under (c) (process (c)) 3-(4-cyano-2,5-difluorophenyl)-6-trifluoromethylpyrimidin-4-one is used as starting material, and the resulting product is reacted according to the process step described above under (a) (process (a)) with, for example, phosgene, then the reaction may be outlined by the following scheme:
The carbonic acid derivatives to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I) are defined in a general way by formula (III). In Formula (III), Z
1
and Z
2
are identical or different and preferably represent fluorine, chlorine, bromine, C
1
-C
4
-alkoxy, phenoxy, imidazolyl or triazolyl, in particular chlorine, methoxy, ethoxy or phenoxy.
Examples of starting materials of the formula (III) are:
Phosgene (and also its “dimers” or “trimers” —diphosgene or triphosgene), dimethyl carbonate, diethyl carbonate, diphenyl carbonate, methyl chloroformate, ethyl chloroformate and also carbonyl-bis-imidazole.
The starting materials of the formula (III) are known chemicals for synthesis.
The cyanophenylpyrimidinones to be used as starting materials in process (c) according to the invention for preparing compounds of the formula (II) are defined in a general way by the formula (IV). In the formula (IV), R
1
, R
2
, R
3
and R
4
preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferred or particularly preferred for R
1
, R
2
, R
3
and R
4
.
The starting materials of the formula (IV) are known and/or ca
Andree Roland
Drewes Mark Wilhelm
Lantzsch Reinhard
Wroblowsky Heinz-Jurgen
Bayer Aktiengesellschaft
Norris & McLaughlin & Marcus
Ramsuer Robert W.
Sackey Ebenezer
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