Organic compounds -- part of the class 532-570 series – Organic compounds – Nitrogen attached directly or indirectly to the purine ring...
Reexamination Certificate
2000-05-08
2001-05-01
Ford, John M. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Nitrogen attached directly or indirectly to the purine ring...
C544S311000, C544S312000, C544S313000, C544S314000
Reexamination Certificate
active
06225470
ABSTRACT:
This is a 371 of PCT/EP90/069,591, filed May 1, 1990.
The invention relates to a novel process for preparing ar(alk)yluracils, which are known as herbicidally active compounds, to novel intermediates for this purpose and to processes for their preparation.
It is known that certain substituted cyanophenyluracils can be prepared by reacting appropriate aminoalkenoic esters with appropriate cyanophenyl isocyanates or cyanophenylurethanes in the presence of reaction auxiliaries, such as, for example, sodium hydride (cf. EP-A-648749). However, in this procedure, the yield and the quality of the resulting products are not always entirely satisfactory and the reaction components which are required are not particularly suitable for industrial purposes.
Furthermore, it is known that certain substituted phenyluracils can be prepared by reacting appropriate substituted N-phenylaminoalkenamides with suitable carbonic acid derivatives (cf. WO-A-95/32952). However, the synthesis route described in this publication involves many steps and is complicated.
Furthermore, it is known that substituted cyanophenyluracils are obtained by reacting appropriate cyanophenylpyrimidinones with bases and reacting the substituted N-cyanophenyl-aminoalkenamides formed with carbonic acid derivatives, such as, for example, phosgene or diphenyl carbonate (cf. DE-A-19604582). However, the desired products are not always obtained in high yields and in satisfactory quality.
The invention provides
(a) a process for preparing ar(alk)yluracils of the general formula (I)
in which
A represents a single bond or represents alkanediyl,
Ar represents optionally substituted aryl,
R
1
represents optionally substituted alkyl and
R
2
represents hydrogen, halogen or alkyl,
characterized in that substituted aminoalkenamides of the general formulae (IIa) or (IIb)
in which
A, Ar, R
1
and R
2
are as defined above
are heated at temperatures between 40° C. and 120° C., if appropriate in the presence of a diluent,
(b) novel substituted amninoalkenamides of the general formulae (IIa) or (IIb)
in which
A represents a single bond or represents alkanediyl,
Ar represents optionally substituted aryl,
R
1
represents optionally substituted alkyl and
R
2
represents hydrogen, halogen or alkyl,
(c) a process for preparing substituted aminoalkenami des of the general formula (IIa), characterized in that substituted pynimidones of the general formula (III)
in which
A, Ar, R
1
and R
2
are as defined above
are reacted at temperatures between 0° C. and 100° C. with an acid, if appropriate in the presence of a diluent,
(d) a process for preparing substituted aminoalkenamides of the general formula (IIb), characterized in that substituted oxazinones of the general formula (IV)
in which
R
1
and R
2
are as defined above
are reacted with ar(alk)ylamines of the general formula (V)
H
2
N—A—Ar (V)
in which
A and Ar are as defined above
at temperatures between 0° C. and 150° C., if appropriate in the presence of a diluent,
(e) novel substituted pyrimidones of the general formula (III)
in which
A represents a single bond or represents alkanediyl,
Ar represents optionally substituted aryl,
R
1
represents optionally substituted alkyl and
R
2
represents hydrogen, halogen or alkyl,
(f) a process for preparing substituted pyrimidones of the general formula (III), characterized in that substituted aminoalkenamides of the general formula (VI)
in which
A, Ar, R
1
and R
2
are as defined above
are reacted with dichloromethylene-dimethylimmonium chloride of the formula (VII)
Cl
2
C═N(CH
3
)
2
Cl (VII)
at temperatures between 0° C. and 100° C. in the presence of a diluent.
The invention also provides the novel route for preparing ar(alk)yluracils of the general formula (I) which involves the steps set forth in a general manner above under (f), (c) and (a).
It is surprising that the ar(alk)yluracils of the general formula (I) can be prepared in a simple manner in high yields and good quality by this novel route.
The oxazinones of the general formula (IV), which are to be used, if appropriate, as intermediates are known and/or can be prepared by processes known per se (cf. Bull. Soc. Chim. Belg. 101 (1992), 313-321; Preparation Examples).
The substituted aminoalkenamides of the general formula (VI) to be used, if appropriate, as intermediates are known and/or can be prepared by processes known per se (cf. DE-A-19604582; Preparation Examples).
Preferred meanings in the formulae (I), (IIa), (IIb), (III) and (VI) are
A represents a single bond or represents straight-chain or branched alkanediyl having 1 to 4 carbon atoms,
Ar represents phenyl or naphthyl, each of which is optionally substituted by amino, cyano, halogen or the grouping —N(R
3
)SO
2
R
4
,
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 or represents in each case optionally fluorine- and/or chlorine-substituted alkyl, alkylcarbonyl or alkylsulphonyl having in each case 1 to 6 carbon atoms in the alkyl groups, represents in each case optionally fluorine- and/or chlorine-substituted cycloalkylcarbonyl or cycloalkylsulphonyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups, or represents in each case optionally fluorine- and/or chlorine-substituted phenylcarbonyl or phenylsulphonyl, and
R
4
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 in each case optionally fluorine- and/or chlorine-substituted phenyl.
Particularly preferred meanings in the formulae (I), (IIa), (IIb), (III) and (IV) are
A represents a single bond or represents a methylene group,
Ar represents phenyl which is optionally substituted by amino, cyano, fluorine, chlorine, bromine or the grouping —N(R
3
)SO
2
R
4
,
R
1
represents in each case optionally fluorine- and or chlorine-substituted methyl or ethyl,
R
2
represents hydrogen, fluorine, chlorine, bromine, methyl or ethyl,
R
3
represents hydrogen or represents in each case optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, acetyl, propionyl, methylsulphonyl or ethylsulphonyl, represents in each case optionally fluorine- and/or chlorine-substituted cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cyclopropylsulphonyl, cyclobutylsulphonyl, cyclopentylsulphonyl or cyclohexylsulphonyl, or represents in each case optionally fluorine- and/or chlorine-substituted phenylcarbonyl or phenylsulphonyl, and
R
4
represents in each case optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case optionally fluorine- and/or chlorine-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or represents in each case optionally fluorine- and/or chlorine-substituted phenyl.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another at will, i.e. including combinations between the given preferred ranges.
The processes according to the invention described above under (a), (c), (d) and (f) are abbreviated below as “process (a)”, “process (c)”, “process (d)” and “process (e)”.
Using, for example, N-(4-cyano-2,5-difluoro-phenyl)-3-amino-4,4,4-trifluoro-2-butenamide and dichloromethylene-dimethylimmonium chloride as starting materials, reacting the product obtained in their reaction according to process (f), for example, with hydrogen bromide according to process (c) and heating the resulting product according to process (a), the course of the reaction can be illustrated by the following formula scheme:
The process (f) according to
Gallenkamp Bernd
Lantzsch Reinhard
Mulder Lubbertus
Rohe Lothar
Bayer Aktiengesellschaft
Ford John M.
Gil Joseph C.
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