Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
1998-08-25
2001-07-17
Raymond, Richard L. (Department: 1624)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
C544S278000
Reexamination Certificate
active
06262058
ABSTRACT:
The present invention relates to novel pyrimidin-4-one derivatives of formula I, which have pesticidal activity, in particular fungicidal activity,
wherein
R
1
=C
1
-C
6
alkyl, C
2
-C
6
alkenyl, C
2
-C
6
alkynyl, C
3
-C
6
cycloalkyl, each of which is unsubstituted or substituted by halogen;
R
2
=OR
5
;
R
3
and R
4
are each independently of the other hydrogen, halogen;
R
5
is C
1
-C
6
alkyl or C
3
-C
6
cycloalkyl each unsubstituted or halogen-substituted; and
A=thienyl.
The invention also relates to the preparation of these compounds, to agrochemical compositions comprising as active ingredient at least one of these compounds, as well as to the use of the active ingredients or compositions for pest control, in particular as fungicides, in agriculture and horticulture.
The compounds I and, optionally, their tautomers may be obtained in the form of their salts. Because the compounds I have at least one basic centre they can, for example, form acid addition salts. Said acid addition salts are, for example, formed with mineral acids, typically sulfuric acid, a phosphoric acid or a hydrogen halide, with organic carboxylic acids, typically acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, with hydroxycarboxylic acids, typically ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or with benzoic acid, or with organic sulfonic acids, typically methane acid or p-toluenesulfonic acid.
Together with at least one acidic group, the compounds of formula I can also form salts with bases. Suitable salts with bases are, for example, metal salts, typically alkali metal salts or alkaline earth metal salts, e.g. sodium salts, potassium salts or magnesiumsalts, or salts with ammonia or an organic amine, e.g. morpholine, piperidine, pyrrolidine, a mono-, di- or trialkylamine, typically ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or trihydroxyalkylamine, typically mono-, di- or triethanolamine. Where appropriate, the formation of corresponding internal salts is also possible. Within the scope of this invention, agrochemically acceptable salts are preferred.
Where asymmetrical carbon atoms are present in the compounds of formula I, these compounds are in optically active form. Owing to the presence of double bonds, the compounds can be obtained in the [E] and/or [Z] form. Atropisomerism can also occur. The invention relates to the pure isomers, such as enantiomers and diastereomers, as well as to all possible mixtures of isomers, e.g. mixtures of diastereomers, racemates or mixtures of racemates.
The general terms used hereinabove and hereinbelow have the following meanings, unless otherwise defined:
Alkyl groups are, in accordance with the number of carbon atoms, straight-chain or branched and will typically be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, tert-amyl, 1-hexyl or 3-hexyl.
Alkenyl will be understood as meaning straight-chain or branched alkenyl such as allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Preferred alkenyl radicals contain 3 to 4 carbon atoms in the chain.
Alkynyl can likewise, in accordance with the number of carbon atoms, be straight-chain or branched and is typically propargyl, but-1-yn-1-yl or but-1-yn-3-yl. The preferred meaning is propargyl.
Halogen and halo substituents will be understood generally as meaning fluoro, chloro, bromo or iodo. Fluoro, chloro or bromo are preferred meanings.
Haloalkyl can contain identical or different halogen atoms, typically fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl, chloro methyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3,3,3-trifluoropropyl.
Cycloalkyl is, depending on the ring size, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
A is thienyl, including all 3 isomers.
A special group within the scope is that of the compounds of formula I, wherein
R
1
=C
3
-C
6
alkyl, cyclopropyl, cyclobutyl;
R
2
=OR
5
;
R
3
and R
4
are each independently of the other hydrogen, chloro, bromo, iodo;
R
5
C
2
-C
6
alkyl, cyclopropyl or cyclobutyl (subgroup D).
A preferred group within the scope of subgroup D is that of the compounds of the formula I, wherein
A=thienyl[2.3-d],
R
1
=C
3
-C
6
alkyl,
R
2
=OR
5
,
R
3
and R
4
are each independently of the other hydrogen, chloro, bromo, iodo and
R
5
=C
2
-C
6
alkyl (subgroup E).
The most preferred compounds of the invention disclosed herein are the following ones:
6-Chloro-2-propoxy-3-propyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.41),
6-Chloro-2-propoxy-3-isobutyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.42),
6-Chloro-2-isobutoxy-3-propyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.83),
6-Chloro-2-propoxy-3-butyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.106),
6-Bromo-2-propoxy-3-butyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.107),
6-Chloro-2-butoxy-3-propyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.112),
6-Bromo-2-butoxy-3-propyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.113),
6-Chloro-2-butoxy-3-butyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.129),
6-Bromo-2-butoxy-3-butyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.130),
6-Chloro-2-butoxy-3-isobutyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.131),
6-Bromo-2-butoxy-3-isobutyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.132),
6-Bromo-2-propoxy-3-isobutyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.133),
6-Chloro-2-ethoxy-3-isobutyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.134),
6-Bromo-2-ethoxy-3-isobutyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.135),
6-Bromo-2-isobutoxy-3-propyl-3H-thieno[2.3-d]pyrimidin-4-one (No. 2.136).
The compounds of formula I can be prepared as follows
The compounds of formula I are preferably prepared starting from &agr;-amino-&bgr;-carboalkoxyheterocycles or &agr;-amino-&bgr;-carbocyclic acid heterocycles, some of which, where Het=thienyl, are commercially available (2 isomers). The methyl thiophene-2-amino-3-carboxylate can be prepared, for example, in accordance with Acta Pharm. Suecica 1968, Vol. 5, p.563, according to S. Gronowitz et al. Other heterocycles can be prepared according to instructions in the literature. The synthesis of, for example, ethyl 5-aminothiazole-4-carboxylate and ethyl 5-amino-2-methylthiazole-4-carboxylate is described by Golankiewicz et al. in Tetrahedron 1985, 41, 5989. The reaction of the &agr;-amino-&bgr;-carboalkoxyheterocycles or &agr;-amino-&bgr;-carbocyclic acid heterocycles with thiophosgene (step 1a in scheme 1) is conveniently carried out in the presence of a base, such as NaOH, KOH, CaCO
3
, Na
2
CO
3
, K
2
CO
3
, NaHCO
3
, N(Et)
3
, pyridine, and others, in solvents, such as CH
2
Cl
2
, CHCl
3
, ether, tetrahydrofuran and others, possibly in a 2 phase mixture consisting of CHCl
3
/water or CH
2
Cl
2
/water, or toluene/water in the temperature range from 0° C. to reflux temperature. The resulting isothiocyanates are then converted with primary amines, such as n-butylamine, n-propylamine, isopropylamine, allylamine, propargylamine, cyclopropylamine, and others, in a solvent (ether, tetrahydrofuran, CH
2
Cl
2
, CHCl
3
, benzene, toluene, dimethylformamide, dimethylsulfoxide) at 0° C. to reflux temperature into the thioureaheterocycles IV (step 2 in scheme 1), which can also be prepared via reaction of the heterocyclic amines II with isothiocyanatoalkanes such as 1-isothiocyanatopropane, 1-isothiocyanatobutane and others in ethanol, n-propanol, n-butanol, dimethylformamide or dimethylsulfoxide as solvents at temperatures between 50° C. and reflux temperature (step 1b in scheme 1). The thioureaheterocycles IV, in most cases, cyclise immediately (step 3 in scheme 1). In some cases, the cyclysation is carried out in the presence of stronger bases, such as potassium tert-butylate, sodium hydride or potassium hydride in solvents such as tetrahydrofuran, di
Raymond Richard L.
Syngenta Crop Protection Inc.
Teoli, Jr. William A.
LandOfFree
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