Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
1998-03-06
2001-02-13
Gerstl, Robert (Department: 1613)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
active
06187927
ABSTRACT:
The invention relates to a process for preparing a known compound of the formula
in which A is chlorine or 3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazin-5-yl, which process comprises
a) reacting a compound of the formula
in which X is a leaving group, if desired in the presence of a base, with a dehydrating agent, a halogenating agent and a sulfurizing agent to give the compound of the formula I, in which A is chlorine, or
b1) reacting a compound of the formula II, if desired in the presence of a base, with a dehydrating agent to give a compound of the formula
in which X is as defined for the formula II, and
b2) reacting the compound thus obtainable of the formula III with a halogenating agent and a sulfurizing agent, if desired in the presence of a base or acid, to give the compound of the formula I, in which A is chlorine, or
c) reacting a compound of the formula
which is known or can be prepared in analogy to corresponding known compounds and in which X is as defined for the formula II, with a compound of the formula
HC(R
1
)(R
2
)R
3
V,
which is known or can be prepared in analogy to corresponding known compounds and in which either R
1
and R
2
together are oxo and R
3
is hydroxy, C
1
-C
6
alkoxy or N(R
4
)R
5
, R
4
and R
5
being, independently of one another, hydrogen or C
1
-C
6
alkyl, or R
1
, R
2
and R
3
, independently of one another, are C
1
-C
6
alkoxy, to give a compound of the formula II and reacting the compound thus obtainable of the formula II either in accordance with the process variant a) or in accordance with the process variant b1)/b2) to give the compound of the formula I, in which A is chlorine, or
d) preparing the compound of the formula I in which A is chlorine, either in accordance with the process variant a) or in accordance with the process variant b1)/b2) or in accordance with the process variant c) and reacting the compound thus obtainable of the formula I, in which A is chlorine, if desired in the presence of a base, with the known compound 3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine or with the known tautomeric compound 3-methyl-4-nitroamino-2,3-dihydro-6H-1,3,5-oxadiazine, respectively, to give the compound of the formula I, in which A is 3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazin-5-yl;
to the compounds of the formulae II and III; to the use thereof; and to a process for the preparation thereof.
The general terms used above and below, unless defined otherwise, are as defined below.
Suitable leaving groups X are, for example, C
1
-C
6
alkoxy, halo-C
1
-C
6
alkoxy, C
1
-C
6
alkanoyloxy, C
1
-C
6
alkylthio, halo-C
1
-C
6
alkylthio, C
1
-C
6
alkylsulfonyloxy, halo-C
1
-C
6
alkylsulfonyloxy, phenylsulfonyloxy, tolylsulfonyloxy or halogen, preferably halogen, particularly bromine, or preferably chlorine.
Suitable dehydrating agents are, for example, thionyl chloride, triphenylphosphine/triethylamine, triphenylphosphine/azodicarboxylic ester, phosphorus oxytrichloride, phosphorus oxytrichloride/amine base, phosgene, phosgene/triethylamine, diphosgene, diphosgene/triethylamine, triphosgene, triphosgene/triethylamine, di-2-pyridylsulfite, benzenesulfonyl chloride, toluenesulfonyl chloride or toluenesulfonyl chloride/quinoline, preferably thionyl chloride or phosphorus oxytrichloride, in particular thionyl chloride.
Suitable halogenating agents are, for example, elemental chlorine, thionyl chloride, poly(sulfur dichloride), sulfur dichloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride or mixtures of two or more than two of these compounds, preferably thionyl chloride, sulfur dichloride or a mixture of these two compounds, particularly sulfur dichloride or a mixture of thionyl chloride and sulfur dichloride.
Suitable sulfurizing agents are, for example, elemental sulfur, poly(sulfur dichloride) or sulfur dichloride, preferably sulfur dichloride.
Preferably, reagents are used which simultaneously act as halogenating agents and sulfurizing agents, such as poly(sulfur dichloride) or sulfur dichloride, preferably sulfur dichloride.
The reactions described above and below are carried out, as required, in the absence or presence of a suitable solvent or diluent or a mixture of the same, with cooling, at room temperature or with heating, for example in a temperature range from about −80° C. to the boiling temperature of the reaction medium, preferably from about −60° C. to about +200° C., in a closed vessel, under atmospheric, elevated or reduced pressure, in an inert-gas atmosphere and/or under anhydrous conditions. Particularly advantageous reaction conditions are described below and can be taken, in particular, from the preparation examples.
Variant a)
The reaction partners can be reacted with one another without addition of a solvent or diluent. However, the addition of an inert solvent or diluent or a mixture of the same can also be advantageous, its amount not being critical. Examples of solvents or diluents of this type are in particular: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphorotriamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. Preferably, the reaction is carried out without addition of an inert solvent or diluent, but in the presence of a, preferably great, excess of the dehydrating agent, if this is liquid at the reaction temperature.
The reaction can be carried out, if desired, in the presence of a base as catalyst. Suitable bases for facilitating the reaction are, for example, alkali metal hydroxides or alkaline earth metal hydroxides, alkali metal hydrides or alkaline earth metal hydrides, alkali metal amides or alkaline earth metal amides, alkali metal alkanolates or alkaline earth metal alkanolates, alkali metal acetates or alkaline earth metal acetates, alkali metal carbonates or alkaline earth metal carbonates, alkali metal dialkylamides or alkaline earth metal dialkylamides or alkali metal alkylsilylamides or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic hetero-cycles, ammonium hydroxides or carbocyclic amines. Examples of such bases as sodium hydroxide, sodium hydride, sodium amide, sodium methanolate, sodium acetate, sodium carbonate, potassium tert-butanolate, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropyl-ethyl-amine, triethylendiamine, cyclohexylamine, N -cyclohexyl-N,N-dimethyl-amine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyl-trimethyl-ammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
The reaction can also be carried out in a two-phase mixture, for example a mixture of an organic solvent and an aqueous solution of a base, if desired in the presence of a phase transfer catalyst, for example a crown ether or a tetraalkylammonium salt.
The reaction is advantageously performed in a temperature range from about 0° C. to about 150° C., preferably from about 20° C. to about 100° C., preferably at the reflux temperature of the reaction mixture.
The molar ratio, in which the compound II and the sulfurizing agent are used in the reaction and which is defined by the quotient “
Gerstl Robert
Novartis Crop Protection, Inc.
Peabody, III John D.
Teoli, Jr. William A.
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