Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2000-12-05
2002-03-19
Higel, Floyd D. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C548S377100, C504S138000, C504S139000
Reexamination Certificate
active
06359143
ABSTRACT:
This application is a 371 of PCT/JP99/02968 filed on Jun. 3, 1990.
1. Field of the Invention
The present invention relates to a novel thiophenol compound substituted with a hetero ring, which is useful as an intermediate to produce agrochemicals, particularly herbicides, an intermediate to produce the said compound, and processes for their preparation.
2. Background Art
The thiophenol compounds substituted with hetero rings of the present invention are important as intermediates to produce benzoyl pyrazole compounds with herbicidal activities, which are disclosed in, for example, WO 96/26206, WO 97/41118 and WO 97/46530.
With regard to reactions to synthesize cyclohexenone derivatives from enol lactones, similar to processes for the preparation of the cyclohexenone compounds of the present invention, for example, a reaction of an enol lactone with a lithioacetate (Reaction Scheme A below) is described in Tetrahedron Letters 31, 3421 (1990) and a reaction between an enol lactone and a Grignard reagent (Reaction Scheme B below) in J. Org. Chem. 54, 4704 (1989).
There are, however, no reports on direct reactions between enol lactones and nitrogen containing hetero ring compounds such as isoxazole.
DISCLOSURE OF THE INVENTION
It is an object of the present invention to provide novel thiophenol compounds substituted with hetero rings, which are useful as intermediates to produce agrochemicals and medicines, particularly compounds with herbicidal activities, intermediates to prepare them, and simpler and more economically advantageous processes for the preparation of thiophenol compounds substituted with hetero rings, which require multistage processes.
The present invention relates to
1. thiophenol compounds substituted with hetero rings represented by Formula (1)
[wherein R
1
is C
1-4
alkyl;
R
2
is hydrogen or C
1-4
alkyl;
R
3
is hydrogen, cyano, amide, C
1-4
alkylcarbonyl or C
1-4
alkoxycarbonyl;
R
4
is C
1-4
alkyl; and
Q is the following Q1, Q2 or Q 3
(wherein r
1
to r
9
are, each independently, hydrogen or C
1-4
alkl, or r
3
and r
5
may join to form a bond)]; and
2. cyclohexenone compounds, intermediates to produce the said compounds, represented by Formula (2)
(wherein R
1
, R
2
, R
3
and Q are as defined above);
3. processes for the preparation of thiophenol compounds substituted with hetero rings, represented by the above Formula (1), characterized in reacting a cyclohexenone compound of the above Formula (2) with an alkane thiol of Formula R
4
SH (wherein R
4
is as defined above) to give a compound represented by Formula (3)
(wherein R
1
to R
4
and Q are as defined above; n is 0, 1 or 2; and the compound of Formula (3) is either a compound of the following Formula (3-1), (3-2), (3-3) or (3-4))
followed by dehydrogenation;
4. compounds represented by Formula (4)
(wherein R
1
to R
3
are as defined above; and R
5
is hydrogen, cyano, C
1-4
alkylcarbonyl or C
1-4
alkoxycarbonyl);
5. processes for the preparation of compounds represented by the above Formula (4), characterized in reacting an enol lactone of Formula (5)
(wherein R
1
to R
3
are as defined above) with a compound of Formula Q—CH
2
R
5
(wherein Q and R
5
are as defined above); and
6. processes for the preparation of cyclohexenone compounds represented by the above Formula (2), characterized in reacting an acid or a base on a compound of the above Formula (4).
An outline of the present invention may be represented by the following reaction scheme:
(wherein R
1
to R
5
, n and Q are as defined above).
The present invention is further described in detail in the following.
IMPLEMENTATION OF THE INVENTION
In the definitions of the compounds represented by the above Formulae (1), (2), (3), (4) and (5),
R
1
is C
1-4
alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl;
R
2
is hydrogen, or C
1-4
alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl;
R
3
is hydrogen, cyano, amide, C
1-4
alkylcarbonyl such as acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl and pivaloyl, or C
1-4
alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, s-butoxycarbonyl and t-butoxycarbonyl;
R
4
is C
1-4
alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl;
Q is either a group of the following Q1, Q2 or Q3
wherein r
1
to r
9
are, each independently, hydrogen, or C
1-4
alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl. r
3
and r
5
may join to form a bond. Of them, r
1
to r
9
are more preferably hydrogen, methyl or ethyl.
More preferred hetero rings represented by Q include isooxazolyl groups such as isooxazol-3-yl, 4-methyl-isooxazol-3-yl, 5-methyl-isooxazol-3-yl, 4,5-dimethylisooxazol-3-yl, 4-ethyl-isooxazol-3-yl, 5-ethyl-isooxazol-3-yl, 4,5-diethylisooxazol-3-yl, isooxazol-5-yl, 3-methyl-isooxazol-5-yl, 4-methyl-isooxazol-5-yl, 3,4-dimethylisooxazol-5-yl, 3-ethyl-isooxazol-
5
-yl, 4-ethyl-isooxazol-5-yl and 3,4-diethylisooxazol-5-yl; isooxazoline groups such as isooxazolin-3-yl, 4-methyl-isooxazolin-3-yl, 5-methyl-isooxazolin-3-yl, 4-ethyl-isooxazolin-3-yl and 5-ethyl-isooxazolin-3-yl; and pyrazolyl groups such as pyrazol-3-yl, 1-methylpyrazol-3-yl, 1-ethylpyrazol-3-yl, 1-propylpyrazol-3-yl and 1,5-dimethylpyrazol-3-yl.
The compounds of the present invention may be produced according to the following processes:
(Process 1) Process for the preparation of a thiophenol compound substituted with a hetero ring represented by Formula (1)
(wherein R
1
to R
4
, n and Q are as defined above).
The process is to obtain a compound of (1) by S-alkylating a compound of Formula (2) to give an intermediate (3), followed by a dehydrogenation reaction.
The S-alkylation reaction is carried out by dissolving a cyclohexenone compound substituted with a hetero ring (2) in an appropriate inert solvent, and reacting it with 1 to 5 equivalents of alkane thiol at temperature between −20° C. and the boiling point of the solvent used. This reaction may proceed more smoothly by adding 0.01 to 2 equivalents of a compound including acids such as p-toluenesulfonic acid and sulfuric acid or Lewis acids such as aluminum chloride, zinc chloride and boron trifluoride etherate.
Solvents that may be used for this reaction include alcohols such as methanol and ethanol; halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene; hydrocarbons such as n-hexane, benzene and toluene; and ethers such as tetrahydrofuran (THF) and dimethoxyethane.
The next dehydrogenation reaction is carried out by dissolving a cyclohexene derivative or cyclohexane derivative (3) in an appropriate solvent and dehyrogenating it in the presence of a dehydrogenating agent at temperature between −10° C. and the boiling point of the solvent used.
Dehydrogenating agents used for the dehydrogenation reaction include quinones such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and tetrachloro-1,4-benzoquinone; halogens such as chlorine and bromine; halogenated imides such as N-chlorosuccinimide and N-bromosuccinimide; oxidizing agents such as manganese dioxide and nickel peroxide, or sulfur and sulfur coexisting with dimethyl sulfoxide.
Proper solvents used include hydrocarbons such as benzene, toluene and mesitylene; halogenated hydrocarbons such as chloroform and chlorobenzene; sulfur containing compounds such as dimethyl sulfoxide and sulfolane; alcohols such as ethanol and ethylene glycol; ethers such as ether and THF; and acetic acid.
(Process 2) Process for the preparation of a cyclohexenone compound of Formula (2) from an enol lactone compound represented by Formula (5)
(wherein R
1
to R
3
, R
5
and Q are as defined above.)
A compound (2) of the present invention can be produced by that an enol lactone (5) and a hetero-ring derivative (6) are reacted in an inert solvent at temperature between 0° C. and the boiling point of the solvent used in the presence of a base, and the obtained compo
Adachi Hiroyuki
Aihara Toshio
Sagae Takahiro
LaPointe Dennis G.
Mason & Assoc., P.A.
Nippon Soda Co. Ltd.
Saeed Kamal
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