Organic compounds -- part of the class 532-570 series – Organic compounds – Four or more ring nitrogens in the bicyclo ring system
Reexamination Certificate
2001-01-12
2004-06-29
Seaman, D. Margaret (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Four or more ring nitrogens in the bicyclo ring system
C548S148000, C548S215000, C548S240000, C548S247000, C548S356100, C546S026000, C568S024000, C568S025000, C568S026000, C568S439000, C568S591000, C549S337000
Reexamination Certificate
active
06756497
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to benzoic acid derivatives useful as intermediates for the preparation of drugs and agricultural chemicals, particularly compounds having herbicidal activity, and to processes for the preparation thereof.
BACKGROUND ART
A method (A) of obtaining benzoic acid derivatives by reactions represented by the following reaction scheme,
between bicycloheptenone derivatives substituted with carboxylates and alcolates or the like is described in Tetrahedron, 42, 1741 (1986) and J. Org. Chem., 26, 2066 (1961).
However, there are no reports on reactions of bicycloheptenone derivatives substituted with hetero rings.
Known methods of dehalogenation of aromatic halogenated compounds include, for example, catalytic hydrogenolysis using palladium-carbon or Raney nickel as a catalyst, a method of using metal and metal salts such as lithium or sodium, hydrogenolytic reduction with tin hydride, reduction with metal-hydrogen complex compounds such as lithium aluminum hydride, and electrolytic reduction, which are described in Shin Jikkenkagakukouza, Vol. 14, Syntheses and Reactions of Organic Compounds [I] pages 22-30 (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.).
DISCLOSURE OF THE INVENTION
Substituted benzoic acid compounds, such as 4-alkylthiobenzoic acid derivatives, are important as intermediates for the preparation of agricultural chemicals and drugs. It has been desired to develop easy and industrially advantageous processes for the preparation of the said benzoic acid derivatives.
The present invention is directed to
(a) a benzoic acid derivative represented by Formula (1)
(wherein R
1
is hydrogen or C
1-4
alkyl,
R
2
is hydrogen or C
1-6
alkyl, and
Q is an optionally substituted, saturated or unsaturated, 5- or 6-membered heterocyclic group containing 1 to 4 N, O or S atoms and combining with the benzene ring via a carbon atom);
(b) a process for the preparation of a benzoic acid derivative of the said Formula (1), characterized by acting a base on a bicycloheptenone derivative of Formula (2)
(wherein R
1
and Q are as defined above), in an appropriate solvent;
(c) a process for the preparation of a benzoic acid derivative of the said Formula (1), characterized by consisting of a stage of preparing a bicycloheptenone derivative of the said Formula (2) by hydrolysis of a bicycloheptene derivative of Formula (3)
(wherein R
1
are as defined above, and X is chlorine or C
1-4
alkoxy and two X's may join to form a C
2-3
alkylenedioxy group optionally substituted with C
1-4
alkyl), and of acting a base and water or alcohol on a bicycloheptenone derivative of the said Formula (2) in an appropriate solvent;
(d) a process for the preparation of a bicycloheptene derivative of the said Formula (3), characterized by reacting a cyclopentadiene derivative of Formula (4)
(wherein X is as defined above) with an ethylene derivative substituted with a hetero ring, of Formula (5)
(wherein R
1
and Q are defined above);
(e) a bicycloheptenone derivative of the said formula (2); and
(f) a process for the preparation of a benzoic acid derivative of Formula (6)
(wherein R
1
, R
2
and Q are as defined above and R
4
is C
1-6
alkyl), characterized by reacting a 4,5-dichlorobenzoic acid derivative of the said Formula (1), with a mercaptan of Formula R
4
SH (wherein R
4
is as defined above) and a base or with a salt of mercaptan of Formula R
4
SH (wherein R
4
is as defined above)
In the definitions of the compounds of the said Formulae (1) and (2), which are the compounds of the present invention, the compounds of Formula (3) of their precursors and the compounds of Formula (6),
R
1
is hydrogen, or C
1-4
alkyl such as methyl, ethyl, propyl, isopropyl n-butyl isobutyl s-butyl or t-butyl;
a R
2
is hydrogen, or C
1-6
alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl or isohexyl;
X is halogen such as chlorine, or C
1-4
alkoxy such as methoxy, ethoxy, propoxy, isopropoxy or butoxy;
Two X's may join to form a C
2-3
alkylenedioxy group, such as ethylenedioxy or trimethylenedioxy;
Further, the said C
2-3
alkylenedioxy group may be substituted with C
1-4
alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl and t-butyl; and
Q is an optionally substituted, saturated or unsaturate 5- or 6-membered heterocyclic group containing 1 to 4 N, O or S atoms and combining with the benzene or bicycloheptane ring via a carbon atom.
Such hetero rings include, for example, 5-membered heterocyclic groups containing 1 to 4 N, O or S atoms, such as
2-furyl, 3-furyl,
2-thienyl, 3-thienyl,
2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,3-dihydrofuran4-yl,2,3-dihydrofuran-5-yl, 2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl,
2,3-dihydrothiophen-2-yl, 2,3-dihydrothiophen-3-yl, 2,3-dihydrothiophen-4-yl, 2,3-dihydrothiophen-5-yl, 2,5-dihydrothiophen-2-yl, 2,5-dihydrothiophen-3-yl,
pyrrol-2-yl, pyrrol-3-yl,
imidazol-2-yl, imidazol-4-yl, imidazol-5-yl,
2-imidazolin-2-yl, 2-imidazolin-4-yl, 2-imidazolin-5-yl,
pyrazol-3-yl, pyrozol-4-yl, pyrazol-5-yl,
oxazol-2-yl, oxazol-4-yl, oxazol-5-yl,
isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl.
1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,5-oxadiazol-3-yl,
4-thiazolyl, 4-thiazolyl, 5-thiazolyl,
isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl,
1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, 1,2,5-thiadiazol-3-yl,
1,2,4-triazol-3-yl, 1,2,4-triazol-5-yl, 1,3,4-triazol-2-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, tetrazol-5-yl,
2-pyrrolin-1-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 2-pyrrolin4-yl, 2-pyrrolin-5-yl,
2-oxazolin-2-yl, 2-oxazolin-4-yl, 2-oxazolin-5-yl, 3-oxazolin-2-yl, 3-oxazolin-4-yl, 3-oxazolin-5-yl, 4-oxazolin-2-yl, 4-oxazolin-4-yl, 4oxazolin-5-yl,
2-isoxazolin-3-yl, 2-isoxazolin-4-yl, 2-isoxazolin-5-yl,
3-isoxazolin-3-yl, 3-isoxazolin-4-yl, 3-isoxazolin-5-yl,
4-isoxazolin-3-yl, 4-isoxazolin-4-yl, 4-isoxazolin-5-yl,
2-thiazolin-2-yl, 4-thiazolin-4-yl, 4-thiazolin-5-yl,
2-isothiazolin-3-yl, 2-isothiazolin-4-yl, 2-isothiazolin-5-yl,
3-isothiazolin-3-yl, 3-isothiazolin-4-yl, 3-isothiazolin-5-yl,
4-isothiazolin-3-yl, 4-isothiazolin-4-yl, 4-isothiazolin-5-yl,
1-pyrazolin-3-yl, 1-pyrazolin-4-yl, 1-pyrazolin-5-yl,
2-pyrazolin-3-yl, 2-pyrazolin-4-yl, 2-pyrazolin-5-yl,
3-pyrazolin-3-yl, 3-pyrazolin-4-yl and 3-pyrazolin-5-yl; saturated 5-membered heterocyclic groups containing 1 to 4 N, O or S atoms, such as
2-pyrrolidinyl, 3-pyrrolidinyl,
2-tetrahydrofuranyl, 3-tetrahydrofuranyl,
2-tetrahydrothienyl, 3-tetrahydrothienyl,
2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl,
3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl,
2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl,
3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl,
2-imidazolidinyl, 4-imidazolidinyl,
1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,3,4-oxadiazolidin-2-yl,
1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,3,4-thiadiazolidin-2-yl,
1,3,4-triazolidin-2-yl,
1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl,
1,3-dithiolan-2-yl, 1,3-dithiolan-4-yl, and
1,3-oxathiolan-2-yl; and
6-membered heterocyclic groups containing 1 to 4 N, O or S atoms, such as
2-pyridyl, 3-pyridyl, 4-pyridyl,
3-pyridazinyl, 4-pyridazinyl,
2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl,
pyrazin-2-yl,
2H-pyran-3-yl, 2H-thiopyran-3-yl,
2-piperidinyl, 3-piperidinyl, 4-piperidinyl
2-piperadinyl,
2-morpholinyl, 3-morpholinyl,
5,6-dihydro-4H-1,3-thiazin-2-yl,
2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl,
2-tetrahydrothiopyranyl, 3-tetrahydrothiopyranyl and 4-tetrahydrothiopyranyl.
These groups may have one or more, same or different, substituents at arbitrary positions of the hetero rings. Such substituents include, for example, C
1-4
alkyl such as methyl, ethyl, propyl isopropyl, n-butyl, isobutyl, s-butyl and t-butyl, and C
1-4
haloalkyl such as chloromethyl, dichlorome
Adachi Hiroyuki
Hatano Masami
Nakagawa Yuuki
Yagihara Tomio
Yamaguchi Masao
Jacobson & Holman PLLC
Nippon Soda Co. Ltd.
Oh Taylor V
Seaman D. Margaret
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