Process for producing organotitanium compound and process...

Details Process for producing organotitanium compound and process... Process for producing organotitanium compound and process...

2001-12-13

2004-06-01

Huang, Evelyn Mei (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C546S002000, C546S324000, C546S339000, C556S052000, C556S012000, C556S465000, C556S432000, C556S489000, C560S008000, C560S009000, C560S103000, C568S034000, C548S101000, C548S406000, C549S466000

Reexamination Certificate

active

06743916

ABSTRACT:

BACKGROUND OF THE INVENTION
The present invention relates to a process for producing an organotitanium compound useful for production of pharmaceuticals and agricultural chemicals and their intermediates and also to a process for addition reaction involving the organotitanium compound. More particularly, the present invention relates to a process for producing an organotitanium compound useful for production of polysubstituted benzene or polysubstituted pyridine.
There is an established process known as Reppe reaction for producing a benzene compound directly from three acetylene compounds in the presence of a catalyst of transition metal catalyst. This reaction, however, has difficulty in producing a polysubstituted benzene compound regioselectively from substituted acetylene compounds.
As for regioselective production of a substituted benzene compound from three acetylene compounds, several processes are disclosed in Chem. Rev. 2000, 100, 2901-2915. These processes are based on condensation of one molecule of diyne compound and one molecule of acetylene compound. Nothing is mentioned about the process of producing a substituted benzene compound regioselectively from three molecules of acetylene compound.
There is known a process for producing a pyridine compound regioselectively from two acetylene compounds and one nitrile compound. (J. Chem. Soc., Dalton 1978, 1278-1282, J. Am. Chem. Soc. 2000, 122, 4994-4995)
The process disclosed in the former literature has the disadvantage of requiring an expensive cobalt complex and being incapable of using two acetylene compounds of different kind. The process disclosed in the latter literature has the disadvantage of requiring an expensive zirconium catalyst and also requiring two-stage reactions with different catalysts. Therefore, both processes are not suitable for industrial production.
SUMMARY OF THE INVENTION
The present invention was completed in view of the foregoing. Accordingly, it is an object of the present invention to provide a process for producing an organotitanium compound capable of regioselectively converting a substituted acetylene compound into a polysubstituted benzene compound or a polysubstituted pyridine compound. It is another object of the present invention to provide a process for addition reaction to produce polysubstituted benzene and polysubstituted pyridine through addition of an electrophilic reagent to the organotitanium compound.
In order to achieve the above-mentioned object, the present inventors carried out extensive studies, which led to the finding that it is possible to produce an organotitanium compound from a titanium reagent as a reaction product of a tetravalent titanium compound (which is commercially inexpensive) and a Grignard reagent, the organotitanium compound being capable of converting three molecules of acetylene compound, or one molecule of acetylene compound and one molecule of diyne compound, into a benzene compound regioselectively, or converting two molecules of acetylene compound and one molecule of nitrile compound into a pyridine compound regioselectively. The present invention is based on this finding.
The present invention provides the following.
[1] A process for producing an organotitanium compound which comprises reacting an acetylene compound represented by the formula (1) below in the presence of a titanium compound represented by the formula (2) below and a Grignard reagent represented by the formula (3) below with an acetylene compound represented by the formula (4) below and further reacting with a compound represented by the formula (5) below, thereby giving the titanium compound represented by the formula (6) and/or (7) below.
[where R
1
and R
2
denote mutually independently a C
1-20
alkyl group {which may be substituted with a C
1-6
alkoxy group (which may be substituted with a phenyl group) or OSiR
7
R
8
R
9
(where R
7
, R
8
, and R
9
denote mutually independently a C
1-6
alkyl group or phenyl group)}, C
3-20
alkenyl group, C
1-6
alkoxy group, C
1-6
alkoxycarbonyl group, C
1-6
alkylaminocarbonyl group, di-C
1-6
-alkylaminocarbonyl group, phenyl group (which may be substituted with a C
1-6
alkyl group, C
1-6
alkoxy group, C
1-6
alkoxycarbonyl group, C
1-6
alkylaminocarbonyl group, or di-C
1-6
-alkylaminocarbonyl group), furyl group, amino group, SiR
7
R
8
R
9
(where R
7
, R
8
, and R
9
denote mutually independently a C
1-6
alkyl group or phenyl group), or SnR
10
R
11
R
12
(where R
10
, R
11
, and R
12
denote mutually independently a halogen atom, C
1-6
alkyl group, or phenyl group).]
TiX
1
X
2
X
3
X
4
  (2)
[where X
1
, X
2
, X
3
, and X
4
denote mutually independently a halogen atom, C
1-6
alkoxy group {which may be substituted with a phenyl group (which may be substituted with a C
1-6
alkyl group, C
1-6
alkoxy group, or phenyl group) or naphthyl group}, phenoxy group (which may be substituted with a C
1-6
alkyl group, C
1-6
alkoxy group, or phenoxy group), or naphthoxy group.]
RMgX
5
  (3)
[where R denotes a C
2-8
alkyl group having a hydrogen atom at the &bgr; position, and X
5
denotes a halogen atom.]
[where R
3
and R
4
denote mutually independently a hydrogen atom, C
1-20
alkyl group, C
1-6
alkoxy group, C
1-6
alkoxycarbonyl group, C
1-6
alkylaminocarbonyl group, di-C
1-6
-alkylamino-carbonyl group, phenyl group (which may be substituted with a C
1-6
alkyl group, C
1-6
alkoxy group, C
1-6
alkoxycarbonyl group, C
1-6
alkylaminocarbonyl group, or di-C
1-6
-alkylaminocarbonyl group), furyl group, amino group, SiR
7
R
8
R
9
(where R
7
, R
8
, and R
9
are defined as above), or SnR
10
R
11
R
12
(where R
10
, R
11
, and R
12
are defined as above).]
[where R
5
denotes a hydrogen atom, C
1-20
alkyl group, or phenyl group (which may be substituted with a C
1-6
alkyl group, C
1-6
alkoxy group, C
1-6
alkoxycarbonyl group, C
1-6
alkylaminocarbonyl group, or di-C
1-6
-alkylaminocarbonyl group); Z denotes CR′ (where R′ denotes a hydrogen atom or C
1-20
alkyl group) or a nitrogen atom; X
6
denotes a halogen atom, C
1-6
alkoxy group {which may be substituted with a phenyl group (which may be substituted with a C
1-6
alkyl group, C
1-6
alkoxy group, or phenyl group) or naphthyl group}, phenoxy group (which may be substituted with a C
1-6
alkyl group, C
1-6
alkoxy group, or phenyl group), naphthoxy group, SO
n
R
6
group {where R
6
denotes a C
1-6
alkyl group or phenyl group (which may be substituted with a halogen atom or C
1-6
alkyl group) and n denotes 1 or 2}, OSO
2
R
6
group (where R
6
is defined as above), or OP(O)(OR
13
)
2
group (where R
13
denotes a C
1-6
alkyl group); and m denotes 0 or 1.]
[where R
1
~R
5
, Z, X
6
, and m are defined as above; and X
p
and X
q
denote any of X
1
~X
4
(which are defined as above).]
[2] A process for producing an organotitanium compound which comprises reacting an acetylene compound represented by the formula (8) below in the presence of a titanium compound represented by the formula (2) below and a Grignard reagent represented by the formula (3) below with a compound represented by the formula (5) below, thereby giving the titanium compound represented by the formula (9) and/or (10) below.
[where R
1
denotes a C
1-20
alkyl group {which may be substituted with a C
1-6
alkoxy group (which may be substituted with a phenyl group) or OSiR
7
R
8
R
9
(where R
7
, R
8
, and R
9
denote mutually independently a C
1-6
alkyl group or phenyl group)}, C
3-20
alkenyl group, C
1-6
alkoxy group, C
1-6
alkoxycarbonyl group, C
1-6
alkylaminocarbonyl group, di-C
1-6
-alkyaminocarbonyl group, phenyl group (which may be substituted with a C
1-6
alkyl group, C
1-6
alkoxy group, C
1-6
alkoxycarbonyl group, C
1-6
alkylaminocarbonyl group, or di-C
1-6
-alkylaminocarbonyl group), furyl group, amino group, SiR
7
R
8
R
9
(where R
7
, R
8
, and R
9
are defined as above), or SnR
10
R
11
R
12
(where R
10
, R
11
, a

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