2-pyridylsilane, processes for producing and using the same

Details 2-pyridylsilane, processes for producing and using the same 2-pyridylsilane, processes for producing and using the same

2000-03-10

2003-04-15

Aulakh, Charanjit S. (Department: 1625)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

active

06548673

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel 2-pyridylsilanes, processes for the same, an intermediates therefor and a process for producing an alcohol compound from the 2-pyridylsilanes.
2. Description of Related Art
In recent years solution(liquid) phase synthesis has been drawing attention since it appears to be superior to solid phase synthesis in that the former has versatile reactivity and scalability in addition to the advantages of cost and facile analysis. Solution phase synthesis, for example, solution phase combinatorial synthesis, however, has problems in that it requires a complicated separating method and a purifying method which are suitably designed for a product.
SUMMARY OF THE INVENTION
An object of the invention is to provide a 2-pyridylsilyl group, as a suitable auxiliary group, a phase tag, that facilitates liquid-liquid extraction for separation and purification of a compound introduced with such a group in a chemical process or sequential processes, particularly in solution phase combinatorial synthesis.
Another object of the invention is to provide a compound introduced with such a group that are useful in solution phase synthesis.
Further objects of the invention are to provide a process for introducing a 2-pyridylsilane group, as an auxiliary group, into a compound that will undergo desired chemical modifications or transformations, and
a process for eliminating the introduced group after desired modifications or transformations, alternatively,
a process for producing an alcohol compound that has desirably modified or transformed.
The present invention provides:
1. a 2-pyridylsilane of formula (1):
wherein R
1
represents an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group or a trisubstituted silyl group,
R
2
and R
3
are the same or different and independently represent an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, an alkenyl group, an alkynyl group or a trisubstituted silyl group,
R
4
, R
5
, R
6
and R
7
are the same or different and independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, an alkenyl group, an alkynyl group, a cyano group, a nitro group, a hydroxy group, an alkylsulfonyl group, an arylsulfonyl group or a trisubstituted silyl group, and
the alkyl groups, alkoxy groups, aryl groups, aryloxy groups, aralkyl groups, aralkyloxy groups, alkenyl groups and alkynyl groups for R
1
to R
7
may have a substituent,
provided that R
1
is not a vinyl group.
2. A process for producing 2-pyridylsilane of formula (1) as defined above, which comprises reacting (2-pyridylsilyl)methyllithium of formula (2):
wherein R
2
, R
3
, R
4
, R
5
, R
6
and R
7
have the same menanings as defined above, with an electrophile,
3. A (2-pyridylsilyl)methyllithium of formula (2) as defined above,
4. A process of producing the 2-pyridylsilylmethyllithium of formula (2) as defined above, which comprises reacting a (2-pyridyl)methylsilane of formula (3):
wherein R
2
, R
3
, R
4
, R
5
, R
6
and R
7
have the same meanings as defined above with a lithiating agent,
5. A process for producing an alcohol of formula (4)
wherein R
1
has the same meaning as defined above, which comprises reacting 2-pyridylsilane of formula (1) with a peroxide, and
6. A process for producing a 2-pyridylsilane derivative of formula (5):
wherein X
1
, X
2
, X
3
, X
4
, X
5
and X
6
have the same meanings as defined below and X
7
represents an ethyl or vinyl group which may have a substituent at its 2-position, which comprises reacting a 1-alkene or a 1-alkyne, in the presence of a transition metal complex catalyst, with a 2-pyridylsilane compound of formula (6):
wherein X
1
and X
2
are the same or different and independently represent an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group or a trisubstituted silyl group,
X
3
, X
4
, X
5
and X
6
are the same or different and independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a cyano group, a nitro group, a hydroxy group, an alkylsulfonyl group, an arylsulfonyl group or a trisubstituted silyl group,
provided that the alkyl groups, alkoxy groups, aryl groups, aryloxy groups, aralkyl groups and aralkyloxy groups for R
1
to R
7
may have a substituent, and
7. A method for liquid-liquid phase acid/base extraction of a compound in liquid phase combinatorial synthesis, which comprises:
(a) subjecting a compound introduced with a 2-pyridylsilylmethylene group to a transformation reaction or reactions in liquid phase combinatorial synthesis to form a desirably modified or transformed compound,
(b) subjecting the resulting reaction mixture containing a so transformed compound to liquid-liquid phase extraction between an organic phase and acidic aqueous phase resulting from the reaction mixture obtained in step (a) and an acidic aqueous solution and optionally an organic hydrophobic solvent to obtain an acidic aqueous phase containing the transformed compound by phase separation, and
(c) liberating the transformed compound in the separated acidic aqueous phase by adding an alkali and extracting the liberated compound with an organic hydrophobic solvent to obtain an organic phase containing the liberated transformed compound by phase separation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
2-pyridylsilane of formula (1) will be explained first.
Examples of the alkyl groups for R
1
, R
2
, R
3
, R
4
, R
5
, R
6
and R
7
in formula (1) include
a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a t-butyl group, a n-amyl group, a neopentyl group, a n-hexyl group, a cyclohexyl group, a n-octyl group, a n-nonyl group, a menthyl group, a 2,3,4-trimethyl-3-pentyl group and a 2,4-dimethyl-3-pentyl group.
The said alkyl group may be substituted with a group selected from:
an alkoxy group having 1 to 12 carbon atoms, such as a methoxy group, an ethoxy group, a n-propoxy group, a t-butoxy group and a 1-methylheptyloxy group,
a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom,
an alkoxycarbonyl group having 2 to 8 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a t-butoxycarbonyl group,
an aralkyloxycarbonyl group such as a benzyloxycarbonyl group,
an aryloxycarbonyl group such as a phenoxycarbonyl group,
a cyano group,
a nitro group,
a hydroxy group and the like.
Specific examples of the alkyl group which may be substituted with such a substituent include, for example, a 3-chloropropyl group and a 1-hydroxycyclohexyl group.
Examples of the aralkyl group for R
1
, R
2
, R
3
, R
4
, R
5
, R
6
and R
7
in formula (1) (C
1
-C
12
)alkyl group substituted with at least one (C
6
-C
10
)aryl group (e.g., a phenyl group and a naphthyl group), and specific examples thereof include, for example,
a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group,
a 3-phenylpropyl group, a 2-naphthylethyl group,
a diphenylmethyl group and the like.
The aralkyl group may be substituted with at least one group selected from the alkyl, alkoxy, alkoxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, cyano, nitro, hydroxy group, a halogen atom or the like as described above. Specific examples of the aralkyl group having such a substituent include, for example, an &agr;-hydroxybenzyl group, a 1-hydroxy-3-phenylpropyl group and a 1-hydroxy-1-phenylethyl group.
Examples of the alkenyl groups for R
1
, R
2
, R
3
, R
4
, R
5
, R
6
and R
7
in formula (1) include an alkenyl group having 3 to 20 carbon atoms such as a 2-propenyl group, a 2-methyl-2-propenyl group, a 2-butenyl group, a &bgr;-styryl group, a 3-phenyl-2-propenyl group.
Examples of the alkynyl groups for R
1
, R
2
, R
3
, R
4
, R
5
, R
6
and R
7

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