Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2002-08-21
2003-09-23
McKane, Joseph K. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C560S129000, C548S237000, C549S477000, C564S463000
Reexamination Certificate
active
06624324
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a process for producing an optically active hemiester.
BACKGROUND OF THE INVENTION
An optically active hemiester, for example, an imidazolidin-2-one hemiester derivative has been known as an intermediate for synthesizing d-biotin (vitamin H) and the like. There have been known a process for producing hemiester intermediate derivatives by ring-opening reactions of a cyclic acid anhydride using a complex of alkaloids and dialkylzinc as described in Bull. Chem. Soc. Jpn, 1993, 66, 2128, and a process of using an optically active diisopropoxytitanium TADDOLate as described in J. Org. Chem, 1998, 63, 1190.
SUMMARY OF THE INVENTION
According to the present invention, an optically active hemiester with good optical activity can be industrially advantageously obtained.
The first aspect of the present invention relates to
a process for producing an optically active hemiester of formula (1):
wherein R
1
, R
2
and R
3
represent the same meanings as described below, which comprises reacting a cyclic acid anhydride of formula (2):
with a hydroxy compound of formula (3):
R
3
OH (3)
in the presence of an asymmetric catalyst comprising
a Lewis acid compound selected from a halide, alkoxide or trifluoromethanesulfonate of an element of Group 3, 4, 13 or 14 of Periodic Table of the Elements, and
an optically active ligand selected from a diol, aminoalcohol or bisoxazoline compound, wherein in formulae (1), (2) and (3)
R
1
and R
2
are different and independently represent
a hydrogen atom, a halogen atom,
an alkyl group optionally substituted with an alkoxy group or a halogen atom,
an alkenyl group optionally substituted with an alkoxy group or a halogen atom,
an aralkyl group optionally substituted with an alkyl group, an alkoxy group or a halogen atom,
an aryl group optionally substituted with an alkyl group, an alkoxy group or a halogen atom, or
a group of formula (10): R
a
O—, R
b
NH, or R
a
R
b
N, wherein
R
a
represents
an alkyl group, an aralkyl group, a silyl group, or an acyl group, and
R
b
represents
an acyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, an alkylsulfonyl group, a haloalkylsulfonyl group or an arylsulfonyl group, or
either R
1
groups or R
2
groups may be bonded at their terminals to form a ring; and
R
3
represents
an alkyl group optionally substituted with an alkoxy group, a phenoxy group, a dialkylamino group or a halogen atom,
an aralkyl group optionally substituted with an alkyl group, an alkoxy group, a phenoxy group, a nitro group or a halogen atom,
an aryl group optionally substituted with an alkyl group, an alkoxy group, a nitro group or a halogen atom.
The second aspect of the present invention relates to
a process for producing an optically active imidazolidin-2-one of formula (4):
wherein R
21
represents the same as defined below and R
3
represent the same as defined above,
which comprises reacting a cyclic acid anhydride of formula (5):
wherein R
21
represents
an alkyl group optionally substituted with an alkoxy group or a halogen atom,
an aralkyl group optionally substituted with an alkyl group, an alkoxy group or a halogen atom,
an aryl group optionally substituted with an alkyl group, an alkoxy group or a halogen atom,
with a hydroxy compound of formula (3):
R
3
OH (3)
wherein R
3
is the same as defined above, in the presence of an optically active alkaloid selected from quinine, epiqunine, cinconine and cinconidine.
DETAILED DESCRIPTION
The first aspect of the present invention will be explained first.
In the cyclic acid anhydride of formula (2), examples of the halogen atom represented by R
1
or R
2
include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group optionally substituted with an alkoxy group or a halogen atom represented by R
1
or R
2
include
a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, which alkyl group may be optionally substituted with a halogen atom, an alkoxy group (e.g., a(C1-C5)alkoxy group such as methoxy, ethoxy, n-propoxy, or i-propoxy group, n-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, i-pentyloxy group, or neo-pentyloxy group) and the like.
Specific examples of the optionally substituted alkyl group include
a methyl group, an ethyl group, a n-propyl group, a i-propyl group, a n-butyl group, a i-butyl group, a s-butyl group, a t-butyl group, a n-pentyl group, isoamyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a 1-chloroethyl group, a 2-chloroethyl group, a 1,2-dichloroethyl group, a 2,2,2-trichloroethyl group, a methoxymethyl group, a 2-metoxyethyl group and the like.
Examples of the alkenyl group optionally substituted with an alkoxy group or a halogen atom include a (C2-C3)alkenyl group optionally substituted with an (C1-C5)alkoxy group or a halogen atom. Specific examples thereof include a vinyl group, a propen-1-yl group, a propen-2-yl group, a 2-methylpropen-1-yl group, a 2,2-dichlorovinyl group, a 2,2-dibromovinyl group, a 2-methoxyvinyl group and the like.
Examples of the aralkyl group optionally substituted with an alkyl group, an alkoxy group or a halogen atom include a (C7-C11)aralkyl group optionally substituted with a (C1-C5)alkyl group (e.g., a methyl group, an ethyl group, n-propyl group, i-propyl group or n-butyl group, s-butyl group, t-butyl group, n-pentyl group, i-pentyl group, or neo-pentyl group), a (C1-C5)alkoxy group, or a halogen atom.
Specific examples thereof include a benzyl group, a 1-phenethyl group, a 2-phenethyl group, an &agr;-naphthylmethyl group, a &bgr;-naphthylmethyl group and the like, of which aromatic rings may be optionally substituted with at least one group selected from the halogen atom, the alkoxy group or the alkyl group as described above.
Examples of the aryl group optionally substituted with an alkyl group, an alkoxy group or a halogen atom include a (C6-C18)aryl (e.g., a phenyl, naphthyl, anthranyl or phenanthryl) group which may be optionally substituted with the halogen atom, the (C1-C5)alkyl or (C1-C5)alkoxy group as described above and the like.
Examples of the alkyl group, aralkyl group, silyl group, or acyl group represented by R
a
respectively include
a (C1-C5)alkyl group such as a methyl group, an ethyl group, a propyl group, a n-butyl group, t-butyl group, a pentyl group or the like
a (C7-C8)aralkyl group such as a benzyl group or a phenethyl group,
a silyl group having three (C1-C4)alkyl groups such as a trimethylsilyl group, a t-butyldimethylsilyl group or the like,
a (C2-C6)acyl group such as an acetyl group, a benzoyl group or the like.
Examples of the acyl group represented by R
b
include the same acyl groups as described above. Examples of the alkyl group in the alkoxycarbonyl group or alkylsulfonyl group, and examples of the aralkyl group in the aralkyloxycarbonyl group respectively include the same groups as defined above for R
a
.
Specific examples of the aryl sulfonyl group include a p-toluenesulfonyl group, or the like. Specific examples of the alkylsulfonyl group include a methylsulfonyl group. Specific examples of the haloalkylsulfonyl group include a trifluoromethanesulfonyl group and the like.
Examples of the group formed by either R
1
groups or R
2
groups include a group of following formula (9):
(9a) —(CH
2
)
n
—, wherein n is an integer of 2 to 4,
(9b) ═C(CH
3
)
2
,
(9c) —NR
21
CON(R
21
)—
wherein R
21
represents the same as defined above in connection with formula (5), or
wherein X represents
—O—, —CH═CH—, —CH
2
—, or —(CH
2
)
2
—, and
Y represents —CH═CH— or —(CH
2
)
2
—.
Substituents represented by R
21
are explained below.
The alkyl group optionally substituted with an alkoxy group or a halogen atom include a linear, branched or cyclic (C1-C10)alkyl group optionally substituted with a halogen atom or a (C1-C
Iwakura Kazunori
Souda Hiroshi
McKane Joseph K.
Shameem Golam M. M.
Sumitomo Chemical Company Limited
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