Methods of acylating adamantane,...

Details Methods of acylating adamantane,... Methods of acylating adamantane,...

1999-10-13

2002-08-06

Lambkin, Deborah C. (Department: 1626)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C568S818000

Reexamination Certificate

active

06429314

ABSTRACT:

TECHNICAL FIELD
The present invention relates to acylating agents which are useful for the production of compounds each containing an acyl group such as acetyl group, to acylation methods using the acylating agents, to methods for the production of acyl group-containing compounds, to methods for the production of vinyl group-containing polycyclic compounds, and to methods for the production of epoxy group-containing polycyclic compounds. It also relates to adamantane derivatives, tricyclo[5.2.1.0
2,6
]decane derivatives and decalin derivatives which are useful as, for example, monomers or their materials for functional polymers, and to methods for the production of these compounds.
BACKGROUND ART
As a method for the introduction of an acyl group directly to a carbon atom of an organic substrate is known a process using an acid halide. For example, a &bgr;-keto-ester is obtained by reacting a ketone and an acid halide in the presence of a base. According to this method, however, it is difficult to introduce an acyl group to a carbon atom not activated such as a carbon atom at the bridgehead position of a polycyclic compound, although a substrate which is activated by, for example, a carbonyl group can be acylated with facility.
J. Org. Chem. 1978, 43, 2370 and J. Org. Chem. 1988, 53, 4369 disclose methods comprising the step of reacting an adamantane derivative with biacetyl under light irradiation to obtain a 1-acetyladamantane derivative. This method, however, requires a special apparatus and, in addition, is low in yield.
As a method for the introduction of an acyl group to the bridgehead position of adamantane, there is known a process comprising the steps of reacting 1-carboxyladamantane with thionyl chloride to give a corresponding acid chloride, reacting this compound with ethyl malonate in the presence of a base to form 1-[2-bis (ethoxycarbonyl) acetyl] adamantane, and subsequently decomposing this compound with an acid to give 1-acetyladamantane. This process, however, requires a large number of steps, and is commercially disadvantageous.
As has been described, there has been no method for the introduction of an acyl group directly to a not-activated carbon atom with facility, up to this time.
On the other hand, adamantane derivatives, tricyclo[5.2.1.0
2,6
decane derivatives and decalin derivatives, in which acetyl group or another acyl group is introduced to its bridgehead position, are useful as manufacturingmaterials for, for example, vinyl group- or epoxy group-containing polycyclic compounds which serve as monomers for functional polymers. Demands have therefore been made to provide simple and efficient methods for the production of these compounds.
DISCLOSURE OF THE INVENTION
Accordingly, it is an object of the present invention to provide an acylating agent and a method for acylation which can introduce an acyl group directly even to a not-activated carbon atom with facility.
Another object of the invention is to provide an acylating agent and a method for acylation which can introduce an acyl group to a methine carbon atom with efficiency.
A further object of the invention is to provide a method for the industrial production of acyl group-containing compounds with efficiency.
It is another object of the invention to provide a simple and efficient method for the production of adamantane derivatives, tricyclo [5.2.1.0
2,6
]decane derivatives, decalin derivatives, and other polycyclic compounds each of which has an acyl group, vinyl group or epoxy group.
Yet another object of the invention is to provide novel adamantane derivatives, tricyclo [5.2.1.0
2,6
] decane derivatives and decalin derivatives.
After intensive investigations to achieve the above objects, the present inventors found that a combination use of a 1,2-dicarbonyl compound or its hydroxy reductant, oxygen and a metallic compound or the like can introduce an acyl group even to a not-activated carbon atom, such as a carbon atom at the bridgehead position of a polycyclic compound, with facility and efficiency. The present invention has been accomplished based on the above finding.
To be more specific, an acylating agent of the invention is composed of (A) a 1,2-dicarbonyl compound or its hydroxy reductant, (B) oxygen, and (C) at least one compound selected from (C1) a metallic compound and (C2) an imide compound represented by the following formula (1):
wherein each of R
1
and R
2
is, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group, or R
1
and R
2
may together form a double bond, or an aromatic or nonaromatic ring; X is an oxygen atom or a hydroxyl group; and to the aforementioned R
1
, R
2
, or to the double bond or aromatic or nonaromatic ring formed together by R
1
and R
2
, one or two N-substituted cyclic imido groups indicated in the formula (1) may be bonded).
Furthermore, according to an acylation method of the invention, an organic substrate is reacted with the aforementioned acylating agent to form an acyl group-containing compound.
According to a method for the production of acyl group-containing compounds of the invention, an organic substrate is reacted with the aforementioned acylating agent to give an acyl group-containing compound.
Furthermore, according to a method for the production of adamantane derivatives of the invention, an adamantane derivative represented by the following formula (3):
wherein each of R
c1
, R
d1
and R
e1
is, identical to or different from one another, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, an amino group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, a nitro group, or an acyl group; and of carbon atoms constituting the adamantane skeleton, the other carbon atoms than those at the bridgehead positions may each have a substituent) is reacted with the aforementioned acylaling agent to give a compound represented by the following formula (4):
(wherein R is an acyl group, and each of R
c2
, R
d2
, and R
e2
is, identical to or different from one another, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, an amino group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, a nitro group, or an acyl group; and of carbon atoms constituting the adamantane skeleton, the other carbon atoms than those at the bridgehead positions may have a substituent).
An adamantane derivative of the invention is represented by the following formula (7):
(wherein R is an acyl group, R
c5
is a hydroxyl group, or an acyl group, and each of R
d5
and R
e5
is, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, an amino group which may be protected by a protective group, a carboxyl group which may be protected by a protective group, a nitro group, or an acyl group; and of carbon atoms constituting the adamantane skeleton, the other carbon atoms than those at the bridgehead positions may each have a substituent).
In a method for the production of tricyclo [5.2.1.0
2,6
] decane derivatives according to the invention, a tricyclo [5.2.1.0
2,6
] decane derivative represented by the following formula (11):
(wherein each of R
p1
, R
q1
, R
r1
and R
s1
is, identical to or different from one another, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group which may be protected by a protective group, a hydroxymethyl group which may be protected by a protective group, an amino group which may

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