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US 6,429,314 B1Granted
Methods of acylating adamantane, tricyclo[5.2.1.02,6], and decalin compounds
AssigneeDaicel Chemical Industries, Ltd.
InventorsYasutaka Ishii, Tatsuya Nakano, Naruhisa Hirai
Life of this patent
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Abstract
An acylating agent of the invention includes (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) N-hydroxyphthalimide or another imide compound. As the 1,2-dicarbonyl compound or its hydroxy reductant (A), biacetyl, 2,3-butanediolor the like canbeused. As the metallic compound (c1), cobalt acetate, or another cobalt compound, for example, can be employed. By reacting an adamantane derivative or another compound having a methine carbon atom with the acylating agent, an acyl group can be introduced to the methine carbon atom with efficiency.
Claims24
An acylating agent being composed of
- (A) a compound represented by the following formula (2a):
- wherein each of Ra1 and Rb1 is, identical to or different from each other, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, or an aryl group, or Ra1 and Rb1 when taken together form a cyclopentyl or cyclohexyl ring with the adjacent two carbon atoms to which they are attached;
- and each of Z1 and Z2 is, identical to or different from each other, an oxygen atom or a hydroxyl group,
- (B) oxygen, and
- (C) at least one compound selected from (C1) a metallic compound selected from the group consisting of an elementary metal, a metallic hydroxide, a metallic oxide, a metallic halide, a metallic salt of an oxo acid, an oxo acid containing a metal, an isopolyacid containing a metal, a heteropolyacid containing a metal, a metallic salt of an organic acid, and a metallic complex and (C2) an imide compound represented by the following formula (1):
- wherein each of R1 and R2 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, and R1 and R2 when taken together form a double bond, or a 5- to 12-membered aromatic or nonaromatic ring;
- X is an oxygen atom or a hydroxyl group;
- and one or two N-substituted cyclic imido groups indicated in the formula (1) may be bonded to the aforementioned R1, R2, or to the double bond or aromatic or nonaromatic ring formed together by R1 and R2.
5 more elements
An adamantane compound represented by the following formula (7):
- wherein R is an acyl group, Rc5 is a hydroxyl group, or an acyl group, and each of Rd5 and Re5 is, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, a hydroxyl group which is protected by a protective group, a hydroxymethyl group, a hydroxymethyl group which is protected by a protective group, an amino group, an amino group which is protected by a protective group, a carboxyl group, a carboxyl group which is protected by a protective group, a nitro group, or an acyl group;
- and the adamantane carbon atoms other than those at the bridgehead position may each have a substituent selected from the group consisting of an oxo group, an alkyl group, an acyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a carboxyl group, an alkoxycarbonyl group, a halogen atom, and a cyano group;
- provided that when Rc5 is a hydroxyl group, at least one of Rd5 and Re5 is other than a hydrogen atom, or provided that one or more of the carbon atoms constituting the adamantane structure, other than those at the bridgehead positions, bears an oxo group.
A tricyclodecane compound represented by the following formula (12):
- wherein each of Rp2, Rq2, Rr2 and Rs2 is, identical to or different from one another, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, a hydroxyl group which is protected by a protective group, a hydroxymethyl group, a hydroxymethyl group which is protected by a protective group, an amino group, an amino group which is protected by a protective group, a carboxyl group, a carboxyl group which is protected by a protective group, a nitro group, or an acyl group, provided that at least one of Rq2 and Rr2 is an acyl group;
- and the tricyclodecane carbon atoms other than those at the bridgehead positions may each have a substituent selected from the group consisting of an oxo group, an alkyl group, an acyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a carboxyl group, an alkoxycarbonyl group, a halogen atom, and a cyano group.
A decalin compound represented by the following formula (14):
- wherein each of Rt2 and Ru2 is, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, a hydroxyl group which is protected by a protective group, a hydroxymethyl group, a hydroxymethyl group which is protected by a protective group, an amino group, an amino group which is protected by a protective group, a carboxyl group, a carboxyl group which is protected by a protective group, a nitro group, or an acyl group, provided that at least one of Rt2 and Ru2 is an acyl group;
- and the decalin carbon atoms other than those at the bridgehead positions are unsubstituted.
A method for the production of a vinyl-substituted polycyclic compound, said method comprising the steps of:
- reacting a polycyclic compound represented by the following formula (15):
- wherein the ring A is a polycyclic group having a methine carbon atom at the bridgehead position, and the single bond indicated in the formula is bonded to said bridgehead position with an acylating agent being composed of (A1) a compound represented by the following formula (2b)
- wherein each of Rf, Rg and Rb is, identical to or different from one another, a hydrogen atom, a hydrocarbon group or a heterocyclic group;
- and each of Z1 and Z2 is, identical to or different from each other, an oxygen atom or a hydroxyl group, (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 R1 and R2 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 R1 and R2 when taken together form a double bond, or a 5- to 12-membered aromatic or nonaromatic ring;
- X is an oxygen atom or a hydroxyl group;
- and to the aforementioned R1, R2, or to the double bond or aromatic or nonaromatic ring formed together by R1 and R2, one or two N-substituted cyclic imido groups indicated in the formula (1) may be bonded to give a compound represented by the following formula (16):
- wherein the ring A, Rf and Rg have the same meanings as defined above, reducing the obtained compound represented by the formula (16) by reduction with a metal hydride complex compound, reduction using borane, or catalytic reduction to give a compound represented by the following formula (17):
- wherein the ring A, Rf and Rg have the same meanings as defined above, and subjecting the compound represented by the formula (17) to dehydration reaction at a temperature of from about 0° C. to about 150° C. to give a compound represented by the following formula (18):
- wherein the ring A, Rf and Rg have the same meanings as defined above.
7 more elements
An adamantane compound represented by the following formula (20):
- wherein each of Rc6, Rd6, and Re1 is, identical to or different from one another, a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, a hydroxyl group which is protected by a protective group, a hydroxymethyl group, a hydroxymethyl group which is protected by a protective group, an amino group, an amino group which is protected by a protective group, a carboxyl group a carboxyl group which is protected by a protective group, a nitro group, an group, a hydroxymethyl group which may have a substituent that is a functional group formed by reducing an acyl group, a vinyl group which may have a substituent that is a functional group formed by dehydrating the hydroxymethyl group which may have a substituent, or an epoxy group which may have a substituent that is formed by oxidation of the vinyl group which may have a substituent, provided that Rc6, Rd6, and Re6 are not concurrently hydrogen atoms;
- each of Rf and Rg is, identical to or different from each other, a hydrogen atom, a hydrocarbon group or a heterocyclic group;
- and the adamantane carbon atoms other than those at the bridgehead positions may each have a substituent selected from the group consisting of an oxo group, an alkyl group, an acyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a carboxyl group, an alkoxycarbonyl group, a halogen atom, and a cyano group.
Dependencies are inferred from the claim text.