US4070382A
Expired / Lapsed
US
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Intermediates for polycyclic quinoid antibiotics
Assignee: Research Corp
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Filing: 1975-11-18
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Granted: 1978-01-24
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Expires: 1995-11-18
Abstract
Abstract There is provided a novel method of synthesizing certain tetracyclic quinones. In particular, there is provided a novel route to the synthesis of (±)-7-deoxydaunomycinone and analogs thereof, which includes the provision of novel tri- and tetracyclic quinone intermediates. The -7-deoxydaunomycinone derived from naturally occurring daunomycin is a known compound, which is itself an intermediate in the preparation of the clinically accepted anti-tumor antibiotics daunomycine and its derivative adriamycin.
Inventors
- 👤 Andrew S. Kende
- 👤 John E. Mills
- 👤 Yuh-Geng Tsay
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 03:42
CPC Classifications
C; C07; C07C; C07C46/00; C07C46/02; A; A61; A61P; A61P35/00; C07C46/06
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
51 words
A mixture of the 1- and 4-regioisomers of the formula: ##STR2## wherein R 1 is lower alkyl of 1-5 carbon atoms; phenyl- or substituted phenyl-lower alkyl wherein the substituent groups are lower alkyl, lower alkoxy, each containing 1-5 carbon atoms, or halo; and lower alkyl contains 1-5 carbon atoms or hydrogen.
Claim 2
Dependent Claim
51 words
A mixture of the 1- and 4-regioisomers of the formula: ##STR2## wherein R 1 is lower alkyl of 1-5 carbon atoms; phenyl- or substituted phenyl-lower alkyl wherein the substituent groups are lower alkyl, lower alkoxy, each containing 1-5 carbon atoms, or halo; and lower alkyl contains 1-5 carbon atoms or hydrogen.
Claim 3
Dependent Claim
13 words
A mixture of claim 1 wherein R 1 is methyl, benzyl or hydrogen.
Claim 4
Dependent Claim
12 words
The component of the mixture of claim 1 having the formula: ##STR3##
Claim 5
Dependent Claim
46 words
A compound having the formula: ##STR4## wherein R 1 is lower alkyl of 1-5 carbon atoms; phenyl- or substituted phenyl-lower alkyl wherein the substituent groups are lower alkyl, lower alkoxy, each containing 1-5 carbon atoms, or halo; and lower alkyl contains 1-5 carbon atoms or hydrogen.
Claim 6
Dependent Claim
46 words
A compound having the formula: ##STR4## wherein R 1 is lower alkyl of 1-5 carbon atoms; phenyl- or substituted phenyl-lower alkyl wherein the substituent groups are lower alkyl, lower alkoxy, each containing 1-5 carbon atoms, or halo; and lower alkyl contains 1-5 carbon atoms or hydrogen.
Claim 7
Dependent Claim
13 words
A compound of claim 4 wherein R 1 is lower alkyl or hydrogen.
Claim 8
Dependent Claim
12 words
A compound of claim 5 wherein R 1 is methyl or hydrogen.
Claim 9
Dependent Claim
31 words
A process of preparing a compound of claim 4 which comprises reacting a compound of the formula: ##STR5## wherein R 1 is as defined in claim 4 with an ethynylating agent.
Claim 10
Dependent Claim
33 words
A process of claim 7 wherein the ethynylating agent is M.C. .tbd. CH or CH .tbd. C.MgX where M is an alkali or alkaline earth metal and X is Cl, Br or I.
Claim 11
Dependent Claim
18 words
A process of claim 8 wherein R 1 is methyl and the ethynylating agent is CH .tbd. C.MgBr.
Claim 12
Dependent Claim
21 words
A process of preparing a compound of the formula: ##STR6## which comprises reacting a compound of claim 4 with hydrating agent.
Claim 13
Dependent Claim
12 words
A process of claim 10 wherein the hydrating agent is mercuric ion.
Claim 14
Dependent Claim
59 words
A process of claim 10 wherein R 1 is other than hydrogen wherein the hydrating agent is a sequence of a mercuric lower alkanoate in the presence of a lower alkyl alkanoate, hydrogen sulphide, aqueous alkali metal hydroxide in a lower alkanol and aqueous mineral acid, wherein lower alkyl, lower alkanoate and lower alkanol each contain 1-5 carbon atoms.
Claim 15
Dependent Claim
44 words
A process of claim 10 wherein R 1 is hydrogen, wherein the hydrating agent is a sequence of a mercuric lower alkanoate in the presence of a lower alkyl alkanoate, and hydrogen sulphide, wherein lower alkyl and lower alkanoate each contain 1-5 carbon atoms.
Claim 16
Dependent Claim
9 words
A compound of claim 4 having the formula: ##STR7##
Claim 17
Dependent Claim
13 words
A compound of claim 14 wherein R 1 is lower alkyl or hydrogen.
Claim 18
Dependent Claim
12 words
A compound of claim 15 wherein R 1 is methyl or hydrogen.
Claim 19
Dependent Claim
31 words
A process of preparing a compound of claim 14 which comprises reacting a compound of the formula: ##STR8## wherein R 1 is as defined in claim 14 with an ethynylating agent.
Claim 20
Dependent Claim
32 words
A process of claim 17 wherein the ethynylating agent is M.C .tbd. or CH .tbd. C.MgX where M is an alkali or alkaline earth metal and X ix Cl, Br or I.
Claim 21
Dependent Claim
18 words
A process of claim 17 wherein R 1 is methyl and the ethynylating agent is CH .tbd. C.MgBr.
Claim 22
Dependent Claim
22 words
A process of preparing a compound of the formula: ##STR9## which comprises reacting a compound of claim 14 with a hydrating agent.
Claim 23
Dependent Claim
12 words
A process of claim 20 wherein R 1 is methyl or hydrogen.
Claim 24
Dependent Claim
12 words
A process of claim 20 wherein the hydrating agent is mercuric ion.
Claim 25
Dependent Claim
59 words
A process of claim 14 wherein R 1 is other than hydrogen wherein the hydrating agent is a sequence of a mercuric lower alkanoate in the presence of a lower alkyl alkanoate, hydrogen sulphide, aqueous, alkali metal hydroxide is a lower alkanol and aqueous mineral acid, wherein lower alkyl, lower alkanoate and lower alkanol each contain 1-5 carbon atoms.
Claim 26
Dependent Claim
44 words
A process of claim 20 wherein R 1 is hydrogen, wherein the hydrating agent is a sequence of a mercuric lower alkanoate in the presence of a lower alkyl alkanoate and hydrogen sulphide, wherein lower alkyl and lower alkanoate each contain 1-5 carbon atoms.
Claim 27
Dependent Claim
87 words
The process which comprises reacting a compound of the formula ##STR10## wherein R 1 is as defined in claim 4 and the group R 1 O is attached to the 1- or the 4- position of the nucleus with a free radical source of bromine in the presence of means for reducing the concentration of the hydrobromic acid produced in the course of the reaction, and replacing the bromine thus introduced with hydroxyl by hydrolyzing with a hydrolyzing agent to yield a mixture of the formula: ##STR11##
Claim 28
Dependent Claim
23 words
A process of claim 25 wherein the hydrolyzing agent is selected from the group consisting of water, mild base, alumina and silica gel.
Claim 29
Dependent Claim
30 words
A process of claim 25 wherein the hydrolyzing agent comprises the sequential treatment of an alkali metal or silver salt of an alkanoic or halo alkanoic acid and a base.
References Cited (Backward Citations)
US3201424A
Cited
US3803124A
Cited
US3686163A
Cited
US3665018A
Cited
US3963760A
Cited
US3976667A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-01-23 | 1981-07-25 | 1982-01-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-01-23 | 1985-07-25 | 1986-01-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-01-23 | 1989-07-25 | 1990-01-24 | $7700.00 | Window Closed / Lapsed |