Patent US4021457A successfully refreshed from Google Patents.
US4021457A
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Intermediates for polycyclic quinonoid antibiotics
Assignee: Research Corp
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Filing: 1976-04-05
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Granted: 1977-05-03
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Expires: 1996-04-05
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 certain analogs of (+)-7-deoxydaunomycinone which includes the provision of novel tri- and tetracyclic quinone intermediates. The products of the synthetic route provided herein may be converted into compounds of known anti-neoplastic activity.
Inventors
- 👤 Andrew S. Kende
- 👤 John E. Mills
- 👤 Yuh-Geng Tsay
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-07 23:06
CPC Classifications
C; C07; C07C; C07C46/00; C07C46/02; C07C46/06
Claims Analysis
Total Claims: 36
Claim 1
Independent Claim
44 words
Ethers having the formula ##STR2## wherein R 1 is a 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.
Claim 2
Dependent Claim
44 words
Ethers having the formula ##STR2## wherein R 1 is a 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.
Claim 3
Dependent Claim
26 words
Ethers of claim 1 wherein R 1 is lower alkyl of 1- 5 carbon atoms or phenyl-lower alkyl containing 1-5 carbon atoms in the alkyl moiety.
Claim 4
Dependent Claim
11 words
Ethers of claim 1 wherein R 1 is methyl or benzyl.
Claim 5
Dependent Claim
81 words
Process for the preparation of a compound of claim 1 which comprises oxidizing a derivative of 1,4,5,8-hydroxy anthraquinone of the formula ##STR3## wherein R 1 has the same definition as in claim 1 R 2 and R 3 are hydrogen, lower alkyl, phenyl-lower alkyl, substituted phenyl-lower alkyl wherein the substituents are lower alkyl, lower alkoxy or halo, wherein the moiety lower alk contains 1-5 carbon atoms and R 1 , R 2 and R 3 may be the same or different.
Claim 6
Dependent Claim
15 words
A process of claim 4 wherein R 1 = R 2 = R 3 .
Claim 7
Dependent Claim
17 words
A process of claim 5 wherein R 1 = R 2 = R 3 = lower alkyl.
Claim 8
Dependent Claim
29 words
A process of claim 4 wherein R 1 = R 2 = R 3 = methyl and the oxidizing agent is argentic oxide in the presence of an acid.
Claim 9
Dependent Claim
18 words
A process of claim 4 wherein the oxidizing agent is argentic oxide in the presence of nitric acid.
Claim 10
Dependent Claim
80 words
A compound of the formula ##STR4## wherein R 7 is lower alkyl of 1-5 carbon atoms or hydrogen, R 9 is R 1 , R 1 O, or hydrogen, where when R 7 is lower alkyl R 9 is hydrogen and when R 9 is R 1 or R 1 O, R 7 is hydrogen, R 8 is selected from a group consisting of the same moieties as R 1 , wherein R 1 is as defined in claim 1.
Claim 11
Dependent Claim
11 words
A compound of claim 9 wherein R 8 = lower alkyl.
Claim 12
Dependent Claim
27 words
A compound of claim 9 where R 7 is methyl or hydrogen R 8 is methyl, phenyl or hydrogen and R 9 is methyl, methoxy, or hydrogen.
Claim 13
Dependent Claim
44 words
The process of preparing a compound of claim 9 which comprises subjecting a compound of the formula ##STR5## to a Diels-Alder condensation with a compound of the formula ##STR6## wherein R 7 , R 8 and R 9 are as defined in claim 9.
Claim 14
Dependent Claim
18 words
A compound of the formula ##STR7## wherein R 7 and R 9 are as defined in claim 9.
Claim 15
Dependent Claim
20 words
A compound of claim 13 wherein R 7 is methyl or hydrogen and R 9 is methyl, methoxy or hydrogen.
Claim 16
Dependent Claim
21 words
A compound having the formula ##STR8## wherein R 1 , R 7 and R 9 are as defined in claim 9.
Claim 17
Dependent Claim
21 words
A compound of claim 15 wherein R 7 is lower alkyl or hydrogen and R 9 is lower alkoxy or hydrogen.
Claim 18
Dependent Claim
20 words
A compound of claim 16 wherein R 7 is methyl or hydrogen and R 9 is methyl, methoxy or hydrogen.
Claim 19
Dependent Claim
34 words
A process of preparing a compound of claim 15 which comprises reacting a compound of the formula ##STR9## wherein R 7 and R 9 are as defined in claim 15 with an ethynylating agent.
Claim 20
Dependent Claim
33 words
A process of claim 18 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 C1, Br or I.
Claim 21
Dependent Claim
26 words
A process of claim 19 wherein R 7 is methyl or hydrogen, R 9 is methoxy or hydrogen and the ethynylating agent is CH .tbd. C.MgBr.
Claim 22
Dependent Claim
32 words
A process of preparing a compound of the formula ##STR10## wherein R 7 and R 9 are defined in claim 15 which comprises reacting a compound of claim 15 with hydrating agent.
Claim 23
Dependent Claim
12 words
A process of claim 21 wherein the hydrating agent is mercuric ion.
Claim 24
Dependent Claim
58 words
A process of claim 21 where R 1 is other than hydrogen, 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 25
Dependent Claim
43 words
A process of claim 21 where R 1 is hydrogen, 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 26
Dependent Claim
18 words
A compound of the formula ##STR11## wherein R 7 and R 9 are as defined in claim 9.
Claim 27
Dependent Claim
13 words
A compound of claim 25 where R 7 = R 9 = hydrogen.
Claim 28
Dependent Claim
15 words
A compound of claim 25 where R 7 = lower alkyl, R 9 = hydrogen.
Claim 29
Dependent Claim
10 words
A compound of claim 27 where R 7 = methyl.
Claim 30
Dependent Claim
16 words
A compound of claim 25 where R 7 = hydrogen and R 9 = lower alkoxy.
Claim 31
Dependent Claim
10 words
A compound of claim 25 where R 9 = methoxy.
Claim 32
Dependent Claim
16 words
A compound of claim 25 where R 7 is hydrogen and R 9 is lower alkyl.
Claim 33
Dependent Claim
10 words
A compound of claim 25 where R 9 is methyl.
Claim 34
Dependent Claim
71 words
The process which comprises reacting a compound of claim 25 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 ##STR12## wherein R 7 and R 9 are as defined in claim 25.
Claim 35
Dependent Claim
23 words
A process of claim 33 wherein the hydrolyzing agent is selected from the group consisting of water, mild base, alumina, and silica gel.
Claim 36
Dependent Claim
29 words
A process of claim 33 wherein the hydrolyzing agent comprises the sequential treatment of an ester or silver salt of an alkanoic or halo alkanoic acid and a base.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-05-02 | 1980-11-01 | 1981-05-03 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-05-02 | 1984-11-01 | 1985-05-03 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-05-02 | 1988-11-01 | 1989-05-03 | $7700.00 | Window Closed / Lapsed |