Patent US4164503A successfully refreshed from Google Patents.
US4164503A
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Quinonoid intermediates from chloroprene
Assignee: Research Corp
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Filing: 1978-10-10
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Granted: 1979-08-14
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Expires: 1998-10-10
Abstract
Abstract There is provided a novel and efficent method of synthesizing 7,10-dihydro-6,11-dihydroxy-5,9,12(8H)-naphthacenetrione and analogs thereof substituted in the 1,2,3 or 4 positions. The novel method comprises reacting the appropriate quinizarinquinone with a haloprene under Diels-Alder conditions, followed by aromatization and treatment with strong acid under very mild temperature conditions. The products of this process are important intermediates in the synthesis of daunomycin and its analogs which are useful in the therapy of neoplastic ailments.
Inventors
- 👤 Andrew S. Kende
- 👤 Yuh-Geng Tsay
- 👤 Takuya Furuta
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 09:43
CPC Classifications
C; C07; C07C; C07C50/00; C07C50/26
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
142 words
A compound of the formula ##STR2## wherein: X is halo, R 1 , r 2 , r 3 , and R 4 are the same or different, R 1 and R 4 are selected from the group consisting of hydrogen, hydroxy, lower alkyl, phenyl or substituted phenyl-lower alkyl wherein the substituent groups are lower alkyl lower alkoxy or halo, lower alkoxy, phenyl-or substituted phenyl-lower alkoxy wherein the substituent groups are lower alkyl lower alkoxy or halo, wherein lower alk signifies a branched chain or straight chain hydrocarbon moiety of 1 to 5 carbon atoms, R 2 and R 3 are selected from the group consisting of the hydrogen, lower alkyl, phenyl-or substituted phenyl-lower alkyl wherein the substituent groups are lower alkyl, lower alkoxy or halo wherein lower alk signifies a branched or straight chain hydrocarbon moiety of 1 to 5 carbon atoms.
Claim 2
Dependent Claim
142 words
A compound of the formula ##STR2## wherein: X is halo, R 1 , r 2 , r 3 , and R 4 are the same or different, R 1 and R 4 are selected from the group consisting of hydrogen, hydroxy, lower alkyl, phenyl or substituted phenyl-lower alkyl wherein the substituent groups are lower alkyl lower alkoxy or halo, lower alkoxy, phenyl-or substituted phenyl-lower alkoxy wherein the substituent groups are lower alkyl lower alkoxy or halo, wherein lower alk signifies a branched chain or straight chain hydrocarbon moiety of 1 to 5 carbon atoms, R 2 and R 3 are selected from the group consisting of the hydrogen, lower alkyl, phenyl-or substituted phenyl-lower alkyl wherein the substituent groups are lower alkyl, lower alkoxy or halo wherein lower alk signifies a branched or straight chain hydrocarbon moiety of 1 to 5 carbon atoms.
Claim 3
Dependent Claim
21 words
A compound of claim 1 wherein: R 1 =R 2 =R 3 =R 4 =hydrogen and X is chloro or bromo.
Claim 4
Dependent Claim
47 words
A regioisomeric mixture consisting substantially of two compounds of claim 1 wherein: R 1 =R 4 =H, R 2 =R 3 or H and R 3 =R 2 or H provided that in one of said compounds R 2 =H and in the other R 3 =H.
Claim 5
Dependent Claim
48 words
A regioisomeric mixture consisting substantially of two compounds of claim 1 wherein: R 2 =R 3 =H, and R 1 =R 4 or H and R 4 =R 1 or H provided that in one of said compounds R 1 =H and in the other R 3 =H.
Claim 6
Dependent Claim
20 words
A compound according to claim 1 wherein: R 1 =R 4 =H and R 2 =R 3 =other than H.
Claim 7
Dependent Claim
20 words
A compound according to claim 1 wherein: R 2 =R 3 =H and R 1 =R 4 =other than H.
Claim 8
Dependent Claim
17 words
A compound of claim 3 wherein: R 2 =methyl or hydrogen and R 3 =hydrogen or methyl.
Claim 9
Dependent Claim
17 words
A compound of claim 4 wherein: R 1 =methyl or hydrogen and R 4 =hydrogen or methyl.
Claim 10
Dependent Claim
18 words
A compound of claim 4 wherein: R 1 =methoxy or hydrogen and R 4 is hydrogen or methoxy.
Claim 11
Dependent Claim
11 words
A compound of claim 5 wherein: R 2 =R 3 =methyl.
Claim 12
Dependent Claim
11 words
A compound of claim 6 wherein: R 1 =R 4 =methyl.
Claim 13
Dependent Claim
11 words
A compound of claim 6 wherein: R 1 =R 4 =methoxy.
Claim 14
Dependent Claim
142 words
A compound of the formula ##STR3## wherein: X is halo, R 1 , r 2 , r 3 , and R 4 are the same or different, R 1 and R 4 are selected from the group consisting of hydrogen, hydroxy lower alkyl, phenyl or substituted phenyl-lower alkyl wherein the substituent groups are lower alkyl lower alkoxy or halo, lower alkoxy, phenyl-or substituted phenyl-lower alkoxy wherein the substituent groups are lower alkyl lower alkoxy or halo, wherein lower alk signifies a branched chain or straight chain hydrocarbon moiety of 1 to 5 carbon atoms, R 2 and R 3 are selected from the group consisting of the hydrogen, lower alkyl, phenyl-or substituted phenyl-lower alkyl wherein the substituent groups are lower alkyl, lower alkoxy or halo wherein lower alk signifies a branched or straight chain hydrocarbon moiety of 1 to 5 carbon atoms.
Claim 15
Dependent Claim
142 words
A compound of the formula ##STR3## wherein: X is halo, R 1 , r 2 , r 3 , and R 4 are the same or different, R 1 and R 4 are selected from the group consisting of hydrogen, hydroxy lower alkyl, phenyl or substituted phenyl-lower alkyl wherein the substituent groups are lower alkyl lower alkoxy or halo, lower alkoxy, phenyl-or substituted phenyl-lower alkoxy wherein the substituent groups are lower alkyl lower alkoxy or halo, wherein lower alk signifies a branched chain or straight chain hydrocarbon moiety of 1 to 5 carbon atoms, R 2 and R 3 are selected from the group consisting of the hydrogen, lower alkyl, phenyl-or substituted phenyl-lower alkyl wherein the substituent groups are lower alkyl, lower alkoxy or halo wherein lower alk signifies a branched or straight chain hydrocarbon moiety of 1 to 5 carbon atoms.
Claim 16
Dependent Claim
21 words
A compound of claim 1 wherein: R 1 =R 2 =R 3 =R 4 =hydrogen and X is chloro or bromo.
Claim 17
Dependent Claim
47 words
A regioisomeric mixture consisting substantially of two compounds of claim 1 wherein: R 1 =R 4 =H, R 2 =R 3 or H and R 3 =R 2 or H provided that in one of said compounds R 2 =H and in the other R 3 =H.
Claim 18
Dependent Claim
48 words
A regioisomeric mixture consisting substantially of two compounds of claim 1 wherein: R 2 =R 3 =H, and R 1 =R 4 or H and R 4 =R 1 or H provided that in one of said compounds R 1 =H and in the other R 3 =H.
Claim 19
Dependent Claim
20 words
A compound according to claim 1 wherein: R 1 =R 4 =H and R 2 =R 3 =other than H.
Claim 20
Dependent Claim
20 words
A compound according to claim 1 wherein: R 2 =R 3 =H and R 1 =R 4 =other than H.
Claim 21
Dependent Claim
17 words
A compound of claim 3 wherein: R 2 =methyl or hydrogen and R 3 =hydrogen or methyl.
Claim 22
Dependent Claim
17 words
A compound of claim 4 wherein: R 1 =methyl or hydrogen and R 4 =hydrogen or methyl.
Claim 23
Dependent Claim
18 words
A compound of claim 4 wherein: R 1 =methoxy or hydrogen and R 4 is hydrogen or methoxy.
Claim 24
Dependent Claim
11 words
A compound of claim 5 wherein: R 2 =R 3 =methyl.
Claim 25
Dependent Claim
11 words
A compound of claim 6 wherein: R 1 =R 4 =methyl.
Claim 26
Dependent Claim
11 words
A compound of claim 6 wherein: R 1 =R 4 =methoxy.
Claim 27
Dependent Claim
59 words
A process for the preparation of a compound having the formula ##STR4## which comprises treating a compound having the formula ##STR5## wherein: R 1 , R 2 , R 3 , R 4 , and X are as in claim 1 with substantially anhydrous strong mineral acid at a temperature of between -5° C. and + about 25° C.
Claim 28
Dependent Claim
19 words
A process in accordance with claim 25 wherein: the mineral acid is concentrated sulfuric acid or concentrated phosphoric acid.
Claim 29
Dependent Claim
27 words
A process in accordance with claim 26 wherein: the concentrated mineral acid is utilized in conjunction with a lower alkanoic acid of 1 to 5 carbon atoms.
Claim 30
Dependent Claim
19 words
A process in accordance with claim 27 wherein: the alkanoic acid is formic acid, acetic acid, or propionic acid.
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) | 1982-08-13 | 1983-02-12 | 1983-08-14 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-08-13 | 1987-02-12 | 1987-08-14 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-08-13 | 1991-02-12 | 1991-08-14 | $7700.00 | Window Closed / Lapsed |