Patent US4089873A successfully refreshed from Google Patents.
US4089873A
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Preparation of menaquinones
Assignee: University of California, San Diego
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Filing: 1975-04-07
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Granted: 1978-05-16
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Expires: 1995-04-07
Abstract
Abstract 3-Prenyl-substituted menaquinones are made by reacting a 3-metalo-2-alkyl-1,4-di(alkoxy or aralkoxy) naphthalene with a prenyl halide, and then oxidizing the resulting 3-prenyl-2-alkyl-1,4-di(alkoxy or aralkoxy) naphthalene to prepare the corresponding 3-prenyl-substituted menaquinone. The metallo substituent at the 3-position may be Li, Li/Cu, Cu or MgBr. The oxidation is advantageously conducted by the use of argenic oxide.
Inventors
- 👤 Henry Rapoport
- 👤 Clinton D. Snyder
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 07:19
CPC Classifications
C; C07; C07C; C07C46/00; C07C46/02; C07C43/00; C07C43/02; C07C43/20; C07C43/202; C07C50/00; C07C50/10; C07C50/14; C07F; C07F1/00; C07F1/02; C07F1/08; C07F3/00; C07F3/02
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
143 words
A method of preparing menaquinones of the formula ##STR4## wherein R is lower alkyl, Z is --CH 2 CH═C(CH 3 )CH 2 ] m , --CH 2 CH 2 CH(CH 3 )CH 2 ] n , or combinations thereof, and in which each of m and n, and their sum is 0 to about 12, comprising reacting at a temperature of about 5 to 60° C. 3-metallo naphthalene of the formula ##STR5## wherein R 1 and R 2 are lower alkyl, or monocyclic, hydrocarbyl aralkyl of 7 to about 12 carbon atoms, and M is selected from the group consisting of Li, (CuLi) 1/2 , MgBr and Cu, with prenyl halide of the formula X--CH.sub.2 CH ═ C(CH.sub.3) CH.sub.2 --Z -- H wherein X is halogen, to provide 1,4-diether naphthalene of the formula ##STR6## oxidizing the 1,4-diether naphthalene to produce the corresponding menaquinone.
Claim 2
Independent Claim
143 words
A method of preparing menaquinones of the formula ##STR4## wherein R is lower alkyl, Z is --CH 2 CH═C(CH 3 )CH 2 ] m , --CH 2 CH 2 CH(CH 3 )CH 2 ] n , or combinations thereof, and in which each of m and n, and their sum is 0 to about 12, comprising reacting at a temperature of about 5 to 60° C. 3-metallo naphthalene of the formula ##STR5## wherein R 1 and R 2 are lower alkyl, or monocyclic, hydrocarbyl aralkyl of 7 to about 12 carbon atoms, and M is selected from the group consisting of Li, (CuLi) 1/2 , MgBr and Cu, with prenyl halide of the formula X--CH.sub.2 CH ═ C(CH.sub.3) CH.sub.2 --Z -- H wherein X is halogen, to provide 1,4-diether naphthalene of the formula ##STR6## oxidizing the 1,4-diether naphthalene to produce the corresponding menaquinone.
Claim 3
Dependent Claim
9 words
The method of claim 1 wherein R is methyl.
Claim 4
Dependent Claim
12 words
The method of claim 1 wherein the prenyl halide is a trans-structure.
Claim 5
Dependent Claim
9 words
The method of claim 3 wherein R is methyl.
Claim 6
Dependent Claim
11 words
The method of claim 4 wherein X is chlorine or bromine.
Claim 7
Dependent Claim
13 words
The method of claim 5 wherein R 1 and R 2 are methyl.
Claim 8
Dependent Claim
9 words
The method of claim 6 wherein X is bromine.
Claim 9
Dependent Claim
12 words
The method of claim 6 wherein the prenyl halide is geranyl chloride.
Claim 10
Dependent Claim
12 words
The method of claim 6 wherein the prenyl halide is geranyl bromide.
Claim 11
Dependent Claim
12 words
The method of claim 6 wherein the prenyl halide is solanesyl bromide.
Claim 12
Dependent Claim
12 words
The method of claim 6 wherein the prenyl halide is phytyl bromide.
Claim 13
Dependent Claim
19 words
The method of claim 1 wherein the oxidation is conducted by using silver (II) oxide as an oxidizing agent.
Claim 14
Dependent Claim
17 words
The method of claim 12 wherein the oxidation is conducted in the presence of a mineral acid.
Claim 15
Dependent Claim
16 words
The method of claim 13 wherein the temperature of oxidation is about 5° to 50° C.
Claim 16
Independent Claim
130 words
A method of preparing 1,4-diether naphthalene of the formula ##STR7## wherein R is lower alkyl, R 1 and R 2 are lower alkyl, or monocyclic, hydrocarbyl aralkyl of 7 to about 12 carbon atoms, and Z is --CH 2 CH═C(CH 3 )CH 2 ] m , --CH 2 CH 2 CH(CH 3 )CH 2 ] n , or combinations thereof, and in which each of m and n, and their sum is 0 to about 12, comprising reacting at a temperature of about 5 to 60° C. 3-metallo naphthalene of the formula ##STR8## wherein M is selected from the group consisting of Li, (CuLi) 1/2 , MgBr, and Cu, with prenyl halide of the formula X--CH.sub.2 CH ═ C(CH.sub.3)CH.sub.2 --Z-- H wherein X is halogen, to provide the 1,4-diether naphthalene.
Claim 17
Independent Claim
130 words
A method of preparing 1,4-diether naphthalene of the formula ##STR7## wherein R is lower alkyl, R 1 and R 2 are lower alkyl, or monocyclic, hydrocarbyl aralkyl of 7 to about 12 carbon atoms, and Z is --CH 2 CH═C(CH 3 )CH 2 ] m , --CH 2 CH 2 CH(CH 3 )CH 2 ] n , or combinations thereof, and in which each of m and n, and their sum is 0 to about 12, comprising reacting at a temperature of about 5 to 60° C. 3-metallo naphthalene of the formula ##STR8## wherein M is selected from the group consisting of Li, (CuLi) 1/2 , MgBr, and Cu, with prenyl halide of the formula X--CH.sub.2 CH ═ C(CH.sub.3)CH.sub.2 --Z-- H wherein X is halogen, to provide the 1,4-diether naphthalene.
Claim 18
Dependent Claim
9 words
The method of claim 15 wherein R is methyl.
Claim 19
Dependent Claim
12 words
The method of claim 16 wherein the prenyl halide is a trans-structure.
Claim 20
Dependent Claim
11 words
The method of claim 17 wherein X is chlorine or bromine.
Claim 21
Dependent Claim
13 words
The method of claim 18 wherein R 1 and R 2 are methyl.
Claim 22
Dependent Claim
9 words
The method of claim 18 wherein X is bromine.
Claim 23
Dependent Claim
12 words
The method of claim 18 wherein the prenyl halide is geranyl chloride.
Claim 24
Dependent Claim
12 words
The method of claim 18 wherein the prenyl halide is geranyl bromide.
References Cited (Backward Citations)
No citation records indexed.
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-05-15 | 1981-11-14 | 1982-05-16 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-05-15 | 1985-11-14 | 1986-05-16 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-05-15 | 1989-11-14 | 1990-05-16 | $7700.00 | Window Closed / Lapsed |