GB2051813A - Adamantylidene succinate esters - Google Patents
Adamantylidene succinate esters Download PDFInfo
- Publication number
- GB2051813A GB2051813A GB8025095A GB8025095A GB2051813A GB 2051813 A GB2051813 A GB 2051813A GB 8025095 A GB8025095 A GB 8025095A GB 8025095 A GB8025095 A GB 8025095A GB 2051813 A GB2051813 A GB 2051813A
- Authority
- GB
- United Kingdom
- Prior art keywords
- succinate
- adamant
- adamantylidene
- ylidene
- diester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
Abstract
The invention relates to adamant -2-ylidene dialkyl succinate esters which are prepared by reacting adamanton-2-one with a succinate diester in a solution of potassium t- butoxide in t-butanol to produce potassium salt of adamantylidene succinate half ester and boiling the product in a benzene/alkanol mixture to yield the diester.
Description
SPECIFICATION
Succinic anhydride derivatives
This invention relates to succinic anhydride derivatives.
In our co-pending patent application number 30720/78 a series of photochromic compounds are described having the general formula (IV):
wherein X represents oxygen or NR6, R6 being hydrogen or an alkyl, aryl or aralkyl group;
R represents hydrogen or an alkyl, aryl, aralkyl or heterocyclic group;
Ar represents a 3furyl, 3-thienyl group, 3-benzofuryl or 3-benzothienyl group or a phenylgroup containing a metal alkoxy or aryloxy substituent; and optionally also substituted in the ortho and/or para-positions.
Ad represents an adamantylidene group.
The present invention is concerned with adamant 2 - ylidene dialkyl succinate esters which are novel chemical compounds and are useful inter alia as intermediates in the preparation of compounds having the general formula (IV) above. The succinate esters of the present invention have other uses and are generally useful as intermediates in the preparation of photochromic succinic anhydride derivatives.
The succinate esters of the present invention have the general formula
Ad = CH-CH2CO2R where R is an alkyl group and Ad represents an adamantylidene group.
Adamantane, the root hydrocarbon is a tricyclodecane having a rigid, strain free cage structure, whose synthesis from dicyclopentadiene is described by Schleyer et al in Organic Synthesis, 1962, volume 42, page 8. Referring to the accompanying formula drawings, the synthesis involves hydrogenation of dicyclopentadiene (1 ) to endotetrahydrodicyclopentadiene (2) and rearrangement of the latter using a catalyst comprising an hydrous aluminium chloride and hydrogen chloride to adamantane (3).
Adamanton - 2 - ol (4) can be prepared by free radical hydroxylation of adamtanane using peracetic acid and U.V. radiation (Schleyeretal. JACS, 1961, 83, p.182) and the product oxidised to Adamantan - 2 - one (5) using a chromic acid/sulphuric acid mixture.
More convenient methods of preparing adaman- tanone by direct oxidation of adamantane are described in U.S. patent 3,257,456 and Geluk et al
Organic Synthesis, 1973, Volume 53, p.8.
Adamantan - 2 - one (5) reacts with methyl magnesium bromide to yield 2 - methyladamantan - 2 - ol (6) which, on heating with 85% phosphoric acid, gives exclusively 2 - methyleneadamantane (7) (Schleyer et al. JACS paper cited above).
Succinate diesters in accordance with the invention may be prepared by a Stobbe condensation reactions. (Chapter 1 of volume 6 of "Organic Reactions"), Wiley, New York, 1951. For example, adamantan - 2 - one (5) is refluxed with diethyl succinate in a solution of potassium t-butoxide in t-butanol to give the potassium salt of the corresponding half ester. Boiling in a benzene/ethanol mixture containing concentrated hydrochloric acid yields adamant- 2 - ylidene - succinate diethyl dies tes(9).
Compounds of formula (IV) can be obtained by reacting the intermediate (9) with an appropriate aldehyde or ketone in the presence of sodium hydride. Formula (10) of the accompanying drawings shows the structure of two specific compounds in accordance with the invention of our co-pending application number 30720/78.
The following Example is given to illustrate the invention and the manner in which it may be carried into effect.
EXAMPLE
Preparation of diethyl adamant - 2 - ylidenesuccinate
Adamantan - 2 - one (50 parts) and diethyl succinate (58 parts) in t-butanol (200 parts by volume) were added to a solution of potassium t-butoxide in t-butanol (prepared by dissolving potassium (13.5 parts) in t-butanol (700 parts by volume). The reaction mixture was boiled (2# hours), cooled, and the solid filtered off and extracted with ether. The ether extracted gave adamantanone (20 parts). The etherinsoluble solid, the potassium salt of the itaconic half ester, was dissolved in water and acidified with 5M hydrochloric acid, giving ethyl adamant - 2 ylidenesuccinate (50 parts), m.p. 85-870C. 82% yield based on adamant - 2 - one consumed.
The half ester was boiled with ethanol (75 parts by volume), benzene (225 parts by volume) and conc.
hydrochloric acid (2 parts by volume) and the water azeotroped off using a Dean and Stark apparatus.
Unchanged half ester was extracted with sodium carbonate solution, the organic layer was dried (magnesium sulphate), filtered and the solvent removed. The diesterwas obtained as a colourless oil (47 parts) 86% yield.
Claims (3)
1. An adamant- 2 - ylidene dialkyl succinate ester.
2. Adamant - 2 - ylidene diethyl succinate ester.
3. A process for the preparation of adamant - 2 ylidene dialkyl succinate esters which comprises reacting adarnantan - 2 - one with a succinate diester in a solution of potassium t-butoxide in t-butanol to produce the potassium salt of the adamantylidene succinate half ester and boiling the product in a benzene/alcohol mixture to yield the diester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8025095A GB2051813B (en) | 1977-07-22 | 1978-07-21 | Adamantylidene succinate esters |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3089477 | 1977-07-22 | ||
| GB8025095A GB2051813B (en) | 1977-07-22 | 1978-07-21 | Adamantylidene succinate esters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2051813A true GB2051813A (en) | 1981-01-21 |
| GB2051813B GB2051813B (en) | 1982-07-14 |
Family
ID=26260650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8025095A Expired GB2051813B (en) | 1977-07-22 | 1978-07-21 | Adamantylidene succinate esters |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2051813B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0136837A2 (en) * | 1983-09-07 | 1985-04-10 | THE PLESSEY COMPANY plc | Heliochromic plastics articles |
| US4685783A (en) * | 1983-09-07 | 1987-08-11 | The Plessey Company P.L.C. | Polychromic tetracyclo-spiro-adamatylidene derivatives, and polychromic lens incorporating said compounds |
-
1978
- 1978-07-21 GB GB8025095A patent/GB2051813B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0136837A2 (en) * | 1983-09-07 | 1985-04-10 | THE PLESSEY COMPANY plc | Heliochromic plastics articles |
| EP0136837A3 (en) * | 1983-09-07 | 1986-03-26 | The Plessey Company Plc | Heliochromic plastics articles |
| US4685783A (en) * | 1983-09-07 | 1987-08-11 | The Plessey Company P.L.C. | Polychromic tetracyclo-spiro-adamatylidene derivatives, and polychromic lens incorporating said compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2051813B (en) | 1982-07-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930721 |