CA1049036A - Process for the preparation of tri-esters and products so obtained - Google Patents
Process for the preparation of tri-esters and products so obtainedInfo
- Publication number
- CA1049036A CA1049036A CA75227232A CA227232A CA1049036A CA 1049036 A CA1049036 A CA 1049036A CA 75227232 A CA75227232 A CA 75227232A CA 227232 A CA227232 A CA 227232A CA 1049036 A CA1049036 A CA 1049036A
- Authority
- CA
- Canada
- Prior art keywords
- reaction
- process according
- rcooh
- carried out
- alkaline
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
Abstract
ABSTRACT OF THE DISCLOSURE:
A process for the preparation of a triester of the formula:
wherein R is an alkyl radical of from 1 to 5 carbon atoms consisting of reacting a ?-halo-epoxide of the formula
A process for the preparation of a triester of the formula:
wherein R is an alkyl radical of from 1 to 5 carbon atoms consisting of reacting a ?-halo-epoxide of the formula
Description
The present invention relates to a process for the preparation of tri-esters of formula:
OCOR OCOR
H ______\ \
C C H
H /
OCOR
wherein R is an alkyl radical of from 1 to 5 carbon atoms and to the so obtained products !
The products according to the invention are useful ` 10 as intermediates for some organic synthesis, such as for example the preparation of~ -hydroxy-aldehydes or -ketones, -acyloxy (or aroyloxy)-aldehydes or -ketones, or ~-hydroxy-aminoacids.
- The process according to the invention consists in reacting q-halo-epoxides of the formula:
. H O Y
\~y H H
wherein: .
Y i8 an halogen atom, with an anhydride of a carboxylic acid RCOOH, wherein R has the above meaning, in the presence of Lewis acids, and, preferably, in a second stage, with .
an alkaline or alkaline-earth metal salt of that RCOOH acid.
More particularly, the reaction of the halo-epoxide with the anhydride is carried out at a temperature ranging from -30 to ~70C at such a pressure as to maintain the mixture in the liquid phase, possibly in the presence of a suitable solvent, selected among the aroma~c'compounds preferably among the nitro- or halo-aromatic compounds, and -. the subsequent reaction with the salt is carried out at a .
'~ ' ` . ' : -' '1. ' ~ :- ' ~0 49 03U6 temperature ranging from +25 to ~180C~ the other condltions remaining unchanged. --~ he ln~ention will be now better under~tood withreference to the following non-restrlctl~e e~ample.
EX~æ
Preparation o~ 1.1.2-triacetoxy-ethane from monochloroeth,~lene oxide To 5.27 g (67.2 mmoles) of monochloroethylene oside were added 40 ml of acetic anh~dride and 0.22 g of anh~drous rerric chloride. ~he mixture ~a8 stirred ior one hour at room temperature under a nltrogen atmosphere. ~hen 5.51 g (67.2 mmoles) Or anhydrous sodium acetate were added, ana, ~tlll under nitrogen, the reaction mi%ture stirred for a further 60 hour~ at room temperature and iinally was re n used ror further 48 hours.
lhe rea¢tion misture, ¢ooled to room temperature, was diluted with 100 ml of methylene chloride. ~he precipitated salts were remo~ed b~ ~iltratinni the precipitate w w hed ~lth meth~lone ohloride and the collected riltrates were dried unaer ~acuum on a rotating e~aporator. The residue diluted ~n methglene chloride was heated and treated wlth acti~e carbo~. ~he aoti~e carbon was washea with a 8mall amount of sol~ent. ~he sol~ent waa removed under ~acuum from the gathered iiltrates and the residue puriiied by distillation.
Dhe 1,1,2-triacetosyethane wa~ distilled at 112-114C under 2 mmHg (bath at 150C). 6.86 g of product pure at the chromatography test (yield 50%) and with a melting point Or 48-50C were obtalned.
OCOR OCOR
H ______\ \
C C H
H /
OCOR
wherein R is an alkyl radical of from 1 to 5 carbon atoms and to the so obtained products !
The products according to the invention are useful ` 10 as intermediates for some organic synthesis, such as for example the preparation of~ -hydroxy-aldehydes or -ketones, -acyloxy (or aroyloxy)-aldehydes or -ketones, or ~-hydroxy-aminoacids.
- The process according to the invention consists in reacting q-halo-epoxides of the formula:
. H O Y
\~y H H
wherein: .
Y i8 an halogen atom, with an anhydride of a carboxylic acid RCOOH, wherein R has the above meaning, in the presence of Lewis acids, and, preferably, in a second stage, with .
an alkaline or alkaline-earth metal salt of that RCOOH acid.
More particularly, the reaction of the halo-epoxide with the anhydride is carried out at a temperature ranging from -30 to ~70C at such a pressure as to maintain the mixture in the liquid phase, possibly in the presence of a suitable solvent, selected among the aroma~c'compounds preferably among the nitro- or halo-aromatic compounds, and -. the subsequent reaction with the salt is carried out at a .
'~ ' ` . ' : -' '1. ' ~ :- ' ~0 49 03U6 temperature ranging from +25 to ~180C~ the other condltions remaining unchanged. --~ he ln~ention will be now better under~tood withreference to the following non-restrlctl~e e~ample.
EX~æ
Preparation o~ 1.1.2-triacetoxy-ethane from monochloroeth,~lene oxide To 5.27 g (67.2 mmoles) of monochloroethylene oside were added 40 ml of acetic anh~dride and 0.22 g of anh~drous rerric chloride. ~he mixture ~a8 stirred ior one hour at room temperature under a nltrogen atmosphere. ~hen 5.51 g (67.2 mmoles) Or anhydrous sodium acetate were added, ana, ~tlll under nitrogen, the reaction mi%ture stirred for a further 60 hour~ at room temperature and iinally was re n used ror further 48 hours.
lhe rea¢tion misture, ¢ooled to room temperature, was diluted with 100 ml of methylene chloride. ~he precipitated salts were remo~ed b~ ~iltratinni the precipitate w w hed ~lth meth~lone ohloride and the collected riltrates were dried unaer ~acuum on a rotating e~aporator. The residue diluted ~n methglene chloride was heated and treated wlth acti~e carbo~. ~he aoti~e carbon was washea with a 8mall amount of sol~ent. ~he sol~ent waa removed under ~acuum from the gathered iiltrates and the residue puriiied by distillation.
Dhe 1,1,2-triacetosyethane wa~ distilled at 112-114C under 2 mmHg (bath at 150C). 6.86 g of product pure at the chromatography test (yield 50%) and with a melting point Or 48-50C were obtalned.
- 2 -
Claims (8)
1. Triesters of the formula:
wherein R is an alkyl radical of 1 to 5 carbon atoms.
wherein R is an alkyl radical of 1 to 5 carbon atoms.
2. A process for the preparation of a triester of the formula:
wherein R is an alkyl radical of 1 to 5 carbon atoms consisting of reacting a ?-halo-epoxide of the formula wherein Y is an halogen atom, with an anhydride of a carboxylic acid RCOOH, wherein R has the above meaning, in the presence of Lewis acids, and with an alkaline or alkaline earth metal salt of that RCOOH acid.
wherein R is an alkyl radical of 1 to 5 carbon atoms consisting of reacting a ?-halo-epoxide of the formula wherein Y is an halogen atom, with an anhydride of a carboxylic acid RCOOH, wherein R has the above meaning, in the presence of Lewis acids, and with an alkaline or alkaline earth metal salt of that RCOOH acid.
3. A process according to claim 2 characterized in that the reaction is carried out in two stages, the first one consisting in reacting the ?-halo-epoxyde with the anhydride of the RCOOH acid, the second one in reacting the product thus obtained with an alkaline or alkaline-earth metal salt of the RCOOH acid.
4. A process according to claim 3 characterized in that the reaction of the first stage is carried out at a temperature ranging from -30 to +70°C.
5. A process according to claim 3 characterized in that the reaction of the second stage is carried out at a temperature ranging from +25 to +180°C.
6. A process according to claim 2 characterized in that the reaction is carried out in the presence of a solvent selected among the aromatic compounds.
7. A process according to claim 6 characterized in that the solvent is selected among the nitro- or halo-aromatic compounds.
8. A process according to claim 2 characterized in that the reaction is carried out at such a pressure as to maintain the reaction mixture in a liquid phase.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2287374A IT1012482B (en) | 1974-05-17 | 1974-05-17 | PROCESS FOR THE PREPARATION OF TRIESTERI AND PRODUCTS SO OBTAINED |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1049036A true CA1049036A (en) | 1979-02-20 |
Family
ID=11201407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA75227232A Expired CA1049036A (en) | 1974-05-17 | 1975-05-16 | Process for the preparation of tri-esters and products so obtained |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS51122013A (en) |
| BE (1) | BE829183A (en) |
| CA (1) | CA1049036A (en) |
| CH (1) | CH605574A5 (en) |
| DE (1) | DE2521500A1 (en) |
| FR (1) | FR2271197B1 (en) |
| GB (1) | GB1503776A (en) |
| IT (1) | IT1012482B (en) |
| LU (1) | LU72493A1 (en) |
| NL (1) | NL7505836A (en) |
-
1974
- 1974-05-17 IT IT2287374A patent/IT1012482B/en active
-
1975
- 1975-05-14 DE DE19752521500 patent/DE2521500A1/en active Pending
- 1975-05-15 CH CH627375A patent/CH605574A5/xx not_active IP Right Cessation
- 1975-05-15 GB GB2073175A patent/GB1503776A/en not_active Expired
- 1975-05-16 BE BE156446A patent/BE829183A/en not_active IP Right Cessation
- 1975-05-16 LU LU72493A patent/LU72493A1/xx unknown
- 1975-05-16 CA CA75227232A patent/CA1049036A/en not_active Expired
- 1975-05-16 NL NL7505836A patent/NL7505836A/en active Search and Examination
- 1975-05-16 FR FR7515526A patent/FR2271197B1/fr not_active Expired
- 1975-05-16 JP JP5749475A patent/JPS51122013A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| LU72493A1 (en) | 1975-08-28 |
| FR2271197A1 (en) | 1975-12-12 |
| IT1012482B (en) | 1977-03-10 |
| GB1503776A (en) | 1978-03-15 |
| BE829183A (en) | 1975-09-15 |
| JPS51122013A (en) | 1976-10-25 |
| JPS5310046B2 (en) | 1978-04-11 |
| DE2521500A1 (en) | 1975-11-20 |
| CH605574A5 (en) | 1978-09-29 |
| NL7505836A (en) | 1975-11-19 |
| FR2271197B1 (en) | 1979-03-02 |
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