CA1175057A - 4-hydroxyacetoacetic acid alkyl ester - Google Patents
4-hydroxyacetoacetic acid alkyl esterInfo
- Publication number
- CA1175057A CA1175057A CA000405280A CA405280A CA1175057A CA 1175057 A CA1175057 A CA 1175057A CA 000405280 A CA000405280 A CA 000405280A CA 405280 A CA405280 A CA 405280A CA 1175057 A CA1175057 A CA 1175057A
- Authority
- CA
- Canada
- Prior art keywords
- acid alkyl
- alkyl ester
- ester
- hydroxyacetoacetic
- acid
- 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
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/716—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
- C07C69/72—Acetoacetic acid esters
Abstract
ABSTRACT OF THE DISCLOSURE
Process for the preparation of 4-hydroxyacetoacetic acid alkyl ester. 4-halogen acetoacetic acid alkyl ester is converted into the 4-benzyloxyacetoacetic acid alkyl ester and the latter is hydrogenolyzed. The hydrogenolysis is preferably carried out under pressure and in the presence of a hydrogenation catalyst. The 4-hydroxyacetoacetic acid alkyl esters include 4-hydroxyacetoacetic acid methyl ester and 4-hydroxyacetoacetic acid ethyl ester.
Process for the preparation of 4-hydroxyacetoacetic acid alkyl ester. 4-halogen acetoacetic acid alkyl ester is converted into the 4-benzyloxyacetoacetic acid alkyl ester and the latter is hydrogenolyzed. The hydrogenolysis is preferably carried out under pressure and in the presence of a hydrogenation catalyst. The 4-hydroxyacetoacetic acid alkyl esters include 4-hydroxyacetoacetic acid methyl ester and 4-hydroxyacetoacetic acid ethyl ester.
Description
~75~57 BAC~G~OUND O'F THE;I~V~TION
1. Field Of The Invention . ~
This invention relates to certain new compounds which are useful for the production of tetronic acid~ This inven~ion also relates to a proces's of preparing such new compounds.
1. Field Of The Invention . ~
This invention relates to certain new compounds which are useful for the production of tetronic acid~ This inven~ion also relates to a proces's of preparing such new compounds.
2. Pr~or Art Tetronic acid~,~hich is used among other things as an accelerator for photo:graphic development, is known to be produced from 4-mono-haloacetoacetic ester or acid.
According to the Swiss Patent N~. 503,'722,,4-chIoroaceto-acetic ester is reacted With an aromatic amine to produce
According to the Swiss Patent N~. 503,'722,,4-chIoroaceto-acetic ester is reacted With an aromatic amine to produce
3-arylaminocrotolactone,,and the'tetronic acid is liberated from such lactone by means o~ ~ mineral acid. The disad-vantage o~ such method is that the isolation of the tetxonic acid only can be realized by means o high vacuum subli~ation. Accordin~ to Swiss Patent No. 529,128,
4-haloacetoacetic acid is reacted with an alkali in an ~queous solution. By treatment wit~'a mineral acid the tetronic acid is liberated. Here too the isolation of the tetronic acid must be accomplished by means of high vacuum sublimation; moreoVer, the achieved yield is only 43 to 44 percent.
~L
~4
~L
~4
5~57 BR{OAD DESCRIPTION OE~ T~ INVENTION
An object of the invention is to provide 4-hydroxy-acetoacetic acid alkyl esters, especially 4-hydroxyaceto-acetic acid methyl ester and 4-hydroxyacetoacetic acid ethyl ester, which can be used Eor the production of tetronic acid, among other things. Another object o~ the invention is to provide a process for prepariny such 4-hydroxyacetoacetic acid alkyl esters. Other objects and advantages of this invention are set out herein or are obvious to one ordinarily skilled in the art.
The objects and advantages o~ this invention are achieved by the process and compound of this invention.
The invention in~olves a process for preparing a 4-hydroxyacetoacetic acid alkyl ester. The process starts out from 4-haloaceto~cetic acid alkyl ester to produce the such new compounds by way of 4-benzyloxyacetoacetic acid alkyl ester by means o~ hydro~enolysis. The process includes converting a 4-haloacetoacetic acid alkyl ester into the corres,ponding ~-benzyloxyacetoacetic acid alkyl ester and hy~enolyzing the'latter into the corresponding 4-hydroxyacetoacetic acid alkyl ester. The hydrogenolysis is preferably carried out under pressure and in the presence o~ a hydrogenation catalyst.
In a preferred met~od of production, 4-haloaceto-acetic ester is converted with an alkali metal salt of ben,zyl alcohol at a temperature of O to 40C. in an organic solvent, prefexably dimethyl sulfoxide or tetra-hydrofuran,and the 4-benzyloxyacetoacetic acid alkyl ester obtained thereby is hydrogenolyzed.
5~7 The invention includes 4-hydroxyacetoacetic acid alkyl esters, which preferably are 4-hydroxyacetoacetic acid methyl ester or 4-hydroxyacetoacetic acid ethyl ester.
The invention also includes the composition composed of a 4-haloacetoacetic acid alkyl ester, an alkali metal salt of benzyl alcohol and an organic solvent. Preferably the alkyl estex of the 4-haloacetoacetic acid alkyl ester has 1 to 4 carbon atoms, and the organic solven-t is dimethyl sulfoxide or tetrahydrofuran. T~e invention further includes the composition composed of a 4-benzyloxyacetoacetic acid alkyl ester, hydrogen, a solvent and a hydrogenation catalyst.
DETAILED DESCRIPTION OF THIS INVENTION
As used herein, all parts, ratios~ percentages and proportions are on a weight basis, unless otherwise stated herein or otherwise obvious herefrom to one ordinarily skilled in the art.
Examples of the 4-haloacetoacetic ester are the bromo- and chloro-derivatives. Preferably~ the 4-halo-acetoacetic acid alkyl ester is a 4-chloroacetoacetic acid alkyl ester, especially the methyl and e~hyl esters.
Examples of the alkali salts of benzyl alcohol are the potassium or sodium salts - preferably the sodium salt is used. The sQdium sa-t of benzyl alcohol is produced preferably from sodium hydride and benzyl alcohol in an organic solyent. The reaction temperature in the conversion step e~fectively is O to 40C.
Hydrogenolysis is the cleavage of a bond in an organic compound with the simultaneous addition of a hydrogen atom to each fragment (by hydrogenolysis one understands the decomposition o~ a compound with concurrent hydrogenation). Hv~ro~enolysis is the combination of hydrogen with another substc~nce, usually an unsaturated organic ~ompound, and usually under the influence of temperature, pressure, and catalysts (usually nickeI). The hydrogeno-lysis reaction is carried out effectively in the invention under a pressure of 1 to 8 atm. Pre~erably, the hydrogena~
tion treatment is carried out in the presence o~ a hydro-generation catalyst, such as, a noble metal. Examples of the noble metals are gold, silver, platinum, palladium, iridium, rhodium, xuthenium, osmium, cobalt, Raney-l~S~
nickel and others. In order to increase the reactionsurface, such catalysts are applied effectively to carriers, for example, pumice stone, coal, silica gel, alumina and others.
Tetronic acid is 2,4-dioxo-tetrahydrofuran or ~ -ketobutyrolactone. Tetronic acid is useful as an accelerator for photographic development.
By way of summary, 4-hydroxyacetoacetic acid alkyl ester is obtained by the hydrogenolysis of the 4-benzyl-oxoacetoacetic acid alkyl ester.
7.56 g o~ 80 percent sodium hydride was freed of white oil by washing three times with 30 ml of petroleum ether (boiling point, 40 to 60C.) and was added to 160 ml of tetrahydrofuran. Then 14.28 g of benzyl alcohol was added in doses while stirring in such a way that a reaction temperature of 40C. was maintained. After hydrogen development was com~leted, a solution of 19.74 g (95.5 percent = 0.1145 mole) of chloroacetoacetic ester in 80 ml of tetrahy~rofuran was addçd during 1 hour drop by drop, whereby a temperature of 40C. prevailed. After 15 hours of stirring, whereby the temperature dropped to ambient temperature, half of the tetrahydrofuran was evaporated on a vacuum rotation evaporator. The still-flowable residue was poured in the form of a thin jet into a mixture of 14.3 g of concentrated HCl in 150 g of ice water, whereby the pH
adjusted itself to S after completion of the addition. Then the residue was extracted four times with ether and~ after washing and drying, the ether was evaporated on the vacuum 75(:357 rotation evaporator. The residue was distilled. 22.52 g (83.2 percent) of 4-benzyloxyacetoacetic acid e~hyl e~ter ~Kpo 4 126C.) resulted.
21.24 g of sUch ester, dissolved in acetic ester (100 ml), was inserted into a 200 rnl steel autoclave provided with a magnetic st:irrer and was hydrogenolized at a pressure of 5 atm in the presence of 1.05 g of Pd 5 percent on coal with hydrogen. A~ter the reaction concluded, which amounted to about 2 hours, and after a 2 hour period after the reaction 10 time ended, the catalyst ~as filtered off and the filtrate was evaporated at 35C. on the vacuum rotation evaporator.
The residue was dried in under high vacuum. 13.4 y of 4-hydroxyacetoacetic acid ethyl ester resulted in the form o a slightly yellowish oil.
Elemental analysis (C6Hl0O4/ MG 146.14) Found: C 49.7 percent i 0.1 H 7~1 percen-t + 0.1 Theory: C 49.3 percent H 6.9 percent IR (thin film) Bands at 3480 (vs), 2950 (m), 1745 (vs), 1725 ~vs), 1325 (m) and 1030 (m) cm 1 NMR (10 percent in GDC13) - 1.30 (t, 3H) ~ = 3.52 (s, 2H) S= 4.27 (q) -- ~4H) J - 4.10 (s) OH at ~ = 3.2 to 3.7 ppm MS: M 164, M/e 1-5, 101, 88 ~75(3S~
EX~MPL~ 2 22.68 g of 80 percent sodium hydride was washed with petroleum ether analogously to Example 1 and was added to 460 ml of tetrahydrofuran. While stirring, 42.84 g of benzyl alcohol was added drop by drop within 45 minutes at 20 to 32C. A~ter the H2 development had stopped, 54.2 g (97.5 percent = 0.35 mole) of 4-chloroacetoacetic acid methyl ester was added drop by drop within 45 minutes at 20 to 30C. The light-brown suspension was tnen stirred for 4 hours at about 20C. and subsequently it was poured into a solution of 92.9 g of concentra~ed hydrochloric acid in 400 ml of water. The light-brown mixture was extracted with three portions of e~her, each of 150 ml, and the extracts were combined. The combined extract was washed twice, each time with 100 ml of saturated NaCl solution.
The ether phase was dried over Na2S04, was fi]tered and was eyaporated in a xotation eyaporator at 30 to 40C. The residue was distilled and 45.1 g (58.1 percent) of 4-benzyl-o~yacetoacetic acid methyl este~ (~p 1 mm = 126 to 129C.) resulted.
IR (thin film) B~nds at 1752 (vs), 1730~(vs), 1325 (m~, ~nd 1100 (m) cms~
NMR (DMSO-d6) - 7.32 (m, 5H~
~ = 4.51 (s, 2H) J ~ 4.25 (s, 2H) _ 3.62 (s, 3~) = 3.60 (s, 2H) ll~S~S~
22.22 g of such ester, dissolved in 100 ml of acetic ester, w~s put into a 200 ml steel autoclave provided with a magnetic stirrer and was hydrogenolyzed in the presence of 1.1 g of Pd 5 percent on coal with water at a pressure of 5 ba~. A~te~ the reaction, the catalyst was filtered off and the filtrate was evaporated in the rotation eyaporator at 30 to.35C. The light-brown residue continued to be dried for another hour in the high vacuum.
As a product, 13.3 g o~ 4-hydroxyacetoacetic acid methyl ester was obtained in the form of a yellow liquid.
IR (thin ~:i;lm) Bands at 3460 (m), 1750 (vs), 1730 (vs), 1440 (m), 1330 (m), 1270 (m) and 1060 (m) cms NM~ (D~SO-;d6) Jr= 5.00 (wide, l~H) = 4.10 (s, 2H) = 3.60 (s, 3H) ~ - 3.54 (s, 2~) EX~MPLE 3 4-Hydroxyacetoacetic acid alkyl ester can be converted into tetronic acid, ~or example, by treating it wit~ a mineralic acid at room temperature. Examples of such mineral or inorganic acids is sul~uric acidl hydrochloric acid (preferred) and phosphoric acid.
4.43 g of 4-hydroxyacetoacetic acid ethyl es~er was treated with 10 ~1 18 percentic aqueous HCl over a 6-hour period at a temperature between 18 and ~5C. Thereafter the HCl was evaporated off at 30C. using a vacuum rotation ~75~57 evaporator. The crystals were washed with water. 3.0 g o~
tetronic acid having purity o~ 95.8 percent resu~ted.
An object of the invention is to provide 4-hydroxy-acetoacetic acid alkyl esters, especially 4-hydroxyaceto-acetic acid methyl ester and 4-hydroxyacetoacetic acid ethyl ester, which can be used Eor the production of tetronic acid, among other things. Another object o~ the invention is to provide a process for prepariny such 4-hydroxyacetoacetic acid alkyl esters. Other objects and advantages of this invention are set out herein or are obvious to one ordinarily skilled in the art.
The objects and advantages o~ this invention are achieved by the process and compound of this invention.
The invention in~olves a process for preparing a 4-hydroxyacetoacetic acid alkyl ester. The process starts out from 4-haloaceto~cetic acid alkyl ester to produce the such new compounds by way of 4-benzyloxyacetoacetic acid alkyl ester by means o~ hydro~enolysis. The process includes converting a 4-haloacetoacetic acid alkyl ester into the corres,ponding ~-benzyloxyacetoacetic acid alkyl ester and hy~enolyzing the'latter into the corresponding 4-hydroxyacetoacetic acid alkyl ester. The hydrogenolysis is preferably carried out under pressure and in the presence o~ a hydrogenation catalyst.
In a preferred met~od of production, 4-haloaceto-acetic ester is converted with an alkali metal salt of ben,zyl alcohol at a temperature of O to 40C. in an organic solvent, prefexably dimethyl sulfoxide or tetra-hydrofuran,and the 4-benzyloxyacetoacetic acid alkyl ester obtained thereby is hydrogenolyzed.
5~7 The invention includes 4-hydroxyacetoacetic acid alkyl esters, which preferably are 4-hydroxyacetoacetic acid methyl ester or 4-hydroxyacetoacetic acid ethyl ester.
The invention also includes the composition composed of a 4-haloacetoacetic acid alkyl ester, an alkali metal salt of benzyl alcohol and an organic solvent. Preferably the alkyl estex of the 4-haloacetoacetic acid alkyl ester has 1 to 4 carbon atoms, and the organic solven-t is dimethyl sulfoxide or tetrahydrofuran. T~e invention further includes the composition composed of a 4-benzyloxyacetoacetic acid alkyl ester, hydrogen, a solvent and a hydrogenation catalyst.
DETAILED DESCRIPTION OF THIS INVENTION
As used herein, all parts, ratios~ percentages and proportions are on a weight basis, unless otherwise stated herein or otherwise obvious herefrom to one ordinarily skilled in the art.
Examples of the 4-haloacetoacetic ester are the bromo- and chloro-derivatives. Preferably~ the 4-halo-acetoacetic acid alkyl ester is a 4-chloroacetoacetic acid alkyl ester, especially the methyl and e~hyl esters.
Examples of the alkali salts of benzyl alcohol are the potassium or sodium salts - preferably the sodium salt is used. The sQdium sa-t of benzyl alcohol is produced preferably from sodium hydride and benzyl alcohol in an organic solyent. The reaction temperature in the conversion step e~fectively is O to 40C.
Hydrogenolysis is the cleavage of a bond in an organic compound with the simultaneous addition of a hydrogen atom to each fragment (by hydrogenolysis one understands the decomposition o~ a compound with concurrent hydrogenation). Hv~ro~enolysis is the combination of hydrogen with another substc~nce, usually an unsaturated organic ~ompound, and usually under the influence of temperature, pressure, and catalysts (usually nickeI). The hydrogeno-lysis reaction is carried out effectively in the invention under a pressure of 1 to 8 atm. Pre~erably, the hydrogena~
tion treatment is carried out in the presence o~ a hydro-generation catalyst, such as, a noble metal. Examples of the noble metals are gold, silver, platinum, palladium, iridium, rhodium, xuthenium, osmium, cobalt, Raney-l~S~
nickel and others. In order to increase the reactionsurface, such catalysts are applied effectively to carriers, for example, pumice stone, coal, silica gel, alumina and others.
Tetronic acid is 2,4-dioxo-tetrahydrofuran or ~ -ketobutyrolactone. Tetronic acid is useful as an accelerator for photographic development.
By way of summary, 4-hydroxyacetoacetic acid alkyl ester is obtained by the hydrogenolysis of the 4-benzyl-oxoacetoacetic acid alkyl ester.
7.56 g o~ 80 percent sodium hydride was freed of white oil by washing three times with 30 ml of petroleum ether (boiling point, 40 to 60C.) and was added to 160 ml of tetrahydrofuran. Then 14.28 g of benzyl alcohol was added in doses while stirring in such a way that a reaction temperature of 40C. was maintained. After hydrogen development was com~leted, a solution of 19.74 g (95.5 percent = 0.1145 mole) of chloroacetoacetic ester in 80 ml of tetrahy~rofuran was addçd during 1 hour drop by drop, whereby a temperature of 40C. prevailed. After 15 hours of stirring, whereby the temperature dropped to ambient temperature, half of the tetrahydrofuran was evaporated on a vacuum rotation evaporator. The still-flowable residue was poured in the form of a thin jet into a mixture of 14.3 g of concentrated HCl in 150 g of ice water, whereby the pH
adjusted itself to S after completion of the addition. Then the residue was extracted four times with ether and~ after washing and drying, the ether was evaporated on the vacuum 75(:357 rotation evaporator. The residue was distilled. 22.52 g (83.2 percent) of 4-benzyloxyacetoacetic acid e~hyl e~ter ~Kpo 4 126C.) resulted.
21.24 g of sUch ester, dissolved in acetic ester (100 ml), was inserted into a 200 rnl steel autoclave provided with a magnetic st:irrer and was hydrogenolized at a pressure of 5 atm in the presence of 1.05 g of Pd 5 percent on coal with hydrogen. A~ter the reaction concluded, which amounted to about 2 hours, and after a 2 hour period after the reaction 10 time ended, the catalyst ~as filtered off and the filtrate was evaporated at 35C. on the vacuum rotation evaporator.
The residue was dried in under high vacuum. 13.4 y of 4-hydroxyacetoacetic acid ethyl ester resulted in the form o a slightly yellowish oil.
Elemental analysis (C6Hl0O4/ MG 146.14) Found: C 49.7 percent i 0.1 H 7~1 percen-t + 0.1 Theory: C 49.3 percent H 6.9 percent IR (thin film) Bands at 3480 (vs), 2950 (m), 1745 (vs), 1725 ~vs), 1325 (m) and 1030 (m) cm 1 NMR (10 percent in GDC13) - 1.30 (t, 3H) ~ = 3.52 (s, 2H) S= 4.27 (q) -- ~4H) J - 4.10 (s) OH at ~ = 3.2 to 3.7 ppm MS: M 164, M/e 1-5, 101, 88 ~75(3S~
EX~MPL~ 2 22.68 g of 80 percent sodium hydride was washed with petroleum ether analogously to Example 1 and was added to 460 ml of tetrahydrofuran. While stirring, 42.84 g of benzyl alcohol was added drop by drop within 45 minutes at 20 to 32C. A~ter the H2 development had stopped, 54.2 g (97.5 percent = 0.35 mole) of 4-chloroacetoacetic acid methyl ester was added drop by drop within 45 minutes at 20 to 30C. The light-brown suspension was tnen stirred for 4 hours at about 20C. and subsequently it was poured into a solution of 92.9 g of concentra~ed hydrochloric acid in 400 ml of water. The light-brown mixture was extracted with three portions of e~her, each of 150 ml, and the extracts were combined. The combined extract was washed twice, each time with 100 ml of saturated NaCl solution.
The ether phase was dried over Na2S04, was fi]tered and was eyaporated in a xotation eyaporator at 30 to 40C. The residue was distilled and 45.1 g (58.1 percent) of 4-benzyl-o~yacetoacetic acid methyl este~ (~p 1 mm = 126 to 129C.) resulted.
IR (thin film) B~nds at 1752 (vs), 1730~(vs), 1325 (m~, ~nd 1100 (m) cms~
NMR (DMSO-d6) - 7.32 (m, 5H~
~ = 4.51 (s, 2H) J ~ 4.25 (s, 2H) _ 3.62 (s, 3~) = 3.60 (s, 2H) ll~S~S~
22.22 g of such ester, dissolved in 100 ml of acetic ester, w~s put into a 200 ml steel autoclave provided with a magnetic stirrer and was hydrogenolyzed in the presence of 1.1 g of Pd 5 percent on coal with water at a pressure of 5 ba~. A~te~ the reaction, the catalyst was filtered off and the filtrate was evaporated in the rotation eyaporator at 30 to.35C. The light-brown residue continued to be dried for another hour in the high vacuum.
As a product, 13.3 g o~ 4-hydroxyacetoacetic acid methyl ester was obtained in the form of a yellow liquid.
IR (thin ~:i;lm) Bands at 3460 (m), 1750 (vs), 1730 (vs), 1440 (m), 1330 (m), 1270 (m) and 1060 (m) cms NM~ (D~SO-;d6) Jr= 5.00 (wide, l~H) = 4.10 (s, 2H) = 3.60 (s, 3H) ~ - 3.54 (s, 2~) EX~MPLE 3 4-Hydroxyacetoacetic acid alkyl ester can be converted into tetronic acid, ~or example, by treating it wit~ a mineralic acid at room temperature. Examples of such mineral or inorganic acids is sul~uric acidl hydrochloric acid (preferred) and phosphoric acid.
4.43 g of 4-hydroxyacetoacetic acid ethyl es~er was treated with 10 ~1 18 percentic aqueous HCl over a 6-hour period at a temperature between 18 and ~5C. Thereafter the HCl was evaporated off at 30C. using a vacuum rotation ~75~57 evaporator. The crystals were washed with water. 3.0 g o~
tetronic acid having purity o~ 95.8 percent resu~ted.
Claims (29)
1. Process for the production of 4-hydroxyacetoacetic acid alkyl ester comprising hydrogenolyzing 4-benzyl-oxyacetoacetic acid alkyl ester, whereby the 4-hydroxy-acetoacetic acid alkyl ester results.
2. Process as claimed in Claim 1 wherein the hydro-genolysis is carried out under pressure and in the presence of a hydrogenation catalyst.
3. Process as claimed in Claim 2 wherein the pressure is 1 to 8 atmospheres.
4. Process as claimed in Claim 2 wherein the hydrogen-ation catalyst is a noble metal.
5. Process as claimed in Claim 4 wherein the nobel metal is palladium.
6. Process as claimed in Claim 4 wherein the nobel metal is on a carrier
7. Process as claimed in Claim 6 wherein the carrier is coal.
8. Process as claimed in Claim 2 wherein the alkyl moiety in the 4-benzyloxyacetoacetic acid alkyl ester has 1 to 4 carbon atoms.
9. Process as claimed in Claim 8 wherein the 4-benzyl-oxyacetoacetic acid alkyl ester is 4-benzyloxyacetoacetic methyl ester.
10. Process as claimed in Claim 8 wherein the 4-benzyl-oxyacetoacetic acid alkyl ester is 4-benzyloxyacetoacetic methyl ester.
11. Process for the production of 4-hydroxyacetoacetic acid alkyl ester comprising converting 4-haloacetoacetic acid alkyl ester into the 4-benzyloxyacetoacetic acid alkyl ester and hydrogenolyzing the latter, whereby the 4-hydroxyacetoacetic acid alkyl ester results.
12. Process as claimed in Claim 11 wherein the alkyl moiety in 4-haloacetoacetic acid alkyl ester has 1 to 4 carbon atoms.
13. Process as claimed in Claim 12 wherein the 4-halo-acetoacetic acid alkyl ester is 4-haloacetoacetic acid methyl ester.
14. Process as claimed in Claim 12 wherein the 4-halo-acetoacetic acid alkyl ester is 4-haloacetoacetic acid ethyl ester.
15. Process as claimed in Claim 11 wherein the 4-halo-acetoacetic acid alkyl ester is 4-chloroacetoacetic acid alkyl ester.
16. Process as claimed in Claim 11 wherein the hydrogenolysis is carried out under pressure and in the presence of a hydrogenation catalyst.
17. Process as claimed in Claim 16 wherein the conver-sion step is achieved by the use of an alkali metal salt of benzyl alcohol.
18. Process as claimed in Claim 17 wherein the alkali metal salt of benzyl alcohol is the sodium salt of benzyl alcohol or the potassium salt of benzyl alcohol.
19. Process as claimed in Claim 16 wherein the conversion step is conducted at a temperature of O° to 40°C.
20. Process as claimed in Claim 16 wherein the conversion step is conducted in an organic solvent.
21. Process as claimed in Claim 20 wherein the organic solvent is dimethyl sulfoxide or tetrahydrofuran.
22. Process as claimed in Claim 16 wherein the pressure is 1 to 8 atmospheres.
23. Process as claimed in Claim 16 wherein the hydrogena-tion catalyst is a noble metal.
24. Process as claimed in Claim 23 wherein the noble metal is palladium.
25. Process as claimed in Claim 23 wherein the noble metal is on a carrier.
26. Process as claimed in Claim 25 wherein the carrier is coal.
27. 4-hydroxyacetoacetic acid alkyl ester.
28. 4-hydroxyacetoacetic acid methyl ester.
29. 4-hydroxyacetoacetic acid ethyl ester.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3984/81A CH649984A5 (en) | 1981-06-17 | 1981-06-17 | 4-HYDROXYACETOACETIC ACID EETHYLESTER. |
| CH3984/81 | 1981-06-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1175057A true CA1175057A (en) | 1984-09-25 |
Family
ID=4267626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000405280A Expired CA1175057A (en) | 1981-06-17 | 1982-06-16 | 4-hydroxyacetoacetic acid alkyl ester |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0067410B1 (en) |
| JP (1) | JPS58936A (en) |
| AT (1) | ATE11275T1 (en) |
| CA (1) | CA1175057A (en) |
| CH (1) | CH649984A5 (en) |
| DD (1) | DD202529A5 (en) |
| DE (1) | DE3261935D1 (en) |
| HU (1) | HU186529B (en) |
| IL (1) | IL66000A (en) |
| IN (1) | IN156668B (en) |
| SU (1) | SU1176829A3 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5936684A (en) * | 1982-08-24 | 1984-02-28 | Shionogi & Co Ltd | Preparation of 1-oxacephem compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1345081A (en) * | 1973-09-14 | 1974-01-30 | Lonza Ag | Process for the preparation of ypsilon-alkoxy-acetoacetic esters |
-
1981
- 1981-06-17 CH CH3984/81A patent/CH649984A5/en not_active IP Right Cessation
-
1982
- 1982-06-07 IL IL66000A patent/IL66000A/en unknown
- 1982-06-08 EP EP82105033A patent/EP0067410B1/en not_active Expired
- 1982-06-08 DE DE8282105033T patent/DE3261935D1/en not_active Expired
- 1982-06-08 AT AT82105033T patent/ATE11275T1/en active
- 1982-06-15 SU SU823450436A patent/SU1176829A3/en active
- 1982-06-16 CA CA000405280A patent/CA1175057A/en not_active Expired
- 1982-06-16 JP JP57103677A patent/JPS58936A/en active Pending
- 1982-06-16 DD DD82240792A patent/DD202529A5/en unknown
- 1982-06-17 HU HU821974A patent/HU186529B/en unknown
- 1982-06-21 IN IN723/CAL/82A patent/IN156668B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DD202529A5 (en) | 1983-09-21 |
| EP0067410A1 (en) | 1982-12-22 |
| SU1176829A3 (en) | 1985-08-30 |
| ATE11275T1 (en) | 1985-02-15 |
| IL66000A0 (en) | 1982-09-30 |
| EP0067410B1 (en) | 1985-01-16 |
| DE3261935D1 (en) | 1985-02-28 |
| IN156668B (en) | 1985-10-12 |
| JPS58936A (en) | 1983-01-06 |
| IL66000A (en) | 1986-08-31 |
| CH649984A5 (en) | 1985-06-28 |
| HU186529B (en) | 1985-08-28 |
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