DE946986C - Process for the production of ª ‡ -acetotetronic acids - Google Patents
Process for the production of ª ‡ -acetotetronic acidsInfo
- Publication number
- DE946986C DE946986C DEB24325A DEB0024325A DE946986C DE 946986 C DE946986 C DE 946986C DE B24325 A DEB24325 A DE B24325A DE B0024325 A DEB0024325 A DE B0024325A DE 946986 C DE946986 C DE 946986C
- Authority
- DE
- Germany
- Prior art keywords
- parts
- acetotetronic
- acid
- acids
- volume
- 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
- 239000002253 acid Substances 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 9
- 150000007513 acids Chemical class 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- -1 aliphatic Alcohols Chemical class 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AEIGUJIDYBREEB-UHFFFAOYSA-N 2-hydroxy-2-(2-methylphenyl)-2-phenylacetic acid Chemical compound CC1=CC=CC=C1C(O)(C(O)=O)C1=CC=CC=C1 AEIGUJIDYBREEB-UHFFFAOYSA-N 0.000 description 1
- 241000114726 Acetes Species 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 description 1
- AIPVNQQMYPWQSX-UHFFFAOYSA-N ethyl 2-hydroxy-2,2-diphenylacetate Chemical compound C=1C=CC=CC=1C(O)(C(=O)OCC)C1=CC=CC=C1 AIPVNQQMYPWQSX-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- LJFIHTFNTGQZJL-UHFFFAOYSA-N methyl 2-hydroxy-2,2-diphenylacetate Chemical compound C=1C=CC=CC=1C(O)(C(=O)OC)C1=CC=CC=C1 LJFIHTFNTGQZJL-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- MKNZKCSKEUHUPM-UHFFFAOYSA-N potassium;butan-1-ol Chemical compound [K+].CCCCO MKNZKCSKEUHUPM-UHFFFAOYSA-N 0.000 description 1
- QDLQVFQAFINMNO-UHFFFAOYSA-N propan-2-yl 2-hydroxy-2,2-diphenylacetate Chemical compound C=1C=CC=CC=1C(O)(C(=O)OC(C)C)C1=CC=CC=C1 QDLQVFQAFINMNO-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
-
- 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
- C07D307/56—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von a-Acetotetronsäuren Gegenstand des Patents 9x6 169 ist ein Verfahren zur Herstellung von a-Acetotetronsäuren der allgemeinen Formel das dadurch gekennzeichnet ist, daB Acetessigester der allgemeinen Formel in der R1 und R2 Wasserstoffatome oder Aryl-, Aralkyl-, niedrige Alkylgruppen oder alicyclische Gruppen oder Alkylengruppen als Teile eines alicychschen Ringsystems und R3 eine niedrige Alkylgruppe bedeuten, mit einem Claisen-Katalysator behandelt werden, wobei eine Alkoholgruppe austritt. Das Verfahren wird zweckmäßig bei erhöhter Temperatur und 1 . in Gegenwart eines inerten organischen Lösungsmittels,-wie Benzol oder Toluol, durchgeführt.Process for the production of α-acetotetronic acids The subject of patent 9x6 169 is a process for the production of α-acetotetronic acids of the general formula which is characterized by the fact that acetoacetic ester of the general formula in which R1 and R2 represent hydrogen atoms or aryl, aralkyl, lower alkyl groups or alicyclic groups or alkylene groups as parts of an alicychic ring system and R3 represent a lower alkyl group, are treated with a Claisen catalyst, an alcohol group emerging. The process is expediently carried out at elevated temperature and 1. carried out in the presence of an inert organic solvent, such as benzene or toluene.
Er wurde nun gefunden, daß bei der Verwendung von solchen Acetes'sigestern, in denen R1 und R2 nicht Wasserstoffatome darstellen, erhöhte Ausbeuten an Acetotetronsäuren erzielt werden, wenn unter Zugabe von aliphatischen Alkoholen mit i bis 6 Kohlenstoffatomen gearbeitet wird.It has now been found that when using such Acetes'sigesters, in which R1 and R2 are not hydrogen atoms, increased yields of acetotetronic acids can be achieved if with the addition of aliphatic alcohols with 1 to 6 carbon atoms is being worked on.
Da während der Umsetzung ein Alkoholmolekül austritt, konnten verbesserte Ergebnisse bei einer-Durchführung des Verfahrens in Gegenwart von Alkohol nicht erwartet werden. Tatsächlich hat man annehmen müssen, daß die Gegenwart eines Alkohols die Umsetzung verzögert und daß eine Alkoholyse des Acetessigesters eintritt.Since an alcohol molecule escapes during the reaction, improvements were made No results when carrying out the process in the presence of alcohol to be expected. In fact one had to assume that the presence of an alcohol the reaction is delayed and that alcoholysis of the acetoacetic ester occurs.
Erfindungsgemäß besteht also die weitere Ausbildung des Verfahrens zur Herstellung von a-Acetotetronsäuren der allgemeinen Formel in der R1 und R2 Aryl-, Aralkyl-, niedrige Alkyl- oder alicyclische Gruppen oder Alkylengruppen als Teile eines alicyclischen Ringsystems bedeuten, durch-Behandlung von Acetessigestern mit einem Claisen-Katalysator gemäß Patent gib 169 -darin, daß unter Zugabe von aliphatischen Alkoholen mit i bis 6 Koblenstoffatomen gearbeitet wird: Die Bildung der a-Acetotetronsäure verläuft bei niedrigen Temperaturen, beispielsweise bei Raumtemperatur, verhältnismäßig langsam. Es ist daher vorteilhaft, bei erhöhten Temperaturen, zweckmäßig beim Siedepunkt der. Mischung unter Rückfluß, zu arbeiten, wobei die Bildung der a-Acetotetronsäuren in wesentlich kürzerer Zeit erfolgt.According to the invention, there is thus the further development of the process for the preparation of α-acetotetronic acids of the general formula in which R1 and R2 mean aryl, aralkyl, lower alkyl or alicyclic groups or alkylene groups as parts of an alicyclic ring system, by treating acetoacetic esters with a Claisen catalyst according to patent 169 - in that with the addition of aliphatic alcohols i to 6 Koblenstoffatomen is worked: The formation of α-acetotetronic acid proceeds relatively slowly at low temperatures, for example at room temperature. It is therefore advantageous at elevated temperatures, expediently at the boiling point of the. Mixture under reflux to work, the formation of the α-acetotetronic acids taking place in a much shorter time.
Anzuwendende Alkohole sind beispielsweise Methanol, Äthanol, Isopropanol, i-Butanol, i-Pentanol und 2-Methyl-2-butanol. Am besten haben sich jedoch Methanol, Äthanol oder i-Butanol bewährt. Mischungen dieser Alkohole können ebenfalls angewendet werden. In der Reaktionsmischung können zusätzlich auch Kohlenwasserstoffe oder andere inerte Lösungsmittel, wie Benzol, Toluol, Tetrachlorkohlenstoff oder Dioxan, vorliegen, beispielsweise, wenn die Temperatur erhöht werden soll, bei welcher die Mischung unter Rückfluß siedet.Applicable alcohols are, for example, methanol, ethanol, isopropanol, i-butanol, i-pentanol and 2-methyl-2-butanol. However, it is best to use methanol Ethanol or i-butanol proven. Mixtures of these alcohols can also be used will. In the reaction mixture can also hydrocarbons or other inert solvents such as benzene, toluene, carbon tetrachloride or dioxane, present, for example, if the temperature is to be increased at which the Mixture boils under reflux.
Die nachfolgenden Beispiele erläutern die praktische Durchführung der Erfindung. Beispiel i y, y-Dimethyl-a-acetotetronsäure Zu einer Lösung von Natriumäthylat aus 5,5 Gewichtsteilen Natrium in ioo Volumteilen Äthanol werden 46 Gewichtsteile des Acetoacetats des a-Oxyisobuttersäuremethylesters (Kp12 = 118 bis i25°; n, 1.44oo) in 25 Volumteilen Toluol unter Rühren zugesetzt. Die Mischung wird dann 4 Stunden am Rückflußkühler erhitzt und über Nacht stehen gelassen. Nach Abdestillieren der Hauptmenge des Lösungsmittels wird der Rückstand mit Äther und Salzsäure (25 Volumteile konzentrierte Säure und 25 Volumteilen Wasser) behandelt. Aus der ätherischen Lösung werden nach Verdampfen des Äthers 37 Gewichtsteile eines festen Rückstandes entsprechend einer Ausbeute von 98 °/o erhalten. Nach dem Behandeln mit wenig kaltem Petroläther werden 35,5 Gewichtsteile y, y-Dimethyl-a-acetotetronsäure mit einem Schmelzpunkt von 58 bis 59°, entsprechend einer Ausbeute von 92 °/o gewonnen.The following examples illustrate the practical implementation of the invention. Example iy, y-dimethyl-a-acetotetronic acid To a solution of sodium ethylate from 5.5 parts by weight of sodium in 100 parts by volume of ethanol are added 46 parts by weight of acetoacetate of methyl a-oxyisobutyrate (bp12 = 118 to 125 °; n, 1.44oo) in 25 parts by volume Toluene added with stirring. The mixture is then refluxed for 4 hours and left to stand overnight. After most of the solvent has been distilled off, the residue is treated with ether and hydrochloric acid (25 parts by volume of concentrated acid and 25 parts by volume of water). After evaporation of the ether, 37 parts by weight of a solid residue are obtained from the ethereal solution, corresponding to a yield of 98%. After treatment with a little cold petroleum ether, 35.5 parts by weight of γ, γ-dimethyl-α-acetotetronic acid with a melting point of 58 to 59 °, corresponding to a yield of 92%.
Beispiel 2 ' - y, y=Diphenyl-a-acetotetronsäure Eine Mischung von Natriumäthylat aus 4,6 Gewichtsteilen Natrium in 7o Volumteilen Äthanol und 62 Gewichtsteilen des Acetoacetats des Benzilsäuremethylesters (F. 9i bis 92°) in ioo Volumteilen Benzol wird am Rückflußkühler 3 Stunden zum Sieden erhitzt und bleibt dann über Nacht stehen. Dann werden 50 V6lumteile des Lösungsmittels abdestilliert, und das Produkt wird nach dem Abkühlen mit einer Mischung von konzentrierter Salzsäure (2o Volumteile) und Wasser (2o Volumteile) angesäuert. Durch Ausschütteln mit Äther werden 52 Gewichtsteile der unreinen y, y-Diphenyl-a-acetotetronsäure, entsprechend einer Ausbeute von 88,5 °/o, gewonnen. Durch Umkristallisation aus n-Butanol wird die reine Verbindung mit einem Schmelzpunkt von io2° erhalten.Example 2 '- y, y = diphenyl-a-acetotetronic acid A mixture of sodium ethylate from 4.6 parts by weight of sodium in 70 parts by volume of ethanol and 62 parts by weight of the acetoacetate of methyl benzilic acid (F. 9i to 92 °) in 100 parts by volume of benzene is refluxed 3 Heated to the boil for hours and then left to stand overnight. Then 50 parts by volume of the solvent are distilled off and, after cooling, the product is acidified with a mixture of concentrated hydrochloric acid (20 parts by volume) and water (20 parts by volume). Shaking out with ether gives 52 parts by weight of the impure γ, γ-diphenyl-α-acetotetronic acid, corresponding to a yield of 88.5%. The pure compound with a melting point of 10 ° is obtained by recrystallization from n-butanol.
Benzilsäüreäthylester und Benzilsäureisopropylester können an Stelle des Benzilsäuremethylesters treten, wobei ähnliche Ausbeuten der gleichen Säure (y, y-Diphenyl-a-acetotetronsäure) erhalten werden.Ethyl benzilate and isopropyl benzilate can be used in place of the methyl benzilate occur, with similar yields of the same acid (y, y-diphenyl-a-acetotetronic acid).
Beispiel 3 a-Methyl-y-benzyl-a-acetotetronsäure 40,7 Gewichtsteile des Acetoacetats des a-Benzylmilchsäuremethylesters (Kpi,b 144 bis i50°; n' 1.5047) in 50 Volumteilen Benzol werden mit einer Natriumäthylatlösung, die aus 3,5 Gewichtsteilen Natrium und 50 Volumteilen Äthanol erhalten worden ist, 4 Stunden am Rückflußkühler erhitzt. Nach Ansäuern mit wäßriger Salzsäure wird das Reaktionsprodukt isoliert, wobei 30 Gewichtsteile einer schwachgelben festen Substanz mit einem Schmelzpunkt von 8o bis 87° erhalten werden. Die Umkristallisation aus wäßrigem Methanol ergibt reine y-Methyl-y-benzyl-a-acetotetronsäure in Form von Nadeln mit einem Schmelzpunkt von 92 bis 93°. Beispiel 4 y-Cyclohexanspiro-a-acetotetronsäure 74,5 Gewichtsteile des Acetoacetats des i-Carbomethoxy-i-oxycyclohexans werden in ioo Volumteilen Benzol zu einer Lösung von Natriummethylat, die aus 7 Gewichtsteilen Natrium und ioo Volumteilen Methanol hergestellt worden ist, zugefügt, und die Mischung wird 4 Stunden am Rückflußkühler erhitzt. Nach dem Ansäuern mit verdünnter Salzsäure wird das Reaktionsprodukt mit Chloroform isoliert, wobei 62 Gewichtsteile rohe y-Cyclohexaä-spiroa-acetotetronsäure anfallen. Durch Umkristallisation aus Methanol wird das reine Produkt mit einem Schmelzpunkt von 125 bis i26° erhalten.Example 3 a-Methyl-γ-benzyl-a-acetotetronic acid 40.7 parts by weight of the acetoacetate of a-benzyllactic acid methyl ester (Kpi, b 144 to 150 °; n '1.5047) in 50 parts by volume of benzene are mixed with a sodium ethylate solution consisting of 3.5 Parts by weight of sodium and 50 parts by volume of ethanol has been obtained, heated under the reflux condenser for 4 hours. After acidification with aqueous hydrochloric acid, the reaction product is isolated, 30 parts by weight of a pale yellow solid substance with a melting point of 80 ° to 87 ° being obtained. Recrystallization from aqueous methanol gives pure γ-methyl-γ-benzyl-α-acetotetronic acid in the form of needles with a melting point of 92 to 93 °. Example 4 γ-Cyclohexanspiro-α-acetotetronic acid 74.5 parts by weight of the acetoacetate of i-carbomethoxy-i-oxycyclohexane are added in 100 parts by volume of benzene to a solution of sodium methylate, which has been prepared from 7 parts by weight of sodium and 100 parts by volume of methanol, and the mixture is refluxed for 4 hours. After acidification with dilute hydrochloric acid, the reaction product is isolated with chloroform, 62 parts by weight of crude γ-cyclohexaä-spiroa-acetotetronic acid being obtained. The pure product with a melting point of 125 to i26 ° is obtained by recrystallization from methanol.
. Diese Arbeitsweise kann auch in n-Butanollösung durchgeführt werden, wobei Benzol und Methanol durch Zoo Volumteile Butanol ersetzt werden und als Katalysator Kalium-n-butylat angewendet wird. Es wird eine Ausbeute von 63 Gewichtsteilen erhalten.. This procedure can also be carried out in n-butanol solution, whereby benzene and methanol are replaced by zoo parts by volume of butanol and as a catalyst Potassium n-butoxide is applied. A yield of 63 parts by weight is obtained.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB425152A GB737458A (en) | 1952-02-18 | 1952-02-18 | Production of alpha-acetotetronic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE946986C true DE946986C (en) | 1956-08-09 |
Family
ID=9773590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB24325A Expired DE946986C (en) | 1952-02-18 | 1953-02-17 | Process for the production of ª ‡ -acetotetronic acids |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE946986C (en) |
| GB (1) | GB737458A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1161260B (en) * | 1960-07-23 | 1964-01-16 | Dr Karl Thomae Gesellschaft mit beschrankter Haftung, Biberach/Riß | Process for the preparation of new alpha-enol acylates of beta-acyl-gamma-phenyl-alpha-tetronic acids. |
-
1952
- 1952-02-18 GB GB425152A patent/GB737458A/en not_active Expired
-
1953
- 1953-02-17 DE DEB24325A patent/DE946986C/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB737458A (en) | 1955-09-28 |
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