DE2257083C3 - - Google Patents
Info
- Publication number
- DE2257083C3 DE2257083C3 DE19722257083 DE2257083A DE2257083C3 DE 2257083 C3 DE2257083 C3 DE 2257083C3 DE 19722257083 DE19722257083 DE 19722257083 DE 2257083 A DE2257083 A DE 2257083A DE 2257083 C3 DE2257083 C3 DE 2257083C3
- Authority
- DE
- Germany
- Prior art keywords
- rcoo
- oxidation
- palladium
- chloride
- ions
- 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
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 3
- 230000000875 corresponding Effects 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- -1 olefin compounds Chemical class 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- IKHGUXGNUITLKF-UHFFFAOYSA-N acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 229960000583 Acetic Acid Drugs 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M Potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 102000014961 Protein Precursors Human genes 0.000 description 2
- 108010078762 Protein Precursors Proteins 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- 101710043771 PDCL Proteins 0.000 description 1
- BWILYWWHXDGKQA-UHFFFAOYSA-M Potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M Sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 229960003212 Sodium propionate Drugs 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000005842 heteroatoms Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000004331 potassium propionate Substances 0.000 description 1
- 235000010332 potassium propionate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N triclene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
Description
2525th
Die Erfindung betrifft die Herstellung von Glykolestern, die zur Herstellung von Aminosäuren geeignete Zwischenprodukte sind.The invention relates to the production of glycol esters which are suitable for the production of amino acids Are intermediates.
Aus J. S mi dt, Ang. Chem., 71 (1959), S. 176 bis 182, ist es bekannt, Olefine in Gegenwart von Palladium enthaltenden Katalysatoren in einem wäßrigen Lösungsmittel zu oxidieren, wobei gesättigte Aldehyde und Ketone mit der gleichen Anzahl von Kohlenstoffatomen erhalten werden. Insbesondere ist es möglich, Acetaldehyd aus Äthylen, Aceton uad Propionaldehyd aus Propylen usw. zu erhalten.From J. S mi dt, Ang. Chem., 71 (1959), pp. 176 to 182, it is known to use olefins in the presence of palladium containing catalysts to oxidize in an aqueous solvent, with saturated aldehydes and ketones having the same number of carbon atoms can be obtained. In particular it is possible to obtain acetaldehyde from ethylene, acetone uad propionaldehyde from propylene, etc.
Es ist auch bekannt, daß bei Anwendung des gleichen Verfahrens auf Olefinverbindungen mit elektronenanziehenden Gruppen, die Heteroatome in den Stellungen 1 oder 2 bezüglich der Doppelbindung enthalten, keine Oxidation bewirkt, sondern eine Eliminierungsreaktion eintritt. Beispielsweise kann das Vinylacetat nicht zum Triacetylglykolaldehyd oxidiert werden, sondern es findet eine Eliminierung der Acetylgruppe unter Bildung von Acetaldehyd statt.It is also known that when using the same Method based on olefin compounds with electron withdrawing groups, the heteroatoms in the Contain positions 1 or 2 with respect to the double bond, causes no oxidation, but one Elimination reaction occurs. For example, the vinyl acetate cannot form triacetyl glycol aldehyde are oxidized, but there is an elimination of the acetyl group with the formation of acetaldehyde instead of.
Es wurde nun gefunden, daß es möglich ist. Olefin- so verbindungen, die in 1-Stellung durch elektronenanziehende Gruppen substituiert sind, zu den entsprechenden Carbonylderivaten zu oxidieren.It has now been found to be possible. Olefin so compounds which are substituted in the 1-position by electron-withdrawing groups to the corresponding To oxidize carbonyl derivatives.
Die Erfindung betrifft daher ein Verfahren zur Herstellung von Glykolestern der allgemeinen FormelThe invention therefore relates to a process for the preparation of glycol esters of the general formula
(RCOO)2CH — HC(RCOO) 2 CH - HC
R1 R 1
6060
worin X die Bedeutung von RCOO oder von Cl hat, RCOG den Acetoxy- oder Propionyloxyrest darstellt, Und R1 ein Wasserstoffatom oder ein Alkyl- oder Cycloalkyirest mit 1 bis 8 Kohlenstoffatomen ist, durch Oxidation der entsprechenden Olefinverbindungen in Gegenwart von Palladium(II)-chlorid bei einer Temperatur von 25 bis 10O0C, das dadurch gekennzeichnet ist, daß man die Oxidation in einem wasserfreien Lösungsmittel der allgemeinen Formel RCÖÖH in Anwesenheit von RCOOe-Ionen, wobei RCOO die vorstehend angegebenen Bedeutungen besitzt, durchführtwhere X has the meaning of RCOO or of Cl, RCOG represents the acetoxy or propionyloxy radical, and R 1 is a hydrogen atom or an alkyl or cycloalkyl radical with 1 to 8 carbon atoms, by oxidation of the corresponding olefin compounds in the presence of palladium (II) - chloride at a temperature of 25 to 10O 0 C, which is characterized in that the oxidation is carried out in an anhydrous solvent of the general formula RCÖÖH in the presence of RCOO e ions, where RCOO has the meanings given above
Unter den erfindungsgemäßen Bedingungen findet die Oxidation der Doppelbindung unter Bildung eines Diesters gemäß der folgenden Reaktionsfolge statt:Under the conditions according to the invention, the double bond is oxidized with formation of a diester according to the following reaction sequence:
CH2=C + Pd++ + 2 RCOOHCH 2 = C + Pd ++ + 2 RCOOH
/
ROCO-CH-HC + Pd + 2H/
ROCO-CH-HC + Pd + 2H
OCOROCOR
R1 R 1
worin R, X und R1 die vorstehend angegebene Bedeutung besitzen.wherein R, X and R 1 are as defined above.
Als Vorläufer für R — COOe-Ionen können Natriumacetat, Kaliumacetat, Kalium- und Natriumpropionat verwendet werden. Vorzugsweise ist die Menge dieser Vorläufer von R — COOe-Ionen den Molen des verwendeten Palladium(II)-chlorids äquivalent.Sodium acetate, potassium acetate, potassium and sodium propionate can be used as precursors for R - COO e ions. The amount of these precursors of R - COO e ions is preferably equivalent to the moles of palladium (II) chloride used.
Die folgenden Beispiele erläutern das Verfahren der Erfindung.The following examples illustrate the process of the invention.
Beispiel 1
Reaktionsschema:example 1
Reaction scheme:
OCOCH3 OCOCH 3
CH2 =CH 2 =
+ Pd++ +2CH3COOH
OCOCH3 + Pd ++ + 2CH 3 COOH
OCOCH 3
(CH3COO)2CH-CH2 + Pd + 2H + (CH 3 COO) 2 CH-CH 2 + Pd + 2H +
O^IMolVinylacetatwurdeineinemKolben zu 25 ml Eisessig und 2 ml Essigsäureanhydrid gefügt. Darauf wurden 0,01 Mol PdCl2 und 0,01 Mol Natriumacetat zugefügt.O ^ IMol vinyl acetate was added to 25 ml of glacial acetic acid and 2 ml of acetic anhydride in a flask. Then 0.01 mol of PdCl 2 and 0.01 mol of sodium acetate were added.
Ein Natriumchlorid-Niederschlag fällt aus. Nach dreistündigem Rühren bei 35° C werden Essigsäure und Essigsäureanhydrid unter vermindertem Druck verdampft. Der Rückstand besteht aus metallischem Palladium, Triacetylglykolaldehyd und anderen Produkten. Nach Extraktion mit Trichlorethylen und Destillation unter vermindertem Druck erhält man 1,5 g Triacetylglykolaldehyd (Ausbeute 75%).A sodium chloride precipitate separates out. After three hours of stirring at 35 ° C., acetic acid becomes and acetic anhydride evaporated under reduced pressure. The residue consists of metallic Palladium, triacetyl glycol aldehyde and other products. After extraction with trichlorethylene and Distillation under reduced pressure gives 1.5 g of triacetyl glycol aldehyde (yield 75%).
Beispiel 2
Reaktionsschema:
ClExample 2
Reaction scheme:
Cl
CH2 = C + Pd++ + 2CH3COOHCH 2 = C + Pd ++ + 2CH 3 COOH
\ j C,
(CH3COO)2CH-CH2 + Pd + 2H+ \ j C,
(CH 3 COO) 2 CH-CH 2 + Pd + 2H +
Die Arbeitsweise von Beispiel 1 wird wiederholt, wobei jedoch von Vinylchlorid, an Stelle von Vinylacetat, ausgegangen wird. Man erhält eine Ausbeute von 75%.The procedure of Example 1 is repeated, but using vinyl chloride instead of vinyl acetate, is assumed. A yield of 75% is obtained.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT31735/71A IT941807B (en) | 1971-11-26 | 1971-11-26 | PROCEDURE FOR THE OXIDATION OF VINYL COMPOUNDS |
| IT3173571 | 1971-11-26 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2257083A1 DE2257083A1 (en) | 1973-05-30 |
| DE2257083B2 DE2257083B2 (en) | 1975-08-14 |
| DE2257083C3 true DE2257083C3 (en) | 1976-04-01 |
Family
ID=11234292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2257083A Granted DE2257083B2 (en) | 1971-11-26 | 1972-11-21 | Process for the production of glycol esters |
Country Status (9)
| Country | Link |
|---|---|
| BE (1) | BE791713A (en) |
| DE (1) | DE2257083B2 (en) |
| FR (1) | FR2160938B1 (en) |
| GB (1) | GB1407480A (en) |
| IE (1) | IE38001B1 (en) |
| IT (1) | IT941807B (en) |
| LU (1) | LU66539A1 (en) |
| NL (1) | NL7215699A (en) |
| NO (1) | NO135821C (en) |
-
0
- BE BE791713D patent/BE791713A/en unknown
-
1971
- 1971-11-26 IT IT31735/71A patent/IT941807B/en active
-
1972
- 1972-11-15 IE IE1575/72A patent/IE38001B1/en unknown
- 1972-11-17 GB GB5337372A patent/GB1407480A/en not_active Expired
- 1972-11-20 NL NL7215699A patent/NL7215699A/xx not_active Application Discontinuation
- 1972-11-21 DE DE2257083A patent/DE2257083B2/en active Granted
- 1972-11-22 FR FR7241407A patent/FR2160938B1/fr not_active Expired
- 1972-11-24 LU LU66539A patent/LU66539A1/xx unknown
- 1972-11-24 NO NO4312/72A patent/NO135821C/no unknown
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