DE277392C - - Google Patents
Info
- Publication number
- DE277392C DE277392C DENDAT277392D DE277392DA DE277392C DE 277392 C DE277392 C DE 277392C DE NDAT277392 D DENDAT277392 D DE NDAT277392D DE 277392D A DE277392D A DE 277392DA DE 277392 C DE277392 C DE 277392C
- Authority
- DE
- Germany
- Prior art keywords
- parts
- reduced
- disecondary
- glycols
- aliphatic aldehydes
- 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.)
- Active
Links
- 150000002334 glycols Chemical group 0.000 claims description 5
- -1 saturated aliphatic aldehydes Chemical class 0.000 claims description 4
- 230000002378 acidificating Effects 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000005591 charge neutralization Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001264 neutralization Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- FXHGMKSSBGDXIY-UHFFFAOYSA-N Heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/29—Coupling reactions
- C25B3/295—Coupling reactions hydrodimerisation
Description
KAISERLICHES.IMPERIAL.
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
Ä 277392 KLASSE 12 o. GRUPPEÄ 277392 CLASS 12 or GROUP
Verfahren zur Darstellung disekundärer Glykole. Patentiert im Deutschen Reiche vom 6.Mai 1913 ab..Process for preparing disecondary glycols. Patented in the German Empire on May 6, 1913 ..
Es ist bekannt, daß sich Ketone unter gleichzeitiger Zusammenlagerung zweier Moleküle zu Pinakonen, aromatische Aldehyde zu Hydrobenzoinen und, ungesättigte aliphatische Aldehyde in vereinzelten Fällen zu ungesättigten disekundären Glykolen (Comptes rendus 128, 736; Journal of chemical Society 1912, 1016; Annales de Chimie et de Physique [6] 26, 369) reduzieren lassen. Im Gegensatz hierzu sind gesättigte aliphatische Aldehyde bisher nie zu disekundären Glykolen reduziert worden.It is known that ketones are formed with the simultaneous assembly of two molecules to pinacones, aromatic aldehydes to hydrobenzoins and, unsaturated aliphatic Aldehydes in isolated cases to unsaturated disecondary glycols (Comptes rendus 128, 736; Journal of chemical Society 1912, 1016; Annales de Chimie et de Physique [6] 26, 369) can be reduced. In contrast, saturated aliphatic aldehydes are so far never been reduced to disecondary glycols.
Es wurde nun gefunden, daß gesättigte aliphatische Aldehyde zu disekundären GIykolen auf elektrolytischem Wege an metallischen Kathoden in sauren Medien reduziert werden können nach der Gleichung:.It has now been found that saturated aliphatic aldehydes give disecondary glycols be reduced electrolytically on metallic cathodes in acidic media can according to the equation:
2R —CHO + 2H
= R — CHOH — CHOH — R (R = Alkyl).2R -CHO + 2H
= R - CHOH - CHOH - R (R = alkyl).
In 900 Teile 3oprozentige Schwefelsäure, die durch Eisstücke auf o° abgekühlt sind, werden 1000 Teile Acetaldehyd unter Rühren eingetragen und mit Wasser auf 3000 Teile aufgefüllt. Dieses Gemisch wird in den Kathodenraum eines Quecksilberelektrolyseurs von etwa 360 qcm wirksamer Kathodenfläche eingefüllt und dort bei 15 bis 20° oder auch höherer Temperatur etwa 60 Stunden lang durch einen Strom von 20 Ampere (Stromdichte pro qdm 5,5 Ampere, Stromkonzentration pro Liter 6,7 Ampere) elektrolytisch reduziert. Das 2 · 3-Butylenglykol kann entweder durch Neutralisation mit Kreide, Ab-. saugen vom Gips und fraktionierte Vakuumdestillation oder durch Aussalzen mit Pottasche, Ausäthern und Fraktionieren oder schließlich nach der Neutralisation mit Kreide durch Aufsaugen in entwässertem Natriumsulfat und darauffolgende Behandlung mit Äther im Soxhlet in guter Ausbeute gewonnen werden^In 900 parts of 3% sulfuric acid, which have been cooled to 0 ° by pieces of ice, 1000 parts of acetaldehyde are introduced with stirring and with water to 3000 parts filled up. This mixture is put into the cathode compartment of a mercury electrolyser of about 360 square cm of effective cathode area and there at 15 to 20 ° or even higher temperature for about 60 hours by a current of 20 amperes (current density per square meter 5.5 amperes, current concentration per liter 6.7 amperes) electrolytically reduced. The 2x3-butylene glycol can either by neutralization with chalk, ab-. sucking off the plaster of paris and fractional vacuum distillation or by salting out with potash, etherifying and fractionating or finally after neutralization with chalk by soaking in dehydrated sodium sulfate and subsequent treatment with ether in the Soxhlet in good yield will ^
Ein Gemisch von 100 Teilen Heptylaldehyd und 300 Teilen 30 prozentiger Schwefelsäure wird mit Alkohol auf 1000 Teile aufgefüllt und, wie im Beispiel ι angegeben, elektrolytisch reduziert. Zur Reduktion sind etwa 200 Ampere-Stunden erforderlich. Das Dihexyläthylenglykol A mixture of 100 parts of heptylaldehyde and 300 parts of 30 percent sulfuric acid is made up to 1000 parts with alcohol and, as indicated in Example ι, electrolytically reduced. Approximately 200 ampere-hours are required for the reduction. The dihexylethylene glycol
CH3-(CH2J5-CH(OH) -CH(OH)- (CH2J5-CH3 CH 3 - (CH 2 J 5 -CH (OH) -CH (OH) - (CH 2 J 5 -CH 3
5555
wird der Kathodenflüssigkeit durch Äther entzogen und befindet sich in der höchstsiedenden Fraktion des Ätherauszugs. Siedepunkt 275 bis 277 °.is withdrawn from the catholyte by ether and is in the highest boiling point Aether Extract faction. Boiling point 275 to 277 °.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE277392C true DE277392C (en) |
Family
ID=533492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT277392D Active DE277392C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE277392C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2457911A1 (en) * | 1979-06-01 | 1980-12-26 | Toyo Soda Mfg Co Ltd | PROCESS FOR THE PRODUCTION OF GLYCOL FROM FORMALDEHYDE BY ELECTROLYSIS |
| EP0024178A2 (en) * | 1979-08-14 | 1981-02-25 | E.I. Du Pont De Nemours And Company | Process for preparing alkanediols by electrochemical coupling of halohydrins and an electrolytic cell suitable for carrying out the process |
-
0
- DE DENDAT277392D patent/DE277392C/de active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2457911A1 (en) * | 1979-06-01 | 1980-12-26 | Toyo Soda Mfg Co Ltd | PROCESS FOR THE PRODUCTION OF GLYCOL FROM FORMALDEHYDE BY ELECTROLYSIS |
| EP0024178A2 (en) * | 1979-08-14 | 1981-02-25 | E.I. Du Pont De Nemours And Company | Process for preparing alkanediols by electrochemical coupling of halohydrins and an electrolytic cell suitable for carrying out the process |
| EP0024178A3 (en) * | 1979-08-14 | 1981-05-20 | E.I. Du Pont De Nemours And Company | Process for preparing alkanediols by electrochemical coupling of halohydrins, alkanediols, when produced by such process, and an electrolytic cell suitable for carrying out the process |
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