DE1000803B - Process for the separation of carbonyl compounds from mixtures with low or insoluble oxy- or ether-group-containing ethynyl compounds in water - Google Patents
Process for the separation of carbonyl compounds from mixtures with low or insoluble oxy- or ether-group-containing ethynyl compounds in waterInfo
- Publication number
- DE1000803B DE1000803B DEB27805A DEB0027805A DE1000803B DE 1000803 B DE1000803 B DE 1000803B DE B27805 A DEB27805 A DE B27805A DE B0027805 A DEB0027805 A DE B0027805A DE 1000803 B DE1000803 B DE 1000803B
- Authority
- DE
- Germany
- Prior art keywords
- compounds
- mixtures
- oxy
- insoluble
- separation
- 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.)
- Pending
Links
- 150000001728 carbonyl compounds Chemical class 0.000 title claims description 14
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 title claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 7
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 title claims description 5
- 238000000926 separation method Methods 0.000 title claims description 3
- 125000001033 ether group Chemical group 0.000 title description 4
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011260 aqueous acid Substances 0.000 claims 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- KDKYADYSIPSCCQ-UHFFFAOYSA-N ethyl acetylene Natural products CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zum Abtrennen von Carbonylverbindungen aus Gemischen mit in Wasser wenig oder unlöslichen oxy- oder äthergruppenhaltigen Athinylverbindungen Oxygruppenhaltige Äthinylverbindungen, wie sie z. B. durch Anlagerung von Acetylen an Carbonylverbindungen entstehen, und die aus ihnen herzustellenden äthergruppenhaltigen Verbindungen lassen sich manchmal nur schwierig von den nicht umgesetzten Carbonylverbindungen abtrennen, insbesondere, wenn es sich um Ausgangsstoffe mit mehr als 3 C-Atomen handelt. Eine fraktionierte Destillation führt meistens nicht zum Ziel. Process for separating carbonyl compounds from mixtures with in water little or insoluble oxy- or ether-group-containing ethynyl compounds Oxy group-containing ethynyl compounds, as they are, for. B. by addition of acetylene of carbonyl compounds and the ether group-containing ones to be produced from them Compounds are sometimes difficult to remove from the unreacted carbonyl compounds separate them, especially if they are starting materials with more than 3 carbon atoms acts. Fractional distillation usually does not achieve its goal.
Es wurde nun gefunden, daß man solche Gemische auf einfache Weise zerlegen kann, wenn man sie mit größeren Mengen von stark sauer reagierenden Stoffen in wäßriger Lösung behandelt und dann die Athinylverbinidungen in reiner Form von der wäßrig-sauren, sämtliche Carbonylverbindungen enthaltenden Lösung abtrennt. It has now been found that such mixtures can be obtained in a simple manner Can decompose if you use them with large amounts of strongly acidic substances treated in aqueous solution and then the Athinylverbinidungen in the pure form of separates the aqueous acidic solution containing all carbonyl compounds.
Solche sauren Stoffe sind z. B. starke Mineralsäuren, wie etwa 30- bis 35 0/oige Salzsäure, Überchlorsäure und etwa 500/oige oder höher konzentrierte Schwefelsättre, ferner etwa 40- bis 700/oige wäßrige Zinkchlorid- oder Kaliumbisulfatlösungen. Such acidic substances are z. B. strong mineral acids such as 30- up to 35% hydrochloric acid, superchloric acid and about 500% or more concentrated Sulfur saturation, furthermore about 40 to 700% aqueous zinc chloride or potassium bisulfate solutions.
Diese bilden mit den Carbonylverbindungen Oxoniumsalze, die wasserlöslich sind und so leicht von den Ä thinyl verbindungen abgetrennt werden können.These form oxonium salts with the carbonyl compounds, which are water-soluble and can thus be easily separated from the ethynyl compounds.
Die Menge und Konzentration der anzuwendenden sauer reagierenden Stoffe richtet sich nach der Art und Menge der abzutrennenden Carbonylverbindungen und kann durch Versuche leicht ermittelt werden. The amount and concentration of acidic reactants to be applied Substances depend on the type and amount of carbonyl compounds to be separated and can easily be determined by experiment.
Die sauer reagierenden Stoffe müssen jedoch in ausreichender Menge vorhanden sein, um alle Carbonylverbindungen in die wasserlöslichen Oxoniumverbindungen überzuführen. In der Regel arbeitet man mit einer den sauren Stoff im Überschuß enthaltenden wäßrigen Lösung bei Temperaturen von etwa -10 bis 4300. Es bilden sich zwei Schichten, die sich leicht trennen lassen. Aus der das Oxoniumsalz der Carl)onylverbindun,g enthaltenden sauren, wäßrigen Schicht kann man die Carbonylverbindung, z. B. durch Verdünnen mit Wasser, durch Aussalzen oder durch Neutralisieren und Ausäthern, wiedergewinnen.However, the acidic reacting substances must be in sufficient quantity present to all carbonyl compounds in the water soluble oxonium compounds convict. As a rule, one works with one of the acidic substances in excess containing aqueous solution at temperatures of about -10 to 4300. It is formed two layers that are easy to separate. From which the oxonium salt of the Carl) onylverbindun, g containing acidic, aqueous layer can be the carbonyl compound, for. B. by Dilute with water, by salting out or by neutralizing and etherifying, recover.
Der Vorteil des Verfahrens besteht darin, daß es auf einfache Weise gelingt, die oxy- oder äthergruppenhaltigen Athinylverbind,ungen rein zu erhalten und die Carbonylverbindung zurückzugewinnen. Es ist überraschend, daß die wenig stabilen Äthinylverbindungen bei der Behandlung des Gemisches mit sauer reagierenden Stoffen unangegriffen bleiben. The advantage of the procedure is that it is easy to use succeeds in keeping the ethynyl compounds containing oxy or ether groups in pure form and recover the carbonyl compound. It is surprising that the little stable ethynyl compounds when the mixture is treated with acidic ones Fabrics remain unaffected.
Es ist zwar bekannt, Carbonylverbindungen aus wäßrigem Propargylalkohol abzutrennen, indem man die Ausgangslösung mit Methanol, zweckmäßig in Gegenwart von geringen Mengen Säure, behandelt und die gebildeten Acetale abdestilliert. It is known to use carbonyl compounds from aqueous propargyl alcohol separated by mixing the starting solution with methanol, expediently in the presence of small amounts of acid, treated and the acetals formed are distilled off.
Gegenüber dieser Arbeitsweise hat das erfindungsgemäße Verfahren den Vorteil, daß sich die Trennung in kürzester Zeit mit äußerst einfachen apparativen Mitteln ohne Mitverwendung weiterer organischer Flüssigkeiten durchführen läßt und die Garbonylverbindungen sich einfacher aus den abgetrennten Verbindungen zufiickerhalten lassen als durch Spaltung von Acetalen. Compared to this procedure, the method according to the invention has the advantage that the separation takes place in a very short time with extremely simple apparatus Can carry out means without the use of other organic liquids and the carbonyl compounds are more easily obtained from the severed compounds let than by cleavage of acetals.
Die nach dem erfindungsgemaßen Verfahren rein erhaltenen ÄthinylverbinSdungen, z. B. das aus Methyläthylketon und Acetylen gewonnene 3-Methylpentin-(1)-ol-(3), können zur Herstellung von pharmazeutischen Stoffen dienen. The ethynyl compounds obtained in pure form by the process according to the invention, z. B. 3-Methylpentin- (1) -ol- (3) obtained from methyl ethyl ketone and acetylene, can be used for the production of pharmaceutical substances.
Beispiel 1 Ein Gemisch von 20 kg Äthinylcyclohexanoi mit 5 kg Cyclohexanon wird unter kräftigem Rühren bei 5° in 100 1 500/oige Schwefelsäure eingetragen. Man rührt etwa 1/4 Stunde weiter und trennt dann die Schichten im Scheidetrichter. Die obere Schicht, die das Äthinylcyclohexanol enthält, ist frei von Cyclohexanon. Aus der schwefelsäurehaltigen Lösung werden durch Neutralisation und Ausäthern 5 kg Cyclohexanon zurückerhalten. Example 1 A mixture of 20 kg of ethynylcyclohexanone with 5 kg of cyclohexanone is introduced into 100 1,500 / o sulfuric acid at 5 ° with vigorous stirring. Stirring is continued for about 1/4 hour and then the layers are separated in a separating funnel. The upper layer, which contains the ethynylcyclohexanol, is free of cyclohexanone. The solution containing sulfuric acid becomes 5 kg of cyclohexanone recovered.
Beispiel 2 Ein Gemisch von 30 kg 3-Methylpentin-(1)-ol-(3) mit 2 kg Methyläthylketon läßt man bei 5° in ein Rührgefäß, in dem 130 1 600/oige Schwefelsäure schnell gerührt werden, einfließen. Nach Beendigung des Eintragens rührt man etwa 15 Minuten weiter undqtrennt die Schichten im Scheidetrichter. Example 2 A mixture of 30 kg of 3-methylpentine- (1) -ol- (3) with 2 kg of methyl ethyl ketone are left at 5 ° in a stirred vessel containing 130 1,600% sulfuric acid be stirred quickly, pour in. After completing the entry, stir for about Continue for 15 minutes and separate the layers in the separatory funnel.
Die obere Schicht enthält kein Methyläthylketon. The upper layer does not contain any methyl ethyl ketone.
Dieses kann aus der schwefelsäu,rehaltigen Lösung zurückgewonnen werden.This can be recovered from the sulfuric acid, rich solution.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB27805A DE1000803B (en) | 1953-10-07 | 1953-10-07 | Process for the separation of carbonyl compounds from mixtures with low or insoluble oxy- or ether-group-containing ethynyl compounds in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB27805A DE1000803B (en) | 1953-10-07 | 1953-10-07 | Process for the separation of carbonyl compounds from mixtures with low or insoluble oxy- or ether-group-containing ethynyl compounds in water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1000803B true DE1000803B (en) | 1957-01-17 |
Family
ID=6962478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB27805A Pending DE1000803B (en) | 1953-10-07 | 1953-10-07 | Process for the separation of carbonyl compounds from mixtures with low or insoluble oxy- or ether-group-containing ethynyl compounds in water |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1000803B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1096896B (en) | 1958-04-03 | 1961-01-12 | Wacker Chemie Gmbh | Process for removing small amounts of carboxylic acids from vinyl esters |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2527358A (en) * | 1948-12-29 | 1950-10-24 | Gen Aniline & Film Corp | Process of purifying propargyl alcohol |
-
1953
- 1953-10-07 DE DEB27805A patent/DE1000803B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2527358A (en) * | 1948-12-29 | 1950-10-24 | Gen Aniline & Film Corp | Process of purifying propargyl alcohol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1096896B (en) | 1958-04-03 | 1961-01-12 | Wacker Chemie Gmbh | Process for removing small amounts of carboxylic acids from vinyl esters |
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