Claims
- 1. In a process for manufacturing and recovering an alkynediol by reacting a ketone, acetylene and potassium hydroxide, the improvement comprising:
- synchronously reacting a C.sub.3-12 ketone, acetylene, potassium hydroxide and C.sub.1-4 alkyl-t-butyl ether solvent, wherein said potassium hydroxide is present as aqueous KOH having a water content of 10 to 24% by weight in a molar ratio relative to said ketone ranging from 1.0:1.0 to 1.6:1.0.
- 2. The process of claim 1, wherein said C.sub.1-4 alkyl-t-butyl ether is methyl-t-butyl ether.
- 3. The process of claim 1, wherein the molar ratio of said potassium hydroxide to said ketone ranges from 1.2:1.0 to 1.5:1.0.
- 4. The process of claim 1, wherein said C.sub.3-12 ketone is acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, or cyclohexanone.
- 5. The process of claim 1, wherein the molar ratio of said ketone to said acetylene ranges from 1.0:1.0 to 3.0:1.0.
- 6. The process of claim 1, wherein the molar ratio of said ketone to said acetylene ranges from 1.8:1.0 to 2.2:1.0.
- 7. The process of claim 1, wherein the water content of the potassium hydroxide powder ranges from 12 to 15% by weight.
- 8. The process of claim 1, wherein said reaction is conducted at a temperature ranging from 20.degree.-55.degree. C.
- 9. The process of claim 8, wherein said temperature ranges from 30.degree.-50.degree. C.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 3711382 |
Apr 1987 |
DEX |
|
BACKGROUND OF THE INVENTION
This application is a Continuation of application Ser. No. 07/176,232, filed on Mar. 31, 1988, now abandoned.
1. Field of the Invention:
This invention relates to the manufacture of alkynediols.
2. Discussion of the Background:
A series of manufacturing procedures have been described for the manufacture of alkynediols of the general formula I ##STR1## In the case of aldehydes, formaldehyde and acetaldehyde can be readily converted with acetylene to the corresponding monoalcohols and glycols using Reppe's ethinylation process which use a copper acetylide catalyst. That method yields unsatisfactory results however if higher aldehydes are used.
Particular difficulties are experienced with the reaction of two moles of a ketone with one mole of acetylene. For that reaction to proceed at least one mole of a base is required. Previously described processes have used a finely divided anhydrous potassium hydroxide powder in organic solvents such as acetaldehyde-dibutyl acetal (U.S. Pat. No. 2 385 546, U.S. Pat. No. 2 385 548 and U.S. Pat. No. 2 455 058), methylal and dioxane (of. W. Ziegenbein; Einfuehrung der Aethinyl- und Alkinyl-Gruppe in organische Verbindungen, Verlag Chemie (1963)), diisopropyl ether (US 2 163 720) or tetrahydrofuran (DE-AS 26 28 145 (=U.S. Pat. No. 4,117,249)). A drawback of this approach is that increase in the water content of the potassium hydroxide used results in an increased consumption of KOH. Furthermore these suspensions in the abovementioned solvents are usually so highly viscous that proper mixing is rendered very difficult, and this viscosity problem cannot be avoided or mitigated by using a relatively high excess of solvent because the solvents used to date have been rather expensive and their recovery for re-use involves expensive procedures, making this approach economically prohibitive.
The process described in DE-PSS 20 08 675 (=GB 1,329,815) and 20 47 446 (=GB 1,354,011) employs, as the base, potassium alcoholates of aliphatic alcohols, and readily accessible aliphatic, cycloaliphatic or aromatic hydrocarbons are used as the solvent. However, this approach has the salient disadvantage that a suspension of finely divided potassium alcoholate in the solvent must be produced in a preliminary reaction.
When relatively long-chain aliphatic methyl ketones are reacted with acetylene, as described e.g. in DE-PS 26 28 145 (=U.S. Pat. No. 4,117,249), only an incomplete conversion of the ketone is attained in tetrahydrofuran when technical potassium hydroxide is used as the base. These unsatisfactory results are obtained even when a ratio of KOH to ketone of 2:1 is used. Moreover, this process usually produces a mixture of the monoalcohol and the desired acetylene glycol of the general formula I.
There is thus a strongly felt need for a process which permits the manufacture of alkynediols by the reaction of ketones with acetylene, providing high yields economically and with a variety of different ketones.
Accordingly, it is an object of this invention to provide a novel process for the manufacture of alkynediols by reacting ketones with acetylene.
It is another object of this invention to provide an economical process for the manufacture of alkynediols from the reaction of ketones with acetylene.
It is another object of this invention to provide a novel process for the manufacture of alkynediols, in high yields, from the reaction of ketones with acetylene.
Briefly, these objects and other objects of the present invention as hereinafter will become more readily apparent can be obtained in a process for producing an alkynediol by reacting a ketone with acetylene in the presence of potassium hydroxide where an alkyl-tert-butyl ether solvent is used and the potassium hydroxide is used in a molar ratio relative to the amount of ketone used of 1.0:1.0 to 1.6:1.0. The solvent used is a C.sub.1-4 alkyl-tertbutyl ether. The ketone which can be used is a C.sub.3-12 ketone.
US Referenced Citations (7)
Foreign Referenced Citations (2)
| Number |
Date |
Country |
| 1329815 |
Sep 1973 |
GBX |
| 1354011 |
May 1974 |
GBX |
Non-Patent Literature Citations (3)
| Entry |
| Weast, Robert, Handbook of Chemistry and Physics, Chemical Rubber Co., Cleveland, Ohio 1970-1971, 51st ed., p. C-293. |
| Jacobs et al., Chemical Analysis of Industrial Solvents, Interscience Publishers Inc., New York, New York, 1953, p. 43. |
| Einfuhrung der Athinyl-und Aklinyl-Gruppe in Organische Verbindungen, Dr. Willi Ziegenbein, Chemische Werke Huls, pp. 48-115. |
Continuations (1)
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Number |
Date |
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| Parent |
176232 |
Mar 1988 |
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Patent Grant
4960959
