JPS6132A - Alcohol separating agent - Google Patents

Abstract

PURPOSE:The titled separating agent that is composed of a specific acetylenic alcohol, thus forming stable complexes with alcohols to enable no-loss separation and recovery of the alcohol from an alcohol-containing solution in high yield and recovery by filtration and drying. CONSTITUTION:The objective alcohol-separating agent is composed of a compound of formula I (R1-R5, R6-R10 are H, lower alkyl where at least one of R1-R5 and R6-R10 are lower alkyls). The agent is added to a solution containing more than 5%, preferably more than 30% of alcohol to form a complex with the alcohol in the form of crystals. The precipitate is filtered, rinsed, dried, then heated to liberate the alcohol whereby pure alcohol or alcohol of high purity is obtained. The compound of formula I is obtained by reaction of a benzophenone derivative of formula II with acetylene in liquid ammonia in the presence of sodium amide.

Description

[Detailed Description of the Invention] "Industrial Application Field" This invention relates to an alcohol-separated type consisting of an acetylene alcohol compound. The alcohol separating agent is a compound that, when added to neutralize a solution containing alcohol, forms complex crystals with the alcohol in the solution and precipitates, thereby separating the alcohol.

"Prior Art" Conventionally, 9-(1-propynyl)-9-hydroxyfluorene and h2.5-
Bis(2,4-dimethylphenyl)hydroquinone is known [38th Autumn Annual Meeting of the Chemical Society of Japan (including the Union Forum)]
・Chemical Studies Association Federation Council Research Presentation・Chubu Chemical Association Branch Federation Autumn Conference Joint Conference Proceedings N2〉-1
, 612 pages “Special compounds that allow you to distinguish between molecules” Incorporated Association
Published by the Chemical Society of Japan (197B); to8m1iitr7Le
tters, PP, 1699-1702 (19
83) (published by the Chemi
cal 5ociety of Japal? l) )
.

"Problems to be Solved by the Invention" The properties of the above compound were discovered by the present inventors, and are useful in allowing easy separation of alcohol from a solution containing alcohol. Alcohol separating agents that can easily separate alcohol and are easy to manufacture have a wide range of uses, and therefore there is a current demand for agents that have good performance and are inexpensive. 'Means for Solving the Problems' Continuing the research and development of the conventional alcohol separating agents mentioned above, the present inventors were further conducting research on this type of alcohol separating agent, and found that a child with the following structure was found. It has been found that a chill alcohol-based compound [hereinafter referred to as compound (1)] exhibits good performance as an alcohol separating agent.

That is, general formula (1) (wherein R, ~R,, R, ~R1° are hydrogen atoms or lower alkyl groups. However, R, NR, and R0~
At least one of each R10 is a lower alkyl group. ). It is an acetylene alcohol compound.

In the definition of RIRs and Re RIo in the above formula (I), the lower alkyl group is a straight or branched alkyl group having 1 to 4 carbon atoms, such as methinepeethyl, nipropyl,
Includes 1-propyl, n-butyl, 1-butyl and the like.

From the viewpoint of ease of complex formation with alcohol, stability of the complex, etc., RI is lower alkyl, at least one of R2 to R4 is a lower alkyl group, R is a hydrogen atom, Ra R,
Compound (1) in which at least one of +o is a lower alkyl group, and at least one of R6 and RIG is a hydrogen atom
is particularly preferred.

Compound (1) is a compound represented by the formula (n) (where R and -R1° have the same meanings as above) and a compound (acetylene) represented by the formula (1). can be prepared by reacting in liquid ammonia in the presence of sodium amide. A small amount of a solvent such as tetrahydrofuran or ethyl ether may be used to dissolve compound (II) or compound (II). The appropriate reaction temperature is about 40 to -65°C. After the reaction is complete, ammonia ftg is released, neutralized with a mineral acid such as hydrochloric acid, and extracted with a solvent such as ethyl ether that dissolves compound (1) but has poor compatibility with water. By distilling off the compound (1
) can be obtained.

Compound (I) forms a complex with alcohol in a solution containing various alcohols, and this complex generally has low solubility in water and precipitates as crystals.

When this is separated into solid and liquid, washed, dried, and heated, alcohol is liberated and pure alcohol or extremely pure alcohol can be obtained. The remaining solid is compound (I) and can be reused.

The alcohols mentioned above include lower alkanols, aliphatic unsaturated alcohols (allyl alcohol, crotyl alcohol, florpargyl alcohol, etc.), alicyclic alcohols (
cyclopentanol, cyclohexanol, etc.), aromatic alcohols (benzyl alcohol, cinnamyl alcohol, etc.), multi-1i-cyclic alcohols (furfuryl alcohol, etc.), lower alkylene glycols, and the like. The above-mentioned lower alkanol is a linear or branched alkanol having 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol, 1-propanol, n-butanol, 1-butanol, 5lIC-butanol, tert
-Includes '7'' tanol, n-pentanol, n-hegisanol, etc.Lower alkylene glycol has 1 carbon number
~6 linear or branched alkylene glycol,
Examples include ethylene glycol, 1.3-7''ropanediol, propylene glycol, 1,3-butanediol, 1,4-butanediopyr, and the like.

The concentration of alcohol in the solution containing alcohol that is brought into contact with compound (1) is not particularly limited, but it is usually 5% or more, particularly 30% or more. Solutions containing alcohol also include alcoholic fermentation broths, reaction solutions for alcohol synthesis, and the like.

As a method of contacting, compound (I) may be simply thrown into a solution containing alcohol, but it is generally more efficient to dissolve or melt the compound (I) by heating if necessary. Also, compound (I) in a small amount of a solvent such as ether? It may be dissolved and then mixed with a solution containing alcohol.

After contact, the mixture is usually left at room temperature or further cooled to precipitate complex crystals with a ratio of alcohol to hydroxyl groups of 1:1, which undergoes solid-liquid separation and releases alcohol when heated. The heating temperature may normally be higher than the boiling point of the alcohol.

"Function" Compound (1) generally has good stability as a complex with alcohol, and there is little or very little loss during drying after filtration. Therefore, according to this compound (X), alcohol in an alcohol-containing solution can be separated and recovered at an extremely high quality ratio.

Next, the present invention will be explained in more detail with reference to Examples.

"Example" Na (49 g
), sodium amide (NaNH*) was adjusted, the mixture was cooled to -40°C to -65°C, and acetylene gas (500meAin) was passed through the mixture for about 1 hour while stirring. Then 2°2' of the above QV) formula, 4. 300 d of an anhydrous tetrahydrofuran bath solution of 4'-tetramethylbenzophenone (580 g) was gradually added and stirred for about 1 hour.

After leaving this at room temperature overnight to evaporate the ammonia,
Add dilute hydrochloric acid (5N-HCe') k500-, this fi
-C-f # (300 ml). After washing this ether layer with water and drying it, the ether was distilled off, leaving a colorless oil.

When petroleum ether (3001 nl) was added to this, colorless needle crystals were obtained. This was identified by the IRCNujol method) and was found to be i, 1-bis (2,4-Llimet), an acetylene alcohol compound.
hyJphanyl ) -2-'prQp7n-1-
ad (formula (ly))] (line A in the figure). Yield: 350 g, melting point: 61-63°C.

This compound 4.09 to 80% ethyl alcohol 1.1r
After adding ulf and dissolving it by heating, it was left to stand at room temperature for 2 hours, and complex crystals of the above compound and ethyl alcohol in a 1=1 molar ratio were precipitated. The formation of a complex with ethyl alcohol was confirmed by the IR (Nujol method) of the crystals shown below (line B in the figure).

Collect the complex crystals by filtration and dry under reduced pressure (20+1llIH
% room temperature for 50 minutes), colorless prismatic crystals (4
, 6 g, melting point 40-48°C) was obtained. When this complex crystal (4.6 g) was heated at about 100°C for 10 minutes, 0.56.9 ethyl alcohol was obtained.
It was 81%.

The above identification by I Tt was carried out based on "Structure Determination of Organic Compounds" published by Sankyo Publishing, written by Fuzo Toda, November 25, 1970.

[Brief explanation of the drawing]

This figure shows the IR spectrum of the alcohol separating agent (acetylene alcohol compound) of one embodiment of the present invention and the complex formed by this compound with ethyl alcohol.

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 to R_5, R_6 to R_1_0 are hydrogen atoms or lower alkyl groups. However, R_1 to R_
At least one of each of 5 and R_6 to R_1_0 is a lower alkyl group. ) An alcohol separating agent consisting of an acetylene alcohol compound represented by (2) R_1 is a lower alkyl group, at least one of R_2 to R_4 is a lower alkyl group, R_5 is a hydrogen atom, R_
At least one of 6 to R_1_0 is a lower alkyl group,
The alcohol separating agent according to claim 1, wherein at least one of R_6 or R_1_0 is a hydrogen atom.