Process for preparing alcohol derivatives

Details Process for preparing alcohol derivatives Process for preparing alcohol derivatives

2000-05-31

2002-04-16

Solola, T. A (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C560S183000, C560S184000, C560S187000, C560S209000, C568S608000, C568S614000, C568S618000, C568S621000

Reexamination Certificate

active

06372923

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a process for preparing an ester, acetal, ketal, ether or alkyl glycoside in the presence of an aluminum catalyst.
BACKGROUND OF THE INVENTION
To prepare a glycidyl ether, two processes have conventionally been known. The first is one-stage process where an alcohol and an &agr;-epihalohydrin are reacted in the presence of an alkali and a phase transfer catalyst such as a quaternary ammonium salt. The second is a two-stage process where an alcohol is reacted with an &agr;-epihalohydrin in the presence of an acid catalyst and the resulting halohydrin ether is subjected to ring closure with an alkali. In the one-step process, an excess amount of the &agr;-epihalohydrin is required to prevent further addition of the alcohol to the resulting glycidyl ether. In the two-step process, the alcohol must be added in an excess amount relative to the &agr;-epihalohydrin, because the conversion ratio of the alcohol is not high enough in the presence of a bronsted acid catalyst, e.g., sulfuric acid. Furthermore, excessive addition reactions of the &agr;-epihalohydrin to the halohydrin ether occurs when a highly active Lewis acid such as boron trifluoride or tin tetrachloride is used as an acid catalyst. Metal chloride such as aluminum chloride, tin chloride or iron chloride used as a Lewis acid catalyst are problematic because of catalyst deactivation by alcoholysis and the reaction of free chlorine with the &agr;-epihalohydrin. Moreover, in the two-stage process a hydrophilic solvent or phase transfer catalyst must be used in order to efficiently close the halohydrin ether ring with an alkali.
Examples of preparing dialkylglyceryl ether are a process of reacting an alcohol with an &agr;-epihalohydrin in the presence of an alkali and a process of reacting glycerin with an alkyl halide in the presence of an alkali. However, these reactions require alcohol or an alkyl halide to be used in large excess which is problematic because simultaneous introduction of two different alkyl groups is considerably difficult. Although it is possible to obtain a dialkylglyceryl ether containing freely selected alkyl groups if an alcohol and a glycidyl ether are reacted in the presence of an alkali or acid catalyst, using alkali is problematic because an excess alcohol must be used to prevent further reaction of the product whereby the glycidyl ether partially undergoes hydrolysis. Using an acid is also problematic because the glycidyl ether is polymerized during the reaction.
A process for preparing an ester, acetal, ketal, ether or alkyl glycoside by using, as a catalyst, a combination of an aluminum alkoxide and a phenol or sulfonic acid or a compound wherein these two have been bonded is described in WO98/50389. However, the yields obtained by this process were not satisfactory and thus further yield improvements are necessary. Additionally, this process is unsatisfactory because of the significant increase of Chemical Oxygen Demand (COD) in the water layer, thereby burdening waste water disposal.
A process for preparing an alkanol alkoxylate product characterized by a narrow-range alkylene oxide adduct distribution and a low content of a residual alkanol, which comprises reacting an alkylene oxide reactant composed of at least one C
2-4
vicinal alkylene oxide with an alkanol reactant composed of at least one C
6-36
alkanol in the presence of a catalytically effective amount of a catalyst, where the catalyst was prepared by contacting (i) at least one sulfur-containing acid and (ii) at least one aluminum compound, e.g., aluminum alcoholates or aluminum phenolates (Japanese Patent Application Laid-open No. SHO 62164641). This process aims to prepare a nonionic surfactant by adding a plurality of moles of a C
2-4
vicinal alkylene oxide to an alcohol. An ether with only 1 mole of an alkylene oxide is not available by this process.
The present inventors have found that the combination of an aluminum alkoxide and sulfuric acid or phosphoric acid makes it possible to effectively prepare an ester, acetal, ketal, ether or alkyl glycoside and in addition to facilitate waste water disposal without raising the COD in the water layer.
SUMMARY OF THE INVENTION
In accordance with this finding, an object of the present invention is a process for preparing an ester, acetal, ketal, ether or alkyl glycoside, which comprises reacting an alcohol with a carbonyl compound, alcohol, olefin, epoxy compound (except C
2-4
vicinal alkylene oxide) or saccharide in the presence of (A) an aluminum alkoxide and (B) sulfuric acid or phosphoric acid.
Another object of the present invention is a process for preparing a glyceryl ether, which comprises reacting an alcohol and an &agr;-epihalohydrin in the presence of the above-described catalyst and reacting the ether obtained with an alkali.
Another object of the present invention is a process for preparing a monoalkylglyceryl ether which comprises; hydrolyzing the glycidyl ether thus obtained.
DETAILED DESCRIPTION OF THE INVENTION
The aluminum alkoxide (A) catalyst can be any aluminum alkoxide in the form of a mono-, di- or tri-alkoxide. Among them, an aluminum trialkoxide is more preferred, with an aluminum tri(C
1-4
alkoxide) being particularly preferred. Specific examples of the aluminum alkoxide include aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide and aluminum triisobutoxide, with aluminum triisopropoxide being particularly preferred. Commercially available aluminum alkoxides can also be used.
Alternatively, a mixture of mono-, di- and tri-alkoxide forms available by reacting an aluminum trihalide or trialkyl aluminum with an alcohol can be used. In this case, it is preferred to select the conditions permitting the preparation of a mixture having a larger trialkoxide content.
Sulfuric acid or phosphoric acid (B) catalyst efficiently catalyzes the above-described reaction when used in combination with the above-described aluminum alkoxide. The reaction does not proceed in the presence of aluminum sulfate. As the catalyst (B), sulfuric acid is preferred, with concentrated sulfuric acid having a concentration of 90% or greater being more preferred and concentrated sulfuric acid or fuming sulfuric acid having a concentration of 96% or greater being particularly preferred. In the present invention, a combination of aluminum triisopropoxide and sulfuric acid or phosphoric acid is preferred, of which the combination of aluminum triisopropoxide and sulfuric acid is particularly preferred.
Alcohols usable in the present invention include those represented by the following formula (1):
R
1
—(OA
1
)
m
—OH  (1)
wherein, R
1
represents a saturated or unsaturated, linear or branched hydrocarbon group having 1 to 36 carbon atoms in total, A
1
represents a C
2-4
alkylene group and m is 0 to 100. Specific examples include saturated aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, 2-ethylhexanol and 3,5-dimethylhexanol; and unsaturated aliphatic alcohols such as oleyl alcohol and linoleyl alcohol; and alkylene oxide adducts thereof. As such an alkylene oxide adduct, an ethylene oxide adduct (an alcohol of the formula (1) wherein A
1
represents ethylene) and the number ((m) in the formula (1)) of moles added is preferably 0 to 20. As alcohols, those free of an alkylene oxide (alcohols of the formula (1) wherein m stands for 0) are preferred.
Examples of the carbonyl compound usable in the present invention include carboxylates, aldehydes and ketones. By the use of, as a raw material, a carboxylate, aldehyde or ketone, the corresponding ester, acetal or ketal can be prepared, respectively. By the reaction of the above-described alcohol with another alcohol, an olefin or an epoxy compound, the corresponding ether can be obtained. Reaction of the above-described alcohol with a saccharide yields the corresponding a

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