JPS58134044A - Preparation of 2-methoxy-1-propanol - Google Patents

Abstract

PURPOSE:In reacting 1,1-dimethoxyethane, and/or acetaldehyde, etc., and methanol with CO and H2, to obtain the titled substance under mild conditions in high yield, by making an aromatic hydrocarbon, an aliphatic hydrocarbon, an ether, etc. exist. CONSTITUTION:In preparing the titled substance by reacting (A) 1,1-dimethoxyethane and/or (B) one or more of acetaldehyde, paraldehyde, and metaldehyde and methanol with CO and H2 in the pressure of a Co-containing catalyst, the reaction is carried out by making one or more solvents selecting a group consisting of an aromatic hydrocarbon (e.g., benzene, or toluene), an aliphatic hydrocarbon (e.g., pentane, or heptane), an ether, an organic ester (e.g., methyl acetate) exist. The amount of the solvent used is especially effectively >=75wt% based on the total amount of the reaction solution. EFFECT:A Co catalyst will not form by-products, has a long catalytic life, makes the separation and purification of a product easy and saves energy.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2-methoxy-1-propertool. More specifically, the present invention relates to a method for producing 2-methoxy-1-propanol by reacting 1,1-dimethoxyethane and/or 7cetaldehyde and methanol with carbon monoxide and hydrogen. 1. Production of 2-methoxy-propertool from 1-dimethoxyethane and synthesis gas The method described in US Pat. No. 2,555,950 is known as an omniscient method. However, this method is not possible under high temperature and high pressure (250℃, 850~95℃).
Despite requiring harsh conditions (0 atrn), the reaction activity is low and the yield (4-15%) is low.

In order to overcome the drawbacks of conventional methods, the present inventors conducted intensive research aimed at relaxing reaction conditions and improving reaction rate and yield, and finally arrived at the present invention. That is, the present invention provides a method of combining (bl-carbon oxide and (c) When producing 2-methoxy-1-propanol by reacting hydrogen, from (1) an aromatic hydrocarbon and (an aliphatic hydrocarbon and (3) an ether and (4) an organic acid ester), This is a method for producing 2-methoxy-1-propatool, characterized by the presence of one or more compounds selected from Narosen.

Although the details of the reaction mechanism of the present invention are not clear, the overall reaction that is thought to occur when 1,1-dimethoxyethane is used as a raw material can be represented by the following chemical reaction formula.

CH= CI(OCHs) * + CO+ 2H*
→ CH, CH-CH, OH+CH, OH b) OCH
s When acetaldehyde and methanol are used as raw materials instead of 1,1-dimethoxyethane, the overall reaction is slightly different and can be expressed by the following 57th chemical reaction equation.

′,) CH, CHO+ CH, OH+ CO 14.

→ OH, CH-CH, OH+ H, 0+110CH.

The features of the present invention are (1) aromatic hydrocarbons;
One or more compounds selected from the group consisting of (2) aliphatic hydrocarbons, (3) ethers, and (4) organic acid esters are present, and this compound is referred to as a solvent throughout this specification. Among these solvents, (1) Aromatic hydrocarbons with a carbon number ranging from 6 to 20 (alphatic hydrocarbons having a carbon number ranging from 5 to 20 (2)) Ethers with a carbon number ranging from 4 to 20 (4)
Organic acid esters having 3 to 20 carbon atoms are preferred. The classification of effective solvents is illustrative, but not limiting.

(1) Aromatic hydrocarbon benzene, ),, i, i, ene, 0-xylene, m-
xylene, p-xylene, mesitylene, 1,2゜5-trimethylbenzene, 1,2.4-)diethylbenzene,
i, 2, 5. , It-tetramethylbenzene, 1,2
．． ! 1.5-tetramethylbenzene, ethylbenzene,
p-diethylbenzene, 〇-ethyltoluene, 1m-ethyltoluene, p-ethyltoluene, cumene, O-inpropylbenzene, m-inpropylbenzene, p-inpropylbenzene, -1-impropylbenzene, i-
Butylbenzene, t-butylbenzene, pt-butyltoluene, $-1-butyl-m-xylene, dodecylpeshizene, cycloxylbenzene, 1-methylnaphthalene, 1.2-:)i-thylnaphthalene, 1 .6-dimethylnaphthalene, 1-ethylnaphthalene, 2-ethylnaphthalene, 4-ia7'ropyru-1,6-dimethylnaphthalene, 3,5'-dimethylbiphenyl, diphenylmethane, 1,1-diphenylethane, indene, Tetralin etc. (2) Aliphatic hydrocarbons n-pentane, n-hexane, isohexane, 3-methylpentane, neohexane, 2,3-dimethylbutane,
n-hebutane, 2-methylhexane, 3-methylhexane, 2. S-dimethylpentane, 2.4-dimethylpentane, n-octane, 2,2.5-)dimethylpentane, inoctane, n-nonane, 2゜2.5-)limethylhexane, n-decane, Zen- (dodecane, cyclobentane, cyclohexane, ethylcyclohexane, ethylcyclohexane, decalin, bicyclohexyl, etc.) Ether diethyl ether, diethyl ether, diisopropyl ether, butyl ethyl ether, dibutyl ether,
Diethyl ether, diypentyl ether, dihexyl ether, tetrahydrocufuran, dioxane, tetrahydrobilane, 1,2-dimethoxyethane, diglyme, anisole, 7-enethole, benzyl methyl ether, benzyl ether, bellatol, m-dimethoxybenzene, diphenyl ether, benzyl ether, 1
-methoxynaphthalene, benzofuran, 2゜3-dihydrobenzofuran, chroman, inchroman, 1,3-dihydro-isobenzofuran, etc. (4) Organic acid esters methyl acetate, ethyl acetate, ethyl propionate, ethyl propionate, methyl butyrate, Ethyl butyrate, methyl valerate, ethyl valerate, methyl hexanoate, ethyl hexanoate, methyl heptanoate, ethyl heptanoate, methyl octoate, ethyl octoate, methyl nonanoate, ethyl nonanoate, methyl decanoate, decane Ethyl acid, methyl laurate, dimethyl sebacate, γ-butyrolactone,
- Monocaprolactone, methyl benzoate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, and the like. Among the above solvents, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, heptane and octane, methyl acetate etc. The use of organic acid esters is a preferred embodiment. In addition, when using an aliphatic hydrocarbon solvent, the reaction solution is separated into an aliphatic hydrocarbon layer and a methanol and/or water layer containing 2-methoxy-1-propanol at room temperature. -1- This is a preferred method of operation since the separation of propatools is a container.

As mentioned above, it is necessary to use a solvent in the reaction of the present invention. This solvent effect is caused by the dielectric constant ε of the solvent, the hydrogen The connectivity parameter r or the cage effect related thereto cannot be simply explained or predicted. In other words, the unpredictable nature of the present invention is
．． 1, l, 1llll+' as partially shown in Examples 1 to 5 of the specification of sss, tjo and the comparison-' mentioned below.
l',,.

This is exemplified by the fact that the desired product can hardly be obtained without a solvent or with water, alcohol, ethanol, etc. The selection of a specific solvent according to the present invention very significantly influenced the progress of the reaction, making it possible to obtain the desired product in high yield with a fast reaction rate.

The amount of the solvent used in the present invention is not particularly critical, but it is usually 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and 75% by weight based on the total amount of the reaction solution. The above is particularly effective.

Regarding the selection and usage amount of the solvent in the present invention, the organic and inorganic properties of the reaction solution at the end of the reaction [(chemical domain% 11.719(
1957)) can be used as an index.

That is, one reaction proceeds suitably when the organic/inorganic ratio of the reaction solution containing the solvent is 0.5 or more, preferably 1.0 or more.

In the present invention, a cobalt compound is used as a catalyst. As a typical cobalt compound, dicobalt octacarbonyl is used, but compounds that form cobalt carbonyl under reaction conditions, such as metallic cobalt, cobalt oxide, cobalt nitrate, etc. , base salts such as primary cobalt carbonate, organic acid salts such as cobalt acetate and cobalt naphthenate, chelate compounds such as bis-7cetyl-7cetonatocobalt, etc. are used in the cobalt catalyst used in the present invention. The amount used is based on the metal atom, the total volume of the reaction solution, 11 0.0
01~1010l-5ie, preferably o,oos~5
1 stam, more preferably in, o 1
~21-atom.

In the present invention, an iodine compound can also be used in combination with a solid compound. Iodine compounds that can be used together include iodine, hydrogen iodide, lithium iodide, sodium iodide, potassium iodide, and magnesium iodide! , inorganic iodides such as calcium iodide, tin iodide, antimonoiodide, and bismuth iodide, and alkyl iodides such as methyl iodide and ethyl iodide. If tritiated cobalt is used as the cobalt compound, it is not necessary to add any other iodine compound.

Cobalt may be added if necessary (if an iodine compound is used in combination, the ratio of cobalt to iodine compound is iodine/
The atomic ratio of Pupart is usually 50 or less, preferably 10 or less.

In the reaction for carrying out the method of the present invention, the reaction temperature is suitably in the range of, for example, 50 to 350°C, preferably 80 to 300°C, more preferably 100 to 250°C. - sufficient to maintain carbon oxides and hydrogen at suitable partial pressures; - preferred partial pressures of carbon oxides and hydrogen are between 1 and 500 atm, optimally between 3 and 300 atm; The optimum partial pressure is between 5 and 200 atmospheres, but a wider range of partial pressures between 0.05 and irlnO atmospheres is also acceptable.

The stoichiometric ratio of the raw material gases in the above-mentioned reaction formula for producing 2-methoxy-1-propatol is 1:2. However, in practice the molar ratio of carbon monoxide to hydrogen is much wider [@1.1:100 to 100:1, preferably
:50 to 50:1, more preferably 1 :, 1.0 to
10:1 can be used. - It is particularly preferable to set the molar ratio of carbon monoxide to hydrogen in the range of 1:0.5 to 1:50 because the worst results are obtained when the gas mixture has a carbon oxide to hydrogen ratio close to the stoichiometric ratio. . Furthermore, the carbon monoxide and hydrogen used in the present invention may be injected into the reaction zone individually, or may be introduced in the form of a so-called "synthesis gas" in which carbon oxide and hydrogen are mixed. , these raw material gases do not necessarily have to be of high purity; they are carbon dioxide, methane,
It may contain nitrogen, rare gas, etc. However, raw material gas of extremely low purity is undesirable because it increases the pressure of the reaction system.

The main raw materials of the present invention, 1,1-dimethoxyethane, 7cetdehyde, paraaldehyde, and metaldehyde, can be supplied by a method that does not derive the basic raw materials from petroleum products such as ethylene, for example, by reacting methanol with synthesis gas. It is also possible (Il!i Kaisho, 48-2525, JP 51-149213, JP 1852 136110)
, JP18. j 2, -1. ,,S,,4. ,,,,
．． 111 etc.). In this case, it is particularly advantageous that methanol, which is an impurity in the raw materials 1,1-dimethoxyethane, acetaldehyde, paraaldehyde, and metaldehyde, is an auxiliary raw material of the present invention. 1. When using an aldehyde and methanol instead of 1-dimethoxyethane, they can be used in any ratio, but usually 0 methanol to 1 mole of aldehyde (based on 7cetaldehyde).
．． The amount ranges from 0.1 to 100 mol, preferably from 0.1 to 50 mol.

In the method of the present invention, a trivalent or trivalent organic nitrogen compound that is commonly used in analogous reactions is not used; trivalent or trivalent organic nitrogen compounds have poor stability; It is necessary to add a new organic nitrogen group compound to prevent a decrease in activity, and a large amount of energy is required to separate and remove by-products such as Saraban. Point 1: The catalyst system of the present invention does not produce any by-products, dramatically extending the life of the catalyst, and also facilitates product separation and purification, contributing to energy savings.

The method of the present invention can be suitably carried out in either batchwise or continuous reaction mode. Recovery of the product and catalyst from the reaction solution can be carried out by any known method such as distillation.

Hereinafter, the present invention will be explained in more detail by way of examples, but the present invention is not limited to the following examples.

Examples 1 to 17 A stainless steel 100-capacity autoclave with an electromagnetic rotary stirrer, a predetermined amount of dimethoxyethane as shown in Table 1,
After a predetermined amount of solvent and a predetermined amount of catalyst were charged and the inside of the autoclave was replaced with nitrogen, hydrogen and carbon monoxide at a predetermined pressure were introduced under pressure.

The mixture was heated to a predetermined temperature shown in Table 1 and reacted for a predetermined time while stirring. After cooling the reactor, the reaction solution was analyzed by gas coomadography.

The results are shown in Table 2.

Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that no solvent was used. The experimental conditions are shown in Table 1#c, and the results are shown in Table 2E.

Comparative Example 2 An experiment was conducted in the same manner as in Example 1 except that methanol was used as the solvent. Experimental conditions! l! 1 shows the results in Table 21.

Table 2 Example 18 In a stainless steel l1tood autoclave equipped with an electromagnetic rotary stirrer, balaldehyde 16.7 mmol, methanol 100 mmol, and toluene 11.611. Jidobalt octacarbonyl, prepared with 5 millimoles,
After the inside of the autoclave was replaced with nitrogen, hydrogen was injected into the autoclave at 8D and then carbon monoxide was injected into the autoclave to obtain 1201EI. 1
The temperature was raised to 60° C., and the mixture was reacted for 1.5 hours while stirring.

After cooling the reactor, the reaction solution was analyzed and 8.4 milliliter of 2-methoxy-1-propanol was detected.

Patent applicant: Mitsubishi Gas Chemical Co., Ltd. ’　as□1. circle.

l□

Claims (1)

[Claims] (at) Ll-dimethoxyethane and/or (a,) 7cetaldehyde, in the presence of a cobalt-containing catalyst;
When producing 2-methoxy-1-propanol by reacting one or more of para-aldehyde and metaldehyde with methanol, (b)-carbon oxide and (c) hydrogen, k,
+11 aromatic hydrocarbons, (2) aliphatic hydrocarbons, (3)
A method for producing 2-methoxy-1-propatool, characterized by the presence of one or more compounds selected from the group consisting of ether and (4) organic acid ester.