DE1279671B - Process for the production of mono-alkoxy-diols - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

German class:

Number:
File number:
Registration date:
Display day:

C07c

BOId
BOIf

12 ο -5/09

12 ο - 5/03

12C-1

P 12 79 671.3-42 (B 84909)

December 9, 1965

October 10, 1968

The invention relates to a method of manufacture of mono-alkoxy-diols, which is characterized is that an epoxy alcohol with an aliphatic monohydric alcohol in the presence of a acidic or basic catalyst capable of opening the oxirane ring.

US Pat. No. 2,902,478 discloses a process for the preparation of polyoxyalkylene ethers known, in which one solid polyhydroxy compounds with at least four hydroxyl groups in Reacts the presence of trimethylamine as a catalyst with alkylene oxides. Thereby all hydroxyl groups oxyalkylated, so that no mono-alkoxy-diols can be obtained.

Furthermore, US Pat. No. 2,870,220 discloses a two-stage process for the production of polyglycol ethers higher, saturated monohydric alcohols known. In the first stage the ethylene oxide is with the alcohol converted to a product which contains 0.2 to 4 moles of the oxide per mole of alcohol, so In the second stage, more ethoxy groups are then introduced into the molecule. In this procedure So it is about the production of common condensates from ethylene oxide and an alcohol, however, these condensates are not monoalkoxydiols.

US Pat. No. 2,654,787 also deals only with the production of unsaturated dialkoxy compounds, whereby ethers containing non-terminal allylic halogen are used with nickel carbonyl Reaction to be brought.

US Pat. No. 2,808,442 also discloses a process for the preparation of hydroxyethers known. A three-component system, which consists of an ethylene compound, a primary or secondary alcohol and hydrogen peroxide, in the presence of an acid catalyst, which reacts with the peroxide to form a peracid. If as Ethylenic compound a corresponding alcohol is used, it is due to the in column 2 given reaction equation theoretically possible, a dihydroxy ether, for example a monoalkoxy diol to manufacture. Such acid catalysts have the disadvantage that they are undesirable Promote oxidation or decomposition of peroxides to oxygen. In the method according to the invention no hydrogen peroxide is used, so these problems do not arise.

In British Patent 696 125, the preparation of monoethers by reacting 1,2-epoxy-2,4,4-trimethylpentene with alcohols in the presence of processes for the preparation of
Monoalkoxy diols

Applicant:

The British Petroleum Company Limited,
London

Representative:

Dipl.-Chem. Dr. W. Koch, Dr.-Ing. R. Glawe
and Dipl.-Ing. K. Delfs, patent attorneys,
8000 Munich 22, Liebherrstr. 20th

Named as inventor:

Gordon Foster, Sunbury-on-Thames,

Middlesex (UK)

Claimed priority: '

Great Britain 17 December 1964 (51 345)

an acidic catalyst described. Although a diol such as ethylene glycol is used as the alcohol no monoalkoxy-diol is obtained by this process, as in Example 12 shows, but 2,2'-hydroxyethoxy- 2,4,4-trimethylpentanol- (l), which contains no alkoxy group. Although there are two hydroxyl groups and one ether bond in the reaction product, the arrangement of these groups does not match that in a monoalkoxy diol.

The monoalkoxy diols formed are generally known compounds and are used as solvents, intermediates for resins and plasticizers, as components of deicing agents and are generally useful intermediates. Some of the connections made are new, e.g. B. 2-alkoxy-2-methylpentane-3,4-diols and 4-alkoxy-2-methylpentane-2,3-diols, which are obtained can be if 3,4-epoxy-4-methylpentanol- (2) or 3,4-epoxy-2-methylpentanol- (2) as an epoxy alcohol component can be used in the reaction.

Suitable catalysts for the process according to the invention are, for example, sodium hydroxide, Mineral acids, zinc and iron (III) chloride and boron trifluoride. The preferred catalyst is boron trifluoride, which is used in the form of an ether or alcohol complex.

The reaction temperatures can be in the range -10 to + 6O ⁰ C, preferably 0 to 25 ⁰ C, are.

809 620/580

The alcohol reactant can be saturated or unsaturated, such as methanol, ethanol, Butanols, propanols and allyl alcohol.

It is ever 'epoxy alcohol regardless of the relative Positions of the oxirane ring and hydroxyl radical in the molecule for use in the method suitable according to the invention. Examples of possible epoxy alcohols are: glycidol, 3,4-epoxy-4-methylpentanol- (2), 3,4-epoxy-2-methylpentanol- (2), 3,4-epoxy-hexanol- (2), 2,3-epoxy-hexanol- (4), 2,3-epoxy-3-methylpentanol- (4 ), 2,3-epoxy-cyclohexanol- (l), 1,2-epoxy-2-ethylbutanol- (3) and 2,3-epoxy-2-ethylbutanol- (l).

The process according to the invention is illustrated in more detail by the following examples.

example 1

20 ml of absolute methanol and 0.1 g of boron trifluoride etherate were mixed and ^{cooled to 0} ° C., then 10 g of 3,4-epoxy-4-methylpentanol- (2) were slowly added with stirring. When the addition was complete, the mixture of a colorless liquid was stirred for 3 hours at 25 ° C, and thereto was added a small amount of potassium carbonate and the mixture is distilled, whereby as 9.8 g was obtained (Kp. = _L5B 6O ⁰ C) . This corresponds to a yield of 78%. The IR and NMR spectrum showed that the product was 2-methoxy-2-methylpentane-3,4-diol.

30th

Example 2

The preparative conditions of Example 1 were repeated using 3,4-epoxy-2-methylpentanol- (2) as the epoxy alcohol; the yield of 4-methoxy-2-methylpentane-2,3-diol was 75 _^0/0; (Bp ₄ = 85 to 89 ° C).

Example 3

The preparative conditions of Example 1 were repeated using absolute ethanol as the alcohol; the yield of 2-ethoxy-2-methylpentane-3,4-diol was 65% (boiling point ₂ = 90 to 94 ° C.).

Claims (5)

Patent claims: 1. A process for the preparation of mono-alkoxydiols, characterized in that an epoxy alcohol with an aliphatic monohydric alcohol in the presence of an acidic or basic catalyst, which is able to open the oxirane ring, is implemented. 2. The method according to claim 1, characterized in that the catalyst boron trifluoride, preferably in the form of an ether or alcohol complex. 3. The method according to claim 1 or 2, characterized in that the reaction temperature is ^{in the range of -10 to 6O 0 C.} 4. The method according to claim 1, characterized in that the alcohol is methanol, ethanol, Butanols, propanols or allyl alcohol is used. 5. The method according to claim 1, characterized in that the epoxy alcohol is glycidol, 3,4-epoxy-4-methylpentanol- (2), 3,4-epoxy-2-methylpentanol- (2), 3,4-epoxy-hexanol- (2), 2,3-epoxyhexanol- (4), 2,3 - epoxy- 3 - methylpentanol- (4), 2,3-epoxycyclohexanol- (1), 1,2-epoxy-2-ethylbutanol- (3) or 2,3-epoxy-2-ethylbutanol- (l) are used will. Considered publications:
British Patent No. 696,125;
U.S. Patents Nos. 2,902,478, 2,870,220,
654 787, 2 808 442. MK 620/580 9.6 SO Bundwdruckerei Berlin