DE4429699A1 - Process for the preparation of butenediols and butenediol derivatives in the presence of oxidic catalysts - Google Patents

Abstract

Process for reacting vinyl oxiranes of the formula <IMAGE> in which R<1> and R<2> are identical or different and represent a hydrogen atom or a C1- to C5-alkyl group, with oxygen nucleophiles in the presence of solid oxidic catalysts which are insoluble in the reaction medium, to give butenediols and butenediol derivatives of the formulae <IMAGE> in which R<3> and R<4> are identical or different and represent a hydrogen atom, an aliphatic radical having 1 to 10 carbon atoms or the radical <IMAGE> , where R<5> is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical having 1 to 15 carbon atoms.

Description

The invention relates to the reaction of vinyl oxiranes with acid nucleophiles such as water, alcohols or carboxylic acids in Ge present from solid oxidic catalysts to butenediols and Butenediol derivatives.

In WO 8 504 392 and WO 8 504 393 is the hydrolysis of oxiranes in the presence of metallates and solid organic materials as described anionic ion exchangers. According to WO 9 115 469, WO 9 115 470 and WO 115 472 address the hydrolysis of vinyloxirane acidic ion exchangers performed. In WO 8 902 883 the Re action of vinyl oxirane with oxygen nucleophiles in the presence of Pd-0 compounds on a polymeric substrate.

Catalyst systems are described in the cited documents, which are heterogeneous in the reaction system. However, you are either organic or non-oxidic in nature. The ion out Exchangers have the disadvantage of low thermal stability. Associated with this is the difficulty of regeneration with Akti decrease in viability. Pd catalysts have the disadvantage of one hand high price, on the other hand they point at the present reak an insufficient service life.

The task was therefore to propose catalysts that on the one hand cheap and readily available, on the other hand among the Reaction conditions are stable.

This task was solved with a procedure for the implementation of Vinyl oxiranes of the formula I.

in which R¹ and R² are the same or different and are hydrogen atom or a C₁ to C₅ alkyl group, to butenediols and Butenediol derivatives of the formulas

in which R³ and R⁴ are the same or different and for one water an atomic aliphatic radical having 1 to 10 carbon atoms or the rest

stand, wherein R⁵ is hydrogen or an aliphatic, cycloali phatic, araliphatic or aromatic radical with 1 to 15 carbon atoms, which is characterized by that vinyloxiranes of the formula I with oxygen nucleophiles R³OH, R⁴OH or R⁵COOH, where R³, R⁴ and R⁵ have the abovementioned meanings gene have, in the presence of solid, insoluble in the reaction medium Chen, oxidic catalysts.

Butenediol derivatives of the formula II and III are precursors, e.g. B. for 1,4-butanediol, tetrahydrofuran or vitamins.

Oxidic catalysts to be used according to the invention oxides of the main groups which are insoluble under the reaction conditions III, IV, V and VI, the subgroups IIIb-VIIb and VIII of Periodic table and the oxides of rare earth metals.

In particular come oxides of silicon, aluminum, titanium, zir cons and hafniums.

Such oxides can advantageously also be combined with one another such as the oxides of silicon with the oxides of Aluminum, titanium, zircon, hafnium, tin, niobs or oxides of zircon with those of chromium, tungsten, molybdenum, selenium and Tellurium.

As a combination of oxides, zeolites or layered silicates such as, for. B. Montmorillonite (Tonsil) suitable. In particular, e.g. B. to name the following oxide catalysts:
Silicon oxide / aluminum oxide, silicon oxide / titanium oxide, silicon oxide / zirconium oxide or silicon oxide / hafnium oxide.

The oxides are produced in a manner known per se. A Precipitation from corresponding alcoholates, especially in the presence of ammonium fluoride or ammonium sulfate has been found to be proven in part.

In addition, those to be used according to the present invention Catalysts still doping in the form of oxygen-containing Sulfur or phosphorus compounds as well as halogen compounds, e.g. B. Contain fluorides.

It is advantageous to use the aforementioned oxides, oxide combinations and doped oxides or oxide combinations before using a thermal treatment at temperatures between 120 to 650 ° C, more advantageous at 250 to 600 ° C and particularly advantageous at 350 to 550 ° C for a period of 0.2 to 25 hours, preferably 2 to 17 To undergo hours.

The catalyst becomes in quantities (weight) of 1 to vinyloxirane 100 to 100: 1, particularly preferably 1:10 to 5: 1 for discontinuous implementation. With continuous implementation be the catalyst load is usually 0.01 to 10 preferred wise 0.1 to 1.

The reaction batches can in addition to the inventive Reaction-promoting compounds are added to catalysts. These additives are mainly halides, preferably iodides Lithium, sodium or potassium, which the content of 1,4-butenediol Increase derivative.

In addition, the reaction-promoting compounds are metallates 4th, 5th and 6th subgroup of the Periodic Table of the Elements in Be traditional, z. B. vanadates, molybdates, tungstates or perrhenates. The total yield is increased by the addition of these metallates of butenediols and derivatives.

The reaction-promoting compounds are usually in one Weight ratio to the catalyst used from 0.01: 1 to 3: 1, preferably 0.1: 1 to 2: 1.

The molar ratios of oxygen nucleophile to vinyl oxirane amount to z. B. 0.5: 1 to 100: 1, preferably 1: 1 to 40: 1, particularly preferably 1: 1 to 20: 1.  

As oxygen nucleophiles come water, alcohols with 1 to 15 carbon atoms or carboxylic acids with 2 to 16 carbon atoms into consideration.

Alcohols to be used according to the invention are primary, secondary or tertiary alcohols or polyols, especially methanol, Ethanol or tert-butanol.

Aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids into consideration, above al lem formic acid, acetic acid and propionic acid.

The reaction is preferred at temperatures between 0 and 200 ° C but carried out between 15 and 100 ° C. The reaction pressure is intrinsic to the system or by injecting inert gases such as Nitrogen to values up to B. set 50 bar. He always will chosen so that the reaction components predominantly liquid lie.

The reaction can be carried out batchwise or continuously, e.g. B. with suspended or fixed catalyst either in Rie Sel or swamp driving style are carried out. The dwell times are usually between one and 300 minutes before trains between 5 to 120 minutes.

After removal of any contained in the reaction discharge NEN catalyst can the products of formula II and III methods known per se, e.g. B. by distillation from each other be separated.

The following examples illustrate the process explained, but not restricted in any way. The specified Yields were determined by gas chromatography. Percentages are Weight percent; in the yield% of theory

example 1

In a 3 liter flask, deionized water and 476 g ammonia solution (25% by weight in water) 74 g ammonium fluoride solved. About dropping funnel as a template were pre-stirred mixed 416 g of tetraethyl orthosilicate and 284 tetraisopropyl ortho titanate added dropwise within 25 minutes. After that the Mix for two hours. The approach has been so far warms that the alcohol mixture resulting from the hydrolysis distilled. After cooling, the hydrolyzate was filtered off and washed with deionized water. The filter cake turned 16  Predried at 120 ° C for hours and then at 5 hours 500 ° C calcined.

The chemical analysis of the catalyst showed ge as wt .-% oxide calculates 59% SiO₂, 38% TiO₂ and 0.25% by weight fluorine. 0.1 g the This catalyst was treated with 0.7 g of vinyl oxirane and 0.45 g of water Heated to 80 ° C for 1 hour. With complete sales found 54% 3,4-butene-1-diol and 7% 1,4-butene-2-diol.

Example 2

0.7 g of vinyl oxirane and 1.8 g of water were mixed with 0.1 g in accordance with match 1 catalyst prepared and the mixture Heated to 80 ° C for 1 hour. With full sales, there was 64% 3,4-butene-1-diol and 13% 1,4-butene-2-diol.

Example 3

0.7 g of vinyl oxirane and 0.45 g of water were mixed with 0.1 g in accordance with match 1 catalyst prepared and 0.1 g of potassium rhenate and the mixture heated to 80 ° C for 1 hour. With complete order 64% of 3,4-butene-1-diol and 7% of 1,4-butene-2-diol were found.

Example 4

0.7 g of vinyl oxirane and 0.45 g of water were mixed with 0.1 g in accordance with game 1 catalyst and 0.1 g of KI added and the Mixture heated to 100 ° C for 1 hour. At 50% sales were found 16% 3,4-butene-1-diol and 12% 1,4-butene-2-diol.

Example 5

0.7 g of vinyl oxirane and 0.8 g of methanol were mixed with 0.1 g in accordance with match 1 catalyst prepared and the mixture Heated to 80 ° C for 1 hour. With 31% sales, 40% were found 3-methoxy-4-hydroxy-but-1-ene.

Example 6

0.7 g of vinyl oxirane and 1.5 g of acetic acid were mixed with 0.1 g Example 1 prepared catalyst was added and mixture 1 Heated to 80 ° C for one hour. With 90% sales, 40% 3,4-Bu were found ten-1-diol monoacetate and 5% 1,4-butene-2-diol monoacetate.  

Example 7

In a 3 1 flask in 360 g of deionized water and 476 g Ammonia solution (25% by weight in water) 264 g of ammonium sulfate solves. About dropping funnel as a template were pre-stirred mixed 416 g of tetraethyl orthosilicate and 467 zirconium (IV) propy added dropwise within 25 minutes and the mixture Hour stirred. The batch was placed in a pressure vessel 180 ° C under an autogenous pressure of 25 bar stirred for 24 hours. After cooling, the solid was filtered off with water washed neutral and dried at 120 ° C for 16 hours and then calcined at 500 ° C for 5 hours. The catalyst obtained had the following composition (calculated as oxide): SiO₂ 45.5%, ZrO₂ 45.5%, sulfate 0.02%.

0.1 g of this catalyst was mixed with 0.7 g of vinyl oxirane and 0.45 g Water heated to 80 ° C for 1 hour. Found with full sales 54% 3,4-butene-1-diol and 0.4% 1,4-butene-2-diol.

Example 8

0.7 g of vinyl oxirane and 0.45 g of water were mixed with 0.1 g of Tonsil sets and the mixture heated to 80 ° C for 1 hour. With 90% sales 50% of 3,4-butene-1-diol and 10% of 1,4-butene-2-diol were found.

Claims (9)

1. Process for the implementation of vinyloxiranes of the formula in which R¹ and R² are the same or different and represent a hydrogen atom or a C₁ to C₅ alkyl group, to butene diols and butenediol derivatives of the formulas in which R³ and R⁴ are the same or different and represent a hydrogen atom, an aliphatic radical having 1 to 10 carbon atoms or the rest stand, where R⁵ is hydrogen or an aliphatic, cyclo aliphatic, araliphatic or aromatic radical having 1 to 15 carbon atoms, characterized in that vinyloxiranes of the formula I with oxygen nucleophiles R³OH, R⁴OH or R⁵COOH, where R³, R⁴ and R⁵ have the meanings given above have, in the presence of solid, insoluble in the reaction medium, oxidic catalysts. 2. The method according to claim 1, characterized in that one as catalysts oxides or oxide combinations of the main groups III, IV, V and VI of the periodic table, the minor groups IIIb-VIIIb and oxides of rare earth metals used.   3. The method according to claim 1, characterized in that the Oxides or combinations of oxides with small amounts of oxygen containing sulfur, phosphorus or halogen compounds do are. 4. The method according to claim 1, characterized in that insoluble catalysts halides of sodium, potassium um or lithium added. 5. The method according to claim 1, characterized in that a molar ratio of oxygen nucleophile to vinyloxy ran from 1: 1 to 1:40. 6. The method according to claim 1, characterized in that works at temperatures of 15-150 ° C. 7. The method according to claim 1, characterized in that one water is used as the oxygen nucleophile. 8. The method according to claim 1, characterized in that as Oxygen nucleophilic primary, secondary or tertiary alcohols hole with 1 to 10 carbon atoms can be used. 9. The method according to claim 1, characterized in that as Oxygen nucleophilic aliphatic or aromatic carbon acids with 1 to 16 carbon atoms can be used.