EP2595990A1

EP2595990A1 - Method for producing diamino-dianhydro-dideoxy-hexitolene, particularly preferably 2,5-diamino-1,4:3,6-dianhydro-2,5-dideoxy-d-hexitol

Info

Publication number: EP2595990A1
Application number: EP11732404.6A
Authority: EP
Inventors: Guido Streukens; Christian Lettmann; Sven Schneider
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2010-07-23
Filing date: 2011-06-28
Publication date: 2013-05-29
Also published as: JP2013533275A; WO2012010385A1; DE102010038310A1; US9029412B2; CN102985427B; CN102985427A; US20130116451A1

Abstract

The invention relates to a method for producing diamino-dianhydro-dideoxy-hexitolene of formulas (I), (II) and (III), particularly preferably 2,5-diamino-1,4:3,6-dianhydro-2,5-dideoxy-D-hexitol.

Description

Process for the preparation of diamino-dianhydrido-dideoxy-hexitols, more preferably 2,5-diamino-1,4: 3,6-dianhydrido-2,5-dideoxy-D-hexitol

The invention relates to a process for the preparation of diamino-dianhydrodideoxy-hexitols, more preferably 2,5-diamino-1, 4: 3,6-dianhydro-2,5-dideoxy-D-hexitol.

The preparation of diamino-dianhydro-dideoxy-hexitols from the corresponding diketone (2,6-dioxabicyclo- (3.3.0) octane-4,8-dione, (IV)) is z. B. from anhydrides of polyhydric alcohols. XIII. The amino derivatives of 1, 4: 3, 6-dianhydromannitol, sorbitol, and L-iditol and their behavior towards nitrous acid. Journal of the Chemical Society 1950; 371-374).

DE 102009000661.3 describes a process for the preparation of diamino-dianhydrodideoxy-hexitols in one stage and preferably in two stages by imination (a) and subsequent hydrogenation (b).

The object of the invention was to find a method that allows high yields and at the same time a simplified work-up and catalyst removal.

The object is achieved by the method according to the invention.

The invention relates to a two-stage process for the preparation of diamino-dianhydro-dideoxy-hexitols from the corresponding diketone by reductive amination, by means of

(a) Imination in the presence of ammonia

and

(b) catalytic hydrogenation in the presence of hydrogen,

characterized in that in step b) at least one fixed bed catalyst is used.

Preferred subject of the process according to the invention is the preparation of 2,5-diamino-1, 4: 3,6-dianhydro-2,5-dideoxy-D-hexitol. Of these, three stereoisomers of formulas (I) - (III) are known, 2,5-diamino-1,4: 3,6-dianhydro-2,5-dideoxy-D-sorbitol, DAS (I), 2.5 Diamino-1, 4: 3,6-dianhydro-2,5-dideoxy-D-mannitol, DAM (II) and 2,5-diamino-1,4: 3,6-dianhydro-2,5-dideoxy L-lditol, DAI (III) prepared from the corresponding diketone (2,6-dioxabicyclo- (3.3.0) -octane-4,8-dione, (IV)):

(I) (I I) (I II)

The three stereoisomers differ in chirality at positions 2 and 5. Here, the amino groups can be in the endo, endo (I), endo, exo (II) or exo, exo (III) position, based on the armchair shape of the annelated five-membered rings.

The process of the invention is carried out by the two-stage reaction of the diketone (IV) to the corresponding diamines (I) to (III) by a reductive amination in the presence of ammonia and hydrogen and a fixed-bed hydrogenation catalyst. In this case, first the diketone (IV) is converted by ammonia into the corresponding diimine (V), the subsequent hydrogenation gives the corresponding diamine isomers (I) to (III).

In the first stage a), at least part of the diketone used is converted into the diimine in the presence or absence of an imination catalyst and / or of organic solvents by reaction with ammonia.

The ammonia can be added in equimolar amounts or in excess. Preferably, ammonia is added in excess, more preferably a more than 10-fold excess of ammonia is used. The ratio of diimine to diketone after imination should be greater than 1, preferably greater than 4, and most preferably greater than 9.

In order to accelerate the equilibration of the imination reaction, it is preferable to use an imination catalyst. For this purpose, the according to the state the technique known Iminierungskatalysatoren be used. Suitable catalysts are, for example, inorganic or organic ion exchangers (see EP 042 1 19), supported heteropolyacids (see DE 44 26 472), acidic metal oxides, in particular aluminum oxide and titanium dioxide (see EP 449 089) organopolysiloxanes containing sulfonic acid groups (DE 196 27 265) and acidic zeolites. Particularly preferred are acidic ion exchangers. When using an imination catalyst, the reaction temperature may be between 10 and 150 ° C, preferably between 15 and 120 ° C, and most preferably between 20 and 80 ° C. The pressure is between the autogenous pressure of the mixture and 500 bar. Preferably, the imination reaction is carried out at the pressure at which the subsequent hydrogenation is carried out.

In the imination in the presence of an imination catalyst, the catalyst may be in the form of a suspension catalyst or fixed bed catalyst. Preference is given to the use of fixed-bed catalysts. In a particularly preferred embodiment, diketone and ammonia are continuously from bottom to top by a with

Imination catalyst filled reaction tube passed.

Although the imination can take place in liquid ammonia, it is preferably carried out with the addition of further solvents. Suitable monohydric alcohols having 1 to 4 carbon atoms, in particular methanol, and ethers, more preferably tetrahydrofuran (THF), methyl tert-butyl ether (MTBE) and dioxane. Preference is given to methanol.

In the second stage b), the reaction product of the first stage a), as it is obtained or after further treatment and / or addition of further ammonia, in the presence of at least ammonia and hydrogen and in the presence or absence of an organic solvent at a temperature of 20 to 150 ° C, preferably 40 to 90 ° C, and a pressure of 3 to 500 bar, preferably 10 to 200 bar, according to the invention to

hydrogenated using fixed bed catalysts.

As hydrogenation catalysts, it is possible in principle to use all catalysts which catalyze the hydrogenation of imine groups with hydrogen. Particularly suitable are nickel, copper, iron, palladium, rhodium, ruthenium and cobalt fixed bed catalysts, especially nickel and cobalt fixed bed catalysts. To increase the activity, selectivity and / or lifetime, the catalysts additionally contain doping metals or other modifiers. Typical dopants are z. As Ti, V, Cr, Mn, Fe, Co, Ni, Mo, Ag, Ga, In, Bi and / or Zr and the rare earths. Typical modifiers are for. For example, those with which the acid-base properties of the catalysts can be influenced, such as z. As alkali and alkaline earth metals or their compounds, preferably Mg and Ca compounds. Particularly preferred are molded nickel and cobalt based

Hydrogenation catalysts.

The catalysts are used according to the invention as a shaped body, such as. B. extrudates or pressed powder. It can be full contacts, Raney type catalysts or

Carrier catalysts are used. Preferred are Raney type and

Supported catalysts. Suitable carrier materials are, for. For example, diatomaceous earth, silica, alumina, aluminosilicates, titanium dioxide, zirconium dioxide, aluminum-silicon mixed oxides, magnesium oxide and activated carbon. Preferred are alumina and silica. The active metal can be applied in a manner known to those skilled in the carrier material, such as. B. by impregnation, spraying or precipitation. Depending on the type of

Catalyst preparation are further known to those skilled preparation steps necessary, such. As drying, calcination, shaping and activation. to

Shaping can optionally other auxiliaries such. As graphite or magnesium stearate.

In the process according to the invention, the catalysts described are used for the step b) of the hydrogenation of the diimine (V) or of the diketone (IV). This process can be carried out batchwise or continuously. The mixture fed to the hydrogenation stage can be directly that which in the imination of the diketone with

Ammonia in the first stage a) is obtained, or as it after addition or removal of components such. As ammonia, organic solvents, bases, co-catalysts and / or water is obtained. Preferably, the hydrogenation is continuously in

Fixed bed reactors that can be operated in trickle or sump mode. Suitable reactor types are z. B. shaft furnaces, Horden reactors or

Tube reactors. It is also possible to connect several fixed bed reactors in series for the hydrogenation, each of the reactors optionally in trickle bed and

Sumpfenweise is operated.

The hydrogen required for the hydrogenation can be added to the reactor either in the

Excess, for example, with up to 10,000 molar equivalents, or only in such an amount that the reaction-consumed hydrogen and the part of the hydrogen, which leaves the reactor dissolved in the product stream, is tracked. In continuous operation, the hydrogen can be supplied in cocurrent or countercurrent become. It is also possible to carry out the hydrogenation in the presence of the solvents already mentioned in the imination stage.

Particular preference is given to using catalysts according to the process of the invention, the use of which achieves an isomer distribution which corresponds to a liquid end product, that is to say having a DAS content of at least 40% by weight (Examples 3-5).

The invention relates to a liquid composition of 2,5-diamino-1, 4: 3,6-dianhydro-2,5-dideoxy-D-sorbitol, DAS (I), 2,5-diamino-1, 4: 3 , 6-dianhydro-2,5-dideoxy-D-mannitol, DAM (II) and 2,5-diamino-1,4: 3,6-dianhydro-2,5-dideoxy-L-lditol, DAI (III) , with a content of DAS (I) of at least 40% by weight.

The following examples are intended to explain the invention in more detail.

Examples

Example 1 :

In a 1 liter stirred tank, a solution of 75 g of the diketone in 325 g of methanol is introduced. The reactor is equipped with 146 g of Lewatit K2621 as a fixed bed catalyst. 89 g of NH 3 are pressed in and the reaction mixture is stirred at 40 ° C. for 18 h.

Subsequently, the reaction mixture is transferred by means of N 2 overpressure in a further 1 -1- stirred tank, which is equipped with 94 g (water wet) of a fixed bed nickel-supported catalyst (10.3 wt .-% Ni / Al 2 O 3). The mixture is heated to 70 ° C and the reaction started by adding hydrogen to a total pressure of 50 bar. The pressure is kept constant at 50 bar for 6 h. After cooling and venting of the reactor, a mixture containing 52 wt .-% diaminomannitol, 33 wt .-%

Diamino sorbitol and 5% by weight diaminoidite isolated. The total yield of diamine is 90% by weight.

Example 2:

A 5% strength by weight solution of the diketone in methanol is admixed with an 80-fold molar excess of NH 3. This solution is continuously added at 50 ml / h over a

Guided imination reactor. The imination reactor is with 50 ml Lewatit K2621 as

Catalyst equipped and is operated in Sumpffahrweise. The reaction temperature of the imination is 50 ° C. After leaving the imination reactor, the reaction mixture is treated with H 2 O (40 NL / h) and passed through a trickle bed reactor. The trickle bed reactor is equipped with 50 ml of a supported nickel catalyst (10.3 wt .-% Ni / Al 2 O 3). The reaction temperature of the hydrogenation is 90 ° C. The total pressure of the reaction is 200 bar in both reaction stages.

The total yield of diamine is 96% by weight. The isomer distribution between DAM, DAS and DAI is 60: 35: 5 wt .-%.

Example 3:

As in Example 2, except that the trickle bed reactor is equipped with a supported nickel-copper-chromium catalyst (7.5 wt .-% Ni, 2.5 wt .-% Cu, 0.8 wt .-% Cr / Al 2 O 3). The total yield of diamine is 95% by weight. The isomer distribution between DAM, DAS and DAI is 46:44:10 wt%.

Example 4:

As in Example 2, except that the trickle bed reactor is equipped with a supported nickel-copper catalyst (7.8 wt .-% Ni, 3.5 wt .-% Cu / Al 2 O 3). The total yield of diamine is 91% by weight. The isomer distribution between DAM, DAS and DAI is 45: 44: 1 1 wt .-%.

Claims

claims

1 . Two-step process for the preparation of diamino-dianhydro-dideoxy-hexitols from the corresponding diketone by reductive amination, by means of

(a) Imination in the presence of ammonia

and

(b) catalytic hydrogenation in the presence of hydrogen,

characterized,

in step b) at least one fixed bed catalyst is used.

2. Two-stage process according to claim 1 for the preparation of 2,5-diamino-1, 4: 3,6-dianhydro-2,5-dideoxy-D-sorbitol, DAS (I), 2,5-diamino-1,4 : 3,6-dianhydro-2,5-dideoxy-D-mannitol, DAM (II) and 2,5-diamino-1,4: 3,6-dianhydro-2,5-dideoxy-L-lditol, DAI ( III), the formulas

(IV)

3. Two-stage process according to claim 1 or 2,

characterized,

that in the first stage a) is reacted with ammonia in the presence of an imination catalyst and / or of organic solvents.

4. Two-stage process according to at least one of the preceding claims,

characterized,

that the reaction temperature in step a) is between 10 and 150 ° C, preferably between 15 and 120 ° C and most preferably between 20 and 80 ° C.

5. Two-stage process according to at least one of the preceding claims,

characterized,

that is reacted in step a) using fixed-bed catalysts.

6. Two-stage process according to at least one of the preceding claims,

characterized,

that in step a) diketone and ammonia is passed continuously from bottom to top through a reaction tube filled with imination catalyst.

7. Two-stage process according to at least one of the preceding claims,

characterized,

in that an acidic ion exchanger is used in stage a).

8. Two-stage process according to at least one of the preceding claims,

characterized,

that the imination in stage a) with the addition of solvents, preference is given to monohydric alcohols having 1 to 4 C atoms, in particular methanol, and / or ethers, preference being given to THF, MTBE and dioxane; most preferably methanol is carried out.

9. Two-stage process according to at least one of the preceding claims,

characterized,

that in step b) nickel, copper, iron, palladium, rhodium, ruthenium and / or cobalt fixed bed catalysts, very particularly nickel and / or cobalt fixed bed catalysts are used as hydrogenation catalysts.

10. Two-stage process according to at least one of the preceding claims,

characterized,

that the hydrogenation catalysts additionally contain doping metals, in particular

Doping metals selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mo, Ag, Ga, In, Bi, and / or Zr and / or the rare earths.

1 1. Two-stage process according to at least one of the preceding claims, characterized

in that the hydrogenation catalysts additionally contain modifiers, preferred modifiers are those with which the acid-base properties of the

Catalysts can be influenced, preferably alkali and alkaline earth metals or their compounds, preferably Mg and / or Ca compounds.

12. Two-stage process according to at least one of the preceding claims,

characterized,

that as hydrogenation catalysts full contacts, Raney type catalysts or

Carrier catalysts are used, preferably Raney type catalysts and supported catalysts.

13. Two-stage process according to at least one of the preceding claims,

characterized,

the hydrogenation catalysts comprise support materials selected from diatomaceous earth, silica, alumina, aluminosilicates, titanium dioxide, zirconium dioxide, aluminum-silicon mixed oxides, magnesium oxide and activated carbon, preferably alumina and silica.

14. Two-stage process according to at least one of the preceding claims,

characterized,

in that the hydrogenation is carried out continuously in fixed bed reactors operated in trickle or bottom mode, preferably selected from reactor types

Shaft furnaces, tray reactors or tube bundle reactors.

15. Two-stage process according to at least one of the preceding claims,

characterized,

that the hydrogenation b) in the presence of the already at the imination stage a)

the solvent used is carried out, preferably methanol.

16. Two-stage process according to at least one of the preceding claims

Preparation of 2,5-diamino-1,4: 3,6-dianhydro-2,5-dideoxy-D-sorbitol, DAS (I), 2,5-diamino-1,4: 3,6-dianhydro-2 , 5-dideoxy-D-mannitol, DAM (II) and 2,5-diamino-1,4: 3,6-dianhydro-2,5-dideoxy-L-lditol, DAI (III) to give an isomer distribution , the a liquid end product, with a content of DAS (I) of at least 40 wt .-%.

17. Liquid composition of 2,5-diamino-1,4: 3,6-dianhydro-2,5-dideoxy-D-sorbitol, DAS (I), 2,5-diamino-1, 4: 3,6- Dianhydro-2,5-dideoxy-D-mannitol, DAM (II) and 2,5-diamino-1,4: 3,6-dianhydro-2,5-dideoxy-L-lditol, DAI (III), with one Proportion of DAS (I) of at least 40% by weight.