DE3802948A1 - Process for the preparation of 1,2-dimorpholino - and/or 1,2-dipiperazinoethane from morpholine or piperazine - Google Patents

Abstract

The aim of the invention is to prepare 1,2-dimorpholino- and/or 1,2-dipiperazinoethane from in each case only one starting material. Surprisingly, it has been found that morpholine or piperazine react at elevated temperature in the presence of a zeolite to give the ethano-bridged dimer. The morpholine and piperazine derivatives are used mainly as catalysts for the preparation of polyurethanes.

Description

The invention relates to a method for producing ethano bridged morpholine and piperazine derivatives of the general formula

with X = 0 and NH.

Such compounds claim interest as catalysts for the production of polyurethanes, polyolefins, epoxy resin hardeners and Foam stabilizers.

It is known from the prior art to use secondary amines Diols and with 1,2-dihaloethanes (J. Am. Chem. Soc. 76, 5158 (1954) to ethano-bridged di-tertiary amines. A only the implementation with the difunctional is of technical importance Acquired alcohol. So from DE-OS 26 24 136 (see Example 5) known a method in which u. a. Piperazine with ethylene glycol in the presence of phosphoric acid under autogenous pressure and temperatures from 275 to 325 ° C within 2 hours to 1,2-dipiperazinoethane implements. An analogous procedure is used for the implementation of morpholine described with 1,2-propylene glycol. These procedures are for technical synthesis due to the unsatisfactory selectivity not suitable. A further disadvantage is that the in Homogeneous phase catalyst must be separated and the Selectivity is unsatisfactory.

European laid-open specification 02 39 934 describes a procedure for mono or diamination of diols by reacting secondary ones Amines such as B. morpholine, with ethylene glycol or 1,3-propanediol in Presence of a ruthenium or iridium catalyst at 10 to 125 ° C.

The advantage of improved selectivity is due to the disadvantage of Use of expensive and not easily reusable catalysts not weighed.  

It goes without saying that amino alcohols can also be converted into diamines. So z. B. from US-PS 41 03 087 known that connections of the formula R₁R₂N-R-OH with secondary amines to di- (N, N-disubstituted can implement amino) alkanes. Example 1 describes the Production of 1,2-dimorpholinoethane with a heterogeneous aluminum phosphate catalyst under autogenous pressure at elevated temperature. Such one 2-step procedure is offered due to the increased effort for the production of ethano-bridged morpholine and piperazine derivatives not at.

From the unpublished German patent applications P 37 35 212.1 and 37 35 214.8 are processes for the preparation of 1,4-di azabicyclo (2.2.2) octane from piperazine or polyamines or amino alcohols known as a catalyst with a zeolite. The table on the Page 8 of the last application shows that the by-product 1,2-Dipiperazinoethane in an amount up to 0.73%. From this Scripture, there are no suggestions for targeted production of ethano-bridged morpholine and piperazine derivatives.

Methods are therefore known throughout from the prior art, at which is an ethylene unit with 2 equivalents of a cyclic secondary Amine is linked. The aim of the invention is a method to develop in which one starts from just one starting product and immediately reaches the desired end products.

It has now surprisingly been found that 1,2-dimorpholino and / or 1,2-dipiperazinoethane by direct reaction of morpholine and / or piperazine in the presence of a zeolite at elevated temperature can get.

The zeolite used preferably has the general formula

(M ^I · M ^II O₂) · a M ^III O₂ · b H₂O

on, where
M ^{I is} an equivalent of a 1-valent alkali metal cation, a proton, the ammonium group or a half equivalent of a 2-valent alkaline earth metal cation,
M ^{II is} an equivalent of one of the following 3-valent cations is Al ³⁺ , B ³⁺ , Sb ³⁺ , As ³⁺ , Cr ³⁺ , V ³⁺ , Ga ³⁺ and Fe ³⁺
M ^III an equivalent of one of the following tetravalent cations is Si ⁴⁺ , Ge ⁴⁺ , Ti ⁴⁺ and Zr ⁴⁺
a has at least the value 1,
and the value of
b The upper limit is only limited by the requirement that a pentasil structure must be maintained.

M ^I is in particular a proton, M ^II B ³⁺ or preferably Al ³⁺ and M ^III Ge ⁴⁺ or preferably Si ⁴⁺ . It is preferably a zeolite with a pentasil and in particular ZSM 5 structure. The process is preferably carried out by using a solution of morpholine and / or piperazine in water or an inert organic solvent.

1,2-Dimorpholinoethane is preferably made by using the gaseous starting products at 200 to 500 ° C, in particular 230 to 350 ° C, over a zeolite fixed bed catalyst. It recommends yourself to add an inert gas and an absolute pressure to the starting product from 0.1 to 10 bar.

1,2-Dipiperazinoethan is preferably under the autogenous pressure of the Reak tion medium at 200 to 400 ° C in the liquid phase.

The exact mechanism of the reaction is unknown.

The following advantages are achieved with the method:

• 1. The only starting connection required is the easily accessible one Morpholine or piperazine.
• 2. The reaction product can be easily removed from the catalyst nen.
• 3. The desired ethano-bridged end products are with high Se maintain selectivity.
• 4. Working up the reaction product is simple. It is done expediently by distillation.

In principle, all known ones can be used in the method according to the invention Zeolites are used. Zeolites and their production for example in Ullmann's Encyclopedia of Technical Chemistry, 4.  Edition, volume 24, page 575 (1983) and volume 17, page 9 (1979) be wrote.

The zeolites have in particular the formula given above. Preferably, a has a value between 15 and 200 and b has a value between 0 and 8. Typically, M ^II stands for Al ³⁺ and M ^{III stands} for Si ⁴⁺ . If one of these two metals is replaced by other metals in the sense of a so-called isomorphic substitution, as stated above, zeolites are obtained whose crystal structure is essentially unchanged (cf. Chem. Ing. Techn. 58, 946-959 and 969 -971 (1986) It is also possible to replace both aluminum and silicon. There is also the possibility of partial substitution. The zeolites can also be doped with transition metals and / or rare earths. These are used to increase the stability of the zeolite often mixed with other materials such as cellulose materials, clays, metal oxides or binders and thus get their shape. Preferred are zeolites which have a pentasil structure. Suitable zeolites are described, for example, in DE-OS 32 39 054. In particular Zeolites with ZSM 5 structure are used, which are listed in the above monograph.

It is appropriate to use morpholine or piperazine together with a diluent agents such. B. water, an inert hydrocarbon, the is liquid at room temperature, or a gas such as. B. nitrogen or ammonia to feed the catalyst. You usually go there so that one dissolves the amine in water and together with the gaseous Component in a suitable warming device on a Temperature heats up at which it is in the gaseous state. Man can also dissolve the amine in liquid hydrocarbons and accordingly method. Depending on whether you have the morpholine or piperazine derivative want to produce, the preferred Reak differ conditions.

In the first case, the starting product is passed in gaseous form over a fixed zeolite catalyst at a temperature of 200 to 500 ° C, preferably 230 to 350 ° C. It is advisable to use an inert gas, such as. As nitrogen, add and set an absolute pressure of 0.1 to 10 bar. It is customary to pass the starting gaseous product in a tube over the fixed zeolite. The catalyst load is preferably set so that the LHSV (liquid hourly space velocity) is 0.1 to 10 hours ^-1 (cf. Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 13, page 550, Verlag Chemie, Weinheim, 1977). The reaction mixture can be worked up by customary methods. A particularly useful form is to collect the reaction mixture and separate it by distillation.

The production of 1,2-piperazinoethane is preferred under the autogenous pressure of the reaction medium in the liquid phase. The reaction temperatures here are between 200 and 400 ° C., in particular between 250 to 350 ° C.

Example 1

A 200 ml stainless steel autoclave with magnetic stirring is included 40 g piperazine, 60 g water and 5 g catalyst A. The mixture is heated to 300 ° C and 3 hours at this temperature and one Pressure of 100 bar stirred. After cooling and separating the catalyst shows the gas chromatographic analysis of the reaction mixture following composition:

53.3% piperazine
36.6% 1,2-dipiperazinoethane
7.3% triethylenediamine
1.8% 1-ethyl piperazine

After separating off water, piperazine and a preliminary fraction by distillation is obtained at a boiling temperature of 165 ° C and one Pressure of 20 mbar pure 1,2-dipiperazinoethane with a melting point of 98 ° C.

Example 2

In the apparatus described in Example 1, 70 g of morpholine, 30 g of water and 5 g of catalyst A heated to 300 ° C and at 3 hours this temperature and a pressure of 80 bar. After cooling and the separation of the catalyst gives the gas chromatographic Analysis of the reaction mixture of the following composition:

79.4% morpholine
13.8% 1,2-dimorpholinoethane
1.7% N-ethylmorpholine

Examples 3 to 6

The conversion of morpholine in the gas phase is carried out in a fixed-bed tubular reactor made of stainless steel (length 1350 mm, diameter 22 mm) with sand fluidized bed heating and an internal temperature measuring tube (diameter 6 mm). The experimental setup is shown schematically in Fig. 1. In the middle of the reactor there is a 350 mm long contact zone ( 1 ) which is filled with 120 ml of catalyst and to which two 500 mm long packing layers ( 2 ) are connected at the top and bottom. The starting product is dosed from the calibrated original (3) via a diaphragm pump (4) and material flow together with a stick, which is regulated by a reducing valve (5), heated up in the Wär exchanger (6) at 200 ° C and from above in passed the reactor. The reaction products are collected in two separators ( 7 and 8 ) connected in series and in a wash bottle ( 9 ) filled with water; the exhaust gas flow is regulated by a valve and a gas meter (FI). The reaction products are worked up by distillation in a packed column (length 1700 mm, diameter 30 mm, filled with V4A wire mesh rings 4 × 4 mm) with a thermostatted column top. After separation of water and unreacted morpholine and distillation of a preliminary fraction, pure 1,2-dimorpholinoethane (melting point 71 ° C.) is obtained at a boiling temperature of 133 ° C. and 10 mbar pressure.

In Examples 1 to 4, the catalyst designated A is a Zeolite in the H form according to Example 1 of DE-OS 32 39 054 (molar Ratio SiO₂ / Al₂O₃ = 30.8), which for assembly with 40 wt .-% an inert binder is formed. The Kata marked B. Analyzer in Examples 5 and 6 corresponds to the zeolite according to Example 4 DE-OS 32 39 054 (molar ratio SiO₂ / Al₂O₃ = 90.0), also made up with 40% by weight of an inert binder.  

table

Claims (9)

1. A process for the catalytic preparation of 1,2-dimorpholino and / or 1,2-dipiperazinoethane at elevated temperature, characterized in that one starts from morpholine or piperazine as the only starting product and uses a zeolite as a catalyst. 2. The method according to claim 1, characterized in that the zeolite has the general formula (M ^I · M ^II O₂) · a M ^III O₂ · b H₂O, wherein
M ^{I is} an equivalent of a 1-valent alkali metal cation, a proton, the ammonium group or a half equivalent of a 2-valent alkaline earth metal cation,
M ^{II is} an equivalent of one of the following 3-valent cations is Al ³⁺ , B ³⁺ , Sb ³⁺ , As ³⁺ , Cr ³⁺ , V ³⁺ , Ga ³⁺ and Fe ³⁺
M ^III an equivalent of one of the following tetravalent cations is Si ⁴⁺ , Ge ⁴⁺ , Ti ⁴⁺ and Zr ⁴⁺
a has at least the value 1,
and the value of
b is limited at the top only by the requirement that a pentasil structure must be maintained. 3. The method according to claim 1 or 2, characterized, that the zeolite used has a pentasil structure. 4. The method according to claim 3, characterized, that the zeolite used has a ZSM 5 structure. 5. The method according to claim 1 or 2, characterized in that
M ^I a proton
M ^II B ³⁺ or preferably Al ³⁺ and
M ^{III is} Ge ⁴⁺ or preferably Si ⁴⁺ . 6. The method according to claims 1 to 5, characterized, that the starting product is the solution of morpholine and / or piperazine in water or an inert organic solvent puts. 7. A process for the preparation of 1,2-dimorpholinoethane according to the claims 1 to 6, characterized, that the starting product in gaseous form over a zeolite Fixed bed catalyst 230 to 350 ° C, conducts. 8. The method according to claim 7, characterized, that an inert gas is added to the gaseous starting product and sets an absolute pressure of 0.1 to 10 bar. 9. A process for the preparation of 1,2-dipiperazinoethane according to the An sayings 1 to 5, characterized, that the reaction in the liquid phase at a temperature of 200 to 400 ° C, especially 250 to 350 ° C, under the autogenous pressure of the reaction medium.