EP2197882A2

EP2197882A2 - Method for producing teda derivatives

Info

Publication number: EP2197882A2
Application number: EP08803391A
Authority: EP
Inventors: Gunther Van Cauwenberge; Johann-Peter Melder; Joachim-Thierry Anders; Christoph Benisch; Rainer Klopsch; Gregor Daun; Christian Dully; Boris Buschhaus; Henning Boeckemeier; Evelyn Pox
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2007-09-03
Filing date: 2008-08-29
Publication date: 2010-06-23
Also published as: CN101842375A; WO2009030649A3; US20100204438A1; WO2009030649A2

Abstract

The invention relates to a method for producing triethylenediamine (TEDA) derivatives, comprising the following steps: a) reaction of a dihydropyrazine with an olefin, b) optionally hydrogenation following step a). The invention also relates to novel TEDA derivatives as such and to the use thereof as built-in polyurethane catalysts.

Description

Process for the preparation of TEDA derivatives

description

The present invention relates to a process for the preparation of triethylenediamine (TEDA) derivatives starting from dihydropyrazines and olefins. Exemplary TEDA derivatives which can be prepared by the process according to the invention correspond to the general formula (Ia) or (Ib)

wherein the substituents R1 to R12 are defined in the following text. Furthermore, the present invention also relates to a selection of novel TEDA derivatives according to the above-defined general formula (Ia) or (Ib) and their use as polyurethane catalysts, preferably as incorporable polyurethane catalysts.

A process for the preparation of TEDA (triethylenediamine, also referred to as 1, 4-diazabicyclo [2.2.2] octane (DABCO)) or derivatives of TEDA are known. For example, WO 01/02404 describes a process for the preparation of TEDA using zeolite catalysts. The educts of TEDA production are ethylenediamine (EDA) and piperazine (PIP). TEDA is an important chemical raw material and is used, among other things, in the production of pharmaceuticals and plastics, in particular as a catalyst in the production of polyurethanes (PUR).

An alternative process for the preparation of TEDA or TEDA derivatives is described in US-A 6,147,185. This process relates in particular to the preparation of TEDA derivatives to which one or two hydrocarbon-containing rings have been condensed. For example, first 6-methylquinoxaline is hydrogenated to 6-methyldecahydroquinoxaline, which subsequently reacts with ethylene oxide. The resulting intermediate, which has a hydroxyethyl substituent on a ring nitrogen atom, is finally in the presence of a phosphate catalyst at 340 ⁰ C with ring closure to the corresponding TEDA derivative (here 6- Methylcyclohexodiazabicyclo-2.2.2-octane). The compounds described in US Pat. No. 6,147,185 are likewise suitable as PUR catalysts.

In particular, the synthesis of TEDA derivatives which have functional groups (for example an ester, ether or amino function) proves to be difficult with the processes described above. Such TEDA derivatives with a functional group are only occasionally known. The use of such substituted TEDA derivatives as PUR catalyst has not yet been described.

Other TEDA derivatives are described, for example, by T. Oishi et al., Tetrahedron Letters, Vol. 33 (5), pp. 639-642 (1992). Starting from the corresponding piperazine derivative, the corresponding TEDA derivatives are synthesized by reaction with 1, 2-dibromoethane in ethanol, which have two benzoxymethyl substituents in position 2 and 3 of TEDA. Alternatively, the corresponding substituents may also have t-butyldimethylsilyl or t-butyldiphenylsilyl-containing ether substituents instead of benzyl.

WO 98/24790 relates to the preparation of TEDA derivatives in which TEDA is linked via a methyl ester bridge with a benzene fragment. The compounds used as drugs are prepared by first reacting piperazine with 2,3-dibromopropionic acid ethyl ester to a TEDA derivative having an ethyl ester function in position 2. This TEDA derivative is then reduced with lithium aluminum hydride to 2-hydroxymethyl-TEDA, which is then reacted with the corresponding benzoic acid derivative to the target molecule.

In L. Street et al., J. Med. Chem., 33 (1990), pages 2690 to 2697, a TEDA substituted with 2-ethylcarboxy is prepared analogously to WO 98/24790 and then with ring closure to the corresponding 1, 2 , 4-oxadiazole TEDA derivative implemented.

G. Shishkin et al., Chem. Heterocycl. Com., 1980, pages 1069 to 1072 describe the reduction of TEDA derivatives which are substituted by carboxy, methylcarboxy or benzoxymethyl, with lithium aluminum hydride or a hydrolysis to 2-hydroxymethyl-TEDA. 2-hydroxymethyl-TEDA can then be reacted with acetic anhydride to give the corresponding acetate.

DE-A 30 48 031 relates to a process for the preparation of substituted pyrazines. In this

Process dihydropyrazines are reacted with carbonyl derivatives in the presence of a base to substituted pyrazine. Suitable carbonyl compounds include carbonyl compounds which contain a double bond, such as terpene aldehydes, unsaturated aliphatic aldehydes, unsaturated aliphatic ketones or furan aldehydes. In particular, due to the use of strong organic bases such as alkali metal alkoxides (alkoxide), alkali metal hydrides or alkali metal amides no TEDA derivatives are obtained with the method described in DE-A 30 48 031. The reason for this difference in reactivity is to be found in a different reaction mechanism underlying the reaction described in DE-A 30 48 031.

The reaction described in DE-A 30 48 031 is based on the following mechanism: First, the strong base used, e.g. an alkoxide, a proton in the saturated position 5 of 5,6-dihydropyrazine, to give the corresponding acid, e.g. the corresponding alcohol. The resulting dihydropyrazine anion then nucleophilically attacks the carbonyl compound to form intermediately a 5- [V-hydroxy-1 '- (substituent) -methyl] -5,6-dihydropyrazine. This can eliminate water and intermediately form a 5'-substituted 5- [V- (substituent) methylidene] -5,6-dihydropyrazine on the exocyclic carbon atom. This, in turn, rearranges to the final product, a 5- [V- (substituent) methyl] pyrazine, with aromatization via a 1, 3-H shift rearrangement.

The fact that the reaction takes place via a deprotonation of dihydropyrazine and not vice versa, ie via formation of an enolate from the carbonyl compound is proved by the fact that it is also possible to use aldehydes which have no proton at the carbonyl group adjacent to the carbon atom, for example benzaldehyde , and therefore can not form enolate. The reaction of dihydropyrazines with carbonyl compounds, optionally also unsaturated carbonyl compounds, described in DE-A 30 48 031 accordingly leads to products in which the atoms of the former carbonyl compound are not linked to the nitrogen atoms of dihydropyrazine.

The object underlying the invention is thus to provide a new, simplified process for the preparation of TEDA derivatives. In the context of the present invention, unsubstituted TEDA is also encompassed by the term "TEDA derivative".

According to the invention, this object is achieved by a process for the preparation of triethylenediamine (TEDA) derivatives comprising the following steps:

a) Reaction of a dihydropyrazine with an olefin b) optionally hydrogenation following step a). In contrast to the process described in DE-A 30 48 031, an additional ring closure ("bridging") takes place in the process according to the invention, the two carbon atoms of the olefin double bond being linked by the reaction with the two ring nitrogen atoms of dihydropyrazine.

By the method according to the invention can be advantageously prepared TEDA and TEDA derivatives, especially those TEDA derivatives containing substituents with functional groups. Substituents with functional groups are to be understood as meaning those substituents which have at least one heteroatom, such as halogen, S, P, O or N. TEDA derivatives with substituents which contain functional groups are particularly advantageously suitable as catalyst for the production of polyurethane (PUR catalyst). The polyurethanes produced in this way, in particular polyurethane foams, are distinguished by the fact that the catalysts used do not outgas from the polyurethane since they are chemically bound into the corresponding polyurethane, in particular in polyurethane foam, or because they have an increased vapor pressure feature.

Furthermore, it is advantageous that to produce such a polyurethane or polyurethane foam no larger or not significantly larger amounts of PUR catalyst are required than in previously established systems, especially unsubstituted TEDA, usual.

The process according to the invention for the preparation of TEDA derivatives is described in more detail below.

In step a), the reaction of a dihydropyrazine with an olefin takes place, wherein in each case one carbon atom of the olefin double bond is linked by the reaction with one ring nitrogen atom of the dihydropyrazine. With regard to the choice of dihydropyrazine and of olefin, in principle there are no restrictions, both educts can be both unsubstituted and substituted. These starting materials are commercially available or can be prepared by methods known to those skilled in the art. Details of the synthesis of the dihydropyrazine starting materials are described in more detail below.

Synthesis of dihydropyrazines

Processes for the preparation of dihydropyrazines are known to the person skilled in the art. A good overview of the preparation of substituted dihydropyrazines is given in Flament, I., Stoll, M., Helvetica Chimica Acta 1967, Vol. 50 (7), no. 180, pages 1754-1758 given. Furthermore, the synthesis of dihydropyrazines is also described in DE 103 21 565 A1. (but with the aim of subsequently dehydrating them to the corresponding pyrazines).

The educt synthesis starting from (optionally substituted) ethylenediamine (s) and dicarbonyl compounds to the dihydropyrazines can be carried out in various solvents. Theoretically, all organic solvents and water are suitable. Less preferred is the use of protic solvents, e.g. 1, 2-propanediol or water, because the reaction in these solvents leads to poorer dihydropyrazine selectivities and to an increased tendency to biopolymerize of polymers. Furthermore, the use of diethyl ether, although chemically useful, but not recommended for safety reasons (low boiling point, auto-oxidizing) on an industrial scale.

Optimum conversion and selectivity were achieved by carrying out the reaction in a moderately polar but water-immiscible solvent. In addition, work should be carried out under N ₂ as protective gas.

Particularly preferred as an optimal solvent is tert-butyl methyl ether (MTBE). This solvent has chemical properties similar to those of diethyl ether (solubility, polarity and mixing behavior with organic solvents or water) but with a higher boiling point and no autoxidisability, making it safer to handle. In addition, in MTBE are obtained by the low miscibility with water benefits because the water formed in the reaction separates as a second phase and this no longer bothers the reaction and because also almost all by-products and residues of ethylenediamine are in the aqueous phase and can be separated very easily after the reaction.

Ethylenediamine or an EDA derivative is initially charged in a subset of MTBE and the dicarbonyl compound (equimolar) in MTBE is slowly added dropwise. It forms an insoluble intermediate which decomposes on subsequent heating to ambient temperature or above in product, EDA and water. The intermediate makes the uniform agitation very difficult, therefore, a relatively large amount of solvent is used. If the amount of solvent is too small, the mixture solidifies, forming lumps that still contain dicarbonyl compound. These lumps heat up a great deal and melt into a tough black mass. Therefore, you can not work solvent-free.

Too high a temperature and the forming water promote the polymerization of the

Product. Tert-butyl methyl ether (MTBE) proved to be ideal because the water separates as the second phase and is separated together with the by-products can. The colorless ethereal phase is dried, concentrated in vacuo and the product mixture is then fractionally distilled in vacuo. The product is air-stable at -20 ⁰ C, but polymerized at ambient temperature in the presence of oxygen.

Particularly positive in this reaction is to assess the fact that you can work with equimolar amounts of EDA (or EDA derivative) to dicarbonyl, because an excess of EDA (derivative) in the next stage can interfere. For example, when the next step is the reaction with an acrylic acid derivative, EDA (derivative) can also perform a 1,4 addition on the olefin to form undesirable by-products. Particular preference is therefore given to working with equimolar amounts of EDA derivative to dicarbonyl compound. A reactant in excess of 1:20 to 20: 1 can also be used, but this procedure is advantageous only if the excess reactant can subsequently be separated off, e.g. by distillation, precipitation or other methods known to those skilled in the art. However, since dihydropyrazines can polymerize under thermal stress, it is particularly advantageous if the separation can be omitted because of the use of equimolar amounts.

The separation of any residual EDA or EDA derivative over a second, aqueous phase which forms is particularly advantageous. This separability is due to the particularly advantageous use of a moderately polar, aprotic, water-immiscible solvent, e.g. MTBE, given. Therefore, the synthesis of the dihydropyrazines in MTBE is particularly preferably carried out.

The synthesis of Dihydropyrazine can be carried out between -80 ⁰ C and 80 ° C. Preferably, the reaction between -20 ⁰ C and 60 ⁰ C, more preferably carried out between 0 ° C and 50 ° C.

The reaction pressure can be between 0.5 and 250 bar (absolute). Preference is given to working at atmospheric pressure.

The synthesis of the dihydropyrazines is particularly preferably carried out without an additionally added catalyst because the reactivity of the dicarbonyl compounds and the ethylenediamine derivatives is very high on its own.

Step a: Reaction of dihvdropyrazine with the olefin

In step a) TEDA derivatives are prepared which have a carbon-carbon double bond (unsaturated TEDA derivatives) in the TEDA skeleton. To obtain TEDA derivatives that have a fully saturated TEDA backbone. If appropriate, a step b) can be carried out, in which the product obtained in step a) is subjected to hydrogenation.

The reaction of the dihydropyrazine with the olefin can be carried out in various solvents. Theoretically, all organic solvents and water are suitable. Examples of suitable solvents are methanol, 1, 2-propanediol, dioxane, tetrahydrofuran or MTBE.

It is advantageous to use the same solvent used in the synthesis of the dihydropyrazines (for example from MTBE), because then no solvent change is required after the synthesis of the dihydropyrazines. Particularly advantageous is the

Use of higher-boiling, aprotic solvents, because it also higher

Reaction temperatures, shorter reaction times and thus a more economical

Space-time yield are possible. The best results in this respect are obtained with dioxane as solvent.

A catalyst can be used. Preferably, step a) is carried out in the absence of bases. It is particularly preferred to work without the addition of a catalyst, since the reaction can also be controlled thermally.

The reaction can be carried out at temperatures of -50 ⁰ C to 200 ⁰ C. Preferably, the reaction is carried out at a reaction temperature between 0 ° C and 150 ⁰ C. The reaction temperature is particularly preferably 60 ^° C. to 130 ^° C.

The molar ratio of dihydropyrazine to olefin can be varied from 20: 1 to 1:20. Particularly advantageous is the use of equimolar amounts.

The reaction can be explained by the mechanism of a cycloaddition between a diene and a dienophile (Diels-Alder reaction) or as a Michael addition. The choice of substituents is therefore largely arbitrary, since especially the diene skeleton of dihydropyrazine and the olefinic double bond are involved in the reaction. However, the rate of reaction and chemoselectivity of cycloadditions often depend on the electronic ratios of the two reactants.

As an example, which does not limit the scope of the invention, is the reaction of

Called 2,3-dimethyl-5,6-dihydropyrazine with ethyl acrylate. This is particularly advantageous because the acrylate is used as electron-deficient dienophile for the ten diene fits well. The same applies, for example, to maleic acid esters. For the same dihydropyrazine, on the other hand, more electron-rich dienophiles (eg, methyl vinyl ether) are less suitable as reactants and therefore react less well, more slowly, or more unselectively with one another. Conversely, as known to those skilled in the art, electron-rich dienophiles can readily react with the dihydropyrazine when the electronic ratios are matched by appropriate substituents.

If necessary, the substituents on both reactants can be varied in their properties by introducing protective groups, derivatization and reversal, to achieve the desired reactivity. The introduction of protective groups is known to the person skilled in the art.

Step b: Hydrogenation of the reaction product from a)

The hydrogenation according to step b) is carried out by methods known to those skilled in the art. Thus, for example, the hydrogenation can be carried out directly after step a) without isolation of the unsaturated TEDA derivative obtained in step a). The products obtained in steps a) and b) can be purified and isolated by methods known to those skilled in the art.

If protected starting materials have been used in step a), the corresponding protective groups can be removed again after step a) or optionally following step b) by methods known to the person skilled in the art (deprotection step c)). Optionally, this deprotection can also be carried out together with the hydrogenation in step b).

In the context of the present invention, unless otherwise stated, the following applies to all educts used and to all products obtained:

Alkyl (Ci-Ci _o alkyl; means this shortcut that the corresponding alkyl group having 1 to 10 carbon atoms) may be unsaturated either linear or branched, acyclic or cyclic and saturated or. This also applies if they are part of another group such as, for example, alkoxy groups (C 1 -C 10 -alkyl-O-), alkoxycarbonyl groups or aminoalkyl groups or if they are substituted. Accordingly, alkyl also includes alkylene radicals (- (CH ₂ ) _n -, with n, for example, 1 to 10). Thus, for example, alkylamino (C 1 -C 10 -alkoxy) means that a C 1 -C 10 -alkoxy radical is in turn substituted by an alkylamino radical.

Examples of alkyl groups are: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl. In this case, both the n-isomers of these radicals and branched isomers such. Isopropyl, isobutyl, isopentyl, sec-butyl, tert-butyl, neophen tyl, 3,3-dimethylbutyl, 2-ethylhexyl, etc. included. In addition, unless otherwise stated, the term alkyl also includes alkyl radicals which are unsubstituted or optionally substituted by one or more further radicals, for example 1 to 10 identical or different radicals, such as, for example, hydroxyl, amino, alkylamino, dialkylamino, aryl, Heteroaryl, alkoxy or halogen. The additional substituents can occur in any position of the alkyl radical. Furthermore, the term alkyl also includes cycloalkyl and cycloalkyl-alkyl- (alkyl which in turn is substituted with cycloalkyl) wherein cycloalkyl has at least 3 carbon atoms. Examples of cycloalkyl radicals are: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. If appropriate, these may also be polycyclic ring systems, such as decalinyl, norbornanyl, bornanyl or adamantanyl. The cycloalkyl radicals may be unsubstituted or optionally substituted by one or more further radicals, as exemplified above for the alkyl radicals.

Halogen is fluorine, chlorine, bromine or iodine.

Aryl is a 5- to 14-membered, aromatic, mono-, bi- or tricycle. The radical aryl is thus derived from mono-, bi- or tricyclic aromatics which contain no ring heteroatoms. Unless they are monocyclic systems, the second or third ring may also be in the saturated or partially unsaturated form, as long as the particular forms are known and stable. Optionally, aryl may also be at least monosubstituted, for example with halogen, alkyl or alkoxy. Examples of aryl are: phenyl, naphthyl, indanyl, 1, 2-dihydro-naphthenyl or 1,2,3,4-tetrahydronaphthyl. Preferably, aryl is phenyl.

A preferred embodiment of the present invention relates to a process for the preparation of triethylenediamine (TEDA) derivatives of the general formulas (Ia) or (Ib)

comprising the following steps: a) Reaction of a Dihydropyrazine (II) with an Olefin (III) to Obtain the TEDA Derivative (Ia)

(") (HD

b) optionally hydrogenation of the TEDA derivative (Ia) to obtain the TEDA derivative (Ib).

where in the formulas (I) to (III):

All carbon atoms may be R- or S- or E- or Z-configured. The representation shown in the structural formulas does not imply a representation of the absolute configuration (eg endo or exo position or an orientation up / down of a particular substituent) on a carbon atom or the absolute configuration of a double bond, the drawing is only to illustrate the To understand connectivity, ie on which C atom which substituents can be situated.

R1 to R10 are independently selected from

H, halogen, - (C _r Cio-alkyl) - _u (R14), -C (O) -RI 3, -CN, -O-aryl (R14) _U, - (Ci-Cio-alkyl) -O -

C (O) R 14, -O - [(C ₁ -C ₁₀ alkyl) - (R 14) _u ] _p H _q , -N - [(C ₁ -C ₁₀ alkyl) - (R 14) _u ] _p H _q A _r!

-P - [(C ₁ -C 10 -alkyl) - (R 14JJpH ₁ A or -S - [(Ci-Cio-alkyl) - (R 14) u] pH _q ; u is 0 to 10. If u = 0, this means that the corresponding (Ci-C _O alkyl) -. fragment of the substituents R1 to R10 is unsubstituted If u> 1, the corresponding (CrCio-alkyl) fragment with the u-times the number substituted at R14, and in the case . of u> 1, the groups R14 are independent of each other substituted residues R14 can thereby in any position of the (Ci-Ci _o alkyl) - fragment is, the upper limit of the residues R14 by the number of hydrogen atoms in the corresponding (Ci-Ci _O alkyl) fragment is fixed.

If a product according to formula (Ib) has arisen from the hydrogenation of a product according to formula (Ia), usually the substituents R 11 and R 12 are H. If appropriate, the substituents R 1 1 and R 12 may be substituted for Hydrogenation according to methods known in the art according to the definitions of R1 to R10 are modified.

R 13 is H, hydroxy, amino, aryl, C 1 -C 10 -alkoxy, amino- (C 1 -C 10 -alkoxy), alkylamino (C 1 -C 10 -alkoxy), dialkylamino (C ₁ -C 10 -alkoxy), amino (Ci -Ci ₀ -alkyl), aminoaryl, -NH (C ₁ -C 10 -alkyl), -N (C ₁ -C 10 -alkyl) ₂ , -NH-aryl, -N- (aryl) ₂ , halogen, hydroxyaryl, -O- aryl or -O- (C _r Cio-alkyl) -aryl;

R14 is hydroxy, amino, aryl, Ci-Ci ₀ alkoxy, amino (Ci-Ci ₀ alkoxy), alkylamino (d- Cio-alkoxy), dialkylamino (C _r Cio-alkoxy), amino (C _{r is} Cio-alkyl), -NH (C 1 -C 10 -alkyl), -N (C 1 -C 10 -alkyl) ₂ , hydroxyaryl, aminoaryl, -NH-aryl, -N (aryl) ₂ , halogen, -PH-aryl, -P (Aryl) ₂ , -O-aryl or -O- (C ₁ -C 10 -alkyl) -aryl,

For p, applies if the remainder [(Ci-C _O alkyl) - (R14) _u] is linked to nitrogen or phosphorus: p is 0 to 3, wherein q may also be 0 to 3rd For the sum of p + q:

If p is 0 then q is equal to 2 or 3.

If p is equal to 1 then q is equal to 1 or 2. If p is equal to 2 then q is equal to 0 or 1.

If the sum of p and q is equal to 2, then the heteroatom is neutral, hence no

Counter-anion A present and thus r = 0.

If the sum of p and q is 3, the heteroatom is positive

Charge, therefore, a counter-anion A is present and thus r = 1. The corresponding TEDA derivative is then present as a salt. Preferably, however, the TE

DA derivatives as a neutral molecule, that is, r is 0.

A can be any anion, preferably A is selected from halogen, sulfate,

Sulfite, nitrate, nitrite, phosphate, phosphite, hypophosphite, formate, acetate, propionate, oxalate and citrate. Halogen is especially chlorine.

For p, applies if the remainder [(Ci-C _O alkyl) - (R14) _u] is linked to oxygen or sulfur: p is 0 or. 1

If p equals 0 then q equals 1. If p equals 1 then q equals 0.

Preferably, in the dihydropyrazine (II) or in the olefin (III) at least one of the substituents R1 to R10 is selected from

- [(C 1 -C ₁₀ -alkyl) - (R 14) _u ], -O - [(C 1 -C ₁₀ -alkyl) - (R 14) _u ], -N [(C 1 -C ₁₀ -alkyl) - (R 14) _u ] ₂ , -NH [(C 1 -C 10 -alkyl) - (R 14) _u ], -C (O) -RI 3 and -CN, where R 13 and R 14 are each independently of the same hydroxy, C ₁ -C 10 -alkoxy, -NH ₂ , - NH (Ci-Cio-alkyl), -N (Ci-Ci _o alkyl) _2, -O-aryl, or -O- (C _r Ci ₀ alkyl) -aryl, and u is from 0 to 10 degrees.

The dihydropyrazine (II) is particularly preferably selected from 2,3-dihydropyrazine, 2-methyl-5,6-dihydropyrazine, 2-ethyl-5,6-dihydropyrazine, 2-propyl-5,6-dihydropyrazine, 2,3- Dimethyl 5,6-dihydropyrazine, 2,3-diethyl-5,6-dihydropyrazine, 2-ethyl-3-methyl-5,6-dihydropyrazine, 2,5-dimethyl-5,6-dihydropyrazine, 2,6- Dimethyl 5,6-dihydropyrazine, 2,3,5-trimethyl-5,6-dihydropyrazine, 2-hydroxy-5,6-dihydropyrazine, 2-methyl-3-hydroxy-5,6-dihydropyrazine, 2-methyl 5-hydroxy-5,6-dihydropyrazine, 2-methyl-6-hydroxy-5,6-dihydropyrazine, 2-dimethylamino-5,6-dihydropyrazine, 5-dimethylamino-5,6-dihydropyrazine or 2-methyl- 3-dimethylamino-5,6-dihydropyrazine.

The olefin (III) is particularly preferably selected from ethylene, propylene, butylene, hydroxypropylene, hydroxybutylene, vinyl methyl ketone, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, vinyl methyl ether, (dimethylaminoethyl) vinyl ether, (2-hydroxyethyl) vinyl ether, (I -Hydroxyethyl) vinyl ethers, allylmethylketone, 3-hydroxybut-1-ene, 3-hydroxypent-1-ene, 3-hydroxyhex-1-ene, 4-hydroxybut-1-ene, 4-hydroxypent-1-ene, 4 Hydroxyhex-1-ene, 5-hydroxypent-1-ene, 5-hydroxyhex-1-ene, 6-hydroxyhex-1-ene, 4-hydroxypent-2-ene, 4-hydroxyhex-2-ene, 2-hydroxybutyl 3-ene, 4-hydroxypent-2-ene, 4-hydroxyhex-2-ene, 5-hydroxypent-2-ene, 5-hydroxyhex-2-ene, 6-hydroxyhex-2-ene, allyl acetate, maleic acid, maleic acid dimethyl ester Diethyl maleate, monomethyl ethyl maleate, maleic anhydride, fumaric acid, dimethyl fumarate, diethyl fumarate, monomethyl monomethyl fumarate or fumaric anhydride.

Preferably, the TEDA derivative (Ia) is a compound according to the formula (Ia1)

where _R _2, R 7 and R 8 independently of one another are H, -OH, - (C _r C ₃ -alkyl) -OH, (C ₁ -C ₃ -alkyl) -O- (C ₁ -C ₃ -alkyl), -CN, -O-phenyl, - (C ₁ -C ₃ -alkyl) -O-phenyl, C ₁ -C ₃ -alkoxy, - C (O) (-C ₃ -alkoxy), -C (O) OH, -N (CH ₃₎ _2, -NH (CH _3), -NH _2, - (C _r C ₃ alkyl) -N ( CH ₃ ) ₂ , - (C ₁ -C ₃ -alkyl) -NH (CH ₃ ), - (C ₁ -C ₃ -alkyl) -NH ₂ , or - (C ₁ -C ₃ -alkyl) -OC (O) (CrC ₃ alkoxy) are, R5 and R6 are independently H, C _r C ₃ alkyl, -C (O) OH, -C (O) (-C ₃ -alkoxy), or - _(Ci-C3 alkyl) -O- (C ₃ -C ₃ -alkyl),

and at least one of the substituents R2, R7 and R8 is not H.

Particularly preferred TEDA derivatives (Ia) are selected in one embodiment

2-Hydroxy-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-carboxy-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-hydroxycarbonyl-1,4-diazabicyclo [ 2.2.2] oct-5-ene, 2-formyloxy-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-acetoxy-1,4-diazabicyclo [2.2.2] oct-5- en, 2-propionyloxy-1, 4-diazabicyclo [2.2.2] oct-5-ene, 2-hydroxy-5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-carboxy 5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-hydroxycarbonyl-5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-formyloxy-5- methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-acetoxy-5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-propionyloxy-5-methyl 1, 4-diazabicyclo [2.2.2] oct-5-ene, 2-hydroxy-6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-carboxy-6-methyl- 1, 4-diazabicyclo [2.2.2] oct-5-ene, 2-hydroxycarbonyl-6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-formyloxy-6-methyl 1, 4-diazabicyclo [2.2.2] oct-5-ene, 2-acetoxy-6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-propionyloxy-6-methyl-1, 4-diazabicyclo [2.2.2] oct-5-ene, 2-hydroxy-5,6-dimethyl-1,4-diazabicyclo [ 2.2.2] oct-5-ene, 2-carboxy-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-hydroxycarbonyl-5,6-dimethyl-1, 4- diazabicyclo [2.2.2] oct-5-ene, 2-formyloxy-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-acetoxy-5,6-dimethyl-1, 4-diazabicyclo [2.2.2] oct-5-ene, 2-propionyloxy-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-hydroxymethyl-1,4-diazabicyclo [ 2.2.2] oct-5-ene, 2-hydroxymethyl-5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-hydroxymethyl-6-methyl-1,4-diazabicyclo [2.2. 2] oct-5-ene, 2-hydroxymethyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (1'-hydroxyethyl) -1, 4-diazabicyclo [2.2.2] oct-5-ene, 2- (1'-hydroxyethyl) -5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (1'-hydroxyethyl) -6 -methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (1'-hydroxyethyl) -5,6-dimethyl-1,4-diazabicyclo-

[2.2.2] oct-5-ene, 2- (2'-hydroxyethyl) -1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (2'-hydroxyethyl) -5-methyl -1, 4-diazabicyclo [2.2.2] oct-5-ene, 2- (2'-hydroxyethyl) -6-methyl-1,4-diacabicyclo [2.2.2] oct-5-ene, 2- (2'-hydroxyethyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-methoxycarbonyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2 Methoxycarbonyl-5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-methoxycarbonyl-6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2 -Methoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-methoxycarbonyl-5-methyl-6-ethyl-1,4-diazabicyclo [2.2.2] oct-5 -en, 2-methoxycarbo- nyl-5-ethyl-6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-ethoxycarbonyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- Ethoxycarbonyl-5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-ethoxycarbonyl-6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-ethoxycarbonyl 5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-ethoxycarbonyl-5-methyl-6-ethyl-1,4-diazabicyclo [2.2.2] oct-5- en, 2-ethoxycarbonyl-5-ethyl-6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-acetoxymethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-acetoxymethyl-5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2-acetoxymethyl-6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- Acetoxymethyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (dimethylamino) -1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (dimethylamino ) -5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (dimethylamino) -6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (Dimethylamino) - 5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (dimethylaminomethyl) -1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (dimethylaminomethyl) -5-methyl- 1, 4-diazabicyclo [2.2.2] oct-5-ene, 2- (dimethylaminomethyl) -6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (dimethylaminomethoxy-S .Θ-dimethyl-i ^-diazabicycloP ^^ oct-S-ene, 2- (dimethylaminoethoxy) -1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (dimethylaminoethoxy) -5-methyl-1 , 4-diazabicyclo [2.2.2] oct-5-ene, 2- (dimethylaminoethoxy) -6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (dimethylaminoethoxy) -5 , 6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2 - [(dimethylaminoethoxy) carbonyl] -1,4-diazabicyclo [2.2.2] oct-5-ene, 2- [(Dimethylaminoethoxy) carbonyl] -5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2 - [(dimethylaminoethoxy) carbonyl] -6-methyl-1,4-diazabicyclo [ 2.2.2] oct-5-ene, 2 - [(dimethylaminoethoxy) carbonyl] -5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (1'-hydroxypropyl ) -1, 4-diazabicyclo [2.2.2] oct-5-ene, 2- (1'-hydroxypropyl) -5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- ( 1'-hydroxypropyl) -6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (1'-hydroxypropyl) -5,6-dimethyl-1,4-diazabicyclo [2.2 .2] oct -5-ene, 2- (2'-hydroxypropyl) -1, 4-diazabicyclo [2.2.2] oct-5-ene, 2- (2'-hydroxypropyl) -5-methyl-1,4-diazabicyclo [2.2 .2] oct-5-ene, 2- (2'-hydroxypropyl) -6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (2'-hydroxypropyl) -5 , 6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (3'-hydroxypropyl) -1, 4-diazabicyclo [2.2.2] oct-5-ene, 2- (3'-hydroxypropyl) -5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2- (S'-hydroxypropyl-θ-methyl-i, -diazabicycloP) -j-octene-S-ene , 2- (3'-Hydroxypropyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2,3-bis (hydroxymethyl) -1, 4-diazabicyclo [2.2 .2] oct-5-ene, 2,3-bis (hydroxymethyl) -5-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2,3-bis (hydroxymethyl) -6-methyl -1, 4-diazabicyclo [2.2.2] oct-5-ene, 2,3-bis (hydroxymethyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 2,3-bis (ethoxycarbonyl) -1,4-diazabicyclo [2.2.2] oct-5-ene, 2,3-bis (ethoxycarbonyl) -5-methyl-1,4-diazabicyclo [2.2.2] -oct -5-ene, 2,3-bis (ethoxycarbonyl) -6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene and 2,3-bis (ethoxycarbonyl) - 5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene.

Preferably, the TEDA derivative (Ib) is a compound according to formula (Ib1),

where R 2, R 7 and R 8 independently of one another are H, -OH, - (C ₁ -C ₃ -alkyl) -OH, - (C ₁ -C ₃ -alkyl) -O- (C ₁ -C ₃ -alkyl), -CN, - O-phenyl, - (C _r C ₃ alkyl) -O-phenyl, C _r C ₃ alkoxy, - C (O) (-C ₃ -alkoxy), -C (O) OH, -N (CH ₃₎ ₂ , -NH (CH ₃ ), -NH ₂ , - (C _r C ₃ -alkyl) -N (CH ₃ ) ₂ , - (dC ₃ -alkyl) -NH (CH ₃ ), - (Ci-C ₃ -Alkyl) -NH ₂ , or - (C ₁ -C ₃ -alkyl) -OC (O) (C ₁ -C ₃ -alkoxy),

R5 and R6 are independently H, C _r C ₃ alkyl, -C (O) OH, -C (O) (-C ₃ -alkoxy), or - _(Ci-C3 alkyl) -O- (CrC ₃ alkyl ) are,

and at least one of the substituents R2, R7 and R8 is not H.

Particularly preferred TEDA derivatives (Ib) are selected in one embodiment

2-hydroxy-1,4-diazabicyclo [2.2.2] octane, 2-carboxy-1,4-diazabicyclo [2.2.2] octane, 2-hydroxycarbonyl-1,4-diazabicyclo [2.2.2] octane, 2- Formyloxy-1,4-diazabicyclo [2.2.2] octane, 2-acetoxy-1,4-diazabicyclo [2.2.2] octane, 2-propionyloxy-1,4-diazabicyclo [2.2.2] octane, 2-hydroxy-5-methyl-1,4-diazabicyclo [2.2.2] octane, 2-carboxy-5-methyl-1,4-diazabicyclo [2.2.2] octane, 2-hydroxycarbonyl-5-methyl-1, 4-diazabicyclo [2.2.2] octane, 2-formyloxy-5-methyl-1,4-diazabicyclo [2.2.2] octane, 2-acetoxy-5-methyl-1,4-diazabicyclo [2.2.2] octane, 2-propionyloxy-5-methyl-1,4-diazabicyclo [2.2.2] octane, 2-hydroxy-6-methyl-1,4-diazabicyclo [2.2.2] octane, 2-carboxy-6- Methyl-1, 4-diazabicyclo [2.2.2] octane, 2-hydroxycarbonyl-6-methyl-1,4-diazabicyclo [2.2.2] octane, 2-formyloxy-6-methyl-1,4-diazabicyclo 2.2.2] octane, 2-acetoxy-6-methyl-1,4-diazabicyclo [2.2.2] octane, 2-propionyloxy-6-methyl-1,4-diazabicyclo [2.2.2] octane, 2- Hydroxy-5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2-carboxy-5,6-dimethyl-1,4-diazabicy clo [2.2.2] octane, 2-hydroxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2-formyloxy-5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2-acetoxy-5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2-propionyloxy-5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2-hydroxymethyl 1, 4-diazabicyclo [2.2.2] octane, 2-

Hydroxymethyl-5-methyl-1,4-diazabicyclo [2.2.2] octane, 2-hydroxymethyl-6-methyl-1,4-diazabicyclo [2.2.2] octane, 2-hydroxymethyl-5,6-dimethyl-1, 4-diazabicyclo [2.2.2] octane, 2- (1'-hydroxyethyl) -1,4-diazabicyclo [2.2.2] octane, 2- (1'-hydroxyethyl) -5-methyl-1,4-diazabicyclo 2.2.2] octane, 2- (1'-hydroxyethyl) -6-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (1 '-hydroxyethyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2- (2'-hydroxyethyl) -1,4-diazabicyclo [2.2.2] octane, 2- (2 '-Hydroxyethyl) -5-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (2'-hydroxyethyl) -6-methyl-1,4-diazabicyclo [2.2.2] octane _! 2- (2'-hydroxyethyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2-methoxycarbonyl-1,4-diazabicyclo [2.2.2] octane, 2-methoxycarbonyl-5-methyl -1, 4-diazabicyclo [2.2.2] octane, 2-methoxycarbonyl-6-methyl-1,4-diazabicyclo [2.2.2] octane, 2-methoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2-methoxycarbonyl-5-methyl-6-ethyl-1,4-diazabicyclo [2.2.2] octane, 2-methoxycarbonyl-5-ethyl-6-methyl-1,4-diazabicyclo [2.2 .2] octane, 2-ethoxycarbonyl-1,4-diazabicyclo [2.2.2] octane, 2-ethoxycarbonyl-5-methyl-1,4-diazabicyclo [2.2.2] octane, 2-ethoxycarbonyl-6-methyl-1 , 4-diazabicyclo [2.2.2] octane, 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2-ethoxycarbonyl-5-methyl-6-ethyl-1,4-diaza - bicyclo [2.2.2] octane, 2-ethoxycarbonyl-5-ethyl-6-methyl-1,4-diazabicyclo [2.2.2] octane, 2-acetoxymethyl-1,4-diazabicyclo [2.2.2] octane, 2 Acetoxymethyl-5-methyl-1,4-diazabicyclo [2.2.2] octane, 2-acetoxymethyl-6-methyl-1,4-diazabicyclo [2.2.2] octane, 2-acetoxymethyl-5,6-dimethyl -1, 4-diazabicyclo [2.2. 2] octane, 2- (dimethylamino) -1,4-diazabicyclo [2.2.2] octane, 2- (dimethylamino) -5-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (dimethylamino ) -6-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (dimethylamino) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2- (dimethylaminomethyl) -1, 4-diazabicyclo [2.2.2] octane, 2- (dimethylaminomethyl) -5-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (dimethylaminomethyl) -6-methyl-1,4-diazabicyclo [ 2.2.2] octane, 2- (dimethylamino-methyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2- (dimethylaminoethoxy) -1, 4-diazabicyclo [2.2.2] octane, 2- (dimethylaminoethoxy) -5-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (dimethylaminoethoxy) -6-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (dimethylamino - ethoxy) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2 - [(dimethylaminoethoxy) carbonyl] -1,4-diazabicyclo [2.2.2] octane, 2 - [(dimethylaminoethoxy) carbonyl ] -5-methyl-1,4-diazabicyclo [2.2.2] octane, 2 - [(dimethylaminoethoxy) carbonyl] -6-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (dimethylaminoethoxy) carboxylic yl] -5,6-dimethyl-1, 4-diazabicyclo [2.2.2] octane, 2- (1'-hydroxypropyl) -1, 4-diazabicyclo [2.2.2] octane, 2- (1'-hydroxypropyl) 5-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (1'-hydroxypropyl) -6-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (1'-hydroxypropyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2- (2'-hydroxypropyl) -1,4-diazabicyclo [2.2.2] octane, 2- (2'-

Hydroxypropyl) -5-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (2'-hydroxypropyl) -6-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (2'- Hydroxypropyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2- (3'-hydroxypropyl) -1, 4-diazabicyclo [2.2.2] octane, 2- (3'- Hydroxypropyl) -5-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (3'-hydroxypropyl) -6-methyl-1,4-diazabicyclo [2.2.2] octane, 2- (3 ') Hydroxypropyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2,3-bis (hydroxymethyl) -1,4-diazabicyclo [2.2.2] octane, 2,3-

Bis (hydroxymethyl) -5-methyl-1,4-diazabicyclo [2.2.2] octane, 2,3-bis (hydroxymethyl) -6-methyl-1,4-diazabicyclo [2.2.2] octane, 2,3- Bis (hydroxymethyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane, 2,3-bis (ethoxycarbonyl) -1, 4-diazabicyclo [2.2.2] octane _! 2,3 Bis (ethoxycarbonyl) -5-methyl-1,4-diazabicyclo [2.2.2] octane, 2,3-bis (ethoxycarbonyl) -6-methyl-1,4-diazabicyclo [2.2.2] octane and 2,3- Bis (ethoxycarbonyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane.

In a further embodiment of the present invention, the dihydropyrazine (II) is prepared by reacting a dicarbonyl compound with ethylenediamine (EDA) or an EDA derivative. Preferably, the carbonyl compound is a diketo compound. Preferred diketo compounds are selected from 2,3-pentanedione, 2,3-butanedione, glyoxal, methylglyoxal. Preferred EDA derivatives are EDA, 1,2-propanediamine, 1,2-butanediamine, 2,3-butanediamine, 1,2-pentanediamine, 2,3-pentanediamine, 1,2-hexanediamine, 2,3-hexanediamine, 3 , 4-hexanediamine. Particularly preferred are the reactions of butanedione with ethylenediamine to 2,3-dimethyl-5,6-dihydropyrazine, of methylglyoxal with ethylenediamine to 2-methyl-5,6-dihydropyrazine and of glyoxal and ethylenediamine to 2,3-dihydropyrazine. The reaction is carried out in organic solvents, for example ethers, esters, alcohols or alkanes. Preferably, the reaction is carried out in a moderately polar but water-immiscible solvent. Tert-butyl methyl ether (MTBE) is particularly preferably used as the solvent and, in addition, it is worked under N ₂ as protective gas.

The synthesis of Dihydropyrazine can be carried out between -80 ⁰ C and 80 ⁰ C. Preferably, the reaction between -20 ° C and 60 ⁰ C, more preferably carried out between 0 ° C and 50 ° C.

The reaction pressure can be between 0.5 and 250 bar (abs.). Preference is given to working at atmospheric pressure.

Another object of the present invention are novel triethylenediamine derivatives which can be prepared by the process according to the invention. These TEDA derivatives according to the invention contain substituents with functional groups, in particular substituents, which have at least one heteroatom, such as halogen, O, P, S or N, preferably O or N. As already mentioned above, isolated TEDA derivatives are already known. These already known TEDA derivatives are not the subject of the present invention with regard to the TEDA derivatives as such. As such, the TEDA derivatives of the invention thus do not include those disclosed in the aforementioned documents by T. Oishi et al., L. Street et al., E. Shiskhin et al. as well as in WO 98/24790 and DE-A 30 48 031 described TEDA derivatives.

The TEDA derivatives according to the invention correspond to the general formula (Ia) or (Ib),

preparable by the process according to the invention, wherein the radicals R 1 to R 12 have the above meanings and wherein at least one of the substituents R 1 to R 10 contains at least one heteroatom selected from halogen, O, P, S or N, preferably O or N, or at least one of R _{1 to} R 10 contains -OH or -NH ₂ , provided that not one of R ₁ to R 12 is -C (O) OH, -C (O) OCH ₃ , -C (O) OC ₂ H ₅ , -CH ₂ -OH, -CH ₂ -O-benzyl or -CH ₂ -OC (O) -CH ₃ when the other radicals from R 1 to R 12 are hydrogen, and not two adjacent radicals R 1 to R 12 equals -CH ₂ -O-benzyl when the other radicals from R _{1 to} R 12 are hydrogen. Adjacent remainder is understood to mean that the respective radicals are bonded to 2 different carbon atoms of the TEDA derivatives according to the invention and these two carbon atoms are in turn themselves connected to one another.

With regard to the preferred and particularly preferred TEDA derivatives according to the invention, reference is made to the corresponding definitions of the method according to the invention, taking into account the above restrictions with respect to the TEDA derivatives as such.

Another object of the present invention is the use of the inventive TEDA derivatives for the production of polyurethanes. The TEDA derivatives according to the invention are preferably used as catalyst, in particular in the production of polyurethane foams. Such processes for the preparation of polyurethanes are known to the person skilled in the art. With regard to the selection of the educts used in the production of polyurethane, in principle there are no restrictions. A further subject of the present invention are thus also polyurethanes comprising at least one TEDA derivative according to the invention. Such polyurethanes, preferably polyurethane foams, are distinguished by the fact that the TEDA derivatives used do not outgas because they chemically enter the corresponding polyurethanes. are involved. In this way, low-odor or odorless polyurethanes can be produced.

The TEDA derivative according to the invention may preferably be used in its capacity as a polyurethane catalyst as a gel catalyst for the crosslinking reaction or as a blowing catalyst for the release of CO 2 with the aid of water. The TEDA derivative according to the invention is particularly preferably used as a gel catalyst which promotes the crosslinking reaction between polyisocyanate and polyol component.

The invention will be explained in more detail with reference to the following examples:

Examples

Examples 1-12: Preparation of 2,3-dimethyl-5,6-dihvdropyrazine

Example 1 :

1 g of 2,3-butanedione are introduced in bulk. 4 ml of a previously prepared solution of 10 g of ethylenediamine in 30 g of H ₂ O are added dropwise, the reaction is exothermic. The reaction solution changes color during the reaction from yellow to dark brown. 2,3-butanedione is presented neat, since an emulsion is formed in water. GC analysis: [GC-FI. %] 10.28% EDA, 76.94% 2,3-dimethyl-5,6-dihydropyrazine, 12.78% Other.

Example 2: Butanedione (52.9 g, 615 mmol, 1 eq.) Is initially charged in 1,2-propanediol (50 g) and EDA (73.8 g, 1.23 mol, 2 eq.) Is added with ice-cooling. The temperature rises to about 40 ⁰ C. The solution turns yellow to black. GC analysis on a 30m RTX-5 amine column shows that the product mixture of 14.7% EDA, 81.5% 1, 2-propanediol and 0.61% 2,3-dimethyl-5,6 -dihydropyrazine composed (solvent-free: 79.5% EDA, 3.29% 2,3-dimethyl-5,6-dihydropyrazine).

Example 3:

EDA (5.58 g, 92 mmol) is initially charged in 1, 2-propanediol (20 mL) at 0 ⁰ C and butanedione (4.00 g, 46.4 mmol, 1 eq.) In 1, 2-propanediol dissolved (20 mL) very slowly added dropwise over 2.5 h and stirred vigorously. The temperature of the mixture does not rise above 5 ° C. In the meantime, a fine white precipitate separates, which slowly dissolves when heated to room temperature. The slightly yellowish solution is in - kept 20 ⁰ C. GC analysis on a 30 m RTX-5 amine column shows that the product mixture of 5.83% EDA, 79.4% 1,2-propanediol and 13.6% 2,3-dimethyl-5,6 - dihydropyrazine (calculated solvent-free: 28.2% EDA, 66.0% 2,3-dimethyl-5,6-dihydropyrazine).

Example 4: EDA (5:58 g, 92 mmol) in MeOH submitted (20 mL) at 0 ⁰ C. Butanedione (4.00 g, 46.4 mmol, 1 eq.) Is dissolved in MeOH (40 ml) and added dropwise very slowly over 2 h to the EDA solution and stirred vigorously. The temperature of the mixture does not rise above 0 ^° C. The resulting white solid is filtered off and washed with cold MeOH. The solid is converted on removal of the solvent at 30 ⁰ C in 2,3-dimethyl-5,6-dihydropyrazine (brown oil). GC analysis on a 30 m RTX-5 amine column shows that the product mixture consists of 74.2% MeOH, 7.12% EDA and 18.2% 2,3-dimethyl-5,6-dihydropyrazine ( calculated solvent-free: 27.6% EDA, 70.5% 2,3-dimethyl-5,6-dihydropyrazine).

Example 5:

EDA (16.7 g, 278 mmol, 2 eq.) Is initially charged in 1,2-propanediol (150 mL) at 0 ° C. Butanedione (12.0 g, 139 mmol) in 1, 2-propanediol (60 ml_) is added dropwise (over 1.5 h) while stirring vigorously. It is stirred for 30 min at 0 ⁰ C and the solution overnight at - 20 ⁰ C stored. GC analysis on a 30 m RTX-5 amine column shows that the product mixture of 3.66% EDA, 86.0% 1, 2-propanediol and 9.90% 2,3-dimethyl-5,6 -dihydropyrazine (calculated solvent-free: 26.1% EDA, 70.7% 2,3-dimethyl-5,6-dihydropyrazine).

Example 6: Work is carried out under N ₂ . EDA (2.79 g, 46.4 mmol, 2 eq.) Is initially charged in MTBE (60 mL) at 0 ° C. Butanedione (4.00 g, 46.4 mmol) in MTBE (6 mL) is added dropwise (over 40 min). Due to the white precipitate, the approach is very firm, it is therefore strongly stirred. It is then heated quickly to 50 ⁰ C to dissolve the precipitate. There are two phases. The mixture is then immediately cooled to 0 ° C to avoid polymerization. The organic phase is fractionally distilled. The desired product boils at 28 mbar / 95 ° C and is collected in the cold trap. GC analysis of the phases shows that the ethereal phase contains almost only product while the aqueous contains all impurities and part of the product. The product can be extracted by shaking out with tert-butyl methyl ether (MTBE) without entraining the by-products. GC analysis on a 30 m RTX-5 amine column shows that the organic phase consists of 0.03% EDA, 88.2% MTBE and 11.5% 2,3-dimethyl-5,6-dihydropyrazine consists of (solvent-free: 0.25% EDA, 97.5% 2,3-dimethyl-5,6-dihydropyrazine). Example 7:

EDA (13.9 g, 232 mmol, 1 eq.) Is initially charged in MTBE (125 mL) at ⁰ ° C. Butanedione (20.0 g, 232 mmol) in MTBE (30 ml) is added dropwise (over 1.5 h). It is then stirred at 0 ⁰ C for 15 min, then warmed to ambient temperature and stirred until two phases form. The resulting phases are separated and the aqueous phase is extracted by shaking with MTBE (3 × 25 ml). The ethereal phases are combined and dried over MgSO ₄ . The ether is removed at 50 ° C / 613 mbar. The product is obtained at 7 mbar / 105 ° C (bottom) / 40 ° C (top). GC analysis on a 30 m RTX-5 amine column shows that the product mixture consists of 83.1% MTBE, 16.5% 2,3-dimethyl-5,6-dihydropyrazine and 0.44% other ( solvent-free: 97.6% 2,3-dimethyl-5,6-dihydropyrazine, 2.60% other).

Example 8:

EDA (25.51 g, 425 mmol, 1 eq.) Is presented in MTBE (130 mL) at 0 ⁰ C. Butanedione (36.56 g, 425 mmol) in MTBE (20 mL) is added dropwise (over 2 h). The batch is stored for 50 h at -20 ⁰ C, then heated to 40 ⁰ C and the aqueous phase separated. This is shaken with MTBE (3 x 25 ml_). The ethereal phases are combined and dried over MgSO ₄ . The ether is removed at 30 ° C / 395 mbar and the residue is fractionally distilled (spinning column).

Example 9:

EDA (20.0 g, 232 mmol, 1 eq.) Is introduced into MTBE (125 mL) at 0 ⁰ C. Butanedione (13.9 g, 232 mmol) in MTBE (30 ml) is added dropwise (over 1.5 h). The mixture is heated to 35 ° C and the aqueous phase separated. This is shaken with MTBE (3 x 15 ml). The ethereal phases are combined and dried over MgSO ₄ . The ether is removed at 33 ° C / 410 mbar. The residue is combined with the residue from Experiment 15 and fractionally distilled. The product is obtained at 43 mbar / 100 ° C (bottom) / 72.2 ° C (top). The isolated molar yield is 66.2%, the purity of the distilled product after GC 99.1%.

Example 10:

The EDA (60 g, 1 mol, 1 eq.) Is introduced into 350 ml of MTBE and the butanedione (86 g, 1 mol, 1 eq.) Was added dropwise at 0 ⁰ C. The approach is determined in places and heats up to 35 ° C in the short term. Add 50 ml of MTBE and wait for the reaction to fade. The solution is kept for 55 h at -20 ⁰ C, then heated to 40 ⁰ C and the two phases separated.

Example 11:

Butanedione (172 g, 2 mol, 1 eq.) Is initially charged in MTBE and EDA (120 g, 2 mol, 1 eq. In 120 ml of MTBE) is slowly added dropwise. The batch is heated to 30 ° C and the aqueous extracted phase with 3 x 100 ml_ MTBE. The combined organic phases are dried with MgSO ₄ and MTBE removed on a rotary evaporator at 55 ° C as far as possible. The residue is fractionally distilled via the rotating band column. The temperature rises during the dropping in the flask to about 35 ° C, since the reaction mixture solidified in places. The dropping is stopped immediately and it is waited until the reaction subsides. The solution does not turn dark. Apparent short-term heating above 30 ⁰ C has no further effects on the course of the reaction.

Example 12:

EDA (240 g, 4 mol, 1 eq.) Is introduced into 750 ml of MTBE and butanedione (320 g, 3.72 mol, 0.93 eq.) Were dissolved was added dropwise mL MTBE at 10 ⁰ C in 200. The reaction is stirred overnight (14 h) at ambient temperature. The phases are separated, the aqueous layer is extracted by shaking with 3 × 50 ml MTBE and the combined organic phases are dried with MgSO ₄ . The ether is removed at 40 ⁰ C on a rotary evaporator. The crude product is not further worked up because the MTBE still contained does not disturb other reactions. GC analysis on a 30 m RTX-5 amine column shows that the product mixture of 25.6% MTBE, 0.14% EDA, 71.9% 2,3-dimethyl-5,6-dihydropyrazine and 2 , 36% other (solvent-free: 0.19% EDA, 96.6% 2,3-dimethyl-5,6-dihydropyrazine, 3.17% other).

Examples 13-17: Preparation of 2,3-dihydropyrazine

2,3-dihydropyrazine shows a strong tendency to dimerization and polymerization, which is why it should be preferred to work at low temperatures. After the synthesis of dihydropyrazine, the next stage should be started as soon as possible.

Example 13:

The ethylenediamine (6.0 g, 0.1 mol, 1 eq.) Is dissolved in MTBE (40 mL) and cooled to 0 ° C. Glyoxal (5.8 g, 0.1 mol, 1 eq., 14.5 g 40% solution in H ₂ O) is so conces- dropwise such that the temperature does not rise above 0 ⁰ C. The heat development of the reaction is much lower than that with the use of methylglyoxal or butanedione. The aqueous phase is almost colorless. The desired product is detected by GC-MS but not isolated. After 1 h at ambient temperature, the discharge becomes rubbery.

Example 14:

30g [0,5mol] of ethylenediamine and 30g [1, 67mol] of water are placed. Then 18.2 g of 40% aqueous glyoxal solution [0.125 mol glyoxal] are added dropwise to the warm solution. There is an exothermic reaction. GC analysis: 75.53% EDA, 15.36% 2,3-dihydropyrazine, 9% unknown, (52.69% H ₂ O) Example 15:

50% EDA solution in water is placed in a test tube and glyoxal (40% solution in water) is added dropwise. There is an exothermic reaction. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) shows the following composition: (in GC-FI%)

50.93% ethylenediamine, 2.11% monoethylene glycol, 26.1 1% 2,3-dihydropyrazine, 20.85% Other. The desired product is confirmed by GC-MS.

Example 16:

60 g [1 mol] of ethylenediamine and 60 g [3.33 mol] of water are placed in a 250 ml flask equipped with magnetic stirrer, dropping funnel and mini-separating column. After the mixture (heating to 50 ⁰ C by mixing heat) is cooled to 38 ° C, within 15 minutes, 36.3 g of a 40% aqueous glyoxal solution [0.25 mol Glyoxal] added dropwise, the approach to 62 ° C heated. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) shows the following composition: (in GC fl.%) 74.5% ethylenediamine, 14.6% 2,3-dihydropyrazine, 10.9% unknown compounds, water content not taken into account.

Example 17:

30 g [0.5 mol] of ethylenediamine and 30 g [1.67 mol] of water are introduced. Then, 18.2 g of 40% aqueous glyoxal solution [0.125 mol glyoxal] are added dropwise to the warm EDA solution. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) shows the following composition: (in GC-FI%): 77.3% ethylenediamine, 12.7% 2,3-dihydropyrazine, 10.0% unknown compounds, water content not included ,

Examples 18-20: Preparation of Other Dihydropyrazines

Example 18: 2-Methyl-5,6-dihvdropyrazine

EDA (6.0 g, 0.1 mol, 1 eq.) Is dissolved in MTBE (40 mL) and cooled to 0 ⁰ C. Methylglyoxal (7.2 g, 0.1 mol, 1 eq., 18 g 40% solution in H ₂ O) is added dropwise so that the temperature does not rise above 5 ° C. The solution turns yellowish. After warming to ambient temperature, the phases separate and the aqueous assumes a black color. For a GC sample, part of the aqueous phase is strongly diluted with acetone. The desired product is detected by GC-MS but not isolated. Example 19: 2-Methyl-5,6-dihvdropyrazine

The EDA (4.5 g, 75 mmol, 3 eq.) Is dissolved in MTBE (40 mL), cooled to ⁰ ° C. and methylglyoxal (1.8 g, 25 mmol, 1 eq., 4.5 g 40% solution in H ₂ O ) (30 min). The batch is warmed overnight to ambient temperature. The organic phase is colorless, the watery tan colored. The aqueous phase contains mainly 3 main products. The desired product is detected in both phases by GC-MS, but not isolated.

Example 20: 2-Ethyl-3-methyl-5,6-dihvdropyrazine To a solution consisting of one part of ethylenediamine in part 1, 2-propanediol, a solution of one part of 2,3-pentanedione is dissolved in part 1 , 2-propanediol added slowly. There is an exothermic reaction. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) has the following composition: (in GC-FI%) 25.28% ethylenediamine, 56.76% 1, 2-propanediol, 16.62% 2-ethyl-3-methyl -5,6-dihydropyrazine, 0.77% Other.

Solvent-free: 58.46% ethylenediamine, 38.42% 2-ethyl-3-methyl-5,6-dihydropyrazine, 3.12% Other. The desired product is confirmed by GC-MS.

Preparation of the TEDA Derivatives (Ia)

Examples 21-33: 2-Ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.21oct-5-ene

Example 21: A portion of the discharge from Example 1 (2,3-dimethyl-5,6-dihydropyrazine 77%) is initially charged, 1 g of ethyl acrylate is added. At room temperature, there is no reaction. The reaction vessel is heated to 100 ^° C. for a few minutes. GC analysis (30 m RTX-5 amines) of the reaction effluent shows the following composition: 0.17% EDA, 4.24% ethyl acrylate,

46.91% 2,3-dimethyl-5,6-dihydropyrazine, 1.03% N-acetyl-EDA,

10.67% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (product),

17.51% N, N-bis [2 '- (ethoxycarbonyl) ethyl] ethylenediamine, 18.09% Other.

Example 22:

2,3-dimethyl-5,6-dihydropyrazine from Example 4 (about 23 mmol, dissolved in 40 mL MeOH, 1 eq.) And ethyl acrylate (2.50 g, 25 mmol, 1.1 eq.) Under N ₂ to 65 ° C (reflux) heated. After 30 min, 1, 1.5, 2 and 3 h, a sample is taken for GC to monitor the course of the reaction. The gas chromatogram of the reactor Onsgemischs (30 m RTX 5 amines) shows after 30 min following composition (in GC-FI%.):

74.8% methanol, 1.43% ethylenediamine, 9.80% 2,3-dimethyl-5,6-dihydropyrazine, 2.31% 2-hydroxyethylpiperazine, 3.04% N-acetyl-EDA,

1.93% N, N-bis [2 '- (ethoxycarbonyl) ethyl] ethylenediamine, 6.69% Other.

The gas chromatogram of the reaction mixture (30 m RTX 5 amines) shows after 90 min the following composition: (in GC-FI%) 69.9% methanol, 1, 59% ethylenediamine, 11, 3% 2,3-dimethyl-5, 6-dihydropyrazine, 3.79% 2-hydroxyethylpiperazine, 2.23% N-acetyl-EDA, 0.71% N, N-bis [2 '- (ethoxycarbonyl) ethyl] ethylenediamine, 10.5% Other.

The gas chromatogram of the reaction mixture (30 m RTX 5 amines) shows after 180 min the following composition: (in GC-FI%).

68.0% methanol, 1, 49% ethylenediamine, 1 1, 6% 2,3-dimethyl-5,6-dihydropyrazine,

4.21% 2-hydroxyethylpiperazine, 1.08% N-acetyl-EDA,

0.17% N, N-bis [2 '- (ethoxycarbonyl) ethyl] ethylenediamine, 13.5% Other.

Solvent-free: 4.66% ethylenediamine, 36.3% 2,3-dimethyl-5,6-dihydropyrazine, 13.2% 2-hydroxyethylpiperazine, 3.38% N-acetyl-EDA,

0.53% N, N-bis [2 '- (ethoxycarbonyl) ethyl] ethylenediamine, 42.2% Other.

Example 23:

2,3-dimethyl-5,6-dihydropyrazine from Example 3 (about 23 mmol in 40 ml of 1,2-propanediol, 1 eq.) And ethyl acrylate (2.50 g, 25 mmol, 1.1 eq.) Are dissolved under N ₂ 100 ⁰ C heated. After 30 min, 1 h and 1.5 h, a sample is taken for GC to monitor the course of the reaction. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) shows after 30 min the following composition: (in GC-FI%) 0.94% ethylenediamine, 81, 5% 1, 2-propanediol, 7.10% 2,3- Dimethyl-5,6-dihydropyrazine, 1.18% N-acetyl-EDA, 0.08% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (product) , 9,20% Other.

The gas chromatogram of the reaction mixture (30 m RTX 5 amines) shows after 90 min the following composition: (in GC-FI%) 1, 28% ethylenediamine, 84.9% 1, 2-propanediol, 0.25% piperazine, 4, 12% 2,3-dimethyl-5,6-dihydropyrazine, 0.31% N-acetyl-EDA, 0.04% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] octane 5-s (product), 9,10% Other.

Solvent-free: 8.48% ethylenediamine, 1.66% piperazine, 27.3% 2,3-dimethyl-5,6-dihydropyrazine, 2.05% N-acetyl-EDA, 0.26% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (product), 60.36% Other.

Example 24: 2,3-dimethyl-5,6-dihydropyrazine (approx. 12 mmol in 20 mL 1, 2-propanediol, 1 eq) and 1, 2- propanediol (30 ml) are heated to 60 ⁰ C. At this temperature, ethyl acrylate (6.0 g, 60 mmol, 0.5 eq. Dissolved in 2.0 ml. 1,2-propanediol) is added dropwise under N ₂ (10 min.) And the mixture is subsequently heated rapidly to 100 ^° C. The reaction solution is left for 5 min at this temperature. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) showed the following composition: (in GC-FI%)

91.0% 1, 2-propanediol, 1.67% 2,3-dimethyl-5,6-dihydropyrazine, 0.03% N-acetyl-EDA,

1, 06% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (product), 6.24%

Other.

Solvent-free: 18.6% 2,3-dimethyl-5,6-dihydropyrazine, 0.33% N-acetyl-EDA, 1 1, 8% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [cf. 2.2.2] oct-5-ene (product), 69.3% Other.

Example 25:

2,3-dimethyl-5,6-dihydropyrazine (about 15 mmol in 20 ml of 1,2-propanediol, 1 eq.) And ethyl acrylate (15 g, 0.15 mmol, 10 eq.) Are heated to 100 under N ₂ ⁰ C heated. The reaction solution is left at this temperature for 22 minutes and turns reddish brown. The yield can not be optimized by a massive excess of acrylic ester.

Example 26:

2,3-Dimethyl-5,6-dihydropyrazine is purified by distillation before the experiment. (Example 9). As a high-boiling, largely inert solvent dioxane is selected. The acrylic acid ester is used only in slight excess (1.2 equivalents). 2,3-Dimethyl-5,6-dihydropyrazine (1.778 g, 16.16 mmol, 1 eq.) Is dissolved under N ₂ in dioxane (25 mL) and heated to 80 ° C. Ethyl acrylate (1939 g, 19.39 mmol, 1.2 eq.) Is dissolved in dioxane (8 mL) and slowly added dropwise (15 min). The mixture is brought to reflux for 4 h at 95 ° C, allowed to stand overnight at 20 ⁰ C and heated again for 4 h. The yield of the desired product can be significantly increased. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) shows the following composition: (in GC-FI%)

95.2% dioxane, 0.61% 2,3-dimethyl-5,6-dihydropyrazine, 1, 26% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5- en (product), 0.64% + 0.35% addition products of the main product plus other equivalents of acrylic esters, 1.94% Other. Solvent-free: 12.7% 2,3-dimethyl-5,6-dihydropyrazine, 26.3% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (product ), 13.3% + 7.29% Addition products of the main product plus other equivalents of acrylic acid ester, 40.4% Other.

Example 27: EDA (. 6.0 g, 0.1 mol, 1 eq) (10 g) were charged and slowly added dropwise butadione (8.6 g, 0.1 mol, 1 eq.) In dioxane (2.0 g) at 0 ⁰ C in dioxane. There are added 12 g of dioxane and the mixture stirred for 15 min. The apparatus is rendered inert with N ₂ and treated with ethyl acrylate (10 g, 0.1 mol, 1 eq.). The solution is heated to boiling (95 ° C) and left at this temperature for 3 h. The desired product can be detected by GC-MS.

Example 28:

Distilled 2,3-dimethyl-5,6-dihydropyrazine (11 g, 0.1 mol, 1 eq., Example 9) is dissolved in

Dioxane (75 ml_) under N ₂ at 80 ⁰ C heated and ethyl acrylate (12 g, 0.12 mol, 1.2 eq.) Was added. The mixture is heated to reflux for 3.5 h (97 ° C) for 14 h at -20 ⁰ C cooled and again heated for 2 hours to reflux. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) has the following composition: (in GC-FI%) 65.8% dioxane, 11.1% 2,3-dimethyl-5,6-dihydropyrazine, 10.1 % 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (product), 13.0% Other. Solvent-free: 32.5% 2,3-dimethyl-5,6-dihydropyrazine, 29.5% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (Product), 38.0% Other.

Example 29:

Distilled 2,3-dimethyl-5,6-dihydropyrazine (34.3 g, 0.321 mol, 1 eq., Example 9) is heated in dioxane (50 mL) under N ₂ at 88 ° C, to ethyl acrylate (44.9 g, 0.499 mol, 1.55 eq.). The mixture 4 h at 105 ⁰ C heated for 14 h at - 20 ⁰ C cooled and again heated for 2 hours at 105 ⁰ C. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) has the following composition: (in GC-FI%) 34.1% dioxane, 11.5% 2,3-dimethyl-5,6-dihydropyrazine, 27.0 % 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (product), 5.40% + 12.2% addition products of the major product plus further equivalents of acrylic acid ester, 9.80 % Other. Solvent-free: 17.5% 2,3-dimethyl-5,6-dihydropyrazine, 41.0% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (product ), 8.19% + 18.5% addition products of the major product plus further equivalents of acrylic acid ester, 14.9% others. This result corresponds to a conversion of 59.5% with respect to dimethyldi- hydropyrazine and a selectivity of dimethyldihydropyrazine to the desired product of 79.0%. Example 30:

2,3-Dimethyl-5,6-dihydropyrazine (40.3 g, 0.367 mol, 1 eq., Example 9) and ethyl acrylate (39.6 g, 0.396 mol, 1.2 eq.) Are dissolved in dioxane (100 ml) under N ₂ heated to 98 ° C and stirred for 4.5 h. The mixture is kept overnight (14 h) at -20 ⁰ C. The resulting crystals are analyzed by GC, they have the same composition as the reaction solution. The reaction is continued for 8 h at 93 ° C. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) has the following composition: (in GC-FI%). 1, 34% ethyl acrylate, 40.8% dioxane, 14.8% 2,3-dimethyl-5,6-dihydropyrazine , 28.4% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (product), 4.50% + 9.75% addition products of the major product plus further equivalents of acrylic acid - ter, 0.41% Other.

Solvent-free: 2.26% ethyl acrylate, 25.0% 2,3-dimethyl-5,6-dihydropyrazine, 48.0% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct -5-ene (product), 7.60% + 16.5% addition products of the major product plus further equivalents of acrylic acid ester, 0.69% Other. This result corresponds to a conversion of 50.3% with respect to dimethyldihydropyrazine or 95.4% with respect to ethyl acrylate and a selectivity of dimethyldihydropyrazine to the desired product of about 90%.

Example 31:

2,3-Dimethyl-5,6-dihydropyrazine (11 g, 0.1 mol, 1 eq.) And ethyl acrylate (10 g, 0.1 mol, 1 eq.) Are dissolved in 20 ml_ THF and under 80 bar H ₂ to 99 ° C heated. It is H ₂ nachgepresst to 200 bar and stirred for a total of 7 h. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) shows the following composition: (in GC-FI%)

48.7% THF, 1.04% ethyl acrylate, 10.6% 2,3-dimethyl-5,6-dihydropyrazine, 23.0% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2. 2] oct-5-ene (product), 5.66% + 9.70% addition products of the main product plus further equivalents of acrylic acid ester, 1.30% others.

Solvent-free: 2.03% ethyl acrylate, 20.7% 2,3-dimethyl-5,6-dihydropyrazine, 44.8% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct -5-ene (product), 1 1, 0% + 18.9% addition products of the main product plus further equivalents of acrylic esters, 2.53% others. This result corresponds to a conversion of 60.5% with respect to dimethyldihydropyrazine and 95.7% with respect to ethyl acrylate and a selectivity of dimethyldihydropyrazine to the desired product of 74%. Example 32:

2,3-Dimethyldihydropyrazine (141 g, 1.28 mol, 1 eq. 196 g of a ca. 72% solution in MTBE) and ethyl acrylate (128 g, 1, 28 mol, 1 eq.) Are heated together to 82 ° C and stirred at this temperature for a total of 11.5 h until no acrylic acid ester can be detected in the GC. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) has the following composition: (in GC-FI%) 7.70% MTBE, 16.9% 2,3-dimethyl-5,6-dihydropyrazine, 46.2% 2 -Ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (product), 8.92% + 17.3% addition products of the major product plus further equivalents of acrylic acid ester, 2.98% Other , Solvent-free: 18.3% 2,3-dimethyl-5,6-dihydropyrazine, 50.1% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (product ), 9.67% + 18.7% addition products of the major product plus further equivalents of acrylic acid ester, 3.23% other. This result corresponds to a conversion of 65.1% with respect to dimethyldi- hydropyrazine or 100% with respect to ethyl acrylate and a selectivity of the dimethyldihydropyrazine to the desired product of 76.1%.

Example 33:

2,3-Dimethyldihydropyrazine (112 g, 1.02 mol, 1 eq. 156 g of an approximately 72% solution in

MTBE) and ethyl acrylate (102 g, 1, 02 mol, 1 eq.) Are heated together to 82 ° C and stirred at this temperature for a total of 6 h. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) shows the following composition: (in GC area%)

19.4% MTBE, 8.10% ethyl acrylate, 20.0% 2,3-dimethyl-5,6-dihydropyrazine, 34.3% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2. 2] oct-5-ene (product), 6.28% + 10.1% addition products of the major product plus further equivalents of acrylic acid ester, 1.82% other.

Solvent-free: 10.0% ethyl acrylate, 24.8% 2,3-dimethyl-5,6-dihydropyrazine, 42.6% 2-ethoxycarbonyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct -5-ene (product), 7.79% + 12.5% addition products of the main product plus further equivalents of acrylic esters, 2.26% others. This result corresponds to a conversion of 52.6% with respect to dimethyldihydropyrazine and 79% with respect to ethyl acrylate and a selectivity of dimethyldihydropyrazine to the desired product of 81.0%.

Examples 34-35: 2,3-bis (ethoxycarbonyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.21oct-5-ene

Example 34:

The experiment is carried out under N ₂ as a protective gas. 2,3-Dimethyldihydropyrazin

(1 1 g, 0.1 mol, 1 eq.) Is introduced and maleic acid dimethyl ester (14.4 g, 0.1 mol,

1 eq.) To 1/3. Immediately, a slight cloudiness occurs, then the approach turns reddish. The residual ester is added and stirred for 3 h. Then it will be 1 h Heated to 85 ° C. The approach is very tough, when cooling, crystals form in the neck of the flask and the contents solidified. A sample is diluted with acetone and analyzed by gas chromatography. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) shows the following composition: (in GC-FI%) 3.40% MeOH, 19.1% acetone, 8.46% 2,3-dimethyl-5,6-dihydropyrazine , 1, 51% diethyl maleate, 40.26% 2,3-bis (ethoxycarbonyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (product), 19 , 5% other.

Solvent-free: 10.95% 2,3-dimethyl-5,6-dihydropyrazine, 1.95% diethyl maleate, 52.13% 2,3-bis (ethoxycarbonyl) -5,6-dimethyl-1, 4- diazabicyclo [2.2.2] oct-5-ene (product), 25.25% Other.

This result corresponds to a conversion of 74.7% with respect to dimethyldihydropyrazine and 96.5% with respect to diethyl maleate and a selectivity of dimethyldihydropyrazine to the desired product of 63.3%.

Example 35:

2,3-Dimethyldihydropyrazin (. 5.5 g, 50 mmol, 1 eq) is dissolved in MTBE (30 ml_) and at about - 30 ⁰ C cooled (ice, dry ice and NaCl). Dimethyl maleate (7.2 g, 50 mmol, 1 eq.) Is slowly added dropwise so that the temperature does not change significantly. The batch is stirred overnight and slowly warmed to ambient temperature. It is allowed to stand for 10 days at ambient temperature, the contents becoming increasingly dark brown but not tenacious as in Example 31. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) shows the following composition: (in GC-FI%) 0.31% MeOH, 70.1% MTBE, 3.84% 2,3-dimethyl-5,6-dihydropyrazine , 11.1% diethyl maleate, 11.6% 2,3-bis (ethoxycarbonyl) -5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene (product), 3 , 05% Other.

Solvent-free: 13.0% 2,3-dimethyl-5,6-dihydropyrazine, 37.5% diethyl maleate, 39.2% 2,3-bis (ethoxycarbonyl) -5,6-dimethyl-1,4-diazabicyclo- [2.2.2] oct-5-ene (product), 10.3% Other. This result corresponds to a conversion of 70.0% with respect to dimethyldihydropyrazine and 33.9% with respect to diethyl maleate and a selectivity of dimethyldihydropyrazine to the desired product of 50.9%.

Examples 36-38: Further diazabicyclooctenes 2-hydroxymethyl-5,6-dimethyl-1,4-diazabicyclo [2.2.2] oct-5-ene

Example 36:

2,3-Dimethyldihydropyrazine (5.50 g, 50 mmol, 1 eq.) Is dissolved in MTBE (30 mL) and

Allyl alcohol (5.00 g, 50 mmol, 5.39 mL, 1 eq.) Was added. It is kept at 62 ° C for 4 h Boiled reflux, then stirred for 65 h at ambient temperature. There is little product (2.83%) detected by GC-MS.

2-Ethoxycarbonyl-5-methyl-6-ethyl-1,4-diazabicyclo [2.2.2] oct-5-ene or 2-ethoxycarbonyl-5-ethyl-6-methyl-1,4-diazabicyclo [2.2.2 ] oct-5-ene,

Example 37:

To 2 parts of the reaction solution from Example 20 (2-ethyl-3-methyl-5,6-dihydropyrazine) is added 1 part of ethyl acrylate and heated to 100 ⁰ C for a few minutes. The gas chromatogram of the reaction mixture (30 m RTX 5 amines) shows the following composition: (in GC-FI%)

3.63% ethanol, 1.53% ethyl acrylate, 43.92% 1,2-propanediol, 7.39% 2-ethyl-3-methyl-5,6-dihydropyrazine, 7.32% 2-ethoxycarbonyl-5 methyl 6-ethyl-1,4-diazabicyclo [2.2.2] oct-5-ene, 36.21% Other, especially Addition products EDA + acrylic ester. The identity of the product was confirmed by GC-MS, via the regioselectivity between the two possible reaction products 2-ethoxycarbonyl-5-methyl-6-ethyl-1, 4-diazabicyclo [2.2.2] oct-5-ene and 2- No statement can be made on ethoxycarbonyl-5-ethyl-6-methyl-1,4-diazabicyclo [2.2.2] oct-5-ene.

Example 38:

2,3-dihydropyrazine from Example 16 is mixed with ethyl acrylate and heated to 80 ⁰ C for a few minutes. There is little product formed (3.4%), which is detected by GC-MS. The reaction conditions are not yet optimized and therefore not yet adapted to the high reactivity of 2,3-dihydropyrazine.

Preparation of the TEDA Derivatives (Ib)

The hydrogenation of the ester function and the double bond takes place by methods known to those skilled in the art, for example with LiAlH ₄ according to the literature description by G. Shishkin et al., Chem. Heterocycl. Com., 1980, pages 1069 to 1072, or with hydrogen on homogeneous or heterogeneous catalysts.

Claims

claims

A process for the preparation of triethylenediamine (TEDA) derivatives comprising the following steps:

a) reaction of a dihydropyrazine with an olefin, b) optionally hydrogenation following step a).

2. Process according to Claim 1 for the preparation of triethylenediamine (TEDA) derivatives of the general formulas (Ia) or (Ib)

comprising the following steps:

a) Reaction of a dihydropyrazine (II) with an olefin (III) to obtain the TEDA derivative (Ia)

(H) (IN)

where in the formulas (I) to (III):

R1 to R10 are independently selected from

H, halogen, - (C _r Cio-alkyl) - ( _R 14) _U! -C (O) -R 13, -CN, -O-aryl (R14) _U, .- (C ₁ -C ₁ 0-

Alkyl) -0-C (0) R14 _! -0 - [(C ₁ -C ₁₀ alkyl) - (R 14) _u ] _p H _q! N - [(C ₁ -C ₁ o alkyl) - (R14) _u] _p H _q A _r! -P - [(C ₁ -C 10 -alkyl) - (R 14JJpH ₁ A or -S - [(Ci-Cio-alkyl) - (R 14) u] pH _q ; u is 0 to 10;

R1 1 and R12 are H;

R 13 is H, hydroxy, amino, aryl, C ₁ -C 10 -alkoxy, amino- (C 1 -C 10 -alkoxy), alkylamino (C 1 -C 10 -alkoxy), dialkylamino (C 1 -C 10 -alkoxy), amino (C 1 -C 10 -alkoxy), alkyl), amino aryl, -NH (Ci-Ci _o alkyl), -N (Ci-Ci _o alkyl) _2, -NH-aryl, -N (aryl) _2, halogen, hydroxy aryl, - O-aryl, or -O- (C _r Ci ₀ alkyl) aryl;

R14 is hydroxy, amino, aryl, Ci-Cio-alkoxy, amino (CrCio-alkoxy), alkylamino (d-Cio-alkoxy), dialkylamino (C _r Cio-alkoxy), amino (C _r Cio-alkyl ), -NH (Ci-Ci ₀ - alkyl), -N (CrCio-alkyl) _2, hydroxyaryl, aminoaryl, -NH-aryl, -N (aryl) _2, halogen, -Ph-aryl, -P (aryl) _2, -O-aryl, or -0- (C _r Cio-alkyl) -aryl;

q is 0 to 3, r is 0 or 1,

p is 0 to 3 in N- or P-containing substituents, with p + q = 2 or 3,

p is 0 or 1 in O- or S-containing substituents, with p + q = 1,

A is an anion.

3. The method according to claim 1 or 2, characterized in that in dihydropyrazine (II) or in the olefin (III) at least one of the substituents R1 to R10 is selected from

- [(Ci-Cio-alkylHR14) u], -0 - [(Ci-Cio-alkyl) - (R14) _u ], -N [(Ci-Cio-alkyl) - (R14) u] 2, -NH [(C 1 -C 10 -alkyl) - (R 14) _u ] -C (O) -R 13 and -CN, where R 13 and R 14 are each independently hydroxy, C 1 -C 10 -alkoxy, -NH ₂ , -NH (C 1 -C 10 -alkyl ), -N (C _r Cio-alkyl) ₂ , -O-aryl or -O- (C _r Cio-alkyl) -aryl, and u is 0 to 10.

4. The method according to any one of claims 1 to 3, characterized in that the TEDA derivative (Ia) is a compound according to the formula (Ia1)

where R 2, R 7 and R 8 independently of one another are H, -OH, - (C ₁ -C ₃ -alkyl) -OH, - (C ₁ -C ₃ -alkyl) -O- (C ₁ -C ₃ -alkyl), -CN, - O-phenyl, - (C _r C ₃ alkyl) -O-phenyl, C _r C ₃ -

Alkoxy, -C (O) (C ₁ -C ₃ -alkoxy), -C (O) OH, -N (CH ₃ ) ₂ , -NH (CH ₃ ), -NH ₂ , - (C ₁ -C ₃ -alkyl ) - N (CH ₃ ) ₂ , - (C _r C ₃ alkyl) -NH (CH ₃ ), - (dC ₃ alkyl) -NH ₂ , or - (C ₁ -C ₃ alkyl) -OC (O ) (-C ₃ alkoxy) are, R5 and R6 are independently H, C _r C ₃ alkyl, -C (O) OH, -C (O) (CrC ₃ -

Alkoxy), or - _(Ci-C3 alkyl) -O- (C _r C ₃ alkyl),

and at least one of the substituents R2, R7 and R8 is not H, and

the TEDA derivative (Ib) is a compound according to formula (Ib1)

where _R _2, R 7 and R 8 independently of one another are H, -OH, - (C ₁ -C ₃ -alkyl) -OH, - (C ₁ -C ₃ -alkyl) -O- (C ₁ -C ₃ -alkyl), -CN, -O- Phenyl, - (C _r C ₃ alkyl) -O-phenyl, C _r C ₃ -

Alkoxy, -C (O) (C 1 -C ₃ -alkoxy), -C (O) OH, -N (CH ₃ ) ₂ , -NH (CH ₃ ), -NH ₂ , - (C 1 -C ₃ -alkyl) -

N (CH ₃₎ _2, - (C _r C ₃ alkyl), -NH (CH _3),

- (C 1 -C ₃ -alkyl) -NH ₂ , or

- (Ci-C ₃ alkyl) -OC (O) (-C ₃ alkoxy) are, R5 and R6 are independently H, C _r C ₃ alkyl, -C (O) OH, -C (O) (CrC ₃ -

Alkoxy), or - _(Ci-C3 alkyl) -O- (C _r C ₃ alkyl),

and at least one of the substituents R2, R7 and R8 is not H.

5. The method according to any one of claims 1 to 4, characterized in that step a) is carried out in the absence of bases.

6. The method according to any one of claims 1 to 5, characterized in that the dihydropyrazine (II) is prepared by reacting a dicarbonyl compound with ethylenediamine (EDA) or an EDA derivative.

7. The method according to claim 6, characterized in that the reaction in a moderately polar, but water-immiscible solvent, in particular in tert-butyl methyl ether, and using equimolar amounts of

EDA derivative to dicarbonyl compound takes place.

8. triethylenediamine (TEDA) derivatives of general formula (Ia) or (Ib)

preparable by a process according to any one of claims 1 to 7, wherein at least one of the substituents R1 to R10 at least one heteroatom selected from halogen, O, P, S or N, preferably O or N, or that at least one of the radicals R1 to R10 Contains -OH or -NH ₂ ,

with the proviso that not one of the radicals R ₁ to R 12 is -C (O) OH, -C (O) OCH ₃ , -C (O) OC ₂ H ₅ , -CH ₂ -OH, -CH ₂ -O- Benzyl or -CH ₂ -OC (O) -CH ₃ is when the other radicals from R 1 to R 12 are hydrogen, and that two adjacent radicals R 1 to R 12 are not -CH ₂ -O-benzyl, when the other radicals from R1 to R12 are hydrogen.

9. Use of a triethylenediamine derivative according to claim 8 for the preparation of polyurethanes.

10. Polyurethane containing at least one triethylenediamine derivative according to claim 8.