WO2018033199A1

WO2018033199A1 - Method for the production of secondary aminoorganosilicon compounds

Info

Publication number: WO2018033199A1
Application number: PCT/EP2016/069436
Authority: WO
Inventors: Alfred Popp; Katja HÜTTL
Original assignee: Wacker Chemie Ag
Priority date: 2016-08-16
Filing date: 2016-08-16
Publication date: 2018-02-22

Abstract

The invention relates to a method for producing the aminoorganosilicon compounds described in the claims by reacting cyclical or acyclical amines with (halogen-organyl)silane, the reaction comprising the following steps: a) reacting the (halogen-organyl)silicon compound of general formula (3) and the amine of general formula (2) at a temperature from 0 to 250°C, the ammonium halide of the amine of general formula (2) being formed as a byproduct in addition to the silicon compound of general formula (1), b) adding a base (B), with complete or partial salt metathesis taking place and the amine of general formula (2) being released again and the halide of the base (B) being formed, at a temperature at which the halide of the base (B) is present as a separate liquid phase, and c) separating the formed liquid halide of the base (B).

Description

Process cur production of secondary

Amlnoorganoeilioiusrverbindungen

The invention relates to a process for the preparation of secondary aminoorganosilicon compounds by reacting primary amine with (haloorganyl) silicon compounds.

Amino-functional silicone oils represent an important class of substances. They are used, for example, for the formulation of auto-care agents (improved polishability with simultaneously improved and longer-lasting water-repellent effect) but are also found in hair (amodimethicones) and textile care products (optimum distribution of the silicones on the Fiber surface for maximum soft grip). Another

Application is, for example, the binding and

Removal of carbon dioxide from the exhaust gases, at the

Combustion of fossil fuels arise.

As a starting material for such amino-functional silicone oils often the corresponding aminoorganosilanes are used.

Various processes for the preparation of aminoorganosilanes are known from the prior art. The preparation of amino-functional organosilanes takes place predominantly by reaction of chloroform-functional organosilanes with organic amines of various types. The procedure is generally such that at least 2 moles of amine are used per mole of chloro-functional organosilane, so that in addition to the formation of the amino-functional organosilane sufficient aminic component is available for conversion of the substituted chlorine into the corresponding amine hydrochloride. From OB 686,068 A, (amino) -, (N-organylamino) -, and (N, N-Diorganylaminomethyl) - or (Ν, Ν-Diorganylamlnoethyl) triorgano-silanes are known. Furthermore, QB 686,068 A notes a process for the reaction of corresponding (chloromethyl) - or (bromomethyl) triorganosilanes with ammonia, a primary or secondary amine at temperatures of at least 50 ° C for the preparation of said (aminoorganyl) (N-Organylaminoorganyl) - and (N , N-Diorganylaminoorganyl) triorganylsilanes. As a rule, the (chloromethyl) - or (bromomethyl) triorganosilanes are initially charged in a flask or autoclave, depending on the boiling points of the amine compounds used, and heated to temperatures above 100 ° C., preferably 110-130 ° C. In the case of higher-boiling amines (eg cyclohexylamine), the

Mixture order be reversed, i. the (chloromethyl) - or (bromomethyl) triorganosilanes will give to the heated amine.

According to a process described in DE 1812564 Al (aminomethyl) silane derivatives are prepared by reacting a (chloroethyl) - or (bromomethyl) silane derivatives with ammonia or a primary amine. The reaction is carried out at temperatures of 80 or 100 ° C in a period of 3 or 2 hours, wherein the amine in a molar excess of 1: 3.2 to 6 was already completely submitted at the beginning of the reaction.

DE 102004 060 627 A describes a variation of these processes in which the abovementioned reactions are carried out continuously. O'Brien et al. describe in Energy Fuels 2014, 28, 3326-3331 the preparation of secondary amino functional disiloxanes by reaction of iodopropyl disiloxanes with primary amines and subsequent release of the free amine from the Hydroiodide salt with NaOH to form Nal. This

Method involves a complicated procedure for the separation of the salt and purification of the final product. A disadvantage of all these processes is the fact that (optionally organically substituted) amonium halides are formed as by-products in quantitative amounts and have to be separated off as solids. A separation of such large amounts of solids is time-consuming and therefore costly and also requires production facilities that have appropriate equipment, eg. B. powerful and therefore expensive centrifuges have. However, this is not the case for many systems - especially for most multi-purpose systems, which are typically used to make fine chemicals.

For example, US Pat. No. 6452033 A describes the preparation of aminoethylaminoorganyltriorganosilanes by reacting the corresponding chlorofunctional organosilanes with ethylenediamine, the above-mentioned phase separation being used in various ways to separate the hydrochlorides. However, a disadvantage of this process is the fact that it is limited to silanes which have an ethylenediamine unit. WO 2009/019161 describes a process for preparing primary and secondary aminoorganyltriorganylsilanes of the general formula by reacting

cyclic or acyclisehen amines of the general formula H-NR ³ R ⁴ with (haloorganyl) silanes of the general formula

wherein first the (haloorganyl) silane and

the amine are reacted and then the amine is liberated by addition of a base from the salt formed, wherein the salt of the base formed at temperature <200 ° C. is liquid and can be separated. However, a disadvantage of this process is the fact that the process remains restricted to radicals R ³ and R ⁴ , which either form an optionally heteroatorase-containing cycle with one another or consist of pure C ₁ -C ₁₀ -carbon radical residues. Through this

Restriction heteroatom-containing linear radicals on Aminoorganosilan not accessible.

The task was the development of a process that no longer has the disadvantages of the prior art.

The invention relates to a process for the preparation of secondary aminoorganyltriorganylsilicon compounds of the general formula (1)

by reaction of acyclic amines of the general formula (2),

with (haloorganyl) silicon compounds of the general formula (3)

in which

R "is an acyloxy radical, an alkoxy radical having 1-10 C

Atoms or a radical of the general formula

an acyloxy radical, an alkoxy radical each having 1-10 C atoms or a radical of the general formula

R ¹ , R ⁴ independently of one another a Kohlenwasserstofoffreet with 1-10 C atoms,

R ² , R ^{5 are} independently a divalent

Hydrocarbon radical with 1-10 C atoms,

R ^{3 is} a hydrocarbon radical having 1-20 C atoms, this by non-adjacent heteroatoms such as N, O, S, P

is interrupted,

n is a number equal to 0, 1, 2 or 3 and

X, Y independently of one another are chlorine, bromine or iodine, the reaction comprising the following steps:

a) Reaction of the (haloorganyl) silicon compound of

the general formula (3) and the amine of the general formula (2) at a temperature of 0 to 250 ° C, wherein in addition to the silicon compound of the general formula ^' (1) as

Byproduct the ammonium halide of amine of

is formed general formula (2),

b) adding a base (B), which leads to a complete or partial salification, wherein the amine of the

the general formula (2) is released and the halide of the base (B) is formed, at a temperature at which the halide of the base (B) is present as a separate liquid phase and

c) separation of the formed liquid halide of the base (B). Based on (haloorganyl) silicon compound of the general formula (3), the amine of the general formula (2) is preferably in excess, ie in molar ratios based on the proportion of the reactive groups Z and Y of 1.1 to 1 to 100 to 1, preferably from 1.5 to 1 to 50 to 1, more preferably from 2 to 1 to 20 to 1, in particular from 3 to 1 to 10 to 1

used. Based on (haloorganyl) silicon compound of the general formula (3), the base (B) is preferably in molar

Ratios based on the proportion of the reactive groups Z and Y of 0.5 to 1 to 10 to 1, preferably from 0.7 to 1 to 5 to 1, particularly preferably from 0.8 to 1 to 2 to 1, in particular from 0 , 9 to 1 to 1.0 to 1 used.

The hydrocarbon radicals can be saturated

or unsaturated, branched or unbranched, substituted or unsubstituted.

The hydrocarbon radicals R ¹ , R ⁴ may be alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. -Pentylrest; Hexyl radicals, such as the n-hexyl radical; Heptyl radicals, such as the n-heptyl radical; Octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; Nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl reagents, such as the n-dodecyl radical; Octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals such as the cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; Alkenyl radicals, such as the vinyl, 1-propenyl and the 2-propenyl radical; Aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical; Alkaryl radicals, such as o-, ra-, p-tolyl radicals; Xylyl radicals and bethylphenyl radicals; and aralkyl radicals, such as the benzyl radical, the alpha- and the beta-phenylethyl radical; Alkoxyalkyl radicals such as the methoxypropyl, methoxyethyl and the bethoxyethyl radicals;

Aminoalkyl radicals, such as the aminoethyl or aminopropyl radical; Alkylaminoalkylrest such as dimethylaminoethyl and the

Diethylaminoethyl radical.

Preferably, independently of one another, R ¹ and R ^{4 are} a methyl, ethyl, iso and n-propyl, iso and n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Phenyl, benzyl or allyl radical.

R ³ preferably has the general formula (4) or (5)

in which

a is a number equal to 1, 2, 3, 4, 5 or 6,

b is a number equal to 1, 2 or 3,

c is a number equal to 1, 2, 3, 4 or 5,

d is a number equal to 0 or 1,

e is a number equal to 1, 2, 3, 4, 5 or 6,

ff is a number equal to 1, 2 or 3,

g is a number equal to 1, 2, 3 or 4,

h is a number equal to 0 or 1,

R ^{6 is} a hydrocarbon radical having 1-6 C atoms, in particular ethyl or methyl and

R ^{7 is} a hydrocarbon radical having 1-6 C atoms, in particular ethyl or methyl.

The radical R ³ is preferably selected from alkoxyalkyl radicals or alkylaminoalkyl radicals. In a particularly preferred embodiment, the radical R ^{3 is} an alkoxyalkyl radical. The radical R "preferably has the meaning of OR ¹ or

and Z - Y are. Especially

preferably R 'is a methoxy, ethoxy, iso and n-propoxy, butoxy, phenoxy, benzyloxy or allyloxy.

The radicals R ² , R ⁵ , independently of each other, preferentially bonds to a divalent hydrocarbon radical having 1-6 C atoms, in particular to a methylene, ethylene and ethylene radical

Propylene oruppe, more preferably around the propylene group.

The radicals Z and Y are preferably chlorine or bromine,

especially chlorine. n preferably has the value 1, 2 or 3.

In principle, steps a) and b) can be carried out successively or simultaneously. Equally conceivable is a

time-delayed execution, in which step b), ie the addition of the base (B), although after the start but before the end of step a) is started. If a base (B) is used in the process according to the invention which has free NH or NH ₂ groups, step b), ie the addition of the base (B) is preferably carried out after the reaction in step a). Preference is given to using bases (B) which, in process step b), form salts which, even at temperatures <150 ° C., are particularly preferably <100 ° C. or <90 ° C.

Form liquids.

Step a) of the process according to the invention is preferably carried out at temperatures of 50 to 250 ° C. To one

To achieve a compromise between economically meaningful reaction times and a reaction leading to as few by-products as possible have temperatures of 50 to 220 ° C, especially from B0 ° C to 150 ° C proved to be particularly advantageous.

Steps b) and c) of the inventive method are at a temperature at which the halide of the base (B) as a separate liquid phase is preferably carried out at temperatures of 0-250 ^e C, preferably at temperatures of 20 to 150 ° C and more preferably carried out at temperatures of 50 to 100 ° C.

All reaction steps are preferably carried out under inert gas, e.g. Nitrogen and argon carried out.

The pressure in reaction steps a), b) and c) is preferably 0.05 to 2 MPa (abs.), More preferably 0.08 to 1.5 MPa (abs.), In particular 0.09 to 1 MPa (abs .).

In a preferred embodiment of the invention, the processes according to the invention can also have one or more of the following additional process steps:

al) if the amine of the general formula (2) in step a) was used in excess, this excess can be completely or partially separated before the addition of the base (B) in step b). The separation is preferably carried out by distillation. This measure preferably serves to reduce the solubility of the respective salts in the organic phase,

d) Adding one or more nonpolar solvents (L) to the product-containing phase. The additional solvent (L) can be added before, during or after the process steps a), al) b) and c). This measure serves to reduce the solubility of the respective salts in the organic phase. Follow the addition of the nonpolar solvent after process step c), the precipitated salts in this step are separated in an additional separation step, for example, a filtration. However, the amounts of salt to be separated are extremely low compared with the original amount of salt in step c), the separation is correspondingly simple. If the addition of the non-polar solvent before or during step c), the respective salts are forced from the product phase into the liquid phase, which consists essentially of the halide of Baee (B), and separated together with this.

Distillative separation or purification of the product (1) and of the liquid used in step a), if appropriate in the flub shot, and during the salination in step b)

released amine (2). At this fractionate

Distillation, the amine of the general formulas (2) is preferably obtained directly in sufficiently high purity, so that it without further work-up in the next

Reaction cycle can be used again. The product of the general formula (1) is in the

corresponding distillation preferably directly in

of sufficient purity.

If halides of Baee (B) remain in the organic phase in the phase separation in step c), these are likewise preferably removed by distillation. The same applies to the solvent (L) additionally optionally added in step d).

It is possible that all components, in particular product of the general formula (1), amine of the general formula (2) and optionally the base (B) and the solvent (L) are separated from each other by a single fractional distillation. Likewise, this can be done by several separate distillation steps. So can For example, initially only the amine of the general formulas (2) are removed by distillation, wherein the crude product initially remains in the distillation bottoms and is then purified in a separate distillation or Dünnschichterschritt.

Additional addition of ammonia to the product-containing phase after the phase separation in step c) and separation of the resulting ammonium halide. This measure may be particularly suitable for reducing the halide content in the final product.

Additional addition of alkali metal alcoholates, preferably sodium or potassium alcoholates, to the product-containing phase after the phase separation in step c) and separation of the resulting alkali metal halides. This measure may be particularly suitable for reducing the halide content in the final product.

Additional addition of polymeric polyamines to the product-containing phase after phase separation in step c). This measure can be used to bind any residues of ionic halides, so that they remain in a final distillation of the product of the general formulas (1) or (4) (see step e) largely in the distillation bottoms and a corresponding low-halide product is obtained.

Recovery or recycling of the step a)

optionally used in excess and the released in step b) amine of the general formula (2). If the amine of the general formula (2) is wholly or at least partially unsubstituted by a simple distillation - cf. Step e) - can be obtained in sufficient cleanliness, the interfering products, by-products or residues of the added in step b) base (B) be separated by one or more further purification steps. To give an example, here's what we mean

• no further purification steps after the first distillation (step e))

sufficiently clean amine fractions

Additional addition of aliphatic ketones or aldehydes to the product-containing phase after step c) or else to the amine fractions distilled under step e). This measure can - if it is in the added in step b) base (B) to

Compounds with primary amino groups serve - to serve in these phases still contained residues of the base (B) in the corresponding imines

convict. The latter can often be removed more easily from the products and above all from the amines of the general formula (2) which are excessively used and / or released again in step b) than the base (B) itself.

Recovery of the base (B) used in step b), preferably by re-salting the halides of this base formed with strong bases, e.g. Alkali or

Alkaline earth hydroxides, carbonates, bicarbonates, etc.

In this case, the respective bases can be used in bulk or else in aqueous or nonaqueous solution or suspension. If aqueous solutions are used and / or water is liberated in the reaction, this is preferably removed by distillation from the base (B). If ethylenediamine was used as the base (B), this distillative separation is preferably carried out at such a high pressure that ethylene diamine and water no longer form an azeotrope. If the base (B) is a compound, e.g. For example, an amine which is itself reactive with the silane of the general formula (3), the amine of the general formulas (2) is preferably purified to such an extent by the said process steps that the content of the base (B) in the amines of the general Formulas (2) is less than 3%, preferably less than 1% and especially less than 0.5%.

In a preferred combination of the described variants of the process according to the invention, the amine of the general formula (2) is used in excess, the excess amine being removed by a step al) by distillation substantially or at least in parts. Subsequently, if appropriate, a solvent (L) (step d)) and the base (B) is added (step b)) and the salt phase is separated off

(Step c)). Subsequently, if present, the solvent (L) and the amine of the general formulas (2) liberated in step b) are removed by distillation (step e)).

In this case, both the solvent (L) and both

Distillates of the amine of the general formulas (2) are preferably obtained with such high purity that they are used directly without further purification.

In a further preferred variant, a solvent (L) whose boiling point is below that of the amine of the general formula (2) but above the boiling point of the base (B) is used in step d), so that any residues of the base (B) in the organic phase together with the solvent (L) are removed and then an amine of the general formula (2) can be obtained by distillation

(Step e)) that contains over the preferred low content of the base (B). Of course, the process can be carried out either batchwise, for example in stirred kettles, or continuously. The latter z. B. by steps a), b) and optionally further steps (see above) in a tubular reactor or a Rührgefäßkaskade done. The individual substances are here together or else - preferably - metered and mixed in succession. Also for the subsequent continuous phase separation (step c) are suitable methods, for. B. using resting or settling vessels, Oekantem, etc., known and widely described in the literature.

The water content of the amines of the general formulas (2) to be used is preferably from 0 to 20 000 ppm, preferably from 0 to 5000 ppm, particularly preferably from 0 to 1000 ppm.

In a preferred embodiment, as base (B)

Selected compounds whose boiling point differs from both the product (1) and the amine of the general formula (2) by at least 40 ° C, preferably at least 60 ° C and more preferably at least 90 ° C, so that residues of the base (B ), which in the phase separation in step c) in the

remain organic, deetillativ sufficiently well separated both from the product of the general formula (1) and from the amine of the general formula (2).

As base (B) it is preferred to use oligoamines (0) containing ethylene or propylenediamine units. The oligoamines preferably contain (0) 1 to 20, in particular 1 to 10, ethylene or propylenediamine units. Preferred oligoamines (O) are ethylenediamine, diethylenetriamine, diazabicyclooctane,

Pentamethyldiethylenetriamine, propylenediamine, N4-amine (BASF AG). Particular preference is given to using ethylenediamine as the base (B). With the process according to the invention, aminoorganyltriorganylsilicon compounds of the general formula (1) can be obtained in good to very good yields in a simple manner. The methods can be implemented on an industrial scale simply and safely.

The purity of the inventively prepared Aminoorganyl- triorganylsiliciumverbindungen the general formula (1) is preferably at least 85%, more preferably at least 95%. This purity can be determined by means of an optional downstream distillation step e) of

Increase products to over 95%.

The process according to the invention offers the advantage over the prior art that the majority of the by-produced ammonium salts of the amines of the general formulas (2) no longer have to be separated off as solids, which is poor on an industrial scale

crystallizing ammonium salts is usually expensive and expensive. In addition, many so-called multi-purpose systems do not have sufficiently powerful equipment elements (e.g., centrifuges) for separating such large quantities of solids. Due to the salting, two liquid phases can now be separated from each other. In addition, washing steps of the filter cake with additional solvent to be used unnecessary. At the same time, through the use of optimized

Excesses of amine according to the general formula (2) the

Formation of by-products are significantly reduced. In addition, it is noteworthy that the process according to the invention is suitable for frequently relatively costly amines of the general formula (2) which would be consumed in step a) for the formation of the corresponding ammonium salts by salification with the generally relatively inexpensive base (B), e.g. As ethylenediamine, and thereby make a recycling accessible.

All the above symbols of the above formulas each have their meanings independently of each other. In all

Formulas is the silicon atom tetravalent.

In the following examples, unless otherwise indicated, all amounts and percentages are by weight, all pressures are 0.10 MPa (abs.) And all temperatures are 20 ° C.

Examples Example la

Preparation of N- (2-sthoxyethyl) -3- (methoxydimethylsilyl) propan-1-amine (variant 1)

In a 4L O-neck flask with reflux condenser, KPG stirrer, thermometer and dropping funnel, 1.71 kg (19.2 mmol) of dry 2-ethoxyethanamine were placed under protective gas (nitrogen) and refluxed with stirring (about 108 ° C.). heated and within 240 min with stirring with 800 g (4.8 mol) of (3-chloro-propyl) (methoxy) dimethylsilane. The sump temperature rose to 125 ° C.

After completion of the addition, the temperature was lowered to 105 ° C and removed at a vacuum of 50 mbar excess Ethoxyethanamin (1117 g, 12.5 mol) by distillation.

After completion of the distillation, the temperature of the clear reaction mixture was lowered to 90 ° C and 288.4 g (4.8 mol) of ethane-1, 2-diamine was added. In the course of a slightly exothermic reaction, a precipitate initially formed, which redissolved at the end of the dosing and emulsified Two-phase system formed, the remaining 120 min at 90 ° C.

was stirred.

After stopping the stirring, the phases separated completely within 10 min. Subsequently, the lower salt phase (ethylenediamine hydrochloride) was separated at 90 ° C in a separatory funnel. The remaining upper phase was passed through a 10 cm Vigreux column at a pressure of 10 mbar

distilled. This gave 843 g (3.8 mol, 80%) of the product as a colorless liquid having a purity of 92.2%. Boiling point - 117-120 ° C / 10 mbar, * H NMR (CDCl ₃ ) δ 3.44 (t, J - 5.3 Hz, 2H), 3.40 (g, J - 7.0 Hz, 2H) , 3.32 (s, 3H), 2.68 (t, J - 5.0 Hz, 2H), 2.52 (t, J = 7.0 HZ, 2H), 1.44 (m, 2H) , 1.25 (br θ, 2H), 1.10 (t, J - 7.0 Hz, 3H), 0.51 (m, 2H), 0.00 (s, 6H). ^a9 Si NMR (CDC13) 17.89 ppm

Example 1b

Preparation of N- (2-Ithoxyethyl) -3- (xaethoxydimethyl) propane-1-amine (variant 2)

Into a 1 L three-necked flask with reflux condenser, KPO stirrer, thermometer and dropping funnel, 456.2 g (5.1 mol) of dry 2-ethoxyethanamine were initially introduced under protective gas (nitrogen) and heated to reflux (about 108 ° C.) with stirring and

214.2 g (1.3 mol) of (3-chloropropyl) (methoxy) dimethylsilane were added over 240 minutes with stirring. The bottom temperature rose to 125 ° C.

After completion of the addition, the temperature was lowered to 90 ° C and 77.4 g (1.3 mol) of ethane-1, 2-diamine added. In the course of a slightly exothermic reaction, it formed

emulsified two-phase system, which was stirred for a further 120 min at 90 ° C. After stopping the stirring, the phases separated completely within 10 min. Subsequently, the lower salt phase (ethylenediamine hydrochloride) was separated at 90 ° C in a separatory funnel. The remaining upper phase was heated to 105 ° C and at a vacuum of 50 mbar excess Bthoxy- ethanamln (278.8 g, 3.0 mol) was removed by distillation. Subsequently, the product was distilled at a pressure of 5 mbar over a 10 cm Vigreux column. This gave 193.0 g (0.88 mol, 69%) of the product as a colorless liquid with a purity of 98.9%.

Example 2

In a 1 L three-necked flask with reflux condenser, KPG stirrer, thermometer and dropping funnel under protective gas (nitrogen) 427.7 g (4.8 mol) of dry 3-methoxypropylamine

and heated to reflux (about 119 ° C) with stirring and within 240 min with stirring with 200.0 g (1.2 mol) of (3-chloropropyl) (methoxy) dimethylsilane. The sump temperature rose to 137 ° C. After completion of the addition, the temperature was lowered to 105 ° C and removed at a vacuum of 50 mbar excess 3-methoxypropylamine (260.4 g, 2, · 9 mol) by distillation. After completion of the distillation, the temperature of the clear reaction mixture was lowered to 90 ° C and 72.1 g (1.2 mol) of Bthan-l, 2-diamine was added. In the course of a slightly exothermic reaction initially formed

Precipitate, which redissolved at the end of the dosing and formed an emulsified two-phase system, which was stirred for a further 120 min at 90 ° C.

After stopping the stirring, the phases separated

completely within 10 minutes. Then, the lower salt phase (ethylenediamine hydrochloride) at 90 ° C in a

Separating funnel separated. The remaining upper phase was distilled at a pressure of 5 mbar over a 10 cm Vigreux column. 166.6 g (0.8 mol, 63%) of the product were obtained as a colorless liquid with a purity of 97.5%.

Bp = 102-105 ° C / 5 mbar, ¹ H NMR (CDCl ₃ ) δ 3.34 (t, J - 6.3 Hz, 2H), 3.32 (s, 3H), 3.22 (s, 3H), 2.58 (t, J = 7.0 Hz, 2H), 2.50 (t, J - 7.3 Hz, 2H), 1.66 (m, 2H), 1.43 (m, 2H), 0.90 (brS, 1H), 0.49 (m, 2H), 0.00 (s, 6H). ²⁹ Si NMR (CDC13) 18.02 ppm

Example 3

Production of

methylethane-1,2-diaxnin

In a 1 L three-necked flask with reflux condenser, KPG stirrer, thermometer and dropping funnel under protective gas (nitrogen) 423.0 g (4.8 mol) of dry

Diamine and heated with stirring to reflux (about 108 ° C) and within 240 min with stirring with 200.0 g (1.2 mol) of (3-chloropropyl) (methoxy) dimethylsilane. The bottom temperature rose to 123 ° C. After completion of the addition, the temperature was lowered to 105 ° C and at a vacuum of 50 mbar excess

(260.9 g, 3.0 mol) removed by distillation. After completion of the distillation, the temperature of the clear reaction mixture was lowered to 90 ° C and added 72.1 g (1.2 mol) of ethane-1, 2-diamine. In the course of a slightly exothermic reaction, a voluminous precipitate initially formed, which dissolved again at the end of the metered quantity and became emulsified

Two-phase system formed, the remaining 120 min at 90 ° C.

was stirred.

After stopping the stirring, the phases separated

Separating funnel separated. The remaining upper phase was distilled at a pressure of 5 mbar over a 10 cm Vigreux column. 109.0 g (0.5 mol, 42%) of the product were obtained ale colorless liquid with a purity of 98.3%.

Example 4

Preparation of 3, 3 '- (1,1,3,3-tetramethyldisiloxanes-l, 3-diyl) - bis (N- (2-ethoxyethyl) propane-1-azoin)

496.3 g (5.6 mol) of dry 2-ethoxyethanamine were placed in a 1 L three-necked flask with reflux condenser, KPQ stirrer, thermometer and dropping funnel under protective gas (nitrogen) and heated to reflux (about 108 ° C.) with stirring and 200.0 g (0.7 mol) of 1,3-bis (3-chloropropyl) -1, 1, 3, 3-tetramethyldisiloxanes are added with stirring over the course of 240 minutes.

The sump temperature rose to 127 ° C. After completion of the addition, the temperature was lowered to 105 ° C and removed at a vacuum of 50 mbar excess 2-ethoxyethanamine (302.0 g, 3.4 mol) by distillation. After completion of the distillation, the temperature of the clear reaction mixture was lowered to 90 ° C and 83.7 g (1.4 mol) of ethane-l, 2-diarain was added. In the course of a slightly exothermic reaction, a voluminous precipitate initially formed, which dissolved again at the end of the metered quantity and formed an emulsified two-phase system which was stirred at 90 ° C. for a further 120 minutes.

After stopping the stirring, the phases separate completely within 10 min. Subsequently, the lower salt phase (ethylenediamine hydrochloride) was separated at 90 ° C in a separatory funnel. The remaining upper phase was distilled at a pressure of 1.1-1.3 mbar over a 10 cm Vigreux column. This gave 187.6 g (0.58 mol, 67%) of the product as a colorless liquid with a purity of 98%. Boiling point - 150 - 154 ° C / 1 mbar, ¹ H NMR (CDCl ₃ ) 3.50 (t, J - 5.0 Hz, 4H), 3.46 (t, J - 7.0 Hz, 4H), 2.73 (t, J - 5.0 Hz, 4H), 2.56 (t, J = 7.0 Hz, 4H), 1.46 (tn, 4H) , 1.36 (br 8, 2H), 1.16 (t, J - 7.0 Hz, 6H), 0.47 (m, 4H), 0.00 (s, 12H). ²⁹ Si NMR (CDC13) 7.49 ppm

Claims

1. Process for the preparation of secondary aminoorganyltriorganylsilicides of the general formula (1)

by reaction of acyclic amines of the general formula (2),

with (haloorganyl) chloride compounds of the general formula (3)

in which

R 'is an acyloxy radical, an alkoxy radical having 1-10 in each case

C atoms or a radical of the general formula O-R ⁴ 2Si-R ⁵ -Y,

R "is an acyloxy radical, an alkoxy radical having 1-10 in each case

C atoms or a radical of the general formula

0-R ⁴ ₂ Si-R ⁵ -NHR ³ ,

R ¹ , R ⁴ independently of one another a hydrocarbon radical having 1-10 C atoms,

R ² , R ^{5 are} independently a divalent hydrocarbon radical with 1-10. C-atoms,

R ^{3 is} a hydrocarbon radical having 1-20 C atoms, this being interrupted by nonadjacent heteroatoms such as N, O, S, P,

a is a number equal to 0, 1, 2 or 3 and

X, Y independently of one another denote chlorine, bromine or iodine, the implementation comprising the following steps:

Reacting the (organohalogeno) silicon compound of the general formula (3) and the amine of the general formula (2) at a temperature of 0 to 250 ° C, wherein in addition to the silicon compound of the general formula (1) as

Byproduct the ammonium halide of amine of

is formed general formula (2),

b) adding a base (B), which leads to a complete or partial salification, in which the amine of the general formula (2) is released again and the halide of the base (B) is formed, at a temperature in the the halide of the base (B) is present as a separate liquid phase and

C) Separation of the formed liquid halide of the base

2. The method of claim 1, wherein R ^{2 is} selected from methylene, ethylene and propylene group.

3. The method according to one or more of the preceding claims, wherein R ^{5 is} selected from methylene, ethylene and propylene group.

4. Process according to one or more of the preceding claims, in which Z and Y are chlorine.

5. The method according to one or more of the preceding claims, wherein R ^{3 is} the general formula (4) or (5)

6. The method according to one or more of the preceding claims, in which as Baee (B) oligoamines (0) are used which have 1 to 20 Bthylen- or Propylendiamineinheiten.

7. The method according to one or more of the preceding claims, wherein ethylenediamine is used as the base (B).