CS269699B1 - Alkanedlamines containing polyalkylpiperidyl groups and processes for their preparation - Google Patents

Abstract

The solution relates to new alkanediamins I of the general formula I CH, CH2-CH-NH-/CH2/n-NH-R2 ff CS 26 969 9 Bl where, n = 2 to-10, R1 means H or CH, and PC means H, 1-(2,2,6,6-tetramethyl-4-piperidyl/-2-propyl or 1-(1,2,2,6,6-pentamethyl-4-piperidyl/-2-propyl and a method for their preparation by reductive amination of 1-(2,2,6,6-tetramethyl-4-piperidyl/-2-propanone or 1-(1,2,2,6,6-pentamethyl-4-piperidyl/-2-propanone with the corresponding alkanediamine at a temperature of 20 to 110 - C, a pressure of 0.5 to 15 MPa in the presence of an organic solvent from the group comprising C, to C.q aliphatic hydrocarbons and lower alcohols, water or mixtures of water with lower alcohols under the catalysis of platinum or palladium catalysts such as PtO,, platinum on activated carbon, palladium on activated carbon, palladium on Al,0,. Alkanediamines of general formula I are intermediates for the production of light stabilizers of polymers and for the production of biologically active substances, including drugs.

Description

The invention relates to novel alkanediamines containing polyalkylpiperidyl groups of the general formula I

CH, ^{1 3} 2 . CH _o -CH-NH-/CH _o /„-NH-R' ^í • 1 c2 n

H-CCHbL ^{3 z1 z} “3 ^C 1,^

R where n = 2 to 10, Rj represents H or CH^ and Rj represents H or a group of general formula II

CH,

I ³

CH ₂ -CHH ₃ ^c CHbk / II / ^H 3 ^C L Gib

R ¹ .

where R ¹ has the meaning already given.

and a method of their preparation. Alkanediamines containing polyalkylpiperidyl groups are intermediates for the preparation of highly effective light stabilizers of polymers and for the preparation of biologically active substances, including drugs.

From the literature and from industrial practice, N,N'-bis/2,2,6,6-tetramethyl-4-piperidyl/alkanediamines, especially 1,6-bis/2,2,6,6-tetramethyl-4-piperidylamino/hexane are known as the main intermediates for the industrial production of a whole range of oligomeric derivatives, which represent the newest group of light stabilizers of polymers. Their synthesis by reductive amination of polyalkyl-4-piperidones with alkanediamines is described in detail in the literature (US 4 104 248, US 4 326 063, DE 3 007 996, US 4 607 104). \

New alkanediamines containing polymethylpiperidyl groups of the general formula I, where n, R and R have the meanings already given, and a method for their preparation by reductive amination of compounds of the general formula III have now been discovered.

/ III / where R ¹ has the meaning already given with alkanediamines of general formula IV

H ₂ N-/CH ₂ / _n -NH ₂ / IV / where n has the above-mentioned meaning, at a temperature of 20 to 110° C, a pressure of 0.5 to 15 MPa in the presence of an organic solvent from the group including up to C^O aliphatic hydrocarbons and lower alcohols, water or mixtures of water with lower alcohols under the catalysis of platinum or palladium catalysts such as PtO _2> platinum on activated carbon, palladium on activated carbon, palladium on A^O^, or others.

CS 269 699 Bl

Alkanediamines containing a polyalkylpiperidine skeleton of general formula I according to the invention can be used as intermediates for the production of oligomeric type light stabilizers suitable for polymeric thermoplastic substrates such as polyolefins, polyethers, polyurethanes, polystyrenes and possibly others and for the production of biologically active substances.

The following examples illustrate, but do not limit, the subject matter of the invention.

Example 1

Into a 100 ml autoclave were charged 19.7 g/0.1 mol/l of (2,2,6,6-tetramethyl-4-piperidyl)-2-propanone, 5.8 g/0.05 mol/l of 1,6-hexanediamine, 40 ml of methanol and 0.25 g of platinum catalyst on activated carbon with a platinum content of 5% in the form of an aqueous suspension. After closing, the autoclave was flushed with hydrogen and after heating to 110° C, the reaction mixture was stirred at a pressure of 0.5 MPa for 4 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, the catalyst was filtered off and after the methanol was distilled off, the crude product was distilled under reduced pressure with the fraction 180-182° C being collected at 40 Pa.

The obtained 1,6-bis/1-(2,2,6,6-tetramethyl-4-piperidyl)/-2-propylamino/-hexane represented a pale yellow liquid.

Elemental analysis for ^C 3q ^H 62 ^N 4 /478.855/ s

Calculated: 75.25% C 13.05% H 11.70% N Determined: 75.12% C 12.97% H 11.78% N

IR spectrum, solution in CCl ₄ s.

335 /»/ -9 2 960 /s/, 2 920 /s/, 2 Έ60 /s/ _as/C -H/,9s/CH/ _f ^{1 * 3 460} “ (T/CH/,

370 + 1 360 /./ - / _/gem . _CH3/ /d/ _; 1,240 /s/ -th ¹ H-NMR spectrum, solution in CDCl ₃ t (f: 0.97 - singlet, CH ₃ -CH /6 H/, 1.12 - 1.15 - doublet, gem. CH ₃ /24 H/, 1.05 - 2.2 - multiplet, -CH-, -CH ₂ -ring, -NH-, -/CH^/ ₄ - ; -CHj-, /26H/; 2.3 - 3.0 multiplet, -CH ₂ -N, -CH-N- /6H/j /ppm/ « ... Example 2

Into a 250 ml autoclave were introduced 31.4 g (0.15 mol) of 1-[1,2,2,6,6-pentamethyl-4-piperidyl]-2-propanone, 8.7 g (0.075 mol) of 1,6-hexanediamine, 90 ml of water and 0.5 g of palladium catalyst on activated carbon with a palladium content of 5%. After sealing, the autoclave was flushed with hydrogen and the reaction mixture was stirred at a temperature of 20° C. at a pressure of 15 MPa for 4 hours. After the reaction was complete, the catalyst was filtered off and after distilling off the water, the crude product was distilled under reduced pressure with the fraction 184-186° C. at 40 Pa being collected, which represented 1,6-bis 1-[1,2,2,6,6-pentamethyl-4-piperidyl]-2-propylamino/hexane as a light yellow liquid.

Elemental analysis for ^C 32 ^H 66 ^N 4 /506.910/ í

Calculated with 75.82% C 13.12% H 11.05% N

Determined with 75.71% C 13.07% H 11.12% N

IC spectrum in CC1 ₄ s

335 /s/ 2960 /s/, 2920 /s/, 2860 /s/ ~ _as/C - _H /,9s/CH/; ^{1 460} ' ~ Č/CH/j ^{1 370 + 1 360} /s/ - cF/gem.CH ₃ /^^^; ^{1 240 /s/}

CS 269 699 Bl

1„ - NMR spectrum in CDCl, :

x* ri 3 (j : 0.97 - singlet, CHj-CH /6H/; 1.12 - 1.15 doublet, gem. CH ₃ /24 H/; 1.05 - 2.2 multiplet, -CH- , -CH ₂ - ring, -NH- , -/CH ₂ / ₄ -, -CH ₂ ~ /24 H/, 2.22 - singlet CH ₃ ~N /6H/;

2.3 - 3.0 - multiplet -CH ₂ -N; CH-N /6H/ /ppm/

Example 3

Into a 100 ml autoclave were charged 19.7 g (0.1 mol) of 1-(2,2,6,6-tetramethyl-4-piperidyl)-2-propanone, 11.6 g (0.1 mol) of 1,6-hexanediamine, 0.1 g of platinum on activated carbon with a content of 5% in 20 ml of water and 20 ml of ethanol. After closing, the autoclave was flushed with hydrogen, heated to a temperature of 80° C. and stirred at a pressure of 5 MPa for 2.5 hours. After the reaction was completed, the reaction mixture was cooled, the catalyst was filtered off and after distillation of ethanol and water, the crude product was distilled under reduced pressure with the collection of the fraction 122-124° C at 36 Pa, which represented N-/1-(2,2,6,6-tetramethyl-4-piperidyl)-2-propyl/-1,6-hexanediamine in the form of a light yellow liquid.

Elemental analysis for C _1O H,_N, /297.532/ :

Λ O J

Calculated: 72.66% C 13.21% H 14.12 » N

Determined: 72.51% C 13.14% H 14.18% N

IC spectrum, solution in CCl ₄ :

380 /sl/ 3 310 /sl/ -9 _S / _NH /; ^{3 190 /sl} / /NH/; ^{2,950 /s/} ' ^{2,930 /s/} '

850 /s/ - _s /cH/; ^{1620 /str/} J/NH/; ^{1450 /s/} cT/C^/; ^{1 380 1 1 378 /s/} -cT/gem.CH,/ 1 230 ^H-NMR spectrum, solution in CDCl ₃ with jf: 0.97 - singlet, CHj-CH /3H/; 1.09 - 1.12 doublet, gem. CH ₃ /12 H/; 1.05 - 2.2 multiplet, -CH-, ring, -CH ₂ - ring, -NH ₂ , -/CH ₂ / ₄ ~, -CH ₂ ~, NH /19 H/; 2.3 - 3.0 multiplet -CH ₂ -N, CH-N /5 H/ /ppm/ Example 4 \

Into a 100 ml autoclave were charged 19.7 g (0.1 mol) of 1-(2,2,6,6-tetramethyl-4-piperidyl)-2-propanone, -3.0 g (0.05 mol) of 1,2-ethanediamine, 40 ml of methanol and 0.1 g of platinum on activated carbon containing 5% Pt in the form of an aqueous suspension. The further procedure was as in Example 3. The product 1,2-bis - / l-(2,2,6,6-tetramethyl-4-piperidyl)-2-propylamino /-ethane with a boiling point of 153 - 5° C/40 Pa, was a light yellow liquid.'

Elemental analysis for C ₂ gHg ₄ N ₄ /422, 747/

Calculated: 73.87% C 12.88% H 13.25% N

Determined: 73.81% C 12.82% H 13.20% N

IR spectrum, solution in CC1 ₄ :

340 /s/ 2955, 2920, 2860 s “^as / _C -H/; 9 s /CH/;

^{1 460} (//CH/; ^{1 370 + 1 360} ~(//gem.CH ₃ / ^{/d/; 1 240} ~9/CN/ ^{cm 1}

Example 5

Into a 100 ml autoclave were charged 20.9 g (0.1 mol) of 1-(1,2,2,6,6-pentamethyl-4-piperidyl)-2-propanone, 6.0 g (0.1 mol) of 1,2-ethanediamine, 40 ml of n-butanol and 0.05 g of PtO ₂ . The entire procedure was as in Example 1.

CS 269 699 Bl

Product, 1-/1-2,2,6,6-pentamethyl-4-piperidyl/2-propylamino/ethane, b.p.

138 - 142° C/65 Pa, presented a yellow liquid.

Elemental analysis for C ₁₅ H ₃₃ N ₃ /255, 450/

Calculated: 70.53% C 13.02% H 16.45% N

Determined with 70.41% C 12.89% H 16.40% N

IC spectrum, solution in CCl^ t ^{3 380} -^/NH ₂ / ^{3 320} -I/NH/ ; ²⁹⁵⁰ ' ²⁹²⁵ ' ²⁸⁵⁵ -^as/CH/^s/CH/;

^1,620 - (f/NH/, ^{1,380 +} 1,370 /Ah 1,235 -

Example 6

Into a 100 ml autoclave were charged 19.7 (0.1 mol) of 1-(2,2,6,6-tetramethyl-4-piperidyl)-2-propanone, 4.4 g (0.05 mol) of 1,4-butanediamine, 20 ml of 2-propanol, 20 ml of water and 0.5 g of palladium on BaSO^ containing 5 * Pd. After sealing, the autoclave was flushed with hydrogen and after heating to 100° C. the reaction mixture was stirred at a pressure of 10 MPa for 3.5 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, the catalyst was filtered off and after distilling off the solvents, the product was distilled under reduced pressure with the fraction 165 - 8° C. /15 Pa being collected. The obtained 1,4-bis /1- /2,2,6,6-tetramethyl-4-piperidyl / /-2-propylamino /butane represented a light yellow liquid. Elemental analysis for ^C 28 ^H 58^4 /«0.800/ ;

Calculated: 74.60% C 12.97% H 12.43% N

Determined with ?4.47% C 12.92% H 12.48 » N.

IC spectrum in CCl ₄ s.

^3,340 -9/mf/ _; 2 2 920, 2 855 - _/C _ _H/ , ý _{s /C} _ _B/ , ^{1 460} V/CH/; ^{1,370 +} 1,360 - ^1,240 /CH/ _t ·

Example 7.

Into a 100 ml autoclave were introduced 19.7 g (0.1 mol) of 1-/2,2,6,6-tetramethyl-4-piperidyl/ /-2-propanone, 7.2 g (0.05 mol) of 1,8-octanediamine, 40 ml of cyclohexane and 0.4 g of platinum on activated carbon containing 10 Pt. The procedure was continued as in Example 3. The product, 1,8-bis/1-/2,2,6,6-tetramethyl-4-piperidyl/-2-propylamino/octane, with a boiling point of 188-191° C/5 Pa, was a light yellow liquid.

Elemental analysis for ^C 32 ^H 66 ^N 4 /5°6, 905/

Calculated: 75.82% C 13.12% H 11.05% N

Determined Τ’ 75.67% C 13.03% H 11.12% N

IC spectrum in CCl^:

340th _{/N_H /} . 2960, 2920, 2860 - )) as/CH/, Ý s/CH/ _ø ¹⁴⁶⁰ -gT/CH/; ^{1 370 + 1 360} -//gem.CH ₃ /; ^{1 240} ~'P/CN/^ ¹ ;

Example 8

19.7 g (0.1 mol) of l-/2,2,6,6-tetramethyl-4-piperidyl/ /-2-propanone, 17.2 g (0.1 mol) of 1,10-decanediamine, 35 ml of n-heptane and 0.2 g of platinum on activated carbon containing 3% Pt were introduced into a 100 ml autoclave. After closing, the autoclave was flushed with hydrogen and the reaction mixture was stirred at a temperature of 90° C. at a pressure of 2 MPa for 2.5 hours. After the reaction was complete, the catalyst was filtered off and after the solvent and reaction water were distilled off,

CS 269 699 B1 the crude product was distilled under reduced pressure with the collection of the fraction 162 - 6° C/25 Pa, which represented N-/1-(2,2,6,6-tetramethyl-4-piperidyl)-2-propyl/-1,10-decanediamine in the form of a brownish-yellow liquid.

Elemental analysis for C22H47N3 /353, 640/

Calculated: 74.72% C 13.40% H 11.88% N

Determined: 74.63% C 13.32% H 11.92% N

IC spectrum in CCl^:

^{3 335} -ý _N -H/ _f ^{2 955} ' ^{2 920} ' ^{2 850} -Ýs, and /cH/; ^{1 460} íf/CH/,·

370 ₊ 1 360 - J _{/gem CH3/} . 1 235 -^ _/C _ _N/ cm' ¹ ·

Claims (2)

OBJECT OF THE INVENTION Alkanediamines containing polyalkylpiperidyl groups of the formula I Wherein n = 2 to 10, R is H or CH 2 and R is H or a group of formula II (II) wherein R ¹ is as defined above 2. A process for the preparation of alkanediamines of the general formula I according to item 1, characterized in that the compounds of the general formula III 0 It (III) wherein R ¹ is as defined above are subjected to reductive amination with alkanediamines of formula IV 6 CS 269 699 Bl H ₂ N - (CH ₂ ) _n - NH ₂ '(IV) wherein n is as defined above, at a temperature of 20 ° C to 110 ° C, a pressure of 0.5 to 15 MPa in the presence of an organic solvent from the group consisting of up to aliphatic hydrocarbons and lower alcohols, water or mixtures of water with lower alcohols catalyzed by platinum or palladium catalysts such as PtO ₂ , platinum on activated carbon, palladium on activated carbon, palladium on α ₂ ° ₃ .