CS210434B1 - 7-Methyl-14,16-dioxo-7,15-diazadiepiro 5,1,5,3 hexadecanes - Google Patents

Abstract

7-methyl-14,16-dioxo-7,15-dizadispiro 5,1,5,3 hexadecanes. The new substances mentioned are intended for organic chemistry and can be used as stabilizers of polymeric materials. They are compounds that best characterize the above derivatives. The compounds mentioned can be used mainly for the effective stabilization of polypropylene and polystyrene.

Description

(54) 7-Methyl-14,16-dioxo-7,15-diazadiepiro 5,1,5,3 hexadecanes

7-methyl-14,16-dioxo-7,15-disadispiro

5,1,5,3 hexadecanes. The new eu substances intended for organic flame and can and have been used as stabilizers of polymeric materials. They are the compounds that best characterize green derivative compounds. The compounds mentioned can be used, in particular, for the evident establishment of polypropylene and polystyrene.

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The present invention relates to novel piperazine derivatives which can be used to stabilize polymeric materials such as polypropylene and polyethylene against the harmful effects of sunlight or other ultraviolet radiation. Sterically hindered piperazines are, in addition to sterically hindered piperidines, the most effective light stabilizers of organic materials. They are characterized by a high degree of protection of organic materials against saturation degradation / U. U.S. Patent 3,992,351, U.S. Patent 3,969,316.

The invention relates to compounds of formula I, wherein R ¹ where R is H, is - ^CH 2 \ C ^ / COOR ^, or where R is CH, R ¹ is a group - CHgCOOR ^, wherein R ^ is alkyl of 1 R ² is H or CH 2 and X is} CH 3 or C = O.

The compounds of the present invention can be used as stabilizers of polymeric materials against ultraviolet radiation.

p

Compounds of formula I when R is H may be prepared by a substituted reaction

"with compounds of formula III

HN

HN t

o / 11 / / 111 /

- C00r \ or - CHgCOOH ^, wherein R ^ is alkyl wherein R ¹ is - CHG having 1 to 18 carbon atoms, and X is Cl, Br ρ

When R is CH 3 of a compound of formula I, it is possible to prepare from compounds of formula Ia

HN (Ia) wherein R ?X is as defined above, by alkylation with formaldehyde in the presence of formic acid (author's certificate 8. 205 432).

The alkylation reaction is carried out by first preparing an alkali salt of the compound of formula II and reacting the alkali metal salt with the corresponding organic halogen of formula III in an organic solvent such as e.g. dimethylformamide, 2-propanol or acetone at

210 434 at a temperature of about 50-100 ° C. The resulting compound is further alkylated with formaldehyde in formic acid to give the final compound.

The compound of formula (II) may be prepared according to the known method of R. Sudo and S. Schuber, Bul. Chem. Soc. Japan 36, 34 (1963) and the hydrolysis of the resulting bis (2-cyanocyclohexyl) amine by the procedure described by E. R. J. Duynetec et al. Remeil de Chemie des Pays-Bus 87, 945 (1968).

Alkylation of nitrogen denoted with the Geneva nomenclature number 7 and formaldehyde in the presence of formic acid is carried out as described in the description of the invention to

X certificate δ. 205 432.

Example 1

4- (14,16-dioxo-7,15-diazadiapiro [5,1,5,3] hexadecylmethyl) butylbenzoate.

To a solution of 3.85 g (0.015 mol) of 7,15-azaadispiro [1,1,5,37-hexadecane-14,16-dione in 63 ml of anhydrous methanol is added 0.86 g (0.015 mol) of potassium hydroxide and refluxed for 30 minutes. minutes. After evaporating the methanol, 63 ml of anhydrous dimethylformamide was added to the residue, and a solution of 4-bromomethylbenzoate butyl in 20 ml of anhydrous dimethylformamide was added with stirring at 50 ° C. The reaction mixture was stirred at the same temperature for 12 hours. After the DMF was distilled off in vacuo, water was added to the residue and extracted with benzene. After drying the benzene solution (NS2SO4) and distilling off, 3.3 g (48.6%) of the product with m.p. t. 75-78 ° C, (petroleum ether).

Calcd for C ₂₆ H ₃₆ H ₂ O ₄ : 70.88% C; H, 8.23; 6.35% N

M = (441.14) found: 70.28% _S C; 8.50% H; 6.80% N

Example 2 / 14,16-Dioxo-7,15-diazadispiro [1,3,5] -15-hexadecyl / methyl acetate

To a solution of 5 g (0.02 mol) of 7,15-diazadispiro [5,1,3,5] hexadecane-14,16-dione in 82 ml of anhydrous methanol is added 1.12 g (0.02 mol) of potassium hydroxide. and reflects for 30 minutes. After evaporation of the methanol, 82 ml of anhydrous dimethylformamide was added to the residue, and a solution of 2.16 g (0.02 mol) of methyl bromoacetate in 20 ml of anhydrous dimethylformamide was added with stirring at 50 ° C. The reaction mixture was stirred at the same temperature for 12 hours. After evaporation of the dimethylformamide in vacuo, water was added to the residue and extracted with benzene. After drying the benzene solution (Na 2 SO 4) and distilling off, 5 g (77.6%) of the product with m.p. t. 142-144 ° C (methanol).

For C ₁₇ H ₂₇ N ₂ O ₄ calculated: 63.39% C; H, 8.12; N, 8.86

M = 322.41 found: 63.80% C; 8.32% H; 8.66% N * 10,434

Example 3 / 14,16-Dioxo-7,15-diazadispirof5,1,5,3] -15-hexadecyl / octyl acetate

To a solution of 5 g (0.02 mol) 7,15-disadispiro [5.1.1.3] hexadecane-14,16-dione in 60 ml of anhydrous dimethylformamide was added in portions at 40 [deg.] C. g (0.047 mol) sodium hydride. After vigorous hydrogen evolution was complete, the reaction mixture was stirred at 40 ° C for one hour and then a solution of 4.14 g (0.02 mol / chlorooctyl acetate) in 15 mL of anhydrous dimethylformamide was added at 65 ° C. After 12 hrs. After stirring at room temperature, dimethylformamide was distilled off in vacuo and the product was extracted from the residue with benzene. After crystallization from methanol, 5.5 g (68%) of the product with m.p. t. Mp 73-75 ° C.

C ₂₄ H ₄₀ N ₂ O ₄ requires C, 68.53; H, 9.58; N, 6.66

M = 420.59 found: 68.44% C; 9.33% H; 6.46% N

Example 4/7-Methyl-14,16-dioxo-7,15-thiazadispiro [eta] < 5 > > 5,3 < 5 > H-hexadecyl / octyl acetate

A mixture of 1.26 g (0.003 mol) of (14,16-dioxo-7,15-diazadispiro [1,1,5] -15-hexadecyl acetate octyl 1 ml of formaldehyde (37 56) and 0.2 ml of formic acid) 98 56) is refluxed for 10 hours. After cooling, 10 ml of potassium hydroxide (10 56) were added and the product was extracted into ether. After drying of K ₂ CO 3 and distilling off the ether, 1.4 g of a substance remained, from which 0.6 g (50%) of the starting material was obtained by fractional crystallization from methanol. 0.7 g of product (oil, 52%) was obtained from the mother liquors after crystallization.

For C ₂₅ H ₄₂ N ₂ O ₄ calculated: 9.74 56 H; 67.24 56 C; 6.46 56 N 1 = 434.62 found: 9.44 56 H; 68.85 56 C; 6.48% N

Example 5/7-Methyl-14,16-dioxo / 7,15-diazadispiro [5 > 1,5,3] -15-hexadecyl / methyl acetate

A mixture of 0.6 g (0.0018 mol) of (14,16-dioxo-7,15-disadispiro [5,1,5,3] -15-hexadecyl) methyl acetate, 0.1 ml of formaldehyde (37%) and 0.13 ml formic acid (98%) was refluxed for 10 hours. After cooling, 10 ml of potassium hydroxide (10%) were added and the product was extracted into ether. After drying (K? CO?) And distilling off the ether, the residue is subjected to fractional crystallization from methanol. 0.4 g (60%) of the starting material and 0.13 g (20%) of the product of m.p. t. Mp 54-57 ° C.

For C ₁₈ H ₂₉ N ₂ O ₄ calculated: 63.69 56 C; 8.61 56 H; 8.25 56 N

M = 339.34 found: 64.02 56 C; 8.31 56 H; 8.47 56 N

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Claims (1)

BRIEF DESCRIPTION OF THE INVENTION Compounds of Formula Z Where R and R is H, the group is --CH2 O m is carbon, or if R is CHp by carbon, R is H or CH - and - cQV COOR3, wherein R3 is an alkyl of 1 to 2 CH 2 COOR 3, R 3 is alkyl s) C 10 R 8 is x is CH 2 12 or 18 βΐό-Ι to 18