CS250593B1 - Ammonium 1,5-dicyano-2,4-dioxo-8,8,10,10-tetramethyl-3,9-diazaspiro [5.5] undecane and its preparation - Google Patents

Ammonium 1,5-dicyano-2,4-dioxo-8,8,10,10-tetramethyl-3,9-diazaspiro [5.5] undecane and its preparation Download PDF

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CS250593B1
CS250593B1 CS951185A CS951185A CS250593B1 CS 250593 B1 CS250593 B1 CS 250593B1 CS 951185 A CS951185 A CS 951185A CS 951185 A CS951185 A CS 951185A CS 250593 B1 CS250593 B1 CS 250593B1
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Prior art keywords
tetramethyl
ammonium
dicyano
undecane
dioxo
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CS951185A
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Czech (cs)
Slovak (sk)
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Frantisek Vass
Anna Bielikova
Jozef Luston
Zdenek Manasek
Gabriela Vassova
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Frantisek Vass
Anna Bielikova
Jozef Luston
Zdenek Manasek
Gabriela Vassova
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Application filed by Frantisek Vass, Anna Bielikova, Jozef Luston, Zdenek Manasek, Gabriela Vassova filed Critical Frantisek Vass
Priority to CS951185A priority Critical patent/CS250593B1/en
Publication of CS250593B1 publication Critical patent/CS250593B1/en

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Abstract

Vynález sa lýka amónium l,5-dikyano-2,4- -dioxo-8,8,10,104etrametyl-3,9-diazaspiro[5,5]undekánu vzorca -A v C H3 ™ 'q( a spósobu jeho pripravy, ktorý sa vyznačuje tým, že sa na 1 mól 2,2,6,6-tetrametyl-4- -oxopiperidínu pósobí 2 mólml metyl alebo etylkyanoacetátu a nasýteným alkoholickým roztokom amoniaku, najvýhodnejšie pri teplote v rozmedzi od —.20 °C do 0 qC po dobu 2 dní. Vynález má použitie v chémii polymérov pre syntézu světelných stabilizátorov polyalkylpiperidínového typu so zvýšenou molekulovou hmotnostou.The invention relates to ammonium 1,5-dicyano-2,4-dioxo-8,8,10,104tetramethyl-3,9-diazaspiro[5,5]undecane of the formula -A in C H3 ™ 'q( and a method for its preparation, which is characterized in that 1 mole of 2,2,6,6-tetramethyl-4-oxopiperidine is treated with 2 moles of methyl or ethyl cyanoacetate and a saturated alcoholic solution of ammonia, most preferably at a temperature in the range from -.20 °C to 0 qC for 2 days. The invention has application in polymer chemistry for the synthesis of polyalkylpiperidine-type light stabilizers with increased molecular weight.

Description

250593

Vynález sa týká amónium l,5-dikyano-2,4--dioxo-8,8,10,10-tetrametyl-3,9-diazaspiro-[5,5]undekánu a sposobu jeho přípravy.

Stéricky bráněné aminy predstavujú novůskupinu světelných stabilizátorov polymérov.Na tieto stabilizátory sú kladené požiadav-ky vysoké] účinnosti, nízkej toxcitiy ia male]vypierateTnosti z polymérov. Okrem apliká-cií v polyolefínoch sú tieto stabilizátory ú-činné i v polystyréne, polyuretánoch a po-lyamidoch.

Podstatou vynálezu je amónium 1,5-dikya-no-2,4-dioxo-8,8,10,10-tetrametyl-3,9-diaza-spiro[5,5]undekán vzorca I

Podstatou vynálezu je ďalej spósob pří-pravy zlúčeniny I, ktorý sa vyznačuje tým,že sa na 1 mól 2,2,6,6-tetnametyl-4-oxopi-peridínu vzorca II CH- (II)

posobí 2 mólmi alkylkyanoacetátu vzorcaIII

O

Z

NC—CH2—C \

OR (ΠΙ) kde va východiskovej látky pre syntézu světel-ných stabilizátorov polymérov polyalkylpi-peridínového typu so zvýšenou molekulovouhmotnosťou, s eliminovanou prchavosťou azníženou extrahovateťnosťou. Příklad 1 K zmesi 9,81 g (0,063 mola] 2,2,6,6-tetra-metyl-4-oxopiperidínu a 12,52 g (0,126 mola]metylkyanoacetátu sa přidá 125 ml meta-nolu sýteného amoniakom. Reakčná zmessa nechá stát 2 dni pri teplote —15 °C.Vzniknutý tuhý podiel sa odsaje a premyjemalým množstvom metanolu. Po vysušenísa získá produkt v podobě biele] práškovi-tej látky s teplotou topenia 184 až 185,5 °C.Elementárna analýza pre: C15H25N5O2 vypočítané: 58,61 % C, 8,20 % H, 22,78 θ/ο N; nájdené: 58,34 % C, 7,91 % H, 23,18 % N.IČ spektrum (nujol) 3 360 (str ]-v(N.H)i 2 960 (s), 2 830-uas, vS(c-H)> 2 700 (S1)-V(nh3+)> 1 665 (s), 1630 (s) “V(C = O amidy)» 1 590 (s)-á(N-H amidy)» 1 450 (s]-á(CH2), 1 375 + 1 360 (s) dublet-á(gem. cm), 1 290-V(C-n amidy), 1 265 (s)-V(c-n) cm-1. Příklad 2

Konkrétným príkladom využitia amóniuml,5-dikyano-2,4-dioxo-8,8,10,10-tetrametyl--3,9-diazaspiro[5,5]undekánu je jeho hydro-lýza kyselinou sírovou na hydrogénsírankyseliny 2,2,6,6-tetrametyl-4-piperidíndiocto-vej, ako východiskovej látky pre přípravupolymérnych světelných stabilizátorov· po-lykondenzačného typu.

Vynález má použitie v chémii polymérovpre syntézu světelných stabilizátorov so zvý-šenou molekulovou hmotnosťou, napříkladhydrogénsíranu kyseliny 2,2,6,6-tetrametyl-4--piperidíndioctovej a jej polykondenzačnýchproduktov s diolmi. R značí metylová alebo etylovú skupinu a nasýteným alkoholickým roztokom amo- niaku najvýhodnejšie pri teplote v rozme- dzí od —20 °C do 0 °C po dobu 2 dní. Výhodou uvedeného vynálezu je prípra-

250593

The present invention relates to ammonium 1,5-dicyano-2,4-dioxo-8,8,10,10-tetramethyl-3,9-diazaspiro [5,5] undecane and to its preparation.

The sterically hindered amines represent a novel group of polymer light stabilizers. High efficiency, low toxicity, and low vapor permeability from polymers are required for these stabilizers. In addition to polyolefin applications, these stabilizers are also effective in polystyrene, polyurethanes and polyamides.

The subject of the invention is ammonium 1,5-dicyano-2,4-dioxo-8,8,10,10-tetramethyl-3,9-diaza-spiro [5,5] undecane of formula I

The invention furthermore relates to a process for the preparation of compound I, characterized in that, for 1 mole of 2,2,6,6-tetnamethyl-4-oxopiperidine of formula II CH- (II)

2 moles of alkyl cyanoacetate of formula III

O

FROM

NC — CH2 — C \ t

OR (ΠΙ) where va is the starting material for the synthesis of light-weight polyolkylpiperidine-type light stabilizers with increased molecular weight, eliminating volatility and reduced extractability. EXAMPLE 1 125 ml of ammonia saturated methanol was added to a mixture of 9.81 g (0.063 mole) of 2,2,6,6-tetramethyl-4-oxopiperidine and 12.52 g (0.126 mole) of methyl cyanoacetate. The solid was filtered off with suction and washed with methanol, dried to give the product as a white powder, mp 184-185.5 ° C, Analysis: C 15 H 25 N 5 O 2 requires: H, 8.20; N, 22.78. Found: C, 58.34; H, 7.91; N, 23.18. -v (NH) i 2,960 (s), 2,830-uas, vS (cH)> 2,700 (S1) -V (nh3 +)> 1,665 (s), 1630 (s) “V (C = O amides) ) »1,590 (s) -α (NH amides)» 1450 (s) -α (CH 2), 1375 + 1360 (s) doublet (gem. Cm), 1,290-V (Cn amides) , 1265 (s) -V (cn) cm -1 Example 2

A particular example of the use of ammonium, 5-dicyano-2,4-dioxo-8,8,10,10-tetramethyl-3,9-diazaspiro [5,5] undecane is its hydrolysis with sulfuric acid to hydrogen sulphate 2,2, 6,6-tetramethyl-4-piperidinedioic acid as a starting material for preparative polymeric stabilizers of the polycondensation type.

DETAILED DESCRIPTION OF THE INVENTION The present invention has utility in polymer chemistry for the synthesis of increased molecular weight light stabilizers, for example 2,2,6,6-tetramethyl-4-piperidinediacetic acid hydrogen sulphate and diol polycondensation products thereof. R represents a methyl or ethyl group and a saturated ammonium alcohol solution most preferably at a temperature in the range of -20 ° C to 0 ° C for 2 days. An advantage of the present invention is the preparation of

Claims (2)

posobí 2 mólmi alkylkyanoacetátu obecného vzorca IIIwith 2 moles of alkyl cyanoacetate of formula III 1. Amónium l,5-dikyano-2,4-dioxo-8,8,10,- 10-tetrametyl-3,9-diazaspiro [ 5,5 ] undekán vzorca I 230593 PREDMET VYNALEZU a-h o·;. Γ·λ! O Z NC—CH2—C /..... H A/ x"Vv. •Z S\ Wh i -J If-ť fj OR (ΠΙ) kde1. Ammonium 1,5-dicyano-2,4-dioxo-8,8,10,10-tetramethyl-3,9-diazaspiro [5.5] undecane of formula I 230593 SUBSTITUTE A-h o. Γ · λ! O Z NC — CH2 — C / ..... H A / x “VV. • Z S i i -J If-ť fj OR (ΠΙ) where 2. Sposob přípravy zlúčeniny vzorca I po-dlá bodu 1, vyznačujúci sa tým, že sa na1 mól 2,2,6,6-tetrametyl-4-oxopiperidínu vzor-ca II R značí metylovú alebo etylovú skupinua nasýteným alkoholickým roztokom amo-niaku pri teplete v rozmedzí od —20 °C do0 °C po dobu 2 dní.2. A process for the preparation of a compound of formula (I) according to claim 1, characterized in that the methyl or ethyl group is saturated per 1 mole of 2,2,6,6-tetramethyl-4-oxopiperidine of the formula c and II R with a saturated alcoholic ammonium solution. at room temperature in the range of -20 ° C to 0 ° C for 2 days. (Π)(Π)
CS951185A 1985-12-19 1985-12-19 Ammonium 1,5-dicyano-2,4-dioxo-8,8,10,10-tetramethyl-3,9-diazaspiro [5.5] undecane and its preparation CS250593B1 (en)

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CS951185A CS250593B1 (en) 1985-12-19 1985-12-19 Ammonium 1,5-dicyano-2,4-dioxo-8,8,10,10-tetramethyl-3,9-diazaspiro [5.5] undecane and its preparation

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Application Number Priority Date Filing Date Title
CS951185A CS250593B1 (en) 1985-12-19 1985-12-19 Ammonium 1,5-dicyano-2,4-dioxo-8,8,10,10-tetramethyl-3,9-diazaspiro [5.5] undecane and its preparation

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