CS231249B1 - Dialkyl esters of α, β-bis (2,2, e, e-tetramethyl-4-piperidyl) adipic acid and its preparation - Google Patents

Dialkyl esters of α, β-bis (2,2, e, e-tetramethyl-4-piperidyl) adipic acid and its preparation Download PDF

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CS231249B1
CS231249B1 CS835071A CS507183A CS231249B1 CS 231249 B1 CS231249 B1 CS 231249B1 CS 835071 A CS835071 A CS 835071A CS 507183 A CS507183 A CS 507183A CS 231249 B1 CS231249 B1 CS 231249B1
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alpha
formula
preparation
tetramethyl
bis
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CS835071A
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Czech (cs)
Slovak (sk)
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CS507183A1 (en
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Jozef Luston
Frantisek Vass
Zdenek Manasek
Anna Papalova
Gabriela Hercegova
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Jozef Luston
Frantisek Vass
Zdenek Manasek
Anna Papalova
Gabriela Hercegova
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Publication of CS231249B1 publication Critical patent/CS231249B1/en

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Abstract

Vynéle$ sa týká dlalkylesteru kyseliny alfa,alfa -bis-(2,2,6,6-tetrametyl-4-piperidylamino)adipovej a spčsobu jeho přípravy. Podstatou vynálezu je dialkylester kyseliny alfa,alfa -bis(2,2,6,6-tetrametyl- -4-piperidylaaino)adipovej vzorca I O .O C—CH - CH,-CH,-CH—C RO NH NH O” v suchou benzéns alebo toluéne pri teplote 20 až 30 °C v přítomnosti trietylaminu. Vynález má použitie v chámii polymérov pre přípravu polymerizovateXného světelného stabilizátore polymérov. h3cJ JzCH3 HjC ( LCH3 h3c h ch3 HaC^SpCHj kde R je metylové alebo etylové skupina. Podstatou vynálezu je dalej spfisob přípravy zlúčeniny vzorca I, ktorý sa vyznačuje tým,,že sa_na dialkylester kyseliny alfa,- alfa'-dibromdipovej vzorca ΙΪ 0^ ^>0 CH - CH, - CH, - CH ir ir Gk (II) OR kde R je metylové alebo etylové skupina, ρβ sobí 4-amino-2,2,6,6-tetrametylpiperidínom vzorca III NH, h3cJ VCH3 h3c^n-^ch3 (III)The invention relates to alpha,alpha-bis-(2,2,6,6-tetramethyl-4-piperidylamino)adipic acid dialkyl ester and its preparation method. The invention is based on the dialkyl ester of alpha,alpha -bis(2,2,6,6-tetramethyl- -4-piperidylamino)adipic acid of the formula I O .O C—CH - CH,-CH,-CH—C RO NH NH O” in dry benzene or toluene at a temperature of 20 to 30 °C in the presence of triethylamine. The invention has application in polymer chemistry for the preparation of polymerizable light stabilizers for polymers. h3cJ JzCH3 HjC ( LCH3 h3c h ch3 HaC^SpCHj where R is a methyl or ethyl group. The invention is further based on the process for preparing a compound of formula I, which is characterized in that the dialkyl ester of alpha,- alpha'-dibromodipic acid of the formula ΙΪ 0^ ^>0 CH - CH, - CH, - CH ir ir Gk (II) OR where R is a methyl or ethyl group, ρβ sobi 4-amino-2,2,6,6-tetramethylpiperidine of formula III NH, h3cJ VCH3 h3c^n-^ch3 (III)

Description

ČESKOSLOVENSKASOCIALISTICKÁREPUBLIKA( 1» ) POPIS VYNÁLEZU 231249 K AUTORSKÉMU OSVEDČENIU ""

(51) lnt Cl.3 (22) Přihlášené 04 07 83(21) (PV 5071-83) C 07 D 211/58

ÚftAD PRO VYNÁLEZYA OBJEVY (40) Zverejnené ,5 02 84(45) Vydané 15 06 86 LUSTOŇ JOZEF ing. CSc., BRATISLAVA. VAŠŠ FRANTIŠEK prom. chea.,, HUMENNÉ, MAŇÁSEK ZDENEK ing. CSc., BRATISLAVA, PAPALOVA ANNA,

Autor vynálezu ZÁZRIVA, HERCEGOVÁ GABRIELA ing., PRIEVIDZA (54) Dialkylester kyseliny a,a'-bis(2,2,6,6-tetrametyl-4-piperidylamtno)-adipovej a spósob jeho prlpravy

Vynále$ sa týká dlalkylesteru kyselinyalfa,alfa -bis-(2,2,6,6-tetrametyl-4-pi-peridylamino)adipovej a spósobu jeho pří-pravy. Podstatou vynálezu je dialkylesterkyseliny alfa,alfa -bis(2,2,6,6-tetrametyl--4-piperidylaaino)adipovej vzorca I

O .O

C—CH - CH,—CH,—CH—C

RO NH NH OR v suchou benzéne alebo toluéne při teplete20 až 30 °C v přítomnosti trietylamínu.Vynález má použitie v chámii polymérovpre přípravu polymerizovateXného světelnéhostabilizátore polymérov. h3cJ JzCH3 HjC ( LCH3h3c h ch3 HaC^SpCHj

kde R je metylová alebo etylová skupina.Podstatou vynálezu je aalej spósob přípra-vy zlúčeniny vzorca I, ktorý sa vyznačujetým,,že sa_na dialkylester kyseliny alfa,-alfa'-dibromdipovej vzorca II 0^ ^>0

CH - CH, - CH, - CH ir ir

Gk (II)OR

kde R je metylová alebo etylová skupina,pó sobí 4-amino-2,2,6,6-tetrametylpiperi-dínoa vzorca III NH, h3cJ VCH3

HjC^N-^CHj (III) 231249 231249 2

Vynález sa týká dialkylesteru kyseliny alfa,alfa'-bis(2,2,6,6-tetrametyl-4-piperidyl-amino)adipověj a spOsobu jeho přípravy.

Stéricky bráněné aminy sú vysokoúčinné světelné stabilizátory polymérov. Inhibujúradikálové procesy, ktoré prebiehajú pri fotooxidácii polymérov. Nevýhodou nízkomolekulo-vých zlúčanín tejto skupiny je ich značná prchavosť a extrahovatel*nost, čo spdsobuje ichpostupný úbytok z užitkového polyméru už pri samotnom spracovaní, alebo neskOr pri skla-dovaní; chemickom čistění alebo praní.

Uvedená nevýhodu tento vynález odstraňuje. Podstatou vynálezu je dialkylester kyselinyalfa,alfa'-bis(2,2,6,6-tetrametyl-4-piperidylamino)adipovej vzorca I

kde R je metylová alebo etylová skupina. Podstatou vynálezu je áalej spBsob přípravyzlúčeniny vzorca I, ktorý sa vyznačuje tým, že sa na dialkylester kyseliny alfa,alfa'--dibrómdipovej vzorca II 0. R0-

C - GH k

CH0 - CH0 - CH - C’£ * I

Br »0

OR (II),

kde R je metylová alebo etylová skupina, pfisobí 4-emino-2,2,6,6-tetrametylpiperidínomvzorca III NH, H3CJ >οη3

HoC^N^CH,3 h 3 (III), v suchom benzéne alebo toluéne, pri teplote 20 až 30 °C, v přítomnosti trietylamínu. Výhodou uvedeného vynálezu je zvaSčenie molekulovej hmotnosti samotného stabilizátorea příprava polymerizovaterného světelného stabilizátore piperidínového typu dávajácehomožnost značného eliminovania spomínaných nedostatkov nízkomolekulových zlúčenín tejtoskupiny. Přikladl / K roztoku 1,552 6 g (0,01 mol) 4-amino-2,2,6,6-tetrametylpiperidínu a 1,4 ml trietyl-amínu v 20 ml suchého benzénu sa pri teplote 20 °C za stálého mieSania pomaly prikvapkároztok 1,801 2 g (0,005 mol) dietylesteru kyseliny alfa,alfa'-dibrómadipovej v 20 mlsuchého benzénu. Reakčná zmes sa mieša po dobu 24 h. Vzniknutý tuhý podiel sa odsaje,rozpustí v nasýtenom roztoku uhličitanu draselného a roztok sa ddkladne vyextrahuje éterom.Benzénový filtrát a éterický extrakt sa spoja, důkladné premyjú destilovanou vodou, vysuiiabezvodým slranom sodným a rozpúštadlá sa odparia. K lepkavému zvyšku sa prileje 10 mlpetroléteru, pričom nastane jeho stuhnutie. Po filtrácii sa získá žltkastá, spréškovatelnálátka s teplotou topenia 131 až 133 °C.

CZECHOSLOVAKCASOCIALISTREPUBLIC (1 ») DESCRIPTION OF THE INVENTION 231249 TO COPYRIGHT CERTIFICATE""

(51) lnt Cl.3 (22) Registered 04 07 83 (21) (PV 5071-83) C 07 D 211/58

ÚftAD FOR INVENTIONS AND DISCOVERIES (40) Published, 5 02 84 (45) Published 15 06 86 LUSTOŇ JOZEF ing. CSc., BRATISLAVA. VAŠŠ FRANTIŠEK prom. chea. ,, HUMENNÉ, MAŇÁSEK ZDENEK ing. CSc., BRATISLAVA, PAPALOVA ANNA,

THE INVENTION ZÁZRIVA, HERCEGOVÁ GABRIELA ing., PRIEVIDZA (54) Dialkyl ester of α, α'-bis (2,2,6,6-tetramethyl-4-piperidylamino) -adipic acid and its method of preparation

The invention relates to alkyl esters of alpha, alpha-bis (2,2,6,6-tetramethyl-4-piperidylamino) adipic acid and a method for its preparation. SUMMARY OF THE INVENTION The present invention relates to dialkyl ester alpha, alpha-bis (2,2,6,6-tetramethyl-4-piperidylaine) adipic formula I

O .O

C-CH-CH, -CH, -CH-C

RO NH NH OR in dry benzene or toluene at a temperature of 20 to 30 ° C in the presence of triethylamine. The present invention has utility in the understanding of polymer for the preparation of a polymerizable light stabilizer of polymers. h3cJ JzCH3 HjC (LCH3h3c h ch3 HaC ^ SpCH3

wherein R is a methyl or ethyl group. The present invention further provides a process for the preparation of a compound of formula I, wherein the dialkyl ester of alpha, -alpha-dibromodipeptide of formula II is 0?

CH - CH, - CH, - CH ir

Gk (II) OR

wherein R is methyl or ethyl, 4-amino-2,2,6,6-tetramethylpiperidine and the formula III NH, h3cJ VCH3

H 1 C 2 N 4 -CH 2 (III) 231249 231249 2

The present invention relates to dialkyl alpha, alpha'-bis (2,2,6,6-tetramethyl-4-piperidinyl-amino) adipic acid ester and its preparation.

The hindered amines are highly efficient light stabilizers of polymers. They inhibit radical processes taking place in photooxidation of polymers. A disadvantage of the low molecular weight compounds of this group is their considerable volatility and extractability, which results in their gradual loss from the utility polymer even during processing or in storage; chemical cleaning or washing.

The present invention overcomes this disadvantage. SUMMARY OF THE INVENTION The present invention provides dialkyl alpha, alpha'-bis (2,2,6,6-tetramethyl-4-piperidylamino) adipic acid (I) dialkyl ester (I).

wherein R is methyl or ethyl. The invention furthermore relates to a process for the preparation of a compound of formula I which is characterized in that the dialkyl alpha, alpha '- dibromodipeptide of formula II is 0.

C - GH k

CH0 - CHO - CH - C '* I

Br »0

OR (II)

wherein R is methyl or ethyl, 4-emino-2,2,6,6-tetramethylpiperidine Formula III is NH, H3CJ >

H 2 Cl 2 N 2 CH 3 3 (III), in dry benzene or toluene, at 20 to 30 ° C, in the presence of triethylamine. An advantage of the present invention is the enhancement of the molecular weight of the stabilizer itself and the preparation of a polymerizable piperidine-type light stabilizer, which makes it possible to remarkably eliminate the aforementioned drawbacks of low molecular weight thiogroup compounds. Example 1 / To a solution of 1.552 6 g (0.01 mol) of 4-amino-2,2,6,6-tetramethylpiperidine and 1.4 ml of triethyl amine in 20 ml of dry benzene slowly dropped a solution of the solution at 20 ° C with stirring. 1.801 2 g (0.005 mol) of .alpha.,. Alpha.-dibromadipic acid diethyl ester in 20 ml of dry benzene. The reaction mixture was stirred for 24 h. The resulting solid was filtered off with suction, dissolved in saturated potassium carbonate solution and extracted with ether thoroughly. The benzene filtrate and ether extract were combined, washed thoroughly with distilled water, dried sodium sulfate and the solvents evaporated. 10 ml of petrol ether are added to the sticky residue, and solidification takes place. After filtration, a yellowish, sprayable substance is obtained, m.p. 131-133 ° C.

Claims (2)

3 231249 Elementárna analýza pře C28H54N4°4 vypočítané: 65,84 % C, 10,66 % H, 10,97 % N;nájdené: 65,75 % C, 10,81 % H, 10,70 % K. IČ spektrum (chloroform) 1 080, 1 170, 1 225, 1 260, 1 380, 1 460, 1 570, 1 650, 1 720, 2 820, 2 950,3 320 cm'1 Příklad 2 K roztoku 1,552 6 g 4-amino-2,2,6,6-tetrametylpiperidínu a 1,4 ml trietylamínuv 20 ml suchého toluému sa pri teplote 30 °C za stéleho miešanía prikvapkéva roztok1,66 g dimetylesteru kyseliny alfa,alfa’-dibrómdipove3 v 20 ml suchého toluénu. Reakčnázmes samieša 20 h, potom sa spracuje ako v příklade 1. Získá sa produkt s teplotoutopenia 126 až 128 °C. Příklad 3 Zo 30 g práškového polypropylénu sa homogenizáciou s 0,072 g zlúčeniny podl’a příkladu1 v plastografe Brabender a lisováním připravili fólie o hrúbke 0,5 mm, ktoré sa ožarovaliv rotačnom ožarovacom zariadení výbojkou Tesla RVL 125 W. Sledoval sa vývoj karbonylovýchskupin v stabilizovanej fólii a fólii bez stabilizátora. Kým nestabilizovaná foliadosiahla karbony1ový index 0,1 za 220 hodin, stabilizovaná vzorka dosiahla ten istýstupeň degradácie za 1 200 hodin. Vynález má použitie pre přípravu polymerlzovateíného světelného stabilizátora pipe-ridínového typu. PREDMET VYNÁLEZUH, 10.66; N, 10.97. Found: C, 65.75; H, 10.81; (chloroform) 1080, 1 170, 1 225, 1 260, 1 380, 1 460, 1 570, 1 650, 1 720, 2 820, 2 950,3 320 cm -1 Example 2 To a solution of 1,552 6 g 4- of amino-2,2,6,6-tetramethylpiperidine and 1.4 ml of triethylamine in 20 ml of dry toluene are added dropwise at 30 ° C with a solution of 1.66 g of dimethyl alpha, .alpha.-dibromodipine in 20 ml of dry toluene. The reaction mixture was stirred for 20 h, then worked up as in Example 1. A product with a temperature of 126-128 ° C was obtained. EXAMPLE 3 0.5 mm thick films were prepared from 30 g of polypropylene powder by 0.072 g of the compound of Example 1 in a Brabender plastograph and pressed by irradiation with a Tesla RVL 125 W rotary irradiation apparatus. and foil without stabilizer. While the non-stabilized foliarexylated carbonyl index was 0.1 for 220 hours, the stabilized sample reached the same degradation rate at 1200 hours. The invention has utility for the preparation of a polymerizable pipe-type light stabilizer. SUBJECT OF THE INVENTION 1. Dialkylester kyseliny alfa,alfa'-bis(2,2,6,6-tetrametyl-4-piperidylamino)adipoveJvzorca I RO <k 7> ;c-ch -ch2--ch2-ch -c^ NH NH OR H3C J 4CH3 H3CHjC ff^CH3H3C CH, ch3 (I), kde R Je metylová alebo etylová skupina. 2312491. The dialkyl ester of alpha, alpha'-bis (2,2,6,6-tetramethyl-4-piperidylamino) adipic formula I RO < 7 >, c-ch2-ch2-ch-c, NH NH OR H3C J 4 CH 3 H 3 CH 3 C 3 H 3 CH 3 H 3 C CH 3 CH 3 (I) wherein R is methyl or ethyl. 231249 2. SpĎsob přípravy zlúčeniny vzorca I podl’a bodu 1, ktorý sa vyznačuje tým, že sa nadialkylester kyseliny alfa,alfa'-dibrómadipovej vzorca II G - CH - GH2 - CH2 - CH - G (II) RO Br Br OR kde R je mytylová alebo etylová skppina, pfisobí 4-Bmino-2,2,6,6-tetrametylpiperidínomvzorca III NH,2. A process for the preparation of a compound of the formula I according to claim 1, characterized in that the alpha-alpha-alpha-dibromodipiperyl ester of formula II G - CH - GH2 - CH2 - CH - G (II) RO is Br Br OR where R is a mythyl or ethyl salt of 4-Bmino-2,2,6,6-tetramethylpiperidine NH 3, CH, (III) H3C ~ CH v suchom benzéne alebo toluéne pri teplote 20 až 30 °G v přítomnosti trimetylamínu. Severografia, n. p., MOST Cena 2,40 KčsCH, (III) H 3 C-CH in dry benzene or toluene at 20-30 ° C in the presence of trimethylamine. Severografia, n. P., MOST Price 2,40 Kcs
CS835071A 1983-07-04 1983-07-04 Dialkyl esters of α, β-bis (2,2, e, e-tetramethyl-4-piperidyl) adipic acid and its preparation CS231249B1 (en)

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