CS254695B1 - 4- (2,3-epoxypropoxy) -1,2,2,6,6-pentamethylpiperidine and its preparation - Google Patents

4- (2,3-epoxypropoxy) -1,2,2,6,6-pentamethylpiperidine and its preparation Download PDF

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CS254695B1
CS254695B1 CS867369A CS736986A CS254695B1 CS 254695 B1 CS254695 B1 CS 254695B1 CS 867369 A CS867369 A CS 867369A CS 736986 A CS736986 A CS 736986A CS 254695 B1 CS254695 B1 CS 254695B1
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formula
preparation
epoxypropoxy
phase
pentamethylpiperidine
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CS867369A
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Slovak (sk)
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CS736986A1 (en
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Jozef Luston
Edita Smieskova
Frantisek Vass
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Jozef Luston
Edita Smieskova
Frantisek Vass
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Publication of CS254695B1 publication Critical patent/CS254695B1/en

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Abstract

Riešenie sa týká 4-(2,3-epoxypropoxy)-l,- 2,2,6,6-pentametylpiperidínu vzorca I s spósobu jeho přípravy, ktorý spočívá v tom, že sa nechá reagovat l,2,2,6,6-pentametyl-4- -bydroxypiperidín vzorca II s epichlórhydrínom za Intenzívneho miešania v heterofázofom systéme, pričom jednu fázu vytvára vodný roztok alkalického hydroxidu a druhů fázu vytvára organické rozpúšťadlo nemiešstelné s vodnou fázou za přítomnosti katalyzátora typu óniových solí v teplotnom rozmedzí 10 až 100 °C. Zlúčenina vzorca I má použitie ako světelný stabilizátor pre polyméry a na přípravu polymérnych světelných stabilizátorov polyadičnými a kopolyadičnými reakciami, na přípravu polyéterov, kopolyéterov, polyesterov a kopolyesterov, alebo umožňuje naviazanie molekuly stabilizátora na vhodné skupiny na polymérnom reťazci.The solution relates to 4-(2,3-epoxypropoxy)-1,- 2,2,6,6-pentamethylpiperidine of formula I and a method for its preparation, which consists in reacting 1,2,2,6,6-pentamethyl-4- -hydroxypiperidine of formula II with epichlorohydrin under intensive stirring in a heterophase system, whereby one phase is formed by an aqueous solution of an alkali hydroxide and the second phase is formed by an organic solvent immiscible with the aqueous phase in the presence of a catalyst of the onium salt type in the temperature range of 10 to 100 ° C. The compound of formula I is used as a light stabilizer for polymers and for the preparation of polymer light stabilizers by polyaddition and copolyaddition reactions, for the preparation of polyethers, copolyethers, polyesters and copolyesters, or enables the attachment of the stabilizer molecule to suitable groups on the polymer chain.

Description

254695 '^Vyn^hBz; .·. sa; í týká 4- (2,3-epoxypropoxy) --^,2/2,6ý6-pehťa,měty]pippriďínu .-á š^Qspbvf ýje-ho přípravy. tu ·; Ln.254695 '^ Vyn ^ hBz; . ·. sa; relates to 4- (2,3-epoxypropoxy) -2,2,6,6,6-pentahydrate, and to the preparation thereof. tu ·; Ln.

Sféricky tienoné aminy patria v súčasnos-ti rnedzi najúčinnejšie; avje^el^é;sja^lizá^ory ,spře polymery [F. E.hlťarrer, t-Makramol.Chem., 181, 595 (1980), F. Gugumus, Deve-lopunenťs 4n Polymer Stabilisation-l, ed. G.Scott, Applied Science Publishers, Londoni,197S, kap. 8, ]. J. Usilton, A. E. Patel. Amer.Ghem. Sec. Polym. Prep., 18 (1), 393 (1977)].Sú to rozličné deriváty 2,2,6,6 tetraalkylpi-peridínu, 1,2,2,6,6-pentaalkylpiperidínu, 2,2,-6,6-tetraalkylpipera.zínu aleho 7,15-diazadi-spiro[ 5,1,5,3 ] hexadekánu.Spherically thienated amines are currently most effective at present; silage, silage, polymers [F. Chem., 180, 595 (1980), F. Gugumus, Deve-lopunen 4n Polymer Stabilization-1, ed. G. Scott, Applied Science Publishers, London, 197S, Chap. 8,]. J. Usilton, A. E. Patel. Amer.Ghem. Sec. Polym. Prep., 18 (1), 393 (1977)] Various derivatives of 2,2,6,6 tetraalkylpiperidine, 1,2,2,6,6-pentaalkylpiperidine, 2,2,6,6- tetraalkylpiperazine but 7,15-diazadiospiro [5,1,5,3] hexadecane.

Tieto zlúčeniny inhibujú nežiadúce degra-dačné procesy, ktoré prebiehajů při inter-akci! světla a kyslíka s pclymérmi. Nevýho-dou tejto triedy světelných stabilizátorov jevysoká prchavosť a extrahovateťnosť nízko-molekulových-derivátov z polyméroiv. Zlúče-nina, kíorá je predmetom vynálezu obsahu-je via svojej molekule reatívnu epoxidováskupinu. Přítomnost' tejto skupiny v moleku-le světelného· stabilizátoru. umožňuje přípra-vu vysokomolekulových. světelných síabill-zátorov polyadičnými reakciami, přípravupolyéterov, kopolyéterov, polyesferov a ko-polyesterciv, ,ako aj naviazaníe molekuly svě-telného stabilizátora na vhodné skupiny nareťazci úžitkového polymeru. Táto zlúčeninaneholá dotpi:a?,.popísaná. viodbprnej literatu-ře.These compounds inhibit the unwanted degradation processes that occur during inter-action! light and oxygen with polymers. The disadvantage of this class of light stabilizers is the high volatility and extractability of low molecular weight derivatives of polymer. The compound of the present invention contains a reatable epoxide group via its molecule. Presence of this group in the light stabilizer molecule. allows the preparation of high molecular weight. the light stabilizers by polyaddition reactions, preparative polyethers, copolyethers, polyesters and co-polyester derivatives, as well as the attachment of a light stabilizer molecule to suitable utility polymer moieties. This compounded dotpi: and?,. viodbprnej literatura.

Podstatou vynálezu je 4- (2,3-epoxypropo-xy ) -1,2,2,6,6-pentametylpiperidín vzorca I. H.f: -N >4N,,-- Cl-l-CC,The subject of the invention is 4- (2,3-epoxypropoxy) -1,2,2,6,6-pentamethylpiperidine of formula I. H.f: -N > 4N ' - Cl-1-CC,

4 λ.....\ / C / \ ' CH,. " Π/4 λ ..... / C / CH ,. "Π /

Podstatou vynálezu je ďalej sposob přípra-vy zlúčeniny vzorca 1, vyznačujúci sa tým,že l,2,2,6,6-pentametyl-4-hydroxypiperidínvzorca II lebo hydroxidu draselného· v koncentračnomrozmedzí ý5 yáž .^0 a druhů fázu vytváraorganické rozpúšťadlo nemiešatefné s vod-nou fázou, ako je například benzen, toluenalebo-^y-l^ny,->^ -přítomnosti katalyzátore. ty-, ‘ pu •óhievýeh solí,, ako je například tetrabu- tylaménium chlorid, tetrabutylamónium bro-mid, tetrabutylamónium hydrogénsíran ale-bo tetrabutylfoisfónium bromid, ktorý sa po-užije v množstve 1 až 10 móju na. množ-stvo zlúčeniny II v rozmedzí -teplot- 10 až100 C. í t ; '! - 1 ‘ - 1 Příklad 1 17.13 g (0.1 molu) l,2,2,6,6-pentametyl-4--hydroxypiperidínu, 3,22 g (0,01 molu) tet-rabutylamónium bromidu, 23 ml (0,25 mola)epichlórhydrínu. 25 ml benzénu a 25 ml 50percentného vodného roztoku hydroxidu sod-ného sa intenzívně mieša pri laboratórnejteplote 24 hodin. Potom sa oddělí organickávrstva, prepiera. sa vodou a solankou a vy-suší sa bezvodým síranom sodným, Oddesti-luje sa rozpúšťadlo a prebytočný epichlór-hydrín na vákuovej odparke a získá sa na-žítlá kvapalina, ktorá sa destiluje za vakua..Odoberá sa frakcia bezfarebnej kvapaliny vteplotnom intervale 84 až 92 C pri tlaku0,07 kPa. Výťažok je 15,5 g čistého produk-tu, t. j. 68 % teoretického- výtažku.The invention furthermore relates to a process for the preparation of a compound of formula 1, characterized in that the 1,2,2,6,6-pentamethyl-4-hydroxypiperidine formula II or the potassium hydroxide in the concentration range of δ 5 and ω 0 and the phase-forming organic solvent is immiscible. with an aqueous phase, such as benzene, toluene or carbonyl, the presence of a catalyst. tetrafluorolammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulphate or tetrabutylfoisphonium bromide, which is used in an amount of 1 to 10 moles per. the amount of compound II in the range of -10 to 100 ° C. '! Example 1 17.13 g (0.1 mol) of 1,2,6,6-pentamethyl-4-hydroxypiperidine, 3.22 g (0.01 mol) of tetrabutylammonium bromide, 23 ml (0, 25 moles of epichlorohydrin. 25 ml of benzene and 25 ml of a 50% aqueous solution of sodium hydroxide are vigorously stirred at room temperature for 24 hours. Then the organic layer is separated, washed. with water and brine, and drying with anhydrous sodium sulfate, distilling off the solvent and excess epichlorohydrin in a vacuum evaporator to obtain a warm liquid which is distilled under vacuum. The colorless liquid fraction is recovered at 84-40 ° C. 92 C at 0.07 kPa. The yield is 15.5 g of pure product, i.e. 68% of theory.

Elementárna analýza pre: C13H25NO2 vypočítané: ,C 68,68 %, H 11,08 %, N 6,16 %,nájdené: C.68,41 «/o, H 11,10 %, N 6,13 %. XH NMR.spektrum (CDCh) (PPmjh 0,93 (s,CH3,ax, 6H), 1,08 (s,-^CH3 eq, 6H), 1,23 až .2,02 (:m, —CPL·-, 4H), 2.13 (s, CHs—N, 3H), 2,45 až 2,33 CH, CH„ w q --<4 >......C" reaguje s epichlórhydrínom za intenzívnehomiešania v heterofázovom systéme, pričomjednu fázu vytvára vodný roztok alkalické-ho hydroxidu, s výhodou hydroxidu sodné-ho v koncentračnom rozmedzí 5 až 50 % a- řm,“ Cn-'-C7o. h Ni, '0 2,92 až'3,25 fm, -C;j· Cl-!., . II) ),Elemental analysis for C 13 H 25 NO 2 calculated: C 68.68%, H 11.08%, N 6.16%, found C.68.41%, H 11.10%, N 6.13%. 1 H NMR spectrum (CDCl 3) (PPmh 0.93 (s, CH 3, ax, 6H), 1.08 (s, - CH 3 eq, 6H), 1.23 to .2.02 (: m, - CPL · -, 4H), 2.13 (s, CH 3 --N, 3H), 2.45 to 2.33 CH, CH "wq - <4> ...... C" reacts with epichlorohydrin under intensive mixing in heterophasic system wherein one phase is formed by an aqueous solution of alkali hydroxide, preferably sodium hydroxide, in a concentration range of 5 to 50% by weight, &quot; C11-C20 &lt; 0 &gt;-C; j · Cl -!, II)),

O 3,35 až 3,83 (m, —CH2—O—, =CH—O—,3H).From 3.35 to 3.83 (m, --CH2 --O--, = CH - O ', 3H).

Claims (5)

1. 4-(2,3-epoxypropoxy)-l,2,2,6,6-pentametylpiperidín vzorca I.1. 4- (2,3-epoxypropoxy) -1,2,2,6,6-pentamethylpiperidine of formula I. te tetote teto 2. Spósob přípravy 4-(2,3-epoxypropoxyj-1,2,2,6,6-pentametylpiperidínu vzorca I podfa bodu 1, vyznačujúei sa tým, že 1,2,2,6.6-pentametyl-4-hydroxypiperidín vzorca II v x 3 te reaguje s epichlórliydrínom za intenzívneho miešania v heterofázovom systéme, pričom jednu fázu vytvára vodný roztok alkalického hydroxidu a druhů fázu vytvára organické rozpúštadlo nemiešatefné s vodnou fázou za přítomnosti katalyzátora typu óniových solí v teplotnom rozmedzí 10 až 100 °C.2. A process for the preparation of 4- (2,3-epoxypropoxy) -1,2,2,6,6-pentamethylpiperidine of the formula I according to claim 1, characterized in that 1,2,2,6,6-pentamethyl-4-hydroxypiperidine of the formula II in x 3 te reacts with epichlorliydrin with vigorous stirring in a heterophasic system, one phase forming an aqueous solution of alkaline hydroxide and the other phase forming an organic solvent immiscible with the aqueous phase in the presence of an onium salt type catalyst at a temperature range of 10 to 100 ° C. 3. Sposob podfa bodu 2, vyznačujúei sa tým, že sa ako alkalický hydroxid použije hydroxid sodný v koncentračnom rozmedzí 5 až 50 % alebo hydroxid draselný v· koncentračnom rozmedzí 5 až 70 %.3. A process according to claim 2, wherein the alkali hydroxide is sodium hydroxide in a concentration range of 5 to 50% or potassium hydroxide in a concentration range of 5 to 70%. 4. Spósob podfa bodu 2, vyznačujúei sa tým, že sa ako· organické rozpúštadlo· nemiešateíné s vodnou tážou použije benzén, toluen alebo xyleny.4. The process of claim 2 wherein benzene, toluene or xylenes are miscible with the aqueous solution as the organic solvent. 5. Spósob podfa bodu 2, vyznačujúei sa tým, že sa ako katalyzátor reakcie použijú óniové soli, ako tetrabutylamónium chlorid, tetrabutylamónium bromid, tetrabutylamónium hydrogénsíran alebo tetrabutylfosfónium bromid v množstve 1 až 10 mól % vztiahnuté na množstvo zlúčeniny 1,2,2,6,6-pentametyl-4-hydroxypiperidínu.5. The process of claim 2, wherein the reaction catalyst used is an onium salt such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate or tetrabutylphosphonium bromide in an amount of 1 to 10 mol% based on the amount of compound 1,2,2,6 , 6-pentamethyl-4-hydroxypiperidine.
CS867369A 1986-10-13 1986-10-13 4- (2,3-epoxypropoxy) -1,2,2,6,6-pentamethylpiperidine and its preparation CS254695B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0634449A3 (en) * 1993-07-13 1995-09-27 Ciba Geigy Ag Polyether with sterically hindered amine side chains as stabilizing agents.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0634449A3 (en) * 1993-07-13 1995-09-27 Ciba Geigy Ag Polyether with sterically hindered amine side chains as stabilizing agents.

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