CS264997B1 - 1,5-dioxo-3,3-bis (ethoxycarbonyl) -8,8,10,10-tetramethyl-9-azaspiro [5.5] undecane - Google Patents
1,5-dioxo-3,3-bis (ethoxycarbonyl) -8,8,10,10-tetramethyl-9-azaspiro [5.5] undecane Download PDFInfo
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- CS264997B1 CS264997B1 CS882670A CS267088A CS264997B1 CS 264997 B1 CS264997 B1 CS 264997B1 CS 882670 A CS882670 A CS 882670A CS 267088 A CS267088 A CS 267088A CS 264997 B1 CS264997 B1 CS 264997B1
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- tetramethyl
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- azaspiro
- ethoxycarbonyl
- undecane
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Abstract
Riešenie sa týká 1,5-dioxa-3,3-bis- (etoxykarbonyl)-8,810,10-tetrametyl-9- -azaspiro[5,5]undekánu. Uvedená zlúčenina sa připraví tak, že sa nechá reagovat 2,2,6,6-tetrametyl-4-oxopiperidín s dietyl bis(hydroxymetyl)malonátom pri teplote spatného toku uhlovodíkového rozpúšťadla, ktoré vytvára s vodou azeotropickú zmes, ako je benzén, toluén alebo xylény, za přítomnosti kyslého katalyzátora, ako je kyselina 4-toluénsulfónová. Zlúčenina má využitie pri príprave polymérnych světelných stabilizátorov.The solution relates to 1,5-dioxa-3,3-bis-(ethoxycarbonyl)-8,810,10-tetramethyl-9-azaspiro[5,5]undecane. The compound is prepared by reacting 2,2,6,6-tetramethyl-4-oxopiperidine with diethyl bis(hydroxymethyl)malonate at the reflux temperature of a hydrocarbon solvent that forms an azeotropic mixture with water, such as benzene, toluene or xylenes, in the presence of an acid catalyst, such as 4-toluenesulfonic acid. The compound is useful in the preparation of polymeric light stabilizers.
Description
264997 2
Vynález sa týká 1,5-dioxa-3,3-bis(etoxykarbonyl)-8,8,10,10-tetrametyl-9-azaspiroQ5,5]-undekánu.
Stéricky tienené aminy patria v súčasnosti medzi najúčinnejšie světelné stabilizátory prepolyméry (F. E.. Karrer, Makromol. chem., 181, 595 (1980), F. Gugumus, Developments in PolymerStabilisation-1, ed. G. Scott, Applied Science Publishers, London, 1979, kap. 8, J. J. UsiltonA. R. Patel. Am. Chem. Soc, Polym. Prep., 18 (1), 393 (1977)). Sú to rozličné deriváty 2,2,6,6-tetraalkylpiperidínu, 1,2,2,6,6-pentaalkylpiperidínu, 2,2,6,6-tetraalkylpiperazínu alebo7,15-diazadispiro[;5,1,5,3]hexadekánu. Tieto zlúčeniny inhibujú nežiadúce degradačné procesy,ktoré prebiehajú pri interakcii světla a kyslíka s polymérmi. Nevýhodou tejto triedy světel-ných stabilizátorov je vysoká prchavosť a extrahovatelnosť nízkomolekulových derivátov z poly-mérov. Zlúčenina, ktorá je predmetom vynálezu, obsahuje vo svojej molekule dve esterovéskupiny. Je to teda bifunkčná zlúčenina. Přítomnost týčhto funkčných skupin v molekule světel-ného stabilizátora umožňuje přípravu vysokomolekulových světelných stabilizátorov poly-kondenzačnými alebo kopolykondenzačnými reakciami s rčznymi diolmi alebo diamínmi. Tátozlúčenina nebola doteraz popísaná v odbornej literatúre.
Podstatou vynálezu je 1,5-dioxa-3,3-bis(etoxykarbonyl)-8,8,10,10-tetrametyl-9-azaspiro[5,5jundekán vzorca I. h3c-h2c- ooc-^-coo-ch2-ch3
SpÓsob přípravy zlúčeniny I spočívá v tom, že 2,2,6,6-tetrametyl-4-oxopiperidín vzorca II
reaguje s dietyl bis(hydroxymetyl)malonátom vzorca III H,C-HqC-00C-C-C00-CH9-CH, (III) 32 /\ 23K2C CH2
HO OH pri teplote spatného toku uhlovodíkového rozpúštadla, ktoré tvoří s vodou azeotropickú zmes,ako je benzén, toluén alebo xylény, za přítomnosti kyslého katalyzátora, ako je kyselina4-toluénsulfónová. Předmětná látka sa mĎže použit ako světelný stabilizátor pre polyméry alebo je medzi-produktom pre přípravu polymérnych světelných stabilizátorov polykondenzačnými reakciami. Přikladl
Do banky opatrenej. nástavcom na azeotropické oddelovanie vody a spátným chladičom savloží 6,21 g (0,04 mol) 2,2,6,6-tetrametyl-4-oxopiperidínu, 8,37 g (0,044 mol) kyseliny4—toluénsulfónovej h2O a 80 ml benzénu. Reakčná zmes sa zahrieva pri teplote spátného tokuza miešania 0,5 hodiny, pričom sa oddělí kryštálová voda z kyseliny a vlhkost zo systému.Súčasne vzniká sol kyseliny derivátu piperidínu. Potom sa přidá 8,81 g (0,04 mol) dietylbis(hydroxymetyl)malonátu a reakčná zmes sa refluxuje za miešania, kým sa nevylúči teoretickémnožstvo vody (14 hodin). Po ochladení sa reakčná zmes vleje do 100 ml 20 %-ného vodného
264997 2
The invention relates to 1,5-dioxa-3,3-bis (ethoxycarbonyl) -8,8,10,10-tetramethyl-9-azaspiro [5,5] -undecane.
Currently, sterically shielded amines are among the most effective light stabilizers of prepolymers (FE. Karrer, Makromol. Chem., 181, 595 (1980), F. Gugumus, Developments in PolymerStabilization-1, ed. G. Scott, Applied Science Publishers, London, 1979, Chapter 8, JJ UsiltonA, R. Patel, Am Chem Soc, Polym Prep, 18 (1), 393 (1977). They are various derivatives of 2,2,6,6-tetraalkylpiperidine, 1,2,2,6,6-pentaalkylpiperidine, 2,2,6,6-tetraalkylpiperazine or 7,15-diazadispiro [; 5,1,5,3] hexadecane. These compounds inhibit unwanted degradation processes that occur when light and oxygen interact with polymers. A disadvantage of this class of light stabilizers is the high volatility and extractability of low molecular weight derivatives from polymers. The compound of the invention contains two ester groups in its molecule. It is thus a bifunctional compound. The presence of these functional groups in the light stabilizer molecule allows the preparation of high molecular weight light stabilizers by polycondensation or copolycondensation reactions with various diols or diamines. The thio compound has not yet been described in the literature.
The present invention provides 1,5-dioxa-3,3-bis (ethoxycarbonyl) -8,8,10,10-tetramethyl-9-azaspiro [5.5] undecane of formula I. ch3
The process for the preparation of compound I is that 2,2,6,6-tetramethyl-4-oxopiperidine of formula II
reacts with diethyl bis (hydroxymethyl) malonate of formula III H, C-HqC-00C-C-COO-CH 9 -CH, (III) 32 / 23K 2 C CH 2
HO OH at the hydrocarbon solvent low flux temperature which forms an azeotropic mixture with water such as benzene, toluene or xylenes in the presence of an acid catalyst such as 4-toluenesulfonic acid. The subject matter can be used as a light stabilizer for polymers or is an intermediate product for the preparation of polymeric light stabilizers by polycondensation reactions. Přikladl
Banked. 6.21 g (0.04 mol) of 2,2,6,6-tetramethyl-4-oxopiperidine, 8.37 g (0.044 mol) of 4-toluenesulfonic acid h 2 O and 80 ml of benzene are deposited by an azeotropic water separator and a back-cooler. The reaction mixture is heated at reflux temperature for 0.5 hour while separating the crystal water from the acid and moisture from the system. Then 8.81 g (0.04 mol) of diethylbis (hydroxymethyl) malonate are added and the reaction mixture is refluxed with stirring until a theoretical amount of water (14 hours) is formed. After cooling, the reaction mixture was poured into 100 mL of 20% aqueous
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS882670A CS264997B1 (en) | 1988-04-20 | 1988-04-20 | 1,5-dioxo-3,3-bis (ethoxycarbonyl) -8,8,10,10-tetramethyl-9-azaspiro [5.5] undecane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS882670A CS264997B1 (en) | 1988-04-20 | 1988-04-20 | 1,5-dioxo-3,3-bis (ethoxycarbonyl) -8,8,10,10-tetramethyl-9-azaspiro [5.5] undecane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS267088A1 CS267088A1 (en) | 1988-10-14 |
| CS264997B1 true CS264997B1 (en) | 1989-09-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS882670A CS264997B1 (en) | 1988-04-20 | 1988-04-20 | 1,5-dioxo-3,3-bis (ethoxycarbonyl) -8,8,10,10-tetramethyl-9-azaspiro [5.5] undecane |
Country Status (1)
| Country | Link |
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| CS (1) | CS264997B1 (en) |
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1988
- 1988-04-20 CS CS882670A patent/CS264997B1/en unknown
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| CS267088A1 (en) | 1988-10-14 |
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