CS264997B1 - 1,5-dioxa-3,3-bis/ethoxycarbonyl/-8,8,10,10-tetramethyl-9-azaspiro/5,5/undecane - Google Patents
1,5-dioxa-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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- Prior art keywords
- tetramethyl
- bis
- azaspiro
- dioxa
- ethoxycarbonyl
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- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 title claims abstract 3
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 title 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000004611 light stabiliser Substances 0.000 abstract description 7
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- WIOHBOKEUIHYIC-UHFFFAOYSA-N diethyl 2,2-bis(hydroxymethyl)propanedioate Chemical compound CCOC(=O)C(CO)(CO)C(=O)OCC WIOHBOKEUIHYIC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 239000003377 acid catalyst Substances 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000008096 xylene Substances 0.000 abstract description 2
- 150000003738 xylenes Chemical class 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- -1 1,5-dioxa-3,3-bis (ethoxycarbonyl) -8,8,10,10-tetramethyl-9-azaspiro [5.5] undecane Chemical compound 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Landscapes
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Hydrogenated Pyridines (AREA)
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. Said compound is prepared by reacting 2,2,6,6-tetramethyl-4-oxopiperidine with diethyl bis (hydroxymethyl) malonate at temperature poor flow of hydrocarbon solvent which forms an azeotropic mixture with water such as benzene, toluene or xylenes; the presence of an acid catalyst such as 4-toluenesulfonic acid. compound it has utility in the preparation of polymeric materials light stabilizers.
Description
Vynález sa týká 1,5-dioxa-3,3-bis(etoxykarbonyl)-8,8,10,10-tetrametyl-9-azaspiroQ5,5]undekánu.The invention relates to 1,5-dioxa-3,3-bis (ethoxycarbonyl) -8,8,10,10-tetramethyl-9-azaspiro [5.5] undecane.
Stéricky tienené aminy patria v súčasnosti medzi najúčinnejšie světelné stabilizátory pre polyméry (F. E.. Karrer, Makromol. chem., 181, 595 (1980), F. Gugumus, Developments in Polymer Stabilisation-1, ed. G. Scott, Applied Science Publishers, London, 1979, kap. 8, J. J. Usilton A. 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 alebo 7,15-diazadispiro[;5,1,5,3]hexadekánu. Tieto zlúčeniny inhibujú nežiadúce degradačné procesy, ktoré prebiehajú pri interakcii světla a kyslika s polymérmi. Nevýhodou tejto triedy světelných stabilizátorov je vysoká prchavosť a extrahovatelnosť nízkomolekulových derivátov z polymérov. Zlúčenina, ktorá je predmetom vynálezu, obsahuje vo svojej molekule dve esterové skupiny. Je to teda bifunkčná zlúčenina. Pritomnosť týchto funkčných skupin v molekule světelného stabilizátora umožňuje přípravu vysokomolekulových světelných stabilizátorov polykondenzačnými alebo kopolykondenzačnými reakciami s róznymi diolmi alebo diaminmi. Táto zlúčenina nebola doteraz popísaná v odbornej literatúre.Sterically shielded amines are currently among the most effective light stabilizers for polymers (FE. Karrer, Macromol. Chem., 181, 595 (1980), F. Gugumus, Developments in Polymer Stabilization-1, ed. G. Scott, Applied Science Publishers, London, 1979, Chapter 8, JJ Usilton AR 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 undesirable degradation processes that occur in the interaction of light and oxygen 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 enables the preparation of high molecular weight light stabilizers by polycondensation or copolycondensation reactions with different diols or diamines. This compound has not been previously described in the literature.
Podstatou vynálezu je 1,5-dioxa-3,3-bis(etoxykarbonyl)-8,8,10,10-tetrametyl-9-azaspiro [5,5jundekán vzorca I.The present invention provides 1,5-dioxa-3,3-bis (ethoxycarbonyl) -8,8,10,10-tetramethyl-9-azaspiro [5,5 ]undecane of formula I.
h3c-h2cooc-^-coo-ch2-ch3 h 3 ch 2 cooc - ^ - coo-ch 2 -ch 3
SpÓsob přípravy zlúčeniny I spočívá v tom, že 2,2,6,6-tetrametyl-4-oxopiperidín vzorca IIA process for the preparation of compound I is characterized in that 2,2,6,6-tetramethyl-4-oxopiperidine of formula II
reaguje s dietyl bis(hydroxymetyl)malonátom vzorca IIIis reacted with diethyl bis (hydroxymethyl) malonate of formula III
H,C-HqC-00C-C-C00-CH9-CH, (III) 32 /\ 23 K2C CH2 H, C q C-00C-C-C00-CH 9 CH, (III) 32 / \ 23 K 2 C 2 CH
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 kyselina 4-toluénsulfónová.HO OH at the reverse flow temperature of a hydrocarbon solvent 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.
Předmětná látka sa mčže použit ako světelný stabilizátor pre polyméry alebo je medziproduktom pre přípravu polymérnych světelných stabilizátorov polykondenzačnými reakciami.The subject substance can be used as a light stabilizer for polymers or is an intermediate for the preparation of polymeric light stabilizers by polycondensation reactions.
PřikladlEXAMPLE
Do banky opatrenej. nástavcom na azeotropické oddelovanie vody a spátným chladičom sa vloží 6,21 g (0,04 mol) 2,2,6,6-tetrametyl-4-oxopiperidínu, 8,37 g (0,044 mol) Kyseliny 4—toluénsulfónovej h2O a 80 ml benzénu. Reakčná zmes sa zahrieva pri teplote spátného toku za miešania 0,5 hodiny, pričom sa oddělí kryštálová voda z kyseliny a vlhkosť zo systému. Súčasné vzniká sol kyseliny derivátu piperidínu. Potom sa přidá 8,81 g (0,04 mol) dietyl bis(hydroxymetyl)malonátu a reakčná zmes sa refluxuje za miešania, kým sa nevylúči teoretické množstvo vody (14 hodin). Po ochladení sa reakčná zmes vleje do 100 ml 20 %-ného vodného roztoku hydroxidu sodného a dobré pretrepe. Oddělí sa organická vrstva, ktorá sa premýva vodou a solankou a vysuší sa bezvodým síranom sodným. Benzén sa oddestiluje na rotačnej vákuovej odparke, pričom sa získá nažltlá kvapalina v množstve 13 g (91 i teoretického výtažku) Produkt sa čistí destiláciou za zničeného tlaku a odoberá sa frakcia v teplotnom intervale 150 až 157 °C pri tlaku 80 Pa.To the bank provided. 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 are charged with azeotropic water separator and reflux condenser. 80 ml benzene. The reaction mixture was heated to reflux with stirring for 0.5 hours, separating the crystal water from the acid and the moisture from the system. At the same time, the acid salt of the piperidine derivative is formed. Then, 8.81 g (0.04 mol) of diethyl bis (hydroxymethyl) malonate are added and the reaction mixture is refluxed with stirring until the theoretical amount of water has precipitated (14 hours). After cooling, the reaction mixture is poured into 100 ml of 20% aqueous sodium hydroxide solution and shaken well. The organic layer was separated, washed with water and brine and dried over anhydrous sodium sulfate. The benzene was distilled off on a rotary evaporator to give a yellowish liquid (13 g, 91%). The product was purified by distillation at a reduced pressure and a fraction was collected at a temperature range of 150-157 ° C at 80 Pa.
Elementárna analýza pre C^gH^NOgElemental analysis for C C gHHNOg
Vypočítané: C = 60,43 %; H = 8,74 i; N = 3,92 %Calculated: C = 60.43%; H = 8.74 i; N = 3.92%
Nájdené: C = 59,62 %; H = 9,03 4; N = 3,77 % XH NMR spektrum (CDC13): o (ppm) = 1,20 (s, =CH3, 12H) , 1,28 (t, CH3-CH2-, 6H, J = 1,5 Hz), 1,68 (s -CH2-, 4H), 4,24 (kv, CH3~CH2-O-, 4H, J = 1,5 Hz), 4,29 (s, -CH2-O-, 4H)Found: C = 59.62%; H = 9.03 4; N = 3.77%; H NMR (CDC1 3):? (Ppm) = 1.20 (s, CH 3, 12H), 1.28 (t, CH 3 CH 2 -, 6 H, J = 1.5 Hz), 1.68 (s -CH 2 -, 4H), 4.24 (kv, CH 3 -CH 2 -O-, 4H, J = 1.5 Hz), 4.29 (s, -CH 2 -O-, 4 H)
Příklad 2Example 2
Postupuje sa rovnako ako v příklade 1 s tým rozdielom, že sa ako rozpúštadlo použije toluén. Doba reakcie je 8 hodin. Získá sa 13,3 g surového produktu (93 % teoretického výtažku).The procedure was as in Example 1 except that toluene was used as the solvent. The reaction time is 8 hours. Yield: 13.3 g (93% of theory);
Vynález má použitie v chemickom priemysle pri príprave polymérov vyznačujúcich sa vysokou svetelnostabilizačnou účinnostou.The invention has application in the chemical industry in the preparation of polymers characterized by high light stabilizing efficiency.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS882670A CS264997B1 (en) | 1988-04-20 | 1988-04-20 | 1,5-dioxa-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-dioxa-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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| Application Number | Title | Priority Date | Filing Date |
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| CS882670A CS264997B1 (en) | 1988-04-20 | 1988-04-20 | 1,5-dioxa-3,3-bis/ethoxycarbonyl/-8,8,10,10-tetramethyl-9-azaspiro/5,5/undecane |
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| Country | Link |
|---|---|
| CS (1) | CS264997B1 (en) |
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1988
- 1988-04-20 CS CS882670A patent/CS264997B1/en unknown
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| Publication number | Publication date |
|---|---|
| CS267088A1 (en) | 1988-10-14 |
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