CS259396B1 - 1,2,2,6,6-Pentamethyl-4- (n-bromoalkoxy) piperidines and a process for their preparation - Google Patents
1,2,2,6,6-Pentamethyl-4- (n-bromoalkoxy) piperidines and a process for their preparation Download PDFInfo
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Abstract
Riešenie sa týká l,2,2,6,6-pentametyl-4- -(<w-brómalkoxy)piperidínov vzorca I a spósobu ich přípravy, ktorý spočívá v tom, že sa nechá reagovat' l,2,2,6,6-pentametyl-4-hydroxypiperidín vzorca II s α,ω-dibrómalkánom vzorca III za intenzívneho miešania v heterofázovom systéme, pričom jednu fázu vytvára vodný roztok alkalického hydroxidu a druhů fázu vytvára organické rozpúsťadlo nemiešatetné s vodnou fázou za přítomnosti katalyzátora typu óniových solí v teplotnom intervale 10 až 100 °C. Zlúčeniny vzorca I majú použitie ako světelné stabilizátory pre polyméryThe solution relates to l,2,2,6,6-pentamethyl-4--(<ω-bromoalkoxy)piperidines of formula I and a method for their preparation, which consists in reacting l,2,2,6,6-pentamethyl-4-hydroxypiperidine of formula II with α,ω-dibromoalkane of formula III 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. Compounds of formula I are used as light stabilizers for polymers
Description
Vynález sa týká l,2,2,6,6-pentametyl-4-(w-brómalkoxy)piperidínov a spQsobu leh přípravy.The present invention relates to 1,2,2,6,6-pentamethyl-4- (n-bromoalkoxy) piperidines and to a method of preparation.
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, ondon, 1979, kap. 8, J. J. Usilton, A. R. Patel, Am. Chem. Soc., Polym. Prep., 18 (1), 393 (1977)].Sterically shielded amines are currently among the most effective light stabilizers for polymers [F. E. Karrer, Makromol. Chem., 181, 595 (1980), F. Gugumus, Developments in Polymer Stabilization-1, ed. G. Scott, Applied Science Publishers, Ondon, 1979, Chap. 8, J. J. Usilton, A.R. Patel, Am. Chem. Soc., Polym. Prep., 18 (1), 393 (1977)].
Sú to rozličné deriváty 2,2,6.6-tetrametylpiperidínu, 1,2,2,6,6-pentaalkylpiperidínu,These are various derivatives of 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentaalkylpiperidine,
2,2,6,6-tetraalkylpiperazínu alebo 7,15-diazadispiro[5,l,5,3]hexadekánu. Tieto zlúčeniny inhibujú nežiaduce degradačné procesy, ktoré prebiehajú pri interakcii světla a kyslíka s polymérmi. Nevýhodou tejto skupiny světelných stabilizátorov je vysoká prchavosť a extrahovatefnosť nízkomolekulových derivátov z polymérov. Zlúčeniny, ktoré sú predmetom vynálezu obsahujú vo svojej molekule funkčně ω-brómalkoxy skupiny. Přítomnost tejto· skupiny v molekule světelného stabilizátor a zvýši jeho molekulovú hmotnost a okrem toho umožňuje ďalšie modifikácie základného skeletu. Takéto zlúčeniny neboli doteraz popísané v odbornej literatúre.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 group of light stabilizers is the high volatility and the extractability of low molecular weight polymer derivatives. The compounds of the invention contain functional ω-bromoalkoxy groups in their molecule. The presence of this group in the light stabilizer molecule increases its molecular weight and, in addition, allows for further modifications of the backbone. Such compounds have not been previously described in the literature.
Podstatou vynálezu sú 1,2,2,6,6-pentametyl-4-(ω-brómalkoxy )piperidíny vzorca IThe present invention provides 1,2,2,6,6-pentamethyl-4- (ω-bromoalkoxy) piperidines of the formula I
C ι' έ f' ^5,C ι 'f f ^ 5,
VIN
ch3 ch 3
0) kde n je 2 až 12.Where n is 2 to 12.
Podstatou vynálezu je ďalej sposob přípravy zlúčenín vzorca I, vyznačujúci sa tým, že l,2,2,6,6-pentametyl-4-hydro'xypiperidín vzorca IIThe present invention further provides a process for the preparation of compounds of formula I, characterized in that 1,2,2,6,6-pentamethyl-4-hydroxypiperidine of formula II
reaguje s «,ω-dibrómalkánom vzorca IIIis reacted with the ω-dibromoalkane of formula III
Br—(CH2)„—Br (III) kde n je 2 až 12, v heterofázovom systéme, pričom jednu fázu vytvára vodný roztok alkalického hydroxidu, s výhodou hydroxidu draselného v koncentračnom rozmedzí 5 až 70 pere. alebo hydroxidu sodného v koncentračnom rozmedzí 5 až 50 % a druhů fázu vytvára organické rozpúšťadio nemiešajúce sa s vodnou fázou, ako je benzén, toluen alebo xylény, za přítomnosti katalyzátoru typu ónlových solí, akoi je tetrabutylamónium chlorid, tetrabutylamónium bromid, tetrabutylamónium hydrogénsíran alebo tetrabutylfosfónium bromid, ktorý sa použije v množstve 1 až 10 mól. % na množstvo zlúčeniny II v rozmedzí teplot 10 až 100 °C.Br - (CH 2 ) n - Br (III) wherein n is 2 to 12, in a heterophasic system, one phase forming an aqueous solution of an alkali hydroxide, preferably potassium hydroxide, in a concentration range of 5 to 70 washes. or sodium hydroxide in a concentration range of 5 to 50% and the other phases form an organic solvent not mixed with the aqueous phase, such as benzene, toluene or xylenes, in the presence of a salt salt type catalyst such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulphate or , which is used in an amount of 1 to 10 mol. % to the amount of compound II in the range of 10 to 100 ° C.
PřikladlEXAMPLE
8,56 g (0,05 molu) l,2,2,6,6-pentametyl-4-hydroxypiperidínu, 1,61 g (0,005 molu) tetrabutylamónium bromidu, 9,4 g (0,05 molu )-l,2-dibrómetánu, 10 ml benzénu a 15 ml 50 %-ného hydroxidu sodného sa intenzívně1 mieša pri izbovej teplote 30 hodin. Potom sa oddělí organická vrstva, ktorá sa prepiera vodou a solankou a vysuší sa bezvodým síranom sodným. Oddestiluje sa rozpúšťadio a produkt sa destiluje za vákua. Odoberá sa frakcia bezfarebnej kvapaliny v teplotnom intervale 120 až 130 °C pri tlaku 333 Pa.8.56 g (0.05 mol) of 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, 1.61 g (0.005 mol) of tetrabutylammonium bromide, 9.4 g (0.05 mol) -1, 2-dibromoethane, 10 ml of benzene and 15 ml of 50% sodium hydroxide solution is vigorously stirred for 1 at room temperature for 30 hours. The organic layer was separated, washed with water and brine, and dried over anhydrous sodium sulfate. The solvent is distilled off and the product is distilled under vacuum. A colorless liquid fraction is collected at a temperature range of 120 to 130 ° C at a pressure of 333 Pa.
Elementárna analýza pre Cf2HMBrNO: Vypočítané:Elemental analysis for C f 2 H M BrNO: Calculated:
51,80 % C, 8,69 % H, 5,03 % N, Nájdené:% C, 51.80;% H, 8.69;% N, 5.03.
51,38 % C, 8,46 % H, 4,89 % N.% C, 51.38;% H, 8.46;% N, 4.89.
1H NMR spektrum (CDC13): 1 H NMR spectrum (CDCl 3 ):
í (ppm) =.delta. (ppm) =
0,97 (s, — CH3ax, 6H),0.97 (s, - CH 3 and x, 6H);
1,12 (s, —CH3 eq, 6H),1.12 (s, —CH 3 eq, 6H),
1,23 až 1,93 (m, —CH2i—, 4H),1.23 to 1.93 (m, CH 2 R -, 4H);
2,17 (s, N—CH3, 3H),2.17 (s, N-CH3, 3H);
3,37 (t, _CH2—O—, 2H, J=6 Hz),3.37 (t, _CH 2-O, 2H, J = 6 Hz);
3,40 (t, —CHa—Br, 2H, J=6 Hz),3.40 (t, —CH and —Br, 2H, J = 6 Hz),
3,40 až 4,00 (m, =CH—O—, 1H). Příklad 23.40 to 4.00 (m, = CH-O-, 1H). Example 2
8,56 g (0,05 molu] l,2,2,6,6-pentametyl-4-hydroxypiperidínu, 0,34 g (0001 molu) tetrabutylamónium hydrogénsíranu, 10,80 g (0,05 molu] 1,4-dibrómbutánu, 10 ml toluénu a 15 ml 30 %-ného hydroxidu draselného· sa intenzívně mieša pri teplote 50 °C 20 hodin.8.56 g (0.05 mol) of 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, 0.34 g (0001 mol) of tetrabutylammonium hydrogen sulphate, 10.80 g (0.05 mol) of 1.4 Dibromobutane, 10 ml of toluene and 15 ml of 30% potassium hydroxide are stirred vigorously at 50 ° C for 20 hours.
Potom sa reakčná zmes spracuje rovnako ako v příklade 1. Pri destilácii sa odoberá frakcia bezfarebnej kvapaliny v teplotnom intervale 130 až 140 °C pri tlaku 333 Pa.Thereafter, the reaction mixture was worked up as in Example 1. A fraction of a colorless liquid was collected by distillation at a temperature range of 130 to 140 ° C at a pressure of 333 Pa.
259390259390
Elementárna analýza pre C14H28BrNO: Vypočítané:Elemental analysis for C 14 H 28 BrNO: Calculated:
54,90 % C, 9,21 % H, 4,57 % N, Nájdené:% C, 54.90;% H, 9.21;% N, 4.57.
54,43 % C, 9,25 % H, 4,49 % N.H, 9.25; N, 4.49.
’HNMR spektrum (CDC13):1 H NMR (CDCl 3 ):
(ppm) —(ppm) -
0,97 (s, —CH3 ax, 6H),0.97 (s, —CH 3 ax, 6H),
1,12 (s, —CH3 eq, 6H),1.12 (s, —CH 3 eq, 6H),
1,23 až 2,00 (m, —CH2—, 8H),1.23 to 2.00 (m, --CH2 -, 8H);
2.17 (s, CH-j—N, 3H),2.17 (s, CH-1-N, 3H),
3,37 (t, — ÓH,i—O—, 2H),3.37 (t, --OH, i - O -, 2H),
3,40 (t, —CH2—Br, 2H),3.40 (t, CH 2 -Br, 2H);
3,40 až 4,00 (m, =CH—O—, 1H).3.40 to 4.00 (m, = CH-O-, 1H).
Příklad 3Example 3
8,56 g (0,05 mólu) 1,2,2,6,6-pentametyl-4-hydroxypiperidínu, 0,68 g (0,002 mólu] tetrabutyífosfónium bromidu, 12,2 g (0,05 mólu) 1,6-dibrómhexánu, 10 ml zmesi xylénov s destilačným rozmedzím 137 až 140 °C a 10 ml 60 %-ného hydroxidu draselného sa intenzívně mieša pri teplote 100 °C po dobu 8 hodin.8.56 g (0.05 mol) of 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, 0.68 g (0.002 mol) of tetrabutylphosphonium bromide, 12.2 g (0.05 mol) of 1.6 Dibromohexane, 10 ml of a mixture of xylenes with a distillation range of 137 to 140 ° C and 10 ml of 60% potassium hydroxide are vigorously stirred at 100 ° C for 8 hours.
Potom sa reakčná zmes spracuje rovnako ako v příklade 1. Pri destilácii sa odoberá frakcia bezfarebnej kvapaliny v teplotnom intervale 180 až 190 °C pri tlaku 333 Pa.Thereafter, the reaction mixture was worked up as in Example 1. A fraction of a colorless liquid was collected by distillation at a temperature range of 180 to 190 ° C at a pressure of 333 Pa.
Elementárna analýza pre Ο16Η33ΒγΝΟ: Vypočítané:Elemental analysis for Ο 16 Η33ΒγΝΟ: Calculated:
57,47 % C, 9,65 % H, 4,19 % N, Nájdené:% C, 57.47;% H, 9.65;% N, 4.19.
57,69 % C, 10,05 % H, 4,11 % N.H, 10.05; N, 4.11.
Ή NMR spektrum (CDC13):Ή NMR Spectrum (CDCl 3 ):
(ppm) =(ppm) =
0,97 (s, — CH. ax, 6H),0.97 (s, --CH. Ax, 6H),
1,11 (s, —CH3 eq, 6H),1.11 (s, —CH 3 eq, 6H),
1.17 až 1,93 (m, —CH2—, 12H),1.17 1.93 (m, -CH2 -, 12 H);
2,15 (s, CH3—N, 3H),2.15 (s, CH 3 -N, 3H),
3,35 (t, —CHS—Ο-, 2H, J=6 Hz),3.35 (t, —CH2 -, -, 2H, J = 6 Hz),
3.39 (t, —CH2—Br, 2H, J=6 Hz),3:39 (t, CH 2 -Br, 2H, J = 6 Hz);
3.40 až 4,00 (m, =CH—O—, 1H).3.40 to 4.00 (m, = CH - O -, 1H).
Příklad 4Example 4
8,56 g (0,05 mólu) l,2,2,6,6-pentametyl-4-hydroxypiperidínu, 1,61 g (0,005 mólu) tetrabutylamónium bromidu, 13,6 g (0,05 mólu) 1,8-dibrómoktánu, 10 ml benzenu a 15 mililitrov 15 %-ného hydroxidu draselného sa intenzívně mieša pri teplote 50 °C po dobu 20 hodin.8.56 g (0.05 mol) of 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, 1.61 g (0.005 mol) of tetrabutylammonium bromide, 13.6 g (0.05 mol) of 1.8 Dibromooctane, 10 ml benzene and 15 ml 15% potassium hydroxide were vigorously stirred at 50 ° C for 20 hours.
Potom sa reakčná zmes spracuje rovnako ako v příklade 1. Pri destilácii sa odoberá frakcia bezfarebnej kvapaliny v teplotnom intervale 185 až 195 °C pri tlaku 300 Pa.Thereafter, the reaction mixture was worked up as in Example 1. A fraction of a colorless liquid was collected by distillation at a temperature range of 185 to 195 ° C at a pressure of 300 Pa.
Elementárna analýza pre C18H36BrNO: Vypočítané:Elemental analysis for C 18 H 36 BrNO: Calculated:
59,65 % C, 10,01 % H, 3,87 % N, Nájdené:% C, 59.65;% H, 10.01;% N, 3.87.
60,16 % C, 10,16 % H, 3,70 % N.H, 10.16; N, 3.70.
’Ή NMR spektrum (CDC13):1 H NMR spectrum (CDCl 3 ):
í (ppm) =.delta. (ppm) =
0,97 (s, — CH3 ax, 6H),0.97 (s, - CH 3 and x, 6H);
1,12 (s, —CH3 eq, 6H),1.12 (s, —CH 3 eq, 6H),
1,20 až 2,00 (ffl, —CH3--, 16H),1.20 to 2.00 (ffl, CH 3 -, 16 H);
2.17 (s, CH3—N, 3H),2.17 (s, CH 3 - N, 3 H),
3,35 (t, —CH2—Ο-, 2H, J=6 Hz),3.35 (t, CH 2 -Ο-, 2H, J = 6 Hz);
3.39 (t, —CH2—Br, 2H, J=6 Hz),3:39 (t, CH 2 -Br, 2H, J = 6 Hz);
3.40 až 4,00 (m, =CH—O—, 1H).3.40 to 4.00 (m, = CH - O -, 1H).
Příklad 5Example 5
8,56 g (0,05 mólu) l,2,2,6,6-pentametyl-4-hydroxyplperidínu, 1,61 g (0,005 mólu) tetrabutylamónium bromidu 15,0 g (0,005 mólu) 1,10-dibrómdekátiu, 10 ml benzenu a 15 mililitrov 50 %-ného hydroxidu sodného sa intenzívně mieša pri izbovej teplote po dobu 30 hodin.8.56 g (0.05 mol) of 1,2,2,6,6-pentamethyl-4-hydroxyplperidine, 1.61 g (0.005 mol) of tetrabutylammonium bromide 15.0 g (0.005 mol) of 1,10-dibromodecium, 10 ml of benzene and 15 ml of 50% sodium hydroxide are stirred vigorously at room temperature for 30 hours.
Potom sa reakčná zmes spracuje rovnako ako v příklade 1. Pri destilácii sa odoberá frakcia bezfarebnej kvapaliny v teplotnom intervale 190 až 200 °C pri tlaku 200 Pa.Thereafter, the reaction mixture was worked up as in Example 1. A fraction of a colorless liquid was collected by distillation at a temperature range of 190 to 200 ° C at a pressure of 200 Pa.
Elementárna analýza pre C2<lH.0BrNO: Vypočítané:Elemental analysis for C 2 < 1 H 0 BrNO: Calculated:
61,52 % C, 10,33 % H, 3,59 % N, Nájdené:% C, 61.52;% H, 10.33;% N, 3.59.
62,48 % C, 10,90 % H, 3,77 % N.% C, 62.48;% H, 10.90;% N, 3.77.
Ή NMR spektrum (CDC13):Ή NMR Spectrum (CDCl 3 ):
(ppm) =(ppm) =
0,97 (s, —CH3 ax, 6H),0.97 (s, —CH 3 ax, 6H),
1,12 (s, —CH3 eq, 6H),1.12 (s, —CH 3 eq, 6H),
1.17 až 2,00 (m, — CH2—, 20H),1.17 to 2.00 (m, - CH2 -, 20 H).
2.17 (s, CH3—N, 3H),2.17 (s, CH 3 - N, 3 H),
3,27 (s, —ÓH2—O—, 2H, J=6 Hz),3.27 (s, --OH 2 - O, 2H, J = 6 Hz),
3,30 (t, —CH2—Br, 2H, J=6,5 Hz),3.30 (t, CH 2 -Br, 2H, J = 6.5 Hz);
3,30 až 4,00 (m, =CH—O—, 1H).3.30 to 4.00 (m, = CH - O -, 1H).
Příklad 6Example 6
8,56 g (0,05 mólu) l,2,2,6,6-pentametyl-4-hydroxypiperidínu, 1,61 g (0,005 mólu) tetrabutylamónium bromidu, 16,41 g (0,05 mólu) 1,12-dibrómdodekánu, 10 ml benzénu a 15 ml 50 %-ného hydroxidu sodného sa intenzívně mieša pri izbovej teplote po dobu 30 hodin. Potom sa reakčná zmes spracuje rovnako ako v příklade 1. Pri destilácii sa odoberá frakcia bezfarebnej kvapaliny v teplotnom intervale 195 až 205 °C pri tlaku 173 Pa.8.56 g (0.05 mol) of 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, 1.61 g (0.005 mol) of tetrabutylammonium bromide, 16.41 g (0.05 mol) of 1.12 Dibromododecane, 10 ml benzene and 15 ml 50% sodium hydroxide are vigorously stirred at room temperature for 30 hours. Thereafter, the reaction mixture was worked up as in Example 1. A fraction of a colorless liquid was collected by distillation at a temperature range of 195 to 205 ° C at a pressure of 173 Pa.
259398259398
Elementárna analýza pre C22H44BrNO: Vypočítané:Elemental analysis for C 22 H 44 BrNO: Calculated:
63,14 % C, 10,60 % H, 3,35 % N, Nájdené:% C, 63.14;% H, 10.60;% N, 3.35.
62,10 % C, 10,21 θ/ο H, 3,41 % N.62.10% C, 10.21 θ / ο H, 3.41% N.
1HNMR spektrum (CDC1S):1 H NMR (CDCl 3 ):
í (ppm) =.delta. (ppm) =
0,97 (s, —CH2 ax, 6H),0.97 (s, CH 2 and x, 6H);
1,12 (s, —CH, eq, 6H),1.12 (s, —CH, eq, 6H),
1.17 až 1,95 (m, —CH2—, 24H),1.17 to 1.95 (m, -CH2 - 24H).
2.17 (a, CH3—N, 3H),2.17 (s, CH 3 -N, 3H);
3,27 (t, — CH2— O—, 2H, J=6 Hz),3.27 (t, - CH 2 - O, 2H, J = 6 Hz);
3,31 (t, —CH2—Br, 2H, J=6,5 Hz),3.31 (t, CH 2 -Br, 2H, J = 6.5 Hz);
3,31 až 4,01 (m, —CH—O—, 1H).3.31 to 4.01 (m, --CH - O -, 1H).
Příklad 7Example 7
100 hmotnostných dielov nestabilizovaného práškovitého polypropylénu sa impregnuje v dichlórmetáne s 0,1 hmot. dielmi 2,6-di-terc.butyl-4-metylíenoíu, 0,15 hmot. dielmi stearanu vápenatého' a s 0,2 hmot. dielmi zlúčeniny pripravenej podlá příkladu 6. Po odpaření rozpúšťadla sa zo zmesi vylisujú fólie 0' hrúbke 0,2 mm pri tlaku 20 MPa a teplote 190 °C po' dobu 3 minut. Takto připravené fólie sa ožarujú ortuťovou výbojkou o výkone 125 W vo vzdialenosti 7 cm od zdroja. Degradácia polyméru sa sleduje vývojom karbonylového pása v infračervených spektrách. Kým doba dosiahnutia karbonylového indexu 0,2 u čistého polypropylénu je 240 hodin, stabilizovaný poolymér dosiahne tuto hodnotu až po 1 560 hodinách.100 parts by weight of unstabilized powdered polypropylene are impregnated in dichloromethane with 0.1 wt. parts by weight of 2,6-di-tert-butyl-4-methylphenyl, 0.15 wt. % of calcium stearate and 0.2 wt. After evaporation of the solvent, 0 'of 0.2 mm film are pressed from the mixture at 20 MPa at 190 ° C for 3 minutes. The films thus prepared are irradiated with a 125 W mercury lamp at a distance of 7 cm from the source. The degradation of the polymer is monitored by the development of the carbonyl band in the infrared spectra. While the time to reach the carbonyl index of 0.2 for pure polypropylene is 240 hours, the stabilized pool polymer does not reach this value until after 1,560 hours.
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US10246690B2 (en) | 2006-10-30 | 2019-04-02 | Promega Corporation | Mutant hydrolase proteins with enhanced kinetics and functional expression |
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