CS264998B1 - 1,2,2,6,6-pentamethyl-4-allyloxypiperidine - Google Patents
1,2,2,6,6-pentamethyl-4-allyloxypiperidine Download PDFInfo
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- CS264998B1 CS264998B1 CS882671A CS267188A CS264998B1 CS 264998 B1 CS264998 B1 CS 264998B1 CS 882671 A CS882671 A CS 882671A CS 267188 A CS267188 A CS 267188A CS 264998 B1 CS264998 B1 CS 264998B1
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- Czechoslovakia
- Prior art keywords
- pentamethyl
- compound
- hydroxide
- mol
- hydroxypiperidine
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- 239000004611 light stabiliser Substances 0.000 abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- HDOWRFHMPULYOA-UHFFFAOYSA-N piperidin-4-ol Chemical compound OC1CCNCC1 HDOWRFHMPULYOA-UHFFFAOYSA-N 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- NWHNXXMYEICZAT-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidin-4-ol Chemical compound CN1C(C)(C)CC(O)CC1(C)C NWHNXXMYEICZAT-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical class CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZOSPIRSWAQIPSU-UHFFFAOYSA-N 7,15-diazadispiro[5.1.5^{8}.3^{6}]hexadecane Chemical compound C1CCCCC21NC1(CCCCC1)CNC2 ZOSPIRSWAQIPSU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000012267 brine Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000004007 reversed phase HPLC Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
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- Hydrogenated Pyridines (AREA)
Abstract
Riešenie sa týká 1 , 2 , 2 , 6 , 6-pentametyl- . -4-alyloxypiperidínu. Uvedená zlúčenina sa připraví tak, že 1 , 2 , 2 , 6 , 6-pentametyl- -4-hydroxypiperidín reaguje s alylbromidom za intenzívneho miešania v heterofázovom systéme, pričom jednu fázu vytvára vodný roztok alkalického hydroxidu, s výhodou hydroxidu sodného alebo hydroxidu draselného a druhů fázu vytvára organické rozpúštadlo nemiešatelné s vodnou fázou za přítomnosti katalyzátora typ óniových solí v teplotnom rozmedzí 10 až 100 °C. Zlúčenina má použitie ako světelný stabilizátor pre polyméry alebo je medzi- produktom pre přípravu polymérnych světelných stabilizátorov polymerizač- nými alebo kopolimerizačnými reakciami.solution the relates to 1 . 2 . 2 . 6 . 6-pentamethyl . 4-alyloxypiperidínu. Stated compound the prepare so, that 1 . 2 . 2 . 6 . 6-pentamethyl 4-hydroxypiperidine reacts with allyl bromide for intensive mixing in heterophasic system while one phase creates aqueous solution alkaline hydroxide, with preferably hydroxide sodium or hydroxide carbonate and species phase creates organic solvent immiscible with water phase for presence catalyst Type onium salt in temperature range 10 until 100 C. compound my the use than light stabilizer for polymers or is a between- products for training polymer light stabilizers polymerizač- BY APPLICABLE or kopolimerizačnými reactions.
Description
. Vynález sa týká 1,2,2,6,6-pentametyl-4-alyloxypiperidinu.. The invention relates to 1,2,2,6,6-pentamethyl-4-allyloxypiperidine.
Stérický tienené aminy patria v súčastnosti medzi najúčinnejšie světelné stabilizátory pre polyméry (F. E. Karrer, Makromol, Chem., 181, 595 (1980), F: Gugumus, Developmenfes in Polymer Stabilisation-1, ed. G. Scott, Applied Science Publishers, London, 1979, kap.Steric shielded amines are currently among the most effective light stabilizers for polymers (FE Karrer, Makromol, Chem., 181, 595 (1980), F: Gugumus, Developmenfes in Polymer Stabilization-1, edited by G. Scott, Applied Science Publishers, London , 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, 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 prchavost a extrahovatelnost nizkomolekulových derivátov z polymérov. Zlúčenina, ktorá je predmetom vynálezu, obsahuje vo svojej molekule funkčnú nenasýtenú vSzbu. Přítomnost tejto skupiny v molekule světelného stabilizátora umožňuje přípravu vysokomolekulových světelných stabilizátorov polymerizáciou alylovej skupiny alebo jej kopolymerizáciou s inými nenasýtenými monomérmi. Táto zlúčenina nebola doteraz popísáná v odbornéj literatúre.8, J. J. Usilton, A.R. Patel, Am. Chem. Soc. Polym. Prep., 18 (1), 393 (1977)). They are various derivatives of 2,2,6,6-tetramethylpiperidine, 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 a functional unsaturated bond in its molecule. The presence of this group in the light stabilizer molecule allows the preparation of high molecular weight light stabilizers by polymerizing an allyl group or copolymerizing it with other unsaturated monomers. This compound has not been previously described in the literature.
Podstatou vynálezu je 1,2,2,6,6-pentametyl-4-alyloxypiperidín vzorca I.The present invention provides 1,2,2,6,6-pentamethyl-4-allyloxypiperidine of formula I.
H3C CH,H3C CH,
VaVa
H3c-N 2—o-ch2-ch-ch2 H 3 CN 2 -O-CH 2 -CH 2
Ál·AL ·
H3c ch3 (i)H 3 c ch 3 (i)
Spósob přípravy zlúčeniny I spočívá v tom, že 1,2,2,6,6-pentametyl-4-hydroxypiperidín vzorca IIA process for the preparation of compound I is characterized in that 1,2,2,6,6-pentamethyl-4-hydroxypiperidine of formula II
reaguje s alylbromidom za intenzívneho miešania v heterofázovom systéme, pričom jednu fázu vytvára vodný roztok alkalického hydroxidu, s výhodou hydroxidu sodného v koncentračnom rozmedzí 5 až 50 % alebo hydroxidu draselného v koncentračnom rozmedzí 5 až 70 % a druhů fázu vytvára organické rozpúštadlo nemiešajúce sa s vodnou fázou, ako je benzén, toluén alebo xylény, za přítomnosti katalyzátore typu óniových solí, ako je tetrabutylamonium chlorid, tetrabutylamónium bromid, tetrabutylamonium hydrogénsíran alebo tetrabutylfosfónium bromid, ktorý sa použije v množstve 1 až 10 mol % na množstvo zlúčeniny II v rozmedzí teplót 10 až 100 °C.reacts with allyl bromide with vigorous stirring in a heterophasic system, one phase forming an aqueous solution of alkaline hydroxide, preferably sodium hydroxide in a concentration range of 5 to 50% or potassium hydroxide in a concentration range of 5 to 70%, and the other phases forming an organic solvent not mixed with aqueous a phase such as benzene, toluene or xylenes in the presence of an onium salt type catalyst such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulphate or tetrabutylphosphonium bromide, which is used in an amount of 1 to 10 mol% Mp 100 ° C.
Předmětná látka sa móže použit ako světelný stabilizátor pre polyméry alebo je medziproduktom pre přípravu polymérnych světelných stabilizátorov polymerizačnými alebo kopolymerizač nými 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 polymerization or copolymerization reactions.
Příklad 1Example 1
5,14 g (0,03 nol) 1,2,2,6,6-pentametyl-4-hydroxypiperidínu, 3,99 g (0,033 mol) alylbromidu, 1,93 g (0,006 mol) tetrabutylamónium bromidu, 10 ml benzénu a 15 ml 50 %-ného vodného roztoku hydroxidu sodného sa intenzivně mieša pri izbovej teplote 24 hodin. Potom sa oddělí organická vrstva, ktorá sa prepiera vodou a solankou a vysuší sa bezvodým síranom sodným. Oddestiluje sa rozpúštadlo a zbytok pri analýze pomocou vysokoúčinnej kvapalinovej chromatografie na obrátnej fáze ukazuje iba jediný pík. Získajú sa 4 g produktu, t. j. 63 % teoretického výtažku.5.14 g (0.03 mol) of 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, 3.99 g (0.033 mol) of allyl bromide, 1.93 g (0.006 mol) of tetrabutylammonium bromide, 10 ml of benzene and 15 ml of 50% aqueous sodium hydroxide solution are stirred vigorously at room temperature for 24 hours. The organic layer was separated, washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off and the residue showed only one peak when analyzed by reverse phase high performance liquid chromatography. 4 g of product are obtained, m.p. j. 63% of the theoretical yield.
Elementárna analýza pre C^^HjjNOElemental analysis for C C ^H HjNONO
Vypočítané: C = 73,88 %; H = 11,92 %; N = 6,63 %Calculated: C = 73.88%; H = 11.92%; N = 6.63%
Nájdené: C = 72,70 i; H = 11,53 %; N = 6,36 % XH NMR spektrum, (CDC13) : δ (ppm) = 0,98 (s, -CH3 ax, 6H) , 1,13 (s, -CH3 eq, 6H) , 1,43 až 2,03 (m, -CH2~, 4H), 2,18 (s, N-CHj, 3H), 3,27 až 3,85 (m, =CH-O, 1H), 3,97 (d, -CH2-O-, 2H, J = 5 Hz), 4,95 až 5,40 (m, =CH2, 2H), 5,57 až 6,25 (m, -CH=, 1H)Found: C = 72.70 i; H = 11.53%; N = 6.36%; H NMR spectrum (CDC1 3): δ (ppm) = 0.98 (s, CH 3 and x, 6H), 1.13 (s, CH 3 eq, 6 H), 1 43 to 2.03 (m, -CH 2 -, 4H), 2.18 (s, N-CH 3, 3H), 3.27 to 3.85 (m, = CH-O, 1H), 97 (d, -CH 2 -O-, 2H, J = 5 Hz), 4.95 to 5.40 (m, = CH 2 , 2H), 5.57 to 6.25 (m, -CH =, 1H)
Přiklad 2Example 2
5,14 g (0,03 mol) 1,2,2,6,6-pentametyl-4-hydroxypiperidínu, 3,99 g (0,033 mol) alylbromidu 0,51 g (0,001 5 mol) tetrabutylamónium hydrogénsíranu, 10 ml toluénu a 15 ml 30 %-ného vodného roztoku hydroxidu draselného sa intenzívně mieša pri teplote 65 °C 7 hodin. Reakčná zmes sa spracuje rovnako ako v příklade 1. Výťažok je 4,5 g produktu, ť. j. 71 i teoretického výtažku.5,14 g (0,03 mol) 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, 3,99 g (0,033 mol) allyl bromide 0,51 g (0,001 5 mol) tetrabutylammonium hydrogen sulphate, 10 ml toluene and 15 ml of a 30% aqueous potassium hydroxide solution are stirred vigorously at 65 ° C for 7 hours. The reaction mixture was worked up as in Example 1. The yield was 4.5 g of product. j. 71 the theoretical extract.
Příklad 3Example 3
5,14 g (0,03 mol) 1,2,2,6,6-pentamety1-4-hydroxypiperidínu, 3,99 g (0,033 mol) alylbromidu 0,34 g (0,001 mol) tetrabutylfosfónium bromidu, 10 ml zmesi xylénov s destilačným rozmedzím 137 až 140 °C a 15 ml 60 %-ného vodného roztoku hydroxidu draselného sa intenzívně mieša pri teplote 100 °C 4 hodiny. Reakčná zmes sa spracuje rovnako ako v příklade 1. Získá sa 4,3 g produktu, t. j. 68 % teoretického výtažku.5.14 g (0.03 mol) of 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, 3.99 g (0.033 mol) of allyl bromide 0.34 g (0.001 mol) of tetrabutylphosphonium bromide, 10 ml of xylene mixture with a distillation range of 137 to 140 ° C and 15 ml of a 60% aqueous potassium hydroxide solution is stirred vigorously at 100 ° C for 4 hours. The reaction mixture was worked up as in Example 1. 4.3 g of product were obtained, m.p. j. 68% of the theoretical yield.
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS882671A CS264998B1 (en) | 1988-04-20 | 1988-04-20 | 1,2,2,6,6-pentamethyl-4-allyloxypiperidine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS882671A CS264998B1 (en) | 1988-04-20 | 1988-04-20 | 1,2,2,6,6-pentamethyl-4-allyloxypiperidine |
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| Publication Number | Publication Date |
|---|---|
| CS267188A1 CS267188A1 (en) | 1988-10-14 |
| CS264998B1 true CS264998B1 (en) | 1989-09-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS882671A CS264998B1 (en) | 1988-04-20 | 1988-04-20 | 1,2,2,6,6-pentamethyl-4-allyloxypiperidine |
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| Country | Link |
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| CS (1) | CS264998B1 (en) |
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1988
- 1988-04-20 CS CS882671A patent/CS264998B1/en unknown
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| Publication number | Publication date |
|---|---|
| CS267188A1 (en) | 1988-10-14 |
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