CS271983B1 - 2,2,6,6-Tetramethyl-4-piperidyl] -2-propanone and its preparation - Google Patents
2,2,6,6-Tetramethyl-4-piperidyl] -2-propanone and its preparation Download PDFInfo
- Publication number
- CS271983B1 CS271983B1 CS888116A CS811688A CS271983B1 CS 271983 B1 CS271983 B1 CS 271983B1 CS 888116 A CS888116 A CS 888116A CS 811688 A CS811688 A CS 811688A CS 271983 B1 CS271983 B1 CS 271983B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- tetramethyl
- piperidyl
- propanone
- pyridine
- piperidylideneacetone
- Prior art date
Links
Landscapes
- Hydrogenated Pyridines (AREA)
Abstract
RieSenie sa týká /2,2,6,6^tetrametyl- -4-piperidyl/-2-propanónu a sposobu jeho přípravy katalytickou hydrogenáciou 2,2,6,6-tetramety1-4-piperidylidénacetónu v atmosféře vodíka, v prostředí organického rozpúšíadla, pri teplote 20 až 120 C, pri atmosférickou! tlaku alebo pri tlaku do 5 MPa, v přítomnosti hydrogenačného katalyzátora, počas 1 až 72 h alebo redukciou 2,2,6,6-tetramety1-4-piperidylidénacetónu komplexným hydridom, v prostředí pyridinu, pri teplote 20 0 až 100 2C» počas 3 až 8 h. Procesy je možné uskutočňovat diskontinuitne alebo kontinuitne. 2,2,6,6-Tetrametyl- -4-piperidyl/-2-propanón je možné použil ako medziprodukt na výrobu vysokoúčinných svetelnýcn stabilizátorov polymérov a biologicky účinných látok, vrátane liečiv.The solution relates to /2,2,6,6^tetramethyl- -4-piperidyl/-2-propanone and a method for its preparation by catalytic hydrogenation of 2,2,6,6-tetramethyl-4-piperidylideneacetone in a hydrogen atmosphere, in an organic solvent environment, at a temperature of 20 to 120 C, at atmospheric pressure or at a pressure of up to 5 MPa, in the presence of a hydrogenation catalyst, for 1 to 72 h or by reduction of 2,2,6,6-tetramethyl-4-piperidylideneacetone with a complex hydride, in a pyridine environment, at a temperature of 20 0 to 100 2C» for 3 to 8 h. The processes can be carried out discontinuously or continuously. 2,2,6,6-Tetramethyl-4-piperidyl-2-propanone can be used as an intermediate for the production of highly effective light stabilizers of polymers and biologically active substances, including pharmaceuticals.
Description
CS 271983 B1
Vynález sa týká /2,2,6,6-tetrametyl-4-piperidyl/-2-propanónu vzorca I
CH CH.
CH.
CH 3 (I) '3 a spSsobu jeho přípravy. /2,2,6,6-Tetrametyl-4-piperidyl/-2-propanón je medziproduktomna přípravu vysokoúčinných světelných stabilizátorov polymérov a biologicky účinných lá-tok, vrátane liečiv. Z literatúry i z priemyselnej praxe je znány 2,2,6,6-tetrametyl-4-piperidón /tri-acetónamín/ ako hlavný východiskový produkt na priemyselnú výrobu světelných stabili-zátorov polymérov ako aj celého radu liečiv na báze polyalkylpiperidínov. 3eho syntézaje v literatúre /□. Am. Chem. Soc. 79, 5444, 1957j SU 520 357 DE 3525 385 ", □ P 1627 /1972/ / podrobné opísaná.
Teraz sa zistil nový derivát tetrametylpiperidínu, /2,2,6,6-tetrametyl-4-piperidyl/--2-propanón vzorca I a spSsob jeho přípravy katalytickou hydrogenáciou 2,2,6,6-tetrame-tyl-4-piperidylidénacetónu v atmosféře vodíka, v prostředí organického rozpúSíadla, přiteplote 20 ° až 120 °C, při atmosférickom tlaku alebo pri tlaku do 5 MPa, v přítomnostihydrogenačného katalyzátore, počas 1 až 72 h, alebo redukciou 2,2,6,6-tetrametyl-4--piperidylidénacetónu komplexným hydridom v prostředí pyridinu, pri teplote 20 0 až100 °C, počas 3 až 8 h. Ako hydrogenačný katalyzátor je možné použit například Raney--Nikel, Ni/AlgOg, Ni/Cr203, paládium na nosiči, platinu na nosiči, PtO2, připadne inéna tento účel používané katalyzátory. Ako komplexný hydrid je vhodný například LiAlH^,
Na BH4, alebo NaAlH2 /0CH2 CH2 0CH3/2. Procesy je možné viest diskontinuitne alebo kon-tinuitne. /2,2,6,6-Tetrametyl-4-piperidyl/-2-propanón vzorca 1 podlá vynálezu je možné po-užit ako medziprodukt na výrobu světelných stabilizátorov, vhodných pře termoplasticképolymérne substráty ako sú polyolefíny, polyestery, polyétery, polyuretány, polystyrény,připadne 3alšie. Je vhodný aj ako medziprodukt na výrobu biologicky účinných látok, vrá-tane liečiv.
Nasledujúce příklady ilustrujú, ale neobmedzujú predmet vynálezu. Příklad l
Do hydrogenačnej banky s magnetickým mieSadlom sa navážilo 19,5 g /0,1 molu/2,2,6,6-tetrametyl-4-piperidylidénacetónu rozpuštěného v 150 ml dietyléteru. κ roztokusa přidalo 1,5 g Pd/Al203 s obsahom Pd 5 % a reakčná zmes sa intenzívně miešalav atmosféře vodíka 72 h pri laboratórnej teplote. Po skončení reakcie sa odfiltrovalkatalyzátor. Po odpaření dietyléteru sa surový produkt destiloval za zníženého tlakus odberora frakcie s teplotou varu 71-2 °C/150 Pa, z ktorej sa získal /2,2,6,6-tetrame-tyl-4-piperidyl/-2-propanón ako slabožltá kvapalina. CS 271983 01
Elementárna analýza pře C12H23 NO :
Vypočítané : 73,04 % C, 11,75 % H,
Stanovené : 73,14 % C, 11,59 % H,
7,10 % N7,03 % N 1H-NMR spektrum v CDCl3: to ppm / skupina 2,27 -ch2-co- 2,11 -co-ch3 1,17 \ 1,04 CH. 1,75 až 0,33 2^-NH, -ch2·
1 M 2 H d 3 H s ax. 6 H s eg. 6 H s - CH - kruh 6 H m IČ-spektrum, roztok v CCl4 : V>/ C - O /- 1735 cm“1, O /NH/volne - 3330 cm“1, J"/ CH / n<a3# - 1380, 1365 cm Γ1, 9 /NH/viaz “ 3 430 cm' -1 Příklad 2
Do 100 ml tlakovej nádoby autoklávu opatřeného miešadlom, teplomerom a tlakomeromsa navážilo 19,5 g /0,1 molu/ 2,2,6,6-tetrametyl-4-piperidylacetónu, přidalo sa 45 mlmetanolu a 0,6 g katalyzátore Raney-Nikel. Po uzatvorení sa nádoba autoklávu prepláchlavodíkom, reakčná zmes sa vyhriala na 120 °C a pri tlaku vodíka 5,0 MPa sa miešala 1,5 h.Po skončení reakcie sa odfiltroval katalyzátor, rozpúštadlo sa oddestilovalo za atmosfe-rického tlaku a surový produkt sa destiloval za zníženého tlaku s odberom frakcie s tep-lotou varu 83-5 °C/400 Pa. Získala sa málo sfarbená priehladná kvapalina produktu/2,2,6,6-tetrametyl-4-piperidyl/-2-propanónu.
Elementárna analýza pre C12H23 N0 :
Vypočítané : 73,04 % C 11,75 % H 7,10 % N
Stanovené : 72,87 % C 11,53 % H 7,03 % N 1 - NMR spektrum v CDCl„ a XČ - spektrum v CCl. boli rovnaké ako v příklade 1. Π ó Příklad 3
Prietokový hydrogenačný reaktor dlžky 0,5 m s vnútorným priemerom 25 mm bol naplně-ný 100 g katalyzátore Ni-Cr203 obsahujúceho 60 % Ni. Po aktivácii katalyzátora vodíkombol do reaktora dávkovaný 30 %-ný roztok 2,2,6,6-tetrametyl-4-piperidylidénacetónuv 2-propanole v množstve 250 g . h”1, pri teplote 70 °C a tlaku vodíka 3,5 MPa. Surovýprodukt sa po oddestilovaní rozpúštadla destiloval za zníženého tlaku, odoberala safrakcia s teplotou varu 71-2 °C/15O pa, z ktorej sa získal /2,2,6,6-tetrametyl-4-pipe-ridyl/-2-propanón ako mierne sfarbená kvapalina.
CS 271983 B1
The invention relates to (2,2,6,6-tetramethyl-4-piperidyl) -2-propanone of formula (I)
CH CH.
CH.
CH 3 (I) 3 and its method of preparation. (2,2,6,6-Tetramethyl-4-piperidyl) -2-propanone is an intermediate for the preparation of high performance light stabilizers of polymers and biologically active substances, including drugs. From literature and industry, 2,2,6,6-tetramethyl-4-piperidone (triacetone amine) is known as the main starting product for the industrial production of polymer light stabilizers as well as a variety of polyalkylpiperidine based drugs. 3e Literature Synthesis / □. Am. Chem. Soc. 79, 5444, 1957, SU 520 357 DE 3525 385, " P 1627/1972] / detailed.
A novel derivative of tetramethylpiperidine, [2,2,6,6-tetramethyl-4-piperidyl] -2-propanone of formula I and its preparation by catalytic hydrogenation of 2,2,6,6-tetramethyl-4-piperidylideneacetone has now been found. under a hydrogen atmosphere, in an organic solvent environment, at a temperature of 20 ° to 120 ° C, at atmospheric pressure or at a pressure of up to 5 MPa, in the presence of a hydrogenation catalyst, for 1 to 72 hours, or reduction of 2,2,6,6-tetramethyl-4 - Piperidylideneacetone with complex hydride in pyridine at 20 ° C to 100 ° C for 3 to 8 h. For example, Raney-Nickel, Ni / AlgOg, Ni / Cr 2 O 3, palladium on support, platinum on support, can be used as the hydrogenation catalyst. , PtO2, other catalysts used in this purpose. Suitable complex hydride is, for example, LiAlH4,
Na BH 4, or NaAlH 2 / OCH 2 CH 2 OCH 3/2. Processes can be discontinuously or continuously. (2,2,6,6-Tetramethyl-4-piperidyl) -2-propanone of the formula I according to the invention can be used as an intermediate for the production of light stabilizers, suitable for thermoplastic polymer substrates such as polyolefins, polyesters, polyethers, polyurethanes, polystyrenes , the third. It is also suitable as an intermediate for the production of biologically active substances, including drugs.
The following examples illustrate, but do not limit the invention. Example 1
19.5 g (0.1 mol) of 2,2,6,6-tetramethyl-4-piperidylideneacetone dissolved in 150 ml of diethyl ether was weighed into a magnetic stirrer. κ solution was added 1.5 g Pd / Al 2 O 3 with a Pd content of 5% and the reaction mixture was vigorously stirred under a hydrogen atmosphere for 72 h at room temperature. After the reaction was complete, the catalyst was filtered off. After evaporation of the diethyl ether, the crude product was distilled under reduced pressure to collect the fraction having a boiling point of 71-2 ° C / 150 Pa from which 2,2,6,6-tetramethyl-4-piperidyl / 2-propanone was obtained as a weak yellow liquid. CS 271983 01
Elemental analysis for C 12 H 23 NO:
C, 73.04; H, 11.75;
Found: C, 73.14; H, 11.59;
7.10% N 7.03% N 1 H-NMR spectrum in CDCl 3: δ ppm / group 2.27 -ch 2 -co- 2.11 -co-ch 3 1.17 1.04 CH. 1.75 to 0.33 2 ^ -NH, -ch2 ·
1 M 2 H d 3 H with ax. 6 H with eg. 6 H s - CH - ring 6 H m IR spectrum, solution in CCl4: V> / C - 0 / - 1735 cm "1, O / NH / free - 3330 cm" 1, J "/ CH / n <a3 # 1380, 1365 cm -1, 9 / NH / viaz "3 430 cm -1 -1 Example 2
19.5 g (0.1 mol) of 2,2,6,6-tetramethyl-4-piperidylacetone were weighed into a 100 ml pressure vessel of an autoclave equipped with a stirrer, thermometer and pressure gauge, 45 ml of methanol and 0.6 g of Raney-Nickel catalyst were added . After the autoclave vessel was sealed, the reaction mixture was heated to 120 ° C and stirred for 1.5 h under a hydrogen pressure of 5.0 MPa. After completion of the reaction, the catalyst was filtered off, the solvent was distilled off under atmospheric pressure and the crude product was distilled under reduced pressure, collecting a fraction with a boiling point of 83-5 ° C / 400 Pa. A slightly colored, clear liquid of (2,2,6,6-tetramethyl-4-piperidyl) -2-propanone was obtained.
Elemental analysis for C 12 H 23 NO:
% C, 11.75; H, 7.10;
Determined: 72.87% C 11.53% H 7.03% N 1-NMR spectrum in CDCl 3 and X 3 - spectrum in CCl. were the same as in Example 1. Example 3
A flow hydrogenation reactor of 0.5 m length with an internal diameter of 25 mm was charged with 100 g of Ni-Cr 2 O 3 catalyst containing 60% Ni. After activation of the catalyst, a 30% solution of 2,2,6,6-tetramethyl-4-piperidylideneacetone in 2-propanol in a quantity of 250 g was fed into the reactor. h ”1, at a temperature of 70 ° C and a hydrogen pressure of 3.5 MPa. The crude product was distilled off under reduced pressure after the solvent was distilled off, and the safraction was collected at 71-2 ° C / 15OmP to give 2,2,6,6-tetramethyl-4-piperidyl-2-propanone as slightly colored liquid.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CS888116A CS271983B1 (en) | 1988-12-08 | 1988-12-08 | 2,2,6,6-Tetramethyl-4-piperidyl] -2-propanone and its preparation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CS888116A CS271983B1 (en) | 1988-12-08 | 1988-12-08 | 2,2,6,6-Tetramethyl-4-piperidyl] -2-propanone and its preparation |
Publications (2)
Publication Number | Publication Date |
---|---|
CS811688A1 CS811688A1 (en) | 1990-03-14 |
CS271983B1 true CS271983B1 (en) | 1990-12-13 |
Family
ID=5431326
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CS888116A CS271983B1 (en) | 1988-12-08 | 1988-12-08 | 2,2,6,6-Tetramethyl-4-piperidyl] -2-propanone and its preparation |
Country Status (1)
Country | Link |
---|---|
CS (1) | CS271983B1 (en) |
-
1988
- 1988-12-08 CS CS888116A patent/CS271983B1/en unknown
Also Published As
Publication number | Publication date |
---|---|
CS811688A1 (en) | 1990-03-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Couturier et al. | Palladium and Raney nickel catalyzed methanolic cleavage of stable borane− amine complexes | |
Hartwig | Directly-Observed β-Hydrogen Elimination of a Late Transition Metal Amido Complex and Unusual Fate of Imine Byproducts | |
Pasumansky et al. | Lithium aminoborohydrides: Powerful, selective, air-stable reducing agents | |
Denmark et al. | Catalytic, nucleophilic allylation of aldehydes with 2-substituted allylic acetates: carbon–carbon bond formation driven by the water–gas shift reaction | |
Thiedemann et al. | Reduction of N-allylamides by LiAlH4: unexpected attack of the double bond with mechanistic studies of product and byproduct formation | |
CN117384199A (en) | Preparation of a new type of organoaluminum hydrogen compound and its catalytic preparation method of unsaturated alcohol compounds | |
Casnati et al. | p-(Benzyloxy) calix [8] arene: one-pot synthesis and functionalization | |
Terhorst et al. | Productivity leap in the homogeneous ruthenium-catalyzed alcohol amination through catalyst recycling avoiding volatile organic solvents | |
CN112892604A (en) | Organic amine and CO2Heterogeneous catalysis method for preparing formamide | |
CN108250165B (en) | A method for preparing N-(5-methylfurfuryl)aniline and derivatives by utilizing biomass carbohydrates | |
CS271983B1 (en) | 2,2,6,6-Tetramethyl-4-piperidyl] -2-propanone and its preparation | |
Yow et al. | A Highly Chemoselective, Zr-Catalyzed C–O Bond Functionalization of Benzofuran | |
Meyer et al. | Lewis acid mediated regioselective ring opening of benzylglycidol with dibenzyl phosphate: short and attractive synthesis of dihydroxyacetone phosphate | |
Toti et al. | Activation of single and multiple C–N bonds by Ru (II) catalysts in homogeneous phase | |
CN113666829B (en) | Preparation method of 4-fluoro-N-isopropylaniline and flufenacet | |
CN1225356A (en) | Synthetic method of 1-[2-amino-1-(P-methoxybenzyl) ethyl] cyclohexanol | |
KR101659163B1 (en) | Preparing method of alkanol | |
Brown et al. | Steric Effects in Elimination Reactions. XII. The Reaction of Potassium t-Butoxide with Cyclic Tosylates. The Effect of Structure on the Rate and Direction of Eliminations in Cyclic Systems1 | |
CN112608207A (en) | Preparation of 4, 6-dimethyl-2-mercaptopyrimidine divalent nickel complexα-Use in alkyl ketones | |
CN108329202B (en) | A kind of method for preparing 3-iodopropionic acid from glyceric acid | |
US6429319B1 (en) | Continuous process for the production of optically pure (S)-beta-hydroxy-gamma-butyrolactone | |
RU2620269C1 (en) | Method of amides obtaining from carbonyl compounds | |
Opačak et al. | Catalytic Transfer Vinylation of Alcohols | |
JP4200704B2 (en) | Method for producing fluorinated benzonitrile | |
Song et al. | 5‐Ammonium‐4, 4‐dimethylvaleryl (Amv) Group: Generation from Acryloyl Group through Decatungstate‐Catalyzed C (sp3)− H Addition and Removal by Base‐Triggered Cyclization |