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 PDF

Info

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
Application number
CS888116A
Other languages
Czech (cs)
Slovak (sk)
Other versions
CS811688A1 (en
Inventor
Peter Rndr Danko
Ema Rndr Jexova
Alojz Balogh
Lubica Rndr Bzduskova
Original Assignee
Danko Peter
Ema Rndr Jexova
Alojz Balogh
Lubica Rndr Bzduskova
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Danko Peter, Ema Rndr Jexova, Alojz Balogh, Lubica Rndr Bzduskova filed Critical Danko Peter
Priority to CS888116A priority Critical patent/CS271983B1/en
Publication of CS811688A1 publication Critical patent/CS811688A1/en
Publication of CS271983B1 publication Critical patent/CS271983B1/en

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, &quot; 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)

CS 271983 81 Elementárna analýza pře C12H23 NO : Vypočítané : 73,04 % C .11,75 % H 7,10 % N Stanovené : 73,11 % C 11,54 % H 7,06 % N 1H - NMR a IČ - spektrum ako v příklade i. Příklad 4 Do 250 ml trojhrdlej banky opatrenej raiešadlom, teplomerom a prikvapkávacím lievi-kom sa navážilo 3,8 g /0,1 molu/ NaBH4 a přidalo sa 150 ml pyridinu. Po rozpuštěníNaBH^ v pyridine sa k roztoku prikvapkalo 4,9 g /0,025 molu/ 2,2,6,6-tetrametyl-4--piperidylidénacetónu počas 1 h. Potom sa reakčná zmes miešala ešte 2 h pri teplote100 °C. Po skončení reakoie sa pri laboratórnej teplote přidal k reakčnej zmesi 5 %-nýroztok NaHCOg a po oddělení pyridínovej vrstvy sa vodná vrstva ešte extrahovala n-hexá-nom. Po vysušení spojených organických roztokov sa n-hexán oddestiloval za vákua, pyri-din za mierne nižšieho tlaku a surový produkt sa destiloval za zníženého tlaku s odbe-rom frakcie s teplotou varu 69 - 70,5 °C pri 100 Pa, z ktorej sa získal /2,2,6,6--tetrametyl-4-piperidyl/-2-propanón ako bezfarebná kvapalina. Elementárna analýza Vypočítané : 73,04 % C 11,75 % H 7,10 % N Stanovené : 72,87 % C 11,68 % H 7,06 % N 1H - NMR a IČ - spektrum ako v příklade l PREDMET VYNÁLEZU 1. /2,2,6,6-Tetrametyl-4-piperidyl/-2-propanón vzorca I 0CS 271983 81 Elemental analysis for C 12 H 23 NO: Calculated: 73.04% C, 11.75% H, 7.10% N, determined: 73.11% C 11.54% H 7.06% N 1H - NMR and IR - EXAMPLE 4 3.8 g (0.1 mol) of NaBH4 were weighed into a 250 ml three-necked flask equipped with a stirrer, thermometer and dropping funnel and 150 ml of pyridine was added. After dissolution of NaBH4 in pyridine, 4.9 g (0.025 mol) of 2,2,6,6-tetramethyl-4-piperidylideneacetone were added dropwise over 1 h. The reaction mixture was then stirred at 100 DEG C. for 2 h. After completion of the reaction, 5% NaHCO 3 solution was added to the reaction mixture at room temperature, and after separation of the pyridine layer, the aqueous layer was extracted with n-hexane. After drying the combined organic solutions, n-hexane was distilled off in vacuo, pyridine at slightly lower pressure, and the crude product was distilled under reduced pressure with fraction withdrawal at 69-70.5 ° C at 100 Pa from which 2,2,6,6-tetramethyl-4-piperidyl] -2-propanone was obtained as a colorless liquid. Elemental analysis Calculated: 73.04% C 11.75% H 7.10% N Found: 72.87% C 11.68% H 7.06% N 1 H-NMR and IR spectra as in Example 1 (2,2,6,6-Tetramethyl-4-piperidyl) -2-propanone of formula (I) 2. Sposob přípravy /2,2,6,6-tetrametyl-4-piperidyl/-2-propanónu podlá bodu 1, vyzna-čujúci sa tým, že 2,2,6,6-tetrametyl-4-piperidylidénacetón sa podrobí katalytickejhydrogenácii v atmosféře vodíka, v prostředí organického rozpúštadla, pri teplote20 až 120 °C, pri atmosférickou! tlaku alebo pri tlaku do 5 MPa, v přítomnosti hydro-genačného katalyzátore, počas 1 až 72 h. CS 271983 B12. A process for preparing 2,2,6,6-tetramethyl-4-piperidyl] -2-propanone according to claim 1, wherein the 2,2,6,6-tetramethyl-4-piperidylideneacetone is subjected to catalytic hydrogenation. in an atmosphere of hydrogen, in an organic solvent environment, at 20 to 120 ° C, at atmospheric! pressure or up to 5 MPa, in the presence of a hydrogenation catalyst, for 1 to 72 hours. CS 271983 B1 3. Sposob přípravy /2,2,6,6-tetrametyl-4-piperidyl/~2-propanónu podlá bodu 1, vyzna-čujúci sa tým, že sa na 2,2,6,6- tetrametyl-4-piperidylidénacetón posobí komplexnýmhydridom, v prostředí pyridinu, při teplote 20 až 100 °C, počas 3 až 8 h. I3. Preparation of (2,2,6,6-tetramethyl-4-piperidyl) -2-propanone according to claim 1, characterized in that the 2,2,6,6-tetramethyl-4-piperidylideneacetone is treated with with complex hydride, in pyridine medium, at 20 to 100 ° C, for 3 to 8 h
CS888116A 1988-12-08 1988-12-08 2,2,6,6-Tetramethyl-4-piperidyl] -2-propanone and its preparation CS271983B1 (en)

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)

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