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CH114106A - Process for the production of pure phenols from their bezyl ethers. - Google Patents

Process for the production of pure phenols from their bezyl ethers.

Info

Publication number
CH114106A
CH114106A CH114106DA CH114106A CH 114106 A CH114106 A CH 114106A CH 114106D A CH114106D A CH 114106DA CH 114106 A CH114106 A CH 114106A
Authority
CH
Switzerland
Prior art keywords
sep
ethers
production
bezyl
hydrogen
Prior art date
Application number
Other languages
German (de)
Inventor
Firma E Merck
Original Assignee
Merck Ag E
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 Merck Ag E filed Critical Merck Ag E
Publication of CH114106A publication Critical patent/CH114106A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D489/00—Heterocyclic compounds containing 4aH-8, 9 c- Iminoethano-phenanthro [4, 5-b, c, d] furan ring systems, e.g. derivatives of [4, 5-epoxy]-morphinan of the formula:
    • C07D489/02—Heterocyclic compounds containing 4aH-8, 9 c- Iminoethano-phenanthro [4, 5-b, c, d] furan ring systems, e.g. derivatives of [4, 5-epoxy]-morphinan of the formula: with oxygen atoms attached in positions 3 and 6, e.g. morphine, morphinone
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

  

      Verfahren    zur     Herstellung    reiner     Phenole    aus deren     Benzylätlier.       Es ist bekannt,     aliphatische    Äther mit  telst Wasserstoff in Gegenwart von Kataly  satoren zu spalten; ebenso ist es bekannt, dass  die     Phenoläther    eine analoge     Zersetzung    er  leiden. Bei     Phenolalkyläthern    tritt die Spal  tung     etwas    leichter ein     (vergleiche        Sabatier.     "Die Katalyse in der organischen Chemie",       1.91.1,        Seite    96).  



  Während nun aber bei der     bekannten          Ausführung    solcher Spaltungen durch kata  lytisehe     Hydrierung    es sich als notwendig  erwiesen hat, mehr oder weniger hohe Tem  peraturen anzuwenden, infolge welcher es  aber nicht zu vermeiden war, dass Zerset  zungsprodukte auftraten, welche die Endpro  dukte verunreinigten und     die        Ausbeute    her  absetzten, wurde die überraschende Beobach  tung gemacht, dass reine     Phenole    gewonnen  werden können durch die Verwendung eines  Edelmetall-,

   zum Beispiel eines Palladium  katalysators bei     gewöhnlicher        Temperatur     zur katalytischen Spaltung der betreffende       Atlier    des     Benzylalkohols    der allgemeinen  Formel  
EMI0001.0024     
    Bei dieser katalytischen Hydrierung ent  steht das entsprechende Phenol einerseits und  ein     Kohlenwasserstoff    anderseits.  



  Das leichte Abspalten der     Benzylgruppe     ohne Erhitzung macht das Verfahren beson  ders wertvoll für den Fall, dass eine freie       Phenolgruppe    zeitweise blockiert     (benzyliert)     werden soll.  



  <I>Beispiel Z:</I>  25     gr        Benzylmorpliinchlorhydrat    werden  in Wasser     suspendiert    und bei Gegenwart  von     Palladiumkohle    mit Wasserstoff ge  schüttelt, wobei     92        Mol.    Wasserstoff absor  biert werden. Nach dem     Abfiltrieren    wird  alkalisch gemacht und     ausgeäthert.    Der  Ätherrückstand besteht aus     Toluol.    Das     al-          ka.lische    Filtrat wird mit     Ammonkarbonat     versetzt, wobei sich     Dihydromorphin    ab  scheidet.

   Ausbeute, fast     quantitativ,       
EMI0002.0001     
  
    <I>Beispiel <SEP> 2:</I>
<tb>  10 <SEP> gr <SEP> Phenylbenzyläthar <SEP> werden <SEP> bei <SEP> Ge  genwart <SEP> von <SEP> Palladiumkohle <SEP> in <SEP> Eisessig  lösung <SEP> mit <SEP> Wasserstoff <SEP> behandelt, <SEP> wobei
<tb>  1. <SEP> Mol. <SEP> Wasserstoff <SEP> aufgenommen <SEP> wird, <SEP> un  ter <SEP> Bildung <SEP> von <SEP> Toluol <SEP> und <SEP> Phenol. <SEP> Aus  beute <SEP> quantitativ.
<tb>  



  <I>Beispiel <SEP> 3:</I>
<tb>  10 <SEP> gr <SEP> Guaja.kphen-#Tläther <SEP> werden <SEP> mit
<tb>  Wasserstoff <SEP> bei <SEP> Gegen-,vart <SEP> von <SEP> Palladinm  kohle <SEP> geschüttelt. <SEP> Auch <SEP> hier <SEP> findet <SEP> die <SEP> Auf  nahme <SEP> von <SEP> 1 <SEP> Mol. <SEP> Wasserstoff <SEP> statt. <SEP> Die
<tb>  Ausbeute <SEP> an <SEP> Guajahol <SEP> und <SEP> Toluol <SEP> ist <SEP> fast
<tb>  quantitativ.



      Process for the production of pure phenols from their benzyl ethers. It is known that aliphatic ethers can be split using hydrogen in the presence of catalysts; It is also known that the phenol ethers suffer an analogous decomposition. With phenol alkyl ethers, the cleavage occurs somewhat more easily (see Sabatier. "Catalysis in organic chemistry", 1.91.1, page 96).



  But while in the known execution of such cleavages by catalytic hydrogenation it has been found necessary to use more or less high temperatures, as a result of which it could not be avoided that decomposition products occurred, which contaminated the end products and the yield the surprising observation was made that pure phenols can be obtained by using a noble metal,

   for example a palladium catalyst at ordinary temperature for the catalytic cleavage of the relevant atlier of the benzyl alcohol of the general formula
EMI0001.0024
    In this catalytic hydrogenation there is the corresponding phenol on the one hand and a hydrocarbon on the other.



  The fact that the benzyl group is easily split off without heating makes the process particularly valuable in the event that a free phenol group is to be temporarily blocked (benzylated).



  <I> Example Z: </I> 25 g of Benzylmorpliinchlorhydrat are suspended in water and shaken with hydrogen in the presence of palladium-carbon, with 92 mol of hydrogen being absorbed. After filtering off, it is made alkaline and etherified. The ether residue consists of toluene. The alkaline filtrate is mixed with ammonium carbonate, with dihydromorphine separating out.

   Yield, almost quantitative,
EMI0002.0001
  
    <I> Example <SEP> 2: </I>
<tb> 10 <SEP> gr <SEP> Phenylbenzyläthar <SEP> are <SEP> with <SEP> in the presence of <SEP> palladium carbon <SEP> in <SEP> glacial acetic acid solution <SEP> with <SEP> hydrogen <SEP> treated, <SEP> where
<tb> 1. <SEP> Mol. <SEP> hydrogen <SEP> is absorbed <SEP>, <SEP> under <SEP> formation <SEP> of <SEP> toluene <SEP> and <SEP> phenol. <SEP> From booty <SEP> quantitative.
<tb>



  <I> Example <SEP> 3: </I>
<tb> 10 <SEP> gr <SEP> Guaja.kphen- # Tläther <SEP> are <SEP> with
<tb> Hydrogen <SEP> at <SEP> counter-, vart <SEP> from <SEP> Palladium carbon <SEP> shaken. <SEP> <SEP> also <SEP> here <SEP> the <SEP> recording <SEP> of <SEP> 1 <SEP> mol. <SEP> hydrogen <SEP> takes place. <SEP> The
<tb> Yield <SEP> of <SEP> guajahol <SEP> and <SEP> toluene <SEP> is <SEP> almost
<tb> quantitative.

Claims (1)

EMI0002.0002 PATENTANSPRUCH: <tb> Verfahren <SEP> zur <SEP> Herstellung <SEP> reiner <SEP> Phenole <tb> dureli <SEP> katalytiseli <SEP> hydrierende <SEP> Spaltung <SEP> von <tb> Phenolbenzt-läthern <SEP> dadurch <SEP> gekennzeichnet, <tb> dass <SEP> die <SEP> l@atalytiseh-hydrieren <SEP> de <SEP> Spaltung <SEP> der <tb> Phenolbeiiz-;l@ither <SEP> mittelst <SEP> eines <SEP> Edelmetall Izatalysators <SEP> bei <SEP> gewöhnlicher <SEP> Temperatur <tb> vorgenommen <SEP> wird. <tb> <B>UNTERANSPRUCH:</B> <tb> Verfahren <SEP> nach <SEP> Patentansprueh, <SEP> dadureh <tb> gekennzeichnet., <SEP> dass <SEP> als <SEP> Edelmetalllatalysa tor <SEP> ein <SEP> @alladiumhatalvatur <SEP> verwendet <SEP> -wird. EMI0002.0002 PATENT CLAIM: <tb> Process <SEP> for <SEP> production of <SEP> pure <SEP> phenols <tb> dureli <SEP> katalytiseli <SEP> hydrogenating <SEP> cleavage <SEP> of <tb> Phenolbenz-läthern <SEP> marked with <SEP>, <tb> that <SEP> the <SEP> l @ atalytiseh-hydrogenate <SEP> de <SEP> cleavage <SEP> the <tb> Phenolic acid; l @ ither <SEP> by means of <SEP> a <SEP> precious metal I catalyst <SEP> at <SEP> normal <SEP> temperature <tb> is made <SEP>. <tb> <B> SUBClaim: </B> <tb> Method <SEP> according to <SEP> patent claim, <SEP> dadureh <tb>., <SEP> that <SEP> <SEP> is used as <SEP> precious metal catalyst <SEP> and <SEP> @alladiumhatalvatur <SEP> <SEP>.
CH114106D 1923-11-26 1924-11-05 Process for the production of pure phenols from their bezyl ethers. CH114106A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEM83152D DE407487C (en) 1923-11-26 1923-11-26 Process for the preparation of phenols

Publications (1)

Publication Number Publication Date
CH114106A true CH114106A (en) 1926-03-01

Family

ID=7319532

Family Applications (1)

Application Number Title Priority Date Filing Date
CH114106D CH114106A (en) 1923-11-26 1924-11-05 Process for the production of pure phenols from their bezyl ethers.

Country Status (2)

Country Link
CH (1) CH114106A (en)
DE (1) DE407487C (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1081017B (en) * 1954-12-16 1960-05-05 Geigy Ag J R Process for the preparation of therapeutically effective 4-substituted 1, 2-diphenyl-3, 5-dioxy-pyrazolidines
US4168388A (en) * 1978-03-23 1979-09-18 Eli Lilly And Company Trifluoromethylphenyl benzyl ethers

Also Published As

Publication number Publication date
DE407487C (en) 1924-12-15

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