CH475242A - Process for the production of aromatic ethers - Google Patents

Process for the production of aromatic ethers

Info

Publication number
CH475242A
CH475242A CH1076965A CH1076965A CH475242A CH 475242 A CH475242 A CH 475242A CH 1076965 A CH1076965 A CH 1076965A CH 1076965 A CH1076965 A CH 1076965A CH 475242 A CH475242 A CH 475242A
Authority
CH
Switzerland
Prior art keywords
sep
propoxy
benzophenone
phenyl
hydroxy
Prior art date
Application number
CH1076965A
Other languages
German (de)
Inventor
Albrecht Dr Edenhofer
Henri Dr Ramuz
Hans Dr Spiegelberg
Original Assignee
Hoffmann La Roche
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
Priority to NL133317D priority Critical patent/NL133317C/xx
Application filed by Hoffmann La Roche filed Critical Hoffmann La Roche
Priority to CH11669A priority patent/CH474513A/en
Priority to CH11769A priority patent/CH474514A/en
Priority to CH11569A priority patent/CH474512A/de
Priority to DE19661695146 priority patent/DE1695146A1/en
Priority to CH1076965A priority patent/CH475242A/en
Priority to CH11469A priority patent/CH474515A/en
Priority to CH11369A priority patent/CH474511A/de
Priority to DE19661695148 priority patent/DE1695148A1/en
Priority to US566214A priority patent/US3528976A/en
Priority to GB33016/66A priority patent/GB1085106A/en
Priority to IL26198A priority patent/IL26198A/en
Priority to BE684600D priority patent/BE684600A/xx
Priority to NL6610566A priority patent/NL6610566A/xx
Priority to BR181621/66A priority patent/BR6681621D0/en
Priority to FR71191A priority patent/FR6263M/fr
Priority to GB34028/66A priority patent/GB1111917A/en
Priority to ES0329683A priority patent/ES329683A1/en
Priority to SE10328/66A priority patent/SE322775B/xx
Priority to NO164109A priority patent/NO121212B/no
Priority to FR111533A priority patent/FR1530783A/en
Priority to CH895667A priority patent/CH479603A/en
Publication of CH475242A publication Critical patent/CH475242A/en
Priority to US39505A priority patent/US3706755A/en
Priority to US00245610A priority patent/US3812129A/en
Priority to US00245609A priority patent/US3816434A/en

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    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
    • C07D203/10—Radicals substituted by singly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • C07D211/52—Oxygen atoms attached in position 4 having an aryl radical as the second substituent in position 4
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/70—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D211/82—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/04—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
    • C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/108—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
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    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/59—Hydrogenated pyridine rings

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  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

  

      Verfahren    zur Herstellung von aromatischen     Äthern            Die    vorliegende Erfindung betrifft ein Verfahren zur  Herstellung von aromatischen     Äthern    der Formel  
EMI0001.0005     
    oder von in den aromatischen Ringen A und B durch  eine oder mehrere     Alkyl-,        Alkoxy-,    Halogen-,     Cyano-,          Carboxy-,        Nitro-,        Amino-    oder     Trifluormethylgruppen     substituierten Derivaten davon,

   in welcher Formel     R1     einen über Stickstoff mit der     Methylengruppe    verbun  denen     ganz    oder teilweise hydrierten, gegebenenfalls       hydroxy-substituierten        Pyridin-    oder     Pyrazinrest    darstellt,  der in     p-Stellung    mit einem gegebenenfalls durch eine  oder mehrere     Alkyl-,        Alkoxy-,    Halogen- oder     Trifluor-          methylgruppen    substituierten     Phenylrest    verknüpft ist,

    X eine     Carbonyl-    oder     Hydroxymethylengruppe    bedeu  tet und Y eine     Carbonyl-,        Methylen-    oder     Hydroxyme-          thylengruppe    bezeichnet, sowie von     Ketalen    und Säure  additionssalzen dieser Verbindungen.  



  Die vorstehend     erwähnten        Alkylgruppen    sind vor  zugsweise niedere     Alkylgruppen    mit bis. zu 5 Kohlen  stoffatomen, wie     Methyl,    Äthyl.     Isopropyl.    Auch die       Alkoxygruppen    enthalten vorzugsweise bis zu 5 Kohlen  stoffatomen, wie     Methoxy,        Äthoxy.    Von den Halogen  atomen sind Fluor, Chlor und Brom bevorzugt.

   Vorhan  dene     Oxogruppen    können durch niedere     Alkanole    oder  Glykole, beispielsweise durch Methylalkohol oder     Äthy-          lenglykol        ketalisiert    sein.  



  Die     Pyridin-    und     Pyrazinreste    sind ganz oder teil  weise hydriert.     Geeignete    Reste sind z. B. der     Dihydro-          pyridin-,        Tetrahydropyridin-;        Piperidin-,        Dihydropyra-          zin-,        Tetrahydropyrazin-    und     Piperazinrest.     



  Das erfindungsgemässe Verfahren ist dadurch ge  kennzeichnet, dass man eine Verbindung der Formel  
EMI0001.0056     
    oder ein in den aromatischen Ringen A und B, wie oben  angegeben, substituiertes Derivat davon, wobei X eine       Carbonyl-    oder     Hydroxymethylengruppe    bezeichnet,     R,     Halogen oder     Alkyl-    bzw.

       Arylsulfonyloxy    bedeutet oder  X und     R2    zusammen mit der endständigen     Methylen-          gruppe    den Rest
EMI0001.0065  
   darstellen,  oder, falls X und/oder Y eine     Carbonylgruppe    be  zeichnen, ein     Ketal    oder     Diketal    dieser Verbindung mit  einer Verbindung der Formel       H-R,        III     umsetzt.  



  Bevorzugt sind Verbindungen der Formel I, in der X  eine     Hydroxymethylengruppe    und Y eine     Carbonyl-          gruppe    darstellt.  



  Verbindungen der Formel    
EMI0002.0001     
    oder der Formel  
EMI0002.0002     
    in denen die gestrichelten Bindungen hydriert und der  aromatische Ring A und/ oder der     Phenylrest    durch Ha  logen     substituiert    sein können, nehmen eine Vorzugs  stellung ein. Folgende durch die Formeln IV und V cha  rakterisierte Verbindungen sind     z.B.    besonders wertvoll.  



       4-[3-(3,6-Dihydro-4-phenyl        -1(2H)pyridyl)-2-hydroxy-          -propoxy]-benzophenon          4-[3-(3,6-Dihydro-4-phenyl        -1(2H)pyridyl)-2-hydroxy-          -propoxy]-4'-chlor-benzophenon          4-[3-(4-(p-Chlor-phenyl)-3,6-dihydro-1(2H)pyridyl)-2-          -hydroxy-propoxy]-benzophenon          4-[3-(4-(p-Chlor-phenyl)-3,6-dihydro-1(2H)pyridyl)-2-          -hydroxy-propoxy]-4'-chlor-benzophenon          4-[3-(3,6-Dihydro-4-phenyl        -1(2H)pyridyl)

  -2-hydroxy-          -propoxy]-4'-fluor-benzophenon          4-[3-(4-(p-Fluor-phenyl)-3,6-dihydro        -1(2H)pyridyl)-2-          -hydroxy-propoxy]-4'-fluor-benzophenon          4-[3-(4-(p-Fluor-phenyl)-3,6-dihydro        -1(2H)pyridyl)-2-          -hydroxy-propoxy]-4'-chlor-benzophenon          4-[3-(4-(p-Chlor-phenyl)-3,6-dihydro-1(2H)pyridyl)-2-          -hydroxy-propoxy]-4'-fluor-benzophenon     4-[     3-(4-(p-Fluor-phenyl)-3,6-dihydro-1(2H)pyridyl)-2-          -hydroxy-propoxy]-4'-brom-benzophenon     4-[     3-(4-(p-Chlor-phenyl)

  -3.6-dihydro-1(2H)pyridyl)-2-          -hydroxy-propoxy]-4'-brom-benzophenon          4-[3-(4-(p-Chlor-phenyl)    -1 -     piperazinyl)    - 2-     hydroxy-          -propoxy]-benzophenon          4-[3-(4-(p-Chlor-phenyl)    -1-     piperazinyl)    - 2     -hydroxy-          -propoxy]-4'-fluor-benzophenon.     Die als Ausgangsverbindungen eingesetzten gegebe  nenfalls ringsubstituierten     Diphenylmethanderivate    der  Formel Il können     z.B.    wie folgt hergestellt werden:

    Verbindungen der Formel il. in der X eine     Hydroxy-          methylengruppe    und Y eine     Carbonylgruppe    darstellen,  lassen sich beispielsweise in der Weise herstellen, dass  man ein gegebenenfalls substituiertes     Benzoylhalogenid     mit einem gegebenenfalls substituierten     Anisol    nach     Frie-          del-Crafts,        d.h.    mit Hilfe einer     Lewis-Säure,    wie beispiels  weise Aluminiumchlorid, Zinkchlorid,     Bortrifluorid        u.a.,     umsetzt,

       entalkyliert    und dass gebildete gegebenenfalls       substituierte        4-Hydroxybenzophenon    vorzugsweise mit  einem Überschuss eines     Epihalogenhydrins,    insbesondere  mit     Epichlorhydrin    tunlich in Gegenwart einer katalyti  schen wirksamen Menge einer organischen Base, wie       z.B.        Piperidin    bei erhöhter Temperatur, bevorzugt     bei     ca. 100 C umsetzt.  



  Ein gegebenenfalls substituiertes     4-Hydroxy-benzo-          phenon    kann ferner auch dadurch gewonnen werden,    dass man eine     4-Alkoxy-benzoesäure    mit einem gege  benenfalls substituierten Benzol in Gegenwart von Poly  phosphorsäure kondensiert und     entalkyliert.     



  Ein gegebenenfalls substituiertes     4-Hydroxybenzo-          phenon    wird bevorzugt in der Weise hergestellt, dass  man einen gegebenenfalls substituierten     Benzoesäure-          phenylester    nach Fries umlagert.  



  Verbindungen der Formel     II,    in der X und Y eine       Hydroxymethylengruppe    darstellen, lassen sich beispiels  weise in der Weise herstellen, dass man ein gegebenen  falls substituiertes     4-Hydroxy-benzophenon    vor oder  nach der Einführung der Seitenkette mit einem gemisch  ten     Metallhydrid,        z.B.    mit     Natriumborhydrid    oder     Li-          thiumaluminiumhydrid    reduziert,

   oder dass man einen  gegebenenfalls substituierten     Benzaldehyd    mit     p-Alkoxy-          brombenzol    mit Hilfe einer     Grignard-Reaktion    in das  entsprechende     4-Alkoxy-benzhydrol    überführt,     entalky-          liert    und mit einer Seitenkette verknüpft.  



  Verbindungen der Formel     II,    in der X eine     Hydroxy-          methylengruppe    und Y eine     Methylengruppe    darstellen,  lassen sich beispielsweise in der Weise herstellen, dass  man ein gegebenenfalls substituiertes     4-Hydroxy-benzo-          phenon    nach     Wolff-Kishner    -     d.h.    nach Überführung  in ein     Hydrazon,

          z.B.    in Gegenwart eines     Alkalialkoho-          lates    bei erhöhter Temperatur - oder nach     Clemmensen     -     d.h.        z.B.    mit Hilfe von amalgamiertem Zink in Gegen  wart von Salzsäure - reduziert und wie vorstehend be  schrieben, mit     Epichlorhydrin    umsetzt.  



  Verbindungen der Formel     1I,    in der X eine     Hydroxy-          methylengruppe    und Y eine     Carbonylgruppe    darstellen,  können mit den üblichen Oxidationsmitteln     z.B.    mit Ka  liumpermanganat oder mit     Natriumdichromat    zu Verbin  dungen der Formel     II,    in der X und Y eine     Carbonyl-          gruppe    bedeuten, oxidiert werden.  



  Verbindungen der Formel     1I,    in der X eine     Hydroxy-          methylengruppe    und Y eine     Methylengruppe    darstellen,  können mit einem Gemisch von     Dimethylsulfoxid    und       Essigsäureanhydrid    zu Verbindungen der Formel     II,    in  der X eine     Carbonylgruppe    und Y eine     Methylengruppe     bedeuten, oxidiert werden.  



  Die gegebenenfalls substituierten Verbindungen der  Formel     1I,    in der R, Halogen oder einen     Alkylsulfonyl-          oder        Arylsulfonyl-oxyrest,    insbesondere den     Tosyloxyrest     darstellt, können in an sich bekannter Weise zu einem       Oxiran    umgesetzt werden.  



  Verbindungen der Formel     III    sind auf üblichem We  ge erhältlich.      Die Umsetzung von Verbindungen der Formel     II    mit  Verbindungen der Formel     III-    erfolgt     zweckmässig    bei  einer Temperatur zwischen der Raumtemperatur und  der Siedetemperatur des Reaktionsgemisches, insbeson  dere bei etwa 70-100 C.

   Es ist zweckmässig, die Reak  tion in einem Lösungsmittel,     z.B.    in einem     Alkanol    wie  Methanol, Äthanol oder     Isopropanol,    oder in einem     cy-          elischen    Äther, wie     Tetrahydrofuran,        Dioxan    oder     Di-          methylsulfoxid,    durchzuführen.  



  Verbindungen der Formel     II,    in denen     R2    Halogen  oder     Alkylsulfonyloxy-    oder     Arylsulfonyloxy    .[insbeson  dere     Mesyloxy-    oder     Tosyloxy]    bedeutet, werden vorzugs  weise in Gegenwart eines säurebindenden Mittels mit  Verbindungen der Formel     III    umgesetzt. Verbindungen  der Formel     1I,    in der     R2    mit der     Hydroxylgruppe    des  Restes X' eine Sauerstoffbrücke bildet, können direkt  mit Verbindungen der Formel     III    umgesetzt werden.  



  Die erhaltenen Verbindungen der Formel I, in der X  und/oder Y eine     Carbonylgruppe    darstellen, können in  an sich bekannter Weise,     z.B.    durch Einwirken niederer       Alkanole    oder Glykole,     insbesondere    durch Methylalko  hol oder     Äthylenglykol        ketalisiert    werden.  



  Die erhaltenen Basen der Formel I bilden Salze so  wohl mit anorganischen als auch mit organischen Säuren,       z.B.    mit     Halogenwasserstoffsäure,    wie Chlorwasserstoff  säure,     Bromwasserstoffsäure,        Jodwasserstoffsäure,    mit  anderen Mineralsäuren, wie Schwefelsäure, Phosphor  säure, Salpetersäure, sowie mit organischen Säuren, wie  Weinsäure,     Citronensäure,        Oxalsäure,        Kampfersulfo-          säure,        Äthansulfosäure,        Toluolsulfosäure,        Salicylsäure,          Ascorbinsäure,

          Maleinsäure,    Mandelsäure usw. Bevor  zugte     Salze    sind. die     Hydrohalogenide,    insbesondere die  Hydrochloride. Die     Säureadditionssalze    werden vorzugs  weise in einem geeigneten     Lösungsmittel    wie Äthanol  durch Behandeln der freien Base mit der entsprechenden  nicht wässerigen Säure hergestellt.  



  Die erfindungsgemäss erhältlichen Verbindungen der  Formel I, deren     Ketale,    und     Säureadditionssalze    zeichnen  sich durch vielfältige Wirkungen auf das Nervensystem,  insbesondere durch eine starke     psychosedierende    Wir  kung aus. Besonders zu erwähnen ist die     reserpinartige          hypotensive    und sedative Wirkung von     4-.[3-(3,6-Dihydro-          4-phenyl-1(2H)pyridyl)-2-hydroxy-propoxy]-benzophenon     sowie von     4-.[3-(4-(p-Fluorphenyl)-3,6-dihydro-1(2H)py-          ridyl)-2-hydroxypropoxy]-4'-chlor-benzophenon.     



  Die Verbindungen der Formel I können als Heilmit  tel in Form pharmazeutischer Präparate Verwendung  finden, welche sie oder ihre Salze in Mischung mit einem  für die     enterale    oder     parenterale    Applikation geeigne  ten pharmazeutischen, organischen oder anorganischen       inerten    Trägermaterial enthalten. Die pharmazeutischen  Präparate können in fester Form oder in flüssiger Form  vorliegen. Gegebenenfalls können sie auch noch andere  therapeutisch wertvolle Stoffe enthalten.

      <I>Beispiel 1</I>  12,7 g     4-[2,3-Epoxy-propoxy]-benzophenon    werden in  50 ml     Dioxan    gelöst und nach Zugabe von 8,0 g     4-Phe-          nyl-1,2,3,6-tetrahydro-pyridin    5 Stunden unter     Rückfluss-          bedingungen    erhitzt. Das Lösungsmittel wird     anschlies-          send    unter vermindertem Druck abgedampft.

   Das zu  rückbleibende     4-[3-(3,6-Dihydro-4-phenyl-1(2H)        pyridyl)-          -2-hydroxy-propoxy]-benzophenon    wird in 20 ml     Ätha-          nol    gelöst und mit     äthanolischer    Salzsäure kongosaurer  gestellt.

   Das sich kristallin abscheidende Hydrochlorid  schmilzt nach dem     Umkristallisieren    aus Äthanol bei     192-          194 C.       In analoger Weise erhält man bei Einsatz von:       4-[2,3-Epoxy-propoxy]-4'-methoxy-benzophenon    und       4-Phenyl-1,2,3,6-tetrahydro-pyridin     das     4-[3-(3,6-Dihydro-4-phenyl-1(2H)pyridyl)-2-hy-          droxy-propoxy]        4'-methoxy-benzophenon-hydrochlorid,          Fp:        185-18611C.     



       4-[2,3-Epoxy-propoxy]-3-methyl-benzophenon    und 4  -Phenyl-1,2,3,6-tetrahydro-pyridin  das     4-[3-(3,6-Dihydro-4-phenyl-1(2H)pyridyl)-2-hy-          droxy-propoxy]-3-methyl-benzophenon,        Fp:    200-203 C.

         4-(2,3-Epoxy-propoxy)-4'-methyl-benzophenon    und       4-Phenyl-1,2,3,6-tetrahydro-pyridin     das     4-[3-(3,6-Dihydro-4-phenyl-1(2H)pyridyl)-2-hy-          droxy-propoxy]    -     4'-        methyl-        benzophenon    -     hydrochlorid,          Fp:        209-2101)C.     



       4-[2,3-Epoxy-propoxy]-benzophenon    und     4-(p-Fluor-          phenyl)-1    2 3     6-tetrahydro-pyridin     das     4-[3-(4-(p-Fluor-phenyl)-3,6-dihydro-1(2H)pyri-          dyl)-2-hydroxy-propoxy]-benzophenon-hydrochlorid,        Fp:     160 C.  



       4-(2,3-Epoxy-propoxy)-4'-chlor-benzophenon    und 4  -(p-Chlor-phenyl)-1,2,3,6-tetrahydro-pyridin  das     4-[3-(4-(p-Chlor-phenyl)-3,6-dihydro-1(2H)pyri-          dyl)    - 2-     hyd        roxy-propoxy]    - 4' -     chlor-benzophenon-hydro-          chlorid,        Fp:

      212 C     (Zers.)          4-(2,3-Epoxy-propoxy)-3',4'-dichlorbenzophenon    und       4-Phenyl-1,2,3,6-tetrahydro-pyridin     das 4 - [3 -     (3,6-Dihydro-4-phenyl-1(2H)pyridyl)-2-hy-          droxy-propoxy]    -     3',4'-dichlor-benzophenon-hydrochlorid,          Fp:

      206 C     (Zers.)          4-(2,3-Epoxy-propoxy)-4'-nitrobenzophenon    und     4-          -Phenyl-1,2,3,6-tetrahydro-pyridin     das 4 - [3 -     (3,6-Dihydro-4-phenyl-1(2H)pyridyl)-2-hy-          droxy-propoxy]-4'-nitro-benzophenon-hydrochlorid,        Fp:     201-203 C.  



       4-(2,3-Epoxy-propoxy)-4'-brom-benzophenon    und     4-          Phenyl-1,2,3,6-tetrahydro-pyridin     das     4-[3-(3,6-Dihydro-4-phenyl-1(2H-pyridyl)-2-hy-          droxy-propoxy]-4'-brom-benzophenon-hydrochlorid,        Fp:     210-212 C.  



       4-(2,3-Epoxy-propoxy)-4'-fluor-benzophenon    und     4-          -Phenyl-1,2,3,6-tetrahydro-pyridin     das 4 - [3 - (3,6-     Dihydro-4-phenyl-1(2H)pyridyl-2-hy-          droxy-propoxy]-4'-fluor-benzophenon-hydrochlorid,        Fp:     198-200 C.  



       4-(2,3-Epoxy-propoxy)-4'-fluor-benzophenon    und     4-          -(p-Fluor-phenyl)-1.2,3,6-tetrahydro-pyridin     das 4 - [3 - (4-     p-Fluor-phenyl)-3,6-dihydro-1(2H)pyri-          dyl)    - 2 -     hydroxy    -     propoxy]    -     4'-chlor-benzophenon-hydro-          chlorid,        Fp:    192-193 C.  



       4-(2,3-Epoxy-propoxy)-4'-chlor-benzophenon    und 4  -(p-Fluor-piienyl)-I,2,3,6-tetrahydro-pyridin  das 4 - [3 - (4-     p-Fluor-phenyl)-3,6-dihydro-1(2H)pyri-          dyl)    - 2 -     hydroxy-propoxy]    - 4'-     chlor-benzophenon-hydro-          chlorid,        Fp:        203-204. C.     



       4-(2,3-Epoxy-propoxy)-4'-ciilor-benzophenon    und 4  -Hydroxy-4-(p-trifluormethyl-phenyl)-piperidin  das     4-[3-(4-Hydroxy-4-(p-trifluormethyl-phenyl)-1-pi-          peridyl)    - 2-     hydroxy    -     propoxy]-4'-chlor-benzophenon-hy-          drochlorid,        Fp:    222-223 C.  



       4-[2,3-Epoxy-propoxy]-4'-chlor-benzophenon    und     4-          -Phenyl-1,2.3,6-tetrahydro-pyridin     das 4 - [3 -     (3,6-Dihydro-4-phenyl-1(2H)pyridyl)-2-hy-          droxy-propoxy]-4'-chlor-benzophenon-hydrochlorid,        Fp:     202 C (Zerr.).  



       4-[2,3-Epoxy-propoxy]-benzophenon    und     4-(p-Chlor-          -phenyl)-1,2,3,6-tetrahydro-pyridin         das     4-[3-(4-(p-Chlor-phenyl)-3,6-dihydro-1(2H)pyri-          dyl)-2-hydroxy-propoxy]-benzophenon-hydrochlorid,        Fp:     217-218 C.  



       4-(2,3-Epoxy-propoxy)    -     4'-trifluor    -     methyl    -     benzophe-          non    und     4-Phenyl-1,2,3,6-tetrahydro-pyridin     das     4-[3-(3,6-Dihydro-4-phenyl-1(2H)pyridyl)-2-hy-          droxy    -     propoxy]    -4' -     trifluormethyl-        benzophenon-hydro-          chlorid,        Fp:    231 C     (Zers.)          4-(2,3-Epoxy-propoxy)-3'-chlor-benzophenon    und     4-          -Phenyl-1;

  2.3,6-tetrahydro-pyridin     das     4-[3-(3,6-Dihydro-4-phenyl-1(2H)pyridyl)-2-hy-          droxy-propoxy]-3'-chlor-benzophenon-hydrochlorid,        Fp:     175 C     (Zers.)          4-(2,3-Epoxy-propoxy)-benzophenon    und     4-Phenyl-4-          -hydroxy-piperidin     das     4-[3-(4-Hydroxy-4-phenyl-piperidyl)-2-hydroxy-          -propoxy]-benzophenon-hydrochlorid,        Fp:    184 C.

         4-(2,3-Epoxy-propoxy)-2',4'-dichlor-benzophenon    und       4-Phenyl-1,2,3,6-tetrahydro-pyridin     das     4-[3-(3,6-Dihydro-4-phenyl-1(2H)pyridyl)-2-hy-          droxy-propoxyl-2',4'-dichlor-benzophenon,        Fp:        132-          134 C.     



  4 - (2,3 -     Epoxy-propoxy)    -3 '-     trifluormethyl-benzophe-          non    und     4-(p-Chlor-phenyl)-1,2,3,6-tetrahydro-pyridin     das 4-[3-(3,6-Dihydro-4-(p-chlor-phenyl)-1(2H)pyri       dyl)-2-hydroxy-propoxy]-3'-trifluormethyl-benzophenon-          -hydrochlorid,        Fp:    130-134 C.

         4-(2,3-Epoxy-propoxy)-4'-fluor-benzophenon    und     4-          -(p-Chlor-phenyl)-1,2,3,6-tetrahydro-pyridin     das     4-[3-(4-(p-Chlor-phenyl)-3,6-dihydro        -1(2H)pyri-          dyl)    - 2 -     hydroxy    -     propoxy]    -4'-     fluor-benzophenon-hydro-          chlorid,        Fp:    204-206 C.  



       4-(2,3-Epoxy-propoxy)-4'-brom-benzophenon    und     4-          -(p-Fluor-phenyl)-1,2,3,6-tetrahydro-pyridin     das 4 - [3 -     (4-(p-Fluor-phenyl)-3,6-dihydro-1(2H)pyri-          dyl)    - 2-     hydroxy-propoxy]        -4-brom-        benzophenon-hydro-          chlorid,        Fp:    233 C.  



       4-(2,3-Epoxy-propoxy)-4'-brom-benzophenon    und     4-          -(p-Chlor-phenyl)-1,2,3,6-tetrahydro-pyridin     das 4 -.[3 - (4     -p-Chlor-phenyl)-3,6-dihydro-1(2H)pyri-          dyl)        -2-hydroxy    -     propoxyl        -4'-brom-benzophenon-hydro-          chlorid,        Fp:    217 C.  



       4-(2,3-Epoxy-propoxy)-diphenylmethan    und     4-Phe-          nyl-1,2,3,6-tetrahydro-pyridin     das a - [     (p-Benzyl-phenyloxy)-methyl]-3,6-dihydro-4-          -phenyl-1(2H)pyridin-äthanol-hydrochlorid,        Fp:    191 C       (Zers.)     Das als Ausgangsverbindung eingesetzte     4-.[2,3-Epo-          xy-propoxy]-benzophenon    ist eine bekannte Verbindung.

    Das     442,3-Epoxy-propoxyl    - 3     -methyl-benzophenon     kann beispielsweise wie folgt hergestellt werden:  10,6 g     4-Hydroxy-3-methyl-benzophenon,    50 g     Epi-          chlorhydrin    und 3 Tropfen     Piperidin    werden 12 Stun  den auf dem Dampfbad erhitzt. Die Reaktionslösung  wird unter vermindertem Druck vom überschüssigen       Epichlorhydrin    befreit. Der obige Rückstand wird in  20 ml Chloroform gelöst und nach Zugabe von 20 ml  3 n Natronlauge 1 Stunde bei Raumtemperatur geschüt  telt. Die organische Phase wird abgetrennt, mit Wasser  gewaschen, über     Calciumchlorid    getrocknet und zur  Trockne eingedampft.

   Das zurückbleibende ölige rohe       4-[2,3-Epoxy-propoxy]-3-methyl-benzophenon    kristalli  siert nach langem Stehen. Die Verbindung kann ohne  weiterer Reinigung weiterverarbeitet werden. Die aus  wässerigem Äthylalkohol umkristallisierte Verbindung    schmilzt bei 56-58 C. Das in analoger Weise aus     4-Hy-          droxy-4'-methoxy-benzophenon    hergestellte     4-[2,3-Epo-          xy-propoxy]-4'-methoxy-benzophenon    schmilzt bei     123-          124 C.     



  <I>Beispiel 2</I>  In analoger Weise, wie im Beispiel 1 angegeben, er  hält man bei Einsatz von:       p-[p-2,3-Epoxy-propoxy)-benzoyl]-benzonitril    und     4-          -(p-Fluorphenyl)-1,2,3,6-tetrahydro-pyridin     das     rac.        p-{p-[3- < 4-(p-Fluorphenyl)-3,6-dihydro-1(2H)          pyridyl>-2-hydroxy-propoxy]-benzoyl}-benzonitril,        Smp.     130-133 C (aus Alkohol).  



  Das hierfür benötigte     p-[p-(2,3-Epoxy-propoxy)-ben-          zoyl]-benzonitril    kann wie folgt hergestellt werden:  Eine Mischung von     4-Brom-4'-methoxy-benzophe-          non,    22 g     Kupfer(I)cyanid    und 400 ml     Dimethylformamid     werden unter Rühren und     Begasen    mit Stickstoff 15 Stun  den unter     Rückflussbedingungen    erhitzt. Anschliessend  wird das Lösungsmittel unter vermindertem Druck ver  dampft.

   Der Rückstand wird mehrmals mit heissem  Chloroform extrahiert, die     Chloroformextrakte    werden  nach dem Trocknen über     Calciumchlorid    zur Trockne  eingeengt. Der Rückstand wird aus Methanol umkristal  lisiert. Das reine     p-(p-Anisoyl)-benzonitril    schmilzt bei  133-134 C.  



  13,5 g     p-(p-Anisoyl)-benzonitril    und 40 g     Pyridinhydro-          chlorid    werden gut vermischt und 30 Minuten auf 220 C  erhitzt. Das heisse Gemisch wird in Wasser gegossen,  die ausfallenden Kristalle werden     abfiltriert    und gründ  lich mit Wasser gewaschen. Das     p-(p-Hydroxybenzoyl)-          benzonitril    schmilzt nach dem     Umkristallisieren    aus Me  thanol bei 188-189 C.  



  9,0 g     p-(p-Hydroxybenzoyl)-benzonitril,    20 ml     Epi-          chlorhydrin    und 3 Tropfen     Piperidin    werden 20 Stunden  auf dem Dampfbad erhitzt. Das überschüssige     Epichlor-          hydrin    wird unter vermindertem Druck verdampft. Der  Rückstand wird in Chloroform gelöst und mit über  schüssiger Natronlauge 30 Minuten geschüttelt. Die       Chloroformphase    wird eingedampft. Das zurück  bleibende     p-[p-(2,3-Epoxy-propoxy)-benzoyl]-benzonitril     schmilzt nach dem     Umkristallisieren    aus Methanol bei  110-113 C.  



  <I>Beispiel 3</I>  5,1 g     4-[2,3-Epoxy-propoxy]-benzophenon    werden in  20 ml     Dioxan    gelöst und nach Zugabe von 3,9 g     1-(p-          -Methoxy-phenyl)-piperazin    5 Stunden unter     Rückfluss-          bedingungen    erhitzt. Das Lösungsmittel wird     anschlies-          send    unter vermindertem Druck abgedampft. Der Rück  stand wird in 10 ml     Äthanol    gelöst und mit     äthanolischer     Salzsäure kongosauer gestellt.

   Das beim Anreiben aus  kristallisierende 4 - [3 -     (o-Methoxy-phenyl)-piperazinyl-2-          -hydroxy-propoxy]-benzophenon-hydrochlorid    schmilzt  nach dem     Umkristallisieren    aus Äthanol bei 210-211 C.  In analoger Weise erhält man bei Einsatz von:       4-[2,3-Epoxy-propoxy]-benzophenon    und     1-(p-Chlor-          -phenvl)-piperazin     das     4-[3-(4-(p-Chlor-phenyl)-1-piperazinyl)-2-hydro-          xy-propoxy]-benzophenon-hydrochlorid,        Fp:    175 C.  



  4 - [23 -     Epoxy-propoxy]    -     benzophenon    und     1-(p-Me-          thoxy-phenyl)-piperazin     das     4-[3-(4-(p-Methoxy-phenyl)-1-piperazinyl)-2-hy-          droxy-propoxy]-benzophenon-hydrochlorid,        Fp:    145 C.       4-(2.3-Epoxy-propoxy)-benzophenon    und     1-(m-Me-          thoxy-phenyl)-piperazin     das 4-[3-(4-(m-Methoxy-phenyl)-1-piperazinyl)-2-hy-           droxy-propoxy]-benzophenon-dihydrochlorid,        Fp:        193-          196 C.     



       4-(2,3-Epoxy-propoxy)-4'-chlor-benzophenon    und     1-          -(o-Methoxy-phenyl)-piperazin     das     4-[3-(4-(o-Methoxy-phenyl)    -1-     piperazinyl)-2-hy-          droxy-propoxy]-4'-chlor-benzophenon-hydrochlorid,        Fp:     201  C.  



       4-(2,3-Epoxy-propoxy)-4'-fluor-benzophenon    und     1-          -(p-Chlor-phenyl)-piperazin     das     4-[3-(4-(p-Chlor-phenyl)-1-piperazinyl)-2-hydro-          xy-propoxy]-4'-fluor-benzophenon-dihydrochlorid,        Fp:     191-193 C.  



       4-(2,3-Epoxy-propoxy)-benzophenon    und     N-Phenyl-          -piperazin     das     4-[2-Hydroxy-3-(4-phenyl-l-piperazinyl)-propo-          xy]-benzophenon-hydrochlorid,        Fp:   <B>210-2110C.</B>       4-(2,3-Epoxy-propoxy)-benzophenon    und     4-(o-Chlor-          -phenyl)-piperazin     das     4-[3-(4-(o-Chlor-phenyl)-1-piperazinyl)-2-hydro-          xy-propoxy]-benzophenon-hydrochlorid,        Fp:    179-180 C.

         4-[2,3-Epoxy-propoxy]-benzophenon    und     1-p-Tolyl-          -piperazin     das     4-[3-(4-p-Tolyl-l-piperazinyl)-2-hydroxy-propo-          xy]-benzophenon,        Fp:    128 C.  



  <I>Beispiel 4</I>  4.5 g     4-[3-(3,6-Dihydro-4-phenyl-1(2H)pyridyl)-2-hy-          droxy-propoxy]-benzophenon    werden in 400 ml Benzol  suspendiert und unter     Rückflussbedingungen    bis zum  Sieden erhitzt. Durch diese Suspension wird 1 Stunde lang  gasförmiger Chlorwasserstoff geleitet. Anschliessend wer  den 6,2 g destilliertes     Äthylenglykol    und 3,44 g     p-Toluol-          sulfonsäure    zugegeben. Die entstehende klare Lösung  wird unter vermindertem Druck eingedampft. Der Rück  stand wird in     Essigsäureäthylester    aufgenommen.

   Die Lö  sung wird dreimal mit 1 n Natronlauge ausgeschüttelt, über  Natriumsulfat getrocknet und unter vermindertem Druck  eingedampft. Das zurückbleibende     3,6-Dihydro-4-phenyl-          -a    - [ (p -     (2-phenyl-1,3-dioxolan-2-yl)-phenoxy)-methyl]-1-          -(2H)pyridin-äthanol    schmilzt nach dem     Umkristallisieren     aus Methanol bei 120 C.  



  In analoger Weise erhält man bei Einsatz von:  4-     [3-(3,6-Dihydro-4-phenyl-1(2H)pyridyl)-2-hydroxy-          -propoxy]-benzophenon    und     1,3-Propandiol     das     3,6-Dihydro-4-phenyl-a        -[(p-(2-phenyl-m-dioxan-          -    2 -     y1)    -     phenoxy)    -     methyl]    -1(2 H)     pyridin    -     äthanol,        Fp:     116,5 C.



      Process for the preparation of aromatic ethers The present invention relates to a process for the preparation of aromatic ethers of the formula
EMI0001.0005
    or of derivatives thereof substituted in the aromatic rings A and B by one or more alkyl, alkoxy, halogen, cyano, carboxy, nitro, amino or trifluoromethyl groups,

   in which formula R1 represents a completely or partially hydrogenated, optionally hydroxy-substituted pyridine or pyrazine radical connected via nitrogen to the methylene group, which is in the p-position with an optionally substituted by one or more alkyl, alkoxy, halogen or trifluoro methyl-substituted phenyl radical is linked,

    X denotes a carbonyl or hydroxymethylene group and Y denotes a carbonyl, methylene or hydroxymethylene group, and of ketals and acid addition salts of these compounds.



  The above-mentioned alkyl groups are preferably lower alkyl groups with up to. to 5 carbon atoms, such as methyl, ethyl. Isopropyl. The alkoxy groups also preferably contain up to 5 carbon atoms, such as methoxy, ethoxy. Of the halogen atoms, fluorine, chlorine and bromine are preferred.

   Existing oxo groups can be ketalized by lower alkanols or glycols, for example by methyl alcohol or ethylene glycol.



  The pyridine and pyrazine residues are fully or partially hydrogenated. Suitable radicals are e.g. B. the dihydropyridine, tetrahydropyridine; Piperidine, dihydropyrazine, tetrahydropyrazine and piperazine residues.



  The inventive method is characterized in that a compound of the formula
EMI0001.0056
    or a derivative thereof substituted in the aromatic rings A and B, as indicated above, where X denotes a carbonyl or hydroxymethylene group, R denotes halogen or alkyl or

       Arylsulfonyloxy or X and R2 together with the terminal methylene group denotes the remainder
EMI0001.0065
   represent, or, if X and / or Y denote a carbonyl group, a ketal or diketal of this compound is reacted with a compound of the formula H-R, III.



  Preferred compounds of the formula I are those in which X is a hydroxymethylene group and Y is a carbonyl group.



  Compounds of the formula
EMI0002.0001
    or the formula
EMI0002.0002
    in which the dashed bonds hydrogenated and the aromatic ring A and / or the phenyl radical can be substituted by halogen, take a preferred position. The following compounds characterized by the formulas IV and V are e.g. especially valuable.



       4- [3- (3,6-Dihydro-4-phenyl -1 (2H) pyridyl) -2-hydroxy-propoxy] -benzophenone 4- [3- (3,6-dihydro-4-phenyl -1 ( 2H) pyridyl) -2-hydroxy-propoxy] -4'-chlorobenzophenone 4- [3- (4- (p-chlorophenyl) -3,6-dihydro-1 (2H) pyridyl) -2- -hydroxy-propoxy] -benzophenone 4- [3- (4- (p-chloro-phenyl) -3,6-dihydro-1 (2H) pyridyl) -2- -hydroxy-propoxy] -4'-chloro-benzophenone 4- [3- (3,6-dihydro-4-phenyl -1 (2H) pyridyl)

  -2-hydroxy-propoxy] -4'-fluoro-benzophenone 4- [3- (4- (p-fluoro-phenyl) -3,6-dihydro -1 (2H) pyridyl) -2- -hydroxy-propoxy ] -4'-fluoro-benzophenone 4- [3- (4- (p-fluoro-phenyl) -3,6-dihydro -1 (2H) pyridyl) -2- -hydroxy-propoxy] -4'-chloro- benzophenone 4- [3- (4- (p-chlorophenyl) -3,6-dihydro-1 (2H) pyridyl) -2- -hydroxy-propoxy] -4'-fluoro-benzophenone 4- [3- ( 4- (p-Fluoro-phenyl) -3,6-dihydro-1 (2H) pyridyl) -2- -hydroxy-propoxy] -4'-bromo-benzophenone 4- [3- (4- (p-chloro- phenyl)

  -3,6-dihydro-1 (2H) pyridyl) -2- -hydroxy-propoxy] -4'-bromo-benzophenone 4- [3- (4- (p-chlorophenyl) -1-piperazinyl) -2-hydroxy -propoxy] -benzophenone 4- [3- (4- (p-chlorophenyl) -1-piperazinyl) -2-hydroxy-propoxy] -4'-fluoro-benzophenone. The optionally ring-substituted diphenylmethane derivatives of the formula II used as starting compounds can e.g. can be produced as follows:

    Compounds of the formula II. in which X is a hydroxymethylene group and Y is a carbonyl group, can be prepared, for example, by mixing an optionally substituted benzoyl halide with an optionally substituted anisole according to Friedel-Crafts, i.e. with the aid of a Lewis acid, such as aluminum chloride, zinc chloride, boron trifluoride, etc.,

       dealkylated and that optionally substituted 4-hydroxybenzophenone formed, preferably with an excess of an epihalohydrin, in particular with epichlorohydrin, if possible in the presence of a catalytically effective amount of an organic base, such as e.g. Piperidine is reacted at an elevated temperature, preferably at about 100.degree.



  An optionally substituted 4-hydroxy-benzophenone can also be obtained by condensing and dealkylating a 4-alkoxy-benzoic acid with an optionally substituted benzene in the presence of polyphosphoric acid.



  An optionally substituted 4-hydroxybenzophenone is preferably prepared in such a way that an optionally substituted phenyl benzoate is rearranged according to Fries.



  Compounds of the formula II in which X and Y represent a hydroxymethylene group can be prepared, for example, in such a way that an optionally substituted 4-hydroxy-benzophenone is mixed with a mixed metal hydride before or after the introduction of the side chain, e.g. reduced with sodium borohydride or lithium aluminum hydride,

   or that an optionally substituted benzaldehyde is converted with p-alkoxybromobenzene into the corresponding 4-alkoxybenzhydrol with the aid of a Grignard reaction, dealkylated and linked with a side chain.



  Compounds of the formula II in which X is a hydroxymethylene group and Y is a methylene group can be prepared, for example, by using an optionally substituted 4-hydroxy-benzophenone according to Wolff-Kishner - i.e. after conversion into a hydrazone,

          e.g. in the presence of an alkali alcohol at elevated temperature - or according to Clemmensen - i.e. e.g. with the help of amalgamated zinc in the presence of hydrochloric acid - reduced and, as described above, reacted with epichlorohydrin.



  Compounds of the formula 1I in which X is a hydroxymethylene group and Y is a carbonyl group can be treated with the usual oxidizing agents, e.g. be oxidized with potassium permanganate or with sodium dichromate to compounds of the formula II in which X and Y are a carbonyl group.



  Compounds of the formula II in which X is a hydroxymethylene group and Y is a methylene group can be oxidized with a mixture of dimethyl sulfoxide and acetic anhydride to give compounds of the formula II in which X is a carbonyl group and Y is a methylene group.



  The optionally substituted compounds of the formula 1I in which R represents halogen or an alkylsulfonyl or arylsulfonyl-oxy radical, in particular the tosyloxy radical, can be converted to an oxirane in a manner known per se.



  Compounds of the formula III are available in the usual way. The reaction of compounds of the formula II with compounds of the formula III is expediently carried out at a temperature between room temperature and the boiling point of the reaction mixture, in particular at about 70-100 C.

   It is convenient to carry out the reaction in a solvent, e.g. in an alkanol such as methanol, ethanol or isopropanol, or in a cyelic ether such as tetrahydrofuran, dioxane or dimethyl sulfoxide.



  Compounds of the formula II in which R 2 is halogen or alkylsulfonyloxy or arylsulfonyloxy [in particular mesyloxy or tosyloxy] are preferably reacted with compounds of the formula III in the presence of an acid-binding agent. Compounds of the formula 1I in which R2 forms an oxygen bridge with the hydroxyl group of the radical X 'can be reacted directly with compounds of the formula III.



  The compounds of formula I obtained, in which X and / or Y represent a carbonyl group, can be prepared in a manner known per se, e.g. be ketalized by the action of lower alkanols or glycols, in particular by methyl alcohol or ethylene glycol.



  The bases of formula I obtained form salts with both inorganic and organic acids, e.g. with hydrohalic acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid, with other mineral acids such as sulfuric acid, phosphoric acid, nitric acid, and with organic acids such as tartaric acid, citric acid, oxalic acid, camphor sulfonic acid, ethanesulfonic acid, toluenesulfonic acid, salicylic acid, ascorbic acid,

          Maleic acid, mandelic acid, etc. Preferred salts are. the hydrohalides, especially the hydrochlorides. The acid addition salts are preferably prepared in a suitable solvent such as ethanol by treating the free base with the appropriate non-aqueous acid.



  The compounds of the formula I obtainable according to the invention, their ketals, and acid addition salts are distinguished by diverse effects on the nervous system, in particular by a strong psycho-sedative effect. The reserpine-like hypotensive and sedative effects of 4-. [3- (3,6-dihydro-4-phenyl-1 (2H) pyridyl) -2-hydroxypropoxy] -benzophenone and of 4-. [3 - (4- (p-Fluorophenyl) -3,6-dihydro-1 (2H) pyridyl) -2-hydroxypropoxy] -4'-chloro-benzophenone.



  The compounds of the formula I can be used as medicinal products in the form of pharmaceutical preparations which contain them or their salts as a mixture with a pharmaceutical, organic or inorganic inert carrier material suitable for enteral or parenteral administration. The pharmaceutical preparations can be in solid form or in liquid form. If necessary, they can also contain other therapeutically valuable substances.

      <I> Example 1 </I> 12.7 g of 4- [2,3-epoxy-propoxy] -benzophenone are dissolved in 50 ml of dioxane and, after adding 8.0 g of 4-phenyl-1,2, 3,6-tetrahydropyridine heated under reflux conditions for 5 hours. The solvent is then evaporated off under reduced pressure.

   The remaining 4- [3- (3,6-dihydro-4-phenyl-1 (2H) pyridyl) -2-hydroxypropoxy] -benzophenone is dissolved in 20 ml of ethanol and made more acidic to congo with ethanolic hydrochloric acid.

   The hydrochloride which separates out in crystalline form melts after recrystallization from ethanol at 192-194 ° C. In an analogous manner, using: 4- [2,3-epoxy-propoxy] -4'-methoxy-benzophenone and 4-phenyl-1 are obtained , 2,3,6-tetrahydropyridine 4- [3- (3,6-dihydro-4-phenyl-1 (2H) pyridyl) -2-hydroxy-propoxy] 4'-methoxy-benzophenone hydrochloride , M.p .: 185-18611C.



       4- [2,3-epoxy-propoxy] -3-methyl-benzophenone and 4-phenyl-1,2,3,6-tetrahydropyridine 4- [3- (3,6-dihydro-4-phenyl- 1 (2H) pyridyl) -2-hydroxy-propoxy] -3-methyl-benzophenone, m.p .: 200-203 C.

         4- (2,3-epoxy-propoxy) -4'-methyl-benzophenone and 4-phenyl-1,2,3,6-tetrahydropyridine 4- [3- (3,6-dihydro-4-phenyl -1 (2H) pyridyl) -2-hydroxy-propoxy] -4'-methyl-benzophenone hydrochloride, m.p .: 209-2101) C.



       4- [2,3-epoxy-propoxy] -benzophenone and 4- (p-fluorophenyl) -1 2 3 6-tetrahydropyridine 4- [3- (4- (p-fluorophenyl) -3) , 6-dihydro-1 (2H) pyridyl) -2-hydroxy-propoxy] -benzophenone hydrochloride, melting point: 160 C.



       4- (2,3-Epoxy-propoxy) -4'-chloro-benzophenone and 4 - (p-chloro-phenyl) -1,2,3,6-tetrahydropyridine 4- [3- (4- ( p-chloro-phenyl) -3,6-dihydro-1 (2H) pyridyl) - 2- hydroxy-propoxy] - 4 '- chlorobenzophenone hydrochloride, mp:

      212 C (dec.) 4- (2,3-Epoxy-propoxy) -3 ', 4'-dichlorobenzophenone and 4-phenyl-1,2,3,6-tetrahydropyridine 4 - [3 - (3, 6-Dihydro-4-phenyl-1 (2H) pyridyl) -2-hydroxy-propoxy] -3 ', 4'-dichloro-benzophenone hydrochloride, mp:

      206 C (dec.) 4- (2,3-Epoxy-propoxy) -4'-nitrobenzophenone and 4- -phenyl-1,2,3,6-tetrahydropyridine the 4 - [3 - (3,6- Dihydro-4-phenyl-1 (2H) pyridyl) -2-hydroxy-propoxy] -4'-nitro-benzophenone hydrochloride, mp: 201-203 C.



       4- (2,3-epoxy-propoxy) -4'-bromo-benzophenone and 4-phenyl-1,2,3,6-tetrahydropyridine 4- [3- (3,6-dihydro-4-phenyl -1 (2H-pyridyl) -2-hydroxy-propoxy] -4'-bromo-benzophenone hydrochloride, mp: 210-212 C.



       4- (2,3-epoxy-propoxy) -4'-fluoro-benzophenone and 4--phenyl-1,2,3,6-tetrahydropyridine the 4 - [3 - (3,6-dihydro-4- phenyl-1 (2H) pyridyl-2-hydroxy-propoxy] -4'-fluoro-benzophenone hydrochloride, m.p .: 198-200 C.



       4- (2,3-epoxy-propoxy) -4'-fluoro-benzophenone and 4- - (p-fluoro-phenyl) -1.2,3,6-tetrahydropyridine the 4 - [3 - (4- p- Fluorophenyl) -3,6-dihydro-1 (2H) pyridyl) -2-hydroxy-propoxy] -4'-chlorobenzophenone hydrochloride, mp: 192-193 C.



       4- (2,3-epoxy-propoxy) -4'-chloro-benzophenone and 4 - (p-fluoro-piienyl) -1, 2,3,6-tetrahydropyridine the 4 - [3 - (4- p -Fluorophenyl) -3,6-dihydro-1 (2H) pyridyl) -2-hydroxy-propoxy] -4'-chloro-benzophenone hydrochloride, mp: 203-204. C.



       4- (2,3-epoxy-propoxy) -4'-ciilor-benzophenone and 4-hydroxy-4- (p-trifluoromethyl-phenyl) -piperidine 4- [3- (4-hydroxy-4- (p- trifluoromethyl-phenyl) -1-piperidyl) -2-hydroxy-propoxy] -4'-chloro-benzophenone hydrochloride, mp: 222-223 C.



       4- [2,3-epoxy-propoxy] -4'-chlorobenzophenone and 4--phenyl-1,2,3,6-tetrahydropyridine the 4 - [3 - (3,6-dihydro-4-phenyl- 1 (2H) pyridyl) -2-hydroxy-propoxy] -4'-chloro-benzophenone hydrochloride, m.p .: 202 C (dis.).



       4- [2,3-epoxy-propoxy] -benzophenone and 4- (p-chloro-phenyl) -1,2,3,6-tetrahydropyridine 4- [3- (4- (p-chloro- phenyl) -3,6-dihydro-1 (2H) pyridyl) -2-hydroxypropoxy] benzophenone hydrochloride, mp: 217-218 C.



       4- (2,3-epoxy-propoxy) -4'-trifluoro-methyl-benzophenon and 4-phenyl-1,2,3,6-tetrahydropyridine 4- [3- (3,6-dihydro -4-phenyl-1 (2H) pyridyl) -2-hydroxy-propoxy] -4 '-trifluoromethylbenzophenone hydrochloride, m.p .: 231 C (dec.) 4- (2,3-epoxypropoxy ) -3'-chloro-benzophenone and 4- -phenyl-1;

  2,3,6-tetrahydropyridine 4- [3- (3,6-dihydro-4-phenyl-1 (2H) pyridyl) -2-hydroxy-propoxy] -3'-chlorobenzophenone hydrochloride, m.p. : 175 C (dec.) 4- (2,3-epoxy-propoxy) -benzophenone and 4-phenyl-4-hydroxy-piperidine 4- [3- (4-hydroxy-4-phenyl-piperidyl) -2 -hydroxy-propoxy] -benzophenone hydrochloride, m.p .: 184 C.

         4- (2,3-epoxy-propoxy) -2 ', 4'-dichloro-benzophenone and 4-phenyl-1,2,3,6-tetrahydropyridine 4- [3- (3,6-dihydro- 4-phenyl-1 (2H) pyridyl) -2-hydroxy-propoxyl-2 ', 4'-dichlorobenzophenone, mp: 132-134 C.



  4 - (2,3 - Epoxy-propoxy) -3 '- trifluoromethyl-benzophenon and 4- (p-chloro-phenyl) -1,2,3,6-tetrahydropyridine 4- [3- (3 , 6-Dihydro-4- (p-chlorophenyl) -1 (2H) pyridyl) -2-hydroxy-propoxy] -3'-trifluoromethyl-benzophenone hydrochloride, mp: 130-134 C.

         4- (2,3-epoxy-propoxy) -4'-fluoro-benzophenone and 4- - (p-chlorophenyl) -1,2,3,6-tetrahydropyridine 4- [3- (4- (p-Chlorophenyl) -3,6-dihydro -1 (2H) pyridyl) -2-hydroxy-propoxy] -4'-fluoro-benzophenone hydrochloride, mp: 204-206 C.



       4- (2,3-epoxy-propoxy) -4'-bromobenzophenone and 4- - (p-fluorophenyl) -1,2,3,6-tetrahydropyridine the 4 - [3 - (4- (p-Fluorophenyl) -3,6-dihydro-1 (2H) pyridyl) -2-hydroxy-propoxy] -4-bromobenzophenone hydrochloride, mp: 233 C.



       4- (2,3-epoxy-propoxy) -4'-bromobenzophenone and 4- - (p-chlorophenyl) -1,2,3,6-tetrahydropyridine the 4 -. [3 - (4 -p-chloro-phenyl) -3,6-dihydro-1 (2H) pyridyl) -2-hydroxy-propoxyl -4'-bromobenzophenone hydrochloride, mp: 217 C.



       4- (2,3-epoxy-propoxy) -diphenylmethane and 4-phenyl-1,2,3,6-tetrahydropyridine the a - [(p-benzyl-phenyloxy) -methyl] -3,6- dihydro-4-phenyl-1 (2H) pyridine-ethanol hydrochloride, melting point: 191 C (decomp.) The 4 -. [2,3-epoxy-propoxy] -benzophenone used as the starting compound is a known compound.

    The 442,3-epoxy-propoxyl-3-methyl-benzophenone can be prepared as follows, for example: 10.6 g of 4-hydroxy-3-methyl-benzophenone, 50 g of epichlorohydrin and 3 drops of piperidine are stored for 12 hours Steam bath heated. The reaction solution is freed from excess epichlorohydrin under reduced pressure. The above residue is dissolved in 20 ml of chloroform and, after the addition of 20 ml of 3N sodium hydroxide solution, shaken for 1 hour at room temperature. The organic phase is separated off, washed with water, dried over calcium chloride and evaporated to dryness.

   The remaining oily crude 4- [2,3-epoxy-propoxy] -3-methyl-benzophenone crystallized after standing for a long time. The compound can be processed further without further purification. The compound recrystallized from aqueous ethyl alcohol melts at 56-58 ° C. The 4- [2,3-epoxy-propoxy] -4'-methoxy- prepared in an analogous manner from 4-hydroxy-4'-methoxy-benzophenone benzophenone melts at 123-124 C.



  <I> Example 2 </I> In a manner analogous to that given in Example 1, it is obtained when using: p- [p-2,3-epoxy-propoxy) -benzoyl] -benzonitrile and 4- (p -Fluorophenyl) -1,2,3,6-tetrahydropyridine the rac. p- {p- [3- <4- (p-fluorophenyl) -3,6-dihydro-1 (2H) pyridyl> -2-hydroxy-propoxy] -benzoyl} -benzonitrile, m.p. 130-133 C (from Alcohol).



  The p- [p- (2,3-epoxy-propoxy) -benzoyl] -benzonitrile required for this can be prepared as follows: A mixture of 4-bromo-4'-methoxy-benzophenone, 22 g of copper ( I) cyanide and 400 ml of dimethylformamide are heated under reflux conditions for 15 hours while stirring and gassing with nitrogen. The solvent is then evaporated off under reduced pressure.

   The residue is extracted several times with hot chloroform, the chloroform extracts are evaporated to dryness after drying over calcium chloride. The residue is recrystallized from methanol. The pure p- (p-anisoyl) -benzonitrile melts at 133-134 C.



  13.5 g of p- (p-anisoyl) benzonitrile and 40 g of pyridine hydrochloride are mixed well and heated to 220 ° C. for 30 minutes. The hot mixture is poured into water, the crystals which precipitate are filtered off and washed thoroughly with water. The p- (p-hydroxybenzoyl) - benzonitrile melts after recrystallization from methanol at 188-189 C.



  9.0 g of p- (p-hydroxybenzoyl) benzonitrile, 20 ml of epichlorohydrin and 3 drops of piperidine are heated on the steam bath for 20 hours. The excess epichlorohydrin is evaporated off under reduced pressure. The residue is dissolved in chloroform and shaken with excess sodium hydroxide solution for 30 minutes. The chloroform phase is evaporated. The remaining p- [p- (2,3-epoxy-propoxy) -benzoyl] -benzonitrile melts after recrystallization from methanol at 110-113 C.



  <I> Example 3 </I> 5.1 g of 4- [2,3-epoxy-propoxy] -benzophenone are dissolved in 20 ml of dioxane and, after adding 3.9 g of 1- (p- -methoxy-phenyl) -piperazine heated under reflux conditions for 5 hours. The solvent is then evaporated off under reduced pressure. The residue was dissolved in 10 ml of ethanol and made Congo acidic with ethanolic hydrochloric acid.

   The 4 - [3 - (o-methoxyphenyl) -piperazinyl-2-hydroxy-propoxy] -benzophenone hydrochloride which crystallizes out on trituration melts after recrystallization from ethanol at 210-211 ° C. In an analogous manner is obtained when used of: 4- [2,3-epoxy-propoxy] -benzophenone and 1- (p-chloro-phenyl) -piperazine the 4- [3- (4- (p-chloro-phenyl) -1-piperazinyl) - 2-hydroxy-propoxy] -benzophenone hydrochloride, mp: 175 C.



  4 - [23 - epoxy-propoxy] - benzophenone and 1- (p-methoxyphenyl) -piperazine 4- [3- (4- (p-methoxyphenyl) -1-piperazinyl) -2-hy - Droxy-propoxy] -benzophenone hydrochloride, m.p .: 145 C. 4- (2.3-Epoxy-propoxy) -benzophenone and 1- (m-methoxy-phenyl) -piperazine the 4- [3- (4- ( m-Methoxyphenyl) -1-piperazinyl) -2-hydroxy-propoxy] -benzophenone dihydrochloride, m.p .: 193-196C.



       4- (2,3-epoxy-propoxy) -4'-chlorobenzophenone and 1- (o-methoxyphenyl) piperazine 4- [3- (4- (o-methoxyphenyl) -1- piperazinyl) -2-hydroxy-propoxy] -4'-chloro-benzophenone hydrochloride, mp: 201 C.



       4- (2,3-Epoxy-propoxy) -4'-fluoro-benzophenone and 1- (p-chloro-phenyl) -piperazine 4- [3- (4- (p-chloro-phenyl) -1- piperazinyl) -2-hydroxy-propoxy] -4'-fluoro-benzophenone dihydrochloride, mp: 191-193 C.



       4- (2,3-Epoxy-propoxy) -benzophenone and N-phenyl-piperazine 4- [2-Hydroxy-3- (4-phenyl-1-piperazinyl) -propxy] -benzophenone hydrochloride, m.p. : <B> 210-2110C. </B> 4- (2,3-epoxy-propoxy) -benzophenone and 4- (o-chloro-phenyl) -piperazine the 4- [3- (4- (o- Chlorophenyl) -1-piperazinyl) -2-hydroxy-propoxy] -benzophenone hydrochloride, mp: 179-180 C.

         4- [2,3-epoxy-propoxy] -benzophenone and 1-p-tolyl-piperazine 4- [3- (4-p-tolyl-1-piperazinyl) -2-hydroxy-propoxy] -benzophenone , M.p .: 128 C.



  <I> Example 4 </I> 4.5 g of 4- [3- (3,6-dihydro-4-phenyl-1 (2H) pyridyl) -2-hydroxy-propoxy] benzophenone are suspended in 400 ml of benzene and heated to boiling under reflux conditions. Gaseous hydrogen chloride is passed through this suspension for 1 hour. Then whoever added 6.2 g of distilled ethylene glycol and 3.44 g of p-toluenesulfonic acid. The resulting clear solution is evaporated under reduced pressure. The residue is taken up in ethyl acetate.

   The solution is extracted three times with 1N sodium hydroxide solution, dried over sodium sulfate and evaporated under reduced pressure. The 3,6-dihydro-4-phenyl-a - [(p - (2-phenyl-1,3-dioxolan-2-yl) -phenoxy) -methyl] -1- - (2H) pyridine-ethanol that remained melts after recrystallization from methanol at 120 C.



  In an analogous manner, when using: 4- [3- (3,6-dihydro-4-phenyl-1 (2H) pyridyl) -2-hydroxy-propoxy] -benzophenone and 1,3-propanediol, the 3, 6-Dihydro-4-phenyl-a - [(p- (2-phenyl-m-dioxan-2-y1) -phenoxy) -methyl] -1 (2H) pyridine-ethanol, m.p .: 116.5 ° C .

Claims (1)

PATENTANSPRUCH Verfahren zur Herstellung von aromatischen Äthern der Formel EMI0005.0061 oder von in den aromatischen Ringen A und B durch eine oder mehrere Alkyl-, Alkoxy-, Halogen-, Cyano-, Car- boxy-, Nitro-, Amino- oder Trifluormethylgruppen substi tuierten Derivaten davon, in welcher Formel R, einen über Stickstoff mit der Methylengruppe verbundenen ganz oder teilweise hydrierten, PATENT CLAIM Process for the production of aromatic ethers of the formula EMI0005.0061 or of derivatives thereof substituted in the aromatic rings A and B by one or more alkyl, alkoxy, halogen, cyano, carboxy, nitro, amino or trifluoromethyl groups, in which formula R, one via nitrogen fully or partially hydrogenated with the methylene group, gegebenenfalls hydroxy- substituierten Pyridin- oder Pyrazinrest darstellt, der in p-Stellung mit einem gegebenenfalls durch eine oder mehrere Alkyl-, Alkoxy-, Halogen- oder Trifluormethyl- gruppen substituierten Phenylrest verknüpft ist, X eine Carbonyl- oder Hydroxymethylengruppe bedeutet und Y eine Carbonyl-, Methylen- oder Hydroxymethylengruppe bezeichnet, optionally hydroxy-substituted pyridine or pyrazine radical which is linked in the p-position to a phenyl radical optionally substituted by one or more alkyl, alkoxy, halogen or trifluoromethyl groups, X is a carbonyl or hydroxymethylene group and Y is a carbonyl -, methylene or hydroxymethylene group, sowie von -Ketalen und Säureadditionssalzen dieser Verbindungen, dadurch gekennzeichnet, dass man EMI0005.0087 eine <SEP> Verbindung <SEP> der <SEP> Formel <tb> II <tb> / <SEP> \ <SEP> 0-<B>CH</B> <SEP> 2 <SEP> X <SEP> -CH <SEP> 2 <SEP> 82 <tb> A <SEP> , <SEP> B <tb> Y oder ein in den aromatischen Ringen A und B wie oben angegeben, substituiertes Derivat davon, in welcher For mel X eine Carbonyl- oder Hydroxymethylengruppe be zeichnet, R, and of ketals and acid addition salts of these compounds, characterized in that one EMI0005.0087 a <SEP> compound <SEP> of the <SEP> formula <tb> II <tb> / <SEP> \ <SEP> 0- <B> CH </B> <SEP> 2 <SEP> X <SEP> -CH <SEP> 2 <SEP> 82 <tb> A <SEP>, <SEP> B <tb> Y or a derivative thereof substituted in the aromatic rings A and B as indicated above, in which formula X denotes a carbonyl or hydroxymethylene group, R, Halogen oder Alkyl- bzw. Arylsulfonyloxy bedeutet oder X und R_ zusammen mit der endständigen Methylengruppe den Rest EMI0005.0096 darstellen, oder, falls X und/oder Y eine Carbonylgruppe bezeichnen, ein Ketal oder Diketal dieser Verbindung mit einer Verbin dung der Formel H-R, III umsetzt. Halogen or alkyl or arylsulfonyloxy or X and R_ together with the terminal methylene group denote the remainder EMI0005.0096 represent, or, if X and / or Y denote a carbonyl group, a ketal or diketal of this compound reacts with a connec tion of the formula H-R, III. UNTERANSPRÜCHE 1. Verfahren nach Patentanspruch, dadurch gekenn zeichnet, dass man eine Verbindung der Formel EMI0005.0103 oder ein in den aromatischen Ringen A und B durch eine oder mehrere Alkyl-, Alkoxy-, Halogen-, Cyano-, Carboxy-, Nitro-, Amino- oder Trifluormethylgruppen substituiertes Derivat davon, wobei R= Halogen bedeutet oder zusammen mit dem Sauerstoffatom der Hydroxyl- gruppe eine Sauerstoffbrücke bildet, SUBClaims 1. The method according to claim, characterized in that a compound of the formula EMI0005.0103 or a derivative thereof substituted in the aromatic rings A and B by one or more alkyl, alkoxy, halogen, cyano, carboxy, nitro, amino or trifluoromethyl groups, where R = halogen or together with the oxygen atom of Hydroxyl group forms an oxygen bridge, oder ein Ketal dieser Verbindung mit einer Verbindung der Formel H-R, III in der R1 einen über Stickstoff mit dem Wasserstoffatom verbundenen, ganz oder teilweise hydrierten gegebenen falls hydroxysubstituierten Pyridin- oder Pyrazinrest dar stellt, der in p-Stellung mit einem gegebenenfalls durch eine oder mehrere Alkyl-, Alkoxy-, Halogen- oder Tri- fluormethylgruppen substituierten Phenylrest verknüpft ist, darstellt, or a ketal of this compound with a compound of the formula HR, III in which R1 represents a completely or partially hydrogenated, optionally hydroxysubstituted pyridine or pyrazine radical connected to the hydrogen atom via nitrogen, which is in the p-position with one or more Alkyl, alkoxy, halogen or trifluoromethyl substituted phenyl radical is linked, umsetzt. 2. Verfahren nach Patentanspruch oder Unteran spruch 1, dadurch gekennzeichnet, dass man eine erhal tene Base in ein Säureadditionssalz überführt. 3. Verfahren nach Patentanspruch oder Unteran- Spruch 1, dadurch gekennzeichnet, dass man eine erhal tene Ketoverbindung in ein Ketal überführt. 4. Verfahren nach Unteranspruch 1, dadurch gekenn zeichnet, dass man 4-[2,3-Epoxy-propoxy]-benzophenon oder 4-[2-Hydroxy-3-halogen-propoxy]-benzophenon mit 4-Phenyl-1,2,3,6-tetrahydropyridin umsetzt. 5. implements. 2. The method according to claim or sub-claim 1, characterized in that a obtained base is converted into an acid addition salt. 3. The method according to claim or sub-claim 1, characterized in that a keto compound obtained is converted into a ketal. 4. The method according to dependent claim 1, characterized in that 4- [2,3-epoxy-propoxy] -benzophenone or 4- [2-hydroxy-3-halo-propoxy] -benzophenone with 4-phenyl-1,2 , 3,6-tetrahydropyridine converts. 5. Verfahren nach Unteranspruch 1, dadurch gekenn zeichnet, dass man 4-[2,3-Epoxy-propoxy]-4'-chlor-ben- zophenon oder 4-[2-Hydroxy-3-halogen (bzw. mesyl- oder tgsyl-oxy)-propoxy]-4'-chlor-benzophenon mit 4-Phenyl- -1,2,3,6-tetrahydro-pyridin umsetzt. 6. Process according to dependent claim 1, characterized in that 4- [2,3-epoxy-propoxy] -4'-chloro-benzophenone or 4- [2-hydroxy-3-halogen (or mesyl- or tgsyl- oxy) propoxy] -4'-chlorobenzophenone is reacted with 4-phenyl-1,2,3,6-tetrahydropyridine. 6th Verfahren nach Unteranspruch 1, dadurch gekenn- zeichnet; dass mang 4-[2,3-Epoxy-propoxy]-4'-chlor-ben- zöphenon oder 4-[2-Hydroxy-3-halogen (bzw. mesyl- oder tosyl-oxy)-propoxy]-4'-chlor-benzophenon mit 4-[p-Chlor- -phenyl]-1,2,3,6-tetrahydro-pyridin umsetzt. 7. Method according to dependent claim 1, characterized in that; that mang 4- [2,3-epoxy-propoxy] -4'-chloro-benzophenone or 4- [2-hydroxy-3-halogen (or mesyl- or tosyl-oxy) -propoxy] -4'- Reacts chlorobenzophenone with 4- [p-chloro-phenyl] -1,2,3,6-tetrahydropyridine. 7th Verfahren nach Unteranspruch 1, dadurch gekenn zeichnet, dass man 4-[2,3-Epoxy-propoxy]-4'-fluor-ben- zophenon oder 4-[2-Hydroxy-3-halogen (bzw. mesyl- oder EMI0006.0029 tosyl-oxy)-propoxy]-4'-fluor-benzophenon <SEP> mit4-[p-Fluor -phenyl]-1,2,3,6-tetrahydro-pyridin <SEP> umsetzt. <tb> B. <SEP> Verfahren <SEP> nach <SEP> Unteranspruch <SEP> 1, <SEP> dadurch <SEP> gekenn zeichnet, <SEP> dass <SEP> man <SEP> 4-[2,3-Epoxy-propoxy]-4'-chlor-ben zophenon <SEP> oder <SEP> 4-[2-Hydroxy-3-halogen <SEP> (bzw. <SEP> mesyl- <SEP> oder <tb> tosyl-oxy)-propoxy]-4'-chlor-benzophenon <SEP> mit <SEP> 4-[p-Fluor -phenyl]-1,2,3,6-tetrahydro-pyridin <SEP> umsetzt. <tb> 9. Process according to dependent claim 1, characterized in that 4- [2,3-epoxy-propoxy] -4'-fluoro-benzophenone or 4- [2-hydroxy-3-halogen (or mesyl or EMI0006.0029 tosyl-oxy) -propoxy] -4'-fluoro-benzophenone <SEP> with 4- [p-fluoro-phenyl] -1,2,3,6-tetrahydropyridine <SEP>. <tb> B. <SEP> method <SEP> according to <SEP> subclaim <SEP> 1, <SEP> characterized by <SEP>, <SEP> that <SEP> man <SEP> 4- [2,3- Epoxy-propoxy] -4'-chloro-ben zophenon <SEP> or <SEP> 4- [2-hydroxy-3-halogen <SEP> (or <SEP> mesyl- <SEP> or <tb> tosyl-oxy) propoxy] -4'-chloro-benzophenone <SEP> with <SEP> 4- [p-fluoro-phenyl] -1,2,3,6-tetrahydropyridine <SEP>. <tb> 9. <SEP> Verfahren <SEP> nach <SEP> Unteranspruch <SEP> 1, <SEP> dadurch <SEP> gekenn zeichnet, <SEP> dass <SEP> man <SEP> 4-[2,3-Epoxy-propoxy]-4'-fluor-ben zophenon <SEP> oder <SEP> 4-[2-Hydroxy-3-halogen <SEP> (bzw. <SEP> mesyl- <SEP> oder <tb> tosyl-oxy)-propoxy]-4'-fluor-benzophenon <SEP> mit <SEP> 4-[p-Chlor -phenyl]-1,2,3,6-tetrahydro-pyridin <SEP> umsetzt. <tb> 10. <SEP> Verfahren <SEP> nach <SEP> Unteranspruch <SEP> 1, <SEP> dadurch <SEP> gekenn zeichnet, <SEP> dass <SEP> man <SEP> 4-[2,3-Epoxy-propoxy]-4'-fluor-ben zophenon <SEP> oder <SEP> 4-[2-Hydroxy-3-halogen <SEP> (bzw. <SEP> mesyl- <SEP> oder <tb> tosyl-oxy)-propoxy]-4'-fluor-benzophenon <SEP> mit <SEP> 4-[p-Chlor -phenyl]-piperazin <SEP> umsetzt. <SEP> method <SEP> according to <SEP> subclaim <SEP> 1, <SEP> characterized by <SEP>, <SEP> that <SEP> one <SEP> 4- [2,3-epoxy-propoxy] - 4'-fluor-ben zophenon <SEP> or <SEP> 4- [2-hydroxy-3-halogen <SEP> (or <SEP> mesyl- <SEP> or <tb> tosyl-oxy) -propoxy] -4'-fluoro-benzophenone <SEP> with <SEP> 4- [p-chloro-phenyl] -1,2,3,6-tetrahydropyridine <SEP>. <tb> 10. <SEP> method <SEP> according to <SEP> subclaim <SEP> 1, <SEP> characterized by <SEP>, <SEP> that <SEP> man <SEP> 4- [2,3- Epoxy-propoxy] -4'-fluoro-ben zophenon <SEP> or <SEP> 4- [2-hydroxy-3-halogen <SEP> (or <SEP> mesyl- <SEP> or <tb> tosyl-oxy) -propoxy] -4'-fluoro-benzophenone <SEP> with <SEP> 4- [p-chloro-phenyl] -piperazine <SEP>.
CH1076965A 1966-06-24 1966-06-24 Process for the production of aromatic ethers CH475242A (en)

Priority Applications (25)

Application Number Priority Date Filing Date Title
NL133317D NL133317C (en) 1966-06-24
CH11669A CH474513A (en) 1966-06-24 1966-06-24 Process for the production of aromatic ethers
CH11769A CH474514A (en) 1966-06-24 1966-06-24 Process for the production of aromatic ethers
CH11569A CH474512A (en) 1966-06-24 1966-06-24
DE19661695146 DE1695146A1 (en) 1966-06-24 1966-06-24 Process for the preparation of substituted oxazolidones
CH1076965A CH475242A (en) 1966-06-24 1966-06-24 Process for the production of aromatic ethers
CH11469A CH474515A (en) 1966-06-24 1966-06-24 Process for the production of aromatic ethers
CH11369A CH474511A (en) 1966-06-24 1966-06-24
DE19661695148 DE1695148A1 (en) 1966-06-24 1966-06-28 Process for the production of aromatic ethers
US566214A US3528976A (en) 1966-06-24 1966-07-19 Process for the preparation of substituted oxazolidones
IL26198A IL26198A (en) 1966-06-24 1966-07-22 Aromatic ethers and process for the manufacture thereof
GB33016/66A GB1085106A (en) 1966-06-24 1966-07-22 Process for the preparation of substituted oxazolidones
BE684600D BE684600A (en) 1966-06-24 1966-07-26
NL6610566A NL6610566A (en) 1966-06-24 1966-07-27
BR181621/66A BR6681621D0 (en) 1966-06-24 1966-07-28 PROCESS FOR THE MANUFACTURE OF AROMATIC ETHERS
FR71191A FR6263M (en) 1966-06-24 1966-07-28
GB34028/66A GB1111917A (en) 1966-06-24 1966-07-28 Diphenylmethane and benzophenone derivatives and a process for the manufacture thereof
ES0329683A ES329683A1 (en) 1966-06-24 1966-07-29 A method for the preparation of aromatic eters. (Machine-translation by Google Translate, not legally binding)
SE10328/66A SE322775B (en) 1966-06-24 1966-07-29
NO164109A NO121212B (en) 1966-06-24 1966-07-29
FR111533A FR1530783A (en) 1966-06-24 1967-06-22 Process for the preparation of substituted oxazolidones
CH895667A CH479603A (en) 1966-06-24 1967-06-23 Process for the preparation of substituted oxazolidones
US39505A US3706755A (en) 1966-06-24 1970-05-21 Certain 4(3-(4-(phenyl)-3,6-dihydro-1(2h)pyridyl)-2 - hydroxy-propoxy)-benzophenones
US00245610A US3812129A (en) 1966-06-24 1972-04-19 Piperazinyl substituted alkoxy benzophenones
US00245609A US3816434A (en) 1966-06-24 1972-04-19 4-(3-(4-phenyl-piperidino)-2-hydroxy-propoxy)-benzophenones

Applications Claiming Priority (1)

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CH1076965A CH475242A (en) 1966-06-24 1966-06-24 Process for the production of aromatic ethers

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CH475242A true CH475242A (en) 1969-07-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023018765A1 (en) * 2021-08-10 2023-02-16 Ecolector, Inc. Cyclooctene-benzophenone monomer, as well as cationic polymer, cross-linked polyelectrolyte, composite material, membrane, electrode and electrochemical device, e.g. electrolyzer, prepared therefrom

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023018765A1 (en) * 2021-08-10 2023-02-16 Ecolector, Inc. Cyclooctene-benzophenone monomer, as well as cationic polymer, cross-linked polyelectrolyte, composite material, membrane, electrode and electrochemical device, e.g. electrolyzer, prepared therefrom

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