3胺基苯乙炔合成专利.docx
- 文档编号:30235999
- 上传时间:2023-08-13
- 格式:DOCX
- 页数:28
- 大小:31.29KB
3胺基苯乙炔合成专利.docx
《3胺基苯乙炔合成专利.docx》由会员分享,可在线阅读,更多相关《3胺基苯乙炔合成专利.docx(28页珍藏版)》请在冰豆网上搜索。
3胺基苯乙炔合成专利
WO1999/003803
PROCESSFORPREPARINGAMINOARYLACETYLENESFIELDOFTHEINVENTION
Thisinventionrelatesgenerallytopreparingaminoarylacetylenes.Morespecifically,itrelatestopreparingaminoarylacetylenesfromaminoarylhalidesandterminalacetylenesandtonovelcompoundswhichareusefulintheirpreparation.Aminophenylacetylenesarevaluableasprecursorstopharmaceuticallyactivecompoundsandtoacetyleneterminatedpolymers.InpartiCuIar,3-aminophenyl-acetyleneisusedasanend-cappingagentforhighperformancepolyimideresins.
BACKGROUNDOFTHEINVENTIONSabourin,Prepr.Div.Pet.Chem.,Am.Chem.Soc.,vol.24,pp.233-239disclosesthepreparationof2-methyl-4-(3-aminophenyl)-3-butyn-2-ol(anaminophenylacetylene)and3-aminophenyl-acetyleneintwoandthreesteps,respectively,from3-bromonitrobenzeneand2-methyl-3-butyn-2-ol.Inthefirststep,3-bromonitrobenzeneand2-methyl-3-butyn-2-olwerereactedinthepresenceofacatalystsystemofbis(triphenylphosphine)palladiumdichloride,additionaltriphenylphosphine,andcuprousiodideintriethylaminesolventattherefluxtemperaturetoobtain2-methyl-4-(3-nitrophenyl)-3-butyn-2-ol.Inthesecondstep,thisnitrophenyl-acetylenewashydrogenatedinisopropanolinthepresenceofaRu/Al203catalysttoobtain2-methyl-4-(3-aminophenyl)-3-butyn-2-ol.Thisreferencestatesthatisessentialtostopthehydrogenationreactionatthestoichiometricpointbecausereductionofthetriplebondensues.Inthethirdstep,thisaminophenylacetylenewasheatedintolueneinthepresenceofsodiumhydroxidepellets,withremovaloftheacetoneco-productbydistillation,toobtain3-aminophenylacetylene.
Thisreferencealsodisclosesanattempttosimilarlyreact3-bromoaniline,insteadof3-bromonitrobenzene,with2-methyl-3-butyn-2-oltoobtain2-methyl-4-(3-aminophenyl)-3-butyn-2-oldirectly,andreportsthat3-bromoanilinefailedtoreactatanyappreciablerateattemperaturesuptoca.100°C.
U.S.Patents4,128,588and4,204,078(eachalsofromthesameSabourinasinventor,withSelwitz)alsodisclosesthispreparationof2-methyl-4-(3-nitrophenyl)-3-butyn-2-olfrom3-bromonitrobenzeneand2-methyl-3-butyn-2-ol.U.S.PatentNo.4,139,561andJ.Org.Chem.,vol.44(1979),pp.1223-1236(bothOnopchenkoaswellasthesameSabourinandSelwitz)alsodisclosesthepreparationof2-methyl-4-(3-aminophenyl)-3-butyn-2-olfrom2-methyl-4-(3-nitrophenyl)-3-butyn-2-olbyhydrogenationwitharutheniumcatalyst,anditssubsequentconversionto3-aminophenylacetylene.BoththepatentandjournaldisclosureshighlightthediffiCuItchallengeofselectivelyhydrogenatingthenitrogroupinthepresenceoftheacetylenegroup.SubsequentU.S.Patents4,215,226;4,216,341;4,219,679andapublicationJOrg.Chem.,vol.44(1979),pp.3671-3674fromOnopchenko,Sabourin,andSelwitzdisclosehydrogenationsof2-methyl-4-(3-nitro-phenyl)-3-butyn-2-olto2-methyl-4-(3-aminophenyl)-3-butyn-2-olusingotherhydrogenationcatalysts.
Synlett,1995,pp.1115-1116disclosesthispreparationof2-methyl-4-(4-nitrophenyl)-3-butyn-2-olfrom4-bromonitrobenzeneand2-methyl-3-butyn-2-olinhighyieldusingacatalystsystemcomprisingpalladiumoncarbon,triphenylphosphine,andcuprousiodideinthepresenceof2.5equivalentsofpotassiumcarbonatein1:
11,2-dimethoxyethane:
waterat80°C.Thisreferencealsodisclosesthepreparationof2-methyl-4-(3-aminophenyl)-3-butyn-2-olin78%isolatedyieldfrom3-iodoaniline(inplaceof4-bromonitrobenzene)usingthesamesystemandthesameconditions.Thereferencedoesnotdiscloseanyattempttosimilarlyreact3-bromoaniline.
OBJECTSOFTHEINVENTIONTheobjectofthisinventionistoprovideaneconomicallypreferable,effectiveandefficientprocessforthepreparationaminophenylacetylenes.Afurtherobjectofthisinventionistoprovideaprocessforthepreparationofaminophenylacetylenesthatavoidstheinherentchallengeofselectivelyhydrogenatinganitrogroupinthepresenceofanacetylenegroup.
Anotherobjectofthisinventionistoprovideaprocessforthepreparationofaminophenyl-acetylenesfromaminophenylhalides.Thepresentinventionisdirectedtowardsoneormoreoftheaboveobjects.Otherobjectsandadvantageswillbecomeapparenttopersonsskilledintheartandfamiliarwiththebackgroundreferencesfromacarefulreadingofthisspecification.
SUMMARYOFTHEINVENTIONInitsmostgeneralterms,thepresentinventionprovidesaprocessforpreparingaminoarylacetylenescomprisingreactinganN-arylmethylideneaminoarylhalidewithaterminalacetyleneinthepresenceofabaseandacatalystsystemcomprisingapalladiumcatalystandacuproussalttoproduceanovelN-arylmethylideneaminoarylacetylene.TheN-arylmethylideneaminoarylacetylenemaybehydrolyzedtoremovetheN-arylmethylidenegroupandprovidetheaminoarylacetylene.ThepresentinventiontherebyprovidesapracticalprocessforpreparinganaminophenylacetylenecomprisingreactingaN-benzylideneaminophenylhalidewithaterminalacetyleneinthepresenceofabaseandacatalystsystemcomprisingapalladiumcatalystandacuproussalttoproduceanovelN-benzylideneaminophenylacetylene,andhydrolyzingtheN-benzylideneaminophenylacetylenetotheaminophenylacetylene.N-benzylideneaminophenylhalidescanbereadilypreparedfromthecorrespondingthecorrespondingbenzaldehydeandthecorrespondingaminophenylhalidebymethodsknownintheart,typicallyinthepresenceofanacidcatalyst.Incertainembodimentsofthepresentinvention,theN-benzylideneaminophenylhalideisprovidedinthereactionbythebenzaldehyde,theaminophenylhalide,andanacidcatalyst.Theinventiontherebyprovidesaprocessforthepreparationofaminophenylacetylenesfromaminophenylhalidesthatavoidstheinherentchallengeofselectivelyhydrogenatinganitrophenylacetylenetoanaminophenylacetylene.
Fromexperimentsusingasubstoichiometricamountofbenzaldehyderelativetotheaminophenylhalide,itwassurprisinglydiscoveredthattheremainingfreeaminophenylhalideinthemixturewiththeresultingN-benzylideneaminophenyl-halidealsoreacts,providingamixtureoftheaminophenylacetyleneandtheN-benzylideneaminophenylacetylene.Apparently,thesubstoichiometricamountofthebenzylidenegroupcatalyzestheconversionofaminophenylhalidetotheaminophenylacetylene.Whilenotintendingtobeboundbytheory,thiscanbeexplainedbythebenzylidenegroupbeingtransferred,duringthereaction,fromtheinitialproduct,theN-benzylideneaminophenyl-acetylene,totheunreactedfreeaminophenylhalide,convertingittothemorereactiveN-benzylideneaminophenylhalide.
Inonepreferredembodiment,thepresentinventionprovidesaprocessforthepreparationof3-aminophenylacetylenecarbinolsfrom3-aminophenylhalidescomprisingreactingaN-benzylidenederivativeofthe3-aminophenylhalidewithaalpha-hydroxyterminalacetyleneinthepresenceofanaminebaseandacatalystsystemcomprisingapalladiumcatalystcomprisingaphosphorusligandandacuproushalide,andhydrolyzingtheresultingnovelN-benzylidene3-aminophenyl-acetylenecarbinoltothe3-aminophenyl-acetylenecarbinol.Optionally,amixtureofthe3-aminophenylhalideandtheN-benzylidene3-aminophenylhalideisreactedtoprovideamixtureofthe3-amino-phenylacetylenecarbinolandthecorrespondingN-benzylideneaminophenylacetylenecarbinol.3-amino-phenylacetylenecarbinolsmaybeconvertedto3-aminophenylacetylenebymethodsknownintheart.Theinventiontherebyprovidesanefficientprocessforthepreparationof3-aminophenylacetylenefrom3-aminophenylhalides.
DETAILEDDESCRIPTIONOFTHEINVENTIONSuitablestartingmaterialsandintermediatesforthepreparationofaminoarylacetylenesbythepresentinventionareaminoarylhalidesingeneral,arylcarboxaldehydesingeneral,terminalacetylenesingeneral,N-arylmethylideneaminoarylhalidesingeneral,andN-arylmethylideneaminoarylacetylenesingeneral.TheN-arylmethylideneaminoaryl-halideandtheN-arylmethylideneaminoarylacetylenemaybecisisomersortransisomers,ormixturesthereof,aboutthecarbon-nitrogendoublebond.
Suitableaminoarylgroupsfortheaminoarylhalide,theN-arylmethylideneaminoarylhalide,theN-arylmethylideneaminoarylacetylene,andtheaminoarylacetyleneincludethoseinwhichthearylringsystemisacarbocyclicaromaticringsystem,havingonlycarbonatomsintheringsystem,andthoseinwhichthearomaticringsystemisaheterocyclicaromaticringsystem,havingoneormoreheteroatomsintheringsystem.Typicalcarbocyclicaromaticringsystemsintheaminoarylgrouphave6-14carbonatomsinthearomaticringsystem.Apreferredcarbocyclicaromaticringsystemsarephenylandsubstitutedphenylgroups.Suitableheterocyclicaromaticringsystemsintheaminoarylgrouphave5-13atomsinthearomaticringsystemwhichcomprisescarbonatomsandoneormoreheteroatoms.Preferredheteroatomsareoxygen,sulfur,andnitrogen.Typicalheterocyclicaromaticringsystemshave5or6atomsinanaromaticringcomprisingoneormoreheteroatomsselectedfromthegroupoxygen,sulfur,andnitrogen,benz-fusedderivativesthereof,andsubstitutedderivativesthereof.Examplesofpreferredheterocyclicaromaticringsystemsintheaminoarylgroupincludepyridyl,furyl,thiophenyl,pyrrolyl,theirbenz-fusedderivativesquinolinyl,isoquinolinyl,benzfuryl,benzthiophenyl,indolyl,isoindolyl,andsubstitutedderivativesthereof.
Suitablearylgroupsforthearylmethylidenegroupofthearylcarboxaldehyde,theN-arylmethylideneaminoarylhalide,andtheN-arylmethylideneaminoaryl-acetyleneincludethosehavingthearomaticringsystemsdescribedaboveassuitabl
- 配套讲稿:
如PPT文件的首页显示word图标,表示该PPT已包含配套word讲稿。双击word图标可打开word文档。
- 特殊限制:
部分文档作品中含有的国旗、国徽等图片,仅作为作品整体效果示例展示,禁止商用。设计者仅对作品中独创性部分享有著作权。
- 关 键 词:
- 胺基 乙炔 合成 专利