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Synthesis_1

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Synthesis_1is_1

    Synthesis

Availableonlineatwww.sciencedirect.com

    ;?:j,ScienceDirect

    ;ChineseChemicalLetters19(2oo8)13981400

    ;CHINE5E

    ;CHEMlCAL

    ;LETTERg

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    ;byntneslsotnewOorazlnescontainingcroSSllnKablegroups

    ;ShaoHuaDong,v,ZhiMinZheng,WeiJianHan,v,TongZhao,CaiHongXu’

    ;BeijingNationalLaboratoryforMolecularScience(BNLMS),InstituteofChemistry,ChineseAcademyofSciences,Beifing100190,China

    ;GraduateSchooloftheChineseAcademyofScience~Beijing10003~China ;Received2June2oo8

    ;Abstract

    ;Threenewfunctionalgroupcontainingborazinederivatives,2,4,6

    tri(allylamino)borazine,2,4,6tri(3ethynylanilino)borazine,

    ;and2,4,6

    tri(4-propargyloxyanilino)borazineweresynthesizedbyaminolysisreactionof2,4,6-trichloroborazineC13B3N3H3

    ;(TCB).Thenewcompoundswerecharacterizedbyinfrared(IR)spectra,nuclearmagneticresonance(NMR),andmass

    ;spectrometry(MS).

    ;?

    2008CalHongXu.PublishedbyElsevierB.VonbehalfofChineseChemicalSociety.Allfightsreserved.

    ;Keywords:Borazine;Aminolysis;Crosslinkablegroups

    ;BCNmaterialshaveattractedincreasinginterestsincethefirstreportontheirsynthesisusingasolidgasreaction.

    ;duetotheiruniqueproperties

    17.Methodstosynthesizethismultinaryceramicsystemsinclude(carbo)nitridation ;ofinorganicoxidesandpyrolysisoforganicprecursors.Recently,manystudiesonpreparingBCNceramicsvia

    ;organicprecursorroutehavebeenreported.However,muchworkisfocusedonpyrolysisofpolymermateriais,suchas

    ;polyborazylene[812

    andpolymericborosesquicarbodiimide[5,13].LittleattentionhasbeenPaidtousingmolecular

    ;monomersasprecursors.Comparedwjtl1polymericprecursors,monomericprecursorsha

veanumberofadvantages,

    ;includinghighpurityandwel1.definedstructures.whichareparticularlyusefu1forinvestigationintothereaction

    ;mechanismfromprecursortofinaiceramicandintotherelationshipbetweenprecursorstructureandceramic

    ;composition.Butcomparativelylowceramicyieldisaseveredrawbackformostmonomericprecursorsduetotheir

    ;lowermolecularweightandvolatility.Aneffectivewaytosolvethisproblemmaybeintroductionofreactivegroups

    ;intomoleculessoastoformcrosslinkedframeworkbeforedecompositionorvolatilizationoftheprecursors,which

    ;hasbeendemonstratedasaneffectivewaytoimprovetheceramicyield[14.

    ;InthisPaper,wewouldliketoreportthesynthesisandcharacterizationofthreenewunsaturatedgroupscontaining

    ;borazinederivatives.Furtherinvestigationontheirthermalpropertiesiscurrentlyunderway.

    ;ThesynthesisrouteisoutlinedinScheme1.2,4,6

    TrichloroborazineC13B3N3H3(TCB)waspreparedaccordingto

    ;literatures

    151andpurifiedbysublimation.TheammonolysisreactionofTCBwithaNylamine,3.ethynylaniline,and

    ;4-propargyloxyaniline[16

    producedcorrespondingunsaturatedgroupscontainingborazinederivatives,respectively. ;Correspondingauthors.

    ;E-mailaddress:caihong@iccas.ac.ca(C.H.Xu)

    ;10018417/5-seefrontmatter?

    2008CaiHongXu.PublishedbyElsevierB.VonbehalfofChineseChemicalSociety.Allfightsreserved.

    ;doi:10.1016/j.cclet.2008.09.046

    ;

    ;1.Experimental

    ;S.H.Dongeta1./ChineseChemicalLetters19(2008)1398-1400

    ;3

    ;+3RNH,

    ;Scheme1

    ;1399

    ;AllmanipulationswereperformedunderaninertatmosphereofnitrogenbystandardSchlenktechniques[17].All

    ;solventsweredistilledfromsodium/benzophenoneketylpriortouse.HNMR,?BN/VlR, ;and3CN/VlRspectrawere

    ;obtmnedonaBrukerAvance400spectrometerusingC6D6assolvent.MSspectrawererecordedonaShimsdzu

    ;GCMS

    2010massspectrometer.Fouriertransformsinfrared(FTIR)spectrawererecordedwithaBru

kerIFS45

    ;spectrometer.

    ;1:2,4,6

    Tri(allylamino)borazine,B3N3H3(NHCH2C}I==CH2).ToamixedsolutionofTCB(1.88g,10.2mmo1)and

    ;triethylamine(4.5mL,31.0mmo1)intoluene(20mL),asolutionofallylamine(2.4mL,32.0mmo1)intoluene

    ;(10mL)wasaddeddropwiseat0.C.Then,themixturewasallowedtowarmtoroomtemperature.Afterstirringat

    ;roomtemperatureovernight.thebyproducttriethylaminehydrochloridewasremovedbvfl1tration.Thefilatewas

    ;concentratedunderreducedpressure.Thecrudeproductwasfurtherpurifiedbyrecrystallizationfromn.pentaneto

    ;give2.28g(9.3mmo1)1in91%yieldasawhitepowder~HNMR(400MHz,C6D6,

    ppm):5.86(m,3H),5.14(m,

    ;6H),3.45(m,6H),2.61(br’3H),1.57(s,3H);”CNMR(100MHz,C6D6,

    ppm):140.02,l13.32,44.07;”B

    ;NMR(128MHz,C6D6,

    ppm):26.49;MS(m/z,EI):Calcd.forC9H21B3N6:246,Found:246[M+;FTIR(v,cm):

    ;3436,3296,3080,1641,1501,1320,993,718.

    ;2:2,4,6-Tri(3-ethynylanilino)borazine,B3N3H3(NHC6H4C

    CH)3.rI11iscompoundwaspreparedasawhitesolidin

    ;90%yieldfromreactionofTCBwith3-ethynylaniline.essentiallyinthesamemannerasdescribedf0r1.HNMR

    ;(400MHz,C6D6,ppm):6.13—6.98(m,12H),3.61(s,3H),2.64(s,3H),1.36(s,3H);”CNMR(100MHz,C6D6,

    ;ppm):147.37,129.77,124.48,123.71,122.62,l15.95,84.86,77.33;”BNMR(128MHz,C6D6):27.75;MS(m/z,

    ;EI):Calcd.forC24H2lB3N6:426,Found:426[M1;FTIR(v,cm

    ):3422,3383,3286,2105,1621,868,1454,1380,

    ;7l0.

    ;3:2,4,6Tri(4

    propargyloxyanilino)borazine,B3N3H3(NHC6I-I4OCHzC~----CH)3.Thiscompoundwaspreparedasa

    ;whitesolidin94%yieldfromreactionofTCBwith4

    propargyloxyaniline.essentiallyinthesamemanneras

    ;describedfor1.HNMR(400MI--Iz,C6D6,6ppm):6.77(d,6H,J=8.38),6.23(d,6H,J=8.38),4.21(s,6H),2.60

    ;(s,3H),1.98(s,3H),1_38(s,3H);”CNMR(100MHz,C6D6,ppm):151.45,142.06,116.86,l16-49,80.15,75.69,

    ;57.04;”BNMR(128MHz,C6D6,ppm):25.65;MS(m/z,EI):Calcd.forC27H21B3N6O3:516,Found:516[M];

    ;FTIR(cm):3417,3422,3285,3040,2073,1595,1456,829,1028,1484,1376,691. ;References

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