Synthesis and Structure of 1-Bromo-1-nitro-2-piperidino(cyclohexylamino)-2-phenylethenes

OriginalRussianTextCopyright+2001byIshmaeva,Berestovitskaya,Litvinov,Vereshchagina,Yarkova,Fattakhova,Krivolapov,Makarenko,Trukhin,Pavlova.

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SynthesisandStructureof1-Bromo-1-nitro-2-piperidino-(cyclohexylamino)-2-phenylethenes

E.A.Ishmaeva,V.M.Berestovitskaya,I.A.Litvinov,Ya.A.Vereshchagina,E.G.Yarkova,G.R.Fattakhova,

D.B.Krivolapov,S.V.Makarenko,E.V.Trukhin,andI.V.Pavlova

KazanStateUniversity,Kazan,Tatarstan,Russia

ArbuzovInstituteofOrganicandPhysicalChemistry,KazanScientificCenter,

RussianAcademyofSciences,Kazan,Tatarstan,Russia

HerzenRussianStatePedagogicalUniversity,St.Petersburg,Russia

ReceivedSeptember12,2000

Abstract-Apreparationmethodwasdevelopedfornewrepresentativesofhalonitroenamines,1-bromo-1-nitro-2-piperidino(cyclohexylamino)-2-phenylethenes.BothmoleculespossessEconfigurationandareof

highpolarity.

Nitroenaminescontaininginvicinalpositionaminoandnitrogroupsattractattentionbothfrompracticalandtheoreticalpointofview(investigationonthespecificfeaturesoftheelectronicstructureofthesemolecules)[137].Inthenitroenamineserieswerefoundcertaincompoundswithpronouncedpharma-cologicalproperties[5].Besides,nowinthemedicalpracticeiswidelyappliedantiulcerdrugranitidinethathasastructureanalogoustonitroenamines,anitro-ketenaminal[6].

Halonitroenamineswerementionedinpublications

ÄÄÄÄÄÄÄÄÄÄÄÄ

asuniqueexamples[739],andtheywereasaruleobtainedbydifficultmethodsandinlow(~30%)yields.

Basingonreactionof1,2-dibromo-1-nitro-2-phenylethene(I)[10]withthecorrespondingaminesweforthefirsttimesynthesized1-bromo-1-nitro-2-piperidino(cyclohexylamino)-2-phenylethenes(II,III).TheprocessoccursatboilingofcompoundIwithdoubleexcessofamineinananhydrousbenzenefor233.5htoaffordtheproductsofSNVin-substitutionIIandIIIin97and91%yieldrespectively.

C=C777776

9NO2N9Br9C6H59C=C79IIBrNO29

NH292C6H5Br

+9C=C777776

NO2NH

III

eiie7

ei7ie

cei7ie7e7

2

7

NH

C6H5

Br

+

NH2Br

+

!

NH2Br

+

!

ÄÄÄÄÄÄÄÄÄÄÄÄ

NotethatdibromonitrostyreneIreactswithaminesunderconsiderablymorestringentconditionsthanthemonohalonitrostyreneswithvicinalorgeminalsubstituents[11317].Thisfactisapparentlyduetolowerste-ricaccessibilityofthereactivesiteC2andbysterichindrancetoconjugationinthemoleculeofcompoundIsincethenitrogroupdeviatesfromthemultiplebond

1070-3632/01/7103-0429$25.00C2001MAIK[Nauka/Interperiodica]

430ISHMAEVAetal.

C6

C5

C4

C7

N3

C8

C2

O2

N1O1

C1

C14

C13

C12

C9

C10

C11

Theconclusionsfrom[13,21]madebasingonUVspectroscopyandX-rayanalysissuggestthat2-mor-pholino-1-nitro-1,2-diphenyletheneinsolutionoccursinEconfiguration,andinthecrystalstateinZconfiguration.ItisquitereasonablesincetheEandZisomersofnitroenaminesasarulehavearelativelylowbarriertoisomerictransformations[22324].Forinstance,bymeansof1H,13C,and14NNMRspec-troscopy[22]itwasshownthata-nitro-b-amino-acrylicestersarestericallynon-rigidinanextendedsetofsolvents.ThisfactBakhmutovetal.ascribedtotheso-called[rotationaroundthedoublebond.]Westudiedthestructuresofthenewtetrasubsti-tutednitroenaminesII,IIIbymeansof1HNMR,IR,andelectronicspectroscopy,dipolemoments,andX-raydiffractionanalysis.Inthe1HNMRspectraofthesecompoundsareseenallprotonsignalsfromstructuralfragments.Forinstance,thespectrumofcompoundIIcontainstheresonancesfromthebenzeneringprotons(d7.60ppm)andfromthepi-peridinering(d1.68and3.15ppm);thesedatashowitsstereohomogeneitybutdonotrevealitsgeometry.TheX-raydiffractionstudyofthepiperidinederiv-ativeofbromonitrostyreneIIdefinitelyshowedthatitsmoleculesinthesolidphasepossessedEcon-figuration.

ThespatialarrangementofcompoundIImoleculeisrepresentedonFig.1,atomcoordinatesandgeo-metricalparametersarelistedinTables133.Itshouldbenotedthatthedoublebondinthemoleculeisnotablytwisted[torsionanglesBrC1C2C930.5(5)andN1C1C2N336.6(6)o](Table3),bondlengthC1=C21.399(6)A(Table2)issomewhatlongerthanthatofnitroethene(1.337A)[25]orthoseofsomesubsti-tutednitroethenes[26,27].OnthecontrarythebondC13N1[1.416(5)A]isshorterthanintheothernitro-ethanes(1.4531.46A)[25327].NotethatsimilarvariationsinbondlengthsC=C(1.378A)andC3NO2(1.426A)areobservedalsoinamoleculeofanothernitroenamine,2-morpholino-1-nitro-1,2-diphenyl-ethene[21].TherewiththeatomsC1andC2aresp2-hybridized[thesumofbondanglesattheseatomsisequalto359.9(4)o].

ThenitrogroupattheC1atomisslightlyturnedwithrespecttothedoublebondplane:thetorsionangleO2N1C1C2is9.1(6)o.Thenitrogenatomofthepiperidinesubstituentisofplane-trigonalcoordination[thesumofbondanglesis359.3(3)o],butitisturnedstrongerwithrespecttothedoublebondplane:thetorsionangleC1C2C9C10is47.9(5)o.ThebondlengthsC13Br[1.879(4)A]andC23C9(C6H5)[1.483(5)A]havecommonvalues.Thecrystalstruc-tureofcompoundIIisdeterminedbyvanderWaals

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Br

Fig.1.NitroenamineIImoleculargeometryinacrystal.

planeaswasreliablyshownbyX-raydiffractionstudy[10].

Theconsiderationofstudiesonthenitroenaminesstructuredemonstratesthattheirgeometrydependsonthesubstituentsandsolventcharacterinacomplicatedway.

Forinstance,theX-raydiffractionstudyrevealedthatinthesolidphasethe2-anilino-1-bromo-1-nitro-ethenehasconfigurationwiththetrans-orientationoftheNHandNO2groups[9].Itisknownhoweverthatinquiteanumberofenamineswithasecondaryaminogroupthecharacteristicconfigurationcorres-pondstothecis-positionoftheaminoandnitrogroups.TherewitharisesanintramolecularhydrogenbondNH...O2Nclosingaquasisix-memberedring[12,18320].Thusto2-anilino-1-nitro-1,2-diphenyl-ethenewasassignedaZ-configuration(cis-positionoftheaminoandnitrogroups)[20]duetotheindepen-denceoftheaminogroupbandintheIRspectrumoftheconcentrationofthecompound.

Themostdifficultistheassignmentofconfigura-tionforthetetrasubstitutednitroenaminescontainingtheaminerestwiththetertiarynitrogenatom.Inparticular,fromtheUVspectraldatafor2-morpholino-1-nitro-1,2-diphenylethene,namelyfromthepositionoftheabsorptionbandinthelongwaveregion[lmax4053408nm(e970039800)],wasconcluded[13]thatinsolutionswaspresentthemoreenergeticallyfeasibleandlessstericallystrainedEisomer(trans-positionoftheaminoandnitrogroups).TheX-raydiffractionstudyofthesamecompounddemonstratedthatitexistedintheformofZisomer(cis-positionoftheaminoandnitrogroups)[21].

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SYNTHESISANDSTRUCTUREOF1-BROMO-1-NITRO-2-PIPERIDINO-...

Table1.Coordinatesofatomsinthestructureofnitro-enamineII,equivalentisotropictemperaturefactorsofnonhydrogenatomsB=4/3SS(aiaj)B(i,j)(A2),andisotropictemperaturefactorsofhydrogenatomsBiso(A2)ÄÄÄÄÂÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄ

³³³³BorAtomxyz

³³³³Biso

ÄÄÄÄÅÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄBr³0.03277(5)³0.20655(3)³0.24005(4)³2.826(8)O1³30.1036(4)³0.3617(2)³0.2392(3)³4.33(8)O2³30.1904(4)³0.3944(2)³0.0018(3)³3.36(7)N1³30.1147(4)³0.3498(2)³0.1085(3)³2.74(8)N3³30.0084(4)³0.3195(2)³30.1457(3)³2.06(7)C1³30.0446(5)³0.2798(2)³0.0794(4)³2.09(8)C2³30.0367(4)³0.2635(2)³30.0604(4)³1.93(8)C4³30.0776(5)³0.3162(3)³30.3132(4)³2.70(9)C5³0.0494(6)³0.3352(3)³30.37(4)³3.3(1)C6³0.1320(6)³0.4137(3)³30.3144(5)³3.8(1)C7³0.2034(6)³0.4141(3)³30.1431(5)³3.7(1)C8³0.0703(5)³0.3955(2)³30.0843(4)³3.0(1)C9³30.0492(5)³0.1810(2)³30.1153(4)³2.14(8)C10³30.1741(5)³0.1320(3)³30.1125(4)³2.8(1)C11³30.1875(6)³0.0558(3)³30.1662(5)³3.8(1)C12³30.0742(8)³0.0274(3)³30.2195(6)³4.6(1)C13³0.0502(6)³0.0752(3)³30.2217(5)³4.1(1)C14³0.0638(5)³0.1517(3)³30.1690(4)³2.8(1)H10³30.243(4)³0.148(2)³30.087(4)³1.8(8)H11³30.277(5)³0.024(2)³30.162(4)³5(1)H12³30.091(6)³30.020(3)³30.259(4)³5(1)H13³0.131(6)³0.057(3)³30.250(5)³5(1)H14³0.152(5)³0.182(2)³30.174(4)³3.0(9)H41³30.126(5)³0.274(2)³30.341(4)³3.2(9)H42³30.160(4)³0.356(2)³30.344(4)³2.4(9)H51³0.131(5)³0.294(2)³30.339(4)³3.0(9)H52³30.012(6)³0.341(3)³30.488(5)³6(1)H61³0.215(5)³0.427(3)³30.341(4)³4(1)H62³0.041(6)³0.460(3)³30.361(5)³6(1)H71³0.2(5)³0.376(2)³30.101(4)³4(1)H72³0.248(5)³0.463(2)³30.098(5)³5(1)H81³0.111(5)³0.392(2)³0.019(4)³3.3(9)H82³30.017(5)³0.439(2)³30.109(4)³4(1)ÄÄÄÄÁÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄ

i=1j=13

3

431

Table2.Bondlengths(d,A)inthemoleculeofnitro-enamineII

ÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÒÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄBond³dºBond³d

ÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄ×ÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄBr3C1³1.879(4)ºC63H62³1.08(4)

³1.528(8)O13N1³1.234(5)ºC73C8

21771

³0.96(4)O3N³1.230(4)ºC3H

11772

³0.94(4)N3C³1.416(5)ºC3H

32881

³0.91(4)N3C³1.342(5)ºC3H

34882

³1.02(4)N3C³1.471(5)ºC3H

310

³1.3(6)N3C³1.468(5)ºC3C

12914

³1.399(6)ºC3C³1.387(7)C3C

291011

³1.483(5)ºC3C³1.378(6)C3C

451010

³1.510(7)ºC3H³0.79(4)C3C

4411112

ºC3C³1.380(9)C3H³0.82(4)

4421111

ºC3H³0.97(5)C3H³0.94(3)

561213

³1.518(7)ºC3C³1.372(8)C3C

5511212

ºC3H³0.88(4)C3H³0.96(4)

5521314

ºC3C³1.379(6)C3H³0.99(4)

671313

³1.503(6)ºC3H³0.91(5)C3C

6611414

ºC3H³0.96(4)C3H³0.(5)

ÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÐÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄ

changedbondlengths)evidenceasignificantelectrondensityredistributionincompoundIImolecule.WedeterminedexperimentallybyDebyemethod[28]thedipolemomentsofnitroenaminesII,IIIinbenzeneanddioxaneat25oC.Thefactorsforcalcula-tionequationsandorientationpolarizationarepre-sentedinTable4.IncalculationofdipolemomentsthevaluesofbondanglesweretakenfromtheresultsofX-rayanalysisofcompoundII,andalsothefollow-ingdipolemomentsofbondsandgroups:m(Csp26Br)0.66Dcalculatedfrommexp(CH2=CHBr),m(Csp26NO2)2.81Dfrommexp(CH2=CHNO2),m(Ph6Csp2)0.33Dfrommexp(C6H5CH=CH2),m(H6N)1.31Dfrommexp(NH3),m(Csp26N)2.12Dfrommexp(C6H5NH2),m(cyclo-C6H116N)1.06Dfrommexp(cyclo-C6H11NH2),m(Csp36N)1.02Dfrommexp(piperidine),m(Csp26N)2.11Dfrommexp(N-phenyl)piperidine.Allexperimentaldipolemomentsofmodelcompoundsusedincalculationofthemomentsforgroupsandbondsweretakenfrom[29].

ThestudyofthestructureofbromonitroenaminesII,IIIbydielcometrymethodrevealedthattheex-perimentalvaluesoftheirdipolemomentsarerelative-lylarge.Thecomparisonoftheexperimentalandcalculateddipolemomentsdoesnotallowdetermina-tionoftheEorZisomerstructure.AlthoughthemomentscalculatedfortheE-formsaremorealike

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contactsandbyinteractionsofthetypeCH...O(weakhydrogenbonds)andC5!H52...O1(x,y,z31).Theparametersofbondsareasfollows:C53H520.99(4),C5...O13.403(4),H52...O12.43(4)A;angleC53H52...O1168(5)o.Duetotheseinteractionsformendlesschainsalongthezaxis(Fig.2).ShortintramolecularcontactsC83H81...N1andC83H82...O2areapparentlyforcedbynitrogenatomsconjugationwiththedoublebond.Thusthedataobtained(plane-trigonalcoordinationofthenitrogenatominthepiperidinesubstituent,

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Table3.Bond(w,deg)andtorsion(t,deg)anglesinthemoleculeofnitroenamineII

ÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÒÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ

Angle³wºAngle³w³Angle³t

ÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄ×ÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ

O1N1O2³122.5(4)ºC6C5H52³108.0(3)³O1N1C1Br³7.95(0.51)111515521112ONC³118.5(3)ºHCH³119.0(4)³ONCC³3174.11(0.40)211567211ONC³119.0(3)ºCCC³110.8(4)³ONCBr³3168.85(0.30)23456612112CNC³122.8(3)ºCCH³115.0(3)³ONCC³9.08(0.62)23856624321CNC³123.5(3)ºCCH³109.0(2)³CNCC³3148.44(0.40)43876614329CNC³113.0(3)ºCCH³106.0(2)³CNCC³35.35(0.56)1176628321BrCN³115.7(3)ºCCH³111.0(3)³CNCC³21.15(0.62)12616628329BrCC³120.8(3)ºHCH³105.0(4)³CNCC³3155.06(0.38)1126782345NCC³123.4(3)ºCCC³111.0(4)³CNCC³3134.06(0.41)32167718345NCC³122.6(3)ºCCH³112.0(3)³CNCC³55.37(0.48)32967722387NCC³117.2(4)ºCCH³114.0(3)³CNCC³133.92(0.39)12987714387CCC³120.1(4)ºCCH³107.0(3)³CNCC³355.59(0.45)3458772123NCC³112.6(3)ºCCH³105.0(3)³BrCCN³3145.56(0.33)344171772129NCH³109.0(3)ºHCH³107.0(3)³BrCCC³30.(0.53)34423871123NCH³104.0(2)ºNCC³110.1(4)³NCCN³36.61(0.63)4138811129CCH³115.0(3)ºNCH³107.0(2)³NCCC³3147.29(0.40)42388232910CCH³110.0(3)ºNCH³110.0(2)³NCCC³3135.76(0.39)41442788132914HCH³106.0(3)ºCCH³113.0(3)³NCCC³44.67(0.52)456788212910CCC³110.2(4)ºCCH³113.0(3)³CCCC³47.93(0.)45518188212914CCH³105.0(3)ºHCH³103.0(3)³CCCC³3131.63(0.42)455229103456CCH³106.0(3)ºCCC³120.2(4)³NCCC³353.(0.47)655129144567CCH³109.0(2)ºCCC³120.6(4)³CCCC³.43(0.52)109141112125678CCC³119.2(4)ºCCH³117.0(4)³CCCC³356.44(0.52)910111312126783CCC³120.2(5)ºCCH³122.0(4)³CCCN³56.30(0.46)91010121314291011CCH³121.0(2)ºCCC³120.1(5)³CCCC³178.82(0.37)111010121313CCH³119.0(2)ºCCH³122.0(3)³³101112141313CCC³119.9(5)ºCCH³118.0(3)³³10111191413CCH³117.0(3)ºCCC³120.3(4)³³12111191414CCH³123.0(3)ºCCH³124.0(2)³³111213131414CCC³120.3(4)ºCCH³116.0(2)³³

ÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÐÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ

experimentalvalues,stillthedifferencebetweenthecalculatedandmeasuredvaluesistoobig:Dm3.934.4DforcompoundIIand2,533.2DforcompoundIII.TheresultsobtainedevidencethehighpolarityofbromonitroenaminesII,III,i.e.indicatethegreatcontributionintotheirstructureofbipolarformcon-+

taininga>C=NThisconclusionisinagreementwiththeelectronabsorptionspectraofcompoundsII,IIIcontainingabsorptionbandsinthelongwaveregion[compoundII:lmax419nm,(e12200);compoundIII:lmax373nm,(e18400)].Thelattervaluesareclosetothoseforthemodelcompound,1-nitro-1,2-diphenyl-2-cyclohexylaminoethenewithcis-positionofcyclo-hexylaminoandnitrogroups(lmax375nm,e20500)

[18].Thereforeitisreasonabletosuggestthatnitro-enamineIIIalsopossessesE-configuration.ThecharacterofIRspectraofnitrostyreneIIinsolidphaseandinchloroformsolutionisfairlyalike.ThereforeitispresumablethatbothinsolutionandsolidphasecompoundIImoleculesarepresentinEconfiguration.ItsIRspectrasimilarlytothespectraofpreviouslydescribednitroenaminescontainstrongabsorptionbandsin160031500cm!1regionthatmaybeattributedtothesystemofconjugatedmultiple+bondswithprevailingcontributionfrom>C=NC=NOO!moiety[1,19,20,30332].Theshifttolowerfre-quenciesofthebandsfrommultiplebondscomparedtothespectrumofE-2-bromo-1-(p-dimethylamino-phenyl)-2-nitroethene[30]maybeascribedtoap-pearanceofthefourthsubstituentatthedoublebond

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SYNTHESISANDSTRUCTUREOF1-BROMO-1-NITRO-2-PIPERIDINO-...433

Table4.ExperimentalandcalculateddipolemomentsofnitroenaminesII,III

ÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄComp.³³³³³³

SolventagPor,cm3mexp,Dmcalc,D

no.³³³³³³

ÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄ

II³C6H6³16.336³1.188³8.344³6.60³E:2.70

³Dioxane³20.617³0.521³1027.239³7.09³Z:2.29III³C6H6³16.769³0.198³1012.938³7.04³ð:4.51

³Dioxane³24.078³0.384³1212.386³7.70³Z:2.

ÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄ

(piperidinogroup)anditscis-orientationwithrespecttonitrogroup[33].Theobservedspectralpatterncharacterizesthemoleculesofthecompoundunderconsiderationashighlypolarized,withasignificantcontributionfromthestricturewithseparatedcharges.

.C6H5

eiqm7

N

+

C=C

Br

NOO!

InsimilarincharacterIRspectraofnitrostyreneIIIinmineraloilandinCHCl3isobservedaweakabsorptionbandat3200cm!1belongingtoNHgroupparticipatinginahydrogenbond;sincethepositionandformofthebanddoesnotchangeatdilutionofthesolutionsinCHCl3andbenzene,itshouldorigi-natefromtheintramolecularhydrogenbondNH...O2N[34].ThereforetheNHandNO2groupsinthemole-culeshavecis-orientation,i.e.themoleculesareofEconfiguration.

ÄÄÄÄÄÄÄÄÄÄÄÄ

H5C6BrBrH5C6

C3CC=C+cyclo-C6H113N.N46cyclo-CH3.NHNOO!611

H_OO

ieieeq󰂀

eiqm

ÄÄÄÄÄÄÄÄÄÄÄÄ

Fig.2.PackingofnitroenamineIImoleculesinacrystal.Projectionalong0–axis.Dottedlinesshowthehydrogenbonds

C3H...O.

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434ISHMAEVAetal.

TheabsorptionbandsintheIRspectraofcom-poundIIIinthe160031100cm!1regionaresome-whatdifferentinpositionandintensityfromthoseinthespectrumofcompoundII;howeverthegeneralpatternofthespectrumisretained:strongbandsat157031562cm!1andanumberofbandsat1350,122031210,113431124cm!1apparentlyoriginatingfromasystemofconjugatedmultiplebondsandionizednitrogroupNOO!.

ItshouldbenotedthatourassignmentsoftheabsorptionbandsintheIRspectraofcompoundsII,IIIarewellconsistentwiththedatadescribedin[1,19,20,30332].HowevertheinterpretationoftheIRabsorptionbandsofthenitroenaminesintheliteratureisnotalwaysunambiguous.Forinstance,in[1]theabsorptionbandsat153031480cm!1wereattributedtotheN3Obondvibrations,andthebandsat128031230cm!1tons(NO2).Thebandat1676cm!1accord-ingtothebook[33]belongingtotheabsorptionoftheC=Nbond,whereasin[35]thebandsinthe165031550cm!1regionaredesignatedas[enaminebands.]Howeverirrespectiveofthedifferenceinassignmentofthebandstodefinitegroupsalltheresearchersmakethesameprincipalconclusionontheprevailingcontributionintothegroundstateofthemoleculesofstructureswithseparatedcharges.

Thusinthecourseofthestudyreportedwerede-velopedconvenientpreparativeproceduresforthesynthesisofnewbromonitroenamines:1-bromo-1-nitro-2-piperidino(cyclohexylamino)-2-phenylethenes.TheirfinestructurewasinvestigatedbymeansofX-raydiffractionanalysis,dipolemoments,IR,1HNMR,andelectronicspectroscopy.WeestablishedEconfigurationandhighpolarizationofthemoleculesofcompoundsstudiedoriginatingfromtheefficientconjugationwithparticipationofthelonepairofpiperidineorcyclohexylaminenitrogen,carbon3carbonmultiplebond,andnitrogroup.

b113.90(2)o,V1312.2(5)A3,Z4,dcalc1.575g/cm3,spacegroupP21/c.Unitcellparametersandintensitiesof2933reflections(11868amongthemwithI>3s)weremeasuredonanautomaticfour-circlediffractometerEnraf-NoniusCAD-4at20oC((lM°K=-irradiation,graphitemonochromator,w/2q-scanning,q<29o).Inthecourseoftherecord-ingwasnointensitydecreaseobservedforthreecontrolreflections.Theabsorptionwastakenintoaccountempirically(mMo30.96cm!1).Thestructurewassolvedbyheavyatommethod.ThebromineatomscoordinateswerecalculatedfromthepeaksofthePatterson’sfunction.Afterrefiningthelatterintheisotropicapproximationallthenonhydrogenatomswererevealedfromthedifferenceseriesoftheelec-trondensity.Thestructurewasrefinedfirstiniso-tropicandtheninanisotropicapproximation.Afterthatfromthedifferenceseriesoftheelectrondensitywererevealedallhydrogenatomsandfinallyrefinedintheisotropicapproximation.Thefinalvaluesofdivergencefactorsareasfollows:R0.037,RW0.047from12independentreflectionswithF2>3s.AllcalculationswerecarriedoutwiththeuseofprogrampackageMolEN[15]onthecomputerAlphaStation200.ThefiguresandanalysisofintermolecularcontactsinthecrystalwasperformedalongPLATONroutine[20].

1,2-Dibromo-1-nitro-2-phenylethene(I)waspre-paredasdescribedin[10].

1-Bromo-1-nitro-2-piperidino-2-phenylethene(II).Amixtureof0.61gofnitrostyreneI,0.4mlofpiperidine,and10mlofanhydrousbenzenewasref-luxedfor2h;duringtheprocessseparatedaprecipi-tate.Themixturewascooled,thepiperidinehydro-chloridewasfilteredoff,andthefiltratewaspouredintoaPetridishforevaporatingthesolvent.There-siduewaswashedwithdistilledwater.Weobtained0.59g(97%)ofcompoundII,mp1493150oC(frommethanol).IRspectrum,n,cm!1:1512,1418,1294,12,1232,1208,1152,1120(mineraloil);1520,1418,1296,12,1232,1208,1156,1120(chloro-form).1HNMRspectrum(CDCl3),d,ppm:1.68,3.15(C5H10N),7.60(C6H5).UVspectrum(CH3CN),lmax,nm(e,lmol!1cm!1):419(12200).Found,%:C50.17,50.22;H4.,4.92;N9.07,9.08.C13H15BrN2O2.Calculated,%:C50.18;H4.82;N9.01.1-Bromo-1-nitro-2-phenyl-2-cyclohexylamino-ethene(III)wasobtainedinasimilarwayfrom1.23gofcompoundI,0.97mlofcyclohexylaminein20mlofanhydrousbenzene(boilingfor3.5h.Weisolated1.18g(91%)ofcompoundIII,mp1613163oC(fromamixturehexane3benzene,1:1).IR

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IRspectrawererecordedonaSpecordM-80spec-trophotometer(insolidphase,inchloroform,andinbenzenesolutions,concn.from0.1to0.001mol/l).1

HNMRspectrawereregisteredonspectrometersBrukerAC-200(200MHz),TeslaBS-487C(80MHz)fromsolutionsinCDCl3;chemicalshiftswereme-asuredeitherfrominternalreference(HMDS,TMS),orfromexternalreference(HMDS),accuracywithin+0.5Hz,dscale.ElectronabsorptionspectraweremeasuredonspectrometerSF-46inquartzcells,solventacetonitrile.

CrystalsofcompoundIImonoclinic,mp1493150oC,At20oCa8.823(2),b16.955(3),c9.594(2)A;

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SYNTHESISANDSTRUCTUREOF1-BROMO-1-NITRO-2-PIPERIDINO-...435

spectrum,n,cm!1:3200,2370,1676,1568,1562,1412,1350,1320,1210,1124(mineraloil);3180,2500,1570,1562,1414,1376,1350,1220,1134,1072(chloroform).1HNMRspectrum(CDCl3),d,ppm:1.1431.,2.96(cyclo-C6H11N),7.29(C6H5),11.05(NH).UVspectrum(CH3CN),lmax,nm(e,lmol!1cm!1:373[18400].Found,%:C51.73,51.74;H5.24,5.26;N8.71,8.69.C14H17BrN2O2.Calculated,%:C51.70;H5.23;N8.62.

14.

ACKNOWLEDGMENTS

ThestudywascarriedoutunderfinancialsupportoftheProgramonSupportoftheLeadingScientificSchools(grantsnos.00-15-97424and96-15-97391)andoftheProgram[RussianUniversities,Funda-mentalResearch])(grantno.015.05.01.17)

15.16.17.18.19.20.

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