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Chapter10
CompoundsofPhosphorusandArsenic
Followingthegenerallyrecognizeddiagonalrelationship,Phosphorusisinmany
respectstheelementthatismostsimilartocarbon.
Phosphorusgivesrisetoanextensiveseriesofheterocycles.
Phosphorusheterocyclescanbestronglydelocalized
phosphorusformsstrongdoubleandtriplebondswithcarbon
Phosphorus(III)compoundssuchasPCl3,P(OMe)3,PR3aresyntheticreagentsand
areextensivelyusedasligandsintransitionmetalchemistry.
Asingletypeoforganophosphoruscompounds,theWittigreagentshasgainedsuch
animportancethatitsdiscoverywashonoredwiththeNobelPrizeinChemistry1979
(jointlyawardedtoG.WittigandH.C.Brown)

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H.C.Brown

G.Wittig

TheNameReactionsofPhosphorusChemistry
Anumberofsyntheticallyimportantreactionsofphosphoruschemistryarereferred
tobythenameoftheirdiscoverer:
WittigOlefinSynthesis
StaudingerReaction
McCormackReaction
KuchtinRamirezReaction
MichaelisArbuzovReaction
MitsunobuReaction
NoyoriReaction

Phosphorus:OxidationStatesandCoordinationNumbers
Theelementphosphorusgivesrisetoalargenumberofstablecompoundsin
differentcoordinationnumbersandoxidationstates.
Theoxidationstateofphosphoruscompoundsisindicatedasusualwithroman
numerals.
Anewnomenclaturetriestoincludethecoordinationnumberofthecentralelement
bytheadditionofagreeklambdawiththeappropriatecoordinationnumberas
subscript:
Ausefulwaytooutlinethebreadthofbondingtypesisaclassificationofphosphorus
compoundsaccordingtocoordinationnumberandoxidationstate:
Coordination Oxidation
Number
State

Examples
Phosphaalkynes,

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RCP

Phosphenium
Cations,[R2P]+

PhosphinesR3P
Phosphites(RO)3P

Phosphonium
Cations[R4P]+

PhosphonatesR
P(O)(OR')2

WittigReagents
R3P=CR'2

PhosphoranesR5P

PhospheniumCations
Phospheniumcationsarebentspeciesthatisoelectronictosingletcarbenes.Theyare
verystrongelectrophilesandusuallyhavesomeformofbondingwitheitherthe
counterionorthesolvent
Likecarbenes,theycanbestabilizedbydonorsubstituentsespeciallyamines.Such
donorstabilizedphospheniumcationsarestableenoughtobeisolatedandsomeof
themhavebeencharacterizedbysinglecrystalXraycrystallography.TheN2Pangles
aretypicallycloseto90oandtheNPbonddistancesindicatedoublebondcharacter.
Asurprisinglysimpleapproachtophospheniumcationswasreportedby
Schmidpeteretal.:reactionofPCl3,Ph3PandAlCl3leadstotheformationofthe
phospheniumcation[(Ph3P)2P]+:

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Tris(dimethylamino)phosphanesreactssimilarlytogive
thecorrespondingtriphosphane:

AromaticPhospheniumCations
Phospheniumcationscanbestabilizedbyaromaticityasthefollowingexample
illustrates:

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TheMcCormackReaction
OneofthemostwidelyusedsyntheticreactionsistheMcCormackreaction:

6,6(Ethylenedioxyl)lmethylA32,4,5,6,7,7a
hexahydro1Hphosphindole1oxide[3]

(2).3Ahexanesolutionof1vinyl4,4ethylendioxycyclohexl
ene1(20.0g,0.12mol)andfreshlydistilledCH3PCl2(18.3g,0.
156mol)andcopperstearate(0.4g)asapolymerization
inhibitor,wasallowedtostandatrtfor5days.Theadductwas
filteredandthefiltratewaskeptfor22daystogetmorecyclo
adduct.ThefirstcropwashydrolyzedbyNaHCO3,extracted
withCHCl3,andafterevaporationgave19.36gof2(72.7%),mp.
156157oC.

TheKuchtinRamirezReaction
TheMcCormackreactioncanbeextendedtoavastnumberof1,3heterodienes.The
reactionofP(III)compoundswith1,2diketonesisparticularlywidelyusedandis
sometimescalledtheKuchtinRamirezReaction:

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References
 McCormack,W.B.,U.S.Pat.2.663.736and2.663.737.
 Hajos,A.G.,J.Org.Chem.1956,30,1213.
 Quin,L.D.,J.Org.Chem.,1981,46,461.
 Kuchtin,V.A.,Doklad.Akad.Nauk.USSR,1958,121,466.
 Ramirez,F.,J.Am.Chem.Soc.1960,82,2651.
 Mitsuo,S.,J.Org.Chem.1981,46,4030.

Phosphaalkynes
Methylidynephosphane,HCP,wasfirstproposedasreactiveintermediatebyAlbers
[1]butwasonlycharacterize10yearslaterbyGier[2]throughthepyrolysisofPH3
inarotatingarcofcarbonelectrodes.

Thecompoundisextremelyreactive,butstericallyshieldedderivativesaremore
stable.ThefirststablephosphaalkynewasreportedbyG.Beckerin1981[3]:

ThestartingmaterialisobtainedfromP(SiMe3)+tBuCOCl[4]:

References
 H.Albers.Angew.Chem.1950,62,443.
 T.E.Gier,JACS,1961,83,1769.
 G.Becker,G.Gresser,W.Uhl,Z.Naturforsch.1981,36b,16.SeealsoW.Rsch,

U.Hees,M.Regitz,Chem.Ber.1987,120,1645.W.Rsch,U.Vogelbacher,T.
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Allspach,M.Regitz,JOM,1986,306,39M.Regitz,W.Rsch,T.Allspach,U.
Annen,K.Blatter,J.Fink,H.Hermesdorf,H.Heydt,U.Vogelbacher,O.
Wagner,PhosphorusSulfur,1987,30,47,.
 G.Becker,Z.Anorg.Allgem.Chem.1976,423,242.

ReactionsofPhosphaalkynes
Phosphaalkyneshaveafascinatingreactionchemistry.At130oC,tBuCP
tetramerisestoatetraphosphacubane:

Arsaalkynes
Arsaalkynesrequireevenlargersubstituentstobekineticallystable:

Phosphites
Phosphites(RO)3PareobtainedfromPCl3andthecorrespondingalkoxides/
phenoxides.

Phosphines
PhosphinesR3Parethephosphoruscompoundscorrespondingtoamines.

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Phosphines:DifferencesBetweenNitrogenandPhosphorus
Thesynthesisofthechelateligandbis(1,2diphenylphosphinoethane)(dppe)
highlightsthesignificantdifferencesbetweennitrogenandphosphorus:

ChelatingPhosphines
Thesynthesisofchelatingphosphineligandshasbeenthesubjectofmanystudies.
EspeciallyusefularethegeneralstrategiesthatweredevelopedbyR.B.Kingetal.
King'sapproachusestheadditionofphosphinesR2PHtosuitablyactivatedolefins
CH2=CHX(Michaelsystems)[1]:

ThephosphinesR2PHandRPH2canbeobtainedfromthephosphonates(via
MichaelisArbusovreaction)orthechlorides(fromPCl3+Grignard)byLiAlH4
reduction.
Thesereactionsarebasecatalyzed(formationofR2PHasnucleophile)andrequire
thepresenceofelectronwithdrawingsubstituentsonthedoublebond.
TheadditionofPHbondsacrossnonactivatedCCdoublebondscanbeachieved
underradicalconditions[2]:

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Theapproachhasrecentlybeenextendedtothesynthesisofphosphanedendrimers
[3]:

ThecompoundsPh2PHareeasilyaccessiblethroughasomewhatsurprising
reductionreaction:

ThesideproductPhLicanbeselectivelyremovedammonia[4].
References
 R.B.KingJ.C.Cloyd,JACS,1975,97,4652and5364
 N.Bampos,L.D.Field,B.A.Messerle,R.J.Smernik,Inorg.Chem.1993,32,

40844088.
 A.Miedaner,C.J.Curtis,R.M.Barkley,D.L.DuBois,Inorg.Chem.1994,33,
54825490.
 A.J.Ashe,J.W.Kampf,D.B.Puranik,J.OrganometalChem.1993,447,197
201.

Phospholes
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Unlikepyrrole,thehigherhomologuesarenonaromaticdiolefinswithpyramidal
heteroelement.

AromaticityisinsufficienttocreateaplanargeometryatP/As,butlowersthe
inversionbarriersofPandAsbyca.50kJ/mol.
InversionbarrierofNH3:24kJ/mol
InversionbarrierofPH3:155kJ/mol

PhospholeComplexes
Phenylgroupscanthusbeusedasprotectivegroupsinthesynthesisofphosphines.
Thisreactionisalsousefulforthesynthesisofarsanes,stibanesandbismutanes:

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PhosphanesasLigands
NumeroustransitionmetalcomplexeshavebeendescribedforPF3,PCl3[1],PBr3[1]
andorganophosphines.
 M.S.Davies,M.J.Aroney,I.E.Buys,T.W.Hambley,J.L.Calvert,Inorg.

Chem.1995,34,330336.

TheTolmanAngle
Thebasicity(pKaofR3PH+)andthestericdemandofphosphinesinfluencesthe
stabilityandreactivityofphosphinecomplexesandcanbothvarysubstantiallyfrom
ligandtoligand.

Thestericdemandofphosphinesintransitionmetalcomplexescanbeestimated
withtheTolmanangle.NotethattheTolmanangledependsontheMPdistance:
Cone
Angle

pKa

US$/
g

Ref.

P(OMe)3

107

2.60

0.38

PMe3

118

8.65

5.55

PhP(OMe)2

120

2.64

6.20

PhPMe2

122

6.5

6.20

Ph2PH

126

0.03

2.59

(PhO)3P

128

2.00

0.02

(OiPr)3P

130

4.04

0.07

Ph2POMe

132

2.69

9.64

Et3P

132

8.69

4.30

(nBu)3P

132

8.43

2.88

Compound

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Ph2PMe

136

4.57

3.77

Ph3P

145

2.73

0.12

(pMeC6H4)3P

145

3.84

8.34

(p
MeOC6H4)3P

145

4.59

14.69

(iPr)3P

160

26.20

(PhCH2)3P

165

6.0

13.66

(mMeC6H4)3P

165

3.30

45.65

(Cy)3P

170

9.70

4.91

(tBu)3P

182

11.40

21.78

(2,6
MeOC6H3)3P

184

9.33

3.67

4,5

(2,4,6
MeOC6H2)3P

184

11.02

2.85

(o
MeOC6H4)3P

194

3.08

8.31

(2,4,6
MeC6H2)3P

212

7.3

18.36

References:
 C.A.Tolman,Chem.Rev.1977,77,313.
 M.Rahmanetal.Organometallics1989,8,1.
 M.Rahmanetal.Organometallics1987,6,650.
 Y.Yamashoui,Chem.Lett.1988,43.
 H.Kurosawaetal.Bull.Chem.Soc.Jpn.1987,60,3563.

PhosphinesasReducingAgents:TheMitsunobuReaction
Interandintramolecularnucleophilicdisplacementofalcoholswithinversionby
meansofdiethylazodicarboxylate(DEAD)triphenylphosphineandanucleophile.
Alsodehydration,esterificationofalcoholsoralkylationofphenols:
()Methylcis3hydroxy4,5oxycyclohexlenecarboxylate(2).[4]

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To()methylshikimate1(220mg,1.06mmol)andtriphenylphosphine(557mg,
2.12mmol)inTHFat0oC,underN2wasaddedwithstirring(DEAD)(370mg,2.12

mmol).After30minat0oCand1hat20oC,itwasvacuumdistilled(Kugelrohr)at
165oC(0.1mm)andtakenupinEt2OCoolinggavebis(carbethoxy)hydrazine(10
mg,mp133oC).Thefiltratewasconcentratedandchromatographed(preparative
TLCsilicagelEt2O)toafford140mgof2(77%)onstandingrecrystallizedfrom
Et2Opetroleumether,mp8182oC,a25=55.4'.
References
1.
2.
3.
4.
5.
6.
7.

Mitsunobu,O.Bull.Chem.Soc.Jpn.1967,40,2380.
Miller,M.J.J.Am.Chem.Soc.1980,102,7026.
Evans,S.A.J.Org.Chem.1988,53,2300.
McGovan,D.A.JOrg.Chem.1981,46,2381.
Mitsunobu,O.Synthesis1981,1.
Crich,D.J.Org.Chem.1988,54,257.
Hassner,A.J.Org.Chem.1990,55,2243.

ChiralPhosphines:TheNoyoriReaction
Thehomogeneouschiralhydrogenationofunsaturatedalcohols,orcarboxylicacids,
enamides,ketonesinthepresenceofBINAPRuorRhcomplex8ascatalyst.
(R)(+)2,2'Bis(diphenylphosphino)1,1'binaphthyl(BINAP)(7).[2]

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(R)(+)2,2'Bis(diphenylphosphino)1,1'binaphthyl(BINAP)(7).[2]
ToMg(2.62g,0.108gat)underN2wasaddediodine(50mg),THF(40mL),1,2
dibromoethane(0.51mL).2.2'Dibromo1,l'binaphthyl1(20g,46.4mmol)in
PhMe(360mL)wasaddeddropwiseoveraperiodof4hat5075oC.After2h
stirringat75oCthemixturewascooledto0oCanddiphenylphosphinylchloride2
(23.2g,98mmol)inPhMe(23mL)wasaddedover30min.Themixturewas
heatedto60oCfor3h,cooled,quenchedwithwater(60mL,stirredat60oCfor10
minandtheorganiclayerconcentratedto60mL.After24hat20oC,theproduct
wasfiltered,stirredwithheptane(45mLandPhMe(5mL),filteredanddriedto
afford27.5gof()3(91%),mp295298oC(pure304305oC).(t)
3(65.4g,0.1mol),(1S)(+)camphorsulfonicacidmonohydrate4(25g,0.1mol)
andEtOAc(270mL)wereheatedtorefluxandHOAc(90ml)wasaddedtogeta
clearsolution.Graduallycoolingto23oC,filtrationandwashing(EtOAc)gave35.3
gofa1:1:1complexof3:4:AcOH.ThecomplexwassuspendedinPhMe(390
mL),treatedwithwater(30mL)at60oCandcooled.Theorganiclayerwas
concentratedto50mLandtreatedwithhexane(50mL).Filtrationanddryinggave
22.2gof(R)(+)5(68%),mp262263oC,J4=+399o(c0.5PhH).(R)5(50g,
76.4mmol),xylene(500mL),Et3N(324g,320mmol)andtrichlorosilane(41.4g,
304mmol)underArwereheated1hat100oC,1hat120oCand5hatreflux30%
NaOH(135mL)wasaddedunderstirringat60oC,theorganiclayerwas
concentratedandtheresiduetreatedwithMeOH(200mL)togive47.5gof(R)
BINAP7(95%),mp241242oC,J4=228o(c0.679PhH).

Methyl(R)3hydroxybutanoate(10).[4]ToRu(OAc)2and(R)7(806mg,
0.975mmol)inCH2Cl2(210mL)wasadded1.42NHOlin90%MeOH(1.41mL,2

mmol).After2.5hstirringat20oCthesolventwasevaporatedtogive(R)BlNAP6
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(722mg)storedunderAr.Catalyst8canalsobepreparedfromRu(COD)Cl2,
BlNAPandTEA.[3]Asolutionofmethyl3oxobutanoate9(100g,0.862mol)in
MeOH(100mL)wastreatedwithcatalyst8(341mg,0.429mmol)and
hydrogenatedat100atmand30oC.Vacuumdistillationafforded97.5gof10
(96%),bp40oC/2mm,a24=24.20(neat),99%ee.
References
1.
2.
3.
4.
5.
6.
7.
8.
9.

Noyori,P,J.Am.Chem.Soc.1980,102,7932.
Noyori,R.J.Org.Chem.1986,51,629.
Noyori,R.J.Am.Chem.Soc.1986,108,7117.
Noyori,R.J.Am.Chem.Soc.1987,109,5858.
Noyori,R.J.Am.Chem.Soc.1989,111,9134.
Noyori,,R.Chem.Soc.Rev.1989,18,187.
Noyori,R.Science1990,248,1194.
Otsuka,S.Synthesis1991,668.
Noyori,R.Acc.Chem.Res.1990,23,345.

SilylatedPhosphines
Silylatedphosphines,especiallytris(trimethylsilyl)phosphine,arecovalentsynthons
fortheanionsR2P,RP2andP3:

P(SiMe3)3canbeobtainedfrom:
P4+Na/Kalloy+Me3SiCl(80%)
PH3+Me3SiOTf+Et3N(90%)
NaPH2+Me3SiF(35%)
PiperidylPCl2+Li+Me3SiCl(71%)
PCl3+Mg+Me3SiClinTHF(62%)
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Thelastmethodisnotonlythemostcosteffectiveonebutalsothesafest.(H.
Schuman,L.Rsch,Chem.Ber.1974,107,854)
PhosphinesRP(SiMe3)2arebestobtainedfromRPCl2viathesaltsRPLi2[13]:

Polyphosphanes(RP)ncanbeisolatedfromthedistillationresidues.
FortheuseofR2P(SiMe3)2see[46]:
 O.I.Kolodiazhnyiin"SyntheticMethodsofOrganometallicandInorganic

Chemistry"(W.A.Herrmann,ed.)ThiemeVerlag,1996,Vol.3,p70.
 G.Becker,O.Mundt,M.Rssler,E.Schneider,Z.Anorg.Allg.Chem.1978,
443,42.
 H.Schuman,L.Rsch,Chem.Ber.1974,107,854.
 Wentrup,H.Briehl,G.Becker,G.Uhl,H.J.Wessely,A.Maquetiau,R.
Flamming,JACS,1983,105,7194.
 R.Appel,W.Paulen,TetrahedronLett.1983,24,2639.
 O.I.Kolodiazhnyi,TetrahedronLett.1982,23,4933.

PhosphorusYlides(WittigReagents)
Wittigreagentsareaccessiblefromphosphines(R=alkyl,aryl)orphosphites(R=
alkoxy)intwosteps:

WittigReagentsarehighlyreactiveusuallygeneratedinsitu.Mesomerically
stabilizedWittigreagentscanbequitestableandaresometimesevenavailable
commercially:
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PhosphorusylidesarenotonlyimportantsynthonsoftheWittigreactionbuthave
alsobeenusedextensivelyasalkylligands,notablybythegroupofSchmidbaur
 H.Schmidbaur,Angew.Chem.Int.Ed.Engl.1983,22,907927.
 W.C.Kaska,Coord.Chem.Rev.1983,48,158.

ArsenicYlides
althoughthefirstarsenicylidewasreportedasearlyas1902byMichaelis[1],arsenic
ylidesremainedvirtuallyuntilthefamousSchmidbaurpublicationin1975[2].
Arsenicismuchmorereluctanttofrom"good"doublebondstocarbonasthe
comparisonbetweenphosphorusylidesandarsenicylidesillustrates:

AlkylidenearsoranescleanlydecomposetoarsinesR3Asandcarbenes(comparethe
syntheticuseofsulfurylidesascarbenetransferreagents)
 A.Michaelis,Annalen1902,321,141ibid.1901,320,271.
 Y.Yamamoto,H.Schmidbaur,J.Chem.Soc.Chem.Commun.1975,668669

andreferencestherein.
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TheWittigOlefinSynthesis
Theterm"olefinsynthesis"shouldbeusedtoavoidtoconfusionwiththeWittig
rearrangement(the[2,3]sigmatropicrearrangementofallylethertohomoallyl
alcohols).
In1953,G.WittigandG.Geisslerreported,thatphosphoraneylidesreactwith
aldehydesorketonestogiveolefines.cisolefinspredominateinaliphaticsystems,
transinconjugatedolefins.
G.WittigandG.Geissler"Reactionsofpentaphenylphosphorusandseveralof
itsderivatives,Annalen,1953,580,4457
trans4Nitro4methoxystilbene[3]
Triphenylphosphine(26.3g,0.1mol)andpnitrobenzylchloride(17.2g,0.1mol)in
PhH(50ml)wererefluxedfor2h.Aftercoolingthesolidwascollectedandwashed
withPhHtogive25gofphosphoniumsalt(58%),mp270276oC.Recrystallized
fromCCl4petroleumether,mp278280oC.
Tostirredphosphoniumsalt(4.3g,10mmol)inPhH(50mL)underN2wasadded
butyllithium(0.85g,13mmol)toproducetheylide.After2hanisaldehyde(1.63g,
12mmol)wasadded,themixturewasdilutedwithpetroleumetherandthedark
solidcollected.Recrystallizationafforded2.23g(89%)trans4Nitro4
methoxystilbene,mp131132.5oC.
References
1.
2.
3.
4.
5.
6.
7.
8.
9.

Wittig,G.,LiebigsAnn.,1949,562,187.
Wittig,G.,Chem.Ber.1961,94,1373.
Ketcham,R.,J.Org.Chem.1962,27,4666.
Angeletti,E.,J.Chem.Soc.PerkinTr.1,1987,713.
Doudon,A.,Tetrahedron1988,44,2021.
Emmons,W.,Angew.Chem.Int.Ed.1966,5,126.
Murphy,P.B.,Chem.Soc.Rev.1988,17,1.
Maercker,A.,Org.React.1965,14,333.
Maryanoff,B.E.,Chem.Rev.1989,89,863.

PentacoordinatePhosphorusCompounds(Phosphoranes)
ThefirstorganicderivativeofpentacoordinatephosphoruswasobtainedbyG.Wittig
in1948:
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Theelementsofgroup15arereluctanttoformcompoundsR5E.NMe5andPMe5are
stillunknownatpresentbutAsMe5,SbMe5andBiMe5havebeenprepared.BiMe5
decomposesabove100oC.

SubstitutionwithphenylgroupsincreasesthestabilityofER5.Ph3SbMe2isstableup
to+70oC.

S.Wallenhauer,K.Seppelt,Inorg.Chem.1995,34,116119.

Phosphoranes:DecompositionPathways
TheexistenceofPCl5as[PCl4]+[PCl6]inthesolidstatedemonstratesawayfor
phosphorustoavoidthecoordinationnumber5.Thetendencydodissociateis
greatlydiminishedincyclicphosphoranes:

Therelativetendencyofsubstituentstooccupytheaxialpositioncanbedetermined
bydynamicNMR(1H,19F,13C,31P).Themostelectronegativesubstituents
occupytheaxialpositions.
Stronglyelectronegativesubstituentsdestabilizethephosphoniumcationandhence
favorthephosphoranestructure:

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Squarepyramidalgeometrieshavebeenreportedforcertaincyclicphosphoranes:

Anotherwayforphosphorustoevadecoordinationnumber5istheeliminationof
arylHoralkylH:

Thisprocessismuchlessfavorableifthephosphorusatomispartofaring.
Whilecyclicphosphitesarethermallyquitestable,cyclicdioxaphospholanesgive
extrusionoftrivalentphosphorusunderringcontraction:

ReferencesonPhosphoranes
 Emsley,J.Hall,C.D.,TheChemistryofPhosphorus,HarperandRow,New

York,1976.
 Hellwinkel,D.,in:OrganicPhosphorusCompounds,Kosolapoff,G.M.Maier,
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L.,eds.,WileyInterscience,1973,vol,3,pp18S339,
 Cadogen,J.1.G.,ed.,OrganophosphorusReagentsinOrganicSynthesis,
AcademicPress,NewYork,1979.
 Sheldrick,W.S.,in:TopicsinCurrentChemistry,SpringerVerlag,NewYork,
1978,vol73,pp.248,andreferencescitedtherein,
 Trippett,S.:OrganophosphorusChemistry,19691979,vols,ITI,Specialist
Reports,ChemicalSociety,London,
 Smith,D.J.H.,inComprehensiveOrganicChemistry,Sutherland,1.0.,Ed.
PergamonPress,NewYork,1979,vol.2.Ch.
 Westheimer,F.,AccountsChem.Res.1968,1,70andreferencescitedtherein.
 Ramirez,F.,lbid,p.168.andreferencescitedtherein.
 Holmes,R.R.,J.Am.Chem.Soc.1974,96,4143.
 Trippett,S.,Phos.Sulfur1976,1,89.,
 Hoffmann,R.Howell,J.M.,Muetterties,E.L,J.Am.Chem.Soc.1972,94,
3047.
 Ramirez,F.etal,Angew.Chem.Int.Ed.Engl.1971,10,687.
 Berry,R.S.,J.Chem.Phys.1960,32,933.
 Muster,J.E.,Tet.Letter.1973,1093.
 Wittig,G.,Bull.Soc.Chim.Fr.1966,1162b.Ramirez,F.,etalJ.Am.Chem.
Soc.1965,87,543C.Ramirez,F.,etal,ibid.,1967,90,751and3531.
 Trippett,S.Waddling,R.E.L.,Tet.Lett.1979,193Trippett,S.FontFreide,
J.,J.Chem.Soc.Chem,Comm.1980,157.
 R.J.P.,etal.Tetrahedron1979,35,2889,andreferencescitedtherein.
 Ramirez,F.,Synthesis,1974,90,andreferencescitedtherein.
 Denney,D.B.,etal,J.Org.Chem.1978,43,4672Denney,D.B.,etal.J.Am.
Chem.Soc.1966,88,1839Denney,D.B.,etal,Ibid,1969,91,S243.
 Voncken,W.G.Buck,H.M.,Recl.Trav.Chim.PaysBas1974,93,14,210.
 Ramirez,F.,etal,J.Am.Chem.Soc.1960,82,2652Ramirez,F.,etal,J.Org,
Chem.1968,33,20Ramirez,F.,J.Am.Chem.Soc.1969,91,496Ramirez,F.,
etal,ibid.,1970,92,6935.
 Corre,E.Foucand,A.,J.Chem.Soc.Chem.Comm.1971,570.
 Stephenson,L.M.Falk,L.C.,J.Org.Chem.1976,41,2928.
 Ramirez,F.,etal,J.Am.Chem.Soc.1965,87,543Ramirez,F.,etal,J.Org.
Chem.1965,30,2575Ramirez,F.,Tet.Lett.1965,261Ramirez,F.,etal,Tet.
1968,24,1931.
 Ramirez,F.etal.,J.Org.Chem.1966,31,3159ibid.1966,31,474ibid.,1967,
32,21943547ibid.,1968,33,1185.
 Ramirez,F.,etal.,Tetrahedron1968,24,3153.
 Inouye,Y.,etal,Bull.Chem.Soc.Japan1969,42,2948.
 David,S.,etal,J.Chem.Soc.Chem.Comm.1976,747.
 David,S.,etal,J.Chem.Soc.Perkin11980,1262.
 Burgada,R.Fauduet,H.Nouv.J.Chim.1980,4,112,
 Ramirez,etal,J.Am.Chem.Soc.1967,89,3026.
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 Ramirez,F.etal,J.Org.Chim.1969,34,376.
 Ramirez,F.etal.,J.Am.Chem.Soc.1967,89,3030Ramirez,F.etal.,ibid.,

1970,92,6935.
 Ramirez,F.etal.,Phos.,1973,2,185.
 Ramirez,F.etal.,Tetrahedron1975,31,2007.
 Ramirez,F.etal.,Heterocycles,1978,11,631.
 Mukaiyama,T.Kumamoto,T.Bull.Chem.Soc.Jpn.1966,39,879.
 Denney,D.B.,etal.,J.Am.Chem.Soc.1969,91,5821.
 Denney,D.B.,etal.,ibid.,1971,93,4004.
 Bartlett,P.D.,etal.,ibid.,1973,95,6486.
 Ramirez,etal.,J.Org.Chem.1968,33,13.
 Denney,D.B.,eta.,Phos.,1971,1,151.
 Ishikawa,M,etal,Chem.Lett.1979,845.Ishikawa,N.,etal.,J.Org.Chem.
1980,45,5052.
 Kobayshi,Y.,Askahi,C.,Chem.Pharm.Bull.1968,16,1009.Witey,G.A.,etal,
J.Am.Chem.Soc.1964,86,964.
 Motoyoshiya,J.,etal,J.Org.Chim.1980,45,5385.
 Ohah,G.A.,etal,Synthesis,1974,506.
 Piers,E.,Nagakura,I.,Syn.Comm.1975,5,193.
 Appel,R.,Chem.Ber.1970,109,814.
 Ramirez,etal,J.Org.Chem.1968,33,1192,
 Harpp,D.N.,Mathiaparanam,P.,Tet.Lett.1970,2089J.Org.Chem.1971,
36,2540ibid.,1972,37,1367.

RingsandCagesofPhosphorusAtoms
Cyclopolyphosphaneshavebeenstudiedingreatdetail,notablybythegroupof
MarianneBaudler
 Chem.Rev.1993,93,16231667

ReactionsofRedandWhitePhosphorus
ReactionofredphosphoruswithM=K,Rb,CsleadstotheformationofsaltsM4P6
withisolated,planarP6anions.ThePPbonddistancesintheseringsareshorter
(215)thantypicalsinglebonds(221p
Attemptstostabilizetheseinterestingringsystemsbythederivatizationwith
electrophilesleadtocomplexrearrangements.Thepredominantproductsareusually
thecagecompoundsP7(E)3:

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Thepentaphosphacyclopentadienylanionisformedassideproductinmanyof
thesereactions.AhighyieldsynthesisisthereactionofredphosphoruswithKPH2in
boilingDMF:

Solutionsof[P5]decomposeuponattemptedconcentrationorifdilutedwithless
polarsolvents.Computationalstudieshaveconfirmedthattheanionisaromatic.
T.P.Hamilton,H.F.Schaefer,Angew.Chem.1989,101,500.
R.Janoschek,Chem.Ber.1989,28,485.
Reactionswithofthearomatic[P5]alkylhalidesproducerearrangedproductsof
typeP7R3andP9R3,butinreactionswithtransitionmetalcompounds,theP5
frameworkispreserved:

Phosphabenzene
sp2hybridizationisprerequisitefortheincorporationofphosphorusintoan
aromaticring.PhosphanesR3Phaveamuchstrongerpreferenceforsp3
hybridizationthannitrogen.Accordingly,phosphaaromaticheterocyclesarerare
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andnotparticularlystable.Thisinstabilitydoesnotreflectalackofdelocalization,
butratherthehighenergyofenergyofsp2hybridizedphosphorus.
ThefirstaromaticphosphoruscompoundwasreportedbyMrklin1966:

Mrkletal.Angew.Chem.Int.Ed.Engl.1966,5,846
UnsubstitutedderivativeswerefirstdescribedbyAshe:

Aninterestingalternativeapproachistheintroductionofelementcarbondouble
bondsthroughretroenesynthesishasbeenintroducedbyOcandoMavarez[1]:

ThestrategyhasbeenadoptedbyMatheyforthesynthesisofphosphabenzeneby
flashvacuumthermolysis:

Underthesameconditions,trisallylphosphinegivesHCP:

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Themechanismofthisreactioninvolvestheformationoftheantiaromaticphospha
cyclobutadiene:

 G.Martin,E.OcandoMavarez,HeteroatomChem.1991,2,651G.Martin,E.

OcandoMavarez,A.Osorio,M.Canestrari,HeteroatomChem.1992,3,395.
 P.LeFloch,F.Mathey,J.Chem.Soc.Chem.Commun.1993,12951296
Thestructuresofphosphabenzene,arsabenzene,stibabenzeneandbismabenzene
showahighdegreeofdelocalization(similarityofformalsingleanddoublebonds):

Inviewofthegreatdistortionsimposedbytheheteroelement,thisuniformsimilarity
ofsingleanddoublebondsseemsevenmoresurprising.
Phosphabenzeneandarsabenzenecanbedistilledwithoutdecomposition,stiba
andbismabenzeneundergoreversibledimerization:

Theofphosphabenzene(indefinitelystableatrtunderexclusionofoxygen)isin
markedcontrasttotheverylowstabilityofsilabenzene.Thisreflectsthefactthat
Si=CbondsaremuchweakerthanP=Cbonds.
TohaveaquantitativeestimateoftherelativestabilityoftheSi=Cvs.P=Cdouble
bond,transferhydrogenationsreactionscanbecalculated:

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RelativestabilityofSiCandPCdouble
bonds
Phosphabenzeneformseta1andeta6complexeswithtransitionmetals.

TheStaudingerReaction
Thebestmethodforthesynthesisofiminophosphoranesisthereactionof
phosphineswithazides:

TrimethylNcyanophosphoroimidate[2]

Cyanogenazide(7.0g,0.1mol)inMeCN(40mL)wasaddedslowlytotrimethyl

phosphite(12.4g,0.1mmol)inEt20(200mL)withcoolingat15oC.Whennitrogen
evolutionwascomplete,thevolatileswereremovedinvacuumandtheresiduewas
washedwithEt2Otogive13.1gof3(80%),mp56.456.8oC.
Ethyl3aminopropanoate[5]

Toa1Msolutionof4inTHF(fromthebromoesterwithNaN3inDMSO)was
addedamolarequivalentofPh3P,1.5equivofwaterandaboilingchip(N2

evolution).After8hat200oCandevaporation,theresiduewastreatedwithEt20
hexaneandPh3POwasfiltered.Thisprocesswasrepeatedand5wasdistilledat40
450and10.5torr(83%).
References
1. Staudinger,H.,Helv.Chim.Acta.1919,2,635.
2. Marsh,F.D.,J.Org.Chem.1972,37,2966
3. Cooper,R.D.G.,PureandAppl.Chem.1987,59,485.
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4. Gololobov,YuG.,Tetrahedron,1981,37,437.
5. Carrie,R.,Bull.Chem.Soc.Fr.1985,815.

TheMichaelisArbuzovPhosphonateSynthesis

TheArbuzovMichaelis reactionisthesynthesisofphosphonatesfromalkylhalides
andphosphites:

isaNicatalyzedphosphonatesynthesisfromphosphitesandarylhalides.Reaction
ofalkylhalideswithphosphitesproceedswithoutnickelsalts.

Diethylphenylphosphonate[3]

Tetrakis(triethylphosphite)nickel(0):stirredNiCl2(5g)andtriethyl
phosphite1(60mL)washeatedandmaintainedfor1hat150o.Thesolid
wasfiltered,trituratedwithMeCNandwashedwithMeOHtogive4.6gof
[(EtO)3P]4Ni,mp106109oC.

Diethylphenylphosphonate:to[(EtO)3P]4Ni(10mg)iniodobenzene

(10.0g.49mmol)at160owasaddedslowly1(9.37g,56.4mmol).The
solution(reduponeachadditionof1),fadedtoyellowandEtIwasdistilled.
Vacuumdistillationafforded9.88gofPhP(O)(OEt)2(94%),bp94101oC
(0.1mm).
References
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1.
2.
3.
4.
5.
6.
7.
8.

&KDSWHUB

Michaelis,A.,Chem.Ber.,1898,31,1048.
Arbuzov,AJ.Russ.Phys.Chem.Soc.1906,38,687.
Balthazar,T.M.J.Org.Chem.1980,45,5425.
Montero,J.L.TetrahedronLett.1987,28,1163.
Brill,Th.B.Chem.Rev.1984,84,577.
Kosolapov,G.M.Org.React.1951,6,276.
Kern,M.K.J.Org.Chem.1970,36,5118.
Redmore,D.J.Org.Chem.1981,46,4114.

TheKuhnWintersteinReaction
OlefinationOlefinformationfromglycolsbymeansofP2I4.
3,4Bis(4,4ethylenedioxocyclohexyi)3hexene1,5diine(2)[3]

P2I4(60g,0.135mol)wasextractedwithCS2inaSoxhlett.Tothisextractwas
added3,4bis(4,4ethylidenedioxcycyclohexyl)3,4hexanedioldiine1(30g,
0.077mol)inpyridine(600mL).Themixturewasstirredat20oCfor2hand
thesolventwasdistilled.TheresiduewastreatedwithEt2Oandafterworkup
theproductwaschromatographedonWoelmAlumina,active.l1.
RecrystallizationfromMeOHafforded12.9gof2(43%).
References
1. Kuhn,R.,Winterstein,A.,Helv.Chim.Acta.1928,11,87.
2. Kuhn,R.,Winterstein,A.,Helv.Chim.Acta.1955,27,309.
3. lnhoffen,C.LiebigsAnn.1965,684,24.

TheOleksyszynAminophosphonicAcidSynthesis
Synthesisof1aminoalkanephosphonicand1aminoalkanephosphinicacidsfrom
ketonesoraldehydes,chlorophosphinesandcarbamates.
1Aminocyclohexylphosphonicacid(4).[1]
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Cyclohexanone1(7.35g,75mmol)wasaddedat20oCtoastirredmixtureof
benzylcarbamate3(7.55g,50mmol)andPCl32(6.87g,50mmol)inAcOH(10
mL).Themixturewasrefluxedfor40min,treatedwith4MHCl(50mL)andagain
refluxedfor0.5h.Aftercooling,theorganiclayerwasremovedandtheaqueous
solutionwasrefluxedwithcharcoal.Afterfiltrationandevaporationinvacuum,the
residuewasdissolvedinMeOH(2540mL).Themethanolicsolutionwastreated
withpropeneoxideuntilpH67isreached.Theprecipitatewasfiltered,washed
withMe2COandrecrystallizedfromMeOHwatertogive7.74gof4(58%),mp
264265oC.

ThePerkowVinylPhosphateSynthesis
Reactionof2haloketoneswithtrialkylphosphitetogiveketophosphonateorvinyl
phosphate.
1,3Butadiene2,3diolbis(diethylphosphate)(3).4

Toastirredsolutionof1,4dibromo2,3butanedione1(12.2g,50mmol)inEt2O
(50mL)wasaddeddropwisetriethylphosphite2(16.6g,100mmol).Thereaction
mixturewasstirredbelow10oCfor2h.Thesolventwasremovedandtheresidue
17.2g3(98%)wasidentifiedbyIR,NMRandMS.
References
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1.
2.
3.
4.
5.
6.

&KDSWHUB

Perkow,W.,Naturwissenschaften1952,39,353.
Perkow,W.,Chem.Ber.1954,87,755.
Borowitz,I.J.,J.Org.Chem.1971,36,3282.
Hennig,M.L.,J.Org.Chem.1973,38,3434.
Mitsunobu,S.,J.Org.Chem.1981,46,4030.
Lichtenthaler,F.W.,Chem.Rev.1961,61,60.

NerveGases
Inthe1930's,GerhardSchraderbeganresearchonthedevelopmentanduseof
chemicalpesticidesforthecompanyIGFarben.Bychance,Gerhardsynthesizedthe
nerveagentTabun.
SarinandSomanwereproducedbyGerhardsoonafter.Gerhard,whohadoriginally
beenlookingforapanaceatotheproblemsofinsectsandcropshadstumbledupona
solutiontoanevenlargerpossiblenuisance,humans.

ThereasonwhyAdolfHitlerdidnotordertheuseofnervegasesinWWIIisstilla
subjectofcontroversy.ThemostpopularexplanationforHitler'sapathystemsback
tothepreviousWorldWarwheretoxicgaseswereusedincombat.Hitlerhadbeen
victimizedbythesechemicalagentsandwasunwillingtointroducenewandmore
toxicagents.ThereisalsoevidencethatsuggeststhatHitlerwasadvisedagainst
usingtheagentsandevenstoppedtheirproduction.Hitler'sMinisterofProduction,
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AlbertSpeer,saidafterthewar,"Allsensiblearmypeopleturnedgaswarfaredown
asbeingutterlyinsane,since,inviewofAmerica'ssuperiorityintheair,itwouldnot
belongbeforeitwouldbringthemostterriblecatastropheuponGermancities."
Another,morepersistentagent,namedVXwasdiscoveredbyBritishchemistR.
Ghoshafterthewar.
AfamouscontemporaryincidentofusewasintheIranIraqwar(19841988).Inthis
conflicttheUNconfirmedthatIraqusedthenerveagentTabunandother
organophosphorousnerveagentsagainstIran.Thisincidentisaprimeexampleof
howchemicalwarfaretechnologywassharedduringtheColdWar.TheSoviets
wouldarmtheirallieswhiletheUSdidthesameforitsallies.Iraqwasobviouslya
benefactorandimplementeditschemicalstockpilesduringthewar.
AnothercontemporaryincidentofnerveagentuseoccurredinJapan.TheAum
ShinrikyoCultwasreportedtohaveusedthenerveagentSarininaTokyosubway.
Thisincidentofusegivessomeclueastothenewrolesthatnerveagentsplay,as
toolsofterroristsinsteadofpowerfulnations.

Symptoms
Nerveagentsaregenerallycolorless,odorless,andarereadilyabsorbablethroughthe
lungs,eyes,skin,andintestinaltractwithoutproducinganyirritation.Theyarealso
extremelypotent,soevenabriefexposurecanbefatal.Deathmayoccurin1to10
minutes,orbedelayedfor1to2hours,dependingontheconcentrationtowhicha
victimhasbeenexposed.
Ifyouweretobeexposedtorealizablefieldconcentrations,inhalationwouldbe
essentiallyimmediatelyincapacitating.Yourgeneralorderofsymptomswouldbeas
follows:
First,yournosewouldbegintorun,thenyourchestwouldfeelconstricted.Your
visionwoulddimasyourpupilscontractedintopinpoints.You'dbegintodrooland
sweatexcessively.Thenwouldcomenauseaandvomiting,intestinalcrampsand
involuntaryurinationordefecation.You'dtwitch,jerk,andstaggerasyou're
overcomewithconvulsionsandpossiblycoma.Finally,you'rebreathingwouldstop
asyourdiaphragmandthemusclesofyourchestfroze,causingyoutodieof
suffocation.
continuedinchapter6:OrganometallicChemistryoftheCopperandZincTriads

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