Synthesis of bifuxctional organophosphorus compounds

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    B. A . ~,rbuzov and G. hi. V~nokuro~a

    A. E. A~buzov Chem,cal Institute. Academ) of Sc,ences, USSR Translated from Iz','estl)a Akadcmli Nauk SSSR, Otdelcnl~. txhlllnchr Nauk, No. 3, pp. ~,02-506, March, I9G:3 Original article submmed May 25. 1902

    We sho~,ed earlier that pl.en)lphosphinc, hkc phosphine itself, adds to urmaturated eon:potmds cot:taming the fiancuo~al groups NH 2, COO~,, Oti, and CN, n:orco~ct, LtS addition to compoundi containing a conjugated sbitc,~: of double bonds proceeds r~adll) and can be brought about in absence of eatal)st but its addmon to an Laokated double bond occurs onl) in presence of a fre~-radical catalyst [1, 2.1. Contmmng our ln~ estigatlon of the addtt ion of pnmar) phosphmes to unsaturated compounds ~,lth the object of s)ntheslzmg nc~, bifmictional phozphoms compom',ds. we considered it to be of lnt,arest to stud), as ~,cll a~ tile reactlol~ of Fhen)lphosphine, sumlar addition reactions of but)'lpho~phme. We now r~.po."t results on reactions of butylphoaphlnc ~lth all) i alcohol, all) l acctate,al l) lamme, and al l) l c)anide [3-butenemtnleJ ~

    1"he addmon of but)Iphosphme to tht-se al l) l derivatives ~,as earned out m sealed tubes b) heating the reac- tants together m presence of azodiisobut)romtrtlc. ~.\pcrtmcnt shov,~.d that but)lpho~phme adds falrl) rca&l) to a[- lyl alcohol, al l) lamme, and aI l) l acetate (the x lchls of the corresponding t~srtlar) phosphmes ~ armd from -t7 to b~ r but with much greater difficult} to 3-butenemtnh. toni) under sc,,erc reactmn conditions could the )~eld of addl~,o':. product be raised to 41.3-74, as will be seen from Table 1. All the but)lphosplun~_ addmon products are color]ess s~r- upy l-qmd~ having a sharp a.palsl~ c odor. the) art. ~er$ readily oxlatzcd with o.x)gen to the corrcspondu~g phosphlu~ oxides and the) combine ~,Lth sul.~ar The constants of the compounds s)~thcslz~.d are hsted m "Iabl~ 1. lhe oxide~ and sulfides of the addmon products arc also colorless liquids, but the) are moa ~ Iscou~ and ha~e a rc lamcl) weak unpleasant'odor Their ph)sical col-stants are hstt.d in 2able 2 B) tLe hydrol)s~s of but)lbis-3-cyanoprop)lpho.,pt,~.:~ oxtde [4,4'-tbutylpho~phidcm.)d:but)ro,l~,rllc] x, ith alcohohc alkah we obtained the corresponding acid, which ts of some interest for polyconden~ation rcactmna. But~lbis-3-carbox)propylpho@ane oxide [4,4'-(but)lphosph~denc)bts- (but)tie acid)l, unhke all the off:or phosphme oxides, ~ a completcly odorless Mute cr)stalhne substa~ce. It~ con- stants are also h~ted m Table 2.

    TABLE 1 , , , , , ,

    t 3/ll B p. "C ~' Fonnula t E, ram) d~, "l J I

    found, calc. t

    Ct l loP[ (- I1J: I I ' -Ci1:011 l : I I* i - - I ~7 t2,5i

    CtlltPiCIl ,C II ,CliiN II ,l., {i ; - - ' i7 fttl, :tJl

    CdI~PIC I IaC l l .C i I .O~.OCI Ia Ia ] 1 ; ; - - ! ~.; t,7,1it

    C l l l l l ' [C l l . .C l l iC l l ! ; \ ] . , t l : J i - 152 I c.',5)

    I 1 t tl,987:~ I ,:.~ ~7't B1,7 o I 6t ,{,7

    (~,,t_u:~ ,5, ,,~11;5,7~ i , b5,4t; 1 ,( l i,St,;lq

    I ' , . 1 i

    iom~d calc. ! % t t

    15,o8 15,oI'56,15

    15.. I | 15.1u t,7,13 ' I

    , ~71:. '~n, 5h i b, i, i,~ i 1' L"~ ~7,36

    , , . . . . . ~,, , . , ,~67,~u[I~,~5' Is..'., , I ,3 t i

    g ~t~en ~,e haJ comph:ted the e.~p~.nn'ental part of flas ln~ estlgation, a paper appeared b) Rauhut and co-~'orker~ oa the free-radical addmon of pho.~pLlnc and prunar) and sccondar) ahphatm p~,o.~phlnes to unsaturated h)drocarboi~ and to eth)l ac t )h ie [31.


  • TABLE 2

    Formula I Bp. , :C rE, ram) lint I *

    17 t,ouq;,,,. C~tH~P{C I IaCII~ 11-.O II).*

    O C~II~P~Clld |! :C|IaN lt.,~a


    C4tt)P(CII;Ctl:( :l!.OCOCIta~: il O

    C4tlt)l'(C tla( "11 "('tt'('N ')..

    (2 CI I I iP( ( ' I I:C I I :(" I I :CO011)]

    C.att tt )(C ! I.C 11.,C I 1 ,_i) 11 )l I

    S Ci l l tP(C li.X'l I .CI I aN It :).,

    S CIII~PiCII.,C II I'I I:OCOClla):

    ,1 S

    C, IIllP(C t t :CI I-CI I aCN)a II


    1:~--!'.)7 (0,8)

    |~q.5 (o,:,)

    l,lO-- 1')2 ~2,5)

    21q~215 t2,-~)

    m.p. 13.5--137

    '220~221 (2)

    173 (:t,5)

    ISs--tql O,5)

    21o--212 (i)

    l,r 7%O1 7;),5~ i

    I,f~85 1,{888 36,11 66,3~ I

    ,, );i .L .l l. ;j t,0_gql,5,~ lr . . . . . 17'-',(~a



    i'! _ I1,2q

    13 "iS! 1

    IS, ~2i

    ', 9,5-' t

    '~ 12,17 t

    1 lO, lqiS3, ~8


    I I, talsa,a

    13,a 2 Sl,~3


    9,62 92,3

    12,10 $5,71

    9 Pecr)stalhz~.d from dr) ac,.ton,..


    Preparation of tJut)lphospt,mc. A lour-tlc~.k~.d flask fitted with stirrer, dropping funnel, cffic~cnt rcfiu\ cond,.n- ~:r, and tubc for the passage of mtrogt.n was charg,.d with an ethereal solutiotl of 11.4 g of litlnuln aluminum h)dr~dr in t00 nil of dr) ~.thcr. A solution of 37 g of but)ldnchlorophosphinc in 100 nil of ether ~,as added ~,lth st,rrmg at ~oo.:~ t,.lnperamre. The rate at ~,htch the but)ldichlorophosphm~ wa~ add~.d was dctcrl~tncd by the rate at ~[atch th~ c:l,t.r boiled. Wl:en it had all been ad&d. tl~e react~o:t mixture was stirred for t)i,c hour and ~a~ then left o~crntgt,,t, O:a t,~. ntaxt da) ~ht: ctl', solut,on wa~ d~.cantt.d under llltrog~.ll illto a dtatillulg flask. Ether was distilled t)fl throl.tgh a t'.,dn,cr co|lll:tll, and the residu,, v, as distilled from all Arbuzov flask, A sceolld fractmnat,on ~as carried ot~t ztolll a flask with a Wtdmcr column W~. obtauted 9.-1 g t-t5.0~,) of butylpl,osplHIlc, b.p 81-85 ". Found P 3-t.49'7.. Ca|cu- lai,.d P 34 -t4~.

    Addttioi: of l~utylphophmc to All)I Alcohol, Allylalmnc, All)I Acetate., and Atlyl C)anide [3-L~utcncllt~rH~_]. "fLc addmon of but)Iphosphulc to th(.se unsaturated compom:ds was tamed out m s~.ah.d mol)bdcnunl-glass tubt~, ~,.h~ch were heated at 130-1 t0 ~ for 5-G hours. -1.3 g of but)'Iphosphme was introduced into a tub

  • p~ne ~-aa dissolved in G rr, l of glacml acetic acid. and 2 g of 30~o h)drogen pero.xldc wal aided at such a rate that tt'~e temperature of the reaction ra~x~care ~as kept at 60". At the end of the addition tt'e reaction mixxm-e ~as heated at IC~0" for 1-2 hours and then vacuum fmcdonated. We then isolated 4.5 g of but}lbts-3-acetox}propylphosphine oxide [3.3"~but}lphosphin}hdene)di-l-pmpanol dmce~ate2; b p 100-192" (2.5 ram); n~) 1A700; d~ 1.0~16. Found P 10 1L~,r .MR ~9.01. CIaHz.tPO ~. Calculated. P 10 13~0; MR79.50.

    The oxidatton of butylhis-O-am,.noprop)lphosphme was effected with oxygen paaim~ tlnrough th.e pho~phme, ~,hieh was heated, first at 100" for two hours, and then for 3-4 hours at t30-140". The co.:~an~ of bulylbt~,-3-c}ano- pmp}-l-, but}-lbis-3-ammopropyl-, and but)lb~s-3-hydroxypropyl-pho~phme ox~des are hated in Table '2_.

    Preparation of Phosphme Sulfides. All the phosphme sulfides were synthesized by t?e addmon of tt~e calculated amo-ant of ~alfur to the corresponding te."har) phosphine. The synthes~s of but}lbts-3-amlnop:opylphosphm,.- sulfide [3,3"-xb,at}lpkosphmothlo}lldcne)b~sp,:opilamme] ma) serve as an example. A mtrogen-fiiled ~urrz flask hawng the ~/de tube in a low positron was charged ~.ttl-, 4.6 g of butylbis-3-ammopropylphosphw~e and 0.'~2 g of sulfur. As the mfl.f'ar ~as ~pnnkled m, there was a spopraneous rise m temperature to 57 ~. The reacher mixture ~a~ heate.d at 130- 140" until the sulfur had d~sappeared con~pierely and ~,as then fracnonated. We obtained ~.'/g CI7.3{.9 of but~lbis-3-

    13.4_-,:, ,XIR ~2 aminoprop~Iphosphmc sulfide b.p. 17q" (2.5 tara), n~ 1.5430, d~ 1.0294, Found P '~- 32. CBHz~PS.'~ ~. Calculated. P 13.135, MR 72.05. The constants of but)lbis-3-h)dro\)pro?}l-, but)lbts-3-acetoxy- ptopyl-, and buty!bis-3-cyanoprop}l-phosphme sulfides are hstcd in Table 2.

    Preparation of Batylbts-3-ca rbox} prop} lphosphme Oxtde [,!,4'-~ But} lphosplud~ne)h.~.hat} ne ac.d)]. But} lb~s- 3-carbox~prop,~ Iphosphme ox~de was prepared by the hydrol}srs of but} lb~s-3-c}aP, oprop)Ip~osph~ne extde wtth aleo- ho!ic alkali. 3 g of but%bts-3-eyanoprop)lphosphme oMde was dissol'~ed m 15 ml of ~nctkanol, and to th~s solutto~ a ~olu~ion of 3.5 g of KOI-t m 3 ral of water ~as added. The contenta of the flask aere hea..ed at the boil for eight houri; t,he2~ ~,ere then aetdifted with ddute hydrochloric acid and vacuum evaporated. The prectpitate forraed ~po- tassium chloride) was filtered off, and the upper, oily la~er of the filtrate ~as separated and left to crystallize. Af- ter recq~taHizatton from dry acetone ~,e obtained 1.8 g ~50%) of the acid, ra.p. 135-13~'. Found P 11,24~o. Cal- culated: P 11.15%,


    1. The additton reactmns of but}Iphosphme with allylamme, allyl alcohol, all}l acetate, and 3-butenemmh: ~ere carried out.

    2. The addLtlon of butylphosphme ~o aIiyl denxan~es proceeds readtt} under the ca'.aI)~ttc influence of azo- di L,,obut } romtrile.

    3. Thirteen new btfunctmnal organophosphorus compounds were prepared,

    l e




    8. A. Arbuzov, G. M. Vlnokurova,and I. A. PerfWcva, Dokl. AN SSS[~, 127, 6, 124; O959). 8. A. Atbuzov, G. M. Vmokuro~a, and I. A. Aleksandtova, Izv, AN SSSR, Otd. khm*., n., 19G2, 290, 5~ M. gauhut, llelen A. Currier. A. M. Sem~cl, and V, P, W)strach, I. Organ. che~:;..2G, No. 12, 5138 (19GI),

    All abbrevzat ton~ of per tod lea ls tn the. above bll) l loltraphy ~re |etter-by-|~eIl~r t ran~hter -

    at ions of the abbrevtat ion~ as ~aven m the. or ig ina l Russ l~ journ.Jl, Some or al l c f th ts pe~-

    odacal h terature may ~*elt he a~a#lab le ~n I'~n~,h~h tr,m~l,~tlon A complete I~st of the


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