S Y N T H E S I S OF B I F U N C T I O N A L O R G A N O P t t O S P H O R U S C O M P O U N D S
CO.M~Mb.~!CATION 2. ADDITION OF 13UT'112ttOSPHINE TO UNSATURATED COMPOUNDS
B. A . ~ , r b u z o v a n d G. hi . V ~ n o k u r o ~ 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 accta te ,a l l ) lamme, and a l l ) l c)anide [3-butenemtnleJ ~
1"he addmon of but)Iphosphme to tht-se a l 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, a l 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. l h e oxide~ and sulfides of the addmon products arc also colorless liquids, but the) are moa ~ Iscou~ and ha~e a r c l a m c l ) 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 a lcohohc 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~, " lJ 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 ; - - ' i 7 ftt l , :tJl
CdI~P IC 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 i C 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,
lii~.tl;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 e th) l a c t ) h i e [31.
451
TABLE 2
Formula I B p . , :C rE, ram)
lint
I *
17 t,ouq;,,,. C~tH~P{C IIaCII~ 11-.O II).*
O C~II~P~Clld |! :C|IaN lt.,~a
,1
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 l i .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
S
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- - tq l 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
09,,!
13'751
i'! _ I1,2q
13 "iS! 1
IS, ~2i
', 9,5-' t
'~ 12,17 t
1 lO, lqiS3, ~8
12,.ql),71,9
I I, talsa,a
13,a 2 Sl,~3
13,1a77,3
9,62 92,3
12,10 $5,71
�9 Pecr)stalhz~.d from dr) ac,.ton,..
E X P E R I M E N T A L
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',crt.al 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 t a m e d 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<: filled with mtro~t.n, and u g of a l l ) l a lcohol and 0.2-0.q g of azodi~mbu~)roultrtle were added. "l be tube ~'as scaled and heated at 1,10- 140" for six hours. At the end of the reaction the reactmn xmxturc was vacuum fracnonated. We ~solat~d <5 8 g t,3v.15~, :} of but ) lb ts -a-hydtox)pmp) tphosphmc ~a.a'-(butylphosph,illdci~cJdt-l-pmpanol]. b p. 140-1-12" t2.5 nun), ~;o = 1.3029, d z~r 0.9873. Found P 15.0t~%, MR GI.'7-i. CI~tlzaPOI. Calculated P 15,04~,~, MR GI.GT. "lhcaddittoil of but)lphosphme to a l lylamlne and to al lyl aceta te was earned out tn an analogous way, the rcactmn with A- buten,.mtrd,, was earned out b) heating the reactants at 180-190 ) for 12 hours. "1 l,c COllSlalits Of the products a~t ttsz~-d in Table 1.
OMdauon of tile Ternary Phosphm~_s. "ihe oxidation of butylbis-3-acetox)propyl- , but)lbis-~-h)droxH~rop)I-. a~.~d butylbls-S-c)anoprop)l-pl ,osp!,mcs v, as carried out with hydrogen pero.x~&. 5 g of but)lb~s-3-acetox)prop)lphos-
4 5 ~
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%,
SUMMARY
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
~m
a.
L ITERATURE CITED
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 a b b r e v z a t t o n ~ of p e r t o d l e a l s tn the. above bl l ) l lol t raphy ~re | e t ter-by- |~eI l~r t r a n ~ h t e r -
a t i o n s of the a b b r e v t a t i o n ~ a s ~aven m the. o r i g i n a l R u s s l ~ journ.Jl, S o m e or a l l c f t h t s p e ~ -
o d a c a l h t e r a t u r e m a y ~*elt h e a ~ a # l a b l e ~n I'~n~,h~h tr ,m~l,~t lon A comple t e I~st o f the c o v e r - t o -
Cover E n g h s h t r a n s l a t i o n s : p p e a r ~ at t h e back of tht,~ i s s u e
453
