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November 9, 2016
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March 5, 1999
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PDF icon CIA-RDP83-00423R001200820004-4.pdf310.59 KB
e- feet of the size and structure of radicals on the rate of Approved For Release 1999/09/10 : CIA-RDP83-00423R001200820004-4 rization o eaters of phosphorous aoit. .,. e?.?.r"k'uzov l?' iNesterov ( .MM.:Rirov Chem. 'eohno1. ust.w, Kazan) Doklad7 Ak d. QUk S.3.034' The natur ?ranee 12, 8 P (OR) of the 77 u zov reaction is sus. . ? ahem. in that the rsa et i.au is a Qhain r 0 m RF(OR) + P(OR) RP(OR) 0 . CPYRGHT oe. P(ORI can aid the loss of RX a.ch'reaot1on link. The iritermediat be regarded as phoshonitu: der 2550), which c.e3ompde of the phase has been regarded as a bitolsouiar (Garrard above) or monomoleoular udo .ky this 1. 84, 519(1052)), depending on the. structure of R. can. be regarded as bein aatalytio with RX being the rdel as being autocatalytic with the rats given eatalyat. it oau be by dx/+ t - k (1 + nx) (1 wx), where i is the relative oonon. of the on product and n is constant for a given expt. (of. awidskit and 8?ta,rouka (.,A,; l l,* 2294(1917))1 also 3taronka, Ohsiu,Cebtrallbl.8, 86(1! sent study several ,e s (hO 4; (P.hO)O.IOBU, 52,,"s. b0 _, 18?s.?.l `, d"1,0967 : nn"J1.55?O t 1 1 ' 7 n 2ZI.Ps47ss (PhO) POCHMe_. S8 _ b,^170-1 6Q , ba180.5-1.00, d 1.0452, ?L15358; PhOP (i e 0531 PhOP (OSt) . 35. 0, b,11$'# l1Ow ed to resat with the correspond and Et sate. iodides below 2000 . &, (Oft) (O It i bile OL found that a smooth reaction took place only or homolog3 apparently ware quite unreaett'Ve temps* deoornpn. ocourred. The produots obta ne b11i35-6a, d.2d1.1914, ivalent. P were prepd. These d201.11544. n!? 1.55281 (PbO } -?O t y 204: S 8 Y _ O%Ald' O a% Me (0) (Oph Approved For Release 1999/09/10 : CIA-RDP83-00423R001200820004-4 :,. b1216 Approved For Release 1999/89/10 : CIA-RDP83-00423R001200820004-4 rl~ 01.541; CAHIcl.) t 100 1.5190-20 {Ph0)!'P wwe: 10O (P-40) 'z tl, m,; 3 crude I (Pho) fC e ". The reactions o:' these (P31HH2 dily gave the e rresponCtin , R--} "Omen, he expeoted P ho ) and The react rder the idomeri a ducts (As. .ut, iso-Pro and oephonates,,_ but also .?re uch tarry Bu, and, so-Bu der above. Thermal baa I aly nd considerable of free iodine. I 4ilatoietrio ez .Z n. of the addn, of 1. i iodide r. )01.518; 8 . tP(Q) ((gip: e o- .'rP (0) (orh) 2 , b1 193-20eox .~ " n"1.53 9; 7s&L Phcl 2p(8) (Oph) o10ted in crystalline st decsua ; iiv of the adduots as tda to fol .ow the reaction L00 j, ) 2029, d 01.179 9, 0 .149'7, 1.b3a 3, ISO -BuF(0) (OP h) Ph0) 3PBu , xxtk&Slx unst a alkyl iodide yield of .1300 ; unstaat ed yield or ( hO) tions, eeled:* on the basis of the dilatometric and was arrays stellar than unity, but the reaction Scribed by the se4uence given by Ste onka (of.above), eplaoer snt of Via O e C -40 toad ,ction rate 7-9 tudied. The rate o so-Prl adds z ost t has a. lone, induc t1 he phosphite by 12M reduces the isomerization rate by Merization and addn, war t ion rite t .at V.;-a3 close to 2 (for 10? rise). The Of an aliphatic radical by Ph reduces i.d. ' C I adds to (PO)3P most rapidly anion ; the halids addii, falls rapidly with increase of size of the alkyl. 7. Addn. of ieo- 'us: i 10 tiries fsater than of Dul on period.. The effect of the iao.lerizatjon product On -r iso.tie rizat is with Ph P (O s) ; to a ui. olar r this phos hit ~,= .- -nd Mel -was ad.ded. J ie ) t;' and the reaction f. at 84.50. S`It1iout such t .ddn. the rsaotion Approved For Release 1999/09/10 : CIA-RDP83-00423R001200820004-4 Approved For Release 1999/090 : CIA-RDP83-00423R001200820004-4 CPYRGHT n 4 in 13*0 J4 in 3` a1+; ; in. , ~ilth G. rba3bon rjel t It In 2 rain ; with 1 mole in 32 8O in 82 min., ?5 in 10? min.,, and 10 udd d. th r U an., M,*;! 100111 1AS.. ~4.