(UNTITLED)
Document Type:
Collection:
Document Number (FOIA) /ESDN (CREST):
CIA-RDP83-00423R000700430003-4
Release Decision:
RIFPUB
Original Classification:
K
Document Page Count:
4
Document Creation Date:
November 9, 2016
Document Release Date:
December 1, 1998
Sequence Number:
3
Case Number:
Content Type:
REPORT
File:
Attachment | Size |
---|---|
![]() | 420.85 KB |
Body:
ro e
6 liseecialff
hiophosphites.
baohnik and T.A.Mastryukova.lzvee
953, No.1 163-76.
Pro ?tropic tautomario a form of protuly
in which 2 aoids with the ems enion exist in a so
- ..4(y21
09/10 ? CIA-RDP83-00423R000700430003-4
miuni.0.eseudomerism, Structure and prope
.Nauk 3.8. LR. , 0
a uils
se which
acta as proton carrier. Attempts were made to eximatne? the possible system
(110)2P38 by means of reactions that would involve the latter
form(addn.of cuprous halides, El, RX); none of these reactions took:plass.
Only forantion of metallic derive. could be possibly placed in this cats
gory these appear to have the structure (B0)0814 but the Na salts in
their action on 1120 do not act as salts of a strong acid and are instantly
hydrolyzed.Hance in the above system the let structure is so predominaut
that the reactions of the 2nd fora do not realize themselves;this fact
ic contrary to the usual concepts of psiudomerismiTheor.examn.of the
kinetics Inherent in pseudomerismiCf.Ingold and Thorpe, Now Aspects of
Tautomer am, indioates &sliest= of auah reaction rates that are not
otually realized,It is believed that reactions of this camp proceed
by transfer of the reactive center without involvement in tautomerio
transformation CC, at this point recants his use of the ideas of resonance
in a previous publication(Vspekhl Xhimil, 17 96(1948)). All properties
thiophosphites indicate structure (RID)P(8)H; these are sol
in org.solvents and a Rt0H but insol in H20; their solns. are neutral
They are Insol.in agialkaliee and are hydrolyzed by acids and alkalies
yielding Be015,T1iey are vigorously oxidized by Treatment with
standard aq,alo.NAOR they slowly coasume alkali because of hydrolysis
to CROP(S)(0Na)14after this the alkali oonsuntlon becomes so 51CM that
it ts possible to actuallytitrate these esters to thts endpoint. This
is similar to behavior of (R0)00R. Acidification of these Na salts yields
solns. of acidic monoalkyl thiophosphites which are stable for months The
mol,r4PRWMP6EVinle99911.glatblarjra=12??):19X2a431C.12-4exptl,
- -
Approved For Release 1999/09/10 : CIA-RDP83-00423R000700430003-4-
re5ulte if the above structure is assumed with ref'raottvity of P take
as 4.27 and that of 3 at 9.70. TO 1.54 g, (Ht0)2PSH in 3 m1.Et011 was
added 2 m1.1200 followed by 0.4 g.NaOR and 5 ml.N20;when the alkaline
reaction disappeared the soln.was avapd,over P20 yielding colorleBs
plates of (BtO)P(S)R(ONa) Similarly was obtained the Bu analogesca
(Bt0)2PSH failed to react
11+6 8.) treated with 5.4
nr1,4711? 401.1918. (Ht0)2P y .1&s the Na dariv. in suspension of
Ns. in 0oR6 and the product forms a crystu.ppt. This is best prepd. as
follows: Na dust in ii converted to BtONa by addn,of BtOB: and this
is treated with ealod.amoun of the ester; finally the Na deriv.can be
in t H.EtONa soln. The produet from 4,62 g. (Ht0)2PSH and 0.69
.Na in 12 m1.006 was mixed with 0.96 g.81 the reaction was wiry exo-
after I hr. the mixture was filtered and the p
extdwitb H20; addn, or basic Pb acetate to the aq.solt.
rn.7S-60. The Na der from 25,1 g.(BtO) PSH and 5,44 g
after heating 5 hrs. at 100 2t0) PSR
t .10? gave (2t0)2P801 40,1)/281-
treated with 22.8 g,
Ina
and the mixture allowed to stand 4 days; th ppt.
of Nal was washe& out with H20 and distn.of tho org.layer gave 50%
b13,582-5.50 pd204 1.0532, 31O1.4563, which is hydrolyzable
t difficulty. Similar reaction with ItC1 gave 46.5% or
lib 990.5.5? ?1.4545,d2?1.0324 The ester (4 g este
tube with 2 vole, :1 NCI 3 hrs.at 145-55? and uad.to dryness
57.8 Heating BtP(8)(01ft) (4 g.) with 1 vol,StI to
00 5 hin eea ed tube gave much Et* X and 1.5 g.ttP(0)(02t)gft
? 401.0709
8 was added 6.82 g.PhOR201 and the mixture allowed to stand
2 *MY Yielding after washing, 5.5 g. PhCH2P(3)(031t)03,5124.5?.d:?
1 10 0 5503,Similar reaction with CION CO Bt gave 72.2% Bt020012
2?1.4730. To Na deriv from. 7.7 g.(Et0)2PSN and 1.5
P(S)(0 bg105-6?,d4 1.1204,no 1.4621,which hydrolyzed with 1:1 RC1 at
150? 3 hrs.in sealed tube to NO,CMPO(OH)0,m4138-9?.Addn.of equiv.amount
Approved For Release 1999/09/n : CTA-ROPT3-00423R0007004300,03-4
O f aq.AgNO3 and a little MR4OH to BtOR soln.of (Zt0)2PS11 yields a
?
Approved For Releas01999/09/10 :CIA-RDP83-00423R000700430003-4
lorless ppt. of th Ag ialt,whioharkena La ugh
slowly in yet forming a sol of Ag. The resuitts are held to be the
Idence for the structure of the Ka deriv. as (ROyslia with trivalent
Their formation is ascribed to transfer of the reactive ea during
*action of formation yielding ions (1:0)EPS" Alkylation with RI appears
to occur by attack of Fa on unshared electron pair at P atom with
elimination of Na which forms EAI, alt bo V
ugh,it 1C_kanion
Approved For Release 1999/09/10: ClA-RIDlio3-00413KUIRMOVitt-4 the ) lb can also participate simialrly.
Si
. k,
oiiipatmeotEepouvigapi; qvbfirmgaveviOuci7cituqb63-ti 81
bachnik and T.A.Mastryakova, Izvest Akad.Nauk 8 8.8.R Otdel Khim
Nauk, 1953, No.1,121-5 Cf.this 3.1952,727.
The dialkyl dithiophosphates obtained from ROH and either PO, i 810
are completely identical. The products are titrated in aq. or alc.medie
as strong monobasic acids and are oxidized with IA in alkaline medium
yielding the corresponding disulfides (R0)2P(S)2SP(.8)(0R) which are
solids, inol.in HO. To 24 g.Me0H was gradually added 33 .P010, the
mixture was warmed on a steam bath until H28 evolution ceased and the
filtered mixture was distd.yielding 73% (Ne0)2PS2H,b4.562-3 5343
dr1.2888 38.87; to neutralized soln.of 3.16 g.of this eater was added
1.29 g. NLC12 and the evapd.soln.gave 3.5 g.[(M40)21)62)2N lila m.124-5?
(from Petr.ether) Reaction of 50.84 8 with 69 g.St0H gave 3.2g.
10 ,
solid residue and 78.% (Bt0)2PSEE,b 5-2.5?41.5076 dr1.1654,82031.7
its Pb salt,14.75-60. Reaction of 11.1 P4S10 with 12 g.PrOH gave 75%
o 20
(PrO)2P8211, b 1 5-2.5 1.4986 P4210(5.& g.) and 6 g.iso-PrOH gave 60%
(iso-PrO) PS2H, b371 2?,34p 1.4916, d01.0911.Thie (4.28 g.)
tralized to
phenolphthalein with NaOH and treated with 3.79 Pb(Oko) gave E(iso-PrO)
P8z)2Pb, m.130
(from? Et011). Reaction of 11.1 g? 810 with 14.8 giBuOil
gave an undietillb1e product; thisoneutralized with 10 MOH and extd with
lt20? was treated with 12 g.Hg012 yielding an oily Hg,salt?which extd.with
Itt 0 and evapd. gave the pure ((B0)2P82)2Hg. m.60-16(from MOH) To 4.8 g.
(MSO)2P equiv'emount of aq.NaOH was added aq.soln.of 3.8 g.12 in KI
yielding 74.3% (Me0)2P(S)S8P(S)(01102,2.51-20(from hexane).The tetra-Et
analog ,AM109veclifmar Rebusis9AW1Pni.g14110WW431gegg9ggp993i4alog,
82.75. m-91-2?(from EtOH). I