SCIENTIFIC ABSTRACT PEREVALOVA, E.G. - PEREVALOVA, E.G.

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• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R001240020012-9
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• Document Creation Date: November 2, 2016
• Document Release Date: June 15, 2000
• Sequence Number: 12
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

Cyclopentadienyl Compounds of Metals and Compounds Related 74-27-1-1/4
to Them
structure, as assumed by Pauson,did absolutely not correspond
with its physical and chemicai properties. The author deals
with the magnetic properties of the ferrocene, discusses the
results of the radiographic investigations of the known
2j crystals of ferrocene, which confirm their so-called sand-
wich-structure. Also the method of electron diffraction was
confirmed by this structure. Then follows a discussion of the
results of the spectroscopic, thermochemical and polaro-
graphic investigation of the properties of ferrocene. Moreover
the author occupies himself with the electron structure of
i" the dicyclopentadienyl derivatives of the transitional metals.
The chemical properties of the ferrocene, its oxidation and
the reactions (with the destruction of the compound of iron
with cyclopentadienyl rings) are discussed in a very detailed
way. A discussion of the acylation of the ferrocene is
following. After the interaction took place (ferrocene-acetyl
chloride) diacetyl ferrocene was obtained; in a similar way
di-o-ohloro-propionyl-chloride ferrocene and di-o-carboxy
benzoyl ferrocene were obtained. The investigations made it
evident that there are acyl groups in all diacyl ferrocenes
Card 2/3 in several rings of the ferrocene nucleus. The investigations

Cyclopentadienyl Compounds of Metals and Compourds Relz.~ted 74-2-1 -1-1/114
to Them
with dibennoyl ferrocene showed similar results. The reactions
of the intramolecular acylation of the ferrocene nLve already
been carried out by Nesmeyanov. Vol 'kenau and others. In
these reactions 1,1-di-(w-carboxyl-propionyl)-ferrocei,,e was
obtained with a yield of 16" . According to the reduction
P;
carried out by Kleiamensen di-(cj-carboxy-propyl)-ferrocene
was obtained with a yield of 775a. Furtlier descriptions of the
synthetization of cyclopentadienyl-ketotetrahydro-indenyl-
-iron and -ferrocene carried out are following. (References
XIII, XIV, XV, formulae p 14). Then a detailed discussion
of the possibility of an alkylation of the ferrocene is
following. There are 11 tablea and 219 references, 39 of which
are Soviet.
1. Cyclic compounds--Analysia 2. Cyclic compowids--Synthesis
Card 3/3

.fo
t r
C r,
03t.,
~11 - II
j)ifern)
jj~rer
t 4
U
Card 1/4 p.

Diforrocenyl Mercury Reactisns
20-
Reaction t.,tXps place un&ir gromter i'l es w. t!:
-ulf on ic acld,3 ch I,-) ran rLy -I Thozi, d. 1 -:-rteen.v. 3111
and phenyll ferr_,;,zr~Yluulfon~ Fire prodlic-,-d ,n P. 1,- 3
5-6 $ on tiv, r-!..~-Ilnz ('r
unhydri&.e :4 11" iv!roc~w, FoA
Or t Il i 8 Cj C, L; 919 1 01 F "It, c f I ; ; C J T P
converted int: !*,!-r~ wi ~. Ri~a:,tlkrt Y, ch
takeo pla~o:(. f-von Und4i gz-~-atEn Ac(-,y.
i'errooer.e (,r v f,:-ma in % yle.el of an,.l f~rrocene farms
in great el-a d,-?scrJl,e,j ijbG\-e. Difol-l-Loeny'.
mercury docs r.,,,,t recL !;t hil &:Ir. h~nrlds~. Reactixis
t,akp_ place nior- eisi2y %'i.h ~ljlfc 's h cc
Vfi th I Odill;~i Fin' i6
ferrocen~l s"!, ;r.i. n a
trercury 1',.m, _-,-rr.3kj)
1 F, 11 t e r i 3 P!, F -I.' : %-, .1 - , f
scd-Jum tti~,sliil V.)rv. :-i., c i. s _i
o " 15 c p I ; U , a 1 h r ~ f , , f '_
wh .' ch te 7-d r-pac v .1
Card 2/ 4 mmul n unch,mae,i. pr

Diferrocenyl Mercury Reactions ;~(J_' 19-2-27/"60
thiocyanogen ferrocene is reduced into disulfide hy the
action of thiosulfate; moreover, 25 % of the diferrocenyl
mercury which entered the reaction are converted into
ferrocene. With Sellr4 the mentioned compound forms
diferrocenyl selenium in a yield of 21 %. On thim occas4on
selenium is reduced to bivalence. In all oases the reaction
product is precipitated either totally or partly In an
oxidized (ferricinium) form and is then reduced bi, sodium
thiosulfate. Thus, the important nucleophilic activity
of the C-atoms in ferrocene (easy electrophilic sub6itutu-
tion of the H atoms of the cyclopentadienyl rings) is ex-
pressed also in the properties of the mercury derivatives
of ferrocene: diferrocenyl mercury reacts with su:fohalides
under slighter conditions than diphenyl mercury (r-~fs 3,4).
The occurrence of ferrocene in all reactions investigatea
(except for SeRr ) as by-product is possibly due to the
forming of the firrooenyl radical which carries [A)ong
tne hydrogen from the solvent or froin other f r? v.
Card 3/4 groups. An experimental part with the usual d,ita !*_?owc.

Diferrocenyl Mercury Reactions 0-, 19- Z- . U"G
There are 4 references, 2 of which are Suv~,et
ASSOC'?~TION: koikovskiy gosudar.9tvennyy universitet im. M. V. Lomonr~---k
llt:.te Univergity imeni, ?A. V. Lomonutiov
~OY
Card 4/4

AUTHORS: Nestrjuyanov, A. N. , Member, Academy of ~-'j 5 9
Sciences, 1199R, Perevalova, E. G.,
Chu r anov , S. S
T1 TLE: The Reactl,in:i rf Ferro(,ene Sulfonic Acids (Fienk t
fervoteeniullfokislot)
PERIODICAL: Doklady Akademii- Nauk 53,3SR, 1058, Vol. '.1.9, Nr 5,
Pp. 949-,);2 (USSR)
A'SSTRA','T: After having ,F-rricpne bv va-io,js
reagpnts and some a-rivat~v,~,s of ferroc-~n& ?,:.c Lit ;,is
4n an garlier pRper (reference i) the nuthors in the
orpsent pap-gr dp%l with a number of furihor N-i,Curo,)s
subutituted ahorh they obtained. Furthor aii
attempt was made *.r) retill2e the excharge reactior. of the
:3111f-~ group. By interaction of Lhe lead efilt if
dis--i-ifoni:, 20 71 i- I h 1) h (' ": p f-lip
t r i r, r i u v , h t a I n ~ a m on o c o r a n hy a r: a q
Ciq_r1')C' H 11 Fou CH so 111. 1 hosphoriis oxych-, ~,T-i do *I I h If tie #4hA
sai t tht.- di d f orms the acid di cf.. rj (if! if Verruo~ t!p
Card 1,14 disulfoniQ a-.id. The ;.pad salt of monns-ilfjnjo aoift is

The Remotj or5 of' Ferrcr-n-, 1.1 1 ! -,-r; :.- cis - 1. 1-- . );, 1, A
oxf di zel by phosphor-,s r,xychlorl de to ferri n iufn-~,a 1. 1 ~r .
on whi eh nco.,tninn an I ntensive dark green c-. , - : q c-r,i o ~,f i
7 t. i s nei the- possl b ~(- t o ob tai n acid ch i r-ri ms~,i no, fr. n
or d-Lsulfonic neld fi-om barium salts. By hf-,;,L-~vg of
fr-rroo~ene with diethylamint. lr-~ li-
(diet~ylamide) 47,'L ferrocene disulfonic ac!id
?efc ff 90 H(C H ) /,- was produced. From MOW-
5 4 2 5 2-
f h, ori -i prAuccA di hy I ami dv, Oj~ im
of sull'Jnjo aeid, dilerrocenyldisi)lfide hn.1
-he 'tatter a.,; 2 derivatives: brnzoate and 9,-1*er,-(-(,-E-n%,.-t114--
at;id. is in iho air iap-i'v
"OrIverted to a dilzo~figi,-. In the ivfraro~-j .I
,st-alned nlca,--Subotl~utva sulfuz,..'U0 compouris of f-rr- :,c-
in the dom;,~n of (taken by L. A. Kazitsyr,,t
arA B. V. ohPrjtAerisC;C maxima eyjet wh~,rb ineli(,ti-i
the pret;ence ot* a frqe ryclopenrad1pnyl rLng. Thiev s3ro ivren*
in all I's-r;,ocenF- atarivativoia -1 this t,lyi~.
This confirn.~; Ot(- Suthoj'St opini~!n expv~F4-i~-d
(ref 1) that Ir.- suifa jroups .1e in differon'
,j.A 2/4 rj~ngF. The ik~tht-,r% airi n,A suc,~,?Pd In repirlin1fig Olf! 8~1

,ioni? of Fprr~)-ine 5 j : f r.Ylj c Avi ds I - I j-- -
Kr-ip by a tiv O-v melting together w. ',n h-~ it
h.v ryo,nng,~--j 'by v~arl of the influence it' pltr.-~:j m
1p?,!-, 'VfIT-0,- rv I
I, ?'My g1-011p (by mC-.fjDS
with 5:-AJ-.im a , 1ttipse attempts -,ea
destriicii-.n of he ferror,~-ne nucleiis, vnpr.~, ei th~:-
hydrc,x)6a or Jr,-n sai, were liberatezi. Thp hv,1r-c,vt-.
sulfrinl,~ unler !irmati n of ferrceemp. alEo fp~ -j.
Tne F-abiji!v at trip iy~kr-.ges of r-n with the c- riv,
r.ing,,; iv, arj)%-pn' 11v hjjTrjtv "Adured under the ini';u4:n,--
cmprrr-!d with ferrocene. Tv-
du-~ t ion of a su c- gr(,up riidi-e s the sil Seep Li V
fu ~-. hor -,.jtp ~, ti ir s hzjrh degr-?A in the pamr
-s~r apid lo a munh to*er aegron in rl--
ot,h6r rll,.g (re. Trie influpnoe exerted by the F?u.t,
gro-ap upon the regot , ,rlty of rho fr-ri-ornne nucle,is
sifio laz Tc, t to - q~!etvl ;crvup t
r.xpir~~ imc-nti. pprL wi 1 n ttin UsuRi d.-Isi !, 'I It'19.
Th-?r- nro ' rof-.r-~rp-n, 4 of which are 'Sov)pt.
3/4

- , 4 - -
Tile No-actl oyis c t S - 1 ",)r I - A~-l cli--
~TP IN: lit) ~-k- "!,~ i v %,Pnnyy uni vergi t c-i in.. V.. '~ I - ~- -
I, tic) t;c,: a ~j, a I 'p. Uni vprei ty impn'. M. V. ",ornor, -, )
AVI TT FD -. Jamzarv '6, ")~8
Clard 4/4

SOV/ 2o-12o-6-2*i',/59
AUTHORS: Nesmeyanovj A* No, Member, Academy of Sciences, USSR.)
Pe evai-S. G.-, Beynoravichute, Z. A., Malygina, 1. L~
TITLE: Reactions of 1,11-Dimethyl Ferrocene (Reakteii 1,11-dimetil-
ferrotsena)
PERIODICAL: Doklady Akedemii nauk SSSR, 1958, Vol, 12o, Nr 6, pp~1265-1 O'U
(USSR)
ABSTRACT: Reports were made already earlier on the influence of the
substituents on the reactivity of the ferrocene nucleus.
In the present paper the metallization- and acylation reach
tions of the substance mentioned in the title were investa
gated. n-amyl sodium was used as metallizing agent, In this
connection two directions of renction are poseible: A sub
stitution of a) the hydrogen of the methyl group, and b) of
the hydrogen of the cyclopentadienyl cycle, The metalliza
tion into the methyl groups expected from the analogy with
t0luene (Ref 8) did not take place; on the contrary, it
takes place into the cyclopentadienyl cycles. The main prod
Card 1/3 uct (yield of 52 ~) is dimethyl ferrocene dicurboxylic acid

Reactions of 1,11-Dimethyl Ferrocene SOV/2o-12o-6-27/59
with a decomposition point at from 196 - 2000. Two ac-,ida
were isolated in small quantities. All 3 acids yield soiid
dimethyl ethers and, hence, none of it is di-(carboxy-meth.v-
-ferrocene which forms liquid ether (Ref 9), The mutual po-
sition of the methyl- and carboxylic groups has not yet been
determined. The acylation of the substance mentioned in the
title was carried out by means of acetyl chloride under tne
presence of AICI The acylated products could not be vepftr~,t
ed. Aftar protra~t'ed storing of the mixture diveetyl d;nroth.v,
ferrocene crystallized out. Two isomers could be separatt'd
from it by means of fractionated cryatallization~ On tho
basis of a comparison with Ref ICI it there is reason to It-,
lieve that they contain stereoisomeric 1,11-diacetyl ferr,,
cenes. The monoacylated dimethyl ferrocene was isolated
chromatographically from the residual liquid mixturn- `ue
to the oxidation of this mixture with sodium hypochlori!k-,
dimethyl ferrocene carboxylic acid was obtained as trimethyl
ether. After the reduction of the same mixture by means of
LiAlH dimethyl triethyl ferrocene was isolated, Thus, M-
contridistinction to ferrocene a triacylated product :F forT
ed. The ferrocene nucleus is thun considerably nativated
Card 2/3 in the reactions of the electrophilic substituents unjer U-

beau ti ,)ns of I,, f -Fj mE:tj-jv I
inf rice cf
E. rroc., ene 30V/ "0-1
C'n n,- r-
1. Ferrocenes--Chemical reactions

..U arc v A 1i i '_7 it %
B Lj' 1.0~-aV i Ci A
TITLE: The of I Yerro(;~nt, t i I f
PERIODICAL: Duklady Akide:aii nauK S!SSH, 195t, Vol. 121, Nr 1,
( j s S,;l )
A3'.TIL',CT-. In r-cc,:-.t tiL.& various and -.1i:11k I
1 L --:(J 1, j..
i -, U f te C U I r t 0e S f
(Ref 6). 1;1 the pre-4e..t iap,r t.,ie uuLhors ac'A-veu I he s,-n-
thesis wei-tioned in the title bj t,;,,o ,ais: a)
methyl ether of ferroccne carbonic acid (Jield 33,j) bi means
of lithium alumohydr3te and b) by reduction ul' t,c
methylate of the 11111-di,-aethy I -amino-m ethyl-ferrocere ~Hefs
by means of ~jodium amal-am (yield In tht; lat
3.:nll -,uantitj of ~aono-~f;rrocenjl cirbir,,,l 2t ,-r
(C5H3FOO5 H4CH 2)20 is prAAced. Ii. ar; e,,.:
Card 112 actions a) and b) are cescribs.~d. The

Th e
'3~,ntheqis of hlcth~,l Ferrocene
spectra of th,~ ;Li~t:ijl furrcc~_n~ inich -r~as
the react _,ons -a ) a na ~, j arc corres ~on~ ~n i. : e:-, - 1 c-_'
-i.ere t-ken in thL laboratori k noy spe~,trosko:)ia
.,a ziole alyar
kafedry crZanichesko,, khimii (Laboratory; Of
copj of tht: FacLilty of Organic ChQmi!3tr~- of th, Mc,sco-~- S".1t,
Universitj,). In a pi A,r on ferrocene a1L;,,1,tion (ittf 2)
1 0
fErrc,_-L-nt.~ Yith -a meltin,7 point of 110 - 11) 7, a s iD cd T
produced i,roduct has a :aLltin, tC-.~ r3t,11'(: 0
Thuse last d-Aa ar, unduabt,c. Th e rt~a.5~,r.3 for 1 c? 1
diVEr.,ence -are (-x-- lainLC la t t~r . There are 9 re-, t~r._~,ces
which are Soviet.
ASSOCIATION: Mosk:)vskij ,csudarstvern,j aniversitet im. M. V. LDmonosc)va
L,
(!4'o8cow State University imeni L. V. Lomonosov)
SUB"'ITTLD: 11"arch 12, 1936
1. Methyl ferro-.ene ---- Synthesis 2. Methyl ethers--Reduction
3. Lithium aluminum hydrates--Chemical reactions 4. Mettlyl
iodide--Reduction 5. Sodium-Chemical reactions
Card 2/2

50)
AUTHORS. Neemoyanov, A. U. t .50V/20-124-2-25/71
Shilovteeva, L. So, Uetynyuk, Yu. A.
TITLE- Synthesis of Ferrocene Derivatives by Means of the
NvN-Dimethyl-Aminomethyl Ferrocene Nethiodide (Sintez
proizvodnykh ferroteena s pomoshch'yu yodmetilata
NpN-dimetilaminometilferrotsena)
PERIODICAL: Doklady kkademii nauk- SSSR, 1959, Vol 124, Nr 2, pp 331-334
(USSR)
ABSTRACT% The compound last mentioned in the title was earlier used by
the authors (Ref 5) for the synthesis of methyl ferrocene. It
proved to be a suitable reagent for the introduction of the
ferrocenyl-methyl group (Refs 2 -8). In the present paper some
substitution reactions of the dimethyl-amino group were carried
out, furthermorelmothyll-!-~forr4)tos'no was aminomethylated and
ferrocene aminoethylated. It was thus possible to obtain the
sodium salt of ferrocenyl-methane sulfonic acid by theinteraction
between the compound mentioned in the title and sodium sulfite.
By the influence of potassium thiocyanate ferrocenyl-methyl
thiocyanate was formed. Sodium phenolate and -f-naphtholate
Card 1/3 yielded the phenyl- and # naphthyl ether of the ferrocenecarbinol.

Synthesis of Ferrocene Derivatives SOV/20-124-2-25/71
by Means of the N,N-Dimethyl-Aminomethyl Forrocene Methiodide
By ferrocenyl methylation of the p-oxy-azo benzene an azo
compound was formed containing a forrocenyl group. This had
hitherto not been possible. On the aminomethylation of the
methyl ferrocone (Hof 5) with a mixture of N,N,U I NI- tetramethyl-
diamino, methane and paraform a homoannular (N,N, dimethyl-amino
methyl) methyl ferrocene was obtained in a 60% yield. The
aminomethylation of the methyl forrocene was carried out in the
substituted cyclopentadiene ring in a yield which was somewhat
higher than for ferrocene (515,, Ref 2). The addition of
phosphoric acid increased the yield up to 80%. Besides,
diaminomethylated mothyl ferrocene is formed (101% yield). Thus
the methyl group in the methyl ferrocene considerably activates
the ferroceno nucleus against electrophilic attacks. The
formation of the homoannular compound suggests that the ring to
which the methyl group is bound, is activated to a more
considerable degree. The successful production of the diamino-
methylated mathyl ferrocene further proves that the influence
exerted by the substituents is transferred from one
cyclopentadienyl ring to the other one by means of the iron atom
Card 2/3 (Ref 9). From the compound mentioned in the title the authors

Synthesis of Perrocene Derivatives SOV/20-124-2-25/71
ty Means of the Ngli-Dimethyl-Aininomethyl Ferrocene Methiodide
synthesized the homoannular dimethyl ferrocene. It may be
assumed from the comparison of infrared spectra that the
alkyl groups are in a 1.3-position. There are 12 references,
2 of which are Soviet.
ASSOCIATION: Moskovskiy gasudarstvennyy universitet im. M. V. Lomonosova
(Roscow State University imeni M. V. Lomonosov)
SUBMITTED. October 14, 1958
Card 3/3

5 (2,3)
AUTHORS: Nesmeyanova, 0. A., Perevalova, E. G. SOV/20-126-5-26/69
TITLE: Diferrocenyl (Diferroteenil)
PERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 126, Nr 5, PP 1007 - 1008
(USSR)
A.BSTRACT: In order to produce diferrocenyl the authors have investigated
the decomposition of diferrocenyl-mercury in the presence of
palladium black. When heating mercury-organic compounds with
metal powders without solvents, a radical doubling occurs (Ref
1). Thus, in the case of diphenyl-mercury, a satisfactory yield
of diphenyl is obtained. In the present case, however, diferro-
cenyl is formed, but the yield is small. The main reaction pro-
duct was ferrocene (Refs 20). Further in organic solvents in-
soluble substances, probably ferrocene-polymers were formed.
The formation of ferrocene can apparently onl:, be explained by
the disproportioning of the ferrocenyl rad1calB formei as in-
termediate products. From these radicals ferrocene is formed,
as well as its polymer or diferrocenylene. Yields are shown by
table 1. The separation of ferrocene and diferrocenyl is de-
scribed. Besides9the existence of the said polymers among the
Card 1/2 reaction products is proved. Diferrocenyl is an orange-colored

Diferrocenyl SOV/20-1 26 -5-26,16- ~
crystalline substance, easily soluble in benzene, but less
easily soluble in petroleum ether, ether, and alcohol. It cry-
stallizes from alcohol. Diferrocenyl is thermally less stable
than ferrocene. It becomes dark at 205 0, and melts at 2300 U!I-
der partial decomposition. In this manner no ferrocene is
Zormed. Consequently, the ferrocene forming in the catal~tlca'
splitting of the diferrocenyl-mercury is not a product of
chemical decomposition of diferrocenyl. There are I table and
3 Soviet references.
ASSOCIATION: Hoskovskiy gosudarstvennyy universitet i=. M. V. Lomonosova
(Moscow State University imeni 121. V. Lomonosov)
PRESENTED: April 14, 1959, by A. N. Neameyanov, Academician
SUBMITTED: April 10, 1959
Card 2/2

PERVALOVA, B.G.; IMSMANOVA, O.A.; LUKIYANUVA, I.G.
Ferrocenesulfinic acids. Dokl.All SSSR 132 no.4:f353-856 Je
l6o. (MIU 13:5)
1. Moskovskiy gosudarstvennyy universitet im. I.I.V.Loinonosova.
Predstavleno akademikom A.N.Neeneyanovym.
(SUfinic acids)

'57 0 O(A~ B011%003
AUTHORS; Perevalova, E. G., Nesmeyanova, 0. A.. Luklyanova, I. G.
Now 1-
TITLE: Perrocenesulfinio Acidel
PERIODICAL: Doklady Akademii nauk SSSR, 1960v Vol. 132, NcF. 4,
pp. 853-856
TEXT: In.a previous paper the authors described the production of
ferrocenesulfinic acid (Ref. 1). In the article under review, they
synthesized terrocenedi8ulfinic acid and examined the properties of
both acids, Ferrocenedieulfinic acid was obtained by reduction of the LY
acid chloride of ferrooenedisulfonic acid with zinc dust. It is
difficultly soluble in water and organic solvents. Its solutions are
rapidly decomposed, and its disodium salt is much more stable. Both
mono- and diferrc-,enesulfinic acid react with sublimates in a similar
way as benzosulfinic acid and yield large quantities of mono- and
di-(chloromercury)-.ferrocene.' The authors tried to obtain in a similar
way a ferrocene derivative of tin by actioh of tinchloride on the
sodium salt of sulfinic acid, They found, however, that a reduction
B102 60/132/04/33/064
Card 113

Ferrooenesulfinic Acids S/02()/60/132/04/33/064
BOII/BO03
I
PRESENTED- January 12, 1960, by A. N. Nesmeyanov, Academician
SUBMITTED: JanuarY 3, 1960
Card 3/3

FXRSTAIDVA, B.G.; NEDWASDVA, O.A.
Synthesis of dlferrocezTl b7 the Ullmnn reaction. Dokl.Alf SSM
132 no-5:1093-1094 Js 160. (MIU 13:6)
1. Moskovskiy gosudaretvanTy universitet imo HaVeloomonosovae
Predstavlem akademikom A.H. Neemayanovyn.
(Iron)
A
I

83136
S/020/60/133/005/014/019
B016/BO60
IF. 3)00(8)
AUTHORS: Nesmeyanov, A. N., Academician, alova. V- ty
Ustynyuk, Yu. A.
TITLE: Ferrocenyl Mothyl Lithiumi.
PERIODICAL: Doklady Akademii nauk SSSR, 1960, Vol. 133, No. 5,
PP- 1105-1107
TEXT: The authors previously described the production of ethers of
ferrocenyl carbinol (Ref. 1). In the present study they used lithium to
cleave ferrocenyl carbinol methyl ether dissolved in tetrahydrofuran.
The resulting ferrocenyl methyl lithium was used to produce ferrocene
derivatives. The authors proved furthermore that ferrocenyl carbinol
ethers can be readily obtained by heating ferrocenyl carbinol with the
respective alcohols in the presence of acetic acid. In this way, the
authors obtained methyl-, othyl-, and benzyl ethers of ferrocenyl
carbinol in yields of 73, 110t and 72/5. The ready formation of thene
ethers is explained by the stability of the ferrocenyl methyl
Card 1/2

HNSMEYANOV, A.N., akad.; PPIRVAWVA, B.G.; Sl.%UYOVb. N.A.; SHL"thl-lit,
Tu.S.; REJ&TOVA, M.D. - -
Formation of the 1.2.3-ozadiazine ring in the r(~actior, of
1.11-diacetylferr-ocene with ary1diazonium compounds. Dokl.AN
SSSR 133 no.4:851-854 Ag 160. (MUM 13:7)
1. Moskovskiy govudarstvennyy universitot imon! M.V.LomonoBova.
(Oxa(Lia2ine) (Yerrocene) (Diazonium compounds)

B10201601' ~r'IOV102
BO, 6/BO60
ATJTHORSi E. G., Yur-yeva, L. P., and Baukov, Yu. 1.
TITLE4 D1TC-It Cyanation of Forricinium SaItFi
PERIODICALi Dnklaay Akademti naik SSSR. 1?60, Vol.
pp. 1402-1405
TEXT: The authors Tep3rt on the substitution of hydrogen atoms in ferri
cinium ferrich",nride and ferricJnium ferribromide. As had been expected,
the ferricinium cation was pasFlvp in the elec+rophillc s,,jbs!ituziDn,
since the positive e~harge, no matter whether localized on the Irnn at7,m
or distributed over the whole me)lecule, prevents electrophil:ic attacK,,i.
Thus the authors did not su,.ceed An performing any elect roptil I ~.c sub-
stitution in ferricinium. They therefore attempted nucleophilic cub-
stitution. Notable yields (-)vEr 50%) cf n1trile of the ferro(,,~ne carbc
xylic acid were obtainod when us-ng 'he solution of liq,14d HCIq in anhydro,;(3
tc-trahydrofuran. A yield Dver 90% was ,.>btained when ferricinium salt was
replaced by a mixture of ferro~,ene and anhydrcus FeCl 3* By this method
one may also obtain the W therl,,-, )rIescribPr.1 nitr; ler3 :)f sub~zt z tu!9d
Card 114

87406
Direct Cyariation of Ferrcn~,im Sa:ts S10201601, ~5/00(,/0-11 ?/'0
B016/BO60
It was fr Dc
(methyl- and ethyl-) ferrDoene acdp-
infrared spectra of these ni tr: ies na* conta., n a itute~
cyclopentadienyl ring. It was co-icluded that *he nitr~le Uoup enterS s-.-,
a ring as contains an elec*rcn donor oubst'tuent. A nnnstlbsttuted cyc.,
pentadienyl ring was missing in the :~Iher rwo compounds produced by the
au t ho rs t i n n I t ri 1 e Df he t e r oanni, :,a r , h I' : -D f '? r ro ~ on e c a rb') xy 1 A c a -_ i ~ a r d
in dinitrile of het-:!roannular ferroce-na dicarboxylic ac'J. This was
spectroscopically :-)nfirmed (Ref. 14)- Electr,~n acceptor sabstit~_ient5
(C1, CN) are therpfDr,7 be.'_,evel tc, render 'he -yariation of the cyc2openf.
dieny! ring w,4*h whi-h they are linked mire difficult; the C11 grrup Pn'e
the free ring. The a,.ithorE 1~,ubt their original a!~Bumption of the ferri-
cinium cat -1,:,n be: ng -apable .- f a n-1cle -,phi I , c subs t itut ion, s ince the
effect of electron doncr and eie,tr-jri acr,qt:~r 3ubqtituentg w;As fo-ind t
be as strong aa in the elc.ctrophilic subs,it,iti-jn. The material yielde-, b.-l-
their experiments ia ri-gar-deJ as beinir -.n~i,ifficient to establish tale re-
action mochtin'sa. Th- -)n.) cf~rtan fa-t -3 that the ro~irtior, rrjj
by an attack of the CN an!-2ri aratrist r)rte of the carbon rit~tn,) -)f the y('~' -
pentadienyl ring-3. Tw,-, api3limpt!-ns put ft-rth ~on-_-rninr *h,- rpfl:-'I~,n
mechan.smi 1) a b-~nd Is f :rm-,i rl-t ~e*ween ?h- CV --inicn 'Ind '~ ir-n
Card 2/4

87406
Direct Cyanat on Fer:'. -,n' um S;,1 * s S/020/160/1 35/006/022/0
B01 6/B060
atom of the ferricinlum cation, and *he pr-)t,,)n thpn -ittacks one of
hydrogen atoms of the cyclolentadienyl rin(;s. This hydrogen is qs~lit -~ff
as a hydride compound and may be used up for the reduction of the ferri-
cinium cation, while CR binds with the carbon atom of the cyclopentadieny'
ring. Possibly, all these stages take place simultaneously within one
single reaction complex (or a cyclic transitional stage). 2) There occlirq
a specific electrophilic (or homolytic) substitution, and ferrocene and
CN4 cation (or CN* radical ') are involved in the reaction. In this case,
tne role of the ferriciniuri cation (cr of FaCl 3) would consist in the
,ransformation of the CN ac~lcn into a cation (or into a radical). L. A.
Kazitsyna is thanked for having taken the spectra. A paper by Ye. M~
Shustorovich and M. Ye. Dyatkina is mentlDned (Ref, 8).
There are 17 references~ 10 S--vipt, 4 US, I German, and 2 Brtish.
ASSOCIATION, Moskov-3)-,,; C,)--,~jdu.-r,-,r43nnyy iniversitet im. M. V. L-clon, ~3-)va
(Hoecow State University impni M. V. LomonDsov)
Card 3/4

87406
Direct Cyanat. :)n --f Fer,-.,- in iun. S~.. , -l~ S/o?0/60/1 ~~,,'Ocrs, O.-Ile-.1,01,
Bol 6/B060
PRESEYTED, T U, y 1 -1 , I '1~0. 11 - i~ ~ i~. ': -- -, -,, i-,- ~ i n -~ " . A r - 1, - U; , - , 11.
SUBT-ITTTED: June P-.), ' 4~0
Cari 4/4

1275
51-700 2,209, U141
89402
5/062/6!/000/001/'00-7,'016
B'0'/B220
AUTHORS: PerevedusajL G., Simukova, N. A., Nikitina, T. V.,
shetov, P. D., and Nesmeyanov, A. N,
TITLE: Interacticn between ferrocene derivatives and aryl diazonia
PERIODICAL- Izvestiya Akademii nauk SSSR. Otdeleniye khimicheskikh nauk,
no. 1, 1961, 77-83
TEXT: The authors have shown in Refs~ !-3 that ferrocene reacts with
aryl diazonia to form aryl ferrocenes. The present paper deals with
the arylation of p-toiyl, methyl, ethyl ferrocene, as we'll as acyl and
carboxy ferrocenes. It was possible to arylate p-tolyl ferrocene by
means of p-tolyl diazonium and this resulted in the formation of hetero-
annular di-(p-to'Ly-) ferrocene:
P-CH-C H N C,
6 4 2 Fe(C Ji C H CH
C5H5 FeC5H4C6H 4CH 3-P 5 4 6 4 5-P12 The yield
amounted to only 9% of the theoretical one; this is attributed to the
poor stability of the cation of this compound, Reaction between phenyl
Card 1/ 3

89402
Interaction between ferrocene S/062/61/000/00!/'007/016
B*Oi/B220
diazonium and methyl ferrocene resulted in a mixture of phenylated methy.'
ferrocenes from which it was possible to isolate the heteroannular meth~l-
phenyl ferrocene in a poor yield-
C'ji N X
C5H5FeC 5H4CH3 o 5 2 % CH 5C9H4FeC5H4C6B5' The ethy.1 ferrocene reacted
similarly (20% yield). Reteroannular d1propionyl, dibutyryl, and di-
benzoyl ferrocene reacted with p-nitro-pheny! diazonium In the same way
as observed in the case of diacetyl ferrocene. The bond between the
iron and1he cyclopentadienyl ring was split, and derivatives of
1,2,3-oxa-diazine were formed. Resinification took place in the reaction
between D-nitro-phenyl diazon:Lum and the dimethy! ester of ferrocene
dicarboxylic acid. It was proved possible to isolate chromatographically
a reduced amount of p-nitro-phenyl-dicarbomethoxy ferrocene. but the
ferrocene ring was destructed at the same time (appearance of iron ions).
Monosubstituted ferrocenes, such as acetyl ferrocene and carbomethoxy
ferrocene, react with p-nitro-phenyl diazonium like ferrocene, but with
a lower yield of arylation products. Monoacetyl ferrocene formed both
homoannular and heteroannular p-n1tro-pheny! acetoferrocene:
Card 2/ 3

89402
Interaction between ferrocene ... 5/062/61/000/001/007/016
BIOI/B220
P-NO2C6H N Cl
C5 H5PeC5H4 COCH3 ...4.2 b CH 3COC5H4FeC 5H4C6H4NO 2-P
+ C5H5FeC5 H3(COCH3)c 6H4NO2-p. The methyl eater of ferrocene carboxylic
acid reacts to form heteroannular p-nitro-phenyl carbomethoxy forrocone
(yield 7%). The presence or absence of the non-substituted cyclopenta-
dienyl ring was always established spectroscopically. The free mono-
and dicarboxylic acide of ferrocene as well as their sodium salts
together with p-nitro-phenyl diazonium gave mixtures from which the
arylation products could not be isolated. L. V. Yershova and M. Kristynyuk
assisted in the experiments. There arp 14 Soviet-bloc references.
ASSOCIATION: Moskovskiy gosudarstvennyy universitet im. M. V. Lomonosova
(Moscow State University imeni, M. V. Lomonosov)
SUBMITTED: July 28., 1959
Card 3/3

NMMYANOV~, A.N., akademik-; PEREVALOVA, E.G.; GUBIN, S.P.; NIKITINA, T.V.;
FONCMRENKO, A.A.,;- SHIJ L7K=..S.
Properties of phonylferrocene. Dokl. All SSSR no-4:888-891 Ag 161.
(MIRA 14:7)
1. Moskovskiy gosudarstvonnyy universitet im. M.V. Lomonosova.
(Ferrocene)

NESMEYANOV, A.I.; PFREVALOVA, E.G.; SHILOVTSEVA, L.S.
Reactions between organomagnesium compounds ard (Ferrocenylmethyl)
trialkylazwr.onium salts. Izv.AN SSSR.Otd.khim.nauk no.11:1982-1985
N 61. (?IIffiL 14: 11
1. Moskovskiy posudarstvennyy universitet im. M.V.Lomonos,.)va.
(Magnesium organic compounds) (Ammonium compounds)

0 25317 S/020/61/136/005/017/025
B103/B215
AUTHORS: Nesmeyanov, A. N., Academician, Perevalova, E. G.,,eLnd
Nikitina, T. V.
TITLE: Synthesis of azoferrocene, its reduction and behavio.r under
the conditions of benzidine rearrangement
PERIODICAL: Akademiya nauk S30SR. Doklady, v. 138, no- 5, 1961, 1118-1121
TEXT: The authors synthesized azoferrocene, examined its interacti~on Vith
reagents transforming azobenzene into benzidine, arid studied the behavior
of azoferrocene under the conditions of the production of hydrazo: compounds
and their subsequent benzidine rearrangement. Azo derivatives of ferrocene
were first synthesized by G. R. Knox (Ref. 11: Proc. Chem. Soo., 1959,
56) (methyl- and phenyl azoferrocene). The authors obtained azoferrocene
by the action of N~O upon, ferrocenyl'lithium (Ref. 12: Tetrahedron
Letters, No. 1, 1 1960)). A similar reaction was described for phenyl
lithium (F. M. Berin'~~r, J. A. Farr, S. Sand6,Ref. 13: J. Am. Chem. Soo.,
75, 3984 (1953); R. Meier, W. Frank, Ref. 14: Ber.., 89, 2747 (1956)).
There is hardly any organic solvent vith which azoferrocene would form
Card 116

S/02 61/138/005/017/025-
Synthesis of azoferroceno, ite..25317 B103YB215
benzidine-type compounds under the action of strong acids (conditions of
benpidine formation from azobenzene). The action of concentrated HCRor
H2C04 partly causes its Jecomponition, and partly its transformation-Into
ferrooenyl amine. The ILthorq explain this pecullar-behuvior of azo-
ferrocene which differs from that of tizobenzene as follows: azoferrocene
is protonized in the presence of a strong acid, and cation I forms whose
positive charge is neutralized due to electrons supplUed by the iron atom,
and due to the formation of ion radical II. Ferroacenyl amine and fission
products of the ferrooene ring iere obtained from Il by acid action;
C4H,FeCH,N = NC6H&FeCsHx -"-* (CjIsFeCH4~ ~CM4Fer4H&I -
+ HCJ
IC4H& Fer-sH,14 NHCH,FeCH,l+
QHjFeC&HdNH, + FeCls + JQH, + C&HINCI I.
The authors assume that tie ion of II has a III structure:
Card 21.6

25317 3/020/61/138/005/Qi7/025
Synthesis of azoferrocene, its ... B103 B215
N - NI-I
Fe* Fe'
III - /-%~. IYO - ;1
0
(W. F. Little, A. K. Clark, Ref. 19: J. Org. Chem, 25, IM (1960)).
Furthermore, the authors studied 'lie reduction of azoferrocene under
c6nditions under which hydrazo benzene is formed from azobenzene with
almost quantitative yield, -,hile almost no aniline is formed. Azoferrocene
proved to react neither w 'ith lithium aluminum hydride, nor with phenyl
magnesium bromide, nor with lithium in tetrahydrofuran medium. In
alkaline medium it is reduced to ferrocenyl amine (yields: 20 %, and 76%,
respectively) by hydrazine hydrate and zinc. This behavior of azoferrooene
is similar to that of benzene derivatives; azobenzenes with donor
substituente canno 't be reduced to hydrazo comDounds as easily as azo-
benzene itself, Phereas the corresponding hydrazo compound can more easily
be reduced to amine. It in known that the donor properties of the
ferrocenyl group are much stronger than those of the phenyl group.
Hydrazo ferrocene probably formed as an intermediate in the reduction with
Card 3/6

S/02 61/138/005/017/025'
25317
Synthesis of azoferrocenti its ... B11D3YB215
zinc dust. Stirring and heating of the reaction mixture makes the violet
color of azoferrocene dialippear gradual'-y. However, it appears again as
soon as stirring has stopped, and zinc has dropped to the bottom.. This is
repeated until the color disappeared irreversibly. The authors assume
a further reduction of hydrazo ferrocene to amine, and also its
disproportionation into szoferrocene and ferrocenyl amine. Without a
reducing agent, only diaproportionation takes place and causes a-rapid
increase in the azoferrocene concentration and violet coloring. If the
reduction is interrupted at the first disappearance of the violet color,
-and if the reaction.mixture is divided into trio equal parts one of ~Phich
is treated nith diluted HC1 whereas the othe 'r one is shaken in the air,
a mixture of azoferrocene and ferrocenyl amine is formed in both cases.
In the second case, however, the amount of azoferrocene is much higher
than that of ferrocenyl amine. In the first case, the disproportionation
of hydrazo ferrooene into amint and azo compound is much faster under the
action of HC1. In the--second half, the hydrazo ferrocene which,so far
has not been disproportionated, is oxidized into azoferrocene by 4e
atmospheric oxygen. Since no other amine besides ferrocenyl amine has
been found, the authors conclude that a benzidine-type rearrangement does
Card 416

S/ 020/-1/ 1 01 02~

'
117
25
-
Synthesio of azoferro~2ene, atri... B 10 El
.
not take pla~,e. Tr,.-,, `.- : -] ' e _~, ir 1 -,T, t e. ~-
under g~: I-, r r.. !rrqnqemen I ch:,r1i_* er be 17e
s -)f' r n series.
An anal oi-,y ~,f f~rrccene benzene 1 roved qucocssf,i;
J in those clasps v.,:ere
the general abi'~ i ty of electro)n suiply of' the syst#?m played 1-ne m~i, 11 !_.,irt
IntrLmolecular rearrant_lement of' benzenp derivatives iu tisuul ly -hura-
terized by a cyclic transition stage in-cludirp quinc-ile- ty-,e qtria:,tures,
In the case of ferrocene derivLitlves, similar transiliDn st~ltes cannot be
of the eame character. The spenifity of' electron interactions Y,,t~iin the
system is very distinct in suc'k structures, and iron plays a decisive rc~le
in ferrocene derivatives Furthermcre , "fulvenoid" structures ( - - III
in scheme no. 2) will correspond to the "qi4inoide" structure of t-!)e
benzene series. A com-,~lete analogy in the conveyance of ele(-tron
influences in these two structuri~q is very unlikely (, I Gershzon is
mentioned. There are 2 1 references ; 7 S~viet-bloe and !.~ nc,n-Soviet ,-bloc .
The four references to English- language publications r3rp wiven in the bod.11
of the abstract,
ASSOCIATION: Moskov,)kiy aosud: rstvenryy universitpt iv.. M, V 1, nf)n0,qova
~Mosco-,% Statq Univer,3ity imeni 1,11. V Lolr,_)n Fi(,~v
Card 5/6

25856
S/020/61/139/004/0'6/C2;1~
B '03/B206
AUTHORSt Nesmeyanov, A. N., Academician, P~- ava:ova, E. G., V'vb;r., j,
P., Nikitina, T. V., Pcnomarer_k6~ -A -A,, and ShTlovtseva,
TITLEi Properties of phenyl ferrocena
PERIODICALs Akademiya nauk SSSR. Doklady, v. 13 C
TEM The authors investigatedt 1) the amino met ati-,n, e, aulf:~ra-
tion, 3) concurrent (with ferrocene) acetylation, a 4~ nitration of
phenyl ferrocene. They established that the alkyl up, if linked w:tt
the ferrocene ring, facilitates the subee-juent elect ~rillic subst-,tution
In this case, the cyciopentadienyl ring to which the t6lkj! group !a bonded,
is more strongly activated. In relation to the ferroqanyl group. the
phenjl group is an electron-acceptor group (A. N, Neemayancv at a.. Lief;
51 DAN, 103, 61 (1955)). These data by the authors were conflrmtd by Y
Rosenbl~m7J, Am. Chem. Soc., 81~4530 (1959))'1 The electrophi,lic su.',ati-
tution of the hydrogen atoms in the forrocene ring is deactivated by the
phenyl group. 1) Amino methylation. To a mixture of 70 ml of
Cardl/ 6

25856
S1O?01611!391j0,11G'6/'12-' I
Properties of phenyl ferrocene B103/B206
acetic acid and 4 g of H 3P6 4' cooled to 100C, e.25 g ~0-019 acie) of
tetramethyldiaminoethane is gradually addedi and then 4 g (G,~),5 molel, of
phenyl ferrocene. The reaction mass was stirred foi ' hr at room
temperature and for 10 hr at 110 - 1150C in a nt,.rogen current and ,;b-
sequently diluted with water to the double amount. The ferrocene gl
which had not entered into reaction was extracted with benzene. 40% NaOH
solution was added to the acidic solution, and the formed (N. N-dimethy'-
aminomethyl)-phenyl ferrocene was extracted with ether. After disti.ling
off the ether, 2.6 g of the above-mentioned oampound was obtained as a
viscous, darK, reddish-brown oil. The yield amounted to 54~~ of the
theoretical one (related to pherVI, ferrocone) and to 66;4 of' the phery.
ferrocene reacted. The final product was distilled In vacuo Its bolling poirt
was 150-1600 C/3 mm Hgj 20 1.6315. In the infrared -spectrum of the final
n. _ I
product, weak absorption bands existed in the range 1000 and '100 cm
From this, the authors assume the formation of a mixture from the hetero-
and homoannular isomers. The latter seems to form in small quantities
The methiodide of the final produot was produced by addition of CH 31 to
Card 2/6

Properties of ph6nyl ferrooene
5/020 61/139/004/016/025
B103 B206
a solution of 3.2 g In absolute Ch 3OH (or in benzene) with precipitafion
after 15 min by a..;reat amount of anhydrous other. An almoot,quantitative
(4-3 g) amount oUnothiodide was produc0d. It is a yellow, cryatalltne
-substance with the decompodItion point 70 - 750C. Since in the infrared
spectrum of the methiodide which was produced from the distIlled fipal
product, absorption at 1000 and 1100 am- I is missing, the authors conclude
that the oubBtituting groups are in Yarious cyclopentadionyl rings.
Through reduction of the methiodide by sodium amalgam, the~hwteroannular
1, 1-mothy.L-phonyl f4rrocene was obtained (Goo reaction no.
C,H, /-\- C'14'
(Cli,4 NCHIN(CH.). \ /
Fe Fe
H.P0. CH,N (CHI)t
CarO. 3/6
CIH, CTi I
cjl.j W No./fir \ /
Fe Fe
Ctl,N (CHo)s J Cli,

S/020/61/1'39/004/01,6/025
Properties of phenyl ferrocene B103/B206
The yield was 1-8 9(71% of the theoretical one). Absorption at ;000 and
1100 0m- was missing in iteinfrared spectrum. A free cyolopentadienyl
ring can only be proved spectroscopically in the substance which was
isolated from the mother liquor. The authors came to the conclusion that,
the hateroannular isomer was the main component of the mixture produced by
amino methylation. Therefnre,,th~j reaction mainly occurs in the free
cyclopentadienyl ring. 2) To a,99lution of 10 g (O.Op mole)'of phenyl
ferrocene in 100 ml of dichlorosthbne,, 10 g (0.060 mole) of freshly
prepared dioxane sulfotrioxide wQs.-added while cooling with ioe. Under
the conditions of formation of fepj!oceno monoeulfonic acid; pheny.1
ferrocene sulfonic acid was obtainq4-1
so -diaxane
C6H5C5H4FeC5H5 3 0 6H5C5N~qY450 3H. This acid was isolated
as lead salt? which crystallizes '-V:L~hW,~,vater molecules. Absorption at
1000 and 1100 om'I was here aIso,m4j4jnsj the phenyl and oulfo grou�o &r
therefore in different oyalopen taoienj~l rings. The formation of hetero-
annular aulfonic aoid is also proof of a lower reactivity of the ring
Card 4A

0
S/020/51 /139/004/016/02 5
Properties of phenvl ferrocene BlOVB206
linked with phenol- 3) The deactivating effect of the phenyl grovp
on the ferrocenyl ring is specially marked during the Friedel-Craft;
reaction. A solution cf 1 .4 ;Ll of acetyl. chic-ride and 2.66 g of AlCl
in 10 ml of absolute et-,).-, t;lded in thO ccor:.,e of 20 min to a
solution of ferrocene ~~:,d pnenyi ferrocene (5-42 g). in 100 ml of
CS 2' All components iialar, riAlo of 1:1i1:1. The authors
obtained acetyl ferrocent, ---iith a yield of' 25-40 of the theoretical one,
and a mixture of acetyl F,~~er.y, of only 5%, 64~,,fa of pher~vl
ferxocene and 3DA' cf rt-c.overed unchanged. From this, the
authors conclude that fer--ocene z-.a'i be acetylated more easily thanphenyl
ferrocene. 4) Pheny! ferrocene was nitrated by means of ethyl nitrate
in CS2 in the presence of AIC1 Thu authors obtained a 13~146 yield (of the
theoretical one) of f~trro--ene
(see reaction no. 2.).
N03
Fe
fo
Card 5/6

Properties of phenyl
3/020/61/1 39/004/01~/025
B105,/B206
The main quantity oil thda final product is isolated together with part of
the nonreacted pheryl ferrocene in nonoxidized state (and not as a cation)-
The authors pres,,ime that nitration does not take place with the phenyl
ferrocene cation but with phenyl ferrocene. The continuance of the forro-
cenyl ring under thetc, e~,ndtions is noticeable, probably as a consequence
of a reduced capability of beinft,, uxidized to a cation as compared with
ferrocene. Ferrocene itsellf caTnot ~~e n:Ltrated under *these conditions.
Attempts of the authors t(., f,~rrocene vi-ith varioua other reagents
(e. g., nitronium borofl_ir_,r~dc" ~.,oo failed. Only, oxidation of fLrrocene
to the catio% which is i-iort n reac~icn,,, of the elE)C.rophilic aubZ;titution,
was brought about. Ther,--- are : ~ Soviet-bloc and 3 licn- *
Soviet-bloc. One r-fer-.~c- t 2n,~__,z;h-_)arqua6e publ'ications _JU ~T-Ver. in*.Ie
body of the ab3tr,-,c-,,, E~ ~ 3 :14. iosunblum, R. B. Icodward,
J. Am. Chem. Soc.,
ASSOCIATION: Yoski.~vok4y universitet, im. 1,1. V. Lomono.,3ova
(!,!o 0 C (3 -C;3L tI V!3 "Y ifliCni V. Lomonosov)
SUBMITTED: Apri.
Card 6/6

FEREVALOVA, Z. G.
Dissertation defended for the degree of Doctor of Chemical
Sciences at the Institute of Elemento-organic Compounds in
1962:
OFerrocene as sai Lromatic System."
Vest. Akad. Nauk SSSR. No. 4, Moscow, 1963, pages 119-145

ACCESSION NR: AP4010040 S/0062/64/000/001/0062/0069
AUTHORS: Ustv*nyuk, Yu. A.; Perovalova, E. G.
TITLE; Reactivity of compounds containing the ferrooenylmethyl
group. 7. Rearrangement of the dimethylbenzyl(ferrooenyl-
methyl)ammonium chloride under the action of nuoleophillo
reagents
SOURCE: AN SSSR. Izvestiya. Ser. kh1m., no. 1, 1964, 62-69
TOPIC TAGS: ferrocenylmethyl compounds, reactivity, rearrangement,
ferrocanylmethyl group, stabilizing action, Isomerization, Intra-
molecular reduction, carbanion stabilization, nuoleop*hillo reagents
dibuttyllithium
ABSTRLCT: The comparative stabilizing action of the benzyl and the
ferrocenyl rings on an adjacent carbanion center was determined
ifrom the rearrangement products. Dimethylbenzvl(ferrooonylmethyl)
ammonium chloride (I) rearranges in the presence of d1butyllithlum
to (alpha-phenyl-beta-forrooenylethvl)-dimethylamine (11), 72% yield.
In the presence of potassium amide, conversion Is 50%,.with benzvl-
1-Card 1/3

'"OESSIOlf - NR:- ~,P4010040
magnesium chloride, 21%.
C4HsFeCoH#CHs\*/CHo C.H. FeC& If,\+/CHS
N N
C,H,CH,/ \Clio c'-"- G11- ul;cl)
C'11& - CH - Clio C4H& FOQH&
Thus the benzene ring stabilizes the adjacent anion center more
than the ferrooenyl ring does. A new type of Isomerization was
observed in the reaction with dibutyllithium; N,N,N't N'-tetramethyl-,
alpha,beta-diphenylethylene diamine and 1.2-diferrocenylethane were
produced In addition to II, the amount of II decreasing on prolonging
the reaction. The following intramoleoular reduction of the ammonium
nitrogen Is suggested:
Ok
J

ACOESSION VR: AP4010040
C,%H&FeC"CVi, 01-01/c"31
C,OW".016 + C0ijd9N(CH,)s
C4"& -HP
"Authors express deep appreciation to A. N. Nesmeyanov for attention
to the work and valuable advice."
Orig. art. has: 10 Equations.
ASSOCIATION: Institut elementoorganicheskikh soyediueniy Akademil
nauk SSSR Moskovskly gosudarstvenny*y universitet im.
M. V., Lomonosova (Institute of Organometallio Compounds,,
Academy of Soienoes SSSR Moscow State University)
SUBMITTED:,06Sep62 DATE ACQ: 10064 ENOL: 00
SUB CODE: CH NR REF SOV: 006 OTHER: 005

AOCESSION NR:
AP4010041
S/0062/64/000/001/0070/0073
AUTHORS: Usty*nyuk, Yu.A.; Perevalova, E.G.; Nesmeyanov, A.N.
TITLE: The reactive ability of compounds containing the ferrooonyl-
methyl group Report No.8. Wittig rearrangement in a series of ferro-:
cenylearbinol others
SOURCE: AN SSSR. Izvestlys. Ser. Mm., no.l. 1964, 70-73
TOPIC TAGS: ferrocenylmethyl group, Wittig rearrangement, ferrocenyl-
carbinol others, butyl lithium, lithium ether linkage, ether isomerl-
zation, anionic center stabilization, I phenyl. 2 forrocenylethanol, 2
phenyl I ferrocenylethanol, 102 diferrocenylethanol, 1,2 diferrocanyl-
ethylene
ABSTRACT: In continuation of earlier work, this rearrangement was
studied for the benzylferroconylmethyl and bisferrocenylmethyl ethers
under the Influence of butyllithium and totrahydrofuran. During re-
action with the first oompound a 55% yield of I-pbenyl-2-ferrooenyl-
ethanol-~.l was obtained without formation of Its 2-ph"q1-1-f9rrocsnyl--:-
Card T/12

ACCESSION NR: A?4010041
ethanol isomer, while reaction of the second yielded 1,2-diferrocenyl-
-ethanol. The latter rearrangemant proceeded with lose eftsev with a
yield of only 23% and a 27% residue of unchanged starter ether. The
product of the second rearrangement was convertea into 1.2-diferro-
cenylethylene by dehydration; this latter Is a red crystalline sub-
-stance, M.P. 264-265, soluble in hot benzene, toluene and chloroform.
The new data confirmed earlier findings, I.e., that the ferrocenyl
nucleus will stabilize the adjoining carbonation center to a lesser
degree than the benzene ring. The laboratory procedure, the products
obtained, and their description and IR spectra are reported. "The
authors wish to thank O.T. Nikitina for determining the molecular
weight." Orig. art, has: 4 formulas.
ASSOCIATION: Institut elementoorganicheek M soodluenty Akademll nauk
=R (Institute of Organoelemental Compounder' - Academy of Bolen-,
ces smh Moskovskly gosudarstenyol unIveraltet In. X.V. Lomo-
nosova (Rdscow State University)
SUBMITTEDs 108op62 DATz Am 14psb64 ZKOLI 00
SVB CODE: ON n RW SM 004 OTMI 004
Card i/2

3326),
S/062/62/000/001,001-11
00 B106/B101
AUTHORS Ne smeyanov, A. N Pereval ova, E. G. , an'] lie smPyanov%
TITLE: Mechanism of ferrocene formation in electrophilic and
homolytic reactions of iodoferrocene and mercury lerivit.v(I
of ferrocene
PERIODICAL: Akademiya nauk SSSR. Izvestiya. Otdeleniye
nauk, no. 1, 196?, 47 - 52
TEXT: In almost all electrophilic and homolytic reactions of iDdofer,rcc~-!e)l
and mercury derivatives of ferrocene, ferrocene is iormed as an unex~e-,~-j
by-product. The mechanism of ferrocene formation was studied wiU-. the
aid of some reactions of diferrocenyl mercury. When boiling diferrecen-.,.
mercury with metallic sodium for 15 min in absolute benzene and
subsequently carboxylating the reaction mixture with dry ice, no
ferrocene carboxylic acid was obtained but ferrocene (10~j of' tne
theoretical value)besides a large portion of the initial proluct.
of diferrocenyl mercury with SnCl in petroleum ether gLve of
2
Card 1/4

33264
S1062/62,'9Do/OD 1, :~-J
Mechanism of ferrocene formation ... B106"B101
ferrocene besides metallic mercury. Reaction of diferrocenyl merc,Ary
with CuCl 2 in dioxane yielded an inseparable mixture of chloroferrocene
and ferrocene. Reaction of copper chloride with 1,11-di-(uierc,iry cr..)r-.Je'
ferrocene yielded a mixture of dichloro ferrocene and ferrocene conta,,!11:t,"
much more ferrocene which could be isolated from the mixture. T~.-
formation of ferrocene can be explained in all these crises, if a
radical is assumed to be involved, which either splits a rijjr,)j-,er,
from the solvent, or, if the latter --~s absent, even from tie ferr,-)cc,-.-?
derivatives. The formation mechanism of this ferrocenyl raJicai i.~
unclear. The radical can not be formed by thermal s~,littinI7 of
mercury because the latter withstands long heating in benzene. Res,11t.;
of previous studies of the authors show that in electrop~iic
of mercury in diferrocenyl mercury according to the pattern
(C5H 5FeC 5H4)2 jIg RXC5115FeC5H4R + (C5H5)2 Fe the yield of ferrocene
decreases with increasing readiness of substitution. The formatio,.
ferrocene during the decomposition of diferrocenyl uercury in tne :rez:e.--
of palladium black without solvent, Dreviously observed 1,y t-ho ~f t:.e
present authors, can be attributed to the fact that a ferr,)cenyll
is formed as an intermel ia- te prol~ic t wh ich z3pl i ts
Card 2/4

33264
S/062/62/000/001/003/015
Mechanism of ferrocene formation ... B106/B101
other radicals or from diferrocenyl mercury. To find out "hether this
was also true for reactions in solvents without hydrogren, the behavior
of the ferrocenyl radical in CCl4was investigated. An unambiguously
radical reaction was already observed when diferrocenyl mercury was heated
in absolute M4* This reaction led to the formation of mercury
chloride ferrocene (57%), ferrocene (22%), and resins which, in addition
4- o carbon, iron, and hydrogen also contained chlorine and mercury (in
;he atomic ratio of 10-12 : 1~. When heating diferrocenyl mercury in
absolute CC14 in the presence of hydroquinone and benzoyl peroxide,
neither resins nor mercury chloride ferrocene were formed, but only 12
and 3% ferrocene, respectively, whereas the bulk of diferrocenyl mercury
did not react. Addition of antioxidants or radical sources inhibited the
reaction, which indicates the chainlike nature of the process. Thus, the
following pattern is suggested for the reaction between diferrocenyl
mercury and M4: WISFOCS Ili + Alf STOC&II 6)111 g - CIII&CIII& + CgIliFeCill j - M? -' C.114Fer.,11j
Csll,FeCsll,- fig -C4If&FeCsIfj+GCI4- C41fjFer41I&- lfg-COUCCO14CC1, 4-Cl*
Cj*+CjIljFoCjIfj- lig-CIIIJeCilfl-
Card 3/4

6,Z/00010~01011'
105, 4 1 't 6 0.4
9,06 sy~~Jo I OT .0ce 'C'es
G 'ro V.
VO. 0'rj 0 G
O.Tlal 01* IA
e e
0*4 OT
Olt, ol Oe
OG~. &
,,Te c Y~e
0
ap ?
,oce 0"0, 0 0
Oile, gle, 1~5 rt e
TO CA a eepe e.~.tco'
0 et ,,pe yLe -be'06,50 fty~e
op .,,o,O ,eeO te e.
&~,Op '0e tea, *1 4rXI "t c e-Ce
ti." TO OT eTl e
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-te 'OeTe
?13 Os ots " (A. ra '0e
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e
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te %e e 01.1
r .4ef to -re. 0
'OD
. 0%, -ro %06
Soyatl 8, J,& G T 0,11,
e.ty~e Ir 't'S.e e
101
e
&e-

S/062/62/000/010/001/00
Aminomethylation of phenyl,... B144/13186
:Initial ferrocene Amino iaomora ludino Mothylaton
number, type R fin benzene of tota l M.P, in IR spoctrum
amines C 1000- 1100 UM
;phenyl 1neterocyc lie 0.14 82 90-95 -
2 homocyclic 0.38; 15 143-145 1004; 1104
0.81 3 167-170 .
~1103i i1o6
:p-tolyl 1hetero cyclic 0.26 83 95-99 -
1 homocyclic 0.57 17 172-175 1004,1106
ichloro 1het6rocyclic 10.22 80 165-190 -
I homocyclic *0-32 11 .-163-166 10o6; 1104
1mixed 9

C H C 1 3:C 6H6 - 1:1
Thus the aminomethylation was e ffected mainly (- 5:1) in the non-cubstituted
cyclopent ane dienyl ring; this was shown also by the I R spectra of iodo-
methylate of the substances obt ained. The spectra of heterocycl ic isomers
showed no 1000-1100 cm-1 bands. iodomethylates were o btained by converting
amines wi th twice the methyl io dide excess in benzene; their compositions
and gross formulas are given. An excess of 1, 11-methy l-p-tolyl ferrocene,
Card 2/3

3/062/62/000/010/001/003
Aminomethylation of phenyl,... B144/B186
C,aH,?Fe (m.p. 93 - 950C) was obtained from the iodomethylate of
1,11- N,N-dimethyl aminomethyl)-p-tolyl ferrocene by reduction with
sodium amalgam. There are 2 tables.
ASSOCIATION: Moskovskiy Losudarstvennyy univeraitet im. M. V. Lomonosova
(Moscow State University imeni It. V. Lomonosov)
SUBMITTED: March 7, 1962
Card

U6391
S/06 62/000/010/002/003
B144YBW
AUTHORS: Nesmeyanov, A. N., Perevalova, E. G., Yurlyeva, L. P., and
Grandberg, K. I.
TITLE: Direct cyanidation of ferrooone derivatives
PERIODICAL: Akademiya nauk SSSR. Izvestiya. Otdoleniye khimicheskikh
nauk, no. 10, 1962, 1772 - 1777
T--*XT-. Bromo, nitro, acetyl, phenyl, p-nitrophenyl ferrocenes (P) and
phenyl ferrocenyl sulfone were cyanidatad; ferricinium borofluoride (1)
and ferricinium chloro platinate (II) were synthesized and I was
cyanidated. Bromo, phenyl, and p-nitrophenyl-Fl were cyanidated by a
method given in Dokl. AN SSSR, 135, 1402 (1960). The cyanidation of.
phenyl-Fl yielded 88-52~ phonyl forrooene carbonic acid nitrile, C 17H 15 NFe,
a reddiah-brown, oily substance with the composition C 71.06, 71-05;
11 4.97, 5.00;, and N 5.19, 5-30~4. The IR absorption bands at 1004 and
1106 cm- 1 showed the homocyclic structure of this nitrile. The substance
was converted into the amide C 17H15 NOFe by adding KOH and H 202 (yield 12~;
bard 1/3
V~

S/06 62/000/010/002/003
Direct cyanidation of ferrocene... B144YBie6
m.p. 155-5 - 156.5 0 C), as it does not crystallize. A heterocyclic nitrile,
C11HaBrJNFe was obtained by cyanidating bromo-Fl (yield: 78~i m.p. 91-92'C;
C 45 ~2, 45-92; H 2.88, 3.09; Br 27.83, 27.67; N 5.00, 5.00; Fe 19.32,
19.4~~O. Cyanidation of p-nitrophenyl-Fl yielded dark red, resin-like
crystals of a heterocyclic n1trile, C 17H 12 NO2Fe (m.p. 134 - 1350c; c 61.42,
61-40; H 3.55, 3.74; N 8.21, b.37; Fe 16 54, 16-46%). Cyanidation of
nitro and acetyl-FI yielded only 3 and 1;A by heating for 2 and 6-5 hrs,
respectively, even with a considerable excess of FeCl 3 and HCN. Treatment
of 1.5 g phenyl ferrocenyl sulfone with 4.6 g FeCl 39 60 mg tetrahydrofuran,
and 3 ml liquid HCN, yielded 52~9 heterocyclic phenyl sulfone ferrocenyl
carbonic acid nitrile, C 17 NO2SPe, (m.P. 141 - 141.5 0C; C 58-30, 58-51;
H 3.88, 4-11; N 4.17, 4.39; S 9.02, 9.13; Fe 15-97, 16.107^a'). Cyanidation
of FI-carbonic acid ni-trile--xith-a considerable excess of FeCl 3 and HCN
added to it, increased the yield in dinitrile from 27 to 62%. F1 was
also cyaraidated immediately into the dinitrile of i,11-ferrocene dicarbonic
acid (yield: 68%). Experiments with an equimolecular FI-mononitrile
mixture showed that cyanidation into mononitriles is much easier than into
Card 2/3

S/06 62/000/010/002/003
Direct cyanidation of ferrocene... B144YB166
dinitriles. I was synthesized by passing BF 3 through a benzene solution
of 5-55 g F1 with 1.62 g quinone. It ia a dark violet crystalline
substance, C 10H10 BF4Fe, which is easily soluble 'in H 20, acetone, and
nitromethane (C 44.06, 44-16; If 3.65, 3.751 F 26-15, 28-43~)- 11 was
obtained from aqueous ferricinium ferrichloride solution and chloroplatinic
acid;.it is a bluish black, crystalline substance, (C 10H10 Fe)2PtC1 60 which
is moderately soluble in H20 and, %hen heated, decomposes into methanol
and nitromethane forming F1 (C 30-39 30,221 H 2.77, 2.73; Cl 27-42,
27-062L). When cyanidating 11 2(C 5 H5~2 FJBF 4+ HCN PC5 H5FeC5 H4CN + Fe(c 5 "5)2
+ 2HBF 44% of the initial compound was converted into nitrile, and 45~
was reTuced into Fl.
ASSOCIATION: Moskovskiy gosudarstvennyy universitet im. M. V. Lomonosova
(Moscow State University imeni M. V. LomonoBov)
SU B-.~ I TTi~D: March 7, 1962
dard 3/-1

119MMOV, A.N.1 PERVAWVA, 9*0.1 -SHIIOVTSKVA, L.S.; TYURINp V.D.
Pbrrocem7lxethylation by means of NpN-dimethylaminomethylferroecmo
and its iodomethylate. Izv.AN MR. Otd.khim.nauk no.1191997-
2001 V 062, 1 (MIRA 15312)
I* Hookovskiy gosudaretvepW universitet im. H.V. Lomonoaova.
(Perrocene)

t
NESNWOV,, A.N.; PEREVALOVA. E.G.. YUROYLVA, L.P.; GRUORRG, K.I.
Direct cyanation of ferrocene derivativea. Izv. AN SSSR.Otd.khim.
nauk no.10:1772,-1777 0 162. (HIRA 15:10)
1. Mmkovakiy gosudarstvennyy universitet im.~'M.V.Mmonosova.
(Ferrocene) (Hydrocyanic acid)

8/062/62/000/011/oo6/o2i
B101/B144
AUTHORSs Nesmeyanov, A. N., Perevalova, E. G., Shilovtseva, L. S.,
and Tyurin, V. D.
TITLEt Ferrocenyl methylation by means of N,N-dimethyl aminomethyl
ferrocene and its iodo methylate
PERIOD1CAL: Akademiya nauK SSSR. Izvestiya. Otdeleniye khimicheskikh
0'2t 1997
nauk, no, 11, 19' - 2001
TEXTs The following syntheses were made with N,N-dimethyl aminomethyl
ferrocene (A), trimethyl(ferrocenyi-metnyl) ammonium iodide (B), and di-
methyl-ettiyl(ferrocenyi-methyl) ammonium bromide (C)3- (1) Reaction of B
with Na2S-IOH 20 on a boiling water bath and extraction with ether produced
di-(ferrocenyl-methyl) sulfiae, yield 50, m.P. 107 - 1080C (with decom-
position). The IR spectrum contained absorption bands at 1000 and
1104 cm- 1. (2) Di-(ferrocenyl mathyl) disulfide, yield 53%, m.p. 125-1270C
(with decomposition), was obtained from B and NaSH, the latter being pro-
duced by bubbling H 2S through NaOH solution. (3) The synthesis of ferro-
Card 1/4

6/062/62/000/011/006/021
Ferrocenyl methylatiog by mearis of ... B101/B144
cenyl methyl acetate was made in three wayss (a) Reaction of B with
glacial acetic acid at 90 - 950C in N 2 atmosphere, yield 25~, m-P. 74-760C,
IR absorption bands at 997, 1104, and 1740 cm- 1. A compound soluble in
benzene,(gross formula C 12H12Fe, m-P. 115-1350C) formed at 110-150OC; it
was not further investigated. (b) Reaction of C with sodium acetate at
150-1550C in vacuum (7 mr. Hg), yield 59~-V', m-P. 75-760C. (c) Reaction of A
with acetic anhydride, yield 89%. Tne compound obtained by (c) was, as to
m.p. and IR spectrum, identical with the compounds obtained by reactions
(a) and (o). (4) Reaction of A with methyl benzoate in N 2 atmosphere at
130 - 1350C, and extraction with benzene, produced ferrocenyl metbyl
1
benzoate, yield 50j;, m-P. 132-1350C, IR bands at 1003, 1098, 1700 cm-
(5) Reaction of A with methyl anthranilate produced ferrocenyl M,athyl
anthranilate, yield 46~;, m.p. 125-1240C, 1R bands at 996, 1102, 16a6 cm
(6) Heating of B with ethyl acetate at 120-1250C produced, instead of the
expected ferrocenyl =ethyl acetate, ferrocenyl carbinol ethyl ether, yield
427-*', b.p. 68-700C/0-3 mm Kg, n20 1.5840. The IR bands at 1002, 1106 cm-1
D
Card 2/4

S/06 62/000/011/006/021
Forrocenyl methylation by means of ... B101YB144
proved the existence of a non--ubstituted cyclopentadienyl ring. Bands of
an eater carbonyl group were riot obaerved. (7) B with butyl acetate pro-
duced ferrocenyl carbinol butyl other, yiold m.p. 31.5-32.50C, b.p.
105-1o6oc/2 mm Hg, n20 1.569~. IR bands at 1004 and 1104 cm-1.
D 1 (8) ifeat-
ing of B with piperiaine at 1100C proaucea N-Jorrocenyl-meLhyl) piperidine,
1
yield 94~, m.p. 84.5 - d5-50G, IR bands at 1002, 1103, 1303 cm- . Reaction
of A with piperiaine aid not lead tQ a substitution of the dimethyl amino
radical. (9) N-(ferzocenyl-metny!) morpholine was obtained from B and
morpholine at 120-13000, yield 95%, m.p. 74-750C, IR bands at IjO6,
1104 em (10) N-(ferrocenyI-zetfjI) aniliiie was obtained from B and
actiline in boiling aqueous sol-tion, y.-Leld 751c;, m.p. 84-64-500, IR bands at
looo, iio6, 1602, 1552-1566, 5930 cm- 01) N-(ferrocenyl-methyl) phthali-
mide was obtained from B and potassium phtnalimide in dimethyl formamide
solution at 150-1400C, yield 97~~, m.p. 209-2100C (with decomposition), IR
-1
bands at 1000, 1102, 1706, 1758 cm - (12) Ferrocenyl methyl amine was ob-
tairied from N-(f errocenyl-methyl) phthalimicke ana hyarazine hydrate heated
at 80-900C in N2atmosphere, by precipitation witn NaOH, b.p.
Card 3/4

6/062/62/000/011/006/021
Ferrocenyl methylatican by means of ... B101/B144
108-11ooc/0.3 ma, fig, n20 baricas at 1002, 1106, 52t38, 5568 cm
D
This compouna decomposes in a,.r. 64ou~in6 of H~! througn its bcnzene solu-
tion yielded ferrocenyl meLnyl amine hyarochloride, decomposition tempera-
ture 255-2350C.
ASSOCIATIONs Moskovukiy t;usuaarstvunnyy univeraitet im. M. V. Lomonosova
(Moscow State University imeni M. V. Lomonosov)
SUBUITTEDs April 2, 1962
Card 4/4

PEREVALOVA,J,..E,G.; BUBIN, S.P.; SMIRNOVA, S.A.; NESMLYANOV, A.N.,
ai~emi~--
Redox potentials of heteroannual disubstituted ferrocenes.
Dokl. AN SSSP 155 no. 4:857-860 Ap 164. (t,1111A 17z5)
1. Moskovskiy gosudarstvennyy universitet im. Lomonosova
Institut elementoorganicheskikh soyedineniy AN SSSR.

9/062,/62/000/012/005/007
B117/B101
AUT1!ORSj Weameyanov, A# B., Purevalovaj,...)~._G.f Yurlyeva, L. F., and
Denisovich, L. 1.
TITLEt Reaction between ferrocene carboxylic acid nitrile with
organometallic compounds and production of di- and triferro-
cenyl-mothyl compounde
PERIODICAL: Akademiya. nauk SSSR. Izvestlya. Otdeleniye khimichaskikh
nauk, no. 12, 1962, 2241-2243
TEXT: Reaction of ferrocene carboxylic acid titrile with ethyl magnesium
bromide yielded propionyl forrocene (m.p. 38-390C) and the same reaction
witi. methyl magnesium iodide yielded acetyl forrocene (M,P- 85-8610).
The ketone yield was found to be 70 and 60~ at a considerable Grignard
reagent excess. Diferrocenyl ketone (m.p. 210-2110C, yield 55-6(Y,~') was
obtained from reaction between farrocenyl lithium and ferrocene carboxylic
acid nitrile. Differrocenyl ketone Aas used for synthesizing compounds
of the triferrocenyl methane ueries, not hitherto described. The reaction
of diferrocenyl ketone with ferrocenyl lithium yielded 60 triferrocenyl
Card 1/2

B/020/62/143/006/016/024
S-1 9 B106/B138
AUTHORSs Gubin, S. P., and Perevalova, E. G.
TITLEt Formal redox potentials of monosubstitUted ferrocenes
PERIODICALt Akademiya nauk SSSR. Doklady, v. 145, no. 6, 1962, 1351-1554
TEXTt The formal redox potentials of 30 monosubstituted ferrocenes WEtre
determined by potentiometric titration with potassium bichromate in a
mixture of acetic acid and aqueous perchloric acid. Relative quantitative
data were thus obtained on the effect of substituents on the oxidation of
the ferrocene nucleus to the ferricinium cation. The determinations were
conducted by the method of J. G. Mason and M. Rosenblum (11cf.2s J..AmIChem.
Soc., 82, 4206 (1960)) at 25 � 0-10C in nitrogeu atmosphere. Table
shows the results. The differences of the logarithms of the equilibrium
constants for the reactions of substituted and unsubstituted ferrocene
were calculated from the corresponding potentials (Column 4, Table 1) and
compared with the constants 0'* and 60 according to Taft (Ref. 10:
11. S. Nlyumen, Prostranstvennyye effekty v organicheskoy khimii (M. S.
Ne,wman, Steric effects In organic chemistry), IL, 1960, 591), and amand
Card 1/0

5/020/62/143/006/016/024
Formal redox potentials of ... B106/B138
published statement that hydrogen ano alkyl substituents cannot interact
with the reaction center bj the field effect mechanisia (Ref. 9:
V. A. Pallm, Uop. khim., 30, 1069 (1961)). The interaction by tn,.- fit-IC
effoot mec!ianiam occurs over a shortor oiatance, %hich It.adll tc, 111i in-
crease in the absolute value of Q. Academician A. N. Nenmeyanov is
thanked for cooperation and advice. There are 1 figure and 1 table. The
most important Englis~,-language references read as follows: T. Kawana,
D. i;. Bublitz, G. Hoh, J. Am. Cnem. loc., 62, 5811 (1960); H. ii. jaffe,
Chem. iev., 53, 191 (1953); D. S. Trifan, R. Baskai, Tetrahedron Letters,
1960, no. 13, 1; J. D. Roberts, R. A. Carboni, J. Am. Chem. Soc., 77, 1P/
5554 (1955).
ASSOCIATION: "oskovskiy gosudarstvcnnyy universitet im. 1- V. Lomonosova
~L',oscor State University imeni M. V. Lomonosov)
?R--5-:-NT1~Di December 12, 1961, by A. N. Nesmeyanov, Academician
SUBMITTLLi November 9, 1961
Card 3/5

5/02 62/14 5/0V,/C,1 6/C,24
Formal redox potentials of ... B106YB136
Table 1. Formal redox potentials of monosubstituted ferrocenes C,H,Fe~ H X
J J 1) 4
(formulas do not take account of changes in the reaction medium).
Legendi (1) Ef I v (according to a standard calomel electrode); '11) x.,
C; (III) b., OC; (IV) under decomposition; 2 calculated from the
mm, Hg
'X - H 3
formula (E 0 E0)/0.0591 - log K/K.; only the primary a n values obtained
from the dissociation constants of the corresponding p-substituted benzoic
acids have been used; 4 the potentials of these compounds differ slightly
from published data; the potential differences bet%een ferrocene and
phenyl ferrocene, and between ferrocene and p-nitrophenyl ferrocene, are
constant within the error limits of the experiment; 5 from published data;
6 the value for the -COOC 2H, group from published data has been used. In
olumn 21 tk--,o - itso; m; rL n p.
Card 4/5

5/020/62/147/002/015/021
B1o6/B101
AUTHORS: Gubin, S. P. , Smirnova, S. A..
Nesmeyanov, A. N., Academician
TITLE; Redox properties of compounds containing two ferrocenyl groups
x3i,'H!ODIC;%L: Akademiya nauk SSSR. Doklady, v. 147, no. 2, 1962,. 364-387
TEXT: The authors studied the effect produced by one ferrocene ring on
the redox properties of a second ferrocene ring bound to the first either
directly (diferrocenyl) or by groups Y of different conductivity (-Jig-,
-CH 2-1 -CH 2- CH 2-1 -CH 2- O-CH 2-1 'CH 2- N+(CH 3)2-CE2-) - They measured the
11
first and second redox potentials E ~o and J~ fo '(Table 1). The signifi.cance
11
of Eio and Efo is evident from the following scheme:
Card 1/4

Redox properties of compounds ...
Y
e Fe +
Eflo
S/02 0/62 /147/002 /015/02 1
B106/B101
Y
Y
+
le Fe Fe i:~ Fe+ Fe* +1e
/I Ell 0
f
Under the chosen conditions diferrocenyl was oxidized at one Fe atom
only. When two ferrocene rings interact, the electron density increaser
at the ring oxidized. The redox potentials indicate that the methylene
group transfers to the other nucleus; hardly any of the electron-donor
effect of the ferrocenyl group, whereas the effect of the positively
charged ferricinium ion is transferred even across bridges of 3 atoms.
The investigations covered also how some substituenta in the methyl group
of methyl farrocene affoot tha redox potentiala (Table 2): in this case,
too, the effect of electron-acceptor substituents was transferred via the
methylene group to a notably greater extent than that of electron-donor
substituents. There are 4 figures and 2 tables. The most important
English-language references are: R.' W. Taft Jr., J. Am. Chem. Soc., 75,
Card 2/4

S/020/62/147/002/015/021
Redox properties of compounds B106/B101
4231 (1953); H- H- Jaffe. Chem. Rev., 53# 191s (1953).
ASSOCIATION: Moskovskiy goBudarstvennyy univeraitet im. M. V. Lomonosova
(Moscow State University imeni Ui V. Lomonosov)
SUBMITTED: July 18, 1962
Table 1. Redox potentials of compounds with two ferrocenyl groups
C5H5Fee5H4- Y-C5H4Fee5H5 (in v, related to the standard calomel electrode).
Legend: (1) melting point, OC; (2) diferrocenyl;-.,r -r obtained by
reduction of diferrocenyl ketone; (3) with de.composition.
Table 2. Redox potentials of some monosubstituted ferrocenes
C5H5Fee5H4CH2X. Legend: (1) v, related to the standard calomel electrode;
mean deviation from the E f values indicated t0.003 v
0
Card 3/4

NESWYANOV, A.N.; PEREVALOVA, E.G., YLTRIYEVA, L.P.; GRANDBERG, K.I.
- - -.1.
Synthesis of ferrocene derivatives from nitriles of
ferrocenecarboxylic acids. Izv.AN SSSR.Ser.khim. no.8:1377-1380
Ag 163. (MIRA 160)
1. Moskovskiy gosudarstvennyy universitet im. Lomonosova.
(Ferrocene) (Nitriles) (Ferrocenecarboxylic acid)

AP30094 ~/042VPAJONA6/1045
AUTHOM Perevalova, E. a i Ustenyuk. Tu. A, zNesmeyanov, A. W. 4P
IT_
TITLIt The reactivity of cospounds containing the ferrooeny 0group. Report
1. Wdrolytic.,cra eking of tetravalent ammonium aalts
SOURG3r'-ANSSSR. Izv. Otdoloniyokbiniehaskikhnauk,no.6,3.963,1036-1045
MFIC UGS: tetravalent, a=onium salts, ferrocenylmetbyl group, hydrolytic crack-
rate.of,bydrolysiv
ABSTRkC.Ti Aseries of tetravalent anmonilm salts, containing the ferrocerylnetbyl
group was synthesized, i.e. compounds of the type shown in. the enclosure, where RM
sub 2 is methyl, ethyl, n-propyl, n-butyl, n-nonyl, benzyl, a3JL;y1, carboVastbyl,
phenacyl or ferrocenyl metbyl, and the anion I is chloro, brcao, iodo orpicryl.
Hydrolytic cracking of these compounds in alkaline, neutral and 30% aqueous div3ane
solutions vas studiedi' rate of hydrolysis vas independent of anions and of BolTent
concentration, but increased with electron acceptor properties of the CH sub 2 R
Hydro2yais proceeded according to the 5 3ub N I mechanism with the imter-
:--mediate formation of the ferrocenylmethyl cation. Orig. art, has: 9 tables, 8
-96ZUU1414 ~4ind I f1gurs.
nose

PEREVALOVA E.G.- USTYNYUK, Yu.A.; NESMEYANOV, A.N.
Reactivity of compounds containing a ferrocenylmethyl group.
Report No.4: Reaction of ferrocenylmthyllithium. Izv. AN
SSSR. Ser. khim. no.11:1967-1972 N 163.
Reactivity of compounds containing a ferrocenyl-methyl group.
R rt NO.5: Preparation of organolithium compounds with
Zrferrocenyl alkyl groups. lbid.:1972-1977 (MIRA 17:1)
1. Moskovskiy gosudarstvennyy universitet imenJ Lomonosova.

ACCESSION M AP3002288 SJUM31owbigm Ab
THOR: Perevalova, S. G.; Usty*roruk, Yu. A.; Nesmoyanov, A. N.
A
U
TIT13: Reactivity of compounds containing a-Terroc 6 1 ~rovp. Report 2.
Regeneration of tetravalent aamonium salts, contair4ng ferrocehylmethyl radical,
Vith Bodium aml by &do
SOURCE: AN-SSSR. Izv. Otdolenlye kbimichesldkh nauk, mo. 6, 196.3, 1045-1049
TOPIC WS: ferrocerq.1metIVI grovp, trimethyl ferroceny2methyl amonium iodide,
dimetbylallyl _firroceny3methyl a=onium iodide, dixetbylbenzyl farrocany1methyl
affmniim iodide, sodium amalgam
ABSTRACT: Mi6 reduction of trizethyl-, dimet~ylallyl_, and &imethylbenzyl ferro-
canylzetbyl ammonium iodide with sodi= -amalgam by the method of Emde and co-
18, 166;
workers (Arch. ftam 247, 1909, 33% 314, 351; v. 249, 1911, 111, 1.
Liebigs Ann.. Chem* 39.1$ 'jqj:2 .1 _88) was investigated. The ferrocany3methyl group
split off from the X of the tatravalant ammonium much more readily than the nothyl,
much less readily than the benzyl, and at about the same rate A3 -the any' group.
Hence, farrocene group stabilizes the neigbboring radical center less than the
bentyl, and more than the methyl, radical, and about equaLUy to the double bond of
Card
------------------ ------- ---------------------- --------

PERVALOVA, USTYNYUK, Yu.A.; USTYMMI, L.A.; NESMEYANOV, A.N.
Reactivity-of compounds containing a ferrocenylmethyl group.
Report No.6.- Steric effects in reactions of alkylation by
quaternary aimnium salts. Izv. AN SSSR. Ser. khim. no.11:
1977-1985 N 163. (MIRA 17-1)
1. Moskovskiy gosudarstvennyy universitet imeni Lomonosova.

ACC NR, AP7012431 SOURCE CODE: UR/0062/66/000/008/1467/1469
AUTHOR: Nesmoyanov, A. N. Perevalove, E. G.; Yurlyeva, L. P.; Gosteyeva, G. N.
ORG: Institute of Heteroorganic Compounds, AN SSSR (Institut elementoorganichoskikh
soyedinenly AN SSSR)
TITLE: Synthesis of nitriles of phenylfcrrocenecarboxylic acids
SOURCE: AN SSSK. izvestiya. Sertya khtmichesknya, no. 8, 1966, 1467-1469
70PIC TAGSt organic n1trile compound, chemical separation, phanylferrocenecarbo)92AC
aeld
SUB CODE: 07
ABSTRACT% The authors describe an improvement on an earlier method for separat-
ing mixtures of amides of isomeric pheuylferrocenecarboxylic acids, prepared by
the hydrolysis of the reaction products of the cyanation of phenylferrocene.
The individual amides of the isomeric phenylferrocencearboxylic acids were con-,
verted to the corresponding nitriles. The nitrile of p-ferrocerylbenzoic acid
was also prepared from the amide of p-ferrocenylbenzoic acid and used as a
standard in gas chromatographic analysis of the mixture of nitriles of 1,2-,
1..3-P and 1jX-)*eny1ferrocvnecarboxylic acids, obtained In 1~be cyanp~ti n of
.JPRS: LAUPE227
phpy1ferrocene.- OrIg. art. haS3 2 formulas and 1 toole. L
Cwd .14 1.. UPCs 542.91-542.957+621.765.666
- 1377

ACC NR: AM12420 SOURCE CODE: UR/0062,166/000'011,1938,1943
AUTHOR: Nesmeyanov, A. N.; Perevalova, E. G. Tyurin, V. D.; Gubin, S. P.
ORG: HDscow State University im. M. V. Lomonosov (11oskovskiy gosudarstvennyy
universitet)
TITLE: Metallation, of alkylferrocenes
SOURCE: AN SSSR. Izvestlya. Serlyn khlmicheskaya, no. 11, 1966, 1938-1943
TOPIC TAGSt ferrocene, lithium compound, ferrocenyllithium
SUB CODE: 07
ABSTRACT: The rretallation of methyl-, ethy3:-, and n-propylferrocene with and
'excess n-butyllithiuM at room temperature was studied. Mixtures of mono-
dimetallated alky1ferrocenes -were obtained. The monometallated alkylferrocenes
were found to possess a heteroannular Structure- The mixture of mono- and dimet-
allated alkylferrocenes, after carboxylation, were converted to a mixture Of
nes proceeded with
'mono- and dicarboxYlic acids. Metallation of alky1ferroce
greater difficulty than that of ferrocene itself. Approximately 2-2-5 times as
much of t~e monometaUated aikylfcrrocene was formed as of the dinetallated
derivative. The metailgLzed. alkylferrocenes were also used for the synthesis
of heteroannular njtroaW3_ferrDcene6 by the reaction with PrOPY1 nitrate.
Ni:tromqjhyl_, nitroethyl-,, and nitr-ppropy1ferrocenes were obtai-ned in low
COYa UDCs - 542.91 + 547-113 + 546.72
073Z 135-4

ACC NR. AP701=
yields. No dinitro-compounds vere Isolated. Orig. art. hast 3 fonculas,
4 tables# PRSS 40,1-iJ2
Ej
"XI

L 35318-66 Dri(m)/EWy(,!)
ACE -NR.AP6026891
AUTHOR: Nesmeyanov. A. N.;
ORG: Moscow State UniversiLy
TITIE: Behavior of m- and
rearrangement
SOURCE CODE: UR/0062/65/000/012/2120/2124
Perevalova, E. G.; Nikitina, T. V.; Kuznetsova, 11.
im. Lomonosov (Moskovskiy posudarstvenny
o- -ferrocenylh drazobenzene5iunder ondil-'L'~1' (,f wnzidine
SOURCE: AN SSSR. Izvestiya. Seriya khimicheskaya, no. 12, 1965, 2120-21124
TOPIC TAGS: benzidine, benzene, substituent, forrocene, molecular structure,
chemical reaction
ABSTRACT: This is a continuation of a previous investigation. The effect
of forroconyl as a substituont on the bonzidino rearrangement of hydrazo-
bonzono was studied. It was established that forroconyl as a uubstituont
on the benzene ring complAcates bonzidino rearrangement: m. and p-
forrooeny1hydrazobonzonos under the conditions of bonzidinn rearrangement
generally got disproportionated rather than rearranged, i.e. the end-produot
is ferrooonylanine and azoforrocone. Compounds of the bonzidino type do not
form. Those findings indicate that the introduction of the forroconyl
substituent. - whether in the para or in the mota position - into the
hydrazobonzeno moleoule impedes bonzidine rearrangement to such an extent
that disproportionation becomes the main Urend of the reaction. [JPRS: 36,4551
SUB CODE: 07 / SUBM DATE: 29ju.163 / CRIG REF: 003 / OTH REF: 005
UDC:

L-35324-66 E;,JT(m)/EWP(j) lul
CC NRs AP6026892 SOURCE CODE: UR/0062/65/000/012/212-4/2128
AUTHOR: NesmVanov, A. N.; Perevalova. E. G.- Nikitina T. V., Kuznetsoina, h.
ORG: Moscow Statc-University im. M. V. Lomon050V (Moskovskiy gosudarstvennyy
universitet)
TITLE: Effect of hydrochloric acid on the azo derivatives of ferrocenel
SOURCE: AN SSSR. Izvestiya. Seriya khimicheskaya, no. 12, 1965, 2124-2128
TOPIC TAGS: hydrochloric acid, ferrocene, organic azo compound, chemical synthesis,
nitrobenzene, chemical decomposition, condensation reaction, chemical reduction, amine;
ABSTRACT: A study was made of the effect of cone. NCI on benzonoazoforroconel
and m... and p,.forroconylazobenzones - azo derivatives of forroceno synthesized
.by condensation of nitrobonzone -,dth forroconylazaino and ra.- and p-ferroconyl-
anilines. It is shown that cone. HC1 causes bonzenoazoforrocono to decompose
and form Fe-froe substances; products of benzidino-type rearrangement have
riot been detected. Cone. HC1 transforms r.- and p-ferrooonylazobenzones Into
ferrocaWlanillne, aniline and substances isomeric to forroceny1hydrazobonzonee
In this case the ferrooenylasobenzonos are protonatod and decompose, to form
FeC12. which then reduces the second molecule of the protonated
ferz~*-OwWlazobsnzene to a hydrazo compound. The hydrazo compound is either
further reftood to awAnee or gets disproportionated mid reamngod.
1JFRS: 36t4551
SUB CODE: )9,7 / SUBM DATE: 29Jul63 / CRIG REF: 006 / OTH REF: 003

L 35316-66 RM
RZ NRs AIP6026698 SOURCE CODE: UR/0062/65/000/012/2196/11!98
AUTHOR: Reshetova. M. D.; Yarysheva, L. M.; Perevalova, E. G.; Ne m Lnrv, It. N
ORG: Moscow State University i1n. Lomon05OV (Moskovskiy gosudarstvenny-j univers"tet)
TITLE: Synthesis of certain substituted ferrocen learbinolsi
SOURCE: AN SSSR. Izvestiya. Seriya khimicheskaya, no. 12, 1965, 2196-219S
TOPIC TAGS: chemical synthesis, ferrocene, hydrolysis, methylation
ABSTRACT: This is a continuation of a previous investigation (PEMWALOVA),
,'which deals with the synthesis of hoteroannular chloro-, bromo- and cyano-
;(alpha-oxyethyl) forroconos and (alpha-oxypropyl) forroceno by reducing the
;corresponding acylforrocones with LiAlH4. The coripounds thus obtained were;
~1.11-chloracotylforrocono. 1,11-chl-oro(a:Lpha-oxyothyl)ferrocone, I'll-
.bromo(alpha-ovethyl)forrocone. 1,11-cyano(alpha-oxyethyl)forrocone, and
,1,11-carbometboxy(alpha-ox7othyl)forrocono. 1,11-eyano(a-lpha-oxyothyl)
ferrocene was converted to 1,11-carbomethoxy(alpha-oxyothyl)ferrocone by
alkaline bAmlysis and subsequent methylation with diazomothano.
1JPRS: 36,4551
SUB CODE: 07 / SUBM DATE: 05Apr65 / ORIG REF.- OW / OTH ld-,F: OW
Card 1/1 UDC: 542-91+547.1'

L 36507-66 E,%'T(m)/17,P(j) 91,
,-CC NR: AP601?876 (4)
i_ SOURCE CODEs 0/0062/66/000/005/0832/C039
AUTHORs Perevalova, E. G.; Grandberg, K. L; ;~ji~ikcTap
sitet);
stitut
()bskovskiy gosudarstvannyy univor-
sj, Academy of Sciences, SSSR (In-
-
TITLE$ Electronic influence of-te-rro-c-emilas a substituent
SOURCES AN SSSR. Izvevtiyas Seriya khimichaskayal, no. 50 19660 832-839
TCPIC TAGS$ ferrocene, dissociation constant, aniline, benzoic acid, phenol, substi-
tuentp amine
ABSTRACTS By determining values of Hammett's if p the authors studied certain elec-
tronic effects of ferrooenyl as a substituent. Using acid-base potentionetric titra-!~
ticnp they determined the dissociation constants of p-, r,-, and o-ferrocenylbenzoic
acids,, a series of substituted benzoic acids and ferrocenecarboxylic acid in 70% di-
oxanev and the dissociation constants of p-ferrocenylphenol and a series of P-substl
tuted phenols In 30% ethanol. The basicity constants of p-j, m-,, and o-fsrrocenylanl:~
linesp a series of peabstituted anilinesp and forroosrorlamine in 80% ethanol were
also determined, The data obtained were treated by the least-squarea method, e val-I
ues were calculated for the reaction series studiadq d values were found for ferro-
UDC1 541 + 541.49 + 347.103s541.132
eftra 1/2

L 35327-66 EIA7 (m)ZZiP( gm
ACC NR, 26836 SOURCE ODDEs UR/0020/60667662W374A377'
AUTH)Rs Nefedova. M.N.i Kursanov, D.N.Norreeponding member AN SSSR)i Setkina, V.N.
her valova E.G.j Nesmeyanov, A.N. (Academician)
ORG s none
TITLE: Effect of substituents on the rate of I L ferrn 01!
derivatives
SOURCEs AN SSSR. Doklady, v. 166, no. 2, 1966, 374-377
TOPIC TAGSt ferrocene, electron donor, dissociation constant, substituent, reaction
rate
ABSTRACT: The authors determined the rate constants for acid isotopic e=hange
of hydrogen in six monosubstituted and four disubstitutod ferrocenes. The
relative rate constants Krel wore then calculated assuming unity for
unsubstitated ferrocone* The substituonts studied included both electro-
donor and olectron-accepter types. An analysis of the resultant data shows
that the effect of the substituent on the renctiDn rate in an aromatic
compound may be described as a combination of induction and conjugation. The
conjugation effect is much less important in this case than it is in oloctro-
phi3io substit6tion in the benzene series. It was found that the substituent
UDCt 546.11.2+542.9574546.79.

L 3`1327-66
ACC NR, AP60268j6--
constants obtained from the dissociation constants for phanylacotic acids may
be used as a quantitative index of the effect which the substituont has on
the reaction rate. Curves for 1n k/ for all substituents studied show a
linear correlation with those constanNs. Heterocyclic disubstituted deriva-
tives Uo on this same line if doubled values of substitutnt, constants are used,
i.e., the subatituents have an additive effect within the limits of experimental
error* The authors thank S.L. Portnova and G.P. Sirrova for taking the nuclear
resonance spectra. The authors further thank V.A, Pallm and N.P. Gambaryan for
participating in the discussions of the results. Orig. art. hast 1 figure and
1 table ZJPP-�2 36v 40
SUB CODE, 07 SUBM DAM 23S-6p65 ORIG REFI 013 OTH RFY9 010

L 313&Q-A66 B~ P ( A ) /~L, :L,~]Pc- _ RY/Will _76-661-002 3
ACC NRi ANL21106 SOURCE CODE: UR/0062766 AD YG~3
AUTHOR: Nesmeyanov, A. H.; Perevalova, E. G., Reshetoya .- M. D.
ORG: Moscow State Uniy~r_sity im. M. V. Lomon;sov ~M-oskovskiy gosudarstv(,,nnyy
universitet)
TITLE: Salts of N-(alpha-ferroce
nylalkyl-Jmmidinium
SOURCE: AN SSSR. Izvestiya. Seriya khimicheekaya, no~ 2, 1966P 335-337
TOPIC TAGS: pyridine, alcohol, esterification, solubility, chemical synthenia,
organic nitrile compound, organic amide, ferrocene
ABSTRACT: The reaction of alcohols with p-toluenesulfochloride in pyridine
is the method by vhich esters of p-toluencoulfonic acid are obtained. How-
ever. in some cases p-toluenesulfonates of pyridinim are formed instead-, for
example, with 2.4-dinitroresorcine or 2,4-dinitronaphthol. The authors found
that ferrocenylearbinol and substituted farrocanyloarbinols react In this
way. In the reaction of oVmethyl-. alpha-oxyethyl-, oVbenzyl, and 1,11-
cy&no_(&lpha_owjethyl)ferrocen9 with p-toluenesulfochloride in absolute pyri-
dine the authors obtained p-toluenesulfonates of the corresponding pyridiuma.
Salts of N-(alpha-forrocenylalkyl)pyridWmne are soluble in water (except
'(ferrooenylbenzyl)pyridinium), alcohol. &Cotanitrile, and certain polar
solvents. Nitriles of ferroconylacetic, ferrocanylproplanio. and forrocanyl
(phenyl)acotlo acids were-obtained. sitrileslof the first two acids were
hydrolyzed to mides, 7be &aides are sU_1T*_*ca_stwjd1ft In alro In contrast
to the nitriles. Orig. art. has: 1 table. [JPRS3
SIJB CODE: 07 SUBM DATE: l9Ma.,r65 / ORIG REF: 002 / OTH REF: 002
Card 1A a UDG: -542.1 +-547.113 +

Ewlw/Ewpu) RM
ACC M AP5027691 ~OMICE CODE: uft/0062j65/000/019/1882/1881L.
AUTHOR: Nesmeyanovs A* W,; Pf?,revalovax E, G.; Ltontlyeva, L
Ustynyukp YU-1 X. ~-bv - I
ORG: Moscow State University.im. M. V. Lomonosova (Moskovskiy
gosudarstvarmyy universitet)
TITLE: Sy#hesis of 1#2-disubstituted ferrocenes
.1, 4 4~
SOURCE: AN SSSR. Izvestiya. Seriya khimicheskaya,, no, 10, 1965,
I RAP-1 AM
TOPIC TAGS: ferroceney chemical reactiong desulfurizationl, chemical
reduction.
I
ABSTRACT: The reduction of 1,92-(21-thia-41-ketotetramethylene)forrocon(
(1) was Investigated in order to find suitable methods for the synthesii
of homoannular disubstituted forroceneso I was desulfurized with
Raney nickel to form ls2-mothylethyl- and 1#2-mothylacetylforracene,
Reduction of I with lithium aluminum hydride gave 102-(21-thia-41-hydix>-
Wytetramethylene)ferrocefie (11). Reduction or I in the presenco-of
iduminum chloride gave Ij,2-(21-thiatetramethylene)-forrocene, a small
amount of II., and methylferrocenes and in one Instance$ 1,,2-12"thia-
31*41-dehydrotetramethylene)ferrocone, Orig, art, has: 2 oquations.
Cwd
i/2 UN: 54201+54705+!1.46,72-

L 27456-66

-L 26555,66 EWP(j)/IEW-1 (m)LT lji'k) NV,
Acc NR, 1,r6oi73631 SOURCE CODE: UR/0062/66/COO/003,10556 0558
AUTHOR: Nesmpvancv, A. N.., Perevalova. E. G.: leonti-vem, L. I.; Ustynyuk, Yu. As
IORG: Moscow State Universit, ov (Moskovakiy gosudire'vvennyy
im. M. V. Lmonos
-universitet)
TITIE:. T,riferrocenylehloromethane hydrochloride
SOURCE: AN SSSRv Izvestiyao Seriya khimicheskaya, no* 3P 1966s 556-558
TOPIC TAGS. organic eyinthatic procese, perchloric acid, parchloratep hydrogen
chloride,, arganoiron compound
ABSTRACT: The ionic triferroceny1methylperchlorate and triferroceny1chloromethane
hydrochloride were synthesized by reaction of triferroceny1carbinol with perchloric
~acid in benzene and anhydrous HC1 in ether, respectively.
HC:LO4
ODH
(003?~V'4)3 (C5H5F'eC5H4)3=04
(C H FOC CM- Ha'
Ha~ __5. 3.,
Iii polar solutions triferrocenylchlorormthane hydrochloride decomposes to'forn
rerrocenylftlvenve. [JPRS1
SUB COO: 07 SUBM DATE-. 22j-al65 ORIG Fff: OD3 OTH REN 002
41,49+546.22
UDGI 542.91
-.4

1 2�22j:0 EWP(j)/EWT(m)/T up(c) PJA
ACC -NA, AP6017364. SOURCE CODE: UR/OD62/66/OD0/M3/O53Qj0359
AUTHOR:' WeM!MqY* A. Perevalova; le2n~!~a Yu. A.
ORG: Moscow State University im,, X. V. Lmonosov Hoskovakiy goaudarstvennyy
TITLE i Reactions of triferrocerw hloromethane hZImehlorid
Lc
SOUM% AN SSSR. Izvestip,, Seriya khimicheakaya, noo. 3. 1966, 558-559
anamagn um ompo md#
TOPIC TAGS: organoiron compound., chlorinated organic compound# org esi c I
-.cganosodlum compound# organolithium compound, chemical reaction
ABSTRACT: TriferTocenylohloromethane hydrochloride reacts with nucleophill-
~-reagentij (organomagnesium and organosodium compounds, lithium aluminohydrides,
sodium metbylate andsodium cyanide) to form the corresponding derivatives of
trifirrocanyluethane ip [JFRS3
SUEN DATE: 22,Tul65 ORIG UP: OW OTH REF.- 001
I SUB CODE 07
Cord 1/1, P UDCt 542,91+5kl. 72
49+546.

L
ACC NR, AP6012083 SOURCE, CODIA UR/0062/65/000/')C)3/()5,'Q/O",Eu-
AUVOR: Nesmeyanov, A. N.-. Kozlovskiv, A. G.: Gubin. F. P.; Perevalova.-E.-
ORG: Moscow State Univ im..M. V. Lomonosov Moskovskiy Cosudarstuvennyy i
universive-0; Institute of a oe i i I ji-co-MP-Ounds. AN SSSR (Institut elewntoorgan-4
icheskikh soyedineniy)
TITLE: Protolysis of'M:~cury derivatives of ferrocene'l
SOURCE: AN SSSR. Izvestiya. Seriya khimicheskaya, no. 3. 19651 580
TOPIC TAGS: titrivetry, ferrocene, mercury compound, dioxane, chlorine compound
ABSTRACT: ?he Rate constants were determined for the protolysis of mercury
iderivatives of ferrocene - chloromercuroferrocene and diferrocene-mercury
:using hydrochloric acid in 90% (by volume) aqueous dioxane. The quantity
of acid not entering into reaction was determined by potentionstric titratim
The reaction rate in all cases is described by a second-order kinetic
.equation. 7he protolysis rate of diferrocene mercury is six times greater
than the cleavage rate of di-p-anisylsercury uDder the same conditions.
Orig. art. has: 1 table. [JPRS1
SUB CODE: 07 SUBM DATE: 18jan65 / GRIG BEF.- OD2
UDCz 531-1+542.
Com 1/1 VE&

NESI-EYANOV, A,N. -:Er,;7Vtd,,JV,A, N,., ilv.
Fm-havi or of
of bsnzidinrt re a 7, ra rm,-
21,24 'b~.
A~-,ticn of
i',lv.All S.SSR.5e.-r.kh'
1. Mo3kovskly Im.
Subm4LLt,r--(j j~jjy

- Yj~y".T!EVj-., I M, F.G,, 4.11.
14.D. )
S-mtheals Of F-c"-c- Co3 r*
c;SS-R.f 1-~ -C
fr.kh'i. I - - - Cb -, t -~,3 1 ";). (, ~ c p I a F, - "4- )
J ~z,, j 6,' -Y ' - r" 1 -1 t 'm- Lotr'- .' ' " -
if Me3kcvpkl-, j, l' - - ~%
Subm' t ted A- T ', , ~, ".

PEREVALOVA, EI.G.; RPSHFTOVA., M.P.; GRANDURG, K.I.; NFSMEYANOV, A.N.
SynthesAls of heter-,tinnular alky1feircceny1carbinols. 1 Z-;, AN
"'.'SR. Ser. khim, no.M1901-1903 0 'U.. (K-FA 17t12)
1. Mcskovskiy gosudarstvennyy universitet,

IYFIA,
syn E.,
n D-3~2
Y

NESMEYANOV, A.N., akademik; KURSANOV, D.N.; N"TFI)OVA, M.N.; SETVNA
V.N,,-FEREVALOVA, E.G.
Substitution of a proton for a halcgen In ferrocene
AN SSSR 161 no.6:1349-11151 AP 165. "M:RA "",
1. Inotttut e'qmentc;orgnnichoskogc- ginb"a ~N SSSR. 2. Ch~ci -K, -, -
T-j
re3pDri,~ent AN SSSH (for K!irsnnov).