SCIENTIFIC ABSTRACT BASHKIROV, A.N. - BASHKIROV, A.N.

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• Sequence Number: 12
• Publication Date: December 31, 1967
• Content Type: SCIENCEAB

KA)4ZOLKIN.V.V.; BASHKIROV, A.N.; MARTYM, M.
Study of the process of continuous oxidation of
paraffin hydrocarbons
to alcohols. Trudy Inst.nefti 12:281-289 158. (MIRA
12:3)
(Paraffins) (Oxidation) (Alcohols)

KANZOLKIN, V.V.; BASHKIRDV, A.B.; MARTYNES, M.
Study of the action of boric acid and boric anhydride
on liquid phase
oxidation of paraffin bydrocarbons. Trudy Inst.nefti
12:290-296 '58.
(Paraffins) (Boric Iacid) (Oxidation) (NIRA 12:3)

BASHKIROV, A.N.; [A)DZIK, S.A., K.AMZOLKIN, V.Y.
Determining the compbeition of primary and eecondaY7
higher alcohols by
the dehydration method. Trudy Inst.nefti 12:297-298 158.
(MIRA 12:3)
(Alcohols) (Dehydration (Chemistry))

KIffUKOV, Yu.B.; BUTTUGIN, V.K. ; LIBEMV, L.G. ;
STXPANOVA, N.A.;
SynthesiR of butyl alcohol containing radioactive carbon
C14. Trudy
Inst.nefti 12:299-303 '58. (MIRA 12:3)
(Butyl alcohol) (Carbon--IsotopeB)

ATEORS s
Bashkiroy, "L,. Kamzolkin, V. V., 9D-1-'4/58

Sokova, K.
h.., Andreyeva, T. P.,
iITLEj
On the Problem of the Oxidation
Mechanism of Paraffinic Hydro-

carbons in the Liquid Phase (K
vckn%W o mekhanizme zhidko-

faznogo okisleniya parafinovykh
igievodorodov)
PERIODICALs
Doklady AN SSSR, 1958, Vol- 118, Nr 1,
pp. 149-152 (USSR)
ABSTRACTt
This process is complicated and
consists of a number of reactions

taking place in parallel or
successively. It is considered an

establishad.fact that this
oxidation under mild conditions pro-

ceeds to water and carbonic
acid through intermediate products

of an incomplete oxidation
(peroxides,,alcohols, ketones, acids

and others). A complicated
mixture of oxygen-containing products

devdops. In an earlier
paper (reference 1) the aathors worked

out the synthesis of
higher alcohols of the aliphatic series by

direct oxidation of
paraffinic hydrocarbons in the presence of.

boric acid. The
Shemism and the mechanism of individual stages

has still to be
determined. For this purpose the oxidation of a

number of
individual hydrocarbons was carried out and the compo-

sition of
the alcohols produced was studied. A nitrogen-oxygen

mixture (3,Q
- 3,5%~ 0 ) with addition of 5~ borio acid (calcu-
Card 1/3
lated
on the initial gydrocarbon) under atmospheric pressure was

On the Problem of the Oxidatiun Mechanism of Paraffinic Hydro-
2ILSA21M
carbons in the Liquid Fhase.
used for the oxidation.-The temperature was 165-1700C and the
duration was 4 hours. The hydrocarbons are characterized in tqble
1, the oxides ("oxydates"?) in table 2. From the latter follows
that alcohols represent the main product (about 70~) of the oxi-
dation. For determining their composition and structure they
were isolated from the oxides. Their characteristics are recorded
in table 3. From this is to be seen that the alcohols hatre hy--;
droxyl numbers corresponding to tri-, tetra-, pent- and hexade-
canole and consequently the same number of carbon atoms in the
molecule as each of the corresponding initial hydrocarbons. In
order to prove this alcohols were reconverted to hydrocarbons,
in order to compare the properties of the latter with the ini-
tial hydrocarbons. The conparison of the two types of hydrocar-
bons showed their identity in the case of every individual al-
cohol. From this result the conclusion may be drawn that alco-
hols containing the same number of carbon atoms inthe molecule
as the initial hydrocarbons predominantly develop in the oxida-
tion of n-paraffinic hydrocarbons by molecular oxygen inthe li-
quid phase and under the conditions described. The molecule of
the initial hydrocarbons is on the whole not destroyed. The de-
Card 2/3 termination of secondary alcohols meets with great
difficulties

On the Problem of the Oxidation Mechanism of Paraffinic Hydro-
2D.1-42/58
carbons in the Liquid Phase.
and does not lead to positive results. The methods known in pu-
blications (referencea3,4) proved to be'useless. In order to
solve this problem the authors worked out a special method of the
quantitative determination of primary and secondary alcohols. For
this purpose alcohols were by means of chromic acid oxidized in
the medium of glacial acetic acid. The accuracy of this method
is about 5~. From the given results of analysis follows that
predominantly secondary alcohols form in the reaction studied
here (87,7 - 88,7 mol.%). The interaction of oxygen with the
molecules of the paraffinic hydrocarbons of normal structure
mainly takes place at the secondary carbon atoms. There are 4
tables, and 5 references, 3 of which are Slavic.
ASSOCIATIONs Petroleum Institute AS USSR (Institut nefti Akademii
nauk
PRESENTED: June 26, 1957, by A.V. Topchiyev, Acadmician
SUBMITTED: June 26, 1957
AVAILABLE: Library of Congress
Card 3/3

AUTHORSt Bashkirov, A.-N., Kamzolkin, V. V., 2o-2-24/66
TITLEs The Synthesis of Ethanol From Carbon Dioxide and Hydrogen (sin-
tez etanole iz dvuokisi ugleroda i vodoroda).
PERIODICALs Doklady AR SSSR, 19589 Vol- 118, Nr 21 pp. 293-296 (USSR)
ABSTRACTs The catalytic reduction of carbon dioxide by means of
hydrogen
under normal pressure leads to the formation of carbon monoxide
and hydrocarbons. Under pressure methanol (references 6-8) and a
oertain quantity of ethanol, propanol, butanol ahd athar higher
alcohols (references 9,1o) on that occasion develop on oxide-
catalysts. Therefore the authors want to realize a directed syn-
thesis as mentioned in the title. The high-pressure apparatus
used for this purpose was already often described (reference 11).
The outgoing gases were led back into the synthesis. The cata-
lysts were before the synthesis reduced by means of hydrogen.
Various precipitated iron-9 cobalt-, and nickel-catalysts as
well as molten iron-catalysts with admixtures (K20 ' A12031 S102)
and others were tried out. Molten iron-catalysts were the most
stable. Table I shows the influence of temperature, pressure and
the composition of the initial mixture upon the produced sub-
stances. The alcohol fraction (up to 9400) yielded methanol,
Card 1/3 ethanol and n-propanol (table 2). Ethanol was represented in
the

The Synthesis of Ethanol From Carbon Dioxide and Hydrogen.
2o-2-24/66
largest quantity of all. About 1% of the condensate was formed
by acids, go% of them acetic acid. Further the product desor-
bed from the activated charcoal was investigated (tables 3A).
It had been adsorbed from the outgoing gases during the syn-
thesis. During the investigations some data on the chemiem of
the synthesis under teview were obtaihed. An essential peculiar-
ity of the process is the fact that it takes place in stages. At
first carbon monoxide forms in quantitaties which do not exceed
those in the water gas. Carbon monoxide represents the main
source of the oxygen-containing compounds and of hydrocarbons.
The concentration of oarbon monoxide decreases with increasing
concentration of water vapor in the reaction mixture. The syn-
thesis comes to a standstill when the concentration of carbon
monoxide sank to about 2%. The reoirbulation is capable of large-
ly suppressing the formation of carbon monoxide. Table 5 gives
some data on the products obtained in this connection, An app
proximate material balance shows a yield per I m3 gas mixture
(C02 : H2 - 1 s 3) in gram oft alcohols 92, hy(trocarbons 81
water 345, carbon monoxide 31 and other oxy#en-containing com-
pounds lo. A lower speed Of passage leads to an increase in the
Card 2/3 amouLt of acids. This may be in favor of the conception
that the

The Synthesis of Ethanol From Carbon Dioxide and-Hydrogen.
2o-2-24/60
main final product, ethanol, develops from aoetio acid by re-
duction. This now synthesis of ethyl alcohol from carbon dioxide
and hydrogen represents a step forward on the way of the deve-
lopment of the at.present not yet numerous methods of convert-
ing carbon dioxide to valuable chemical products.
There are 5 tables, II references, 4 of which are Slavic.
ASSOCIATIONs Petroleum Institute, AS USSR (Institut nefti
Akademii
nault
PRESENTEDt July 12, 1957, by A. V. Topchiyev, Academician
SUBMITTEDs July 12, 1957
AVAIIABLEz Library of Congress
Cord 3/3

AUTHORSt
Bashkirov, A. N., Kamzol~in, V. V, Sokova,K.M., 2o-119-4-21/6o

Andreyeva)
TITLE%
The Composition of Alcohols Produced by Liquid Phase
Oxydat-

ion of n-Paraffinio Hydrocarbons (0 sostave ipirtovt polu-

ohayushohikhoya pri zhidkofasnom okialerxii n-parafinovykb

uglevodorodov)
PERIODICALs
Doklady Akademii Nauk SSSR, 1958, Vol.. 119,
Nr 4, PP, 705-

-707 (USSR)
ABSTRAM
Teh investigation of the chemical
composition and the struc-

ture of higher aliphatic alcohols is very
important for the

explanation of their formation mechanism as well as
for the

selection of the right method for their rational exploitat-

ion.
In the present paper the authors occupied themselves

with the hydroxyl
group in the alcohol molecule. They paid

special attention to the
method of oxydation of Alcohols with

sodium biohromate an& with
sulfuric acid. The weigth ratios

between alcohol and sodium bichromate
were 123, the quantity

of the diluted sulfuric acid and of alcohol
loil. The oxidat-

ion waa carried out at different temperatures. The
existence
Card 1/3
of certain methyl ethers was found in single
fractions. The
M

The Composition of Alcohols Produced by Liquid Phase
2o-119-4-21/6o
Oxydation of n-Paraffinic Hydrocarbons
computation could be carried out also according to the
following formula:
A(M-1)-Io7.9(1oo_A)
X loo
14A
whereby X denotes the content of acid C (mol.%)*, A denotes
the content of silver in the existing sEver salt (percents-
ge by weight); M denotes the molecular weight of the acid
On 11 The numerical empirical data prove that this method of
oxtdation of alcohols can be.used very well for the detection
of the position of the hydroxyl group. The experimental re-
sults show furthermore that the alcohols obtained form a bi-
nary mixture of- n-hexadecyl alcohols. The quantityat various
alcohol molecules in this group is equal. Comprisingly was
said that the alcohle produced by the oxidation of n-para-
ffinic hydrocarbons aremainly of secondary nature and repre-
sent a mixture of various isomeric substances.
The reactivity of the atoms of the molecules of higher para-
ffin hydrogens of normal structure does not display any con-
siderable differences and is equal in comparison to oxygen.
Card 2/3 This is theoondition for the production ofisome'rio
substances

The Composition of Alcohols Produced by Liquid Phase 2o-119-4-21/6o
Oxydation of n-Paraffinic Hydrocarbons
of secondary alcohols during the oxidation process of hydro-
carbons in liquid state.
There are 1 table and 5 references, 4 of which are Soviet.
ASSOCIATIONt Inati tut nef ti Akademii nauk SSSR (Petroleum BMUUM of.
the
AS USSR)
PRESENTEDi December 14, 1957 by A. V. Topohiyev, Member, Academy of
Sciences, USSR
SUBMITTED: December 14, 1957
Ca-rd 3/3

2o- 119-6-27/56
AUTHORS: Kryakov, Yu. B, Bashkirov, A* N Batyugin, V. K.,,
Liberov, L. Go 91 a, No Do
TITLE: On the Uniformity of the Meohanism of Synthesis of HydTo,-
carbons and Oxygen Containing Compounds of CO and HI,
(0 yedinatve mekhamizma sinteza uglevodorodo7 i kislorod-
s(~derzhashchlkh soyedinezxiy iz CO i H2)
PERIODICAL: Dok*laly kkademii nauk SSSR. 1958, Vol.. 119, NT 6~,
pp-1152-1155
(USSR)
ABSTRACT:
Card 1/3
Fpr the 3yuthesis c-f 00 and H2. diffsrent sethemas vere pr;,Po!ed.
Ac--cording t~o ihem bk-th procasaer, mantioned ir. th-a title
asei ktdq)end~,.-a! ,-,f eacb otber irt two d'fferett ways. (Refs
1--5)-
Cz~atrz-T,'i-~his fa.)t ixPexim,,z,-~aI date exi-,AT ., which permit
th-~ 3tis-.xmpti that % mi~7hanizqm exiets in introducing
ths :of syrAtheals and in the struf~tv:c-~ of ,~arbcn chains
of 4-1hs compoiii,41-9 CO under the of hydro-
g6n. In tri6r te prnve:, thst,the authors hav,~ expe.,timental.ly
investidatstl the ways rf conversi*n -,f ale,~hols under the
rsaL cordit-A'.*D.a ff syn-';Ib,~slq, ~S.f thq primary products of
syn-

2o-' 19.,6-,2'1 /56
On the Uniformity ef thi, Vei,,hanlam Qf Syntheflis of
Hyd--rr:ar'bonQ and Orygen
Containing Compoaad~.: ~f CO and H2
ths.,~fs ri5,pvjaft_*,q4 a Butanol marked
by, C 4 and m4thq_nol, whlh wvre added to the g~i,~ of syntheals
in suh quantitie.-i ihat t1v; coniiitictv% extotiag on the suz.,
face of the -~ataly*t wevz~s di~,*.urbe(i, s-~rosd as indicator&
of the behavi,:lr of ths ;_%'.1.cchoLF fDrweri of CO and H..
Molten
iron catalysts und,4t high presss-ur6 '5(1 atmoaphr-res ex.-
cess pz,;,9siee) se7ved fo7 this pirp~sa. PigvLr~! 1 shows typic..
al xesultE. From 2 is t^ 'te z~q-?n that methanol is muoh
more eaaily Pub.4e%,.'-- fk) diff:~T-emt cora---,~rsiors thin
b-atanol..
Prcim the tc4;alJ-V of the cbitairied r~isv_'.tq foll,_ws that the
pr%,_%cess4~-q of syntbaisis cf ard ~.xygpn. containing
compoujads cf CO and R, aro conne-ted. wi-th ecich vtbear. On the
molterA cata'.'ystsethi~ afor,--mentione(l comp'..).ind?.; and
th;~
alenhols po.,_z4sees a common source of origin. This is an un-
stable intermediate complex on the surface of the catalyat,
which forme during tbe primaxy interaction betve-?n CO and H2'
This compl.ex contaln!3 C-, H.- and 0--atoms. It is named C1 by
the authors. It is able to condsnse villh its aquals~ whar6by
the formation of the ~~arbon-earbon bonA, furthermore that
Card 2/3 of a new oxygern eontalnii:.g comp,,atAl with 2
~7,arbcn-.C2-r&toMs

2o,A 19-6-27/56
On the Uniformity of the Mechanism of Synthesis of E[ydrocarbons and
Oxygen
Containing Compounds of CO and H 2
is guaranteed. The further growth takes place thanks to the
continuous connection of C, to the growing complexes 07~ 032
0 and so on. Also the molec.-ales CO and H 2 car-, be takeh up
a9d a f-arther hydration of the gr-owing ccimp3exes until the
formation of a stable compoard (aldehyde, alcohol, olefin,
or paraffin) seems to be not impossible. There are 2 figur6s
and 11 r,-f"rarArias, 3 of whil-h Arab 3,~iet-
ASSOCIATION: Instita-~ nsifti, Aka&em~.i. Y;.a,,zA. SSSH
lnai-V;~.itG AS USSR"
PRESENTED; Det~em*r',.~ 26, 1957~ 1-y A. V. Tnp-'-;q*,'yev. Academy of
USSR
SUBMITTED: De-i~~mb.-~3~ 24, 14ST
Card 3/3

ITN 0 V rr:- TT77
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log., I
all
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I I ;. "s 14
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ri
5(2) SOV/156-5.1-1-42/54
AUTHORS: Bashkirov, A. IT., Kamzolkina, Ye. V., Kagan, Yu. B.
TITLE: On Catalysts of the Peactions of the Decomposition of Carbon.
Monoxide (0 katalizatorakh roal:toiy razlozheiiiya okisi ugleroda)
PERIODICAL: llaucln~yye doklady vysshey shkoly. Khimiya I khimichaskaya
tekhnolcgiya, 1959, Ur 1, pp 162 - 165 (USSn)
A3STI~ACT: For the systematic investi,~aticn of the influence of
catalysts
on the reactions: 1) 2 Fe+2 CO --) Fe 2C + CO 2, and
2) 2C0 -4 C + CC 20 melted iron catalysts with actiNating
additivos (Al 2 03v Sio 21 K201 Cr 2031 B203' Y003' V205, MeOjl~nOj
and combinations thereof), as employed in tho synth,.~ois Co+II,
were investiCated. The rosults are lisied in a table. Carbide
forration (reaction 1) and reaction 2 were accelerated by
Al203 and V 2 03' K2 0 accelerates only reaction 1. MoO 3 is
inefl"ectivo, Cr 20 30 PeCr, and In particular S'02 and B203
exercise inhibitory effects. With c-,evu---al additives to the
Card 1/2 catalyst, the havc, as n rule, a cumulative effect.

On Catalysts of the Reactions of the Decomposition of
Carbon Monoxide
SOV/156-59-1-42/54
Only ~Wrj whichg when added exclusively, inhibits the
reaction, increases the reaction velocity in the presence of
other additives. Thus an iron catalyst with kaolin (as an
Sio 2 vehicle), K2 0 and FeCr showed the highest reactivity.
In this caset even B20 3 inhibits only reaction 2. A further
test series concerned industrial iron catalysts, which were also
given additives. The table of the results shows that also in
this case the same rules apply. There are 2 tables and I
Soviet reference.
ASSOCIATIOV: Kafodra neftekhimicheskogo sinteza i iskusstvennogo
zhidkogo
topliva Moskovskogo institut-a tonkoy khimicheskoy tekhnologii
im. M. V. Lomonosova (Chair of retroleum-chemical Synthesis
and Artificial Liquid Fuels of the Moscow Institute of Pine
Chemical Technology imeni It. V. Lomonozov)
SUBMITTED: October 6, 1958
Card 2/2

5(3) S(,V/62-59-7-34/38
AUTHORS: Ka0an, Yu. B., Bachkirov, A. N., Kliger, G. A., fermakov,
Yu. I.
TITLE: Transformation of n-Batyl Amine Under SvnthesiE; Conditions
From Carbon Oxide and %-dro-,cn (Prevrashchen-lyc n.butilamina
v usloviyakh 3intt;za iz okisi ucyleroda i vodoroda)
6~
PERIODICAL: Izvestija Akademii nauk SSSTZ. Otdeleniye kiiinicheskikh.
nauk,
1959, Nr 7, PP 1345 - 1346 (USSR)
ACT: It had been found in previoui invcsti-.-atiors that -.Ihen s~7n-
thesizing n-butyl amine froL, CO, H2 and IM3 in the presence
of iron catalysts, di- and trialkyls ar,~ formed in addition
to monoalkyl amines. Iloreovt-r, the forziation of the 61- and
trialkyls was found to be dependent in tho courLe of reaction
b~, the facilitated reacting possibility of jri,4,arj aminer, vith
oxygen-containing products frOL, tho hydroenation of the
carbon oxide (alcohols, aldehydes, rtc). Viv conclusion was
dra,wn therefrom that the secondary and tertiari a;iines nay be
obtained from CO, H 21 and the pri-tiary araire, here n-butyl
Card 1/3 amine. This conclusion is submiticd to i-xu=ination in the

Transformation of n-Butjl Amine Under S~nthi~8is
Conditions From Carbon Oxide and lljdroL~en
SOV/62-55-7-34/38
prcsent papcr. The synthesis conditiors were the sa~,..,.! as
in references -1 and 2. A molten iron cata-1yGt ran also usT-.d
in tho investi-tation. The amines obtained icrc potentiometri-
cally titrated. The following vias investi.7ated in the course
of sinthesist the influence oxerted by tht, avinc aCditiozi r3te
upon the catalyst, by touperature, pre-3sure, and "he ~:atlo
CO/H in the initial mixture on the yild and the prodacts of
the sylithesis. The data obtained are specified in thm, table. It
may be observed from the latter that occon6ary aff t(trtiary
sai.nes may be actually obtainQd in th,~ awinner defcribed, and
that, by chan6ing the conditiozis, the reaction may be dirtotcd
to the production of either secondary or tertiary amines. In-
crease in the concentration of n-butyl amine and tUTeratare
leaes to the predominant forma 'tion of zzoondary amille., dilu-
tion of hydro3en, lor templurature, and nlow addition of n-but~~l
araine on the catalist for the icrination of tcrtiary aviiiie.
Rising pressure increanes the foriiation of the tro amir,es. At
80-1500 the laraest porctnta3e jicld of secondary and t,~-rtlarj
uwines is obtained (49;j). The additionally obtain~;d priuary
Card 2113 awine (50;o') is caiascd by di3proportionation. There
are j

Transformation of n-Butyl Aiaine Under Synth~!sis
-,GV/'C2-59-7-3.A/38
Conditions Frou Carbon Oxide and Hydrogen
table and 10 referenocs, 7 of rhich art Soviet.
ASSOCIATION; Institut nefti Akademii nauk SSSR
(I:-.1-titute of Petraltum
of the Academy of Sciences, USSR)
SUMMED: January 19, 1959
Card 3/3

SISEKIWV, A.-It.; L01m, S*X6 rial YuSBG% SABIROVA G.T.
Oldrogenation of compowids containing a carbonyl, group (over fused
Iron catalysts). Trudy Inst.nefti IUM4195 159o (MIRA l3t12)
(Carbonyl cowpounds) (Hydrogenation)
(Catalyata)

5 (3)
AUTHORS: Kamsolkin, V. V., Bashkirov, A. N.v SOT/20-126-6-38/67
Corresponding Membl~r
Potaring M. M.
TITLE: On the Synthesis of Higher Ketones by Means of the
Oxidation of
Paraffin Hydrocarbons (0 sinteze sehikh ketonov metodom oki-.
sleniya parafinovykh uglevodorodovi
PERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 126, Nr 6,
pp 1282 - 1285
(USSR)
ABSTRACT: The formation of the carbonyl compounds take" lace
in the oxi-
dation of the paraffin hydrocarbons ai 120-1608 such more ra-
pidly in the initial stage than the formation of the alcohols
and acids. On the basis of the concepts on the order of the
for-
mation of oxygen containing compounds (see scheme, Refs 1,2) it
may be maintained that in this case ketones are formed mainly
directly from hydroperoxide. Because of this observation ex-
periments were carried out to determine whether a directed syn-
thesis of higher ketones by means of the oxidatlon of paraffin
hydrocarbons is possible in the liquid phase. For this purpose
the authors studied the action of the reaet!.on conditions as
Card 1/0 well as of some additions on the rate of oxidation
and on the

on the Synthesis of Higher Ketones by Means of the SOV/20-126-6-38/67
Oxidation of Paraffin Hydrocarbons A
composition of some forming products. The fraction of synthetic
hydrogenated paraffin hydrocarbons which boils out between 105
and 1300 0 torr) and which consists of carbons with 16 to 18
carbon atoms, was oxidized. The apparatus used and the method
applied are desoribed in reference 3. The temperature effects
are shown by table 1. Their increase to 1650 considerably in-
tensifies the conversion of the initial hydrocarbons. A further
increase to 1850 remains practically without effect. The aaxi-
mum yield of ketones was obtained at 120-1400. Also in the oxi-
dation by a nitrogen oxygen mixture (3.5~ 02) the above regular-
ities existed. By increasing this content to 21% 02 the ketone
portion in the reaction products decreased (Table 2). At the
same time, howeverp the degree of conversion of the initial hy-
drooarbons increased. It is possible that other oxidation con-
ditions may be found under which high ketone yields are obtain-
ed. Such e.g. the reduction of the specific consumption of the
oxidizing gae (oxygen) from 1000 llkg h to 200 1/kg h leads
to ketone yields of about 55% computed with respect to the re-
Card 2/~ acted paraffin (Table 2). Table 3 shows the effect exercised
by

On the Synthesis of Higher Ketones by Means of the
Oxidation of Paraffin Hydrocarbons
Card 3/
30V/20-126-6-36/67
the duration of oxidation on the composition of the oxide (3-5%
02+N2 at 1400). The oxidation intensity increases and the ke-
tone yield decreases with the longer duration. The ottimum i du-
ration is 3-4 hours in the oxidation with air at 140 . It may
be seen from figure I that at 1200 the oxidation in inhibited
after a certain maximum degree of conversion (which depends on
the reaction conditions) is attained. Later, the ketone and acid
portion increases somewhat at the expense of the alcohol por-
tions (Fig I and experiments Nr 1,2,4,5 in table 2). In this
case an alcohol oxidation may take place. The oxidation process
of the hydrocarbons concerned takes place according to the chain
mechanism of the free radicals where a bimolecular decomposition
of hydroperoxide leads to a branching of the chain, see scheme
(Ref 4). The self-acceleration of the reaction at relatively
low temperatures is due to the peroxide decomposition. The oxi-
dation rate depends on the formation rate and the concentration
of the free radicals in the reaction zone. The decomposition may
take place also due to an interaction with the radical of reac-
tion III according to reference 1. The mentioned inhibition is

On the Synthesis of Higher Ketones by Means of the BOV/20-126-6-38/67
Oxidation of Paraffin Hydrocarbons
"ASSOCIATION:
Card 4/
probably due to a rapid reduction or stoppage of the formation
of free radicals which are responsible of the reaction course*
At higher temperatures no inhibition occurs and the oxidation
taken place to a considerable degree of conversion (Fig 2). Al-
cohols, eaters, acids and other oxygen containing compounds so-
oumulatet however, in high quantities. Additions of KMnO 41 78804
eto. could not bring about an increase of the ketone. yield. The
results obtained indicate that the formation of free radicals
takes place mainly according to reaction (III)'and not accord-
ing to (I) and (II). Thusp it was proved that the higher ali-
phatic ketones may be produced by direct oxidation of paraffin
hydrocarbons with yields of approximately 65 mol% of-the trans-
formed hydrocarbon and at a degree of conversion of 10-15 mol%-
There are 2 figures, 3 tables, and 5 referencest 3 of which are
Soviet.
Institut neftekhimicheskogo sinteza kkademii nauk SSSR (Insti-
tute of Petrochemical Synthesis of the Academy of Sciences,
USSR)

5(2)
AUTHORS: ..Bashkirovv A. N-9 Corresponding Member, SOV/20--127-1-24/65
AS USSRt Potarin-9 M. M.i Kamzolking V. V.
TITLE:
The Synthesis of Higher Ketones by Liquid Phase Oxidation of

Speondary Alcohols (Sintez vysehikh ketonov metodom zhidko-

faznogo
okisleniya vtorichnykh spirtov)
PERIODICAL;
Doklady Akademii nauk SSSR,
1959P Vol 127P Nr 19 pp 93-96

(USSR)
ABSTRACT:
The oxidation of the
paraffin hydrocarbons in the liquid phase

is considered to be a
process of various stages. The succession

of these stages is shown by
a scheme (Refs 1-3). A considerable

number of carbonyl compounds are
formedv as a rule, in the

production of synthetic sebacic acids by the
oxidation of solid

paraffins. The oxidation products of the higher
paraffin hydro-

carbons contain besides secondary alcohols (in
the,presence

of boric acid) always a certain quantity'of katon
s ~Ref 5)-

:d
The carbonyl compounds (see Scheme) may be produc a) by

the
decomposition of hydroperoxide (Ref 6); b) by the oxidation

of the
alcohols in the reaction zone. The authors attempted

to clarify the
possibility of oxidizing the alcohols to ketones
Card 1/4
under
conditions similar to those of the oxidation of

The Synthesis of Higher Ketones by Liquid Phase
SOV/20-127-1-24/65
Oxidation of Secondary Alcohols
hydrocarbons in the liquid phaser furthermorep the
possibility
of an orientated oxidation of secondary alcohols toketones.
For this purpose bigher aliphatic alcohols (fracti:oA boiling
out within the range of from 125-17009 produced according to
the method of reference 5) were used with a content of secon-
dary alcohols of approximately 90 mole% (Ref 7 The apparatus
and the method were already earlier described 4ef 5). The
quantity of acids in the reaction products increases with
rising temperature in the oxidation by means of an oxygen-
nitrogen mixture (6.0..6-5 Wt% 02 ) during 4 hours at
120-18009
in contrast to that of ketones which is reduced from 63.6 to
55.3 mole% (Table 1). Carbonyl compounds apparently cannot be
accumulated in greater quantities at higher temperatures
since
they are rapidly oxidized to acids. These acids occur either
free or as eaters. The transformation.degree of the initial
alcohols is increased by the increase of 0 2- concentration
in
the reaction zonev the relative yield of ketoneaq howeverl is
reduced (Table 2). The reaction kate depends as a 'rule to a
Card 2A considerable extent on the 0 2-concentration in the
oxidizing

The Synthesis of Higher Ketones by Liquid Phase SOV/20-127-1-24/65
Oxidation of Secondary Alcohols
gas. Its increase leads to greater yields of acids. The pro-
longation of the oxidation (Table 3, Fig 1) increases the
transformation degree of1he alcohols and the acid yield at the
expense of the ketone yield. On the strength of the experi-
mental results an oxidation method for alcohols coula be
chosen which.guaranteed a ketone yield of 60 mole% in the
case of a tranformatton degree of 40-45 mole% of alcohols4
i.e.: temperature 16509 O.-content in the gas mixture h
6.0-6.5 %p the specific consumption of the latter 19000 1/k9 P
oxidation duration '3 hours. A higher yield of ketones may be
obtained in the oas*p-of a lower transformation degree of the
alcohols. Additions of Co-, Ni-, Un-, Fe-, Cr-, Cu-, and Sn-
salts are ineffective. Iron pentacarb6nyl has a considerably
inhibiting effect on the reaction. This proves its radical
character. The data obtained Am well in line with referenee
8 with respect to the effect of boric acid and boric anhydri-
de on the process mentioned in the title. There are 1 figure,
3 tables, and 8 Soviet references.
Card 3/4

The Synthesis of Higher Ketones by Liquid Phase
SOV/20-127-1-24/65
Oxidation of Sec7ondary Alcohols
ASSOCIATION: Institut'neftekhimicheskogo sinteza Akademii
nauk SSSR
(Instituto of Petrochemical Synthesis of the Academy
I of Scienceel USSR)
SUBMITTED: March 16, 1959
Card 4/4

TITLE:
On the Composition of Ketones Formed in Oxidation in the

Liquid
Phase From n-Paraffin Hydrocarbons
PERIODICAL:
Doklady Akademii nauk
SSSR, 1959, Vol 128, Nr 5,

pp 956 - 959 (USSR)
ABSTRACT:
Secondary
alcohols with a normal structure are the main

products in the oxidation
of n-paraffin hydrocarbons by mole-

cular oxygen in ihe liquid phase
under mild conditions in the

presence of boric acid (Refs 1-3). The
molecules of these

alcohols have the same number of carbon atoms as the
initial

hydrocarbon. Thesq alcohols form a mixture of all isomers

possible with regard to the position of the hydroxyl group.

Compounds
with a carbonyl group, acids, and polyfunctional

compounds are formed
as side products. The authors paid special

attention to the carbonyl
compounds and used n-hexadecane

as initial product. Its oxidation took
place in a device de-

scribed in reference 2. The oxidized substances
enumerated in
Card 1/3
table 1 were formed by the effect of a
nitrogen-oxygen mixture

LK

66172
On the Composition of Ketones Formed in Oxidation SOV/2o-128-5-26/67
in the Liquid Phase From n-Paraffin I~ydrocarbons
(with 3-5% 02) at 165-1700 and 5% boric acid within 4 ~rs.
Among them were rJ 19 mol% compounds with a carbonyl group.
The oarbonyl compounds were separated from the oxidized sub-
stance for the purpose of determining their composition. About
4Wo of their total amount remained with the products which
had reacted with boric acid. For this reason the authors assume
that the afore-mentioned compounds containing carbonyl consist
of ketones and polyfunctional compounds with a carbonyl group
(mainly ketoaloohols). The distillate was chromatographically
separated into paraffin hydrocarbons and compounds containing
oxygen in order to determine the composition of the ketones.
Table 2 shows the melting temperatures of semicarbazones.
Comparison with them did not yield a final conclusion regard-
ing the composition of the ketonesinvestigated. Thus, they..
were oxidized with potassium bichromate in diluted R so ef 3).
2 4 VP
Table 3 shows the results of the rectification of the methyl
esters of the acids formed in the oxidized substance. Table 4
shows the weight- and per cent ratios of these acids. On
Card 2/3 account of the above results, the authors ascertain that
mainly

66172
On the Composition of Ketones Formcd in Oxidation
BOV/2o-128-3-26/67
in the Liquid Phase From n-Paraffin Hydrocarbons
ketones are represented among carbonyl compounds in the
reaction mentioned. These ketones have the same chain length
as the initial hydrocarbon. They form a mixture of all iso-
mers theoretically possible with regard to the position of the
carbonyl group. Polyfunctional compounds containing a carbonyl
group are formed in addition to the ketones. There are 4 tables,
and 4 references, 3 of which are Soviet.
ASSOCIATION: Institut neftekhimicheskogo sinteza Akademii nauk
SSSR (In-
stitute of Petroleum-chemioal.Synthesis of the Academy of
Sciences, USSR)
SUBMITTIEDt June 26, 1959
Card 3/3

I..; x
a
+44T3-)- 3 1/ 0 0 66417
AUTHORS: 8-6-21/63
jorresponding Member SOV/20-12
AS USSR9 Shinan Pal
TITLE: Liquid-phase Oxidation of Olefines in the Presence of Boric
Acid
PERIODICAL: Doklady Akademii nauk SSSR9 19599 Vol 128, fir 6, PP 1175
- 1178
(USSR)
ABSTRACT: The molecule of the initial hydrocarbon Is not destroyed in
the
initial stage of oxidation of the hydrocarbons of normal struc-
ture (stage of-alcohol formation) (Refs 192). Under the condi-
tions chosen by the authors, secondary alcohols are primarily
formed in the presence of boric acid. They form a mixture of all
possible Isomers with the same number of carbon atoms in the
molecule as there had been in the initial hydrocarbon* As the
isomers mentioned are formed in equal molar quantities, it ap-
pears that the reactivity of the secondary carbon atoms in the
molecule of the higher paraffin hydrocarbons is practically the
same with respect to the oxygen* Primary alcohols with the same
C-atom number as in the initial substance are missing in the
oxidation products of normal paraffin hydrooarbons6 This is ap-
Card 1/3 parently due to the higher stability of the C-H-bond in the
~,

Liquid-phase Oxidation of Olefines in the Presence of
Boric Acid
66417
BOY/20-128-6-21/63
methyl group as compared with the methylene groups. The authors
oxidized synthetic n-dodecene-le The pressure of the normal
nitrogen-oxygen mixture was normal, the 0 -content was about 4%t
2
boric acid 5-7%, temperature 165-1750# duration 2-3 hours. The
apparatus was described in reference 1, The oxidates obtained
are characterized in table 1. Table 2 presents the hydroxyl-
containing products of this reaction. Alcohols (about 75 molar %)
were formed as a main product at an oxidation intensity of about
27%. Table 2 suggests that the let fraction (about 38% of the
hydroxyl-oontaining compounds) represents n-nonyl alcoholt which
was confirmed later on, The 2nd fraction had - besides a high
hydroxyl number - also a high iodine number. This fraction pri-
marily consists of unsaturated alcohols C H On. W selective
12 23
hydrogenation and aoid formation (Ref 2), several acids were
isolated and identified (Table 3). Hence it was found that the
alcohols of this fraction represent a mixture of unsaturated
secondary alcohols. About 60 molar % fall to the share of
dodeconol-3t the remaining 40% are represented by other possible
Card 2/3 isomers of the alcohol group C,2H2,OH. The 3rd fraction
was a

crystalline substance: n-dodsoanol-192. Synthetic n-dodsc*n*-2
was oxidized in addition. The results show that the double bond
in the carbon molecule considerably influences the direction of
oxidative transformations. The formation of glycol suggests an
analogy in the oxidation process with Prileshayev's reaction.
There are 4 tables and 8 reforenoesi 7 of which are Soviet.
ASSOCIATION: Institut neftekhimiohookogo sinteza Akademii nauk
SSSR (Insti-
tute for the Chemical Synthesis of Petroleum of the Academy of
Sciences, USSR). Moakovskiy institut tonkoy kbimioheskoy
tekhnologii im. M. V. Lomonosova (Moscow Institute of Fine
Chemical Technology imoni M. V. Lomonosov)
SUBMITTED: June 26, 1959
Card 3/3

BASHKIROV., A.N.; KAMZOLKIN., V.V.; SOKOVA, K.M.; ANDREYEVA, T.P.
Determination of primary and secondary higher alcohols of
the aliphatic xeriewin their mixtures. Hatod.anal.org.
soed.nefti,ikh man i proizv. no.1:170-177 t6O. (MIRA 14:8)
(Alcohols; (HxOrocarbons)

TITLE: Compopition of oxygen-containing compounds forming during
the-liquid phase aerial oxidation of n-pentadecane
SOURCE: Akaaemi.~&'nauk SSSR. Institut neftio Tru'4y, v. 14, 1960,
ladriiya niefti, 65 - 75
TEXT; R6sul ti.are-presented of the study of the composition of the
products of,o'lidaiidg o~ n-pentadecane in the presence of boric
acid. More-oxygeri 'was ubeT in this work than previously (Bashkirov
A.N., Khimic)29skayi nauka i promyshlennost'. 1, no. 3, 272 (1956)).
The aim of'.th6.protent investigation was to obtain additional data
on the oxidaUve" ~oo~nve'rsions of hydrocarbons and on some
intermedia-~
,te oxygen-aoll'iIiiniAg coiupound8o It was found that the increase
of 0
in the oxidising~g4q from 3.5 % to 21 % doubles the quantity of 0 -
containing .-oomyouXi4s. At the same time the proportion of OH - con-
taining 6ovip~*ida.'-'decreAses from 70 % to 50 % -and COOH -
containing
compounds' in'ct4idse..-from 12 % to 31 The amour-t of oarbonyl com-
Card 1/2

-8/510,/60/014/000/004/006
D244/D307
AUTHORS: Baahkirov, AeNe, Loktev, S*Mop Sabirovat G.V., and
Novakt P.I.
TITLE: ComposItion of liquid products of the synthesis from CO
and H on talc catalysts
2
-SOURCE: "Ak~demiya nauk SSSR. Institut nefti, Trudyp v. 14# 19609
-Yhimiya.nefti, 76 - 84
TEXT: Results "are presented of the chemical composition of CO -
H2
synthesis on talc catalysts and of the influence of the~-'bhemical
composition of the catalysts and the synthesis c6nditions on the
com-
position of th 'e reaction products. It was found that the
products
were a coiaplex mikture of alcohols, hydrocarbons, aldehydes,
ketones
and small,;quantities of acids and eaters. The water of the
reaction
contained .1.9 %-of organic acids and 12.5 % of neutral
O-containing
compounds (-alcohols axed ketones). There were about 30 % of
carbonyl
oompounds'in.;the~products. Addition to the catalyst of.25 % of
cal-
cium aluminite'inoreased the ketone content to 36.6 % 39.7 %. With
Card 1/2

S/51Y60/014/000/004/006
Composition of liquid products of D244 D307
50 % of bdrium aluminate the content increased to 40 - 55 %. Selec-
.tive hydrogenation of the liquid products could give liquids contain-
ing 75 - 80.%.alcohols. The 0-containing compounds 'Oefore and after
hydrogenat-iont contained uneatuTated bonds. Increase of the space
velocity,from 100 h-1 to 500 h- gave 1.5 - to 4-fold increase in
the alcohol content of the products and a decrease in-the content
of unsatu:raUd compounds. Further increases to 1000 h-1 gave only V,
small changos-in.the yields and composition of the products. Regene-
ration of th.9 catalyst by air at 380 - 4500 enabled the authors to
conduct the reaction at lower temperatures, Increase of the reaction
temperature,frozd,350 - 37500 to 400 - 4300C gave some inciease in
the content of alcohols, ketonesp complex esters and caftoxylic
acids in the'.products and a decrease of the content of unsaturated
compounds. There are 8 tables.
Card 2/2

S/195/60/001/002/006/010
B004/B067
AUTHORS: Kryukov, Yu. B., Bgjghkirov~ A- N. Liberov, L. G.,
Butyugin, V. K., Stepanova, N. ff-., Kagant Yu. B.
TITLEs Conversions of Iron Carbide Under the Conditions of the
Synthesis of Hydrocarbons From Carbon Monoxide and Hydrogen
PERIODICALi Kinetika i kataliz, 1960, Vol. 1, No. 2, pp. 274 - 281
TEXTt The present paper was presented at the All-Union Conference on
Organic Catalysis in November 1959. The authors attempted to explain
the
part played by carbides as intermediate compounds in the synthesis of
hydrocarbons. They used a standard 19on catalyst with chromA um
admixture, which was reduced at 100O.C and activated at'300 C and 20
atm
with the initial gas mixture CO + H2 (1 : 1), which contained C14 0.
The
catalyst, enriched with radioactive iron carbide, was then treated
with
pure CO + H 2' The radioactivity of the products formed was then
measured.
The authors found that mainly the following reactions took place in
iron
Card 1/2

Conversions of Iron Carbide Under the S/195/60/001/002/006/010
Conditions of the Synthesis of Hydrocarbons B000067
From Carbon Monoxide and Hydrogen
carbide (90%)s hydrogenation to methane, exchange of C isotopes
between
00 and carbide. The rate of these reactions is low as compared
to that
of the synthesis reaotion. Of 3000 CO molecules, only one
exchanges its
carbon; of 3000 CH4 molecules, only five are formed by carbide
hydrogens-
tion. Henoe, only 0-03% of the hydrocarbons with C> 1 was
formed und
the action of carbide. These data rebut the hypothesis
according to which
carbide products are intermediates in hydrocarbon synthesis
from CO and
H2' There are 2 figures, 2 tables, and 22 references: 13
Soviet, 5 US,
1 British, and 3 German.
ASSOCIATIONs Institut neftekhimicheskogo sinteza AN SSSR
(Institute of
Petrochemical Synthesis of the AS USSR)
SUBMITTEDt Janwtry 23, 1960
Card 2/2

s/fl95/60/001/003/008/013
B013/BO58
AUTHORS: Kagan, Yu. B.-,~ Kaftolkina, Ye. V.,
Loktev, S. M.
TITLE: On the Activation Process of Molten Iron Catalysts for
for CO and H2 Synthesis Under the Effect of the Reaction
Mixture
PERIODICAL: Kinetika i kataliz, 1960, Vol. 1, No~ 3, PP. 393 - 400
TEXT: The activation of molten iron catalysts for the hydrocarbon
synthesis from CO and H2 under the effect of the reaction mixture was
studied in this paper. The following catalysts were used:
1) 10OFe30 4+ 6A120 3 + 4-23i02 + 1.2K20 + O.3Crj
2) IOOFe30 4+ 6A120 3 + 4.28102 + 1.2K20 + 0-5V;
3) 10OFe30 4+ 6A12 03+ 4.23102 + 1,2K 0 + 1-OB 203' They were reduced
Card 1/4

On tho Activation Process of Holton Iron S/195/60/001/003/008/013
Cataiysts for CO and H2 Synthesis Under the B0131BO58
Effect of the Reaction Mixture
within 1.5 hre in hydrogen current at 10000C. The study was made in
a
highpressure apparatus (Ref- 4) in the laboratory. For each of the
catalysts studied, thelowest temperatures and pressures were
initially
chosen, at which, over the freshly and reduced catalysts (in
comparable
time intervals), a high degree of transformation of the carbon
monoxide
(84 to 86%) entering at a volume rate of the initial. gas (CO and H
2 1 :1)
0f-01500 h- I was obtained. The catalysts were gradually activated
under
these conditions. The duration of the tests varied. The tests of
catalyats
of equal composition were conducted under the same conditions and
in the
same reaction vessel. The indices of the synthesis were well
reproducible.
The results determined could therefore also be compared with each
other.
The samples were hydrogenated after termination of the synthesis
test.
Subsequentlyp the hydrogenated samples were treated with CO at
atmospherio
pressure, a volume rate of 800 h-1 and temperatures by 100 higher
than
at the end of the synthesis test, with carbide bbeing formed. The
studies
Card 2/4

On the Activation Process of Molten Iron S/195J60/001/003/008/013
Catalysts for 00 and H2 Synth~sis Under the BO13/B058
Effect of the Reaction Mixture
produced the following resultat the previously (Refs. 1, 2) made
statement
that the iron catalysts molten at high temperatures (10000C)
immediately
after reduction, are inactive in the synthesis of CO and H2 and
obtain
activity only during the course of this synthesis, was confirmed.
Activa-
tion also continues after reaching activity, which warrants a
practically
complete transformation of the initial carbon monoxide. This process
is not
terminated until 3 to 4 days after conduction of the synthesis.
Simultan-
eously with the activation of the catalysts under the effect of the
reac-
tion mixture, their reactivity with respect to carbide formation is
also
increased. Those catalysts which have reached equal activity in
consequence
of the 00 + H synthesis, have also a similar reactivity with regard
to
carbide formahon. The activation of the catalysts during the
synthesis is
accompanied by an increase of their activity during CO decomposition
under
formation of elementary carbon. The conditions under which the
activation
of catalysts occur- (pressure, temperature, 002 content of the gas)
have
a noticeable effect on their properties. Of the methods investigated
of
Card 3/4

On the Activation Processof Molten Iron 5/195/60/001/003/008/013
Catalysts for 00 and H2Synthesis Under the B0131BO58
Effect of the Reaction Mixture
the activ4tion of the catalyst for the synthesis, its treatment at
the
synthesis temperature is suited best. In this case the catalysts get
speci-
ally active, but simultaneously show a lower activity with regard to
CO
decomposition. There are 3 figures, 4 tables, and 6 Soviet
references.
ASSOCIATION: Institut neftekhimicheskogo sinteza AN SSSR
(Institute of Petrochemical Synthesis AS USSR)
SUBMITTED: January 19, 1960
Card 4/4

AUTHORS: B"hkirovq Ae Not Corresponding 8/02 60/131/04/030/073
V Ab UUZXP Llexanovas A. 1. BOI I YBO17
TITLE: Oxidation of Naphthene Hydrocarbons in the Liquid Phase in the
Presence of rorio Acid
PERIODICAL: Doklady Akademii nauk SSSR, 19609 Vol.131t Nr 4, pp
827-829 (USSR)
TEXT: Under the conditions mentioned in the title, the oxidation of
nephthenes
takes place widely under the formatioji of alcohols. For the purpose
of studying
this oxidation, the authors synthesized (according to Grignard) a
series of
naphthene hydrocarbons with side chains of varying lengths in the
molecule:
n-amyloyclohexane, n-hoptyloyolohexanot and n-nonyloyclohexane. Their
constants
are shown in table 1. These compounds were oxidized at normal
pressure by means
of a nitrogen-oxygen mixture (0 -content 3.5%). ThS specific
oonsumption of the
oxidizing gas was 1000 1/kg.h, he temperature 165 , the duration of
the experi-
ment 4 h, the added amount of boric acid 5%. The apparatus used was
described in
reference 1. The oxidized substance was saponified with hot water.
Table 2 gives
the characteristics of the oxidized substances. They show that the
reaction
products are mainly alcohols. After having saponified the boric acid
eaters, the
not reacted hydrocarbons were separated chromatographically on silica
gel of 0type
ASK from the oxygen-containing compounds, Petroleum ether (boiling
out at 60
and methanol were used as displacing liquids. The eaters were
saponified b_
Card 1/3

of caustic potash. The alcohols obtained were separated from
ketonseby the formation
of boric acid asters. Bifunctional compounds which are formed in
small quantities
during oxidation were separated chromatographically (this method
devised by the
authors will be-publish*d shortly). Here benzene and methanol were
used as dis-
placing liquids. Pure alcohols were distilled in the vacuum (Table
3). Their
primary and secondary alcohol content was determined (Table 4).
Furthermore, the
authors wanted to find out whether the oxidation described takes
place under the
destruction of the molecule. For this purpose, they dehydrated the
alcohols which
they obtained from the oxidized product of n-nonyloyclohexane over
anhydrous
aluminum oxide at 270 0 in the vacuum. The unsaturated hydrocarbons
formed had an -
iodine number of 120 (for C 15H30 it should be 122). They were
hydrogenated in
n-haptane Wedium. over a Raney nickel catalyst at a hydrogen pressure
of 30 atm.
and at 180 . n-Heptane was distilled off in the vacuum. Table 5 shows
the oompara-
tive characteristics of the hydrocarbon obtained from alcohols and of
the n-nonyl-
oyclohexans used. These two substances are identical. Thus, the
authors proved that
alcohols are formed by oxidation of naphthenes with a side chain of
normal struc-
ture in the presence of boric acid. In this case, no destruction of
the molecule
of the oxidized substance takes place. The alcohols formed are mainly
secondaryp
and have the same number of carbon atoms in the molecule as the
hydrocarbon us6d.
Card 2/3

Oxidation of Naphthene Hydrooarbons in the Liquid
8/02Y60/131/04/030/073
Phase in the Presenci of Borio Aoid BOll B017
There are 5 tablea and 4 referenoes, 3 of whiob are Soviet,
ASSOCIATION: Institut neftakhimichaskogo sinteza Akademii nauk SSSR
(Institute gf retroleum-ohomioal Synthesis of the Aoademy of
Soienoest USSR), Mookovskiy inetitut tonkoy khimichaskoy tekbno-
logii im- M. V. Lomonosova (mosoov Institute of Fine Chemloal
Toohnology imeni M. V. Lomonosov)
SUBMITTn: Ootober 20v 1959
Card 3/3

"17 a 4 00
69993
AUTHORS: Bas Irov. A, Corresponding Member of
S1020J60113110510221069
the AS USSR9 aMZ01Jdn, Ve V.9 Potarin, B011/B117
M. M., J~oloverrn_ov, G. D.
TITLE: Preparation of Higher Aliphatic Ketones by the Method of
Dehydrogenationlof Secondary Alcohols
PERIODICAL: Doklady Akademii nauk SSSR, 1960, Vol 131, Wr 5, pp
io67-1o68 (USSR)
TEXT: The topic mentioned in the title has been studied using an
industrial-
type skeleton nickel catalyst. It was proved by the authors that
it is possible
to obtain a high yield (85% by weight), if the above-mentioned
liquid-phace
preparation method is used. The amount of the catalyst was 10% of
the alcohol.
Commercially produced C 16 - C19 alcohols containing 6% of
hydrocarbons were
0
dehydrogenated. The reaction temperature was 185 , the residual
pressure 33 torr.
From the kinetic curves of the reaction it follows that the
reaction proceeds
rapidly in the liquid phase, and is practically completed within
two hours. The
conversion degree of the alcohols reaches 95 mole % (Fig 1). At
first, a vigorous
separation of hydrogen takes place, the iodine number of the
product decreases,
probably as a result of the hydrogenation of the unsaturated
compounds in the
alcohols used. Then, the iodine number is somewhat increased
which is due to a
side reaction involving the dehydration of the alcohols. It could
be established
Card 1/2

by chromatography on silica gel that the carbohydrate content was
thereby increased
from 6 to 10% by weight. The acid and ester content in the reaction
products
remains the same as the one in the alcohols ueed. The curves in
figure 2 show
that the dehydrogenation of the alcohols is accelerated by higher
temperatures.
Low pressure (33 torr) favors the reaction. The small quantity of
unreacted
alcohols was removed from the dehydrogenation product by
esterification with
boric acid. Substances not reacting with boric acid were distilled
from the boric
esters in vacuo (7 torr). The boiling-point range of the distillate
was 115 to
1200. After removal of the hydrocarbons by means of chromatography
on silica gel,
a fraction oV*higher aliphatic ketones with d'o 0.8362, n211 1.4446
and a carbonyl
4 D
number of 202.0 was obtained. There are 2 figures and 5 references,
4 of which
are Soviet.
ASSOCIATION: Institut neftekhimicheekogo sinteza Akademii nauk SSSR
(I
of Petroleum-ohemical Synthesis of the Academy of Science
USSR)
SUBMITTED: November 30, 1959
Card 2/2

KOZOLKINX V.V.;-BASHKIROV A.N.; KHOTIWKAYAS M.I.; GROZHALN., M.M.;
Synthesis of aliphatic C6 - Clo alcohols by the liquid phase
oxidation of paraffins under pressure. Neftekbimiia I no.2:
2"-254 Mr-Ap 161. (MM 15:2)
1. Institut neftelchimaicheskogo sinteza AN SSSR.
(Alcohols) (oxidation) (Paraffins)

KLIGER, G.AO; -WHKIROY, A*Ne; REZINGER, N,N.; KAGAN, Yu.B.
Method for ana3,vzing products obtained by the interaction
of aliphatic alcohols with ammonia in the presence of
hydrogen. Neftekhimia I no,3:397-402 My-Je 161,
(MIRA 16:U)
1. Institut neftekhimichaskogo sinteza AN SSSR.

KAGAN, Yu.B.j AgW2U,.Aj.j MLIGEFt,
MAK-,N.Ye.
G,A.; CHZHOU CHZHAO-DI (Chou Chao-tili
Reaction between oetyl alcohols and ammonia under the I.Wdro-
gen pressure on a fused iron catalyst. Neftekhimia 1 no-31
403-410 YqTe 161. (K 16:11)
i
1. Institut neftakhimichaskogo sinteza AN SSSR Inatitut
tonkoy khImichookoy tokhnologii imeni Lomonosova.'

-BASHKMOT-p-A.N.4,,-,UMMKINO Y.V,;'SONDVAp Us; ANDRMVA.. T.P.1
KORNEVAP V.V.j ZAKRARKIN, L.I.
Synthesio of cyclododecanol by the liquid-phaae oxidation
of oyclododeoane. Neftekhimiia 1 no.4:527-534 JI-Ag 161.
(MMA 16til)
1. Institut neftekbimicheskogo ainteza, AN SSSR i Institut
elementoorganicheakikh soyedineniy AN SSSR.

XAGANj NOB IGGMtq 0 A.; CHZHOU CRZHAO-DI
hou Chao-ti I MAKj, N.Ye.
Effect of the molecular weight of alcohol on the proce"
of its amination. Neftekhimiia I no-48555-563 JI-Ag 161,
(MM 16: 13.)
1. Institut neftekhimichookogo sinteza AN SSSR i Moskovskiy
inBtitut tonkoy khimicbeskoy tekhnologii imeni Lumonosova,

33496
.s/195/61/002/005/023/027
z7.)/'9a EO4O/El85
AUTHORS: Kryukov, Yu.B., Bashkirovi-A.-R- Liberov, L.G.,
Butyugin, V.K*, and Stepanoval NoDe
TITlEi on the mechanism of chain growth in the synthesis of
organic compounds from CO and H2 on iron catalysts
PERIODICAL: Kinetika i kataliz, v.2, no-5, 1961, 780-787
TEXT: A brief survey of the previous investigations of the
syntheals of organic compounds from CO and H2 mixtures on cobalt
and iron catalysts showed that the mechanism of the chain growth
can be visualised either as 1) condensation of oxygen-containing
complexes, with separation of water, or 2) the growth of the
carbon chain can be assumed an being preceded by the splitting off 1/
of oxygen atoms from the carbon monoxide molecule and a subsequent Vr'
chain growth by the mechanism of polymerisation of methyl
radicals. The experimental evidence at present available appears
to be somewhat contradictory and for this reason a study was made
of the role played in the above synthesis by oxygen-fro*
intermediate complexes of the methyl and hydrocarbon type
Card 1/4

33496
on the mechanism of chain growth... 5/193/61/002/005/023/027
E040/E185
radicals. The study was made with the help of radioisotope
tracer technique using carbon monoxide labelled with C14 carbon
(9000 pulse/min per m?). In the tests, a mixture of C140 + H2
(in the 1:1 by volume ratio) was passed'over freshly prepared
iron catalyst heated to 295 OC, the reaction was allowed to
proceed for various periods and the products were then separated.
The radioactivity of the separated hydrocarbons was then plotted
against the reaction time and the number of carbon atoms in the
synthetised hydrocarbons. The results obtained indicated that
botb the condensation and polymerisation mechanisms are involved
in the synthesis of the products* The actual mechanism prevailing
at any stage of the reaction was found to depend on the
experimental eonditlons. A general scheme was formulated for the
various reactions that can occur when a stream of carbon
monoxide/hydrogen mixture is passed over iron catalyst heated to
about 300 OCi
Card 2/~'

33496
On the mechanism of chain growth ... S/195/61/002/005/023/027
Eo4o/El.85
Carbon chain growth by #4 Carbon chain growth by
4
polymerisation mechanism 0 condensation mechanism
to
.*., '-V
Vo
C HS-C."I C H 2.014 r-Hjc $I C if o 0
CH 20 H ;Loll C04 W). HoH
it
Scheme 2
C H
Card 3/4 growth by polymerisation mechanism

on the mechanism of chain growth s~?9'5"/61/002/005/023/027
E040/E185
There are 4 figures, 2 schemes and 20 references: 11 Soviet-bloc
and 9 non-Soviet-bloc. The four most recent English language
references read as followss
Ref.12: E.J. Gibson, Chem. and Ind., 649, 1957.
Ref.15s G. Blyholder, P.H. Emmett,
J.Phys.Chem.~ v.63, 962, 19.59.
Ref.17s G. Blyholder, P.H. Emmett,
J.Phys.Chem., v.64, 470, 196o.
Ref.18t W.K. Hall, R.J. Cokes, P.H. Emmett,
J.Amer.Chem.Soc., v.82, 1027, lg6o.
ASSOCIATIONs Institut neftekhimicheskogo sinteza AN SSSR
(Institute of Petrochemical Synthesis, AS USSR)
Card 4/4

z/oll/62/019/001/012/017
E073/E136
AUTHORS:
TITLE;
Kamzolkin, V.V., and BWUj4vnv-_A,N.
Preparation of higher glycols by oxidation of
paraffinic hydrocarbons in the liquid phase
PERIODICALt Chemie a chemickA technologie. Prehled technicke' a
hospodAfskA literatury, v.19, no,l, 1962, 34,
abstract Ch 62-473. (Neftekhimiya, v.1, no.3, 1961,
411-417)
TEXT: The experimental results indicate that during oxidation
of paraffin hydrocarbons in the liquid phase in the presence of
boric acid, secondary oxidation occurs of monofunctional oxygen
compounds to multifunctional. During oxidation of eaters by
means
of acetic acid the proportion of hydroxyl, carbonyl and multi-
functional ester groups increases, which leads to the same
conclusion. In the presence of acetic anhydride, the described
method permits the preparation of glycol eaters in addition to
keto-alcohols.
I figure, 4 tables, 7 references.
[Abstractor-s note: Complete translation.]
Card 1/1

KAMWLKINt V.V.; BASHKIROVp A.N.; SONDVAI N.M.; MARTYNESs
M.; ANDREYEVAv T.P.
Transformations of higher aliphatic aloohols during their
34quid phas oxidation. Neftekhimiia 1 no.5:675482 S-0
161.
(MIRA 15s2)
1. Inotitut neftakhimichaskogo sinteza, AN SSSR.
(Ald0hols)(Oxidation)

ROZOVSKIY, A.Ya.; IROV, A.N.j KAGAN, Yu.B.;
POKROVSKAYA, Ye.G.
Water and water vapor oxidation of the iron
catalysts for
synthesis from CO and H2. Kin.i kat. 2 no.6.830-637
N-D 161.
(MIRA 14:12)
1. Institut neftekbimicheakogo sinteza AN SSSR.
(Carbon monoxide)
(Hydrogen) (Catalysts.. Iron)

ZAKRAMM,t LIZ.; KOlWVAj V.V..- MMOLIKINp V-V-; SOKOVAt X-M-;
ANDIMYEVA,, T.P.,-AQJKP~IDVA.~N.
Preparation of w-dodecalactam from 1.,5,,9-cyclododecatriens.
Neftekbimla 2 nool:106-109 la-F 862. (NMU l5s5)
1. Institut elementoorganicheakikh soyedinoniy AN SWR.
(Lactams) (Cyolododsoatrione)

UMER) G6Aj- BLIHKPOV, AN. LM GUAX-YUX [IA Kuang-A];
LESIK,, Ok,;
EEZ I&M.V N.N.; KAGAN, Yu.B.
Method of analyzing producto of reaction between
aliphatic
alcohole and al]WI amines, NertekbInIa 2 nool:121-226
Ja-F
162. 1 OM 15:5)
1. Institut neftekbimicheskogo sinteza AN SWR.
(Alcohol;) (Amines)

--------- --- ------ - ---- --
TAGAWj-Yu.B.;,WIIKIROV, A.N.; KLIGER., G.A. 1 ROZOVSKIY, A.Ya.
Certain problems involved in the microkinetics of amination of
alcoholq on fused iron catalysts. Neftekhimiia 2 no.2:253-,2-56
Mr-Ap 162. (MM 15:6)
I* Institut neftekhimicheakogo ainteza All SSSR~
(Alcohols) (Amination)

KLIGER, G.A.; BASHKIJMV,-A.N.; LYMMAN-YUY (Ui Kuang-y;il; KWAN, Yu.B.
Effect of-ths.struietw*6 and,molecular weight of initial compounds
on the interaction of aliphatic alcohols with primary alkyl
amines, Neftekhimiia, 2 no.3:384-390 Yw-Je 162. (MbRA 15:8)
1. Inatitut neftakhimiahaskogo sinteza AN SSSR.
(Alcohols) (Amines)

KAGANi Yu.B.; BASHKIROV, A.N.; KLIGER, G.A.; LYUY GUAN-YUY [Mi
Kuang-yU]
Synthesis of-secondary alkyl amines from aliphatic alcohols
and primary amineo. Neftekbimiia 2 no.3091-397 Yq-Je '62.
(RIRA 15:8)
1. Institut neftekhimicheakogo sintesa AN SSSR.
(Aminea) (Alcohols)

XAMZMXIN V.V.; Bjfk~~v NAO Y%Vep LODZIX, S.A*
Certain lave governing the liquid-phase oxidation of olefinB.
Neftek&miia 2 no.5050455 S-0 162. (KMA 16%1)
1. Institut neftekbildc-h--eskogo sinteza AN SSSR.
(Olefins) (Oxidation)

ROZOVBKIY., A.Ya.,- BIRYUKOVICHO H.K.j ITA)IOV, A.A.j LIMOV, L.G.;
BUTYUGIN, V.K.; UGAN, Yu.B.; IRYUKOV, Yu.B.; BASHKEOV, A.N.
I-----------
Mechanism of the oarbide-forming reaction of fused iron
catalysts for synthesis from CO apd H2, -Neftekhimiia
3 nools97-103 44 163, (MMA 16t2)
(Iron catalysts) (Iron carbides)
(Chemistry, Organic-Synthesis)

KRYUKOV.. Yu.B.; SMRNOVA, R.M. VAZZNEVt V.I.; KAHZOLKIN, V.V.;
BASHKIROV
Intermediate stages in the liquid phase oxidation of secondary.
alcohols to ketones. lleftekhimiia 3 no.2t238-245 Mr-AP( 163-
XM 16'5)
1. Institut neftekhimicheakogo sinteza AN SSM imeni A.V.Topddyeva.
(Alcohols) (Oxidation) (Ketones)

ROZOVSXIY# A.Ya*j IVANOV, A.A.; UGAN.. Yu.B.;_ BASHKMV, A.M.
Kinetics of reactions involving the solid phase, Part 2: Hydrogenation
of iron carbides. Kin.i kat. 4 no,,1&97-108 Ja-F 163. (MM 16&3)
19 Institut, nof tokhimioheukogo uIntesa AN 83SR i Institut tonkoy
kbimichaskoy tekbnologit imeni H.V.1,omonooova,
(Iron carbides) (Hydrogenation)

RMOVSKIYj A.ra.1 BIRYUKOVICHO MMO; IVANOVp A,Aol
KAGAN,, Yu,B,;
BAS __
Kinetics of reactions involving the solid phase.
Part 3:
Carbide formation in fused iron catalysts
induced by carbon
monoxide. Kin* i kat. 4 no,3:313-381 Yq-Je 163.
(MMA 16:7)
1. Institut nefteldhinic skogo sintess. AN SSSR.
Carbides) (Iron catalysts)
temical reaction, Rate of)

S
120/63/148/006/014/023
/C
B117/BI86
AUTHORS i Bashkirov". N., Corresponding Member AS USSR,
--S Kaykhutdinovp Ye.. U., Gilyarovskayap L. A.
(PITLE& Oxidation-of monomethylsubstituted paraffins in liquid phase
in the presence'of borio acid
PERIODICALi Akademiya nauk SSSR. Dokladyj v. 148 1311
no. 6, 1963, 1309
TEXT: The effeot-of the tertiary-oarbon-atom on the conversion of mono-
substituted-paraffins during oxidation and on the composition of the
alcohols formed is studied.. For this purpose, 2-methyldodecane and
8-methylpentadecano-were synthetized according to Grignard's method.
These
hydrocarbons were oxidized in-an apparatus described previously
(A. N. Bashkirovp Xhim. nauka i prom.p 11 273 (1956)) under normal
pressure
at 165 - 1700C for 3 - 4 hre, using a mixture of nitrogen and oxygen
with
3.0 - 3.5% 0 (consumption 800 1/kg-hr). The main conversion products
were
compounds coitaining hydroxyl with a yield of oj75 mole%. The alcohols
formed were identified as a mixture of tertiary (cj25 - 30 mole%) and
secondary alcohols having the same carbon skeleton and the same number
of
C-atome in the molecule as the original hydrocarbon. The secondary
Card 1/2

/63/148/006/014/0?3
S/020
Oxidation of monomethylsubst it ut ed... B117/B186
alcohols proved to be*a,mixture of a variety of isomers. Hence it was.
assumed thats under the oxidation conditions described, the tertiary
C-atoms are more reactive with respect to oxygen than the Be6ondary
C-atoms'
of the highest monosubstituted paraffin molecules. There are 3 tables.
ASSOCIATIONi Institut neftekhimioheskogo sinteza Akademii nauk SSSR
(Institute of Petrochemical Synthesis of the Academy of
Sciences USSR); Moskovskiy ii4stitut tonkoy khimicheskoy
tekhmlogii im. M. V. Lomonosova (Moscow Institute of Fine
Chemical Technology imeni M. V. Lomonosov)
SUBUITTEDs
July 26j 1962

NEVOLIN, Fedor Vasillyevichl TYUTYUKNIKOV~ B.N., doktor tekbn. nauk,
prof.p retsenzent; BASHKIROV,_A.!!,p spets. red.; MOROZOVA,
I.I., red.
[Chemistry and technology of synthetic detergents) Khimiia i
tekhnologiia sinteticheskikh moiushchikh sredstv. Moskva,
Izd-vo "Pishchevaia pronyshlennostl," 1964. 362 p.
(MIRA 17:7)
1. Chlen-korrespondent AN SSSR (for Bashkirov).

ACCESSION NR; AP4024408 9/0204/64/004/001/010610110
AUTHOR: Kagan, - Yu# Bo; Bashkirav, A* No; KliXere 0. A*; Itup
MAAB-yu
TITIX: Synthesis of secondary alkylamines from carbon monoxide,
hydrogen and:
M
SOURCE: Nefteknimiya, v. 4. no. 1, 1964, 106-110
TOPIC TAGS; secondary alkylamins, synthesis, amination, process
condition,
reaction mechaaLsmp methylalkylemine
ABSTPACT: Continuing earlier work (Yuo B. Kagan, A* N* Baskirov,
G. A. Kliger,
Yu. L, Yermakovo Izvo. AN SSSRP Otd, khLme n. (1959), 1345), the
inteiraction of
GO$ H2 and methylamine to form secondary alkylamines was studied*
Using a fused I
iron cataly3 t, the optimum synthesis conditions are 100-140
atmospheres pressurep
1250 hours-,, volume flow of the initial gas mixture, a
temperature of 168-175 C,
and an R2:CO:CH3NHZ ratio of 4:1:1925o The yield of secondary
amines was 77-78o5.
mol.%. The product also contained small amounts of alcohols and
carbonyl com-
pounds, indicating the synthesis probably proceeded In two
stages; (1) the
formation of the oxygen-containing compounds from CO and %g (2)
followad'by
i!:G.rd 1/2

ACCESSION NR.- AP4024408
their amination with methylamins, The ami6ted products are 5-20 carbon
atom
methylalkylamines of normal structure. Synthesis of secondary amineo
by this
method was realized for the first times Orige arts bast 6 tableas
ASSOCTATION; Inatitut uaftakhimichookoso sinteza AN MR ime As Vs
Topchiyeva
(Institute of Petrochemical Synthesis,,AN SSSR)
SUBMITTED: O3Hay63 DATE ACQ: 17Apr" MMt '00
SUB CODE: NO RV SOVt 007 OnMRI 008"~*-~~
Card 2/2

LOKTEV, Sergey Minovich; BASHKIR07,_A,N. otv red.
7-
[Higher aliphatic alcohols) Vysshie zhirnya lqpirty. Mo-
skvaj Nauka, 1964. 165 p, (MIRA 17:10)
1. Chlen-korrespondent AN SSSR (for Bashk-irov).

KAMZOIXIN, V.V.; BASHMOVo A,N.; SOKOVAO K.M.; ANDREYEVA, T.P.
By-products of the liquid-phaeo oxidation of cyclododeeme with
molecular oxygen in the presence of boric acid. Neftekh'mii!~
4 no.lt96-j99 J&-F'64 WRA 17&61
1. Institub neftekhimicheokogo sinteza AN SSSR imeni A.V.
Topchiyeva.

M-T-dA., G.A*; LYUY.GUAN-M
Synthesis of secondary alkylamines from carbon monoxidep hydrogen..
and methylamine, Neftekhimiia 1+ no.ltIO6-110 Ja-FI64
(MIRA 17 t6)
1. Institut neftelchimicheskogo sinteza AN SSSR Imeni Me
Topohiyeva.

ROZOVSKIY, A. Ta.; BIRIUKOVICH~ H.M.; rVANOV, A.Aq KAGAN, Yu.B.;
ftetics and mechanism of the carbidizing treatment of iron
catalysts for synthesis from CO and IL
,,. Neftekhimiia. 4 no.2t
269-.Z74 Mr-AP"64 (MIRA 1798)
lo Institut neftekhimichaskogo sinteza. AN SWR imeni Topchiym.

'ILKIV, vv.
ObtainLng higher ketorei by the d6~y3rogm,--Llon or secondary
alcohols over nopper-:hr-omium ri-n-d nl2hel-chrlcmium ca+nl -.t9.
NeftekhlmiJa 4 no.2t29F-X,;-) Mr-Ap'64 (I-r: RA 17:8)
1. Institut nertekhIralch(rkogo rinteze. IN imeni A.V. Topchi-
yevue

NOVAK, F.I.;.KAMZOLKY-N, V.V.; BASHKIROV, A.N.
Catalytic activity of the natural silicates of minerals in the
synthesis of hydrocarbons from carbon monoxide and hydrogen.
Neftakhimia 4 n0-3:447-451 Yq-Je 164. (MIRA 1812)
1, Institut, neftekhimicheskogo sinteza AN SSSR im. A.V.Topchiyeva.

ALENTIYEVAp Ye.S.
Liquid-phase oxidation of alkyl bonzenes in the prenenne of esterifyin
agonta. Neftekhimia. 4 no.4:593-598 JI-Ag 164. (MIRA 17: Of
1. Moskovakiy institut tonkoy khimicheskoy tekhnologii im. M.V.
Lonenosova i Institut neftekhimichoskogo sinteza im. A.V. Topchlyeva.
Ali SSSR.

BASHKIROVI-AIIN.; GILYAROVSKIY, L.A.; AISUTIYEVAj Ye.O'.-,
KOZLENKOVAt R.V..*
--RROGHKTNA, A.K.
Effect or aromatic hydrocarbons on Lho oxidation of paraffins in the
liquid phase in the prosence of boric acids Neftekbimila 4 no65077-
779 3-0 164, (MIRA 180)
1, Moskovakty Institut tonkay khimicheekoy tekhnologii iment M*VO
Lomonosova. i Inatitut nertakhImicheakogo ainteza, Imeni
kA.T.3pahiYova
AN SSSR.

L 16673-65 E-T.- ilml ilrPrfe- I f i I /-r /=-,m i +I
/,,r iL, i . - - , - - -... )- - - - I . I

!,
. , . . . I

IA'i-W ttE~ dMANEW -f4

i-z A, V, Topchlvf~va, AN SSSR