SCIENTIFIC ABSTRACT BELSKIY, I. F. - BELSKIY, I. F.

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• Collection: Scientific Abstracts
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• Sequence Number: 9
• Publication Date: December 31, 1967
• Content Type: SCIENCEAB

BOV/ 20-!?0-3-31/67
f2omeric Transformation of y-Uxi4es (Tetrahyd-rofuranes) of Aliphatic Carbonyl
Compounds
There are 2 tables and 7 references, 2 of which are Soviet,
AS11OCIATION: Inatitut organicheekoy khi,-.ii im. Ho Do Zelinskogo olkademii
nauk fiSSR
(Jnstitute of Organic Chemistry Imeni N. Do ZelineklY AS USS)R)
SUBMITTEP: January 11, 1958
1. Furan derivativea--Isomerism. 2. Aliphatic compounds--Chemical
reactions 3. Carbonyls--Chemical reactions.
Card 3/3

AUTHORS: Shuykin, N. I., Corresponding Member's SOV/20-122.-4-24/57
Academy of Sciences, USSR, Bellskiy, 1. F.,
Karakhanov, R. A. e
TITLE: On the Reaction Mechanism of the Furane Cycle Catalytic
Hydrogenolysis (0 mekhanizme reaktsii kataliticheskogo
gidrogenoliza furanovogo tsikla)
PERIODICALg Doklady Akademii nauk SSSR, 1958, Vol 122, Nr 4, pp 625 -
628 (USSR)
ABSTRACTs The problem whether the reaction mentioned in the title
passes the hydration stage of double bonds of the cycle,
i.e. with a subsequent cleavage of the formed tetra-
hydrofurane cycle at one of the C-0-bonds, was raised
several times. This problem was rejected by several scien-
tists (Refs 1 - 5). It was proved that the tetra-hydro-
furane-cycle does not hydrogenolyze at all under the condi-
tions of the hydration in the liquid phase, whereas the
iurane cycle hydrogenolyzes to a great extent. The authors
proved recently (Ref 6) that the homologs of tetia-hydro-
furane can be isomerized on Rt-coal at 250 - 300 in
Card 1/3 aliphatic ketones. However, this reaction passes much more

On the Reaction Mechanism of the Furane Cyolb BOV/20-122-4-24/57
Catalytic Hydrogenolysis
slowly than an immediate hydroger-olysis of the alkyl furanes
themselves under the same conditions. Therefore, the tetra-
hydrofuranea cannot be considered to be intermediate products
in the hydrogenolysis reaction of the furane-compounds. All
mentioned investigations led thus to the conclusion that the
hydrogenolysis of the C-0-bond may take place either in the
cycle of furane itself or in the dihydrofurane cycle. The
formation of the latter as an intermediate product is con-
firmed by the transformation of silvane into r-acetone-
propylalcohol in the presence of water (Ref 7). In the
present paper the authors investigated the hydration of the
dihydrosilvane in the gaseous phase_on p~atinized charcoal
and on nickel to zinc oxide at 250 260 . Thus it was
proved that not the hydrogenolysis of the C-0-bondv but the
hydration of the C-C-bond in the cycle is the main reaction.
The formation of methyl-propylketone in the hydration of the
dihydrosilvane on Pt-C may take place in consequence of a
secondary isomerization reaction of tetra-hydrosilvane.
Tetra-hydrosilvane is not isomerized to methyl-propylketone
Card 2/3 on Ni-ZnO. The above results are interpreted differently

On the Reaction Mechanism of the Furane Cycle SOT/20-122-4-24/57
Catalytic Hydrogenolysis
by the authors. There are 13 references, 3 of which are
Soviet.
ASSOCIATIONt Institut organicheskoy khimii im. N. D. Zelinskogo Akademii
nauk SSSR (Institute of Organic Chemistry Imeni
N. D. Zelinskiy2AS USSR)
SUBMITTEDi June 20, 1958
Card 3/3

AUTHCHS: Shuykin, N. I., Bel'skily, I. F. SOV/79-29-2-19/71
TITLE: Hydrogenation of Furane Compounds Over the Ni-ZnO Catalyst
(Gidrirovaniye furanovykh soyedineniy na Ni-ZnO-katalizatore)
PERIOXCALt Zhurnal obahchey khimii, 1959, Vol 29, Nr 2, PP 442-445 (USSR)
ABSTRJiCT: Investigations carried out by Shuykin and other chemists (Refs 1.
5) show that tl,.e properties of nickel catalysts are considerably
dependent on the nature of the carrier. This is confirmed by the
present investigation. The authors found that nickel stored upon
ZnO hydrogenates the double bond in the side chain of a-alkenyl
furane under conditions of hyd--ogenatioD in the vapor phase or)
at higher tempexatures, it allows hydrogenolysis of the furane
cycle to take place only on the bond C-0, which is not close to
the alkyl radical. This catalyst does not have the function of
hydrogenating the double bonds in the furane cycle in the vapor
phase. Thus, for example, silvane, that had been left over the
above catalyst at 140 , was not transformed. Under the same
conditions, a-propenyl furane was hydrated almost quantitatively
into a-propyl furane:
Card 1/2

SOY/79-29-2-19/71
Hydrogenation of Furane Compounda Over the Ri-ZnO Catalyst
CH == CHCh H21 K' CH2CH2 CH
3 1400 3'
0 0
The0hydrogenation of Bilvane, of a-ethyl and a-propyl faranes at
250 led to the complete cleavage of the cycle at the C-0 bond
1-5 and, correspondingly, to the formation of pentanone-2,
hexanone-3 and heptanone-4 (up to gr-% yield) (Scheme 2)~ Thus,
depending on temperature, the Ki-ZnO catalyst hydrogenates the
olefin bond in the side chain of the alkenyl furanea in the
selectiwe ay, or it may allow hydrogenolysis of the furane cycle
at the C-0 bond, which is not close to the alkyl radical,, In the
latter case, ec-reeponding aliphatic ketones in y'Lelds up to
95% form at 250 b~ There are I table and 10 references, 5 of
which are Soviet.
ASSOCIATION: Institut organ-icheskoy khimii Akademii nauk SSSR (Institute of
Organic Chemis-try of the Academy of Sciences, USSR)
SUBMITTED: November 28, 1957
Card 2/2

5 (3) SOV/79-29-3-25/61
AUTHORS: Shuykin, N. I., Bel'skly, 1. F.j Savekina, 0. N.
TITLE: Hydrogenation of Silvan on Nickel Catalysts in the Liquid Phase
(Gidrirovaniye sillvana n& nikelevykh katalizatorakh v zhid-
koy faze)
PERIODICAL: Zhurnal obshchey khimii, 1959, ~01 29,-Ar 3P pp 869-874 (USSR)
.ABSTRACT: In the present paper the authors investigated the hydrogenation
capability of the skeleton-Ni-Al- and -Ni-ZnO-catalyst in the
liquid phase to determine the influence of the phase conditions
in carrying out the reaction upon the hydrogenation of the
furan ring. The experimental data obtained were compared with
the rules which were earlier -found by the authors on hydro-
genation of the furan homologues on the same catalysts intthe
vapor phase. These data led to the conclusion that the hyd--O-
genation of the furan ring can proceed on one and the same
catal5a~ in different directions, according to the reaction in
the liquid or vapor phaseh Silvan-and a-propenyl furan were
hydrogenated in-the autoclave at 120-1500 under a hydrogen
pressure of 50-150 atmo heres excess pressure on the skeleton-
Ni-Al-catalyst. The pri"
Card 1/3 ntipal reaction products were, accord-

SOV/79-29-3-25/61
Hydrogenation of Silvan on Nickel Catalysts.in the Liquid Phase
ingly, tetrahydrosilvan and a-propyltetrahydrofuran (65-95~)-
on this hydrogenation of silvan in addition to tetrahydrosilvan
(90%) the pentanediol-1~4 is formed, in which connection a
certain part.of the silvan molecule is.subject to cleavage,
forming H20 and high-molecular compounds. Under the above re-
action conditions, but on addition of water, about the same
quantities of tetrahydrosilvan and pentanediol-1,4 are formed
as well as about 7% of butanol-2 and pentanol-2 which are
products of hydrogenolysis of the ring. The hydrogenolysis of
the furan ring in silvan on hydrogenation on the skeleton-
nickel-catalyst at 120-1500 in the liquid phase proceeds
similarly as in the vapor phase, i.e. on the C-0-bond 1-5 and
on the bonds 1-5 and 4-5, yielding pentanol-2 and butanol-2~
accordingly. The nickel on the ZnO is capable of hydrogenating
the double bonds in the furan ring in the liquid phase at
200-2500, as contrasted with the vapor phase. Here, hydro-
genolysis of the ring takes place only on the C-0-bond 1-5
yielding pentanone-2 as Principal product which is not the
case on the other catalysts. Thus the direction of the hydro-
Card 2/3 genation of the furan ring depends on the nature of the catalyst

SOV/79-29-3-25/61
Hydrogenation of Silvan on Nickel Catalysts In the Liquid Phase
and on the phase conditions of the reaction* There are 1 table
and 9 references, 7 of which are Soviet.
ASSOCIATION: Institut organicheskoy khimii Akademii nauk SSSR (Institute of
Organic Chemistry of the Academy of Sciencesp USSR)
SUBMITTED: December 20,-1957
Card 3/3

-,If ( 3 )
AUTHORS: Shuykin, ff. I.,- Pel'skiy I F SOV/79-29-3-26/61
TITLE: Catalytic Reduction of the Phenyl Carbinols in Aromatic
Hydrocarbons (Kataliticheakoye voestanovleniye fenilkarbinolov
v aromatichaskiye uglevodorody)
PERIODICAL: Zhurnal obahchey khimii, 1959, Vol 29, Nr 3, PP 875-077 (USSR)
ABSTRACT: If R in the compounds of the R-CH-Alk type represents an
OH
alkyly no reduction of the hydroxyl group takes place on the
catalysts Pd-C and Ni-ZnOj but more or less a dehydrogenation
of the alcohol into the ketone, The question was of which
chemical nature R should be, in order that an activated hydro-
gen could be substituted for the hydroxyl group by the cata-
lytic method. The results of the investigations reported in
the present paper show that with R-C6H 5? using the catalysts
Pt-C, Pd-C, Ni-ZnO and skeleton-Ili-Al, at 250 0 in the vapor
phase a reduction of the hydroxyl group and a transformation
of the phenyl carbinols into the aromatic hydrocarbons take
place. Thus, e.g. ethyl phenyl carbinol is reduced at 250 0
in the vapor phase on all catalysts used to propyl benzene
Card 1/3 (yield 88-95%). On the Ni-Al"catalyst in addition to proiyl

SOV/79-29-3-26/61
Catalytic Reduction of the Phenyl Carbinols in Aromatic Hydrocarbons
benzil benzene (3~) and toluene (A are formad, owing to
the hydrolysis process of the C-C-bonds in the side chains.
The dehydrogenation of ethyl phenyl carbinol to the correspond-
ing ketone takes place only to a small extent:
_CH2CH2CH 3+$o
CH-CH2CH H 86-
1 3 2
0
Un - Pt,Pd,Ni CH2CH3+H2
'The catalytic reduction of benzene alcohol proceeds under the
same conditions yielding toluene and dehydrogenation to benz-
0
aldehyde which is readily decarbonylated into benzene at 250
The aliphatic alcohols (pentanol-2 and heptanol-1) are not
reduced on the platinum and nickel catalyst, but, accordingly,
dehydroGenated to give pentanone-2 and heptanall with the lat-
ter being decarbonylated to n.-hexane (scheme 2). There are
Card 2/3 1 table and I Soviet reference.

SOV/79-29-3-26/61
Catalytic Reduction of the Phenyl Carbinols in Aromatic Hydrocarbons
ASSOCIATION: Institut organicheskoy khimii Akademii nauk SSSR
(Institute of Organic Chemistry of the Academy of Sciences,
~ USSR)
SUBMITTED: December 2o, 1957
Card 3/3

50) SOV/79-29-4-10/77
AUTHORS: Shuykin, N. I., Bellskiy, I. F.
TITLE; Hydrogenation of Furan Compounds on Platinum and Rhodium
Catalyste(Gidrirovaniye furanovykh soyedineniy na platinovom i
rodiyevom katalizatorakh)
PERIODICAL: Zhurnal obshchey khimii, 1959, Vol 29, Nr 4, PP 1093-1096 (USSR)
ABSTRACT; The hydrogenation results of furan compounds in the presence of
catalysts containing metals of the group VIII of the periodic
system lead to the conclusion that some of them are active pre-
dominantly in the hydrogenolyS18 Of the double bond in the furan
ring, and othezedevelop, a high activity in the hydrogenolysis
of the ether bonds of the furan ring. As regards the action of
the catalysts also the phases and temperatures play an important
part in one and the same catalyst. Many examples are presented
for this fact which underline that in general the comparison data
on the properties of the catalysts can only be obtained under
certain standard conditions during the reaction. For this reason
the hydrogenation of-silvan and a-vinyl furan on rhodium
dep8sited on active charcoal in the vapor phase at 150, 200, and
Card 1/3 300 was investigated. For comparison purposes also the hydro-

BOV/79-29-4-10/77
Hydrogenation of Furan Compounds on the Platinum- and Rhodium Catalyst
genation of silvan and a-propenyl furan on platinated charcoal
in the vapor phase at 150 0 was carried out. On the rhodium
catalyst at 150 the furan. ring hydrogenates very slowly which
makes it possible to reduce the olefin bond in the side chain,
maintaining the double bonds in the ring. a-vinyl furan is
transformed at this temperature into a-ethyl furan (94 yield)
(Scheme 1). The hydrogenation of silvan on Rh-C at 200 yields a
mixture of tetrahydrosilvan (40%) and pentanone-2 (60%); at
3000 only pentanone-2 is found in the hydrogenation products
(Scheme 2). Similar results are offered by the hydrogenation
products of both compounds on Pt-C at 1500, The Pd-C catalyst is
found to be a specific catalyst of the hydrogenolysis of double
bonds in the furan ring during the hydrogenation in the vapor
phase (140-275*1). The Pt-C catalyst proved to be a specific
catalyst of the hydrogenolysis of the furan ring on the
C-0-bond 1-5 under the given conditions. The effect of theo
Rh-S catalyst is equal to that of the Ft-C catalyst at 300 ; at
200 it assumes an intermediary position between Pd-C and Pt-C
as far as its properties are concerned. There are I table and
Card 2/3 7 references, 6 of which are Soviet.

SOV/79-29-4-10/77
Hydrogenation of Puran Compounds on the Platinum- and Rhodium Catalyst
ASSOCIATION: Institut organicheskoy khimii Akademii nauk SSSR (institute Of
Organic Chemistry of the Academy of Sciences, USSR)
SUBMITTED: March 6, '958
Card 3/3

50)
AUTHORSs Shuykin, N. I., Bel'skiy, 1. P. SOV/79-29-4-11/77
TITLEt Catalytic Reduction of 2-Methyl-5-acetyl Puran
Into 241ethyl-5-ethyl Furan (Kataliticheakoye
vosetanovleniye 2-metil-5-atsetilfurana v 2-metil-5-etilfuran)
PERIODICALt Zhurnal obehchey ~chimiij 1959P Vol 29p Nr 4, pp 1096-1099
(USSR)
ABSTRACT: In addition to the reports of some chemists (Refs I - 6)
on the part played by various catalysts under different
conditions in the hydrogenation of furan ketones the authors
investigated inthe present paper the hydrogenation of
2-methyl-5-acetyl furan in the vapor phase at 2500 on the
catalysts Ni-ZnO, Ni-CdO and Pd-C. As was already earlier
shown by the authors (Ref 7), on the hydrogenation of alkyl
furyl carbinols on Pd-C and Ni-ZnO first the reduction of
the hy1roxyl group takes place, under forming the corresponding
alkyl furanes H
-CH-R :t -OR R + R 0
k. I I CfNi-zno 2 2
Card 1/3 OH

Catalytic Reduction of 2-kethyl-5-acetYl Furan BOV/79-29-4-11/77
Into 2-MethYl-5-dthyl Furan
,As was to be expected, on the hydrogenation of the
2-meth7l-5-aoetyl furan the resulting methyl-(5-mothylfuryl)-
carbinol on Ni-ZnO and Ni-CdO in the vapor phase at 2500
was subject to a further reduction into the 2-metbyl-5-ethYl
furan (Scheme 2), in contrast with the Pd-C catalyst nearly
ineffective as regards the reduction of the carbonyl group
and the hydrogenolysis of the furan ring into the
2-methYl-5-acetyl furan. As aide reaction on the hydrogenation
of the 2-methyl-5-acetyl furan on Ni-ZnO the hyctrogenolysis
of the ring takes placep thus yielding heptanone-2, which
is scarcely,the case on Ni-CdO (Scheme 3). The definite
solution of this problem requires further investigations.
The direct catalytic reduction of alkyl furyl ketones into
alkyl furans mV be of preparative importance since it is
more convenient than the method of Kizhner (Ref 8) by way
of the hydrazones, with subsequent reduction of these
intermediate products. There are 9 references, 4 of which
are Soviet.
Card 2/3

Catalytic Reduction of 2-Mothyl-5-acetyl Furan SOV/79-29-4-11/77
into 2-Methyl-5-ethyl Furan
ASSOCIATIONj Institut organicheskoy khimii Akademii nauk SSSR
(Institute of Organic Chemistry of the Academy of Sciences,
USSR)
SUBMITTED: March 6, 1958
Card 3/3

50) SOV/79-29-6-23/72
AUTHORS: Shuykin, Y. I., Bel'skiy, I. F., Grushko, I. Ye.
TITLE: On the Reaction of Tetrahydrofuran With Halogen Silanes (0 vzai-
modeystvii tetragidrofurana s galoidsilanami)
PERIODICAL: Zhurnal obshchey khimii, 1959, Vol 29, Nr 6,
pp 1882 - 1885 (USSR)
ABSTRACT: From among all organic oxides those chemical transformations
of the ethylene oxides are investigated most thoroughly, which
yield the aliphatic compounds with reactive groups by the ready
opening of the a-oxide ring under the influence of various
agents. Par less investigated are the chemical transformations
of the oxides of tetrahydrofuran and its homologs. They possess
a consAerably lower reactivity and are of great importance for
the organic synthesis since they can yield the 1,4-bifunctional
derivatives of the aliphatic setiest the dihalogen-alkanes, di-
glycolst hhlogen-hydrinal.besides the totrahydrofuran
derivatives are a sufficiently accessible and cheap material. In
the present paper the reaction of tetrahydrofuran with alkyl-
and aryl-chloro-silanes with two or three chlorine atoms in the
Card 1/2 molecule was investigated. It takes place only in the presence

On the Reaction of Tatrahydrofuran With Halogen Silanes SOV/79-29-6-23/72
of anhydrous zinc (II) chloride in different directions according
to the number of chlorine atoms in the chloro silane molecule.
Methyl-dichloro-silane and ditaethyl-dichloro-silane split up
the tetrahydrofuran ring at both C-0 bonds with 1,4-dichloro-
butane being formed as main product (Scheme 1). In contrast to
the dichloro-silanes the reaction of tetrahydrofuran with alkyl
and aryl-trichloro-silanes takes place with ring opening only
at one C-0-bond and yields the chlorine-substituted ester of the
ortho-silioic acid (Scheme 2). In all cases the yields in
mono-(6-chloro-butoxy)-dichloro-silanes are very high (8o-9o%)
Two chlorine atoms in the molecule of the mono (6-chlorobutoxy;_
dichloro-silane are activej but react mainly under forzation of
1,4-dichloro-butane (Scheme 3). An interpretation of this reaction
is suggested. The compounds synthesized are listed in two tables.
There are 2 tables and 11 references, I of which is Soviet.
ASSOCIATION: Institut organicheskoy khimii Akademii nauk SSSR (Institute of
Organic Chemistry of the Academy of Sciences, USSR)
SUBMITTEDt April 18, 1958
Card 2/2

50) SOV179-29-649181,
AUTHORSs Shuykin, N. I., Bel'skiy, 1. F., Grushko, I. Ye.
TITLE: On the Reaction of TetrahydrosylvareWith Silicon Tetrachloride.
PLRIODICAL: Zhurnal obshchey khimii, 1959, Vol 29,' Nr 8,
pp 2591 - 2594 (USSR)
ABSTRACTt In the present paper, the authors investigated the reaction
of tetrahydrosylvane with silicon tetrachloride, This reactior,
takes place only in the presence of anhydrous zinc chloride.
The reaction products underwent an intense decomposition in
the vacuum distillation. For this reason, they were previously
subjected to a hydrolysis with water. The products of this
hydrolysis had to be fractionated at reduced pressare with a
column top section* In this connection, the 1,4-dichloro-
pentane (15-2o%) and the chlorine-substituted amyl alcohol
(70-80%) were separated, the latter of which was likewise ob-
tained on hydrolysis of the chlorine esters of silicic acid
(Scheme 1). Depending on the cleavaEe of the C-0 bond in posi-
tion 1-2 or 1-5, the alcohol can be formed with a primarily
Card 1/2 (1) or secondarily (II) bound hydroxyl group (4-chloro-pen-

On the Reaction of Tetrahydrosylvane With Silicon SOV/79-29-8-29/81
Tetrachloride
tanol-1 or 5-chloro-pentanol-2). The structure of the chloro-
hydrin obtained by hydrolysis was confirmed according to the
transformations of scheme 2, The reducing dehalogenation of
2-chloro-5-acetoxy-pentane (III) on platinized carbon in the
vapor phase proceeds smoothly and with high yields (95a/,) at
the primary amyl acetate (IV). The chlorohydrin obtained by.
hydrolysis of the reaction products of tetrahydrosylvane with
Sicl4 thus represents the 4-ohloro-pentanol-1. This means that
the ring in the tetrahydrosylvane is cleft at the C-0 bond
adjoining the methyl group, under the influence of SiCl 4# There
are lo references, 4 of which are Soviet.
ASSOCIATIONi Institut organicheskoy khimii Akademii nauk SSSR (Institute
of Organic Chemistry of the Academy of Sciences, USSR)
SUBMITTED: July 4, 1958
Card 2/2

3(5) SOV/79-29-9-34/76
AUTHORS: Shuykin, N. I., Bellakiy, I. F., Minachev, Kh. M.
TITLE: Hydrogenation of the-Furan Compounds by Means of Metals.
VIII. Groups of the Periodic System
PERIODICAL: Zhurnal obahchey khimii, 1959, Vol 29, Nr 9, pp 2969-2973 (USSR)
ABSTRACT: Owing to the results of previous investigations (Refs 1-5) the
problem arose which of the metals of group VIII are like pal-
ladium, capable of bringing about the catalytic hydrogenation of
the furan cycle in a wide temperature range, and which of them
are the most active ones. The catalytic properties of oemium,
iridium, and ruthenium, applied to carbon, were investigated in
the hydrogenation of silvane and a-vinyl furan in the vapor
phase and at various temperatures. a-Vinyl furan is hydrogenated
on all these catalysts at 1500 into a-ethyl furan in yields of
95-100% (Scheme 1). On Ir-C and Ru-C a small portion (-5%) of
a-ethyl furan formed is subjected to hydrogenolySiB on the
C-0 bond 1-5 (Scheme 2). Hydrogenation of silvane on Os-C, Ir-C,
Ru-C at,higher temperatures shows that these catalysts are not
able to reduce the furan cycle, but are only capable of
Card 1/3 hydrogenolysis on the C-0 bond 1-5 under the formation of the

SOY/73-29-9-34/T6
Hydrogenation of the Furan Compounds by Means of Metals. VIII. Groups of the
Periodic System
methylpropyl ketone (Scheme 3). The results of this paper as
well as those already previously obtained permit to draw some
general conclusions. All catalysts containing metals of
group VIII, applied to carbon could be in hydrogeqation oonditio
ally. divided in the vapor phase under comparable temperature
conditions into two groups, depending on their effect upon the
furan eyelet 1) The catalysts of the platinum type (Pt, Os, Ir,
Ru, Rh) show either a weak or practically no capability of
hydrogenation of the double bond in the furan cycle. On these
catalysts only hydrogenolysis 8f the furan cycle on the
C-0 bond 1-5 occurs at 200-300 - 2) The catalysts of the pal-
ladium type are in a sufficiently wide temperature range capable
of hydrogenating the double bond in the furan cycle. Hydro-
genolysis of this cycle occurs only at highe.- temperatures.
There are 7 Soviet references.
ASSOCIATION: Institut organicheskoy khimii Akademii nauk S33R (Institute of
Organic Chemistry of the Academy of Sciences, USSR)
Card 2/3

SOV/79-29-9-35/76
-7 4UTHORS: 9huykin, N. I.,,Bellakiyl I. P.
TITLE: On the Reaction of Propylene Oxide With Some Compounds Contain-
ing an Active Chlorine Atom
PERIODICAL; Zhurnal obehohey khimii, 1959, Vol 29, Nr 9, pp 2973-2975 (USSR)
ABSTRACT% The present paper dasoribes the investigation of the reaction'of
propylene oxide with AlCl,, TiCl 41 and PM 3' The two first
chlorides were previously (Ref 9) used in the reaction with
tetrahydrooilvane so that it was po3sible to compare their ef-
fecto upon a- and y-oxides. The reaction products of propylene
oxide with A101 TiCl , and decomposed in distillation
3', 4 PC13
already at reduced pressure; for this reason they were sub-
jected to hydrolysis. An analysis of the products yielded the
following resultst 1) The reaction with AICI
proceeds in a
3
similar way as the reaction of tetrahydrosilvane (Ref 9), i.e.
under the formation of 1,2-dichloro propane (Scheme 2). The
products of hydrolysis do not contain chlorohydrin. 2) PC1 3and
Card 1/3 TiCl
open propyleneoxide on the C-0-bond next to the methyl
4

SOV/79-29-9-35/76
On the Reaction of Propylene-Oxide With Some Compounds Containing an-Active
Chlorine Atom
.group, which leads to unstable chlorine-substituted esters of
phosphorous.- and titanic acid. Hydrolysis of these esters yields
70-85% 2-chloropropanol-1 (Scheme 3). In order to prove the
structure of the final product (chlorohydrin), the latter was
transformed into the acetate. which ~y reducing dehalogenation
in the vapor phase over Pt-C at 300 could be smoothly quanti-
tatively transformed into propyl acetate without difficulty
(Scheme 4)- This method of proving the structure of halohydrin
is more convenient than the usual oxidation method. Titanium
tetrachloride is known to cause a splitting of the y-oxide
cycle under elimination of the oxygen atom and formation of
1,4-dichloropentarie in the reaction with tetrahydrosilvane.
PCI3 and TiCl4 therefore have the same effectlupon the a-oxide
cycle as the other acid chlorides of inorganic acids, e.g.
AC1 3P Sici 49 etc. There are 11 references, 8 of which are Soviet.
ASSOCIATION: Institut organicheskoy khimii Akademii nauk SSSR (Institute of
Card 2/3 Organic Chemistry of the Academy of Sciences, USSR)

SHTYMN, N. 1.;-.1 RM ......
I I.- .-
Hydrogenation of furan compounds on skeletal catalysts. Doklo
AN SSM 125 no.2:343-347 Mr 159. (MIRA 12:4)
I
I* Chlen-korrespondent AN SSM (for Phuvidn). 2. Inatitut
orgLnichaskoy khimii imeni I.D.Zelinakogo AN SSSR.
(Puran) (Hydrogenation)

'50)
AUTHORSs Shuykin, N. I.,.Corresponding Member, BOV/20-125-5-27/61
AS USSR, B_ellakiy, I.-Yof Xarakhanov, R. A.
TITLE: Thermal Isomerization of 2-Methyl-4-5-dihydrofuran to
Methyl-cyclopropyl Ketone (Termicheskaya izomerizatsiya
2-metil-415 digidrofurana v metiltaiklopropilketon)
PERIODICAL; Doklady Akademii nauk SSSR, 1959, Vol 125, Nr 5,
PP 1051-1052 (USSR)
ABSTRACTs According to reference 1 2.3-dihydrofuran isomerizes at 375
to cyclopropane aldehyde. A small quantity of croton aldehyde
is formed therein, which is partially de,carbonylated to
propylene under the experimental conditions. The gas
development increases with rising temperature. The first
reaction is reversible. The inequivalence of the C-0 bonds
depends in the dihydrofuran, molecule only on the presence
of the double bond. This verj fact is bound to determine
the place of rupture of the dihydrofuran ring. Wilson (Ref 1)
assumed that 2-3-dihydrofuran behives in the aforeeaid
isomerization like simple.vinyl ethers. According to
Card 1/3 formal-structural coneider,~tions it is, however, clear that

Thermal Isomerization of 2-lethyl-4-5-dihydrofuran to SOV/20-125-5-27/61
Methyl-cyclopropyl Ketone
the formation of cyclopropane aldehyde in the rupture of
the dihydrofuran ring is possible at the C-0 bond 1.2 as
well as at the C-0 bond-1.5. Therefore the results of the
isomerization of the 2.3-dihydrofuran cannot indicate
definitely the place of rupture of the dihydrofuran ring.
In the case of the isomerization of (X-alkyl-dihydrofurans
two different producte - aldehyde or ketone - are bound to
be produced according to the C-0 bond which has been
ruptured. The authors tried to investigate the isomerization
of such M-alkyl-substituted 2.3-dihydrofurans mentioned in
the title, the alkyl group of which is found at the double
bond. They found that 2-methyl-4-5-dihydrofuran isomerizes
to methyl-cyclopropyl ketone at 475 - 5000 (Reaction 11,
see Sohemt). Thus, the C-0 bond 1.5 is ruptured and a new
bond is formed between the-C-atome 3 and 5 and the keto-
-group in the side chain. The reaction carried out here is
irreversible, in contrast with the isomerization of
2.3-dihydrofuran to cyclopropane aldehyde which is reversible.
Card 2/3 There are 2.references.

Thermal Isomerization of 2-MethYl-4.5-dihydrofuran to SOY/20-125-5-27/61
Methyl-cyclopropyl Ketone.
ASSOCIATIONs Institut organicheakoy khimii im..N. D. Zelinskogo Akademii
nauk SSSR (Institute of Organic Chemistry imeni H. D.
Zelinskiy of the kcademy of Sciences,USSR)
SUBMITTEDs February*5, 1959
Card 3/3

50)
AUTHORS: Bellsklyg I. F.9 Shuykinp N. I.p BOY/20-127-1-23/65
'C-orreap-Ming Member, AS USSR
TITLE: Catalytic Isomerization of d'-Oxides (Tetrahydropyrans) to
Aliphatic Carbonyl Compounds (Kataliticheakaya izomerizataiya
d'-okisey (tetragidropiranov) v alifaticheskiye karbonillnyye
soyedineniya)
PERIODICAL:: Doklady Akademii 'nauk SSSR, 19599 Vol 1279 Nr 1, pp 91-92
(USSR)
ABSTRACT:: Hitherto it has been assumed that the y- and S-oxides cannot
be isomerized by the opening of the ring to the compounds men-
tioned in the title, in contrast to the a-'oxides. The authors
provedg howeverg ~(Ref 1) that this is possible as well in the
case of the d-oxides (tetrahydrofuran and its homologs) in the
vapor phase on platinized charcoal at 2500. They are transformed
mainly into aliphatic ketones. The reaction of the &-oxides
mentioned in the title could be carried out as well with an
alkyl substituent in an a-position at 300-3500, as was ex-
pected. The corresponding aliphatic ketones (yield 70-80 %) and
alkafies (20-30 %) are formed also in this case (see Scheme).
Card 1/2 This speaks in favor of the fact that the isomerization of

Catalytic Isomerization of 6-Oxides (Tetral4ydro- SOV/20-127-1-23/65
pyrans) to Aliphatic Carbonyl Compounds
a-a,:Lkyl-tetrahydropyranerproceeds like in the case of the
I-oxides, mainly by the opening,.of the ting of the 0-0
bond which is farthest away from the Alk~l substituent . '
(bond 1-6). The reaction proceeds as ~mo6thly as that of the
I-oxides; the reaction products are the same. An analogy with
-'the Y-oxides exists with respect to the easiness of opening
_(raskrytiye) of the ringas-well. The transformation degree
of the d-oxides into ketone ana aldehydes was higher than that
of the I-oxides (50-60 % per passage over the catalyst), since
.their isomerization was carried out at a higher lepperature.
There are 2 references, 1 of which is Soviet.
ASSOCIATION: Inatitut organicheakoy khimii im. N. D. Zelinskogo Akademii
nauk SSSR (Institute of Organic Chemistry imeni N. D. Zelinskiy
of the Academy of Sciencesq USSR)
SUBMITTED: April 18~ 1959
Card 2/2

5,(3)
ADTHORS: Shuykin) ff. I.) Corresponding Member SOT/20-127-2-34/70
AS USSR, Bellskl,~j 1. F.
TITLE: Hydrogenolysis of Carbonyl-containing Furan Compounds, Trans-
formation of Alkyl-acyl-furans Into Six-membered Carbocyclic
Compouiids
PERIODICAL: Doklady Akademii nauk SSSR, 1959Y Vol 127Y Nr 21 PP 359-361 (USSR)
ABSTRACTi The direction of the bydrogenolysis of the furan ring depends on
various factors, in the first place on'the nature of the catalyst
and on the properties of the lateral substitutents (Refs 1-5).
Strict oonolusionB on the influence of the latter on the mentioned
direction of the ring cleavage are possible only an the strength
of the comparison of experimental results obtained under equal
conditions of phase state and pressure. In a previous paper
(Ref 5) the authors f ound a ring aperture in the ccralkyl-furans
on Pt-C only at the C--O-bond at normal pressure which is not
adjacent to the alkyl radloal, Aliphatic ketones are fo=oa here.
In tho present pap*r the hydration reaction of pyro=oio acid-
metbyl-ester and 2-methyl-5-acetyl-furan was investigated under
conditions completely analogous to the last mentioned ones. In
Card 1/3 this case the carbonyl-oontaining groups influence decisively

HjFdrogenolysis of Carbonyl-containing F=an Compounds. BOV/20-127-2-34/70
Transformation of Alkyl-acyl-furans Into Six-membered Carbocyclic Compounds
the direction of the aperture of the furan ring. The effect of
these groups is opposed to that of the alkyl radical. The hydro-
genolysis mentioned in the title proceeds in all substances
investigated easily and only at the C--O-bond adjacent to
oarbonyl-oontaining groups. The primary products produced by this
are subjected to further changes in the vapor phase under +he
hydration conditions. This hydration is interesting not only from
the theoretical point of view9 but also opens now ways of
catalytic synthesis of valuable compounds on the furfarol I~ase,
The mentioned ester forms methyl butyrate with a yield of 95 %
in the hydration on Pt-C at 2750. This is a deoarbonylization
product of the esters of the corresponding aldehyde aoid produced
meanwhile (see Scheme)- 3-methyl-cyclohezanona, 3-methyl-
oyclohexanol as well as metacresol are produced as main pr6duots
from 2-methYl-5-acetyl-faran, under the mentioned hydration
conditionso This formation of carbocyclic compounds is based
!Apon profound structural changes in the molecule of this
heterocyclic ketone (2-methyl-5-acetyl-furan) and is certainly
a result of several subsequent reactions '(see Scheme). Thus a
Card 213 hydrogenolysis of the furan ring at the'C-0-bond adjacent to the

Hyarogenolysis of Carbonyl-containing Puran Compounds. SOT/20-127-2-34/TO
Transformation of Alkyl-acyl-furans Into Six-membered Carbocyclic Compounds
carbonyl group proceeds first on rt-c (iu contrast to Ni
catalysts)* This leads to the formation of carbocyolic compounds.
A primary reduction of the oarbonyl-group in 2-motbyl-.5-acetyl-
furan takes as well place on Pt-C, however, to a much lower
extent than on Ni catalysts. An immediate transformation of I
into IV and V (see Scheme) has obviously a general'imp'ortance
and may serve as a catalytic synthesis method of the alkyl-
oyclokoxanongs and,alkyl-phanols from 2-alkyl-5-aeyl-furans'.
Finally the hydration appal-atus the reaction conditions # wd *9
siabl- -ocestants of the obtained substances are described. There'
are 6 references, 3 of which are Soviet.
ASSOCIATIONs Institut organicheskoy khimii im..N. D. Zelinskogo Akademii nauk
SSSR (Institutei~of organic Chemistry imeni X. D. Zelinekly of
the Academy of Sciences, USSR)
SUBMITTED: April 18,1959
Card 3/3

5.0) SOV/20-127-4-24/60
.TAUT S- Shuyk-In, R. I., Correspondin- LiemberXS USS17, -Bell akiyj I,* Fo#.
Karakhanov, R. A.
TITLE. Isomerization of r-Oxides to Aliphatic Carbonyl Compounds.
Effect of the temperature and Str-,ture of These Compounds
PERIODICAL: Doklady Akademi
i nauk SSSR,1959,vol 127, Nr 4tPP 815-817 (USSR)

,UST.-4ACT: ,
i
Four problems are solved in this article: (1) That is the a;--tion
exercised by the length of the carbon chain of the alkyl radicals
placed in OC-position on the capacity of the tetrahydrofuran
cycle to isomerize: Does this action proceed In the direction I
(splitting of the 10-bond), or in the direction II (splitting
of the 1,2-bond, Scheme)? (2) What is the effect of temperature
on the relative capacity of the 1,2- and 1,5-bonds to be split
by the isorierization of co