PROGRESS IN ACETYLENE CHEMISTRY

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000600290442-9
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 4
• Document Creation Date: December 22, 2016
• Document Release Date: September 28, 2011
• Sequence Number: 442
• Publication Date: March 14, 1950
• Content Type: REPORT

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CLASSIFICA 1
y~P
CENTRAL INTELLIGENCE AGENCY
INFORMATION FROM
FOREIGN DOCUMENTS OR RADIO BROADCASTS
COUNTRY USSR ..
SUBJECT Scientific - Chemistry, acetylene
HOW
PUBLISHED Monthly p iodicals
WHERE
PUBLISHED USSR
DATE
PUBLISHED 1949
LANGUAGE
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In an article (1) on the chemistry of acetylene and its derivatives which
appeared in Veatnik Akademii Nauk SSSR, No 1.1, 1949, the author stated that
extensive studies in this field have been carried on for a number of years in
a laboratory supervised by I. N. Nazarov, Corresponding Member, Academy of
Sciences USSR. In his laboratory, a unit of the Institute of Organic Chemistry,
Academy of Sciences USSR, a simple method was developed 10 years ago for syn-
thesizino various vinylacetylene alcohols (vinylethinylcarbinols).
Vinylethinylcarbinols are easily polymerized into a solid vitreous mass
and can be used as a reliable adhesive for firmly gluing metals, glass, porce-
lain, marble, minerals, plastics, and other materials. These carbinols were
quickly adopted for actual use and have proved themselves of value in the opti-
cal, instrument and tool, marble, automobile repair, public utilities, and other
branches of USSR industry, particularly during World War 11.
Systematic research on vinylethinvlcarbinols instituted in this laboratory
has revealed the unusual richness and variety of synthetics. Of the many new
reactions discovered by Nazarov and his colleagues, the one for the hydration
and cyclization of divinylacetylene hydrocarbons into cyclopentenones is most
significant since it permits the development of a very simple method for the
conversion of acetylene into compounds of the cyclopentane series which are
difficult to synthesize. These compounds are found in petroleum and other im-
portant natural products.
Recent examples of this phase of acetylene chemistry are afforded by two
investigations, resumes of which follow:
In the first investigation (2), Nazarov and S. S. Bakhmutskaya began by
hydrating 1, 2-bis(1' - cyclohexenyl) acetylene in an aqueous solution of
methanol in the presence of sulfuric acid and HgS04 and obtained good yields of
1-hexenyl 1-hexenylmethyl ketone which was hydrogenated with a Pt catalyst to
form cyclohexyl cyclohexylmethyl ketone. The cyclization of 1-hexenyl -1 hexenyl-
methyl ketone VYh HP04 gave spiro Zc-yclohexane-1, l'-indan-3-on7, and the
condensation of vinylacetylene with cyclohexl cyclohexylmethy.l ketone gave good
yields of 1, 2-dicyc'ohexyl-5-hexen-3-yn-2-ol which was hydrogenated with Pt
catalyst to 1, 2-dicyclohexyl-2-hexanol and dehydrated to 1, 2-dicyclohexyl-1,5-
hexadien-3-yne? The latter compound was hydrogenated to 1, 2-dicyclohexylhexane
NSRB
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DISTRIBUTIOO
CD NO.
DATE OF
INFORM,ITION 1949
DATE DIST. / Mar 1950
NO. OF PAGES 4
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and was also hydrated in an aqueous methanol solution to 1,3-dicyclohexyl-l,5-
hexadiene-3-one which was easily cyclized with H3P04 to l,2-dicyclohexyl-3-
methyl-l-cyclopenten-5-one.
A similar procedure was carried out in the second investigation (3) in which
Nazarov collaborated with L. N. Pinkina: who showed that upon condensation of
isobutyrone with vinylacetylele, 5-isopropyl-6-methyl-l-hepten-3-yn-5-ol was
formed with good yields. Then thin compound was easily dehydrated .by dilute
sulfuric acid to 5-isopropyl-6-methyl-l,5-heptadien-3-yne. Upon heating this
latter substance In aqueous methanol with H2SO4 and HgS04, 5-isopropyl-6-
methyl-l,5-heptadien?4-one was formed which, under the action of acid (phosphoric
sulfuric, hydrochloric, and p-tolenesulfonic acids), was transformed into 2-iso-
propyl-3,3,4-trimethyl-li-cyclopenten-l-one.
The Vestnik Akademii Nauk SSSR article (1) also notes another very interesting
phase of acetylene c emiscry sealing with the synthesis of heterocyclic cpmp..usds
of the pyran, thiopyran, and piperidine series which form the basis for many
natural and synthetic medicinal preparations and physiologically active sub-
stances.
Three current studies on such compounds are available. In one of these,
Nazarov and I. V. Torgov (4) began with the condensation of 2,2-dimethyltetra-
hydro-l,4-pyrone with acetylene in the presence of powdered KOH giving 30 percent
2,2-dimethyl-4-ethynyl tetrahydro-4-pyranoi, which during partial hydrogenation
with a Pd catalyst was transformed into the corresponding vinyltetrahydropyranol.
This latter compound upon dehydration with p-toluene sulfonic acid then gave
68 percent 2,2-dimethyl-4-vinyl-3,6-dihydropyran which easily condensed with
maleic anhydride forming the normal additional product. At 160-185 degrees centi-
grade, 2,2-dimethyl-4-vinyl-3,6-dihydropyran condensed easily with 1,3-dimethyl-
1-cyclopenten-5-one with the formation of a tricyclic ketone of the pyran series
containing a cyclopentanone nucleus with an angular methyl group. The oxidation
of 1,3-dimethyl-l-cyclopenten-5-one with SeO in a glacial acetic acid solution
gave 1,3-dimethyl-l-cyclopenten-4,5-dione which condensed with 2,2-dimethyl-4-
vinyl-1.6-dihvropyran forming a tricyclic diketone.
Three colleagues, V. Ya. Raygorodskaya, F. I. Gorman, and V. A. Rudenko,
worked with Nazarov in another research effort (5) on heterocyclic compounds.
They first reacted ethylamine and ethanola:.ine with allyl isopropenyl ketone and
its methoxy derivatives (obtained by the addition of Cii3OH across one or both
double bonds) to obtain l-ethyl-2,5-dine thyl-+-pii:eridone and 1-(beta-hydroxy-
ethyl)-2,5-dimethyl-4-piperidone in good yields. The latter compound did not re-
act with acetylene, vinylacetylene, or Grignard reagents, but the former compound
condensed with acetylene to give 85 percent 1-ethyl-2,5-dimethyl-4-ethynyl-4-
piperidol which was then selectively hydrogenated with a Pd catalyst to 1-ethyl-
2,5-dimethyl-4-vinyl-4-piperidol., and was exhaustively hydrogenated to give 1,4-
diethyl-2,5-dimethyl-4-piperidol. The 1-(beta-hvdroxyethyl)-^,5-dimethyl-4-
piperidone readily gave the crystalline 2,4-dinitro-phenyl-hydrazone but was
catalytically hydrogenated with a Ni catalyst to l-(beta-hydroxyethyl)-2,5-
dimethyl-b-piperidol.
1,2,5-trimethyl-4-piperidols were synthesized by iazarov, Raygorodskaya,
and Rudenko (6) as follows: The condensation of i,2,5-trimethyi-4-piperidone
with acetylene in the presence of powdered KOH gave 80 percent 1,2,5-trimethyl-
4-ethynyl-4-piperidcl which was isolated in the form of two itereoisomers. Both
isomers, upon heating with powdered FOR, decomposed into acetylene and the initial
piperidone. Selective hydrogenation of the piperidol gave the vinylpiperidol, and
exhaustive hydrogenation gave the ethylpiperidoi. The condensation of the
original piperidone with vinylacetylene produced good yields of 1,2.5-trimethyl-
4-vinylethynyl-4-piperidol. Phenyllithium reacted with the original piperidona
to yield 1,2,5-trimethyl.-4-pipe ridol. The esters (acetates, propionates, and
benzoates) of the piperidyl alcohols were urepared and found to possess physicc-
logical (p..rticularl.y anesthetic) properties.
SECRET
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sl-RtONF(DEN11
The latter work of Nazarov (1) and his collaborators with steroid compounds
is also of very great importance, for these constitute the basis for the syn-
thesis of animal and plant sterols, steroid hormones, bile acids, antirachitic
vitamin D, cardiac aglucones, and other biologically active compounds which play
important roles in the activity of animal and plant organisms. It has required
almost 100 years to define the structures of these steroid compounds, and the
efforts of foreign chemists to synthesize them on the basis of carbon skeletons
have not led to positive results.
Nazarov and his fellow-workers, however, developed a very simple and ele-
gant method for the complete synthesis of steroid skeletcne, opening up wide
horizons for further advances in this field.
The investigation by Nazarov and Torgov (4) form a good example of work
in the field of steroids, in view of the fact that tricyclic ketones, similar
to cyclo-penta-phenanthrenones, have been synthesized and the introduction of
the angular methyl group is dealt with.
In the last 10 years, Nazarov's group has prepared over 1,000 new substances
on the basis of acetylene -- substances falling into all classes and subdivis-
ions of organic compounds (1).
For many yearn, large quantities of acetic acid, rubber, plastics, synthetic
fibers, adhesive and impregnating substances, solvents, and numerous other
chemical products have been manufactured on the basis of acetylene. In fact,
acetylene is one of the basic starting materials in contemporary industrial syn-
thesis. The trend, which was started by Nazarov's school, makes acetylene a
promising material for the synthesis of su h complicated and important fine or-
ganic compounds as the steroids, alkaloids, and substances related to them.
Recently, another series ~)f articles in the field of acetylene chemistry have
been initiated by the Chair on the Structure of Organic Compounds of the Order
of Lenin State University imeni A. A GGhdennv to Leningrad. In the first article
of the series (7), 1. A. Favorskaya described the preparation of the unsaturated
ketone, 4.4'-dimethyl-3-methenepentanone-2, by the hydration of beta-tertiary-
butylvinylacetylene, as well as a method for preparing beta-tertiary-butylvinyl-
acetylenecerbonic acid and beta terti&ry-b,.itylviny]acetylenecarbonate.
1. "Organic Synthesis on the Basis of Acetylene," Vestnik Akademii Nauk SSSR,
No 11, PP 103-h,
2. I. N. Nazarov and S. S. Bakhmutskaya. "Acetylene Derivatives. 102. Mechanism
of Hydration and Cyclization of Dienines. XX. Hydration and Cyclization of
Di-delta-l-dichlcohexenylacetylene and 1 2-Dicyclohexyl-l,5-hexadien-3-ine,"
ihurnal Obahchey Khimii, Vol XIX, No ?, pp 1777-36, 1y49.
3. I. N. Nazarov and L. :;. Pinkina. "Acety:ene Derivatives. 103. Mechanic, m c`
Hydration and Cyclization of Dienines. XXI. Hydration of 5-Isopropyl-6-
methly-1,5-pentadien-3-ine into 1-Iso_,ro;;1i-6-methyl-l,5-heptadien-4-one and
its Cyclization into 1-Isopropyl-2,2,3-trimethvl-delta-3,4-cycl,6penten-5-one.
A New Instance of the Cyclization of Substituted Vinylallylketones Which Do
Not Have a Free Hydrogen in the Vinyl Radical,. "'Lhurnal Obshchey Khimii, Vol
XIX, No 10, pp 1870-81, 11.hp.
It. I. N. Nazarov and 1. V. Torgov. "Acetylene Derivatives. 101. Synthesis of
Polycyclic Compounds With an Angular ?:ethyl Group. II. Condensation of 2,2-
Dimethyl-4-vinyl-3,6-dihydropyran With 1,3-Dimethyl-l-ciopentene-5-one and 1,3-
Dimethyl-l-cyclopentene-4,5-dione," _,hurnal Obshchey Khimii, Vol XIX, No 9,
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5. I. N. Nazarov, V. Ya. Raygorodskaya, F. I. Gotman, and V. A. Rudenko.
"Acetylene Derivatives. Report 95. Heterocyclic Compounds. VIII. The
Activity of Ethylamine and Ethanolamine on Allylisopropenylketone and
Methoxyketone Derived From It. Preparation of Gamma-piperidones Containing
with Nitrogen an Ethyl and a Beta-hydroxyethyl Radical, Izveeti a Akademii
Nauk SSSR, Otdeleniye Khimicheakikh Nauk, No .5, pp 493-503, 1949.
6. I. N. Nazarov, V. Ya. Raygorodskaya, and V. A Rudenko. "Acetylene Derivatives. Re-
port 96. Heterocyclic Compounds. IX. Synthesis of 1,2,5-Trimethyl-4-piperidole and
Their Eaters,'Izves Akademii? ukSSSR, Otdelen13eItIImicbesldlChNaikND5, pp 9D4-4-19 49.
7. I. A. Favorekaya. "Monovinylacetylene Homologues. 1. Beta-tertiary-butyl-
vinylacetylene," Zhurnal Obehchey Khimii, Vol XIX, No 11, pp 2051-6, 1949.
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