.

ACETYLENE CHEMISTRY
W. E. HANFORDl AND D. L. FULLER
General Aniline and Film Corporation, Easton, Pa.

Acetylene chemistry has taken rapid strides, especially in Europe, during the past twenty
years as a result of the extensive research and development by Reppe and his co-workers of
I. G. Farbenindustrie. These advances were due primarily to the fact that they found
how to handle acetylene at 200 to 300 pounds per square inch at temperatures up to 200' C.
This was accomplished in general by diluting the acetylene with an inert material, such
as nitrogen, or by constructing suitable apparatus. Data on the explosive behavior of
acetylene and certain mixtures are presented. Two types of reactions of acetylene have
been developed: reactions where the product resulting from a reactant and acetylene
seems to be best explained by migration of an acetylenic hydrogen, and those which can
best be explained by addition of a reactant to the acetylene linkage. Topics discussed are
vinylation, ethynylation, carboxylation, and cyclic polymerization.

A CETYLENE chemistry was one of the major contributions

of the German scientists to their war effort. United
States scientists also were actively engaged i n trying to make
acetylene chemistry a real contribution of organic chemistry to
the American cause and did add several small parts from this
field to the Allies' war effort.
Because this is an extremely broad subject this paper is limited
to the f i s t member of the acetylene series, CaH2. The chemistry
of the oxidation of acetylene is excluded, as are the conventional
methods for the manufacture of such compounds a8 vinyl acetate,
divinyl acetylene, ethylidene diacetate, tetrachloroethane,
trichloroethylene, and tetrachloroethylene. Each represents a
major development in the field of chemistry that has been prac-
ticed in this country for many years.
The reactions of acetylene discussed below are not as well
known, but many believe they will become as important in the
future development of organic chemistry in this country. They
differ from those excluded in that in the majority of cases the
acetylene must be used under pressure in order td obtain a re-
action rate fast enough for commercial operation. A great deal
of the information given was taken from the reports obtained
from the I. G. Farbenindustrie by technical missions sent to
Germany and also from data obtained in the authors' laboratory
(1,3,6,16, I!?).
The development of this field is due to a very large extent to
the work of Reppe and his associates a t the main I. G. Farben-
industrie research laboratory a t Ludwigshafen, Germany.
This paper may be looked upon, in general, as experiences a t
General Aniline and Film Corporation with these reactions.
HANDLING OF COMPRESSED ACETYLENE
Because the development of new techniques for handling
acetylene under pressure of several atmospheres is the factor
that has made these new reactions possible, before the chemistry
is considerkd, a discussion of these pressure techniques is in order
(8, 4). '
decomposition of acetylene, but unfortunately this reaction can
and does in many cases go so rapidly that the result is a detona-
tion. Under these conditions, the I. G. has reported instan-
taneous pressures up to 20 times that calculated for the straight
thermal decomposition or over 200 times the initial pressure.
HAZARDS. The characteristics of acetylene have not changed
as a result of any research. What has changed is a better under-
standing of the factors that enter into the control of the tre-
mendous force that can be developed during its decomposition.
I n the General Aniline laboratory an explosion test was made
on a nitrogen-acetylene mixture in an extra heavy pipe carrying a
right-angle bend, Because of interest in the safety and design of
acetylene feed lines, the test was carried out a t room tempera-
ture with an 80 to 90% acetylene mixture and nitrogen a t 175
pounds per square inch gage in a 1-inch extra heavy flanged steel
p i p 6 feet long. This pipe had a working pressure of 1361 pounds
m t h a safety factor of 8.
At one end, the explosion was set off by fusing a n i r o n wi.re;
the flange a t the other end held a steel plate 0.130 inch thick
which had been used many times in static strain gage tests with
nitrogen a t 2000 pounds per square inch without taking a perma-
nent set. In view of the current rule that tenfold pressure in-
creases occur when acetylene mixtures explode, this plate was
expected to be satisfactory for the test.
When the explosion occurred the 10,000-pound gage connected
by st steel tube '/le inch in insfde diameter did not have time to
move appreciably. The report was loud, more like a shot un than
a rifle, and there was an instantaneous bright yellow fight (of
burning carbon as it hit the air) in the barricade. There was no
damage, no windows or light bulbs were broken, and the pipe
held, but a 1.25-inch hole was cleanly punched out of the steel
plate. This slug knocked chips out of the concrete floor, SO I t
came out at high speed.
If we assume the ultimate shearing stress of the plate t o be
42,000 pounds per square inch, we find the shearing force to be
21,500 pounds and the pressure on the slug t o be 17,500 pounds
per square inch. This is about ten times the tenfold pressure in-
crease expected. The effective pressure then was considerably
greater than that given by the usual rule.
The uantity of acetylene present in this pipe was about 10
grams &igure I).

Thermodynamically, acetylene is unstable with respect to its
elements a t room temperature and when decomposed to its
elements a t 18' C. liberates 53,500 calories per gram mole.
As the usual decomposition products are mainly carbon and
hydrogen, the rise in pressure must be due to an increase in
temperature. On this basis, and assuming no heat loss, the
temperature would increase from 15" to around 3100' C. and
thus result in a pressure of some twelve times the initial pressure.
This theoretical calculation checks very well with the experi-
ment$alresults that have been obtained for the straight thermal
1 Present address, M. W. Kellogg Company, 225 Broadway, New York,
N. Y.
1171
This force surely belongs t o the top group of explosives.
However, it is possible to run acetylene reactions under pressure
without hazard, i f the proper precautions are taken a t all times.
Two general procedures have been worked out for controlling
the.hazardous behavior of acetylene: (1) diluting the acetylene
with some inert gas, such as nitrogen or carbon dioxide; and
(2) keeping the amount of free space present in the system t o a
minimum by using bunches of small tubes and by filling all large
voids with a packing material, such as steel or porcelain Raschig
rings (Figure 2). Both methods have their particular uses,
depending on the reaction which is to be carried out.
For autoclave operation, the first method is probably the brst;
1172 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 40, No. 7

I\ BARRICADE Since the authors were initially interested

KWALL
in carrying out these reactions of acetylenr
in autoclaves, they employed for the explosion
tests a 1200-cc. Aminco bomb, 3 inches 111
diameter, which had been pressure-tested at
CzHz -Nz 6000 pounds. (The volume of the correspond-
SUPPLY
ing reactor used by I. G. for this study m-ah
730 cc.) As with most gas explosion reactions,
the size and shape of the reaction vessel have
~1 large effect on the pressure developed. The
presence of a diluent in the acetylene, how-
ever, greatly reduces the possibility of detona-
tion regardless of the size and shape of the
bomb.
As the temperature of acetylene is increased,
the pressure a t which i t will decompose is dr-
creased (Table 111).
The results of the decomposition of mix-
Figure 1. Acetylene Explosion Test in Bent Pipe tures of acetylene with hydrogen, acetylene
with nitrogen. and acetvlene with ethvlene are
- I

for continuous operation, especially where a solid contact cata- summarized on Figures 3 and 4. The areas below the curves
lyst is to be used, the second method is preferred. represent safe operating conditions and those above the lincs
I n determining the eGplosive characteristics of acetylene, some represent unsafe operating conditions.
means must be selected for initiating the decomposition. A great I n the running of organic reactions in autoclaves in batch
deal of thought and experimental work has been expended in operations, another constituent is always present in the gas
deciding on the best method for initiating this reaction. Con- phase-the vapor of the liquid or diluent used in the reactor. This
sideration has been given to a spark plug, fusion of a wire, and means that with volatile solvents the reaction conditions in the
dynamite caps. autoclave are safer, as far as detonation is concerned, than those
The fusion of a wire has been used by all investigators in that exist in the acetylene supply lines. However, the acetylene
determining the explosive characteristics of acetylene. In will be safe in the lines, provided the diameter is less than 0.5
attempting to select ignition material, the I. G. studied the inch.
critical pressure for decomposition of pure acetylene with variouq Before all the I. G. data became available the authors studied
kinds of wires (Table I). many of these reactions and their approach to the problem was a
very practical one. If they had decided to run, say, the vinylatiori
of methanol with a mixture of 35y0 acetylene and 65% nitrogen
TABLEI. LIMITINGPRESSURE OF ACETI-
FOR DECOMPOSITION at 250 pounds gage pressure and 180" C. with an excesb of
OF MELTING
LENE AS 4 FUNCTION POIKTOF WIRE methanol present at all times, they would ask: Is this mixture
Melting Point, Pressuie
Element c. Lb./Sq In , 'Ab? safe or can it decompose under these Conditions? The bomh
N O 2550 20.6 mentioned above was loadrd with the desired reaction mixture
Pt 1760 20.6
Fe 1530 25.2
cu 1080 27.0
A1 660 38.9
Pb 330 110.0 TABLE 111. LIMITINGPRWSEREFOR 'DECONPOSITION OF
ACETYLENEAS A FWWTION
O F TEMPERATURE O F GAS A T T I h r E ?F
IGNITIONOF T T 7 1 ~ ~
Temperature, Pressure,
From these data i t is apparent that the lover the temprraturr c. Lb./Sq. In., Abc;.
of fusion of the wire, the higher the pressure can be before decom- 16 20.6
position occurs. 100 18.4
150 16.6
Other factors which must be considered are the diameter of tlir 180 15.6
wire, the length of the wire, and the rate a t which the energy is
put into the wire., The I. G. decided to use platinum wire 0.5
mm. in diameter and 10 em. long fo rall decomposition studies.
In their work the authors have used iron wire, rrhich gives slightly
higher values for the pressure than are obt,ained with platinum.
Explosive decomposit,ions of this type also depend upon the
dimensions of the vessel. The I. G. studied the effect of the
size of the vessel on the decomposition of pure acetylene under
pressure (Table 11) and concluded that the critical pressure for.
decomposition is independent of the diameter for vessels greater
than 7.9 inches in diameter, and that it is very markedly a func-
tion of diameter for smaller vessels.

TABLE11. L I N I T I X G PRESSURE FOR DECOMPOSITIOK O F ACETY-

LENE AS A FUXCTION O F DL4METER O F VESSEL
Vessel Diameter, Pressure,
Inches Lb./Sq. In., Abs.
2.0 26 5
3.9 23.5
5.9 21.3
7.9 20.6
10.6 20.6 CROSS SECTION
Figure 2. Pipe Packing to Prevent Acetylene Detonation
July 1948 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY 1173

The I. G. concluded from the results that pure acetylene

can be handled safely at pressures up to 15 atmospheres absolute,
provided the large pipes are filled with bundles of tubes having
diameters of 0.5 inch or less and that the free spaces at bends,
etc., are filled with Raschig rings. Under these conditions ther-
mal decompositions did occur, but no detonations; provided
detonations can be avoided, safe plant designs are feasible.
As the Reppq synthesis of butynediol from acetylene and
formaldehyde operated at pressures of 5 to 10 atmospheres, usu-
ally 5 to 6, ample margin of safety was afforded by building the
unit for 100 atmospheres operation. For long continuous
runs the bundles of tubes are preferred to the Raschig ring
packing.
As for the chemistry of acetylene under pressure, there are
four important. types of reactions of acetylene: vinylation
ethynylation, carboxylation, and cyclic polymerization.
VINY LATION
For the vinylation of alcohols (12, 16-18,26, 28) with acetylene,
a bas? is used as the catalyst. For this reaction, potassium
HC=CH + RON +H,C=CHOR
hydroxide or potassium alcoholate gives better results than any
of the other alkalies tested. The general reaction conditions
PRESSURE OF MIXTURES, PSI. required for the vinylation of alcohols from methyl to octadecyl
are: addition of 1to 5% of potassium hydroxide to the anhydrous
and an attempt made to decompose i t by fusing an iron wire in alcohol; heating to a temperature of 160' to 185' C.; then treat-
the gas phase. If no reaction occurred, the operation was ing with a mixture of 1 part of acetylene and 2 parts of nitrogen
repeated once or twice. The acetylene pressure was raised and at a total pressure of 100 to 300 pounds gage. The method for
the operation repeated two or three times more. Finally the carrying out this reaction in a batch operation is as follows:
decision was made on the basis of data of this type whether or not
the experiments were justified. Mixtures used in these testjs A stainless steel autoclave provided with an efficient stirrer
and capable of withstanding a pressure of 2000 pounds is charged
and the conditions are summarized briefly in Table IV. with the alcohol-say, anhydrous butanol-and to this is added
23% of anhydrous potassium hydroxide. The autoclave is closed,
evacuated, and flushed with nitrogen which contains less than
0,2y0oxyg!n. The flushing o eration is continued until the ni-
IV.
TABLE OF TEST
CONDITIONS trogen leaving the autoclave sgows less than 0.5% oxygen when
Compositions Other Component Pressure tested. The autoclave is heated to 160"C. and the nitrogen pres-
Present in Liquid Temp., Lb./Sq. I;., sure adjusted to about 130 pounds gage. Acetylene is then intro-
% CzHa % N t and Gas Phases C. Abs. Explosion
duced through a regular high pressure feeding system until the
70 30 Cyclohexane 151 235 Yes pressure in the autoclave is 200 pounds gage. Under these condi-
67 33 Cyclohexane 165 285 No
50 50 Cyclohexane 98 205 Yes tions the acetylene is absorbed rapidly and the drop in pressure is
38 62 Cyclohexane 98 205 NO made up by the addition of fresh acetylene.
50 50 Cyclohexane , 151 260 NO I n the authors' laboratory acetylene at 250 pounds pressure is
100 0 Methanol 120 205 No
100 0 Methanol 120 215 Y e8 generally used directly from cylinders. The reaction proceeds
71 29 Methanol 120 215 No
67 33 Butanol 120 135 No
100 0 Isobutanol 120 85 Yes
100 0 Vinyl isopropyl ether 120 245 No
Neglecting vapor pressure of organic liquids,

It is surprising how accurately this type of experiment can be

run. Using data of this type, work in the field of acetylene
under pressure has been carried on €or over four years without
any serious accidents; there was only one rupture of any equip-
ment during these four years and this was in one of the feed lines.
The seaond method of preventing the detonation of acetylene
by keeping every acetylene molecule within a certain maximum
distance from a solid such as a wall has been studied in great
detail by I. G. Following the preliminary work on the diameter
of vessels, etc., the I. G. decided to investigate the explosion
characteristics of acetylene on a commercial plant scale.
These experiments were conducted by burying pipes of differ-
ent sizes, from'0.5 to 8 inches in diameter and over 100 feet long,
in deep trenches and covering them with earth and heavy ties.
Instruments were installed for determining the pressures at
several points along the pipes. I n these pipes were placed various
types of steel plugs or arrestors, bundles of small tubes running
the complete length of the pipe, bundles of small tubes with voids
at the ends, and similar bundles of tubes in which the voids a t
the ends were filled with Raschig rings, etc. These assemblies
were filled with acetylene mixtures and decomposition was initi-
ated by fusion of a platinum wire. PRESSURE OF Ps.1.
MIXTURE,
1174 INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY
Figure 5. Flow Sheet for Vinylation of Alcohols
smoothly. The autoclave is checked from time to time to see that
the reaction mixture does not contain more than 33% acetylene
at any time during the run. When reaction has ceased, the auto-
clave is cooled, the acetylene and nitrogen are vented, and the
product is worked u p by distillation.
Under the conditions outlined, one can obtain yields of 80 to
95% based on the alcohol with all of the primary alcohols from
methyl to octadecyl.
With the secondary alcohols, such as isopropyl or see-butyl,
vinylation occurs but the yields are lo-wer. The reaction does
not proceed nearly as well p i t h tertiary alcohols, such as t e r t
butanol. Polyhydric alcohols, such as ethylene glycol, glycerol,
sorbitol, and sugar derivatives, can also be vinylated under these
same conditions. The products of polyhydroxy compounds are
generally divinyl, trivinyl, etc., derivatives, or the cyclic acetals
or mixtures of the two.
CHzOH CHzOCH=CHz CHr-O\
HC-CH + 1
CH~OH
+I
CHzOH
4- L H 2 - d C H C H s + CH20CH=CH2
Other functional groups can also be present in the alcohols,
provided they do not react with potassium alcoholate at 160' C.
It is more difficult to vinylate the lower alcohols, such as
methyl and ethyl, than the higher alcohols by a batch operation
because of the high vapor pressure which results at the elevated
temperatures. The lower members can best be obtained by
carrying out the operation in a continuous fashion, although the
same equipment can be used for the higher vinyl ethers. The
way in which the reaction is carried out in a continuous manner
is shown diagrammatically in Figure 5 ,
The tower, A , is charged with the anhydrous alcohol and the
potassium hydroxide or alcoholate as catalyst. On the top of A
is a column, B, to separate the vinyl ether from the unused alco-
hol, acetylene, and nitrogen. The nitrogen diluent is brought
down to about 15 pounds pressure, acetylene is added, and the
mixture of acetylene and nitrogen is passed through the compres-
sor to obtain the desired pressure and then into the bottom of A .
Continuous operation is maintained by adding make-up alcohol
by means of pump C. The synthesis of methyl vinyl ether by
this process is carried out at about 300 pounds gage pressure, due
to the vapor pressure of methanol at 160" to 185' C. %-Butanol,
on the other hand, can be vinylated at 100 pounds pressure and
octadecyl alcohol from atmospheric pressur; to about 100
pounds.
The only side reaction that occurs to any appreciable extent
in this reaction is the gradual conversion of potassium alcoholate
to the potassium salt of the corresponding fatty acid and hy-
Vol. 40, No. 1
drogen. This, of course, is what one would anticipate, for when
potassium butylate is heated to a temperature of about 185 C.,
potassium butyrate is formed. The control of this side reaction
is an important variable in the successful commercial operation
of this process for two reasons: (1) -4s the catalyst is consumed,
the rate of reaction is reduced; this, of course, adds to the COST
of the operation. (2) The hydrogen concentration in the inert
gas and unconverted acetylene recycled gradually builds up and
some method of removing i t or venting i t from the system muqt
be used.
The vinylation of alcohol has also been studied in the vapoi
phase, using potassium hydroxide on calcium oxide as a contact
catalyst. The life of this catalyst is short and the extreme
difficulty in removing the heat of reaction makes the liquid
system more attractive.
The vinyl ethers so prepared are colorless liquids or solid.
which can be utilized for the preparation of a wide variety 01
organic chemicals and polymers. They can be polymerized ai
low temperature with acid catalysts, such as boron trifluondt.,
and interpolymerized with a variety of unsaturated compound.
by means of a peroxygenated catalyst such as benzoyl peroxidc
The double bond in the vinyl ethers is extremely reactive and
undergoes all the characteristic reactions of a carbon-carbo11
double bond.
Vinyl nitrogen compounds, such as vinyl carbazole (17, 2.5
aiid vinyl diphenylamine, can be prepared by the direct reactioii
of the amine with acetylene in the presence of potassium hydrox-
ide.
HC=CH + q-'?-(j-i", "/
G \ NH/ C i I
HC=CHz
Here the reaction conditions are essentially the same, except
that in those cases where the amine is high melting, a solvent is
generally employed. The easiest to prepare and most stablp of
thp vinyl compounds of this series is vinyl carbazole.
This was DreDared in cvclohexane with
potassium hidrdxide and zi"nc oxide as cata-
C H 2 0 C H ~ C H 2 lyst
I
a t 180" C., 200 pounds gage pressure,
and using a mixture of 2 parts of nitrogen
with 1 part of acetylene. The vinylation is
rapid, but the duration of the reaction de-
pends to a large extent on the degree of
agitation. When acetylene is no longer absorbed, the reaction
mixture is allowed to cool. The unreacted carbazole and the
inorganic materials are removed by filtration, the cyclohexane
is distilled, and the vinyl carbazole purified by distillation, or
by crystallization from such materials as cyclohexane, benzene,
and methanol. The yields are above 85%.
Diphenylamine can be vinylated under the same conditil Iris,
but the yield is lower and tlie product is extremely sensitive to air
and difficult to obtain in a pure form. Vinyl carbazole is readill
polymerized by acid- or peroxide-type catalysts to produce
polyvinyl carbazole. It can also be polymerized by thermal
methods. It has been used for eIectrical insulation because of
its high electrical resistance and low power factor. It is sold
under the tradc-mark of Polectron and its main war use was in
making condensers for the proximity fuse.
Because the less basic nitrogen compounds in the amine clash
vinylate readily, i t is natural to suppose that certain amides will
also vinylate easily. The compound that has been studird i 1 1
greatest detail is the cyclic amide, pyrrolidone (11).
HzC-CH2
 July 1948 INDUStRIAL AND ENGINEERING CHEMISTRY
For the vinylation, it is best to form first the potassium salt
of the pyrrolidone. This can be done by mixing potassium hy-
droxide with pyrrolidone and distilling out about one third of
the pyrrolidone, which carries with it the water from foremation
of the potassium pyrrolidone: This reaction mixture 1s then
charged into an autoclave, heated to about 160 " C. and treated
with dilute acetylene at 200 pounds per square inch gage. The
absorption is very rapid a t first, then gradually dies off. TJsually
vinylation reaction is not run to completion, because the rate
drops off very rapidly near the end. A 70% conversion seems t o
be a good point t o stop. At this time the reaction mixture is dis-
charged and the vinyl pyrrolidone boiling a t 95" c. a t 14mm.
pressure is separated from the unchanged pyrrolidone. This ma-
terial can then be polymerized by either a peroxide catalyst 01: a
boron trifluoride catalyst to a solid material, which is readily
soluble in water with the formation of a very viscous solution.
Polyvinyl pyrrolidone has been used in Europe as a synthetic
blood plasma and also for offset printing. How far these de-
velopments will go in this country is still to be determined.
. The higher acids, such as lauric, stearic, and oleic, can be
vinylated with acetylene by using the potassium or zinc salt
as catalyst under essentially the same conditions as those em-
ployed for the vinyl ethers (90).
ClrHaa(!
0
8
- OH + HC=CH +CIJH~I, - OCH=CH2
The best yields are obtained when the system is anhydrous.
Vinyl stearate is readily obtained from a reaction mixture of 5%
zinc stearate and 95% stearic acid heated in an autoclave at
165O C., using diluted acetylene a t 200 pounds pressure. Vinyl
stearate resulting from this reaction mixture is purified by dis-
tillation. It can be polymerized under about the same condi-
tions as are used for the lower molecular weight vinyl esters.
Potassium stearate is also a good catalyst for this reaction.
Although it is extremely difficult t o vinylate acetic acid with
potassium acetate as a catalyst, the potassium salt is a good
catalyst for the higher fatty acids. Relative solubilities of the
salts may be part of the answer.
The same general reaction conditions can be employed for the
preparation of vinyl laurate, vinyl oleate, etc. It has been
reported that the polyvinyl esters of the unsaturated acids of
high molecular weight have interesting drying characteristics.
Phenols, especially the monoalkylated phenols, react with acety-
lene very readily in the presence of organic bases and selected
zinc salts, such as zinc naphthenate, a t approximately 160" C.
and 200 pounds total pressure t o give resinouq materials.
This is the basis for the synthesis of the rubber tackifier de-
veloped in Germany known as Koresin and now offered by Gen-
eral Aniline and Film Corporation (91).
The specific prod-
iYY
uct is prepared by
mixing p-tertbutyl
phenol with about
+ HC=CH -+- 10% by weight of
zinc naphthenate,
heating the reaction
Hac-C-CHa
mixture to 160" C.,
ClHa
CHr
OH I /
1175
and introducing a mixture of 2 parts of nitrogen and 1 part of
acetylene t o a total pressure of 200 pounds. The reactants are
kept under these conditions until a resinous material with certain
predetermined physical constants has been obtained. The de-
gree of polymerization in this reaction is not large, being of the
order of 7, and the product contains many products including
some unchanged alkyl phenol.
Practically all the monoalkyl phenols give a similar product
under the same conditions. There has been a great deal of
speculation by Reppe and others as to the mechanism of f o r m s
tion and the structure of this resin. It seems probable that the
hydroxyl of the alkyl phenol reacts with acetylene to form a sub-
stituted vinyl phenyl ether. Under the conditions of the reaction
however, this vinyl ether reacts like any other vinyl ether with a
phenol to give a resin which probably has an ethylidine structure.
Reppe, in his formulation of Koresin, has given it the alternative
ethylene structure. Because infrared absorption shows the
presence of CHI and OH groups and nearly the same type of
material can be made from p-tertbutyl phenol and acetaldehyde
or p-tert-butyl phenol and a vinyl ether, this formulation does
not seem possible, It would be interesting to prepare the vinyl
tert-butyl phenyl ether and heat it under the conditions used in
the vinylation to see if polymerization of this type will occur.
Mercaptans (thiols), according t o the Reppe patents, form
vinyl thioethers. The reaction proceeds under approximately
the conditions outlined for the other active hydrogen compounds.
I n general, all the active hydrogen compounds which will form
stable potassium salts-alcohols, amines, acids, phenols, and mer-
captans-will react with acetylene under pressure a t 160" C. to
give in the majority of cases good yield of vinyl derivatives.
What is the mechanism of these reactions? So far, no basic
data have been published, so guesses will need verification.
With phenols and alcohols the following series of reactions looks
reasonable.
KOH + ROH ROK + HOH
ROK += OR- + K +
H
HC=CH + OR- HC=COR-
H
HCFZCOR- + ROH CHz=CHOR + OR-
A similar set of reactions appears suitable for acetylene and
amines such as carbazole, or with phenols and acetylene with
amines as catalysts. I n the case of acetylene and aqueous tri-
methylamine with no added catalyst, we can write a number of
untested mechanisms, such as
HC=CH+ HOH HCCHz+ + OH-
(CHJsN + HC=CHz+ + OH- +[(CHa),NCH=CHd+ OH-
ETHYNY LATION
In addition to its unsaturated characteristics, acetylene pos-
sesses active hydrogen atoms which should add to unsaturated
systems. This reaction is called ethynylation. Sodium acety-
1176 INDUSTRIAL AND ENGINEERING CHEhISTRY
lide and the Grignard derivative of acetylene will react with a
carbonyl group to form an acetylenic alcohol. Nieuwland found
that both the unsaturated nature and the hydrogen of acetylenr
could be activated by an aqueous mixture of potassium chloride,
ammonium chloride, cuprous chloride, and hydrochloride acid to
form monovinyl acetylene and higher polymers. Reppe has
found another copper salt, copper acetylide, which will catalyze
the hydrogen addition reaction to several types of unsaturated
systems, especially aldehydes and ketones. Because the only
details that have reached this country from I. G. on this general
reaction are for the synthesis of butynediol-1,4 and propargyl
alcohol, the present discussion is limited to the reaction condi.
tions used for the preparation of these two products (2, 6, 7 , 9.
13-1 8, 22-24).
HCECH + CHZO +HCZEECCH~OH
HC=CCHsOH + CHZO +HOCHZC-CCHeOH
The catalyst for these reactions is prepared by impregnating
silica withcopper nitrateand bismuthnitrateand heating to 500 "C.
to convert thc nitrates into a mixed oxide; the best one con-
tains at this step about 12% copper and 3% bismuth. The mix-
ture is packed into a tower and a formaldehyde solution and then
acetylene a t 5 to 6 atmospheres is passed down the tower to gen-
erate the catalyst, which is a copper acetylide-formaldehyde-
acetylene-water addition complex. When on stream a 15%
formaldehyde solution and pure acetylene are passed over this
catalyst a t 100" to 120" C.; it is important to keep the tempera-
ture below 130" C. This control can be accomplished by evapo-
rating some of the water or by using reactors of small diameter.
As catalysts go, a t least to a petroleum chemist, the copper acety-
lide is relatively inactive and requires a long contact time, from
0.33 t,o 3.5 hours, depending on the recycling system and the per-
centage of unchanged formaldehyde that can be tolerated in the
crude product. The reaction mixture is filtered to remove any
copper acetylide which may have come into the reaction product,
and the reaction product is then distilled.
The men who have seen the operation in Germany and those
who have operated i t in this country have found that the opera-
tion is not nearly so bad as i t sounds, if proper equipment is used.
As pure acetylene was used in this reaction, the acetylene was
handled under pressure by the second method outlined above
--that is, bundles of tube.
By the hydrogenation of butynediol, butenediol and bu-
tanediol are produced. The latter formed the basis of a butadiene
synthesis via tetrahydrofurane, and it also can be converted to
butyrolactone via dehydrogenation and then to pyrrolidone with
ammonia. All these materials and many others were used to
produce a great variety of compounds for practically all the fields
of organic chemistry.
Carbonyl compounds reported to react in a similar mannei
with acetylene are acetaldehyde, propionaldehyde, n-butyral-
dehyde, dodecanal, benzaldehyde, and acetone. Both the mono-
and di- addition products have been reported.
Another reaction which was found earlier by Reppe but has
not been studied in great detail is the reaction of meLhylolamine$
with acetylene in the presence of copper acetylide ( 1 7 ) . Thr
reaction of dimethylmethylolamine and acetylene with coppei
acetylide as the catalyst is as follows:
Vol. 40, No. 7
Both the mono- and di- addition products have been isolated.
Similarly, dimethyl01 urea and trimethylol melamine react with
acetylene to form addition compounds, the structures of which
are not accurately known because they have never been isolated.
On the basis of analogy, one would formulate the reaction as
follolrs:
F-IOCHzNHCNHCHzOH + HC-(>H ---+
II
0
' HOCH~NHCNHCH~CZZZCHHOH +
I1
0
CARBOXY LATlON
Another interesting reaction which has been developed b>
Reppe and his eo-workers is the synthesis of acrylic acid deriva-
tives from acetylene (8, 16). Apparently Reppe was initially
interested in trying to make propargyl aldehyde by the combina-
tion of carbon monoxide and acetylene in the way in which
he made propargyl alcohol, by the combination of acetylene and
formaldehyde. He studied the reaction of nickel carbonyl and
acetylene in the presence of acids. Instead of obtaining pro-
pargyl aldehyde, he obtained acrylic acid as the main product of
the reaction.
A gas, acetylene, reacts in a 2-phase liquid system with both
components as rapidly as the acetylene can be added and the
temperature kept under control.
A 500-cc. 4-necked flask was equipped with a condenser, stirrer,
thermometer, and bubbling tube. The flask was charged with 96
grams of methanol and 128 grams of nickel carbonyl. During
vigorous agitation, 133 grams of concentrated hydrochloric acid
and 90 liters of acetylene (25 C. and 760 mm., washed with water
and dried) were added during 3 hours. T i t h an ice bath the tem-
perature was held a t 25" to 30" C. At the end of this time, 40
liters of acetylene were added (during 30 minutes) as long as there
was liberation of heat.
About 300 cc. of water and 100 cc. of ether were added and the
two layers were separated. I n the reaction 181.3 grams of methyl
acrylate (78.7%theoretical based on nickel chloride), 4 grams of
methyl propionate, and 86.8 grams of nickel chloride were formed
The reaction ran as well as an Organic Syntheses preparation.
The method as outlined here requires the use of a stoichio-
metric quantity of nickel carbonyl. Reppe found that it is
possible to convert the nickel chloride back to nickel carbonyl'
by the reaction of nickel chloride with ammonia and then treat-
ment of the nickel ammonium chloride with carbon monoxide.
Ni(NH3)sCL + 5CO + 2H20 --+
Ni(C0)4 + 2NHaCI + (NH4)&03+ 2Pu'H1
Whether or not this synthesis will compete with some of the
other syntheses that have Seen and are being developed in this
c?untry, remains to be seen. Regardless of its economics or
commercial importance, it is an extremely interesting reaction and
a worth-while addition to our knowledge.
Reppe has found that if the alcohol contains water, hydrogena-
tion of the double bond of the acrylic acid does not occur; but if
the system is anhydrous, dehydrogenation occurs and the yield
of the acrylic ester is lower. The same reaction is stated t o go
July 1948 INDUSTRIAL AND ENGINEERING CHEMISTRY
for all the alcohols and also for the synthesis of amides by replac-
ing the alcohol with ammonia and amines.
Reppe believes that the formation of cyclopropenone occurs
by the direct combination of carbon monoxide and acetylene, and
this is then opened through the addition of the active hydro-
gen of the alcohol t o the system to give acrylic ester. This
mechanismis substantiated by the fact that substituted acetylenes
give both isomers expected by a ring opening.
Another very interesting reaction in this same field is the
reaction of carbon monoxide with acetylene in the presence of
cobalt carbonyl hydride, H.Co (CO)r, to yield hydroquinone.
OH
I The authors wish to thank their associates in the laboratory for
2HC=CH + 3CO + HzO --+
CYCLO-OCTATETRAENE
Q + COz
One of the reactions of acetylene developed by Reppe which
has probably caused more discussion than any other is the direct
formation of cyclo-octatetraene from acetylene under pressure
(10,37).
H H
. Hd
C=C
/ \
CH
4HC=CH -3
HJ AH
\ /
c=c
‘H H
The catalyst for this reaction IS nickel, cyanide, which is pre-
pared by the reaction of nickel chloride with hydrogen cyanide.
The catalyst is suspended in a selected solvent, anhydrous
tetrahydrofurane, and is charged to the reactor along with a
small amount of calcium carbide which is added to maintain
anhydrous conditions. The direct polymerization of acetylene
then occurs a t a temperature of 60 O to 70 O C. and with an acety-
lene pressure of about 250 pounds. Under slightly higher
pressures and somewhat higher temperatures] some of the higher
vinylogs of cyclo-octatetraene are obtained. Their structures,
however, have not yet been elucidated. After the acetylene
has been absorbed, the catalyst is filtered from the reaction mix-
t8ure,and the cyclo-octatetraene is isolated by distillation.
The physical properties of cyclo-octatetraene obtained by this
process agree with those previously repoxted by Willstiitter.
Numerous reactions of cyclo-octatetraene have been studied by
I. G. chemists, and it has been found to undergo some very
unusual transformations. It can be hydrogenated to a hexa-
hydro derivative and then oxidized by means of nitric acid to gfve
a good yield of suberic acid, shqwing that the ring hexahydro
derivative is an eight-member ring. This compound will un-
doubtedly be the subject of many papers within the next few
years.
SUMMARY
Omitted from this discussion are acetylene reactions such as
reduction of acetylene to ethylene, addition of hydrogen fluoride,
hydrogen sulfide, hydrogen cyanide, and ammonia. For work
with acetylene under pressure some means must be selected
of determining whether the reaction conditions to be used
are safe or unsafe. To run a vinylation with acetylene] the
best catalyst to test first is a potassium salt in an anhydrous
medium. If this is not satisfactory, then the zinc or cadmium
salt of the active hydrogen compound should be tried, or one of
1117
its higher homologs which is more likely to be soluble in the
reaction medium. If one wishes to run an ethynylation with
acetylene, the best catalyst will probably be copper acetylide,
some other copper compound, or some other acetylide. For
the addition of carbon monoxide to acetylene, the only effective
catalyst which has been reported to date is nickel carbonyl.
There is a wonderful field here for academic study of the
nature of the catalysts used in these acetylene reactions, and also
for obtaining further information on the mechanism and cont(ro1
of the decomposition of acetvlene.
ACKNOWLEDGMENT
their assistance.
LITERATURE CITED
(1) Alt, “Acetylene Chemistry,” U. S. Dept. Commerce OTS,
PB L60,285 (Mar. 28, 1947).
(2) Appleyard, C. G. S., and Gartshore, J. F. C., “Manufacture of
Butynediol a t I. G. Ludwigshafen, Germany,” Ibid., PB
28,556 (Aug. 9, 1946).
(3) Callott, W. S., “Researches in Acetylene Chemistry at I. G. Far-
benindustrie, Ludwigshafen, Germany,” Ibid., PB 9626
(April 19, 1946).
(4) Copeland, N. A,, and Youker, M. A,, “German Techniques
for Handling Acetylene in Chemical Operations,” Ibid., PB
20,078 (July 26, 1946).
(5) Evans, D. C., “New Technical Applications of Acetylene.”
Ibid., PB 18,953 (June 7, 1946).
(6) Fuller, D. L., et al., “Manufacture of Butynediol (and Certain
Related Materials) from Acetylene and Formaldehyde,”
Ibid., PB 80,334.
(7) Hopkinson, R., et al., “I. G. Farbenindustrie, Synthetic Rubber
Plant at Ludwigshafen, Germany,” Ibid., PB 1763 (Feb. 15,
1946).
(8) I. G. Farbenindustrie, Modern Plastics, 23, 162 (1945).
(9) I. G. Farbenindustrie, “Preparation of Butynediol,” U. S. Dept.
Commerce OTS, PB 19,320 (June 7, 1946).
(10) Kammermeyer, K., “Cyclo-octatetraene,” Ibid., PB 62,593 (May
30, 1947).
(11) Kline, G. M., Modern Plastics, 23, 157 (1945).
(12) Ibid., 24, 159 (1947).
(13) Monrad, C. C., “Reppe Butadiene Proccss,” U. S. Dept. Com-
merce OTS, PB 4604 (Mar. 8, 1946)
(14) Niemann, G., “State of the Reppe Process,” Ibid., PB 50,458
(Feb. 28, 1947).
(15) Reppe, J. W., “Acetylene as a Basis of a New Industrial Chem-
istry,” Ibid., PB 2437 (Feb. 8, 1946).
(16) Reppe, J. W., “Advances in Acetylene Chemistry,” Ibid., PB
1112 (Jan. 25, 1946).
(17) Reppe, J. W., “Advances in Acetylene Chemistry at I. G. Lud-
wigshafen,” Ibid., PB 13,366 (May 24, 1946).
(18) Reppe, J. W., “Butynediol ap a Basis for Plastics Intermediatez,”
Ibid., PB 11,394 (April 5, 1946).
(19) Reppe, J. W., “Synthesis of Intermediates for Polyamides on a n
Acetylene Basis,’’ Ibid., PB 25,553 (Aug. 2,1946).
(20) Reppe, J. W., et al., U . S. Patent 2,066,075 (Dec. 29, 1936)
(21) Ibid., 2,072,825 (March 2; 1937).
(22) Ibid., 2,300,969 (Nov. 3, 1942).
(23) Ibid., 2,319,707 (May 18, 1943).
(24) Ibid., 2,232,867 (Feb. 25, 1941).
(25) Rose, J. D., “Products Formed by the Interaction of Acetylene
and Amines,” U. S. Dept. Commerce OTS, PB 25,667 (Aug.
16, 1946).
(26) Schildknecht, C. E., et al., IND. ENG.CHEM.,39, 180 (1947) ; 63
references given.
(27) Textile Research Institute, “Synthetic Fiber Developments i n
Germany,” U. S. Dept. Commerce OTS, PB 7416 (March 29,
1946).
(28) Zoss, A. O., and Fuller, D. L., “Oppanol C,” Ibid., PB 67,694
(May 30, 1947).
REC~IVED March 26, 1947. Presented before the Division of Organic
Chemistry, Symposium on Some Contributions of Organic Chemistry t o the
War Effort, a t the 110th Meeting of the AMERICAN CHEMICALSOCIETY,
Chicago, Ill.
L