[CONTRIBUTION FROM TEE CHEMICAL LABORATORIES OF TEE UNIVERSITY OF

NOTRE DAME]
A PROPOSED MECHANISM FOR MERCURY CATALYSIS I N
ACETYLENE ADDITION REACTIONS*
G. F. HENNI ON, R. R. VOGT AND J . A. NI EUWLANDt
Received March 27, 19%
DISCUSSION
The many well-known reactions of acetylene with water, alcohols,
glycols, carboxylic acids, oxy-acids, phenols, etc., which yield acetaldehyde,
acetals, vinyl and ethylidene esters, and the like, are too numerous to
permit of review here. Some corresponding reactions with alkylacetylenes
have recently been described in publications from our 1aboratory.l
These reactions are similar in that they all proceed quite readily when
carried out in an appropriate acid medium in the presence of mercuric
oxide or a suitable mercuric salt. Considerable interest attaches to the
r61es played by the mercury and acid in these reactions. The amounts of
mercuric salt and acid required are so small that these substances must
undoubtedly undergo a definite cycle of reactions which may be repeated
until the mercuric salt is reduced by secondary reactions. Such recurring
reactions may well explain the nature of the so-called mercury catalysis
in acetylene chemistry. The mercuric salt must presumably be ionized
since slightly ionizable salts and conditions which depress ionization are,
in general, not suitable.
A small quantity of boron fluoride, when used with an alcohol, forms a
strongly acidic medium. Boron fluoride has been found to be an extremely
effective acid-forming catalyst. Nieuwland, Vogt and Foohey2 showed
* Paper XI11 on the chemistry of the alkylacetylenes and their addition com-
pounds; previous paper, J . Am. Chem. Soc., 68, 892 (1936).
t Editorial note: Dr. Nieuwland, a member of the Board of Editors of THIS J OURNAL,
died suddenly of a heart attack on J une 11th [Znd. Eng. Chem., News Ed., 14, 248
(J une 20, 1936)l. His many friends will welcome this outline of his views on a re-
action to the knowledge of which he was an outstanding contributor.
1 HENNION, NIEUWLAND AND COWORKERS, J . Am. Chem. Soc., ( a) 66, 1130 (1934);
(b) 56, 1384 (1934); ( c ) 66, 1786 (1934); ( d ) 66, 1802 (1934); ( e ) 67, 2006 (1935); (f) 68,
80 (1936).
2 NIEUWLAND, VOGT AND FOOHEY, ibid., 62, 1021 (1930).
159
160 G. F. HENNION, R. R. VOGT AND J . A. NIEUWLAND
that 0.142 grams of boron fluoride was sufficient to catalyze the conversion
of 250 grams of glycerol to the ethylidene acetal. Later Vaughn3 pointed
out that (50 f 2) X lo4 grams of boron fluoride per milliliter of glycol
is sufficient to catalyze the formation of glycol acetal. I n other casesleJ
a small amount of a strong acid, such as trichloroacetic acid, promotes the
catalytic effect of boron fluoride. The lower limit of the quantity of re-
quired mercuric oxide (or salt) has not been determined but is known to
be largely dependent upon experimental conditions.
A great deal of work concerning mercury-acetylene addition compounds
-much of which is questionable or indefinite-has been reported in the
literature. Kutscheroff4 was probably the first to recognize the existence
and catalytic effect of complex mercury-acetylene addition compounds;
nevertheless in many subsequent discussions the r81eof either the mercuric
salt or acid has been unjustifiably ignored.
A consideration of these catalytic effects should, in the light of present
experimental experience, include the following points.
1. Both a mercuric salt (or mercuric oxide which, no doubt, forms the
salt) and a strong acid are required. A notable exception to this rule is
the hydration of the acetylenic triple bond. Some acetaldehyde is formed,
for example, by passing acetylene through boiling 20% sulfuric acid.
Certain alkylacetylenes may be converted to ketones5 by dissolving in
strong sulfuric acid followed by dilution with water. Even in these in-
stances, however, the reactions are certainly more advantageously carried
out with the aid of a mercuric salt and a more dilute acid.
2. Acetylenic hydrogen cannot be concerned, or is at least unnecessary
for catalysis. It has been shown that the dialkylacetylenes form typical
derivatives by addition. For example, methylamylacetylene yields, with
methanol, 3 , 3-dimethoxyo~tane~~.
3. It is logical to believe that the catalytic mercury salt reacts with the
acetylene by addition, being subsequently replaced by the adding molecule.
It is quite probable that the mercury content of the catalytic intermediate
may depend upon whether acetylene, a monosubstituted acetylene or a
disubstituted acetylene is used. The authors are of the opinion that re-
placement of acetylenic hydrogen by mercury may be of secondary impor-
tance and not immediately concerned with the catalytic mechanism.
4. Vinyl ethers add alcohols to form ketals (acetals) with extreme ease
when catalyzed by a trace of strong acid only.6 It is significant that
mercuric compounds are not required in this step.
a VAUQHN, PTOC. Ind. Acad. Sci., 4, 129 (1933).
4 KUTSCEEROFF, Ber., 17, 13 (1884).
6 BEHAL, Ann. chim., [6], 16, 270 (1888).
* KILLIAN, HENNION AND NIEUWLAND, J . Am. Chem. SOC., 67, 544 (1935).
PROPOSED MECHANISM FOR MERCURY CATALYSIS
3
m
.3
F9
d
*
3
64
m
.rl
I
I
e-. 0
u
P4
161
162 G. F. HENNION, R. R. VOGT AND J. A. NIEUWLAND
5. The alkylacetylenes react with acetic acid to form monoaddition
compounds, e.g., 2-acetoxy-1-heptene from amylacetyleneld. With acety-
lene either mono- or diaddition compounds may be obtained.
6. The small amount of catalyst needed seems to indicate that its addi-
tion product is extremely reactive and easily decomposed.
7. I t is logical to believe that the mechanism of this catalysis is, in its
essential features, independent of the nature of the acetylene and the type
of hydroxylated compound being added.
The authors have formulated and here present a mechanism consistent
with these points, plausible, and useful as working tool.
NomencEature.-R and R are independently hydrogen atoms or alkyl
groups originating in the acetylene used. A represents the acid radical
contained in the mercuric salt and (or) the acid used. For example when
boron trifluoride and methyl alcohol are employed A becomes -OCHs.
BF,. The existence of the salt Hg(OCH3.BF3)2 was established by
OLeary and Wenzke. B represents the group attached to the hydroxyl
group of the adding molecule such as hydrogen (in the case of water),
alkyl groups (in the case of alcohols), or acyl groups (in the case of acids).
We are fully aware of the fact that such a mechanism is incapable of
rigid proof; hence none is offered. I n fact the extreme reactivity of the
intermediate mercury compounds and their susceptibility to reduction
(not infrequently to metallic mercury) argues against the possibility of
their isolation and characterization.
It is readily seen that the proposed scheme of reactions is generally
applicable to the addition of any hydroxy compound to any type of acet-
ylene. I n the event that the acetylene in question is a conjugate enyne
or diyne, where there is a possibility that reagents may add in the 1, 4
positions, it is only necessary to assume that the catalytic mercuric salt
previously added in that fashion.
SUMMARY
A mechanism for mercury catalysis in acetylene addition reactions is
The proposed scheme of reactions is plausible, consistent with offered.
experimental results, and useful as a working tool.
7 OLEARY AND WENZKE, i bi d. , 66, 2118 (1933).