Promotion of raney nickel hydrogenation catalyst

There is disclosed a number of processes for the promotion of the Raney Nickel catalyzed hydrogenation of carbon-carbon double bonds. (a) One process uses tertiary amines to promote the Raney Nickel catalyzed hydrogenation. (b) Another process uses acetylene and acetylene derivatives to promote the Raney Nickel catalyzed hydrogenation. The promotion of Raney Nickel catalyst is particularly suited for the reduction of unsaturated hydantoins to saturated hydantoins and also for the reduction of cyclic and acyclic olefins and diolefins to the corresponding cyclic and acyclic alkanes.

FIELD OF THE INVENTION 
The present invention relates to improved processes for the promotion of 
Raney Nickel catalyzed hydrogenation, or reduction, of carbon-carbon 
double bond containing compounds. 
BACKGROUND OF THE INVENTION 
The reduction of carbon-carbon double bond containing compounds is a widely 
used chemical process having a large variety of applications. For 
instance, a desired alkane can be easily produced by reduction of the 
corresponding alkene. 
One commonly employed technique for the reduction of these carbon-carbon 
double bonds is catalytic hydrogenation wherein a catalyst is employed to 
hydrogenate, or reduce, the double or olefinic bonds. Examples of 
catalysts which have been employed to reduce carbon-carbon double bonds 
include noble metal catalysts such as platinum or palladium. Other 
commonly employed catalysts include copper chromite, cobalt molybdate, and 
finely divided nickel or cobalt. 
One of the most commonly used hydrogenation catalysts is Raney Nickel. 
While a somewhat effective hydrogenation catalyst, the Raney Nickel 
catalyst exhibits declining catalytic activity upon prolonged storage 
necessitating the use of either a freshly prepared or newly purchased 
catalyst for maximum catalytic activity. Since preparation or purchase of 
a new batch of Raney Nickel can be expensive, an alternative procedure for 
ensuring maximum catalytic activity is to use a promoting agent. Various 
promoting agents for Raney Nickel catalyzed hydrogenation are known. 
In Pizey, Synthetic Reagents, Volume II, John Wiley and Sons, it is 
reported that the addition of organic bases to a Raney Nickel catalyst 
results in retardation of the hydrogenation of ketones, with the use of 
low concentrations of triethylamine and N,N-dimethylaniline being 
exceptions to the above rule. It is also reported in the above reference 
that triethylamine retards hydrogenation of the carbon-carbon double bond 
in alpha, beta unsaturated ketones while increasing hydrogenation of the 
keto group. 
In order to ensure maximum efficiency, an effective promoting agent for the 
Raney Nickel catalyzed hydrogenation of carbon-carbon double bonds is 
needed. 
SUMMARY OF THE INVENTION 
In accordance with the present invention, there are disclosed a number of 
processes for the promotion of Raney Nickel catalyzed hydrogenation of 
aliphatic carbon-carbon double bonds. One embodiment of the present 
invention comprises the addition of a tertiary amine as a promoting agent. 
Another embodiment of the present invention comprises the use of 
acetylenic compounds as promoting agents. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention is directed to the promotion of the Raney Nickel 
catalyzed hydrogenation of carbon-carbon double bonds. While the processes 
of the present invention may be used for the promotion of the Raney Nickel 
catalyzed hydrogenation of carbon-carbon double bonds in any aliphatic 
compound containing said bonds, they are particularly suited for the 
promotion of the Raney Nickel catalyzed hydrogenation, or reduction, of 
unsaturated hydantoins to saturated hydantoins. The remainder of the 
application will be discussed in relation to the reduction of unsaturated 
hydantoins although it is to be understood that the processes of the 
present invention are equally applicable to the promotion of Raney Nickel 
catalyzed hydrogenation of carbon-carbon double bonds in a wide variety of 
compounds, for example, dienes and cyclic dienes. Generally, the compounds 
which can be reduced by the process of the present invention are those 
which contain aliphatic carbon-carbon double bonds, i.e., non-aromatic 
compounds. These compounds include the aforementioned cyclic and acyclic 
dienes as well as cyclic and acyclic compounds containing one double bond. 
Hereinafter the term "compound containing an aliphatic carbon-carbon 
double bond" refers to the above mentioned non-aromatic compounds. 
The process of the invention is particularly suited for the promotion of 
the Raney Nickel catalyzed reduction of substituted unsaturated hydantoins 
of the general formula. 
##STR1## 
where A is X or Y, and X is an unbranched or branched alkyl or alkenyl 
group, a cycloalkyl group, a cycloalkenyl group, an alkylthio group, a 
haloalkyl group, a haloalkenyl group, a hydroxyalkyl group, an aralkyl 
group, a mono- or dialkylaminoalkyl group, an acylaminoalkyl group, or a 
mercaptoalkyl group. Preferably the alkyl groups contain 1 to about 20, 
especially 1 to about 10 carbon atoms, the alkenyl groups 2 to about 10, 
especially 2 to about 5 carbon atoms, the cycloalkyl and cycloalkenyl 
groups from about 3 to about 15, preferably from about 3 to about 10 
carbon atoms. In a given case in the cycloalkyl or cycloalkenyl group, one 
or more --OH.sub.2 - units can a1so be replaced by --O--, 15, preferably 
from about 3 to about 10 ring atoms. The alkoxy, alkylthio, hydroxyalkyl, 
mercaptoalkyl, mono or dialkylaminoalkyl and acylaminoalkyl groups contain 
preferably 1 to about 10, especially 1 to about 6 carbon atoms in the 
alkyl or acyl groups, and 
##STR2## 
in which Y.sub.1, Y.sub.2, and Y.sub.3 are the same or different and can 
be X as defined above, hydrogen, halogen, e.g. of atomic weight 9 to 80, a 
hydroxy group, a nitro group, a cyano group, an amino group, an aralkyl 
group, or an alkaryl group. Preferably, the aralkyl and the alkaryl groups 
contain from about 7 to about 15 carbons in the alkylene or alkyl groups. 
In a given case, two of the groups Y.sub.1 to Y.sub.3 together can form an 
alkylene or alkenylene group with from about 3 to about 5 carbon atoms 
whereby in this case one or more --OH.sub.2 -- units can be replaced by 
--O--, --S--, or --NH-- or --OH.dbd. can be replaced by --N.dbd.. 
R.sub.1 and R.sub.2 are the same or different and are hydrogen, alkyl, 
aryl, or amino. 
The unsaturated hydantoin to be reduced can be purchased commercially or 
can be synthesized, for example, through the condensation reaction of an 
aliphatic or aromatic aldehyde with a substituted or unsubstituted 
hydantoin. 
One such condensation reaction is disclosed in U.S. copending application 
Ser. No. 641,888, now U.S. Pat. No. 4,582,903, entitled "New Inexpensive 
Catalyst for the Production of Unsaturated Hydantoins", in which the 
condensation reaction of an aldehyde and hydantoin is carried out in the 
presence of a basic salt of an inorganic acid. In this process, 
representative aldehydes which may be used include, but are not limited 
to, aliphatic aldehydes such as butyraldehyde, isobutyraldehyde, 
valeraldehyde, isovaleraldehyde, caproaldehyde, enanthaldehyde, 
nonaldehyde, cyclobutylaldehyde, cyclopentylaldehyde, cyclohexylaldehyde, 
furfural, 2-thiophenealdehyde, 2-pyrrolealdehyde, imidazolealdehyde, 
oxazolealdehyde, 3-indolealdehyde, pyridylaldehyde, pyrimidylaldehyde, 
malonic acid half aldehyde, as well as the monoaldehyde derivatives of 
dicarboxylic acids such as, for example, succinic, oxalic, glutaric and 
adipic acid. 
Aromatic aldehydes can also be used. Examples of aromatic aldehydes 
include, but are not limited to, benzaldehyde, tolylaldehyde, 
4-isopropylbenzaldehyde, 4-hydroxybenzaldehyde, 
8,4,5-trimethoxybenzaldehyde, 3-bromo-4-methoxybenzaldehyde, 
3,4-methylenedioxybenzaldehyde, 2-hydroxy-4-nitrobenzaldehyde, 
4,5-dimethoxy-2-nitrobenzaldehyde, salicylaldehyde, vanillin, 
4-phenylbenzaldehyde, 4-benzylbenzaldehyde, 4-fluorobenzaldehyde, 
4-dimethylaminobenzaldehyde, 4-acetoxybenzaldehyde, 
4-acetaminobenzaldehyde, 4-methylthiobenzaldehyde, and 
3,5-dichloro-4-hydroxybenzaldehyde. Additional aldehydes include 
p-tolylaldehyde, m-tolylaldehyde, 4-chlorobenzaldehyde, 
4-hexylbenzaldehyde, 2-allylbenzaldehyde, 4-allylbenzaldehyde, 
2-vinylbenzaldehyde, 3-vinylbenzaldehyde, 4-methallylbenzaldehyde, 
4-crotylbenzaldehyde, 2-nitrobenzaldehyde, 8-nitrobenzaldehyde, 
4-nitrobenzaldehyde, 2-aminobenzaldehyde, 4-aminobenzaldehyde, 
4-cyclopropylbenzaldehyde, 2-cyclopropylbenzaldehyde, 
4-cyclohexylbenzaldehyde, 2,6-dichlorobenzaldehyde, anisaldehyde, 
3-hydroxybenzaldehyde, 2-hydroxybenzaldehyde, 
2-hydroxy-4-methylbenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 
veratraldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 
4-cyclohexenylbenzaldehyde, 4-cyclooctylbenzaldehyde, 
4-piperidinylbenzaldehyde, 4-pyridinebenzaldehyde, 4-furylbenzaldehyde, 
4-thienylbenzaldehyde, 4-phenylethylbenzaldehyde, 4-sec.butylbenzaldehyde, 
4-morpholinobenzaldehyde, 4-isopropoxybenzaldehyde, 2-propoxybenzaldehyde, 
3-exthoxybenzaldehyde, 4-hexoxybenzaldehyde, 2-isopropylaminobenzaldehyde, 
4-hexylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 
4-dipropylaminobenzaldehyde, 4-methylethylaminobenzaldehyde, 
3,4-ethylenedioxybenzaldehyde, 4-acetylthiobenzaldehyde, 
4-propionoxybenzaldehyde, 4-formoxybenzaldehyde, 4-butyroxybenzaldehyde, 
8,4-tetramethylenebenzaldehyde, 3,4-trimethylenebenzaldehyde, 
3,4-dihyroxybenzaldehyde, alphanaphthaldehyde, beta-naphthaldehyde, and 
3-indenecarboxaldehyde. 
In addition, the above process is also suited to the condensation reaction 
of hydantoins substituted at the N-1 and N-3 position such as 
3-methylhydantoin, 1,3-diacetylhydantoin, 1,3-diphenylhydantoin, 
3-benzylhydantoin, 1,3-dibenzylhydantoin and the like. 
It has now been discovered that the unsaturated hydantoin produced in the 
above reaction, available commercially or produced through other means, 
can be reduced in a fast reaction time to the corresponding saturated 
hydantoin by carrying out the hydrogenation step using Raney Nickel 
catalyst in the presence of a promoting agent to increase the 
hydrogenation rate. 
The Raney Nickel catalyst employed is available commercially (for example, 
from the Davison Division of W. R. Grace). Briefly, the preparation of 
this catalyst involves fusing about 50 parts nickel with about 50 parts 
aluminum as described in U.S. Pat. Nos. 1,628,190 and 1,915,473, 
pulverizing the alloy and dissolving out most of the aluminum with sodium 
hydroxide solution [J. Am. Chem. Soc. 54, 4116 (1932)]. The nickel is then 
washed to remove any residual sodium hydroxide [Ind. and Eng. Chem. 33 
1199 (1940)]. The exact mechanism through which Raney Nickel exerts its 
catalytic activity is not known. Various theories have been put forth 
including absorbed hydrogen or the formation of a nickel hydride. A 
complete discussion of this subject can be found in Freifelder, Practical 
Catalytic Hydrogenation, Wiley Interscience, 1971 pp. 6-7, the discussion 
therein being incorporated by reference. As is known to those skilled in 
the art, the Raney Nickel catalyst must be kept under water. The Raney 
Nickel catalyst produced through the above procedure will hereinafter be 
referred to as a "nickel catalyst". 
An example of the Raney Nickel catalyzed hydrogenation of unsaturated 
hydantoins to saturated hydantoins is disclosed in copending U.S. 
application Ser. No. 641,886, now abandoned, entitled "Reduction of 
Unsaturated, Substituted Hydantoins to Saturated, Substituted Hydantoins" 
filed Aug. 17, 1984, the material therein being incorporated by reference. 
While the above application discloses the reduction of unsaturated 
hydantoins by using Raney Nickel catalyst in the presence of more than a 
stoichiometric amount of caustic, the present invention is directed to the 
promotion of Raney Nickel catalyzed hydrogenation of carbon-carbon double 
bonds under a wide variety of reaction conditions, including in the 
presence of stoichiometric or less than stoichiometric amounts of caustic. 
In one embodiment of the present invention, it has now surprisingly been 
discovered that the Raney Nickel catalyzed hydrogenation of carbon-carbon 
double bonds is promoted in the presence of a tertiary amine. This result 
is rather surprising in light of the literature which reports that the 
presence of the tertiary amine actually retards hydrogenation of the 
carbon-carbon double bond. 
The tertiary amines which can be employed as promoting agents in the 
present invention are those corresponding to the general formula 
EQU N(R).sub.3 
wherein R is C.sub.1 to C.sub.12 straight or branched chain alkyl, aryl, 
substituted aryl, alkaryl, substituted alkaryl, aralkyl and substituted 
aralkyl. Suitable amines will have some degree of solubility in the 
hydrogenation media. 
Examples of tertiary amines which can be used as promoting agents in the 
present invention include, for example, triethylamine, trimethylamine, 
tripropylamine, triisobutylamine, tricyclohexylamine, 
dimethylcyclohexylamine, N,N-dimethylaniline, N-methyl-N-ethylaniline, and 
the like. Combinations of the above amines can also be used. However, it 
is preferred to use tertiary alkyl amines with at least some degree, i.e., 
partial solubility in the hydrogenation medium. 
The amount of tertiary amine used as a promoting agent can range from about 
0.10 to about 50 weight percent, preferably from about 0.5 to about 25 
weight percent based on the amount of Raney Nickel. In the case of the 
promotion of the Raney Nickel catalyzed reduction of unsaturated 
hydantoins, the tertiary amine can be used at a level ranging from about 
0.01 to about 20 weight percent, preferably from about 0.05 to about 10 
weight percent based on the unsaturated hydantoin. 
It has also surprisingly been found that tertiary amines function as 
efficient promoting agents for different grades (types) of Raney Nickel 
catalyst. Thus, consistent hydrogenation of carbon-carbon double bonds can 
be achieved through the use of any Raney Nickel catalyst plus the 
promoting agent. 
The media in which the hydrogenation reaction is conducted is dependent 
upon the particular carbon-carbon double bond containing compound which is 
to be reduced. For instance, if the carbon-carbon double bond containing 
compound to be reduced is an unsaturated hydantoin, the Raney Nickel 
catalyst and tertiary amine can be added to an aqueous alkaline media. 
Organic solvents and especially alcohols can also be used alone or in 
combination with other solvents and/or water. 
Since the tertiary amine is functioning as a promoting agent, it can be 
added at any time to the reaction medium although it is preferable that 
the tertiary amine promoting agent be present at the start of the reaction 
with the Raney Nickel. 
The hydrogenation reaction in the presence of the promoting agent can be 
carried out at atmospheric pressure. If faster reaction times are desired, 
elevated pressures ranging from about 0.25 to about 200 atmospheres may be 
used. 
The temperature at which the hydrogenation reaction is carried out is 
preferably from about room temperature (25.degree. C.) to about 58.degree. 
C. If desired, temperatures ranging from about 0.degree. C. to about 
150.degree. C. can also be used. In the case of the Raney Nickel catalyzed 
hydrogenation of unsaturated hydantoins, particularly 5-alkenyl 
hydantoins, it is preferred to keep the temperature below 60.degree. C. to 
avoid hydrolysis of the unsaturated hydantoins to the corresponding 
pyruvic acid or salt thereof. Such hydrolysis can occur to a degree at 
reaction temperatures of 60.degree. C. or higher and particularly in the 
presence of caustic. 
In another embodiment of the present invention, it has also been found that 
acetylenes and acetylenic compounds function as efficient promoting agents 
for the Raney Nickel catalyzed hydrogenation of carbon-carbon double 
bonds. 
The acetylene, or acetylenic compounds which are useful promoting agents in 
the present invention are those corresponding to the formula 
EQU R.tbd.R.sub.1 
wherein R and R.sub.1 are the same or different and are C.sub.1 to C.sub.10 
straight or branched chain substituted or unsubstituted alkyl, substituted 
or unsubstituted cycloalkyl, substituted unsubstituted cycloalkenyl, 
substituted or unsubstituted alkaryl or aryl or substituted aryl up to 
three fused rings, substituted or unsubstituted cycloalkyl or cycloalkenyl 
groups wherein one or more of the --CH.sub.2 -- units is replaced by 
--O--, --S-- or --NH-- or --C.dbd. is replaced by --N-- so that there is 
present the corresponding heterocyclic ring with 3 to about 15 carbon 
atoms. By "unsubstituted" as used herein is meant the parent compound, 
i.e., benzene, pyridine, etc. By "substituted" as used herein is meant any 
substituent which is non-reactive under the reaction conditions employed. 
Examples of such substituents include, but are not limited to, amino, 
thio, alkoxy, sulfono, amido, hydroxy, alkyamino, aminoalkyl, alkylthio 
and the like. 
Since the presence of the carbon-carbon triple bond is the important factor 
which theoreticially imbues the promoting properties upon the acetylenic 
compounds, it is also within the scope of the present invention to use as 
promoting agents compounds containing more than one carbon-carbon triple 
bond. Hereinafter, the term "acetylenic compound" refers to the parent 
compound, acetylene, as well as derivatives thereof, e.g., 
phenylacetylene, tolylacetylene, 1,7-octadiyne, and hexynes-1 and -2. 
Preferably, the acetylenic compound will have some degree of solubility in 
the hydrogenation medium. 
The reaction conditions employed when using acetylenic compounds as 
promoting agents for the Raney Nickel catalyzed hydrogenation of 
carbon-carbon double bonds are essentially similar to those employed when 
a tertiary amine is used as a promoting agent. Thus, the temperature, 
pressure and medium conditions under which the reaction is conducted are 
those hereinbefore described. Similarly, acetylnic compounds with at last 
partial solubility also act as promoting agents for different grades 
(types) of Raney Nickel. 
The amount of acetylenic compound employed as a promoting agent can range 
from about 0.10 to about 50 weight percent preferably from about 0.5 to 
about 25 weight percent based upon the amount of Raney Nickel used. If the 
acetylenic compound is used as a promoting agent for the Raney Nickel 
catalyzed hydrogenation of unsaturated hydantoins, the amount of 
acetylenic compound used can range from about 0.10 io to about 50 weight 
percent based on the amount of Raney Nickel needed to reduce the 
unsaturated hydantoin. 
The present invention is illustrated by the following Examples. 
COMATIVE EXAMPLE 1 
A 500 milliliter, round bottomed, 3 necked flask was fitted with a 
mechanical stirrer, thermometer, dip tube for hydrogen or nitrogen flow, 
heating mantle and condenser. The flask was preflushed with nitrogen and 
then 30 grams (0.15 mole) of benzalhydantoin, 270 grams of deoxygenated 
distilled water, and 6.5 grams (0.16 mole) of sodium hydroxide were added. 
Under a nitrogen purge, 3 grams of 50% No. 2800 Raney Nickel (Davison 
Division of W. R. Grace) in water (1.5 gram dry basis or 5 wt. % (dry 
basis) based on benzalhydantoin) were added. Under atmospheric pressure, 
the hydrogen flow was turned on, the reaction mixture was vigorously 
stirred and the temperature was raised to 50.degree. C. and held 
throughout the reaction. Samples were periodically withdrawn and submitted 
for liquid chromatographic analysis. The hydrogenation reaction was 85% 
complete in 83 hours, 96% complete in 48.5 hours and 100% complete in 56.5 
hours. A subsequent repeat run required 56 hours for 83% completion and 
71 hours for 100% completion.

EXAMPLE 1 
The procedure was essentially that of Comparative Example 1 except 2 drops 
of triethylamine were added at the start of the reaction. The 
hydrogenation was 85% complete in 20 hours, 97% complete in 27.5 hours and 
100% complete in 35 hours. 
COMATIVE EXAMPLE 2 
The procedure was that of Comparative Example 1 except 3 grams of No. 200 
Raney Nickel (Davison Division of W. R. Grace) were used. The 
hydrogenation was 87% complete in 35 hours, 92% complete in 66 hours and 
100% complete in 74 hours. 
EXAMPLE 2 
The procedure was that of Comparative Example 2 except 2 drops of 
triethylamine were added at the beginning of the reaction. The 
hydrogenation was 81% complete in 26 hours, 91% complete in 33 hours and 
100% complete in 40 hours. 
COMATIVE EXAMPLE 3 
The procedure was essentially that of Comparative Example 1 except 3 grams 
of No. 2400 Raney Nickel (Davison Division of W. R. Grace) were used. The 
hydrogenation was 75% complete in 19 hours, 89% complete in 42 hours and 
100% complete in 57 hours. 
EXAMPLE 3 
The procedure was essentially that of Comparative Example 3 except 2 drops 
of triethylamine were added at the beginning of the reaction. The 
hydrogenation was 84% complete in 18 hours, 92% complete in 24 hours and 
100% complete in 33 hours. 
COMATIVE EXAMPLE 4 
This Example shows the need for a soluble tertiary amine. Instead of using 
2 drops of triethylamine as in Examples 1 to 3, 3 grams of 
poly(vinylpyridine) were used with the No 2400 Raney Nickel. The 
hydrogenation was 75% complete in 19 hours, 89% complete in 42 hours and 
100% complete in 57 hours. 
EXAMPLE 4 
The catalyst from Example 3 (No. 2400 Raney Nickel (Davison Division of W. 
R. Grace)) was recycled and used with 2 drops of triethylamine. The 
hydrogenation results were exactly those seen in Example 3, i.e., 100% 
complete in 33.5 hours. 
EXAMPLE 5 
Similar to Example 8 except the reaction was run at 10 psig hydrogen 
pressure and with better agitation. Oomplete hydrogenation was seen in 11 
hours. 
The following Examples illustrate the reduction of dodecene-1: 
COMATIVE EXAMPLE 5 
To a well stirred reactor was added 25 g. of dodecene-1 in 100 ml. of 
methyl alcohol and under an atmosphere of nitrogen, 1.5 g. of NaOH and 3 
g. of 50% No. 2800 Raney Nickel in water (1.5 g. dry basis) (from Davison) 
and 3 g. of 50% No. 2400 Raney Nickel (from Davison) (1.5 g. dry basis) 
were added. With vigorous stirring at 40-45.degree. C., hydrogen was 
bubbled in at atmospheric pressure. The reaction was periodically 
monitored by GC analysis. After 2 hrs. the hydrogenation was 61% complete. 
The hydrogenation was 100% complete in about 4 hrs. 
EXAMPLE 6 
This reaction was carried out identical to Comparative Example 5 except 
that 0.4 g. of triethylamine was also included. The reaction was 69% 
complete in 2 hrs. and was 100% done in 3.25 hrs. 
The following Examples illustrate the reduction of dicyclopentadiene: 
COMATIVE EXAMPLE 6 
a. With 40 wt. % Raney Nickel 
A well stirred reaction vessel was charged with 25 g. of dicyclopentadiene 
and 100 ml. of methanol. Under nitrogen was added 3 g. of NaOH and then 10 
g. of 50% No. 2400 Raney Nickel (from Davison) in water (5 g. dry basis) 
and 10 g. of 50% No. 2800 Raney Nickel (from Davison) in water (5 g. dry 
basis). With good stirring at 50.degree. C., hydrogen was bubbled in at 
atmospheric pressure. The hydrogenation was sampled periodically for GC 
analysis After 2.5 hrs., the reaction was 52% complete and the reaction 
was 100% complete in 4.5-4.75 hrs. 
EXAMPLE 7 
The same reaction as in Comparative Example 6 above was done with 1 g. of 
triethylamine also present. The reaction was 59% complete in 2.5 hrs. and 
was 100% complete in 3.75 hrs. 
COMATIVE EXAMPLE 7 
b. With 16 wt. % Raney Nickel 
The same reaction as in Comparative Example 6 above was carried out except 
that 4 g. of 50% No. 2800 (2 g. dry basis), and 4 g. of 50% No. 2400 (2 g. 
dry basis) Raney Nickels (from Davison) were used. The reaction was 63% 
complete in 4 hrs. and 100% in 6 hrs. 
EXAMPLE 8 
The same reaction as in Comparative Example 7 above was carried out except 
that 0.4 g. of triethylamine was also used. The reaction was 72% complete 
in 4 hrs. and 100% complete in 5-5.25 hrs. 
The following proposed Examples illustrate that the tertiary amine 
promotion of the Raney Nickel catalyzed reduction of carbon-carbon double 
bond containing compounds can be extended to other unsaturated compounds. 
PROPOSED EXAMPLE 1 
By essentially following the procedure of Examples 1 to 8 the nickel 
catalyzed reduction of an unsaturated alcohol containing at least one 
aliphatic carbon-carbon double bond is promoted in the presence of a 
tertiary amine. 
PROPOSED EXAMPLE 2 
By essentially following the procedures of Examples 1 to 8, the nickel 
catalyzed reduction of an alpha, beta, or other unsaturated carboxylic 
acids or esters containing at least one aliphatic carbon-carbon double 
bond is promoted in the presence of a tertiary amine. 
EXAMPLE 9 
This Example shows the use of an acetylenic compound as a promoting agent. 
The procedure was that of Comparative Example 1 except 2 drops of 
phenylacetylene (0.3 wt. % based on benzalhydantion) were added at the 
beginning of the reaction. The hydrogenation was 92% complete in 85 hours 
and 100 % complete in 43 hours. 
PROPOSED EXAMPLE 3 
By essentially following the procedure of Example 9 and substituting 
therein compounds containing aliphatic carbon-carbon double bonds such as 
dicyclopentadiene, 1-dodecene, unsaturated alcohols or unsaturated 
carbonyl-containing compounds as enumerated in Proposed Example 2, the 
nickel catalyzed reduction of these compound containing at least one 
aliphatic carbon-carbon double bond is promoted in the presence of an 
acetylenic compound. 
Additional features of the preferred and most preferred embodiments of the 
present invention are found in the claims hereinafter.