Promotion of Raney Nickel Catalyst

EuropSiscnes Paterrtamt European Patent Office © Publication number: 0 210 683 Office europeen des brevets A1

EUROPEAN PATENT APPLICATION

S) Application number 86201150.9 C07D © int. ci.<: 233/76 , C07D 233/78 C07D 233/80 C07C 51/36 g) Date , , of filing: 30.06.86 C07C 67/303 C07C , 5/03 , C07C 9/15 , C07C 13/61 , C07B 35/02

® Priority: 01.07.85 US 749971 <3> Applicant: STAUFFER CHEMICAL COMPANY

@ Date of publication of application: Westport Connecticut 06881 (US) 04.02^7 Bulletin 87/06 @ Inventor: Mlrviss, Stanley Burton ® Designated Contracting States: 90 Surrey Road BE DE FR GB IT NL Stamford Connecticut 06903(US)

0 Representative: Smuiders, Theodorus A.H.J. etal Vereenlgde Octrooibureaux Nieuwe Parldaan 107 NL-2587 BP 's-Gravenhage(NL)

® Promotion of raney nickel 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 satu- ^. rated hydantoins and also for the reduction of cyclic ^and acyclic olefins and dioiefins to the correspond- ^_ ing cyclic and acyclic alkanes. 00

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Xerox Copy Centre 0 210 683

PROMOTION OF RANEY NICKEL CATALYST

In order to ensure maximum efficiency, an ef- FIELD OF THE INVENTION fective promoting agent for the Raney Nickel catalyzed hydrogenation of carbon-carbon double The present invention relates to improved pro- bonds is needed. cesses for the promotion of Raney Nickel catalyzed hydrogenation, or reduction, of carbon-carbon double bond containing compounds. SUMMARY OF THE INVENTION

In accordance with the present invention, there BACKGROUND OF THE INVENTION 10 are disclosed a number of processes for the promotion of Raney Nickel catalyzed hydrogenation of The reduction of carbon-carbon double bond aliphatic carbon-carbon double bonds. One em- containing compounds is a widely used chemical bodiment of the present invention comprises the process having a large variety of applications. For addition of tertiary amine as a promoting agent. instance, a desired alkane can be easily produced 75 Another embodiment of the present invention com- by reduction of the corresponding alkene. prises the use of acetylenic compounds as promot- One commonly employed technique for the ing agents. reduction of these carbon-carbon double bonds is catalytic hydrogenation wherein a catalyst is employed to hydrogenate, or reduce, the double or 20 DETAILED DESCRIPTION OF THE INVENTION olefinic bonds. Examples of catalysts which have been employed to reduce carbon-carbon double The present invention is directed to the promo- bonds include noble metal catalysts such as plati- tion of the Raney Nickel catalyzed hydrogenation num or palladium. Other commonly employed cata- of carbon-carbon double bonds. While the pro- lysts include copper chromite, cobalt molybdate, 25 cesses of the present invention may be used for and finely divided nickel or cobalt. the promotion of the Raney Nickel catalyzed hy- One of the most commonly used hydrogena- drogenation of carbon-carbon double bonds in any tion catalysts is Raney Nickel. While a somewhat aliphatic compound containing said bonds, they are effective hydrogenation catalyst the Raney Nickel particularly suited for the promotion of the Raney catalyst exhibits declining catalytic activity upon 30 Nickel catalyzed hydrogenation, or reduction, of prolonged storage necessitating the use of either a unsaturated hydantoins to saturated hydantoins. freshly prepared or newly purchased catalyst for The remainder of the application will be discussed maximum catalytic activity. Since preparation or in relation to the reduction of unsaturated hydan- purchase of a new batch of Raney Nickel can be toins although it is to be understood that the pro- expensive, an alternative procedure for ensuring 35 cesses of the present invention are equally ap- maximum catalytic activity is to use" a promoting plicable to the promotion of Raney Nickel catalyzed agent. Various promoting agents for Raney Nickel hydrogenation of carbon-carbon double bonds in a catalyzed hydrogenation are known. wide variety of compounds, for example, dienes In Pizey, Synthetic Reagents, Volume II, John and cyclic dienes. Generally, the compounds which Wiley and Sons, it is reported that the addition of 40 can be reduced by the process of the present organic bases to a Raney Nickel catalyst results in invention are those which contain aliphatic carbon- retardation of the hydrogenation of ketones, with carbon double bonds, i.e., non-aromatic com- the use of low concentrations of triethylamine and pounds. These compounds include the aforemen- N,N-dimethylaniline being exceptions to the above tioned cyclic and acyclic dienes as well as cyclic rule. It is also reported in the above reference that 45 and acyclic compounds containing one double triethylamine retards hydrogenation of the carbon- bond. Hereinafter the term "compound containing carbon double bond in alpha, beta unsaturated an aliphatic carbon-carbon double bond" refers to ketones while increasing hydrogenation of the keto the above mentioned non-aromatic compounds. group. The process of the invention is particularly so suited for the promotion of the Raney Nickel catalyzed reduction of substituted unsaturated hydantoins of the general formula. 0 210 683

H // A - C c - c

RjNN NR, \ / C n

where A is X or Y, and X is an unbranched or from about 3 to about 10 carbon atoms. In a given branched alkyl or alkenyl group, a cyctoalkyl group, case in the cycloalkyl or cycioalkenyl group, one or a cyctoalkenyl group, an alkytthio group, a hatoalkyl is more -CH2-units can also be replaced by -O, 15, group, a hatoaikenyl group, a hydroxyalkyl group, preferably from about 3 to about 10 ring atoms. an araikyl group, a mono-or diaikylaminoaikyl The afkoxy, alkytthio, hydroxyalkyl, mercaptoaikyl, group, an acyiaminoaikyl group, or a mercaptoaikyl mono or diaikylaminoaikyl and acyiaminoaikyl group. Preferably the aHcyi groups contain 1 to groups contain preferably 1 to about 10, especially about 20, especially 1 to about 10 carbon atoms, 20 1 to about 8 carbon atoms in the alkyl or acyl the alkenyl groups 2 to about 10, especially 2 to groups, and about 5 carbon atoms, the cycloalkyl and cyctoat- kenyl groups from about 3 to about 15, preferably Yis

»^iV>- or

in which Y,, Yt, and Y3 are the same or different aldehydes which may be used include, but are not and can be X as defined above, hydrogen, halo- limited to, aliphatic aldehydes such as butyral- gen, e.g. of atomic weight 9 to 80, a hydroxy dehyde, isobutyraidehyde, vaieraidehyde, group, a nitro group, a cyano group, an amino 35 isovaleraldehyde, caproaldehyde, enanthaidehyde, group, an araikyl group, or an alkaryl group. Prefer- nonaidehyde, cyclobutyialdehyde, cyclopentylal- ably, the araikyl and the alkaryl groups contain dehyde, cyctohexylaldehyde, furfural, 2- from about 7 to about 15 carbons in the alkylene or thiopheneakJehyde, 2-pyrroieatdehyde, imidazoteai- alkyl groups. In a given case, two of the groups Y, dehyde, oxazoteakJehyde, 3-indotealdehyde, to Y, together can form an alkylene or alkenylene 40 pyridyiaktehyde, pyrimidylaldehyde, matonic acid group with from about 3 to about 5 carbon atoms half aldehyde, as well as the monoaldehyde deriva- whereby in this case one or more -CHj-units can tives of dicarboxylic acids such as, for example, be replaced by -O-, -S-, or -NH-or -CH= can be succinic, oxalic, glutaric and adipic acid. replaced by -N = . Aromatic aldehydes can also be used. Exam- R, and R, are the same or different and are 45 pies of aromatic aldehydes include, out are not hydrogen, alkyl, aryl, or amino. limited to, benzaldehyde, tolylatdehyde, 4- The unsaturated hydantotn to be reduced can isopropyibenzaidehyde, 4-hydroxybenzaldehyde, be purchased commercially or can be synthesized, 3,4,5-trimethoxybenzaktehyde, 3-bromo-4-methox- for example, through the condensation reaction of ybenzakJehyde, 3,4-methylenedioxy-benzaldehyde, an aliphatic or aromatic aldehyde with a substituted 50 2-hydroxy-4-nitrobenzaldehyde, 4,5-dimethoxy2- or unsubstituted hydantoin. nitrobenzaldehyde, saiicylaldehyde, vanillin, 4- One such condensation reaction is disclosed in phenylbenzaldehyde, 4-benzyibenzaldehyde, 4- United States copending application Serial No. fluorobenzaldehyde, 4-dimethylaminobenzai- 641,888 entitled "New Inexpensive Catalyst for the dehyde, 4-acetoxybenzaldehyde, 4-acetaminoben- Protection of Unsaturated Hydantoins", in which the 55 zaldehyde, 4-methytthiobenzaldehyde, and 3,5- condensation reaction of an aldehyde and hydan- dichkxo-4-hydroxybenzaidehyde. Additional al- toin is carried out in the presence of a basic salt of dehydes include p-tolyialdehyde, m-tolylaklehyde, an inorganic acid. In this process, representative 4-chiorobenzaidehyde, 4-hexylbenzaidehyde, 2-al- 0 210 683 tylbenzaldehycte, 4-allylbenzaldehyde, 2-vinylben- this subject can be found in Freifelder, Practical zakSehyda, 3-vmyfbenzaktehyde, 4-methallylbenzal- Catalytic Hvdroaenation. Wiley Interscience, 1971 dehyde, 4-crotylbenzaldehyde, 2-nitrobenzal- pp. 6r7, the discussion therein being incorporated dehyde, 3-nttrobenzakfehyde, 4-nitrobenzaldehyde, by reference. As is known to those skilled in the 2-aminobenzaldehyde, 4-aminobenzaldehyde, 4- 5 art, the Raney Nickel catalyst must be kept under cycloprapylbenzaldehyde, 2-cyclopropylbenzal- water. The Raney Nickel catalyst produced through dehyde, 4-cyclohexylbenzaldehyde, 2,6-dich- the above procedure will hereinafter be referred to lorobenzaldehyde, anisaldehyde, 3-hydroxybenzaI- as a "nickel catalyst". dehyde, 2-hydroxybenzaldehyde, 2-hydroxy-4- An example of the Raney Nickel catalyzed methylbenzaldehyde, 2-hydroxy-3-methoxybenzal- w hydrogenation of unsaturated hydantoins to satu- dehyde, veratraldehyde, 2,4-dihydroxybenzal- rated hydantoins is disclosed in copending United dehyde, 2,5-dihydroxybenzaldehyde, 4-cyclohex- States Application Serial No. 641,886 entitled enylbenzaldehyde, 4-cyclooctyIbenzaIdehyde, 4- "Reduction of Unsaturated, Substituted Hydantoins piperidinylbenzaklehyde, 4-pyridinebenzaldehyde, to Saturated, Substituted Hydantoins" filed August 4-furylbenzaldehyde, 4-thienylbenzaldehyde, 4- 75 17, 1984, the material therein being incorporated phenylethylbenzaldehyde, 4-sec.butyl benzal- by reference. While the above application discloses dshyde, 4-morphoBnobenzaldehyde, 4-isopropox- the reduction of unsaturated hydantoins by using ybenzaldehyde, 2-propoxybenzaldehyde, 3-ethox- Raney Nickel catalyst in the presence of more than ybenzaldehyde, 4-hexoxybenzaldehyde, 2- a stoichiometric amount of caustic, the present isopropylaminobenzaldehyde, 4-hexylaminobenzal- 20 invention is directed to the promotion of Raney dehyde, 4-diethylaminobenzaldehyde, 4- Nickel catalyzed hydrogenation of carbon-carbon dipropylaminobenzaldehyde, 4- double bonds under a wide variety of reaction methylethylaminobenzaldehyde, 3,4-ethylenediox- conditions, including in the presence of ybenzaldehyde, 4-acetylthiobenzaldehyde, 4-pro- stoichiometric or less than stoichiometric amounts pionoxybenzaldehyde, 4-formoxybenzakJehyde, 4- 25 of caustic. butyroxybenzaldehyde, 3,4-tetramethylenebenzal- In one embodiment of the present invention, it dehyde, 3,4-trimethylenebenzaldehyde, 3,4- has now surprisingly been discovered that the dihyroxybenzaldehyde, alphanaphthaldehyde, beta- Raney Nickel catalyzed hydrogenation of carbon- naphthaldehyde, and 3-indenecarboxaldehyde. carbon double bonds is promoted in the presence In addition, the above process is also suited to 30 of a tertiary amine. This result is rather surprising the condensation reaction of hydantoins substituted in light of the literature which reports that the at the N-1 and N-3 position such as 3-methyl- presence of the tertiary amine actually retards hy- hydantoin, 1 ,3-diacetylhydantoin, 1 ,3-diphenylhy- drogenation of the carbon-carbon double bond. dantoin, 3-benzylhydantoin, 1 ,3-dibenzylhydantoin The tertiary amines which can be employed as and the like. 35 promoting agents in the present invention are those It has now been discovered that the unsatu- corresponding to the general formula rated hydantoin produced in the above- reaction, available commercially or produced through other N(R), means, can be reduced in a fast reaction time to the corresponding saturated hydantoin by carrying 40 wherein R is C, to C, straight or branched chain out the hydrogenation step using Raney Nickel alkyl, aryl, substituted aryl, alkaryl, substituted al- catalyst in the present of a promoting agent to karyl, aralkyl and substituted aralkyl. Suitable increase the hydrogenation rate. amines will have some degree of solubility in the The Raney Nickel catalyst employed is avail- hydrogenation media. able commercially (for example, from the Davison 45 Examples of tertiary amines which can be used Division of W.R. Grace). Briefly, the preparation of as promoting agents in the present invention in- this catalyst involves fusing about 50 parts nickel clude.for example, triethylamine, trimethylamine, with about 50 parts aluminum as described in U. S. tripropylamine, triisobutylamine, tricyclohexylamine, Patent Nos. 1,628,190 and 1,915,473, pulverizing dimethylcyclohexyiamine, N,N-dimethylaniline, N- the alloy and dissolving out most of the aluminum 50 methyl-N-ethylaniline, and the like. Combinations of with sodium hydroxide solution [J. Am.Chem. Soc. the above amines can also be used. However, it is 54, 4116 (1932)]. The nickel is then washed to preferred to use tertiary alkyl amines with at least remove any residual sodium hydroxide [Ind. and some degree, i.e., partial solubility in the hydroge- Eng. Chem. 33 1199 (1940)]. The exact mechanism nation medium. through which Raney Nickel exerts its catalytic 55 The amount of tertiary amine used as a pro- activity is not known. Various theories have been moting agent can range from about 0.10 to about put forth including absorbed hydrogen or the for- 50 weight percent, preferably from about 0.5 to mation of nickel hydride. A complete discussion of about 25 weight percent based on the amount of 0 210 683

Raney Nrckei. In the case of the promotion of the The acetylene, or acetylenic compounds which Raney Nickel catalyzed reduction of unsaturated are useful promoting agents in the present inven- hydantoins, the tertiary amine can be used at a tion are those corresponding to the formula level ranging from about 0.01 to about 20 weight percent preferably from about 0.05 to about 10 s R»R, weight percent based on the unsaturated hydantoin. wherein R and R, are the same or different and are It has also surprisingly been found that tertiary C, to C« straight or branched chain substituted or amines function as efficient promoting agents for unsubstituted alkyl, substituted or unsubstituted different grades (types) of Raney Nickel catalyst io cydoalkyi, substituted unsubstituted cyctoalkenyl, Thus, consistent hydrogenation of carbon-carbon substituted or unsubstituted alkaryl or aryl or sub- double bonds can be achieved through the use of stituted aryl up to three fused rings, substituted or any Raney Nickel catalyst plus the promoting unsubstituted cydoalkyi or cyctoalkenyl groups agent. wherein one or more of the -CHrunrts is replaced The media in which the hydrogenation reaction 75 by -O-, -S-or -NH-or -CH= is replaced by -N-so is conducted is dependent upon the particular that there is present the corresponding heterocyclic carbon-carbon double bond containing compound ring with 3 to about 15 carbon atoms. By which is to be reduced. For instance, if the carbon- "unsubstituted" as used herein is meant the parent carbon double bond containing compound to be compound, i.e., benzene, pyridine, etc. By reduced is an unsaturated hydantotn, the Raney 20 "substituted" as used herein is meant any substitu- Nickel catalyst and tertiary amine can be added to ent which is non-reactive under the reaction con- an aqueous alkaline media. Organic solvents and ditions employed. Examples of such substituents especially alcohols can also be used alone or in include, but are not limited to, amino, thio, alkoxy, combination with other solvents and/or water. suifono, amido, hydroxy, alkyamino, aminoalkyi, ah 25 kylthio and the like. alcohols can also be used alone or in combination Since the presence of the carbon-carbon triple with other solvents and/or water. bond is the important factor which tneoreticially Since the tertiary amine is functioning as a imbues the promoting properties upon the acety- promoting agent it can be added at any time to the lenic compounds, it is also within the scope of the reaction medium although it is preferable that the » present invention to use as promoting agents com- tertiary amine promoting agent be present at the pounds containing more than one carbon-carbon start of the reaction with the Raney Nickel. triple bond. Hereinafter, the term "acetyienic com- The hydrogenation reaction in the presence of pound" refers to the parent compound, acetylene, the promoting agent can be carried out at at- as well as derivatives thereof, e.g., mospheric pressure, if faster reaction times are 35 phenylacetytene, toiylacetylene, 1 ,7-octadiyne, and desired, elevated pressures ranging from about hexynes-1 and -2. Preferably, the acetylenic com- 0.25 to about 200 atmospheres may be used. pound will have some degree of solubility in the The temperature at which the hydrogenation hydrogenation medium. reaction is carried out is preferably from about The reaction conditions employed when using room temperature (25°C) to about 58"C. If desired, 40 acetylenic compounds as promoting agents for temperatures ranging from about 0°C to about Raney Nickel catalyzed hydrogenation of carbon- 1S0°C can also be used. In the case of the Raney carbon double bonds are essentially similar to Nickel catalyzed hydrogenation of unsaturated those employed when a tertiary amine is used as a hydantoins, particularly 5-alkenyl hydantoins, it is promoting agent. Thus, the temperature, pressure preferred to keep the temperature below 60 °C to 46 and medium conditions under which the reaction is avoid hydrolysis of tie unsaturated hydantoins to conducted are those hereinbefore described. Simi- the corresponding pyruvic acid or salt thereof. larly, acetylenic compounds with at least partial Such hydrolysis can occur to a degree at reaction solubility also act as promoting agents for different temperatures of 60 °C or higher and particularly in grades (types) of Raney Nickel. the presence of caustic. so The amount of acetylenic compound employed In another embodiment of the present inven- as a promoting agent can range from about 0.10 to tion, it has also been found that acetylenes and about 50 weight percent preferably from about 0.5 acetylenic compounds function as efficient promot- to about 25 weight percent based upon the amount ing agents for the Raney Nickel catalyzed hy- of Raney Nickel used. If the acetyienic compound drogenation of carbon-carbon double bonds. 55 is used as a promoting agent for the Raney Nickel catalyzed hydrogenation of unsaturated hydantoins, 0 0 210 683 10 the amount of acetyienic compound used can EXAMPLE 2 range from about Q.10 to about 50 weight percent based on the amount of Raney Ntckei needed to The procedure was that of Comparative Exam- reduce the unsaturated hydantotn. ple 2 except 2 drops of triethylamine were added The present invention is illustrated by the fol- at the beginning of the reaction. The hydrogenation lowing Examples. was 81% complete in 26 hours, 91% complete in 33 hours and 100% complete in 40 hours.

COMPARATIVE EXAMPLE 1 w COMPARATIVE EXAMPLE 3 A 500 milliliter, round bottomed, 3 necked flask was fitted with a mechanical stirrer, thermometer, The procedure was essentially that of Com- dip tube for hydrogen or nitrogen flow, heating parative Example 1 except that 3 grams of No. mantle and condenser. The ffesk was preflushed 2400 Raney Nickel (Davison Division of W.R. with nitrogen and then 30 grams (0.15 mole) of 75 Grace) were used. The hydrogenation was 75% benzalhydantoin, 270 grams of deoxygenated dis- complete in 19 hours, 89% complete in 42 hours tilled water, and 6.5 grams (0.16 mole) of sodium and 100% complete in 57 hours. hydroxide were added. Under a nitrogen purge, 3 grams of 50% No. 2300 Raney Nickel (Davison Division of W. R. Grace) in water (1.5 gram dry 20 EXAMPLE 3 basis or 5 wt. % (dry basis) based on benzalhydantoin) were added. Under atmospheric pressure, the The procedure was essentially that of Com- hydrogen flow was turned on, the reaction mixture parative Example 3 except 2 drops of triethylamine was vigorously stirred and the temperature was were added at the beginning of the reaction. The raised to 50°C and held throughout the reaction. 25 hydrogenation was 84% complete in 18 hours, Samples were periodically withdrawn and submit- 92% complete in 24 hours and 100% complete in ted for liquid chromatographic analysis. The hy- 33 hours. drogenation reaction was 85% complete in 33 hours, 96% complete in 48.5 hours and 100% complete in 56.5 hours. A subsequent repeat run 30 COMPARATIVE EXAMPLE 4 required 56 hours for 83% completion and 71 hours for 100% completion. 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 EXAMPLE 1 35 poly(vinylpyridine) were used with the No. 2400 Raney Nickel. The hydrogenation was 75% com- The procedure was essentially that of Com- plete in 19 hours, 89% complete in 42 hours and parative Example 1 except 2 drops of triethylamine 100% complete in 57 hours. were added at the start of the reaction. The hydrogenation was 85% complete in 20 hours, 97% 40 complete in 27.5 hours and 100% complete in 35 EXAMPLE 4 hours. The catalyst from Example 3 (No. 2400 Raney Nickel (Davison Division of W. R. Grace)) was COMPARATIVE EXAMPLE 2 45 recycled and used with 2 drops of triethylamine. The hydrogenation results were exactly those seen The procedure was that of Comparative Exam- in Example 3, i.e., 100% complete in 33.5 hours. ple 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, 50 EXAMPLE 5 92% complete in 66 hours and 100% complete in 74 hours. Similar to Example 3 except the reaction was run at 10 psig hydrogen pressure and with better agitation. Complete hydrogenation was seen in 11 55 hours. 11 0 210 683 12

The following Examples illustrate the reduction COMPARATIVE EXAMPLE 7 of dodecene-1: b. With 16 wt % Raney Nickel

COMPARATIVE EXAMPLE 5 5 The same reaction as in Comparative Example 6 above was carried out except that 4 g. of 50% To a well stirred reactor was added 25 g. of No. 2800 (2 g. dry basis), and 4 g. of 50% No. dodecene-1 in 100 ml. of methyl alcohol and under 2400 (2 g. dry basis) Raney Nickels (from an atmosphere of nitrogen, 1.5 g. of NaOH and 3 g. Davison) were used. The reaction was 63% com- of 50% No. 2800 Raney Nickel in water (1.5 g. dry ia plete in 4 hrs. and 100% in 6 hrs. 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<>C, EXAMPLE 8 hydrogen was bubbled in at atmospheric pressure. The reaction was periodically monitored by GC rg The same reaction as in Comparative Example analysis. After 2 hrs. the hydrogenation was 61% 7 above was carried out except that 0.4 g. of complete. The hydrogenation was 100% complete triethylamine was also used. The reaction was 72% in about 4 hrs. complete in 4 hrs. and 100% complete in 5-5.25 hrs. 20 The following Proposed Examples illustrate that EXAMPLES the tertiary amine promotion of the Raney Nickel catalyzed reduction of carbon-carbon double bond This reaction was carried out identical to Com- containing compounds can be extended to other parative Example 5 except that 0.4 g of unsaturated compounds. triethylamine was also included. The reaction was 25 69% complete in 2 hrs. and was 100% done in 3.25 hrs. PROPOSED EXAMPLE 1 The following Examples illustrate the reduction of dicyctopentadiene: By essentially following the procedure of Ex- 30 amples 1 to 8 the nickel catalyzed reduction of an unsaturated alcohol containing at least one aliphatic COMPARATIVE EXAMPLE 6 carbon-carbon double bond is promoted in the presence of a tertiary amine. a. With 40 wt. % Raney Nickel 35 A well stirred reaction vessel was charged with PROPOSED EXAMPLE 2 25 g. of dicyctopentadiene and 100 ml. of metha- nol. Under nitrogen was added 3 g. of NaOH and By essentially following the procedures of Ex- then 10 g. of 50% No. 2400 Raney Nickel (from amples 1 to 8, the nickel catalyzed reduction of an Davison) in water (5 g. dry basis) and 10 g. of 50% 40 alpha, beta, or other unsaturated carboxyiic acids No. 2800 Raney Nickel (from Davison) in water (5 or esters containing at least one aliphatic carbon- g. dry basis). With good stirring at 50 °C, hydrogen carbon double bond is promoted in tie presence of was bubbled in at atmospheric pressure. The hy- a tertiary amine. drogenation was sampled periodically for GC analysis. After 2.5 hrs., the reaction was 52% complete « and the reactions was 100% complete in 4.5-4.75 EXAMPLE 9 hrs. This Example shows the use of an acetylenic compound as a promoting agent. The procedure EXAMPLE 7 50 was that of Comparative Example 1 except 2 drops of phenylacetylene (0.3 wt. % based on benzal- The same reaction as in Comparative Example hydantion) were added at the beginning of the 8 above was done with 1 g. of triethylamine also reaction. The hydrogenation was 92% complete in present. The reaction with 59% complete in 2.5 35 hours and 100% complete in 43 hours. hrs. and was 100% complete in 3.75 hrs. 55 13 0 210 683 14

PROPOSED EXAMPLE 3 Claims

By essentially following the procedure of Ex- 1. A process for the promotion of the nickel ample 9 and substituting therein compounds con- catalyzed reduction of compounds containing at taining aliphatic carbon-carbon double bonds such least one aliphatic carbon-carbon double bond as dicyclopentactiene, 1-dodecene, unsaturated al- which comprises using a tertiary amine as a pro- cohols or unsaturated carbonyl-containing com- moting agent. pounds as enumerated in Proposed Example 2, the 2. A process according to Claim 1 wherein the nickel catalyzed reduction of these compound con- tertiary amine is triethylamine. taining at least one aliphatic carbon-carbon double 70 3. A process according to Claim 1 wherein the bond is promoted in the presence of an acetylenic compound containing at least one aliphatic carbon- compound. carbon double bond is an unsaturated hydantoin of Additional features of the preferred and most the formula: preferred embodiments of the present invention are found in the claims hereinafter. 75

H i // A - C » C C i RjN NR, \ / C it

wherein A is X and X is unbranched or branched kenyl having a -CH = replaced by -O-, -S-, or -N-; alkyl or alkenyf, cycloalkyl, cycloalkenyl alkylthio, hydroxyalkyl, aralkyl, mono or dialkyalkylaminoalkyl 30 R, and R2 are the same or different and are hy- acylaminoalkyl, mercaptoalkyl, cydoalkyl having a - drogen, alkyl, aryl, acyl or amino. CH2 group replaced by -O-, -S-, or -NH-, cycloal- 4. A process according to Claim 1 wherein the compound containing at least one aliphatic carbon- carbon double bond is an unsaturated hydantoin of 35 the formula:

H // A - C = C - C i RjN NR, \ / C

wherein A is Y and Y is 50

55 15 0 210 683 . 16

w wherein Y,, Yz and Y3 are the same or different and 6. A process according to Claim 1 wherein the are hydrogen, alkyl, alkenyl, cycloalkyl, compound containing at least one aliphatic carbon- cydoakienyl, aryl, hatogen, hydroxy, nrtro, cyano, carbon double bond is dodecene-1 . amino, atkylaminoalkyl, dialkylaminoalkyl, alkoxy, 7. A process according to Claim 1 wherein the alkytthio, acyloxy, mercaptoalkyl, atkaryl, aralkyl, T5 compound containing at least one aliphatic carbon- acylaminoalkyl, cycloalkyl having a -CH,-group re- carbon double bond contain is dicyclopentadiene. placed by -O-, -S-, or -NH-cycloalkenyl having a - 8. A process for the promotion of the nickel CH= replaced by -N-or where two of the mem- catalyzed hydrogenation compounds containing at bers. Y,, Y2, and Y, are joined together to form an least one aliphatic carbon-carbon double bond alkylene group having at least one -CH,-group re- 20 which comprises using an acetylenic compound as placed by -O-. -S-, or -NH= or an alkenylene a promoting agent. group having at least one -CH = group replaced by 9. A process according to Claim 8 wherein the -NH = ; acetylenic compound is phenylacetylene. 10. A process according to Claim 8 wherein the R, and R, are the same or different and are hy- 25 compound containing at least one aliphatic carbon- drogen, alkyl, aryl, acyl or amino. carbon double bond is an unsaturated hydantoin of 5. A process according to Claim 4 wherein the the formula: unsaturated hydantoin is 5-benzalhydantoin.

H // A - C C - C i i RjM NR, \ / C u

4O wherein A is X and X is unbranched or branched having a -CH » replaced by -O-, -S-, or -N-; alkyl or alkenyl, cycloalkyl, cycloalkenyl, alkylthio, hydroxyalkyl aralkyl, mono or dialkyalkylaminoikyl R, and R2 are the same or different and are hy- acylaminoalkyl, mercaptoalkyl, cycloalkyi having a - drogen, alkyl, aryl, acyl or amino. 45 CH, group replaced by -O-, -S-, or -NH-, cycloalkyl 1 1 . A process according to Claim 8 wherein the compound containing at least one aliphatic carbon- carbon double bond is an unsaturated hydantoin of the formula:

55 17 0 210 683 18

H // A - C C - C i i RXN NR, \ / C ii

wherein A is Y and Y is

wherein Y,, Y2 and Y3 are the same or different and alkylene group having at least one -CH2-group re- are hydrogen, alkyl, alkenyl, cycloalkyl, cycloal- placed by -O-, -S-, or -NH= or an alkenylene kenyl, aryl, halogen, hydroxy, nitro, cyano, amino, group having a -CH = group replaced by -N = ; alkylaminoaJkyl, dialkylaminoalkyl, alkoxy, alkylthio, 25 acyloxy, mercaptoalkyl, alkaryl, aralkyl, ac- R, and R2 are the same or different and are hy- ylaminoalfcyt, cycloalkyl having a -CH2-group re- drogen, alkyl, aryl, acyl or amino. placed by -O, -S-, or -NH-cycloalkenyl having a - 12. The process of Claim 11 wherein the un- CH= replaced by -N-or where two of the mem- saturated hydantoin is 5-benzalhydantoin. bers, Yu Y2, and Yj are joined together to form an 30

10 CUfOpMMI P&tMtt Application nombar J EUROPEAN SEARCH REPORT . Offk»

DOCUMENTS CONSIDERED TO BE RELEVANT EP 86201150.9 "tnttfirr nf rtnninnntirritft inHrnion tthara ■ppiopiian. CLASSIFICATION OF TH6 Catagwy to claim APPLICATION (kit CM)

C 07 D 233/76 A CH - A5 - 646 426 (WELLCOME FOUN- 1,3 DATION) C 07 D 233/78 ' * Claim 1; page 3, right column C 07 D 233/80 lines 52-68 - page 4, left C 07 column, lines 1-13 * C 51/36 C 07 C 67/303 C 07 C 5/03 CH - A5 - 639 650 (LILLY) 1.3 C 07 C 9/15 * Claim 1; page 2, right column lines 27-42 * C 07 C 13/61 C 07 B 35/02 GB - A - 1 595 694 (WELLCOME FOUN- 1,3 DATION ) * Claims 1,88; page 4, lines 40-50 - page 5, lines 1-9 *

TECHNICAL REUDS US - A - 3 919 271 (DU PONT) SEARCHED (Int. CM) * Claims * C 07 B 233/00

DE - A - 1 668 248 (JOHNSON) C 07 C 51/00 * Claims * C 07 C 67/00 C 07 C 5/00 C 07 C 9/00 GB - A - 1 219 763 (JOHNSON) 1.2 C 07 C * Claims 1,7; example ♦ 13/00 C 07 B 35/00

US - A - 3 150 203 (SHEPHERD) C 07 B 31/00 * Claim 1; example 1 *

Thapr thaabaan drawn up tor aRcMma Piaca or March Data of compMkM of tha VIENNA 08-10-1986 BRUS a CATEGORY OF CTTEO 0OCUM6NTS T : thaorywixkKiptaundarty+ngttw invention E: aarMaf patinl documant, but pubMihad on. or particularly ralavant if takanatona aftar tha (Ming data particularly raiavant if combinad with anothar 0: docuwan«cHad>nthaappweatton documant of thasama category L : documant citad for ofhar i aaauna I A: tachnoiogicai background O: non-writt dosura « : mambarotthai iMy( corraapoi wJiny I intarmadiata documant documant