GB1569334A - Creation of Inventions and Patents with Artificial Intelligence

GB1569334A – Process for the selective hydrogenation of the keto group in nonconjugated olefinic keytones
– Google Patents

GB1569334A – Process for the selective hydrogenation of the keto group in nonconjugated olefinic keytones
– Google Patents
Process for the selective hydrogenation of the keto group in nonconjugated olefinic keytones

Download PDF
Info

Publication number
GB1569334A

GB1569334A
GB40571/77A
GB4057177A
GB1569334A
GB 1569334 A
GB1569334 A
GB 1569334A
GB 40571/77 A
GB40571/77 A
GB 40571/77A
GB 4057177 A
GB4057177 A
GB 4057177A
GB 1569334 A
GB1569334 A
GB 1569334A
Authority
GB
United Kingdom
Prior art keywords
process according
methyl
ketone
reaction
chromium
Prior art date
1976-09-30
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Expired

Application number
GB40571/77A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Rhone Poulenc Industries SA

Original Assignee
Rhone Poulenc Industries SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1976-09-30
Filing date
1977-09-29
Publication date
1980-06-11

1977-09-29
Application filed by Rhone Poulenc Industries SA
filed
Critical
Rhone Poulenc Industries SA

1980-06-11
Publication of GB1569334A
publication
Critical
patent/GB1569334A/en

Status
Expired
legal-status
Critical
Current

Links

Espacenet

Global Dossier

Discuss

Classifications

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone

C07C403/02—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains containing only carbon and hydrogen atoms

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring

C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group

C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH

C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones

C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms

C07C403/08—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by hydroxy groups

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C2601/00—Systems containing only non-condensed rings

C07C2601/12—Systems containing only non-condensed rings with a six-membered ring

C07C2601/14—The ring being saturated

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C2601/00—Systems containing only non-condensed rings

C07C2601/12—Systems containing only non-condensed rings with a six-membered ring

C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Description

PATENT SPECIFICATION ( 11) 1569 334
” ( 21) Application No 40571/77 ( 22) Filed 29 Sept 1977 n ( 31) Convention Application No 728346 1 ( 32) Filed 30 Sept 1976 in C ( 33) United States of America (US) ( 44) Complete Specification published 11 June 1980 ( 51) INT CL 3 C 07 C 33/02 35/08 ( 52) Index at acceptance C 2 C 200 209 20 Y 220 221 225 226 227 22 Y 304 30 Y 351 353 355 360 362 36 Y 386 507 509 50 Y 623 625 652 655 662 66 Y 67 Y 776 779 FE UE UU WP YF YK ( 72) Inventors PETER S GRADEFF and GIUSEPPE FORMICA ( 54) PROCESS FOR THE SELECTIVE HYDROGENATION OF THE KETO GROUP IN NONCONJUGATED OLEFINIC KETONES ( 71) We, RHONE-POULENC INDUSTRIES, a French Body Corporate of 22, Avenue Montaigne, 75-Paris, 8 eme, France, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to
be performed, to be particularly described in and by the following statement:-
This invention relates to a process for the preparation of ethylenic alcohols by 5 selective hydrogenation of ethylenic ketones in the presence of a Raney nickel catalyst.
Although viewed as a difficult problem (c f Chemtech, June, 1975, p 382), the selective hydrogenation of unsaturated aldehydes to unsaturated alcohols has been achieved in several instances using a variety of catalytic systems The case of 10 unsaturated ketones is quite different Rylander in Catalytic Hydrogenation over Platinum Metals (Academic Press, 1967, p 271) has indicated that “generally hydrogenation of an unsaturated olefinic ketone proceeds with preferential saturation of the olefinic function ” There are indeed very few exceptions: 4 phenyl 2 oxo but 3 ene is said to be hydrogenated to 4 phenyl 2 15 hydroxy but 3 -ene in the presence of colloidal Pd and promoters (Chemical Abstracts, 41 ( 1947), p 109) and another tetrasubstituted olefinic ketone, ethyl 2,3 dimethyl 5 carbethoxy 6 oxo 2 heptenoate is converted to the corresponding unsaturated carbinol using platinum oxide in ethanol (R Adams and M Ginaturco, J Am Chem Soc, 79 ( 1957), p169) 20 Reduction of 6 methyl hep 5 ene 2 one (hereinafter called methyl heptenone) and homologues thereof to the corresponding secondary unsaturated alcohols, which are valuable ingredients for perfumery and intermediates for organic syntheses, is presently done primarily by the aluminium isopropylateisopropanol method, as none of the known catalytic hydrogenation processes can 25 be used satisfactorily The platinum oxide/ethanol indicated by Adams and Gianturco, the palladium, ruthenium and nickel on carbon, the Raney nickel, the chromium and cobalt-promoted Raney-nickels and other widely used catalytic systems, all are unsuccessful.
We have now discovered reaction conditions which permit selective catalytic 30 hydrogenation of the keto group in methyl heptenone and derivatives thereof to give the corresponding ethylenic alcohol.
The present invention provides a process for the preparation of an olefinically unsaturated alcohol which comprises selectively hydrogenating the keto group in a non-conjugated olefinic ketone of the general formula: 35 R 3 wherein R, is hydrogen, methyl or ethyl; or R 1 together with one of R 4 and R, and the carbon atoms to which they are attached form an unsaturated cycloaliphatic ring, the other of R 4 and R, then being hydrogen or a hydrocarbon group as defined below; 5 R 2 is hydrogen, or when R 3 is methyl, R 2 may be methyl; R 3 is methyl, ethyl or phenyl; or R 2 and R 3 together with the carbon atoms to which they are attached and the CO group linking those carbon atoms form a sixmembered saturated cycloaliphatic ring comprising the keto group; R 4 and R 5, which may be the same or different, each is an alkyl, aryl, alkaryl, 10 aralkyl, cycloalkyl, alkcycloalkyl or cycloalkalkyl, group having from one to fifty carbon atoms; or R 4 and R, together with the carbon atom to which they are attached form a cycloaliphatic ring; with hydrogen in the presence of (a) a chromiumpromoted Raney nickel; (b) a strong base which is an alkali metal hydroxide or alkali metal 15 alcoholate having from one to thirty carbon atoms, the alkali metal being sodium or potassium; and (c) an alkanol which is methanol or ethanol.
The chromium-promoted Raney nickel is known, and is available commercially It can be obtained by alkaline digestion of the commercially available alloy of nickel, aluminium and chromium Chromium-promoted Raney 20 nickel containing 0 5-20 % by weight chromium is normally satisfactory.
Preferably, the chromium content is 1 to 10 % by weight.
The active chromium-promoted Raney nickel can be used without a support, but if desired, a suitable inert support can be used Suitable supports are the conventional supports and include, for example, carbon, silica gel, barium, 25 charcoal, calcium carbonate, aluminium sulphate, and kieselguhr.
The chromium-promoted Raney nickel can be purchased already activated, i.e most of the aluminium digested by one of the standard procedures Prior to use most of the water is decanted, and the wet catalyst employed as such.
In the absence of the strong base and the methanol or ethanol, the chromium 30 promoted Raney nickel is inactive, as is also plain Raney nickel When the strong base and the methanol or ethanol are present, chromium-promoted Raney nickel is active, but plain Raney nickel is still not active in this hydrogenation.
The amount of strong base to be used is preferably, 0 05 to 5 grams per mole of ketone A larger amount than 5 grams can be used, but does not give any 35 irnprovement in the catalytic etffcf Nbormally, 0 1-05 g of strong base per mole of ketone is employed, since these amounts give good selectivity and good conversions.
Surprisingly, only the very strong bases, i e the hydroxides or alcoholates of sodium or potassium, are effective The alkali metal alcoholates of alcohols having 40 from one to thirty carbon atoms can be used Alcoholates of the higher alcohols having from six to thirty carbon atoms, in the presence of methanol or ethanol, will ultimately revert to the lower alcoholate Weak bases are not effective.
The strong base can be added to the reaction mixture as a solid, or in solution in water, methanol or ethanol 45 Methanol or ethanol are integral parts of the catalytic system The reactions where methanol or ethanol is omitted are very slow, or do not proceed at all, and the selectivity of the hydrogenation of the keto group is quite poor Ethanol is not as effective as methanol, giving a slower reaction rate, although it does give good selectivity Surprisingly, alcohols higher than ethanol are effective, resulting in 50 very poor yields; only a few percent of ketone is hydrogenated in the presence of npropyl and isopropyl alcohols, for example.
The reaction does not proceed with other conventional inert organic solvents, such as benzene and tetrahydrofuran.
The amount of methanol and/or ethanol is also important to obtain a 55 satisfactory hydrogenation rate and good selectivity For example, 20 ml of methanol per mole of ketone gives only a negligible reaction An effective amount of methanol and/or ethanol is 25 to 250 ml per mole of ketone and preferably, the amount is 40 to 150 ml per mole of ketone.
It has surprisingly been found that a small amount of water also increases the 60 hydrogenation rate In the absence of water, i e, in essentially anhydrous reaction mixture, good selectivity is obtained, but a relatively slow reaction occurs Thus, in an anhydrous system, after 22 hours of reaction, although selectivity was good, there was still about 17 % ketone remaining unreacted On the other hand, in the 1,569,334 3 1,569,334 3 presence of 1 % to 5 % of water, based on the weight of the reaction mixture, the reaction rate is good and so is the selectivity.
An excessive amount of water lowers the reaction rate When the amount of water present in the reaction mixture is increased to 5 /% to 8 %, the reaction rate is as slow as in the anhydrous system Accordingly, it is preferred that the amount of 5 water be not more than 5 %, and particularly within the range from 1 C/ to 3 %.
The presence of nitrogen base in the reaction mixture also increases the reaction rate, although it does not apparently improve selectivity Effective nitrogen bases include ammonia, amines, and quaternary ammonium hydroxides.
Aliphatic, cycloaliphatic, aromatic and heterocyclic mono and poly amines and 10 quaternary ammonium hydroxides can be used The strength of the nitrogen base does not appear to be critical Weak bases, such as aniline, are as effective as strong bases, such as the lower aliphatic monoamines and diamines and quaternary ammonium hydroxides.
Amines which can be used include cyclohexylamine, cyclohexylene diamine, 15 cyclopentyl amine, dicyclopentylene diamine, methyl amine, dimethyl amine, trimethyl amine, ethyl amine, dikthyl amine, triethyl amine, propyl amine, dipropyl amine, tripropyl amine, butyl amine, dibutyl amine, tributyl amine, monoethanolamine, diethanolamine, triethanolamine, aniline, ortho-, meta and para-toluidine, ethylene diamine, diethylene triamine, triethylene tetramine, 20 pyridine, piperidine, pyrazine, piperazine, morpholine, and quaternary ammonium hydroxides such as tetramethyl quaternary ammonium hydroxide, trimethyl benzyl quaternary ammonium hydroxide and pyridinium hydroxide.
The amount of nitrogen base can be 0 05 to 15 grams per mole of ketone.
Although larger amounts than 15 grams can be used, a proportionate enhancement 25 of the reaction rate is not noted Preferably, the amount of nitrogen base is about 1 to 5 g per mole of ketone.
Ketones which can be used in the process of the invention include:
5-cyclohexylidene-pentan-2-one, 4-(cyclohex 1-enyl)-butan-2-one, 30 6-methyl-hept-5-en-2-one, 6-ethyl-hept-5-en-2-one, 6-ethyl-oct-5-en-2-one, 3,6-dimethyl-oct-5-en-2-one, 7-methyl-oct-6-en-3-one, 35 7-ethyl-non-6-en-3-one, 5,6-dimethyl-hept-5-en-2-one, 2-( 3 ‘-methyl-but-2-enyl)-cyclohexanone, 2-( 3 ‘-ethyl-pent-2-enyl)-cyclohexanone, 3-methyl-6-ethyl-oct-5-en-2-one, 40 I-phenyl-5-methyl-hex-4-en 1-one, I -phenyl-5-ethyl-hept-4-en 1 l-one, and mixtures of 3,6-dimethyl-hept-5-en-2-one and 7-methyl-oct-6-en-3-one.
A small amount of the chromium-promoted Raney nickel is quite sufficient to catalyse the reaction The larger the amount used, the more rapid the rate of 45 hydrogenation Satisfactory results are obtained with amounts as small as 1 % by weight of the ketone; in some cases, amounts as small as 0 5 % by weight can be used Normally, an amount in excess of about 25 % by weight of the ketone is not required, and in most cases, an amount of 2 to 15 % by weight of the ketone is sufficient 50 It is well known that freshly-prepared chromium-promoted Raney nickel catalysts are more active than catalysts that have been stored for some time.
The reaction can be carried out at from 5 C to about room temperature, but is faster at elevated temperatures There is no upper limit on reaction temperature, except that imposed by the stability of the starting ketone and/or unsaturated 55 alcohol reaction product Temperatures from 20 to 100 C are preferred, but the reaction temperature may in some cases be as high as 200 C.
The reaction proceeds rapidly, depending upon temperature, hydrogen concentration, and catalyst concentration Usually, the reaction does not require more than forty-eight hours for completion, and depending upon the end product 60 desired, may be complete in as little as one-half hour Usually, from four to twelve hours are sufficient.
The reaction can be started by charging the ketone, the strong base, the amine (if used), the alkanol, and the chromium-promoted Raney nickel into a suitable pressure vessel equipped with stirring and optionally with heating or cooling facilities After appropriate purging of the system, a hydrogen atmosphere is then established, and hydrogen supplied to the system under pressure for a time sufficient to produce the desired reaction product 5 In a preferred procedure, the chromium-promoted Raney nickel is stirred for a few minutes with the strong base, the amine (if used) and some of the alkanol, and then added to the autoclave, containing the ketone and the rest of the alkanol.
As the amount of unsaturated alcohol increases, small amounts of saturated alcohol tend to be formed and consequently, if this impurity is not desired it is well 10 to halt the hydrogenation at a stage before the saturated alcohol begins to be formed.
The reaction time required to reach the desired reaction product depends on a number of factors including, for example, the amount and reactivity of the catalyst ingredients, the pressure, the temperature, and the desired composition of the final 15 product Consequently, the reaction conditions best adapted for a particular objective are normally determined by trial and error, but will be found to lie within the above parameters.
It is normally preferred to operate the process in a manner so as to halt the hydrogenation before saturated alcohol begins to be formed in significant quantity 20 However, the time selected for halting the hydrogenation will of course depend upon the other parameters chosen.
It is possible to carry out the hydrogenation reaction at atmospheric pressure.
However, the hydrogenation reaction then proceeds rather slowly A suitable reaction rate is obtained at a reaction pressure of 0 14-0 35 kg/cm 2 The higher the 25 pressure, the more rapid the hydrogenation Consequently, pressures of at least 0 7 kg/cm 2 are preferred, preferably, 2 8-7 kg/cm 2, but higher pressures can be used, if desired There is in fact no upper limit except as may be imposed by practicality, and the pressure vessels available, which indicate an upper limit of 14 kg/cm 2.
The following Examples are given to illustrate the invention 30 In all the Examples below, the reactions were carried out either in a stainlesssteel autoclave or in a PARR hydrogenator (a 200 ml glass reactor shakertype apparatus designed to operate at pressures up to 4 2 kg/cm 2) The progress of the hydrogenation was followed by taking samples at the intervals indicated.
EXAMPLE 1 35
A mixture of 3,6 dimethyl hept 5 en 2 one and 7 methyl oct 6 ene 3 one 140 g chromium-promoted Raney nickel 4 g, in suspension in 5 g of water; 56 g methanol; 4 5 g of a 10 % solution of potassium methoxide in methanol; and 5 g of triethylamine, were placed in a stainless steel autoclave The reactor was purged of air, and pressurized with hydrogen to 2 8 kg/cm 2 Agitation of 40 the autoclave was then begun at room temperature, and samples were taken at the times indicated in Table I below The samples were analyzed by gas liquid chromatography (GLC) for (a) unreacted ketone and the three possible mixtures of reaction products, (b) the saturated ketone, (c) the saturated alcohol, and (d) the unsaturated alcohol (which was the desired product, representing selective 45 hydrogenation of the keto group to the exclusion of the olefinic group) The following results were obtained:
TABLE I % of Components after Hydrogenation by GLC Analysis After Hours 50 Components 14 3 4 + 6 7 + 9 (a) Unreacted ketones 56 9 31 1 16 0 7 8 4 9 4 1 (b) Saturated ketones 1 7 2 8 2 4 2 2 2 1 1 8 (c) Saturated alcohols Trace 0 9 2 9 3 5 4 5 6 1 55 (d) Unsaturated alcohols 41 4 65 2 78 7 86 5 88 5 88 The results show an excellent yield of unsaturated alcohols (d) after six hours of reaction, which was not materially improved in three hours further reaction.
Selectivity was quite good, as evidenced by the relatively small proportion of saturated ketones, the non-selectively hydrogenated by-products, and saturated 60 alcohols, the fully hydrogenated by-product.
In a continuous hydrogenation process, it would be possible to withdraw the 1,569,334 reaction mixture after a three-hour dwell time in the reactor, and recycle the unreacted ketones for further reaction, since at this reaction stage the proportion of saturated alcohol is at a minimum, and therefore loss of the starting material in this by-product would be substantially eliminated.
It is also apparent from the results that saturated ketones are converted to 5 saturated alcohols in later stages of the reaction.
In contrast with the above results, the use in substitution for potassium methoxide by the bases listed in Table II gives both poor yields and poor selectivity.
In experiments carried out exactly as the above, with the only change being the substitution of the base indicated, the following results were obtained 10 TABLE II % of Components after Hydrogenation Reaction by GLC Analysis 3 Control No Base glmol Time (hours) a b c d F Li OH 1 0 3 1/4 7 0 8 1 15 2 69 7 G 1 None 2 1/2 9 0 20 4 23 0 47 5 H 2 None 3 18 3 14 5 11 9 55 3 1 (CH 3)4 NOH 1 0 4 33 7 14 3 5 0 46 9 K Na 2 CO 3 1 0 16 7 8 25 26 2 41 0 L Borax 1 0 3 1/2 17 2 27 9 16 2 38 7 18 g cat/mol 2 4 g cat/mol 3 a, b, c, and d are as defined for Table I.
It is apparent from the above results that lithium hydroxide is not acceptable.
Poor selectivity and/or a poor reaction rate are obtained with it and the other 25 alkalis In fact, the results with the other bases are no better than the results obtained in the absence of base, Controls G and H In all cases, selectivity is unacceptable.
EXAMPLE 2
A mixture of 3,6 dimethyl hept 5 ene 2 one and 7 methyl oct 30 6 ene 3 one 140 g: chromium-promoted Raney nickel 4 g in suspension in 5 g of water: 56 g methanol and 4 5 g of a 10 % solution potassium methoxide in methanol were placed in a stainless-steel autoclave The system was purged of air and pressurized with hydrogen to 2 8 kg/cm 2 Agitation of the autoclave was then begun at room temperature and samples were taken at the times indicated in Table 35 III below The samples were analyzed by gas liquid chromatography (GLC) as in Example 1 The following results were obtained:
TABLE III % of Components after Hydrogenation by GLC Analysis 40 After Hours Components 3 6 + 25 33 49 (a) Unreacted ketones 69 4 53 4 12 1 7 7 4 9 (b) Saturated ketones 1 8 2 8 3 2 3 1 2 6 (c) Saturated alcohols 4 7 4 7 7 3 45 (d) Unsaturated alcohols 28 7 43 6 80 0 84 5 85 1 The results show an excellent yield after six hours of reaction, which was not materially improved in three hours further reaction Selectivity was quite good, as evidenced by the relatively small proportion of saturated ketones and saturated 50 alcohols, the fully hydrogenated and non-selectively hydrogenated byproducts In the absence of the amine, reaction rate was slower than in Example 1.
In a continuous hydrogenation process, it would be possible to stop the reaction early, and recycle the unreacted ketones for further reaction, since, before this reaction stage, the proportion of saturated alcohol is at a minimum, and 55 therefore loss of the starting material in this by-product would be substantially eliminated It is apparent from the results that saturated ketones are converted to saturated alcohols in later stages of the reaction.
I 1,569,334 6 1,569,334 6 These results show that the presence of amine is quite beneficial in increasing the reaction rate although not affecting the selectivity However, good yields are obtained after the longer reaction time.
EXAMPLES 3 TO 8 A mixture of 3,6 dimethyl hept 5 ene 2 one and 7 methyl oct 5 6 ene 3 one, 140 g; chromium promoted Raney nickel 4 g in suspension in 5 g of water; the amount of alcohol listed below in Table IV; 4 5 g of a 10 solution of potassium methoxide in methanol and 5 g of triethylamine were placed in a stainless steel autoclave The system was purged of air and pressurized with hydrogen to 2 8 kg/cm 2 Agitation of the autoclave was then begun at room 10 temperature, and reaction continued for the time indicated in Table IV below The products were analyzed by gas liquid chromatography (GLC) as in Example 1 The following results were obtained:
TABLE IV % of Components after Hydrogenation by GLC Analysis Example or Reaction Control No Solvent mi/mole Time (hrs) a b c d 3 Methanol 4 7 97 6 1 8 Trace Trace 22 + 97 6 1 8 Trace Trace 4 Methanol 20 20 96 1 3 Trace Trace Methanol 35 23 64 0 2 0 Trace 31 7 6 Methanol 50 7 32 9 3 2 1 2 602 14 2 0 1 9 11 7 82 7 Methanol 140 1 + 31 4 9 5 4 2 53 3 3 + 5 4 7 9 14 5 68 1 8 Ethanol 70 14 + 35 3 4 0 1 4 57 7 Controls A n-Butanol 70 7 97 2 0 9 0 3 B iso-Butanol 70 21 94 5 1 1 2 7 C n-Propanol 70 21 95 4 09 1 9 D Tetrahydro 70 3 98 3 0 7 1 0 furan E Benzene 70 16 86 7 6 1 7 2 3 a, b, c and d are as defined for Table I 35 The above results show that the methanol and ethanol definitely contribute to selectivity and increase the reaction rate In Controls A to E, in the presence of nand iso-butyl alcohol, and n-propyl and isopropyl alcohol, tetrahydrofuran and benzene, the reaction rate is virtually negligible, and nearly all of the starting ketone is recovered unreacted 40 The results for Examples 3 to 7 also show that the influence of the methanol is proportionate to the amount In amounts below 25 ml per mole, the methanol also was virtually ineffective, no better than the higher alcohols in the Controls At amounts within the range from 35 to 140 ml per mole, a good reaction rate is obtained (Examples 5 to 7) The same is true of ethanol, in the proportion of 70 ml 45 per mole, as shown in Example 8.
EXAMPLES 9 and 10 A mixture of 3,6 dimethyl hept 5 ene 2 one and 7 methyl oct 6 ene 3 one 140 g; chromium-promoted Raney nickel 4 g, 56 g methanol, 4 5 g of a 10 % solution of potassium methoxide in methanol, 5 g of triethylamine and the 50 amount of water noted in Table V were placed in a stainless-steel autoclave The reactor was purged of air and pressurized with hydrogen to 40 psi Agitation of the autoclave was then begun at room temperature, and reaction continued for the times indicated in Table V below The products were analyzed by gas liquid chromatography (GLC) as in Example 1 The following results were obtained: 55 TABLE V % of Components after Hydrogenation by GLC Analysis Water Reaction Example No g/mole Time(hrs) a b c d 5 11 5 4 + 16 0 2 4 2 9 78 7 7 + 4 9 2 1 4 5 88 5 9 0 7 58 0 2 4 36 1 22 16 8 5 5 3 6 71 8 10 15 4 + 84 2 1 3 12 2 10 21 47 3 4 0 0 9 46 4 from Table I (Example 1) 3 a, b, c and d are as defined in Table I.
The above results include Example 1, to show the importance of the water in increasing the reaction rate When no water is present, the reaction is rather slow 15 (Example 9) When 15 g of water per mole of ketone are present, the reaction rate is even slower (Example 10) However, in each case selectivity is good The product could be accepted in a continuous process, and the unreacted ketone recycled.
EXAMPLES 11 to 31 A mixture of 3,6 dimethyl hept 5 en 2 one and 7 methyl oct 20 6 en 3 one 140 g; chromium-promoted Raney nickel 4 g in suspension with 5 g of water, 70 ml methanol, and the amount of alkali and amine noted in Table VI were placed in a stainless steel autoclave The reactor was purged of air and pressurized with hydrogen to 2 8 kg/cm 2, or as indicated in Table VI Agitation of the autoclave was then begun at room temperature, and reaction continued at 20 to 25 C for the times indicated in Table VI below The products were analyzed by gas liquid chromatography (GLC) as in Example 1 The following results were obtained:
1,569,334 Amine/g/mole TEAV/5 0 12 TEA/1 O 13 TEA/1 0 142 TEA/5 0 153 TEA/5 0 Base/g KOH/4 5 Na OH/1 0 KO Me /2 0 KO Me /4 5 . 16 TEA/2 0 174 TEA/5 0 Aniline/5 0 NH 40 H/5 0 28 %o 205 Hexadecyl amine/5 0 215 Cyclohexyl amine/5 0 225 Ethylene diamine/5 0 235 Dimethyl amine 40 %/5 0 24 Butyl amine/5 O Dibutyl amine/5 0 26 Tributyl amine/5 0 275 Diethyl amine/5 0 286 TEA 1/5 0 297 308 318 Control M 9 Control N 9 Tributyl amine /5 O Butyl amine/5 0 TEA/5 O TEA/5 O KOH/1 O KOH/1 O KO-t-But.
/1.5 KOH/4 5 KO Me/4 5 KO Me/4 5 , Reaction Time (hrs) 3 18 1/2 3 4 1 1/2 8 7 7 23 18 1/2 24 16 1/2 24 1/2 1/2 24 3 1/2 3 4 I 1/2 3 2 1/2 22 % of Components after Hydrogenation by GLC Analysis a 14.4 5.4 25.8 5.2 3.3 54.6 0.7 1.2 33.3 10.1 3.2 21.0 23.7 26.2 82.5 35.5 84.5 63.9 36.0 b 2.9 2.3 5.3 4.0 2.4 3.4 1.2 1.4 3.6 3.0 2.6 1.7 1.6 1.8 2.3 1.4 0.8 4.1 19.9 71.6 2 6 15.8 7 9 53.7 61.8 46.8 60.9 36.6 3.1 3.9 1.2 16.1 21.4 c 3.8 6.2 7.1 9.4 7.8 0.6 11.7 10.4 1.4 5.0 7.4 0.5 0.4 0.2 6.3 d 79.0 86.0 61.8 81.3 86.5 41.4 86.2 86.4 61.6 81.9 84.5 75.2 73 69.3 11.4 61.2 14.5 31.9 37.7 9 9.1 66 3 1.2 42 0 33 6 2.3 20 6 6.7 33 6 o KO Me=KOCH 3 1 TEA=Triethyl amine 2 8 g/mole Chromium-Raney nickel 3 w/recycled Chromium-Raney nickel 4 2 g/mole Chromium-Raney nickel in PARR Hydrogenator 6 4 2 kg/cm 2 autoclave 7 50 C 4 2 kg/cm 2 autoclave 8 2 8 kg/cm 2 autoclave 9 Raney nickel without chromium a, b, c and d are as defined in Table I TABLE VI
Example No.
O ui t.,o -P oo It is apparent from the above results that using chromium-promoted Raney nickel good yields and good selectivity are obtained using a variety of strong bases and amines over a wide range of reaction times.
In contrast Raney nickel without chromium gives very poor selectivity and a slow reaction rate 5 EXAMPLES 32 to 34 One mole of the ketone listed in Table VII below, 3 g of chromiumpromoted Raney nickel, 70 to 170 ml methanol, 5 g of a 10/ solution of potassium methoxide in methanol and 5 g of triethyl amine were placed in a stainless-steel autoclave The reactor was purged of air and pressurized with hydrogen to 2 8 kg/cm 2 Agitation of 10 the autoclave was then begun at room temperature, and the reaction continued for the times indicated in Table VII below The products were analyzed by gas liquid chromatography (GLC) as in Example 1.
TABLE VII
IS % of Components after 15 Hydrogenation by GLC Analysis Example or Reaction Control No Ketone Time (hrs) a b c d 32 6-methyl-hept-5-en-2-one 2 2 3 8 O 8 4 4 88 5 16 0 3 15 4 82 5 33 2-( 3 ‘-methyl-but-2 ‘-enyl) 7 26 6 2 7 69 4 cyclohexanone 24 4 7 2 8 1 6 89 3 34 phenyl-4-methyl-pent-3 2 1 21 9 O 7 1 5 72 8 enyl ketone O 4-methyl-pent-3-en-2-one 16 10 89 3 P 4,7-dimethyl-oct-6-en-3-one 20 5 94 7 1 8 O 1 1 6 i:Q 3-iso-propyl-6-methyl 7 93 2 1 2 4 hept-5-en-2-one R 6,10-dimethyl-undeca-5,9 6 97 8 1 8 O 4 dien-2-one 491 45 5 27 5 2 6 24 4 S 3-ethyl-6-methyl-hept-5 24 49 7 14 8 5 5 27 2 en-2-one T 3-phenyl-6-methyl-hept-5 3 92 6 1 1 5 9 en-2-one 23 5 38 7 13 3 5 4 41 8 U 2-allyl-cyclohexanone 16 19 8 80 2 1 O 98 5 O 4 I using double the amounts of methanol and chromium-Raney nickel.
3 a, b, c and d are as defined in Table I.
The above data show that ketones falling within the invention Examples 32 to 34 give good results under these conditions, while the other ketones do not The 40 undue steric hindrance of the keto group causes interference, as shown by Controls P, Q, S and T The effect of an unshielded double bond is shown by its preferential hydrogenation in Control U which is also the result in Control O where the double bond is a,/ to the carbonyl The Control R shows the steric effects exercised by the spatial arrangement of the relatively long carbon chain 45

Claims (1)

WHAT WE CLAIM IS:-
1 A process for the preparation of an olefinically unsaturated alcohol which comprises selectively hydrogenating the keto group in a non-conjugated olefinic ketone of the general formula:
R 5 e R 4 S z y so O 50 R 3 1,569,334 1,569,334 10 wherein R 1 is hydrogen, methyl or ethyl; or R, together with one of R 4 and R, and the carbon atoms to which they are attached form an unsaturated cycloaliphatic ring, the other of R 4 and R, then being hydrogen or a hydrocarbon group as defined below; R 2 is hydrogen, or when R 3 is methyl, R 2 may be methyl; R 3 is methyl, ethyl or phenyl; or R 2 and R 3 together with the carbon atoms to which they are attached 5 and the CO group linking those carbon atoms form a six-membered saturated cycloaliphatic ring comprising the keto group; R 4 and R 5, which may be the same or different, each is an alkyl, aryl, alkaryl, aralkyl, cycloalkyl, alkcycloalkyl or cycloalkalkyl group having from one to fifty carbon atoms; or R 4 and R 5 together with the carbon atoms to which they are attached form a cycloaliphatic ring; with 10 hydrogen in the presence of (a) a chromium-promoted Raney nickel; (b) a strong base which is an alkali metal hydroxide or alkali metal alcoholate having from one to thirty carbon atoms; the alkali metal being sodium or potassium and (c) an alkanol which is methanol or ethanol.
2 A process according to claim 1 carried out in the presence of water in an 15 amount of 1-5 % by weight of the total reaction mixture.
3 A process according to claim 1 or 2 carried out in the presence of 0 0515 g of nitrogen base per mole of ketone.
4 A process according to any one of the preceding claims wherein the Raney nickel contains 0 5-20 % by weight chromium 20 A process according to claim 4 wherein the Raney nickel contains 1-10 % by weight chromium.
6 A process according to any one of the preceding claims wherein the amount of chromium-promoted Raney nickel present is 0 5 % to 25 % by weight of the ketone 25 7 A process according to any one of the preceding claims wherein the hydrogen pressure is 1 kg/cm 2 to 14 kg/cm 2.
8 A process according to any one of the preceding claims wherein the reaction is carried out at a temperature of 5 C to 200 C.
9 A process according to any one of the preceding claims wherein the ketone 30 is 3,6 dimethyl 5 heptene 2 one, 7 methyl 6 octene 3 one, 6 methyl 5 heptene 2 one, 2 ( 3 methyl 2 butenyl) cyclohexanone or phenyl 4 methyl pent 3 enyl ketone.
A process according to any one of the preceding claims wherein the alkanol is methanol 35 11 A process according to any one of the preceding claims wherein the strong base is potassium hydroxide.
12 A process according to any one of claims 1 to 10 wherein the strong base is potassium methoxide.
13 A process according to any one of the preceding claims wherein 0 1-5 g of 40 strong base are used per mole of ketone.
14 A process according to any one of the preceding claims wherein 25-250 ml alkanol are used per mole of ketone.
A process for the preparation of an olefinically unsaturated alcohol according to claim 1 substantially as hereinbefore described with reference to any 45 one of Examples I to 34.
16 An olefinically unsaturated alcohol obtained by a process according to any one of the preceding claims.
J A KEMP & CO, Chartered Patent Agents, 14, South Square, Gray’s Inn, London, W.C IR SEU.
Printed for Her Majesty’s Stationery Office, by the Courier Press Leamington Spa 1980 Published by The Patent Office 25 Southampton Buildings, London WC 2 A IAY, from which copies may be obtained.

GB40571/77A
1976-09-30
1977-09-29
Process for the selective hydrogenation of the keto group in nonconjugated olefinic keytones

Expired

GB1569334A
(en)

Applications Claiming Priority (1)

Application Number
Priority Date
Filing Date
Title

US05/728,346

US4041083A
(en)

1976-09-30
1976-09-30
Process for the selective hydrogenation of the keto group in nonconjugated olefinic ketones

Publications (1)

Publication Number
Publication Date

GB1569334A
true

GB1569334A
(en)

1980-06-11

Family
ID=24926471
Family Applications (1)

Application Number
Title
Priority Date
Filing Date

GB40571/77A
Expired

GB1569334A
(en)

1976-09-30
1977-09-29
Process for the selective hydrogenation of the keto group in nonconjugated olefinic keytones

Country Status (11)

Country
Link

US
(1)

US4041083A
(en)

JP
(1)

JPS5344506A
(en)

BE
(1)

BE859220A
(en)

CA
(1)

CA1086332A
(en)

CH
(1)

CH624372A5
(en)

DE
(1)

DE2744134A1
(en)

ES
(1)

ES462810A1
(en)

FR
(1)

FR2366247A1
(en)

GB
(1)

GB1569334A
(en)

IT
(1)

IT1084796B
(en)

NL
(1)

NL7710677A
(en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

DE2934251A1
(en)

1979-08-24
1981-03-26
Basf Ag, 67063 Ludwigshafen

METHOD FOR PRODUCING UNSATURATED ALCOHOLS.

IT1129758B
(en)

1980-01-23
1986-06-11
Montedison Spa

PROCESS FOR THE CATALYTIC REDUCTION OF UNSATURATED KETONES

CH648281A5
(en)

1981-04-21
1985-03-15
Firmenich & Cie

MACROCYCLIC COMPOUNDS AND THEIR USE.

DE3130805A1
(en)

1981-08-04
1983-02-24
Basf Ag, 6700 Ludwigshafen

NEW RUTHENIUM / COAL HYDRATING CATALYSTS, THEIR PRODUCTION AND USE FOR THE SELECTIVE HYDROGENATION OF UNSATURATED CARBONYL COMPOUNDS

GB2215330A
(en)

1988-03-04
1989-09-20
Shell Int Research
Hydrogenation of esters into alcohols

DE3824518A1
(en)

1988-07-20
1990-01-25
Bayer Ag

METHOD FOR PRODUCING 4,4-DIMETHYL-1- (P-CHLORINE-PHENYL) -PENTAN-3-ON

DE3824625A1
(en)

1988-07-20
1990-01-25
Bayer Ag

METHOD FOR HYDROGENATING (ALPHA), (BETA) -UNSATURATED KETONES

JPH0753680B2
(en)

1989-07-17
1995-06-07
高砂香料工業株式会社

Method for producing optically active ketone

DE19505938A1
(en)

1995-02-21
1996-08-22
Bayer Ag

Process for the preparation of 1- (4-chlorophenyl) -4,4-dimethyl-pentan-3-one

CN102603473A
(en)

2012-01-13
2012-07-25
河北科技大学
Method for preparing corresponding alcohol through carbonyl compound selective hydrogenation

CN112469685A
(en)

2018-07-23
2021-03-09
西姆莱斯股份公司
Novel flavoring agent with rose smell

Family Cites Families (16)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

US2983734A
(en)

1961-05-09

Catalytic hydrogenation

US2009948A
(en)

1931-08-27
1935-07-30
Ig Farbenindustrie Ag
Production of unsaturated alcohols

US2448047A
(en)

1947-02-15
1948-08-31
Burton T Bush Inc
Preparation of unsaturated alcohols

US2767221A
(en)

1953-06-11
1956-10-16
Shell Dev
Production of unsaturated alcohols

US3102150A
(en)

1960-02-19
1963-08-27
Exxon Research Engineering Co
Process for hydrogenating carbonyl compounds

US3109865A
(en)

1961-10-24
1963-11-05
Standard Oil Co
Manufacture of allyl alcohol

US3471575A
(en)

1962-04-28
1969-10-07
Shiro Kudo
Catalytic hydrogenation of alpha,beta-unsaturated carbonyl compounds,unsaturated fatty acids,and unsaturated fatty acid esters

US3268589A
(en)

1963-05-29
1966-08-23
Reynolds Tobacco Co R
Process for preparing 4-(2-butenylidene)-3, 5, 5-trimethyl-2-cyclohexene-1-one

US3284517A
(en)

1963-09-11
1966-11-08
Engelhard Ind Inc
Hydrogenation of alpiia, beta-unsaturated aldehydes to alpha, beta-unsaturated alcohols

US3463818A
(en)

1966-01-25
1969-08-26
Int Flavors & Fragrances Inc
Unsaturated aldehydes and alcohols

US3991127A
(en)

1967-03-18
1976-11-09
Basf Aktiengesellschaft
Production of saturated aliphatic alcohols

NL6712077A
(en)

1967-09-01
1969-03-04

US3655777A
(en)

1968-11-12
1972-04-11
Engelhard Min & Chem
Hydrogenation of unsaturated aldehydes to unsaturated alcohols

DE2200650A1
(en)

1971-01-13
1972-07-20
Yeda Res & Dev

Process for the preparation of alcohols by reducing carbonyl compounds using a system of aluminum silicate and a secondary alcohol

CH566113A5
(en)

1973-02-09
1975-09-15
Firmenich & Cie

CH576926A5
(en)

1973-03-21
1976-06-30
Hoffmann La Roche

1976

1976-09-30
US
US05/728,346
patent/US4041083A/en
not_active
Expired – Lifetime

1977

1977-09-29
BE
BE181329A
patent/BE859220A/en
unknown

1977-09-29
NL
NL7710677A
patent/NL7710677A/en
not_active
Application Discontinuation

1977-09-29
CA
CA287,795A
patent/CA1086332A/en
not_active
Expired

1977-09-29
GB
GB40571/77A
patent/GB1569334A/en
not_active
Expired

1977-09-29
FR
FR7729903A
patent/FR2366247A1/en
active
Granted

1977-09-29
CH
CH1193077A
patent/CH624372A5/fr
not_active
IP Right Cessation

1977-09-30
DE
DE19772744134
patent/DE2744134A1/en
not_active
Withdrawn

1977-09-30
ES
ES462810A
patent/ES462810A1/en
not_active
Expired

1977-09-30
JP
JP11696277A
patent/JPS5344506A/en
active
Pending

1977-09-30
IT
IT28175/77A
patent/IT1084796B/en
active

Also Published As

Publication number
Publication date

ES462810A1
(en)

1978-05-16

CH624372A5
(en)

1981-07-31

FR2366247A1
(en)

1978-04-28

NL7710677A
(en)

1978-04-03

CA1086332A
(en)

1980-09-23

US4041083A
(en)

1977-08-09

JPS5344506A
(en)

1978-04-21

BE859220A
(en)

1978-03-29

FR2366247B1
(en)

1980-04-25

DE2744134A1
(en)

1978-04-06

IT1084796B
(en)

1985-05-28

Contact information