WO2012025559A2 - Process for the manufacture of 3,7-dimethyl-1-octen-3-ol - Google Patents

Process for the manufacture of 3,7-dimethyl-1-octen-3-ol Download PDF

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WO2012025559A2
WO2012025559A2 PCT/EP2011/064531 EP2011064531W WO2012025559A2 WO 2012025559 A2 WO2012025559 A2 WO 2012025559A2 EP 2011064531 W EP2011064531 W EP 2011064531W WO 2012025559 A2 WO2012025559 A2 WO 2012025559A2
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range
catalyst
process according
dimethyl
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PCT/EP2011/064531
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WO2012025559A3 (en
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Werner Bonrath
Johannes Tschumi
Jonathan Medlock
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Dsm Ip Assets B.V.
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Priority to ES11752170.8T priority Critical patent/ES2678472T3/en
Priority to CN2011800411200A priority patent/CN103080055A/en
Priority to JP2013525301A priority patent/JP2013536216A/en
Priority to BR112013004208-7A priority patent/BR112013004208B1/en
Priority to EP11752170.8A priority patent/EP2609063B1/en
Priority to KR1020137007173A priority patent/KR20130100141A/en
Publication of WO2012025559A2 publication Critical patent/WO2012025559A2/en
Publication of WO2012025559A3 publication Critical patent/WO2012025559A3/en

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    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • 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
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
    • C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
    • C07C33/03—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond in beta-position, e.g. allyl alcohol, methallyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms

Definitions

  • 6-methyl-5-hepten-2-on (MH) is hydrogenated to 6-methyl-2-heptanone (MHA) (step a), which is then reacted with acetylene to 3,7-dimethyl-l -octin-3-ol (DMOI) (step b). DMOI is then hydrogenated to 3,7-dimethyl-l -octen-3-ol (DMOE, step c).
  • MHA 6-methyl-2-heptanone
  • DMOI 3,7-dimethyl-l -octin-3-ol
  • DMOE 3,7-dimethyl-l -octen-3-ol
  • MH itself can be prepared by reaction of isopropenyl methyl ether with 2-methyl-3- buten-2-ol as described by G. Saucy and R. Marbet in Helv. Chim. Acta 1967, 50, 2091 - 2095.
  • DMOE as well as tetrahydrolinalool (THLL, 3,7-dimethyl-octan-3-ol) are base products for the flavour and fragrance industry.
  • THLL tetrahydrolinalool
  • DMOE a colourless to pale yellow liquid, has a rose odour and is used in a variety of perfumery applications. It is seen as an alternative to geraniol.
  • DMOE and THLL are furthermore possible intermediates for isophytol (see e.g. P.
  • 6,10-dimethyl-5-undecen-2-one may be manufactured starting from DMOE according to processes known to the person skilled in the art like e.g. described in US 2,783,257 (see scheme in column 1) and DE-AS 1 193 490 (see example 10). 6,10-Dimethyl-5-undecen- 2-one may then be hydrogenated to obtain hexahydropseudoionone (HPI) (see US 2,783,257: column 2, line 58-64), which may be further reacted to (iso)phytol according to processes as e.g. disclosed in Appl. Catal. 2005, 280, 55-73 and Catal. Today 2007, 121, 45-57.
  • HPI hexahydropseudoionone
  • the disadvantage of the procedure is that stoichiometric amounts of the ethynylation agent are used, the hydrogenations are performed with an expensive catalyst, no yields are given (the analysis is not discussed), the reactions are carried out in solvents, and low yields are obtained if we assume that 20 g of MH give 8 g of THLL, based on the experimental procedures reported.
  • the THLL obtained is used for the synthesis of isophytol.
  • DMOE (named as 1,5 -dimethyl- 1 -vinyl- 1 -hexanol) is synthesized starting from MHA which is ethynylated in presence of sodium in liquid ammonia followed by Lindlar hydrogenation in the presence of a catalyst which is Pd/Pb on CaCC .
  • the hydrogenation was carried out in petroleum ether at 20-30°C.
  • EP-A 754 664 describes the partial hydrogenation of alkynes using a solid-bed catalyst as described in EP-A 412 415, whereby the Lindlar hydrogenation was carried out in presence of CO (10-180 ppm).
  • EP-A 816 321 claimed the synthesis of MHA by aldol reaction of acetone and isovaleraldehyde in presence of hydrogen and a conventional hydrogenation catalyst at 15-150°C and 1 -100 bar, (example 3 : Pd/C).
  • a conventional hydrogenation catalyst at 15-150°C and 1 -100 bar, (example 3 : Pd/C).
  • step c 2 hours, 4-6°C, KOH in water, ammonia).
  • the object of the present invention was to provide a process which may be used for the industrial production of DMOE, i.e. a process which is economic. Furthermore, the process according to the present invention should not have the disadvantages of the processes of the prior art.
  • a preferred object of the present invention was also to achieve a selectivity > 90% at a conversion of > 95%.
  • the present invention is directed to a process for the manufacture of 3,7-dimethyl-l- octen-3-ol comprising the following steps:
  • step a) may be used in step c), and that steps a) and c) may be performed without the use of an organic solvent such as petroleum ether, ligroin, hexane and heptane.
  • organic solvent such as petroleum ether, ligroin, hexane and heptane.
  • step a) is performed in the absence of any organic solvent, i.e. that no organic solvent is added to MH or the reaction mixture used in step a). This encompasses also the case that minor amounts of solvent may be present as "impurity" of the MH used.
  • the catalyst used in step a) is the same catalyst as used in step c). More preferably this catalyst has a Pd content, based on the total weight of the catalyst, of 1-10, preferred 2.5-8 more preferred, especially preferred 3-7 weight-% Pd. This catalyst is even more preferably Pd on aluminum oxide.
  • the catalyst is Pd on aluminum oxide, it preferably has a BET surface area in the range of 50 to 500 m7g, more preferably it has a BET surface area in the range of 80 to 300 m /g, most preferably it is an egg-shell catalyst.
  • An “egg-shell” catalyst in the context of the present invention is a catalyst where the catalytically active metal (Pd) has a non-uniform distribution on the support and is located mainly on the shell of such catalyst.
  • the catalyst is Pd on carbon, it preferably has a BET surface area in the range of 800 to 1500 m 2 /g, more preferably it has a BET surface area in the range of 900-1200 m 2 /e. Even more preferably 50% of the catalyst also have a size ⁇ 20-50 ⁇ (i.e. the so-called particle size D50 ⁇ 20-50 ⁇ ). Most preferably the bulk density is in the range of 100 to 500 g/L, more preferably in the range of 200 to 300 g/L.
  • the catalyst is Pd on CaCC , it preferably has a BET surface area in the range of 5 to 15
  • m /g more preferably it has a BET surface area in the range of 7 to 10 m /g. Most preferably 50% of the particles of this catalyst also have a size ⁇ 3-30 ⁇ (i.e. the so- called particle size D50 ⁇ 3-30 ⁇ ).
  • pulverous catalysts including egg-shell catalysts are used. These can be separated easily after the reaction from the reaction mixture by filtration or centrifugation. Furthermore, these catalysts can be recycled and used several times.
  • step a) is carried out at a temperature in the range of 20 to 100 °C, more preferably at a temperature in the range of 25 to 80 °C.
  • step a) is carried out at a pressure in the range of 1.1 bar to 15 bar, more preferably at a pressure in the range of 1.5 to 6 bar, even more preferably at a pressure in the range of 1.8 to 4 bar.
  • the amount in weight-% of catalyst used in step a) is in the range of 1 : 50 to 1 : 5000, more preferably in the range of 1 : 100 to 1 : 2500, even more preferably in the range of 1 : 250 to 1 : 1000, based on the amount of 6-methyl-5-hepten-2-on in weight-%.
  • Preferred embodiments of the present invention are also embodiments where several preferred embodiments of step a) as listed above are combined.
  • the molar ratio of 6-methyl-2-heptanon to acetylene in step b) is in the range of 1 : 1 to 1 : 2, more preferably in the range of 1 : 1.01 to 1 : 1.5.
  • the molar ratio of 6-methyl-2-heptanon to potassium hydroxide in step b) is in the range of 30 : 1 to 250 : 1, more preferably in the range of 40 : 1 to 100 : 1.
  • the molar ratio of 6-methyl-2-heptanon to ammonia in step b) is in the range of 1 : 15 to 1 : 50, more preferably in the range of 1 : 20 to 1 : 30.
  • step b) is carried out at a temperature in the range of -10 °C to 25 °C, more preferably at a temperature in the range of 0 to 20 °C.
  • the pressure used is preferably in the range of 5 to 25 bar, more preferably in the range of 10 to 20 bar.
  • Preferred embodiments of the present invention are also embodiments where several preferred embodiments of step b) as listed above are combined. Step c)
  • step c) is performed in the absence of any organic solvent, i.e. that no organic solvent is added to DMOI or the reaction mixture used in step c). This encompasses also the case that minor amounts of solvent may be present as "impurity" of the DMOI used.
  • the catalyst used in step c) is a palladium containing catalyst on a carrier selected from the group consisting of calcium carbonate, aluminum oxide, silica, porous glass (especially TRISOPERL®), with the proviso that the catalyst additionally contains lead when the carrier is calcium carbonate.
  • the catalyst used in step c) has an amount of palladium in the range of 1 to 10 weight-%, more preferably in the range of 1 to 5 weight-%, based on the total weight of the catalyst, if the carrier is aluminum oxide, silica, porous glass, carbon or graphite and barium sulphate.
  • a preferred catalyst used in step c) is palladium on calcium carbonate, wherein lead is present.
  • this catalyst has an amount of lead in the range of 0 to 9 weight-%, more preferably in the range of 1 to 5 weight-%, based on the total weight of the catalyst.
  • the amount of palladium of this catalyst is preferably in the range of 1 to 10 weight-%, more preferably in the range of 3 to 8 weight-%, even more preferably in the range of 5 to 7 weight-%, based on the total weight of the catalyst,
  • the catalyst is Pd + Pb on CaCC , it preferably has a BET surface area in the range of 2 to 15 m 2 /g, more preferably it has a BET surface area in the range of 5 to 15 m 2 /g, even more preferably it has a BET surface area in the range of 7 to 10 m /g.
  • Most preferably 50% of the particles of this catalyst also have a size ⁇ 2 to 50 ⁇ (i.e. the so-called particle size D50 ⁇ 3-30 ⁇ ), preferably ⁇ 2 to 30 ⁇ , more preferably ⁇ 3 to 10 ⁇ .
  • the catalyst used in step c) is the same catalyst as used in step a).
  • This catalyst is more preferably Pd on aluminum oxide.
  • the catalyst is Pd on aluminum oxide or silica or any mixture thereof it preferably has a BET surface area in the range of 50 to 500 m g, more preferably it has a BET surface area in the range of 80 to 300 m /g, most preferably it is an egg-shell catalyst.
  • step c) is carried out at a temperature in the range of 10 °C to 100 °C, more preferably at a temperature in the range of 15 to 60 °C.
  • step c) is carried out at a pressure in the range of 1.1 bar to 15 bar, more preferably at a pressure in the range of 1.5 to 6 bar, even more preferably at a pressure the range of 1.8 to 4 bar.
  • the amount in weight-% of the catalyst used in step c) is in the range of 1 : 50 to 1 : 5000, more preferably in the range of 1 : 100 to 1 : 2500, even more preferably in the range of 1 : 250 to 1 : 1000, based on the amount of 3,7-dimethyl-l -octin-3-ol in weight-%.
  • Preferred embodiments of the present invention are also embodiments where several preferred embodiments of step c) as listed above are combined.
  • the present invention is not only directed to the synthesis of DMOE, but also to the synthesis of (iso)phytol (derivatives) and vitamin E (acetate), especially to 0 a process for the manufacture of isophytol comprising the following steps
  • a process for the manufacture of vitamin E comprising the following steps - reacting 2,3,6-trimethylhydroquinone (TMHQ) or 2,3,6-trimethylhydroquinone-l - acetate (TMHQA) with (iso)phytol or derivatives thereof or any mixture thereof to obtain vitamin E or its acetate.
  • TMHQ 2,3,6-trimethylhydroquinone
  • THQA 2,3,6-trimethylhydroquinone-l - acetate
  • a 5 % Pd/C catalyst with a specific surface area of 1000 m 2 /g, a volume of the micropores of 0.30 ml/g, a volume of the mesopores of 0.40 ml/g, a volume of the macropores of 0.40 ml/g, a bulk density in the range of 200 and 300 g/L; a volume of the pores of 1.10 ml/g and a mixed metal localisation, which is e.g. commercially available from Evonik under the tradename "10 % Pd/C Evonik E 101 N/D" ("catalyst C");
  • Such a catalyst with a BET area of 800 m 2 /g, whereby 50 % of the particles have a size ⁇ 21 ⁇ is e.g. commercially available from Engelhard under the tradename "5 % Pt/C Engelhard Lot. 07608" ("catalyst G");
  • Rh/C catalyst which is e.g. commercially available from Evonik under the tradename "5 % Rh/C, Evonik G 101 XB/D" ("catalyst H");
  • a catalyst with 5 % Pd and 3.5 % Pb supported on CaC03 with a BET area in the range of 5 to 15 m 2 /g and a bulk density in the range of 0.2 to 1.0 kg/1, whereby 50 % of the particles have a size ⁇ 2 to 10 ⁇ .
  • Such a catalyst with a BET area of 8 m /g and a bulk density of 0.37 kg/1, whereby 50 % of the particles have a size ⁇ 5 ⁇ is e.g.
  • a catalyst with 5 % Pd and 5 % Pb supported on CaC03 with a BET area in the range of 2 to 15 m /g, a bulk density in the range of 0.2 to 1.0 kg/1 and a pore volume in the range of 1.0 to 2.0 ml/g, whereby the particles have a size ⁇ 100 ⁇ .
  • Such a catalyst with a BET area of 5 m /g, a bulk density of 0.45 kg/L and a pore volume of 1.6 ml/g, whereby the particles have a size ⁇ 100 ⁇ is e.g. commercially available from Heraeus under the tradename "5 % Pd 5 % Pb CaC0 3 Heraeus"("catalyst M");
  • Catalyst S a 1 % Pd/TP catalyst
  • TRISOPERL® by the Schuller GmbH, Wertheim/Germany, is a porous Silica glass with an average particle size in the range of 100 to 200 ⁇ , an average pore size of 54.47 nm, a specific surface of 93.72 m 2 /g and an average pore volume of 1255.5 mm 3 /g.
  • a 125 mL-autoclave (Hastelloy) was charged with 30 g of MH with a purity of 96.7 % and the catalyst as given in table 1.
  • the amount of catalyst was 33.3 mg in all examples.
  • the mixture was heated to 60 °C and hydrogen was added at 2 bar. After reaction, when no up-take of hydrogen was observed any more, the mixture was cooled to 20 °C, the catalyst separated by filtration and the mixture analyzed by gas chromatography.
  • the catalysts used in examples 5 and 6 are pulverous catalysts.
  • Step a Examples 8 to 11
  • Example 2 was repeated at various temperatures and/or pressures. The results are shown in table 2.
  • the catalyst used was catalyst B (5 % Pd/C).
  • Example 1 was repeated but different metals used as catalyst.
  • the results are summarized in table 3. As the results show platinum on carbon as well as rhodium on carbon give less conversion and less selectivity, thus also less yield on the desired product, than palladium on carbon.
  • the experiment was repeated three times.
  • the conversion was 97.3 % in average, the yield was 96.0 % in average before washing and 95.3 % afterwards, and the selectivity was 98.7 %.
  • Step c Examples 13 to 30
  • a 150 mL-autoclave (Hastelloy) was charged with 40 g of DMOI with a purity of 99.8 % and the amount and catalyst as given in table 4. 4.7 mg of the modifier 2,2'ethylene-dithiodiethanol were added. The mixture was heated to 30 °C and hydrogen was added at 2 bar. After reaction, when no up-take of hydrogen was observed any more, the mixture was cooled to 20 °C, the catalyst separated by filtration and the mixture analyzed by gas chromatography.
  • Example 13 was repeated at different temperature and/or pressure. The results are shown in table 5.
  • the catalyst used was catalyst I (5 % Pd 3.5% Pb on CaC0 3 ).
  • Example 13 was repeated with different modifiers. The reactions were all performed at 2 bar and 30 °C. The results are shown in 6.
  • Step c Example 39 and comparison examples 40 to 41
  • Example 13 was repeated with different metal catalysts, but no modifier was used. The reactions were all performed at 2 bar and 30 °C. The results are shown in table 7.

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Abstract

The present invention is directed to a process for the manufacture of 3,7-dimethyl-l-octen-3-ol comprising the following steps: a) hydrogenation of 6-methyl-5-hepten-2-on to 6-methyl-2-heptanon in the presence of hydrogen and a palladium containing catalyst on a carrier selected from the group consisting of carbon, calcium carbonate and aluminum oxide. b) reaction of 6-methyl-2-heptanon with acetylene to 3,7-dimethyl-l-octin-3-ol in the presence of ammonia and potassium hydroxide and in the absence of any additional organic solvent; c) hydrogenation of 3,7-dimethyl-l -octin-3-ol to 3,7-dimethyl-l-octen-3-ol in the presence of hydrogen and a palladium containing catalyst on a carrier selected from the group consisting of calcium carbonate, aluminum oxide, silica, porous glass, carbon or graphite, and barium sulphate, with the proviso that the catalyst additionally contains lead when the carrier is calcium carbonate. The present invention is further directed to a process for the manufacture of isophytol and vitamin E, where a thus produced 3,7-dimethyl-l-octen-3-ol is used as starting material.

Description

Process for the manufacture of 3,7-dimethyl-l -octen-3-ol
According to the process of the present invention (see Fig. 1) 6-methyl-5-hepten-2-on (MH) is hydrogenated to 6-methyl-2-heptanone (MHA) (step a), which is then reacted with acetylene to 3,7-dimethyl-l -octin-3-ol (DMOI) (step b). DMOI is then hydrogenated to 3,7-dimethyl-l -octen-3-ol (DMOE, step c).
MH itself can be prepared by reaction of isopropenyl methyl ether with 2-methyl-3- buten-2-ol as described by G. Saucy and R. Marbet in Helv. Chim. Acta 1967, 50, 2091 - 2095.
DMOE as well as tetrahydrolinalool (THLL, 3,7-dimethyl-octan-3-ol) are base products for the flavour and fragrance industry. DMOE, a colourless to pale yellow liquid, has a rose odour and is used in a variety of perfumery applications. It is seen as an alternative to geraniol.
DMOE and THLL are furthermore possible intermediates for isophytol (see e.g. P.
Karrer, K.S. Yap, Helv. Chim. Acta 1940, 23, 581), which may be used to manufacture vitamin E (see UUmann's Encyclopedia of Industrial Chemistry, Editors: Barbara Elvers, Stephen Hawkins, 5th completely revised edition, VCH Verlagsgesellschaft mbH, D-
69451 Weinheim, 1996, Volume A27 (Thor to Vita), Chapter 4.11.2 - 4.11.5, page 484- 488; especially Chapter 4.11.2 (page 484-485)).
6,10-dimethyl-5-undecen-2-one may be manufactured starting from DMOE according to processes known to the person skilled in the art like e.g. described in US 2,783,257 (see scheme in column 1) and DE-AS 1 193 490 (see example 10). 6,10-Dimethyl-5-undecen- 2-one may then be hydrogenated to obtain hexahydropseudoionone (HPI) (see US 2,783,257: column 2, line 58-64), which may be further reacted to (iso)phytol according to processes as e.g. disclosed in Appl. Catal. 2005, 280, 55-73 and Catal. Today 2007, 121, 45-57.
Processes for the manufacture of THLL and DMOE are already known: P. Karrer and K. S. Yap (Helv. Chim. Acta 1940, 23, 581 -584.) describe a procedure for the synthesis of THLL starting from MH. The MH reduction was carried out in the presence of a Pt catalyst, yields were not given. The resulting methylheptanone (MHA) was ethynylated using ethyne and sodium amide. 3,7-Dimethyl-octin-l -3-ol was catalytically reduced in presence of a Pt catalyst. The disadvantage of the procedure is that stoichiometric amounts of the ethynylation agent are used, the hydrogenations are performed with an expensive catalyst, no yields are given (the analysis is not discussed), the reactions are carried out in solvents, and low yields are obtained if we assume that 20 g of MH give 8 g of THLL, based on the experimental procedures reported. The THLL obtained is used for the synthesis of isophytol.
According to US 2,780,658 DMOE (named as 1,5 -dimethyl- 1 -vinyl- 1 -hexanol) is synthesized starting from MHA which is ethynylated in presence of sodium in liquid ammonia followed by Lindlar hydrogenation in the presence of a catalyst which is Pd/Pb on CaCC . The hydrogenation was carried out in petroleum ether at 20-30°C. For the hydrogenation of 308 g of the starting material 20 g of the catalyst (s/c ~ 15) were required.
A similar procedure was claimed in GB 788,301. MHA was ethynylated in ether in presence of ammonia using sodium and ethyne followed by Lindlar hydrogenation in ligroin as solvent. The ethynylation was described to proceed in 82.2 % yield.
I. N. Nazarov et al. described in Seriya Khimicheskaya 1957, 1267-1270 and in Zhurnal Obshchei Khimii 1958, 28, 1444-1448 the semi hydrogenation of alkynols in presence of Pd on CaC03. MHA was ethynylated in 87% yield in presence of solid KOH at 0-20°C at 5-8 atmospheres, followed by hydrogenation (90%), no conditions were given.
A. Ofner et al. described in Helv. Chim. Acta 1959, 42, 2577-2584 the Pd/CaC03 (5% Pd loading) catalyzed hydrogenation of MH to MHA at 34 atm pressure, followed by sodium acetylide treatment to give the corresponding alkynol and Lindlar hydrogenation to DMOE (named as dihydro-linalool).
F. J. Brocker et al. claimed the preparation and application of hydrogenation catalysts. In EP-A 412 415 the preparation of a Pd catalyst on a support by metal vapour deposition was claimed (300-800°C), and especially the hydrogenation of 3,7-dimethyl-oct-l-in-3-ol (named as hydro-dehydrolinalool (HDHL)) to DMOE (named as hydro-linalool (HLIN)) was demonstrated (examples 2 and 3: 100% conversion, 99.3% - 99.5% selectivity).
EP-A 754 664 describes the partial hydrogenation of alkynes using a solid-bed catalyst as described in EP-A 412 415, whereby the Lindlar hydrogenation was carried out in presence of CO (10-180 ppm).
In EP-A 1 110 932 the above applications are combined and more examples are presented. A similar procedure of alkyne hydrogenation in presence of CO was carried out.
EP-A 816 321 claimed the synthesis of MHA by aldol reaction of acetone and isovaleraldehyde in presence of hydrogen and a conventional hydrogenation catalyst at 15-150°C and 1 -100 bar, (example 3 : Pd/C). For the ethynylation of MHA standard protocols were used (example 3, step c, 2 hours, 4-6°C, KOH in water, ammonia).
Solvents like NMP, DMSO, and DMF had to be used. These solvents are difficult to separate from the product, (and) especially they could have a negative impact on flavour and fragrance applications. The Lindlar hydrogenation was carried out in a solvent, e.g. hexane, heptane, at 1-130°C and at 1 -50 bar. The preferred catalyst was Pd on CaCC (selectivity 95-96 %, conversion 97.3-99.7%). In the examples (step 3c, page 20) the Lindlar hydrogenation was carried out in hexane.
The object of the present invention was to provide a process which may be used for the industrial production of DMOE, i.e. a process which is economic. Furthermore, the process according to the present invention should not have the disadvantages of the processes of the prior art.
A preferred object of the present invention was also to achieve a selectivity > 90% at a conversion of > 95%.
The present invention is directed to a process for the manufacture of 3,7-dimethyl-l- octen-3-ol comprising the following steps:
a) hydrogenation of 6-methyl-5-hepten-2-on to 6-methyl-2-heptanon in the presence of hydrogen and a palladium containing catalyst on a carrier selected from the group consisting of carbon, calcium carbonate and aluminum oxide.
b) reaction of 6-methyl-2-heptanon with acetylene to 3,7-dimethyl-l-octin-3-ol in the presence of ammonia and potassium hydroxide and in the absence of any additional organic solvent;
c) hydrogenation of 3,7-dimethyl-l-octin-3-ol to 3,7-dimethyl-l-octen-3-ol in the presence of hydrogen and a palladium containing catalyst on a carrier selected from the group consisting of calcium carbonate, aluminum oxide, silica, porous glass, carbon or graphite, and barium sulphate, with the proviso that the catalyst additionally contains lead when the carrier is calcium carbonate.
Big advantages of the process of the present invention are that the same catalyst as used in step a) may be used in step c), and that steps a) and c) may be performed without the use of an organic solvent such as petroleum ether, ligroin, hexane and heptane. The single steps are described in more detail in the following.
Step a)
Preferably step a) is performed in the absence of any organic solvent, i.e. that no organic solvent is added to MH or the reaction mixture used in step a). This encompasses also the case that minor amounts of solvent may be present as "impurity" of the MH used.
Preferably the catalyst used in step a) is the same catalyst as used in step c). More preferably this catalyst has a Pd content, based on the total weight of the catalyst, of 1-10, preferred 2.5-8 more preferred, especially preferred 3-7 weight-% Pd. This catalyst is even more preferably Pd on aluminum oxide.
If the catalyst is Pd on aluminum oxide, it preferably has a BET surface area in the range of 50 to 500 m7g, more preferably it has a BET surface area in the range of 80 to 300 m /g, most preferably it is an egg-shell catalyst.
An "egg-shell" catalyst in the context of the present invention is a catalyst where the catalytically active metal (Pd) has a non-uniform distribution on the support and is located mainly on the shell of such catalyst.
If the catalyst is Pd on carbon, it preferably has a BET surface area in the range of 800 to 1500 m2/g, more preferably it has a BET surface area in the range of 900-1200 m2/e. Even more preferably 50% of the catalyst also have a size < 20-50 μηι (i.e. the so-called particle size D50 < 20-50 μηι). Most preferably the bulk density is in the range of 100 to 500 g/L, more preferably in the range of 200 to 300 g/L.
If the catalyst is Pd on CaCC , it preferably has a BET surface area in the range of 5 to 15
2 2
m /g, more preferably it has a BET surface area in the range of 7 to 10 m /g. Most preferably 50% of the particles of this catalyst also have a size < 3-30 μηι (i.e. the so- called particle size D50 < 3-30 μηι).
Even more preferably pulverous catalysts including egg-shell catalysts are used. These can be separated easily after the reaction from the reaction mixture by filtration or centrifugation. Furthermore, these catalysts can be recycled and used several times.
Preferably step a) is carried out at a temperature in the range of 20 to 100 °C, more preferably at a temperature in the range of 25 to 80 °C. Preferably step a) is carried out at a pressure in the range of 1.1 bar to 15 bar, more preferably at a pressure in the range of 1.5 to 6 bar, even more preferably at a pressure in the range of 1.8 to 4 bar.
Preferably the amount in weight-% of catalyst used in step a) is in the range of 1 : 50 to 1 : 5000, more preferably in the range of 1 : 100 to 1 : 2500, even more preferably in the range of 1 : 250 to 1 : 1000, based on the amount of 6-methyl-5-hepten-2-on in weight-%.
Preferred embodiments of the present invention are also embodiments where several preferred embodiments of step a) as listed above are combined.
Step ω
Preferably the molar ratio of 6-methyl-2-heptanon to acetylene in step b) is in the range of 1 : 1 to 1 : 2, more preferably in the range of 1 : 1.01 to 1 : 1.5.
Preferably the molar ratio of 6-methyl-2-heptanon to potassium hydroxide in step b) is in the range of 30 : 1 to 250 : 1, more preferably in the range of 40 : 1 to 100 : 1. Preferably the molar ratio of 6-methyl-2-heptanon to ammonia in step b) is in the range of 1 : 15 to 1 : 50, more preferably in the range of 1 : 20 to 1 : 30.
Preferably step b) is carried out at a temperature in the range of -10 °C to 25 °C, more preferably at a temperature in the range of 0 to 20 °C. The pressure used is preferably in the range of 5 to 25 bar, more preferably in the range of 10 to 20 bar.
Preferred embodiments of the present invention are also embodiments where several preferred embodiments of step b) as listed above are combined. Step c)
Preferably step c) is performed in the absence of any organic solvent, i.e. that no organic solvent is added to DMOI or the reaction mixture used in step c). This encompasses also the case that minor amounts of solvent may be present as "impurity" of the DMOI used. Preferably the catalyst used in step c) is a palladium containing catalyst on a carrier selected from the group consisting of calcium carbonate, aluminum oxide, silica, porous glass (especially TRISOPERL®), with the proviso that the catalyst additionally contains lead when the carrier is calcium carbonate. Preferably the catalyst used in step c) has an amount of palladium in the range of 1 to 10 weight-%, more preferably in the range of 1 to 5 weight-%, based on the total weight of the catalyst, if the carrier is aluminum oxide, silica, porous glass, carbon or graphite and barium sulphate. A preferred catalyst used in step c) is palladium on calcium carbonate, wherein lead is present. Preferably this catalyst has an amount of lead in the range of 0 to 9 weight-%, more preferably in the range of 1 to 5 weight-%, based on the total weight of the catalyst. The amount of palladium of this catalyst is preferably in the range of 1 to 10 weight-%, more preferably in the range of 3 to 8 weight-%, even more preferably in the range of 5 to 7 weight-%, based on the total weight of the catalyst,
If the catalyst is Pd + Pb on CaCC , it preferably has a BET surface area in the range of 2 to 15 m2/g, more preferably it has a BET surface area in the range of 5 to 15 m2/g, even more preferably it has a BET surface area in the range of 7 to 10 m /g. Most preferably 50% of the particles of this catalyst also have a size < 2 to 50 μηι (i.e. the so-called particle size D50 < 3-30 μπι), preferably < 2 to 30 μιτι, more preferably < 3 to 10 μηι.
Most preferably, however, the catalyst used in step c) is the same catalyst as used in step a). This catalyst is more preferably Pd on aluminum oxide.
If the catalyst is Pd on aluminum oxide or silica or any mixture thereof it preferably has a BET surface area in the range of 50 to 500 m g, more preferably it has a BET surface area in the range of 80 to 300 m /g, most preferably it is an egg-shell catalyst.
Preferably step c) is carried out at a temperature in the range of 10 °C to 100 °C, more preferably at a temperature in the range of 15 to 60 °C.
Preferably step c) is carried out at a pressure in the range of 1.1 bar to 15 bar, more preferably at a pressure in the range of 1.5 to 6 bar, even more preferably at a pressure the range of 1.8 to 4 bar.
Preferably the amount in weight-% of the catalyst used in step c) is in the range of 1 : 50 to 1 : 5000, more preferably in the range of 1 : 100 to 1 : 2500, even more preferably in the range of 1 : 250 to 1 : 1000, based on the amount of 3,7-dimethyl-l -octin-3-ol in weight-%. Preferred embodiments of the present invention are also embodiments where several preferred embodiments of step c) as listed above are combined.
Further preferred embodiments of the present invention are embodiments where one or more of the preferred embodiments of step a) and/or step b) and/or step c) as listed above are combined.
The present invention is not only directed to the synthesis of DMOE, but also to the synthesis of (iso)phytol (derivatives) and vitamin E (acetate), especially to 0 a process for the manufacture of isophytol comprising the following steps
preparing DMOE according to the process of the present invention;
preparing 6,10-dimethyl-5-undecen-2-one starting from a thus prepared DMOE; hydrogenating a thus prepared 6,10-dimethyl-5-undecen-2-one to obtain hexahydropseudoionone;
- preparing (iso)phytol or derivatives thereof from a thus prepared hexahydropseudoionone. as well as to
0 a process for the manufacture of vitamin E (acetate) comprising the following steps - reacting 2,3,6-trimethylhydroquinone (TMHQ) or 2,3,6-trimethylhydroquinone-l - acetate (TMHQA) with (iso)phytol or derivatives thereof or any mixture thereof to obtain vitamin E or its acetate.
Derivatives of phytol and isophytol are especially those as disclosed in EP-A 694-541 : page 4, line 39 to page 5, line 14 and in WO 2005/1211 15: page 4, line 11 to 19 with n = 3, whose content is incorporated herein by reference.
The invention is now further illustrated in the following non-limiting examples. Examples
In the examples the following catalysts were used:
- a 5 % Pd/C catalyst which was oxidized and dried and is e.g. commercially available from Evonik under the tradename "5 % Pd/C E 101 O/D" ("catalyst A");
- a 5 % Pd/C catalyst with a BET surface area of 1000 m /g, a bulk density in the range of 200 and 300 g/L and the following particle size distribution: 10 % of the particles < 6 μπι, 50 % of the particles < 28 μπι, and 90 % of the particles < 79 μπι, which is e.g.
commercially available from Evonik under the tradename "5 % Pd/C E 101 N/D" ("catalyst B");
- a 5 % Pd/C catalyst with a specific surface area of 1000 m2/g, a volume of the micropores of 0.30 ml/g, a volume of the mesopores of 0.40 ml/g, a volume of the macropores of 0.40 ml/g, a bulk density in the range of 200 and 300 g/L; a volume of the pores of 1.10 ml/g and a mixed metal localisation, which is e.g. commercially available from Evonik under the tradename "10 % Pd/C Evonik E 101 N/D" ("catalyst C");
- a 5 % Pd/CaCC egg-shell catalyst with a BET surface area of 8 m2/g, a bulk density of 0.37 kg/1, and whereby 50 % of the particles have a size < 5 μπι which is e.g.
commercially available from Evonik under the tradename "5 % Pd/CaCC^ Evonik E 407 R/D" ("catalyst D );
- a 5 % Pd/Al203 egg-shell catalyst with a surface area in the range of 50 - 300 m2/s, a bulk density in the range of 0.5 - 1 kg/1 and a pore volume in the range of 0.1 to 0.5 ml/g. Such a catalyst with a surface area of 93 m2/g, a bulk density of 0.8 kg/1 and a pore volume of 0.3 ml/g is e.g. commercially available from Evonik under the tradename "5 % Pd/Al203 Evonik E 213 XR/D" ("catalyst E");
- a 5 % Pd/Al2C>3 catalyst as e.g. commercially available from Engelhard under the tradename "5 % Pd/Al203 Engelhard Lot. 09784" ("catalyst F");
- a 5 % Pt/C catalyst with a BET area in the range of 500 to 1000 m2/g, whereby 50 % of the particles have a size < 21 μπι. Such a catalyst with a BET area of 800 m2/g, whereby 50 % of the particles have a size < 21 μηι, is e.g. commercially available from Engelhard under the tradename "5 % Pt/C Engelhard Lot. 07608" ("catalyst G");
- a 5 % Rh/C catalyst which is e.g. commercially available from Evonik under the tradename "5 % Rh/C, Evonik G 101 XB/D" ("catalyst H");
- a catalyst with 5 % Pd and 3.5 % Pb supported on CaC03 with a BET area in the range of 5 to 15 m2/g and a bulk density in the range of 0.2 to 1.0 kg/1, whereby 50 % of the particles have a size < 2 to 10 μπι. Such a catalyst with a BET area of 8 m /g and a bulk density of 0.37 kg/1, whereby 50 % of the particles have a size < 5 μπι is e.g.
commercially available from Evonik under the tradename "5 % Pd 3.5% Pb CaC03 Evonik CE 407 R D" ("catalyst I");
- a catalyst with 5 % Pd and 1 % Pb supported on CaC03 as e.g. commercially available from J & M under the tradename "5 % Pd 1% Pb CaC03 J & M A-304050-5" ("catalyst
J");
- a catalyst with 7 % Pd and 9 % Pb supported on CaC03 as e.g. commercially available from Evonik under the tradename "7 % Pd 9 % Pb CaC03 Evonik CE 407 R/D"
("catalyst K");
- an egg-shell catalyst with 5 % Pd and 2.5 % Pb supported on CaC03 with a BET area in the range of 5 to 15 m2/g, whereby 50 % of the particles have a size < 20 to 50 μπι which may be manufactured according to processes known to the person skilled in the art
("catalyst L");
- a catalyst with 5 % Pd and 5 % Pb supported on CaC03 with a BET area in the range of 2 to 15 m /g, a bulk density in the range of 0.2 to 1.0 kg/1 and a pore volume in the range of 1.0 to 2.0 ml/g, whereby the particles have a size < 100 μπι. Such a catalyst with a BET area of 5 m /g, a bulk density of 0.45 kg/L and a pore volume of 1.6 ml/g, whereby the particles have a size < 100 μπι is e.g. commercially available from Heraeus under the tradename "5 % Pd 5 % Pb CaC03 Heraeus"("catalyst M");
- a 5 % Pd/SiG"2 catalyst as e.g. commercially available from Engelhard under the tradename "5 % Pd/Si02 Engelhard A 596033" ("catalyst N"); - a 1 % Pd/C catalyst as e.g. commercially available from Evonik under the tradename "1 % Pd/charcoal Degussa E 101 N/D" ("catalyst O");
- a 5 % Pd/graphite reduced catalyst as e.g. commercially available from Engelhard under the tradename "5 % Pd/graphite Engelhard" ("catalyst P");
- a 5 % Pd/BaS04 catalyst as e.g. commercially available from Evonik under the tradename "5 % Pd/BaS04 Evonik E 50 N/D" ("catalyst Q");
- a 3.7 weight-% Pd/A^C catalyst, whereby the Pd is in the form of nano-particles as e.g. commercially available from SDC under the tradename "3.7 % Pd/A^C SDC Nanokat" ("catalyst R");
- a 1 % Pd/TP catalyst ("catalyst S") whose manufacture is described below.
1 % Pd/TP was manufactured as follows:
21 mg Pd(OAc)2 (0,09 mmol) were suspended in 50 rriL of dichloromethane. 1 g of TRISOPERL® were added and the solvent was removed (bath temperature: 40 °C / pressure: 950 mbara). The carrier doped with Pd(OAc)2 was calcinated for 2 hours at 300 °C in an oven (pre-heating of the oven for 20 minutes for 1000 W to 300 °C). The loading of the catalyst on the carrier was then ca. 1 weight-% Pd, i.e. 10 mg of Pd onl g of carrier. TRISOPERL® by the Schuller GmbH, Wertheim/Germany, is a porous Silica glass with an average particle size in the range of 100 to 200 μπι, an average pore size of 54.47 nm, a specific surface of 93.72 m2/g and an average pore volume of 1255.5 mm3/g.
5 Step a: Examples 1 to 7
A 125 mL-autoclave (Hastelloy) was charged with 30 g of MH with a purity of 96.7 % and the catalyst as given in table 1. The amount of catalyst was 33.3 mg in all examples. The mixture was heated to 60 °C and hydrogen was added at 2 bar. After reaction, when no up-take of hydrogen was observed any more, the mixture was cooled to 20 °C, the catalyst separated by filtration and the mixture analyzed by gas chromatography.
10
Table 1 : Synthesis of MHA by use of various catalysts
Figure imgf000014_0001
The catalysts used in examples 5 and 6 are pulverous catalysts.
Step a: Examples 8 to 11
Example 2 was repeated at various temperatures and/or pressures. The results are shown in table 2. The catalyst used was catalyst B (5 % Pd/C).
Table 2: Synthesis of MHA at various temperatures and/or pressures
Figure imgf000015_0001
5 Step a: Comparison examples 1 and 2
Example 1 was repeated but different metals used as catalyst. The results are summarized in table 3. As the results show platinum on carbon as well as rhodium on carbon give less conversion and less selectivity, thus also less yield on the desired product, than palladium on carbon.
10 Table 3 : Synthesis of MHA by use of different metals on carbon as catalyst
Figure imgf000016_0001
Step b: Example 12
In a 2 liter autoclave under nitrogen, 860 g of liquid ammonia were added to 319.4 g of methylheptanone. The mixture was cooled
15 down to 15 °C (pressure: 9.8 bar). Then acetylene was added until a pressure of 12 bar was achieved. Then 6.4 g of an aqueous 45
weight-% KOH solution was added. The reactor pressure of 12 bar was maintained by continued addition of acetylene. In total 66.7 g of acetylene were used. At the end of the reaction (after ca. 3.3 hours) 10 g of an aqueous 90 weight-% acetic acid solution were added, the pressure was relieved whereby the main part of ammonia was evaporated. By heating to 40 °C the remaining ammonia was removed. Then the reaction mixture was washed twice with 100 ml of de-ionized water, twice with 100 ml of an aqueous 8 weight-% sulphuric acid solution and again twice with 100 ml of de-ionized water.
The experiment was repeated three times. The conversion was 97.3 % in average, the yield was 96.0 % in average before washing and 95.3 % afterwards, and the selectivity was 98.7 %.
Step c: Examples 13 to 30
A 150 mL-autoclave (Hastelloy) was charged with 40 g of DMOI with a purity of 99.8 % and the amount and catalyst as given in table 4. 4.7 mg of the modifier 2,2'ethylene-dithiodiethanol were added. The mixture was heated to 30 °C and hydrogen was added at 2 bar. After reaction, when no up-take of hydrogen was observed any more, the mixture was cooled to 20 °C, the catalyst separated by filtration and the mixture analyzed by gas chromatography.
Table 4: Synthesis of DMOE by use of various catalysts
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Example 13 was repeated at different temperature and/or pressure. The results are shown in table 5. The catalyst used was catalyst I (5 % Pd 3.5% Pb on CaC03).
Table 5: Synthesis of DMOE at different temperature and/or pressure
Figure imgf000020_0001
Example 13 was repeated with different modifiers. The reactions were all performed at 2 bar and 30 °C. The results are shown in 6.
Table 6: Synthesis of DMOE, whereby the catalysts were modified with different modifiers
Figure imgf000021_0001
Step c: Example 39 and comparison examples 40 to 41
Example 13 was repeated with different metal catalysts, but no modifier was used. The reactions were all performed at 2 bar and 30 °C. The results are shown in table 7.
Table 7: Synthesis of DMOE with different catalysts, whereby no modifier was used
Figure imgf000022_0001

Claims

Claims
A process for the manufacture of 3,7-dimethyl-l-octen-3-ol comprising the following steps:
a) hydrogenation of 6-methyl-5-hepten-2-on to 6-methyl-2-heptanon in the presence of hydrogen and a palladium containing catalyst on a carrier selected from the group consisting of carbon, calcium carbonate and aluminum oxide.
b) reaction of 6-methyl-2-heptanon with acetylene to 3,7-dimethyl-l-octin-3- ol in the presence of ammonia and potassium hydroxide and in the absence of any additional organic solvent;
c) hydrogenation of 3,7-dimethyl-l-octin-3-ol to 3,7-dimethyl-l-octen-3-ol in the presence of hydrogen and a palladium containing catalyst on a carrier selected from the group consisting of calcium carbonate, aluminum oxide, silica, porous glass, carbon or graphite, and barium sulphate, with the proviso that the catalyst additionally contains lead when the carrier is calcium carbonate.
The process according to claim 1, wherein the catalyst used in step a) is the same catalyst as used in step c).
The process according to claim 2, wherein the catalyst is Pd on aluminum oxide.
The process according to claim 1 , wherein the catalyst used in step c) is palladium on calcium carbonate, wherein lead is present.
5. The process according to any of the preceding claims, wherein step a) is carried out at a temperature in the range of 40 °C to 80 °C, preferably at a temperature in the range of 50 to 70 °C.
6. The process according to any of the preceding claims, wherein step a) is carried out at a pressure in the range of 1.1 bar to 10 bar, preferably at a pressure in the range of 1.5 to 6 bar, more preferably at a pressure in the range of 1.8 to 4 bar.
7. The process according to any of the preceding claims, wherein the amount in
weight-% of catalyst used in step a) is in the range of 1 : 50 to 1 : 5000, preferably in the range of 1 : 100 to 1 : 2500, more preferably in the range of 1 : 250 to 1 : 1000, based on the amount of 6-methyl-5-hepten-2-on in weight-%.
8. The process according to any of the preceding claims, wherein the molar ratio of 6- methyl-2-heptanon to acetylene in step b) is in the range of 1 : 1 to 1 : 2, preferably in the range of 1 : 1.01 to 1 : 1.5.
9. The process according to any of the preceding claims, wherein the molar ratio of 6- methyl-2-heptanon to potassium hydroxide in step b) is in the range of 30 : 1 to 250 : 1 , preferably in the range of 40 : 1 to 100 : 1.
10. The process according to any of the preceding claims, wherein the molar ratio of 6- methyl-2-heptanon to ammonia in step b) is in the range of 1 : 15 to 1 : 50, preferably in the range of 1 : 20 to 1 : 30.
11. The process according to any of the preceding claims, wherein step b) is carried out at a temperature in the range of -10 °C to 25 °C, preferably at a temperature in the range of 0 to 20 °C, and at a pressure in the range of 5 to 25 bar, preferably at a pressure in the range of 10 to 20 bar.
12. The process according to any of the preceding claims, wherein step c) is carried out at a temperature in the range of room temperature (20 °C) to 100 °C, preferably at a temperature in the range of 30 to 80 °C.
13. The process according to any of the preceding claims, wherein step c) is carried out at a pressure in the range of 1.1 bar to 10 bar, preferably at a pressure in the range of 1.5 to 6 bar, more preferably at a pressure in the range of 1.8 to 4 bar.
14. The process according to any of the preceding claims, wherein the amount in
weight-% of the catalyst used in step c) is in the range of 1 : 50 to 1 : 5000, preferably in the range of 1 : 100 to 1 : 2500, more preferably in the range of 1 : 250 to 1 : 1000, based on the amount of 3,7-dimethyl-l-octin-3-ol in weight-%.
15. The process according to any of the preceding claims, wherein the catalyst used in step c) has an amount of palladium in the range of 1 to 10 weight-%, based on the total weight of the catalyst.
16. The process according to claim 4, wherein the catalyst used in step c) has an amount of lead in the range of 0 to 9 weight-%, preferably in the range of 1 to 5 weight-%, based on the total weight of the catalyst.
17. A process for the manufacture of phytol, isophytol or derivatives thereof comprising the following steps
preparing DMOE according to any of the preceding claims;
preparing 6,10-dimethyl-5-undecen-2-one starting from a thus prepared DMOE; hydrogenating a thus prepared 6,10-dimethyl-5-undecen-2-one to obtain hexahydropseudoionone;
preparing phytol, isophytol or derivatives thereof from a thus prepared
hexahydropseudoionone.
18. A process for the manufacture of vitamin E or its acetate comprising the following step:
reacting 2,3,6-trimethylhydroquinone (TMHQ) or 2,3, 6-trimethylhydroquinone-l -acetate (TMHQA) with phytol, isophytol or derivatives thereof or any mixture thereof as manufactured according to claim 17 to obtain vitamin E or its acetate.
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KR20150023423A (en) * 2012-06-22 2015-03-05 디에스엠 아이피 어셋츠 비.브이. New catalytic system
JP2015526276A (en) * 2012-06-22 2015-09-10 ディーエスエム アイピー アセッツ ビー．ブイ． New catalyst system
KR102159414B1 (en) * 2012-06-22 2020-09-24 디에스엠 아이피 어셋츠 비.브이. New catalytic system
US10953393B2 (en) 2015-10-12 2021-03-23 The University Of Chicago Stabilization of active metal catalysts at metal-organic framework nodes for highly efficient organic transformations
US11673125B2 (en) 2016-08-18 2023-06-13 The University Of Chicago Metal oxide-supported earth-abundant metal catalysts for highly efficient organic transformations

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