CN106946673A - The method for manufacturing the ketone of 6,10,14 trimethylpentadecane 2 - Google Patents

The method for manufacturing the ketone of 6,10,14 trimethylpentadecane 2 Download PDF

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CN106946673A
CN106946673A CN201611144925.9A CN201611144925A CN106946673A CN 106946673 A CN106946673 A CN 106946673A CN 201611144925 A CN201611144925 A CN 201611144925A CN 106946673 A CN106946673 A CN 106946673A
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catalyst
mixture
hydrogen
acetone
group
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沃纳·邦拉蒂
乔纳森·艾伦·米德洛克
托马斯·穆尔勒
彼得·里布尔
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DSM IP Assets BV
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    • 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
    • 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
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
    • C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention relates to manufacture 6,10, the method of the ketone of 14 trimethylpentadecane 2, methods described includes making (5E with hydrogen in the presence of a catalyst, 9E) farnesyl acetone and (5Z, the step of 9E) mixture of farnesyl acetone is hydrogenated, wherein relative to C=O bond, catalyst can preferentially hydrogenate carbon-carbon double bond.Preferably, catalyst includes the metal selected from the group being made up of palladium, platinum, rhodium, iridium and nickel and its mixture.

Description

The method for manufacturing 6,10,14- trimethylpentadecane -2- ketone
The present invention relates to the method for 6,10,14- trimethylpentadecane -2- ketone of manufacture (" C18- ketone "), methods described includes Make the step that the mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone is hydrogenated with hydrogen in the presence of a catalyst Suddenly, wherein relative to carbon-oxygen double bond, the catalyst can preferentially hydrogenate carbon-to-carbon double bond.Preferably, catalyst is included and is selected from The metal for the group being made up of palladium, platinum, rhodium, iridium and nickel and its mixture.It is highly preferred that catalyst include be selected from by palladium, platinum and its The metal of the group of mixture composition.Even further preferably, catalyst is the gold selected from the group being made up of palladium, platinum and its mixture Category.Most preferably, catalyst is palladium.
It is surprising that it was found by the inventors of the present invention that when use (5E, 9E)-farnesyl acetone and (5Z, 9E)-method The mixture of Thessaloniki acetone is prepared during C18- ketone, and hydrogenation reaction ratio uses (5E, 9E)-farnesyl acetone, (5Z, 9E)-Fa Ni The situation of the mixture of benzylacetone, (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone is faster.Therefore, it is favourable It is (for up to a hundred tons of commercial run of production), uses (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl third The mixture of ketone as obtain C18- ketone parent material because the saving time there is tremendous influence to total cost of production.
Brief description of the drawings
Fig. 1 schematically shows farnesyl acetone to the conversion of C18- ketone.
Manufacture the mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone
It can be extended by the C3 of (E)-nerolidol, to obtain (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl The mixture of acetone.One example is, in the presence of a catalyst (E)-nerolidol reacted with isopropenyl methyl ether or with The reaction of isopropenyl ethylether obtains the mixture of (E, E)-farnesyl acetone and (E, Z)-farnesyl acetone.Can use acid or Ammonium salt is used as catalyst.
The method that wherein catalyst is acid is further described in WO 2009/019132, preferably wherein catalyst is selected The group that free phosphoric acid, sulfuric acid, p-methyl benzenesulfonic acid, methanesulfonic acid, trichloroacetic acid, oxalic acid and its mixture are constituted, WO 2009/ 019132 content is incorporated herein by reference.
The method that wherein catalyst is ammonium salt is further described in WO 2010/046199, is preferably wherein catalyzed Agent is selected from the group being made up of ammonium bromide, ammonium chloride or Diammonium phosphate (DAP), and WO 2010/046199 content is incorporated herein by reference.
Or, the C3 that can also carry out (E)-nerolidol according to the method described in JP-A 2002-121 165 prolongs Stretch.
Further, it is also possible to which (E)-orange is carried out using one kind in following reagent with method known to those skilled in the art The C3 extensions of the flower tertiary alcohol.
The example of the method wherein using diketene is described in GB 788,301.In such as CN 102 115 437 Describe the example of the method (so-called " Carroll reactions ") wherein using acetoacetic ester.
Manufacture (E)-nerolidol
(E)-nerolidol as parent material can come from natural origin or any other source, or be obtained by fermentation , or can be obtained with synthetic method synthesis, and if desired, by any method known to those skilled in the art To separate with (Z)-nerolidol.
Another method for obtaining (E)-nerolidol is that since (E)-geranyl acetone, (E)-geranyl acetone is in itself It can extract and obtain from natural origin or any other source, or be obtained by fermenting, or can be obtained with synthetic method synthesis, And if desired, come to separate with (Z)-geranyl acetone by any method known to those skilled in the art.
Then ethinylation, Ran Hou are carried out to (E)-geranyl acetone according to any method well known by persons skilled in the art Hydrogenated in the presence of Lindlar catalyst.Ethinylation (ethyinylation) can use acetylene, ammonia and alkali (such as potassium hydroxide) Carry out, or carried out with acetenyl RMgBr.Or, (E)-perfume can be used according to method known to those skilled in the art Phyllopodium acetone reacts with vinyl RMgBr.
Obtain (E)-nerolidol another method be by (2E, 6E)-farnesol, (2Z, 6E)-farnesol or The rearrangement of its mixture, such as, by S.Matsubara, T.Okazoe, K.Oshima, K. Takai, H.Nozaki exists Bull.Chem.Soc.Jpn.1985, described by 58,844-849 and by J.Jacob, J.H.Espenson, J.H.Jensen, M.S.Gordon is in Organometallics 1998, described by 17,1835-1840.
(2E, 6E)-farnesol can extract from natural origin obtain in itself, or be obtained by fermenting, or can synthesize Method synthesis is obtained, and if desired, is come by any method known to those skilled in the art and (2Z, 6E)-method Buddhist nun's alcohol, (2E, 6Z)-farnesol and (2Z, 6Z)-farnesol are separated.
(2Z, 6E)-farnesol can be obtained with synthetic method synthesis in itself, and if desired, pass through this area skill Any method known to art personnel to separate with (2E, 6E)-farnesol, (2E, 6Z)-farnesol and (2Z, 6Z)-farnesol.
The mixture of (2E, 6E)-farnesol and (2Z, 6E)-farnesol can be obtained with synthetic method synthesis in itself, and such as If fruit needs, come by any method known to those skilled in the art and (2E, 6Z)-farnesol and (2Z, 6Z)-farnesol Separation.
The method for manufacturing isophytol, alpha-tocopherol and its acetic acid esters
Because the mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone is a kind of important of isophytol Parent material, thus be also a kind of important parent material of alpha-tocopherol and its acetic acid esters, therefore the present invention is also related to respectively And the method for the method and manufacture alpha-tocopherol and its acetic acid esters of manufacture isophytol, methods described is including according to side of the invention Method.
Therefore, another target of the invention is the method for manufacturing isophytol, described to comprise the following steps：
A) (E)-nerolidol is made to carry out C3 extensions in the presence of a catalyst, it is preferred to use isopropenyl methyl ether makes Isopropenyl ethylether is used, to obtain the mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone；
B) mixing of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone is made with hydrogen in the presence of a catalyst Thing is hydrogenated, to obtain 6,10,14- trimethylpentadecane -2- ketone, wherein relative to carbon-oxygen double bond, catalyst can be hydrogenated preferentially Carbon-to-carbon double bond；
C1 6,10,14- trimethylpentadecane -2- ketone ethinylations) are made, to obtain the carbon -1- of 3,7,11,15- tetramethyl 16 Alkynes -3- alcohol；
D1 the hydrogenation of the carbon -1- alkynes -3- alcohol of 3,7,11,15- tetramethyl 16) is made to obtain isophytol.
Or, isophytol can be produced according to the method comprised the following steps, this method is also the mesh of the present invention Mark：
A) (E)-nerolidol is made to carry out C3 extensions in the presence of a catalyst, it is preferred to use isopropenyl methyl ether makes Isopropenyl ethylether is used, to obtain the mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone；
B) mixing of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone is made with hydrogen in the presence of a catalyst Thing is hydrogenated, to obtain 6,10,14- trimethylpentadecane -2- ketone, wherein relative to carbon-oxygen double bond, catalyst can be hydrogenated preferentially Carbon-to-carbon double bond；
C2) 6,10,14- trimethylpentadecane -2- ketone vinylations are made to obtain different plant by adding vinyl RMgBr Alcohol.
Another target of the present invention is the method for manufacture alpha-tocopherol and its acetic acid esters respectively, and methods described includes as follows Step：
A) (E)-nerolidol is made to carry out C3 extensions in the presence of a catalyst, it is preferred to use isopropenyl methyl ether makes Isopropenyl ethylether is used, to obtain the mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone；
B) mixing of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone is made with hydrogen in the presence of a catalyst Thing is hydrogenated, to obtain 6,10,14- trimethylpentadecane -2- ketone, wherein relative to carbon-oxygen double bond, catalyst can be hydrogenated preferentially Carbon-to-carbon double bond；
C1 6,10,14- trimethylpentadecane -2- ketone ethinylations) are made, to obtain the carbon -1- of 3,7,11,15- tetramethyl 16 Alkynes -3- alcohol；
D1 the hydrogenation of the carbon -1- alkynes -3- alcohol of 3,7,11,15- tetramethyl 16) is made to obtain isophytol；
E) isophytol is made to be coupled with TMHQ or its acetic acid esters, to obtain alpha-tocopherol or its acetic acid esters.
Or, alpha-tocopherol or its acetic acid esters can be produced according to the method comprised the following steps, this method is also this One target of invention：
A) (E)-nerolidol is made to carry out C3 extensions in the presence of a catalyst, it is preferred to use isopropenyl methyl ether makes Isopropenyl ethylether is used, to obtain the mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone；
B) mixing of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone is made with hydrogen in the presence of a catalyst Thing is hydrogenated, to obtain 6,10,14- trimethylpentadecane -2- ketone, wherein relative to carbon-oxygen double bond, catalyst can be hydrogenated preferentially Carbon-to-carbon double bond；
C2) 6,10,14- trimethylpentadecane -2- ketone vinylations are made to obtain different plant by adding vinyl RMgBr Alcohol；
E) isophytol and TMHQ or its acetic acid ester condensation are made, to obtain alpha-tocopherol or its acetic acid esters.
Step c1), d1), c2) and e) can be carried out according to method known to those skilled in the art.For example, ethinylation can To be carried out with acetylene, ammonia and potassium hydroxide, or carried out with acetenyl RMgBr.Then carried out such as with Lindlar catalyst Under the keys of CC tri- be hydrogenated to C=C double bonds.
Describe in detail
The synthesis of isophytol is needed to be optimized, isophytol is the important parent material of alpha-tocopherol and its acetic acid esters. 6,10,14- trimethylpentadecane -2- ketone (hereinafter referred to as " C18- ketone ") are the parent materials of isophytol.Therefore, C18- ketone The improvement of synthesis also causes the improvement that isophytol is synthesized.
Present invention accomplishes the needs, the present invention relates to manufacture 6,10,14- trimethylpentadecane -2- ketone (hereinafter referred to For " C18- ketone ") method, the described method comprises the following steps：In the presence of a catalyst, (5E, 9E)-Fa Ni is made with hydrogen The mixture of benzylacetone and (5Z, 9E)-farnesyl acetone is hydrogenated, wherein relative to carbon-oxygen double bond, the catalyst can be preferential Hydrogenate carbon-carbon double bond.The step b) that this method corresponds in the method for manufacture isophytol and alpha-tocopherol or its acetic acid esters.
Parent material
Preferably, the mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone is used, wherein based on institute The total amount of mixture is stated, less than 43 moles % of content of (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone, preferably Ground is less than 20 moles of %, is more preferably less than 10 moles of %.Therefore, following mixtures can also be used successfully, the mixture In, the total amount based on mixture, the amount of (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone be at most 43 moles of %, Preferably no more than the 20 moles % of %, more preferably up to 10 moles.It is highly preferred that use (5E, 9E)-farnesyl acetone with (5Z, The mixture of 9E)-farnesyl acetone, wherein (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone are only deposited with trace It is that less than 0.5 mole %, preferably respective amount are less than 0.1 mole % in, i.e., respective amount.Most preferably, use (5E, The mixture of 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone, wherein (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-method Thessaloniki acetone is not present.
Catalyst
Preferably, catalyst includes the metal selected from the group being made up of palladium, platinum, rhodium, iridium and nickel and its mixture.More preferably Ground, catalyst includes the metal selected from the group being made up of palladium, platinum and its mixture.Even further preferably, catalyst be selected from by The metal of the group of palladium, platinum and its mixture composition.Most preferably, catalyst is palladium.
In above-mentioned catalyst, those catalyst comprising support/carrier be even more preferably, the support/ Carrier selects the group of free carbon, graphite, inorganic oxide, inorganic carbonate, mineral sulfates and its mixture composition, wherein activity Composition (that is, metal) is deposited on the support/carrier.It is preferred that support/carrier material be carbon, silica, oxidation Aluminium and calcium carbonate and its mixture.The example of this mixture has silica-alumina-mixture.Most preferred support/ Carrier material is silica, aluminum oxide and calcium carbonate and its mixture.
If using the active component (that is, metal) on support/carrier material, then (that is, golden based on active component Category) and support gross weight, the content of active component (that is, metal) preferably in the range of 0.5-20 weight %, it is more excellent Selection of land is in the range of 2-5 weight %, most preferably in the range of about 5 weight %.
Based on parent material：The weight of the mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone, is urged The amount of the active component (metal preferably selected from the group being made up of palladium, platinum, rhodium, iridium and nickel and its mixture) of agent is preferred Ground is in the range of 0.0001-1 weight %, more preferably in the range of 0.001-0.5 weight %, most preferably in 0.01- In the range of 0.1 weight %.
Reaction condition
Temperature of the hydrogenation preferably at a temperature in the range of 10-150 DEG C, more preferably in the range of 20-100 DEG C Under, most preferably at a temperature in the range of 50-90 DEG C carry out.
Hydrogenation preferably in 1-25bar hydrogen absolute value ranges hydrogen pressure, it is more preferably absolute in 2-10bar hydrogen Hydrogen pressure in the range of value, hydrogen even more preferably still in 2-6bar hydrogen absolute value ranges are depressed, even more preferably existed Hydrogen in 2.5-4bar hydrogen absolute value ranges is depressed, most preferably in the hydrogen pressure progress of about 3bar hydrogen absolute values.
Solvent
Hydrogenation can be carried out in the absence of solvent or in the case of there is organic solvent.
It should be understood that " organic solvent " in linguistic context of the present invention is represented：It is inert for claimed process conditions And keep the organic solvent of non-chemical change.
Organic solvent is preferably chosen from hydrocarbon, halogenated hydrocarbons, alcohol, ether, ester, acid amides, nitrile and ketone and its mixture.More preferably C4-C10Aliphatic hydrocarbon, C6-C10Aromatic hydrocarbon, by one or more C1-C4Straight chained alkyl or C3-C4Branched alkyl or the C of halogen substitution6- C10Aromatic hydrocarbon, C1-C4Straight chain alcohol or C3-C4Branched-chain alcoho, the C of acyclic and cyclic4-C10Ether, C3-C10Ester, C3-C10Ketone and its mixed Compound.
Especially preferred organic solvent is selected from by hexane, heptane, toluene, methanol, ethanol, normal propyl alcohol, 2- propyl alcohol, positive fourth What alcohol, tetrahydrofuran, 2- methyl-tetrahydros furans, dioxanes, ethyl acetate, isopropyl acetate, acetone and its mixture were constituted Group.
Based on parent material：The volume of the mixture of (E, E)-farnesyl acetone and (E, Z)-farnesyl acetone, solvent Measure preferably in the range of 0-100 volumes (0=is solvent-free), more preferably in the range of 0.1-10 volumes, most preferably In the range of 1-5 volumes.
Preferably, reaction is carried out under no organic solvent.
Now so that further explaination is of the invention in following non-limiting examples.
Embodiment
The normal process of Solvent-free hydrogenation reaction
Farnesyl acetone (4g) is added in glass reactor.Add catalyst and closed reactor.By mixture nitrogen Gas purifies 3 times (are pressurized to 5bar, then discharge) and with hydrogen cleaning 3 times (being pressurized to 5bar, then release).By reactor plus Heat is to desired temperature, then with hydrogen pressurization to desired pressure.Start to stir and record hydrogen-sucking amount with 1000rpm.18 is small When total experimental period after, reactant mixture is cooled to room temperature, then discharge pressure and sample for GC analysis.
Table 1：The catalyst used=Evonik E 101O/D (5% carbon loaded palladium catalyst)
For embodiment 1 and embodiment 3, reaction not exclusively, then made it so stop and carry out after 1300 minutes Analysis.Parent material fully converts but is found that the mixture of desired C18- ketone and intermediate product.
Table 2：The catalyst used=Evonik E 213R/D (5% alumina load palladium catalyst)
For embodiment 8, after filtration catalytic agent, 4.0g (5E, 9E)/(5Z, 9E) farnesyl acetone (90% purity) is given The rate of output is 86% C18- ketone.

Claims (12)

1. manufacturing the method for the method (" C18- ketone ") of 6,10,14- trimethylpentadecane -2- ketone, methods described is included in catalysis Make the step of mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone is hydrogenated with hydrogen in the presence of agent, wherein Relative to carbon-oxygen double bond, the catalyst can preferentially hydrogenate carbon-to-carbon double bond.
2. according to the method described in claim 1, wherein the catalyst preferably include be selected from by palladium, platinum, rhodium, iridium and nickel and The metal of the group of its mixture composition, more preferably wherein described catalyst, which is included, is selected from what is be made up of palladium, platinum and its mixture The metal of group, even more preferably still wherein described catalyst is the metal selected from the group being made up of palladium, platinum and its mixture, optimal The wherein described catalyst of selection of land is palladium.
3. the method according to claim 1 and/or 2, wherein the metal is preferably deposited on carrier/support, Carrier/the support selects free carbon, graphite, inorganic oxide, inorganic carbonate, mineral sulfates and its mixture composition Group, more preferably described metal is deposited on carrier/support, and the carrier/support selects free carbon, silica, oxygen Change the group of aluminium and calcium carbonate and its mixture composition.
4. according to one or more described methods in claims 1 to 3, wherein hydrogenation is in the range of 10 to 150 DEG C At a temperature of, preferably at a temperature in the range of 20 to 100 DEG C, more preferably at a temperature in the range of 50 to 90 DEG C carry out.
5. according to any one or more described methods in Claims 1-4, wherein hydrogenation is absolute to 25bar hydrogen 1 Hydrogen in the range of value is depressed, the hydrogen preferably in 2 to 10bar hydrogen absolute value ranges is depressed, more preferably exhausted to 6bar hydrogen 2 To the hydrogen pressure in the range of value, hydrogen pressure even more preferably still in 2.5 to 4bar hydrogen absolute value ranges, most preferably about The hydrogen pressure of 3bar hydrogen absolute values is carried out.
6. according to any one or more described methods in claim 1 to 5, wherein based on parent material：(5E, 9E)-method The weight of the mixture of Thessaloniki acetone and (5Z, 9E)-farnesyl acetone, (it is preferably choosing to the active component of the catalyst Free palladium, platinum, rhodium, iridium and nickel and its mixture composition group metal) amount in the range of 0.0001 to 1.0 weight %, it is excellent Selection of land is in the range of 0.001 to 0.5 weight %, more preferably in 0.01 to 0.1 weight % scopes ground.
7. according to any one or more described methods in claim 1 to 6, wherein hydrogenation is in no organic solvent Lower progress.
8. according to any one or more described methods, wherein parent material in foregoing Claims：(5E, 9E)-farnesyl The mixture of acetone and (5Z, 9E)-farnesyl acetone is by making (E)-nerolidol and isopropenyl in the presence of a catalyst Methyl ether reacts what is obtained with isopropenyl ethylether.
9. method according to claim 8, wherein the catalyst is acid, preferably wherein described catalyst is selected from by phosphorus The group that acid, sulfuric acid, p-methyl benzenesulfonic acid, methanesulfonic acid, trichloroacetic acid, oxalic acid and its mixture are constituted.
10. method according to claim 8, wherein the catalyst is ammonium salt, preferably wherein described catalyst is selected from The group being made up of ammonium bromide, ammonium chloride or Diammonium phosphate (DAP).
11. manufacturing the method for isophytol, methods described is included according to any one or more described sides in foregoing Claims Method.
12. manufacture the method for alpha-tocopherol or its acetic acid esters, methods described include according to any one in foregoing Claims or Multiple described methods.
CN201611144925.9A 2015-12-11 2016-12-12 The method for manufacturing the ketone of 6,10,14 trimethylpentadecane 2 Pending CN106946673A (en)

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CN113891870A (en) * 2019-05-27 2022-01-04 帝斯曼知识产权资产管理有限公司 Selective hydrogenation of alkynols to enols in the presence of phosphorus compounds

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