CN106928039A - 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 PDFInfo
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- CN106928039A CN106928039A CN201611144054.0A CN201611144054A CN106928039A CN 106928039 A CN106928039 A CN 106928039A CN 201611144054 A CN201611144054 A CN 201611144054A CN 106928039 A CN106928039 A CN 106928039A
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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
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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
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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
- C07C29/36—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
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- 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
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- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to manufacture 6,10, the method of the ketone of 14 trimethylpentadecane 2, it includes making (5E with hydrogen in the presence of a catalyst, 9E) farnesyl acetone, (5Z, 9E) farnesyl acetone, (5E, 9Z) farnesyl acetone and (5Z, the step of 9Z) mixture of farnesyl acetone is hydrogenated, wherein the total amount based on mixture, (5E, 9Z) farnesyl acetone and (5Z, 9Z) content of farnesyl acetone is less than 50mol %, 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
Method the present invention relates to manufacture 6,10,14- trimethylpentadecane -2- ketone (" C18- ketone "), methods described includes
Make the step of the mixture hydrogenation of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone with hydrogen in the presence of a catalyst
Suddenly, wherein relative to carbon-oxygen double bond, catalyst can preferentially hydrogenate carbon-to-carbon double bond.Preferably, catalyst comprising be selected from by palladium,
The metal of the group of platinum, rhodium, iridium and nickel and its mixture composition.It is highly preferred that catalyst is comprising selected from by palladium, platinum and its mixture
The metal of the group of composition.Even further preferably, catalyst is the metal selected from the group being made up of palladium, platinum and its mixture.It is optimal
Selection of land, 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)-
The mixture of farnesyl acetone is prepared during C18- ketone, and hydrogenation reaction ratio uses (5E, 9E)-farnesyl acetone, (5Z, 9E)-method
The situation of the mixture of Thessaloniki acetone, (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone is faster.Therefore, favorably
Be (for particularly with up to a hundred tons of commercial run of production) to use (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl
The mixture of acetone as obtain C18- ketone parent material because time-consuming have tremendous influence to total cost of production.
Brief description of the drawings
Fig. 1 schematically shows farnesyl acetone/different farnesyl acetone to the conversion of C18- ketone.
Fig. 2 schematically shows β-farnesene to the conversion of farnesyl acetone/different farnesyl acetone.
The mixture of manufacture (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone
Can extend to obtain this (5E, 9E)-farnesyl acetone and (5Z, 9E)-method by the C3 of (E)-nerolidol
The mixture of Thessaloniki acetone.One example is, in the presence of a catalyst (E)-nerolidol reacted with isopropenyl methyl ether or
Person obtains the mixture of (E, E)-farnesyl acetone and (E, Z)-farnesyl acetone with the reaction of isopropenyl ethylether.Can use
Acid or ammonium salt are used as catalyst.
The method that wherein catalyst is acid is further described in WO 2009/019132, preferably wherein catalyst choosing
The group of free phosphoric acid, sulfuric acid, p-methyl benzenesulfonic acid, methanesulfonic acid, trichloroacetic acid, oxalic acid and its mixture composition, 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 the content of WO 2010/046199 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 (E)-orange is carried out using the one kind in following reagent with method known to those skilled in the art
The C3 of the flower tertiary alcohol extends.
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.
Alternative parent material is β-farnesene, can carry out β-farnesene by any suitable chemical conversion
C3- extends, to obtain different farnesyl acetone (carbon -9 of=(9E) -10,14- dimethyl -6- methylene 15,13- diene -2-
Ketone), the mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone (referring to Fig. 2), preferably chemical conversion exists
Acetacetic acid alkyl ester, such as WO 2015/165959, CN-A 105 859 534, CN-A 104 are used in the presence of catalyst
478 679, institute is public in EP 1 008 582, WO 2000/014046, EP 983 988, EP 909 750 and EP 842 917
Open;More preferably chemical conversion uses methyl acetoacetate in the presence of a transition metal catalyst.
Different farnesyl acetone, (5E, 9E)-farnesyl third can also successfully be made under the reaction condition of the method for the present invention
The mixture of ketone and (5Z, 9E)-farnesyl acetone is hydrogenated.
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 be separated with (Z)-nerolidol.
The method that another kind obtains (E)-nerolidol is that since (E)-geranyl acetone, (E)-geranyl acetone is in itself
Can be extracted from natural origin or any other source and obtained, or obtained by fermenting, or can synthesized with synthetic method
Arrive, and if desired, come to be separated 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)-spiceleaf can be made according to method known to those skilled in the art
Benzylacetone 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 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, by this area skill
Any method known to art personnel to be separated 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
Separate.
The method of manufacture 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 alpha-tocopherol and its acetic acid esters a kind of important parent material, therefore the present invention also relates to respectively
And the method for the method and manufacture alpha-tocopherol and its acetic acid esters of manufacture isophytol, it includes the method according to the invention.
Therefore, another target of the invention is the method for manufacturing isophytol, and it comprises the following steps:
A) making (E)-nerolidol in the presence of a catalyst carries out C3 extensions, 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 carbon -1- alkynes -3- the alcohol of 3,7,11,15- tetramethyl 16) is made to hydrogenate to obtain isophytol.
Or, isophytol can be produced according to the method for comprising the following steps, the method is also an object of the invention:
A) making (E)-nerolidol in the presence of a catalyst carries out C3 extensions, 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 invention is the method for manufacture alpha-tocopherol and its acetic acid esters respectively, and methods described includes as follows
Step:
A) making (E)-nerolidol in the presence of a catalyst carries out C3 extensions, 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, and to obtain 6,10,14- trimethylpentadecane -2- ketone, wherein relative to carbon-oxygen double bond, catalyst being capable of preferential hydrogen
Change 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 carbon -1- alkynes -3- the alcohol of 3,7,11,15- tetramethyl 16) is made to hydrogenate 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 for comprising the following steps, the method is also this hair
A bright target:
A) making (E)-nerolidol in the presence of a catalyst carries out C3 extensions, 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.
* wherein, it is also possible to carry out step a) and b) as follows.
A1) β-farnesene is carried out C3- extensions by any suitable chemical conversion, with obtain different farnesyl acetone,
The mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone, preferably chemical conversion makes in the presence of a catalyst
Use Acetacetic acid alkyl ester;More preferably chemical conversion uses methyl acetoacetate in the presence of a transition metal catalyst.
B1) different farnesyl acetone, (5E, 9E)-farnesyl acetone and (5Z, 9E)-method are made with hydrogen in the presence of a catalyst
The mixture hydrogenation of Thessaloniki acetone, to obtain 6,10,14- trimethylpentadecane -2- ketone, wherein relative to carbon-oxygen double bond, catalysis
Agent can preferentially hydrogenate carbon-to-carbon double bond.
Step c1), d1), c2) and e) can be carried out according to method known to those skilled in the art.For example, ethinylation can
Carried out with acetylene, ammonia and potassium hydroxide, or carried out with acetenyl RMgBr.Then carried out with Lindlar catalyst as
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 synthesizes.
Present invention accomplishes the needs, the present invention relates to manufacture 6,10,14- trimethylpentadecane -2- ketone (hereinafter referred to
Be " C18- ketone ") method, the described method comprises the following steps:In the presence of a catalyst, (5E, 9E)-Fa Ni is made with hydrogen
Benzylacetone is hydrogenated with the mixture of (5Z, 9E)-farnesyl acetone, wherein relative to C=O bond, the catalyst can be preferential
Hydrogenation carbon-carbon double bond.The method corresponds to the step in the method for manufacture isophytol and alpha-tocopherol or alpha-tocopherol acetate
b)。
Parent material
Preferably, the mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone is used, wherein based on institute
State the total amount of mixture, the content of (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone less than 43 moles of %, preferably
Ground is less than 20 moles of %, is more preferably less than 10 moles of %.Therefore, following mixtures can also be successfully used, 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 % of 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 less than 0.5 mole of %, preferably respective amount is less than 0.1 mole of % to be 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 does not exist.
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.Preferred support/carrier material is 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 their mixture.
If using the active component (that is, metal) on support/carrier material, then based on active component (that is, gold
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, urges
The amount of the active component (preferably selected from the metal of the group being made up of palladium, platinum, rhodium, iridium and nickel and its mixture) of agent is preferred
Ground 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 carry out at a temperature in the range of 50-90 DEG C.
Hydrogenation preferably in 1-25bar hydrogen absolute value ranges hydrogen pressure, it is absolute more preferably 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 are existed
In 2.5-4bar hydrogen absolute value ranges hydrogen pressure, most preferably about 3bar hydrogen absolute values hydrogen pressure carry out.
Solvent
Hydrogenation can be carried out in the absence of solvent or in the case of there is organic solvent.
In the context of the present invention, " organic solvent " it will be appreciated that to process conditions of the invention be inertia and
Chemically keep constant organic solvent.
Organic solvent is preferably chosen from the group being made up of 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 halogen
The C of element 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 mixture.
Especially preferred organic solvent is selected from by hexane, heptane, toluene, methyl alcohol, ethanol, normal propyl alcohol, 2- propyl alcohol, positive fourth
Alcohol, tetrahydrofuran, 2- methyl-tetrahydros furans, dioxanes, ethyl acetate, isopropyl acetate, acetone and its mixture composition
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 in the case of no organic solvent.
Further explaination is of the invention in following non-limiting examples now.
Embodiment
The normal process of Solvent-free hydrogenation reaction
By in farnesyl acetone (4g) addition 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 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 for the using=O/D of Evonik E 101 (5% carbon loaded palladium catalyst)
For embodiment 1 and 3, reaction was not yet completed after 1300 minutes, is now stopped and is analyzed.Initial material
Material is converted completely, but is found that the mixture of desired C18- ketone and intermediate product.
Table 2:The catalyst for the using=R/D of Evonik E 213 (5% alumina load palladium catalyst)
For embodiment 8, after filtering catalyst, 4.0g (5E, 9E)/(90% is pure for (5Z, 9E) farnesyl acetone
Degree) provide the C18- ketone of 86% yield.
Claims (12)
1. the method for manufacturing the method (" C18- ketone ") of 6,10,14- trimethylpentadecane -2- ketone, methods described is included in catalysis
The step of mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone being hydrogenated in the presence of agent with hydrogen, wherein
Relative to carbon-oxygen double bond, the catalyst can preferentially hydrogenate carbon-to-carbon double bond.
2. method according to claim 1, wherein the catalyst preferably comprising being selected from by palladium, platinum, rhodium, iridium and nickel and
The metal of the group of its mixture composition, more preferably wherein described catalyst is included and 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. the method according to one or more in claims 1 to 3, wherein hydrogenation is in the range of 10 to 150 DEG C
At a temperature of, carry out 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.
5., according to any one or more described methods in Claims 1-4, wherein hydrogenation is absolute in 1 to 25bar hydrogen
Hydrogen in the range of value is depressed, the hydrogen preferably in 2 to 10bar hydrogen absolute value ranges is depressed, exhausted more preferably in 2 to 6bar hydrogen
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 the range of 0.01 to 0.1 weight %.
7., according to any one or more described methods in claim 1 to 6, wherein hydrogenation is in no organic solvent
In the case of carry out.
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 of acid, sulfuric acid, p-methyl benzenesulfonic acid, methanesulfonic acid, trichloroacetic acid, oxalic acid and its mixture composition.
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).
The method of 11. manufacture isophytols, methods described is included according to any one or more described sides in foregoing Claims
Method.
12. manufacture alpha-tocopherols or its acetic acid esters method, methods described include according in foregoing Claims any one or
Method described in multiple.
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EP15199574 | 2015-12-11 |
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CN201611144052.1A Pending CN106946671A (en) | 2015-12-11 | 2016-12-12 | The method for manufacturing the ketone of 6,10,14 trimethylpentadecane 2 |
CN201611144054.0A Pending CN106928039A (en) | 2015-12-11 | 2016-12-12 | The method for manufacturing the ketone of 6,10,14 trimethylpentadecane 2 |
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US2411969A (en) * | 1938-03-31 | 1946-12-03 | Hoffmann La Roche | Process for the preparation of synthetic dl-tocopherols |
GB788301A (en) | 1954-02-26 | 1957-12-23 | Hoffmann La Roche | A process for the manufacture of 6, 10-dimethyl-undecanone-(2) |
DE19647117A1 (en) | 1996-11-14 | 1998-05-28 | Basf Ag | Process for the production of gamma, delta-unsaturated ketones by Caroll reaction in cyclic carbonates or gamma-lactones as solvents |
US6051741A (en) | 1997-10-17 | 2000-04-18 | Basf Aktiengesellschaft | Preparation of γ,δ-unsaturated ketones by the Carroll reaction, novel catalysts therefor and the preparation thereof |
DE19840747A1 (en) | 1998-09-07 | 2000-03-09 | Basf Ag | Continuous process for the production of unsaturated ketones |
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DE19853908A1 (en) | 1998-12-07 | 2000-06-08 | Basf Ag | Process for the production of unsaturated ketones |
JP2002121165A (en) | 2000-10-16 | 2002-04-23 | Kuraray Co Ltd | Method for producing unsaturated ketone |
EP2188240B1 (en) | 2007-08-08 | 2016-04-13 | DSM IP Assets B.V. | Process for the preparation of (e, e)-farnesyl acetone |
JP5481712B2 (en) | 2008-10-21 | 2014-04-23 | ディーエスエム アイピー アセッツ ビー.ブイ. | Production of γ, δ-unsaturated ketones |
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CN106946673A (en) | 2017-07-14 |
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