CN106946672A - 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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- CN106946672A CN106946672A CN201611144924.4A CN201611144924A CN106946672A CN 106946672 A CN106946672 A CN 106946672A CN 201611144924 A CN201611144924 A CN 201611144924A CN 106946672 A CN106946672 A CN 106946672A
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- farnesyl acetone
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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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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, (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
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.
In the context of the present invention, " mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone " refers to
Be (5E, 9E)-farnesyl acetone, (5Z, 9E)-farnesyl acetone, (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl
The mixture of acetone, wherein with (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone in all isomer mixtures
Amount compare, the amount of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone is higher, wherein " all isomers mixing
Thing " is (5E, 9E)-farnesyl acetone, (5Z, 9E)-farnesyl acetone, (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl
The mixture of acetone.Therefore, the mixture of (5Z, 9E)-farnesyl acetone " (5E, 9E)-farnesyl acetone and " refer to (5E,
9E)-farnesyl acetone, (5Z, 9E)-farnesyl acetone, (5E, 9Z)-farnesyl acetone are mixed with (5Z, 9Z)-farnesyl acetone
Compound, wherein the content of the total amount based on mixture, (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone is less than
50mol-%, preferably less than 43mol-%, even more preferably less than 20mol-%, more preferably less than 10mol-%.
It is surprising that it was found by the inventors of the present invention that as use (5E, 9E)-farnesyl acetone, (5Z, 9E)-Fa Ni
The mixture of benzylacetone, (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone and the wherein total amount based on mixture
When the content of (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone prepares C18- ketone less than 50mol-%, hydrogenation is anti-
Should be than using (5E, 9E)-farnesyl acetone, (5Z, 9E)-farnesyl acetone, (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-method
The mixture of Thessaloniki acetone and total amount (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone wherein based on mixture
Content >=50mol-% situation it is faster.It would thus be advantageous to (for up to a hundred tons of commercial run of production),
Use (5E, 9E)-farnesyl acetone, (5Z, 9E)-farnesyl acetone, (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl
The mixture of acetone is used as the parent material for obtaining C18- ketone and total amount (5E, 9Z)-farnesyl acetone wherein based on mixture
The content of (5Z, 9Z)-farnesyl acetone is less than 50mol-%, because the saving time has huge shadow to total cost of production
Ring.
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.
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, wherein (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone only exist with trace, i.e. every kind ofization
Compound is less than 5mol-%, preferably every kind of compound and is less than 1mol-%, more preferably every kind of compound less than 0.5mol-%.
One example is, in the presence of a catalyst (E)-nerolidol reacted with isopropenyl methyl ether or with isopropenyl ethylether
Reaction obtains the mixture of (5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone.Acid or ammonium salt can be used as urging
Agent.
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, preferably wherein catalyst
Selected from the group being made up of ammonium bromide, ammonium chloride or Diammonium phosphate (DAP), 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.
Alternative parent material is β-farnesene, and it can carry out C3- extensions to obtain by any suitable chemical conversion
Obtain different farnesyl acetone (=(9E) -10,14- dimethyl -6- methylene pentadecane -9,13- diene -2- ketone), (5E, 9E)-method
The mixture of Thessaloniki acetone and (5Z, 9E)-farnesyl acetone (referring to Fig. 2)；Preferably, chemical conversion is in the presence of a catalyst
Using Acetacetic acid alkyl ester, such as such as WO 2015/165959, CN-A 105 859 534, CN-A 104 478 679, EP
1 008 582, disclosed in WO 2000/014046, EP 983 988, EP 909 750 and EP 842 917；More preferably
Ground, chemical conversion uses methyl acetoacetate in the presence of transition metal catalysts.
Under the reaction condition of the inventive method, different farnesyl acetone, (5E, 9E)-farnesyl acetone and (5Z, 9E)-method
The mixture of Thessaloniki acetone also can be hydrogenated successfully.
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.
* herein, step a) and b) can also be carried out as follows：
A1) by any suitable chemical conversion make farnesene carry out C3- extension with obtain different farnesyl acetone, (5E,
The mixture of 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone；Preferably, chemical conversion makes in the presence of a catalyst
Use Acetacetic acid alkyl ester；It is highly preferred that chemical conversion uses methyl acetoacetate in the presence of transition metal catalysts；
B1) in the presence of a catalyst, using hydrogen hydrogenate different farnesyl acetone, (5E, 9E)-farnesyl acetone and (5Z,
The mixture of 9E)-farnesyl acetone, to obtain 6,10,14- trimethylpentadecane -2- ketone, wherein relative to carbon-oxygen double bond, institute
Carbon-carbon double bond can preferentially be hydrogenated by stating catalyst.
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 catalyst is palladium on alumina.
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：(5E, 9E)-farnesyl acetone, (5Z, 9E)-farnesyl acetone, (5E, 9Z)-farnesyl acetone
The weight of the mixture of (5Z, 9Z)-farnesyl acetone, the active component of catalyst is (preferably selected from by palladium, platinum, rhodium, iridium
The metal of the group constituted with nickel and its mixture) amount preferably in the range of 0.0001-1 weight %, more preferably exist
In the range of 0.001-0.5 weight %, most preferably in the range of 0.01-0.1 weight %, wherein based on the total of mixture
Less than 50 moles % of the content of amount, (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone.
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.Preferably, the reaction is organic
Carried out in solvent.
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.Most preferably heptane.
Based on parent material：(5E, 9E)-farnesyl acetone, (5Z, 9E)-farnesyl acetone, (5E, 9Z)-farnesyl acetone
The volume of the mixture of (5Z, 9Z)-farnesyl acetone, the amount of solvent is preferably in the scope of 0-100 volumes (0=is solvent-free)
It is interior, more preferably in the range of 0.1-10 volumes, most preferably in the range of 1-5 volumes, wherein based on the total of mixture
Less than 50 moles % of the content of amount, (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone.
Now so that further explaination is of the invention in following non-limiting examples.
Embodiment
The normal process of hydrogenation
The mixture of substrate farnesyl acetone (20g) and heptane (20g) is added in 125ml steel autoclaves.Addition is urged
Agent and closed reactor.Mixture nitrogen is purified into 3 times (are pressurized to 5bar, then discharge) and with hydrogen cleaning 3 times
(being pressurized to 5bar, then discharge).Reactor is heated to desired temperature, then with hydrogen pressurization to desired pressure.With
1000rpm starts to stir and record hydrogen-sucking amount.After 18 hours total experimental periods, reactant mixture is cooled to room temperature, then
Release pressure is simultaneously sampled for qualitative GC-analysis.
Hydrogenate result
" all isomers " represents (5E, 9E)-farnesyl acetone, (5Z, 9E)-farnesyl acetone, (5E, 9Z)-farnesyl
The mixture of acetone and (5Z, 9Z)-farnesyl acetone, wherein the ratio determined by chromatography of gases with area % is as follows：31 faces
(5E, the 9Z) of product % (5E, 9E)-farnesyl acetone, 12 area % (5Z, 9E)-farnesyl acetone and 55 area %-
Farnesyl acetone and (5Z, 9Z)-farnesyl acetone
" (5E, 9E) -/(5Z, 9E)-farnesyl acetone " expression mol ratio is 65%-57% to 35%-43%, preferably
(5E, 9E)-farnesyl acetone and (5Z, 9E)-farnesyl acetone mixture that mol ratio is 65%-35%.
Use following catalyst：
- 5%Pd/Al2O3Eggshell catalyst, its BET surface area is 93m2/ g and pore volume are 0.3ml/g, for example can be from
Evonik is with trade name " 5%Pd/Al2O3The R/D of E 213 " are commercially available；
- 5%Pd/CaCO3 eggshell catalysts, its BET surface area is 8m2/ g and bulk density are 0.37kg/l, and wherein
Size≤5 μm of 50% particle, for example can be from Evonik with trade name " 5%Pd/CaCO3The R/D of E 407 " are commercially available；
- 5% carbon loaded palladium catalyst, for example from Evonik with trade name " O/D of 5%Pd/C E 101 " commercially available from；
- 5% silicon dioxide carried palladium catalyst, it is commercially available from Johnson Matthey.
Table 1：The catalyst the used=O/D of Evonik E 101 (5% carbon loaded palladium catalyst)
Table 2：The catalyst the used=R/D of Evonik E 213 (5% alumina load palladium catalyst)
Table 3：5% silicon dioxide carried palladium catalyst of the catalyst used=commercially available from Johnson Matthey
Table 4：The catalyst the used=R/D of Evonik E 407 (5% calcium carbonate loaded palladium catalyst)
In both embodiment 9 and embodiment 10, unrealized hydrogenation completely in 900 minutes is utilized.Therefore, the period it
After sample and analyzed.As a result show the mixture of desired C18- ketone and partially hydrogenated intermediate, without rise
Beginning material is remaining.
Claims (15)
1. manufacturing the method for the method (" C18- ketone ") of 6,10,14- trimethylpentadecane -2- ketone, methods described is included in catalysis
In the presence of agent with hydrogen make (5E, 9E)-farnesyl acetone, (5Z, 9E)-farnesyl acetone, (5E, 9Z)-farnesyl acetone and
The step of mixture of (5Z, 9Z)-farnesyl acetone is hydrogenated, wherein relative to carbon-oxygen double bond, the catalyst being capable of preferential hydrogen
Change carbon-to-carbon double bond, wherein the total amount based on the mixture, (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone
Content is less than 50mol-%.
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 mixture of Thessaloniki acetone, (5Z, 9E)-farnesyl acetone, (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone
Weight, (it is preferably selected from the group being made up of palladium, platinum, rhodium, iridium and nickel and its mixture for the active component of the catalyst
Metal) amount in the range of 0.0001 to 1.0 weight %, preferably in the range of 0.001 to 0.5 weight %, more preferably exist
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 to enter in organic solvent
Capable.
8. method according to claim 7, wherein the organic solvent be selected from by hydrocarbon, halogenated hydrocarbons, alcohol, ether, ester, acid amides,
The group of nitrile and ketone and its mixture composition；More preferably wherein described organic solvent is selected from by C4-C10Aliphatic hydrocarbon, C6-C10Aromatics
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 the group that its mixture is constituted.
9. method according to claim 8, wherein the organic solvent be selected from by hexane, heptane, toluene, methanol, ethanol,
Normal propyl alcohol, 2- propyl alcohol, n-butanol, tetrahydrofuran, 2- methyl-tetrahydros furans, dioxanes, ethyl acetate, isopropyl acetate, acetone
And its group of mixture composition, preferably wherein described organic solvent is heptane.
10. according to any one or more described methods in claim 7 to 9, wherein based on parent material：(5E, 9E)-method
The mixture of Thessaloniki acetone, (5Z, 9E)-farnesyl acetone, (5E, 9Z)-farnesyl acetone and (5Z, 9Z)-farnesyl acetone
Volume, the amount of solvent is in 0.01 to 100 volume range, more preferably in 0.1 to 10 volume range, most preferably 1 to 5
In volume range.
11. according to any one or more described methods in foregoing Claims, wherein parent material is (5E, 9E)-Fa Ni
The mixture of benzylacetone and (5Z, 9E)-farnesyl acetone, and wherein described mixture is by making in the presence of a catalyst
(E)-nerolidol reacts what is obtained with isopropenyl methyl ether or with isopropenyl ethylether.
12. method according to claim 11, wherein the catalyst is acid, preferably wherein described catalyst be selected from by
The group that phosphoric acid, sulfuric acid, p-methyl benzenesulfonic acid, methanesulfonic acid, trichloroacetic acid, oxalic acid and its mixture are constituted.
13. method according to claim 11, 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).
14. manufacturing the method for isophytol, methods described is included according to any one or more described sides in foregoing Claims
Method.
15. 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.
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| CN201611144924.4A Pending CN106946672A (en) | 2015-12-11 | 2016-12-12 | The method for manufacturing the ketone of 6,10,14 trimethylpentadecane 2 |
| CN201611144925.9A Pending CN106946673A (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 |
| DE19840746A1 (en) | 1998-09-07 | 2000-03-09 | Basf Ag | Process for the production of gamma, delta-unsaturated ketones by Carroll reaction |
| DE19840747A1 (en) | 1998-09-07 | 2000-03-09 | Basf Ag | Continuous process for the production of unsaturated ketones |
| 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 |
| EP2346805B1 (en) | 2008-10-21 | 2014-12-10 | DSM IP Assets B.V. | Manufacture of gamma-delta-unsaturated ketones |
| CN102115437B (en) | 2010-04-12 | 2014-05-07 | 上海海嘉诺医药发展股份有限公司 | Method for preparing gamma and delta unsaturated ketone |
| ES2764153T3 (en) | 2014-04-30 | 2020-06-02 | Basf Se | Procedure for the preparation of farnesilacetone |
| CN104478679B (en) | 2014-11-21 | 2016-08-24 | 山东新和成药业有限公司 | The preparation technology of γ, δ-higher unsaturated ketone and method of purification |
| CN105859534A (en) | 2016-04-07 | 2016-08-17 | 能特科技有限公司 | Method for synthesizing ketone compounds by continuous cyclic catalytic reaction |
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