CN105330515B - A kind of preparation method of optical voidness citronellol - Google Patents
A kind of preparation method of optical voidness citronellol Download PDFInfo
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- 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
- C07C29/175—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 with simultaneous reduction of an oxo group
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Abstract
The invention discloses a kind of method that optical voidness citronellol is prepared by neral or geranial.The present invention uses optically pure transition-metal catalyst, so that neral or geranial obtain optically pure citronellol by selective asymmetric hydrogenation, chemo-selective reaches 98% 99.9%, stereoselectivity reaches 96% 99%, solves and prepares the defects such as optical voidness lemongrass raw polyol limited, synthetic route length, cost height in the prior art.
Description
Technical field
The present invention relates to a kind of preparation method of optical voidness citronellol, and in particular to neral or geranial are with optics
By the asymmetric hydrogenation of selectivity in the presence of pure transition-metal catalyst, optical voidness citronellol is prepared, is belonged to not
Asymmetric catalytic field.
Background technology
Citronellol has fresh rose fragrant, is a kind of very important perfume base, is deployed into usually as spices
Various bouquet type compositions, tool has been widely used.Citronellol has left-handed and two kinds of optical isomers of dextrorotation, and rhodinol leads to
In frequently referred to rhodinol, the essential oil for being primarily present in attar of rose and storksbill, with rose like special aroma, left-handed perfume (or spice)
The fragrance of thatch alcohol is more quiet and tastefully laid out than dextrorotation citronellol, is the type-odor of rose scent essence, it can also be used in flavoring essence.Optical voidness
Left-handed citronellol has higher economic value compared to racemization citronellol.
Natural rhodinol is primarily present in the essential oil of plant, and because separation is difficult, left-handed citronellal is mainly by changing
The approach for learning synthesis is obtained.
CN03817019.1 discloses a kind of by method of the citronellal continuous hydrogenation for citronellol；CN201110261275.7
Disclose a kind of method that utilization interval hydrogenization method direct-reduction citral obtains citronellol；CN200710008530.0 is disclosed
A kind of method for using dihydromyrcene to prepare citronellol for raw material, the method described by three patents of the above is by non-hand
Property catalyst choice catalytic hydrogenation obtain citronellol, have the disadvantage to can only obtain that citronellol is left-handed and two kinds of optical isomers of dextrorotation
Mixture.
The method for carrying out asymmetric reduction in US20100035315 to unsaturated olefin using enzyme, using citral as raw material
By the catalytic action of enzyme, rhodinol is prepared, the conversion ratio based on raw material is 99%, the ee values for obtaining product are
95%, but enzymatic reaction have enzyme be difficult to product separation and Extraction, the difficulty such as be difficult to recycle, it is difficult to realize big
Technical scale metaplasia is produced.
Chinese publication CN200580040615.6 discloses one kind using geraniol as raw material, is catalyzed using Ru/BINAP
System, prepares ee values for 95.2% dextrorotation citronellol, yield is 97.2% by asymmetric hydrogenation.Due to used original
Material geraniol is industrially that, by selective hydration citral, and the method purified by rectifying is obtained, and passes through two step hydrogen
Change reaction, which obtains product, has the shortcomings that flow complexity, equipment investment are high, does not have advantage in cost.
It is, thus, sought for a kind of new method for preparing citronellol, realizes that high selectivity, low cost prepare optical voidness fragrant
Thatch alcohol.
The content of the invention
It is an object of the invention to provide a kind of preparation method of citronellol, the citral that can inexpensively obtain on a large scale is used
Cis-isomer neral or transisomer geranial are raw material, the catalysis constituted in transistion metal compound and Phosphine ligands
In the presence of agent, and alkali metal salt co-catalyst, selective asymmetric hydrogenation prepares left-handed or dextrorotation citronellol.The party
Method has the advantages that simple to operate, high income, the three wastes are few.
To realize above goal of the invention, the present invention is adopted the following technical scheme that：
A kind of preparation method of optical voidness citronellol：
In the presence of transition-metal catalyst and co-catalyst, asymmetry catalysis hydrogen is carried out to neral or geranial
Change, prepare optical voidness citronellol；
In the present invention, the structural formula of the optical voidness citronellol (I) is respectively
The structural formula of the reaction substrate neral (II) and geranial (III) is respectively With
In the present invention, the catalytic asymmetric hydrogenation process is as follows：
The present invention obtains optical voidness citronellol by asymmetric hydrogenation substrate neral (II) or geranial (III)
(I), the neral and geranial E/Z double bond isomers each other.
In the present invention, described transition-metal catalyst is made up of transistion metal compound and Phosphine ligands.
In the present invention, described transition metal is the metal of the VIIIth race in the periodic table of elements, preferably Ru, Rh, Pd, Ir
Or Pt, more preferably Rh.
In the present invention, the transistion metal compound is the transistion metal compound for dissolving in reactant mixture, including but
It is not limited to transition metal halide, transition metal carbonate, transition metal and carbonyls, acetic acid acetonide, hydroxyl
Compound, cyclo-octadiene, norbornadiene, cyclo-octene, methoxy compound, acetyl compounds, aliphatic carboxylic acid or fragrance
The complex of race's carboxylic acid coordination, preferably transition metal halide, transition metal and carbonyls, cyclo-octadiene or acetylating
The complex of compound coordination.
As preferred scheme, the example of the workable transistion metal compound of the present invention is RhCl3、Rh(OAc)3、Rh
(cod)2BF4、[Rh(cod)Cl]2、Rh(CO)2acac、[Rh(cod)OH]2、[Rh(cod)OMe]2、Rh4(CO)12、Rh6
(CO)16、Ir4(CO)12Or [Ir (cod) Cl]2Deng, wherein, " acac " is acetyl acetone ligands, and " cod " is cyclo-octadiene part.
In the present invention, the Phosphine ligands of the transition-metal catalyst contain 1-2 phosphorus atoms, with below general formula：
It is preferred that Phosphine ligands beThe part has 2 phosphorus atoms and chelated with transition metal formation
Thing.
Wherein, R1、R2、R3And R4It is identical or different, separately represent C1-C3Alkyl, C4-C5It is branched, unbranched
Alkyl or cyclic alkyl and optionally identical or different be selected from C containing 1-2 olefinic double bond and/or 1-41-C4Alcoxyl
Base, halogen, C5-C10Heteroaryl substituent, or C6-C20Branched, nonbranched alkyl or cyclic alkyl and can optionally contain 1-4
Individual olefinic double bond and/or 1-4 it is identical or different be selected from C1-C4Alkoxy, halogen, C5-C10Heteroaryl substituent.
As preferred scheme, the part that the following compound listed by way of example uses for the present invention：
As further preferred scheme, the Phosphine ligands that the present invention is used are
(1,1 '-Bis [dimethylphospholane-1-yl]-ferrocene) or(1,1’-Bis[diphenylphospholane-1-yl]-ferrocene)。
In the present invention, the Phosphine ligands can each be used in the form of its two kinds of enantiomers (R, R) or (S, S).
In principle, in the present invention, the enantiomter type of raw material E/Z double bond isomers ratio and Phosphine ligands used is equal
The optical purity of obtained product citronellol can be influenceed.
In the present invention, in the transition-metal catalyst, the chiral mol ratio containing Phosphine ligands and transition metal atoms is
(0.5-10)：1, be preferably (1-4)：1.
In the present invention, the reaction substrate neral or geranial rub with transition metal atoms in transition-metal catalyst
You are than being 5000:1~100:1；Preferably 1000:1~500:1.
In the present invention, catalytic asymmetric hydrogenation is carried out under conditions of co-catalyst is added.The co-catalyst is
Alkali/alkaline earth metal salt, preferably anion are the alkali/alkaline earth metal salt of halogen, including but not limited to sodium chloride, sodium iodide, fluorine
Change sodium, sodium bromide, potassium chloride, KI, potassium fluoride, KBr, potassium chloride, calcium iodide, calcium bromide, calcirm-fluoride, calcium chloride, iodine
Change one or both of magnesium, magnesium fluoride, magnesium bromide and magnesium chloride or a variety of, more preferably KI.
In the present invention, the mol ratio of the co-catalyst and metallic atom in transition-metal catalyst is 1:10~50:1；
It is preferred that 1:1~10:1.
In the present invention, the asymmetric catalytic hydrogenation can be carried out in the case where there is solvent condition, can also be in condition of no solvent
It is lower to carry out.The solvent is that can dissolve transition-metal catalyst and reaction substrate neral or geranial of the present invention, and with
Solvent of the reactor product without reactivity；The solvent is preferably C5-C20Aliphatic hydrocarbon, C6-C20Aromatic hydrocarbon, C1-C10's
Alcohol, C3-C10Ketone and C2-C10One or both of ether or a variety of, more preferably methanol.
In the present invention, the initial concentration of the reaction substrate is 5~100wt%, preferably 10~50wt%, based on solvent and
The gross mass of reaction substrate.
In the present invention, the reaction temperature of the asymmetric catalytic hydrogenation is 0~120 DEG C, preferably 20~80 DEG C；Reaction time
For 1~48 hour, preferably 10~20 hours.
In the present invention, the reaction pressure (absolute pressure) of the asymmetric catalytic hydrogenation is 1~100 bar, preferably 10~50 bars.
In the present invention, the bulk purity for the hydrogen that the asymmetric catalytic hydrogenation is used is 99-100%.
In the present invention, the reaction vessel of the asymmetric hydrogenation allows in reaction condition of the present invention to be all in principle
Under, reaction pressure especially of the present invention carries out the container of hydrogenation, including but not limited to autoclave, tubular type with a temperature of
Reactor and bubble column etc..
The inventive method is applicable to laboratory lab scale and commercial scale.
The inventive method is successfully excessive with high antimer, i.e., provide optical purity more than 90ee% enantiomeric excesses
Nerol.Typically, obtainable maximum enantiomeric excess depends on the purity of substrate used, raw material especially to be hydrogenated
The purity of reaction substrate is in middle E/Z double bond isomers ratio, the purity of the invention depending on neral or geranial, the present invention
50-100mol%, preferably 90-100mol%.
In the present invention, the chemo-selective that neral or the selective asymmetric hydrogenation of geranial obtain optical voidness citronellol reaches
To 98%-99.9%, stereoselectivity reaches 96%-99%, and product yield can reach 88%-99%, and feed stock conversion is reachable
To 90%-99.9%, optical purity of products is up to 89-99ee%.
In the inventive method, the transition metal atoms in transition-metal catalyst are lured by aldehyde radical in neral or geranial
Effect α preferentially with substrate, β-unsaturated double-bond coordination are led, and due to the space steric effect of chiral phosphine ligand so that catalysis
When agent and Binding Capacity, the chiral environment of a closely substrate is formd, the vertical of catalytic hydrogenation has been efficiently controlled
Body selectivity, so as to obtain optically pure intermediate i.e. citronellal；With the progress of reaction, α, β-unsaturated double-bond constantly subtracts
It is few, transition-metal catalyst and then continue that aldehyde radical hydrogenate to obtain optics pure products citronellol.Alkali/alkaline earth metal salt, which is helped, urges
The anionicsite of agent forms a part more stablized by the interaction with transition-metal catalyst, improves and urges
The catalytic activity and stability of agent, so that the recycling number of times increase of the conversion ratio and catalyst of reaction.
In the present invention, catalyst system can be separated with product, realize recycling for catalyst, and the separation can be with
In several ways, including but not limited to distill, extract or crystallization etc. method, the preferably way of distillation.Rhodinol passes through distillation
The pressure (absolute pressure) separated with catalyst system is 10-5000Pa, and preferably 100-1000Pa, temperature is 25-150 DEG C, preferably 50-
120℃；Catalyst system after separation is reusable.
The beneficial effects of the present invention are：
1st, in asymmetric catalytic hydrogenation system, while using transition-metal catalyst and co-catalyst, significantly improving
The chemo-selective and stereoselectivity of reaction, and the presence of co-catalyst improves the stability of major catalyst；Realize
Selective asymmetric hydrogenation obtains optically pure citronellol using neral or geranial as the step of raw material one.
2nd, selected Phosphine ligands obtain suitable dihedral angle in the coordination with rhodium salt, should have suitable dihedral angle
Catalyst, when with substrate reactions, its chiral atmosphere is more nearly substrate, so as to more effectively control the hand of product
Property；The Phosphine ligands are coordinated the catalyst to be formed with rhodium salt also has catalytic hydrogenation activity to aldehyde radical, it is achieved thereby that with neral
Or geranial is that the step of raw material one obtains optically pure citronellol.
3rd, the chemo-selective of product reaches that 99.9%, optical purity reaches 99ee%.
4th, raw material of the present invention is easy to get, and technique is simple, reaction condition is gently easily controlled, product is easily isolated purifying, has
Industrial production value.
Accompanying drawing
Fig. 1 is the gas chromatogram of dextrorotation citronellol product；
Fig. 2 is the gas chromatogram of rhodinol product；
Embodiment
The inventive method is described further below by way of specific embodiment, but the invention is not restricted to listed implementation
Example, should also be included in other any known changes in scope of the presently claimed invention.
Gas chromatograph：Agilent7890, chromatographic column Supelco β-DEXTM225, injector temperature：220℃；Shunting
Than 50:1；Heating schedule：100 DEG C of initial temperature；120 DEG C are risen to 5 DEG C/min speed, 0min is kept；With 20 DEG C/min's
Speed rises to 200 DEG C, keeps 7min, detector temperature：300℃；
As shown in Figures 1 and 2, wherein, retention time 8.7min chromatographic peak is dextrorotation citronellol；Retention time
8.2min chromatographic peak is rhodinol.
Neral, 99wt%, Aldrich；
Citral, 96wt%, Aldrich；
Rh(cod)2BF4, 98wt%, Aldrich；
1,1 '-Bis [(2S, 5S)-dimethylphospholane-1-yl]-ferrocene, 97wt%, Aldrich；
1,1 '-Bis [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 97wt%, Aldrich；
1,1 '-Bis [(2S, 5S)-diphenylphospholane-1-yl]-ferrocene, 97wt%, Aldrich；
KI, 99wt%, lark prestige Science and Technology Ltd.；
Embodiment 1
By 41.4mg1,1 '-Bis [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 40.6mg
Rh(cod)2BF4, 16.58mg KIs are dissolved in 40mL methanol, and are transferred in 100mL autoclaves, by 15.22g nerals
(neral/geranial=99.1:0.9 (mol), substrate/catalyst=1000 (mol)) injection autoclave, it is passed through hydrogen displacement
Regulation pressure is to 50 bars after gas reactor three times.Stirring is opened, in being reacted at 40 DEG C after 10h, conversion is measured using gas-chromatography
Rate is 99.9%, and product is rhodinol, and yield 99.8%, optical purity is 99ee%.
Embodiment 2
By-the Bis of 41.4mg 1,1 ' [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 40.6mg
Rh(cod)2BF4, KI 16.58mg is dissolved in 130mL methanol, and is transferred in 200mL autoclaves, by 15.22g nerals
(neral/geranial isomer proportion is 95:5 (mol), substrate catalyst ratio=1000 (mol)) injection autoclave, leads to
Enter after hydrogen displacement gas reactor three times regulation pressure to 50 bars.Stirring is opened, in being reacted at 40 DEG C after 10h, gas phase color is used
It is 99.9% that spectrometry, which measures conversion ratio, and product is rhodinol, and yield 99.8%, optical purity is 89ee%.
Embodiment 3
By-the Bis of 41.4mg 1,1 ' [(2S, 5S)-dimethylphospholane-1-yl]-ferrocene, 40.6mg
Rh(cod)2BF4, KI 82.9mg is dissolved in 9.7mL methanol, and is transferred in 50mL autoclaves, by 7.61g nerals (orange
The ratio of flower aldehyde/geranial double bond isomer is 99.1:0.9 (mol), substrate catalyst ratio=500 (mol)) injection high pressure
Kettle, is passed through after hydrogen displacement gas reactor three times regulation pressure to 60 bars.Stirring is opened, in being reacted at 40 DEG C after 12h, gas is used
It is 99.8% that phase chromatography, which measures conversion ratio, and product is dextrorotation citronellol, and yield 99.7%, optical purity is 90ee%.
Embodiment 4
By-the Bis of 41.4mg 1,1 ' [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 40.6mg
Rh(cod)2BF4, KI 16.58mg is dissolved in 40mL methanol, and is transferred in 100mL autoclaves, by 11.41g geranials
(ratio of neral/geranial double bond isomer is 1:99, substrate catalyst ratio=750 (mol)) injection autoclave, leads to
Enter after hydrogen displacement gas reactor three times regulation pressure to 25 bars.Stirring is opened, in being reacted at 80 DEG C after 10h, gas phase color is used
It is 96.8% that spectrometry, which measures conversion ratio, and product is dextrorotation citronellol, and yield 96.7%, optical purity is 90ee%.
Embodiment 5
By-the Bis of 66.2mg 1,1 ' [(2S, 5S)-diphenylphospholane-1-yl]-ferrocene, 40.6mg
Rh(cod)2BF4, KI 165.8mg is dissolved in 40mL methanol, and is transferred in 100mL autoclaves, by 15.22g nerals
(ratio of neral/geranial double bond isomer is 99.1:0.9, substrate catalyst ratio=1000) inject autoclave is led to
Enter after hydrogen displacement gas reactor three times regulation pressure to 15 bars.Stirring is opened, in being reacted at 20 DEG C after 20h, gas phase color is used
It is 91.5% that spectrometry, which measures conversion ratio, and product is rhodinol, and yield 90.8%, optical purity is 97ee%.
Embodiment 6
By-the Bis of 103.5mg 1,1 ' [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 40.6mg
Rh(cod)2BF4, KI 165.8mg is dissolved in 40mL methanol, and is transferred in 100mL autoclaves, by 15.22g nerals
(ratio of neral/geranial double bond isomer is 99.1:0.9, substrate catalyst ratio=1000 (mol)) injection high pressure
Kettle, is passed through after hydrogen displacement gas reactor three times regulation pressure to 40 bars.Stirring is opened, in being reacted at 30 DEG C after 18h, gas is used
It is 93.7% that phase chromatography, which measures conversion ratio, and product is rhodinol, and yield 91.5%, optical purity is 96ee%.
Embodiment 7
By-the Bis of 1.65g 1,1 ' [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 406mg Rh
(cod)2BF4, KI 165.8mg is dissolved in 40mL methanol, and is transferred in 100mL autoclaves, by 15.22g nerals (orange
The ratio of flower aldehyde/geranial double bond isomer is 99.1:0.9, substrate catalyst ratio=100 (mol)) injection autoclave, leads to
Enter after hydrogen displacement gas reactor three times regulation pressure to 50 bars.Stirring is opened, in being reacted at 60 DEG C after 2h, gas-chromatography is used
It is 99.9% that method, which measures conversion ratio, and product is rhodinol, and yield 99.8%, optical purity is 99ee%.
Embodiment 8
By-the Bis of 414mg 1,1 ' [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 406mg Rh
(cod)2BF4, KI 165.8mg is dissolved in 152.2g nerals, and (ratio of neral/geranial double bond isomer is 99.1:
0.9, substrate catalyst ratio=1000 (mol)), and be transferred in 250mL autoclaves, it is passed through hydrogen displacement gas reactor three
Pressure is adjusted after secondary to 10 bars.Stirring is opened, in being reacted at 20 DEG C after 18h, measuring conversion ratio using gas chromatography is
74.6%, product is rhodinol, and yield 74.3%, optical purity is 99ee%.
Embodiment 9
Catalyst is applied mechanically
Reaction condition according to embodiment 1 is reacted, and reaction steams solvent at 65 DEG C of normal pressure first after terminating
Methanol, is then decompressed to 10torr, and product is steamed at 110 DEG C, then using 40mL methanol dilution bottoms, and adds
15.22g nerals (neral/geranial=99.1:0.9, substrate/catalyst=1000), it is passed through hydrogen displacement gas reactor
Pressure is adjusted after three times to 50 bars.Stirring is opened, carries out applying mechanically experiment in reacting 10h at 40 DEG C, table 1, which is shown, applies mechanically result
The catalyst system life-span of table 1 is investigated
| Apply mechanically number of times | Conversion ratio | Yield | Optical purity ee values |
| 1 | 99.9% | 99.8% | 99% |
| 5 | 98.9% | 98.7% | 99% |
| 10 | 98.0% | 97.8% | 98% |
| 20 | 97.5% | 97.3% | 96% |
| 50 | 97.0% | 96.8% | 94% |
Comparative example 1
By 41.4mg1,1 '-Bis [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 40.6mg
Rh(COD)2BF4, it is dissolved in 40mL methanol, and be transferred in 100mL autoclaves, by 15.22g nerals (neral/geranial
The ratio of double bond isomer is 99.1:0.9, substrate catalyst ratio=1000) inject autoclave is passed through in hydrogen displacement kettle
Regulation pressure is to 50 bars after gas three times.Stirring is opened, in being reacted at 60 DEG C after 20h, conversion ratio is measured using gas chromatography
For 74%, product is rhodinol, and yield 57%, optical purity is 44ee%.
Comparative example 2
Metallic cobalt, nickel, molybdenum, aluminium are subjected to high-temperature molten according to 25wt%, 30wt%, 5wt%, 40wt% ratio respectively
Close, alloy is cooled to room temperature, crush, the alloying pellet more than 400 mesh of screening below 50 mesh.Configure the hydrogen-oxygen of 20wt% concentration
Change sodium solution 500g, boil, be slowly added to alloying pellet 100g, continue to boil 4 hours, cool down.Topple over the turbid liquid in upper strata of grey,
Cyclic washing 3 times under clear water normal temperature are added, liquid layer is Clear ＆ Transparent after standing, pH value is less than 10.The catalyst prepared
It is stored under water seal liquid level, it is standby.Clear water 58g, di-n-propylamine 2.0g are successively added in 500ml hydrogenation reaction pressure kettle,
Moistening aqueous catalyst 5g, n-hexane 25g, citral 60g (content 96wt%, remaining 4wt% are impurity).Seal pressure
Kettle, is respectively replaced 3 times using nitrogen, hydrogen, is filled with hydrogen to 2.0Mpa, begun to warm up, stir, 75 DEG C of controlling reaction temperature, hydrogen
Atmospheric pressure maintains 2.0Mpa by supplementing.Reaction finishes sampling and testing, removes solvent peak, and gas-chromatography is shown：Citronellal
2.5%th, dihydro-citronellol 0.85%, citronellol 92.3%, geraniol 0.63%, citral 0.32%.
Claims (16)
1. a kind of preparation method of optical voidness citronellol, it is characterised in that：In the effect of transition-metal catalyst and co-catalyst
Under, asymmetric catalytic hydrogenation is carried out to neral or geranial, optical voidness citronellol is prepared；
The transition-metal catalyst is made up of transistion metal compound and Phosphine ligands；
The Phosphine ligands areOr, the Phosphine ligands be respectively enantiomer (R,R) or it is right
Reflect body (S,S)；
The transition metal be the periodic table of elements in the VIIIth race metal；
The transistion metal compound is transition metal halide, transition metal carbonate, transition metal and carbonyls, second
Sour acetonide, hydroxy compounds, cyclo-octadiene, norbornadiene, cyclo-octene, methoxy compound, acetyl compounds,
Aliphatic carboxylic acid or the complex of aromatic carboxylic acid coordination；
The co-catalyst is KI.
2. according to the method described in claim 1, it is characterised in that
The transition metal is Ru, Rh, Pd, Ir or Pt；
The transistion metal compound is transition metal halide, transition metal and carbonyls, cyclo-octadiene or acetyl group
The complex of compound coordination.
3. method according to claim 2, it is characterised in that the transition metal is Rh；
The transistion metal compound is RhCl3、Rh(OAc)3、Rh(cod)2BF4、[Rh(cod)Cl]2、Rh(CO)2acac、[Rh
(cod)OH]2、[Rh(cod)OMe]2、Rh4(CO)12、Rh6(CO)16、Ir4(CO)12Or [Ir (cod) Cl]2, wherein, " acac " is
Acetyl acetone ligands, " cod " is cyclo-octadiene part.
4. according to the method described in claim 1, it is characterised in that the mol ratio of the Phosphine ligands and transition metal atoms is
（0.5-10）：1.
5. method according to claim 4, it is characterised in that the mol ratio of the Phosphine ligands and transition metal atoms is
（1-4）：1.
6. the method according to any one of claim 1-5, it is characterised in that the co-catalyst with it is transition metal-catalyzed
The mol ratio of agent is 1:10~50:1.
7. method according to claim 6, it is characterised in that the mol ratio of the co-catalyst and transition-metal catalyst
For 1:1~10:1.
8. the method according to any one of claim 1-5, it is characterised in that the neral or geranial and transition gold
The mol ratio of transition metal atoms is 5000 in metal catalyst:1~100:1.
9. method according to claim 8, it is characterised in that in the neral or geranial and transition-metal catalyst
The mol ratio of transition metal atoms is 1000:1~500:1.
10. the method according to any one of claim 1-5, it is characterised in that the asymmetric catalytic hydrogenation it is absolute
Pressure is 1 ~ 100 bar；Reaction temperature is 0 ~ 120 DEG C；Reaction time is 1 ~ 48 hour.
11. method according to claim 10, it is characterised in that the absolute pressure of the asymmetric catalytic hydrogenation is 10 ~
50 bars；Reaction temperature is 20 ~ 80 DEG C；Reaction time is 10 ~ 20 hours.
12. the method according to any one of claim 1-5, it is characterised in that the asymmetric catalytic hydrogenation is without molten
Under the conditions of agent or have under solvent condition carry out, the solvent be C5-C20Aliphatic hydrocarbon, C6-C20Aromatic hydrocarbon, C1-C10Alcohol,
C3-C10Ketone and C2-C10Ether in one or more.
13. method according to claim 12, it is characterised in that the solvent is C1-C10Alcohol.
14. method according to claim 13, it is characterised in that the solvent is methanol.
15. the method according to any one of claim 1-5, it is characterised in that the starting of the neral or geranial
Concentration is 5-100wt%, the gross mass based on solvent and neral or geranial.
16. method according to claim 15, it is characterised in that the initial concentration of the neral or geranial is 10-
50wt%, the gross mass based on solvent and neral or geranial.
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| CN201510683769.2A CN105330515B (en) | 2015-10-20 | 2015-10-20 | A kind of preparation method of optical voidness citronellol |
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| CN105330515B true CN105330515B (en) | 2017-07-21 |
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| CN106905124B (en) * | 2017-02-24 | 2020-05-08 | 万华化学集团股份有限公司 | Method for preparing optically active aldehyde or ketone |
| CN108083980B (en) * | 2017-11-27 | 2021-02-02 | 万华化学集团股份有限公司 | Method for preparing optically pure L-menthol |
| CN108732289B (en) * | 2018-08-14 | 2020-10-09 | 东莞波顿香料有限公司 | Method for identifying natural citronellol and synthetic citronellol |
| CN110963888B (en) * | 2019-11-26 | 2022-09-16 | 万华化学集团股份有限公司 | Method for preparing nerol and geraniol from citral |
| CN110963902B (en) * | 2019-12-05 | 2023-01-13 | 万华化学集团股份有限公司 | Method for synthesizing R-citronellal by water-oil two-phase asymmetric hydrogenation and catalyst used in method |
| CN114149301B (en) * | 2021-11-29 | 2023-12-19 | 万华化学集团股份有限公司 | Method for preparing citronellol by hydrogenating citral |
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