CN105330515A - Preparation method for optically-pure citronellol - Google Patents
Preparation method for optically-pure citronellol Download PDFInfo
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- 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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Abstract
The invention discloses a method for preparing optically-pure citronellol from neral or geranial. According to the method, an optically-pure transition metal catalyst is used, and neral or geranial is subjected to selective asymmetric hydrogenation for obtaining the optically-pure citronellol, the chemical selectivity reaches 98%-99.9%, and the stereoselectivity reaches 96%-99%, and the defects that raw materials are limited, the synthesis route is long, cost is high and the like in the process for synthesizing optically-pure citronellol in the prior art are solved.
Description
Technical field
The present invention relates to a kind of preparation method of optical purity geraniol, be specifically related to neral or geranic acid under the effect with optically pure transition-metal catalyst by optionally asymmetric hydrogenation, prepare optical purity geraniol, belong to asymmetric catalysis field.
Background technology
Geraniol has fresh Muscat Hamburg, and be a kind of very important perfume base, be deployed into various bouquet type composition usually used as spices, tool has been widely used.Geraniol has left-handed and dextrorotation two kinds of optical isomers, rhodinol is commonly referred to rhodinol, mainly be present in the essential oil of rose oil and storksbill, there is rose like special aroma, quiet and tastefully laid out than dextrorotation geraniol of the fragrance of rhodinol, be the type-odor of rose scent essence, also can be used in food flavour.The left-handed geraniol of optical purity has higher economic worth compared to racemization geraniol.
Natural rhodinol mainly exists in the essential oil of plant, and due to separation difficulty, left-handed geranial obtains mainly through the approach of chemosynthesis.
It is the method for geraniol by geranial continuous hydrogenation that CN03817019.1 discloses a kind of; CN201110261275.7 discloses a kind of method utilizing interval hydride process direct-reduction citral to obtain geraniol; It is the method that geraniol prepared by raw material that CN200710008530.0 discloses a kind of dihydromyrcene that adopts, method described by above three sections of patents is and obtains geraniol by achiral catalyst selective catalytic hydrogenation, and shortcoming is the mixture that can only obtain the left-handed and dextrorotation two kinds of optical isomers of geraniol.
Enzyme is used to carry out the method for asymmetric reduction to unsaturated olefin in US20100035315, take citral as the katalysis of raw material by enzyme, prepare rhodinol, transformation efficiency based on raw material is 99%, the ee value obtaining product is 95%, but in enzymatic reaction, there is enzyme to be difficult to extract with product separation, be difficult to difficulties such as recycling, be difficult to realize large-scale industrial production.
It is raw material with Geraniol that China publication CN200580040615.6 discloses a kind of, and use Ru/BINAP catalyst system, preparing ee value by asymmetric hydrogenation is 95.2% dextrorotation geraniol, and yield is 97.2%.Because used raw material Geraniol is industrially by selective hydration citral, and obtained by the method for rectifying purifying, obtain product by two step hydrogenations and there is the shortcoming such as flow process complexity, facility investment height, cost does not have advantage.
Therefore, need to find a kind of method preparing geraniol newly, realize highly selective, low cost prepares optical purity geraniol.
Summary of the invention
The object of this invention is to provide a kind of preparation method of geraniol, use can the cis-isomeride neral of the cheap citral obtained or trans-isomer(ide) geranic acid be raw material on a large scale, at the catalyzer that transistion metal compound and Phosphine ligands form, and under the effect of an alkali metal salt promotor, selectivity asymmetric hydrogenation prepares left-handed or dextrorotation geraniol.The method has the advantages such as simple to operate, yield is high, the three wastes are few.
For realizing above goal of the invention, the present invention adopts following technical scheme:
A kind of preparation method of optical purity geraniol:
Under the effect of transition-metal catalyst and promotor, asymmetric catalytic hydrogenation is carried out to neral or geranic acid, prepares optical purity geraniol;
In the present invention, the structural formula of described optical purity geraniol (I) is respectively
the structural formula of described reaction substrate neral (II) and geranic acid (III) is respectively
with
In the present invention, described catalytic asymmetric hydrogenation process is as follows:
The present invention obtains optical purity geraniol (I) by asymmetric hydrogenation substrate neral (II) or geranic acid (III), and described neral and geranic acid be E/Z double bond isomer 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, is preferably Ru, Rh, Pd, Ir or Pt, is more preferably Rh.
In the present invention; described transistion metal compound is the transistion metal compound dissolving in reaction mixture; include but not limited to transition metal halide; transition metal carbonate; the title complex of transition metal and carbonyl compound, acetic acid acetonide, oxy-compound, cyclooctadiene, norbornadiene, cyclooctene, methoxy compound, acetyl compounds, aliphatic carboxylic acid or aromatic carboxylic acid coordination, the title complex of preferred transition metal halide, transition metal and carbonyl compound, cyclooctadiene or acetyl compounds coordination.
As preferred scheme, the example of the spendable transistion metal compound of the present invention is RhCl
3, Rh (OAc)
3, Rh (cod)
2bF
4, [Rh (cod) Cl]
2, Rh (CO)
2acac, [Rh (cod) OH]
2, [Rh (cod) OMe]
2, Rh
4(CO)
12, Rh
6(CO)
16, Ir
4(CO)
12or [Ir (cod) Cl]
2deng, wherein, " acac " is acetyl acetone ligands, and " cod " is cyclooctadiene part.
In the present invention, the Phosphine ligands of described transition-metal catalyst contains 1-2 phosphorus atom, has following general formula:
Preferred Phosphine ligands is
this part has 2 phosphorus atom and forms inner complex with transition metal.
Wherein, R
1, R
2, R
3and R
4identical or different, separately represent C
1-C
3alkyl, C
4-C
5branching, nonbranched alkyl or cyclic alkyl optionally containing 1-2 olefinic double bond and/or 1-4 is individual identical or different is selected from C
1-C
4alkoxyl group, halogen, C
5-C
10heteroaryl substituent, or C
6-C
20branching, nonbranched alkyl or cyclic alkyl can optionally containing 1-4 olefinic double bond and/or 1-4 is individual identical or different is selected from C
1-C
4alkoxyl group, halogen, C
5-C
10heteroaryl substituent.
As preferred scheme, the following compound listed by way of example is the part that the present invention uses:
As further preferred scheme, the Phosphine ligands that the present invention uses is
(1,1 '-Bis [dimethylphospholane-1-yl]-ferrocene) or
(1,1 '-Bis [diphenylphospholane-1-yl]-ferrocene).
In the present invention, described Phosphine ligands can use with the form of its two kinds of enantiomorphs (R, R) or (S, S) separately.
In principle, in the present invention, the enantiomer type of raw material E/Z double bond isomer ratio and Phosphine ligands used all can affect the optical purity of obtained product geraniol.
In the present invention, in described transition-metal catalyst, chirality is (0.5-10) containing the mol ratio of Phosphine ligands and transition metal atoms: 1, is preferably (1-4): 1.
In the present invention, in described reaction substrate neral or geranic acid and transition-metal catalyst, the mol ratio of transition metal atoms is 5000:1 ~ 100:1; Be preferably 1000:1 ~ 500:1.
In the present invention, under the condition adding promotor, carry out catalytic asymmetric hydrogenation.Described promotor is alkali/alkaline earth metal salt, be preferably the alkali/alkaline earth metal salt that negatively charged ion is halogen, include but not limited to the one or two or more in sodium-chlor, sodium iodide, Sodium Fluoride, Sodium Bromide, Repone K, potassiumiodide, Potassium monofluoride, Potassium Bromide, Repone K, calcium iodide, Calcium Bromide, Calcium Fluoride (Fluorspan), calcium chloride, magnesium iodide, magnesium fluoride, magnesium bromide and magnesium chloride, more preferably potassiumiodide.
In the present invention, in described promotor and transition-metal catalyst, the mol ratio of atoms metal is 1:10 ~ 50:1; Preferred 1:1 ~ 10:1.
In the present invention, described asymmetric catalytic hydrogenation can carry out having under solvent condition, also can carry out under condition of no solvent.Described solvent is solubilized transition-metal catalyst of the present invention and reaction substrate neral or geranic acid, and does not have reactive solvent with reactor product; Described solvent is preferably C
5-C
20aliphatic hydrocarbon, C
6-C
20aromatic hydrocarbon, C
1-C
10alcohol, C
3-C
10ketone and C
2-C
10ether in one or two or more, more preferably methyl alcohol.
In the present invention, the initial concentration of described reaction substrate is 5 ~ 100wt%, preferably 10 ~ 50wt%, based on the total mass of solvent and reaction substrate.
In the present invention, the temperature of reaction of described asymmetric catalytic hydrogenation is 0 ~ 120 DEG C, preferably 20 ~ 80 DEG C; Reaction times is 1 ~ 48 hour, preferably 10 ~ 20 hours.
In the present invention, the reaction pressure (absolute pressure) of described asymmetric catalytic hydrogenation is 1 ~ 100 bar, preferably 10 ~ 50 bar.
In the present invention, the bulk purity of the hydrogen that described asymmetric catalytic hydrogenation uses is 99-100%.
In the present invention, the reaction vessel of described asymmetric hydrogenation is that all permissions are under reaction conditions of the present invention in principle, especially carry out the container of hydrogenation at reaction pressure of the present invention and temperature, include but not limited to autoclave, tubular reactor and bubble-plate column etc.
The inventive method is applicable to laboratory lab scale and industrial-scale production.
The inventive method is successfully excessive with high antimer, is namely greater than the vernol that 90ee% enantiomeric excess provides optical purity.Typically, obtainable maximum enantiomeric excess depends on the purity of substrate used, E/Z double bond isomer ratio in raw material especially to be hydrogenated, and the purity of neral or geranic acid is depended in the present invention, in the present invention, the purity of reaction substrate is 50-100mol%, preferred 90-100mol%.
In the present invention, the chemo-selective that neral or geranic acid selectivity asymmetric hydrogenation obtain optical purity geraniol reaches 98%-99.9%, stereoselectivity reaches 96%-99%, product yield can reach 88%-99%, feed stock conversion can reach 90%-99.9%, and optical purity of products can reach 89-99ee%.
In the inventive method, the α of and the substrate preferential by the inducing action of aldehyde radical in neral or geranic acid of the transition metal atoms in transition-metal catalyst, β-unsaturated double-bond coordination, and due to the space steric effect of chiral phosphine ligand, when making catalyzer and Binding Capacity, define the chiral environment of a closely substrate, effectively control the stereospecificity of catalytic hydrogenation, thus obtain optically pure intermediate and geranial; Along with the carrying out of reaction, α, β-unsaturated double-bond constantly reduces, and transition-metal catalyst and then continuation are carried out hydrogenation to aldehyde radical and obtained optical purity product geraniol.The anionicsite of alkali/alkaline earth metal salt promotor is by forming a more stable part with the interaction of transition-metal catalyst, improve catalytic activity and the stability of catalyzer, thus the number of times that recycles of the transformation efficiency of reaction and catalyzer is increased.
In the present invention, catalyst system can be separated with product, realizes the recycle of catalyzer, and described separation in several ways, can include but not limited to the methods such as distillation, extraction or crystallization, preferred distillation method.Rhodinol is 10-5000Pa by distilling the pressure (absolute pressure) be separated with catalyst system, preferred 100-1000Pa, and temperature is 25-150 DEG C, preferred 50-120 DEG C; Catalyst system after separation is reusable.
Beneficial effect of the present invention is:
1, in asymmetric catalytic hydrogenation system, use transition-metal catalyst and promotor simultaneously, significantly improve chemo-selective and the stereoselectivity of reaction, and the existence of promotor improves the stability of Primary Catalysts; Achieve selectivity asymmetric hydrogenation with neral or geranic acid for raw material one step obtains optically pure geraniol.
2, selected Phosphine ligands, with the coordination of rhodium salt, obtains suitable interfacial angle, and this has the catalyzer of suitable interfacial angle, and when with substrate reactions, its chirality atmosphere more close to substrate, thus controls the chirality of product more effectively; The catalyzer that this Phosphine ligands and the coordination of rhodium salt are formed also has catalytic hydrogenation activity to aldehyde radical, thus achieves with neral or geranic acid as raw material one step obtains optically pure geraniol.
3, the chemo-selective of product reaches 99.9%, optical purity reaches 99ee%.
4, raw material of the present invention is easy to get, and technique is simple, the gentle easy control of reaction conditions, product are easy to separation and purification, has industrial production value.
Accompanying drawing
Fig. 1 is the gas chromatogram of dextrorotation geraniol product;
Fig. 2 is the gas chromatogram of rhodinol product;
Embodiment
Below by way of specific embodiment, the inventive method is described further, but the invention is not restricted to listed embodiment, also should be included in other any known changes in right of the present invention.
Gas chromatograph: Agilent7890, chromatographic column Supelco β-DEX
tM225, injector temperature: 220 DEG C; Splitting ratio 50:1; Heating schedule: initial temperature 100 DEG C; Rise to 120 DEG C with the speed of 5 DEG C/min, keep 0min; Rise to 200 DEG C with the speed of 20 DEG C/min, keep 7min, detector temperature: 300 DEG C;
As shown in Figures 1 and 2, wherein, the chromatographic peak of retention time 8.7min is dextrorotation geraniol; The chromatographic peak of retention time 8.2min is rhodinol.
Neral, 99wt%, Aldrich;
Citral, 96wt%, Aldrich;
Rh(cod)
2BF
4，98wt％，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；
Potassiumiodide, 99wt%, lark prestige Science and Technology Ltd.;
Embodiment 1
By 41.4mg1,1 '-Bis [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 40.6mgRh (cod)
2bF
416.58mg potassiumiodide is dissolved in 40mL methyl alcohol, and be transferred in 100mL autoclave, by 15.22g neral (neral/geranic acid=99.1:0.9 (mol), substrate/catalyst=1000 (mol)) inject autoclave, pass into hydrogen exchange gas reactor and regulate for three times pressure to 50 to cling to afterwards.Open and stir, react 10h at 40 DEG C after, using gas-chromatography to record transformation efficiency is 99.9%, and product is rhodinol, productive rate 99.8%, and optical purity is 99ee%.
Embodiment 2
By 41.4mg1,1 '-Bis [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 40.6mgRh (cod)
2bF
4potassiumiodide 16.58mg is dissolved in 130mL methyl alcohol, and be transferred in 200mL autoclave, by 15.22g neral, (neral/geranic acid isomer proportion is 95:5 (mol), substrate catalyst ratio=1000 (mol)) inject autoclave, pass into hydrogen exchange gas reactor and regulate for three times pressure to 50 to cling to afterwards.Open and stir, react 10h at 40 DEG C after, using vapor-phase chromatography to record transformation efficiency is 99.9%, and product is rhodinol, productive rate 99.8%, and optical purity is 89ee%.
Embodiment 3
By 41.4mg1,1 '-Bis [(2S, 5S)-dimethylphospholane-1-yl]-ferrocene, 40.6mgRh (cod)
2bF
4potassiumiodide 82.9mg is dissolved in 9.7mL methyl alcohol, and be transferred in 50mL autoclave, by 7.61g neral, (ratio of neral/geranic acid double bond isomer is 99.1:0.9 (mol), substrate catalyst ratio=500 (mol)) inject autoclave, pass into hydrogen exchange gas reactor and regulate for three times pressure to 60 to cling to afterwards.Open and stir, react 12h at 40 DEG C after, using vapor-phase chromatography to record transformation efficiency is 99.8%, and product is dextrorotation geraniol, productive rate 99.7%, and optical purity is 90ee%.
Embodiment 4
By 41.4mg1,1 '-Bis [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 40.6mgRh (cod)
2bF
4potassiumiodide 16.58mg is dissolved in 40mL methyl alcohol, and be transferred in 100mL autoclave, by 11.41g geranic acid, (ratio of neral/geranic acid double bond isomer is 1:99, substrate catalyst ratio=750 (mol)) inject autoclave, pass into hydrogen exchange gas reactor and regulate for three times pressure to 25 to cling to afterwards.Open and stir, react 10h at 80 DEG C after, using vapor-phase chromatography to record transformation efficiency is 96.8%, and product is dextrorotation geraniol, productive rate 96.7%, and optical purity is 90ee%.
Embodiment 5
By 66.2mg1,1 '-Bis [(2S, 5S)-diphenylphospholane-1-yl]-ferrocene, 40.6mgRh (cod)
2bF
4potassiumiodide 165.8mg is dissolved in 40mL methyl alcohol, and be transferred in 100mL autoclave, by 15.22g neral, (ratio of neral/geranic acid double bond isomer is 99.1:0.9, substrate catalyst ratio=1000) inject autoclave, pass into hydrogen exchange gas reactor and regulate for three times pressure to 15 to cling to afterwards.Open and stir, react 20h at 20 DEG C after, using vapor-phase chromatography to record transformation efficiency is 91.5%, and product is rhodinol, productive rate 90.8%, and optical purity is 97ee%.
Embodiment 6
By 103.5mg1,1 '-Bis [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 40.6mgRh (cod)
2bF
4potassiumiodide 165.8mg is dissolved in 40mL methyl alcohol, and be transferred in 100mL autoclave, by 15.22g neral, (ratio of neral/geranic acid double bond isomer is 99.1:0.9, substrate catalyst ratio=1000 (mol)) inject autoclave, pass into hydrogen exchange gas reactor and regulate for three times pressure to 40 to cling to afterwards.Open and stir, react 18h at 30 DEG C after, using vapor-phase chromatography to record transformation efficiency is 93.7%, and product is rhodinol, productive rate 91.5%, and optical purity is 96ee%.
Embodiment 7
By 1.65g1,1 '-Bis [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 406mgRh (cod)
2bF
4potassiumiodide 165.8mg is dissolved in 40mL methyl alcohol, and be transferred in 100mL autoclave, by 15.22g neral, (ratio of neral/geranic acid double bond isomer is 99.1:0.9, substrate catalyst ratio=100 (mol)) inject autoclave, pass into hydrogen exchange gas reactor and regulate for three times pressure to 50 to cling to afterwards.Open and stir, react 2h at 60 DEG C after, using vapor-phase chromatography to record transformation efficiency is 99.9%, and product is rhodinol, productive rate 99.8%, and optical purity is 99ee%.
Embodiment 8
By 414mg1,1 '-Bis [(2R, 5R)-dimethylphospholane-1-yl]-ferrocene, 406mgRh (cod)
2bF
4potassiumiodide 165.8mg is dissolved in 152.2g neral, and (ratio of neral/geranic acid double bond isomer is 99.1:0.9, substrate catalyst ratio=1000 (mol)), and be transferred in 250mL autoclave, pass into hydrogen exchange gas reactor and regulate for three times pressure to 10 to cling to afterwards.Open and stir, react 18h at 20 DEG C after, using vapor-phase chromatography to record transformation efficiency is 74.6%, and product is rhodinol, productive rate 74.3%, and optical purity is 99ee%.
Embodiment 9
Catalyzer is applied mechanically
React according to the reaction conditions of embodiment 1, first at normal pressure 65 DEG C, solvent methanol is steamed after reaction terminates, then 10torr is decompressed to, product is steamed at 110 DEG C, then 40mL methanol dilution distillation residue are used, and add 15.22g neral (neral/geranic acid=99.1:0.9, substrate/catalyst=1000), pass into hydrogen exchange gas reactor and regulate for three times pressure to 50 to cling to afterwards.Open and stir, at 40 DEG C, react 10h carry out applying mechanically experiment, table 1 shows applies mechanically result
The table 1 catalyst system life-span is investigated
| Apply mechanically number of times | Transformation efficiency | Productive rate | Optical purity ee value |
| 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, 40.6mgRh (COD)
2bF
4be dissolved in 40mL methyl alcohol, and be transferred in 100mL autoclave, by 15.22g neral, (ratio of neral/geranic acid double bond isomer is 99.1:0.9, substrate catalyst ratio=1000) inject autoclave, pass into hydrogen exchange gas reactor and regulate for three times pressure to 50 to cling to afterwards.Open and stir, react 20h at 60 DEG C after, using vapor-phase chromatography to record transformation efficiency is 74%, and product is rhodinol, productive rate 57%, and optical purity is 44ee%.
Comparative example 2
Cobalt metal, nickel, molybdenum, aluminium are carried out high temperature fusion according to the ratio of 25wt%, 30wt%, 5wt%, 40wt% respectively, alloy is cooled to room temperature, pulverize, screen the alloying pellet of below more than 400 orders 50 order.The sodium hydroxide solution 500g of configuration 20wt% concentration, boils, slowly adds alloying pellet 100g, continue to boil 4 hours, cooling.Topple over the turbid liquid in upper strata of grey, to add under clear water normal temperature repetitive scrubbing 3 times, after leaving standstill, liquid layer is Clear & Transparent, and pH value is less than 10.The catalyzer prepared is kept under water seal liquid level, for subsequent use.Successively clear water 58g is added, dipropyl amine 2.0g, moistening moisture catalyzer 5g, normal hexane 25g, citral 60g (content 96wt%, all the other 4wt% are impurity) in the hydrogenation reaction pressure still of 500ml.Sealing load still, use nitrogen, hydrogen respectively replace 3 times, are filled with hydrogen to 2.0Mpa, start heating, stir, control temperature of reaction 75 DEG C, and hydrogen pressure maintains 2.0Mpa by supplementary.React complete sampling and testing, remove solvent peak, gas-chromatography shows: geranial 2.5%, dihydro-citronellol 0.85%, geraniol 92.3%, Geraniol 0.63%, citral 0.32%.
Claims (9)
1. a preparation method for optical purity geraniol, is characterized in that: under the effect of transition-metal catalyst and promotor, carry out asymmetric catalytic hydrogenation, prepare optical purity geraniol to neral or geranic acid.
2. method according to claim 1, is characterized in that, described transition-metal catalyst is made up of transistion metal compound and Phosphine ligands;
Described Phosphine ligands contains 1-2 phosphorus atom, has following general formula:
Preferably
Wherein, R
1, R
2, R
3and R
4identical or different, separately represent C
1-C
3alkyl, C
4-C
5branching, nonbranched alkyl or cyclic alkyl optionally containing 1-2 olefinic double bond and/or 1-4 is individual identical or different is selected from C
1-C
4alkoxyl group, halogen, C
5-C
10heteroaryl substituent, or C
6-C
20branching, nonbranched alkyl or cyclic alkyl can optionally containing 1-4 olefinic double bond and/or 1-4 is individual identical or different is selected from C
1-C
4alkoxyl group, halogen, C
5-C
10heteroaryl substituent;
Described transition metal is the metal of the VIIIth race in the periodic table of elements, is preferably Ru, Rh, Pd, Ir or Pt, is more preferably Rh.
Described transistion metal compound is transition metal halide; transition metal carbonate; the title complex of transition metal and carbonyl compound, acetic acid acetonide, oxy-compound, cyclooctadiene, norbornadiene, cyclooctene, methoxy compound, acetyl compounds, aliphatic carboxylic acid or aromatic carboxylic acid coordination; the title complex of preferred transition metal halide, transition metal and carbonyl compound, cyclooctadiene or acetyl compounds coordination, is more preferably RhCl
3, Rh (OAc)
3, Rh (cod)
2bF
4, [Rh (cod) Cl]
2, Rh (CO)
2acac, [Rh (cod) OH]
2, [Rh (cod) OMe]
2, Rh
4(CO)
12, Rh
6(CO)
16, Ir
4(CO)
12or [Ir (cod) Cl]
2, wherein, " acac " is acetyl acetone ligands, and " cod " is cyclooctadiene part.
3. method according to claim 2, is characterized in that, the described mol ratio containing Phosphine ligands and transition metal atoms is (0.5-10): 1, is preferably (1-4): 1.
4. method according to claim 1, it is characterized in that, described promotor is alkali/alkaline earth metal salt, be preferably the alkali/alkaline earth metal salt that negatively charged ion is halogen, be more preferably the one or two or more in sodium-chlor, sodium iodide, Sodium Fluoride, Sodium Bromide, Repone K, potassiumiodide, Potassium monofluoride, Potassium Bromide, Repone K, calcium iodide, Calcium Bromide, Calcium Fluoride (Fluorspan), calcium chloride, magnesium iodide, magnesium fluoride, magnesium bromide and magnesium chloride, more preferably potassiumiodide.
5. the method according to any one of claim 1-4, is characterized in that, the mol ratio of described promotor and transition-metal catalyst is 1:10 ~ 50:1; Preferred 1:1 ~ 10:1.
6. the method according to any one of claim 1-5, is characterized in that, in described neral or geranic acid and transition-metal catalyst, the mol ratio of transition metal atoms is 5000:1 ~ 100:1; Be preferably 1000:1 ~ 500:1.
7. the method according to any one of claim 1-6, is characterized in that, the absolute pressure of described asymmetric catalytic hydrogenation is 1 ~ 100 bar, preferably 10 ~ 50 bar; Temperature of reaction is 0 ~ 120 DEG C, preferably 20 ~ 80 DEG C; Reaction times is 1 ~ 48 hour, preferably 10 ~ 20 hours.
8. the method according to any one of claim 1-7, is characterized in that, described asymmetric catalytic hydrogenation carries out under condition of no solvent or under having solvent condition, and described solvent is C
5-C
20aliphatic hydrocarbon, C
6-C
20aromatic hydrocarbon, C
1-C
10alcohol, C
3-C
10ketone and C
2-C
10ether in one or two or more, be preferably C
1-C
10alcohol, more preferably methyl alcohol.
9. the method according to any one of claim 1-8, is characterized in that, the initial concentration of described neral or geranic acid is 5-100wt%, preferred 10-50wt%, based on the total mass of solvent and neral or geranic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106905124A (en) * | 2017-02-24 | 2017-06-30 | 万华化学集团股份有限公司 | A kind of method for preparing optical activity aldehydes or ketones |
| CN108083980A (en) * | 2017-11-27 | 2018-05-29 | 万华化学集团股份有限公司 | A kind of method for preparing optical voidness l-menthol |
| CN108732289A (en) * | 2018-08-14 | 2018-11-02 | 东莞波顿香料有限公司 | The method for differentiating natural citronellol and synthesizing citronellol |
| CN110963888A (en) * | 2019-11-26 | 2020-04-07 | 万华化学集团股份有限公司 | Method for preparing nerol and geraniol from citral |
| CN110963902A (en) * | 2019-12-05 | 2020-04-07 | 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 |
| CN114149301A (en) * | 2021-11-29 | 2022-03-08 | 万华化学集团股份有限公司 | Method for preparing citronellol by hydrogenating citral |
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| CN106905124A (en) * | 2017-02-24 | 2017-06-30 | 万华化学集团股份有限公司 | A kind of method for preparing optical activity aldehydes or ketones |
| 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 |
| CN108083980A (en) * | 2017-11-27 | 2018-05-29 | 万华化学集团股份有限公司 | A kind of method for preparing optical voidness l-menthol |
| 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 |
| CN108732289A (en) * | 2018-08-14 | 2018-11-02 | 东莞波顿香料有限公司 | The method for differentiating natural citronellol and synthesizing citronellol |
| 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 |
| CN110963888A (en) * | 2019-11-26 | 2020-04-07 | 万华化学集团股份有限公司 | Method for preparing nerol and geraniol from citral |
| 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 |
| CN110963902A (en) * | 2019-12-05 | 2020-04-07 | 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 |
| 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 |
| CN114149301A (en) * | 2021-11-29 | 2022-03-08 | 万华化学集团股份有限公司 | Method for preparing citronellol by hydrogenating citral |
| 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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