CN105481715A - Camphor Schiff base, and preparation method and application thereof - Google Patents
Camphor Schiff base, and preparation method and application thereof Download PDFInfo
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- CN105481715A CN105481715A CN201510988604.6A CN201510988604A CN105481715A CN 105481715 A CN105481715 A CN 105481715A CN 201510988604 A CN201510988604 A CN 201510988604A CN 105481715 A CN105481715 A CN 105481715A
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- GMOXUSLGCYTWEW-UHFFFAOYSA-N CC1(C)C23NC2CC1CC3O Chemical compound CC1(C)C23NC2CC1CC3O GMOXUSLGCYTWEW-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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Abstract
The invention discloses camphor Schiff base, and a preparation method and application of the camphor Schiff base. A structural formula of the camphor Schiff base is as shown in the description. The preparation method the camphor Schiff base comprises the steps of obtaining optically pure camphor amino alcohol through reduction and hydrolysis of 1-isocyanate-2-camphorquinone, and obtaining the camphor Schiff base by enabling the optically pure camphor amino alcohol to react with 4-hydroxyl salicylaldehyde. The camphor Schiff base disclosed by the invention can be used as a ligand so as to be used for an asymmetric Henry reaction of aromatic aldehyde and nitromethane which are catalyzed by cuprous chloride, and an obtained product, namely beta-nitroalcohol, has higher enantioselectivity and higher yield.
Description
Technical field
The invention belongs to the asymmetric synthesis technical field of β-nitroalcohol, be specifically related to a kind of camphor Schiff's base and preparation method thereof and the application in the asymmetric Henry reaction of aromatic aldehyde and Nitromethane 99Min..
Background technology
β-nitroalcohol is the very important organic synthesis intermediate of a class, has nitro and the very useful functional group of hydroxyl two kinds, can by functional group's conversion compound that synthesis is as useful in carboxylic acid, aldehyde, alpha-alcohol ketone, amino alcohol etc. further; The chiral amino alcohol obtained by reduction chiral beta-nitroalcohol can be widely used in asymmetric catalysis as part.It is prepare that chiral beta-nitroalcohol is main, the most direct method that chiral ligand and transition metal are used for asymmetric Henry reaction.The chiral ligand invented at present mainly comprises and derives the ligand classes such as bisoxazoline, amino alcohol, diamine, aminopyridine and Schiff's base by different chiral source.Camphor is a kind of natural chiral source, has low toxicity, cheap, the advantage such as be easy to get, but chiral camphor schiff base ligand is used for asymmetric Henry reaction never studies report.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of camphor Schiff's base, and provides a kind of preparation method and novelty teabag for it.
Solving technical scheme that above technical problem adopts is that the structural formula of above-mentioned camphor Schiff's base is as follows:
The preparation method of above-mentioned camphor Schiff's base is made up of following step:
1,1-isocyanic ester-2-camphorphorone is dissolved in methyl alcohol completely, at 0 ~ 10 DEG C, adds Cerous chloride heptahydrate, be cooled to-78 ~-70 DEG C, add sodium borohydride, stir 1 ~ 2 hour, be warming up to-40 ~-30 DEG C, stir 1 ~ 3 hour, rise to room temperature, steam except methyl alcohol, add the KOH aqueous solution, reflux 2 ~ 4 hours, be cooled to room temperature, separation and purification product, obtain the camphor amino alcohol that structural formula is following.
2, take dehydrated alcohol as solvent, by camphor amino alcohol and 4-hydroxyl salicylic aldehyde under anhydrous sodium sulphate effect, reflux 10 ~ 12 hours, separation and purification product, obtains camphor Schiff's base.
In above-mentioned steps 1, the mol ratio of preferred 1-isocyanic ester-2-camphorphorone and Cerous chloride heptahydrate, sodium borohydride, KOH is 1:(0.2 ~ 0.3): (5 ~ 6): (10 ~ 15).
In above-mentioned steps 2, the mol ratio of preferred camphor amino alcohol and 4-hydroxyl salicylic aldehyde, anhydrous sodium sulphate is 1:1:(2 ~ 3).
The structural formula of above-mentioned 1-isocyanic ester-2-camphorphorone (CASNO:137329-22-7) is as follows:
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis aromatic aldehyde and Nitromethane 99Min.; concrete grammar is: take the trimethyl carbinol as solvent; under protection of inert gas; be 10:(300 ~ 500 in molar ratio by aromatic aldehyde, Nitromethane 99Min., cuprous chloride, camphor Schiff's base according to claim 1): 1:1 room temperature reaction, obtains β-nitroalcohol.
Above-mentioned aromatic aldehyde is any one in phenyl aldehyde, nitro substituted benzaldehyde, halogenated benzaldehyde, trifluoromethyl substituted benzaldehyde, cyano group substituted benzaldehyde, alkoxy substituted formaldehyde, concrete as any one in phenyl aldehyde, 4-nitrobenzaldehyde, 3-nitrobenzaldehyde, 2-nitrobenzaldehyde, 4-fluorobenzaldehyde, 3-fluorobenzaldehyde, 4-bromobenzaldehyde, 3-bromobenzaldehyde, 4-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-trifluoromethylated benzaldehyde, 3-trifluoromethylated benzaldehyde, 4-cyanobenzaldehyde, 4-methoxybenzaldehyde.
Camphor Schiff's base of the present invention, as part, has high catalytic efficiency in the asymmetric Henry reaction of cuprous chloride catalysis aromatic aldehyde and Nitromethane 99Min., can high yield, obtain chiral beta-nitroalcohol high enantioselectivity.
Concrete embodiment
Below in conjunction with embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these embodiments.
Embodiment 1
1, 5.01g (28mmol) 1-isocyanic ester-2-camphorphorone is dissolved in 100mL absolute methyl alcohol, be cooled to 0 DEG C, add 2.6g (7mmol) Cerous chloride heptahydrate, after finishing, reaction solution is cooled to-78 DEG C, 5.3g (140mmol) sodium borohydride is added in batches in 1 hour, and at-78 DEG C, continue stirring 1 hour, reaction solution is warming up to-40 DEG C afterwards, and continue stirring 2 hours at such a temperature, then reacting liquid temperature slowly rises to room temperature, the KOH aqueous solution of 50mL6mol/L is added in debris, and reflux 3 hours, reaction solution is cooled to room temperature, with dichloromethane extraction (3 × 100mL), merge organic phase, anhydrous sodium sulfate drying, filter, filtrate removes methylene dichloride through Rotary Evaporators, obtain the camphor amino alcohol crude product of white, further by pillar layer separation, (silica gel is sorbent material, sherwood oil and ethyl acetate mixtures are eluent), obtain 2.83g optical purity camphor amino alcohol, its productive rate is 65%.
2,0.62g (4mmol) optical purity camphor amino alcohol and 0.554g (4mmol) 4-hydroxyl salicylic aldehyde are dissolved in 30mL absolute ethanol, add 1.14g (8mmol) anhydrous sodium sulphate, reflux 12 hours, be cooled to room temperature, filter, filtrate removes dehydrated alcohol through Rotary Evaporators, (silica gel is sorbent material to pillar layer separation, sherwood oil and ethyl acetate mixtures are eluent), obtain 0.83g camphor Schiff's base, its productive rate is 75%, fusing point 220 ~ 221.8 DEG C, [α] 2D0=-174.59 ° of (c0.95, CH
2cl
2), structural characterization data are as follows:
1HNMR(400MHz，DMSO)δ：14.63(s，1H)，9.90(d，J＝22.4Hz，1H)，8.26(d，J＝6.0Hz，1H)，7.13(d，J＝8.4Hz，1H)，6.09(dd，J＝8.8、2.0Hz，1H)，5.98(d，J＝2Hz，1H)，5.24-5.25(m，1H)，3.75-3.78(m，1H)，1.91-1.94(m，1H)，1.76-1.83(m，4H)，1.19-1.31(m，2H)，1.12(s，3H)，0.81(s，3H)。
13CNMR(101MHz，DMSO)δ：171.6，163.0，162.2，134.2，111.2，105.9，103.6，75.6，71.4，47.3，42.4，40.4，28.44，26.6，19.7，19.7。
HRMS (ESI, M+H
+) C
16h
22nO
3: theoretical value 276.1594, measured value 276.1599.
Embodiment 2
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis 4-nitrobenzaldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection; 0.014g (0.05mmol) camphor Schiff's base, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol is added in reaction flask; at room temperature stir 2 hours; then 0.54mL (20mmol) Nitromethane 99Min. is added; and stir 30 minutes; add 0.76g (0.5mmol) 4-nitrobenzaldehyde again; after TLC detection reaction is complete; low boiling component is removed with Rotary Evaporators; crude product is through pillar layer separation; obtain (R)-1-(4-nitrophenyl)-2-nitroethyl alcohol, its productive rate is 90%, ee value is 84%.
Embodiment 3
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis 3-nitrobenzaldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection; 0.014g (0.05mmol) camphor Schiff's base, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol is added in reaction flask; at room temperature stir 2 hours; then 0.54mL (20mmol) Nitromethane 99Min. is added; and stir 30 minutes; add 0.76g (0.5mmol) 3-nitrobenzaldehyde again; after TLC detection reaction is complete; low boiling component is removed with Rotary Evaporators; crude product is through pillar layer separation; obtain (R)-1-(3-nitrophenyl)-2-nitroethyl alcohol, its productive rate is 82%, ee value is 80%.
Embodiment 4
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis 2-nitrobenzaldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection; 0.014g (0.05mmol) camphor Schiff's base, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol is added in reaction flask; at room temperature stir 2 hours; then 0.54mL (20mmol) Nitromethane 99Min. is added; and stir 30 minutes; add 0.76g (0.5mmol) 2-nitrobenzaldehyde again; after TLC detection reaction is complete; low boiling component is removed with Rotary Evaporators; crude product is through pillar layer separation; obtain (R)-1-(2-nitrophenyl)-2-nitroethyl alcohol, its productive rate is 80%, ee value is 68%.
Embodiment 5
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis 4-fluorobenzaldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection; 0.014g (0.05mmol) camphor Schiff's base, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol is added in reaction flask; at room temperature stir 2 hours; then 0.54mL (20mmol) Nitromethane 99Min. is added; and stir 30 minutes; add 0.62g (0.5mmol) 4-fluorobenzaldehyde again; after TLC detection reaction is complete; low boiling component is removed with Rotary Evaporators; crude product is through pillar layer separation; obtain (R)-1-(4-fluorophenyl)-2-nitroethyl alcohol, its productive rate is 72%, ee value is 73%.
Embodiment 6
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis 3-fluorobenzaldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection; 0.014g (0.05mmol) camphor Schiff's base, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol is added in reaction flask; at room temperature stir 2 hours; then 0.54mL (20mmol) Nitromethane 99Min. is added; and stir 30 minutes; add 0.62g (0.5mmol) 3-fluorobenzaldehyde again; after TLC detection reaction is complete; low boiling component is removed with Rotary Evaporators; crude product is through pillar layer separation; obtain (R)-1-(3-fluorophenyl)-2-nitroethyl alcohol, its productive rate is 81%, ee value is 76%.
Embodiment 7
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis 4-bromobenzaldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection; 0.014g (0.05mmol) camphor Schiff's base, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol is added in reaction flask; at room temperature stir 2 hours; then 0.54mL (20mmol) Nitromethane 99Min. is added; and stir 30 minutes; add 0.92g (0.5mmol) 4-bromobenzaldehyde again; after TLC detection reaction is complete; low boiling component is removed with Rotary Evaporators; crude product is through pillar layer separation; obtain (R)-1-(4-bromophenyl)-2-nitroethyl alcohol, its productive rate is 78%, ee value is 81%.
Embodiment 8
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis 3-bromobenzaldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection; 0.014g (0.05mmol) camphor Schiff's base, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol is added in reaction flask; at room temperature stir 2 hours; then 0.54mL (20mmol) Nitromethane 99Min. is added; and stir 30 minutes; add 0.92g (0.5mmol) 3-bromobenzaldehyde again; after TLC detection reaction is complete; low boiling component is removed with Rotary Evaporators; crude product is through pillar layer separation; obtain (R)-1-(3-bromophenyl)-2-nitroethyl alcohol, its productive rate is 75%, ee value is 83%.
Embodiment 9
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis 4-chlorobenzaldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection; 0.014g (0.05mmol) camphor Schiff's base, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol is added in reaction flask; at room temperature stir 2 hours; then 0.54mL (20mmol) Nitromethane 99Min. is added; and stir 30 minutes; add 0.70g (0.5mmol) 4-chlorobenzaldehyde again; after TLC detection reaction is complete; low boiling component is removed with Rotary Evaporators; crude product is through pillar layer separation; obtain (R)-1-(4-chloro-phenyl-)-2-nitroethyl alcohol, its productive rate is 76%, ee value is 87%.
Embodiment 10
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis 3-chlorobenzaldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection; 0.014g (0.05mmol) camphor Schiff's base, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol is added in reaction flask; at room temperature stir 2 hours; then 0.54mL (20mmol) Nitromethane 99Min. is added; and stir 30 minutes; add 0.70g (0.5mmol) 3-chlorobenzaldehyde again; after TLC detection reaction is complete; low boiling component is removed with Rotary Evaporators; crude product is through pillar layer separation; obtain (R)-1-(3-chloro-phenyl-)-2-nitroethyl alcohol, its productive rate is 68%, ee value is 74%.
Embodiment 11
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis 4-trifluoromethylated benzaldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection; 0.014g (0.05mmol) camphor Schiff's base, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol is added in reaction flask; at room temperature stir and within 2 hours, then add 0.54mL (20mmol) Nitromethane 99Min.; and stir 30 minutes; add 0.87g (0.5mmol) 4-trifluoromethylated benzaldehyde again; after TLC detection reaction is complete; low boiling component is removed with Rotary Evaporators; crude product is through pillar layer separation; obtain (R)-1-(4-trifluoromethyl)-2-nitroethyl alcohol; its productive rate is 78%, ee value is 78%.
Embodiment 12
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis 3-trifluoromethylated benzaldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection, 0.014g (0.05mmol) camphor Schiff's base is added in reaction flask, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol, at room temperature stir 2 hours, then 0.54mL (20mmol) Nitromethane 99Min. is added, and stir 30 minutes, add 0.87g (0.5mmol) 3-trifluoromethylated benzaldehyde again, after TLC detection reaction is complete, low boiling component is removed with Rotary Evaporators, crude product is through pillar layer separation, obtain (R)-1-(3-trifluoromethyl)-2-nitroethyl alcohol, its productive rate is 68%, ee value is 86%.
Embodiment 13
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis 4-cyanobenzaldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection; 0.014g (0.05mmol) camphor Schiff's base, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol is added in reaction flask; at room temperature stir 2 hours; then 0.54mL (20mmol) Nitromethane 99Min. is added; and stir 30 minutes; add 0.66g (0.5mmol) 4-cyanobenzaldehyde again; after TLC detection reaction is complete; low boiling component is removed with Rotary Evaporators; crude product is through pillar layer separation; obtain (R)-1-(4-cyano-phenyl)-2-nitroethyl alcohol, its productive rate is 82%, ee value is 81%.
Embodiment 14
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis phenyl aldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection; 0.014g (0.05mmol) camphor Schiff's base, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol is added in reaction flask; at room temperature stir 2 hours; then 0.54mL (20mmol) Nitromethane 99Min. is added; and stir 30 minutes; add 0.53g (0.5mmol) phenyl aldehyde again; after TLC detection reaction is complete; low boiling component is removed with Rotary Evaporators; crude product is through pillar layer separation; obtain (R)-1-phenyl-2-nitroethyl alcohol, its productive rate is 75%, ee value is 66%.
Embodiment 15
Camphor Schiff's base of the present invention is applied in the asymmetric Henry reaction of cuprous chloride catalysis 4-methoxybenzaldehyde and Nitromethane 99Min., and concrete using method is as follows:
Under nitrogen protection; 0.014g (0.05mmol) camphor Schiff's base, 0.005g (0.05mmol) cuprous chloride and the 2mL trimethyl carbinol is added in reaction flask; at room temperature stir 2 hours; then 0.54mL (20mmol) Nitromethane 99Min. is added; and stir 30 minutes; add 0.68g (0.5mmol) 4-methoxybenzaldehyde again; after TLC detection reaction is complete; low boiling component is removed with Rotary Evaporators; crude product is through pillar layer separation; obtain (R)-1-(4-p-methoxy-phenyl)-2-nitroethyl alcohol, its productive rate is 45%, ee value is 69%.
Claims (8)
1. a camphor Schiff's base, is characterized in that the structural formula of this compound is as follows:
2. the preparation method of camphor Schiff's base according to claim 1, is characterized in that it is made up of following step:
(1) 1-isocyanic ester-2-camphorphorone is dissolved in methyl alcohol completely, at 0 ~ 10 DEG C, adds Cerous chloride heptahydrate, be cooled to-78 ~-70 DEG C, add sodium borohydride, stir 1 ~ 2 hour, be warming up to-40 ~-30 DEG C, stir 1 ~ 3 hour, rise to room temperature, steam except methyl alcohol, add the KOH aqueous solution, reflux 2 ~ 4 hours, be cooled to room temperature, separation and purification product, obtain the camphor amino alcohol that structural formula is following;
(2) take dehydrated alcohol as solvent, by camphor amino alcohol and 4-hydroxyl salicylic aldehyde under anhydrous sodium sulphate effect, reflux 10 ~ 12 hours, separation and purification product, obtains camphor Schiff's base.
3. the preparation method of camphor Schiff's base according to claim 2, it is characterized in that: in step (1), the mol ratio of described 1-isocyanic ester-2-camphorphorone and Cerous chloride heptahydrate, sodium borohydride, KOH is 1:(0.2 ~ 0.3): (5 ~ 6): (10 ~ 15).
4. the preparation method of camphor Schiff's base according to claim 2, is characterized in that: in step (2), and the mol ratio of described camphor amino alcohol and 4-hydroxyl salicylic aldehyde, anhydrous sodium sulphate is 1:1:(2 ~ 3).
5. camphor Schiff's base according to claim 1 is applied in the asymmetric Henry reaction of cuprous chloride catalysis aromatic aldehyde and Nitromethane 99Min..
6. camphor Schiff's base according to claim 5 is applied in the asymmetric Henry reaction of cuprous chloride catalysis aromatic aldehyde and Nitromethane 99Min.; it is characterized in that: take the trimethyl carbinol as solvent; under protection of inert gas; be 10:(300 ~ 500 in molar ratio by aromatic aldehyde, Nitromethane 99Min., cuprous chloride, camphor Schiff's base according to claim 1): 1:1 room temperature reaction, obtains β-nitroalcohol.
7. the application of camphor Schiff's base according to claim 6 in the asymmetric Henry reaction of cuprous chloride catalysis aromatic aldehyde and Nitromethane 99Min., is characterized in that: described aromatic aldehyde is any one in phenyl aldehyde, nitro substituted benzaldehyde, halogenated benzaldehyde, trifluoromethyl substituted benzaldehyde, cyano group substituted benzaldehyde, alkoxy substituted formaldehyde.
8. the application of camphor Schiff's base according to claim 6 in the asymmetric Henry reaction of cuprous chloride catalysis aromatic aldehyde and Nitromethane 99Min., is characterized in that: described aromatic aldehyde is any one in phenyl aldehyde, 4-nitrobenzaldehyde, 3-nitrobenzaldehyde, 2-nitrobenzaldehyde, 4-fluorobenzaldehyde, 3-fluorobenzaldehyde, 4-bromobenzaldehyde, 3-bromobenzaldehyde, 4-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-trifluoromethylated benzaldehyde, 3-trifluoromethylated benzaldehyde, 4-cyanobenzaldehyde, 4-methoxybenzaldehyde.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109384769A (en) * | 2018-12-07 | 2019-02-26 | 陕西师范大学 | A kind of synthetic method of R configuration 3- substitution -3- hydroxyl oxidized indole compounds |
| CN113683529A (en) * | 2021-09-22 | 2021-11-23 | 中国林业科学研究院林产化学工业研究所 | Tetrahydroaryl schiff base compound and preparation method and weeding application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003853A (en) * | 2014-04-15 | 2014-08-27 | 汕头大学医学院 | Chalcone derivative and application thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003853A (en) * | 2014-04-15 | 2014-08-27 | 汕头大学医学院 | Chalcone derivative and application thereof |
Non-Patent Citations (2)
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| 刘伟春: "手性樟脑三齿席夫碱配体的合成及催化性能研究", 《中国优秀硕士学位论文全文数据 工程科技I辑》 * |
| 周晓聪: "手性三齿席夫碱配体的合成及其在不对称Henry反应中的应用", 《中国优秀硕士学位论文全文数据 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109384769A (en) * | 2018-12-07 | 2019-02-26 | 陕西师范大学 | A kind of synthetic method of R configuration 3- substitution -3- hydroxyl oxidized indole compounds |
| CN113683529A (en) * | 2021-09-22 | 2021-11-23 | 中国林业科学研究院林产化学工业研究所 | Tetrahydroaryl schiff base compound and preparation method and weeding application thereof |
| CN113683529B (en) * | 2021-09-22 | 2023-08-11 | 中国林业科学研究院林产化学工业研究所 | Tetrahydrolinalyl Schiff base compound and preparation method and weeding application thereof |
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| CN105481715B (en) | 2017-12-05 |
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