CN101967165A - Bridge chain bis-Schiff base-cobalt complex and synthesis method thereof as well as application thereof - Google Patents
Bridge chain bis-Schiff base-cobalt complex and synthesis method thereof as well as application thereof Download PDFInfo
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Abstract
The invention relates to a new bridge chain bis-Schiff base-cobalt complex and a synthesis method thereof as well as the catalyst application thereof in the tehhydrolysis reactions of various epoxy compounds. Experiments show that the bridge chain bis-Schiff base-cobalt complex has high catalytic activity and excellent enantioselectivity in the hydrolytic kinetic resolution (HKR) of racemic epoxy compounds, especially can achieve high efficient synthesis of chiral epoxy compounds and chiral 1, 2-glycol compounds.
Description
Technical field
The present invention relates to two schiff bases (Salen) complex compounds of a kind of novel bridge chain, specifically, relate to two schiff bases-cobalt complexs of a kind of bridge chain and preparation method and use thereof.
Background technology
Chiral epoxy compound and chirality 1, the 2-diol compound is important organic synthesis intermediate.With chiral epoxy compound or chirality 1, the 2-diol compound is a starting raw material, can prepare the medicine and the pesticide intermediate of multiple high-optical-purity.The hydrolytic kinetic resolution of racemation epoxy is a kind of efficient synthesizing chiral epoxy compound and chirality 1, the method for 2-diol compound.1997, (Jacobsen in the fractionation that the hydrolytic kinetic resolution method is applied in terminal epoxy of Jacobsen group success first, E.N.Science, 1997,277,936), used catalyzer is monokaryon schiff bases-Co complex compound (US5929232, WO03018520A1, US2003073855A1).A plurality of afterwards catalyst system are reported in succession, for example immobilized schiff bases-Co catalyzer (Jacobsen to polystyrene resin, E.N.J.Am.Chem.Soc., 1999,121,4147), the dimer schiff bases of methylene bridge chain-Co catalyzer (Kureshy, R.I.Journal of Molecular Catalysis A:Chemical, 2002,179,73) and the schiff bases of oligopolymer form-Co catalyzer (Jacobsen, E.N.Tetrahedron:Asymmetry, 2003,14,3633) etc., however there is the shortcoming that catalytic activity is low or selectivity is low in existing these catalyzer overwhelming majority.
Summary of the invention
Weak point at above-mentioned existing catalyzer, the invention provides two schiff bases-cobalt complexs of the novel bridge chain of a class and synthetic method thereof, hope improves this class activity of such catalysts and efficient by the synergistic effect of catalyzer bimetal coordination center, for catalyst field increases a class product innovation; The present invention also provides a kind of purposes of the two schiff bases-cobalt complexs of described bridge chain, promptly, be used for the hydrolytic kinetic resolution reaction of catalysis end-rings oxygen compound after activated, for example: the epoxy compounds and the diol compound that are used for the synthetic high-optical-purity of catalysis.
Two schiff bases-the cobalt complexs of bridge chain provided by the invention have following a kind of general formula:
Wherein:
R
1, R
2, R
3Independently be selected from hydrogen, C respectively
1-6Alkyl or R
x, R
X 'The phenyl that replaces is recommended as C
1-6Alkyl, for example: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, sec-butyl, isobutyl-, isopentyl, cyclopentyl or cyclohexyl further are recommended as the tertiary butyl;
Represent chirality
Wherein: the integer of n=2～6, R
4Be C
1-6Alkyl, the cycloalkyl that contains 4～8 carbon or R
x, R
X 'The phenyl that replaces; Recommend
Represent chirality
The bridge chain is the covalent bond structure unit that is selected from the diprotic acid with following structure:
The link position of bridge chain generally is on the position of the carboxyl of above-mentioned group.
Above-mentioned R
x, R
X 'Be selected from hydrogen, C respectively
1-4Alkyl, C
1-4Alkoxyl group, phenyl, benzyl, 1-naphthyl or 2-naphthyl.
Two schiff bases-the cobalt complexs of bridge chain provided by the invention, the another kind of general formula that has is as follows:
R wherein
1, R
2, R
3,
And the bridge chain as mentioned above; X is an organic acid, and described organic acid derives from carboxylic acid, camphorsulfonic acid, phenylformic acid, methylsulfonic acid, Phenylsulfonic acid or the phenylformic acid of the organic acid of the following group of following group or replacement: C1-C4; Described substituting group is the alkyl of halogen, nitro or C1-C4, and described substituting group is single replacement or polysubstituted, for example: acetate, trifluoroacetic acid, trifluoromethanesulfonic acid, 2,4-dinitrobenzene sulfonic acid, 3-nitrobenzene-sulfonic acid, p-methyl benzenesulfonic acid, Phenylsulfonic acid, camphorsulfonic acid, p-nitrobenzoic acid, phenylformic acid etc.
The synthetic method of the two schiff bases-cobalt complexs of bridge chain provided by the invention: be the two schiff bases parts of earlier synthetic bridge chain, then itself and four hydration Cobaltous diacetates reacted in organic solvent; Here used organic solvent can be selected from chloroform, methylene dichloride, tetracol phenixin, 1,2-ethylene dichloride, tetrahydrofuran (THF), ether, methyl alcohol, ethanol, Virahol, N, dinethylformamide or dimethyl sulfoxide (DMSO) etc.
The synthetic method of the two schiff bases parts of bridge chain involved in the present invention is as follows:
1) by structural formula is
The 5-hydroxyl salicylic aldehyde and the dicarboxylic acid of replacement
In organic polar solvent, the 4-Dimethylamino pyridine of condensing agent and catalytic amount exists down, reacts under the room temperature 1～60 hour, makes the double salicylaldehyde of bridging
The molar feed ratio of described substituted salicylic aldehydes, dicarboxylic acid, condensing agent and 4-Dimethylamino pyridine is 10: 5: 10: 1;
2) structural formula is
Substituted salicylic aldehydes list imines and the double salicylaldehyde of the product-bridging of step 1), in organic solvent, under 0～60 ℃ of the temperature of reaction, with 1～4: 1 molar ratio reaction 10～80 hours makes the two schiff bases parts of bridging
The concrete recommendation is shown below:
With the methylene dichloride is solvent, N, the 4-Dimethylamino pyridine (DMAP) of N '-di-isopropyl carbodiimide (DIC) and catalytic amount exists down, substituted salicylic aldehydes 1 and dicarboxylic acid 2 react under room temperature and obtained bridge chain double salicylaldehyde 3 in 1～60 hour, and feed ratio is: the mol ratio of salicylic aldehyde 1, carboxylic acid 2, DIC and DMAP is 10: 5: 10: 1; By diamines 5 and the salicylic aldehyde 4 that replaces with 1: 1 molar feed ratio in chloroform under zero degrees celsius prepared in reaction reaction intermediate 6, and synthesize the two schiff bases parts 7 of bridge chains with resulting bridge chain double salicylaldehyde 3 without separating directly, this step temperature of reaction is 0 ℃ and arrives room temperature that compound 6 is 1～4: 1 with the molar feed ratio of double salicylaldehyde 3.
Preparation method's (being shown below) of the two schiff bases-cobalt complexs 8 of bridge chain involved in the present invention: two schiff bases parts 7 and four hydration Cobaltous diacetates by covalent linkage bridge chain react the two schiff bases-cobalt complexs 8 that obtain by covalent linkage bridge chain in organic solvent, the reaction mol ratio of the described pair of schiff bases part 7 and four hydration Cobaltous diacetates is 1: 1～10, temperature of reaction is-10 ℃～100 ℃, and the reaction times is 1～48 hour; Used organic solvent is recommended to be selected from: chloroform, methylene dichloride, tetracol phenixin, tetrahydrofuran (THF), 1,2-ethylene dichloride, ether, alcohol (for example methyl alcohol, ethanol, Virahol), toluene, N, at least a in dinethylformamide or the dimethyl sulfoxide (DMSO).
Activate with the organic acid effect having under the condition of oxygen by two schiff bases-cobalt complexs 8 of covalent linkage bridge chain, generation is by two schiff bases-cobalt complexs 9 of covalent linkage bridge chain, described pair of schiff bases-cobalt complex 8 is 1: 2～10 with organic acid reaction mol ratio, temperature of reaction is 0～50 ℃, and the reaction times is 1～24 hour; Organic acid as previously mentioned;
The structural formula of the described pair of schiff bases part 7, two schiff bases-cobalt complex 8, two schiff bases-cobalt complex 9 is as follows:
R wherein
1, R
2, R
3, R
4, X and bridge chain are as previously mentioned.
The concrete recommendation: part 7 is dissolved in organic solvent, drips the methanol solution of four hydration Cobaltous diacetates then, finishes, and stirring at room 1～48 hour, the red solid that the filtration collection is separated out are also with methyl alcohol thorough washing, vacuum-drying.Here the mol ratio of four hydration Cobaltous diacetates and part 7 is 1～10: 1.
The two schiff bases of bridge chain provided by the invention-cobalt complex useful as catalysts, recommendation is used for the hydrolytic kinetic resolution reaction of catalysis end-rings oxygen compound, further recommendation is used for the hydrolytic kinetic resolution reaction of the end-rings oxygen compound of catalysis racemization, synthesizes to have optically active two pure and mild epoxy compoundss.React used catalyzer for example complex compound 9 can be on-the-spot the generation.The complex compound 9 that obtains through organic acid for activating has good catalytic effect.
The structure of the end-rings oxygen compound of described racemization is:
R wherein is selected from alkyl, aryl or the terminal alkyl that has functional groups such as ether, carboxylicesters, halogen of C1-C20, can for: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, isopentyl, cyclopentyl, cyclohexyl and other various straight chains or branched alkyl also can be chloromethyl, benzyloxymethyl, carbalkoxy or R
x, R
X 'The phenyl that replaces, R here
x, R
X 'As hereinbefore; Recommendation is selected from following structure:
With complex compound 8 catalytic reactions is that example is described as follows:
Two schiff bases-the cobalt complexs 8 of the epoxy compounds of racemization, organic solvent and bridging, organic acid, water (are recommended to keep the reaction system ingress of air, are dripped H gradually
2O), after reaction finishes, recommend to distill chiral epoxy and diol product.The mol ratio that wherein adds the two schiff bases-cobalt complexs 8 of organic acid and bridging is 2～20: 1, the mol ratio of the two schiff bases-cobalt complexs 8 of the epoxy compounds of racemization and bridging is 100000～100: 1, the mol ratio of racemation epoxy compound and water is 1～10: 5, temperature of reaction is recommended room temperature, further recommend 0～50 ℃, the reaction times recommended 3～200 hours.Described organic solvent is recommended chloroform, methylene dichloride, tetracol phenixin, 1,2-ethylene dichloride, tetrahydrofuran (THF), ether, alcohol (for example methyl alcohol, ethanol, Virahol), toluene, N, dinethylformamide or dimethyl sulfoxide (DMSO).
Description of drawings
Fig. 1 is the X ray crystallogram of the embodiment 1 synthetic compound 8a that obtains.
Specific implementation method
The present invention is described in further detail and completely below in conjunction with embodiment, but do not limit content of the present invention.
Embodiment 1
The synthetic method of the two schiff bases-cobalt complexs of bridge chain of the present invention describes (synthetic reaction process is as shown below) in detail with the example that synthesizes of the two schiff bases of bridging-cobalt complex 8a:
The first step: from compound 1a and 2a synthetic compound 3a
In the 50mL there-necked flask, add compound 1a (775mg, 4.0mmol), cis-5-norbornylene-endo-2,3-dicarboxylic acid (363mg, 2.0mmol) and DMAP (4-Dimethylamino pyridine) (49mg, 0.4mmol), substitute and add methylene dichloride (8mL) and DMF (N-N-dimethyl formamide) behind the argon gas (0.8mL), stir 10 minutes postcooling to 0 ℃, add DIC (N, N '-di-isopropyl carbodiimide) (0.53g, 4.2mmol) keep 0 ℃ to stir 10 minutes, rising to stirring at room 72 hours, the TLC detection reaction finishes, in reaction solution, add methylene dichloride (50mL), add 0.1M hydrochloric acid (20mL) washing, and saturated NaCl solution washing (3 * 30mL), anhydrous Na
2SO
4Dry after-filtration, removal of solvent under reduced pressure, column chromatography for separation (sherwood oil: ethyl acetate=8: 1) get white solid 0.816g, yield 86%.m.p.167-168℃；
1H?NMR(300MHz，CDCl
3)δ1.32(s，18H)，1.52(d，1H，J＝8.7Hz)，1.65(d，1H，J＝8.4Hz)，3.41(s，2H)，3.68(s，2H)，6.41(s，2H)，7.13(d，2H，J＝2.7Hz)，7.15(d，2H，J＝3.0Hz)，9.72(s，2H)，11.69(s，2H)ppm；MALDI-MS，m/z＝534.9[M+H]
+；Anal.Calcd?for?C
31H
34O
8：C，69.65；H，6.41％.Found：C，69.64；H，6.32％。
Second step: from compound 4a and 5a synthetic compound 6a
In the 100mL there-necked flask that constant pressure funnel is housed, add R, R-cyclohexanediamine 5a (0.493g, 4.32mmol), add chloroform (10mL) dissolving, be cooled to 0 ℃, drip 3 by constant pressure funnel, 5-di-tert-butyl salicylaldehyde 4a (1.012g, 4.32mmol) chloroformic solution (10mL), drip the back and keep 0 ℃ to stir and obtained compound 6a in 48 hours and be directly used in next step reaction without separation.
The 3rd step: from compound 3a and 6a synthetic compound 7a
In the solution of 6a, drip the chloroformic solution (400mg, 0.72mmol, in 10mL) of 3a, rise to room temperature after dripping, add
Molecular sieve stirred 48 hours, filtered back washed with dichloromethane, concentrating under reduced pressure.With the gained crude product through column chromatography for separation (sherwood oil: ethyl acetate=30: 1) yellow blister solid 150mg, yield 58%.m.p.159-160℃；[α]
D 20＝-256.4(c＝0.52，CHCl
3)；
1H?NMR(300MHz，CDCl
3)δ1.28(s，18H)，1.29(s，9H)，1.32(s，9H)，1.44(s，18H)，1.47-1.61(m，6H)，1.69-1.77(m，4H)，1.87-1.99(m，8H)，3.34(br，6H)，3.60(s，2H)，6.34(br，2H)，6.67(s，1H)，6.74(d，1H，J＝2.7Hz)，6.88，(t，2H，J＝3.0Hz)，7.02(t，2H，J＝3.0Hz)，7.35(d，2H，J＝2.4Hz)，8.08(s，1H)，8.17(s，1H)，8.34(d，2H，J＝3.3Hz)，13.61(br，2H)13.86(br，2H)ppm；MALDI-MS，m/z＝1159.7[M+H]
+；Anal.Calcd?for?C
73H
98N
4O
8：C，75.61；H，8.52；N，4.83％.Found：C，75.27；H，8.58；N，4.68％。
The 4th step: from the two schiff bases of the synthetic bridge chain of part 7a-cobalt complex 8a
In the 100mL reaction tubes, add part 7a (1.16g, 1.0mmol), add methylene dichloride (10mL) dissolving, be added drop-wise in the dichloromethane solution of above-mentioned part after four hydration Cobaltous diacetates, 0.5 gram (2.0mmol) is dissolved in methyl alcohol (20mL), stirred 2 hours, separate out red solid, filter and use methanol wash, get red solid 1.02 grams after the vacuum-drying, yield 80%, complex structure is through X ray crystalline diffraction analysis confirmation (referring to shown in Figure 1).
The 5th step: the activation of the two schiff bases-cobalt complexs of bridge chain:
Cobalt complex 8a (127mg) is dissolved in the toluene (2mL), adds acetate (48mg), and the reaction of room temperature lower open mouth is 2 hours then, and concentrating under reduced pressure removes and desolvates.Resulting crude product is dissolved in a small amount of methylene dichloride, adds normal hexane complex compound sediment is come out, filtration, vacuum-drying obtain brown solid 132mg, yield 95%.MALDI-MS，m/z＝1273.4；Anal.Calcd?for?C
77H
100Co
2N
4O
12：C，66.46；H，7.24；N，4.03％.Found：C，66.38；H，7.26；N，4.12％。
With the hydrolysis reaction of the two schiff bases of bridge chain of the present invention-cobalt complex catalysis epoxidation compound, be that example is described in detail as follows with the two schiff bases of bridge chain-cobalt complex 8a or 9a:
The hydrolytic kinetic resolution reaction of embodiment 2 usefulness 9a catalysis propylene oxide
(7mL 0.1mol) with the two schiff bases of bridge chain-cobalt complex 9a (0.01mol%), drips H gradually to add racemic epoxide propane in the 50mL there-necked flask
2O (0.9mL, 0.05mol), after the GC detection reaction finished, air distillation got (R)-1,2 epoxy prapane (97%ee), and underpressure distillation gets (S)-1,2-propylene glycol (95%ee).
The hydrolytic kinetic resolution reaction of embodiment 3 usefulness 9a catalysis propylene oxide
The two schiff bases of bridge chain-cobalt complex 8a (127mg) is dissolved in the toluene (2mL), adds acetate (48mg), the reaction of room temperature lower open mouth is 6 hours then, and concentrating under reduced pressure removes and desolvates.Resulting crude product is dissolved in a small amount of methylene dichloride, adds normal hexane complex compound sediment is come out, filtration, vacuum-drying obtain brown solid 136mg, yield: 98%.
Propylene oxide (7mL in racemization, 0.1mol) the middle above-mentioned activatory catalyzer (0.01mol%) that adds, keep reaction system can touch air, drip water (0.9mL under the room temperature, 0.05mol), GC monitoring reaction process finishes after two kinds of products of rectifying separation: (R)-1,2-propylene oxide (96%ee) and (S)-1,2-propylene glycol (95%ee).
Embodiment 4 is with the organic acid of camphorsulfonic acid as activation divalence cobalt complex
(7mL, 0.1mol) with the two schiff bases of bridge chain-cobalt complex 8a (0.01mol%), the sulfonic acid that camphorates (0.05mol%) keeps reaction system energy ingress of air, slowly drips H then under the room temperature to add racemic epoxide propane in reactor successively
2O (0.7 equivalent), after the GC detection reaction finished, rectifying separation got (R)-1,2 epoxy prapane (96%ee) and (S)-1,2-propylene glycol (92%ee).
Embodiment 5 is with 2, and 4-dinitrobenzene sulfonic acid is as the organic acid of activation divalence cobalt complex
(7mL 0.1mol) with the two schiff bases of bridge chain-cobalt complex 8a (0.01mol%), adds 2, and 4-dinitrobenzene sulfonic acid (0.05mol%) keeps reaction system energy ingress of air, slowly drips H then under the room temperature to add racemic epoxide propane in reactor successively
2O (0.5 equivalent), after the GC detection reaction finished, rectifying separation got (R)-1,2 epoxy prapane (98%ee) and (S)-1,2-propylene glycol (94%ee).
Embodiment 6 is with the organic acid of trifluoroacetic acid as activation divalence cobalt complex
(7mL 0.1mol) with the two schiff bases of bridge chain-cobalt complex 8a (0.01mol%), adds trifluoroacetic acid (0.05mol%), keeps reaction system energy ingress of air, slowly drips H then under the room temperature to add racemic epoxide propane in reactor successively
2O (0.6 equivalent), after the GC detection reaction finished, rectifying separation got (R)-1,2 epoxy prapane (96%ee) and (S)-1,2-propylene glycol (92%ee).
Embodiment 7: synthesized the two schiff bases of bridge chain as shown below-cobalt complex 8b-8v respectively with reference to the synthetic method of the two schiff bases of bridge chain-cobalt complex 8a:
The bridge chain=
Embodiment 8:8e is through the hydrolysis reaction of p-methyl benzenesulfonic acid activating catalytic propylene oxide
(7mL 0.1mol) with the two schiff bases of bridge chain-cobalt complex 8e (0.01mol%), adds tosic acid (0.05mol%), keeps reaction system energy ingress of air, slowly drips H then under the room temperature to add racemic epoxide propane in reactor successively
2O (0.7 equivalent), after the GC detection reaction finished, rectifying separation got (R)-1,2 epoxy prapane (98%ee) and (S)-1,2-propylene glycol (93%ee).
Embodiment 9:8e is through the hydrolysis reaction of trifluoromethanesulfonic acid activating catalytic propylene oxide
(7mL 0.1mol) with the two schiff bases of bridge chain-cobalt complex 8e (0.005mol%), adds trifluoromethanesulfonic acid (0.05mol%), keeps reaction system energy ingress of air, slowly drips H then under the room temperature to add racemic epoxide propane in reactor successively
2O (0.7 equivalent), after the GC detection reaction finished, rectifying separation got (R)-1,2 epoxy prapane (95%ee) and (S)-1,2-propylene glycol (90%ee).
Embodiment 10:8e is through the hydrolysis reaction of 3-nitrobenzene-sulfonic acid activating catalytic propylene oxide
(7mL 0.1mol) with the two schiff bases of bridge chain-cobalt complex 8e (0.007mol%), adds 3-nitrobenzene-sulfonic acid (0.05mol%), keeps reaction system energy ingress of air, slowly drips H then under the room temperature to add racemic epoxide propane in reactor successively
2O (0.7 equivalent), after the GC detection reaction finished, rectifying separation got (R)-1,2 epoxy prapane (97%ee) and (S)-1,2-propylene glycol (92%ee).
Embodiment 11: with the two schiff bases of every kind of bridge chain of embodiment 7 synthetic-cobalt complex 8a-8v after the on-the-spot activation of p-nitrobenzoic acid as catalyzer, test method with reference to previous embodiment epoxy hydrolysis reaction, carry out the hydrolysis reaction of propylene oxide respectively, the result as shown in Table 1.
Table one: the two catalytic propylene oxide hydrolytic kinetic resolution of schiff bases-cobalt complex of bridge chain
Reaction conditions: propylene oxide 100mmol, the two schiff bases-cobalts (0.01mol%) of bridge chain, p-nitrobenzoic acid (0.06mol%), water 50mmol, solvent-free reaction.
Embodiment 12: according to the reaction result of embodiment 11, we as catalyst precursor, make activator with p-nitrobenzoic acid with 8e, and the check catalyst system is to the suitability of substrate.
As shown in Table 2, select different epoxy substrates for use, carry out kinetic resolution, the results are shown in table two, the substrate that this catalyst system was suitable for listed structure in being not limited only to show with reference to the experiment condition that with the propylene oxide is substrate.
Table two: the two schiff bases of the bridging-catalytic epoxy compounds hydrolytic kinetic resolution of cobalt complex 8e
Reaction conditions: epoxy compounds 200mmol, 8e (0.005mol%), p-nitrophenyl sulfonic acid (0.05mol%), water 100mmol, solvent-free reaction.
By above-mentioned experimental result as seen: the two schiff bases-cobalt complexs of bridge chain of the present invention show very high catalytic activity and outstanding enantioselectivity in the hydrolytic kinetic resolution of racemation epoxy, especially can realize efficient synthesizing chiral epoxy compound and chirality 1, the 2-glycol.
Claims (16)
1. two schiff bases-cobalt complexs of a bridge chain is characterized in that having following general formula:
Wherein:
R
1, R
2, R
3Independently be selected from hydrogen, C respectively
1-6Alkyl or R
x, R
X 'The phenyl that replaces;
Represent chirality
The integer of n=2 wherein～6, R
4Be C
1-6Alkyl, the cycloalkyl that contains 4～8 carbon or R
x, R
X 'The phenyl that replaces;
The bridge chain is the covalent bond structure unit that is selected from the diprotic acid with following structure:
2. two schiff bases-cobalt complexs of a bridge chain is characterized in that having following general formula:
R wherein
1, R
2, R
3,
And the bridge chain according to claim 1; X is an organic acid.
3. the two schiff bases-cobalt complexs of bridge chain according to claim 1 is characterized in that R
1, R
2, R
3Independently be selected from C respectively
1-6Alkyl.
4. the two schiff bases-cobalt complexs of bridge chain according to claim 3 is characterized in that R
1, R
2, R
3Independently be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, sec-butyl, isobutyl-, isopentyl, cyclopentyl or cyclohexyl respectively.
5. the two schiff bases-cobalt complexs of bridge chain according to claim 1 is characterized in that,
Represent chirality
6. the two schiff bases-cobalt complexs of bridge chain according to claim 1 is characterized in that described R
x, R
X 'Be selected from hydrogen, C respectively
1-4Alkyl, C
1-4Alkoxyl group, phenyl, benzyl, 1-naphthyl or 2-naphthyl.
7. the two schiff bases-cobalt complexs of bridge chain according to claim 2, it is characterized in that described organic acid derives from carboxylic acid, camphorsulfonic acid, phenylformic acid, methylsulfonic acid, Phenylsulfonic acid or the phenylformic acid of the organic acid of the following group of following group or replacement: C1-C4; Described substituting group is the alkyl of halogen, nitro or C1-C4, and described substituting group is single replacement or polysubstituted.
8. the two schiff bases-cobalt complexs of bridge chain according to claim 7, it is characterized in that, described organic acid derives from acetate, trifluoroacetic acid, trifluoromethanesulfonic acid, 2,4-dinitrobenzene sulfonic acid, 3-nitrobenzene-sulfonic acid, p-methyl benzenesulfonic acid, Phenylsulfonic acid, camphorsulfonic acid, p-nitrobenzoic acid or phenylformic acid.
9. the synthetic method of described pair of schiff bases-cobalt complex of a claim 1 is characterized in that, comprises the steps:
A) by structural formula be
The 5-hydroxyl salicylic aldehyde and the dicarboxylic acid of replacement
In organic polar solvent, the 4-Dimethylamino pyridine of condensing agent and catalytic amount exists down, reacts under the room temperature 1～60 hour, makes the double salicylaldehyde of bridge chain
The molar feed ratio of described substituted salicylic aldehydes, dicarboxylic acid, condensing agent and 4-Dimethylamino pyridine is 10: 5: 10: 1;
B) structural formula is
Substituted salicylic aldehydes list imines and the double salicylaldehyde of the product-bridge chain of step 1), in organic solvent, under 0～60 ℃ of the temperature of reaction, with 1～4: 1 molar ratio reaction 10～80 hours makes the two schiff bases parts of bridging
C) two schiff bases parts of bridging and the four hydration Cobaltous diacetates that made by step b) react in organic solvent, the reaction mol ratio of two schiff bases parts of described bridging and four hydration Cobaltous diacetates is 1: 1～10, temperature of reaction is-10 ℃～100 ℃, and the reaction times is 1～48 hour.
10. the synthetic method of pair schiff bases-cobalt complex according to claim 9, it is characterized in that, described organic solvent is selected from chloroform, methylene dichloride, tetracol phenixin, tetrahydrofuran (THF), 1,2-ethylene dichloride, ether, methyl alcohol, ethanol, N, at least a in dinethylformamide and the dimethyl sulfoxide (DMSO).
11. the synthetic method of described pair of schiff bases-cobalt complex of a claim 2, it is characterized in that, described pair of schiff bases-cobalt complex of claim 1 had under the condition of oxygen and the organic acid effect, described pair of schiff bases-cobalt complex of claim 1 and organic acid reaction mol ratio are 1: 2～10, temperature of reaction is 0～50 ℃, and the reaction times is 1～24 hour.
12. the synthetic method of according to claim 11 pair of schiff bases-cobalt complex, it is characterized in that, described organic acid is selected from acetate, trifluoroacetic acid, trifluoromethanesulfonic acid, 2, at least a in 4-dinitrobenzene sulfonic acid, 3-nitrobenzene-sulfonic acid, 4-nitrobenzene-sulfonic acid, p-methyl benzenesulfonic acid, Phenylsulfonic acid, camphorsulfonic acid, p-nitrobenzoic acid and the phenylformic acid.
13. the purposes of a claim 1 or 2 described pairs of schiff bases-cobalt complexs is characterized in that, is used for the hydrolytic kinetic resolution reaction of the end-rings oxygen compound of catalysis racemization, synthesizes to have optically active two pure and mild epoxy compoundss.
14. the purposes of described pair of schiff bases-cobalt complex of a claim 1, it is characterized in that, described pair of schiff bases-cobalt complex of end-rings oxygen compound, organic solvent and claim 1 and organic acid reaction with racemization add entry, react chiral epoxy and diol product; Wherein: the mol ratio of described pair of schiff bases-cobalt complex of organic acid and claim 1 is 2～20: 1, the mol ratio of the end-rings oxygen compound of racemization and described pair of schiff bases-cobalt complex of claim 1 is 100000～100: 1, and the end-rings oxygen compound of racemization and the mol ratio of water are 1～10: 5.
15. the purposes according to claim 13 or 14 described pairs of schiff bases-cobalt complexs is characterized in that, the structure of the end-rings oxygen compound of described racemization is:
R wherein is selected from alkyl, aryl or the terminal alkyl that has ether, carboxylicesters, cyano group, halogen functional group of C1-C20.
16. the purposes of according to claim 15 pair of schiff bases-cobalt complex, it is characterized in that described R is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, isopentyl, cyclopentyl, cyclohexyl, chloromethyl, benzyloxymethyl, carbalkoxy or R
x, R
X 'The phenyl that replaces, R wherein
x, R
X 'Described identical with claim 6.
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| CN113087640A (en) * | 2021-04-02 | 2021-07-09 | 合肥工业大学 | Chiral ONO tridentate Schiff base carboxylic acid ligand and preparation method and application thereof |
| CN113087640B (en) * | 2021-04-02 | 2023-04-25 | 合肥工业大学 | Chiral ONO tridentate Schiff base carboxylic acid ligand and preparation method and application thereof |
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