CN107311890B - A kind of method of synthesis of carboxylic acid cyanomethyl ester - Google Patents
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- 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
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- 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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- B01J2231/49—Esterification or transesterification
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Abstract
The invention discloses a kind of methods of synthesis of carboxylic acid cyanomethyl ester, i.e., with molecular formula be [(tBuNCH2CH2NtBu)CH][FeBr4] ionic iron (III) complex of the Imidazole cation Han 1,3- di-t-butyl be catalyst, using di-t-butyl peroxide as oxidant, by the oxidative coupling reaction of carboxylic acid and acetonitrile come synthesis of carboxylic acid cyanomethyl ester.The carboxylic acid substrate that the present invention is applicable in is related to aliphatic carboxylic acid, aromatic carboxylic acid and heterocyclic carboxylic acid.This is the first case that carboxylic acid cyanomethyl ester is prepared by the oxidative coupling reaction through carboxylic acid and acetonitrile of Fe-series catalyst realization.
Description
Technical field
The invention belongs to the preparation technical fields of organic compound, and in particular to the preparation method of carboxylic acid cyanomethyl ester.
Background technique
Carboxylic acid cyanomethyl ester is present in many natural products and drug molecule, also there is extensive fortune in organic synthesis
With the method for the such compound of conventional synthesis needs the halide using preparatory functionalization, such as chloroacetonitrile, and such method is not
Enough Atom economies, and generally require to give off the halide of chemical contamination, therefore develop synthesis of carboxylic acid cyanomethyl ester
New method has very strong practical application value.
In recent years, the direct esterification reaction of carbon-hydrogen link has been increasingly becoming a kind of new method of synthesizing carboxylate.Among these
Someone reports the direct esterification reaction at oxygen atom ortho position, benzyl position and allyl position carbon-hydrogen link successively, and directly passes through itrile group neighbour
The report that the esterification of position carbon-hydrogen link carrys out synthesis of carboxylic acid cyanomethyl ester not yet has been reported, novel synthesis of carboxylic acid cyanomethyl ester
The method report of class compound is also less.Existing reaction is that direct esterification is realized by α-itrile group acetic acid decarboxylation, but the party
The inadequate Atom economy of method, catalyst amount are also larger.Therefore develop relatively higher effect green synthesis method, i.e., by carboxylic acid with
The direct esterification reaction of acetonitrile is great innovative and application value.
Within past 10 years, Fe-series catalyst is because having many advantages, such as cheap and easy to get, less toxic or nontoxic, good biocompatibility
And it is developed rapidly, but the reaction kinetic for being related to carbon-hydrogen link in the acetonitrile of Fe-series catalyst catalysis also only has two at present
Piece report, i.e., reacted with difunctionalization of aryl acrylamide by acetonitrile and construct a series of oxidized indole compounds, second
The oxidative coupling reaction of nitrile and 1,3- dicarbonyl compound.It is related to acetonitrile carbon-hydrogen of Fe-series catalyst catalysis to yet there are no
The document report of the esterification of key.Therefore, the esterification for the carboxylic acid and acetonitrile that Fe-series catalyst is catalyzed is realized to construct carboxylic
Sour cyanomethyl ester is the original innovation with application prospect.
Summary of the invention
The object of the present invention is to provide a kind of new methods of synthesis of carboxylic acid cyanomethyl ester, i.e., are with molecular formula
[(tBuNCH2CH2NtBu)CH][FeBr4] ionic iron (III) complex of the Imidazole cation of di-t-butyl containing 1,3- be
Catalyst synthesizes corresponding carboxylic acid with the oxidative coupling reaction of acetonitrile as oxidant, by carboxylic acid using di-t-butyl peroxide
Cyanomethyl ester.Catalyst is iron (III) complex simple and easy to get, stable in the air, with clear structure.
To achieve the above object of the invention, the technical solution adopted by the present invention is that:
A kind of method of synthesis of carboxylic acid cyanomethyl ester, using carboxylic acid compound and acetonitrile as raw material, in catalyst and organic oxygen
In the presence of agent, reaction obtains carboxylic acid cyanomethyl ester；
The chemical structural formula of the catalyst is as follows:
。
In above-mentioned technical proposal, catalyst, carboxylic acid compound, organic oxidizing agent molar ratio be (0.08~0.12): 1:
(2~3)；Preferably 0.10: 1: 2.5
In above-mentioned technical proposal, reaction temperature is 90~130 DEG C, and the time is 15~40 hours；Preferably reaction temperature is
100~120 DEG C, the time is 20~30 hours.
In above-mentioned technical proposal, be cooled to room temperature after reaction, product column Chromatographic purification, for example, with ethyl acetate/
The mixed solvent that petroleum ether volume ratio is 1: 20 is solvent, obtains carboxylic acid cyanomethyl ester.
In above-mentioned technical proposal, carboxylic acid compound includes aryl carboxylic acid compound, substituted aryl carboxylic acid compound, heteroaryl
Carboxylic acid compound, such as benzoic acid, 4- methoxy benzoic acid, 4- methyl benzoic acid, 1- naphthoic acid, 2- thiophenic acid, 4- chlorobenzene
Formic acid, 4- bromobenzoic acid, 4- nitrobenzoic acid, 4- cyanobenzoic acid, cinnamic acid, phenylacetic acid, benzenpropanoic acid.
In above-mentioned technical proposal, organic oxidizing agent is organic peroxide, such as di-t-butyl peroxide.
The invention also discloses a kind of catalyst catalysis carboxylic acid compound in acetonitrile reaction using and one kind urge
Application of the agent in synthesis of carboxylic acid cyanomethyl ester；The chemical structural formula of the catalyst is as follows:
。
Reaction process of the invention can be expressed as follows:
Since above-mentioned technical proposal is used, the invention has the following advantages that
1. the present invention realizes the esterification of carboxylic acid and acetonitrile for the first time using iron (III) complex as catalyst.This is first
The esterification of carbon-hydrogen link, provides a kind of new method for synthesis of carboxylic acid cyanomethyl ester class compound in example acetonitrile.Relative to existing
There is synthetic method, the present invention has better Atom economy, reduces the chemical contamination of halide and the discharge of carbon dioxide,
Meet Green Chemistry concept.
2. iron (III) series catalysts component of the present invention is single, structure is clear, synthesis is simple, steady in air
It is fixed to exist, and show good catalytic activity, be conducive to large-scale commercial synthesis application.
Specific embodiment
The present invention will be further described below with reference to examples:
Embodiment one: the Imidazole cation of di-t-butyl containing 1,3- (molecular formula be [(tBuNCH2CH2NtBu)CH]
[FeBr4]) ionic iron complex synthesis
Successively by 1,3- di-t-butyl imidazoline villaumite (0.22 gram, 1.0 mMs) and NaBr(0.15 grams, 1.5 mmoles
You) it is added in the tetrahydrofuran solution of ferric bromide (0.29 gram, 1.0 mMs), it is reacted 24 hours at 60 DEG C, vacuum pumps
Solvent, hexane washing, drains, is extracted with tetrahydrofuran, and hexane recrystallization is added, at room temperature in centrifugal clear liquid transfer in clear liquid
Red-brown crystals, yield 90% is precipitated.
Chemical structural formula is as follows:
Elemental analysis is carried out to product, as a result as follows:
Elemental analysis
| C:(%) | H:(%) | N:(%) | |
| Theoretical value | 23.64 | 4.15 | 5.01 |
| Actual value | 23.88 | 4.31 | 5.34 |
This complex [(tBuNCH2CH2NtBu)CH][FeBr4] be in the form of ion pair existing for, wherein [FeBr4]-
It is characterized by Raman spectrum, finds it in 204 cm-1There is characteristic peak at place, is consistent with reported in the literature.
Complex cationic portion [(tBuNCH2CH2NtBu)CH]+Characterized by mass spectrum, find its
There is a molecular ion peak at 183.1861, theoretically this molecular ion peak is surveyed consistent with theory, it was demonstrated that institute 183.1861
Obtaining compound is target compound.
Embodiment two: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis benzoic acid and acetonitrile esterification
It is sequentially added in reaction flask benzoic acid (61.1 milligrams, 0.5 mM), and catalyst (28 milligrams, 0.05 mmoles
You), di-t-butyl peroxide (232 microlitres, 1.25 mMs), acetonitrile (10 milliliters) reacts 24 hours at 110 DEG C, reaction
After be cooled to room temperature, product column Chromatographic purification, (with ethyl acetate/petroleum ether volume ratio be 1: 20 mixed solvent be
Solvent), yield 80%.
It is sequentially added in reaction flask benzoic acid (61.1 milligrams, 0.5 mM), and catalyst (28 milligrams, 0.05 mmoles
You), di-t-butyl peroxide (186 microlitres, 1 mM), acetonitrile (10 milliliters) reacts 24 hours at 110 DEG C, and reaction terminates
After be cooled to room temperature, product column Chromatographic purification, (with the mixed solvent that ethyl acetate/petroleum ether volume ratio is 1: 20 be expansion
Agent), yield 78%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 8.13-8.07 (m, 2H), 7.67 (t, 1H), 7.52 (t,
2H), 5.01 (s, 2H)。
Embodiment three: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis 4- methoxy benzoic acid and acetonitrile esterification it is anti-
It answers
It is sequentially added in reaction flask 4- methoxy benzoic acid (76.1 milligrams, 0.5 mM), catalyst (28 milligrams,
0.05 mM), it is small to react 30 at 100 DEG C for di-t-butyl peroxide (232 microlitres, 1.25 mMs), acetonitrile (10 milliliters)
When, it is cooled to room temperature after reaction, product column Chromatographic purification, (the mixing for being 1: 5 with ethyl acetate/petroleum ether volume ratio
Solvent is solvent), yield 85%.
It is sequentially added in reaction flask 4- methoxy benzoic acid (76.1 milligrams, 0.5 mM), catalyst (28 milligrams,
0.05 mM), it is small to react 30 at 100 DEG C for di-t-butyl peroxide (278 microlitres, 1.5 mMs), acetonitrile (10 milliliters)
When, it is cooled to room temperature after reaction, product column Chromatographic purification, (the mixing for being 1: 5 with ethyl acetate/petroleum ether volume ratio
Solvent is solvent), yield 84%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 8.02 (d, 2H), 6.96 (d, 2H), 4.96 (s, 2H),
3.89 (s, 3H)。
Example IV: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis 4- methyl benzoic acid and acetonitrile esterification
It is sequentially added in reaction flask 4- methyl benzoic acid (68.1 milligrams, 0.5 mM), and catalyst (28 milligrams, 0.05
MM), di-t-butyl peroxide (232 microlitres, 1.25 mMs), acetonitrile (10 milliliters) reacts 20 hours at 120 DEG C,
It is cooled to room temperature after reaction, product column Chromatographic purification, it is (molten with the mixing that ethyl acetate/petroleum ether volume ratio is 1: 20
Agent is solvent), yield 83%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 7.99 (d, 2H), 7.32 (d, 2H), 4.99 (s, 2H),
2.47 (s, 3H)。
Embodiment five: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis 1- naphthoic acid and acetonitrile esterification
It is sequentially added in reaction flask 1- naphthoic acid (86.1 milligrams, 0.5 mM), and catalyst (28 milligrams, 0.05 mmoles
You), di-t-butyl peroxide (232 microlitres, 1.25 mMs), acetonitrile (10 milliliters) reacts 28 hours at 110 DEG C, reaction
After be cooled to room temperature, product column Chromatographic purification, (with ethyl acetate/petroleum ether volume ratio be 1: 10 mixed solvent be
Solvent), yield 62%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 8.97 (d, 1H), 8.30 (dd, 1H), 8.11 (t, 1H),
7.93 (d, 1H), 7.72-7.66 (m, 1H), 7.58 (ddd, 2H), 5.06 (s, 2H)。
Embodiment six: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis 2- thiophenic acid and acetonitrile esterification
It is sequentially added in reaction flask 2- thiophenic acid (64.1 milligrams, 0.5 mM), and catalyst (28 milligrams, 0.05 milli
Mole), di-t-butyl peroxide (232 microlitres, 1.25 mMs), acetonitrile (10 milliliters) reacts 24 hours at 110 DEG C, instead
It is cooled to room temperature after answering, product column Chromatographic purification, (the mixed solvent for being 1: 20 with ethyl acetate/petroleum ether volume ratio
For solvent), yield 42%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 7.94 (dd, 1H), 7.72 (dd, 1.2 Hz, 1H), 7.21
(dd, 1H), 4.99 (s, 2H)。
Embodiment seven: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis 4- chlorobenzoic acid and acetonitrile esterification
It is sequentially added in reaction flask 4- chlorobenzoic acid (78.3 milligrams, 0.5 mM), and catalyst (28 milligrams, 0.05 milli
Mole), di-t-butyl peroxide (232 microlitres, 1.25 mMs), acetonitrile (10 milliliters) reacts 20 hours at 110 DEG C, instead
It is cooled to room temperature after answering, product column Chromatographic purification, (the mixed solvent for being 1: 10 with ethyl acetate/petroleum ether volume ratio
For solvent), yield 80%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 8.05-8.01 (m, 2H), 7.52-7.47 (m, 2H), 5.01
(s, 2H)。
Embodiment eight: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis 4- bromobenzoic acid and acetonitrile esterification
It is sequentially added in reaction flask 4- bromobenzoic acid (100.5 milligrams, 0.5 mM), and catalyst (28 milligrams, 0.05
MM), di-t-butyl peroxide (232 microlitres, 1.25 mMs), acetonitrile (10 milliliters) reacts 24 hours at 110 DEG C,
It is cooled to room temperature after reaction, product column Chromatographic purification, it is (molten with the mixing that ethyl acetate/petroleum ether volume ratio is 1: 10
Agent is solvent), yield 76%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 7.94 (d, 2H), 7.66 (d, 2H), 5.01 (s, 2H)。
Embodiment nine: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis 4- nitrobenzoic acid and acetonitrile esterification
It is sequentially added in reaction flask 4- nitrobenzoic acid (83.6 milligrams, 0.5 mM), and catalyst (28 milligrams, 0.05
MM), di-t-butyl peroxide (232 microlitres, 1.25 mMs), acetonitrile (10 milliliters) reacts 30 hours at 120 DEG C,
It is cooled to room temperature after reaction, product column Chromatographic purification, (the mixed solvent for being 1: 5 with ethyl acetate/petroleum ether volume ratio
For solvent), yield 54%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 8.36 (d, 2H), 8.27 (d,2H), 5.05 (s, 2H)。
Embodiment ten: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis 4- cyanobenzoic acid and acetonitrile esterification
It is sequentially added in reaction flask 4- cyanobenzoic acid (73.6 milligrams, 0.5 mM), and catalyst (28 milligrams, 0.05
MM), di-t-butyl peroxide (232 microlitres, 1.25 mMs), acetonitrile (10 milliliters) reacts 28 hours at 110 DEG C,
It is cooled to room temperature after reaction, product column Chromatographic purification, it is (molten with the mixing that ethyl acetate/petroleum ether volume ratio is 1: 10
Agent is solvent), yield 55%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 8.21 (d, J = 8.5 Hz, 2H), 7.84 (d, J = 8.5
Hz, 2H), 5.05 (d, J = 5.9 Hz, 2H)。
Embodiment 11: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis cinnamic acid and acetonitrile esterification
It is sequentially added in reaction flask cinnamic acid (74.1 milligrams, 0.5 mM), and catalyst (28 milligrams, 0.05 mmoles
You), di-t-butyl peroxide (232 microlitres, 1.25 mMs), acetonitrile (10 milliliters) reacts 24 hours at 110 DEG C, reaction
After be cooled to room temperature, product column Chromatographic purification, (with ethyl acetate/petroleum ether volume ratio be 1: 10 mixed solvent be
Solvent), yield 67%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 7.78 (d, 1H), 7.54-7.50 (m, 2H), 7.45-7.37
(m, 3H), 6.44 (d, 1H), 4.84 (s, 2H)。
Embodiment 12: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis phenylacetic acid and acetonitrile esterification
It is sequentially added in reaction flask phenylacetic acid (68.0 milligrams, 0.5 mM), and catalyst (28 milligrams, 0.05 mmoles
You), di-t-butyl peroxide (232 microlitres, 1.25 mMs), acetonitrile (10 milliliters) reacts 24 hours at 110 DEG C, reaction
After be cooled to room temperature, product column Chromatographic purification, (with ethyl acetate/petroleum ether volume ratio be 1: 10 mixed solvent be
Solvent), yield 60%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 7.31-7.28 (m, 2H), 7.23-7.18 (m, 3H), 5.10
(s, 2H), 3.72 (t, 2H)。
Embodiment 13: [(tBuNCH2CH2NtBu)CH][FeBr4] catalysis benzenpropanoic acid and acetonitrile esterification
It is sequentially added in reaction flask benzenpropanoic acid (75.1 milligrams, 0.5 mM), and catalyst (28 milligrams, 0.05 mmoles
You), di-t-butyl peroxide (232 microlitres, 1.25 mMs), acetonitrile (10 milliliters) reacts 24 hours at 110 DEG C, reaction
After be cooled to room temperature, product column Chromatographic purification, (with ethyl acetate/petroleum ether volume ratio be 1: 10 mixed solvent be
Solvent), yield 60%.
Product is dissolved in CDCl3In (about 0.4 mL), tube sealing measures on Unity Inova-400 type NMR instrument at room temperature
Characterization:1H NMR (400 MHz, CDCl3, TMS): 7.31-7.28 (m, 2H), 7.23-7.18 (m, 3H), 4.67
(s, 2H), 2.97 (t, 2H), 2.72 (t, 2H).
Claims (5)
1. a kind of method of synthesis of carboxylic acid cyanomethyl ester, using carboxylic acid compound and acetonitrile as raw material, in catalyst and organic oxidation
In the presence of agent, reaction obtains carboxylic acid cyanomethyl ester；The carboxylic acid compound is benzoic acid, 4- methoxy benzoic acid, 4- methylbenzene
Formic acid, 1- naphthoic acid, 2- thiophenic acid, 4- chlorobenzoic acid, 4- bromobenzoic acid, 4- nitrobenzoic acid, 4- cyanobenzoic acid, cortex cinnamomi
Acid, phenylacetic acid, benzenpropanoic acid；The organic oxidizing agent is di-t-butyl peroxide；
The chemical structural formula of the catalyst is as follows:
。
2. the method for synthesis of carboxylic acid cyanomethyl ester according to claim 1, which is characterized in that catalyst, has carboxylic acid compound
The molar ratio of machine oxidant is (0.08~0.12): 1: (2~3).
3. the method for synthesis of carboxylic acid cyanomethyl ester according to claim 1, which is characterized in that reaction temperature is 90~130 DEG C,
Time is 15~40 hours.
4. the method for synthesis of carboxylic acid cyanomethyl ester according to claim 3, which is characterized in that preferred reaction temperature is 100
~120 DEG C, the time is 20~30 hours.
5. the method for synthesis of carboxylic acid cyanomethyl ester according to claim 1, which is characterized in that be cooled to room after reaction
Temperature, product column Chromatographic purification, obtains carboxylic acid cyanomethyl ester.
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| WO2020087233A1 (en) * | 2018-10-29 | 2020-05-07 | 南通纺织丝绸产业技术研究院 | Application of ionic iron (iii) complex as catalyst in preparation of benzylamine compound |
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| "Iron-catalyzed esterification of allylic sp3 C–H bonds with carboxylic acids: Facile access to allylic esters";Lu Bing等;《Tetrahedron Letters》;20170512;第58卷;第2490-2494页 * |
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