CN107474090A - Double aza ring carbene precursor salts of carbohydrate and its production and use - Google Patents

Double aza ring carbene precursor salts of carbohydrate and its production and use Download PDF

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CN107474090A
CN107474090A CN201710747341.9A CN201710747341A CN107474090A CN 107474090 A CN107474090 A CN 107474090A CN 201710747341 A CN201710747341 A CN 201710747341A CN 107474090 A CN107474090 A CN 107474090A
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carbohydrate
double
carbene precursor
aza ring
precursor salts
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周中高
元洋洋
李美
谢永荣
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Gannan Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
    • C07H19/02—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing nitrogen
    • C07H19/04—Heterocyclic radicals containing only nitrogen atoms as ring hetero atom
    • C07H19/052—Imidazole radicals
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • 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
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • 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
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium

Abstract

The invention provides double aza ring carbene precursor salts of a kind of carbohydrate and its production and use, structure is shown in formula I：

Description

Double aza ring carbene precursor salts of carbohydrate and its production and use
Technical field
The present invention relates to double aza ring carbene precursor salts of a kind of carbohydrate and its production and use, belong to organic Synthesis technical field.
Background technology
Not only toxicity is big for Phosphine ligands, and extremely sensitive to air, steam, and the condition for the catalytic reaction for making to be related to Phosphine ligands is different Often harsh, N-heterocyclic carbine is excellent electron donor, " imitative Phosphine ligands " is referred to as in catalytic reaction, in the reaction to sky Gas and water vapour is relatively stable.The Buchwald-Hartwig reactions of palladium/Phosphine ligands catalysis are the important channels for preparing C-N keys, generally It is considered what is carried out by Pd (0)/Pd (II) catalytic cycle, i.e., fragrant halogen first aoxidizes addition on zeroth order palladium, and following amine is in alkali In the presence of slough proton complete turn metallization, finally by reduction eliminate obtaining final arylamine product.2,2', 7,7'- tetra- The fluorenes (Spiro-OMeTAD) of [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells two and its derivative be a kind of perovskite too Positive one kind that can be in battery efficiently hole material and be widely used, document report is catalyzed by palladium/Phosphine ligands Buchwald-Hartwig reactions are prepared, in addition the synthesis step of Spiro-OMeTAD and its derivative complexity, product Component is more, not easy purification, low yield the shortcomings of, make its expensive, be ten times of the price of gold or so.So it is badly in need of exploitation Green, inexpensive, high catalytic activity, the new catalyst for being easily isolated purification.Double aza ring carbene precursor salts have double urge Change activated centre, be advantageous to the raising of aza ring carbene precursor salt catalytic activity.The introducing of glycosyl is not only increased on azacyclo- The steric hindrance of nitrogen-atoms, while multiple chiral centers are also introduced aza ring carbene precursor by the spatial chemistry that monose enriches Salt, the excellent aqueous solubility of monose, it is water-soluble that it also increases aza ring carbene precursor salt in organic solvents in particular while introducing Dissolubility in liquid, saccharide compound are considered as the desirable feedstock for preparing high performance catalyst, and it is additional can to greatly improve it Value, generally speaking, being introduced into of glycosyl improve the dissolubility in organic solvents in particular is water of aza ring carbene precursor salt with Catalytic activity.
The content of the invention
For in the prior art the defects of, it is an object of the invention to provide a kind of carbohydrate dinitrogen heterocyclic carbene precursors Salt and its production and use.
The present invention is achieved by the following technical solutions：
A kind of double aza ring carbene precursor salts of carbohydrate, its structure is shown in formula I：
A kind of preparation method of the double aza ring carbene precursor salts of carbohydrate as the aforementioned, it comprises the following steps：
By the 1- (- O- acetyl group-β-D- glucopyranosyls of 2,3,4,6- tetra-) imidazoles and 1,4- to benzyl dichloride anhydrous four In hydrogen furans, under inert gas shielding, back flow reaction, compound shown in Formula II is obtained；
By compound shown in Formula II and N- benzyl imidazoles in anhydrous tetrahydro furan, under inert gas shielding, back flow reaction, Obtain the double aza ring carbene precursor salts of the carbohydrate；
Reaction scheme is：
Preferably, 1- (2,3,4, the 6- tetra--O- acetyl group-β-D- glucopyranosyls) imidazoles and Isosorbide-5-Nitrae-right The mol ratio of benzyl dichloride is 1:The mol ratio of (1~5), compound shown in Formula II and N- benzyl imidazoles is 1:(1~5).
A kind of preparation method of the double aza ring carbene precursor salts of carbohydrate as the aforementioned, it comprises the following steps：
By N- benzyl imidazoles and Isosorbide-5-Nitrae-to benzyl dichloride in anhydrous tetrahydro furan, under inert gas shielding, back flow reaction, obtain To compound shown in formula III；
By compound shown in formula III with 1- (- O- acetyl group-β-D- the glucopyranosyls of 2,3,4,6- tetra-) imidazoles anhydrous In tetrahydrofuran, under inert gas shielding, back flow reaction, the double aza ring carbene precursor salts of the carbohydrate are obtained；
Reaction scheme is as follows：
Preferably, the N- benzyl imidazoles and Isosorbide-5-Nitrae-be 1 to the mol ratio of benzyl dichloride:(1~5)；Formula III chemical combination The mol ratio of thing and 1- (- O- acetyl group-β-D- the glucopyranosyls of 2,3,4,6- tetra-) imidazoles is 1:(1~5).
A kind of double aza ring carbene precursor salts of carbohydrate as the aforementioned are preparing Spiro-OMeTAD and its derivative In purposes, the structure of the Spiro-OMeTAD derivatives is as shown in formula IV：
Wherein, R1For H or OCH3, R2For H or OCH3, R3For H or OCH3。
The chiral source for being used as chiral catalyst by cheap and easy to get, spatial chemistry is abundant monose of the present invention, with two kinds Different methods has synthesized the double aza ring carbene precursor salts of carbohydrate, as urging for Buchwald-Hartwig reactions Agent, Spiro-OMeTAD and its derivative of the synthesis with application value realistic, overcome and prepare Spiro-OMeTAD and its spread out Biological step is complicated, product component is more, not easy purification, low yield the shortcomings of, be in particular in following aspect：
1st, the double aza ring carbene precursor salts of carbohydrate containing have good catalytic activity and three-dimensional selection to the reaction Property, efficiently can quickly catalyze and synthesize series has practical application in perovskite solar cell hole transport layer material field The Spiro-OMeTAD and its derivative of value；
2nd, there is the substrate of different substituents for the reaction, reaction can be smoothed out and show very high conversion Rate, show that the double aza ring carbene precursor salts of carbohydrate as catalyst, have good universality；
3rd, there is the substrate of passivation substituent for the reaction, also show higher conversion ratio herein, illustrate the catalyst With very high catalytic activity；
4th, the mild condition that the reaction is related to, the reaction time is short, and convenient post-treatment is quick, and yield is high；
5th, the reaction auxiliary chemicals dosage is small, and discharge is low, green, meets new and old kinetic energy conversion theory, have compared with High application value.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention Protection domain.
Embodiment 1
The present embodiment is related to a kind of preparation method of the double aza ring carbene precursor salts of carbohydrate, and it includes following step Suddenly：
First, 1.0mmol the 1- (- O- acetyl group-β-D- pyrroles of 2,3,4,6- tetra- are sequentially added in 50mL twoport round-bottomed flasks Glucopyranoside base) imidazoles 1 and 3.0mmol Isosorbide-5-Nitrae-to benzyl dichloride, react 3 hours in 10mL dry THFs, after reaction is complete, Stop reaction, post processing, column chromatography purification, obtain colorless viscous shape compound II, yield 89%,1H NMR(400MHz,CDCl3): δ=1.99 (s, 3H, CH3),2.00(s,3H,CH3),2.06(s,3H,CH3),2.08(s,3H,CH3), 4.17 (d, 1H, J= 12Hz), 4.27 (m, 1H), 4.33 (q, 1H, J=12.8Hz), 4.57 (s, 2H), 5.19-5.24 (m, 2H), 5.50 (t, 1H, J =9.5Hz), 5.64 (s, 2H), 6.49 (d, 1H, J=9.2Hz), 7.23 (s, 1H), 7.44 (m, 4H), 7.48 (s, 1H), 11.28(s,1H)；13C NMR(100MHz,CDCl3):δ=20.42,20.50,20.69,45.28,53.38,61.27, 67.41,70.76,72.18,75.09,84.17,119.22,122.01,129.29,129.70,132.75,138.70, 139.17,169.37,169.54,169.90,170.40；MS(ES):M/z (%)=609 (100) [M+Cl]- .Anal.Calcd. (%) for C25H30Cl2N2O9:C,52.36；H,5.27.Found:C,52.32；H,5.32；
2nd, 1.0mmol compound II and 1.5mmol N- benzyl miaows are sequentially added in 50mL twoport round-bottomed flasks Azoles, reacted 3 hours in 10mL dry THFs, after reaction completely, stop reaction, post processing, column chromatography purifies to obtain carbohydrate Double aza ring carbene precursor salts, yield 98%.1H NMR(400MHz,MeOD)δ9.70(s,1H),9.24(s,1H),7.91(d, J=1.7Hz, 1H), 7.85 (s, 1H), 7.74 (s, 1H), 7.61 (s, 1H), 7.47 (dd, J=7.7,1.6Hz, 2H), 7.39 (dt, J=12.8,4.3Hz, 3H), 6.06 (d, J=8.9Hz, 1H), 5.51 (t, J=9.4Hz, 1H), 5.46 (s, 2H), 5.44-5.37 (m, 1H), 5.28 (t, J=9.6Hz, 1H), 4.52-4.43 (m, 2H), 4.4-4.32 (m, 2H), 4.29 (dt, J =8.8,5.5Hz, 2H), 4.20 (t, J=7.0Hz, 1H), 2.64-2.45 (m, 2H), 2.01 (s, 3H), 2.01 (s, 3H), 1.97(s,3H),1.94(s,3H).13C NMR(101MHz,MeOD)δ170.79,169.83,169.75,169.68,136.08, 133.53,128.88,128.84,128.50,122.83,122.63,122.49,120.94,84.52,74.80,71.85, 71.39,67.50,61.36,52.81,29.93,19.28,19.09,19.02,18.97。
Embodiment 2
The present embodiment is related to a kind of preparation method of the double aza ring carbene precursor salts of carbohydrate, and it includes following step Suddenly：
First, 1.0mmol N- benzyl imidazoles and 3.0mmol 1,4- are sequentially added in 50mL twoport round-bottomed flasks to two Benzyl chloride, reacted 3 hours in 10mL dry THFs, after reaction completely, stop reaction, post processing, column chromatography purifies to obtain compound III, yield 90%.1H NMR(400MHz,CDCl3) δ 10.45 (s, 1H), 7.39 (s, 1H), 7.29 (d, J=8.0Hz, 2H), 7.25 (s, 1H), 7.22 (dd, J=6.4,2.8Hz, 2H), 7.04 (dd, J=6.7,3.7Hz, 5H), 5.34 (s, 2H), 5.27 (s,2H),4.25(s,2H)；
2nd, sequentially added in 50mL twoport round-bottomed flasks 1.0mmol compound III and 1.5mmol 1- (2,3,4, - O- acetyl group-β-D- the glucopyranosyls of 6- tetra-) imidazoles, reacts 3 hours in 10mL dry THFs, after reaction completely, stops Reaction, post processing, column chromatography purify to obtain the double aza ring carbene precursor salts of carbohydrate, yield 95%.1H NMR(400MHz, MeOD) δ 9.70 (s, 1H), 9.24 (s, 1H), 7.91 (d, J=1.7Hz, 1H), 7.85 (s, 1H), 7.74 (s, 1H), 7.61 (s, 1H), 7.47 (dd, J=7.7,1.6Hz, 2H), 7.39 (dt, J=12.8,4.3Hz, 3H), 6.06 (d, J=8.9Hz, 1H), 5.51 (t, J=9.4Hz, 1H), 5.46 (s, 2H), 5.44-5.37 (m, 1H), 5.28 (t, J=9.6Hz, 1H), 4.52-4.43 (m, 2H), 4.43-4.32 (m, 2H), 4.29 (dt, J=8.8,5.5Hz, 2H), 4.20 (t, J=7.0Hz, 1H), 2.64-2.45 (m,2H),2.01(s,3H),2.01(s,3H),1.97(s,3H),1.94(s,3H).13C NMR(101MHz,MeOD)δ 170.79,169.83,169.75,169.68,136.08,133.53,128.88,128.84,128.50,122.83,122.63, 122.49,120.94,84.52,74.80,71.85,71.39,67.50,61.36,52.81,29.93,19.28,19.09, 19.02,18.97。
Embodiment 3
The present embodiment is related to a kind of double aza ring carbene precursor salt catalysis of carbohydrate obtained using embodiment 1 The method of Buchwald-Hartwig reaction synthesis Spiro-OMeTAD derivatives, specifically comprises the following steps：
By the double aza ring carbene precursor salts (1.1mmol%) of carbohydrate, Pd2dba3(1mmol%), base agent NaOBut (6.0mmol), raw material V (8.0mmol) and VI (1.0mmol) are placed in 50mL twoport round-bottomed flasks, by displacement, are made System is full of nitrogen, then adds 10mL deoxidations toluene/water (V/V=3/1) with syringe, back flow reaction, is kept for 12 hours.It is cold But to room temperature, reaction mixture is poured into dry ethyl acetate, adds saturated aqueous common salt, washed three times, collected organic layer, MgSO4Dry, then be spin-dried for solvent with Rotary Evaporators.Gained solid is purified by column chromatography (ethyl acetate/n-hexane= 1:3) final product IV, is obtained, reaction scheme is as follows：
Embodiment 4
The present embodiment is related to a kind of double aza ring carbene precursor salt catalysis of carbohydrate obtained using embodiment 1 Buchwald-Hartwig, which reacts, synthesizes 2,2,2', 2', 7,7,7', 7'- eight [N, N- bis- (4- methoxyphenyls) amino] -9, The method of the fluorenes of 9'- spiral shells two (shown in formula IV -1), specifically comprises the following steps：
By the double aza ring carbene precursor salts (1.1mmol%) of carbohydrate, Pd2dba3(1mmol%), base agent NaOBut(6.0mmol), raw material 4,4'- dimethoxys diphenylamines (8.0mmol) and 2,2', 7, the 7'- tetra- bromo- fluorenes of 9,9'- spiral shells two (1.0mmol) is placed in 50mL twoport round-bottomed flasks, by displacement, system is full of nitrogen, then adds 10mL with syringe Deoxidation toluene/water (V/V=3/1), back flow reaction, kept for 12 hours.Room temperature is cooled to, reaction mixture is poured into dry second Acetoacetic ester, saturated aqueous common salt is added, washed three times, collected organic layer, MgSO4Dry, then be spin-dried for solvent with Rotary Evaporators. Gained solid is purified into (ethyl acetate/n-hexane=1 by column chromatography:3) final product IV-1, is obtained.
1H NMR(CDCl3, 400MHz) and δ=7.35 (d, 4H), 6.90 (d, 16H), 6.79 (br d, 4H), 6.75 (d, 16H),6.55(s,4H),3.76(s,24H).13C NMR(CDCl3, 100MHz) and δ=154.94,149.92,147.10, 141.44,135.45,124.95,122.66,119.71,118.02,114.30,65.44,55.41.m/z 1124(M+)。
Embodiment 5
The present embodiment is related to a kind of double aza ring carbene precursor salt catalysis of carbohydrate obtained using embodiment 1 Buchwald-Hartwig reaction synthesis 2,7,2', 7'- tetra- (3- methoxyphenyls) (4- methoxybenzenes of -2,7,2', 7'- tetra- Base)-the fluorenes of 9,9'- spiral shells two (shown in formula IV -2) method, specifically comprise the following steps：
By the double aza ring carbene precursor salts (1.1mmol%) of carbohydrate, Pd2dba3(1mmol%), base agent NaOBut(6.0mmol), raw material 3- methoxyl groups-N- (4- methoxyphenyls) aniline (8.0mmol) and 2,2', 7,7'- tetra- bromo- 9, The fluorenes of 9'- spiral shells two (1.0mmol) is placed in 50mL twoport round-bottomed flasks, by displacement, system is full of nitrogen, is then used syringe 10mL deoxidations toluene/water (V/V=3/1) is added, back flow reaction, is kept for 12 hours.Room temperature is cooled to, reaction mixture is poured into Dry ethyl acetate, adds saturated aqueous common salt, washes three times, collected organic layer, MgSO4Dry, then will with Rotary Evaporators Solvent is spin-dried for.Gained solid is purified into (ethyl acetate/n-hexane=1 by column chromatography:3) final product IV-2, is obtained.
1H NMR(CDCl3, 400MHz) and δ=7.41 (d, 4H), 7.04 (t, 4H), 6.96 (d, 8H), 6.87 (d, 4H), 6.80(d,8H),6.64(d,4H),6.29-6.50(m,12H).13C NMR(CDCl3, 100MHz) and δ=160.16,155.86, 129.79,149.36,146.582,140.44,136.18,129.43,126.79,123.97,120.07,119.17, 114.51,114.00,107.34,106.43,65.50,55.39,55.10.m/z 1124(M+)。
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow Ring the substantive content of the present invention.

Claims (6)

1. the double aza ring carbene precursor salts of a kind of carbohydrate, it is characterised in that structure is shown in formula I：
A kind of 2. preparation method of the double aza ring carbene precursor salts of carbohydrate as claimed in claim 1, it is characterised in that Comprise the following steps：
By the 1- (- O- acetyl group-β-D- glucopyranosyls of 2,3,4,6- tetra-) imidazoles and 1,4- to benzyl dichloride in anhydrous tetrahydrochysene furan Mutter, under inert gas shielding, back flow reaction, obtain compound shown in Formula II
By compound shown in Formula II and N- benzyl imidazoles in anhydrous tetrahydro furan, under inert gas shielding, back flow reaction, obtain The double aza ring carbene precursor salts of the carbohydrate.
3. the preparation method of the double aza ring carbene precursor salts of carbohydrate as claimed in claim 2, it is characterised in that described The 1- (- O- acetyl group-β-D- glucopyranosyls of 2,3,4,6- tetra-) imidazoles is 1 to the mol ratio of benzyl dichloride with 1,4-:(1~5), Compound shown in Formula II and the mol ratio of N- benzyl imidazoles are 1:(1~5).
A kind of 4. preparation method of the double aza ring carbene precursor salts of carbohydrate as claimed in claim 1, it is characterised in that Comprise the following steps：
By N- benzyl imidazoles and Isosorbide-5-Nitrae-to benzyl dichloride in anhydrous tetrahydro furan, under inert gas shielding, back flow reaction, formula is obtained Compound shown in III
By compound shown in formula III and 1- (- O- acetyl group-β-D- the glucopyranosyls of 2,3,4,6- tetra-) imidazoles in anhydrous tetrahydrochysene In furans, under inert gas shielding, back flow reaction, the double aza ring carbene precursor salts of the carbohydrate are obtained.
5. the preparation method of the double aza ring carbene precursor salts of carbohydrate as claimed in claim 4, it is characterised in that described N- benzyl imidazoles are 1 to the mol ratio of benzyl dichloride with 1,4-:(1~5)；Formula III compound and the 1- (- O- acetyl of 2,3,4,6- tetra- Base-β-D- glucopyranosyls) imidazoles mol ratio be 1:(1~5).
6. a kind of double aza ring carbene precursor salts of carbohydrate as claimed in claim 1 prepare Spiro-OMeTAD and its Purposes in derivative, the structure of the Spiro-OMeTAD derivatives is as shown in formula IV：
Wherein, R1For H or OCH3, R2For H or OCH3, R3For H or OCH3。
CN201710747341.9A 2017-08-23 2017-08-23 Double aza ring carbene precursor salts of carbohydrate and its production and use Pending CN107474090A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108929349A (en) * 2018-07-02 2018-12-04 赣南师范大学 The derivative benzoglioxaline salt of bromo-glucopyranose and its N-heterocyclic carbine palladium (II) complex preparation method and purposes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103228135A (en) * 2010-10-15 2013-07-31 新加坡科技研究局 An antimicrobial composition
CN105131042A (en) * 2015-07-22 2015-12-09 河南工业大学 Chelate-type N-heterocyclic carbene palladium compound containing heteroaromatic group and preparation method of same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103228135A (en) * 2010-10-15 2013-07-31 新加坡科技研究局 An antimicrobial composition
CN105131042A (en) * 2015-07-22 2015-12-09 河南工业大学 Chelate-type N-heterocyclic carbene palladium compound containing heteroaromatic group and preparation method of same

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
NAM JOONG JEON等: "o-Methoxy Substituents in Spiro-OMeTAD for Efficient Inorganic-Organic Hybrid Perovskite Solar Cells", 《J. AM. CHEM. SOC.》 *
SHEILA RUIZ-BOTELLA等: "Phenylene- and Biphenylene-Bridged Bis-Imidazolylidenes of Palladium. Influence of the Presence of Pyrene Tags on the Catalytic Activity of the Complexes", 《ORGANOMETALLICS》 *
YOSUKE IMANAKA等: "Incorporation of a Sugar Unit into a C-C-N Pincer Pd Complex Using Click Chemistry and Its Dynamic Behavior in Solution and Catalytic Ability toward the Suzuki-Miyaura Coupling in Water", 《CHEM. LETT.》 *
YOSUKE IMANAKA等: "Syntheses and Catalytic Ability of Sugar-Incorporated N-Heterocyclic Carbene Pincer Pd Complexes Possessing Various N-Substituents", 《BULL. CHEM. SOC. JPN.》 *
ZHONGGAO ZHOU等: "Green, Efficient and Reusable Bis(imidazolium) Ionic Liquids Promoted Pd-Catalyzed Aqueous Suzuki Reaction for Organic Functional Materials", 《CATALYSIS LETTERS》 *
ZHONGGAO ZHOU等: "Synthesis of Chiral Imidazolium Salts from a Carbohydrate and Their Application in Pd-Catalyzed Suzuki-Miyaura Reaction", 《CATAL LETT》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108929349A (en) * 2018-07-02 2018-12-04 赣南师范大学 The derivative benzoglioxaline salt of bromo-glucopyranose and its N-heterocyclic carbine palladium (II) complex preparation method and purposes

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