CN108929349A - The derivative benzoglioxaline salt of bromo-glucopyranose and its N-heterocyclic carbine palladium (II) complex preparation method and purposes - Google Patents
The derivative benzoglioxaline salt of bromo-glucopyranose and its N-heterocyclic carbine palladium (II) complex preparation method and purposes Download PDFInfo
- Publication number
- CN108929349A CN108929349A CN201810709612.6A CN201810709612A CN108929349A CN 108929349 A CN108929349 A CN 108929349A CN 201810709612 A CN201810709612 A CN 201810709612A CN 108929349 A CN108929349 A CN 108929349A
- Authority
- CN
- China
- Prior art keywords
- base
- glucose
- complex
- tetra
- acetyl group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 CCO[C@@]([C@](*C(*)=O)C(OCC*)O[C@@]1CO*C(C)=O)[C@@]1OC(*C)=O Chemical compound CCO[C@@]([C@](*C(*)=O)C(OCC*)O[C@@]1CO*C(C)=O)[C@@]1OC(*C)=O 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/26—Acyclic or carbocyclic radicals, substituted by hetero rings
-
- 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
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H23/00—Compounds containing boron, silicon, or a metal, e.g. chelates, vitamin B12
-
- 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
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
Abstract
The present invention provides a kind of bromination 1- [2- (2,3,4,6- tetra--O- acetyl group-β-D- glucopyranosyl oxygroup)-ethyl] -3-R base benzoglioxaline salt, structure is shown in formula I:Wherein, R is alkyl, benzyl or aryl.The present invention is by being naturally easy to get, chiral source of the spatial chemistry D-Glucose abundant as bromo-glucopyranose derivative benzoglioxaline salt and Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex, it is simple and fast with one kind, environmentally protective one kettle way route has synthesized a series of derivative benzoglioxaline salt of bromo-glucopyranoses and its Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex, using glucose benzimidazole type N-heterocyclic carbine palladium (II) complex as catalysis Suzuki coupling reaction catalyst, success has efficiently synthesized 9, 9- dibenzyl fluorenes is the organic conjugate small molecule material of parent nucleus.
Description
Technical field
The present invention relates to the derivative benzoglioxaline salt of a kind of bromo-glucopyranose and chiral glucose benzimidazole type azacyclo- cards
Guest's palladium (II) complex and its preparation method and application belongs to Organometallic Chemistry synthesis and transition metal-catalyzed research field.
Background technique
Saccharide compound and its derivative steric hindrance are huge, possess multiple chiral centers, are extraordinary natural chirals
Source, but only obtains seldom concern, the preparation route complexity and purification difficult of this and it have much relations [Chem.Eur.J.2007,
13,8648-8659；Coord.Chem.Rev.2010,254,2007-2030；Coord.Chem.Rev.2017,339, 1-
16].Currently, N-heterocyclic carbine (NHCs) ligand and its N-heterocyclic carbine palladium (NHCs-Pd) about chiral Derived from D-Glucose are matched
It closes object and [Organometallics 2010,29,5959-5971 has been reported；Eur.J.Inorg.Chem. 2007,2007,
2221-2224；J.Organomet.Chem.2007,692,4593-4602；Organometallics 2007, 26,1126-
1128；Organometallics 2010,29,403-408；Dalton Trans.2011,40,4826-4829； Dalton
Trans.2011,40,6778-6784；.Bull.Chem.Soc.Jpn.2017,90(1),59-67；Bull.Chem.
Soc.Jpn.2017,90(9),1050-1057].But what the method for synthesizing NHCs-Pd complex was all made of is two-step method, usually
It is that first synthesis NHCs-Ag complex shifts synthesis NHCs-Pd complex, not only severe reaction conditions, same time-division by NHCs again
From purification difficult, yield is not high, can not be mass produced, and this not only adds complexity, also brings uncertainty to reaction,
It is simultaneously imidazole type N-heterocyclic carbine.
Derived from D-Glucose chirality benzimidazole type azacyclo- card precursor imidazole salts are prepared in high yield here, having invented for the first time,
In addition it there is no the preparation method of the benzimidazole type NHCs-Pd complex about the group containing glucose, while having invented one kettle way
Prepare Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex, while by Derived from D-Glucose benzimidazole type azepine
Ring Cabbeen palladium (II) complex for palladium chtalyst Suzuki coupling reaction prepare 9,9- dibenzyl fluorenes for parent nucleus organic conjugate it is small
Molecular functional materials, the reaction is mild, product easy purification separates, and illustrates Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium
(II) complex is a kind of new and effective chiral N-heterocyclic carbine palladium catalyst.
Summary of the invention
For the defects in the prior art, the object of the present invention is to provide the derivative benzoglioxaline salt of a kind of bromo-glucopyranose and
Chiral glucose benzimidazole type N-heterocyclic carbine palladium (II) complex and its preparation method and application.
The present invention is achieved by the following technical solutions:
The present invention provides a kind of bromination 1- [2- (tetra--O- acetyl group-β-D- glucopyranosyl oxygroup of 2,3,4,6-)-
Ethyl] -3-R base benzoglioxaline salt, structure is shown in formula I:
Wherein, R is alkyl, benzyl or aryl.
A kind of bromination 1- as the aforementioned [2- (tetra--O- acetyl group-β-D- glucopyranosyl oxygroup of 2,3,4,6-)-second
Base] -3-R base benzoglioxaline salt preparation method comprising following steps:
In anhydrous tetrahydro furan, make 2- (2,3,4,6- tetra--O- acetyl group-β-D- glucopyranosyl oxygroup)-bromine second
Alkane and 1-R base benzimidazole heating carry out back flow reaction after, purified by column chromatography for separation, obtain the bromination 1- [2- (2,
Tetra--O- acetyl group-β-D- glucopyranosyl oxygroup of 3,4,6-)-ethyl] -3-R base benzoglioxaline salt.
Reaction route are as follows:
Preferably, 2- (2,3,4,6- tetra--O- acetyl group-β-D- glucopyranosyl the oxygroup)-bromoethane
Molar ratio with 1-R base benzimidazole is 1:(1~10).
A kind of Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex, structure is as shown in Formula II:
A kind of preparation method of Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex as the aforementioned, packet
Include following steps:
Under nitrogen protection, by [(2,3,4, the 6- tetra--O- acetyl group-β-D- pyrans Portugals 2- bromination 1- described in claim 1
Grape glycosyl oxygroup)-ethyl] -3-R base benzoglioxaline salt and palladium acetate and dry pyridine be dissolved in anhydrous tetrahydro furan, carry out
It after back flow reaction, is purified through column chromatography for separation, obtains Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) cooperation
Object.
Reaction route are as follows:
Preferably, the bromination 1- [2- (2,3,4,6- tetra--O- acetyl group-β-D- glucopyranosyl oxygroup)-
Ethyl] molar ratio of -3-R base benzoglioxaline salt and palladium acetate is 1:(1~10), bromination 1- [2- (2,3,4,6- tetra--O- acetyl
Base-β-D- glucopyranosyl oxygroup)-ethyl] molar ratio of -3-R base benzoglioxaline salt and pyridine is 1:(1~10).
A kind of Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex as the aforementioned is even in catalysis Suzuki
Purposes in the derivative conjugation small molecule functional material of connection reaction synthesis fluorenes.
Preferably, the structure of the derivative conjugation small molecule functional material of the fluorenes is as shown in formula III:
Wherein, Ar is with following substituent group H, 4-CH3-、3-CH3-、2-CH3-、4-C6H5-O、3-C6H5-O、 2-
C6H5The aromatic ring of-O, 4-F-, 3-F- or 2-F.Number before substituent group represents connection site of the substituent group on aromatic ring, such as 4-
CH3Methyl is represented to be connected on 4 carbon of aromatic ring (with the carbon that is connected on aromatic ring with fluorenyl as 1).
Reaction route are as follows:
The present invention by be naturally easy to get, spatial chemistry D-Glucose abundant as bromo-glucopyranose derivative benzoglioxaline salt
It is simple and fast with one kind with the chiral source of Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex, it is environmentally protective
One kettle way route synthesized a series of derivative benzoglioxaline salts of bromo-glucopyranoses and its Derived from D-Glucose benzimidazole type azepine
Ring Cabbeen palladium (II) complex, using glucose benzimidazole type N-heterocyclic carbine palladium (II) complex as catalysis Suzuki coupling
Catalysts, success have efficiently synthesized the organic conjugate small molecule material that 9,9- dibenzyl fluorenes is parent nucleus, have been in particular in
Following aspect:
1, the derivative benzoglioxaline salt of bromo-glucopyranose and Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) cooperation
The synthesis condition of object is mild, the reaction time is short, post-processing is convenient, high income；
2, one kettle way prepares Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex, and no extra condition alkali helps
Agent does not need to be separated purification, using only the pyridine and bromination 1- [2- (2,3,4,6- tetra--O- acetyl group-β-D- pyrans being coordinated with palladium
Glucosyl group oxygroup)-ethyl] -3-R base benzimidazole reactant salt, expensive intermediate steps have been saved, have kept operation simple,
Simplify post-processing, meets environmentally protective trend；
3, have containing chiral Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex to C-C coupling reaction good
Good catalytic activity and reaction selectivity efficiently can quickly catalyze and synthesize series in perovskite solar battery hole transmission layer
Research field and organic photoelectric diode research field have the small organic molecule hole mobile material of potential using value, described
Small molecule hole transport material is the compound that 9,9- dibenzyl fluorenes is parent nucleus；
4, there is the substrate of different substituents for the reaction, reaction can go on smoothly and show very high conversion
Rate shows that chiral Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex as catalyst, has good
Universality；
5, involved in the complex-catalyzed Suzuki reaction of Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II)
Reaction condition is mild, the time is short, post-processing is convenient, high income；
6, involved in the complex-catalyzed Suzuki reaction of Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II)
Auxiliary chemicals dosage is small, and discharge is low, environmentally protective, meets new and old kinetic energy conversion theory, application value with higher.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the mass spectrogram of the catalysis reaction solution obtained after 5 coupling reaction of embodiment in the present invention；
Fig. 2 is the mass spectrogram of the catalysis reaction solution obtained after 6 coupling reaction of embodiment in the present invention；
Fig. 3 is the mass spectrogram of the catalysis reaction solution obtained after 7 coupling reaction of embodiment in the present invention；
Fig. 4 is the mass spectrogram of the catalysis reaction solution obtained after 8 coupling reaction of embodiment in the present invention.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
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 scope.
Embodiment 1
The present embodiment is related to a kind of preparation method of derivative benzoglioxaline salt of chiral bromo-glucopyranose comprising following step
It is rapid:
Bromination 2- (tetra--O- acetyl group-β-the D- of 2,3,4,6- of 1.0mmol is sequentially added in 50mL twoport round-bottomed flask
Glucopyranosyl oxygroup)-bromoethane, the N- benzyl benzimidazole of 2.0mmol, vigorous reflux is reacted in 10mL dry THF
12 hours, thin-layer chromatography tracked (methylene chloride: methanol=20:1), after fully reacting, stopped reaction, post-processing, column chromatography mentions
Pure (methylene chloride: methanol=20:1), obtains yellow, viscous compound I-1, yield 91%,1H NMR(400MHz,CDCl3)δ
0.92(s,3H),1.17(s,3H),1.21(s,3H),1.25(s,3H),3.00 (m,1H),3.30(dd,J1=12.0Hz, J2
=2.2Hz, 1H), 3.38 (dd, J1=12.4Hz, J2=4.6Hz, 1H), 3.52 (m, 1H), 3.64 (m, 1H), 3.90 (d, J=
8.0Hz, 1H), 4.04 (t, J=8.0Hz, 1H), 4.16 (m, 2H), 4.25 (m, 1H), 4.36 (t, J=8.0Hz, 1H), 5.04
(d, J=1.6Hz, 2H), 6.59 (m, 3H), 6.76 (m, 5H), 7.09 (d, J=8.0Hz, 1H), 10.03 (s, 1H)13C NMR
(100MHz,CDCl3)δ 20.2,20.3,20.4,20.6,47.6,51.4,61.5,67.9,68.9,70.8,71.7,72.5,
100.1,113.1,114.2, 126.8,127.0,128.1,129.1,129.2,130.6,132.2,132.4,142.7,
169.3,169.4,169.8,170.5. MS (ESI): m/z (%)=664.51 (100) [M+1]+；Its structure such as -1 institute of Formulas I
Show:
Embodiment 2
The present embodiment is related to a kind of preparation method of derivative benzoglioxaline salt of chiral bromo-glucopyranose comprising following step
It is rapid:
Bromination 2- (tetra--O- acetyl group-β-the D- of 2,3,4,6- of 1.0mmol is sequentially added in 50mL twoport round-bottomed flask
Glucopyranosyl oxygroup)-bromoethane, the N- decyl benzimidazole of 2.0mmol, vigorous reflux is reacted in 10mL dry THF
12 hours, thin-layer chromatography tracked (methylene chloride: methanol=20:1), after fully reacting, stopped reaction, post-processing, column chromatography mentions
Pure (methylene chloride: methanol=20:1), obtains yellow, viscous compound I-2, yield 95%,1H NMR(400MHz,CDCl3)δ
0.49 (t, J=8.0Hz, 3H), 0.88-0.96 (br, 10H), 1.07 (m, 4H), 1.40 (m, 4H), 1.45 (s, 3H), 1.60
(s, 3H), 1.64 (s, 3H), 1.70 (s, 3H), 1.73 (m, 2H), 3.52 (m, 1H), 3.75 (d, J=12.0Hz, 1H), 3.86
(dd,J1=12.4Hz, J2=4.0Hz, 1H), 3.92 (m, 1H), 4.05 (m, 1H), 4.26 (t, J=8.0Hz, 2H), 4.41
(d, J=8.0Hz, 1H), 4.49 (t, J=8.0Hz, 1H), 4.62 (t, J=10.0Hz, 1H), 4.68 (m, 2H), 4.80 (t, J
=9.2Hz, 1H), 5.02 (s, 1H), 7.31 (m, 2H), 7.48 (m, 1H), 7.66 (d, J=8.0Hz, 1H), 10.10 (s,
1H).13C NMR(100MHz,CDCl3) δ13.2,19.5,19.6,19.7,19.9,21.7,25.6,28.1,28.2,28.3,
28.4,28.5,30.9,46.8,46.9, 48.8,53.0,60.8,67.0,67.2,70.1,70.9,71.7,99.4,112.0,
113.6,126.2,126.3,130.1,131.1,141.5,168.5,168.6,168.9,16 9.6.MS (ESI): m/z (%)
=714.76 (100) [M+1]+；Its structure is as shown in Formulas I -2:
Embodiment 3
The present embodiment is related to a kind of preparation of chiral Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex
Method comprising following steps:
Bromination 1- [2- (tetra--O- acetyl group-the β of 2,3,4,6--of 1.0mmol is sequentially added in 50mL twoport round-bottomed flask
D- glucopyranosyl oxygroup)-ethyl] -3- allyl benzene benzimidazole salt, the palladium acetate of 1.0mmol, 3.0mmol drying pyrrole
Pyridine, vigorous reflux is reacted 4 hours in 10mL dry THF, and thin-layer chromatography tracks (methylene chloride: methanol=20:1), has been reacted
Quan Hou stops reaction, post-processing, and column Chromatographic purification (methylene chloride: methanol=20:1) obtains yellow, viscous compound II-1,
Yield 92%,1H NMR(400MHz,CDCl3)δ1.89(s,3H),1.93(s, 3H),1.97(s,3H),2.02(s,3H),
3.65 (m, 1H), 4.03 (m, 2H), 4.22 (m, 1H), 4.56 (m, 2H), 4.70 (m, 1H), 4.85 (m, 2H), 5.01 (t, J=
8.0Hz), 5.07 (t, J=8.0Hz), 5.23 (t, J=8.0Hz), 6.11 (d, J=3.3Hz), 6.94 (d, J=8.0Hz,
1H), 7.03 (t, J=8.0Hz, 1H), 7.28 (m, 5H), 7.42 (d, J=4.0Hz, 2H), 7.70 (t, J=8.0Hz, 1H),
8.98(m,2H).13C NMR(100MHz,CDCl3) δ14.2,20.1,20.4,20.5,20.7,21.0,48.2,51.8,
60.3,61.7,68.1,69.0,71.0,71.6,72.9, 100.7,110.5,111.5,119.6,123.0,123.5,
124.6,131.8,133.8,135.8,138.1,152.4,162.7, 169.0,169.3,170.0,170.5,171.0.MS
(ESI): m/z (%)=878.88 (100) [M+1]+；Its structure is as shown in Formula II -1:
Embodiment 4
The present embodiment is related to a kind of preparation method of chiral glucose benzimidazole type N-heterocyclic carbine palladium (II) complex,
It includes the following steps:
Bromination 1- [2- (tetra--O- acetyl group-the β of 2,3,4,6--of 1.0mmol is sequentially added in 50mL twoport round-bottomed flask
D- glucopyranosyl oxygroup)-ethyl] -3- benzyl benzimidazole salt, the palladium acetate of 1.0mmol, 3.0mmol drying pyrrole
Pyridine, vigorous reflux is reacted 4 hours in 10mL dry THF, and thin-layer chromatography tracks (methylene chloride: methanol=20:1), has been reacted
Quan Hou stops reaction, post-processing, and column Chromatographic purification (methylene chloride: methanol=20:1) obtains yellow, viscous compound II-2,
Yield 94%.1H NMR(400MHz,CDCl3)δ1.89(s,3H),1.93(s,3H),1.97(s, 3H),2.02(s,3H),
3.65 (m, 1H), 4.03 (m, 2H), 4.22 (m, 1H), 4.56 (m, 2H), 4.70 (m, 1H), 4.85 (m, 2H), 5.01 (t, J=
8.0Hz), 5.07 (t, J=8.0Hz), 5.23 (t, J=8.0Hz), 6.11 (d, J=3.3Hz), 6.94 (d, J=8.0Hz,
1H), 7.03 (t, J=8.0Hz, 1H), 7.28 (m, 5H), 7.42 (d, J=4.0 Hz, 2H), 7.70 (t, J=8.0Hz, 1H),
8.98(m,2H).13C NMR(100MHz,CDCl3)δ14.2, 20.1,20.5,20.6,20.8,21.0,48.3,53.6,
60.3,61.7,68.1,69.0,71.1,71.6,72.9,100.7, 111.0,111.5,123.0,123.5,124.7,
128.0,128.2,128.8,133.8,134.7,136.1,138.2,151.9, 152.5,163.4,169.1,169.3,
170.6,171.0.MS (ESI): m/z (%)=928.91 (100) [M+1]+；Its structure is as shown in Formula II -2:
Embodiment 5
The present embodiment is related to a kind of chiral Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium obtained using embodiment 3
(II) complex II-1 is catalyzed the method that Suzuki coupling reaction prepares the derivative small molecule material of fluorenes, specifically comprises the following steps:
By chiral Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex (0.01mmol%), base agent
K2CO3(4.0mmol), 9,9- dibenzyl -2,7- dibromo fluorenes (1.0mmol) and phenyl boric acid (4.0mmol) are placed in 50mL twoport circle
In the flask of bottom, by displacement, makes system full of nitrogen, 10mL deoxidation acetone/water (V/V=5/1) then is added, is heated to 90
DEG C, it being kept for 0.5 hour, stops reaction, be spin-dried for, be extracted with ethyl acetate, distillation washing collects organic phase repeatedly three times,
It is spin-dried for, column Chromatographic purification (ethyl acetate/petroleum ether=20/1-10/1), obtains final product III-1, yield 95%,1HNMR
(400MHz,CDCl3) δ 8.24 (dd, J=13.0,5.9Hz, 4H), 8.00-7.83 (m, 4H), 7.73-7.42 (m, 12H),
7.01 (d, J=5.9Hz, 6H), 6.89 (d, J=7.4Hz, 4H), 3.57 (s, 4H)13C NMR(101MHz,CDCl3)δ
149.21,140.56,139.68,139.00,138.85,137.66, 136.92,136.32,135.91,130.41,
127.54,127.27,126.99,126.88,126.03,125.16,124.63, 124.47,122.72,121.83,
120.43,120.19,57.56,45.68.MS (ESI): m/z (%)=499.7 (100) [M+1]+。
Reaction route are as follows:
The product species that coupling reaction obtains in the present embodiment can be carried out by carrying out mass spectral analysis in situ to reaction solution
Judgement, mass spectrogram only detect Suzuki coupling reaction as shown in Figure 1, by carrying out Mass Spectrometer Method in situ to catalysis reaction solution
Product III-1's, its molecular ion peak i.e. 499.7 [M+1] as we can see from the figure+, by not detecting to mass spectrogram analysis
To aryl boric acid self-coupling reaction product and dehalogenated product, illustrate that catalysis reaction has selectivity well, only Suzuki
Coupling reaction product.
Embodiment 6
The present embodiment is related to a kind of chiral Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium obtained using embodiment 3
(II) method that complex II-1 is catalyzed the derivative small molecule material of fluorenes, specifically comprises the following steps:
By chiral Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex (0.01mmol%), base agent
K2CO3(4.0mmol), 9,9- dibenzyl -2,7- dibromo fluorenes (1.0mmol) and 4- (ethoxy carbonyl) phenyl boric acid (4.0 mmol)
It is placed in 50mL twoport round-bottomed flask, by displacement, makes system full of nitrogen, 10mL deoxidation acetone/water (V/V=is then added
5/1) it, is heated to 90 DEG C, is kept for 0.5 hour, stop reaction, be spin-dried for, be extracted with ethyl acetate, distillation washing, repeatedly three
It is secondary, organic phase is collected, is spin-dried for, column Chromatographic purification (ethyl acetate/petroleum ether=20/1-10/1) obtains final product III-2, produces
Rate 97%,1H NMR(400MHz,CDCl3) δ 8.18 (d, J=8.2Hz, 4H), 7.71 (d, J=8.3Hz, 4H), 7.59 (s,
2H), 7.56-7.45 (m, 4H), 7.03 (dt, J=20.8,7.0Hz, 6H), 6.79 (d, J=7.2Hz, 4H), 4.46 (q, J=
7.1Hz, 4H), 3.47 (s, 4H), 1.46 (t, J=7.1 Hz, 6H)13C NMR(101MHz,CDCl3)δ166.56,149.67,
145.75,140.29,138.19,137.09, 130.41,130.15,129.16,127.41,127.21,126.92,
126.61,126.23,123.60,120.44,61.02,56.78, 45.36,14.43.MS (ESI): m/z (%)=642.8
(100)[M+1]+。
Reaction route are as follows:
The product species that coupling reaction obtains in the present embodiment can be carried out by carrying out mass spectral analysis in situ to reaction solution
Judgement, mass spectrogram only detect Suzuki coupling reaction as shown in Fig. 2, by carrying out Mass Spectrometer Method in situ to catalysis reaction solution
Product III-2's, its molecular ion peak i.e. 624.8 [M+1] as we can see from the figure+, by not detecting to mass spectrogram analysis
To aryl boric acid self-coupling reaction product and dehalogenated product, illustrate that catalysis reaction has selectivity well, only Suzuki
Coupling reaction product.
Embodiment 7
The present embodiment is related to a kind of chiral Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium obtained using embodiment 4
(II) method that complex II-2 is catalyzed the derivative small molecule material of fluorenes, specifically comprises the following steps:
By chiral Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex (0.01mmol%), base agent
K2CO3(4.0mmol), 9,9- dibenzyl -2,7- dibromo fluorenes (1.0mmol) and 4- (diphenyl amino) phenyl boric acid (4.0 mmol)
It is placed in 50mL twoport round-bottomed flask, by displacement, makes system full of nitrogen, 10mL deoxidation acetone/water (V/V=is then added
5/1) it, is heated to 90 DEG C, is kept for 0.5 hour, stop reaction, be spin-dried for, be extracted with ethyl acetate, distillation washing, repeatedly three
It is secondary, organic phase is collected, is spin-dried for, column Chromatographic purification (ethyl acetate/petroleum ether=20/1-10/1) obtains final product III-3, produces
Rate 96%,1H NMR(400MHz,CDCl3) δ 7.54 (d, J=8.4Hz, 6H), 7.46 (s, 4H), 7.30 (t, J=7.7Hz,
8H), 7.19 (t, J=6.5Hz, 12H), 7.06 (t, J=7.3 Hz, 4H), 7.03-6.92 (m, 6H), 6.78 (d, J=
7.2Hz,4H),3.43(s,4H).13C NMR(101MHz, CDCl3)δ149.27,147.77,147.08,139.42,
138.52,137.26,135.62,130.40,129.30,127.70, 127.26,126.01,125.79,124.41,
124.07,122.93,122.81,119.94,56.65,45.52.MS (ESI): m/z (%)=834.1 (100) [M+1]+。
Reaction route are as follows:
The product species that coupling reaction obtains in the present embodiment can be carried out by carrying out mass spectral analysis in situ to reaction solution
Judgement, mass spectrogram only detect Suzuki coupling reaction as shown in figure 3, by carrying out Mass Spectrometer Method in situ to catalysis reaction solution
Product III-3's, its molecular ion peak i.e. 834.1 [M+1] as we can see from the figure+, by not detecting to mass spectrogram analysis
To aryl boric acid self-coupling reaction product and dehalogenated product, illustrate that catalysis reaction has selectivity well, only Suzuki
Coupling reaction product.
Embodiment 8
The present embodiment is related to a kind of chiral Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium obtained using embodiment 4
(II) method that complex II-2 is catalyzed the derivative small molecule material of fluorenes, specifically comprises the following steps:
By chiral Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex (0.01mmol%), base agent
K2CO3(4.0mmol), 9,9- dibenzyl -2,7- dibromo fluorenes (1.0mmol) and 4- (9H- carbazole -9- base) phenyl boric acid (4.0
Mmol it) is placed in 50mL twoport round-bottomed flask, by displacement, makes system full of nitrogen, 10mL deoxidation acetone/water is then added
(V/V=5/1), 90 DEG C are heated to, is kept for 0.5 hour, stops reaction, is spin-dried for, is extracted with ethyl acetate, distillation washing, so
Repeatedly for three times, organic phase is collected, is spin-dried for, column Chromatographic purification (ethyl acetate/petroleum ether=20/1-10/1) obtains final product
III-4, yield 97%,1H NMR(400MHz,CDCl3) δ 8.20 (d, J=7.8Hz, 4H), 7.90 (d, J=8.2Hz, 4H),
7.77-7.68 (m, 6H), 7.61 (q, J=8.0Hz, 4H), 7.55 (d, J=8.2Hz, 4H), 7.48 (t, J=7.6Hz, 4H),
7.34 (t, J=7.4Hz, 4H), 7.05 (q, J=6.0Hz, 6H), 6.86 (d, J=6.8Hz, 4H), 3.54 (s, 4H)13C
NMR(101MHz,CDCl3)δ149.61,140.97,140.61, 140.04,138.37,137.17,136.84,130.42,
128.43,127.43,127.39,126.40,126.17,125.99, 123.51,123.40,120.36,120.02,
109.87,56.90,45.57.MS (ESI): m/z (%)=830.1 (100) [M+1]+。
Reaction route are as follows:
The product species that coupling reaction obtains in the present embodiment can be carried out by carrying out mass spectral analysis in situ to reaction solution
Judgement, mass spectrogram only detect Suzuki coupling reaction as shown in figure 4, by carrying out Mass Spectrometer Method in situ to catalysis reaction solution
Product III-4's, its molecular ion peak i.e. 830.1 [M+1] as we can see from the figure+, by not detecting to mass spectrogram analysis
To aryl boric acid self-coupling reaction product and dehalogenated product, illustrate that catalysis reaction has selectivity well, only Suzuki
Coupling reaction product.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to 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 substantive content of the invention.
Claims (8)
1. a kind of bromination 1- [2- (tetra--O- acetyl group-β-D- glucopyranosyl oxygroup of 2,3,4,6-)-ethyl] -3-R base benzo
Imidazole salts, which is characterized in that structure is shown in formula I:
Wherein, R is alkyl, benzyl or aryl.
2. a kind of bromination 1- as described in claim 1 [2- (tetra--O- acetyl group-β-D- glucopyranosyl oxygen of 2,3,4,6-
Base)-ethyl] -3-R base benzoglioxaline salt preparation method, which comprises the steps of:
In anhydrous tetrahydro furan, make 2- (2,3,4,6- tetra--O- acetyl group-β-D- glucopyranosyl oxygroup)-bromoethane and
After the heating of 1-R base benzimidazole carries out back flow reaction, is purified by column chromatography for separation, obtain the bromination 1- [2- (2,3,4,6-
Four-O- acetyl group-β-D- glucopyranosyl oxygroups)-ethyl] -3-R base benzoglioxaline salt.
3. bromination 1- [2- (tetra--O- acetyl group-β-D- glucopyranosyl oxygroup of 2,3,4,6-)-second as claimed in claim 2
Base] -3-R base benzoglioxaline salt I preparation method, which is characterized in that 2- (2,3,4, the 6- tetra--O- acetyl group-β-D- pyrans
Glucosyl group oxygroup) molar ratio of-bromoethane and 1-R base benzimidazole is 1:(1~10).
4. a kind of Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex, which is characterized in that structure such as Formula II institute
Show:
5. a kind of preparation side of Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex as claimed in claim 4
Method, which comprises the steps of:
Under nitrogen protection, by bromination 1- described in claim 1 [2- (2,3,4,6- tetra--O- acetyl group-β-D- glucopyranoses
Base oxygroup)-ethyl] -3-R base benzoglioxaline salt and palladium acetate and dry pyridine be dissolved in anhydrous tetrahydro furan, flow back
It after reaction, is purified through column chromatography for separation, obtains Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex.
6. the preparation side of Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex II as claimed in claim 5
Method, which is characterized in that the bromination 1- [2- (2,3,4,6- tetra--O- acetyl group-β-D- glucopyranosyl oxygroup)-ethyl]-
The molar ratio of 3-R base benzoglioxaline salt and palladium acetate is 1:(1~10), bromination 1- [2- (2,3,4,6- tetra--O- acetyl group-β-D-
Glucopyranosyl oxygroup)-ethyl] molar ratio of -3-R base benzoglioxaline salt and pyridine is 1:(1~10).
7. a kind of Derived from D-Glucose benzimidazole type N-heterocyclic carbine palladium (II) complex as claimed in claim 4 is being catalyzed
Suzuki coupling reaction synthesizes the purposes in the derivative conjugation small molecule functional material of fluorenes.
8. purposes as claimed in claim 7, which is characterized in that the structure such as formula of the derivative conjugation small molecule functional material of the fluorenes
Shown in III:
Wherein, Ar is with following substituent group H, 4-CH3-、3-CH3-、2-CH3-、4-C6H5-O-、3-C6H5-O-、2-C6H5-
The aromatic ring of O-, 4-F-, 3-F- or 2-F.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810709612.6A CN108929349A (en) | 2018-07-02 | 2018-07-02 | The derivative benzoglioxaline salt of bromo-glucopyranose and its N-heterocyclic carbine palladium (II) complex preparation method and purposes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810709612.6A CN108929349A (en) | 2018-07-02 | 2018-07-02 | The derivative benzoglioxaline salt of bromo-glucopyranose and its N-heterocyclic carbine palladium (II) complex preparation method and purposes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108929349A true CN108929349A (en) | 2018-12-04 |
Family
ID=64447244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810709612.6A Pending CN108929349A (en) | 2018-07-02 | 2018-07-02 | The derivative benzoglioxaline salt of bromo-glucopyranose and its N-heterocyclic carbine palladium (II) complex preparation method and purposes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108929349A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942656A (en) * | 2019-03-27 | 2019-06-28 | 赣南师范大学 | Based on the chiral Pd nano particle and preparation method thereof that glucose N-heterocyclic carbine is stable |
| JP2020164518A (en) * | 2019-03-26 | 2020-10-08 | 大阪ガスケミカル株式会社 | Fluorene compound and method for producing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474089A (en) * | 2017-08-23 | 2017-12-15 | 赣南师范大学 | Chiral glucose bidentate aza ring carbene precursor salt and its production and use |
| CN107474090A (en) * | 2017-08-23 | 2017-12-15 | 赣南师范大学 | Double aza ring carbene precursor salts of carbohydrate and its production and use |
| CN107501372A (en) * | 2017-09-07 | 2017-12-22 | 赣南师范大学 | Chiral N-heterocyclic carbine gold compound and its production and use |
-
2018
- 2018-07-02 CN CN201810709612.6A patent/CN108929349A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474089A (en) * | 2017-08-23 | 2017-12-15 | 赣南师范大学 | Chiral glucose bidentate aza ring carbene precursor salt and its production and use |
| CN107474090A (en) * | 2017-08-23 | 2017-12-15 | 赣南师范大学 | Double aza ring carbene precursor salts of carbohydrate and its production and use |
| CN107501372A (en) * | 2017-09-07 | 2017-12-22 | 赣南师范大学 | Chiral N-heterocyclic carbine gold compound and its production and use |
Non-Patent Citations (3)
| Title |
|---|
| EMINE ÖZGE KARACA，等: "Pd-N-Heterocyclic carbene catalysed Suzuki-Miyaura coupling reactions in aqueous medium", 《ARKIVOC》 * |
| ZHONGGAO ZHOU，等: "Synthesis of Chiral Imidazolium Salts from a Carbohydrate and Their Application in Pd-Catalyzed Suzuki–Miyaura Reaction", 《CATAL. LETT.》 * |
| 周中高，等: "葡糖衍生手性N-杂环卡宾前体波谱学数据分析", 《波谱学杂志》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020164518A (en) * | 2019-03-26 | 2020-10-08 | 大阪ガスケミカル株式会社 | Fluorene compound and method for producing the same |
| CN109942656A (en) * | 2019-03-27 | 2019-06-28 | 赣南师范大学 | Based on the chiral Pd nano particle and preparation method thereof that glucose N-heterocyclic carbine is stable |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Du et al. | A general and efficient synthesis of substituted furans and dihydrofurans via gold-catalyzed cyclization of (Z)-2-en-4-yn-1-ols | |
| US9434665B2 (en) | Ruthenium complex and method for preparing methanol and diol | |
| CN106749139B (en) | Polysubstituted condensed benzofuran derivative of one kind and preparation method thereof | |
| CN103772297B (en) | Chirality six-membered heterocycle carbene precursor compound and its preparation method and application | |
| CN105838104A (en) | Thiophene and pyrrole quinoid compound and preparation method thereof | |
| CN108929349A (en) | The derivative benzoglioxaline salt of bromo-glucopyranose and its N-heterocyclic carbine palladium (II) complex preparation method and purposes | |
| CN112480130A (en) | Macrocyclic extended porphyrin compounds and methods of making the same | |
| CN106243105A (en) | Methylene-bridged 1,8 naphthyridines part and copper (I) coordination compound, preparation method and application | |
| Yang et al. | Abnormal bis-NHC mediated aerial oxidation of arylaldehydes: highly efficient transformation of arylaldehydes to the corresponding carboxylic acids catalyzed by organic catalysts | |
| CN102718768B (en) | Chiral five-membered bicyclic guanidine compound, preparation method and application thereof | |
| CN108821975B (en) | Hydrogenated phenanthrene derivative containing exocyclic double bond and preparation method thereof | |
| CN100482644C (en) | Chiral diene ligand, synthesis method and its application in asymmetric reaction | |
| CN102030721B (en) | Method for synthesizing chiral benzosultam via palladium-catalytic asymmetric hydrogenation | |
| CN105017150B (en) | A kind of method of the outer amine of the amine asymmetric hydrogenation synthesis of chiral ring of palladium chtalyst quinoline 3 | |
| CN108586558A (en) | Carbohydrate alkyl bond connects imidazole type N-heterocyclic carbine palladium complex and its preparation method and application | |
| CN106008346B (en) | A kind of method of palladium chtalyst synthesis aromatic aldehyde under normal pressure | |
| CN103145769B (en) | Bis-cyclometallated compound of heteronuclear ruthenium palladium and its preparation method and application | |
| CN103724151A (en) | Method for synthesizing 9-aryl fluorene compound | |
| CN102153483B (en) | Axial chirality vicinal diamine compound and preparation method thereof | |
| CN111100124B (en) | Linear o-phenanthroline compound and preparation method and application thereof | |
| Meng et al. | Metal-free access to 3-allyl-2-alkoxychromanones via phosphine-catalyzed alkoxy allylation of chromones with MBH carbonates and alcohols | |
| CN111303096B (en) | Synthesis method of polysubstituted 1, 3-dihydronaphtho [2,3-c ] furan derivative | |
| CN104803829B (en) | A kind of method of asymmetric syntheses chirality diarylcarbinols | |
| CN110283040B (en) | Synthetic method of 3-methyl-D3-benzyl bromide | |
| CN108101755A (en) | A kind of method for preparing chiral 4- (2- propargyls) phenol compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181204 |
|
| RJ01 | Rejection of invention patent application after publication |