CN104910076B - The preparation of bis-benzimidazole salt and its application in intramolecular coupling reaction - Google Patents
The preparation of bis-benzimidazole salt and its application in intramolecular coupling reaction Download PDFInfo
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- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/12—Radicals substituted by oxygen atoms
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- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
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Abstract
The invention discloses the preparation of bis-benzimidazole salt and its application in intramolecular coupling reaction.It is preparation method and its palladium chtalyst C C coupling reaction of the bis-benzimidazole salt by xenol bridging.With benzimidazole in the present invention, 2,2 ' xenols, 2-chloroethyl alcohol, thionyl chloride etc. is Material synthesis double-benzimidazoles part, using the slaine of palladium, part is carried out with catalysis and obtain intramolecular C C coupling compound, to studying intramolecular coupling reaction under catalyzing by metal palladium for such bis-benzimidazole salt.Have and prepare succinct, catalytic effect clear advantage, can be used to synthesize the biaryl unit containing benzimidazole, the coupling field in catalytic molecular that is expected to is applied.
Description
With regard to subsidizing the statement of research or exploitation
The present invention is in state natural sciences fund（Fund number is 21172172）, Tianjin Natural Science Fund In The Light（Fund
Number be 11JCZDJC22000）, Tianjin innovation team of institution of higher education training plan（Fund number is TD12-5038）With Tianjin teacher
Model university research for application and development fund (fund number：Carry out under 52XK1202) subsidizing.
Technical field
The invention belongs to organic synthesiss and Molecular modelling technical field, it is related to the bis-benzimidazole salt of xenol bridging
Synthesis, and the intramolecular C-C coupling reaction of its generation under palladium salt catalysis.In particular it is the double benzene containing xenol bridging
And the research of the preparation method as precursor for the imidazoles and its intramolecular C-C coupling reaction.
Background technology
Coupling reaction is that two molecules are passed through the process that reaction forms a recruit.And form new carbon-carbon bond and exist
It is extremely important in organic chemistry.In organic substances such as synthetic drug, plastics, need carbon atom with little organic molecule
Link together and build new complicated macromole, thus in organic synthesiss, the efficient method connecting carbon-carbon bond is organic synthesiss
Important tool in chemistry.Because carbon atom chemical property torpescence, it is difficult between carbon atom to be combined with each other, so being related to two
Chemical reaction between individual carbon atom, condition requires will be harsher.With, 20 generation further deep to the research of organic synthesiss
Record the later stage, scientists are found that a large amount of reactions to create new organic molecule by transition metal-catalyzed, promote organic synthesiss
Chemistry is fast-developing.
It is known that transition metal-catalyzed C-C coupling reaction is widely used in organic synthesiss and industry.Urge numerous
In agent, the catalyst based on Metal Palladium is building C-C key, plays important role in C-N key and other C- heteroatomic bonds.
The cross-coupling reaction of palladium chtalyst is one of the most efficient method, and is widely used in synthesis biaryl unit.Palladium chtalyst is even
In the study on the synthesis of natural product, the aspect such as pharmaceuticals industry and new material synthesis is all widely used for connection reaction.Existing at present
Lot of documents reports using palladium catalysed cross coupling reaction synthesising macromolecule copolymer, feature complicated molecule etc..Benzoglioxaline salt
Because it is in Organic Light Emitting Diode, ionic liquid, fluorescence identifying, the application in the field such as battery and cell and receive much concern.
Content of the invention
It is an object of the invention to provide by the bisbenzimidazole of xenol bridging as precursor intramolecular coupling
Compound.
The present invention also relates to the method preparing such intramolecular coupling compound precursor.
The present invention has further related to the method preparing such intramolecular coupling compound simultaneously, and carries out crystallography table to it
Levy.
The present invention relates to the crystal of such intramolecular coupling compound form method, the research of measurement data data.
Intramolecular coupling compound involved in the present invention is all to be obtained by the method culture spread or volatilize.
Intramolecular coupling compound in the present invention is all measured data by x-ray diffractometer and characterizes.
The present invention further discloses the bis-benzimidazole salt part of xenol bridging in intramolecular coupling compound
The application of aspect processed.
For completing above-mentioned items goal of the invention, technical solution of the present invention is as follows：
The invention discloses a kind of bis-benzimidazole salt part with xenol bridging, it has following structure：
The present invention further discloses the preparation method of described intramolecular coupling compound it is characterised in that：
（1）In organic solvent 2,2 '-xenol, potassium carbonate are protected in nitrogen and stirred 0.5 h under 50 C, then slowly
Deca 2-chloroethyl alcohol；Mixed solution reacts 24 h in 110 C, and post processing obtains 2,2 '-and bis-（2- ethoxy）The white of biphenyl
Solid；
（2）In organic solvent by 2,2 '-bis-（2- ethoxy）Biphenyl and pyridine are uniformly mixed, then slowly Deca
Thionyl chloride；Mixed solution reacts 6 h in 70 C, and post processing obtains 2,2 '-and bis-（2- chloroethoxy）Biphenyl light yellow
Solid；
（3）By 2,2 '-bis-（2- chloroethoxy）The tetrahydrofuran solution of biphenyl is stirred at room temperature 10-20 min, adds
NaI and the tetrahydrofuran solution containing N- ethyl benzo imidazole, this mixed solution stirs 5 days under 60-70 C has white heavy
Starch generates, and obtains the white solid of 2,2 '-bis- [2- (N- ethyl benzo imidazole base) ethyoxyl] biphenyl iodine salt after post processing；To
Add the methanol of ammonium hexafluorophosphate molten in the methanol solution of 2,2 '-bis- [2- (N- ethyl benzo imidazole base) ethyoxyl] biphenyl iodine salt
Liquid, has white precipitate to separate out, obtains 2,2 '-bis- [2- (N- ethyl benzo imidazole base) ethyoxyl] biphenyl hexafluorophosphoric acids after post processing
Salt（1）；
Wherein step（1）In 2,2 ' xenols：Potassium carbonate：The mol ratio of 2-chloroethyl alcohol is 1：4：4.
Step（2）In 2,2 '-bis-（2- ethoxy）Biphenyl：Pyridine：The mol ratio of thionyl chloride is 1：5：5.
Step（3）In 2,2 '-bis-（2- ethoxy）Biphenyl：N- ethyl benzo imidazole：NaI：The mol ratio of ammonium hexafluorophosphate
For 1：1.3：1.6：1.6.
Described organic solvent be selected from oxolane, dichloromethane, chloroform, absolute ether, acetonitrile, absolute methanol,
The mixture of one or more of DMF.
The present invention further discloses to be had by the bis-benzimidazole salt part of xenol bridging in intramolecular coupling
The application of the aspect processed of compound.Experiment proves：Urged in the slaine of palladium by the bis-benzimidazole salt part of xenol bridging
Under changing, intramolecular C-C coupling reaction can occur.
In the present invention, crystal data and structure refinement parameter are included in supportive information.In Bruker SMART 1000
Carry out on CCD diffractometer, experimental temperature is 113 (2) K, under 50kV and 20mA, operated with Mo-K α radiation (0.71073),
Carry out data collection and reduction with SMART and SAINT software,θScope be 1.8<θ< 25º.Application SADABS program
Carry out empirical absorption rectification.Crystal structure is solved by direct method, with SHELXTL bag to whole non-hydrogen atom coordinate anisotropy
Thermal parameter carries out complete matrix least square method correction.
The crystal structure figure of the coupling compound that application example 1 obtains is shown in Figure of description 1.
Brief description：
Fig. 1 is the intramolecular coupling compound crystal structure chart obtained by application example 1.
Specific embodiment
For purposes of simplicity and clarity, the hereafter appropriate description eliminating known technology, in order to avoid those are unnecessary
The description to the technical program for the details impact.Below in conjunction with preferred embodiment, the present invention will be further described, especially in addition
Illustrate, prepare the initial substance N- ethyl benzo imidazole of the compounds of this invention, 2,2 ' xenols, 2-chloroethyl alcohol, thionyl chloride
Can commercially or easily by known method be obtained Deng all.
Prepare the reagent used in the compounds of this invention all to stand and Ke Wei Chemical Co., Ltd. from Tianjin unit, level
Wei not analyze pure.
Additionally need be illustrated be：Solvent used by all of experimental implementation is through normal process purification.Institute is useful
It is all that analysis is pure in the reagent synthesizing and analyze, through further process.Fusing point is surveyed by Boetius block apparatus
Fixed.1H H NMR spectroscopy passes through hydrargyrum variable V x400 spectrophotometer record, and surveying range is 400 MHz and 100 MHz respectively.Chemistry
Displacement, δ, the TMS with reference to international standard measures.Elementary analysiss are to be measured by Perkin-Elmer 2400C elemental analyser
's.
Embodiment 1（1）
2,2 '-xenol (1.000 g, 5.4 mmol) is added to N,N-dimethylformamide（150ml）Potassium carbonate
In (2.980 g, 21.6 mmol) suspension, lower 50 C of nitrogen protection stir Deca 2-chloroethyl alcohol after 0.5 h (1.740 g,
21.6 mmol), after completion of dropping, 110 C stir 24 h.Deep yellow solution is obtained after filtration.400 ml water are added in filtrate,
Extract (30 mL × 3) with dichloromethane.Extract anhydrous magnesium sulfate is dried.2,2 ' are obtained after removing dichloromethane-bis-
（2- ethoxy）The white solid of biphenyl.Yield： 1.296 g (87%).Fusing point：42-44 ˚C.
1H NMR (400 MHz, CDCl3): δ 7.36 (t, J = 7.8 Hz, 2H, PhH), 7.26 (q, J
= 2.9 Hz, 2H, PhH), 7.10 (t, J = 7.4 Hz, 2H, PhH), 7.02 (d, J = 8.0 Hz, 2H,
PhH), 4.05 (t, J = 4.2 Hz, 4H, CH2), 3.72 (t, J = 4.4 Hz, 4H, CH2), 2.80 (s,
2H, OH).13C NMR (100 MHz, CDCl3): δ 155.8, 131.3, 129.0, 122.1 and 114.1
(PhC), 71.5 (OCH2CH2), 61.1 (OCH2CH2).
To 2,2 '-bis-（2- ethoxy）Biphenyl (1.000 g, 3.65 mmol) and pyridine (1.440 g, 18.2 mmol)
Chloroform soln in Deca thionyl chloride (2.170 g, 18.2 mmol).Mixed solution stirs 6 h in 70 C.React
It is added thereto to 300 ml water, point liquid obtains chloroform layer, is dried with anhydrous magnesium sulfate after finishing.Remove chloroform and obtain 2,
2 '-bis-（2- chloroethoxy）The light yellow solid of biphenyl.Yield：0.738 g (65%).Fusing point：52-54 ˚C.
1H NMR (400 MHz, CDCl3): δ 7.31 (m, 2H, PhH), 7.28 (m, 2H, PhH), 7.06
(t, J = 7.4 Hz, 2H, PhH), 6.96 (d, J = 8.0 Hz, 2H, PhH), 4.18 (t, J = 6.2 Hz,
4H, CH2), 3.65 (t, J = 6.2 Hz, 4H, CH2).13C NMR (100 MHz, CDCl3): δ 155.6,
131.8, 128.2, 121.2 and 112.7(PhC), 68.7 (OCH2CH2), 41.8 (OCH2CH2).
Addition N- ethyl benzo imidazole (1.690 g, 11.6 mmol) in 100 ml oxolanes, 2,2 '-bis-（2- chlorine
Ethyoxyl）Biphenyl (1.500 g, 8.9 mmol) and sodium iodide (2.170 g, 14.5 mmol) return stirring 5 days.There is white
Precipitation.Bis-benzimidazole salt 2,2 '-bis- [2- (N- ethyl benzo imidazole base) are obtained with a small amount of oxolane drip washing after sucking filtration
Ethyoxyl] biphenyl iodine salt white solid.To 100 ml 2,2 '-bis- [2- (N- ethyl benzo imidazole base) ethyoxyl] biphenyl iodine
Add ammonium hexafluorophosphate (2.360 g, 14.5 mmol) in the methanol solution of salt, have white precipitate to separate out immediately.Use after sucking filtration
A small amount of methanol drip washing obtains 2,2 '-bis- [2- (N- ethyl benzo imidazole base) ethyoxyl] biphenyl hexafluorophosphates.Yield：2.417
g (61%).Fusing point：104-106 ˚C.
Anal. Calc. For C34H36N4O2P2F12: C, 49.64; H, 4.41; N, 6.81. Found: C,
49.53; H, 4.25; N, 6.62.1H NMR (400 MHz, DMSO-d6): δ 9.33 (s, 2H, 2-bimiH), δ
8.02 (d, J = 7.6 Hz, 2H, PhH), 7.64 (t, J = 6.8 Hz, 2H, PhH), 7.55 (d, J =
8.0 Hz, 2H, PhH), 7.45 (d, J = 6.8 Hz, 2H, PhH), 7.32 (d, J = 1.6 Hz, 2H,
PhH), 6.98 (d, J = 8.0 Hz, 2H, PhH), 6.86 (s, 4H, PhH), 4.68 (s, 4H, CH2),
4.41 (d, J = 6.4 Hz, 4H, CH2). 4.26 (s, 4H, CH2), 1.45 (s, 6H, CH3).13C NMR
(100 MHz, DMSO-d6): δ 154.6 (PhC), 141.7 (bimi-NCN), 131.1, 130.7, 130.5,
128.7, 126.4, 126.2, 120.9, 113.5, 113.4 and 112.5 (PhC), 65.7 (OCH2CH2), 48.5
(OCH2CH2), 42.1 (CH2CH3), 13.9 (CH3) (bimi = benzimidazole).
Its experiment flow is shown below：
Application example 1
Sodium Acetate Trihydrate (0.199 g, 2.4 mmol), palladium is added in 10 ml acetonitriles and 10 ml dichloromethane
(0.080 g, 0.36 mmol) and part（1）(0.200 g, 0.2 mmol), lower 50 C of nitrogen protection stir 24 h.Filter
Obtain filtrate, filtrate is placed in ether slowly to be spread, after two weeks, grow suitable X-ray single crystal diffraction test in test tube wall
Yellow transparent bulk crystals（2）.Yield：0.083 g (38%), fusing point：192-194 ˚C. Anal. Calc. for
C38H38F12N6O2P2: C, 50.67; H, 4.25; N, 9.33. Found: C, 49.95; H, 3.87; N, 6.96.1H NMR (400 MHz, DMSO-d6): δ 8.26 (m, 4H, PhH), 8.02 (t, J = 7.6 Hz, 4H, PhH),
7.80 (m, 4H, PhH), 7.75 (t, J = 7.8 Hz, 2H, PhH), 4.80 (t, J = 5.4 Hz, 4H,
CH2) 4.72 (q, J = 7.2 Hz, 4H, CH2), 4.64 (t, J = 5.6 Hz, 4H, CH2), 1.60 (t, J
= 7.2 Hz, 6H, CH3).13C NMR (100 MHz, DMSO-d6): δ 151.0 (bimi-NCN), 146.0,
135.3, 130.8, 129.6, 128.9, 125.2, 123.5, 116.4, 115.1, 112.2 and 111.4
(PhC), 74.6 (OCH2CH2), 41.0 (OCH2CH2), 40.0 (CH2CH3), 12.8 (CH3).
Its experiment flow is as follows：
Crystal structure is shown in Figure of description 1.
The intramolecular coupling compound crystal structural parameters of application example 1 preparation
In sum, present disclosure is not limited in example, and the knowledgeable people in same area can be at this
Other examples can be proposed easily within bright technological guidance's thought, but this example be included in the scope of the present invention it
Interior.
Claims (2)
1. a kind of preparation method of the bis-benzimidazole salt part of xenol bridging it is characterised in that：
（1）In organic solvent 2,2 '-xenol, potassium carbonate are protected in nitrogen and stirred 0.5 h under 50 C, then slowly Deca
2-chloroethyl alcohol；Mixed solution reacts 24 h in 110 C, and post processing obtains 2,2 '-and bis-（2- ethoxy）The white solid of biphenyl；
（2）In organic solvent by 2,2 '-bis-（2- ethoxy）Biphenyl and pyridine are uniformly mixed, then slowly Deca dichloro
Sulfoxide；Mixed solution reacts 6 h in 70 C, and post processing obtains 2,2 '-and bis-（2- chloroethoxy）The light yellow solid of biphenyl；
（3）By 2,2 '-bis-（2- chloroethoxy）The tetrahydrofuran solution of biphenyl is stirred at room temperature 10-20 min, add NaI and
Tetrahydrofuran solution containing N- ethyl benzo imidazole, this mixed solution stirs 5 days under 60-70 C has white depositions to give birth to
Become, after post processing, obtain the white solid of 2,2 '-bis- [2- (N- ethyl benzo imidazole base) ethyoxyl] biphenyl iodine salt；To 2,2 '-
Add the methanol solution of ammonium hexafluorophosphate in the methanol solution of double [2- (N- ethyl benzo imidazole base) ethyoxyl] biphenyl iodine salt, have
White precipitate separates out, and obtains 2,2 '-bis- [2- (N- ethyl benzo imidazole base) ethyoxyl] biphenyl hexafluorophosphates after post processing
（1）；
Wherein step（1）In 2,2 '-xenol：Potassium carbonate：The mol ratio of 2-chloroethyl alcohol is 1：4：4；
Step（2）In 2,2 '-bis-（2- ethoxy）Biphenyl：Pyridine：The mol ratio of thionyl chloride is 1：5：5；
Step（3）In 2,2 '-bis-（2- ethoxy）Biphenyl：N- ethyl benzo imidazole：NaI：The mol ratio of ammonium hexafluorophosphate is 1：
1.3：1.6：1.6；Described organic solvent is selected from oxolane, dichloromethane, chloroform, absolute ether, acetonitrile, no water beetle
Alcohol or DMF；The structure of the bis-benzimidazole salt part of xenol bridging is as follows：
.
2. the preparation method of the bis-benzimidazole salt part of xenol bridging described in claim 1 is for intramolecular coupling chemical combination
The application of the preparation aspect of thing.
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