CN105294776A - Method for preparing symmetric dimer of nitrogen heterocyclic ring aromatic compound - Google Patents
Method for preparing symmetric dimer of nitrogen heterocyclic ring aromatic compound Download PDFInfo
- Publication number
- CN105294776A CN105294776A CN201510903111.8A CN201510903111A CN105294776A CN 105294776 A CN105294776 A CN 105294776A CN 201510903111 A CN201510903111 A CN 201510903111A CN 105294776 A CN105294776 A CN 105294776A
- Authority
- CN
- China
- Prior art keywords
- reaction
- formula
- natural number
- aromatic compound
- nitrogen heterocyclic
- 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.)
- Granted
Links
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a method for preparing a symmetric dimer of a nitrogen heterocyclic ring aromatic compound, a product prepared by the method and application of the product. The method comprises the following steps: adding a solvent in which a Grignard reagent is dissolved into a reaction container under protection of an inert gas, and slowly dropwise adding secondary amine into the Grignard reagent solution; then, adding a second kind of solvent into the reaction container to dissolve the product obtained in the reaction of the Grignard reagent and the secondary amine, adding a nitrogen complex reagent into the mixture, complexing, and adding a nitrogen heterocyclic ring aromatic compound to react at 20-200 DEG C; and quenching the reaction after the reaction is completed, and oxidizing the reaction product with air or oxygen to transform the reaction product into the symmetric dimer of the nitrogen heterocyclic ring aromatic compound. The method does not need transition metal, can be used for reducing production cost and environmental pollution, has an environment-friendly process, and can be used for preparing a series of novel compounds with illumination performance or pharmacological activity.
Description
Technical field
The present invention relates to the symmetrical dimeric preparation method of a kind of nitrogen heterocyclic ring aromatic compound, product prepared by this method and purposes.
Background technology
The symmetrical dimer of heterocyclic aromatic compounds such as 2,2'-dipyridyl or 2,2'-diquinolyl are the important organic compound of a class, and they are widely used in the preparation of luminescent material, in the mark of biomacromolecule, bioanalysis.Owing to being the excellent part of metal, be thus widely used in and the various organic reaction of metal complex then catalysis.Meanwhile, this compounds self also has multiple biological activity.Such as 2,2'-diquinolyls can form title complex with metal, have huge effect in metal assay.2,2'-diquinolyl is conventional survey α-benzoinoxime.2,2'-diquinolyl-4,4'-dioctyl phthalate disodium can be used for the concentration for measuring protein.2,2'-dipyridyl not only can be used for organic synthesis, medicine intermediate, electroless copper additive can also be used for, when with yellow prussiate of potash with the use of time, not only can effectively control copper sedimentation velocity, avoid Red copper oxide to be formed, also can be used as analytical reagent, for examining and determine ferrous iron, silver, cadmium, molybdenum, also oxidation-reduction indicator can be made.
At present this compounds with transition metal be mainly catalyst functionalized or activation in advance nitrogen heterocyclic aromatic compound (as halo azepine aromatic compound etc.) between linked reaction synthesize.The synthetic method of a large amount of uses of bibliographical information is mainly transition metal-catalyzed to be activated or coupling between nitrogen heterocyclic aromatic compound functionalized in advance, comprising: with halo nitrogen-containing heterocycle compound for raw material, (Catal.Sci.Technol.2013 is reacted using transition metal as the UllmannCoupling of catalyst halo azepine aromatic compound coupling, 3,3030-3035, J.Org.Chem.2014,79,777-782); Reacted (J.Org.Chem.2010,75,424 – 433) by the tributyl tin derivative of transition metal-catalyzed nitrogen heterocyclic aromatic compound and the StillCoupling of corresponding halo nitrogen heterocyclic aromatic compound coupling; (Chem.AsianJ.2008 is reacted by the organozinc derivatives of transition metal-catalyzed nitrogen heterocyclic aromatic compound and the NegishiCoupling of corresponding halo nitrogen heterocyclic aromatic compound coupling, 3,1046-1049, Org.Lett.2013,15,5754 – 5757); Reacted (Org.Lett.2013,15,4308 – 4311) by the organic boronic acid derivative of transition metal-catalyzed nitrogen heterocyclic aromatic compound and the SuzukiCoupling of corresponding halo nitrogen heterocyclic aromatic compound coupling.These methods are all first heterocyclic aromatic compounds will be changed into the corresponding nitrogen heterocyclic aromatic compound derivative activated, and drastically increase the cost of reaction raw materials; Use transition metal in its secondary response and make catalyzer.Transition metal in general price comparison is expensive, and considerable transition metal is all to bad environmental.Medicine or precision electronic industries material all need the transition metal removing trace.But these have nitrogen heterocyclic fragrance dimer compound and the transition metal complex of symmetrical structure closely, the transition metal removing these traces is extremely time-consuming, require great effort, expensive.The report of the second type does not use transition metal, but use the sulfonate derivatives of nitrogen heterocyclic aromatic compound and corresponding Grignard reagent cross-coupling to form the symmetrical dimer (Bull.Chem.Soc.Jpn.1989 of heterocyclic aromatic compounds, 62,2338-41), two kinds of reaction raw materials are wherein that sulphonate or the corresponding Grignard reagent of nitrogen heterocyclic aromatic compound is all the raw material that price is very expensive.The third patented method take quinoline as raw material, take Pd/C as catalyzer, with water and polyoxyethylene glycol for solvent synthesis 2,2'-diquinolyl (Chinese invention patent: CN101134742A), its advantage is that cost of material is cheap, and reaction solvent is water, more green, but employ expensive transition-metal catalyst equally, productive rate is moderate, and is only applicable to the reaction of a kind of raw material of quinoline.Thus how to avoid using transition metal, using the nitrogen heterocyclic aromatic compound of the functionalized wider range of the relatively cheap non-pre-of price to synthesize its symmetrical dimer for the direct coupling of reaction raw materials is an interesting and important problem.
Summary of the invention
The present invention is raised the price and can be overcome prior art deficiency for one, avoid transition metal, with the nitrogen heterocyclic aromatic compound of the functionalized wider range of the non-pre-using price relatively cheap for reaction raw materials, the symmetrical dimeric method of preparation nitrogen heterocyclic ring aromatic compound, the associated products prepared in this way is provided simultaneously, and the purposes of part of compounds in this compounds.
The symmetrical dimer preparation method of a kind of nitrogen heterocyclic ring aromatic compound of the present invention is: under protection of inert gas condition, a kind of solvent being dissolved with Grignard reagent is joined in reaction vessel, – 30 DEG C to 50 DEG C is slowly added dropwise to a kind of secondary amine and reacts in grignard reagent solution, then under 0 DEG C to 100 DEG C temperature condition, the solvent in reaction vessel is drained, be filled with rare gas element under – 30 DEG C to 100 DEG C temperature condition and continue protective reaction, the product that the aforementioned Grignard reagent of the second dissolution with solvents and secondary amine are obtained by reacting is added again in reaction vessel, and add a kind of nitrogenous complexometric reagent wherein, nitrogen heterocyclic aromatic compound is added wherein again after complexing, react at 20 DEG C to 200 DEG C, after question response completes, pass into air or dioxygen oxidation reaction product, reaction product is made to change the symmetrical dimer of nitrogen heterocyclic aromatic compound into, in described reaction: the solvent dissolving Grignard reagent is ether, tetrahydrofuran (THF), methyl ethyl ether, methyltetrahydrofuran, metopryl, methyl tertiary butyl ether, Di Iso Propyl Ether, n-butyl ether, isobutyl ethyl ether, IVE, any one or several mixture in any proportion arbitrarily of toluene, Grignard reagent is any one or several mixture in any proportion arbitrarily of RMgBr or RMgCl or ArMgBr or ArMgCl, R group is wherein C
nh
2n+1, n is the natural number of 1 ~ 10, Ar group is wherein
or furyl or thienyl or naphthyl, wherein R
1and R
2h or MeO or Me or F or F
3c or Cl or C
nh
2n+1, n is the natural number of 1 ~ 10, described secondary-amine compound be Pyrrolidine or pyrroles or piperidines or morpholine or 2,2,6,6-tetramethyl piperidine (TMPH) or 2,5-dimethyl pyrrole or 2,2,5,5-tetramethyl-Pyrrolidine or ring imines in heptan or
(n=0,1,2) or
(n=1,2) or
(n=1,2) or benzhydrylamine or R
1r
2nH, R
1and R
2c
nh
2n+1, n is the natural number of 1 ~ 10, any one or aforementioned secondary amine in several mixture in any proportion arbitrarily, the second solvent added is several mixture in any proportion arbitrarily in any one or aforementioned solvents of tetrahydrofuran (THF), methyltetrahydrofuran, methyl tertiary butyl ether, Di Iso Propyl Ether, n-butyl ether, isobutyl ethyl ether, IVE, glycol dimethyl ether, dioxane, benzene, toluene, ethylbenzene, dimethylbenzene, described nitrogenous complexometric reagent is: R
1r
2r
3n, two [(N, N-dimethyl-N ', N '-dimethyl) amino] ethyl ether, N-methylmorpholine, Tetramethyl Ethylene Diamine, hexamethylenetetramine, DMAP, pyridine, 2,2 '-dipyridyl, 2,2 '-diquinolyl or N, N, N ', any one or several mixture in any proportion arbitrarily in N '-tetraethylethylenediamine, wherein: R
1=C
xh
2x+1, in formula, x is the natural number of 1 ~ 10, R
2=C
yh
2y+1, in formula, y is the natural number of 1 ~ 10, R
3=C
zh
2z+1, in formula, z is the natural number of 1 ~ 10, described nitrogen heterocyclic aromatic compound for such as formula the nitrogen heterocyclic aromatic compound described in I to formula IV structure,
That is: quinoline and substd quinolines, isoquinoline 99.9 and substituted isoquinoline, pyridine and 3-substituted pyridines or quinoxaline and substituted quinoxaline, R wherein
1, R
2, R
3, R
4, R
5, R
6can be H or Br or Cl or F or F
3c or Ph or naphthalene or C
nh
2n+1in any one, n is the natural number of 1 ~ 10; R
7with R
8in: have at least one to be H, remaining is H or Br or Cl or F or F
3c or Ph or naphthalene or C
nh
2n+1in any one, n is the natural number of 1 ~ 10; R
13, R
14, R
15, R
16, R
17, R
18h or Br or Cl or F or F
3c or naphthalene or
or C
nh
2n+1in any one, n is the natural number of 1 ~ 10, R
1and R
2h or MeO or Me or F
3c or F or Cl or Br or C
nh
2n+1in any one, n is the natural number of 1 ~ 10.
In the dimeric preparation method of symmetry of a kind of nitrogen heterocyclic ring aromatic compound of the present invention, preferred Grignard reagent is nBuMgCl; Be tetrahydrofuran (THF) for dissolving the solvent of Grignard reagent; Preferred secondary-amine compound is 2,2,6,6-tetramethyl piperidine (TMPH), and it is 0 DEG C that secondary amine adds temperature, and the reaction times is 15 minutes; Temperature when draining solvent from reaction vessel is 50 DEG C; The second solvent of the reactant in solubilizing reaction container is toluene, and the temperature adding the reactant in the second dissolution with solvents reaction vessel in reaction vessel is 25 DEG C; Adding the complexation time that selects after nitrogenous complexometric reagent is 10 minutes; Adding the temperature of reaction after nitrogen heterocyclic aromatic compound is 60 DEG C to 80 DEG C; Preferred nitrogenous complexometric reagent is Tetramethyl Ethylene Diamine.
The symmetrical dimer of the nitrogen heterocyclic aromatic compound adopting the inventive method to prepare can be such as formula the structure shown in 1 to formula 5,
Wherein: R in 2,2'-diquinolyls of formula 1
1, R
2, R
3, R
4, R
5, R
6for H or Br or Cl or F or F
3c or Ph or naphthalene or C
nh
2n+1in any one, n is the natural number of 1 ~ 10; R in 1,1'-connection isoquinoline 99.9 of formula 2
8, R
9, R
10, R
11, R
12for H or Br or Cl or F or F
3c or Ph or naphthalene or C
nh
2n+1in any one, n is the natural number of 1 ~ 10; R in 3,3'-connection isoquinoline 99.9 of formula 3
7, R
9, R
10, R
11, R
12for H or Br or Cl or F or F
3c or Ph or naphthalene or C
nh
2n+1in any one, n is the natural number of 1 ~ 10; R in 2,2'-dipyridyls of formula 4
13for H or Br or Cl or F or F
3c or naphthalene or
or C
nh
2n+1in any one, n is the natural number of 1 ~ 10, R
1and R
2for H or MeO or Me or F
3c or F or Cl or Br or C
nh
2n+1in any one, n is the natural number of 1 ~ 10; R in 2,2'-connection quinoxalines of formula 5
14, R
15, R
16, R
17, R
18h or Br or Cl or F or F
3c or naphthalene or
or C
nh
2n+1in any one, n is the natural number of 1 ~ 10, R
1and R
2for H or MeO or Me or F
3c or F or Cl or Br or C
nh
2n+1in any one, n is the natural number of 1 ~ 10.
The symmetrical dimer product of the nitrogen heterocyclic aromatic compound adopting method of the present invention to prepare
the new composite I r-DMBQ (NBT) shown such as formula 6 formed with metal Ir title complex
2show
Good red light-emitting performance.Detected known by ultraviolet-visible light, this mixture has strong absorption at Uv and visible light region 230nm, 277nm, 358nm, has a faint photoabsorption at 456nm.And 607nm and 661nm two peaks are had in phosphorescence absorption region, showing strong red light absorption, is a kind of potential material.
The symmetrical dimer product of the nitrogen heterocyclic aromatic compound such as formula structure arbitrary shown in 7 prepared with the method for the invention is more a kind of new compound, these compounds and various metal have good complex ability, be used as part can with different metal complexes after have the potential ability of the multiple organic chemical reactions of catalysis, and organifying reaction may show the reactive behavior different from the chemical reaction reported in the past and selectivity, such as, F.DeanToste teach problem group uses 4, 4'-di-t-butyl-2, 2'-dipyridyl completes fluoridizing of propylamine compound first efficiently as part and palladium complexing and reacts (J.Am.Chem.Soc.2015 with the difunctionality dough of arylation, 137, 12207-12210), these new symmetrical dimer compounds show different luminescent properties after can also belonging to Ir complexing with different metals like gold, many photoelectric materials having potential use can be synthesized accordingly, in such as the present invention 6,6'-dimethyl-2, the metal Ir mixture of 2'-diquinolyl has good red light-emitting performance, and the people such as Chung-ChihWu report 2, the mixture that the Ir of 2'-diquinolyl and 2-phenylpyridine is formed has good white-light emitting performance (J.Am.Chem.Soc.2008,130,3413-3419), due to the compound structure in the past reported on have large difference, thus also the biological activity different from the similar compound of known structure can be shown, potential multiple biology or pharmacologically active can be shown, as the people such as IkukoMurakami-Kubo find 2,2'-diquinolyl derivative has certain curative effect (J.Virology2004 for statural spongiosus damage, 78,1281-1288).
Advantage of the present invention is:
1) whole reaction is without the need to any transition metal, reduces production cost, reduces environmental pollution, and technique is green;
2) reaction is oxygenant with air or oxygen, without the need to adding other oxygenant any specially, reducing reaction cost and product purification difficulty, reducing by product;
3) substrate applicability is extensive, is conducive to the preparation promoting heterocyclic aromatic compounds autoimmunity syndrome;
4), after reacting extensive magnitude, do not affect productive rate, have good industrial applications prospect;
5) method of the present invention can prepare a series of new compound, and in these compounds, some have good luminescent properties, and other show potential multiple biology or pharmacologically active.
Accompanying drawing explanation
Fig. 1 is the spectrogram of embodiment 21 product, wherein: Ir-DMBQ (NBT)
2the spectral absorption of A in dichloromethane solution, concentration is 1.0 × 10
-6mol/L, left side is UV-Visible absorption, and right side is that phosphorescence absorbs.
Embodiment
Following examples will contribute to understanding the present invention, but be not limited to content of the present invention.
Embodiment 1.
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, add 1mmol quinoline at normal temperatures, 20h is reacted again at 60 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 2 of faint yellow solid, the product of 2 '-diquinolyl 116.5mg, structural formula is shown in formula 8, its productive rate 91%2, 2 '-diquinolyl characterizes: Mp.190.1 – 191.4 DEG C,
1hNMR (400MHz, CDCl
3): δ 8.87 (d, J=8.8Hz, 2H), 8.35 (d, J=8.8Hz, 2H), 8.25 (d, J=8.4Hz, 2H), 7.90 (d, J=8.0Hz, 2H), 7.77 (t, J=7.4Hz, 2H), 7.59 (t, J=7.4Hz, 2H).
Embodiment 2
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol4-toluquinoline, 20h is reacted again at 60 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 4 of faint yellow solid, 4'-dimethyl-2, 2'-diquinolyl 58.3mg, structural formula is shown in formula 9, productive rate 42%.4,4'-dimethyl-2,2'-diquinolyl characterizes: Mp.180.5 – 181.9 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.68 (s, 2H), 8.26 (d, J=8.4Hz, 2H), 8.08 (d, J=8.4Hz, 2H), 7.76 (t, J=7.4Hz, 2H), 7.60 (t, J=7.8Hz, 2H), 2.85 (s, 6H).
Embodiment 3
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol6-toluquinoline, 24h is reacted again at 60 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 6 of faint yellow solid, 6'-dimethyl-2, 2'-diquinolyl 130.8mg, structural formula is shown in formula 10, productive rate 92%.6,6'-dimethyl-2,2'-diquinolyl characterizes: Mp.253.8 – 256.8 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.79 (d, J=8.8Hz, 2H), 8.24 (d, J=8.8Hz, 2H), 8.12 (d, J=8.8Hz, 2H), 7.64 (s, 2H), 7.60 (d, J=8.8Hz, 2H), 2.57 (s, 6H).
Embodiment 4
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol7-toluquinoline, 24h is reacted again at 60 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 7 of faint yellow solid, 7'-dimethyl-2, 2'-diquinolyl 115.2mg, structural formula is shown in formula 11, productive rate 81%.7,7'-dimethyl-2,2'-diquinolyl characterizes: Mp.273.2 – 274.9 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.77 (d, J=8.4Hz, 2H), 8.29 (d, J=8.4Hz, 2H), 8.01 (s, 2H), 7.79 (d, J=8.4Hz, 2H), 7.42 (d, J=8.4Hz, 2H), 2.61 (s, 6H).
Embodiment 5
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol6-normal-butyl quinoline, 24h is reacted at 60 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 6 of faint yellow solid, 6'-dibutyl-2, 2'-diquinolyl 165.8mg, structural formula is shown in formula 12, productive rate 90%.6,6'-dibutyl-2,2'-diquinolyl characterizes: Mp.135.4 – 136.4 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.79 (d, J=8.0Hz, 2H), 8.25 (d, J=8.0Hz, 2H), 8.14 (d, J=8.0Hz, 2H), 7.63-7.59 (m, 4H), 2.82 (t, J=8.0Hz, 4H), 1.76-1.69 (m, 4H), 1.47-1.39 (m, 4H), 0.97 (t, J=8.0Hz, 6H);
13cNMR (100MHz, CDCl
3): δ 155.70,146.78,141.85,136.31,131.25,129.67,128.49,126.05,119.43,35.80,33.51,22.53,14.12; HR-ESIMScalcdforC
26h
28n
2([M+H]
+) 369.2252, found369.2325..
Embodiment 6
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol isoquinoline 99.9, 24h is reacted at 60 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 1 of faint yellow solid, 1'-joins isoquinoline 99.9 111.5mg, structural formula is shown in formula 13, productive rate 87%.1,1'-joins isoquinoline 99.9 and characterizes: Mp.312.4 – 315.3 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.73 (d, J=5.6Hz, 2H), 7.96 (d, J=8.0Hz, 2H), 7.83 (d, J=5.6Hz, 2H), 7.77-7.70 (m, 4H), 7.49 (t, J=7.8Hz, 2H).
Embodiment 7
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol1-methylisoquinolinium, 48h is reacted at 80 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after solvent evaporated, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 1 of faint yellow solid, 1'-dimethyl-3, 3'-bis-isoquinoline 99.9 24.2mg, structural formula is shown in formula 14, productive rate 17%.1,1'-dimethyl-3,3'-bis-isoquinoline 99.9 characterizes: Mp.217.1 – 218.5 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.50 (d, J=5.6Hz, 2H), 8.27 (d, J=8.4Hz, 2H), 7.82 (d, J=8.4Hz, 2H), 7.67-7.61 (m, 2H), 7.56 (d, J=5.6Hz, 2H), 3.91 (s, 6H);
13cNMR (100MHz, CDCl
3): δ 161.17,141.86,136.18,129.85,127.23,127.09,125.29,119.44,22.81; HR-ESIMScalcdforC
20h
16n
2([M+H]
+) 285.1392, found285.1388.
Embodiment 8
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol3-chloropyridine, 48h is reacted at 80 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 3 of faint yellow solid, 3'-bis-chloro-2, 6'-dipyridyl 43.9mg, structural formula is shown in formula 15, productive rate 39%.Chloro-2, the 6'-dipyridyls of 3,3'-bis-characterize: Mp.114.7 – 115.9 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.84 (s, 1H), 8.62 (s, 1H), 7.54-7.46 (m, 3H), 7.41 (d, J=5.2Hz, 1H).
Embodiment 9
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol3-(betanaphthyl) pyridine, 4d is reacted at 80 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 3 of faint yellow solid, 3'-bis-(betanaphthyl)-2, 6'-dipyridyl 33mg, structural formula is shown in formula 16, productive rate 16%.3,3'-bis-(betanaphthyl)-2,6'-dipyridyl characterizes: Mp.107.6 – 109.9 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.93 (s, 1H), 8.82 (d, J=3.6Hz, 1H), 8.01 (s, 1H), 7.96-7.82 (m, 7H), 7.72-7.61 (m, 2H), 7.48 (s, 6H), 7.26-7.09 (m, 2H);
13cNMR (100MHz, CDCl
3): δ 156.61,155.59,148.57,148.02,139.05,137.24,136.64,135.13,134.66,134.41,133.38,132.84,132.34,128.79,128.18,128.07,127.74,127.62,126.53,126.39,126.25,126.06,124.86,123.19; HR-ESIMScalcdforC
30h
20n
2([M+H]
+) 409.1705, found409.1682.
Embodiment 10
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol3-phenylpyridine, 48h is reacted at 80 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 3 of faint yellow solid, 3'-phenylbenzene-2, 6'-dipyridyl 134.2mg, structural formula is shown in formula 17, productive rate 87%.3,3'-phenylbenzene-2,6'-dipyridyl characterizes: Mp.100.1 – 101.5 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.83 (s, 1H), 8.76 (d, J=1.0Hz, 1H), 7.81-7.75 (m, 2H), 7.59 (d, J=7.2Hz, 2H), 7.48-7.36 (m, 6H), 7.29-7.28 (m, 2H), 7.23-7.21 (m, 2H);
13cNMR (100MHz, CDCl
3): δ 156.77,155.63,148.49,147.80,139.55,138.58,137.48,136.64,135.11,134.03,129.32,129.30,128.98,128.30,128.32,128.07,127.22,127.04,124.71,123.05; HR-ESIMScalcdforC
22h
16n
2([M+H]
+) 309.1386, found309.1388.
Embodiment 11
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol3-(p-aminomethyl phenyl) pyridine, 4d is reacted at 100 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 3 of faint yellow solid, 3'-bis-(p-aminomethyl phenyl)-2, 6'-dipyridyl 131.2mg, structural formula is shown in formula 18, productive rate 78%.3'-bis-(p-aminomethyl phenyl)-2,6'-dipyridyl characterizes: Mp.109.2 – 112.9 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.85 (s, 1H), 8.75 (d, J=3.6Hz, 1H), 7.79-7.73 (m, 2H), 7.50 (d, J=7.2Hz, 2H), 7.50-7.41 (m, 1H), 7.40-7.26 (m, 3H), 7.10 (s, 4H), 2.40 (s, 3H), 2.34 (s, 3H);
13cNMR (100MHz, CDCl
3): δ 156.41,155.48,148.27,147.66,138.59,138.02,137.05,136.49,134.97,134.56,133.79,129.71,129.17,129.09,126.84,124.74,123.01,21.09; HR-ESIMScalcdforC
24h
20n
2([M+H]
+) 337.1705, found337.1688.
Embodiment 12
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol3-(p-p-methoxy-phenyl) pyridine, 4d is reacted at 90 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 3 of faint yellow solid, 3'-bis-(p-p-methoxy-phenyl)-2, 6'-dipyridyl 81.1mg, structural formula is shown in formula 19, productive rate 44%.3,3'-bis-(p-p-methoxy-phenyl)-2,6'-dipyridyl characterizes: Mp.143.8 – 146.8 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.83 (s, 1H), 8.73 (d, J=3.6Hz, 1H), 7.78-7.71 (m, 2H), 7.54 (d, J=8.4Hz, 2H), 7.40-7.37 (m, 1H), 7.31 (d, J=8.4Hz, 1H), 7.15 (d, J=8.0Hz, 2H), 7.01 (d, J=8.4Hz, 2H), 6.84 (d, J=8.4Hz, 2H), 3.85 (s, 3H), 3.79 (s, 3H);
13cNMR (100MHz, CDCl
3): δ 159.77,158.93,156.20,148.15,147.47,138.47,136.17,134.62,133.51,131.78,130.47,129.88,128.13,124.70,123.01,114.50,113.83,55.34,55.17; HR-ESIMScalcdforC
24h
20n
2o
2([M+H]
+) 369.1603, found369.1591.
Embodiment 13
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol3-(m-p-methoxy-phenyl) pyridine, 3d is reacted at 90 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 3 of faint yellow solid, 3'-bis-(m-p-methoxy-phenyl)-2, 6'-dipyridyl 104.9mg, structural formula is shown in formula 20, productive rate 57%.3,3'-bis-(m-p-methoxy-phenyl)-2,6'-dipyridyl characterizes: Mp.36.1 – 37.4 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.85 (s, 1H), 8.77 (d, J=4.4Hz, 1H), 7.82-7.75 (m, 2H), 7.43-7.35 (m, 3H), 7.22-7.16 (m, 2H), 7.10 (s, 1H), 6.94 (d, J=8.0Hz, 1H), 6.79 (t, J=7.2Hz, 2H), 6.75 (s, 1H), 3.86 (s, 3H), 3.66 (s, 3H);
13cNMR (100MHz, CDCl
3): δ 160.05,159.32,156.82,155.51,148.50,147.76,140.73,138.85,138.42,136.42,134.98,134.09,130.04,129.33,124.62,123.04,121.78,119.45,114.66,113.33,113.17,112.81,55.25,55.05; HR-ESIMScalcdforC
24h
20n
2o
2([M+H]
+) 369.1603, found369.1598.
Embodiment 14
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol3-(m, m-3,5-dimethylphenyl) pyridine, 4d is reacted at 90 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 3 of pale yellow oily liquid body, 3'-bis-(m, m-3,5-dimethylphenyl)-2, 2'-dipyridyl 76.5mg, structural formula is shown in formula 21, productive rate 42%.3,3'-bis-(m, m-3,5-dimethylphenyl)-2,2'-dipyridyl characterizes: Mp.199.6 – 201.3 DEG C,
1hNMR (400MHz, CDCl
3): δ 8.83 (s, 1H), 8.74 (d, J=4.4Hz, 1H), 7.79-7.74 (m, 2H), 7.39-7.33 (m, 2H), 7.19 (s, 2H), 7.03 (s, 1H), 6.90 (s, 1H), 6.82 (s, 2H), 2.38 (s, 6H), 2.22 (s, 6H);
13cNMR (100MHz, CDCl
3): δ 156.62,155.55,148.24,147,68,139.28,138.58,138.48,137.72,137.46,136.75,135.17,133.92,129.67,128.82,127.15,124.84,124.63,122.91,21.29,21.17; HR-ESIMScalcdforC
24h
20n
2o
2([M+H]
+) 365.2001, found365.2005.
Embodiment 15
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol3-phenyl quinoxaline, 4h is reacted at 60 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 3 of red solid, 3'-phenylbenzene-2, 2'-joins quinoxaline 110.8mg, structural formula is shown in formula 22, productive rate 54%.3,3'-phenylbenzene-2,2'-joins quinoxaline and characterizes: Mp.210.2 – 211.2 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.39-8.37 (m, 2H), 8.19-8.17 (m, 2H), 7.88-7.85 (m, 4H), 7.21 (t, J=7.4Hz, 2H), 7.02 (t, J=7.6Hz, 4H), 6.80 (d, J=7.6Hz, 4H);
13cNMR (100MHz, CDCl
3): δ 153.23,151.98,141.91,141.06,137.27,130.89,130.17,129.65,129.32,128.96,128.74,128.07; HR-ESIMScalcdforC
28h
18n
4([M+H]
+) 411.1610, found411.1608.
Embodiment 16
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol3-(p-aminomethyl phenyl) quinoxaline, 4h is reacted at 60 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 3 of red solid, 3'-bis-(p-aminomethyl phenyl)-2, 2'-joins quinoxaline 135.9mg, structural formula is shown in formula 23, productive rate 62%.3,3'-bis-(p-aminomethyl phenyl)-2,2'-joins quinoxaline and characterizes Mp.204.8 – 205.2 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.37-8.34 (m, 2H), 8.18-8.15 (m, 2H), 7.86-7.84 (m, 4H), 6.84 (d, J=7.6Hz, 4H), 6.70 (d, J=8.0Hz, 4H), 2.27 (s, 6H);
13cNMR (100MHz, CDCl
3): δ 153.39,152.16,141.92,140.91,138.84,134.50,130.75,129.92,129.63,129.25,128.87,128.74,21.09; HR-ESIMScalcdforC
30h
22n
4([M+H]
+) 439.1923, found439.1917.
Embodiment 17
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol3-(p-p-methoxy-phenyl) quinoxaline, 24h is reacted at 60 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 3 of red solid, 3'-bis-(p-p-methoxy-phenyl)-2, 2'-joins quinoxaline 97mg, structural formula is shown in formula 24, productive rate 41%.3,3'-bis-(p-p-methoxy-phenyl)-2,2'-joins quinoxaline and characterizes: Mp.152.5 – 153.5 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.30-8.22 (m, 2H), 8.16-8.11 (m, 2H), 7.87-7.81 (m, 4H), 7.48 (d, J=8.8Hz, 4H), 6.85 (d, J=8.4Hz, 4H), 3.79 (s, 6H);
13cNMR (100MHz, CDCl
3): δ 153.28,152.44,141.95,140.97,131.29,131.17,130.65,130.55,130.38,130.10,129.96,129.64,55.28; HR-ESIMScalcdforC
30h
22n
4o
2([M+H]
+) 471.1821, found471.1815.
Embodiment 18
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol3-(m, m-3,5-dimethylphenyl) quinoxaline, 24h is reacted at 60 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 3 of red solid, 3'-bis-(m, m-3,5-dimethylphenyl)-2, 2'-joins quinoxaline 94mg, structural formula is shown in formula 25, productive rate 40%.3,3'-bis-(m, m-3,5-dimethylphenyl)-2,2'-joins quinoxaline and characterizes: Mp.199.6 – 201.3 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.38-8.36 (m, 2H), 8.18-8.16 (m, 2H), 7.87-7.84 (m, 4H), 6.85 (s, 2H), 6.38 (s, 4H), 2.02 (s, 12H);
13cNMR (100MHz, CDCl
3): δ 153.65,152.40,141.73,140.88,137.42,136.98,130.74,130.27,129.94,129.54,129.10,127.05,20.95; HR-ESIMScalcdforC
32h
26n
4([M+H]
+) 467.2236, found467.2233.
Embodiment 19
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol3-(m-aminomethyl phenyl) quinoxaline, 12h is reacted at 60 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 3 of red solid, 3'-bis-(m-aminomethyl phenyl)-2, 2'-joins quinoxaline 122.8mg, structural formula is shown in formula 26, productive rate 56%.3,3'-bis-(m-aminomethyl phenyl)-2,2'-joins quinoxaline and characterizes: Mp.207.3 – 208.0 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.39-8.37 (m, 2H), 8.19-8.17 (m, 2H), 7.87-7.85 (m, 4H), 7.04 (d, J=7.6Hz, 2H), 6.85 (t, J=7.6Hz, 2H), 6.64 (s, 2H), 6.51 (d, J=7.6Hz, 2H), 2.11 (s, 6H);
13cNMR (100MHz, CDCl
3): δ 153.46,152.17,141.86,141.06,138.03,137.10,130.82,130.04,129.87,129.66,129.39,129.24,127.55,126.02,21.11; HR-ESIMScalcdforC
30h
22n
4([M+H]
+) 439.1923, found439.1917.
Embodiment 20
Under argon shield, the tetrahydrofuran solution (0.8mmol/mL) of the freshly prepd nBuMgCl of 1.5mmol is added to the 5mL round-bottomed flask putting into the clean dried stirring magneton, 2 of 1.5mmol is slowly added dropwise in 0 DEG C of downhill reaction bottle, 2, 6, 6-tetramethyl piperidine (TMPH), react after 15 minutes, by tetrahydrofuran (THF) decompressing and extracting under 50 DEG C of conditions, re-fill argon shield reaction, add 2mL toluene after cooling reaction flask to 25 DEG C and dissolve generated in-situ TMP-MgCl, add the Tetramethyl Ethylene Diamine of 1.2mmol again, complexing is after ten minutes, normal temperature adds 1mmol3-(fluorophenyl) quinoxaline, 18h is reacted at 60 DEG C, thin plate chromatography detection reaction, room temperature is chilled to after having reacted, go out with shrend, with 4 × 15mL dichloromethane extraction, saturated common salt water washing, anhydrous sodium sulfate drying, cross and filter sodium sulfate, crude product is obtained after evaporated under reduced pressure solvent, be washing and dehydrating integrated machine by petrol ether/ethyl acetate, column chromatography purification obtains 3 of green solid, 3'-bis-(p-fluorophenyl)-2, 2'-joins quinoxaline 104.5mg, structural formula is shown in formula 27, productive rate 39%.3,3'-bis-(p-fluorophenyl)-2,2'-joins quinoxaline and characterizes: Mp.125.6 – 132.4 DEG C;
1hNMR (400MHz, CDCl
3): δ 8.39-8.37 (m, 2H), 8.20-8.18 (m, 2H), 7.92-7.88 (m, 4H), 7.09-6.93 (m, 2H), 6.83 (d, J=7.6Hz, 2H), 6.62 (d, J=9.2Hz, 2H), 6.55 (d, J=6.8Hz, 2H);
13cNMR (100MHz, CDCl
3): δ 164.65,162.18,150.40,142.96,142.18,141.84,138.99,130.72,130.63,130.47,129.90,129.67,129.15,123.03; HR-ESIMScalcdforC
28h
16n
4f
2([M+H]
+) 447.1421, found447.1416..
Embodiment 21 (two (2-(Alpha-Naphthyl) benzo [d] thiazole)-6,6'-the preparation of dimethyl-2,2'-diquinolyl iridium mixture)
Under room temperature and nitrogen protection condition, InCl
3nH
2o (1.0g, 3.12mmol) with 2-(Alpha-Naphthyl) benzo [d] thiazole (NBT, 2.04g, 7.79mmol) add in the cellosolvo of 30mL and the mixed solvent of 10mL water successively, temperature of reaction is progressively increased to 135 DEG C, and reacts 24h at this temperature.Reaction being cooled to room temperature, adding 30mL water in reaction solution, filter and collect the red precipitate obtained, then washing precipitation twice respectively with water, is MeOH and H of 1:2 by volume ratio
2the mixing liquid washing of O once, this red precipitate decompressing and extracting, does not need purifying, is directly used in next step reaction.
Under room temperature and nitrogen protection condition; prepare with preceding method 6; 6'-dimethyl-2; 2'-diquinolyl (142.5mg; red precipitate (300mg 0.5mmol) prepared with previous step; 0.2mmol) in 1, the 2-ethylene dichloride of 20mL and the methanol mixed solvent of 10mL.Heating lucifuge back flow reaction liquid 24h, cooling reaction solution, to room temperature, disposablely carefully in reaction solution adds KPF
6(1.84g, 10mmol), after making reaction continue reaction 0.5h at this temperature, adds a small amount of water, with dichloromethane extraction three times in reaction solution.Merge organic phase, with a small amount of water washing twice, use anhydrous sodium sulfate drying organic phase, filter out sodium sulfate, concentrating under reduced pressure removing organic solvent, with silica column purification (methylene dichloride: methyl alcohol-10:1, volume ratio) obtain two (2-(Alpha-Naphthyl) benzo [d] thiazole)-6,6'-dimethyl-2,2'-diquinolyl iridium mixture 160mg of red powder, structure is shown in formula 6, productive rate 35%.
Two (2-(Alpha-Naphthyl) benzo [d] thiazole)-6,6'-dimethyl-2,2'-diquinolyl iridium mixture characterize:
Ir-DMBQ(NBT)
2complex)：
1HNMR(400MHz,CDCl
3)δ9.03(d,J＝8.0Hz,2H),8.65(d,J＝8.0Hz,2H),8.39(d,J＝8.0Hz,2H),7.90(d,J＝8.0Hz,2H),7.75(d,J＝8.0Hz,2H),7.65-7.59(m,4H),7.44(t,J＝8.0Hz,2H),7.33-7.25(m,6H),6.95(t,J＝8.0Hz,2H),6.73(dd,J＝20.0,8.0Hz,4H),6.51(d,J＝8.0Hz,2H),2.20(s,6H).
13CNMR(100MHz,CDCl
3):δ177.6,160.0,158.4,147.8,146.4,141.2,139.2,133.9,133.0,132.4,131.0,130.9,130.8,130.5,130.2,129.8,128.4,128.2,127.5,127.0,125.9,124.4,123.0,122.7,121.5,118.0,21.1；HR-ESIMScalcdforC
54H
36IrN
4S
2PF
6([M–PF
6])
+997.2005,found997.2025。
Use Shimadzu UV-2550 photometer measurement to carry out ultraviolet-visible light detection above-mentioned product, and phosphorescence absorb and produces LS-55 type photometer measurement by platinum-Ai Ermo (Perkin-Elmer) company and obtain spectrogram and see that Fig. 1 shows.As can be seen from measured spectrogram 1, this mixture has strong absorption at Uv and visible light region 230nm, 277nm, 358nm, has a faint photoabsorption at 456nm.And 607nm and 661nm two peaks are had in phosphorescence absorption region, show strong red light absorption.
More a kind of new compound is with the symmetrical dimer product of nitrogen heterocyclic aromatic compound that the method for the invention can be prepared such as formula structure shown in 7, these compounds and various metal have good complex ability, be used as part can with different metal complexes after have the potential ability of the multiple organic chemical reactions of catalysis, and organifying reaction may show the reactive behavior different from the chemical reaction reported in the past and selectivity, such as, F.DeanToste teach problem group uses 4, 4'-di-t-butyl-2, 2'-dipyridyl completes fluoridizing of propylamine compound first efficiently as part and palladium complexing and reacts (J.Am.Chem.Soc.2015 with the difunctionality dough of arylation, 137, 12207-12210), these new symmetrical dimer compounds show different luminescent properties after can also belonging to Ir complexing with different metals like gold, many photoelectric materials having potential use can be synthesized accordingly, in such as the present invention 6,6'-dimethyl-2, the metal Ir mixture of 2'-diquinolyl has good red light-emitting performance, and the people such as Chung-ChihWu report 2, the mixture that the Ir of 2'-diquinolyl and 2-phenylpyridine is formed has good white-light emitting performance (J.Am.Chem.Soc.2008,130,3413-3419), due to the compound structure in the past reported on have large difference, thus also the biological activity different from the similar compound of known structure can be shown, potential multiple biology or pharmacologically active can be shown, as the people such as IkukoMurakami-Kubo find 2,2'-diquinolyl derivative has certain curative effect (J.Virology2004 for statural spongiosus damage, 78,1281-1288).
。
Claims (7)
1. the symmetrical dimer preparation method of a nitrogen heterocyclic ring aromatic compound, it is characterized in that: under protection of inert gas condition, a kind of solvent being dissolved with Grignard reagent is joined in reaction vessel, – 30 DEG C to 50 DEG C is slowly added dropwise to a kind of secondary amine and reacts in grignard reagent solution, then under 0 DEG C to 100 DEG C temperature condition, the solvent in reaction vessel is drained, be filled with rare gas element under – 30 DEG C to 100 DEG C temperature condition and continue protective reaction, the product that the aforementioned Grignard reagent of the second dissolution with solvents and secondary amine are obtained by reacting is added again in reaction vessel, and add a kind of nitrogenous complexometric reagent wherein, nitrogen heterocyclic aromatic compound is added wherein again after complexing, react at 20 DEG C to 200 DEG C, after question response completes, pass into air or dioxygen oxidation reaction product, reaction product is made to change the symmetrical dimer of nitrogen heterocyclic aromatic compound into, in described reaction: the solvent dissolving Grignard reagent is ether, tetrahydrofuran (THF), methyl ethyl ether, methyltetrahydrofuran, metopryl, methyl tertiary butyl ether, Di Iso Propyl Ether, n-butyl ether, isobutyl ethyl ether, IVE, any one or several mixture in any proportion arbitrarily of toluene, Grignard reagent is any one or several mixture in any proportion arbitrarily of RMgBr or RMgCl or ArMgBr or ArMgCl, R group is wherein C
nh
2n+1, n is the natural number of 1 ~ 10, Ar group is wherein
or furyl or thienyl or naphthyl, wherein R
1and R
2h or MeO or Me or F or F
3c or Cl or C
nh
2n+1, n is the natural number of 1 ~ 10, described secondary-amine compound be Pyrrolidine or pyrroles or piperidines or morpholine or 2,2,6,6-tetramethyl piperidine (TMPH) or 2,5-dimethyl pyrrole or 2,2,5,5-tetramethyl-Pyrrolidine or ring imines in heptan or
(n=0,1,2) or
(n=1,2) or
(n=1,2) or benzhydrylamine or R
1r
2nH, R
1and R
2c
nh
2n+1, n is the natural number of 1 ~ 10, any one or aforementioned secondary amine in several mixture in any proportion arbitrarily, the second solvent added is several mixture in any proportion arbitrarily in any one or aforementioned solvents of tetrahydrofuran (THF), methyltetrahydrofuran, methyl tertiary butyl ether, Di Iso Propyl Ether, n-butyl ether, isobutyl ethyl ether, IVE, glycol dimethyl ether, dioxane, benzene, toluene, ethylbenzene, dimethylbenzene, described nitrogenous complexometric reagent is: R
1r
2r
3n, two [(N, N-dimethyl-N ', N '-dimethyl) amino] ethyl ether, N-methylmorpholine, Tetramethyl Ethylene Diamine, hexamethylenetetramine, DMAP, pyridine, 2,2 '-dipyridyl, 2,2 '-diquinolyl or N, N, N ', any one or several mixture in any proportion arbitrarily in N '-tetraethylethylenediamine, wherein: R
1=C
xh
2x+1, in formula, x is the natural number of 1 ~ 10, R
2=C
yh
2y+1, in formula, y is the natural number of 1 ~ 10, R
3=C
zh
2z+1, in formula, z is the natural number of 1 ~ 10, described nitrogen heterocyclic aromatic compound for such as formula the nitrogen heterocyclic aromatic compound described in I to formula IV structure,
That is: quinoline and substd quinolines, isoquinoline 99.9 and substituted isoquinoline, pyridine and 3-substituted pyridines or quinoxaline and substituted quinoxaline, R wherein
1, R
2, R
3, R
4, R
5, R
6can be H or Br or Cl or F or F
3c or Ph or naphthalene or C
nh
2n+1in any one, n is the natural number of 1 ~ 10; R
7with R
8in: have at least one to be H, remaining is H or Br or Cl or F or F
3c or Ph or naphthalene or C
nh
2n+1in any one, n is the natural number of 1 ~ 10; R
13, R
14, R
15, R
16, R
17, R
18h or Br or Cl or F or F
3c or naphthalene or
or C
nh
2n+1in any one, n is the natural number of 1 ~ 10, R
1and R
2h or MeO or Me or F
3c or F or Cl or Br or C
nh
2n+1in any one, n is the natural number of 1 ~ 10.
2. the dimeric preparation method of symmetry of a kind of nitrogen heterocyclic ring aromatic compound according to claim 1, is characterized in that Grignard reagent used is nBuMgCl; Be tetrahydrofuran (THF) for dissolving the solvent of Grignard reagent.
3. the dimeric preparation method of symmetry of a kind of nitrogen heterocyclic ring aromatic compound according to claim 1, is characterized in that: described secondary-amine compound is 2,2,6,6-tetramethyl piperidine (TMPH), it is 0 DEG C that secondary amine adds temperature, and the reaction times is 15 minutes; Temperature when draining solvent from reaction vessel is 50 DEG C; The second solvent of the reactant in solubilizing reaction container is toluene, and the temperature adding the reactant in the second dissolution with solvents reaction vessel in reaction vessel is 25 DEG C; Adding the complexation time that selects after nitrogenous complexometric reagent is 10 minutes; Adding the temperature of reaction after nitrogen heterocyclic aromatic compound is 60 DEG C to 80 DEG C.
4. the symmetrical dimeric preparation method of any one the nitrogen heterocyclic aromatic compound according to claims 1 to 3, is characterized in that described nitrogenous complexometric reagent is Tetramethyl Ethylene Diamine.
5. the method described in Claims 1-4 prepare such as formula the symmetrical dimer of the nitrogen heterocyclic aromatic compound shown in 1 to formula 5,
Wherein: R in 2,2'-diquinolyls of formula 1
1, R
2, R
3, R
4, R
5, R
6for H or Br or Cl or F or F
3c or Ph or naphthalene or C
nh
2n+1in any one, n is the natural number of 1 ~ 10; R in 1,1'-connection isoquinoline 99.9 of formula 2
8, R
9, R
10, R
11, R
12for H or Br or Cl or F or F
3c or Ph or naphthalene or C
nh
2n+1in any one, n is the natural number of 1 ~ 10; R in 3,3'-connection isoquinoline 99.9 of formula 3
7, R
9, R
10, R
11, R
12for H or Br or Cl or F or F
3c or Ph or naphthalene or C
nh
2n+1in any one, n is the natural number of 1 ~ 10; R in 2,2'-dipyridyls of formula 4
13for H or Br or Cl or F or F
3c or naphthalene or
or C
nh
2n+1in any one, n is the natural number of 1 ~ 10, R
1and R
2for H or MeO or Me or F
3c or F or Cl or Br or C
nh
2n+1in any one, n is the natural number of 1 ~ 10; R in 2,2'-connection quinoxalines of formula 5
14, R
15, R
16, R
17, R
18h or Br or Cl or F or F
3c or naphthalene or
or C
nh
2n+1in any one, n is the natural number of 1 ~ 10, R
1and R
2for H or MeO or Me or F
3c or F or Cl or Br or C
nh
2n+1in any one, n is the natural number of 1 ~ 10.
6. show compound such as formula 6
7. the method described in Claims 1-4 prepare such as formula the arbitrary compound shown in 7
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510903111.8A CN105294776B (en) | 2015-12-09 | 2015-12-09 | A kind of preparation method of the symmetrical dimer of nitrogen heterocyclic ring aromatic compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510903111.8A CN105294776B (en) | 2015-12-09 | 2015-12-09 | A kind of preparation method of the symmetrical dimer of nitrogen heterocyclic ring aromatic compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105294776A true CN105294776A (en) | 2016-02-03 |
| CN105294776B CN105294776B (en) | 2018-06-15 |
Family
ID=55192678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510903111.8A Expired - Fee Related CN105294776B (en) | 2015-12-09 | 2015-12-09 | A kind of preparation method of the symmetrical dimer of nitrogen heterocyclic ring aromatic compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105294776B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947898A (en) * | 2018-08-02 | 2018-12-07 | 南京工业大学 | Organic photoelectric functional material and application thereof |
| CN110862381A (en) * | 2019-12-04 | 2020-03-06 | 宁波卢米蓝新材料有限公司 | Organic electroluminescent compound and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002163926A (en) * | 1999-11-29 | 2002-06-07 | Canon Inc | Electric conduction element and its manufacturing method |
-
2015
- 2015-12-09 CN CN201510903111.8A patent/CN105294776B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002163926A (en) * | 1999-11-29 | 2002-06-07 | Canon Inc | Electric conduction element and its manufacturing method |
Non-Patent Citations (6)
| Title |
|---|
| ALVAREZ M.等: "Product class 5: isoquinolines", 《SCIENCE OF SYNTHESIS》 * |
| ARKADY KRASOVSKIY等,: "Mixed Mg/Li Amides of the Type R2NMgCl·LiCl as Highly Efficient Bases for the Regioselective Generation of Functionalized Aryl and Heteroaryl Magnesium Compounds", 《ANGEW. CHEM. INT. ED.》 * |
| RUGGLI PAUL等: "Syntheses in the 1,4-diphenylbutane series. III.Reduction of diphenyl tetraketone and of benzoylformoin", 《HELVETICA CHIMICA ACTA》 * |
| ZHIBING DONG等,: "Direct Zincation of Functionalized Aromatics and Heterocycles by Using a Magnesium Base in the Presence of ZnCl2", 《CHEM. EUR. J.》 * |
| ZHUO FANGFANG等: "Site-Specific ortho-Arylation of N-Heteroarenes with Aryl Grignard Reagents Assisted by TMEDA", 《中国化学会·第八届有机化学学术会议暨首届重庆有机化学国际研讨会论文集》 * |
| 谢雯雯等: "TMEDA协助的芳基格氏试剂对N-杂环芳香化合物的高效位置选择性加成反应", 《甘肃省化学会第二十八届年会暨第十届中学化学教学经验交流会论文集》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947898A (en) * | 2018-08-02 | 2018-12-07 | 南京工业大学 | Organic photoelectric functional material and application thereof |
| CN108947898B (en) * | 2018-08-02 | 2021-11-05 | 南京工业大学 | Organic photoelectric functional material and application thereof |
| CN110862381A (en) * | 2019-12-04 | 2020-03-06 | 宁波卢米蓝新材料有限公司 | Organic electroluminescent compound and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105294776B (en) | 2018-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Oi et al. | Nitrogen-directed ortho-arylation and-heteroarylation of aromatic rings catalyzed by ruthenium complexes | |
| Xie et al. | A novel highly selective probe with both aggregation-induced emission enhancement and intramolecular charge transfer characteristics for CN− detection | |
| Adam | Catalytic activity of nickel (II), copper (II) and oxovanadium (II)‐dihydroindolone complexes towards homogeneous oxidation reactions | |
| Gossage et al. | Application of an air stable Pd oxazoline complex for Heck, Suzuki, Sonogashira and related C–C bond-forming reactions | |
| Mishra et al. | Cobalt coordination induced functionalized molecular clefts: isolation of {CoIII− ZnII} heterometallic complexes and their applications in Beckmann rearrangement reactions | |
| Rawat et al. | Iron-catalyzed borylation reactions of alkynes: an efficient synthesis of E-vinyl boronates | |
| Sindhuja et al. | Palladium (ii) thiocarboxamide complexes: synthesis, characterisation and application to catalytic Suzuki coupling reactions | |
| Yeom et al. | Silver (I)-catalyzed direct route to isoquinoline-N-oxides | |
| Abdolmaleki et al. | Novel pyridinedicarboxamide derivatives and a polymeric copper (II) complex: Synthesis, structural characterization, electrochemical behavior, catalytic and cytotoxic studies | |
| Li et al. | Mercapto thiadiazole-based sensor with colorimetric specific selectivity for AcO− in aqueous solution | |
| US20150112066A1 (en) | Asymmetric catalysts | |
| Odago et al. | Thioamide, urea and thiourea bridged rhenium (I) complexes as luminescent anion receptors | |
| Batista et al. | Novel optical chemosensors for anions and cations based on an amino acid core functionalised with benzimidazoles | |
| Adiyala et al. | Continuous-flow photo-induced decarboxylative annulative access to fused imidazole derivatives via a microreactor containing immobilized ruthenium | |
| Ay et al. | Hydrothermal synthesis, structure, heterogeneous catalytic activity and photoluminescent properties of a novel homoleptic Sm (III)-organic framework | |
| Ozboya et al. | A Late-Stage Strategy for the Functionalization of Triazolium-Based NHC Catalysts | |
| Lee et al. | Pd (II) complexes with mono-and bis-chelate carbene ligands tagged with pyridinium cation: Synthesis, structures, and their catalytic activities toward Heck reaction | |
| Wang et al. | Highly sensitive fluorescence detection of nitrofurazone and nitrofurantoin in milk and honey using a hydrostable Cd (Ⅱ) metal-organic framework | |
| Chen et al. | Iron-catalyzed nitrene insertion reaction for facile construction of amide compounds | |
| Shukla et al. | Host-guest interaction of rotaxane assembly through selective detection of ferric ion: insight into hemin sensing and switching with sodium ascorbate | |
| Kumar et al. | A facile approach for the synthesis of novel 1-oxa-and 1-aza-flavonyl-4-methyl-1 H-benzo [d][1, 3] oxazin-2 (4 H)-ones by microwave enhanced Suzuki–Miyaura coupling using bidentate chromen-4-one-based Pd (II)–diimine complex as catalyst | |
| Nasr-Esfahani et al. | Multi-component synthesis of highly substituted imidazoles catalyzed by nanorod vanadatesulfuric acid | |
| CN105294776A (en) | Method for preparing symmetric dimer of nitrogen heterocyclic ring aromatic compound | |
| Wang et al. | Two zinc coordination polymers constructed by 4′-hydroxy-[1, 1′-biphenyl]-3, 5-dicarboxylic acid (H2BDA) and 4-hydroxy-[1, 1′-biphenyl]-3, 3′, 5, 5′-tetracarboxylic acid (H3BTA): Synthesis, structures and luminescence identifying properties | |
| Kargar et al. | Dioxovanadium (V) complex incorporating tridentate ONO donor aminobenzohydrazone ligand: synthesis, spectral characterization and application as a homogeneous lewis acid catalyst in the Friedländer synthesis of substituted quinolines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180615 Termination date: 20211209 |