CN109053556A - Pyridyl group bridging-phenyl-amino pyridine compounds and their, complex and its synthesis and application - Google Patents
Pyridyl group bridging-phenyl-amino pyridine compounds and their, complex and its synthesis and application Download PDFInfo
- Publication number
- CN109053556A CN109053556A CN201811067601.9A CN201811067601A CN109053556A CN 109053556 A CN109053556 A CN 109053556A CN 201811067601 A CN201811067601 A CN 201811067601A CN 109053556 A CN109053556 A CN 109053556A
- Authority
- CN
- China
- Prior art keywords
- reaction
- compound
- phenyl
- methyl
- pyridyl 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0046—Ruthenium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses pyridyl group bridging-phenyl-amino pyridine compounds and their, complex and its synthesis and applications.It is reacted with 2,6- dibromo pyridine and o-aminopyridine (pyrimidine or s-triazine), then is reacted with (to first) phenyl boric acid and generate pyridyl group bridging-phenyl-amino pyridine compounds and their.The ligand can be used for the metal complex catalysts of synthesizing efficient.The present invention has many advantages, such as that raw material is cheap and easy to get, easy to operate, synthesis step is few, synthetic reaction condition is mild and high-efficient.
Description
Technical field
The present invention relates to pyridyl group bridging-phenyl-amino pyridine compounds and their, complex and its synthesis and applications.With 2,
6- dibromo pyridine and o-aminopyridine (pyrimidine or s-triazine) reaction, then reacted with (to first) phenyl boric acid and generate pyridyl group bridging-
Phenyl-amino pyridine compounds and their.The compound can be used for the metal complex catalysts of synthesizing efficient.The present invention has raw material
It is cheap and easy to get, easy to operate, synthesis step is few, synthetic reaction condition is mild and it is high-efficient the advantages that.
Background technique
Three tooth NNC compounds not only have potential bioactivity as a kind of widely used N- heterocyclic compound,
It can be used for preparing complex luminescent material or high activity composition catalyst.2012 and 2018, Yu Zhengkun study group reported respectively
Ruthenium complex of the two class NNC compounds as ligand has been led, the hydrogen transfer reaction of ketone, the Oppenauer oxygen of alcohol are being catalyzed
Higher catalytic activity is shown in change and N- heterocyclic compound, alcohol compound dehydrogenation reaction
(Chem.Eur.J.2012,18,11550；Organometallics 2018,37,584.).
The pyridyl group NNC series ligand of Baratta group report is one of ligand the most outstanding in transfer hydrogenation,
It remains the advantages of 2- methylamino pyridine, while phenyl ring is introduced on ligand, has played the high advantage of ring ruthenium complex activity,
A kind of completely new ligand is obtained.Obtained NNC-Ru complex is catalyzed acetophenone back flow reaction 5 under 0.005mol% dosage
98% conversion ratio can be obtained in minute, and half way TOF value is 1.1 × 106h-1.Chiral radicals and chirality (S, R)-are introduced into ligand
Josiphos ligand, obtains chiral ruthenium complex, and in 60 DEG C, 0.005mol% dosage, acetophenone, which reacts 10 minutes, be can get
98% conversion ratio and 95%ee is realizing the high activity that catalyst is maintained while asymmetric reaction.Then get back
NNC-Os complex, under the same conditions, acetophenone react 30 minutes available 97% conversion ratios and 93%ee, are that Os is urged
Change a quantum jump (Angew.Chem.Int.Ed.2005,44,6214 of asymmetric transfer hydrogenation reaction；
Angew.Chem.Int.Ed.2008,47,4362；Chem.Eur.J.2008,14,5588；Organometallics 2010,
29,3563；Organometallics 2012,31,1133；Organometallics 2013,32,3339.).In addition contain
The Annular metal complex of asymmetric NNC ligand can generally also be used as the luminous material in organic luminescent device and chemical sensor
Material, therefore there is important application value (Adv.Mater.2011,23,926.).
The present invention is reacted with 2,6- dibromo pyridine and o-aminopyridine (pyrimidine or s-triazine), then anti-with (to first) phenyl boric acid
Pyridyl group bridging-phenyl-amino pyridine compounds and their should be generated, the present invention has reaction step few, and raw material is cheap and easy to get, operates
Easy, the advantages that synthetic reaction condition is mild and high-efficient, and gained compound also can be used as complex luminescent material or height
The ligand of active complex catalysts uses, and has very important scientific meaning and application value.
Summary of the invention
The purpose of the present invention is to provide a kind of raw materials to be easy to get, reaction condition is mild, wide adaptability, can be efficiently synthesized pyrrole
Piperidinyl bridging-phenyl-amino pyridine compounds and their method.
To achieve the goals above, technical scheme is as follows:
Buchwald-occurs in organic solvent for 2,6- dibromo pyridines 2 and aminopyridine (pyrimidine or s-triazine) compound 3
Hartwig cross-coupling reaction obtains compound 4 (reaction equation 1), and it is even that with (to first) phenyl boric acid 5 suzuki occurs for compound 4 again
Connection reaction obtains compound 1a (reaction equation 2), and compound 1a further can occur methylation reaction with iodomethane and obtain chemical combination
Object 1b (reaction equation 3).
Substituent R2=R3=C or R2=C, R3=N or R2=R3=N, substituent R4For hydrogen, methyl, ethyl, (just,
It is different) propyl or normal-butyl.
Technical solution is characterized in that:
1, aminopyridine (pyrimidine or s-triazine) compound 3 is synthon.
2, Buchwald-Hartwig friendship occurs for 2,6- dibromo pyridine 2 and aminopyridine (pyrimidine or s-triazine) compound 3
Coupling reaction prepare compound 4 is pitched, reaction dissolvent is toluene, dimethylbenzene, tetrahydrofuran, dichloroethanes, dioxane, NN- bis-
Methylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide, one of methanol or two kinds or more, preferably in toluene or dioxy six
It is carried out in ring.
3, the molar ratio of 2,6- dibromo pyridine 2 and aminopyridine (pyrimidine or s-triazine) compound 3 is 1:1-1:4；Reaction
Temperature is 20-150 DEG C；Reaction time is 1-24 hours.
4, compound 4 is reacted with (to first) phenyl boric acid 5, and reaction dissolvent is toluene, methanol, acetonitrile, one of water or two
Kind or more；The molar ratio of compound 4 and (to first) phenyl boric acid 5 is 1:1-1:10；Reaction temperature is 50-200 DEG C；Reaction time is
2-24 hours.
5, compound 1a and iodomethane reaction, reaction dissolvent are dioxane, toluene, tetrahydrofuran, dimethyl sulfoxide, dichloro
One or more of methane；The molar ratio of compound 1a and iodomethane is 1:1-1:20；Reaction temperature is 50-150 DEG C；
Reaction time is 6-28 hours.
The invention has the following advantages that
1) raw material sources are extensive, cheap and easily-available or easily prepared.
2) pyridyl group bridging -1 synthetic method of phenyl-amino pyridine compounds and their is simple, preparation efficiency is high, product application is wide
It is general, be easy to derivatization.
3) pyridyl group bridging -1 purposes of phenyl-amino pyridine compounds and their is wider, can be used for preparing high activity complex and urges
The ligand of agent or complex luminescent material etc..
In short, the present invention prepares pyridyl group bridging-phenyl-amino pyridine compounds and their using three step synthetic methods, synthesis
Method is easy, preparation efficiency is high and product is easy to derivatization.
Specific embodiment
The present invention with 2,6- dibromo pyridine 2 and o-aminopyridine (pyrimidine or s-triazine) 3 for starting material, then with (to first)
Phenyl boric acid 5 reacts, and efficiently synthesizes pyridyl group bridging-phenyl-amino pyridine compounds and their 1.By following embodiments facilitate into
One step understands the present invention, but the contents of the present invention are not limited to that.
Embodiment 1
2,6- dibromo pyridines 2 (2.37g, 10.0mmol), o-aminopyridine 3a (1.41g, 15.0mmol), three (two benzal
Benzylacetone) two palladium Pd2(dba)3(183mg, 0.2mmol), 1,1 '-bis- (diphenylphosphine) ferrocene dppf (222mg,
0.4mmol), the mixture of sodium tert-butoxide (1.92g, 20.0mmol) and 30mL dimethylbenzene is stirred to react 12 hours at 110 DEG C.
It is cooled to after room temperature by suction filtered through kieselguhr, and with 100mL eluent methylene chloride, filtrate is concentrated through column chromatography for separation and obtains white
Solid 4a is target product (2.15g, yield 86%).Target product measures to obtain really by nuclear magnetic resoance spectrum and high resolution mass spectrum
Recognize.
Embodiment 2
Compound 4a (2.50g, 10.0mmol), to toluene boric acid 5a (2.04g, 15.0mmol), cesium carbonate CsCO3
(6.50g, 20.0mmol), palladium acetate Pd (OAc)2The mixture of (112mg, 0.5mmol) and 50mL NN- dimethylformamide
It is stirred to react at 80 DEG C 15 hours.50mL ethyl acetate and 50mL water is added after being cooled to room temperature, separates organic phase, water phase is used again
Ethyl acetate (3 × 20mL) extraction, collects organic phase, and anhydrous magnesium sulfate drying is added, and is spin-dried for solvent, and by column chromatography point
From obtaining white solid 1a-1 (2.34g, yield 90%).Target product is measured by nuclear magnetic resoance spectrum and high resolution mass spectrum
To confirmation.
Embodiment 3
The mixture of compound 1a-1 (261mg, 1.0mmol), NaH (80mg, 2.0mmol) and 8mL tetrahydrofuran is in room
Half an hour is stirred to react under temperature.Then iodomethane (284mg, 2.0mmol) is added, temperature rising reflux reacts 10 hours, is cooled to room temperature
20mL methanol quenching reaction is added afterwards, is spin-dried for solvent, mixture obtained by column chromatography for separation, obtain white solid 1b-1 (253mg,
Yield 92%).Target product is confirmed by nuclear magnetic resoance spectrum and high resolution mass spectrum measurement.
Embodiment 4
With embodiment 1, difference from Example 1 is for reaction step and operation, the reaction time 24 hours.Stop anti-
It answers, is equally post-processed to obtain target product 4a (2.15g, yield 86%).Target product passes through nuclear magnetic resoance spectrum and high-resolution
Mass spectroscopy is confirmed.Illustrate that the extension reaction time is unhelpful to target product yield is increased.
Embodiment 5
With embodiment 2, difference from Example 2 is for reaction step and operation, and reaction temperature is 50 DEG C.Stop anti-
It answers, is equally post-processed to obtain target product 1a-1 (1.30g, yield 50%), target product passes through nuclear magnetic resoance spectrum and high score
Distinguish that mass spectroscopy is confirmed.Illustrate that temperature reduction is unfavorable for target product generation.
Embodiment 6
Reaction step and operation are with embodiment 2, and difference from Example 2 is, reaction dissolvent is methanol.Stop anti-
It answers, is equally post-processed to obtain target product 1a-1 (0.65g, yield 25%).Target product passes through nuclear magnetic resoance spectrum and high score
Distinguish that mass spectroscopy is confirmed.Illustrate to be unfavorable for target product generation using protonic solvent.
Embodiment 7
With embodiment 3, difference from Example 3 is for reaction step and operation, the reaction time 28 hours.Stop anti-
It answers, is equally post-processed to obtain target product 1b-1 (253mg, yield 92%).Target product passes through nuclear magnetic resoance spectrum and high score
Distinguish that mass spectroscopy is confirmed.Illustrate that the extension reaction time is unhelpful to target product yield is increased.
Embodiment 8
With embodiment 3, difference from Example 3 is for reaction step and operation, and reaction temperature is 30 DEG C.Stop anti-
It answers, is equally post-processed to obtain target product 1b-1 (69mg, yield 25%).Target product passes through nuclear magnetic resoance spectrum and high-resolution
Mass spectroscopy is confirmed.Illustrate that reaction temperature is too low and is unfavorable for target product generation.
Embodiment 9
With embodiment 3, difference from Example 3 is for reaction step and operation, and reaction dissolvent is Isosorbide-5-Nitrae-dioxane,
100 DEG C of reaction temperature.Stop reaction, is equally post-processed to obtain target product 1b-1 (153mg, yield 56%).Target product
It is confirmed by nuclear magnetic resoance spectrum and high resolution mass spectrum measurement.Illustrate that Isosorbide-5-Nitrae-dioxane can also be used as reaction dissolvent, but
It is not optimum response solvent.
Embodiment 10
Reaction step and operation with embodiment 2, difference from Example 2 is, addition be compound 4b (2.52g,
10.0mmol), stop reaction, equally post-processed to obtain desired product as white solid 1a-2 (2.23g, yield 85%).Target
Product is confirmed by nuclear magnetic resoance spectrum and high resolution mass spectrum measurement.
Application examples 1
Under nitrogen protection, sequentially added into 25mL Schlenk reaction flask ligand 1 b-1 (28mg, 0.1mmol),
RuCl2(PPh3)3(99mg, 0.1mmol), triethylamine (0.5mL) and 10mL isopropanol, back flow reaction 7h.After being cooled to room temperature, mistake
Filter, solid wash (3 × 20mL) with ether.Brick-red solid product 6a (65mg, yield 70%) is obtained after vacuum drying.Target
Product is confirmed by nuclear magnetic resoance spectrum and determination of elemental analysis.
Under nitrogen protection, catalyst 6a (5.6mg, 0.006mmol) is dissolved in 30.0mL isopropanol and is made into catalyst
Solution.Under nitrogen protection, acetophenone (2.0mmol), 10.0mL catalyst solution and 9.8mL isopropanol are stirred 5 at 82 DEG C
Minute.Then the aqueous isopropanol (0.1M) of 0.2mL potassium isopropoxide is injected in reaction system, it is interior at the appointed time, it extracts
The reaction solution of 0.1mL, and immediately with doing gas chromatographic analysis after 0.5mL isopropanol.Under the described conditions, benzene second when 30s
Ketone is reduced to corresponding alcohol product with 98% conversion ratio, illustrates pyridyl group bridging of the invention-phenyl-amino pyridines chemical combination
Object can be used as potential ketone reducing catalyst and use.
Comparative example 1
The known compound shown in above formula and metal ruthenium precursor with reaction equation (8) under the same conditions (instead of application
Ligand 1 b-1 in example 1) it is reacted (reaction equation (10)), discovery raw material is largely remaining, fails to react, the reason is that known chemical combination
Object hydrogen atom at the position a is replaced by isopropyl group, and the compound that the present invention protects has hydrogen atom at a, this is just
Determine that the compound protected of the present invention can be used as the ligand of high activated catalyst and use, and known compound can not, because
Being had in terms of catalyst synthesis based on pyridyl group bridging-phenyl-amino pyridine compounds and their for this this patent report is bigger
Application value.
Typical compound characterize data
Compound 4a, white solid.1H NMR(CDCl3,400MHz):δ8.28(d,1H),8.10(br,NH),7.61(m,
2H),7.43(m,2H),7.00(d,1H),6.89(m,1H)。
Compound 1a-1, white solid, 130-132 DEG C of fusing point.1H NMR(CDCl3,400MHz):δ8.32(d,1H),
7.94(d,2H),7.86(m,2H),7.66(t,2H),7.31(m,4H),6.89(m,1H),2.44(s,3H).13C{1H}NMR
(CDCl3,100MHz)δ155.8,154.2,153.7,147.9,138.9,138.5,137.9,136.8,129.5,126.8,
116.5,112.8,111.9,109.9,21.4.HRMS calcd for C17H15N3 261.1266,found 261.1260。
Claims (9)
1. a kind of pyridyl group bridging-phenyl-amino pyridine compounds and their, structural formula as shown in following formula 1,
Substituent R1For hydrogen or methyl；
Substituent R2=R3=C or R2=C, R3=N or R2=R3=N；
R4For hydrogen, methyl, ethyl, n-propyl, isopropyl or normal-butyl.
2. a kind of bridging of pyridyl group described in claim 1-phenyl-amino pyridine compounds and their synthetic method, it is characterised in that:
It is starting material with dibromo pyridine 2 and aminopyridines 3, by the way that Buchwald-Hartwig cross-coupling reaction occurs
Compound 4 is obtained, compound 4 occurs suzuki coupling reaction with (to first) phenyl boric acid again and obtains compound 1a；Compound 1a can
Compound 1b is obtained so that methylation reaction further occurs with iodomethane；
Wherein, aminopyridines 3 are aminopyridine or aminopyrimidine or amino s-triazine, and structure is as follows,
Substituent R2=R3=C or R2=C, R3=N or R2=R3=N；
Synthetic route is divided into two steps or three steps carries out as shown in following reaction equations,
Substituent R2=R3=C or R2=C, R3=N or R2=R3=N；
Substituent R4For hydrogen, methyl, ethyl, n-propyl, isopropyl or normal-butyl.
3. synthetic method according to claim 2, it is characterised in that:
Wherein: 2,6- dibromo pyridines 2 occur Buchwald-Hartwig with aminopyridine (pyrimidine or s-triazine) compound 3 and intersect
Coupling reaction prepare compound 4, reaction dissolvent are toluene, dimethylbenzene, tetrahydrofuran, dichloroethanes, dioxane, NN- diformazan
Base formamide, N-Methyl pyrrolidone, dimethyl sulfoxide, one of methanol or two kinds or more；2,6- dibromo pyrrole in reaction process
The molar ratio 1:1-1:4, preferably 1:1.5 of pyridine 2 and aminopyridine (pyrimidine or s-triazine) compound 3；Reaction temperature is 20-150
DEG C, preferably 110 DEG C；Reaction time is 1-24 hours, preferably 12 hours.
4. according to synthetic method described in claim 2 or 3, it is characterised in that: 2,6- dibromo pyridines 2 and aminopyridine (pyrimidine
Or s-triazine) reaction of compound 3 preferably carries out in one kind of non-protonic solvent toluene or dimethylbenzene or two kinds.
5. synthetic method according to claim 2, it is characterised in that: compound 4 and phenyl boric acid or to toluene acid reaction,
Reaction dissolvent is toluene, methanol, acetonitrile, water, one or more of NN- dimethylformamide；Compound 4 and (to first)
The molar ratio of phenyl boric acid 5 is 1:1-1:10, preferably 1:1.5；Reaction temperature is 50-200 DEG C, preferably 80 DEG C；Reaction time is 2-
24 hours, preferably 15 hours.
6. synthetic method according to claim 2, it is characterised in that: compound 1a and iodomethane reaction, reaction dissolvent are
One or more of dioxane, toluene, tetrahydrofuran, dimethyl sulfoxide, methylene chloride；Compound 1a and iodomethane
Molar ratio is 1:1-1:20, preferably 1:2；Reaction temperature is 50-150 DEG C, preferably 66 DEG C；Reaction time is 6-28 hours, preferably
10 hours.
7. a kind of pyridyl group bridging-phenyl-amino pyridines ruthenium complex, structural formula as shown in following formula 6,
Substituent R1For hydrogen or methyl；
Substituent R2=R3=C or R2=C, R3=N or R2=R3=N
R4For hydrogen, methyl, ethyl, n-propyl, isopropyl or normal-butyl.
8. a kind of application of pyridyl group bridging-phenyl-amino pyridines ruthenium complex in the reaction of ketone reduction catalysts.
9. applying according to claim 8, it is characterised in that: the ketone be on acetophenone and various phenyl ring containing fluorine, chlorine,
One or more of the acetophenone compounds of one or more of bromine, methyl, methoxyl group, trifluoromethyl,
It is reduced on corresponding benzyl carbinol and phenyl ring contain one or more of fluorine, chlorine, bromine, methyl, methoxyl group, trifluoromethyl
One or more of phenylethanol compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811067601.9A CN109053556A (en) | 2018-09-13 | 2018-09-13 | Pyridyl group bridging-phenyl-amino pyridine compounds and their, complex and its synthesis and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811067601.9A CN109053556A (en) | 2018-09-13 | 2018-09-13 | Pyridyl group bridging-phenyl-amino pyridine compounds and their, complex and its synthesis and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109053556A true CN109053556A (en) | 2018-12-21 |
Family
ID=64761432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811067601.9A Pending CN109053556A (en) | 2018-09-13 | 2018-09-13 | Pyridyl group bridging-phenyl-amino pyridine compounds and their, complex and its synthesis and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109053556A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175019A (en) * | 2020-10-14 | 2021-01-05 | 青岛理工大学 | Pyridyl-bridged NNP cobalt complex and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997013763A1 (en) * | 1995-10-13 | 1997-04-17 | The Penn State Research Foundation | Asymmetric synthesis catalyzed by transition metal complexes with new chiral ligands |
| JP2001104795A (en) * | 1999-10-13 | 2001-04-17 | Mitsubishi Chemicals Corp | Ruthenium catalyst composition |
| CN102924450A (en) * | 2012-11-01 | 2013-02-13 | 西安交通大学 | 6-(5-pyridyl)-1,2,4-triazolopyridine compound, and preparation method and application thereof |
| CN105693696A (en) * | 2014-11-25 | 2016-06-22 | 中国科学院大连化学物理研究所 | Aminopyrazolyldipyridine and preparation method thereof |
| CN108148046A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of pyridyl group bridged pyrazolate base indole derivatives and preparation and application |
-
2018
- 2018-09-13 CN CN201811067601.9A patent/CN109053556A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997013763A1 (en) * | 1995-10-13 | 1997-04-17 | The Penn State Research Foundation | Asymmetric synthesis catalyzed by transition metal complexes with new chiral ligands |
| JP2001104795A (en) * | 1999-10-13 | 2001-04-17 | Mitsubishi Chemicals Corp | Ruthenium catalyst composition |
| CN102924450A (en) * | 2012-11-01 | 2013-02-13 | 西安交通大学 | 6-(5-pyridyl)-1,2,4-triazolopyridine compound, and preparation method and application thereof |
| CN105693696A (en) * | 2014-11-25 | 2016-06-22 | 中国科学院大连化学物理研究所 | Aminopyrazolyldipyridine and preparation method thereof |
| CN108148046A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of pyridyl group bridged pyrazolate base indole derivatives and preparation and application |
Non-Patent Citations (3)
| Title |
|---|
| JEANNE L. BOLLIGER ET AL.: "Access to 2-Aminopyridines – Compounds of Great Biological and Chemical Significance", 《ADV. SYNTH. CATAL.》 * |
| JUN-ICHI ITO ET AL.: "Recent topics of transfer hydrogenation", 《TETRAHEDRON LETTERS》 * |
| MADHAV S. MANE ET AL.: "Designing and Synthesis of N-(6-phenylpyridin-2-yl) Pyridine-2-amine Derivatives as a Novel Antimicrobial Agent", 《J. ENVIRON. NANOTECHNOL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175019A (en) * | 2020-10-14 | 2021-01-05 | 青岛理工大学 | Pyridyl-bridged NNP cobalt complex and application thereof |
| CN112175019B (en) * | 2020-10-14 | 2022-11-25 | 青岛理工大学 | Pyridyl-bridged NNP cobalt complex and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108101733B (en) | Method for preparing polyaryl substituted naphthalene derivative by ruthenium catalysis reaction of fluoroarylone and tolane | |
| CN109651202B (en) | Method for synthesizing carbamate by using dimethyl sulfoxide ylide, amine and carbon dioxide | |
| CN105001028A (en) | Synthesis method for asymmetric conjugate diyne compound | |
| CN105085208B (en) | A kind of preparation method using palladium as catalyst benzfluorene ketone compounds | |
| CN111362895A (en) | Synthesis method of naphthofuran derivative, naphthofuran derivative and application | |
| CN108864147B (en) | Octanitrogen oxygen heterocyclic spiro indolone compound and preparation method thereof | |
| CN104910104A (en) | Method for synthesizing dihydrofuran derivatives under catalytic action of copper | |
| CN104628643A (en) | Preparation method of isoquinolone and derivatives thereof | |
| KR102207333B1 (en) | Novel Production Method for Quadruple Cyclic Compounds | |
| CN105732619A (en) | Synthesizing method of 5,6,7,8-tetrahydropyridino-[2,3-d]pyrimidine compound | |
| CN109053556A (en) | Pyridyl group bridging-phenyl-amino pyridine compounds and their, complex and its synthesis and application | |
| CN101643378A (en) | Method for synthesizing aryl-linking compound | |
| CN110606829A (en) | Method for synthesizing 4-substituted quinoline derivative under palladium catalysis | |
| CN111484436A (en) | Method for introducing isopentenyl group to C3 position of indole | |
| CN105693696A (en) | Aminopyrazolyldipyridine and preparation method thereof | |
| CN114082446A (en) | Chiral zirconium catalyst for preparing chiral alpha-hydroxy-beta-keto ester compound and preparation method thereof | |
| CN101143331B (en) | Non-palladium catalyst system used for coupling reaction | |
| CN111116450B (en) | Axial chiral naphthylamine squaramide organic catalyst, and preparation method and application thereof | |
| KR101614887B1 (en) | Method for preparation of amide and imide from alcohol and nitrogen Containing Compound | |
| CN112624998A (en) | Azacyclolactone compound and preparation method thereof | |
| JP7088690B2 (en) | Method for producing aromatic compounds | |
| CN106831522B (en) | Lactam compound and preparation method thereof | |
| CN111704558A (en) | Method for preparing phenyl-2- (2' -cyanophenyl) acetylene compounds by palladium catalysis | |
| CN115232163B (en) | Silicon center chiral molecular compound and preparation method and application thereof | |
| CN105801578B (en) | A kind of synthetic method of semi-saturation pyrazines derivatives and application |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181221 |