CN103980317B - Dipyridyl tetradentate ligand ruthenium complex as well as preparation method and application thereof - Google Patents
Dipyridyl tetradentate ligand ruthenium complex as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a dipyridyl tetradentate ligand ruthenium complex as well as a preparation method of the complex and application of the complex to a reaction for hydrogenating ester compounds into alcohol compounds. A method for catalytically hydrogenating the ester compounds into the alcohol compounds by using the dipyridyl tetradentate ligand ruthenium complex is characterized by comprising the following steps: by taking 0.001mol% to 0.3mol% of the dipyridyl tetradentate ligand ruthenium complex based on the ester compounds, as a catalyst, adding 1mol%-10mol% of alkali based on the ester compounds, and catalytically hydrogenating the ester compounds into the corresponding alcohol compounds under the conditions that the temperature is 25-100 DEG C and the hydrogen pressure is 1-10MPa. The dipyridyl tetradentate ligand ruthenium complex is convenient to prepare, stable in structure and excellent in catalytic activity in hydrogenation reaction of the ester compounds. According to the preparation method, the shortcomings of requirements on high-temperature high-pressure reaction conditions and high catalyst consumption in an existing homogeneous or non-homogeneous catalytic hydrogenation system of the ester compounds are overcome, the catalyst consumption is low, the reaction conditions are mild, the reaction selectivity is good, and the economy and the safety of a production system are improved.
Description
Technical field
The present invention relates to a kind of new bipyridyl tetradentate ligandses ruthenium complex and preparation method thereof and in ester type compound hydrogen
Turn to the application in alcohol compound reaction.
Background technology
The important reaction that alcohol compound is in organic synthesiss is prepared in ester type compound reduction, no matter in basic scientific research
Or important meaning is had on commercial production.Ester type compound be reduced to alcohol compound in the lab commonly use be hydrogen
Change the negative hydrogen reagents such as aluminum lithium, and these negative hydrogen reagents can produce substantial amounts of inorganic wastes in post processing, and these are active
Negative hydrogen reagent can bring potential safety hazard in a large amount of use, limits its application in commercial production.Using catalytic hydrogenation also
Former ester type compound is a kind of method of high atom economy for alcohol compound, therefore for the hydrogenation of ester type compound
The development of catalyst causes the extensive concern of people.
At present, the heterogeneous catalysis hydrogenation of ester type compound generally requires the harsh conditions of High Temperature High Pressure, such as cu-cr or
The catalyst such as cu-zn-cr are the catalyst being used in ester type compound hydrogenation earliest, but during these catalyst hydrogenations
Generally require very high temperature (200～300 DEG C) and Hydrogen Vapor Pressure (20～30mpa).Chinese patent cn103566933a is open
A kind of using silicon dioxide carried cu catalyst, add mg, one of zn, ni, zr element or mg-zn, mg-zr conduct
Auxiliary agent, is 200～270 DEG C in reaction temperature, the method that Hydrogen Vapor Pressure prepares ethanol for catalytic hydrogenation acetate under the conditions of 3mpa,
Acetic acid ester conversion rate 98%, ethanol selectivity 98%.Cn102976892a disclose a kind of using mesoporous molecular sieve carried cu
Catalyst, the oxide adding at least one element in la, ce is that auxiliary agent is 220 DEG C in reaction temperature, and Hydrogen Vapor Pressure is
The method that under the conditions of 3mpa, catalytic hydrogenation acetate prepares ethanol, acetic acid ester conversion rate 98.5%, ethanol selectivity 99.6%.
Cn102649694a discloses a kind of cu catalyst of the composite carrier load of use silicon oxide and aluminium oxide, adds re, w gold
Belong to element and its oxide as auxiliary agent, be 170～270 DEG C in reaction temperature, Hydrogen Vapor Pressure is urged under the conditions of 1.5～10mpa
Change the method that hydrogenation oxalate prepares ethylene glycol, the conversion ratio of oxalate can reach 100%, and the selectivity of ethylene glycol is more than
95%.Cn101602005b disclose a kind of using silicon dioxide carried pd-cu bimetallic catalyst reaction temperature be 120
～180 DEG C, Hydrogen Vapor Pressure is catalytic hydrogenation 3 under the conditions of 1～5mpa, and 3- acid dimethyl methyl ester synthesizes 3,3- dimethyl butyrate alcohol
Method, the yield 95.6% of 3,3- dimethyl butyrate alcohols.Cn1097038c discloses one kind and is used containing cu, mn, al as basic
The catalyst of composition is 150～230 DEG C in reaction temperature, and Hydrogen Vapor Pressure is by adipate ester and 6- hydroxyl under the conditions of 1～7mpa
Caproic acid ester hydrogenation prepare 1,6- hexanediol method, feed stock conversion 100%, generate 1,6- hexanediol selectivity be higher than
95%.Cn1974510a discloses a kind of ru, rh or ru-zn of use zirconia-supported, ru-co, ru-sn catalyst anti-
Temperature is answered to be 100～150 DEG C, Hydrogen Vapor Pressure is the method that the multiple fatty acid ester of catalytic hydrogenation prepares alcohol under the conditions of 3～7mpa, former
Material conversion ratio is 75.0～99.5%, and selectivity of product is 68.2～99.5%.These heterogeneous catalysis hydro genation system are generally deposited
In the problem of severe reaction conditions (for example: high temperature, high pressure), lead to production cost high, be unfavorable for large-scale production.
No matter the development of the homogeneous catalytic hydrogenation catalyst of ester type compound is obtained in academia or in industrial quarters
Concern.Recent years, more research is obtained based on the ester type compound homogeneous catalytic hydrogenation catalyst of ruthenium, corresponding report
May refer to nearest survey article (acs catalysis2012,2,1718-1741；org.process
Res.dev.2014,18,289-302) and wherein literature cited.Industrial quarters also has more ester type compound homogeneous catalytic hydrogenation
Patent report, such as ep1970360a1 discloses and a kind of prepares alcohol using double ruthenium complex catalysed hydrogenation of carboxylic acid esters of phosphine diamine
Method, wherein for aromatic carboxylic acid esters such as essence of Niobe the s/c ratio of the amount of the material of catalyst (substrate with)=
Under the conditions of 500,100 DEG C and 5mpa Hydrogen Vapor Pressure, reaction 8h can obtain benzyl alcohol with 97.7% yield, for fatty acid ester such as
In s/c=500,100 DEG C and 5mpa Hydrogen Vapor Pressure conditioned response 16h can obtain capryl alcohol with 92.9% yield to methyl caprylate, right
In lactone such as Phthalide in s/c=500,100 DEG C and 5mpa Hydrogen Vapor Pressure conditioned response 18h can obtain adjacent benzene with 98.5% yield
Dimethanol.Ep2141142a1 discloses a kind of method using the ruthenium complex catalysed hydrogenation of carboxylic acid esters of three Phosphine ligands to prepare alcohol, its
In for aromatic carboxylic acid esters such as essence of Niobe in s/c=632, under the conditions of 100 DEG C and 4mpa Hydrogen Vapor Pressure, reaction 15h is permissible
54.1% yield obtains benzyl alcohol, for fatty acid ester such as methyl lactate in s/c=16,377,120 DEG C and 4mpa hydrogen pressure
Under the conditions of power, reaction 16h can obtain 1,2-PD with 88.5% yield, for lactone such as gamma-butyrolacton in s/c=679,
Under the conditions of 100 DEG C and 4mpa Hydrogen Vapor Pressure, reaction 13h can obtain BDO with 69.0% yield.jp2012224600a
Disclose one kind and prepare 2- (l- Herba Menthae using pnp tri- tooth pincer ligand ruthenium complex catalysed hydrogenation l- Herba Menthae ethoxyacetic acid methyl ester
Epoxide) ethanol method, in s/c=2000, under the conditions of 85 DEG C and 4.5mpa Hydrogen Vapor Pressure, reaction 6h can be obtained with 90% yield
To target product.Us20100125144 discloses one kind using the preparation of pnnp tetradentate ligandses ruthenium complex catalysed hydrogenation of carboxylic acid esters
The method of alcohol, wherein for aromatic carboxylic acid esters such as essence of Niobe in s/c=2000,100 DEG C and 5mpa Hydrogen Vapor Pressure condition
Reaction 2.5h can obtain 99% conversion ratio, for fatty acid ester such as methyl caprylate in s/c=2000,100 DEG C and 5mpa hydrogen
Atmospheric pressure conditioned response 2.5h can obtain 97% conversion ratio, for such as third nonalactone of lactone in s/c=2000,100 DEG C
94% conversion ratio can be obtained with 5mpa Hydrogen Vapor Pressure conditioned response 2.5h.W02006106483a1 discloses one kind and uses phosphine
The method that the ruthenium complex catalysed hydrogenation of carboxylic acid esters of amine ligand prepares alcohol, wherein for aromatic carboxylic acid esters such as essence of Niobe in s/
C=2000, the 100 DEG C and 5mpa Hydrogen Vapor Pressure conditioned response 2.5h conversion ratios that can obtain 98%, for example pungent for fatty acid ester
, in s/c=2000, the 100 DEG C and 5mpa Hydrogen Vapor Pressure conditioned response 2.5h conversion ratios that can obtain 86%, for interior for sour methyl ester
Such as third nonalactone of ester in s/c=2000, the 100 DEG C and 5mpa Hydrogen Vapor Pressure conditioned response 2.5h conversions that can obtain 98%
Rate.Wo2012052996a2 discloses a kind of ruthenium complex catalysed hydrogenation of carboxylic acid esters of use pnn tri- tooth pincer ligand and prepares alcohol
Method, wherein for methyl formate in s/c=5000, under the conditions of 110 DEG C and 5mpa Hydrogen Vapor Pressure, reaction 14h can be with 93.7%
Yield obtains methanol, and for dimethyl carbonate in s/c=5000, under the conditions of 110 DEG C and 5mpa Hydrogen Vapor Pressure, reaction 14h is permissible
87.6% yield obtains methanol, for hexyl hexanoate in s/c=4000, reacts 16h under the conditions of 110 DEG C and 5mpa Hydrogen Vapor Pressure
Hexanol can be obtained with 82.1% yield.
On the whole, the homogeneous catalytic hydrogenation of ester type compound can be carried out under conditions of relatively gentle, but mostly
Number report reaction temperatures remain a need for 100 DEG C and more than, the large usage quantity of catalyst, thus increased production cost, be unfavorable for
Industrialized production.Therefore, develop efficient ester type compound homogeneous catalytic hydrogenation catalyst to be particularly important.
Content of the invention
It is an object of the invention to proposing a kind of new bipyridyl tetradentate ligandses ruthenium complex and preparation method thereof and in ester
Class hydrogenation of compounds is the application in alcohol compound reaction.Will be generated in-situ to bipyridyl tetradentate ligandses and metal ruthenium precursor
Pyridine tetradentate ligandses ruthenium complex solution or directly using synthetically prepared solid bipyridyl tetradentate ligandses ruthenium complex as catalysis
Agent is applied in the reaction that alcohol compound is prepared in ester type compound hydrogenation.The bipyridyl tetradentate ligandses ruthenium complex system of the present invention
Standby convenient, Stability Analysis of Structures, show excellent catalysis activity in esters chemical combination hydrogenation.Instant invention overcomes existing esters
Compound is homogeneous or heterogeneous catalysis hydro genation system needs high-temperature high-voltage reaction condition and the shortcoming of high catalyst consumption, catalyst
Consumption is little, and reaction condition is gentle, and the selectivity of reaction is good, improves economy and the safety of production system.
New bipyridyl tetradentate ligandses provided by the present invention have a general structure as shown in i:
Wherein, coordinating group l1And l2Can be independently selected from phosphorous (pr1r2), nitrogen (nr1r2) or sulfur (sr) group, coordination
Group l1、l2Can be identical, also can be different.
r、r1And r2Can be independently selected from c1～c8Alkyl, c3～c8Cycloalkyl, phenyl, the phenyl replacing, 1- naphthyl, 2- naphthalene
The group that base, heteroaryl, benzyl etc. have no adverse effect to reaction.Substituent group on described substituted phenyl is c1～c8Alkyl,
c3～c8The group that cycloalkyl, phenyl, alkoxyl and halogen etc. have no adverse effect to reaction, substituent group quantity is 1～5；Described
Heteroaryl be furyl, thienyl or pyridine radicals etc.；r1、r2Can be identical, also can be different.r1、r2Can and be c3～c8Fat
Ring or aromatic rings.
x1、x2Can be independently selected from h, c1～c8Alkyl, c3～c8Cycloalkyl, phenyl, the phenyl replacing, 1- naphthyl, 2- naphthalene
The group that base, heteroaryl, benzyl, halogen etc. have no adverse effect to reaction；Substituent group on described substituted phenyl is c1～c8
Alkyl, c3～c8Cycloalkyl, phenyl, alkoxyl and halogen etc. to the group that has no adverse effect of reaction, substituent group quantity is 1～
5；Described heteroaryl is furyl, thienyl or pyridine radicals etc.；M=0～3, n=0～3；When m >=2, two adjacent x1
Can and be c3～c8Cycloaliphatic ring or aromatic rings；When n >=2, two adjacent x2Can and be c3～c8Cycloaliphatic ring or aromatic rings；x1、
x2Can be identical, also can be different；
Alternatively, above-described c1～c8Alkyl is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, tert-butyl group etc.；
Described c3～c8Cycloalkyl is cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl etc.；Described alkoxyl be methoxyl group, ethyoxyl,
Positive propoxy, isopropoxy, n-butoxy, tert-butoxy etc..
The present invention is well known to those of ordinary skill in the art, here and hereafter no longer do in detail with regard to the definition of group
Explanation.
Alternatively, bipyridyl tetradentate ligandses include shown in following structural formula:
The in-situ preparation that the present invention provides or synthetically prepared bipyridyl tetradentate ligandses ruthenium complex have as shown in ii
General structure:
Wherein, l1、l2、x1、x2, m, n definition identical with described in formula i；Y, z are h or other complex anion such as halogen
(cl、br、i)、clo4、pf6、bph4、b(c6f5)4、bf4、bh4、ocor、ococf3、oso2r、oso2cf3、cn、or、nr2、sr；r
For h, c1～c8Alkyl, c3～c8Cycloalkyl, phenyl, the phenyl replacing, 1- naphthyl, 2- naphthyl, heteroaryl, benzyl etc. are to reaction
The group having no adverse effect, the substituent group on described substituted phenyl is c1～c8Alkyl, c3～c8Cycloalkyl, phenyl, alcoxyl
The group that base and halogen etc. have no adverse effect to reaction, substituent group quantity is 1～5；Described heteroaryl is furyl, thiophene
Base or pyridine radicals etc.；Y, z can be identical, also can be different.
Alternatively, y, z are identical halogen: cl, br, i.
Y in formula ii, z are that bipyridyl tetradentate ligandses ruthenium complex during identical halogen (cl, br, i) can be by such as lower section
Method is by bipyridyl tetradentate ligandses and metal ruthenium precursor in-situ preparation or synthetically prepared:
1) in-situ preparation: in dichloromethane, oxolane, toluene, n, n- dimethylformamide, dimethyl sulfoxide etc. are organic molten
In agent, the bipyridyl tetradentate ligandses of the present invention of metal ruthenium precursor and amount 1.0～1.5 times amount with respect to ruthenium atom material,
React 4～16 hours at 25～120 DEG C, you can obtain bipyridyl tetradentate ligandses ruthenium complex solution.Or
2) synthetically prepared: in dichloromethane, oxolane, toluene, n, n- dimethylformamide, dimethyl sulfoxide etc. are organic molten
In agent, the bipyridyl tetradentate ligandses of the present invention of metal ruthenium precursor and amount 1.0～1.5 times amount with respect to ruthenium atom material,
React 4～16 hours at 25～120 DEG C, solution rotating is evaporated to original volume～1/10.The solution of concentration is added under agitation
The poor solvent such as ether or normal hexane, separates out dark purple black solid, vacuum filtration, is washed with poor solvents such as ether or normal hexane
Filter cake, obtains solid bipyridyl tetradentate ligandses ruthenium complex after filter cake vacuum drying.
Described metal ruthenium precursor can be rucl3·nh2o、[rucl2(co)3]2、[ru(cod)cl2]n、[ru(nbd)
cl2]n、[rucl2(benzene)]2、[rubr2(benzene)]2、[rui2(benzene)]2、[rucl2(η6-p-cymene)]2、
[rubr2(η6-p-cymene)]2、[rui2(η6-p-cymene)]2、[rucl2(mesitylene)]2、[rubr2
(mesitylene)]2、[rui2(mesitylene)]2、rucl2(pph3)3, rubr2(pph3)3、rui2(pph3)3、rucl2
(dmso)4, wherein: cod=1,5- cyclo-octadiene, nbd=2,5- norbornadiene, dmso=dimethyl sulfoxide) etc..
Alternatively, in-situ preparation or synthetically prepared bipyridyl tetradentate ligandses ruthenium complex include shown in following structural formula:
Y in formula ii, z can be by y for bipyridyl tetradentate ligandses ruthenium complex when h or other complex anion, and z is identical
Halogen (cl, br, i) when bipyridyl tetradentate ligandses ruthenium complex and the sodium hydride of respective amount, Sodium Acetate Trihydrate, sodium perchlorate, four
The inorganic salts such as phenyl boron sodium, Silver Trifluoroacetate exchange anion in-situ and generate and obtain corresponding bipyridyl tetradentate ligandses ruthenium complex
Solution or synthetically prepared obtain corresponding solid bipyridyl tetradentate ligandses ruthenium complex.
The present invention will be molten with metal ruthenium precursor generated in-situ bipyridyl tetradentate ligandses ruthenium complex for bipyridyl tetradentate ligandses
Liquid or synthetically prepared solid bipyridyl tetradentate ligandses ruthenium complex are applied to ester type compound catalytic hydrogenation as catalyst and are
In the reaction of alcohol compound, the ester type compound that is suitable for can be aliphatic carboxylic acid esters, aromatic carboxylic acid esters, formic acid esters,
Carbonic ester and lactone etc., can contain one or more ester groups, can be with the substituent group arbitrarily not affecting hydrogenation.
Described ester type compound is as shown in formula iii:
Wherein, ra、rbCan be independently selected from c1～c30Alkyl, c3～c30Cycloalkyl, c2～c30Thiazolinyl, c3～c30Cycloalkenyl group,
Aryl etc., can contain in these groups does not arbitrarily affect the substituent group of hydrogenation, ra、rbCan be identical, also can be different；ra、
rbCan be connected and form the c of ring-type4～c30Lactone, lactonic ring can contain arbitrarily does not affect the replacement of hydrogenation
Base, on lactonic ring, the carbon atom of correct position can be replaced by hetero atoms such as o, n, s, lactonic ring can be monocyclic or
Multi-ring, described lactone can be saturation lactone or unsaturated lactone.
Described alcohol compound is as shown in formula iv-a, iv-b:
ra、rbDefinition identical with described in formula iii.Work as ra、rbBe not connected when described in alcohol compound such as iv-a,
Shown in iv-b；Work as ra、rbAlcohol compound described in when connected is the dihydroxylic alcohols of gained after corresponding lactone reduction；When hydrogenation is used
Ester type compound in containing multiple ester group when, the alcohol compound of gained is corresponding polyhydric alcohol.
The non-limiting examples of ester type compound include essence of Niobe, ethyl acetate, ethylene carbonate, levulic acid
Methyl ester, dimethyl succinate, gamma-butyrolacton, gamma-valerolactone, Alpha-Methyl-gamma-butyrolacton, methyl glycollate, methyl lactate, first
Ethoxyacetic acid methyl ester, methyl laurate, methyl stearate, trilaurin, glyceryl tristearate, dimethyl oxalate.,
1,2- phthalic acid methyl ester, 1,3- phthalic acid methyl ester, methyl caproate, hexyl hexanoate etc..
The method of the catalytic hydrogenation application to ester type compound for the present invention comprises the steps:
Under argon or nitrogen are protected, catalyst is bipyridyl tetradentate ligandses ruthenium complex (generated in-situ bipyridyl
Tetradentate ligandses ruthenium complex solution or synthetically prepared solid bipyridyl tetradentate ligandses ruthenium complex) and alkali addition reactor inner tube
In, add substrate to be dissolved in the solution of coordinative solvent, tighten reactor and with the careful displacement of hydrogen 3～5 times, adjust Hydrogen Vapor Pressure to
After desirable pressure, stirring reaction no longer changes to pressure at appropriate temperatures, and reactor is recovered room temperature, slowly discharges residual hydrogen
Gas.Product carries out separating-purifying by the conventional organic compound purification process such as column chromatography, distillation.
It is alcohol compound method that the present invention uses bipyridyl tetradentate ligandses ruthenium complex catalysed hydrogenation ester type compound
Be characterised by: catalyst amount be substrate materials amount 0.001～0.3mol%, alkali consumption be substrate materials amount 1～
10mol%, Hydrogen Vapor Pressure 1～10mpa, reaction temperature is 25～100 DEG C, and the response time is 2～64 hours.
The present invention can be carried out to the catalytic hydrogenation of ester type compound under condition of no solvent, but preferably uses solvent.Institute
With the non-limiting examples of solvent be oxolane, in the organic solvent such as ether, 2- methyltetrahydrofuran, isopropanol, toluene
A kind of or wherein several mixed solvents.
The present invention is Feldalat NM, Sodium ethylate, isopropyl to the non-limiting examples of ester type compound alkali used by catalytic hydrogenation
Sodium alkoxide, sodium tert-butoxide, Feldalat KM, potassium ethoxide, potassium isopropoxide, potassium tert-butoxide etc..Alkali used can be added directly in reactor
In pipe or be dissolved in coordinative solvent and be added in reactor inner tube.
The present invention will be molten with metal ruthenium precursor generated in-situ bipyridyl tetradentate ligandses ruthenium complex for bipyridyl tetradentate ligandses
Liquid or directly synthetically prepared solid bipyridyl tetradentate ligandses ruthenium complex is applied to ester type compound hydrogenation as catalyst
Prepare in the reaction of alcohol compound.The bipyridyl tetradentate ligandses ruthenium complex preparation of the present invention is convenient, and Stability Analysis of Structures, in esters
Excellent catalysis activity, good reaction selectivity is shown, yield is high in chemical combination hydrogenation.Instant invention overcomes existing esters
Compound is homogeneous or heterogeneous catalysis hydro genation system needs high-temperature high-voltage reaction condition and the shortcoming of high catalyst consumption, and catalyst is used
Amount is little, and reaction condition is gentle, and reaction temperature and pressure are far below other homogeneous or heterogeneous catalysis systems, the selectivity of reaction
Good, improve economy and the safety of production system, have broad application prospects.
Specific embodiment
Following non-limiting examples can make those of ordinary skill in the art that the present invention is more fully understood, but not with
Any mode limits the present invention.The experimental technique of unreceipted actual conditions in embodiment, generally according to normal condition and handbook
Described in condition, or according to the condition proposed by manufacturer；Material used, reagent etc., if no special instructions, all can be from
Commercial sources obtain.
All Air-sensitive compounds weigh and on vacuum line all in mbraun labstar argon atmosphere glove box
In strict accordance with the technical operation of standard schlenk.1h nmr、13c nmr、31P nmr nuclear magnetic resoance spectrum is respectively by bruker av400
Nuclear magnetic resonance analyser (operating frequency is respectively 400mhz, 101mhz and 162mhz) measures, and the unit of chemical shift is ppm,1h
Nmr spectrum tetramethylsilane as internal standard,13C nmr composes with listed deuterated solvent as internal standard,31Pnmr spectrum uses 85%
h3po4As external standard；High resolution mass spectrum is measured by apexii type ft-icr mass spectrograph, with esi (electron spray ionisation) or maldi (base
The attached ionization of matter assisted laser desorption) it is ion source；Elementary analysiss are measured by elementar vario el elemental analyser；Monocrystalline
Diffraction is measured by rigaku007saturn70 single crystal diffractometer；Gas chromatographic analysiss use agilent7890a gas chromatograph.
Embodiment 1
The preparation of ligand 1
2- methyl -6- (tri-n-butyl tin base) pyridine (8): equipped with constant pressure funnel, turned welt plug and magnetic stir bar
Two mouthfuls of round-bottomed bottles of 500ml of dried and clean in add 2- methyl -6- bromopyridine (20.0g, 116mmol), system is replaced into
Argon atmosphere, adds anhydrous tetrahydro furan (200ml).By system liquid nitrogen-acetone cryostat temperature control to -78 DEG C, dropwise Deca is being just
The hexane solution (2.4m, 56.0ml, 134mmol) of butyl lithium, time for adding is 30 minutes.Drip and finish, continue to stir at -78 DEG C
2 hours.With syringe in system dropwise Deca tri-n-butyltin chloride (45.4g, 140mmol), time for adding is 30 minutes.
Drip and finish, continue to stir 30 minutes at -78 DEG C, clear-cutting forestland is stirred at room temperature reaction overnight (14 hours).By system rotary evaporation
Instrument precipitation, residue with diethyl ether (300ml) dilutes, and is washed with water (200ml) and saturated aqueous common salt (200ml) successively, organic faciess
With anhydrous sodium sulfate drying, stand.Sucking filtration removes desiccant, and filtrate uses Rotary Evaporators precipitation, residue vacuum distillation, collects
145 DEG C/0.4mmhg fraction, obtains nearly colourless oil liquid product 40.0g, yield: 90%.1H nmr (400mhz, cdcl3)δ
7.36 (t, j=7.5hz, 1h), 7.18 (d, j=7.4hz, 1h), 6.95 (d, j=7.6hz, 1h), 2.54 (s, 3h), 1.69-
0.76 (m, 27h).13C nmr (101mhz, cdcl3) δ 173.11 (s), 158.70 (s), 133.40 (s), 129.48 (s),
121.62 (s), 29.22 (s), 27.47 (s), 24.98 (s), 13.82 (s), 9.95 (s) .hrms (esi) calcd for
c18h34nsn+([m+h]+): 384.1708；Found:384.1712.
2- (to Methyl benzenesulfonyl oxygen methyl) -6- bromopyridine (9): stirring equipped with constant pressure funnel, turned welt plug and magnetic force
Mix and in tri- mouthfuls of round-bottomed bottles of 500ml of son, add 2- methylol -6- bromopyridine (11.2g, 59.6mmol) and oxolane
(200ml).By system with ice salt bath temperature control to 0 DEG C, the naoh of ice-water bath that disposable addition is prepared in advance cooling (7.20g,
Water (50ml) solution 180mmol), dropwise Deca paratoluensulfonyl chloride (12.6g, 66.1mmol) be dissolved in oxolane (50ml)
Solution, time for adding be 30 minutes.Drip and finish, be naturally warmed to room temperature, stirring reaction overnight (14 hours), reacted by tlc monitoring
Entirely.By system Rotary Evaporators precipitation, residue from dichloromethane (300ml) dilutes, and uses water (200ml) and saturation food successively
Saline (200ml) washs, organic faciess anhydrous sodium sulfate drying, standing.Sucking filtration removes desiccant, and filtrate is taken off with Rotary Evaporators
Molten, obtain faint yellow solid product, be directly completely used for next step reaction.1H nmr (400mhz, cdcl3) δ 7.81 (d, j=
8.3hz, 2h), 7.56 (d, j=8.0hz, 1h), 7.40 (d, j=7.8hz, 2h), 7.34 (d, j=8.1hz, 2h), 5.09 (s,
2h), 2.44 (s, 3h).13C nmr (101mhz, cdcl3) δ 155.18 (s), 145.38 (s), 141.47 (s), 139.36 (s),
132.48 (s), 130.06 (s), 128.12 (s), 127.82 (s), 120.61 (s), 70.73 (s), 21.73 (s) .hrms (esi)
calcd for c13h13brno3s+([m+h]+): 341.9794；Found:341.9789.
2- (diethylin methyl) -6- bromopyridine (10): in two mouthfuls of round bottoms of the 250ml equipped with turned welt plug and magnetic stir bar
Add 9, diethylamine (43.9g, 600mmol) and oxolane (120ml) in bottle, reaction is stirred at room temperature overnight (14 hours), tlc
Monitoring reaction is completely.By system Rotary Evaporators precipitation, residue from dichloromethane (300ml) dilutes, and uses saturated carbon successively
Sour hydrogen sodium water solution (200ml), water (200ml) and saturated aqueous common salt (200ml) washing, organic faciess anhydrous sodium sulfate drying,
Standing.Sucking filtration removes desiccant, and filtrate uses Rotary Evaporators precipitation, residue vacuum distillation, collects 56 DEG C/0.1mmhg fraction,
Obtain pale yellow oily liquid product 14.0g, two-step reaction yield: 96%.1H nmr (400mhz, cdcl3) δ 7.50 (d, j=
4.9hz, 2h), 7.32 (t, j=4.8hz, 1h), 3.70 (s, 2h), 2.56 (q, j=7.1hz, 4h), 1.03 (t, j=7.1hz,
6h).13C nmr (101mhz, cdcl3) δ 163.09 (s), 141.04 (s), 138.73 (s), 125.85 (s), 121.37 (s),
59.09 (s), 47.51 (s), 12.08 (s) .hrms (esi) calcd for c10h16brn2 +([m+h]+): 243.0491；
Found:243.0487.
6- methyl -6 '-(diethylin methyl) -2,2 '-bipyridyl (11): dry equipped with turned welt plug and magnetic stir bar
8 (14.5g, 37.9mmol), 10 (7.71g, 31.7mmol), four (triphenyls are added in dry clean 100ml schlenk bottle
Phosphine) palladium (1.28g, 1.11mmol) and anhydrous Lithium chloride (4.10g, 96.7mmol), system is deaerated three times with frozen-thawed,
Rearmounted it is changed to argon atmosphere.By system oil bath heating to 120 DEG C, stirring reaction produces a large amount of palladium blacks to system in 16 hours, this
When gc show 10 oneself convert completely.System is cooled to room temperature, adds ethyl acetate (100ml) dilution, kieselguhr is filtered to remove not
Molten thing, adds 6n hydrochloric acid that system is adjusted to acid (ph=3), point liquid.Aqueous phase 6n sodium hydrate aqueous solution is adjusted to alkaline (ph=
13), extracted with ether (3 × 100ml), organic faciess are washed with saturated aqueous common salt (100ml), anhydrous sodium sulfate drying, standing.Take out
Filter desiccant, filtrate uses Rotary Evaporators precipitation, residue vacuum distillation, collects 130 DEG C/0.1mmhg fraction, obtains yellowish
Color oily liquids product 6.40g, yield: 79%.1H nmr (400mhz, cdcl3) δ 8.24 (d, j=7.8hz, 1h), 8.19 (d,
J=7.8hz, 1h), 7.75 (t, j=7.7hz, 1h), 7.68 (t, j=7.7hz, 1h), 7.48 (d, j=7.6hz, 1h), 7.14
(d, j=7.6hz, 1h), 3.83 (s, 2h), 2.65-2.58 (m, overlap ofq and s, 7h), 1.09 (t, j=7.1hz,
6h).13C nmr (101mhz, cdcl3) δ 160.10 (s), 157.87 (s), 156.07 (s), 155.64 (s), 137.12 (s),
137.05 (s), 123.09 (s), 122.73 (s), 119.15 (s), 118.27 (s), 59.53 (s), 47.51 (s), 24.77 (s),
12.18(s).hrms(esi)calcd for c16h22n3 +([m+h]+): 256.1808；Found:256.1807.
6- (diethylin methyl) -6 '-(di-t-butyl phosphinomethyl) -2,2 '-bipyridyl (1): equipped with turned welt plug and
Diisopropylamine (2.38g, 23.5mmol) and anhydrous four are added in the 50ml schlenk bottle of the dried and clean of magnetic stir bar
Hydrogen furan (20ml), system is deaerated three times with frozen-thawed, is finally replaced into argon atmosphere.By system with ice salt bath temperature control extremely
0 DEG C, with the hexane solution (2.4m, 9.8ml, 23.5mmol) of syringe dropwise Deca n-BuLi in system, during Deca
Between be 15 minutes.Drip and finish, continue to stir 1 hour at 0 DEG C, set aside for use.
In the 100ml schlenk bottle of the dried and clean equipped with turned welt plug and magnetic stir bar add 11 (4.01g,
15.7mmol) with anhydrous tetrahydro furan (10ml), system is deaerated three times with frozen-thawed, is finally replaced into argon atmosphere.Will
System ice salt bath temperature control to 0 DEG C, with syringe in system dropwise the oxolane of the above-mentioned lda well prepared in advance of Deca molten
Liquid, time for adding is 15 minutes.Drip and finish, continue to stir 2 hours at 0 DEG C.By system liquid nitrogen-acetone cryostat temperature control to -78
DEG C, it is diluted in anhydrous with the syringe di-t-butylchlorophosphine (5.69g, 31.5mmol) that dropwise Deca freeze thawing deaerates in system
The solution of oxolane (10ml), time for adding is 30 minutes.Drip and finish, continue in -78 DEG C of stirring reactions 30 minutes, clear-cutting forestland
Reaction is stirred at room temperature overnight (14 hours).Ether (30ml) and the water (30ml) of freeze thawing degassing is added after system vacuum desolvation, point
Liquid, ether extraction (2 × 10ml) that aqueous phase freeze thawing deaerates, merge organic faciess, under argon protection, use anhydrous sodium sulfate drying, quiet
Put.It is filtered to remove desiccant, filter vacuum precipitation, residue vacuum distillation, collect 180 DEG C/0.1mmhg fraction, obtain faint yellow
Viscous oil-like liquid, standing gradually solidifies, and obtains faint yellow solid product 3.30g, yield: 53%.1H nmr (400mhz, cdcl3)
δ 8.26 (d, j=7.7hz, 1h), 8.18 (d, j=7.7hz, 1h), 7.74 (t, j=7.7hz, 1h), 7.68 (t, j=7.7hz,
1h), 7.46 (d, j=7.7hz, 1h), 7.40 (d, j=7.7hz, 1h), 3.82 (s, 2h), 3.14 (d, j=2.4hz, 2h),
2.62 (q, j=7.0hz, 4h), 1.18 (d, j=11.0hz, 18h), 1.09 (t, j=7.0hz, 6h).13C nmr (101mhz,
cdcl3) δ 161.46 (d, j=13.7hz), 159.88 (s), 155.70 (s), 155.49 (s), 137.16 (s), 137.00 (s),
123.82 (d, j=8.5hz), 122.75 (s), 119.14 (s), 117.99 (s), 59.46 (s), 47.53 (s), 32.09 (d, j
=21.6hz), 31.97 (d, j=23.9hz), 29.86 (d, j=13.2hz), 12.18 (s).31P nmr (162mhz, cdcl3)
δ37.12(s).hrms(esi)calcd for c24h39n3p+([m+h]+): 400.2876；Found:400.2867.
Embodiment 2
The preparation of part 2
2- [(t-Butyldimethylsilyl) methyl] -6- bromopyridine (12): dry equipped with turned welt plug and magnetic stir bar
Add in dry clean 100ml schlenk bottle 2- methylol -6- bromopyridine (10.6g, 56.4mmol) and imidazoles (15.4g,
226mmol), system is replaced into argon atmosphere, adds anhydrous dmf (50ml), the disposable addition tert-butyl group in argon stream
Dimethylchlorosilane (10.2g, 67.7mmol).Finish, reaction 1 hour is stirred at room temperature, tlc monitoring reaction completely, adds water
(50ml) reaction is quenched, with ether (3 × 100ml) extraction product, organic faciess priority water (100ml) and saturated aqueous common salt
(100ml) wash, anhydrous sodium sulfate drying, standing.Sucking filtration removes desiccant, and filtrate uses Rotary Evaporators precipitation, and residue subtracts
Pressure distillation, collects 92 DEG C/0.1mmhg fraction, obtains colourless oil liquid product 15.3g, yield: 90%.1H nmr (400mhz,
cdcl3) δ 7.56 (t, j=7.7hz, 1h), 7.47 (dd, j=7.6,0.8hz, 1h), 7.33 (dd, j=7.8,0.7hz, 1h),
4.80 (s, 2h), 0.95 (s, 9h), 0.11 (s, 6h).
2- [(t-Butyldimethylsilyl) methyl] -6- (tri-n-butyl tin base) pyridine (13): equipped with turned welt plug and magnetic
Add 12 (15.5g, 51.3mmol) in tetra- mouthfuls of round-bottomed bottles of the 250ml of the dried and clean of power stirrer, system is replaced into argon
Atmosphere, adds anhydrous thf (150ml), by system liquid nitrogen-acetone cryostat temperature control to -78 DEG C, with syringe in system dropwise
The hexane solution (2.4m, 25ml, 60.0mmol) of Deca n-BuLi, time for adding is 30 minutes.Drip and finish, continue -78
DEG C stirring reaction 1 hour.It is diluted in anhydrous thf with syringe to Deca tributyltin chloride (20.0g, 61.4mmol) in system
(30ml) solution, time for adding is 30 minutes.Drip and finish, after continuing to stir 30 minutes at -78 DEG C, clear-cutting forestland is stirred at room temperature instead
Should overnight (14 hours).System Rotary Evaporators precipitation, residue with diethyl ether (200ml) dilute, successively use water (200ml) and
Saturated aqueous common salt (200ml) washs, organic faciess anhydrous sodium sulfate drying, standing.Sucking filtration removes desiccant, and filtrate is steamed with rotation
Send out instrument precipitation, residue vacuum distillation, collect 170 DEG C/0.1mmhg fraction, obtain colourless oil liquid product 23.0g, yield:
87%.1H nmr (400mhz, cdcl3) δ 7.49 (t, j=7.6hz, 1h), 7.31 (d, j=7.4hz, 1h), 7.24 (d, j=
7.8hz, 1h), 4.83 (s, 2h), 1.60-1.49 (m, 6h), 1.36-1.28 (m, 6h), 1.12-1.05 (m, 6h), 0.95 (s,
9h), 0.87 (t, j=7.3hz, 9h), 0.12 (s, 6h).13C nmr (101mhz, cdcl3) δ 172.63 (s), 161.56 (s),
133.78 (s), 130.57 (s), 118.49 (s), 66.77 (s), 29.22 (s), 27.46 (s), 26.10 (s), 18.52 (s),
13.84 (s), 9.98 (s), -5.16 (s) .hrms (esi) calcd for c24h48nosisn+([m+h]+): 514.2522；
Found:514.2530.
6- methylol -6 '-(diethylin methyl) -2,2 '-bipyridyl (14): equipped with turned welt plug and magnetic stir bar
10 (8.51g, 35.0mmol), 13 (21.5g, 42.0mmol), four (triphens are added in the 100ml schlenk bottle of dried and clean
Base phosphine) palladium (1.42g, 1.23mmol) and anhydrous Lithium chloride (4.49g, 106mmol), system is deaerated three times with frozen-thawed,
Finally it is replaced into argon atmosphere.By system oil bath heating to 120 DEG C, stirring reaction produces a large amount of palladium blacks to system in 10 hours,
Now gc shows that 10 convert completely.System is cooled to room temperature, adds ethyl acetate (100ml) dilution, kieselguhr is filtered to remove
Insoluble matter, adds 6n hydrochloric acid that system is adjusted to acid (ph=3), point liquid.Aqueous phase 6n sodium hydrate aqueous solution is adjusted to alkaline (ph
=13), extracted with ether (3 × 100ml), organic faciess are washed with saturated aqueous common salt (100ml), anhydrous sodium sulfate drying, standing.
Sucking filtration removes desiccant, and filtrate uses Rotary Evaporators precipitation, residue vacuum distillation, collects 150 DEG C/0.1mmhg fraction, obtains light
Yellow oily liquid product 8.00g, yield: 84%.1H nmr (400mhz, cdcl3) δ 8.36 (d, j=7.8hz, 1h), 8.26
(d, j=7.8hz, 1h), 7.81,7.79 (2t, partially overlapped, j=7.8hz, 2h), 7.52 (d, j=
7.8hz, 1h), 7.22 (d, j=7.7hz, 1h), 4.83 (s, 2h), 4.06 (s, 1h), 3.84 (s, 2h), 2.63 (q, j=
7.1hz, 4h), 1.10 (t, j=7.1hz, 6h).13C nmr (101mhz, cdcl3) δ 160.26 (s), 158.22 (s), 155.30
(s), 154.76 (s), 137.67 (s), 137.23 (s), 123.19 (s), 120.29 (s), 119.89 (s), 119.06 (s),
64.05 (s), 59.46 (s), 47.53 (s), 12.16 (s) .hrms (esi) calcd for c16h22n3o+([m+h]+):
272.1757；Found:272.1762.
Chloro- 6 '-(the diethylin methyl) -2 of 6-, 2 '-bipyridyl (15): in the drying equipped with turned welt plug and magnetic stir bar
Add 14 (5.81g, 21.4mmol) in clean two mouthfuls of round-bottomed bottles of 250ml, system is replaced into argon atmosphere, add anhydrous two
Chloromethanes (80ml), by 0 DEG C of ice salt bath temperature control of system, with syringe in system dropwise Deca thionyl chloride (13.0g,
109mmol) it is diluted in the solution of dichloromethane (20ml), time for adding is 30 minutes.Drip and finish, remove cryostat, use oil bath heating
To 45 DEG C of stirring reactions 3 hours, tlc monitoring reaction completely, system was cooled to and pours the beaker filling ice cube (100g) after room temperature into
In, be adjusted to alkaline (ph=13) with 6n naoh aqueous solution, with dichloromethane (3 × 50ml) extraction, use successively water (100ml) and
Saturated aqueous common salt (100ml) washs, organic faciess anhydrous sodium sulfate drying, standing.Sucking filtration removes desiccant, and filtrate is steamed with rotation
Send out instrument precipitation, obtain pale brown oil product liquid, this compound is unstable, be all directly used in next step reaction.1h nmr
(400mhz, cdcl3) δ 8.36 (d, j=7.9hz, 1h), 8.28 (d, j=7.7hz, 1h), 7.83 (t, j=7.7hz, 1h),
7.77 (t, j=7.7hz, 1h), 7.50,7.48 (2d, partially overlapped, j=8.8hz and8.4hz, 2h),
4.75 (s, 2h), 3.83 (s, 2h), 2.62 (q, j=7.0hz, 4h), 1.09 (t, j=7.1hz, 6h).13C nmr (101mhz,
cdcl3) δ 160.19 (s), 156.25 (s), 156.07 (s), 154.86 (s), 137.93 (s), 137.25 (s), 123.20 (s),
122.56 (s), 120.49 (s), 119.33 (s), 59.47 (s), 47.54 (s), 47.13 (s), 12.18 (s) .hrms (esi)
calcd for c16h21cln3 +([m+h]+): 290.1419；Found:290.1427.
6- (diethylin methyl) -6 '-(diphenylphosphinomethyl) -2,2 '-bipyridyl (2): equipped with turned welt plug and magnetic
Add potassium tert-butoxide (3.40g, 30.3mmol) in the 250ml schlenk bottle of the dried and clean of power stirrer, system is replaced
For argon atmosphere, add the anhydrous tetrahydro furan (50ml) of freeze thawing degassing, by system with ice salt bath temperature control to 0 DEG C.Use syringe
To in system, the diphenylphosphine (4.69g, 25.2mmol) of dropwise Deca freeze thawing degassing is diluted in anhydrous tetrahydro furan (15ml)
Solution, time for adding is 15 minutes.Drip and finish, continue to keep 0 DEG C of stirring reaction 1 hour, obtain a peony settled solution.With injection
15 solution being dissolved in anhydrous tetrahydro furan (15ml) of device dropwise Deca freeze thawing degassing in system, time for adding is 30 minutes.
Drip and finish, continue to keep 0 DEG C of stirring reaction 30 minutes, clear-cutting forestland is stirred at room temperature reaction overnight (14 hours).With syringe to body
The distilled water (30ml) of freeze thawing degassing, point liquid is added, aqueous phase with ether (2 × 10ml) extraction of freeze thawing degassing, merges again in system
Organic faciess, use anhydrous sodium sulfate drying, standing under argon protection.It is filtered to remove desiccant, filter vacuum precipitation, residue subtracts
Pressure distillation, collects 230 DEG C/0.1mmhg fraction, obtains pale yellow oily liquid product 5.00g, two-step reaction yield: 54%.1h
Nmr (400mhz, cdcl3) δ 8.18 (d, j=7.8hz, 1h), 8.02 (d, j=7.7hz, 1h), 7.69 (t, j=7.7hz,
1h), 7.60 (t, j=7.7hz, 1h), 7.53-7.47 (m, 4h), 7.45 (d, j=7.7hz, 1h), 7.37-7.28 (m, 6h),
7.02 (d, j=7.6hz, 1h), 3.81 (s, 2h), 3.71 (s, 2h), 2.62 (q, j=7.1hz, 4h), 1.09 (t, j=
7.1hz, 6h).13C nmr (101mhz, cdcl3) δ 159.93 (s), 157.46 (d, j=7.5hz), 156.02 (s), 155.49
(s), 138.59 (d, j=14.9hz), 137.06 (s, 2c, one carbon missing due to overlap), 133.15
(d, j=19.0hz), 128.74 (s), 128.47 (d, j=6.8hz), 123.47 (d, j=5.5hz), 122.81 (s),
119.42 (s), 118.45 (d, j=1.4hz), 59.53 (s), and 47.55 (s), 38.72 (d, j=16.3hz), 12.23 (s).31p
Nmr (162mhz, cdcl3)δ-11.09(s).hrms(esi)calcd for c28h31n3p+([m+h]+): 440.2250；
Found:440.2258.
Embodiment 3
The preparation of part 3
6,6 '-dihydroxymethyl -2,2 '-bipyridyl (16): in the dried and clean equipped with turned welt plug and magnetic stir bar
12 (8.49g, 28.1mmol), 13 (16.9g, 33.0mmol), tetrakis triphenylphosphine palladium is added in 100mlschlenk bottle
(1.14g, 0.99mmol) and anhydrous Lithium chloride (3.60g, 84.9mmol), system is deaerated three times with frozen-thawed, the most rearmounted
It is changed to argon atmosphere.By system oil bath heating to 120 DEG C, stirring reaction produces a large amount of palladium blacks, now gc to system in 12 hours
Display 12 converts completely.System is cooled to room temperature, adds ethyl acetate (100ml) dilution, kieselguhr is filtered to remove insoluble matter,
Add 6n hydrochloric acid that system is adjusted to acid (ph=3), point liquid.Aqueous phase 6n sodium hydrate aqueous solution is adjusted to alkaline (ph=13),
Extracted with ether (3 × 100ml), organic faciess are washed with saturated aqueous common salt (100ml), anhydrous sodium sulfate drying, standing.Sucking filtration removes
Remove desiccant, filtrate uses Rotary Evaporators precipitation, obtain white solid product 5.20g, yield: 85%.1H nmr (400mhz,
Dmso) δ 8.23 (d, j=7.7hz, 2h), 7.93 (t, j=7.8hz, 2h), 7.52 (d, j=7.6hz, 2h), 5.48 (t, j=
5.8hz, 2h), 4.65 (d, j=5.7hz, 4h).
6,6 '-dichloromethyl -2,2 '-bipyridyl (17): in the dried and clean equipped with turned welt plug and magnetic stir bar
Add 16 (1.71g, 7.91mmol) in 100ml schlenk bottle, system is replaced into argon atmosphere, add anhydrous methylene chloride
(40ml), by 0 DEG C of ice salt bath temperature control of system, with syringe in system dropwise Deca thionyl chloride (4.81g, 40.4mmol)
It is diluted in the solution of dichloromethane (10ml), time for adding is 15 minutes.Drip and finish, remove cryostat, stirred to 45 DEG C with oil bath heating
Mix reaction 3 hours, tlc monitoring reaction completely, system is cooled to and pours into after room temperature in the beaker filling ice cube (100g), use 6n
Naoh aqueous solution is adjusted to alkaline (ph=13), with dichloromethane (3 × 50ml) extraction, organic phase washed with water (100ml) and satisfying
With saline solution (100ml) washing, anhydrous sodium sulfate drying, standing.Sucking filtration removes desiccant, and filtrate uses Rotary Evaporators precipitation,
Obtain faint yellow solid product 1.80g, yield: 90%.1H nmr (400mhz, cdcl3) δ 8.40 (d, j=7.9hz, 2h), 7.85
(t, j=7.8hz, 2h), 7.51 (d, j=7.7hz, 2h), 4.75 (s, 4h).
6,6 '-bis- (di-t-butyl phosphinomethyl) -2,2 '-bipyridyl (3): dry equipped with turned welt plug and magnetic stir bar
Add 17 (1.01g, 3.99mmol) in dry clean 50ml schlenk bottle, system is replaced into argon atmosphere, add freeze thawing
The di-t-butyl phosphine (2.34g, 16.0mmol) of degassing is diluted in the solution of absolute methanol (30ml), is heated to system with oil bath
60 DEG C of stirring reactions 48 hours, obtain a white suspension.System is cooled to room temperature, adds freeze thawing to deaerate in system with syringe
Triethylamine (2.10g, 20.8mmol), mixture continues to be stirred at room temperature reaction overnight (14 hours).By system vacuum desolvation,
Residue adds the dichloromethane (50ml) of freeze thawing degassing, is washed with the distilled water (3 × 10ml) of freeze thawing degassing, organic faciess are in argon
Anhydrous sodium sulfate drying is used, standing under gas shielded.Filtered with short neutral aluminium sesquioxide post, filter vacuum precipitation, obtain white
Solid product 1.30g, yield: 69%.1H nmr (400mhz, cdcl3) δ 8.17 (d, j=7.7hz, 2h), 7.67 (t, j=
7.7hz, 2h), 7.39 (d, j=7.7hz, 2h), 3.13 (d, j=3.2hz, 4h), 1.18 (d, j=11.0hz, 36h).13c
Nmr (101mhz, cdcl3) δ 161.33 (d, j=13.8hz), 155.49 (s), 136.91 (s), 123.67 (d, j=8.4hz),
117.87 (s), 32.03 (d, j=21.7hz), 31.91 (d, j=23.9hz), 29.81 (d, j=13.2hz).31p nmr
(162mhz, cdcl3)δ37.02(s).hrms(esi)calcd for c28h47n2p2 +([m+h]+): 473.3209；Found:
473.3213.
Embodiment 4
The preparation of part 4
Two mouthfuls of round-bottomed bottles of 100ml of dried and clean equipped with reflux condensing tube, turned welt plug and magnetic stir bar add
17 (1.50g, 5.93mmol), diethylamine (4.30g, 58.8mmol) and oxolane (50ml), by system with oil bath heating extremely
70 DEG C of stirring reactions 4 hours, tlc monitoring reaction is completely.System is cooled to room temperature, uses Rotary Evaporators precipitation, residue uses two
Chloromethanes (50ml) dilute, and are washed with saturated sodium bicarbonate aqueous solution (50ml), water (50ml) and saturated aqueous common salt (50ml) successively
Wash, organic faciess anhydrous sodium sulfate drying, standing.Sucking filtration removes desiccant, and filtrate uses Rotary Evaporators precipitation, and residue reduces pressure
Distillation, collects 120 DEG C/0.1mmhg fraction, obtains pale yellow oily liquid product 1.50g, yield: 78%.1H nmr (400mhz,
cdcl3) δ=8.25 (d, j=7.7,2h), 7.76 (t, j=7.7,2h), 7.48 (d, j=7.6,2h), 3.83 (s, 4h),
2.62 (q, j=7.1,8h), 1.09 (t, j=7.1,12h).13C nmr (101mhz, cdcl3) δ=160.06 (s), 155.69
(s), 137.18 (s), 122.78 (s), 119.23 (s), 59.52 (s), 47.53 (s), 12.21 (s) .hrms (esi) calcd
for c20h31n4 +([m+h]+): 327.2543；Found:327.2550.
Embodiment 5
The preparation of complex 5
In the 15ml schlenk pipe of the dried and clean equipped with turned welt plug and magnetic stir bar add 1 (600mg,
1.50mmol) with [rucl2(η6-p-cymene)]2(400mg, 0.65mmol), system is replaced into argon atmosphere, adds freeze thawing
The anhydrous methylene chloride (5ml) of degassing.Stirring reaction 4 hours under room temperature, obtain a dark purple black suspension, directly use rotary evaporation
Instrument precipitation, residue with diethyl ether (3 × 10ml) washs, sucking filtration, vacuum drying, obtains dark purple black solid powder 740mg, yield:
99%.1H nmr (400mhz, cdcl3) δ 7.93 (d, j=8.0hz, 1h), 7.80-7.71 (m, 2h), 7.48 (d, j=7.6hz,
1h), 7.45-7.33 (m, 2h), 4.45 (s, 2h), 3.62 (d, j=8.5hz, 2h), 3.57,3.54 (2q, partially
Overlapped, j=6.8hz and6.7hz, 2h), 3.25,3.22 (2q, partially overlapped, j=6.6hz
And6.6hz, 2h), 1.44 (d, j=11.8hz, 18h), 1.18 (t, j=7.0hz, 6h).13C nmr (101mhz, cdcl3)δ
169.25 (d, j=3.3hz), 161.58 (d, j=2.0hz), 161.00 (s), 158.56 (s), 134.17 (s), 131.69
(s), 121.16 (d, j=1.9hz), 120.56 (s), 120.47 (s), 120.30 (s), 67.79 (s), 51.42 (s), 38.67
(d, j=14.5hz), 38.31 (d, j=7.1hz), 30.78 (d, j=3.9hz), 10.71 (s).31P nmr (162mhz,
cdcl3)δ63.21(s).anal.calcd.for c24h38cl2n3Pru:c, 50.44；H, 6.70；N, 7.35.found:c,
50.34；H, 6.92；N, 7.31.
Embodiment 6
The preparation of complex 6
In the 15ml schlenk pipe of the dried and clean equipped with turned welt plug and magnetic stir bar add 2 (210mg,
0.48mmol) with [rucl2(η6-p-cymene)]2(122mg, 0.20mmol), system is replaced into argon atmosphere, adds freeze thawing
The dry toluene (5ml) of degassing.System oil bath heating, to 120 DEG C of stirring reactions 16 hours, obtains a dark purple black suspension, very
Empty precipitation, residue with diethyl ether (3 × 5ml) and ethanol (3 × 5ml) washing, sucking filtration, vacuum drying, obtain dark purple black solid powder
Last 210mg, yield: 86%.1H nmr (400mhz, cdcl3) δ 8.00 (d, j=8.3hz, 1h), 7.88-7.81 (m, 2h),
7.80-7.70 (m, 4h), 7.57-7.47 (m, 3h), 7.41-7.31 (m, 6h), 4.54 (s, 2h), 4.27 (d, j=10.2hz,
2h), 3.38,3.35 (2q, partially overlapped, j=6.8hz and6.7hz, 2h), 3.20,3.17 (2q,
Partially overlapped, j=6.4hz and6.6hz, 2h), 1.08 (t, j=7.0hz, 6h).13C nmr (101mhz,
cdcl3) δ 165.93 (d, j=5.1hz), 160.76 (d, j=3.1hz), 160.53 (s), 157.62 (s), 137.24 (d, j=
34.5hz), 134.74 (s), 133.61 (d, j=10.4hz), 132.12 (s), and 129.27 (s), 127.82 (d, j=8.9hz),
121.45 (d, j=2.9hz), 120.82 (s), 120.69 (s), 120.56 (d, j=9.3hz), 66.63 (s), 51.28 (s),
(48.59 d, j=25.4hz), 10.53 (s).31P nmr (162mhz, cdcl3)δ45.75(s).hrms(esi)calcd for
c28h30cln3pru+([m-cl]+): 576.0904；Found:576.0897.
Embodiment 7
The preparation of complex 7
In the 15ml schlenk pipe of the dried and clean equipped with turned welt plug and magnetic stir bar add 3 (113mg,
0.24mmol) with [rucl2(η6-p-cymene)]2(61mg, 0.10mmol), system is replaced into argon atmosphere, adds freeze thawing
The anhydrous methylene chloride (5ml) of degassing.Stirring reaction 4 hours under room temperature, obtain a dark purple black suspension, directly use rotary evaporation
Instrument precipitation, residue with diethyl ether (3 × 5ml) washs, sucking filtration, vacuum drying, obtains dark purple black solid powder 117mg, yield:
91%.1H nmr (400mhz, cdcl3) δ 7.87 (d, j=7.8hz, 2h), 7.63 (t, j=7.8hz, 2h), 7.57 (d, j=
7.7hz, 2h), 3.87 (d, j=8.3hz, 4h), 1.45 (d, j=11.3hz, 36h).13C nmr (101mhz, cdcl3)δ
166.50 (s), 159.51 (s), 134.04 (s), 122.30 (vt, j=4.8hz), 120.45 (s), 39.25 (dd, j=11.8,
6.7hz), 37.46 (vt, j=3.8hz), 30.70 (s).31P nmr (162mhz, cdcl3)δ66.25(s)
.anal.calcd.for c28h46cl2n2p2Ru:c, 52.17；H, 7.19；N, 4.35.found:c, 52.29；H, 6.91；N,
4.56.
Embodiment 8
The operation of elaboration ester type compound catalytic hydrogenation taking gamma-valerolactone as a example:
A) use generated in-situ bipyridyl tetradentate ligandses ruthenium complex solution
Ligand 1 (1.4mg, 3.6 μm of ol) and [rucl is weighed in glove box2(η6-p-cymene)]2(0.9mg, 1.5 μ
Mol) in the 10ml schlenk pipe equipped with turned welt plug and magnetic stir bar, add the oxolane (2.0ml) of freeze thawing degassing,
Under 25 DEG C and the protection of argon ball, stirring reaction 30 minutes, obtains the tetrahydrofuran solution of bipyridyl tetradentate ligandses ruthenium complex 5.Claim
Take Feldalat NM (17mg, 0.3mmol) in the glass reaction inner tube equipped with magnetic stir bar, be put in rapidly in autoclave, displacement
For argon atmosphere.With syringe by the tetrahydrofuran solution of above-mentioned bipyridyl tetradentate ligandses ruthenium complex 5 and freeze thawing degassing pre-
Oxolane (3.0ml) solution of the gamma-valerolactone (300mg, 3.0mmol) first prepared is added in high-pressure hydrogenation kettle, uses hydrogen
Gas replaces the gas five times in autoclave, and finally adjusting Hydrogen Vapor Pressure is 5mpa, and 25 DEG C of stirring reactions 6 hours are to pressure gauge no longer
Change, slowly releases the hydrogen in autoclave, adds 1,5-PD as internal standard, takes a small amount of sample to filter through short silicagel column
The yield using gas Chromatographic Determination Isosorbide-5-Nitrae-pentanediol afterwards is 96%.
Using part 2 and [rucl2(η6-p-cymene)]2Generated in-situ bipyridyl tetradentate ligandses ruthenium complex solution is urged
After changing hydrogenation gamma-valerolactone reaction 14 hours, Isosorbide-5-Nitrae-pentanediol yield is 67%；Using part 3 and [rucl2(η6-p-
cymene)]2After generated in-situ bipyridyl tetradentate ligandses ruthenium complex solution catalyzing hydrogenation gamma-valerolactone reacts 14 hours, 1,
4- pentanediol yield is 25%；Using part 4 and [rucl2(η6-p-cymene)]2Generated in-situ bipyridyl tetradentate ligandses ruthenium
After complex solution catalytic hydrogenation gamma-valerolactone reacts 14 hours, Isosorbide-5-Nitrae-pentanediol yield is 15%.
Analytical conditions for gas chromatography is: agilent db-35 chromatographic column (30m × 0.32mm × 0.25 μm), fid detection
Device, injector temperature is 230 DEG C, and detector temperature is 250 DEG C, and carrier gas is nitrogen, and constant flow rate is 1.0ml/min.Program liter
Temperature: initial temperature is 50 DEG C, rises to 250 DEG C with the heating rate of 10 DEG C/min, keeps 10 minutes at such a temperature.Isosorbide-5-Nitrae-penta two
Alcohol, gamma-valerolactone, the retention time of 1,5-PD are respectively 7.92min, 8.30min, 9.04min.
B) use synthetically prepared solid bipyridyl tetradentate ligandses ruthenium complex
Glove box weighs bipyridyl tetradentate ligandses ruthenium complex 5 (1.7mg, 3.0 μm of ol) and Feldalat NM (17mg,
0.3mmol) in the glass reaction inner tube equipped with magnetic stir bar, it is added thereto to the preparation in advance of freeze thawing degassing with syringe
Gamma-valerolactone (300mg, 3.0mmol) oxolane (5.0ml) solution, stir, be put in rapidly in autoclave, put
It is changed to argon atmosphere.With the gas in hydrogen exchange autoclave five times, finally adjusting Hydrogen Vapor Pressure is 5mpa, 25 DEG C of stirring reactions
No longer change to pressure gauge within 4 hours, slowly release the hydrogen in autoclave, add 1,5-PD as internal standard, take a small amount of
The yield of gas Chromatographic Determination Isosorbide-5-Nitrae-pentanediol used through short silicagel column by sample after filtering be 98%.
Anti- for catalyst hydrogenation gamma-valerolactone using synthetically prepared solid bipyridyl tetradentate ligandses ruthenium complex 6
After answering 7 hours, Isosorbide-5-Nitrae-pentanediol yield is 96%；The use of synthetically prepared solid bipyridyl tetradentate ligandses ruthenium complex 7 is to urge
After agent catalytic hydrogenation gamma-valerolactone reacts 14 hours, Isosorbide-5-Nitrae-pentanediol yield is 30%.
Embodiment 9
Optimized using synthetically prepared bipyridyl tetradentate ligandses ruthenium complex 5 for substrate with gamma-valerolactone and compare catalysis hydrogen
Change the experiment condition of reaction, the reaction result of the experiment condition such as different catalysts, solvent, alkali and Hydrogen Vapor Pressure is shown in Table 1.
The comparison of table 1 gamma-valerolactone hydrogenation experiment conditiona
aReaction condition: s/c=1000,3.0mmol gamma-valerolactone, 3.0 μm of ol5,5.0mllProh, 25 DEG C.bComposed by gas
Measure, be separation yield in bracket, in all reactions, all only observe that Isosorbide-5-Nitrae-pentanediol and unreacted gamma-valerolactone are deposited
?.cS/c=10,000,12mmol gamma-valerolactone, 1.2 μm of ol5,1.0mllProh, 1.2mmol naome.dS/c=100,
000,36mmol gamma-valerolactone, 0.36 μm of ol5,4.0mllProh, 3.6mmol naome.e40℃.
Embodiment 10
Hydrogenation using synthetically prepared bipyridyl tetradentate ligandses ruthenium complex 5 catalytic hydrogenation other ester type compound
The results are shown in Table 2:
The hydrogenation of the other ester type compound of table 2a
aReaction condition: s/c=1000,3.0mmol substrate, 3.0 μm of ol5,3.0mllProh, 0.3mmol naome, 5mpa
h2, 25 DEG C.bGas composes yield, is separation yield in bracket, all only observes target product and unreacted former in all reactions
Material exists.cSurplus materialss are gamma-valerolactone.d100℃.eS/c=333,100 DEG C, 1.0mmol substrate.fOxolane is molten
Agent.gS/c=10,000,12mmol substrate, 1.2 μm of ol5,1.2mmol naome.hS/c=100,000,100mmol benzoic acid
Methyl ester, 1.0 μm of ol5,20mllProh, 10.0mmol naome.l40℃.j10mpa h2.kS/c=100,000,200mmol second
Acetoacetic ester, 2.0 μm of ol5,20.0mmol naoet.
The preparation of bipyridyl tetradentate ligandses ruthenium complex is demonstrated conveniently by above-described embodiment, good stability, and in ester
Excellent catalysis activity is shown, catalyst amount is little, reaction condition is gentle, the selectivity of reaction in class chemical combination hydrogenation
Good, show very high industrial application value.
Claims (10)
1. a kind of bipyridyl tetradentate ligandses are it is characterised in that it has a structural formula as shown in i:
Wherein, coordinating group l1And l2Independently selected from: pr1r2、nr1r2, but it is not simultaneously selected from pr1r2、nr1r2；
r1And r2Independently selected from: c1～c8Alkyl, c3～c8Cycloalkyl, phenyl, the phenyl replacing, 1- naphthyl, 2- naphthyl, heteroaryl
Base, benzyl；Substituent group on described substituted phenyl is c1～c8Alkyl, c3～c8Cycloalkyl, phenyl, alkoxyl and halogen
Element, substituent group quantity is 1～5；Described heteroaryl is furyl, thienyl or pyridine radicals；r1、r2Identical or different；Or r1、
r2And be c3～c8Cycloaliphatic ring or aromatic rings；
x1、x2Independently selected from: h, c1～c8Alkyl, c3～c8Cycloalkyl, phenyl, the phenyl replacing, 1- naphthyl, 2- naphthyl, miscellaneous
Aryl, benzyl, halogen；Substituent group on described substituted phenyl is c1～c8Alkyl, c3～c8Cycloalkyl, phenyl, alkoxyl
And halogen, substituent group quantity is 1～5；Described heteroaryl is furyl, thienyl or pyridine radicals；M=0～3, n=0～
3；When m >=2, two adjacent x1Can and be c3～c8Cycloaliphatic ring or aromatic rings；When n >=2, two adjacent x2Can and be c3
～c8Cycloaliphatic ring or aromatic rings；x1、x2Identical or different.
2. according to the bipyridyl tetradentate ligandses described in claim 1 it is characterised in that described c1～c8Alkyl be methyl, ethyl,
N-pro-pyl, isopropyl, normal-butyl, the tert-butyl group；Described c3～c8Cycloalkyl is cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl；Institute
The alkoxyl stated is methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, tert-butoxy.
3. according to the bipyridyl tetradentate ligandses described in claim 1 it is characterised in that described bipyridyl tetradentate ligandses are structure
Shown in formula 1,2:
4. a kind of bipyridyl tetradentate ligandses ruthenium complex by the bipyridyl tetradentate ligandses preparation described in claim 1, its feature
It is that it has a structural formula as shown in ii:
Wherein, l1、l2、x1、x2, m, n definition identical with described in formula i；Y, z are h, cl, br, i, clo4、pf6、bph4、b
(c6f5)4、bf4、bh4、ocor、ococf3、oso2r、oso2cf3、cn、or、nr2、sr；R is h, c1～c8Alkyl, c3～c8Cycloalkanes
Base, phenyl, the phenyl replacing, 1- naphthyl, 2- naphthyl, heteroaryl, benzyl；Substituent group on described substituted phenyl is c1~
c8Alkyl, c3～c8Cycloalkyl, phenyl, alkoxyl and halogen, substituent group quantity is 1～5；Described heteroaryl be furyl,
Thienyl or pyridine radicals；Y, z are identical or different.
5. it is characterised in that described y, z is identical halogen to bipyridyl tetradentate ligandses ruthenium complex according to claim 4
Element: cl, br, i.
6. bipyridyl tetradentate ligandses ruthenium complex according to claim 4 is it is characterised in that described bipyridyl four tooth is joined
Body ruthenium complex is shown in structural formula 5,6:
7. the preparation method of the bipyridyl tetradentate ligandses ruthenium complex described in claim 4 is it is characterised in that include following method:
1) in-situ preparation: in dichloromethane, oxolane, toluene, n, in n- dimethylformamide or dimethyl sulfoxide organic solvent,
Metal ruthenium precursor and the described bipyridyl tetradentate ligandses of amount 1.0～1.5 times amount with respect to ruthenium atom material, at 25～120 DEG C
Reaction 4～16 hours, you can obtain bipyridyl tetradentate ligandses ruthenium complex solution；
Or
2) synthetically prepared: in dichloromethane, oxolane, toluene, n, n- dimethylformamide, dimethyl sulfoxide organic solvent,
Metal ruthenium precursor and the described bipyridyl tetradentate ligandses of amount 1.0～1.5 times amount with respect to ruthenium atom material, at 25～120 DEG C
Reaction 4～16 hours, solution rotating is evaporated to original volume 1/10；The solution of concentration is added ether or normal hexane under agitation,
Separate out dark purple black solid, vacuum filtration, wash filter cake with ether or normal hexane, after filter cake vacuum drying, obtain solid bipyridyl
Tetradentate ligandses ruthenium complex；
Described metal ruthenium precursor is rucl3·nh2o、[rucl2(co)3]2、[ru(cod)cl2]n、[ru(nbd)cl2]n、
[rucl2ph]2、[rubr2ph]2、[rui2ph]2、[rucl2(p -Methylisopropylbenzene)]2、[rubr2(to isopropyl methyl
Benzene)]2、[rui2(p -Methylisopropylbenzene)]2、[rucl2(1，3，5-trimethyl-benzene)]2、[rubr2(1，3，5-trimethyl-benzene)
]2、[rui2(1，3，5-trimethyl-benzene)]2、rucl2(pph3)3、rubr2(pph3)3、rui2(pph3)3、rucl2(dmso)4, its
In, cod=1,5- cyclo-octadiene, nbd=2,5- norbornadiene, dmso=dimethyl sulfoxide.
8. the application of the bipyridyl tetradentate ligandses ruthenium complex described in claim 4 is it is characterised in that it is used for as catalyst
Ester type compound catalytic hydrogenation synthesizes in the reaction of alcohol compound, and described ester type compound is as shown in formula iii:
Wherein, ra、rbSelected from c1～c30Alkyl, c3～c30Cycloalkyl, c2～c30Thiazolinyl, c3～c30Cycloalkenyl group, aryl, these bases
The substituent group arbitrarily not affecting hydrogenation, r is contained in groupa、rbIdentical or different；Or ra、rbIt is connected and form the c of ring-type4~
c30Lactone, lactonic ring contains arbitrarily does not affect the substituent group of hydrogenation, and on lactonic ring, the carbon atom of correct position can quilt
O, n, s hetero atom replaces, and lactonic ring is monocyclic or multi-ring；Described lactone is saturation lactone or unsaturated lactone；
Described alcohol compound is as shown in formula iv-a, iv-b:
ra、rbDefinition identical with described in formula iii；Work as ra、rbAlcohol compound such as iv-a, iv-b institute described in when not being connected
Show；Work as ra、rbAlcohol compound described in when connected is the dihydroxylic alcohols of gained after corresponding lactone reduction；When hydrogenation esters used
When containing multiple ester group in compound, the alcohol compound of gained is corresponding polyhydric alcohol.
9. the application of bipyridyl tetradentate ligandses ruthenium complex according to claim 8 is it is characterised in that described esters
Compound is: essence of Niobe, ethyl acetate, ethylene carbonate, methyl ester levulinate, dimethyl succinate, gamma-butyrolacton,
Gamma-valerolactone, Alpha-Methyl-gamma-butyrolacton, methyl glycollate, methyl lactate, methoxy menthyl acetate, methyl laurate, Hard Fat
Sour methyl ester, trilaurin, glyceryl tristearate, dimethyl oxalate., 1,2- phthalic acid methyl ester, 1,3- phthalic acid
Methyl ester, methyl caproate, hexyl hexanoate.
10. the application of bipyridyl tetradentate ligandses ruthenium complex according to claim 8 is it is characterised in that to ester type compound
Catalytic hydrogenation application method comprise the steps:
Under argon or nitrogen are protected, by catalyst be bipyridyl tetradentate ligandses ruthenium complex and alkali adds in reactor inner tube,
Add substrate to be dissolved in the solution of coordinative solvent, tighten reactor and with the careful displacement of hydrogen 3～5 times, adjust Hydrogen Vapor Pressure to institute
After needing pressure, stirring reaction no longer changes to pressure at appropriate temperatures, and reactor is recovered room temperature, slowly discharges residual hydrogen
Gas；Product carries out separating-purifying by column chromatography, the conventional organic compound purification process of distillation；
Catalyst amount be substrate materials amount 0.001～0.3mol%, alkali consumption be substrate materials amount 1～
10mol%, Hydrogen Vapor Pressure 1～10mpa, reaction temperature is 25～100 DEG C, and the response time is 2～64 hours；
Solvent for use is one of oxolane, ether, 2- methyltetrahydrofuran, isopropanol, toluene organic solvent or wherein
Several mixed solvents；Alkali used is Feldalat NM, Sodium ethylate, sodium isopropylate, sodium tert-butoxide, Feldalat KM, potassium ethoxide, isopropanol
Potassium, potassium tert-butoxide；The consumption of alkali is 1～10mol% of the amount of ester type compound material.
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