CN103980317A - 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 Novel connected pyridine tetradentate ligands ruthenium complex and preparation method thereof and be the application in alcohol compound reaction in ester compound hydrogenation.
Background technology
It is the important reaction in organic synthesis that alcohol compound is prepared in ester compound reduction, still in industrial production, all has important meaning at basic scientific research.It is the negative hydrogen reagents such as lithium aluminum hydride that ester compound is reduced to alcohol compound conventional in laboratory, and these negative hydrogen reagents can produce a large amount of inorganic wastes in the time of aftertreatment, and these active negative hydrogen reagents can bring potential safety hazard in the time of a large amount of use, have limited its application in industrial production.Adopting catalytic hydrogenation ester reduction compounds is that alcohol compound is a kind of method of atom economy, has therefore caused people's extensive concern for the development of the hydrogenation catalyst of ester compound.
At present, the heterogeneous catalysis hydrogenation of ester compound often needs the severe condition of High Temperature High Pressure, the such as catalyzer such as Cu-Cr or Cu-Zn-Cr is the catalyzer being used in the earliest in ester compound hydrogenation, but often needs very high temperature (200～300 DEG C) and hydrogen pressure (20～30MPa) when these catalyst hydrogenations.Chinese patent CN103566933A discloses a kind of silicon dioxide carried Cu catalyzer that uses, add Mg, Zn, Ni, a kind of element or Mg-Zn in Zr, Mg-Zr is as auxiliary agent, it is 200～270 DEG C in temperature of reaction, hydrogen pressure is the method that under 3MPa condition, catalytic hydrogenation acetic ester is prepared ethanol, acetic ester transformation efficiency 98%, ethanol selectivity 98%.CN102976892A discloses a kind of mesoporous molecular sieve carried Cu catalyzer that uses, the oxide compound that adds at least one element in La, Ce is that auxiliary agent is 220 DEG C in temperature of reaction, hydrogen pressure is the method that under 3MPa condition, catalytic hydrogenation acetic ester is prepared ethanol, acetic ester transformation efficiency 98.5%, ethanol selectivity 99.6%.CN102649694A discloses a kind of Cu catalyzer of the composite carrier load that uses silicon oxide and aluminum oxide, add Re, W metallic element and its oxide compound as auxiliary agent, it is 170～270 DEG C in temperature of reaction, hydrogen pressure is the method that under 1.5～10MPa condition, catalytic hydrogenation barkite is prepared ethylene glycol, the transformation efficiency of barkite can reach 100%, and the selectivity of ethylene glycol is greater than 95%.CN101602005B discloses that a kind of to use silicon dioxide carried Pd-Cu bimetallic catalyst be 120～180 DEG C in temperature of reaction, hydrogen pressure is catalytic hydrogenation 3 under 1～5MPa condition, 3-acid dimethyl methyl esters synthetic 3, the method of 3-dimethyl butyrate alcohol, the yield 95.6% of 3,3-dimethyl butyrate alcohol.CN1097038C discloses that a kind of use contains Cu, Mn, Al is 150～230 DEG C as the catalyzer of basal component in temperature of reaction, hydrogen pressure is, under 1～7MPa condition, adipic acid ester and 6 hydroxycaproic acid ester hydrogenation are prepared to 1, the method of 6-hexylene glycol, feed stock conversion 100%, generate the selectivity of 1,6-hexylene glycol higher than 95%.CN1974510A discloses a kind of Ru, Rh that uses zirconia-supported or Ru-Zn, Ru-Co, Ru-Sn catalyzer is 100～150 DEG C in temperature of reaction, hydrogen pressure is the method that under 3～7MPa condition, the multiple fatty acid ester of catalytic hydrogenation is prepared alcohol, feed stock conversion is 75.0～99.5%, and selectivity of product is 68.2～99.5%.These heterogeneous catalysis hydro genation system ubiquities the problem of severe reaction conditions (for example: high temperature, high pressure), cause production cost high, are unfavorable for large-scale production.
The development of the homogeneous catalytic hydrogenation catalyzer of ester compound is in academia or all obtained concern in industry member.Recent years, the ester compound homogeneous catalytic hydrogenation catalyzer based on ruthenium has obtained more research, and corresponding report can be referring to nearest survey article (ACS Catalysis2012,2,1718-1741; Org.Process Res.Dev.2014,18,289-302) and literature cited wherein.Industry member also has the patent report of more ester compound homogeneous catalytic hydrogenation, for example EP1970360A1 discloses a kind of method that uses pair ruthenium complex catalysed hydrogenation of carboxylic acid esters of phosphine diamine to prepare alcohol, wherein for aromatic carboxylic acid esters if methyl benzoate is in the S/C ratio of the amount of substance of catalyzer (substrate with)=500, under 100 DEG C and 5MPa hydrogen pressure condition, react the yield that 8h can 97.7% and obtain phenylcarbinol, for fatty acid ester if methyl caprylate is at S/C=500, 100 DEG C and 5MPa hydrogen pressure conditioned response 16h can 92.9% yield obtain octanol, for lactone if phthalide is at S/C=500, 100 DEG C and 5MPa hydrogen pressure conditioned response 18h can 98.5% yield obtain phthalyl alcohol.EP2141142A1 discloses a kind of method that uses the ruthenium complex catalysed hydrogenation of carboxylic acid esters of triphosphine part to prepare alcohol, wherein for aromatic carboxylic acid esters if methyl benzoate is at S/C=632, under 100 DEG C and 4MPa hydrogen pressure condition, react the yield that 15h can 54.1% and obtain phenylcarbinol, for fatty acid ester if methyl lactate is at S/C=16, 377, under 120 DEG C and 4MPa hydrogen pressure condition, react the yield that 16h can 88.5% and obtain 1, 2-propylene glycol, for lactone if gamma-butyrolactone is at S/C=679, under 100 DEG C and 4MPa hydrogen pressure condition, react the yield that 13h can 69.0% and obtain 1, 4-butyleneglycol.JP2012224600A discloses the method that the ruthenium complex catalysed hydrogenation L-of a kind of use PNP tri-tooth pincer ligand peppermint ethoxyacetic acid methyl esters is prepared 2-(L-peppermint oxygen base) ethanol, at S/C=2000, under 85 DEG C and 4.5MPa hydrogen pressure condition, react the yield that 6h can 90% and obtain target product.US20100125144 discloses the method that the ruthenium complex catalysed hydrogenation of carboxylic acid esters of a kind of PNNP of use tetradentate ligands is prepared alcohol, wherein for aromatic carboxylic acid esters if methyl benzoate is at S/C=2000, can obtain 99% transformation efficiency with 5MPa hydrogen pressure conditioned response 2.5h for 100 DEG C, for fatty acid ester if methyl caprylate is at S/C=2000, can obtain 97% transformation efficiency with 5MPa hydrogen pressure conditioned response 2.5h for 100 DEG C, if third nonalactone is at S/C=2000, can obtain 94% transformation efficiency with 5MPa hydrogen pressure conditioned response 2.5h for lactone for 100 DEG C.W02006106483A1 discloses a kind of method that uses the ruthenium complex catalysed hydrogenation of carboxylic acid esters of phosphine amine ligand to prepare alcohol, wherein for aromatic carboxylic acid esters if methyl benzoate is at S/C=2000, can obtain 98% transformation efficiency with 5MPa hydrogen pressure conditioned response 2.5h for 100 DEG C, for fatty acid ester if methyl caprylate is at S/C=2000, can obtain 86% transformation efficiency with 5MPa hydrogen pressure conditioned response 2.5h for 100 DEG C, if third nonalactone is at S/C=2000, can obtain 98% transformation efficiency with 5MPa hydrogen pressure conditioned response 2.5h for lactone for 100 DEG C.WO2012052996A2 discloses the method that the ruthenium complex catalysed hydrogenation of carboxylic acid esters of a kind of PNN of use tri-tooth pincer ligand is prepared alcohol, wherein for methyl-formiate at S/C=5000, under 110 DEG C and 5MPa hydrogen pressure condition, react the yield that 14h can 93.7% and obtain methyl alcohol, for methylcarbonate at S/C=5000, under 110 DEG C and 5MPa hydrogen pressure condition, react the yield that 14h can 87.6% and obtain methyl alcohol,, under 110 DEG C and 5MPa hydrogen pressure condition, react the yield that 16h can 82.1% and obtain hexanol at S/C=4000 for hexyl hexanoate.
On the whole, the homogeneous catalytic hydrogenation of ester compound can carry out under relatively relatively mild condition, but the temperature of reaction of great majority reports still need 100 DEG C and more than, the large usage quantity of catalyzer, thus increased production cost, be unfavorable for suitability for industrialized production.Therefore, develop efficient ester compound homogeneous catalytic hydrogenation catalyzer and seem particularly important.
Summary of the invention
The object of the invention is to propose a kind of Novel connected pyridine tetradentate ligands ruthenium complex and preparation method thereof and be the application in alcohol compound reaction in ester compound hydrogenation.By dipyridyl tetradentate ligands and the generated in-situ dipyridyl tetradentate ligands of metal Ru precursor ruthenium complex solution or directly the solid dipyridyl tetradentate ligands ruthenium complex of synthetic preparation is applied to ester compound hydrogenation as catalyzer and prepares in reacting of alcohol compound.Dipyridyl tetradentate ligands ruthenium complex of the present invention is easy to prepare, and Stability Analysis of Structures shows excellent catalytic activity in ester class chemical combination hydrogenation.The present invention has overcome the shortcoming that existing ester compound homogeneous phase or heterogeneous catalysis hydro genation system need high-temperature high-voltage reaction condition and high catalyst consumption, catalyst levels is little, reaction conditions gentleness, the selectivity of reaction is good, has improved economy and the security of production system.
Novel connected pyridine tetradentate ligands provided by the present invention has the general structure as shown in I:
Wherein, coordinating group L
1and L
2can be independently selected from phosphorous (pR
1r
2), nitrogen (NR
1r
2) or the group of sulphur (SR), coordinating group L
1, L
2can be identical, also can be different.
R, R
1and R
2can be independently selected from C
1～C
8alkyl, C
3～C
8the group that the phenyl of cycloalkyl, phenyl, replacement, 1-naphthyl, 2-naphthyl, heteroaryl, benzyl etc. have no adverse effect to reaction.Substituting group on the phenyl of described replacement is C
1～C
8alkyl, C
3～C
8the group that cycloalkyl, phenyl, alkoxyl group and halogen etc. have no adverse effect to reaction, substituting group quantity is 1～5; Described heteroaryl is furyl, thienyl or pyridyl etc.; R
1, R
2can be identical, also can be different.R
1, R
2can and be C
3～C
8cycloaliphatic ring or aromatic nucleus.
X
1, X
2can be independently selected from H, C
1～C
8alkyl, C
3～C
8the group that the phenyl of cycloalkyl, phenyl, replacement, 1-naphthyl, 2-naphthyl, heteroaryl, benzyl, halogen etc. have no adverse effect to reaction; Substituting group on the phenyl of described replacement is C
1～C
8alkyl, C
3～C
8the group that cycloalkyl, phenyl, alkoxyl group and halogen etc. have no adverse effect to reaction, substituting group quantity is 1～5; Described heteroaryl is furyl, thienyl or pyridyl etc.; M=0～3, n=0～3; In the time of m>=2, two adjacent X
1can and be C
3～C
8cycloaliphatic ring or aromatic nucleus; In the time of n>=2, two adjacent X
2can and be C
3～C
8cycloaliphatic ring or aromatic nucleus; X
1, X
2can be identical, also can be different;
Alternatively, above-described C
1～C
8alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl etc.; Described C
3～C
8cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc.; Described alkoxyl group is methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy etc.
The present invention is well known to those of ordinary skill in the art about the definition of group, at this and be below no longer described in detail.
Alternatively, dipyridyl tetradentate ligands comprises below shown in structural formula:
Original position provided by the invention generates or the dipyridyl tetradentate ligands ruthenium complex of synthetic preparation has the general structure as shown in II:
Wherein, L
1, L
2, X
1, X
2, m, n definition with identical described in general formula I; Y, Z is that H or other complex anion are as halogen (Cl, Br, I), ClO
4, PF
6, BPh
4, B (C
6f
5)
4, BF
4, BH
4, OCOR, OCOCF
3, OSO
2r, OSO
2cF
3, CN, OR, NR
2, SR; R is H, C
1～C
8alkyl, C
3～C
8the group that the phenyl of cycloalkyl, phenyl, replacement, 1-naphthyl, 2-naphthyl, heteroaryl, benzyl etc. have no adverse effect to reaction, the substituting group on the phenyl of described replacement is C
1～C
8alkyl, C
3～C
8the group that cycloalkyl, phenyl, alkoxyl group and halogen etc. have no adverse effect to reaction, substituting group quantity is 1～5; Described heteroaryl is furyl, thienyl or pyridyl etc.; Y, Z can be identical, also can be different.
Alternatively, Y, Z is identical halogen: Cl, Br, I.
Y in general formula I I, dipyridyl tetradentate ligands ruthenium complex when Z is identical halogen (Cl, Br, I) can be generated or synthetic preparation by dipyridyl tetradentate ligands and metal Ru precursor original position as follows:
1) original position generates: at methylene dichloride, tetrahydrofuran (THF), toluene, N, in the organic solvent such as dinethylformamide, methyl-sulphoxide, metal Ru precursor and with respect to the dipyridyl tetradentate ligands of the present invention of 1.0～1.5 times of amounts of ruthenium atom amount of substance, 25～120 DEG C of reactions 4～16 hours, can obtain dipyridyl tetradentate ligands ruthenium complex solution.Or
2) synthetic preparation: at methylene dichloride, tetrahydrofuran (THF), toluene, N, in the organic solvent such as dinethylformamide, methyl-sulphoxide, metal Ru precursor and with respect to the dipyridyl tetradentate ligands of the present invention of 1.0～1.5 times of amounts of ruthenium atom amount of substance, 25～120 DEG C of reactions 4～16 hours, solution rotating was evaporated to original volume～1/10.Concentrated solution is under agitation added to the poor solvent such as ether or normal hexane, separate out dark purple black solid, vacuum filtration, with the poor solvent such as ether or normal hexane washing leaching cake, obtains solid dipyridyl tetradentate ligands ruthenium complex after filter cake vacuum-drying.
Described metal Ru precursor can be RuCl
3nH
2o, [RuCl
2(CO)
3]
2, [Ru (cod) Cl
2]
n, [Ru (nbd) Cl
2]
n, [RuCl
2(benzene)]
2, [RuBr
2(benzene)]
2, [RuI
2(benzene)]
2, [RuCl
2(η
6-p-cymene)]
2, [RuBr
2(η
6-p-cymene)]
2, [RuI
2(η
6-p-cymene)]
2, [RuCl
2(mesitylene)]
2, [RuBr
2(mesitylene)]
2, [RuI
2(mesitylene)]
2, RuCl
2(PPh
3)
3,, RuBr
2(PPh
3)
3, RuI
2(PPh
3)
3, RuCl
2(DMSO)
4, wherein: cod=1,5-cyclooctadiene, nbd=2,5-norbornadiene, DMSO=methyl-sulphoxide) etc.
Alternatively, original position generates or synthesizes the dipyridyl tetradentate ligands ruthenium complex of preparing and comprises below shown in structural formula:
Y in general formula I I, dipyridyl tetradentate ligands ruthenium complex when Z is H or other complex anion can be by Y, and the inorganic salt exchange anion in-situs such as dipyridyl tetradentate ligands ruthenium complex when Z is identical halogen (Cl, Br, I) and the sodium hydride of respective amount, sodium-acetate, sodium perchlorate, tetraphenyl boron sodium, Silver Trifluoroacetate generate and obtain corresponding dipyridyl tetradentate ligands ruthenium complex solution or syntheticly prepare corresponding solid dipyridyl tetradentate ligands ruthenium complex.
It is in reacting of alcohol compound that the present invention is applied to ester compound catalytic hydrogenation with the solid dipyridyl tetradentate ligands ruthenium complex of the generated in-situ dipyridyl tetradentate ligands of metal Ru precursor ruthenium complex solution or synthetic preparation as catalyzer using dipyridyl tetradentate ligands, applicable ester compound can be aliphatic carboxylic acid esters,, aromatic carboxylic acid esters, manthanoate, carbonic ether and lactone etc., can contain one or more ester groups, can be with the substituting group that does not affect arbitrarily hydrogenation.
Described ester compound is as shown in general formula III:
Wherein, R
a, R
bcan be independently selected from C
1～C
30alkyl, C
3～C
30cycloalkyl, C
2～C
30thiazolinyl, C
3～C
30cycloalkenyl group, aryl etc., can contain the substituting group that does not affect arbitrarily hydrogenation, R in these groups
a, R
bcan be identical, also can be different; R
a, R
bcan be connected and form the C of ring-type
4～C
30lactone, on lactonic ring, can contain the substituting group that does not affect arbitrarily hydrogenation, on lactonic ring, the carbon atom of correct position can be replaced by heteroatomss such as O, N, S, and lactonic ring can be monocycle, also can be many rings, described lactone can be saturated lactone or unsaturated lactone.
Described alcohol compound is as shown in general formula I V-a, IV-b:
R
a, R
bdefinition with identical described in general formula III.Work as R
a, R
balcohol compound described in while not being connected is as shown in IV-a, IV-b; Work as R
a, R
balcohol compound described in while being connected is the dibasic alcohol of gained after corresponding lactone reduction; In the time containing multiple ester group in hydrogenation ester compound used, the alcohol compound of gained is corresponding polyvalent alcohol.
The limiting examples of ester compound comprises methyl benzoate, ethyl acetate, ethylene carbonate, methyl ester levulinate, Succinic acid dimethylester, gamma-butyrolactone, γ-valerolactone, Alpha-Methyl-gamma-butyrolactone, methyl glycolate, methyl lactate, methoxy menthyl acetate, Laurate methyl, methyl stearate, trilaurin, Tristearoylglycerol, dimethyl oxalate, 1,2-phthalic acid methyl esters, 1,3-phthalic acid methyl esters, methyl caproate, hexyl hexanoate etc.
The method of the catalytic hydrogenation application of the present invention to ester compound comprises the steps:
Under argon gas or nitrogen protection; be that dipyridyl tetradentate ligands ruthenium complex (the solid dipyridyl tetradentate ligands ruthenium complex of generated in-situ dipyridyl tetradentate ligands ruthenium complex solution or synthetic preparation) and alkali add in reactor inner tube by catalyzer; add substrate to be dissolved in the solution of coordinative solvent; tighten reactor and replace 3～5 times with hydrogen is careful; regulate hydrogen pressure to required pressure; under suitable temp, stirring reaction to pressure no longer changes; reactor is recovered to room temperature, slowly discharge remaining hydrogen.Product carries out separating-purifying by the conventional organic compound purification process such as column chromatography, distillation.
The present invention uses the ruthenium complex catalysed hydrogenated ester compounds of dipyridyl tetradentate ligands to be characterised in that for alcohol compound method: catalyst levels is 0.001～0.3mol% of substrate amount of substance, alkali consumption is 1～10mol% of substrate amount of substance, hydrogen pressure 1～10MPa, temperature of reaction is 25～100 DEG C, and the reaction times is 2～64 hours.
The present invention can carry out the catalytic hydrogenation of ester compound under condition of no solvent, but preferably uses solvent.The limiting examples of solvent for use is a kind of in the organic solvents such as tetrahydrofuran (THF), ether, 2-methyltetrahydrofuran, Virahol, toluene or several mixed solvent wherein.
The limiting examples of the catalytic hydrogenation used alkali of the present invention to ester compound is sodium methylate, sodium ethylate, sodium isopropylate, sodium tert-butoxide, potassium methylate, potassium ethylate, potassium isopropoxide, potassium tert.-butoxide etc.Alkali used can directly join in reactor inner tube or be dissolved in coordinative solvent and join in reactor inner tube.
The present invention is by dipyridyl tetradentate ligands and the generated in-situ dipyridyl tetradentate ligands of metal Ru precursor ruthenium complex solution or directly the solid dipyridyl tetradentate ligands ruthenium complex of synthetic preparation is applied to ester compound hydrogenation as catalyzer and prepares in reacting of alcohol compound.Dipyridyl tetradentate ligands ruthenium complex of the present invention is easy to prepare, and Stability Analysis of Structures shows excellent catalytic activity in ester class chemical combination hydrogenation, good reaction selectivity, and productive rate is high.The present invention has overcome the shortcoming that existing ester compound homogeneous phase or heterogeneous catalysis hydro genation system need high-temperature high-voltage reaction condition and high catalyst consumption, catalyst levels is little, reaction conditions gentleness, temperature of reaction and pressure are far below other homogeneous phases or heterogeneous catalysis system, the selectivity of reaction is good, the economy and the security that have improved production system, have broad application prospects.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.The experimental technique of unreceipted actual conditions in embodiment, conventionally according to the condition described in normal condition and handbook, or the condition of advising according to manufacturer; Material, reagent etc. used, if no special instructions, all can obtain from commercial channels.
All Air-sensitive compounds all in MBRAUN LABstar argon atmosphere glove box weigh and on vacuum line in strict accordance with standard Schlenk technological operation.
1h NMR,
13c NMR,
31p nuclear magnetic resonance spectrum is measured by Bruker AV400 nuclear magnetic resonance analyser (operating frequency is respectively 400MHz, 101MHz and 162MHz) respectively, and the unit of chemical shift is ppm,
1h NMR spectrum uses tetramethylsilane as interior mark,
13c NMR spectrum with listed deuterated solvent as interior mark,
31pNMR spectrum 85%H
3pO
4as external standard; High resolution mass spectrum is measured by APEXII type FT-ICR mass spectrograph, taking ESI (electron spray ionisation) or MALDI (matrix assisted laser desorption ionization ionization) as ion source; Ultimate analysis is measured by Elementar Vario EL elemental analyser; Single crystal diffraction is measured by Rigaku007Saturn70 single crystal diffractometer; Gas chromatographic analysis is used Agilent7890A gas chromatograph.
Embodiment 1
The preparation of ligand 1
2-methyl-6-(tri-n-butyl tin base) pyridine (8): add 2-methyl-6-bromopyridine (20.0g in two mouthfuls of round-bottomed bottles of 500mL of dried and clean that constant pressure funnel, turned welt plug and magnetic stir bar are housed, 116mmol), system is replaced into argon atmosphere, adds anhydrous tetrahydro furan (200mL).Liquid nitrogen-acetone cryostat temperature control for system, to-78 DEG C, is dropwise dripped to the hexane solution (2.4M, 56.0mL, 134mmol) of n-Butyl Lithium, and time for adding is 30 minutes.Drip and finish, continue to stir 2 hours at-78 DEG C.In system, dropwise drip tri-n-butyltin chloride (45.4g, 140mmol) with syringe, time for adding is 30 minutes.Drip and finish, continue to stir 30 minutes at-78 DEG C, naturally recovery room temperature stirring reaction spend the night (14 hours).By system Rotary Evaporators precipitation, ether for resistates (300mL) dilution, water (200mL) and saturated aqueous common salt (200mL) washing successively, organic phase anhydrous sodium sulfate drying, leaves standstill.Suction filtration is removed siccative, and filtrate is used Rotary Evaporators precipitation, and 145 DEG C/0.4mmHg cut is collected in resistates underpressure distillation, obtains nearly colourless oil liquid product 40.0g, yield: 90%.
1H?NMR(400MHz，CDCl
3)δ7.36(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，CDCl
3)δ173.11(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?C
18H
34NSn
+([M+H]
+)：384.1708；Found：384.1712.
2-(to Methyl benzenesulfonyl oxygen methyl)-6-bromopyridine (9): add 2-methylol-6-bromopyridine (11.2g, 59.6mmol) and tetrahydrofuran (THF) (200mL) in tri-mouthfuls of round-bottomed bottles of 500mL that constant pressure funnel, turned welt plug and magnetic stir bar are housed.System is bathed to temperature control to 0 DEG C with cryosel, the disposable cooling NaOH (7.20g of ice-water bath of preparation in advance that adds, water (50ml) solution 180mmol), dropwise drip Tosyl chloride (12.6g, 66.1mmol) be dissolved in the solution of tetrahydrofuran (THF) (50mL), time for adding is 30 minutes.Drip and finish, naturally rise to room temperature, stirring reaction spends the night (14 hours), and TLC monitoring reacts completely.By system Rotary Evaporators precipitation, methylene dichloride for resistates (300mL) dilution, water (200mL) and saturated aqueous common salt (200mL) washing successively, organic phase anhydrous sodium sulfate drying, leaves standstill.Suction filtration is removed siccative, and filtrate is used Rotary Evaporators precipitation, obtains faint yellow solid product, directly all for next step reaction.
1H?NMR(400MHz，CDCl
3)δ7.81(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，CDCl
3)δ155.18(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?C
13H
13BrNO
3S
+([M+H]
+)：341.9794；Found：341.9789.
2-(diethylin methyl)-6-bromopyridine (10): add 9 in two mouthfuls of round-bottomed bottles of 250mL that turned welt plug and magnetic stir bar are housed, diethylamine (43.9g, 600mmol) and tetrahydrofuran (THF) (120mL), stirring at room temperature reaction is spent the night (14 hours), and TLC monitoring reacts completely.By system Rotary Evaporators precipitation, methylene dichloride for resistates (300mL) dilution, use successively saturated sodium bicarbonate aqueous solution (200mL), water (200mL) and saturated aqueous common salt (200mL) washing, organic phase anhydrous sodium sulfate drying, leaves standstill.Suction filtration is removed siccative, and filtrate is used Rotary Evaporators precipitation, and 56 DEG C/0.1mmHg cut is collected in resistates underpressure distillation, obtains pale yellow oily liquid body product 14.0g, two-step reaction yield: 96%.
1H?NMR(400MHz，CDCl
3)δ7.50(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，CDCl
3)δ163.09(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?C
10H
16BrN
2 +([M+H]
+)：243.0491；Found：243.0487.
6-methyl-6 '-(diethylin methyl)-2,2 '-dipyridyl (11): add 8 (14.5g in the 100mL Schlenk bottle of dried and clean that turned welt plug and magnetic stir bar are housed, 37.9mmol), 10 (7.71g, 31.7mmol), tetrakis triphenylphosphine palladium (1.28g, 1.11mmol) and Lithium chloride (anhydrous) (4.10g, 96.7mmol), by degassed three times of frozen-thawed of system, be finally replaced into argon atmosphere.System is heated to 120 DEG C with oil bath, and stirring reaction 16 hours to system produces a large amount of palladium blacks, now GC show 10 oneself transform completely.System is chilled to room temperature, adds ethyl acetate (100mL) dilution, diatomite filtration is removed insolubles, adds 6N hydrochloric acid that system is adjusted to acidity (pH=3), separatory.Water is adjusted to alkalescence (pH=13) with 6N aqueous sodium hydroxide solution, and with ether (3 × 100mL) extraction, saturated aqueous common salt for organic phase (100mL) washing, anhydrous sodium sulfate drying, leaves standstill.Suction filtration is removed siccative, and filtrate is used Rotary Evaporators precipitation, and 130 DEG C/0.1mmHg cut is collected in resistates underpressure distillation, obtains pale yellow oily liquid body product 6.40g, yield: 79%.
1H?NMR(400MHz，CDCl
3)δ8.24(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，CDCl
3)δ160.10(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?C
16H
22N
3 +([M+H]
+)：256.1808；Found：256.1807.
6-(diethylin methyl)-6 '-(di-t-butyl phosphinomethyl)-2,2 '-dipyridyl (1): add diisopropylamine (2.38g in the 50mL Schlenk bottle of dried and clean that turned welt plug and magnetic stir bar are housed, 23.5mmol) and anhydrous tetrahydro furan (20mL), by degassed three times of frozen-thawed of system, be finally replaced into argon atmosphere.Cryosel for system is bathed to temperature control to 0 DEG C, and with syringe, to the hexane solution (2.4M, 9.8mL, 23.5mmol) that dropwise drips n-Butyl Lithium in system, time for adding is 15 minutes.Drip and finish, continue at 0 DEG C, to stir 1 hour set aside for use.
In the 100mL Schlenk bottle of dried and clean that turned welt plug and magnetic stir bar are housed, add 11 (4.01g, 15.7mmol) and anhydrous tetrahydro furan (10mL), by degassed three times of frozen-thawed of system, be finally replaced into argon atmosphere.Cryosel for system is bathed to temperature control to 0 DEG C, and with syringe, to the tetrahydrofuran solution that dropwise drips above-mentioned previously prepared good LDA in system, time for adding is 15 minutes.Drip and finish, continue at 0 DEG C, to stir 2 hours.By extremely-78 DEG C of liquid nitrogen-acetone cryostat temperature controls for system, in system, dropwise drip the degassed di-t-butylchlorophosphine (5.69g of freeze thawing with syringe, 31.5mmol) be diluted in the solution of anhydrous tetrahydro furan (10mL), time for adding is 30 minutes.Drip and finish, continue-78 DEG C of stirring reactions 30 minutes, naturally recovery room temperature stirring reaction spend the night (14 hours).After system vacuum desolvation, add the degassed ether of freeze thawing (30mL) and water (30mL), separatory, the degassed extracted with diethyl ether (2 × 10mL) of freeze thawing for water, merges organic phase, under argon shield, with anhydrous sodium sulfate drying, leaves standstill.Remove by filter siccative, filtrate vacuum desolvation, resistates underpressure distillation, collects 180 DEG C/0.1mmHg cut, obtains faint yellow thickness oily liquids, leaves standstill gradually and solidifies, and obtains faint yellow solid product 3.30g, yield: 53%.
1H?NMR(400MHz，CDCl
3)δ8.26(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，CDCl
3)δ161.46(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，CDCl
3)δ37.12(s).HRMS(ESI)calcd?for?C
24H
39N
3P
+([M+H]
+)：400.2876；Found：400.2867.
Embodiment 2
The preparation of part 2
2-[(t-Butyldimethylsilyl) methyl]-6-bromopyridine (12): in the 100mL Schlenk bottle of dried and clean that turned welt plug and magnetic stir bar are housed, add 2-methylol-6-bromopyridine (10.6g, 56.4mmol) and imidazoles (15.4g, 226mmol), system is replaced into argon atmosphere, add dry DMF (50mL), the disposable TERT-BUTYL DIMETHYL CHLORO SILANE (10.2g, 67.7mmol) that adds in argon stream.Finish, in stirring at room temperature reaction 1 hour, TLC monitoring reacts completely, add water (50mL) cancellation reaction, with ether (3 × 100mL) extraction product, organic phase is water (100mL) and saturated aqueous common salt (100mL) washing successively, and anhydrous sodium sulfate drying, leaves standstill.Suction filtration is removed siccative, and filtrate is used Rotary Evaporators precipitation, and 92 DEG C/0.1mmHg cut is collected in resistates underpressure distillation, obtains colourless oil liquid product 15.3g, yield: 90%.
1H?NMR(400MHz，CDCl
3)δ7.56(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): in the 250mL four-hole round-bottomed bottle of dried and clean that turned welt plug and magnetic stir bar are housed, add 12 (15.5g, 51.3mmol), system is replaced into argon atmosphere, add anhydrous THF (150mL), by extremely-78 DEG C of liquid nitrogen-acetone cryostat temperature controls for system, with syringe to the hexane solution (2.4M that dropwise drips n-Butyl Lithium in system, 25mL, 60.0mmol), time for adding is 30 minutes.Drip and finish, continue-78 DEG C of stirring reactions 1 hour.With syringe, to the solution that drips tributyltin chloride (20.0g, 61.4mmol) in system and be diluted in anhydrous THF (30mL), time for adding is 30 minutes.Drip and finish, continue to stir after 30 minutes naturally recovery room temperature stirring reaction spend the night (14 hours) at-78 DEG C.System Rotary Evaporators precipitation, ether for resistates (200mL) dilution, water (200mL) and saturated aqueous common salt (200mL) washing successively, organic phase anhydrous sodium sulfate drying, leaves standstill.Suction filtration is removed siccative, and filtrate is used Rotary Evaporators precipitation, and 170 DEG C/0.1mmHg cut is collected in resistates underpressure distillation, obtains colourless oil liquid product 23.0g, yield: 87%.
1H?NMR(400MHz，CDCl
3)δ7.49(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，CDCl
3)δ172.63(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?C
24H
48NOSiSn
+([M+H]
+)：514.2522；Found：514.2530.
6-methylol-6 '-(diethylin methyl)-2,2 '-dipyridyl (14): add 10 (8.51g in the 100mL Schlenk bottle of dried and clean that turned welt plug and magnetic stir bar are housed, 35.0mmol), 13 (21.5g, 42.0mmol), tetrakis triphenylphosphine palladium (1.42g, 1.23mmol) and Lithium chloride (anhydrous) (4.49g, 106mmol), by degassed three times of frozen-thawed of system, be finally replaced into argon atmosphere.System is heated to 120 DEG C with oil bath, and stirring reaction 10 hours to system produces a large amount of palladium blacks, and now GC shows that 10 transform completely.System is chilled to room temperature, adds ethyl acetate (100mL) dilution, diatomite filtration is removed insolubles, adds 6N hydrochloric acid that system is adjusted to acidity (pH=3), separatory.Water is adjusted to alkalescence (pH=13) with 6N aqueous sodium hydroxide solution, and with ether (3 × 100mL) extraction, saturated aqueous common salt for organic phase (100mL) washing, anhydrous sodium sulfate drying, leaves standstill.Suction filtration is removed siccative, and filtrate is used Rotary Evaporators precipitation, and 150 DEG C/0.1mmHg cut is collected in resistates underpressure distillation, obtains pale yellow oily liquid body product 8.00g, yield: 84%.
1H?NMR(400MHz，CDCl
3)δ8.36(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，CDCl
3)δ160.26(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?C
16H
22N
3O
+([M+H]
+)：272.1757；Found：272.1762.
Chloro-6 '-(the diethylin methyl)-2 of 6-, 2 '-dipyridyl (15): add 14 (5.81g in two mouthfuls of round-bottomed bottles of 250mL of dried and clean that turned welt plug and magnetic stir bar are housed, 21.4mmol), system is replaced into argon atmosphere, add anhydrous methylene chloride (80mL), system is bathed to 0 DEG C of temperature control with cryosel, in system, dropwise drip thionyl chloride (13.0g with syringe, 109mmol) be diluted in the solution of methylene dichloride (20mL), time for adding is 30 minutes.Drip and finish, remove cryostat, be heated to 45 DEG C of stirring reactions 3 hours with oil bath, TLC monitoring reacts completely, and pours in the beaker that fills ice cube (100g) after system is chilled to room temperature, is adjusted to alkalescence (pH=13) with the 6N NaOH aqueous solution, extract with methylene dichloride (3 × 50mL), water (100mL) and saturated aqueous common salt (100mL) washing successively, organic phase anhydrous sodium sulfate drying, leaves standstill.Suction filtration is removed siccative, and filtrate is used Rotary Evaporators precipitation, obtains light brown oily product liquid, and this compound is unstable, is all directly used in next step reaction.
1H?NMR(400MHz，CDCl
3)δ8.36(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，CDCl
3)δ160.19(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?C
16H
21ClN
3 +([M+H]
+)：290.1419；Found：290.1427.
6-(diethylin methyl)-6 '-(diphenylphosphine ylmethyl)-2,2 '-dipyridyl (2): add potassium tert.-butoxide (3.40g in the 250mL Schlenk bottle of dried and clean that turned welt plug and magnetic stir bar are housed, 30.3mmol), system is replaced into argon atmosphere, add the degassed anhydrous tetrahydro furan of freeze thawing (50mL), system is bathed to temperature control to 0 DEG C with cryosel.With syringe, to the solution that dropwise drips the degassed diphenylphosphine (4.69g, 25.2mmol) of freeze thawing in system and be diluted in anhydrous tetrahydro furan (15mL), time for adding is 15 minutes.Drip and finish, continue to keep 0 DEG C of stirring reaction 1 hour, obtain a scarlet settled solution.With syringe, to dropwise dripping the 15 degassed solution that are dissolved in anhydrous tetrahydro furan (15mL) of freeze thawing in system, time for adding is 30 minutes.Drip and finish, continue to keep 0 DEG C of stirring reaction 30 minutes, naturally recovery room temperature stirring reaction spend the night (14 hours).In system, add the degassed distilled water of freeze thawing (30mL) with syringe, separatory, water is used the degassed ether of freeze thawing (2 × 10mL) extraction again, merges organic phase, under argon shield, with anhydrous sodium sulfate drying, leaves standstill.Remove by filter siccative, filtrate vacuum desolvation, resistates underpressure distillation, collects 230 DEG C/0.1mmHg cut, obtains pale yellow oily liquid body product 5.00g, two-step reaction yield: 54%.
1H?NMR(400MHz，CDCl
3)δ8.18(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，CDCl
3)δ159.93(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)，47.55(s)，38.72(d，J＝16.3Hz)，12.23(s).
31p?NMR(162MHz，CDCl
3)δ-11.09(s).HRMS(ESI)calcd?for?C
28H
31N
3P
+([M+H]
+)：440.2250；Found：440.2258.
Embodiment 3
The preparation of part 3
6,6 '-dihydroxymethyl-2,2 '-dipyridyl (16): add 12 (8.49g in the 100mLSchlenk bottle of dried and clean that turned welt plug and magnetic stir bar are housed, 28.1mmol), 13 (16.9g, 33.0mmol), tetrakis triphenylphosphine palladium (1.14g, 0.99mmol) and Lithium chloride (anhydrous) (3.60g, 84.9mmol), by degassed three times of frozen-thawed of system, be finally replaced into argon atmosphere.System is heated to 120 DEG C with oil bath, and stirring reaction 12 hours to system produces a large amount of palladium blacks, and now GC shows that 12 transform completely.System is chilled to room temperature, adds ethyl acetate (100mL) dilution, diatomite filtration is removed insolubles, adds 6N hydrochloric acid that system is adjusted to acidity (pH=3), separatory.Water is adjusted to alkalescence (pH=13) with 6N aqueous sodium hydroxide solution, and with ether (3 × 100mL) extraction, saturated aqueous common salt for organic phase (100mL) washing, anhydrous sodium sulfate drying, leaves standstill.Suction filtration is removed siccative, and filtrate is used Rotary Evaporators precipitation, obtains white solid product 5.20g, yield: 85%.
1H?NMR(400MHz，DMSO)δ8.23(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 '-dipyridyl (17): add 16 (1.71g in the 100mL Schlenk bottle of dried and clean that turned welt plug and magnetic stir bar are housed, 7.91mmol), system is replaced into argon atmosphere, add anhydrous methylene chloride (40mL), system is bathed to 0 DEG C of temperature control with cryosel, in system, dropwise drip thionyl chloride (4.81g with syringe, 40.4mmol) be diluted in the solution of methylene dichloride (10mL), time for adding is 15 minutes.Drip and finish, remove cryostat, be heated to 45 DEG C of stirring reactions 3 hours with oil bath, TLC monitoring reacts completely, and pours in the beaker that fills ice cube (100g) after system is chilled to room temperature, is adjusted to alkalescence (pH=13) with the 6N NaOH aqueous solution, extract with methylene dichloride (3 × 50mL), organic phase is water (100mL) and saturated aqueous common salt (100mL) washing successively, and anhydrous sodium sulfate drying, leaves standstill.Suction filtration is removed siccative, and filtrate is used Rotary Evaporators precipitation, obtains faint yellow solid product 1.80g, yield: 90%.
1H?NMR(400MHz，CDCl
3)δ8.40(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 '-dipyridyl (3): add 17 (1.01g in the 50mL Schlenk bottle of dried and clean that turned welt plug and magnetic stir bar are housed, 3.99mmol), system is replaced into argon atmosphere, add the degassed di-t-butyl phosphine (2.34g of freeze thawing, 16.0mmol) be diluted in the solution of anhydrous methanol (30mL), system is heated to 60 DEG C of stirring reactions 48 hours with oil bath, obtains a white suspension liquid.System is chilled to room temperature, adds the degassed triethylamine (2.10g, 20.8mmol) of freeze thawing with syringe in system, mixture continues at stirring at room temperature reaction spend the night (14 hours).By system vacuum desolvation, resistates adds the degassed methylene dichloride of freeze thawing (50mL), and with degassed distilled water (3 × 10mL) washing of freeze thawing, organic phase with anhydrous sodium sulfate drying, leaves standstill under argon shield.With short neutral aluminium sesquioxide post filtration, filtrate vacuum desolvation, obtains white solid product 1.30g, yield: 69%.
1H?NMR(400MHz，CDCl
3)δ8.17(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，CDCl
3)δ161.33(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，CDCl
3)δ37.02(s).HRMS(ESI)calcd?for?C
28H
47N
2P
2 +([M+H]
+)：473.3209；Found：473.3213.
Embodiment 4
The preparation of part 4
In two mouthfuls of round-bottomed bottles of 100mL of dried and clean that reflux condensing tube, turned welt plug and magnetic stir bar are housed, add 17 (1.50g, 5.93mmol), diethylamine (4.30g, 58.8mmol) and tetrahydrofuran (THF) (50mL), system is heated to 70 DEG C of stirring reactions 4 hours with oil bath, and TLC monitoring reacts completely.System is chilled to room temperature, use Rotary Evaporators precipitation, methylene dichloride for resistates (50mL) dilution, use successively saturated sodium bicarbonate aqueous solution (50mL), water (50mL) and saturated aqueous common salt (50mL) washing, organic phase anhydrous sodium sulfate drying, leaves standstill.Suction filtration is removed siccative, and filtrate is used Rotary Evaporators precipitation, and 120 DEG C/0.1mmHg cut is collected in resistates underpressure distillation, obtains pale yellow oily liquid body product 1.50g, yield: 78%.
1H?NMR(400MHz，CDCl
3)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，CDCl
3)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?C
20H
31N
4 +([M+H]
+)：327.2543；Found：327.2550.
Embodiment 5
The preparation of complex compound 5
In the 15mL Schlenk pipe of dried and clean that turned welt plug and magnetic stir bar are housed, add 1 (600mg, 1.50mmol) and [RuCl
2(η
6-p-cymene)]
2(400mg, 0.65mmol), is replaced into argon atmosphere by system, adds the degassed anhydrous methylene chloride of freeze thawing (5mL).Stirring reaction 4 hours under room temperature, obtains a dark purple black suspension, directly uses Rotary Evaporators precipitation, ether for resistates (3 × 10mL) washing, and suction filtration, vacuum-drying, obtains dark purple black solid powder 740mg, productive rate: 99%.
1H?NMR(400MHz，CDCl
3)δ7.93(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，CDCl
3)δ169.25(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，CDCl
3)δ63.21(s).Anal.Calcd.for?C
24H
38Cl
2N
3PRu：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 compound 6
In the 15mL Schlenk pipe of dried and clean that turned welt plug and magnetic stir bar are housed, add 2 (210mg, 0.48mmol) and [RuCl
2(η
6-p-cymene)]
2(122mg, 0.20mmol), is replaced into argon atmosphere by system, adds the degassed dry toluene of freeze thawing (5mL).System is heated to 120 DEG C of stirring reactions 16 hours with oil bath, obtains a dark purple black suspension, vacuum desolvation, ether for resistates (3 × 5mL) and ethanol (3 × 5mL) washing, suction filtration, vacuum-drying, obtain dark purple black solid powder 210mg, productive rate: 86%.
1H?NMR(400MHz，CDCl
3)δ8.00(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，CDCl
3)δ165.93(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)，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，CDCl
3)δ45.75(s).HRMS(ESI)calcd?for?C
28H
30ClN
3PRu
+([M-Cl]
+)：576.0904；Found：576.0897.
Embodiment 7
The preparation of complex compound 7
In the 15mL Schlenk pipe of dried and clean that turned welt plug and magnetic stir bar are housed, add 3 (113mg, 0.24mmol) and [RuCl
2(η
6-p-cymene)]
2(61mg, 0.10mmol), is replaced into argon atmosphere by system, adds the degassed anhydrous methylene chloride of freeze thawing (5mL).Stirring reaction 4 hours under room temperature, obtains a dark purple black suspension, directly uses Rotary Evaporators precipitation, ether for resistates (3 × 5mL) washing, and suction filtration, vacuum-drying, obtains dark purple black solid powder 117mg, productive rate: 91%.
1H?NMR(400MHz，CDCl
3)δ7.87(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，CDCl
3)δ166.50(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，CDCl
3)δ66.25(s).Anal.Calcd.for?C
28H
46Cl
2N
2P
2Ru：C，52.17；H，7.19；N，4.35.Found：C，52.29；H，6.91；N，4.56.
Embodiment 8
Set forth the operation of ester compound catalytic hydrogenation as an example of γ-valerolactone example:
A) use generated in-situ dipyridyl tetradentate ligands ruthenium complex solution
In glove box, take ligand 1 (1.4mg, 3.6 μ mol) and [RuCl
2(η
6-p-cymene)]
2(0.9mg; 1.5 μ mol) in the 10mL Schlenk pipe of turned welt plug and magnetic stir bar is housed; add the degassed tetrahydrofuran (THF) of freeze thawing (2.0mL); protect lower stirring reaction 30 minutes in 25 DEG C with argon gas ball, obtain the tetrahydrofuran solution of dipyridyl tetradentate ligands ruthenium complex 5.Take sodium methylate (17mg, 0.3mmol) in the glass reaction inner tube of magnetic stir bar is housed, be put in rapidly in autoclave, be replaced into argon atmosphere.With syringe by the tetrahydrofuran solution of above-mentioned dipyridyl tetradentate ligands ruthenium complex 5 and freeze thawing degassed in advance preparation γ-valerolactone (300mg, tetrahydrofuran (THF) (3.0mL) solution 3.0mmol) joins in high-pressure hydrogenation still, with the gas in hydrogen exchange autoclave five times, finally regulating hydrogen pressure is 5MPa, 25 DEG C of stirring reactions 6 hours to tensimeter no longer changes, slowly release the hydrogen in autoclave, add 1, 5-pentanediol is as interior mark, the sample that takes a morsel is used gas Chromatographic Determination 1 after short silicagel column filters, the yield of 4-pentanediol is 96%.
Use part 2 and [RuCl
2(η
6-p-cymene)]
2generated in-situ dipyridyl tetradentate ligands ruthenium complex solution catalyzing hydrogenation γ-valerolactone reaction is after 14 hours, and Isosorbide-5-Nitrae-pentanediol yield is 67%; Use part 3 and [RuCl
2(η
6-p-cymene)]
2generated in-situ dipyridyl tetradentate ligands ruthenium complex solution catalyzing hydrogenation γ-valerolactone reaction is after 14 hours, and Isosorbide-5-Nitrae-pentanediol yield is 25%; Use part 4 and [RuCl
2(η
6-p-cymene)]
2generated in-situ dipyridyl tetradentate ligands ruthenium complex solution catalyzing hydrogenation γ-valerolactone reaction is after 14 hours, and Isosorbide-5-Nitrae-pentanediol yield is 15%.
Analytical conditions for gas chromatography is: and Agilent DB-35 chromatographic column (30m × 0.32mm × 0.25 μ m), fid detector, 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.Temperature programming: initial temperature is 50 DEG C, rises to 250 DEG C with the temperature rise rate of 10 DEG C/min, keeps 10 minutes at this temperature.The retention time of Isosorbide-5-Nitrae-pentanediol, γ-valerolactone, 1,5-PD is respectively 7.92min, 8.30min, 9.04min.
B) use the synthetic solid dipyridyl tetradentate ligands ruthenium complex of preparing
In glove box, take dipyridyl tetradentate ligands ruthenium complex 5 (1.7mg, 3.0 μ mol) and sodium methylate (17mg, 0.3mmol) in the glass reaction inner tube of magnetic stir bar is housed, with syringe add wherein freeze thawing degassed in advance preparation γ-valerolactone (300mg, tetrahydrofuran (THF) (5.0mL) solution 3.0mmol), stir, be put in rapidly in autoclave, be replaced into argon atmosphere.With the gas in hydrogen exchange autoclave five times, finally regulating hydrogen pressure is 5MPa, 25 DEG C of stirring reactions 4 hours to tensimeter no longer changes, slowly release the hydrogen in autoclave, add 1,5-pentanediol is as interior mark, and the sample that takes a morsel is 98% with the yield of gas Chromatographic Determination Isosorbide-5-Nitrae-pentanediol after short silicagel column filters.
The solid dipyridyl tetradentate ligands ruthenium complex 6 that uses synthetic preparation is that catalyst hydrogenation γ-valerolactone reacted after 7 hours, and Isosorbide-5-Nitrae-pentanediol yield is 96%; The solid dipyridyl tetradentate ligands ruthenium complex 7 that uses synthetic preparation is that catalyst hydrogenation γ-valerolactone reacted after 14 hours, and Isosorbide-5-Nitrae-pentanediol yield is 30%.
Embodiment 9
Use the dipyridyl tetradentate ligands ruthenium complex 5 of synthetic preparation to optimize the relatively experiment condition of catalytic hydrogenation taking γ-valerolactone as substrate, the reaction result of the experiment conditions such as different catalysts, solvent, alkali and hydrogen pressure is in table 1.
The comparison of table 1 γ-valerolactone hydrogenation experiment condition
a
areaction conditions: S/C=1000,3.0mmol γ-valerolactone, 3.0 μ mol5,5.0mL
lprOH, 25 DEG C.
bbeing measured by gas spectrum, be separation yield in bracket, all only observe Isosorbide-5-Nitrae-pentanediol and the existence of unreacted γ-valerolactone in responding.
cs/C=10,000,12mmol γ-valerolactone, 1.2 μ mol5,1.0mL
lprOH, 1.2mmol NaOMe.
ds/C=100,000,36mmol γ-valerolactone, 0.36 μ mol5,4.0mL
lprOH, 3.6mmol NaOMe.
e40℃。
Embodiment 10
Use the hydrogenation of dipyridyl tetradentate ligands ruthenium complex 5 other ester compounds of catalytic hydrogenation of synthetic preparation to the results are shown in Table 2:
The hydrogenation of other ester compound of table 2
a
areaction conditions: S/C=1000,3.0mmol substrate, 3.0 μ mol5,3.0mL
lprOH, 0.3mmol NaOMe, 5MPa H
2, 25 DEG C.
bgas spectrum yield, be separation yield in bracket, all only observe target product and the existence of unreacted raw material in responding.
csurplus materials is γ-valerolactone.
d100℃。
es/C=333,100 DEG C, 1.0mmol substrate.
ftetrahydrofuran (THF) is solvent.
gs/C=10,000,12mmol substrate, 1.2 μ mol5,1.2mmol NaOMe.
hs/C=100,000,100mmol methyl benzoate, 1.0 μ mol5,20mL
lprOH, 10.0mmol NaOMe.
l40℃。
J10MPa?H
2。
ks/C=100,000,200mmol ethyl acetate, 2.0 μ mol5,20.0mmol NaOEt.
Prove that by above-described embodiment dipyridyl tetradentate ligands ruthenium complex is easy to prepare, good stability, and show excellent catalytic activity in ester class chemical combination hydrogenation, catalyst levels is little, reaction conditions gentleness, the selectivity of reaction is good, has demonstrated very high industrial application value.
Claims (10)
1. a dipyridyl tetradentate ligands, is characterized in that it has the structural formula as shown in I:
Wherein, coordinating group L
1and L
2be selected from: PR
1r
2, NR
1r
2or SR group, coordinating group L
1, L
2identical, or different.
R, R
1and R
2independently selected from: C
1～C
8alkyl, C
3～C
8the phenyl of cycloalkyl, phenyl, replacement, 1-naphthyl, 2-naphthyl, heteroaryl, benzyl; Substituting group on the phenyl of described replacement is C
1～C
8alkyl, C
3～C
8cycloalkyl, phenyl, alkoxyl group and halogen, substituting group quantity is 1～5; Described heteroaryl is furyl, thienyl or pyridyl; R
1, R
2identical, or different; Or R
1, R
2and be C
3～C
8cycloaliphatic ring or aromatic nucleus;
X
1, X
2independently selected from: H, C
1～C
8alkyl, C
3～C
8the phenyl of cycloalkyl, phenyl, replacement, 1-naphthyl, 2-naphthyl, heteroaryl, benzyl, halogen; Substituting group on the phenyl of described replacement is C
1～C
8alkyl, C
3～C
8cycloalkyl, phenyl, alkoxyl group and halogen, substituting group quantity is 1～5; Described heteroaryl is furyl, thienyl or pyridyl; M=0～3, n=0～3; In the time of m>=2, two adjacent X
1and be C
3～C
8cycloaliphatic ring or aromatic nucleus; In the time of n>=2, two adjacent X
2and be C
3～C
8cycloaliphatic ring or aromatic nucleus; X
1, X
2identical, or different.
2. according to dipyridyl tetradentate ligands claimed in claim 1, it is characterized in that described C
1～C
8alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl; Described C
3～C
8cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; Described alkoxyl group is methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy.
3. according to dipyridyl tetradentate ligands claimed in claim 1, it is characterized in that described dipyridyl tetradentate ligands is shown in structural formula 1-4:
4. a dipyridyl tetradentate ligands ruthenium complex of being prepared by dipyridyl tetradentate ligands claimed in claim 1, is characterized in that it has the structural formula as shown in II:
Wherein, L
1, L
2, X
1, X
2, m, n definition with identical described in general formula I; Y, Z is H, Cl, Br, I, ClO
4, PF
6, BPh
4, B (C
6f
5)
4, BF
4, BH
4, OCOR, OCOCF
3, OSO
2r, OSO
2cF
3, CN, OR, NR
2, SR; R is H, C
1～C
8alkyl, C
3～C
8the phenyl of cycloalkyl, phenyl, replacement, 1-naphthyl, 2-naphthyl, heteroaryl, benzyl; Substituting group on the phenyl of described replacement is C
1～C
8alkyl, C
3～C
8cycloalkyl, phenyl, alkoxyl group and halogen, substituting group quantity is 1～5; Described heteroaryl is furyl, thienyl or pyridyl; Y, Z is identical or different.
5. dipyridyl tetradentate ligands ruthenium complex according to claim 4, is characterized in that described Y, and Z is identical halogen: Cl, Br, I.
6. dipyridyl tetradentate ligands ruthenium complex according to claim 4, is characterized in that described dipyridyl tetradentate ligands ruthenium complex is shown in structural formula 5-7:
7. the preparation method of dipyridyl tetradentate ligands ruthenium complex claimed in claim 6, is characterized in that comprising following method:
1) original position generates: at methylene dichloride, tetrahydrofuran (THF), toluene, N, in dinethylformamide or methyl-sulphoxide organic solvent, metal Ru precursor and with respect to the described dipyridyl tetradentate ligands of 1.0～1.5 times of amounts of ruthenium atom amount of substance, 25～120 DEG C of reactions 4～16 hours, can obtain dipyridyl tetradentate ligands ruthenium complex solution;
Or
2) synthetic preparation: at methylene dichloride, tetrahydrofuran (THF), toluene, N, in dinethylformamide, methyl-sulphoxide organic solvent, metal Ru precursor and with respect to the described dipyridyl tetradentate ligands of 1.0～1.5 times of amounts of ruthenium atom amount of substance, 25～120 DEG C of reactions 4～16 hours, solution rotating was evaporated to original volume 1/10; Concentrated solution is under agitation added to ether or normal hexane, separate out dark purple black solid, vacuum filtration, with ether or normal hexane washing leaching cake, obtains solid dipyridyl tetradentate ligands ruthenium complex after filter cake vacuum-drying.
Described metal Ru precursor is RuCl
3nH
2o, [RuCl
2(CO)
3]
2, [Ru (cod) Cl
2]
n, [Ru (nbd) Cl
2]
n, [RuCl
2(benzene)]
2, [RuBr
2(benzene)]
2, [RuI
2(benzene)]
2, [RuCl
2(η
6-p-cymene)]
2, [RuBr
2(η
6-p-cymene)]
2, [RuI
2(η
6-p-cymene)]
2, [RuCl
2(mesitylene)]
2, [RuBr
2(mesitylene)]
2, [RuI
2(mesitylene)]
2, RuCl
2(PPh
3)
3,, RuBr
2(PPh
3)
3, RuI
2(PPh
3)
3, RuCl
2(DMSO)
4, wherein: cod=1,5-cyclooctadiene, nbd=2,5-norbornadiene, DMSO=methyl-sulphoxide.
8. the application of dipyridyl tetradentate ligands ruthenium complex claimed in claim 4, is characterized in that its reaction for ester compound catalytic hydrogenation synthol compounds as catalyzer, and described ester compound is as shown in general formula III:
Wherein, R
a, R
bbe selected from C
1～C
30alkyl, C
3～C
30cycloalkyl, C
2～C
30thiazolinyl, C
3～C
30cycloalkenyl group, aryl, contain the substituting group that does not affect arbitrarily hydrogenation, R in these groups
a, R
bidentical or different; Or R
a, R
bbe connected and form the C of ring-type
4～C
30lactone, on lactonic ring, contain the substituting group that does not affect arbitrarily hydrogenation, on lactonic ring, the carbon atom of correct position can be replaced by O, N, S heteroatoms, lactonic ring is monocycle or encircles more; Described lactone is saturated lactone or unsaturated lactone;
Described alcohol compound is as shown in general formula I V-a, IV-b:
R
a, R
bdefinition with identical described in general formula III; Work as R
a, R
balcohol compound described in while not being connected is as shown in IV-a, IV-b; Work as R
a, R
balcohol compound described in while being connected is the dibasic alcohol of gained after corresponding lactone reduction; In the time containing multiple ester group in hydrogenation ester compound used, the alcohol compound of gained is corresponding polyvalent alcohol.
9. the application of dipyridyl tetradentate ligands ruthenium complex according to claim 8, it is characterized in that described ester compound is: methyl benzoate, ethyl acetate, ethylene carbonate, methyl ester levulinate, Succinic acid dimethylester, gamma-butyrolactone, γ-valerolactone, Alpha-Methyl-gamma-butyrolactone, methyl glycolate, methyl lactate, methoxy menthyl acetate, Laurate methyl, methyl stearate, trilaurin, Tristearoylglycerol, dimethyl oxalate, 1, 2-phthalic acid methyl esters, 1, 3-phthalic acid methyl esters, methyl caproate, hexyl hexanoate.
10. the application of dipyridyl tetradentate ligands ruthenium complex according to claim 8, is characterized in that the method for the catalytic hydrogenation application to ester compound comprises the steps:
Under argon gas or nitrogen protection, be that dipyridyl tetradentate ligands ruthenium complex and alkali add in reactor inner tube by catalyzer, add substrate to be dissolved in the solution of coordinative solvent, tighten reactor and replace 3～5 times with hydrogen is careful, regulate hydrogen pressure to required pressure, under suitable temp, stirring reaction to pressure no longer changes, and reactor is recovered to room temperature, slowly discharges remaining hydrogen; Product carries out separating-purifying by column chromatography, the conventional organic compound purification process of distillation;
Catalyst levels is 0.001～0.3mol% of substrate amount of substance, and alkali consumption is 1～10mol% of substrate amount of substance, hydrogen pressure 1～10MPa, and temperature of reaction is 25～100 DEG C, the reaction times is 2～64 hours;
Solvent for use is a kind of in tetrahydrofuran (THF), ether, 2-methyltetrahydrofuran, Virahol, toluene organic solvent or several mixed solvent wherein; Alkali used be sodium methylate, sodium ethylate, sodium isopropylate, sodium tert-butoxide, potassium methylate, potassium ethylate, potassium isopropoxide, potassium tert.-butoxide; The consumption of alkali is 1～10mol% of ester compound amount of substance.
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