CN107445995A - The method that a kind of new manganese catalysis ethanol condensation prepares butanol - Google Patents
The method that a kind of new manganese catalysis ethanol condensation prepares butanol Download PDFInfo
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- CN107445995A CN107445995A CN201710669609.1A CN201710669609A CN107445995A CN 107445995 A CN107445995 A CN 107445995A CN 201710669609 A CN201710669609 A CN 201710669609A CN 107445995 A CN107445995 A CN 107445995A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic System
- C07F13/005—Compounds without a metal-carbon linkage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
- C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
Abstract
The invention discloses a kind of method that new manganese catalysis ethanol condensation prepares butanol.The Mn catalyst that methods described uses is the manganese complex shown in Formulas I, Formula II, formula III or formula IV.Based on manganese complex of the present invention, there is provided a kind of method that ethanol coupling based on the catalysis of cheap metal manganese prepares butanol, show very high catalytic activity (TON=114120, wherein preceding 12h TOF is 3078h‑1) and 92% butanol selectivity (Fig. 1)；The present invention will be to the efficient utilization of biomass resource, particularly to the production of high-quality bio-fuel, the catalytic activation of biomass platform chemicals and conversion and corresponding cheap, effective catalyst design, there is provided important technical support and theoretical direction.
Description
Technical field
The present invention relates to the method that a kind of new manganese catalysis ethanol condensation prepares butanol, belongs to Catalytic processes technology neck
Domain.
Background technology
The energy is the important substance basis of human survival and development of civilization, while energy and power is provided for us,
And the most important source of numerous basic chemicals.The chemicals required for production and living and fuel are mainly provided using fossil at present
Source is transformed, and the increasingly consumption of this nonrenewable resources promotes the other alternative renewable carbon sources of people's development to be fired
The production of material and chemicals.And and the bio-fuel that obtains it is important side that regenerative resource develops by bioconversion
To there are good storing properties and rodability, it is possible to provide substitute the liquid fuel of oil.The whole world produces height altogether within 2015
Up to the biomass fuel equivalent to 74,900,000 tons of crude oil energy, wherein the bio-fuel more than 70% is by biomass ferment work
Skill and the bio-ethanol obtained.
The mainly purposes of bio-ethanol is to mix to be directly used in not engineered internal combustion engine with gasoline at present, so as to have
Effect reduces the consumption of petroleum resources.Ethanol has many shortcomings as bio-fuel, is primarily due to the water-soluble easy moisture absorption of ethanol, vapour
Oil must close on use before carry out the mixing of ethanol and gasoline, the problem of so as to cause storage and transportation complexity.Secondly,
Ethanol can produce acetic acid in combustion, have corrosivity to metal parts particularly copper, in addition the energy density of ethanol compared with
It is low, when using a high proportion of the problem of containing ethanol petrol fuel value and dynamic property being caused to decline, the above shortcoming can all limit
Ethanol processed is as additive package using in the oil.And higher alcohol is used, for example, the alcohol of butanol and more long-chain, due to fourth
The long-chain alcohols such as alcohol, can be even independent to be mixed more at high proportion with gasoline with higher energy density and with relatively low vapour pressure
Fuel as gasoline engine uses.Although the long-chain alcohols such as butanol are more high-quality fuel, but still lack at present efficient
Method pass through the direct synthetic long chain alcohol of biomass resource.The method of known best biosynthesis, i.e., so-called ABE fermentations
Method, only the mixture of acetone, butanol and ethanol can be obtained with low yield, because separation is difficult, and cost is higher, therefore by with
Propylene is substituted by the chemical synthesis process of raw material.
Based on the large-scale production of global range endogenous substance ethanol, ethanol is effectively converted into length by development one kind
The production technology of chain alcohol is by as being produced the important technology of the high-quality bio-fuel of long-chain alcohols by biomass resource.From certain meaning
Upper theory, Guerbet reactions are a kind of ideal methods that butanol or long-chain alcohol are synthesized by ethanol, because anti-for such
Its accessory substance is only water for answering.And with use ethanol as Guerbet reaction substrate right and wrong often with challenging.It is first
First, the dehydrogenation reaction of ethanol is the very unfavorable course of reaction of thermodynamics, Δ G0=12.87kcal/mol；Secondly, among reaction
The aldol condensation reactions of body acetaldehyde also face the problem of poor selectivity often.At present, only a smaller number of example reports
Guerbet reacts, and wherein heterogeneous catalysis usually requires more harsh reaction condition or has to low butanol selection
Property.In contrast, although being catalyzed using homogeneous catalyst, the reaction is generally lower can to obtain higher activity, preferably selection
Property.But the report up to the present about homogeneous catalysis Guerbet reactions is all concentrated mainly on the noble metals such as Ru and Rh (figure
1)。
It is one of catalytic science research field in recent years important to substitute noble metal catalyst using cheap metal catalyst
Developing direction.However, the C-C coupling reaction of the low-carbon alcohols micromolecular such as ethanol that up to the present homogeneous cheap metal is catalyzed
Long-chain alcohol compound is prepared to have not been reported.Therefore, the corresponding efficiently homogeneous cheap metal catalyst of development realizes (biology)
The C-C coupling reaction of the low-carbon alcohols micromolecular such as ethanol is by as preparing a key technology of high-quality bio-fuel.
The content of the invention
The invention provides the reaction that a kind of new manganese catalysis ethanol coupling prepares butanol, used manganese complex is
A kind of NNP or PNP complex compounds based on cheap metal manganese, the reaction show very high catalytic activity (TON=
114120, wherein preceding 12h TOF is 3078h-1) and 92% butanol selectivity, therefore, new method provided by the invention will be right
Biomass resource efficiently utilizes, particularly to the production of high-quality bio-fuel, the catalytic activation of biomass platform chemicals and conversion
And the corresponding cheap, design of effective catalyst, there is provided important technical support and theoretical direction.
Present invention firstly provides manganese complex, its structural formula is as shown in Formulas I, Formula II, formula III or formula IV：
In Formulas I, Formula II and formula III,Represent NNP parts or PNP parts；
Wherein, X2It is methyl, ethyl, isopropyl, the tert-butyl group, cyclopenta, cyclohexyl, phenyl or 2- pyridines for N or P, R
Base；R1For H, methyl, ethyl, benzyl or 2- picolyls；
In Formulas I, X and X1Independently selected from H, Cl, Br, I, CO (carbonyl), OAc (acetate), OEt (ethyoxyl), OMe
(methoxyl group), OBn (benzyloxy), OH and OTf (trifyl), and X and X1It is asynchronously CO.
The structural formula of the NNP parts is as shown in Formula V or Formula IV：
In Formula V and Formula IV, A represents C or N；
In Formula V, R is expressed as methyl, ethyl, isopropyl, the tert-butyl group, cyclopenta, cyclohexyl or phenyl；
R1It is expressed as H, methyl, ethyl, benzyl or 2- picolyls；
R3、R4、R5And R6Independently represent H, C1~C6Alkyl, C1~C6Alkoxy, phenyl, C1~C6Alkyl substituted benzene
Base, halogen, benzyl, hydroxyl, naphthyl, furyl or thienyl；
In Formula IV, R7、R8And R9Independently represent H, C1~C6Alkyl, C1~C6Alkoxy, phenyl, C1~C6Alkyl takes
For phenyl, halogen, benzyl, hydroxyl, naphthyl, furyl or thienyl.
The structural formula of the PNP parts is as shown in Formula VII：
In Formula VII, R is expressed as methyl, ethyl, isopropyl, the tert-butyl group, cyclopenta, cyclohexyl or phenyl；
R1It is expressed as H, methyl, ethyl, benzyl or 2- picolyls.
In the present invention, C1~C6Alkyl refers specifically to methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, uncle
Butyl, n-pentyl, isopentyl, neopentyl, sec-amyl, tertiary pentyl, cyclopenta, n-hexyl, isohesyl, new hexyl, Sec-Hexyl, uncle
Hexyl or cyclohexyl.
C1~C6Alkoxy is methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tertiary fourth oxygen
It is base, n-pentyloxy, isoamoxy, neopentyl oxygen, secondary amoxy, tertiary amoxy, cyclopentyloxy, positive hexyloxy, dissident's epoxide, new
Hexyloxy, secondary hexyloxy, tertiary hexyloxy or cyclohexyloxy.
Manganese complex of the present invention is specifically as shown in formula 1- formulas 16, preferred formula 2, formula 3, formula 8, formula 11 and formula 12：
In various, tBu represents the tert-butyl group, and Ph represents phenyl, and Cy represents cyclohexyl, and iPr represents isopropyl.
Invention further provides the preparation method of the manganese complex, comprise the following steps：
Under the protection of inert atmosphere, pentacarbonyl halogenation manganese salt is reacted with the NNP parts or the PNP parts,
Produce the manganese complex；
The chemical formula of the pentacarbonyl halogenation manganese salt is Mn (CO)5X3, wherein, X3Represent Cl, Br or I.
In above-mentioned preparation method, the pentacarbonyl halogenation manganese salt and the mol ratio of the NNP parts or the PNP parts
Can be 1:1.05~1.1, such as 1:1.1；
The temperature of the reaction can be 70~110 DEG C, and the time can be 6~20 hours, and it is small that 8~20 are reacted such as at 70 DEG C
When, 8 hours, 15 hours or 20 hours.
In above-mentioned preparation method, the reaction is carried out in a solvent, and the solvent can be toluene, dimethylbenzene and tetrahydrochysene furan
At least one of mutter.
Manganese complex of the present invention is capable of the Guerbet reactions of catalysis ethanol, the butanol of acquisition and its chemical combination of higher level alcohol
Thing can be as the additive in gasoline.
The reaction equation of the Guerbet reactions is specifically such as formula (1)
Wherein, [Mn] represents the manganese complex；
In the Guerbet reactions, the mole dosage of the manganese complex can be the 0.00001%~0.01% of ethanol,
Concretely 0.01%, the mole dosage of the ethanol can 50mmol~1300mmol；
The temperature of the Guerbet reactions can be 100~180 DEG C, and the time can be 2~168 hours, anti-such as at 160 DEG C
Answer 24 hours；
The Guerbet reactions are carried out under the conditions of existing for caustic alcohol；
The concentration of caustic alcohol can be 0.1~2M described in the system of the Guerbet reactions, concretely 1M.
Based on manganese complex of the present invention, there is provided a kind of ethanol coupling based on the catalysis of cheap metal manganese prepares butanol
Method, show very high catalytic activity (TON=114120, wherein preceding 12h TOF is 3078h-1) and 92% butanol
Selectivity (Fig. 1)；The present invention will be to the efficient utilization of biomass resource, particularly to the production of high-quality bio-fuel, biomass platform
The catalytic activation of compound and conversion and the corresponding cheap, design of effective catalyst, there is provided important technical support and theory refers to
Lead.
The present invention achieves following technique effect：
1st, the present invention provides a kind of new manganese-NNP of report or the ethanol condensed reaction into butanol of PNP complex catalysis,
It is capable of the synthesis butanol Compound of high selectivity, the complex compound has high catalytic activity, has very high researching value and answers
Use prospect.
2nd, present invention also offers a kind of method for preparing manganese-NNP or PNP complex compounds, by the NNP of three teeth or
PNP parts with manganese salt react in a solvent by heating stirring, and filtering gained precipitation is new manganese-NNP or PNP complex compound, system
It is standby simple, it is easy to operate.
Brief description of the drawings
Fig. 1 is the homogeneous catalyst and its catalytic effect for the Guerbet reactions that ethanol can be achieved.
Fig. 2 is the structural formula and its x-ray crystal structure of manganese complex shown in formula 7.
Fig. 3 is the structural formula and its x-ray crystal structure of manganese complex shown in formula 9.
Fig. 4 is the structural formula and its x-ray crystal structure of manganese complex shown in formula 11.
Fig. 5 is the structural formula and its x-ray crystal structure of manganese complex shown in formula 15.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material used, reagent etc., unless otherwise specified, are commercially obtained in following embodiments.
In following embodiment, Me represents methyl, and tBu represents the tert-butyl group, and nBu represents normal-butyl, and Ph represents phenyl, Bn tables
Show benzyl, Cy represents cyclohexyl, and iPr represents isopropyl, and PE represents petroleum ether, and EA represents ethyl acetate, and TLC represents thin layer color
Spectrum, NMR represent nuclear magnetic resonance.
Double [2- (di-t-butyl phosphino-) ethyl] amine of part in following embodiments (tBuPNP), double [2- (dicyclohexylphosphontetrafluoroborates
Base) ethyl] amine (CyPNP) and double [2- (diisopropyl phosphino-) ethyl] amine (iPrPNP), bought from Alfa-Aesar Reagent Companies,
Purity>95%；The equal bibliography synthesis of remaining part：(Organometallics2003,22,445.；
Organometallics, 2009,28,6331.；Organometa-llics2012,31,5239.；Dalton Trans.,
2011,40,10397.)。
Mn(CO)5Br is bought from Alfa-Aesar Reagent Companies, purity>97%, directly use.
Solvent for use is bought from Shanghai traditional Chinese medicines Reagent Company, and drying is purified with standard method using preceding.
First, the preparation of Py-NNP parts：
1st, (trimethyl silicon substrate) ethylamine of 2- chloros-N, N- bis- is synthesized
2- chloros ethylamine hydrochloride (4.6g, 40mmol), NEt are successively added into Shrek bottle3(18mL,132mmol)
The dichloromethane 50mL of sum.Reaction be stirred at room temperature in the case of, toward the system add trim,ethylchlorosilane (90mmol, 9.8g,
Dichloromethane solution (20mL) 11.4mL).Reaction is stirred overnight at room temperature, and after reaction terminates, excessive triethylamine is removed under reduced pressure,
Trim,ethylchlorosilane and dichloromethane, 60mL n-hexane is added into the residue of gained, reaction is stirred at room temperature 30 minutes, mistake
Filter out NEt3·HCl.After filtrate concentration, target product (6.0g, 68%) is obtained by vacuum distillation.1H NMR(400MHz,
CDCl3)δ3.37–3.21(m,2H),3.18–2.99(m,2H),0.14(s,18H).13C NMR(101MHz,CDCl3)δ
47.38,44.83,1.89.
2nd, 2- isopropyl phosphine ethamine borane complexes are synthesized
Under the conditions of argon gas, into 100mL Shrek bottle, diisopropyl phosphine (2.92g, 20mmoL) and n-hexane are added
(20ml), above-mentioned mixed liquor is cooled to -78 degree, n-BuLi (2.5M, 8.8mL, 22mmoL) is added dropwise into the system.
After adding, reaction is warmed to room temperature, and is continued after stirring 1h, is obtained LiPiPr2White suspended things.
Under argon gas protection, by 2- chloros-N, N- bis- (trimethyl silicon substrate) ethylamine (4.46g, 20mmoL) and 20mL just
Hexane, it is added in Shrek bottle, under agitation, above-mentioned LiPiPr is added toward the mixture2Suspension.React room temperature
After stirring 30min, 8h is heated to reflux.After reaction terminates, 10mL de aerated waters and 2M 10mL H are added into reaction2SO4Solution,
Reaction is stirred at room temperature one hour, continues stirring one hour toward addition 11mL 4M NaOH solutions, reaction in the reaction afterwards.Separation
Organic phase, aqueous phase merge organic phase with n-hexane extraction (2 × 15mL), anhydrous sodium sulfate drying, filtering, after draining crude product
2- isopropyl phosphine ethamine.
By resulting 2- isopropyl phosphine ethylamines in the THF (30mL) of degassing, 1M boron is added into the solution
Alkane tetrahydrofuran solution, reaction be stirred at room temperature 2 hours after, drain, residue through column chromatography for separation obtain target product (0.75g,
41%).1H NMR(400MHz,CDCl3) δ 2.98 (td, J=8.7,6.2Hz, 2H), 1.99 (ddt, J=14.3,10.4,
7.1Hz, 1H), 1.84-1.69 (m, 2H), 1.35 (s, 2H), 1.18 (ddd, J=10.9,7.1,4.3Hz, 12H), 0.82-
0.11(brs,3H).δ13C NMR(101MHz,CDCl3) δ 37.55,23.46 (d, J=29.1Hz), 22.08 (d, J=
33.5Hz), 16.91 (d, J=20.3Hz)31P NMR(162MHz,CDCl3)δ29.42(q).HR-MS(ESI)calcd.for
C14H29BN2P[M+H]+:176.1734；found:176.1720.
3-1, the borane complex for synthesizing Py-NNP parts
Under the conditions of argon gas, into Shrek bottle, 2- pyridine carboxaldehydes (0.44g, 4.14mmol) and 5mLTHF are added, it is past to be somebody's turn to do
THF (5mL) solution of 2- wopropyl ethyl amines borane complex (0.73g, 4.14mmol) is added in solution.Reaction stirring 0.5h,
THF solvents are drained, the borane complex of gained pyridine-imine-NNP parts direct plunges into without purifying to react in next step
In.
Under the conditions of ice-water bath, 20mL first is added into the borane complex of the pyridine-imine-NNP parts of above-mentioned gained
Benzene, 1.2M DIBAL toluene solution (1.3mL, 1.56mmoL) is slowly added dropwise into the solution.It is small that reaction is stirred at room temperature 0.5
Shi Hou, add 3mL water quenchings and go out, toluene is extracted twice (2 × 5mL), merges organic phase.Sodium sulphate is dried, and filtering, solvent is drained
Afterwards, the borane complex (0.65g, 59%) of pure pyridine NNP parts is obtained through column chromatography for separation.1H NMR(400MHz,
CDCl3) δ 8.55 (d, J=4.8Hz, 1H), 7.64 (td, J=7.7,1.8Hz, 1H), 7.37-7.26 (m, 1H), 7.16 (dd, J
=7.4,4.9Hz, 1H), 3.93 (d, J=4.9Hz, 2H), 2.93 (dt, J=12.0,7.1Hz, 2H), 1.99 (ddt, J=
14.3,10.4,7.1Hz, 3H), 1.83 (ddd, J=11.0,9.6,8.1Hz, 2H), 1.17 (ddd, J=12.1,7.1,
5.5Hz,12H),0.75–0.14(brs,3H).13C NMR(101MHz,CDCl3)δ159.09,149.31,136.51,
122.28,122.05,54.75,44.34,22.11 (d, J=33.4Hz), 19.87 (d, J=30.2Hz), 16.94 (d, J=
21.8Hz).31P NMR(162MHz,CDCl3)δ32.25(q).HR-MS(ESI)calcd.for C14H29BN2P[M+H]+:
267.2155；found:267.2136.
3-2, synthesis Py-NNP parts
Borane complex (0.32g, 1.2mmol) containing Py-NNP parts is dissolved in the Et of degassing2NH, will be above-mentioned molten
Liquid is added in 20mL Schlenk bottles under argon gas protection, is reacted and is carried out 24 hours at 95 degree.After reaction terminates, Et is drained2NH,
Post separation (eluent ratio was descended in argon gas protection to residue again：Petrol ether/ethyl acetate=3:1to petrol ether/ethyl acetates/
Methanol=3:1:0.2) target product (0.22g, 72%), is obtained.
1H NMR(400MHz,CDCl3) δ 8.48 (d, J=4.2Hz, 1H), 7.56 (td, J=7.7,1.8Hz, 1H), 7.24
(d, J=7.8Hz, 1H), 7.08 (dd, J=6.7,5.2Hz, 1H), 3.86 (s, 2H), 2.81-2.56 (m, 2H), 2.10 (s,
2H),1.79–1.60(m,2H),1.60–1.48(m,2H),0.95-1.03(m,12H).13C NMR(101MHz,CDCl3)δ
(159.09,149.31,136.51,122.28,122.05,54.75,44.34,22.11 d, J=33.4Hz), 19.87 (d, J=
30.2Hz), 16.94 (d, J=21.8Hz)31P NMR(162MHz,CDCl3)δ-0.91(s).HR-MS(ESI)called for
C14H26N2P[M+H]+:253.1828；found:253.1828.
2nd, the preparation of N-Me-PNP (Cy) part
Under argon gas protection, into 50mL Schlenk bottles, dicyclohexylphosphontetrafluoroborate (1.00g, 5mmol) and degassing THF are added
(10mL), by above-mentioned solution be cooled to -20 degree, be slowly added into above-mentioned solution nBuLi (2.2mL, 2.5M in hexanes,
5.5mmol), room temperature is slowly increased to after adding and is flowed back 1 hour.Under argon gas protection, into another 50mL Schlenk bottles
Add MeN (CH2CH2Cl)2HCl (0.49g, 2.52mmol) and THF (10mL), above-mentioned solution is cooled to -20 degree, up
State and nBuLi (1.1mL, 2.5M in hexanes, 2.52mmol) be slowly added in solution, be slowly increased to after adding room temperature and after
Continuous stirring 2 hours.Above-mentioned solution the THF solution for the dicyclohexylphosphontetrafluoroborate lithium being slowly added to, is reacted afterwards under -78 degree afterwards
Liquid is slowly increased to room temperature, and heated overnight at reflux.After reaction terminates, THF is drained, 5mL de aerated waters, solution are added into raffinate
With the extraction of degassing ether three times (3 × 10mL), organic phase, anhydrous sodium sulfate drying, filtering are merged, and organic phase is concentrated into
5mL, there are a large amount of white solids to separate out after putting -20 degree refrigerator 30min, the filtering of low temperature argon gas, obtain white solid (0.45g, 38%).
1H NMR(400MHz,Tol-d8) δ 2.71 (dt, J=9.4,6.2Hz, 4H), 2.31 (s, 3H), 2.13 (dt, J=4.3,
2.1Hz,4H),1.91–1.74(m,24H),1.56(m,4H),1.25(m,18H).13C NMR(101MHz,Tol-d8)δ56.76
(d, J=29.4Hz), 41.65,33.58 (d, JC-P=14.9Hz), 30.51 (d, JC-P=15.4Hz), 29.14 (d, JC-P=
8.7Hz),27.32(d,JC-P=5.5Hz), 26.63.20.61,20.41,20.22,20.03,19.84,19.76,19.65,
19.46.31P NMR(162MHz,Tol-d8)δ-8.00(s).HR-MS(ESI)called for C29H56NP2[M+H]+:
480.3883；found:480.3880.
Embodiment 1, pyridine synthesis NNP-Mn (CO)2Br complex compounds (shown in formula 7)
Reaction equation is as follows：
Under argon atmosphere, into 25mL Schlenk bottles, [Mn (CO) is added5Br] (129mg, 0.47mmol), [Py-
NNP-iPr] L5 (132mg, 0.52mmol) and degassing THF (10mL), reaction is stirred overnight at room temperature.With entering for reaction time
OK, solution is gradually separated out by faint yellow solid.After reaction terminates, argon gas filtering, filter cake is eluted with degassing ether, after vacuum drying
Obtain light yellow solid (192mg, 87%).
Nuclear-magnetism：1H NMR(400MHz,CD2Cl2) δ 8.62 (d, J=4.9Hz, 1H), 8.20 (s, 1H), 7.72 (d, J=
7.0Hz, 1H), 7.33 (d, J=6.8Hz, 1H), 7.29-7.25 (m, 1H), 4.79 (d, J=18.7Hz, 1H), 3.88 (d, J=
17.8Hz, 1H), 3.11-2.79 (m, 2H), 2.41 (m, 1H), 2.08 (t, J=13.6Hz, 1H), 1.62-0.94 (m, 14H)
.13C NMR(101MHz,CD2Cl2)δ162.54,152.49,138.92,124.66,121.87,59.99,29.67,24.43
(d, J=17.0Hz), 24.05,23.84 (d, J=17.8Hz), 20.26,19.32 (d, J=2.3Hz), 18.85,17.82 (d,
J=6.0Hz)31P NMR(162MHz,CD2Cl2)δ77.54(s).
High-resolution：HR-MS(ESI)called for C17H25MnN2O3P[M]+:391.0978；found:391.0979.
It is infrared：IR:3029,2905,2018,1924,1459,1104,1056,779,682,640,618cm-1.
X-ray crystal structure is as shown in Figure 2.
Understand that prepared target manganese complex structure is correct by above-mentioned analysis result.
Embodiment 2, synthesis N-Me-PNP (iPr)-Mn (CO)2Br complex compounds (shown in formula 9)
Under argon atmosphere, into 25mL Schlenk bottles, [Mn (CO) is added5Br] (120mg, 0.44mmol), [N-
Me-PNP-iPr] (153mg, 0.48mmol) and degassing toluene (10mL), react and are heated to 100 degree, be stirred overnight.Reaction
After end, drain toluene, add 10mL degassing n-hexanes, argon gas filtering, after filter cake vacuum drying light yellow solid (175mg,
78%).
Nuclear-magnetism：1H NMR(400MHz,C6D6) δ 3.46 (t, J=10.9Hz, 2H), 3.07 (dt, J=14.7,7.3Hz,
2H),2.26–2.13(m,2H),2.07(s,3H),1.74–1.63(m,8H),1.51(m 3H),1.41–1.28(m,8H),
1.26–1.10(m,11H).13C NMR(101MHz,C6D6) δ 232.06,227.14,58.59 (t, J=4.5Hz), 48.34,
28.31 (t, J=10.2Hz), 25.71 (t, J=8.1Hz), 24.79 (t, J=5.3Hz), 20.72,19.31,19.21,
18.85.31P NMR(162MHz,C6D6)δ77.82(s).
High-resolution：HR-MS(ESI)called for C19H39MnNO2P2[M]+:430.1831；found:430.1834.
It is infrared：IR:2907,2871,1900,1807,1458,1053,1021,925,816,739,686,652,621cm-1.
X-ray crystal structure is as shown in Figure 3.
Understand that prepared target manganese complex structure is correct by above-mentioned analysis result.
Formula 1, formula 2, formula 3, formula 4, formula 5, formula 6, formula 8 and the institute of formula 10 has been prepared according to method same as Example 2
Show cobalt complex.
Embodiment 3, synthesis PNP-Mn (CO)2Complex compound (shown in formula 11)
Under argon atmosphere, into 10mL Schlenk bottles, PNP is successively addediPr-Mn(CO)2Br(0.15g,
0.3mmol), caustic alcohol (61mg, 0.9mmol) and anhydrous and oxygen-free THF (4mL).Reaction is stirred at room temperature 2 hours, with reaction
Carry out, solution is gradually changed into red from yellow, after reaction terminates, drains solvent.Then toward addition 5mL anhydrous and oxygen-frees in residue
N-hexane, argon gas filtering, gained filtrate are drained, as amino manganese complex formula 11 (87mg, 69%).
Nuclear-magnetism：1H NMR(400MHz,C6D6) δ 2.96 (s, 1H), 1.99 (d, J=4.7Hz, 1H), 1.38 (s, 1H),
0.98 (d, J=5.7Hz, 3H), 0.84 (d, J=4.2Hz, 3H)13C NMR(101MHz,C6D6) 64.89 (J=of δ
10.1Hz), 26.29 (J=10.1Hz), 22.85 (J=5.6Hz), 18.08,17.48.31P NMR(162MHz,C6D6)δ
112.99(s).
X-ray crystal structure is as shown in Figure 4.
Understand that prepared target manganese complex structure is correct by above-mentioned analysis result.
Embodiment 4, synthesis PNP-Mn (CO)2OAc complex compounds (shown in formula 15)
Under argon atmosphere, into 10mL Schlenk bottles, PNP is successively addediPr-Mn(CO)2(0.1mmol,
41.4mg), anhydrous and oxygen-free n-hexane (2mL) and acetic acid (0.3mmol, 18mg).Reaction is stirred at room temperature 0.5 hour, afterwards will be mixed
Close liquid and be put into -20 degree refrigerator overnights, upper strata hexane solution is siphoned away, obtains pale yellow crystals (36mg, 75%).
Nuclear-magnetism：1H NMR(400MHz,C6D6)δ8.16(s,1H),3.57(s,3H),2.95(s,2H),2.28–1.56(m,
11H),1.52–0.64(m,24H).13C NMR(101MHz,C6D6)δ67.45,52.44,31.58,27.42,26.46,
25.44,24.30,22.67,19.95 (d, J=24.3Hz), 18.14 (d, J=59.4Hz) .13.96.31P NMR(162MHz,
C6D6)δ87.68(s).
X-ray crystal structure is as shown in Figure 5.
Understand that prepared target manganese complex structure is correct by above-mentioned analysis result.
Manganese complex shown in formula 12 and formula 16 has been prepared according to method same as Example 1
Embodiment 5, synthesizing cis PNPiPr-Mn(CO)2H complex compounds (shown in formula 13)
In glove box, amino manganese complex formula 11 (0.01mmol, 4.1mg) and toluene (1mL) are added to containing syringe needle
Bottle in, bottle is put into 100mL autoclaves afterwards.The hydrogen of 10 atmospheric pressure is filled in kettle, room temperature reaction 14 is small
When.Question response terminates, phosphine spectrum tracking reaction product after hydrogen is slowly discharged.
31P NMR(162MHz,Toluene)：109.38ppm.
Understand that prepared target manganese complex structure is correct by above-mentioned analysis result.
Embodiment 6, synthesis of trans PNPiPr-Mn(CO)2H complex compounds (shown in formula 14)
In glove box, by amino manganese complex formula 11 (0.01mmol, 4.1mg), ethanol (0.3mmol, 13.8mg) and
Toluene (1mL) is successively added in the bottle containing syringe needle, after question response 15min forms ethyoxyl manganese complex (formula 12) completely,
Bottle is put into 100mL autoclaves.The hydrogen of 30 atmospheric pressure is filled in kettle, is reacted at room temperature 14 hours.Question response terminates,
Phosphine spectrum tracking reaction product after hydrogen is slowly discharged.
31P NMR(162MHz,Toluene)：106.86ppm.
Understand that prepared target manganese complex structure is correct by above-mentioned analysis result.
The research of embodiment 7, different Mn catalysts to Guerbet reaction results[a]
The different Mn catalyst effects of table 1 compare
[a]Reaction condition:(6mL, 100mmol) ethanol, (6mmol) caustic alcohol, (0.01mol%) catalyst is 25ml's
24h. is reacted in pressure-resistant kettle[b]Total conversion ratio is the amount that ethanol is converted into higher alcohol, and yield (is made for the yield of butanol with biphenyl
Quantified for internal standard GC)[c]Selectivity compares for the amount of the amount of the material of butanol material shared in higher alcohols product[d]TON
Can be with total amount (mmol) of ethanol conversion to higher alcohols product for every mmol catalyst[e]The selectivity of crotonyl alcohol is
21%.
Under the protection of argon gas, by Mn catalyst (0.01mmol, 0.01mol%), caustic alcohol (6mmol, 408.3mg,
6mol%) successively it is added in the pressure-resistant kettles of 25mL containing magnetic stir bar with ethanol (100mmol, 6mL), it is anti-at a temperature of being given
Answer 24h.After reaction terminates, cooled down with frozen water, slowly release gas caused by inside kettle, biphenyl is added into reaction system
As internal standard, diluted with THF, the yield and its selectivity of product butanol are quantitatively drawn by GC.
By to screening of catalyst result it can be found that using the less cyclohexyl of steric hindrance and isopropyl PNP types
Pincer [Mn] (+1) catalyst (entry1-7) has preferable conversion ratio and yield to ethanol；For the uncle that steric hindrance is larger
Butyl PNP catalyst or the weaker NNP catalyst of coordination ability and [Mn] (+2) catalyst fail successfully to make ethanol
Generation converts (entry7-11).
Embodiment 8, Different Alkali and other reaction conditions are catalyzed the research of Guerbet reaction results to manganese[a]
The condition optimizing of table 2
[a]Reaction condition:(6mL, 100mmol) ethanol, (6-12mmol) caustic alcohol, 0.01mol% [Mn]-formula 8 exist
160 DEG C of reaction 12-168h. conversion ratios, yield, selectivity and TON and the Computational Methods one of example 1 in 25mLl pressure-resistant kettle
Cause[b]The extra water for adding 10mmol[c]Reaction temperature is 180 DEG C of[d]0.02mol% [Mn]-formula 8.[e]0.1mol% [Mn]-
Formula 8.[f](12mL, 200mmol) ethanol, (12mmol) caustic alcohol[g]60mL reactors, (0.0025mmol) [Mn]-formula 8,
(30mL, 510mmol) ethanol, (30mmol) caustic alcohol[h]60mL reactors, (0.00125mmol) [Mn]-formula 8, (45mL,
765mmol) ethanol, (46mmol) caustic alcohol[i]100mL reactors, (0.00125mmol) [Mn]-formula 8, (75mL,
1275mmol) ethanol, (76mmol) caustic alcohol[j]The selectivity of crotonyl alcohol is 11%.[i]100mL reactors,
(0.00125mmol) [Mn]-formula 8, (75mL, 1275mmol) ethanol, (150mmol) caustic alcohol
Condition optimizing discovery is carried out by being reacted to more than, it is catalyst to use [Mn] (formula 8), and alkali is screened
(entry1-5), when using highly basic when all there is preferable reaction result, at that time with weak base (such as sodium acetate) when, although the reaction
With preferable selectivity (entry 5), but its conversion ratio and yield are poor；Increase the dosage of alkali and the dosage of catalyst,
Its conversion ratio and yield can be further improved (entry 10-12)；It has also been found that, reacted simultaneously for the reaction
, can for the selectivity of product ethanol when increasing the dosage but identical other reaction conditions of its substrate ethanol when device is identical
Therewith increase (entry 1,13), it is believed that, due to reactor can accommodate gas space it is less when, generated in-situ hydrogen
Atmospheric pressure will increase, and can so accelerate the hydrogenation rate of reaction intermediate, so as to prevent its conversion to higher alcohol (to pass through
GC detections are carried out to caused gas in reaction system, as a result show 81%) content of hydrogen in its gas phase has reached.Finally,
After carrying out a series of optimization to reaction condition, the reaction can obtain up to 114120 TON (entry 19), wherein preceding 12h
TOF be 3078h-1。
Embodiment 9, poison experiment repercussion study
The part of table 3 poisons results contrast
Under the protection of argon gas, by catalyst [Mn] (formula 8) (0.01mmol, 0.01mol%), caustic alcohol (408.3mg,
6mmol, 6mol%), the Hg or PMe of ethanol (100mmol, 6mL) and respective amount3Successively it is added to the 25mL containing magnetic stir bar
In pressure-resistant kettle, 24h is reacted at 160 DEG C.After reaction terminates, cooled down with frozen water, slowly release gas caused by inside kettle, to
Biphenyl is added in reaction system as internal standard, is diluted with THF, the yield and its selectivity of product butanol is quantitatively drawn by GC.
Result above shows that addition poisons reagent Hg or PMe3Conversion ratio and yield to whole catalytic reaction do not have
Any detrimental effect, it is the process of a homogeneous reaction to illustrate the catalytic reaction.
The research of embodiment 10, the Mn catalyst of N-Me protections in ethanol conversion process
Table 4N-Me catalyst results contrasts
Under the protection of argon gas, by catalyst [Mn] formula 9 or formula 10 (0.01mmol, 0.01mol%), caustic alcohol
(408.3mg, 6mmol, 6mol%) and ethanol (100mmol, 6mL) are successively added to the pressure-resistant kettles of 25mL containing magnetic stir bar
In, react 24h at 160 DEG C.After reaction terminates, cooled down with frozen water, gas caused by inside kettle is slowly released, to reaction
Biphenyl is added in system as internal standard, is diluted with THF, the yield and its selectivity of product butanol is quantitatively drawn by GC.
From the point of view of from the result of table 4, after N-H structures are changed into N-Me, the conversion for ethanol generates strong influence.
Its conversion ratio, yield and selectivity, which have, obviously to be declined, and therefore, the presence of N-H structures is for ethanol in part
Whole conversion to butanol plays very important effect.
The condensation reaction research of embodiment 11, manganese catalysis acetaldehyde and crotonaldehyde
Under the protection of argon gas, by Mn catalyst formula 8 (0.01mmol) (or being added without catalyst), caustic alcohol (1mmol),
Acetaldehyde or crotonaldehyde (1mL) are successively added in the pressure-resistant kettles of 25mL containing magnetic stir bar, react 4h at 160 DEG C.Reaction knot
Shu Hou, cooled down with frozen water, slowly release gas caused by inside kettle, biphenyl is added into reaction system as internal standard, is used
THF is diluted, and the selectivity and yield of raw material condensation product are quantitatively drawn by GC.
From the point of view of above-mentioned acquired results, catalyst will be added and be added without condensation of the catalyst to acetaldehyde or crotonaldehyde and produced
Thing is analyzed, and its C4 selectivity does not have obvious difference, i.e. the introducing of catalyst fails to improve C4 selectivity
So as to suppress the generation of C4+ products.Therefore, it is presumed that, the conversion reaction for ethanol, the high selectivity of its product butanol is
Caused by efficiently hydrogenation can occur for condensation intermediate crotonaldehyde.
The hydrogenation research of embodiment 12, manganese catalysis acetaldehyde and crotonaldehyde
Under the protection of argon gas, by Mn catalyst-formula 8 or 9 (0.01mmol), caustic alcohol (0.12mmol), acetaldehyde or bar
Beans aldehyde (2mmol) is successively added in the 25mL autoclaves containing magnetic stir bar, using THF as solvent, is put with inert gas argon gas
10bar H are filled with after the gas changed in autoclave three times2, react 24h at 160 DEG C.After reaction terminates, cooled down with frozen water,
Kettle internal hydrogen is slowly released, biphenyl is added into reaction system as internal standard, is diluted with THF, is quantitatively drawn by GC
The selectivity and yield of hydrogenated products.
From the point of view of above-mentioned hydrogenation result, the addition of [Mn]-formula 8 has brighter for the C4 products of acetaldehyde or crotonaldehyde
Aobvious facilitation, the selectivity of its C4 product are improved significantly, the result again illustrate acetaldehyde and hydrogen be ethanol to
The intermediate of butanol conversion process；In addition, the Mn catalyst formula 9 protected using N-Me, no matter for acetaldehyde or the hydrogen of crotonaldehyde
Change for reaction, all obtain relatively low C4 selectivity.Therefore, this also further illustrates its metal of the catalyst containing N-H structures
It is vital that hydrogenation of the mode that hydrogen migration occurs for its reaction intermediate crotonaldehyde is cooperateed with part.
As can be seen from the above-described embodiment, the invention provides the anti-of a kind of new manganese catalysis ethanol condensation generation butanol
Should, the reaction shows very high catalytic activity (TON=114120, wherein preceding 12h TOF is 3078h-1) and 92% fourth
Alcohol selectivity, has very high researching value and application prospect.
In this description, the present invention describes with reference to specific embodiment.But it is clear that it can still make
Go out various modifications and alterations without departing from the spirit and scope of the present invention.Therefore, specification and drawings are considered as illustrative
And it is nonrestrictive.
Claims (10)
1. the manganese complex of catalysis ethanol condensation generation butanol, its structural formula is as shown in Formulas I, Formula II, formula III or formula IV：
In Formulas I, Formula II and formula III,Represent NNP parts or PNP parts；
Wherein, X2It is methyl, ethyl, isopropyl, the tert-butyl group, cyclopenta, cyclohexyl, phenyl or 2- pyridine radicals for N or P, R；R1For
H, methyl, ethyl, benzyl or 2- picolyls；
In Formulas I, X and X1Independently selected from H, Cl, Br, I, CO, OAc, OEt, OMe, OBn, OH and OTf, and X and X1When different
For CO.
2. manganese complex according to claim 1, it is characterised in that：The structural formula such as Formula V of the NNP parts or Formula IV institute
Show：
In Formula V and Formula IV, A represents C or N；
In Formula V, R is expressed as methyl, ethyl, isopropyl, the tert-butyl group, cyclopenta, cyclohexyl or phenyl；
R1It is expressed as H, methyl, ethyl, benzyl or 2- picolyls；
R3、R4、R5And R6Independently represent H, C1~C6Alkyl, C1~C6Alkoxy, phenyl, C1~C6Alkyl-substituted phenyl, halogen
Element, benzyl, hydroxyl, naphthyl, furyl or thienyl；
In Formula IV, R7、R8And R9Independently represent H, C1~C6Alkyl, C1~C6Alkoxy, phenyl, C1~C6Alkyl substituted benzene
Base, halogen, benzyl, hydroxyl, naphthyl, furyl or thienyl.
3. manganese complex according to claim 1, it is characterised in that：The structural formula of the PNP parts is as shown in Formula VII：
In Formula VII, R is expressed as methyl, ethyl, isopropyl, the tert-butyl group, cyclopenta, cyclohexyl, phenyl and 2- pyridine radicals；
R1It is expressed as H, methyl, ethyl, benzyl or 2- picolyls.
4. the preparation method of manganese complex, comprises the following steps any one of claim 1-3：
Under the protection of inert atmosphere, pentacarbonyl halogenation manganese salt is reacted with the NNP parts or the PNP parts, is produced
The manganese complex；
The chemical formula of the pentacarbonyl halogenation manganese salt is Mn (CO)5X3, wherein, X3Represent Cl, Br or I.
5. preparation method according to claim 4, it is characterised in that：The pentacarbonyl halogenation manganese salt and the NNP parts
Or the mol ratio of the PNP parts is 1：1.05~1.1.
The temperature of the reaction is 70~110 DEG C, and the time is 6~20 hours.
6. the preparation method according to claim 4 or 5, it is characterised in that：The reaction is carried out in a solvent, the solvent
For at least one of toluene, dimethylbenzene and tetrahydrofuran.
7. the answering in the Guerbet reaction generation butanol of manganese catalysis ethanol of manganese complex any one of claim 1-3
With.
8. application according to claim 7, it is characterised in that：The Guerbet of the manganese catalysis ethanol reacts to obtain butanol
Reaction equation it is as follows：
Wherein, [Mn] represents manganese complex any one of claim 1-3.
9. the application according to claim 7 or 8, it is characterised in that：The Guerbet reactions are under the protection of inert atmosphere
Carry out.
10. the application according to any one of claim 8 or 9, it is characterised in that：In the Guerbet reactions, right will
The mole dosage for seeking manganese complex any one of 1-3 is the 0.00001%~0.01% of ethanol；
The temperature of the Guerbet reactions is 100~180 DEG C, and the time is 2~168 hours；
The Guerbet reactions are carried out under the conditions of existing for caustic alcohol；
The concentration of caustic alcohol is 0.1~2M described in the system of the Guerbet reactions.
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