CN108144612A - It is a kind of for the cobalt-base catalyst of one pot process carboxylate and its preparation and application - Google Patents
It is a kind of for the cobalt-base catalyst of one pot process carboxylate and its preparation and application Download PDFInfo
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Abstract
The invention belongs to liquid phase oxidation technical fields, disclose a kind of cobalt-base catalyst preparation method and applications for one pot process carboxylate, the form of the cobalt-base catalyst is Co N C@MxOy；The grain size of the cobalt-base catalyst cobalt nano-particle is 2~20nm.For the cobalt-base catalyst using vitamin B12 as precursor, oxide or carbon are carrier, are prepared by way of pyrolysis in an inert atmosphere.In the presence of the cobalt-base catalyst, using oxygen or air as oxidant, without other additives, two kinds of alcohol reactions prepare carboxylate.Cobalt-base catalyst of the present invention is very easy to largely synthesize, which has magnetism, easy recycling.Reaction condition is mild, environmentally protective, and product is very easy to detach, and the selectivity and yield of product are all very high, have a good application prospect.
Description
Technical field
The invention belongs to liquid phase catalytic oxidation technical fields, are related to a kind of cobalt-base catalyst, and in particular to one kind is used for one
The cobalt-base catalyst preparation method and applications of pot method synthesizing carboxylate
Background technology
Ester is a kind of very important chemical products and organic synthesis intermediate, is widely used in food, organic synthesis, painting
The fields such as material, fragrance, cosmetics, medicine and high molecular material.Therefore, esterification is used as and prepares ester type compound being of approach
Important organic reaction in.Traditional esters synthetic method is raw material generally by acid and alcohol, using the concentrated sulfuric acid as catalyst,
Long-time heating, direct esterification synthesis.Although making catalyst with high activity with the concentrated sulfuric acid, lacked there is also more
Point：Poor selectivity, side reaction is more, and product purity is poor, and strong acid causes environmental pollution and equipment corroded also very serious.Then
The acyl chlorides or acid anhydrides of high activity is generally first made in carboxylic acid by the esters synthetic method of the mild condition of development, then anti-with alcohol again
Corresponding ester should be generated.If these methods first prepare ester using aldehyde as starting material, need through peroxidating, activation and esterification three
Step reaction, these methods usually can all reduce the yield of ester and need the longer reaction time.Then, it is further to make great efforts always
It is dedicated to the direct oxidation esterification one-step synthesis Ester of aldehyde, but this kind of method is often using the oxygen of stoichiometry or excess
Agent for example, manganese dioxide, potassium hydrogen persulfate, peroxide, although these methods are useful, but have and largely has
Malicious unwanted byproduct generation, and the aldehyde as substrate is typically to be aoxidized by alcohol.So from Atom economy and efficiency profit
From the point of view of, the direct oxidation esterification one-step synthesis Ester of alcohol is a method highly studied, and is grasped in this way
Make simply, to reduce cost, environmental pollution is small, with more industrial application value, because alcohol compound is than carbonyl class chemical combination
Object more " green ", classes of compounds is more, stablizes in air, is commercially easy to get, cheap low toxicity is easy to operate.
From the point of view of economy and environment, air or oxygen is ideal oxidant, and not only cheap, resource is rich
Richness, and the by-product after oxidation is water.At present, document report using molecular oxygen as terminal oxidized dose, catalysis oxidation alcohol one
Catalyst system used in step synthesizing ester compound relates generally to homogeneous and two kinds of multiphase.
Homogeneous catalysis system is mainly using Pd as catalyst, 2011, Matthias Beller seminars and Lei
Almost simultaneously, the alcohol direct oxidation that Pd catalysis is reported in Angew.Chem.Int.Ed. is ester type compound for aiwei seminars
Method.Matthias Beller seminars (Angew.Chem.Int.Ed.2011,50,5139-5143) report method be
With the Pd (OAc) of 2-5mol%2As catalyst, addition 4-5mol%nBuP (1-adamantyl)2As ligand, 4- is added in
10mol%AgPF6With the K of 50-120mol%2CO3As additive, 50-80 DEG C, 1bar O2Under the conditions of react 20-40h.Lei
Method 5mol% [the PdCl of aiwei seminars (Angew.Chem.Int.Ed.2011,50,5144-5148) report2
(CH3CN)2] as catalyst, the AgBF of 10mol%4With the NaOtBu of 2 equivalents as additive, 45 DEG C, oxygen ball pressure
Under, realize the synthesis of first ester type compound.When other short chain fatty alcohols are as solvent, need to add in the P- of 20mol%
Olefin is as ligand, the Ag of 20mol%2CO3With the K of 4.5 equivalents3PO4It is 60 DEG C, real under oxygen ball pressure as additive
The synthesis of other existing ester type compounds.Although two methods realize Pd catalytic alcohol oxidative esterification reactions for the first time, item is reacted
Part is complicated, needs to add in ligand and multiple additives, and the yield of product has to preferable level.
Homogeneous catalysis system has apparent limitation：Catalyst cannot recycle, and product separation is more complicated,
To obtain high catalytic activity, need to add in ligand or multiple additives.Therefore, heterogeneous catalyst system, Neng Gouke are developed
Homogeneous catalysis system shortcoming is taken, receives the favor of researcher.In recent years, the heterogeneous catalyst master of ester is oxidized to for catalytic alcohol
If precious metals pd, Au.Especially nano catalyst has a wide range of applications in alcohol oxidative esterification.At present, it has reported
Nano gold catalysis system largely needs to add a large amount of alkali, higher reaction temperature and high reaction pressure (0.3MPa-
2MPa) only has a small amount of catalyst system and catalyzing (Au/K2TiO13, Au/MgAl-HT, PI-Au) and alcohol oxidation can be realized under the conditions of slightly warm
For ester.Seldom, the Stahl seminars in 2013 (Organic Letters, 2013,15,5072) of multiphase Pd catalyst system and catalyzings report
Pd/charcoal catalyst is reported, in the presence of bismuth nitrate and metal Te, can efficiently realize that alcohol is oxidized to ester, but
It is that the reaction system is also required to the potassium methoxide of addition equivalent.
One kettle way is increasingly paid close attention to using alcohol as raw material direct oxidation synthetic ester by researcher, and that has reported is homogeneous
This conversion can be effectively realized with heterogeneous catalytic system, but these catalyst system and catalyzings generally require to add in a certain amount of alkali
(equivalent is excessive), reaction can just carry out.Homogeneous catalysis system also needs to add in ligand or other additives, multiphase are urged
Change system is directed to greatly noble metal catalyst, and catalyst preparation is limited by many conditions, and catalytic activity is by preparation condition shadow
There are many factor of sound.Therefore, research with base metal heterogeneous catalyst come to replace noble metal catalyst be to realize that alcohol direct oxidation is given birth to
Into the key of ester commercial Application.
Invention content
The shortcomings that overcome the prior art, preparation had the non-precious metal catalyst of high activity, and is applied with insufficient
The synthesizing ester compound under temperate condition.It is an object of the present invention to provide a kind of cobalt-based catalysts for one pot process carboxylate
Agent preparation method and applications.
The purpose of the present invention is achieved through the following technical solutions：
A kind of cobalt-base catalyst preparation method and applications for one pot process carboxylate.The cobalt-base catalyst
Form is Co-N-C@MxOy；The grain size of cobalt nano-particle is 2~20nm in the cobalt-base catalyst.Using oxygen or air as oxygen
Agent, the cobalt-base catalyst prepare carboxylate for two kinds of alcohol reactions.
It is a kind of according to the above-mentioned cobalt-base catalyst preparation method that carboxylate is prepared for two kinds of alcohol reactions, it is as follows：It weighs
Vitamin B12 is added in ethyl alcohol, and more than 30min is stirred at room temperature, and then adds in carrier, and gained mixture stirs at room temperature
Mix 3-24 hours, then reduced vacuum rotates ethyl alcohol, the vacuum drying of gained red solid.Sample is pulverized, is transferred to
In quartz cell, it is put into tubular type kiln roasting.Roasting condition：Nitrogen atmosphere rises to required target roasting from room temperature with 5-10 DEG C/min
600-1000 DEG C of temperature is burnt, then keeps certain time at this temperature.Heating finishes, cooled to room temperature, whole process
Keep nitrogen atmosphere.As described prepares carboxylate cobalt-base catalyst for two kinds of alcohol reactions.
Above-mentioned preparation method, carrier are one in magnesia, aluminium oxide, zirconium oxide, activated carbon, hydroxyapatite, SBA-15
Kind or two or more, preferential oxidation magnesium.
The mass ratio 1 of above-mentioned preparation method, vitamin B12 and carrier:1~5.
Above-mentioned preparation method, solid is is vacuumized 12-24 hours by vacuum drying treatment at 60-100 DEG C.
Above-mentioned preparation method, heating target temperature are 600-1000 DEG C.
Above-mentioned preparation method, isothermal pyrolysis time are 1-8 hours.
It is described that prepare carboxylate method for two kinds of alcohol reactions as follows：Using oxygen or air as oxidant, two kinds of alcohol
For raw material, the one of which alcohol in reaction is solvent, and reaction temperature is 60~150 DEG C, and the reaction time is 12-24 hours, reaction
After detach, obtain to obtain carboxylate compound.Above-mentioned to prepare carboxylate method, alcohol is C7-C20 fragrance primary alconol, C1-C10 fat
One or two or more kinds in fat primary alconol or C8-C20 aromatic diols, C4-C10 aliphatic glycols.
Above-mentioned to prepare carboxylate method, the pressure of required oxidation or air is 0.1-0.5MPa.
Above-mentioned to prepare carboxylate method, the molar ratio of alcohol and cobalt atom in cobalt-base catalyst is：1: 0.05~0.15.
Above-mentioned to prepare carboxylate method, reaction temperature is preferably 80 DEG C, and the reaction time is preferably 24 hours.
It is above-mentioned to prepare carboxylate method, it is cooled to room temperature after reaction, solid filtering, vacuum distillation concentration removes molten
Agent, crude product is through column chromatography for separation to get carboxylate compound.
The present invention is had the following advantages relative to the prior art and effect：
(1) it is raw materials used simple and easy to get to prepare cobalt-base catalyst by the present invention, does not need to synthesize；Preparation condition is also very simple,
Therefore a large amount of synthesis are very easy to.In addition, the catalyst has magnetism, mixed after reaction using Magnetic Isolation catalyst and reaction
Liquid, post-processing operation are very simple.
(2) cobalt-base catalyst provided by the present invention is heterogeneous non-precious metal catalyst, avoids that your traditional gold used
Metal catalyst (Au, Pd).Catalystic converter system does not need to add in additional alkali.Catalyst system and catalyzing has reaction condition mild, locates afterwards
Manage the advantages that simple.
(3) cobalt-base catalyst of the present invention has good low cycle performance.It does not need to carry out high temperature regeneration processing, instead
After answering, simple washing drying is reusable, and catalytic activity does not change with selective.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention and not only danger in
This：
Cobalt-base catalyst of the present invention for one pot process carboxylate can be by described in embodiment any one of 1-10
Method prepared
Embodiment 1
It weighs 1g vitamin B12s to be added in 100ml ethyl alcohol, 30min is stirred at room temperature, then add in 1g magnesia,
Gained mixture is stirred at room temperature 24 hours, and then reduced vacuum rotates ethyl alcohol, and vacuum is done at 60 DEG C of gained red solid
Dry 12 hours.Sample is pulverized, is transferred in quartz cell, is put into tubular type kiln roasting.Roasting condition：Nitrogen atmosphere, from
Room temperature is risen to required 800 DEG C of target temperature, is then kept for 2 hours at this temperature with the speed of 5 DEG C/min.Heating finishes, from
It is so cooled to room temperature, gained black powder is the cobalt-base catalyst Co-N-C@MgO-800 for one pot process carboxylate.
Embodiment 2
It weighs 1g vitamin B12s to be added in 100ml ethyl alcohol, 30min is stirred at room temperature, then add in 1g aluminium oxide,
Gained mixture is stirred at room temperature 24 hours, and then reduced vacuum rotates ethyl alcohol, and vacuum is done at 60 DEG C of gained red solid
Dry 12 hours.Sample is pulverized, is transferred in quartz cell, is put into tubular type kiln roasting.Roasting condition：Nitrogen atmosphere, from
Room temperature is risen to required 800 DEG C of target temperature, is then kept for 2 hours at this temperature with the speed of 5 DEG C/min.Heating finishes, from
It is so cooled to room temperature, gained black powder is the cobalt-base catalyst Co-N-C@Al for one pot process carboxylate2O3-800。
Embodiment 3
It weighs 1g vitamin B12s to be added in 100ml ethyl alcohol, 30min is stirred at room temperature, then add in 1g zirconium oxides,
Gained mixture is stirred at room temperature 24 hours, and then reduced vacuum rotates ethyl alcohol, and vacuum is done at 60 DEG C of gained red solid
Dry 12 hours.Sample is pulverized, is transferred in quartz cell, is put into tubular type kiln roasting.Roasting condition：Nitrogen atmosphere, from
Room temperature is risen to required 800 DEG C of target temperature, is then kept for 2 hours at this temperature with the speed of 5 DEG C/min.Heating finishes, from
It is so cooled to room temperature, gained black powder is the cobalt-base catalyst Co-N-C@ZrO for one pot process carboxylate2-800。
Embodiment 4
It weighs 1g vitamin B12s to be added in 100ml ethyl alcohol, 30min is stirred at room temperature, then add in 1g activated carbons,
Gained mixture is stirred at room temperature 24 hours, and then reduced vacuum rotates ethyl alcohol, and vacuum is done at 60 DEG C of gained red solid
Dry 12 hours.Sample is pulverized, is transferred in quartz cell, is put into tubular type kiln roasting.Roasting condition：Nitrogen atmosphere, from
Room temperature is risen to required 800 DEG C of target temperature, is then kept for 2 hours at this temperature with the speed of 5 DEG C/min.Heating finishes, from
It is so cooled to room temperature, gained black powder is the cobalt-base catalyst Co-N-C@C-800 for one pot process carboxylate.
Embodiment 5
It weighs 1g vitamin B12s to be added in 100ml ethyl alcohol, 30min is stirred at room temperature, then add in 1g hydroxyapatites
(HAP), gained mixture is stirred at room temperature 24 hours, and then reduced vacuum rotates ethyl alcohol, at 60 DEG C of gained red solid
Vacuum drying 12 hours.Sample is pulverized, is transferred in quartz cell, is put into tubular type kiln roasting.Roasting condition：Nitrogen atmosphere
It encloses, from room temperature with the speed of 5 DEG C/min, rises to required 800 DEG C of target temperature, then kept for 2 hours at this temperature.It has heated
Finish, cooled to room temperature, gained black powder is the cobalt-base catalyst Co-N-C@HAP- for one pot process carboxylate
800。
Embodiment 6
It weighs 1g vitamin B12s to be added in 100ml ethyl alcohol, 30min is stirred at room temperature, then add in 1g SBA-15,
Gained mixture is stirred at room temperature 24 hours, and then reduced vacuum rotates ethyl alcohol, and vacuum is done at 60 DEG C of gained red solid
Dry 12 hours.Sample is pulverized, is transferred in quartz cell, is put into tubular type kiln roasting.Roasting condition：Nitrogen atmosphere, from
Room temperature is risen to required 800 DEG C of target temperature, is then kept for 2 hours at this temperature with the speed of 5 DEG C/min.Heating finishes, from
It is so cooled to room temperature, gained black powder is the cobalt-base catalyst Co-N-C@SBA-15- for one pot process carboxylate
800。
Embodiment 7
It weighs 1g vitamin B12s to be added in 100ml ethyl alcohol, 30min is stirred at room temperature, then add in 1g magnesia,
Gained mixture is stirred at room temperature 24 hours, and then reduced vacuum rotates ethyl alcohol, and vacuum is done at 60 DEG C of gained red solid
Dry 12 hours.Sample is pulverized, is transferred in quartz cell, is put into tubular type kiln roasting.Roasting condition：Nitrogen atmosphere, from
Room temperature is risen to required 600 DEG C of target temperature, is then kept for 2 hours at this temperature with the speed of 5 DEG C/min.Heating finishes, from
It is so cooled to room temperature, gained black powder is the cobalt-base catalyst Co-N-C@MgO-600 for one pot process carboxylate.
Embodiment 8
It weighs 1g vitamin B12s to be added in 100ml ethyl alcohol, 30min is stirred at room temperature, then add in 1g magnesia,
Gained mixture is stirred at room temperature 24 hours, and then reduced vacuum rotates ethyl alcohol, and vacuum is done at 60 DEG C of gained red solid
Dry 12 hours.Sample is pulverized, is transferred in quartz cell, is put into tubular type kiln roasting.Roasting condition：Nitrogen atmosphere, from
Room temperature is risen to required 700 DEG C of target temperature, is then kept for 2 hours at this temperature with the speed of 5 DEG C/min.Heating finishes, from
It is so cooled to room temperature, gained black powder is the cobalt-base catalyst Co-N-C@MgO-700 for one pot process carboxylate.
Embodiment 9
It weighs 1g vitamin B12s to be added in 100ml ethyl alcohol, 30min is stirred at room temperature, then add in 1g magnesia,
Gained mixture is stirred at room temperature 24 hours, and then reduced vacuum rotates ethyl alcohol, and vacuum is done at 60 DEG C of gained red solid
Dry 12 hours.Sample is pulverized, is transferred in quartz cell, is put into tubular type kiln roasting.Roasting condition：Nitrogen atmosphere, from
Room temperature is risen to required 900 DEG C of target temperature, is then kept for 2 hours at this temperature with the speed of 5 DEG C/min.Heating finishes, from
It is so cooled to room temperature, gained black powder is the cobalt-base catalyst Co-N-C@MgO-900 for one pot process carboxylate.
Embodiment 10
It weighs 1g vitamin B12s to be added in 100ml ethyl alcohol, 30min is stirred at room temperature, then add in 1g magnesia,
Gained mixture is stirred at room temperature 24 hours, and then reduced vacuum rotates ethyl alcohol, and vacuum is done at 60 DEG C of gained red solid
Dry 12 hours.Sample is pulverized, is transferred in quartz cell, is put into tubular type kiln roasting.Roasting condition：Nitrogen atmosphere, from
Room temperature is risen to required 1000 DEG C of target temperature, is then kept for 2 hours at this temperature with the speed of 5 DEG C/min.Heating finishes,
Cooled to room temperature, gained black powder are the cobalt-base catalyst Co-N-C@MgO- for one pot process carboxylate
1000。
The catalytic applications of cobalt-base catalyst of the present invention for one pot process carboxylate can pass through embodiment 11-30
In scheme realize：
Embodiment 11
Table 1：Above-mentioned prepared catalyst is for the synthesis comparison of benzyl alcohol methyl esters
Reaction condition:3mol% catalyst, 1mmol benzyl alcohol 2ml MeOH, 80 DEG C, for 24 hours, 0.1MPa O2.a15mol%
Catalyst
The synthesis of 12 methyl benzoate of embodiment
By Co-N-C@MgO (15mol%), 108mg benzyl alcohols (1mmol), 2mL methanol is added sequentially to 25mL polytetrafluoros
In the autoclave pressure of ethylene liner, closed reactor, with oxygen by kettle pressurising power to 0.1MPa, 80 DEG C of reactions obtain crude product for 24 hours,
Room temperature is cooled to, slowly bleed, vacuum rotary steam goes out solvent methanol, and residue object column chromatography obtains product methyl benzoate
123.7mg, colourless liquid, yield 91%.Product：1H NMR(400M,CDCl3)δppm:3.91 (s, 3H), 7.43 (t, J=
7.6Hz, 2H), 7.55 (t, J=8.0Hz, 1H), 8.04 (d, J=7.6Hz, 2H)；13C NMR(100M,CDCl3)δppm:
167.1,132.9,130.2,129.6,128.3,52.0。
The synthesis of 13 methyl p-methyl benzoate of embodiment
Examination on experimental operation, to replace benzyl alcohol to methylbenzyl alcohol, obtains target product to methylbenzene first with embodiment 1
Sour methyl esters 135.9mg, yellowish liquid, yield 91%.Product：1H NMR(400M,CDCl3)δppm:2.38(s,3H),3.89
(s,3H),7.28-7.35(m,2H),7.82-7.85(m,2H)；13C NMR(100M,CDCl3)δppm:167.1,143.5,
129.6,129.0,127.4,51.8,21.6。
The synthesis of 14 o-methyl benzoic acid methyl ester of embodiment
Examination on experimental operation replaces benzyl alcohol with o-methyl-benzene methanol, obtains target product as methylbenzene first with embodiment 1
Sour methyl esters 140.3mg, colourless liquid, yield 94%.Product：1H NMR(400M,CDCl3)δppm:2.60(s,3H),3.88(s,
3H),7.21-7.24(m,2H),7.36-7.40(m,1H),7.89-7.91(m,1H)；13C NMR(100M,CDCl3)δppm:
168.1,140.2,132.0,131.7,130.6,129.6,125.7,51.8,21.7。
The synthesis of 15 m-methyl benzoic acid methyl ester of embodiment
Examination on experimental operation replaces benzyl alcohol with embodiment 1, with methylbenzyl alcohol, obtain target product be between methylbenzene
Methyl formate 129.7mg, colourless liquid, yield 86%.Product：1H NMR(400M,CDCl3)δppm:2.38(s,3H),3.89
(s,3H),7.28-7.35(m,2H),7.82-7.85(m,2H)；13C NMR(100M,CDCl3)δppm:167.2,138.1,
133.6,130.1,128.2,126.7,52.0,21.2。
The synthesis of 16 3,4- dimethylbenzoate methyl esters of embodiment
Examination on experimental operation replaces benzyl alcohol, it is 3,4- to obtain target product with embodiment 1 with 3,4- dimethylphenylcarbinols
Dimethylbenzoate methyl ester 154.9mg, colourless liquid, yield 94%.Product：1H NMR(400M,CDCl3)δppm:2.27(s,
6H), 3.87 (s, 3H), 7.16 (d, J=8.0Hz, 1H), 7.75 (d, J=8.8Hz, 1H), 7.80 (s, 3H)；13C NMR
(100M,CDCl3)δppm:167.9,142.7,137.2,131.2,130.2,128.3,127.7,52.4,20.5,20.2。
The synthesis of 17 methyl p-methoxybenzoate of embodiment
Examination on experimental operation replaces benzyl alcohol with P-methoxybenzyl alcohol, obtains target product as methoxyl group with embodiment 1
Methyl benzoate 140.4mg, white solid, yield 84%.48-51 DEG C of fusing point.1H NMR(400M,CDCl3)δppm:3.85(s,
3H), 3.88 (s, 3H), 6.91 (d, J=8.8Hz, 2H), 7.99 (d, J=8.8Hz, 2H)；13C NMR(100M,CDCl3)δ
ppm:166.9,163.4,131.6,122.6,113.6,55.4,51.9。
The synthesis of 18 m-methoxybenzoic acid methyl esters of embodiment
Examination on experimental operation replaces benzyl alcohol with embodiment 1, with meta-methoxy benzyl alcohol, obtain target product be between methoxy
Yl benzoic acid methyl esters 144.4mg, colourless liquid, yield 87%.1H NMR(400M,DMSO)δppm:3.77(s,3H),3.81
(s, 3H), 7.17-7.20 (m, 1H), 7.37-7.41 (m, 2H), 7.51 (d, J=7.6Hz, 1H)；13C NMR(100M,DMSO)δ
ppm:166.1,159.3,131.0,129.9,121.4,119.3,113.8,55.3,52.2。
The synthesis of 19 parachlorobenzoic-acid methyl esters of embodiment
Examination on experimental operation, to replace benzyl alcohol to chlorobenzene methanol, obtains target product as parachlorobenzoic-acid with embodiment 1
Methyl esters 158.4mg, white solid, yield 95%.42-44 DEG C of fusing point.1H NMR(400M,CDCl3)δppm:3.86(s,3H),
7.91 (d, J=8.0Hz, 2H), 7.35 (d, J=8.4Hz, 2H)；13C NMR(100M,CDCl3)δppm:166.1,139.3,
130.9,128.6,128.5,52.2。
The synthesis of 20 m-chlorobenzoic acid methyl esters of embodiment
Examination on experimental operation replaces benzyl alcohol with chlorobenzene methanol, obtains target product as m-chlorobenzoic acid with embodiment 1
Methyl esters 164.7mg, yellowish liquid, yield 90%.1H NMR(400M,CDCl3)δppm:3.92 (s, 3H), 7.37 (t, J=
8.0Hz, 1H), 7.52 (d, J=8.0Hz, 1H), 7.92 (d, J=7.6Hz, 1H), 8.02 (s, 1H)；13C NMR(100M,
CDCl3)δppm:165.9,134.6,133.0,131.9,129.7,127.8,122.0,52.5。
The synthesis of 21 0-chloro-benzoic acid methyl esters of embodiment
Examination on experimental operation replaces benzyl alcohol with adjacent chlorobenzene methanol, obtains target product as 0-chloro-benzoic acid with embodiment 1
Methyl esters 159.6mg, yellowish liquid, yield 90%.1H NMR(400M,CDCl3)δppm:3.91(s,3H),7.29-7.31(m,
1H),7.37-7.44(m,2H),7.79-7.81(m,1H)；13C NMR(100M,CDCl3)δppm:166.1,133.7,132.6,
131.4,131.1,130.1,126.6,52.4。
The synthesis of 22 1- naphthoic acid methyl esters of embodiment
Examination on experimental operation replaces benzyl alcohol with 1- naphthalenes alcohol, obtains target product as 1- naphthoic acid methyl esters, nothing with embodiment 1
Color liquid, 141.2mg, yield 77%.1H NMR(400M,CDCl3)δppm:4.01(s,1H),7.48-7.56(m,1H),
7.60-7.64 (m, 1H), 7.89 (d, J=8.4Hz, 1H), 8.02 (d, J=8.4Hz, 1H), 8.20 (d, J=7.2Hz, 1H),
8.92 (d, J=8.4Hz, 1H)；13C NMR(100M,CDCl3)δppm:168.1,133.9,133.4,131.4,130.3,
128.6,127.8,127.2,126.3,125.9,124.6,52.2。
The synthesis of 23 3,4- dimethoxy p-methyls of embodiment
Examination on experimental operation replaces benzyl alcohol with embodiment 1, with 3,4- 3,5-dimethoxybenzoic alcohols, and it is 3 to obtain target product,
4- dimethoxy p-methyl 176.9mg, white solid, yield 92%.59-62 DEG C of fusing point.1H NMR(400M,CDCl3)δ
ppm:3.88 (s, 3H), 3.92 (s, 6H), 6.88 (d, J=8.4Hz, 1H), 7.53 (d, J=1.6,1H), 7.67 (dd, J1=J2
=1.6Hz, 1H)；13C NMR(100M,CDCl3)δppm:167.4,153.5,149.2,124.1,123.2,112.5,110.8,
56.6,52.6。
The synthesis of 24 3,4,5- tri-methoxybenzoates of embodiment
Examination on experimental operation replaces benzyl alcohol, obtaining target product is with embodiment 1 with 3,4,5- trimethoxybenzyl alcohols
3,4,5- tri-methoxybenzoate 169.5mg, white solid, yield 78%.82-84 DEG C of fusing point.1H NMR(400M,
CDCl3)δppm:3.89(s,12H),7.29(s,2H)；13C NMR(100M,CDCl3)δppm:166.8,153.0,142.2,
125.2,106.8,103.1,61.0,56.3,52.3。
The synthesis of 14 parabromobenzoic acid methyl esters of embodiment
Examination on experimental operation, to replace benzyl alcohol to bromobenzene methanol, obtains target product as parabromobenzoic acid with embodiment 1
Methyl esters 193.5mg, white solid, yield 90%.77-81 DEG C of fusing point.1H NMR(400M,DMSO)δppm:3.83(s,3H),
7.71 (d, J=8.8Hz, 2H), 7.85 (d, J=8.4Hz, 2H)；13C NMR(100M,DMSO)δppm:166.6,133.0,
132.1,129.8,128.4,51.4。
The synthesis of 25 methyl p-nitrobenzoate of embodiment
Examination on experimental operation replaces benzyl alcohol with p nitrobenzyl alcohol, obtains target product as p-nitrophenyl with embodiment 1
Methyl formate 153.8mg, white solid, yield 85%.94-96 DEG C of fusing point.1H NMR(400M,CDCl3)δppm:2.38(s,
3H),3.89(s,3H),7.28-7.35(m,2H),7.82-7.85(m,2H)；13C NMR(100M,CDCl3)δppm:167.1,
143.5,129.6,129.0,127.4,51.8,21.6。
The synthesis of 26 methyl cinnamate of embodiment
Examination on experimental operation replaces benzyl alcohol with cinnamyl alcohol, obtains target product as methyl cinnamate with embodiment 1
129.6mg, yellowish solid, yield 80%.34-36 DEG C of fusing point,1H NMR(400M,CDCl3)δppm:3.81(s,3H),6.45
(d, J=16Hz, 1H), 7.39 (s, 3H), 7.52 (s, 2H), 7.70 (d, J=16Hz, 1H)；13C NMR(100M,CDCl3)δ
ppm:167.5,145.0,134.4,130.4,129.0,128.1,117.9,51.8。
The synthesis of 27 methylfuroate of embodiment
Examination on experimental operation replaces benzyl alcohol with embodiment 1, with furfuryl alcohol, obtains target product as methylfuroate 100.8mg,
Colourless liquid, yield 80%.1H NMR (400MHz, CDCl3)δppm：3.87(s,3H),6.80(dd,J1=1.8Hz, J2=
3.3Hz, 1H), 7.17 (d, J=3.6Hz, 1H), 7.58 (d, J=0.6Hz, 1H)；13C NMR(100MHz,CDCl3)δppm:
159.8,146.8,144.6,118.3,112.3,52.2。
The synthesis of 28 methyl methacrylate of embodiment
Examination on experimental operation replaces benzyl alcohol with methylallyl alcohol, obtains target product as methacrylic acid with embodiment 1
Methyl esters 75mg, colourless liquid, yield 75%.1H NMR (400MHz, CDCl3)δppm：1.94(s,3H),3.75(s,3H),6.13
(s,1H),5.57(s,1H)；13C NMR(100MHz,CDCl3)δppm:167.8,136.6,125.3,118.3,52.1。
The synthesis of 29 propyl benzoate of embodiment
Examination on experimental operation replaces methanol with embodiment 1, with normal propyl alcohol, obtains target product propyl benzoate 147.6mg,
Colourless liquid, yield 90%.Product：1H NMR(400M,CDCl3)δppm:1.04 (t, J=7.2Hz, 3H), 1.77-1.83 (m,
2H), 4.28 (t, J=6.4Hz, 2H), 7.44 (t, J=7.6Hz, 1H), 7.55 (t, J=7.2Hz, 1H), 8.04-8.06 (m,
2H)；13C NMR(100M,CDCl3)δppm:166.8,132.9,130.2,129.6,128.4,66.6,22.2,10.6.
The synthesis of 30 δ-valerolactone of embodiment
By Co-N-C@MgO (15mol%), 104mg 1,5-PDs (1mmol), 1mL normal heptanes are added sequentially to 25mL
In the autoclave pressure of polytetrafluoroethyllining lining, closed reactor, with oxygen by kettle pressurising power to 0.1MPa, 80 DEG C of reactions obtain for 24 hours
Crude product is cooled to room temperature, slowly bleed, and vacuum rotary steam goes out solvent methanol, and residue object column chromatography is obtained in product δ-penta
Ester 93mg, light yellow liquid, yield 90%.Product：1H NMR(400MHz,CDCl3):δ1.80-1.92(m,4H),2.53(t,J
=7.2Hz, 2H), 4.32 (t, J=5.6Hz, 2H)13C NMR(100MHz,CDCl3):δ18.8,22.1,29.6,69.3,
171.4。
Claims (10)
1. a kind of preparation method for one pot process carboxylate cobalt-base catalyst, it is characterised in that：Include the following steps, claim
Vitamin B12 is taken to be added in ethyl alcohol, more than 30min is stirred at room temperature, then adds in carrier, gained mixture is at room temperature
Stirring 3-24 hour, then reduced vacuum rotate ethyl alcohol, gained red solid is dried in vacuo；Sample is pulverized, is shifted
Into quartz cell, it is put into tubular type kiln roasting；Roasting condition：Nitrogen atmosphere rises to required target from room temperature with 5-10 DEG C/min
Then 600-1000 DEG C of calcination temperature is kept for 1-8 hours at this temperature；Heating finishes, cooled to room temperature, whole process
Keep nitrogen atmosphere；As described prepares carboxylate cobalt-base catalyst for two kinds of alcohol reactions.
2. preparation method according to claim 1, it is characterised in that：The carrier for magnesia, aluminium oxide, zirconium oxide,
It is more than one or two kinds of in activated carbon, hydroxyapatite, SBA-15.
3. preparation method according to claim 1, it is characterised in that：The vacuum drying treatment is in 60-100 by solid
It DEG C vacuumizes 12-24 hours.
4. preparation method according to claim 1, it is characterised in that：The mass ratio 1: 1~5 of vitamin B12 and carrier.
5. the cobalt-base catalyst for one pot process carboxylate that a kind of claim 1-4 either method prepares, special
Sign is：The form of the cobalt-base catalyst is Co-N-C@MxOy；MxOyFor carrier；Cobalt nano-particle in the cobalt-base catalyst
Grain size be 2~20nm.
6. a kind of application of the cobalt-base catalyst in two kinds of alcohol reactions prepare carboxylate described in claim 5, it is characterised in that：
Using oxygen and/or air as oxidant, two kinds of alcohol A, B are raw material, and the one of which alcohol in reaction is solvent, and reaction temperature is
60~150 DEG C, the reaction time is 12-24 hours, is cooled to room temperature after reaction, and separation obtains carboxylate compound；
Wherein A is C7-C20 fragrance primary alconol, in C1-C10 primary aliphatic alcohols, C8-C20 aromatic diols, C4-C10 aliphatic glycols
One or two or more kinds；
Wherein B is C7-C20 fragrance primary alconol, in C1-C10 primary aliphatic alcohols, C8-C20 aromatic diols, C4-C10 aliphatic glycols
One or two or more kinds.
7. application according to claim 6, it is characterised in that：The pressure of required oxygen and/or air is 0.1-
0.5MPa。
8. application according to claim 6, it is characterised in that：The molar ratio of alcohol and cobalt atom in cobalt-base catalyst is：1∶
0.05~0.15.
9. application according to claim 6, it is characterised in that：Reaction temperature is preferably 80 DEG C, and the reaction time is preferably 24
Hour.
10. application according to claim 6, it is characterised in that：It is cooled to room temperature after reaction, solid filtering, decompression
Distillation and concentration removes solvent, and crude product is through column chromatography for separation to get carboxylate compound.
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