CN109265319A - The preparation method of two (miscellaneous) aryl first alcohol compounds - Google Patents
The preparation method of two (miscellaneous) aryl first alcohol compounds Download PDFInfo
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- C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
- C07C33/24—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part polycyclic without condensed ring systems
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
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- C07C215/68—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
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- C07C29/36—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 with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—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 with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
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- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
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- C07C67/00—Preparation of carboxylic acid esters
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- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
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Abstract
The invention belongs to organic synthesis fields, and in particular to the preparation method of two (miscellaneous) aryl first alcohol compounds.It is that catalyst prepares two (miscellaneous) aryl first alcohol compounds in high yield that method of the invention, which is using available (miscellaneous) the aryl aldehyde in market and divalent nickel source of (miscellaneous) aryl boric acid as raw material, inexpensively stable,.Method of the invention is improved usually using metal reagent severe reaction conditions, side reaction is more and post-processes the deficiencies of difficult, also avoids the defect that is at high cost, being difficult to the preparation of scale amount of the catalysis such as precious metal palladium reaction.Have the characteristics that mild condition, easy to operate, inexpensive, high efficiency and environmental-friendly, convenient for extending in practical scale amount preparation.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to the preparation method of two (miscellaneous) aryl first alcohol compounds.
Background technique
Two (miscellaneous) aryl first alcohol compounds are a kind of important organic synthesis intermediates, and most common synthetic method is
Utilize (miscellaneous) aryl ketones reduction or using the metal reagents such as (miscellaneous) aryl grignard reagent, (miscellaneous) aryl lithium, organotin with
It is prepared by the addition of (miscellaneous) aryl aldehyde.But two (miscellaneous) aryl first alcohol compounds are prepared by reaction substrate of two (miscellaneous) aryl ketones
Reduction reaction conditions it is harsh, need to carry out in anhydrous conditions, be unfavorable for being widely applied.On the other hand, since grignard is tried
Agent and lithium reagent activity are higher, so that the compatibility of reaction is not high, thus by the very day of one's doom in the preparation of complicated organic molecule
System；Meanwhile the reasons such as high toxicity of the reagents such as organotin, significantly limit the application range of above-mentioned reaction.
Aryl borane reagent is extensive because having preferable functional group compatibility, to the characteristics such as water and air-stable, low toxicity
In organic reaction.From Miyaura in 1998 etc. [M.Sakai, M.Ueda, N.Miyaura.Angew.Chem.,
Int.Ed.1998,37,3279.] aryl boric acid of rhodium catalysis has been reported for the first time to since the addition reaction of aryl formaldehyde, transition
The aryl boric acid of metal catalytic makes great progress the addition reaction of aryl formaldehyde.But these work are concentrated mainly on expensive
The noble metals such as metal Pd, Rh, the also toxic and higher Ni of risk (cod)2、Ni(ClO4)2As being obtained under catalysts conditions
?.Due to palladium, rhodium it is expensive, catalysis reaction needed for ligand it is special；In addition, the toxicity and nickelous perchlorate of zero-valent nickel are not
Stability, limiting these methods can be only applied to during laboratory prepares in a small amount, it is difficult to scale amount or productivity preparation is suitble to want
It asks, the preparation method of two (miscellaneous) aryl first alcohol compounds of practicability can't be become.
In conclusion two (miscellaneous) aryl first alcohol compounds have important and being widely applied property, in existing synthesis side
In method, some synthesis condition harshness yields are not high, and some mild conditions are high-efficient but expensive.For this reason, it may be necessary to develop such
The reaction condition of compound is easy, efficiently, convenient for the preparation method of scale.
Summary of the invention
To improve the above problem, the present invention provides the preparation method such as 3 compound of following formula, comprising:
If 1 compound of following formula and 2 compound of formula react in the presence of catalyst, Cabbeen class ligand are with alkali, the change of formula 3 is obtained
Close object:
Wherein, A1、A2It is identical or different, it is independently from each other aryl or heteroaryl unsubstituted or replace；
The substituted aryl or heteroaryl may include the aryl or substituted heteroaryl replaced, the substituted aryl
Or the heteroaryl replaced can be for optionally by one or more R aryl replaced or heteroaryl；
Each R can be independently selected from group-CHO ,-B (OH)2Or the group inert to above-mentioned reaction, such as can
To be selected from F, Cl, Br, I, OH, NH2, SH, CN, it is unsubstituted or optionally by one or more RaSubstituted following groups: alkyl, alkene
Base, alkynyl, naphthenic base, heterocycle, aryl, heteroaryl, alkyl oxy, alkenyl oxygroup, alkynyl oxygroup, cycloalkyl oxy, heterocycle
Base oxygroup, aryloxy, heteroaryl oxygroup, NRbRc；
Ra、Rb、RcCan independently have meaning described in group R；As example, RaCan selected from F, Cl, Br, I, OH,
NH2、SH、CN、-OC(O)CH3；
As example, Rb、RcIt is identical or different, it is independently from each other unsubstituted or optionally by one or more RaReplace
C1-40Alkyl；
The alkali can be organic base or inorganic base, such as can be in sodium carbonate, potassium carbonate, sodium acetate, potassium phosphate etc.
One or more, preferably potassium phosphate；
The catalyst can be Raney nickel, such as containing the compound of nickelous or its complex, for example NiCl2·
6H2O、Ni(acac)2、NiCl2(PPh3)2、Ni(PPh3)2One of (1- naphthalene) Cl etc. or a variety of, preferably NiCl2
(PPh3)2；
The Cabbeen class ligand is preferably N-heterocyclic carbine, bis- (2, the 6- diisopropyl phenyl) imidazolitm chlorides of for example, 1,3-
(IPrHCl), 1,3- di-t-butyl imidazolitm chloride (ItBuHCl), 1,3- dicyclohexyl imidazolitm chloride (ICy
HCl), bis- (2,6- 3,5-dimethylphenyl) imidazolitm chlorides (IXyHCl) of 1,3-, bis- (2,4,6- trimethylphenyl) chlorinations of 1,3-
One of imidazoles (IMesHCl) etc. is a variety of, bis- (2, the 6- diisopropyl phenyl) imidazolitm chlorides of preferably 1,3-
(IPr·HCl)。
The molar ratio of preparation method according to the present invention, the catalyst and 1 compound of formula is (0.001-0.1): 1.
The molar ratio of 1 compound of formula and 2 compound of formula is 1:(1-4), for example, 1:1.5 or 1:3.
The molar ratio of the alkali and 1 compound of formula can be (0.5-5): 1, preferably (2-4): 1, for example, 2.5:1.
Preparation method according to the present invention, the reaction can carry out in organic solvent, such as in toluene, dimethylbenzene etc.
It carries out in organic solvent, is carried out preferably in toluene.
Preparation method according to the present invention, the temperature of the reaction can be 80-130 DEG C.
Preparation method according to the present invention, the time of the reaction can be 5-15 hours.
Preparation method according to the present invention, the reaction carry out preferably in inert gas, for example, under nitrogen protection into
Row.
As an embodiment, preparation method of the invention can use following steps:
1 compound of formula, 2 compound of formula, catalyst, Cabbeen class ligand and alkali are sequentially added in reaction tube；
Reaction tube first vacuumizes leads to nitrogen again, repeats operation three times, adds organic solvents into reaction tube later,
It is reacted 5-15 hours at 80-130 DEG C；
To after reaction, remove organic solvent under reduced pressure, separation is carried out to the mixture in reaction solution using column chromatography and is mentioned
It is pure, obtain 3 compound of formula.
The present invention also provides a kind of carbon monoxide-olefin polymeric, the carbon monoxide-olefin polymeric include catalyst, Cabbeen class ligand with
Alkali；
The alkali can be organic base or inorganic base, such as can be in sodium carbonate, potassium carbonate, sodium acetate, potassium phosphate etc.
One or more, preferably potassium phosphate；
The catalyst can be Raney nickel, such as can be containing the compound of nickelous or its complex, for example
NiCl2·6H2O、Ni(acac)2、NiCl2(PPh3)2、Ni(PPh3)2One of (1- naphthalene) Cl etc. or a variety of, preferably
NiCl2(PPh3)2；
The Cabbeen class ligand is preferably N-heterocyclic carbine, such as can be bis- (2, the 6- diisopropyl phenyl) chlorinations of 1,3-
Imidazoles (IPrHCl), 1,3- di-t-butyl imidazolitm chloride (ItBuHCl), 1,3- dicyclohexyl imidazolitm chloride
(ICyHCl), bis- (2,6- 3,5-dimethylphenyl) imidazolitm chlorides (IXyHCl) of 1,3-, bis- (the 2,4,6- trimethylbenzenes of 1,3-
Base) one of imidazolitm chloride (IMesHCl) etc. or a variety of, such as 1, bis- (2, the 6- diisopropyl phenyl) imidazolitm chlorides of 3-
(IPrHCl)；
Catalyst in the carbon monoxide-olefin polymeric, Cabbeen class ligand, alkali and reaction substrate molar ratio can be (0.001-
0.1):(0.001-0.1):(0.5-5):1。
Carbon monoxide-olefin polymeric as described above reacts preparation formula 3 with 2 compound of formula for above-mentioned 1 compound of formula as catalyst
The purposes of compound.
Term and definition
The present invention is used alone or " alkyl " as suffix or prefix is intended to include the branch with 1 to 40 carbon atom
With linear saturation aliphatic hydrocarbyl.For example, " C1-6Alkyl " indicates the straight chain and branched alkane with 1,2,3,4,5 or 6 carbon atom
Base.The example of alkyl include but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl,
Amyl and hexyl.
The present invention is used alone or " alkenyl " as suffix or prefix is intended to include including with 2 to 40 carbon atoms
The branch and linear aliphatic hydrocarbon group of alkenyl or alkene.For example, " C2-6Alkenyl " indicates the alkene with 2,3,4,5 or 6 carbon atoms
Base.The example of alkenyl includes but is not limited to vinyl, allyl, 1- acrylic, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 2-
Methyl but-2-ene base, 3- methyl but-1-ene base, 1- pentenyl, 3- pentenyl and 4- hexenyl.
The present invention is used alone or " alkynyl " as suffix or prefix is intended to include including with 2 to 40 carbon atoms
The branch and linear aliphatic hydrocarbon group of alkynyl or alkynes.Such as acetenyl, propinyl (such as l- propinyl, 2-propynyl), 3- fourth
Alkynyl, pentynyl, hexin base and the amyl- 2- alkynyl of 1- methyl.
Terminology used in the present invention " aryl " is intended to include the aromatic ring structure being made of 5 to 20 carbon atoms.Such as: packet
Aromatic ring structure containing 5,6,7 and 8 carbon atoms can be mono-cyclic aromatic group such as phenyl；Include 8,9,10,11,12,13
Or the ring structure of 14 carbon atoms can be polycyclic such as naphthalene.Aromatic ring can one or more ring positions replace have it is above-mentioned that
A little substituent groups.Term " aryl " further includes the polycyclic ring system with two or more rings, and two of them or more carbon is two
(ring is " condensed ring ") common to a adjacent ring, wherein at least one ring is aromatics and other rings for example can be cycloalkanes
Base, cycloalkenyl, cycloalkynyl radical, aryl and/or heterocycle.Polycyclic example includes but is not limited to 2,3- dihydro -1,4- benzo dioxy
Heterocycle hexadiene and 2,3- dihydro -1- benzofuran.
Terminology used in the present invention " naphthenic base " is intended to include the saturated cyclic with 3 to 40 carbon atoms.These arts
Language may include condensed or bridge joint multi-loop system.For example, naphthenic base has 3 to 20 carbon atoms in its ring structure.At one
In embodiment, naphthenic base has 3,4,5 or 6 carbon atoms in its ring structure.For example, " C3-6Naphthenic base " indicates such as ring
Propyl, cyclobutyl, cyclopenta or cyclohexyl group.
" heteroaryl " that the present invention uses refers to the heteroaromatic miscellaneous of at least one ring hetero atom (such as sulphur, oxygen or nitrogen)
Ring.Heteroaryl includes single loop system and multi-loop system (such as with 2,3 or 4 condensed ring).The example of heteroaryl includes but unlimited
In pyridyl group, pyrimidine radicals, pyrazinyl, pyridazinyl, triazine radical, furyl, quinolyl, isoquinolyl, thienyl, imidazole radicals, thiophene
Oxazolyl, indyl, pyrrole radicals, oxazolyl, benzofuranyl, benzothienyl, benzothiazolyl, isoxazolyl, pyrazolyl, three
Oxazolyl, tetrazole radical, indazolyl, 1,2,4- thiadiazolyl group, isothiazolyl, benzothienyl, purine radicals, carbazyl, benzimidazole
Base, benzoxazolyl, azepine benzoxazolyl, Imidazothiazole base, benzo [1,4] dioxine base, benzo [1,3] two
Oxole base etc..In some embodiments, heteroaryl has 3 to 40 carbon atoms and has in other embodiments
3 to 20 carbon atoms.In some embodiments, heteroaryl includes that 3 to 14,4 to 14,3 to 7 or 5 to 6 cyclization are former
Son.In some embodiments, heteroaryl has 1 to 4,1 to 3 or 1 to 2 hetero atom.In some embodiments, miscellaneous
Aryl has 1 hetero atom.
Unless otherwise indicated, terminology used in the present invention " heterocycle " refer to the saturation comprising 3 to 40 atoms, insatiable hunger and/or
The monocyclic, bicyclic or tricyclic of fractional saturation, wherein 1,2,3,4 or 5 annular atom is selected from nitrogen, sulphur or oxygen, unless otherwise indicated,
It can be connected by carbon or nitrogen, wherein-CH2Group is optionally replaced by-C (O)-；And wherein unless otherwise indicated, ring nitrogen
Atom or ring sulfur atom are optionally oxidized to form N- oxide or S- oxide or theheterocyclic nitrogen atom and optionally be quaternized；Its middle ring
In-NH optionally replaced by acetyl group, formoxyl, methyl or mesyl；And ring is optionally replaced by one or more halogens.It answers
It should be appreciated that these hetero atoms are not adjacent to each other when the sum of S atom in heterocycle and O atom is more than 1.If described miscellaneous
Ring group is two rings or tricyclic, then at least one ring may optionally be heteroaromatic rings or aromatic ring, and condition is that at least one ring is non-miscellaneous
Aromatics.It is not centainly aromatics if the heterocycle is monocycle.The example of heterocycle include but is not limited to piperidyl,
N- acetylpiperidinyl, N- methyl piperidine base, N- formyl piperazine base, N- mesylpiperazinyl, high piperazine base, piperazinyl,
Azetidinyl, oxetanyl, morpholinyl, tetrahydro isoquinolyl, tetrahydric quinoline group, indolinyl, oxinane
Base, dihydro -2H- pyranose, tetrahydrofuran base, tetrahydro thiapyran base, tetrahydric thiapyran -1- oxide, tetrahydric thiapyran -1,1- titanium dioxide
Object, 1H- pyridin-2-ones and 2,5- dioxoimidazolidin alkyl.
The above-mentioned definition to term is equally applicable to other terms containing the term, such as term " alkyl " is also applied for
" alkoxy " etc..
Beneficial effects of the present invention:
Preparation method of the invention has the characteristics that easy, efficient.The system of two (miscellaneous) aryl methanol scale amount easy to accomplish
It is standby.Method of the invention be using available (miscellaneous) the aryl aldehyde in market and (miscellaneous) aryl boric acid as raw material, cheap stable nickelous
Source is that catalyst prepares two (miscellaneous) aryl first alcohol compounds in high yield.Method of the invention improves the prior art and is preparing
The deficiencies of harsh, side reaction is mostly using metal reagent condition in two (miscellaneous) aryl methanol process and post-processing is difficult, also avoids
The defect that is at high cost, being difficult to the preparation of scale amount of noble metal palladium-catalyzed reaction.
Preparation method reaction condition of the invention is mild, and product yield high, the catalyst used is at low cost, is suitble to two (miscellaneous)
The industrialized production of aryl methanol.
Specific embodiment
Further detailed description is done to preparation method of the invention below in conjunction with specific embodiment.It should be appreciated that
The following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.
In the range of all technologies realized based on above content of the present invention are encompassed by the present invention is directed to protect.
Unless otherwise indicated, raw materials and reagents used in the following embodiment are commercial goods, or can be by
Perception method preparation.
Embodiment 1: the preparation of benzohydrol
Sequentially added in 25mL reaction tube 0.106 gram of (1.0mmol) benzaldehyde, 0.183 gram of (1.5mmol) phenylboric acid,
0.0327 gram of (0.05mmol) NiCl2(PPh3)2, 0.0424 gram of (0.1mmol) IPrHCl, 0.53 gram of (2.5mmol) K3PO4；
Reaction tube first vacuumizes leads to nitrogen again, repeats operation three times, 5mL toluene is added in reaction tube；It reacts at 110 DEG C
It carries out 5-15 hours, to after reaction, remove organic solvent under reduced pressure, the reaction solution after concentration is separated using column chromatography
Purification, can be obtained 0.149 gram of target product benzohydrol (yield 81%).
Embodiment 2: phenyl -3,4,5- trimethoxyphenyl-methanol preparation
By 1 the method for embodiment and step, benzaldehyde is changed to 3,4,5- trimethoxy-benzene first unlike the first embodiment
Aldehyde.Finally obtain 0.238 gram of target product (yield 87%).
Embodiment 3: phenyl -4- hydroxymethyl phenyl-methanol preparation
By 1 the method for embodiment and step, benzaldehyde is changed to 4- hydroxymethylbenzaldehyde unlike the first embodiment.Most
0.150 gram of target product (yield 70%) is obtained afterwards.
Embodiment 4: the preparation of phenyl -4- acetyl-o-methyl phenvl-methanol
By 1 the method for embodiment and step, benzaldehyde is changed to 4- formoxyl benzyl acetate unlike the first embodiment.
Finally obtain 0.197 gram of target product (yield 77%).
Embodiment 5: phenyl -6- methoxyl group -2- naphthalene-methanol preparation
By 1 the method for embodiment and step, benzaldehyde is changed to 6- methoxy-2-naphthaldehyde unlike the first embodiment.
Finally obtain 0.235 gram of target product (yield 89%).
Embodiment 6:3,4,5- trimethoxyphenyl-naphthalene-methanol preparation
By 1 the method for embodiment and step, benzaldehyde is changed to 3,4,5- trimethoxy-benzene first unlike the first embodiment
Aldehyde, phenylboric acid are changed to 1- naphthalene boronic acids.Finally obtain 0.269 gram of target product (yield 83%).
Embodiment 7: phenyl -4- dimethylamino phenyl-methanol preparation
By 1 the method for embodiment and step, benzaldehyde is changed to paradime thylaminobenzaldehyde unlike the first embodiment,
The phenylboric acid measured using 3 times, 0.0392 gram of (0.06mmol) NiCl2(PPh3)2, finally obtain 0.184 gram of (yield of target product
81%).
The preparation of embodiment 8:4- trifluoromethyl -6- methoxyl group -2- naphthalene-methanol
By 1 the method for embodiment and step, benzaldehyde is changed to 6- methoxy-2-naphthaldehyde unlike the first embodiment,
Phenylboric acid is changed to 3 times of equivalent p-trifluoromethyl phenyl boric acid.Finally obtain 0.309 gram of target product (yield 93%).
The preparation of embodiment 9:4- fluorophenyl -6- methoxyl group -2- naphthalene-methanol
By 1 the method for embodiment and step, benzaldehyde is changed to 6- methoxy-2-naphthaldehyde unlike the first embodiment,
Phenylboric acid is changed to 3 times of equivalent p-fluorophenyl boric acid.Finally obtain 0.243 gram of target product (yield 86%).
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. as following formula 1,2 compound of formula react 3 compound of preparation formula in the presence of catalyst, Cabbeen class ligand are with alkali,
Wherein, A1、A2It is identical or different, it is independently from each other aryl or heteroaryl unsubstituted or replace；
The substituted aryl or heteroaryl may include the aryl or substituted heteroaryl replaced, the substituted aryl or take
The heteroaryl in generation can be for optionally by one or more R aryl replaced or heteroaryl；
Each R can be independently selected from group-CHO ,-B (OH)2Or the group inert to above-mentioned reaction, such as can be selected from
F、Cl、Br、I、OH、NH2, SH, CN, it is unsubstituted or optionally by one or more RaSubstituted following groups: alkyl, alkenyl, alkynes
Base, naphthenic base, heterocycle, aryl, heteroaryl, alkyl oxy, alkenyl oxygroup, alkynyl oxygroup, cycloalkyl oxy, heterocyclyloxy
Base, aryloxy, heteroaryl oxygroup, NRbRc；
Ra、Rb、RcCan independently have meaning described in group R；
For example, RaF, Cl, Br, I, OH, NH can be selected from2、SH、CN、-OC(O)CH3；
For example, Rb、RcIt is identical or different, it is independently from each other unsubstituted or optionally by one or more RaSubstituted C1-40Alkane
Base.
2. preparation method as described in claim 1, wherein the alkali is organic base or inorganic base, for example, sodium carbonate, carbonic acid
One of potassium, sodium acetate, potassium phosphate etc. are a variety of, preferably potassium phosphate.
3. preparation method as claimed in claim 1 or 2, wherein the catalyst is Raney nickel, for example, containing nickelous
Compound or its complex, for example NiCl2·6H2O、Ni(acac)2、NiCl2(PPh3)2、Ni(PPh3)2In (1- naphthalene) Cl etc.
One or more, preferably NiCl2(PPh3)2。
4. preparation method as described in any one of claims 1-3, wherein the Cabbeen class ligand is preferably N-heterocyclic carbine, example
Bis- (2,6- diisopropyl phenyl) imidazolitm chlorides of for example 1,3-, 1,3- di-t-butyl imidazolitm chloride, 1,3- dicyclohexyl chlorine
Change imidazoles, bis- (2,6- 3,5-dimethylphenyl) imidazolitm chlorides of 1,3-, bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 1,3-
One of or it is a variety of, such as 1, bis- (2, the 6- diisopropyl phenyl) imidazolitm chlorides (IPrHCl) of 3-.
5. preparation method according to any one of claims 1-4, wherein the molar ratio of the catalyst and 1 compound of formula is
(0.001-0.1):1；
The molar ratio of 1 compound of formula and 2 compound of formula is 1:(1-4), for example, 1:1.5 or 1:3；
The molar ratio of the alkali and 1 compound of formula is (0.5-5): 1, preferably (2-4): 1, for example, 2.5:1.
6. preparation method as described in any one in claim 1-5, wherein the reaction carries out in organic solvent, such as in first
It carries out in the organic solvents such as benzene, dimethylbenzene, is carried out preferably in toluene；
The temperature of the reaction can be 80-130 DEG C；
The reaction carries out preferably in inert gas, such as carries out under nitrogen protection.
7. preparation method as claimed in any one of claims 1 to 6 can use following steps:
1 compound of formula, 2 compound of formula, catalyst, Cabbeen class ligand and alkali are sequentially added in reaction tube；
Reaction tube first vacuumizes leads to nitrogen again, repeats operation three times, adds organic solvents into reaction tube later, in
It is reacted 5-15 hours at 80-130 DEG C；
To after reaction, remove organic solvent under reduced pressure, separating-purifying is carried out to the mixture in reaction solution using column chromatography, is obtained
To 3 compound of formula.
8. a kind of carbon monoxide-olefin polymeric, including catalyst, Cabbeen class ligand and alkali.
9. carbon monoxide-olefin polymeric as claimed in claim 8, wherein the alkali is organic base or inorganic base, for example, sodium carbonate, carbon
One of sour potassium, sodium acetate, potassium phosphate are a variety of, preferably potassium phosphate；
The catalyst can be Raney nickel, such as containing the compound of nickelous or its complex, for example NiCl2·6H2O、Ni
(acac)2、NiCl2(PPh3)2、Ni(PPh3)2One of (1- naphthalene) Cl or a variety of, preferably NiCl2(PPh3)2；
The Cabbeen class ligand is preferably N-heterocyclic carbine, bis- (2, the 6- diisopropyl phenyl) imidazolitm chlorides of for example, 1,3-,
Bis- (2,6- 3,5-dimethylphenyl) imidazolitm chlorides of 1,3- di-t-butyl imidazolitm chloride, 1,3- dicyclohexyl imidazolitm chloride, 1,3-
, one of bis- (2,4,6- trimethylphenyl) imidazolitm chlorides of 1,3- or a variety of, such as 1, bis- (2, the 6- diisopropyl benzenes of 3-
Base) imidazolitm chloride；
Catalyst in the carbon monoxide-olefin polymeric, Cabbeen class ligand, alkali and reaction substrate molar ratio can be (0.001-
0.1):(0.001-0.1):(0.5-5):1。
10. carbon monoxide-olefin polymeric as claimed in claim 8 or 9 is as catalyst for above-mentioned 1 compound of formula and 2 compound of formula
The purposes of 3 compound of preparation formula is reacted,
Wherein, A1With A2With definition described in claim 1.
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| CN101456790A (en) * | 2008-11-04 | 2009-06-17 | 大连理工大学 | Method for preparing diaryl alcohol by catalyzing addition reaction of aryl boric acid and aldehyde by nickel |
| CN102584511A (en) * | 2011-01-05 | 2012-07-18 | 郑建鸿 | Preparation method for secondary alcohol |
| CN105732249A (en) * | 2016-01-27 | 2016-07-06 | 中国科学院上海有机化学研究所 | Synthesis method of aryl alcohol compound and Escitalopram |
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| CN102584511A (en) * | 2011-01-05 | 2012-07-18 | 郑建鸿 | Preparation method for secondary alcohol |
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