CN110054557A - A kind of 1,3- bis- replaces the preparation method of alkyl phenyl acetone - Google Patents
A kind of 1,3- bis- replaces the preparation method of alkyl phenyl acetone Download PDFInfo
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- CN110054557A CN110054557A CN201910380428.6A CN201910380428A CN110054557A CN 110054557 A CN110054557 A CN 110054557A CN 201910380428 A CN201910380428 A CN 201910380428A CN 110054557 A CN110054557 A CN 110054557A
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- alkyl
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- diol silica
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- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 125000005037 alkyl phenyl group Chemical group 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000007853 buffer solution Substances 0.000 claims abstract description 5
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229940127003 anti-diabetic drug Drugs 0.000 claims abstract description 4
- 239000003472 antidiabetic agent Substances 0.000 claims abstract description 4
- 239000004020 conductor Substances 0.000 claims abstract description 3
- 230000005622 photoelectricity Effects 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 51
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 238000011097 chromatography purification Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- FSQCARXEMZOCLZ-UHFFFAOYSA-N C1=CC(=CC(=C1)CN)CC(=O)CC2=CC(=CC=C2)CN Chemical compound C1=CC(=CC(=C1)CN)CC(=O)CC2=CC(=CC=C2)CN FSQCARXEMZOCLZ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- -1 graphite alkene Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000003279 phenylacetic acid Substances 0.000 description 2
- 229960003424 phenylacetic acid Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RNPGHTOGQOCBQK-UHFFFAOYSA-N 1,3-bis(3-methoxyphenyl)propan-2-one Chemical compound COC1=CC=CC(CC(=O)CC=2C=C(OC)C=CC=2)=C1 RNPGHTOGQOCBQK-UHFFFAOYSA-N 0.000 description 1
- RMMRRRLPDBJBQL-UHFFFAOYSA-N 1-(3-methoxyphenyl)propan-2-one Chemical compound COC1=CC=CC(CC(C)=O)=C1 RMMRRRLPDBJBQL-UHFFFAOYSA-N 0.000 description 1
- KIEOMRYTVQSFBX-UHFFFAOYSA-N 2,3,4-triphenyl-2h-furan-5-one Chemical compound O=C1OC(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 KIEOMRYTVQSFBX-UHFFFAOYSA-N 0.000 description 1
- GJMPSRSMBJLKKB-UHFFFAOYSA-N 3-methylphenylacetic acid Chemical compound CC1=CC=CC(CC(O)=O)=C1 GJMPSRSMBJLKKB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- MOIPGXQKZSZOQX-UHFFFAOYSA-N carbonyl bromide Chemical class BrC(Br)=O MOIPGXQKZSZOQX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- GGRQLKPIJPFWEZ-UHFFFAOYSA-N cycloprop-2-en-1-one Chemical compound O=C1C=C1 GGRQLKPIJPFWEZ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/213—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings
- C07C49/215—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing six-membered aromatic rings polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/58—One oxygen atom, e.g. butenolide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
One kind 1,3- bis- replaces the preparation method of alkyl phenyl acetone, belongs to medical science and field of photovoltaic materials.The present invention first reacts Alkyl-diol silica with DMAP, adding DCC, the reaction was continued, pH finally is adjusted using Potassium Hydrogen Phthalate buffer solution and obtains compound, and compound obtains this product by column Chromatographic purification, and this product can be used for the preparation of antidiabetic drug and photoelectricity crystallization conductor material.The present invention replaces alkyl phenyl acetone using Alkyl-diol silica reaction preparation 1,3- bis-；Operation is easy, carries out under mild reaction conditions.Synthetic method provided by the invention is simple and easy, scientific and reasonable, environmentally protective, economical and practical, is suitble to large-scale production.
Description
Technical field
The present invention relates to medical science and field of photovoltaic materials, relate generally to one kind 1,3- bis- and replace alkyl phenyl acetone
Preparation method.
Background technique
1,3- bis- replace alkyl phenyl acetone due to its unique molecular structure, photoelectric characteristic and they in p- electronics material
Application on material, make its poromerics, crystallization photoconductor, synthesizing graphite alkene in terms of using more and more extensive.
Meanwhile 1,3- bis- replaces alkyl phenyl acetone to can be used as a kind of cheap precursor, fast and effeciently prepares relative complex construction
Object, so also there is important application in terms of pharmaceutical synthesis.Based on this, this field needs easier, green, economic method
It synthesizes 1,3- bis- and replaces alkyl phenyl acetone.The present invention using Alkyl-diol silica or with 3- alkyl benzyl chloride p-toluenesulfonyl first
Base isocyanide reaction preparation 1,3- bis- replaces alkyl phenyl acetone.Operation is easy, and simple acid-base accommodation PH is used only
Value, carries out under mild reaction conditions.
Summary of the invention
To make up the deficiencies in the prior art, the present invention provides operate to synthesize the substitution alkane of 1,3- bis- under easy, temperate condition
The method of base phenylacetone.
The present invention adopts the following technical scheme: 1,3- bis- replaces alkyl phenyl acetone, there is the structure as shown in general formula I:
Wherein, R1With R2For identical-CH3Or-OCH3。
Replace the preparation method of alkyl phenyl acetone the purpose of the present invention is above-mentioned 1,3- bis- is claimed, it may be assumed that by alkyl
(1mmol:(0.2~0.5mL) is added in 1~10:1~3 in molar ratio for phenylacetic acid and DMAP (4-dimethylaminopyridine)) dry
In methylene chloride, stirring to whole dissolutions.It will be equivalent to 0.1~2 DCC (N, the N'- dicyclohexyl of Alkyl-diol silica molal quantity
Carbodiimide) it is dissolved in (1mmol:(0.5~1mL)) in dry methylene chloride, be then slowly added dropwise with constant pressure funnel
To in above-mentioned solution.After being stirred for 24 hours at being 20~30 DEG C in temperature, it is added (1mmol:(1~3mL)) n-hexane and ethyl acetate
Mixed solution (the two volume ratio is n-hexane: ethyl acetate=1:1), then uses Potassium Hydrogen Phthalate buffer solution by PH tune
To 4.Organic phase is extracted with separatory funnel, and removes DMAP.With saturated sodium bicarbonate solution quenching reaction, and use saturated salt solution
Washing three times, extracts organic matter, with the dry organic phase of anhydrous sodium sulfate.It is rotated later, using column chromatography for separation
It closes object (eluant, eluent is ethyl acetate: petroleum ether=1:5).
The volume number of the methylene chloride, n-hexane and ethyl acetate is using the mole of Alkyl-diol silica as standard
's.
Preferably, the Alkyl-diol silica are as follows:Wherein R is-CH3Or-OCH3；
Preferably, fragrant phenylacetic acid are as follows:One kind.
Above-mentioned 1,3- bis- is claimed simultaneously and replaces alkyl phenyl acetone in medicine preparation and field of photovoltaic materials by the present invention
On application.
For example it is used for antidiabetic drug intermediateOr photoelectricity crystallizes conductor materialPreparation.
The beneficial effects of the present invention are:
The present invention replaces alkyl phenyl acetone using Alkyl-diol silica reaction preparation 1,3- bis-；Operation is easy, in temperature
It is carried out under reaction condition.Synthetic method provided by the invention is simple and easy, scientific and reasonable, environmentally protective, economical and practical, is suitble to
Large-scale production.
Specific embodiment
The present invention is described in detail below by specific embodiment, but is not limited the scope of the invention.Unless otherwise specified, originally
Experimental method used by inventing is conventional method, and experiment equipment used, material, reagent etc. can chemically company be bought.
Embodiment 1
Take a 250mL round-bottomed flask, by m-Tolylacetic acid (3.0036g, 20mmol) and DMAP (0.9773g,
It 8mmol) is added in dry methylene chloride, stirring to whole dissolutions.It is dry that DCC (2.0633g, 10mmol) is dissolved to 12mL
In dry methylene chloride, then it is slowly added dropwise with constant pressure funnel into above-mentioned solution.Stirring for 24 hours after, be added 30mL just oneself
Alkane and ethyl acetate (n-hexane: ethyl acetate=1:1), are then adjusted to 4 for PH with Potassium Hydrogen Phthalate buffer solution.With point
Liquid funnel extracts organic phase, and removes DMAP.With saturated sodium bicarbonate solution quenching reaction, and with saturated common salt water washing three
It is secondary, organic phase is extracted, with the dry organic phase of anhydrous sodium sulfate.Be spin-dried for, then through pillar layer separation (eluant, eluent is ethyl acetate:
Petroleum ether :=1:5) to obtain target compound.It is characterized as below.
1,3- bis- (3- aminomethyl phenyl) acetone: yield: 60%.1H NMR(500MHz,CDCl3) δ 7.28 (dt, J=6.2,
3.9Hz, 2H), 7.15 (d, J=7.6Hz, 2H), 7.04 (d, J=5.6Hz, 4H), 3.75 (s, 4H), 2.39 (d, J=8.2Hz,
6H).
Embodiment 2
Take a 250mL round-bottomed flask, by meta-methoxy phenylacetic acid (3.3234g, 20mmol) and DMAP (0.9773g,
It 8mmol) is added in dry methylene chloride, stirring to whole dissolutions.It is dry that DCC (2.0633g, 10mmol) is dissolved to 12mL
In dry methylene chloride, then it is slowly added dropwise with constant pressure funnel into above-mentioned solution.Stirring for 24 hours after, be added 30mL just oneself
Alkane and ethyl acetate (n-hexane: ethyl acetate=1:1), are then adjusted to 4 for PH with Potassium Hydrogen Phthalate buffer solution.With point
Liquid funnel extracts organic phase, and removes DMAP.With saturated sodium bicarbonate solution quenching reaction, and with saturated common salt water washing three
It is secondary, organic phase is extracted, with the dry organic phase of anhydrous sodium sulfate.Be spin-dried for, then through pillar layer separation (eluant, eluent is ethyl acetate:
Petroleum ether :=1:5) to obtain target compound.It is characterized as below:
1,3- bis- (3- methoxyphenyl) acetone: yield: 58%.1H NMR(500MHz,CDCl3) δ 7.27 (dd, J=
11.1,4.7Hz, 2H), 6.86-6.83 (m, 2H), 6.79 (d, J=7.5Hz, 2H), 6.73-6.71 (m, 2H), 3.81 (d, J=
2.0Hz,6H),3.72(s,4H).
Embodiment 3
The application of antidiabetic drug intermediate
By 1,3- bis- (3- aminomethyl phenyl) acetone solution in acetic acid, the acetic acid solution of bromine (2.05 equivalent) is added dropwise.3 hours
Afterwards, reactant is poured into water, product is collected by filtration.Crude product (two bromoketones) is air-dried into a few hours, is then dissolved in dry
In methylene chloride.The solution is added in the dichloromethane solution of the triethylamine (2.5 equivalent) of stirring, and is stirred at room temperature 1
Hour.Then reaction mixture is washed with 1M HCl, is then washed with saturated sodium chloride solution, it is dry with sodium sulphate, and subtract
Pressure concentration.By silica gel chromatography, 'beta '-ketoester is obtained.Sequentially added in 10mL test tube cyclopropenone (0.15mmol,
1.5 equivalents), 'beta '-ketoester (0.1mmol, 1 equivalent), catalyst DBU (0.02mmol, 20mol%) and solvent DME (1mL).It will pipe
It seals and is stirred at room temperature.It (is detected after completion of the reaction by TLC), directly removes solvent under reduced pressure, and pass through silica gel
Flash column chromatography crude mixture (PE:EA=20:1), obtains target compound.It is characterized as below:
2- (5- oxo -2,3,4- triphenyl -2,5- dihydrofuran -2- base) ethyl acetate: yield: 91%；Colorless oil
Object.1H NMR(300MHz,CDCl3)δ7.45-7.34(m,5H),7.33-7.28(m,1H),7.27-7.18(m,7H)6.88-
6.84 (m, 1H), 6.83-6.80 (m, 1H), 4.25-4.08 (m, 2H), 3.43-3.26 (AB, J=15.3Hz, 2H), 1.22 (t,
J=7.1Hz, 3H).
Embodiment 4
The application of photoelectric material
Benzil is added into the mixture of (3- methoxyphenyl) acetone of 1,3- bis- (0.78g, 3.02mmol)
(0.64mg, 3.02mmol) and EtOH (10ml/ grams of ketone), are stirred at 85 DEG C, and KOH (0.5 equivalent) is added at EtOH (3mL)
In.Mixture is heated 1 hour, is then filtered out.Obtained solid is first washed with water, then is washed to obtain black powder with EtOH
Solid.It is characterized as below:
2,5- is bis--the amyl- 2,4- dienone of (3- methoxyl group-phenyl) -3,4- diphenyl-ring: yield: 70%；Fusing point: 150-
152℃。1H NMR(500MHz,CDCl3) δ 7.22 (m, 6H), 6.97 (m, 6H), 6.78 (d, J=8.5Hz, 2H), 6.70 (d, J
=1.9Hz, 2H), 3.85 (s, 6H).
The preferable specific embodiment of the above, only the invention, but the protection scope of the invention is not
It is confined to this, anyone skilled in the art is in the technical scope that the invention discloses, according to the present invention
The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection scope it
It is interior.
Claims (8)
1. one kind 1,3- bis- replaces the preparation method of alkyl phenyl acetone, which is characterized in that method includes the following steps:
S1. Alkyl-diol silica and DMAP are added in round-bottomed flask, and dry methylene chloride is added and stirs evenly；
S2. DCC is dissolved in the reaction solution for being added dropwise to step S1 in dichloromethane solution, 20~30 DEG C of reactions are for 24 hours；
S3. n-hexane is added and PH is adjusted to 4 with Potassium Hydrogen Phthalate buffer solution by the mixed solution of ethyl acetate, liquid separation takes
Organic phase removes DMAP；
S4. saturated sodium bicarbonate solution quenching reaction is used, and three times with saturated common salt water washing, extracts organic matter, use is anhydrous
Sodium sulphate dries organic phase, and revolving removes solvent；
S5. column chromatography for separation obtains product.
2. the preparation method that a kind of 1,3- bis- according to claim 1 replaces alkyl phenyl acetone, which is characterized in that described
The molar ratio of Alkyl-diol silica and DMAP are 1~10:1~3 in step S1.
3. the preparation method that a kind of 1,3- bis- according to claim 1 replaces alkyl phenyl acetone, which is characterized in that described
The proportionate relationship of methylene chloride and Alkyl-diol silica is Alkyl-diol silica in step S1: methylene chloride=1mmol:0.2~
0.5mL。
4. the preparation method that a kind of 1,3- bis- according to claim 1 replaces alkyl phenyl acetone, which is characterized in that step
The molal quantity of DCC is equivalent to the 0.1~2 of Alkyl-diol silica molal quantity in S2.
5. the preparation method that a kind of 1,3- bis- according to claim 1 replaces alkyl phenyl acetone, which is characterized in that described
The proportionate relationship of methylene chloride and Alkyl-diol silica is Alkyl-diol silica: methylene chloride=1mmol:0.5~1mL in step S2.
6. the preparation method that a kind of 1,3- bis- according to claim 1 replaces alkyl phenyl acetone, which is characterized in that step
The volume ratio of the mixed solution of n-hexane and ethyl acetate is n-hexane: ethyl acetate=1:1, n-hexane and ethyl acetate in S3
Mixed solution and Alkyl-diol silica proportionate relationship be Alkyl-diol silica: the mixed solution of n-hexane and ethyl acetate=
1mmol:1~3mL.
7. the preparation method that a kind of 1,3- bis- according to claim 4 replaces alkyl phenyl acetone, which is characterized in that step
The eluant, eluent that S5 column chromatography uses is ethyl acetate: petroleum ether=1:5.
8. the preparation that the products application prepared using method for claim 4 method crystallizes conductor material in antidiabetic drug and photoelectricity.
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| CN101805266A (en) * | 2008-10-13 | 2010-08-18 | 葛来西雅帝史派有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
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| CN101805266A (en) * | 2008-10-13 | 2010-08-18 | 葛来西雅帝史派有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
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| JICHAO LI等: "An efficient synthesis of heptaarydipyrromethenes from tetraarylcyclopentadienones and ammonium acetate and their extension to the corresponding BODIPYs", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 * |
| XUANYI LI等: "Supporting Information: Organocatalyzed[3+2] Annulation of Cyclopropenones and β-Ketoesters: An Approach to Substituted Butenolides with a Quaternary Center", 《ORGANIC LETTERS》 * |
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