CN104177238B - Synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the method for 5-diphenyl cyclopentadienone - Google Patents
Synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the method for 5-diphenyl cyclopentadienone Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- 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
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- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
Abstract
The invention discloses a kind of synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the method for 5-diphenyl cyclopentadienone, taking 3,4,5-Trimethoxybenzaldehyde as raw material, with Cobastab1For catalyst, under alkali condition, make 4,4 '-bis-(3 by condensation reaction, 4,5-trimethoxy) benzoin, then in glacial acetic acid solution, using Schweinfurt green and ammonium nitrate as co-oxidants, oxidation 4,4 '-bis-(3,4,5-trimethoxy) benzoin obtains 4,4 '-bis-(3,4,5-trimethoxy) benzil, finally taking ethanol as solvent, under potassium hydroxide alkalescence condition, 4,4 '-bis-(3,4,5-trimethoxy) benzils and dibenzyl ketone condensation prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone; Method reaction raw materials of the present invention is cheap and easy to get, and synthesis step is simple, and the reaction time is short, reaction condition gentleness, and course of reaction is easy to control, and is applicable to suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the method for 5-diphenyl cyclopentadienone, belongs toOrganic compound synthesis technical field.
Background technology
Polyaryl substituted-cyclopentadienyl ketone is the important organic synthesis intermediate of a class. As the raw material of organic synthesis, its ringAlmost can there is Diels-Alder addition reaction with any unsaturated bond in two C=C conjugated double bonds on pentadienone ring, be syntheticPolyaryl substituted phenyl compounds one of method the most easily. In industrialized fine chemical product is produced, polyaryl substituted ring pentaDienone is widely used in the industries such as rubber, resin, coating, agricultural chemicals, spices.
3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone is cyclopentadiene ketone with regard to its skeleton structureCompound. The introducing of phenyl substituent, increases its molecular weight, and Melting point elevation, becomes solid-state under normal temperature. Two keys in ring withSubstituted benzene ring height conjugation, the spontaneous dimerization reaction activity decreased of cyclopentadienone, chemical stability is improved. Methoxy simultaneouslyThe pi-conjugated effect of p-based on lone electron pair and phenyl ring on inductive effect and oxygen atom between base and phenyl ring, presents special chemistryMatter. These characteristics have determined 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone have higher research andUsing value.
About 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the synthetic method of 5-diphenyl cyclopentadienone is also not relevant at presentBibliographical information. RhysShort etc. with 2-(3,4-Dimethoxyphenyl) acetic acid for raw material, by after its chloride again with O-phthalicEther carries out Friedel-Crafts reaction, obtains 4,4 '-bis-(3,4 – dimethoxy) benzoin. Then with selenium dioxide by 4,4 '-bis-(3,4 –Dimethoxy) benzoin is oxidized to 4,4 '-bis-(3,4 – dimethoxy) benzil, then carries out Knoevenagel with dibenzyl ketoneReaction obtains 3,4-bis-(3,4-Dimethoxyphenyl)-2,5-diphenyl cyclopentadienone (R.Shortetal., Chem.Commun.,2011,47:6822-6824). This method not only complex steps is consuming time, the relative fancy price of reaction raw materials and to human body, ringThe harm in border has also limited it in industrial application. In addition, with respect to 3,4-bis-(3,4-Dimethoxyphenyl)-2,5-diphenylCyclopentadienone, along with increasing of methoxy substitution base number, 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-hexichol basic ring pentaPolarity, dissolubility, chemical stability and the heat endurance of dienone are all improved. Therefore, seek that a kind of raw material is easy to get, workSkill is simple, product purity is high, yield is high, safe and reliable, pollute little, be applicable to carrying out 3 of suitability for industrialized production, 4-bis-(3,4,5-tri-Methoxyphenyl)-2, the synthetic method of 5-diphenyl cyclopentadienone seems particularly important.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)The method of-2,5-diphenyl cyclopentadienone. The method raw material is easy to get, technique is simple, the reaction time is short, product is easily separated, productProduct purity is high, yield is high, safe and reliable, pollute little, be suitable for carrying out suitability for industrialized production.
For achieving the above object, the present invention adopts following technical scheme:
A kind of synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the method for 5-diphenyl cyclopentadienone, comprises the following steps:
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzoin
In reactor, add successively Cobastab1, distilled water, ethanol, 3,4,5-Trimethoxybenzaldehyde, in ice-water bath slowlyStir 10～20min, then dropwise add NaOH ethanolic solution, pH value to 8～10 of regulator solution, and constantly addNaOH ethanolic solution makes the pH value of solution keep 40～50min, is heated to, after 55～75 DEG C of reaction 2～4h, be chilled to room temperature,Leave standstill, suction filtration, filter cake is washed with distilled water to filtrate for neutral, obtains yellow solid, with ethyl alcohol recrystallization, can obtain 4,4 '-Two (3,4,5-trimethoxy) benzoin;
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
In reactor, add Schweinfurt green, ammonium nitrate, glacial acetic acid, distilled water, stirring and dissolving, then adds 4,4 '-bis-(3,4,5-Trimethoxy) benzoin, be warming up to backflow, reaction 1～3h, cooling after, the precipitation of separating out is leached, be washed to filtrate beingNeutrality, with ethyl alcohol recrystallization, the yellow acicular crystal obtaining is 4,4 '-bis-(3,4,5-trimethoxy) benzil;
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone
In reactor, add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil, dibenzyl ketone, ethanol, agitating heating,Question response system is micro-while boiling, drips potassium hydroxide-ethanol solution to solution and is aterrimus and keeps half a minute colour-fast, continues heatingTo refluxing, reaction 15～45min, cooling rear suction filtration obtains rufous powder, is (1～2): (1～2) by it in volume ratioIn ethanol/toluene mixed solvent, be recrystallized, obtain 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone;
Wherein, in step (1), Cobastab1, distilled water, ethanol, 3,4,5-Trimethoxybenzaldehyde mass ratio be (1～3):(4～6):(11～14):15；
In step (2), 4,4 '-bis-(3,4,5-trimethoxy) benzoin, Schweinfurt green, ammonium nitrate, glacial acetic acid, distilled waterMass ratio is 9:(1～2): (4～6): (29～34): (4～6);
In step (3), the mass ratio of 4,4 '-bis-(3,4,5-trimethoxy) benzil, dibenzyl ketone, ethanol be 7:(4～5):(14～18)。
In described step (1), time of repose is 24h.
In described step (1), NaOH ethanolic solution concentration is 3.0mol/L.
In described step (3), potassium hydroxide-ethanol solution concentration is 3.6mol/L.
Preferably, in described step (1), Cobastab1, distilled water, ethanol, 3,4,5-Trimethoxybenzaldehyde mass ratioFor 2:5:13:15.
Preferably, in described step (3), the volume ratio of ethanol/toluene mixed solvent is 1:1.
Reaction equation of the present invention is as follows:
Beneficial effect of the present invention:
(1) the present invention is taking 3,4,5-Trimethoxybenzaldehyde as raw material, with Cobastab1For catalyst, under alkali condition, pass throughCondensation reaction makes 4,4 '-bis-(3,4,5-trimethoxy) benzoin, then, in glacial acetic acid solution, does with Schweinfurt green and ammonium nitrateFor co-oxidants, oxidation 4,4 '-bis-(3,4,5-trimethoxy) benzoin obtains 4,4 '-bis-(3,4,5-trimethoxy) benzil,After taking ethanol as solvent, under potassium hydroxide alkalescence condition, 4,4 '-bis-(3,4,5-trimethoxy) benzil and dibenzyl ketone condensationsPreparation 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone; Synthesis technique is simple, and the reaction time is short, produceRate is high, and product is easy to separation and purification.
(2) the present invention adopts Cobastab1, Schweinfurt green, ammonium nitrate be catalyst, NaOH, potassium hydroxide regulate pH value,Distilled water, glacial acetic acid, ethanol are reaction dissolvent, and required reagent is the low evil of cheap and easy to get, low toxicity all, meet sending out of " Green Chemistry "Exhibition direction.
(3) the present invention is without the harsh reaction condition such as high temperature, high pressure, and course of reaction is safe and reliable, be easy to control, and is applicable to largeTechnical scaleization is produced.
(4) the present invention, by adopting ice-water bath reaction and controlling the pH value of reacting, has effectively avoided overheated and has crossed alkali to catalystCobastab1Structural damage, stable reaction, favorable reproducibility.
(5) the present invention adopts Schweinfurt green to replace copper sulphate, has avoided the introducing of foreign atom.
Brief description of the drawings
Fig. 1 be the embodiment of the present invention 1 prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the core of 5-diphenyl cyclopentadienoneMagnetic resonance hydrogen spectrogram;
Fig. 2 be the embodiment of the present invention 1 prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone redExternal spectrum figure.
Detailed description of the invention
The present invention is further illustrated in conjunction with the embodiments, should be noted that following explanation is only in order to explain the present invention,Its content is not limited.
Embodiment 1:
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzoin
Add successively Cobastab to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, thermometer12g, distilled water 5mL,Ethanol 16mL, 3,4,5-Trimethoxybenzaldehyde 15.3g slowly stir 15min in ice-water bath. Then by condenser dropwiseAdd 3.0mol/L NaOH ethanolic solution, the pH value to 8 of regulator solution, and constantly add 3.0mol/L NaOH secondAlcoholic solution makes the pH value of solution keep 45min. Be heated to, after 55 DEG C of reaction 3h, be cooled to room temperature. Suction filtration after standing 24h,After filter cake is washed 3 times with distillation, filtrate is neutral, obtains yellow solid. With after ethyl alcohol recrystallization, obtain 9.2g4,4 '-bis-(3,4,5-Trimethoxy) benzoin, productive rate 60.2%, m.p:165.2～165.6 DEG C (literature value (WO2010050720A2): 165～166℃)。
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To be equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, add Schweinfurt green 1g, ammonium nitrate 5g, glacial acetic acid 30mL,Distilled water 5mL, starts stirring, and heating makes dissolution of solid. Then add 4,4 '-bis-(3,4,5-trimethoxy) benzoin 9g,Be warming up to backflow, reaction 1h. After cooling, the precipitation of separating out is leached, with filtrate after distillation washing 3 times be neutral. Use ethanolRecrystallization, obtains 7.2g4, the yellow acicular crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, and productive rate 80.4%, m.p:192.3～192.9 DEG C (literature value (WO2010050720A2): 192～193 DEG C).
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone
Add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device7g, dibenzyl ketone 4g, ethanol 15mL, agitating heating. Question response system is micro-while boiling, drips 3.6mol/L by condenserPotassium hydroxide-ethanol solution to solution is aterrimus and keeps half a minute colour-fast. Continue to be heated to reflux, after 30min, stop anti-Should. Fully cooling rear suction filtration obtains rufous powder, it is recrystallized in the mixed solvent of ethanol/toluene (V/V=1:1),To 8.8g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone, productive rate 86.9%, m.p:165.2～165.7 DEG C.
Prepared 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the hydrogen nuclear magnetic resonance spectrogram of 5-diphenyl cyclopentadienone and infraredSpectrogram as depicted in figs. 1 and 2.
δH(400MHz，CDCl3)3.4711(12H，s，4OCH3)，3.8573(6H，s，2OCH3)，6.1910(4H，s)，7.3010～7.3108(10H，m)。
υmax(KBr/cm-1): 3006.9 (phenyl ring C-H stretching vibrations), 2937.5,2835.3 (methoxyl group C-H stretching vibrations)1708.9 (C=O stretching vibrations), 1577.7,1507.2,1462.0 (phenyl ring skeletal vibrations), 1411.8,1350.1 (methoxiesBase C-H flexural vibrations), 1240.2,1126.4,1001.0 (aryl oxide C-O stretching vibrations), 846.7 (1,2,3,5 four getFor benzene C-H flexural vibrations), 734.8,696.3 (single-substituted C-H flexural vibrations).
From Fig. 1 and Fig. 2, prepared compound is 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-hexichol basic ring penta 2Ketenes.
Embodiment 2:
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzoin
Add successively Cobastab to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, thermometer14g, distilled water10mL, ethanol 32mL, 3,4,5-Trimethoxybenzaldehyde 30.6g slowly stir 15min in ice-water bath. Then by coldCondenser dropwise adds 3.0mol/L NaOH ethanolic solution, the pH value to 8 of regulator solution, and constantly add 3.0mol/L hydrogenSodium oxide molybdena ethanolic solution makes the pH value of solution keep 45min. Be heated to, after 65 DEG C of reaction 3h, be cooled to room temperature. Leave standstill 24hRear suction filtration, after filter cake is washed 3 times with distillation, filtrate is neutral, obtains yellow solid. With after ethyl alcohol recrystallization, obtain 19.2g4,4 '-Two (3,4,5-trimethoxy) benzoin, productive rate 62.8%, m.p:165.2～165.6 DEG C.
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To be equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, add Schweinfurt green 2g, ammonium nitrate 10g, glacial acetic acid 60mL,Distilled water 10mL, starts stirring, and heating makes dissolution of solid. Then add 4,4 '-bis-(3,4,5-trimethoxy) benzoin 18g,Be warming up to backflow, reaction 2h. After cooling, the precipitation of separating out is leached, with filtrate after distillation washing 3 times be neutral. Use ethanolRecrystallization, obtains 15.8g4, the yellow acicular crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, and productive rate 88.2%, m.p:192.3～192.9℃。
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone
Add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device14g, dibenzyl ketone 8g, ethanol 30mL, agitating heating. Question response system is micro-while boiling, drips 3.6mol/L by condenserPotassium hydroxide-ethanol solution to solution is aterrimus and keeps half a minute colour-fast. Continue to be heated to reflux, after 30min, stop anti-Should. Fully cooling rear suction filtration obtains rufous powder, it is recrystallized in the mixed solvent of ethanol/toluene (V/V=1:1),To 17.6g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone, productive rate 86.9%, m.p:165.2～165.7 DEG C.
Embodiment 3
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzoin
Add successively Cobastab to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, thermometer12g, distilled water 5mL,Ethanol 16mL, 3,4,5-Trimethoxybenzaldehyde 15.3g slowly stir 15min in ice-water bath. Then by condenser dropwiseAdd 3.0mol/L NaOH ethanolic solution, the pH value to 8 of regulator solution, and constantly add 3.0mol/L NaOH secondAlcoholic solution makes the pH value of solution keep 45min. Be heated to, after 75 DEG C of reaction 3h, be cooled to room temperature. Suction filtration after standing 24h,After filter cake is washed 3 times with distillation, filtrate is neutral, obtains yellow solid. With after ethyl alcohol recrystallization, obtain 9.0g4,4 '-bis-(3,4,5-Trimethoxy) benzoin, productive rate 58.9%, m.p:165.2～165.6 DEG C.
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To be equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, add Schweinfurt green 1g, ammonium nitrate 5g, glacial acetic acid 30mL,Distilled water 5mL, starts stirring, and heating makes dissolution of solid. Then add 4,4 '-bis-(3,4,5-trimethoxy) benzoin 9g,Be warming up to backflow, reaction 3h. After cooling, the precipitation of separating out is leached, with filtrate after distillation washing 3 times be neutral. Use ethanolRecrystallization, obtains 7.9g4, the yellow acicular crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, and productive rate 88.2%, m.p:192.3～192.9℃。
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone
Add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device7g, dibenzyl ketone 4g, ethanol 15mL, agitating heating. Question response system is micro-while boiling, drips 3.6mol/L by condenserPotassium hydroxide-ethanol solution to solution is aterrimus and keeps half a minute colour-fast. Continue to be heated to reflux, after 30min, stop anti-Should. Fully cooling rear suction filtration obtains rufous powder, it is recrystallized in the mixed solvent of ethanol/toluene (V/V=1:1),To 8.9g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone, productive rate 87.9%, m.p:165.2～165.7 DEG C.
Embodiment 4
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzoin
Add successively Cobastab to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, thermometer12g, distilled water 5mL,Ethanol 16mL, 3,4,5-Trimethoxybenzaldehyde 15.3g slowly stir 15min in ice-water bath. Then by condenser dropwiseAdd 3.0mol/L NaOH ethanolic solution, the pH value to 9 of regulator solution, and constantly add 3.0mol/L NaOH secondAlcoholic solution makes the pH value of solution keep 45min. Be heated to, after 65 DEG C of reaction 2h, be cooled to room temperature. Suction filtration after standing 24h,After filter cake is washed 3 times with distillation, filtrate is neutral, obtains yellow solid. With after ethyl alcohol recrystallization, obtain 9.5g4,4 '-bis-(3,4,5-Trimethoxy) benzoin, productive rate 62.1%, m.p:165.2～165.6 DEG C.
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To be equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, add Schweinfurt green 1g, ammonium nitrate 5g, glacial acetic acid 30mL,Distilled water 5mL, starts stirring, and heating makes dissolution of solid. Then add 4,4 '-bis-(3,4,5-trimethoxy) benzoin 9g,Be warming up to backflow, reaction 2h. After cooling, the precipitation of separating out is leached, with filtrate after distillation washing 3 times be neutral. Use ethanolRecrystallization, obtains 7.8g4, the yellow acicular crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, and productive rate 87.1%, m.p:192.3～192.9℃。
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone
Add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device7g, dibenzyl ketone 4g, ethanol 15mL, agitating heating. Question response system is micro-while boiling, drips 3.6mol/L by condenserPotassium hydroxide-ethanol solution to solution is aterrimus and keeps half a minute colour-fast. Continue to be heated to reflux, after 15min, stop anti-Should. Fully cooling rear suction filtration obtains rufous powder, it is recrystallized in the mixed solvent of ethanol/toluene (V/V=1:1),To 7.8g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone, productive rate 77.1%, m.p:165.2～165.7 DEG C.
Embodiment 5
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzoin
Add successively Cobastab to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, thermometer14g, distilled water10mL, ethanol 32mL, 3,4,5-Trimethoxybenzaldehyde 30.6g slowly stir 15min in ice-water bath. Then by coldCondenser dropwise adds the NaOH ethanolic solution of 3.0mol/L, the pH value to 9 of regulator solution, and constantly add 3.0mol/LNaOH ethanolic solution makes the pH value of solution keep 45min. Be heated to, after 65 DEG C of reaction 3h, be cooled to room temperature. Leave standstill 24hRear suction filtration, after filter cake is washed 3 times with distillation, filtrate is neutral, obtains yellow solid. With after ethyl alcohol recrystallization, obtain 21.0g4,4 '-Two (3,4,5-trimethoxy) benzoin, productive rate 68.7%, m.p:165.2～165.6 DEG C.
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To be equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, add Schweinfurt green 2g, ammonium nitrate 10g, glacial acetic acid 60mL,Distilled water 10mL, starts stirring, and heating makes dissolution of solid. Then add 4,4 '-bis-(3,4,5-trimethoxy) benzoin 18g,Be warming up to backflow, reaction 2h. After cooling, the precipitation of separating out is leached, with filtrate after distillation washing 3 times be neutral. Use ethanolRecrystallization, obtains 15.8g4, the yellow acicular crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, and productive rate 88.2%, m.p:192.3～192.9℃。
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone
Add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device14g, dibenzyl ketone 10g, ethanol 30mL, agitating heating. Question response system is micro-while boiling, drips 3.6mol/L by condenserPotassium hydroxide-ethanol solution to solution be aterrimus and keep half a minute colour-fast. Continue to be heated to reflux, after 30min, stopReaction. Fully cooling rear suction filtration obtains rufous powder, it is recrystallized in the mixed solvent of ethanol/toluene (V/V=1:1),Obtain 18.0g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone, productive rate 88.9%, m.p:165.2～165.7℃。
Embodiment 6
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzoin
Add successively Cobastab to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, thermometer12g, distilled water 5mL,Ethanol 16mL, 3,4,5-Trimethoxybenzaldehyde 15.3g slowly stir 15min in ice-water bath. Then by condenser dropwiseAdd the NaOH ethanolic solution of 3.0mol/L, the pH value to 9 of regulator solution, and constantly add the hydroxide of 3.0mol/LSodium ethoxide solution makes the pH value of solution keep 45min. Be heated to, after 65 DEG C of reaction 4h, be cooled to room temperature. After leaving standstill 24h, take outFilter, after filter cake is washed 3 times with distillation, filtrate is neutral, obtains yellow solid. With after ethyl alcohol recrystallization, obtain 10.5g4,4 '-Two (3,4,5-trimethoxy) benzoin, productive rate 68.7%, m.p:165.2～165.6 DEG C.
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To be equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, add Schweinfurt green 1g, ammonium nitrate 5g, glacial acetic acid 30mL,Distilled water 5mL, starts stirring, and heating makes dissolution of solid. Then add 4,4 '-bis-(3,4,5-trimethoxy) benzoin 9g,Be warming up to backflow, reaction 2h. After cooling, the precipitation of separating out is leached, with filtrate after distillation washing 3 times be neutral. Use ethanolRecrystallization, obtains 7.8g4, the yellow acicular crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, and productive rate 87.1%, m.p:192.3～192.9℃。
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone
Add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device7g, dibenzyl ketone 4g, ethanol 15mL, agitating heating. Question response system is micro-while boiling, drips 3.6mol/L by condenserPotassium hydroxide-ethanol solution to solution be aterrimus and keep half a minute colour-fast. Continue to be heated to reflux, after 45min, stopReaction. Fully cooling rear suction filtration obtains rufous powder, it is recrystallized in the mixed solvent of ethanol/toluene (V/V=1:1),Obtain 8.9g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone, productive rate 87.9%, m.p:165.2～165.7℃。
Embodiment 7:
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzoin
Add successively Cobastab to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, thermometer16g, distilled water15mL, ethanol 48mL, 3,4,5-Trimethoxybenzaldehyde 45.9g slowly stir 15min in ice-water bath. Then by coldCondenser dropwise adds the NaOH ethanolic solution of 3.0mol/L, the pH value to 10 of regulator solution, and constantly add 3.0mol/LNaOH ethanolic solution make solution pH value keep 45min. Be heated to, after 65 DEG C of reaction 3h, be cooled to room temperature. Leave standstillSuction filtration after 24h, after filter cake is washed 3 times with distillation, filtrate is neutral, obtains yellow solid. With after ethyl alcohol recrystallization, obtain27.0g4,4 '-bis-(3,4,5-trimethoxy) benzoin, productive rate 58.9%, m.p:165.2～165.6 DEG C.
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To be equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device, add Schweinfurt green 3g, ammonium nitrate 15g, glacial acetic acid 90mL,Distilled water 15mL, starts stirring, and heating makes dissolution of solid. Then add 4,4 '-bis-(3,4,5-trimethoxy) benzoin 27g,Be warming up to backflow, reaction 2h. After cooling, the precipitation of separating out is leached, with filtrate after distillation washing 3 times be neutral. Use ethanolRecrystallization, obtains 23.4g4, the yellow acicular crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, and productive rate 87.1%, m.p:192.3～192.9℃。
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone
Add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil to being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, agitating device21g, dibenzyl ketone 12g, ethanol 45mL, agitating heating. Question response system is micro-while boiling, drips 3.6mol/L by condenserPotassium hydroxide-ethanol solution to solution be aterrimus and keep half a minute colour-fast. Continue to be heated to reflux, after 30min, stopReaction. Fully cooling rear suction filtration obtains rufous powder, it is recrystallized in the mixed solvent of ethanol/toluene (V/V=1:1),Obtain 26.7g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone, productive rate 87.9%, m.p:165.2～165.7℃。
Claims (8)
1. synthetic 3 a, 4-bis-(3,4,5-trimethoxyphenyl)-2, the method for 5-diphenyl cyclopentadienone, is characterized in that,Comprise the following steps:
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzoin
In reactor, add successively Cobastab1, distilled water, ethanol, 3,4,5-Trimethoxybenzaldehyde, mix, regulatePH value to 8～10 of solution, and make the pH value of solution keep 40～50min, be heated to 55～75 DEG C, after reaction 2～4h,Be chilled to room temperature, leave standstill, filter, with ethyl alcohol recrystallization, obtain 4,4 '-bis-(3,4,5-trimethoxy) benzoin;
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
In reactor, add Schweinfurt green, ammonium nitrate, glacial acetic acid, distilled water, stirring and dissolving, then adds 4,4 '-bis-(3,4,5-Trimethoxy) benzoin, be warming up to backflow, reaction 1～3h, leaches the precipitation of separating out, and is washed to filtrate for neutral, usesEthyl alcohol recrystallization, obtains 4,4 '-bis-(3,4,5-trimethoxy) benzil;
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone
In reactor, add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil, dibenzyl ketone, ethanol, agitating heating,Question response system is micro-while boiling, drips potassium hydroxide-ethanol solution to solution and is aterrimus and keeps half a minute colour-fast, continues heatingTo refluxing, reaction 15～45min, filters, and is (1～2): in the ethanol/toluene mixed solvent of (1～2) by it in volume ratioRecrystallization, obtains 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone;
Wherein, in step (1), Cobastab1, distilled water, ethanol, 3,4,5-Trimethoxybenzaldehyde mass ratio be (1～3):(4～6):(11～14):15；
In step (2), 4,4 '-bis-(3,4,5-trimethoxy) benzoin, Schweinfurt green, ammonium nitrate, glacial acetic acid, distilled waterMass ratio is 9:(1～2): (4～6): (29～34): (4～6);
In step (3), the mass ratio of 4,4 '-bis-(3,4,5-trimethoxy) benzil, dibenzyl ketone, ethanol be 7:(4～5):(14～18)；
In step (1), adopt and dropwise add NaOH ethanolic solution to carry out the pH value of regulator solution, and constantly add hydrogen-oxygenChanging sodium ethoxide solution makes the pH value of solution keep 40～50min;
In step (1), the mode of mixing is in ice-water bath, slowly to stir 10～20min.
2. synthetic 3, the 4-bis-(3,4,5-trimethoxyphenyl)-2 of one as claimed in claim 1,5-diphenyl cyclopentadienoneMethod, is characterized in that, in step (1), the mode of filtration is suction filtration, and filter cake is washed with distilled water to filtrate for neutral.
3. synthetic 3, the 4-bis-(3,4,5-trimethoxyphenyl)-2 of one as claimed in claim 1,5-diphenyl cyclopentadienoneMethod, is characterized in that, in step (1), the pH value of regulator solution NaOH ethanolic solution concentration used is 3.0mol/L.
4. synthetic 3, the 4-bis-(3,4,5-trimethoxyphenyl)-2 of one as claimed in claim 1,5-diphenyl cyclopentadienoneMethod, is characterized in that, in described step (1), time of repose is 24h.
5. synthetic 3, the 4-bis-(3,4,5-trimethoxyphenyl)-2 of one as claimed in claim 1,5-diphenyl cyclopentadienoneMethod, is characterized in that, in described step (3), potassium hydroxide-ethanol solution concentration is 3.6mol/L.
6. synthetic 3, the 4-bis-(3,4,5-trimethoxyphenyl)-2 of one as claimed in claim 1,5-diphenyl cyclopentadienoneMethod, is characterized in that, in described step (1), and Cobastab1, distilled water, ethanol, 3,4,5-TrimethoxybenzaldehydeMass ratio is 2:5:13:15.
7. synthetic 3, the 4-bis-(3,4,5-trimethoxyphenyl)-2 of one as claimed in claim 1,5-diphenyl cyclopentadienoneMethod, is characterized in that, in described step (3), the volume ratio of ethanol/toluene mixed solvent is 1:1.
8. synthetic 3, the 4-bis-(3,4,5-trimethoxyphenyl)-2 of one as claimed in claim 1,5-diphenyl cyclopentadienoneMethod, is characterized in that, comprises the following steps:
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzoin
In reactor, add successively Cobastab12g, distilled water 5mL, ethanol 16mL, 3,4,5-Trimethoxybenzaldehyde 15.3g,In ice-water bath, slowly stir 15min, then dropwise add the NaOH ethanolic solution of 3.0mol/L by condenser, regulateThe pH value to 8 of solution, and constantly add NaOH ethanolic solution and make the pH value of solution keep 45min, be heated to 55 DEG C anti-Answer after 3h, be cooled to room temperature, suction filtration after standing 24h, after filter cake is washed 3 times with distillation, filtrate is neutral, with ethyl alcohol recrystallization,Obtain 4,4 '-bis-(3,4,5-trimethoxy) benzoin;
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
In reactor, add Schweinfurt green 1g, ammonium nitrate 5g, glacial acetic acid 30mL, distilled water 5mL, start stirring, heating makesDissolution of solid, then adds 4,4 '-bis-(3,4,5-trimethoxy) benzoin 9g, is warming up to backflow, reaction 1h, cooling after,The precipitation of separating out is leached, with filtrate after distillation washing 3 times be neutral, with ethyl alcohol recrystallization, obtain 4,4 '-bis-(3,4,5-front threesOxygen base) benzil;
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-diphenyl cyclopentadienone
In reactor, add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil 7g, dibenzyl ketone 4g, ethanol 15mL, stirMix heating, question response system is micro-while boiling, and potassium hydroxide-ethanol solution to the solution that drips 3.6mol/L by condenser is aterrimusAnd keep half a minute colour-fast, and continue to be heated to reflux, after 30min, stop reaction, fully cooling rear suction filtration obtains rufous powder,In the ethanol/toluene mixed solvent that is 1:1 in volume ratio by it, be recrystallized, obtain 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-Diphenyl cyclopentadienone.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010050720A2 (en) * | 2008-10-27 | 2010-05-06 | (주)아이씨비 | Near infrared absorbent consisting of dithiol metal complex, method for preparing said dithiol metal complex, and optical filter and thermal infrared shielding filter containing same |
| CN103467265A (en) * | 2013-09-16 | 2013-12-25 | 山东大学 | Preparation method of 4,4'-di-trifluoromethyl benzil |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010050720A2 (en) * | 2008-10-27 | 2010-05-06 | (주)아이씨비 | Near infrared absorbent consisting of dithiol metal complex, method for preparing said dithiol metal complex, and optical filter and thermal infrared shielding filter containing same |
| CN103467265A (en) * | 2013-09-16 | 2013-12-25 | 山东大学 | Preparation method of 4,4'-di-trifluoromethyl benzil |
Non-Patent Citations (4)
| Title |
|---|
| Hexaphenylbenzene-based polymers of intrinsic microporosity;Rhys Short等;《Chem. Commun.》;20110517;第47卷;第6822-6824页 * |
| The Synthesis of Rigid Polycyclic Structures for the study of Diatropic or Steric Effects of a Phenyl Ring on CF Bond;Yung-Yu Chang等;《J. Org. Chem.》;20131210;第78卷;第12790-12794页 * |
| Thermal oxidation of tetracyclones (2,3,4,5-tetraarylcyclopentadienones);Thies Thiemann等;《 Journal of Chemical Research》;20081231;第173-180页 * |
| α-吡喃酮衍生物的合成及聚集荧光增强性质研究;唐海云等;《化学学报》;20111231;第69卷(第19期);第2241-2247页 * |
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