CN104177238A - Method for synthesizing 3, 4-di(3, 4, 5-trimethoxy phenyl)-2, 5-diphenyl cyclopentadienone - Google Patents
Method for synthesizing 3, 4-di(3, 4, 5-trimethoxy phenyl)-2, 5-diphenyl cyclopentadienone Download PDFInfo
- Publication number
- CN104177238A CN104177238A CN201410360539.8A CN201410360539A CN104177238A CN 104177238 A CN104177238 A CN 104177238A CN 201410360539 A CN201410360539 A CN 201410360539A CN 104177238 A CN104177238 A CN 104177238A
- Authority
- CN
- China
- Prior art keywords
- bis
- trimethoxy
- cyclopentadienone
- phenylbenzene
- trimethoxyphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
-
- 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
- C07C45/27—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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 3, 4-di(3, 4, 5-trimethoxy phenyl)-2, 5-diphenyl cyclopentadienone. The method comprises the following steps: carrying out condensation reaction on 3, 4, 5-trimethoxy benzaldehyde serving as a raw material in the presence of vitamin B1 serving as a catalyst under an alkaline condition to prepare 4, 4'-di(3, 4, 5-trimethoxy) benzoin; then, in a glacial acetic acid solution, oxidizing 4, 4'-di(3, 4, 5-trimethoxy) benzoin in the presence of copper acetate and ammonium nitrate serving as cooxidation agents to obtain 4, 4'-di(3, 4, 5-trimethoxy) benzoin; and finally, by using ethanol as a solvent and under a potassium hydroxide alkaline condition, carrying out condensation reaction on 4, 4'-di(3, 4, 5-trimethoxy) benzoin and dibenzyl ketone to prepare 3, 4-di(3, 4, 5-trimethoxy phenyl)-2, 5-diphenyl cyclopentadienone. According to the method disclosed by the invention, the reaction raw materials are cheap and easily available, the synthesis steps are simple, the reaction time is short, the reaction conditions are mild and the reaction process is easy to control; therefore, the method is suitable for industrial 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-phenylbenzene cyclopentadienone, belongs to organic 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, almost can there is Diels-Alder addition reaction with any unsaturated link(age) in two C=C conjugated double bonds on its cyclopentadienone ring, is synthetic polyaryl substituted phenyl compounds one of method the most easily.In industrialized fine chemical product is produced, polyaryl substituted-cyclopentadienyl ketone is widely used in the industries such as rubber, resin, coating, agricultural chemicals, spices.
3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone is cyclopentadiene ketone compounds with regard to its skeleton structure.The introducing of phenyl substituent, increases its molecular weight, and Melting point elevation, becomes solid-state under normal temperature.Two keys in ring and substituted benzene ring height conjugation, the spontaneous dimerization reaction activity decreased of cyclopentadienone, chemical stability is improved.The pi-conjugated effect of p-based on lone electron pair and phenyl ring on inductive effect and Sauerstoffatom between methoxyl group and phenyl ring, presents special chemical property simultaneously.These characteristics have determined 3,4-bis-(3,4,5-trimethoxyphenyl)-2, and 5-phenylbenzene cyclopentadienone has higher research and using value.
About 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the synthetic method of 5-phenylbenzene cyclopentadienone, does not also have pertinent literature report at present.Rhys Short etc., react carrying out Friedel-Crafts with 1,2-dimethoxy benzene again after its chloride for raw material with 2-(3,4-Dimethoxyphenyl) acetic acid, obtain 4,4 '-bis-(3,4 – dimethoxy) bitter almond oil camphor.Then with tin anhydride by 4,4 '-bis-(3,4 – dimethoxy) bitter almond oil camphor is oxidized to 4,4 '-bis-(3,4 – dimethoxys) benzil, carrying out Knoevenagel with dibenzyl ketone again reacts and obtains 3,4-bis-(3,4-Dimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone (R.Short et al., Chem.Commun., 2011,47:6822-6824).This method not only complex steps is consuming time, the relative fancy price of reaction raw materials and the harm of human body, environment has also been limited to it in industrial application.In addition, with respect to 3,4-bis-(3,4-Dimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone, along with increasing of methoxy substitution base number, 3,4-bis-(3,4,5-trimethoxyphenyl)-2, polarity, solvability, chemical stability and the thermostability of 5-phenylbenzene cyclopentadienone are all improved.Therefore, seek that a kind of raw material is easy to get, technique 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-trimethoxyphenyl)-2, the synthetic method of 5-phenylbenzene 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)-2, the method for 5-phenylbenzene cyclopentadienone.The method raw material is easy to get, technique is simple, the reaction times is short, product is easily separated, product 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-phenylbenzene cyclopentadienone, comprises the following steps:
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor
In reactor, add successively vitamins B
1, distilled water, ethanol, 3,4,5-TMB, in ice-water bath, slowly stir 10～20min, then dropwise add sodium hydroxide ethanolic soln, pH value to 8～10 of regulator solution, and constantly add the pH value that sodium hydroxide ethanolic soln makes solution and keep 40～50min, be heated to, after 55～75 ℃ of reaction 2～4h, be chilled to room temperature, standing, suction filtration, filter cake is washed with distilled water to filtrate for neutral, obtains yellow solid, with ethyl alcohol recrystallization, can obtain 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor;
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
In reactor, add neutralized verdigris, ammonium nitrate, Glacial acetic acid, distilled water, stirring and dissolving, then adds 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor, be warming up to backflow, reaction 1～3h, cooling after, the precipitation of separating out is leached, be washed to filtrate for neutral, with ethyl alcohol recrystallization, the yellow needle crystal obtaining is 4,4 '-bis-(3,4,5-trimethoxy) benzil;
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone
In reactor, add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil, dibenzyl ketone, ethanol, stirring heating, question response system is micro-while boiling, and drips potassium hydroxide-ethanol solution to solution and is aterrimus and keeps half a minute colour-fast, continues to be heated to reflux, reaction 15～45min, cooling rear suction filtration obtains reddish-brown powder, by it, in volume ratio, is (1～2): recrystallization in the ethanol/toluene mixed solvent of (1～2), obtains 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone;
Wherein, in step (1), vitamins B
1, distilled water, ethanol, 3,4,5-Trimethoxybenzaldehyde mass ratio be (1～3): (4～6): (11～14): 15;
In step (2), the mass ratio of 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor, neutralized verdigris, ammonium nitrate, Glacial acetic acid, distilled water 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 is 7:(4～5): (14～18).
In described step (1), time of repose is 24h.
In described step (1), sodium hydroxide ethanolic soln concentration is 3.0mol/L.
In described step (3), potassium hydroxide-ethanol solution concentration is 3.6mol/L.
Preferably, in described step (1), vitamins B
1, distilled water, ethanol, 3,4,5-Trimethoxybenzaldehyde mass ratio be 2:5:13:15.
Preferably, in described step (3), the volume ratio of ethanol/toluene mixed solvent is 1:1.
Reaction formula of the present invention is as follows:
Beneficial effect of the present invention:
(1) the present invention be take 3,4,5-Trimethoxybenzaldehyde as raw material, with vitamins B
1for catalyzer, under alkaline condition, by condensation reaction, make 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor, then in glacial acetic acid solution, using neutralized verdigris and ammonium nitrate as co-oxidants, oxidation 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor obtains 4,4 '-bis-(3,4,5-trimethoxy) benzil, finally take 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-phenylbenzene cyclopentadienone; Synthesis technique is simple, and the reaction times is short, productive rate is high, and product is easy to separation and purification.
(2) the present invention adopts vitamins B
1, neutralized verdigris, ammonium nitrate be catalyzer, sodium hydroxide, potassium hydroxide regulate pH value, distilled water, Glacial acetic acid, ethanol are reaction solvent, required reagent is the low evil of cheap and easy to get, low toxicity all, meets the developing direction of " Green Chemistry ".
(3) the present invention is without the harsh reaction conditions such as high temperature, high pressure, and reaction process is safe and reliable, be easy to control, and is applicable to large-scale industrial production.
(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 catalyzer vitamins B
1structural damage, stable reaction, favorable reproducibility.
(5) the present invention adopts neutralized verdigris to replace copper sulfate, has avoided the introducing of impurity atoms.
Accompanying drawing explanation
Fig. 1 is 3 of the embodiment of the present invention 1 preparation, 4-bis-(3,4,5-trimethoxyphenyl)-2, the hydrogen nuclear magnetic resonance spectrogram of 5-phenylbenzene cyclopentadienone;
Fig. 2 is 3 of the embodiment of the present invention 1 preparation, 4-bis-(3,4,5-trimethoxyphenyl)-2, the infrared spectrogram of 5-phenylbenzene cyclopentadienone.
Embodiment
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, does not limit its content.
Embodiment 1:
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, thermometer, add successively vitamins B
12g, distilled water 5mL, ethanol 16mL, 3,4,5-Trimethoxybenzaldehyde 15.3g slowly stir 15min in ice-water bath.Then by condenser, dropwise add 3.0mol/L sodium hydroxide ethanolic soln, the pH value to 8 of regulator solution, and constantly add the pH value maintenance 45min that 3.0mol/L sodium hydroxide ethanolic soln makes solution.Be heated to, after 55 ℃ 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) bitter almond oil camphor, productive rate 60.2%, m.p:165.2～165.6 ℃ (literature value (WO 2010050720 A2): 165～166 ℃).
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add neutralized verdigris 1g, ammonium nitrate 5g, Glacial acetic acid 30mL, distilled water 5mL, start stirring, heating makes dissolution of solid.Then add 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor 9g, be warming up to backflow, reaction 1h.After cooling, the precipitation of separating out being leached, is neutral with filtrate after distillation washing 3 times.With ethyl alcohol recrystallization, obtain 7.2g4, the yellow needle crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, productive rate 80.4%, m.p:192.3～192.9 ℃ (literature value (WO2010050720A2): 192～193 ℃).
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil 7g, dibenzyl ketone 4g, ethanol 15mL, stirring heating.Question response system is micro-while boiling, and drips 3.6mol/L potassium hydroxide-ethanol solution to solution be aterrimus and keep half a minute colour-fast by condenser.Continue to be heated to reflux, stopped reaction after 30min.Fully cooling rear suction filtration obtains reddish-brown powder, by its recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1), obtains 8.8g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone, productive rate 86.9%, m.p:165.2～165.7 ℃.
Prepared 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the hydrogen nuclear magnetic resonance spectrogram of 5-phenylbenzene cyclopentadienone and infrared spectrogram are as depicted in figs. 1 and 2.
δ
H(400MHz，CDCl
3)3.4711(12H，s，4OCH
3)，3.8573(6H，s，2OCH
3)，6.1910(4H，s)，7.3010～7.3108(10H，m)。
υ
max(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 vibration), 1577.7,1507.2, (1462.0 phenyl ring skeletal vibration), 1411.8,1350.1 (methoxyl group C-H flexural vibration), 1240.2,1126.4,1001.0 (aryl oxide C-O stretching vibrations), 846.7 (1,2,3,5 four substituted benzene C-H flexural vibration), 734.8,696.3 (single-substituted C-H flexural vibration).
From Fig. 1 and Fig. 2, prepared compound is 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone.
Embodiment 2:
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, thermometer, add successively vitamins B
14g, distilled water 10mL, ethanol 32mL, 3,4,5-Trimethoxybenzaldehyde 30.6g slowly stir 15min in ice-water bath.Then by condenser, dropwise add 3.0mol/L sodium hydroxide ethanolic soln, the pH value to 8 of regulator solution, and constantly add the pH value maintenance 45min that 3.0mol/L sodium hydroxide ethanolic soln makes solution.Be heated to, after 65 ℃ 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 19.2g4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor, productive rate 62.8%, m.p:165.2～165.6 ℃.
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add neutralized verdigris 2g, ammonium nitrate 10g, Glacial acetic acid 60mL, distilled water 10mL, start stirring, heating makes dissolution of solid.Then add 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor 18g, be warming up to backflow, reaction 2h.After cooling, the precipitation of separating out being leached, is neutral with filtrate after distillation washing 3 times.With ethyl alcohol recrystallization, obtain 15.8g4, the yellow needle crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, productive rate 88.2%, m.p:192.3～192.9 ℃.
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil 14g, dibenzyl ketone 8g, ethanol 30mL, stirring heating.Question response system is micro-while boiling, and drips 3.6mol/L potassium hydroxide-ethanol solution to solution be aterrimus and keep half a minute colour-fast by condenser.Continue to be heated to reflux, stopped reaction after 30min.Fully cooling rear suction filtration obtains reddish-brown powder, by its recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1), obtains 17.6g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone, productive rate 86.9%, m.p:165.2～165.7 ℃.
Embodiment 3
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, thermometer, add successively vitamins B
12g, distilled water 5mL, ethanol 16mL, 3,4,5-Trimethoxybenzaldehyde 15.3g slowly stir 15min in ice-water bath.Then by condenser, dropwise add 3.0mol/L sodium hydroxide ethanolic soln, the pH value to 8 of regulator solution, and constantly add the pH value maintenance 45min that 3.0mol/L sodium hydroxide ethanolic soln makes solution.Be heated to, after 75 ℃ 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) bitter almond oil camphor, productive rate 58.9%, m.p:165.2～165.6 ℃.
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add neutralized verdigris 1g, ammonium nitrate 5g, Glacial acetic acid 30mL, distilled water 5mL, start stirring, heating makes dissolution of solid.Then add 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor 9g, be warming up to backflow, reaction 3h.After cooling, the precipitation of separating out being leached, is neutral with filtrate after distillation washing 3 times.With ethyl alcohol recrystallization, obtain 7.9g4, the yellow needle crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, productive rate 88.2%, m.p:192.3～192.9 ℃.
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil 7g, dibenzyl ketone 4g, ethanol 15mL, stirring heating.Question response system is micro-while boiling, and drips 3.6mol/L potassium hydroxide-ethanol solution to solution be aterrimus and keep half a minute colour-fast by condenser.Continue to be heated to reflux, stopped reaction after 30min.Fully cooling rear suction filtration obtains reddish-brown powder, by its recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1), obtains 8.9g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone, productive rate 87.9%, m.p:165.2～165.7 ℃.
Embodiment 4
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, thermometer, add successively vitamins B
12g, distilled water 5mL, ethanol 16mL, 3,4,5-Trimethoxybenzaldehyde 15.3g slowly stir 15min in ice-water bath.Then by condenser, dropwise add 3.0mol/L sodium hydroxide ethanolic soln, the pH value to 9 of regulator solution, and constantly add the pH value maintenance 45min that 3.0mol/L sodium hydroxide ethanolic soln makes solution.Be heated to, after 65 ℃ 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) bitter almond oil camphor, productive rate 62.1%, m.p:165.2～165.6 ℃.
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add neutralized verdigris 1g, ammonium nitrate 5g, Glacial acetic acid 30mL, distilled water 5mL, start stirring, heating makes dissolution of solid.Then add 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor 9g, be warming up to backflow, reaction 2h.After cooling, the precipitation of separating out being leached, is neutral with filtrate after distillation washing 3 times.With ethyl alcohol recrystallization, obtain 7.8g4, the yellow needle crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, productive rate 87.1%, m.p:192.3～192.9 ℃.
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil 7g, dibenzyl ketone 4g, ethanol 15mL, stirring heating.Question response system is micro-while boiling, and drips 3.6mol/L potassium hydroxide-ethanol solution to solution be aterrimus and keep half a minute colour-fast by condenser.Continue to be heated to reflux, stopped reaction after 15min.Fully cooling rear suction filtration obtains reddish-brown powder, by its recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1), obtains 7.8g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone, productive rate 77.1%, m.p:165.2～165.7 ℃.
Embodiment 5
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, thermometer, add successively vitamins B
14g, distilled water 10mL, ethanol 32mL, 3,4,5-Trimethoxybenzaldehyde 30.6g slowly stir 15min in ice-water bath.Then by condenser, dropwise add the sodium hydroxide ethanolic soln of 3.0mol/L, the pH value to 9 of regulator solution, and constantly add the pH value maintenance 45min that 3.0mol/L sodium hydroxide ethanolic soln makes solution.Be heated to, after 65 ℃ 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 21.0g4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor, productive rate 68.7%, m.p:165.2～165.6 ℃.
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add neutralized verdigris 2g, ammonium nitrate 10g, Glacial acetic acid 60mL, distilled water 10mL, start stirring, heating makes dissolution of solid.Then add 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor 18g, be warming up to backflow, reaction 2h.After cooling, the precipitation of separating out being leached, is neutral with filtrate after distillation washing 3 times.With ethyl alcohol recrystallization, obtain 15.8g4, the yellow needle crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, productive rate 88.2%, m.p:192.3～192.9 ℃.
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil 14g, dibenzyl ketone 10g, ethanol 30mL, stirring heating.Question response system is micro-while boiling, and potassium hydroxide-ethanol solution to the solution that drips 3.6mol/L by condenser is aterrimus and keeps half a minute colour-fast.Continue to be heated to reflux, stopped reaction after 30min.Fully cooling rear suction filtration obtains reddish-brown powder, by its recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1), obtains 18.0g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone, productive rate 88.9%, m.p:165.2～165.7 ℃.
Embodiment 6
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, thermometer, add successively vitamins B
12g, distilled water 5mL, ethanol 16mL, 3,4,5-Trimethoxybenzaldehyde 15.3g slowly stir 15min in ice-water bath.Then by condenser, dropwise add the sodium hydroxide ethanolic soln of 3.0mol/L, the pH value to 9 of regulator solution, and the sodium hydroxide ethanolic soln of constantly adding 3.0mol/L makes the pH value of solution keep 45min.Be heated to, after 65 ℃ of reaction 4h, 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 10.5g4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor, productive rate 68.7%, m.p:165.2～165.6 ℃.
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add neutralized verdigris 1g, ammonium nitrate 5g, Glacial acetic acid 30mL, distilled water 5mL, start stirring, heating makes dissolution of solid.Then add 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor 9g, be warming up to backflow, reaction 2h.After cooling, the precipitation of separating out being leached, is neutral with filtrate after distillation washing 3 times.With ethyl alcohol recrystallization, obtain 7.8g4, the yellow needle crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, productive rate 87.1%, m.p:192.3～192.9 ℃.
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil 7g, dibenzyl ketone 4g, ethanol 15mL, stirring heating.Question response system is micro-while boiling, and potassium hydroxide-ethanol solution to the solution that drips 3.6mol/L by condenser is aterrimus and keeps half a minute colour-fast.Continue to be heated to reflux, stopped reaction after 45min.Fully cooling rear suction filtration obtains reddish-brown powder, by its recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1), obtains 8.9g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone, productive rate 87.9%, m.p:165.2～165.7 ℃.
Embodiment 7:
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, thermometer, add successively vitamins B
16g, distilled water 15mL, ethanol 48mL, 3,4,5-Trimethoxybenzaldehyde 45.9g slowly stir 15min in ice-water bath.Then by condenser, dropwise add the sodium hydroxide ethanolic soln of 3.0mol/L, the pH value to 10 of regulator solution, and the sodium hydroxide ethanolic soln of constantly adding 3.0mol/L makes the pH value of solution keep 45min.Be heated to, after 65 ℃ 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 27.0g4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor, productive rate 58.9%, m.p:165.2～165.6 ℃.
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add neutralized verdigris 3g, ammonium nitrate 15g, Glacial acetic acid 90mL, distilled water 15mL, start stirring, heating makes dissolution of solid.Then add 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor 27g, be warming up to backflow, reaction 2h.After cooling, the precipitation of separating out being leached, is neutral with filtrate after distillation washing 3 times.With ethyl alcohol recrystallization, obtain 23.4g4, the yellow needle crystal of 4 '-bis-(3,4,5-trimethoxy) benzil, productive rate 87.1%, m.p:192.3～192.9 ℃.
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone
To being equipped with in three mouthfuls of round-bottomed flasks of reflux condensation mode, whipping appts, add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil 21g, dibenzyl ketone 12g, ethanol 45mL, stirring heating.Question response system is micro-while boiling, and potassium hydroxide-ethanol solution to the solution that drips 3.6mol/L by condenser is aterrimus and keeps half a minute colour-fast.Continue to be heated to reflux, stopped reaction after 30min.Fully cooling rear suction filtration obtains reddish-brown powder, by its recrystallization in the mixed solvent of ethanol/toluene (V/V=1:1), obtains 26.7g3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone, productive rate 87.9%, m.p:165.2～165.7 ℃.
Claims (10)
1. one kind is synthesized 3,4-bis-(3,4,5-trimethoxyphenyl)-2, and the method for 5-phenylbenzene cyclopentadienone, is characterized in that, comprises the following steps:
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor
In reactor, add successively vitamins B
1, distilled water, ethanol, 3,4,5-Trimethoxybenzaldehyde, mix, pH value to 8～10 of regulator solution, and make the pH value of solution keep 40～50min, be heated to 55～75 ℃, after reaction 2～4h, be chilled to room temperature, standing, filter, with ethyl alcohol recrystallization, obtain 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor;
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
In reactor, add neutralized verdigris, ammonium nitrate, Glacial acetic acid, distilled water, stirring and dissolving, then adds 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor, be warming up to backflow, reaction 1～3h, leaches the precipitation of separating out, be washed to filtrate for neutral, with ethyl alcohol recrystallization, obtain 4,4 '-bis-(3,4,5-trimethoxy) benzil;
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone
In reactor, add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil, dibenzyl ketone, ethanol, stirring heating, question response system is micro-while boiling, and drips potassium hydroxide-ethanol solution to solution and is aterrimus and keeps half a minute colour-fast, continues to be heated to reflux, reaction 15～45min, filtering, is (1～2) by it in volume ratio: recrystallization in the ethanol/toluene mixed solvent of (1～2), obtains 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone;
Wherein, in step (1), vitamins B
1, distilled water, ethanol, 3,4,5-Trimethoxybenzaldehyde mass ratio be (1～3): (4～6): (11～14): 15;
In step (2), the mass ratio of 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor, neutralized verdigris, ammonium nitrate, Glacial acetic acid, distilled water 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 is 7:(4～5): (14～18).
2. as claimed in claim 1 a kind of synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the method of 5-phenylbenzene cyclopentadienone, is characterized in that, in step (1), adopt and dropwise add sodium hydroxide ethanolic soln to carry out the pH value of regulator solution, and constantly add pH value maintenance 40～50min that sodium hydroxide ethanolic soln makes solution.
3. a kind of synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2 as claimed in claim 1, the method for 5-phenylbenzene cyclopentadienone, is characterized in that, in step (1), the mode of mixing be slow stirring 10～20min in ice-water bath.
4. a kind of synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2 as claimed in claim 1, the method for 5-phenylbenzene cyclopentadienone, is characterized in that, and in step (1), the mode of filtration is suction filtration, and filter cake is washed with distilled water to filtrate for neutral.
5. a kind of synthetic 3,4-bis-(3,4 as claimed in claim 2,5-trimethoxyphenyl)-2, the method for 5-phenylbenzene cyclopentadienone, is characterized in that, in step (1), the pH value of regulator solution sodium hydroxide ethanolic soln concentration used is 3.0mol/L.
6. a kind of synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2 as claimed in claim 1, the method for 5-phenylbenzene cyclopentadienone, is characterized in that, in described step (1), time of repose is 24h.
7. a kind of synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2 as claimed in claim 1, the method for 5-phenylbenzene cyclopentadienone, is characterized in that, in described step (3), potassium hydroxide-ethanol solution concentration is 3.6mol/L.
8. a kind of synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2 as claimed in claim 1, the method for 5-phenylbenzene cyclopentadienone, is characterized in that, in described step (1), vitamins B
1, distilled water, ethanol, 3,4,5-Trimethoxybenzaldehyde mass ratio be 2:5:13:15.
9. a kind of synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2 as claimed in claim 1, the method for 5-phenylbenzene cyclopentadienone, is characterized in that, in described step (3), the volume ratio of ethanol/toluene mixed solvent is 1:1.
10. a kind of synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2 as claimed in claim 1, the method for 5-phenylbenzene cyclopentadienone, is characterized in that, comprises the following steps:
(1) prepare 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor
In reactor, add successively vitamins B
12g, distilled water 5mL, ethanol 16mL, 3,4,5-TMB 15.3g, in ice-water bath, slowly stir 15min, then by condenser, dropwise add the sodium hydroxide ethanolic soln of 3.0mol/L, the pH value to 8 of regulator solution, and constantly add the pH value maintenance 45min that sodium hydroxide ethanolic soln makes solution, be heated to after 55 ℃ 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, with ethyl alcohol recrystallization, obtain 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor;
(2) prepare 4,4 '-bis-(3,4,5-trimethoxy) benzil
In reactor, add neutralized verdigris 1g, ammonium nitrate 5g, Glacial acetic acid 30mL, distilled water 5mL, start stirring, heating makes dissolution of solid, then add 4,4 '-bis-(3,4,5-trimethoxy) bitter almond oil camphor 9g, is warming up to backflow, reaction 1h, after cooling, the precipitation of separating out being leached, is neutral with filtrate after distillation washing 3 times, with ethyl alcohol recrystallization, obtain 4,4 '-bis-(3,4,5-trimethoxy) benzil;
(3) prepare 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone
In reactor, add successively 4,4 '-bis-(3,4,5-trimethoxy) benzil 7g, dibenzyl ketone 4g, ethanol 15mL, stirring heating, question response system is micro-while boiling, and potassium hydroxide-ethanol solution to the solution that drips 3.6mol/L by condenser is aterrimus and keeps half a minute colour-fast, continues to be heated to reflux, stopped reaction after 30min, fully cooling rear suction filtration obtains reddish-brown powder, and recrystallization in the ethanol/toluene mixed solvent that is 1:1 in volume ratio by it, obtains 3,4-bis-(3,4,5-trimethoxyphenyl)-2,5-phenylbenzene cyclopentadienone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410360539.8A CN104177238B (en) | 2014-07-25 | 2014-07-25 | Synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the method for 5-diphenyl cyclopentadienone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410360539.8A CN104177238B (en) | 2014-07-25 | 2014-07-25 | Synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the method for 5-diphenyl cyclopentadienone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104177238A true CN104177238A (en) | 2014-12-03 |
| CN104177238B CN104177238B (en) | 2016-05-25 |
Family
ID=51958621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410360539.8A Expired - Fee Related CN104177238B (en) | 2014-07-25 | 2014-07-25 | Synthetic 3,4-bis-(3,4,5-trimethoxyphenyl)-2, the method for 5-diphenyl cyclopentadienone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104177238B (en) |
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 |
-
2014
- 2014-07-25 CN CN201410360539.8A patent/CN104177238B/en not_active Expired - Fee Related
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 |
|---|
| RHYS SHORT等: "Hexaphenylbenzene-based polymers of intrinsic microporosity", 《CHEM. COMMUN.》, vol. 47, 17 May 2011 (2011-05-17), pages 6822 - 6824 * |
| THIES THIEMANN等: "Thermal oxidation of tetracyclones (2,3,4,5-tetraarylcyclopentadienones)", 《 JOURNAL OF CHEMICAL RESEARCH》, 31 December 2008 (2008-12-31), pages 173 - 180 * |
| YUNG-YU CHANG等: "The Synthesis of Rigid Polycyclic Structures for the study of Diatropic or Steric Effects of a Phenyl Ring on CF Bond", 《J. ORG. CHEM.》, vol. 78, 10 December 2013 (2013-12-10), pages 12790 - 12794 * |
| 唐海云等: "α-吡喃酮衍生物的合成及聚集荧光增强性质研究", 《化学学报》, vol. 69, no. 19, 31 December 2011 (2011-12-31), pages 2241 - 2247 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104177238B (en) | 2016-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101891606B (en) | New method for synthesizing rhodium caprylate (II) | |
| CN103804223A (en) | 2-hydroxy-3-(2-hydroxy-3-ethyoxyl-N-methyl benzene) acetophenone and synthesis method thereof | |
| CN109575014B (en) | Benzimidazo [2,1-a ] isoquinolinone compound and preparation method thereof | |
| CN103342649A (en) | 3-amino-2, 4, 6-trinitro-distyrene compounds and preparation method thereof | |
| CN103172480B (en) | Method for preparing iodo aromatic hydrocarbon | |
| Corey et al. | O, 2-Dilithio derivative of allyl alcohol, a useful synthetic reagent | |
| CN111747831B (en) | Method for preparing cyclopentanone | |
| CN101323567B (en) | Process for preparing cinnamate and derivates thereof | |
| CN103553878B (en) | A kind of novel preparation method of cyclohexyl phenol class liquid crystal intermediates compound | |
| CN109336753B (en) | Synthetic method of alpha-benzyl substituted 1, 3-diketone compound | |
| CN104177238A (en) | Method for synthesizing 3, 4-di(3, 4, 5-trimethoxy phenyl)-2, 5-diphenyl cyclopentadienone | |
| CN108586405A (en) | A kind of preparation method of tetrahydro pyrone | |
| CN107501338B (en) | Preparation method of 2, 6-diaminopyridine condensed 4-carboxybenzaldehyde bis-Schiff base cobalt complex | |
| CN107353245A (en) | A kind of synthetic method of quinolines | |
| CN106749135B (en) | Substituted benzofuran formyl hydrazone analog derivative and preparation method thereof | |
| CN107513078B (en) | Preparation method of 2, 6-diaminopyridine condensed 3-carboxybenzaldehyde bis-Schiff base cobalt complex | |
| CN111116339A (en) | Method for artificially synthesizing curcumin and derivatives thereof | |
| CN111253358A (en) | Synthetic method of isocoumarin aromatic ether compound | |
| CN106316819B (en) | A kind of synthetic method of 2- substitution -1,4-naphthoquinone class compound | |
| CN104788324A (en) | Synthetic method of aminofluorene compounds | |
| CN108191887A (en) | A kind of synthetic method of dibenzo spiral shell [4,5] dodecane ketone derivatives | |
| CN106349073B (en) | A kind of synthetic method of phenacylidene malonic acid ester type compound | |
| CN103058803A (en) | Biphenyl compound and synthesis method for same | |
| CN111187181B (en) | Preparation method of 2- (4-aminophenyl) -2-methylpropanenitrile compound | |
| CN101555225B (en) | Method for preparing poly-substituted quinoline compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160525 Termination date: 20190725 |