CN102746104A - Synthesizing method of 1,4-diphenylbutane - Google Patents
Synthesizing method of 1,4-diphenylbutane Download PDFInfo
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- CN102746104A CN102746104A CN2012101642622A CN201210164262A CN102746104A CN 102746104 A CN102746104 A CN 102746104A CN 2012101642622 A CN2012101642622 A CN 2012101642622A CN 201210164262 A CN201210164262 A CN 201210164262A CN 102746104 A CN102746104 A CN 102746104A
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Abstract
The invention relates to a synthesizing method of 1,4-diphenylbutane. The invention relates to a synthetic preparation method of organic micro-molecular 1,4-diphenylbutane. With an iodination substitution reaction, low-activity 2-phenyl-1-ethyl bromide is prepared into high-activity 2-phenyl-1-iodoethane; water is adopted as a solvent; 2-phenyl-1-iodoethane is added into a solvent containing Zn or Mn and CuCl2 as catalyst, and the mixture is fully stirred for reaction; and a product is distilled and purified, such that 1,4-diphenylbutane is obtained. A molar ratio of water to 2-phenyl-1-iodoethane to Mn to CuCl2 is 10-20:1:0.5-1:0.05-0.1. The reaction process requires an ice-water bath, a temperature is controlled at 10-40 DEG C, and an optimal reaction rate is reached. According to the invention, CuCl2, and Mn or Zn are adopted as the catalyst, and water is adopted as the solvent. The reaction is easy to control, the reaction rate is greatly improved, and the reaction yield is further improved. The product yield is high. The synthesized organic micro-molecular model can be applied in researches of polymer solvent system thermodynamic properties.
Description
Technical field
The present invention relates to the synthetic field of organic molecule, relate to a kind of compound method of small molecules 1,4 diphenyl butane more specifically.
Background technology
To the PS (PS) of different chain structures like isotactic, a rule, in the research of the spectrum peak ownership of the ir spectra of random polystyrene, small molecules model substances such as toluene and verivate thereof have played very large effect.Usually people adopt 2; 4-Diphenylheptane, 2,4,6-triphenyl heptane, 2; 4; 6, series model small molecules such as 8-tetraphenyl nonane carry out infrared and Raman spectrum analysis, to these small molecules Study of model achievements be after this in the many decades people through one of molecular orientation, molecular relaxation, glass transition and the structure relaxation phenomenon of infrared method research PS, foundation of yield phenomenon.Yet the report in its infrared signature absorption peak zone of above-mentioned these small molecules models is not comprehensive, and these model segments all exist methyl (CH
3), make methylene radical (CH on the PS main chain
2-) the C-H stretching vibration (comprise that symmetry is flexible and asymmetric flexible, at 2800-3000cm
-1The zone) and C-H (at 1450cm
-1Regional) flexural vibration are very approaching and partially overlap the analysis that influence changes the PS molecular motion.
The dimeric purpose of synthesizing styrene is to prepare in order to study polymkeric substance-solvent system thermodynamic property.Fox has proposed the experimental formula to the variation formed of second-order transition temperature in compatible polymer/solvent system in 1956; After this Couchman explains this phenomenon with thermodynamic entropy alter opinion; This theory is to the very success of polymer/Polymer Systems; But just be suitable for for high score/solvent system at solvent composition more after a little while, when the composition overweight of solvent than 40%, actual observation to second-order transition temperature and theoretical value very big-difference is arranged.People propose fluctuation of concentration theory (concentration fluctuation) and self aggregation theoretical (self-concentration) again and explain departing from of kinetics heterogencity and second-order transition temperature in the compatible polymer co-mixing system in recent years.People generally with the difference of this experimental value and theoretical value general be summed up as the special interaction between polymer and the solvent; Yet we are furtheing investigate the back discovery to gather (alpha-methyl styrene) studied before with the glass transition behavior of the mixed system of its oligopolymer; Although in this system because the chemical structure of polymer monomer and solvent is identical; There is not any special interaction; But when the composition of oligopolymer compares above 40% quality; The second-order transition temperature of mixed system still departs from the predictor of thermodynamic argumenies such as Couchman, shows that this deviation is not because special interaction causes, and this and other investigator's conclusion is inconsistent.In order to obtain the reasonableness of conclusion before further verifying, we study p-poly-phenyl ethylene/styrene oligomer system.System does not certainly have special interaction between macromole and small molecules hereto.
The medicine that research is used adopts the PS and the styrene dimer body of narrow molecular weight distributions.The styrene dimer body has three kinds of isomer, is respectively: 1, and 3-diphenyl butane, 1,4-diphenyl butane and 2, the 3-diphenyl butane, the suitability for industrialized production but these several kinds of dimers are unrealized is bought difficulty, and this has just determined the synthesizing styrene dimer.Directly use 2-phenyl-1-monobromethane preparation 1, the productive rate of 4-diphenyl butane is less than 30%, and this experimental technique obtains 1, and 4-diphenyl butane productive rate is high, can reach 50% ~ 70%; Through Finkelstein (Finkelstein) reaction, prepare 2-phenyl-1-iodoethane by 2-phenyl-1-monobromethane, cost is low; Experiment is reacted mild condition in that the water anaerobic is arranged under the lower temperature.
Summary of the invention
The objective of the invention is design and prepare a kind of styrene dimer body 1,4-diphenyl butane.1, the 4-diphenyl butane can be used for studying polymkeric substance-solvent system thermodynamic property.
Technical scheme of the present invention is following:
A kind of 1, the compound method of 4--diphenyl butane, step is following:
1) at first in being dissolved with the acetone soln of NaI, prepares 2-phenyl 1-iodoethane by 2-phenyl 1-monobromethane through the iodination reaction backflow through the Finkelstein reaction; Sodium Bromide is insoluble to acetone; Remove through layered filtration; With the volatilization of the acetone in the organic liquid fully, temperature is 20 ° of C-60 ° of C; 2-phenyl 1-monobromethane: NaI: the mol ratio of acetone is 0.6 ~ 1: 1 ~ 2: 7 ~ 10;
2) with Catalysts Cu Cl
2Be dissolved in the water; H
2O: CuCl
2Molar ratio be 167: 1 ~ 3;
3) the 2-phenyl-1-iodoethane that step 1) is obtained joins step 2) Catalysts Cu Cl
2In the solvent, fully stir, again with catalyzer Mn or Zn within 10 seconds in the adding system, reaction system feeds nitrogen; H
2O: CuCl
2: Zn or Mn: the molar ratio of 2-phenyl 1-iodoethane is 167: 1 ~ 3: 10 ~ 30: 10; Under 10 ° of C-40 ° of C, stirring reaction 24-32 hour, reaction finished, and quenched with hydrochloric acid acid, and used ether extraction product 1,4 diphenyl butane;
1, the 4 diphenyl butane system that contains that 5) will obtain is washed with frozen water, keeps organic layer, uses MgSO
4Dry water removes and desolvates;
The dry organism that 6) will obtain distills processing, and air distillation is to remove low-boiling point material, and the separation of product is carried out in underpressure distillation, and the cut that obtains carries out recrystallization, and recrystallization obtains purified 1,4 diphenyl butane.
Described recrystallization adopts induction method: with the glass stick container inner wall of swiping, form small glass particles as nucleus, and induced crystallization, and make liquid level coarse, be beneficial to the orientation of surface crystallization.
The present invention at first utilizes the iodate substitution reaction that SA 2-phenyl-1-monobromethane is changed into highly active 2-phenyl-1-iodoethane through Finkelstein (Finkelstein) reaction.The present invention adopts the CuCl of inexpensive and better catalytic activity
2With Mn or Zn as catalyzer.Said solvent adopts this simple solvent of water, but need under the condition of anaerobic, carry out.2-phenyl 1-monobromethane need distill the back of purifying to be used, entire reaction course at acetone as solvent.
The product system that obtains is all transferred in the exsiccant separating funnel, leaves standstill to complete layering, removes sub-cloud, keeps the upper strata.Repeatedly wash with frozen water on the upper strata, keeps organic layer, drying.The dry organism that obtains is distilled processing: air distillation is to remove low-boiling point material, and the separation of product is carried out in underpressure distillation; Wherein, 2-phenyl-1-monobromethane boiling point is 106 ° of C (15mmHg), n
D 20Be 1.5802,2-phenyl-1-iodoethane boiling point is 114 ° of C (15mmHg), n
D 20Be 1.596; 1,157 ° of C of 4-diphenyl butane (14mmHg), n
D 20Be 1.5578, density is 0.9801g/cm
3The cut that obtains is carried out recrystallization.Cut is crystal at normal temperatures, and its recrystallization need be induced.Induction method can be: 1. glass stick scraping container inner wall, form small glass particles as nucleus, and induced crystallization, and make liquid level coarse, be beneficial to the orientation of surface crystallization.2. cryosel or dry ice/ether mixture cools off.3. solution places refrigerator, long-time processing under cooling.
The productive rate of present technique method is 50% ~ 70%, adopts 2-phenyl 1-iodoethane, and activity is higher than 2-phenyl 1-monobromethane, and it is higher to react resulting product productive rate.
Embodiment
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1:
1, prepare 2-phenyl 1-iodoethane through Finkelstein (Finkelstein) reaction by 2-phenyl 1-monobromethane 27.8g (0.15mol) effect backflow through first Soiodin 27g (0.18mol) in acetone 61.0g (1.05mol) solution earlier.Mol ratio, 2-phenyl 1-monobromethane: NaI: acetone=1: 1.2: 7, temperature are controlled at 20 ° of C, reaction times 6h.Distill the 2-phenyl 1-iodic ether of purifying out.
2, in flask, pour the nitrogen of circulation, evacuation of air is with water 30ml, CuCl
2140mg (0.01mol), 2-phenyl 1-iodoethane 23.2g (0.1mol) add successively, fully stir, and after cupric chloride dissolved fully, time spent 5S added metal M n1.65g (0.3mol) powder wherein.Reaction in the nitrogen environment of circulation-hour, continue to stir.Mol ratio, H
2O: CuCl
2: Mn: 2-phenyl 1-iodoethane=167: 1: 30: 10.
3, bath temperature is controlled at 10 ° of C.Constantly stir in the dropping process, make to mix.Then at 10 ° of C lower seal reaction 28h.
4, product is carried out separatory, distillation, recrystallization is respectively organized cut.Needed cut is white crystals at normal temperatures, need induce its recrystallization.Induction method is: glass stick scraping container inner wall, form small glass particles as nucleus, and induced crystallization, and make liquid level coarse, be beneficial to the orientation of surface crystallization.
The reaction yield of 5,1,4 diphenyl butanes is 60%.
Embodiment 2:
1, prepare 2-phenyl 1-iodoethane through Finkelstein (Finkelstein) reaction by 2-phenyl 1-monobromethane 27.8g (0.15mol) effect backflow through first Soiodin 27g (0.18mol) in acetone 61.0g (1.05mol) solution earlier.Mol ratio, 2-phenyl 1-monobromethane gets: aI: acetone=1: 1.2: 7, temperature are controlled at 30 ° of C, reaction times 4h.Distill the 2-phenyl 1-iodic ether of purifying out.
2, in flask, pour the nitrogen of circulation, evacuation of air is with water 30ml, CuCl
2140mg (0.01mol), 2-phenyl 1-iodoethane 23.2g (0.1mol) add successively, fully stir, and after cupric chloride dissolved fully, time spent 6S added metal M n1.65g (0.3mol) powder wherein.Reaction in the nitrogen environment of circulation-hour, continue to stir.Mol ratio, H
2O: CuCl
2: Mn: 2-phenyl 1-iodoethane=167:1:30:10.
3, bath temperature is controlled at 20 ° of C.Constantly stir in the dropping process, make to mix.Then at 20 ° of C lower seal reaction 24h.
4, product is carried out separatory, distillation, recrystallization is respectively organized cut.Needed cut is white crystals at normal temperatures, need induce its recrystallization.Induction method is: glass stick scraping container inner wall, form small glass particles as nucleus, and induced crystallization, and make liquid level coarse, be beneficial to the orientation of surface crystallization.
The reaction yield of 5,1,4 diphenyl butanes is 65%.
Embodiment 3:
1, prepare 2-phenyl 1-iodoethane through Finkelstein (Finkelstein) reaction by 2-phenyl 1-monobromethane 27.8g (0.15mol) effect backflow through first Soiodin 27g (0.18mol) in acetone 70.0g (1.20mol) solution earlier.Mol ratio, 2-phenyl 1-monobromethane: NaI: acetone=1:1.2:8, temperature is controlled at 40 ° of C, reaction times 4h.
2, in flask, pour the nitrogen of circulation, evacuation of air is with water 30ml, CuCl
2140mg (0.01mol), 2-phenyl 1-iodoethane 23.2g (0.1mol) add successively, fully stir, and after cupric chloride dissolved fully, time spent 8S added Metal Zn 1.31g (0.2mol) powder wherein.Reaction in the nitrogen environment of circulation-hour, continue to stir.Mol ratio, H
2O:CuCl
2: Zn:2-phenyl 1-iodoethane=167:1:20:10.
3, bath temperature is controlled at 30 ° of C.Constantly stir in the dropping process, make to mix.Then at 30 ° of C lower seal reaction 24h.
4, product is carried out separatory, distillation, recrystallization is respectively organized cut.Needed cut is white crystals at normal temperatures, need induce its recrystallization.Induction method is: glass stick scraping container inner wall, form small glass particles as nucleus, and induced crystallization, and make liquid level coarse, be beneficial to the orientation of surface crystallization.
5,1, the reaction yield of 4--diphenyl butane is 70%.
Embodiment 4:
1, prepare 2-phenyl 1-iodoethane through Finkelstein (Finkelstein) reaction by 2-phenyl 1-monobromethane 46.3g (0.25mol) effect backflow through first Soiodin 45g (0.30mol) in acetone 145.25g (2.50mol) solution earlier.Mol ratio, 2-phenyl 1-monobromethane: NaI: acetone=1:1.2:10, temperature is controlled at 60 ° of C, reaction times 2h.
2, in flask, pour the nitrogen of circulation, evacuation of air is with water 45ml, CuCl
2210mg (0.015mol), 2-phenyl 1-iodoethane 34.8g (0.15mol) add successively, fully stir, and after cupric chloride dissolved fully, time spent 7S added Metal Zn 2.94g (0.45mol) powder wherein.Reaction in the nitrogen environment of circulation-hour, continue to stir.Mol ratio, H
2O:CuCl
2: Zn:2-phenyl 1-iodoethane=167:1:30:10.
3, bath temperature is controlled at 40 ° of C.Constantly stir in the dropping process, make to mix.Then at 40 ° of C lower seal reaction 32h.
4, product is carried out separatory, distillation, recrystallization is respectively organized cut.Needed cut is white crystals at normal temperatures, need induce its recrystallization.Induction method is: glass stick scraping container inner wall, form small glass particles as nucleus, and induced crystallization, and make liquid level coarse, be beneficial to the orientation of surface crystallization.
5,1, the reaction yield of 4--diphenyl butane is 55%.
Embodiment 5:
1, prepare 2-phenyl 1-iodoethane through Finkelstein (Finkelstein) reaction by 2-phenyl 1-monobromethane 46.3g (0.25mol) effect backflow through first Soiodin 56.3g (0.375mol) in acetone 145.25g (2.50mol) solution earlier.Mol ratio, 2-phenyl 1-monobromethane: NaI: acetone=1:1.5:10, temperature is controlled at 30 ° of C, reaction times 3h.
2, in flask, pour the nitrogen of circulation, evacuation of air is with water 45ml, CuCl
2210mg (0.015mol), 2-phenyl 1-iodoethane 34.8g (0.15mol) add successively, fully stir, and after cupric chloride dissolved fully, time spent 9S added metal M n2.43g (0.45mol) powder wherein.Reaction in the nitrogen environment of circulation-hour, continue to stir.Mol ratio, H
2O:CuCl
2: Zn:2-phenyl 1-iodoethane=167:1:30:10.
3, bath temperature is controlled at 40 ° of C.Constantly stir in the dropping process, make to mix.Then at 40 ° of C lower seal reaction 24h.
4, product is carried out separatory, distillation, recrystallization is respectively organized cut.Needed cut is white crystals at normal temperatures, need induce its recrystallization.Induction method is: 1. glass stick scraping container inner wall, form small glass particles as nucleus, and induced crystallization, and make liquid level coarse, be beneficial to the orientation of surface crystallization.
5,1, the reaction yield of 4--diphenyl butane is 65%.
Embodiment 6:
1, prepare 2-phenyl 1-iodoethane through Finkelstein (Finkelstein) reaction by 2-phenyl 1-monobromethane 46.3g (0.25mol) effect backflow through first Soiodin 56.3g (0.375mol) in acetone 145.25g (2.50mol) solution earlier.(2-phenyl 1-monobromethane: NaI: acetone=1:1.5:10), temperature is controlled at 30 ° of C, reaction times 3h.
2, in flask, pour the nitrogen of circulation, evacuation of air is with water 45ml, CuCl
2210mg (0.015mol), 2-phenyl 1-iodoethane 34.8g (0.15mol) add successively, fully stir, and after cupric chloride dissolved fully, time spent 5S was with Metal Zn 1.57g (0.225mol), and Mn1.22g (0.225mol) powder adds wherein.Reaction in the nitrogen environment of circulation-hour, continue to stir.Mol ratio, H
2O:CuCl
2: Zn/Mn:2-phenyl 1-iodoethane=167:1:15/15:10.
3, bath temperature is controlled at 20 ° of C.Constantly stir in the dropping process, make to mix.Then at 20 ° of C lower seal reaction 24h.
4, product is carried out separatory, distillation, recrystallization is respectively organized cut.Needed cut is white crystals at normal temperatures, need induce its recrystallization.Induction method is: 1. glass stick scraping container inner wall, form small glass particles as nucleus, and induced crystallization, and make liquid level coarse, be beneficial to the orientation of surface crystallization.
5,1, the reaction yield of 4--diphenyl butane is 50%.
Claims (2)
1. the compound method of a 4--diphenyl butane is characterized in that step is following:
1) at first in being dissolved with the acetone soln of NaI, prepares 2-phenyl 1-iodoethane by 2-phenyl 1-monobromethane through the iodination reaction backflow through the Finkelstein reaction; Sodium Bromide is insoluble to acetone; Remove through layered filtration, with the volatilization of the acetone in the organic liquid fully, temperature is 20 ℃-60 ℃; 2-phenyl 1-monobromethane: NaI: the mol ratio of acetone is 0.6～1:1～2:7～10;
2) with Catalysts Cu Cl
2Be dissolved in the water; H
2O:CuCl
2Molar ratio be 167:1～3;
3) the 2-phenyl-1-iodoethane that step 1) is obtained joins step 2) Catalysts Cu Cl
2In the solvent, fully stir, again with catalyzer Mn or Zn within 10 seconds in the adding system, reaction system feeds nitrogen; H
2O:CuCl
2: the molar ratio of Zn or Mn:2-phenyl 1-iodoethane is 167:1～3:10～30:10; Under 10 ℃-40 ℃, stirring reaction 24-32 hour, reaction finished, and quenched with hydrochloric acid acid, and used ether extraction product 1,4 diphenyl butane;
1, the 4 diphenyl butane system that contains that 4) will obtain is washed with frozen water, keeps organic layer, uses MgSO
4Dry water removes and desolvates;
The dry organism that 5) will obtain distills processing, and air distillation is to remove low-boiling point material, and the separation of product is carried out in underpressure distillation, and the cut that obtains carries out recrystallization, and recrystallization obtains purified 1,4 diphenyl butane.
2. compound method according to claim 1 is characterized in that described recrystallization adopts induction method: with the glass stick container inner wall of swiping, form small glass particles as nucleus, and induced crystallization, and make liquid level coarse, be beneficial to the orientation of surface crystallization.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100113800A1 (en) * | 2005-08-05 | 2010-05-06 | Shasun Pharma Solutions Limited | Formation of Carbon-nitrogen bond |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100113800A1 (en) * | 2005-08-05 | 2010-05-06 | Shasun Pharma Solutions Limited | Formation of Carbon-nitrogen bond |
Non-Patent Citations (3)
| Title |
|---|
| JIHAI MA等: "Organometallic-type Reactions in Aqueous Media Wurtz-coupling of Alkyl Halides with Manganese/Cupric Chloride", 《TETRAHEDRON LETTERS》, vol. 39, 23 April 1998 (1998-04-23), pages 2499 - 2502, XP004112079, DOI: doi:10.1016/S0040-4039(98)00348-7 * |
| 仝海江: "高效相变储能材料的研究与1，3-二苯基丁烷的合成", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 4, 7 April 2009 (2009-04-07), pages 20 - 49 * |
| 申凤娟等: "水相合成1 2- 二苯乙烷", 《河北科技大学学报》, vol. 26, no. 3, 30 September 2005 (2005-09-30), pages 197 - 198 * |
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