CN104710284A - Method for preparing 2,2'-dihydroxy diphenyl - Google Patents
Method for preparing 2,2'-dihydroxy diphenyl Download PDFInfo
- Publication number
- CN104710284A CN104710284A CN201510103332.7A CN201510103332A CN104710284A CN 104710284 A CN104710284 A CN 104710284A CN 201510103332 A CN201510103332 A CN 201510103332A CN 104710284 A CN104710284 A CN 104710284A
- Authority
- CN
- China
- Prior art keywords
- dihydroxybiphenyl
- solution
- boron
- reaction
- xenol
- 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.)
- Pending
Links
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 46
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 229910052796 boron Inorganic materials 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000012074 organic phase Substances 0.000 claims description 14
- 239000003205 fragrance Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- ZXSSXAUYKUTLBP-UHFFFAOYSA-N hexane;trichloroborane Chemical compound ClB(Cl)Cl.CCCCCC ZXSSXAUYKUTLBP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 6
- 239000000010 aprotic solvent Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 5
- 238000005859 coupling reaction Methods 0.000 abstract description 6
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000006400 oxidative hydrolysis reaction Methods 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000012230 colorless oil Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- MSVMSXHTHSWNAU-UHFFFAOYSA-N 2-phenylcyclohexa-2,4-diene-1,1-diol Chemical group OC1(O)CC=CC=C1C1=CC=CC=C1 MSVMSXHTHSWNAU-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940031815 mycocide Drugs 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000651 prodrug Substances 0.000 description 1
- 229940002612 prodrug Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 2,2'-dihydroxy diphenyl. The method comprises the following steps: taking 2-hydroxy diphenyl as a starting material; under the catalytic action of aluminum chloride, enabling reaction between 2-hydroxy diphenyl and boron chloride to generate 10-hydroxy-10,9-boron-oxygen hetero-phenanthrene; taking 10-hydroxy-10,9-boron-oxygen hetero-phenanthrene as an intermediate, and further carrying out oxidative hydrolysis to obtain the target product 2,2'-dihydroxy diphenyl. The method avoids the defects of poor coupling reaction selectivity, harsh reaction condition and low yield, has the advantages of being mild in reaction condition, short in reaction time, high in yield, safe in process route, low in cost and high in purity of target product, and is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to organic chemical industry field, being specifically related to a kind of is that raw material prepares 2 by 2-xenol, the method for 2 '-dihydroxybiphenyl.
Background technology
10-hydroxyl-10,9-boron oxa-phenanthrene is a kind of white cotton fluffy solid, and fusing point 205-210 DEG C, is dissolved in methylene dichloride, water insoluble, normal hexane etc.10-hydroxyl-10,9-boron oxa-phenanthrene is synthesized in 1956 first by people such as Dewar, and research shows that this type of material has the dual nature of aromatic compound and boric acid fat, and the widespread use of this type of material of its special boron oxygen aromatic heterocycle structures shape is worth.Its application mainly comprises antioxidant, lubricant, mycocide and synthetic intermediate.
2,2 '-dihydroxybiphenyl is a kind of gray powdery solid, and fusing point 108-111 DEG C is dissolved in ethanol, ethyl acetate, methylene dichloride etc., is insoluble to normal hexane, sherwood oil, benzene.2,2 '-dihydroxybiphenyl structure is present in and much has in bioactive natural product, medicine and prodrug and asymmetry catalysis part.In organic synthesis field, there is very large application potential.
Well-known 2,2 '-dihydroxybiphenyl can be prepared by the way of coupling.Such as CN1802339A, US6077979 all describe and utilize the method for coupling two kinds of phenol to prepare 2,2 '-dihydroxybiphenyl.
The method of coupling prepares 2, and 2 '-dihydroxybiphenyl Problems existing is poor selectivity, and phenolic hydroxyl group needs group to protect, and step many condition is harsh and efficiency is low.
Summary of the invention
The invention provides one break away from coupling thinking prepare 2, the method for 2 '-dihydroxybiphenyl.The method with 2-xenol for Material synthesis 10-hydroxyl-10,9-boron oxa-is luxuriant and rich with fragrance as intermediate, by obtaining 2,2 '-dihydroxybiphenyl to the oxydrolysis of 10-hydroxyl-10,9-boron oxa-phenanthrene.
One prepares 2, the method for 2 '-dihydroxybiphenyl, can carry out successively as follows:
(1) add aprotic solvent, boron trichloride hexane solution, 2-xenol solution in a reservoir, mixed solution adds aluminum trichloride (anhydrous) after at room temperature stirring 10-20min, and stirring and refluxing is reacted;
(2), after reaction terminates, the reaction solution of step (1) is cooled to room temperature and adds frozen water and stir, point isolated product 10-hydroxyl-10,9-boron oxa-is luxuriant and rich with fragrance;
(3) product 10-hydroxyl-10, the 9-boron oxa-obtained in step (2) is luxuriant and rich with fragrance and sodium hydroxide solution is dissolved in tetrahydrofuran (THF) and joins in reactor, under agitation in above-mentioned reactor, slowly drips H
2o
2, dropwise stirred at ambient temperature reaction;
(4) reaction terminates rear hydrochloric acid soln regulating step (3) reaction solution to acid, and add water and ethyl acetate, be separated organic phase, vacuum rotary steam recycling design obtains target product 2,2 '-dihydroxybiphenyl.
As a kind of preferred version, in step of the present invention (1), described aprotic solvent is selected from the one in normal hexane, hexanaphthene or toluene etc.; The concentration of boron trichloride hexane solution is the concentration of 1mol/L ~ 10mol/L, 2-xenol solution is 1mol/L ~ 10mol/L; The mol ratio of 2-xenol and boron trichloride is 1: 1 ~ 5; The mol ratio of 2-xenol and aluminum trichloride (anhydrous) is 1: 0.02 ~ 0.05; Reflux temperature is 50 ~ 150 DEG C, and return time is 0.5 ~ 20h.As a kind of preferred version, in step of the present invention (2), the add-on of described frozen water and the mol ratio of 2-xenol are 10: 1 ~ 100: 1; Stir 5 ~ 30min.
As a kind of preferred version, in step of the present invention (3), the concentration of described sodium hydroxide solution is 1mol/L ~ 10mol/L, and the mol ratio of sodium hydroxide and 10-hydroxyl-10,9-boron oxa-phenanthrene is 1: 1 ~ 1: 1.5; H
2o
2mass concentration be 30% ~ 50%, H
2o
2be 1: 1 ~ 5: 1 with the mol ratio of 10-hydroxyl-10,9-boron oxa-phenanthrene; The temperature of stirring reaction is 25 ~ 50 DEG C, and the reaction times is 0.5 ~ 20h.
As a kind of preferred version, in step of the present invention (4), the concentration of hydrochloric acid soln is 1mol/L ~ 10mol/L.
Compared with prior art, advantage of the present invention is:
1, this approach avoid coupling reaction poor selectivity, severe reaction conditions and the low shortcoming of productive rate;
2, reaction conditions of the present invention is gentle, and the reaction times is short;
3, productive rate is high, operational path safety, and cost is low, and object product purity is high, is suitable for large-scale industrial and produces.
Embodiment
Below by embodiment, the invention will be further described.Protection scope of the present invention is not only confined to the statement of following content.
The invention provides a kind of organic intermediate 2, the chemical synthesis process of 2 '-dihydroxybiphenyl, with 2-xenol for starting raw material, 10-hydroxyl-10 is generated with boron trichloride reaction under the katalysis of aluminum chloride, 9-boron oxa-is luxuriant and rich with fragrance, make intermediate with this and obtain object product 2 by further oxydrolysis, 2 '-dihydroxybiphenyl.
Its reaction equation is:
The solvent adopted in 2-xenol solution in following embodiment can be the aprotic solvent such as toluene, m-xylene, hexanaphthene.
It is luxuriant and rich with fragrance that embodiment 1 synthesizes 10-hydroxyl-10,9-boron oxa-:
100mL normal hexane is added in the 250mL round-bottomed flask of drying, the boron trichloride hexane solution (18.5mL, 18.5mmol) of 1mol/L, adds 2-xenol (2.10g in above-mentioned mixing solutions, 12.3mmol, is dissolved in 10ml toluene); At room temperature stir 10min, add dry AlCl
3(60mg, 0.44mmol); Above-mentioned reaction solution is warming up to 75 DEG C, stirring and refluxing 6h.After backflow terminates, reaction solution is cooled to room temperature, after adding frozen water, stirs 30min, separate out white cotton fluffy solid, filter, and with water, n-hexane solid product.Yield 93%, fusing point 205 ~ 21 DEG C, purity > 90%.Product structure warp
1h NMR
13c NMR characterizes.
Analytical results is as follows:
1H NMR(500MHz，DMSO-d
6)：δ7.27-7.17(m，2H)，7.39(ddd，J＝8.4，7.1，1.6Hz，1H)，7.47(td，J＝7.3，1.0Hz，1H)，7.71(ddd，J＝8.3，7.3，1.5Hz，1H)，8.07(dd，J＝7.4，1.4Hz，1H)，8.31-8.22(m，2H)，9.40(s，1H)；
13C NMR(125MHz，DMSO-d
6)：δ122.85(d，J＝10.8Hz)，122.31，124.3。
Embodiment 2-in-1 one-tenth 10-hydroxyl-10,9-boron oxa-is luxuriant and rich with fragrance:
100mL normal hexane is added in the 250mL round-bottomed flask of drying, the boron trichloride hexane solution (13mL, 13mmol) of 1mol/L, adds 2-xenol (2.10g in above-mentioned mixing solutions, 12.3mmol, is dissolved in 10mL toluene); At room temperature stir 10min, add dry AlCl
3(60mg, 0.44mmol); Above-mentioned reaction solution is warming up to 75 DEG C, stirring and refluxing 6h.After backflow terminates, reaction solution is cooled to room temperature, adds frozen water and stir 30min, separate out white cotton fluffy solid, filter, and with water, n-hexane solid product.Yield 70%, fusing point 205 ~ 210 DEG C, purity > 90%.Product structure warp
1h NMR
13c NMR characterizes.Analytical results is consistent with embodiment 1.
It is luxuriant and rich with fragrance that embodiment 3 synthesizes 10-hydroxyl-10,9-boron oxa-:
100mL normal hexane is added in the 250mL round-bottomed flask of drying, the boron trichloride hexane solution (18.5mL, 18.5mmol) of 1mol/L, adds 2-xenol (2.10g in above-mentioned mixing solutions, 12.3mmol, is dissolved in 10ml toluene); At room temperature stir 10min, add dry AlCl
3(60mg, 0.44mmol); Above-mentioned reaction solution is warming up to 100 DEG C, stirring and refluxing 8h.After backflow terminates, reaction solution is cooled to room temperature, adds frozen water and stir 30min, separate out white cotton fluffy solid, filter, and with water, n-hexane solid product.Yield 85%, fusing point 190 ~ 195 DEG C, purity > 90%.Product structure warp
1h NMR
13c NMR characterizes.Analytical results is consistent with embodiment 1.
It is luxuriant and rich with fragrance that embodiment 4 synthesizes 10-hydroxyl-10,9-boron oxa-:
100mL normal hexane is added in the 250mL round-bottomed flask of drying, the boron trichloride hexane solution (18.5mL, 18.5mmol) of 1mol/L, adds 2-xenol (2.10g in above-mentioned mixing solutions, 12.3mmol, is dissolved in 10ml toluene); At room temperature stir 10min, add dry AlCl
3(60mg, 0.44mmol); Above-mentioned reaction solution is warming up to 75 DEG C, stirring and refluxing 12h.After backflow terminates, reaction solution is cooled to room temperature, adds frozen water and stir 30min, separate out white cotton fluffy solid, filter, and with water, n-hexane solid product.Yield 92%, fusing point 190 ~ 195 DEG C, purity > 90%.Product structure warp
1h NMR
31c NMR characterizes.Analytical results is consistent with embodiment 1.
Embodiment 5 synthesizes 2,2 '-dihydroxybiphenyl:
Add tetrahydrofuran (THF) (10mL) in the reactor and make solvent, and add 10-hydroxyl-10 successively subsequently, luxuriant and rich with fragrance (the 0.76g of 9-boron oxygen fragrance, 3.88mmol) under agitation in above-mentioned reactor, slowly add H with 1mol/L aqueous sodium hydroxide solution (1mL, 1mmol)
2o
2(30%, 1mL); 20h is stirred at 20 ~ 30 DEG C.Reaction terminates rear 1mol/L aqueous hydrochloric acid and regulates above-mentioned reaction solution to PH=2, adds water and each 30mL of ethyl acetate, is separated organic phase, and washs aqueous phase by ethyl acetate (2 × 20mL), merges organic phase.Colorless oil drop is obtained after vacuum rotary steam removes solvent after NaCl solution washing organic phase, normal hexane (10mL) is joined and fills both stirrings fully mixing rear precipitation gray powdery solid and object product 2 in colorless oil drop reactor, 2 '-dihydroxybiphenyl.Yield 80%, fusing point 108-111 DEG C.Product structure warp
1h NMR
13c NMR characterizes.Analytical results is as follows:
1H NMR(500MHz，DMSO-d
6)：δ6.91-6.85(m，2H)，6.81(td，J＝7.4，1.2Hz，2H)，7.12(td，J＝6.9，6.4，1.9Hz，4H)，9.17(s，2H)；
13C NMR(125MHz，DMSO-d
6)：δ128.49，116.15，131.94，119.26，154.88，126.34。
Embodiment 6 synthesizes 2,2 '-dihydroxybiphenyl:
Add tetrahydrofuran (THF) (10mL) in the reactor and make solvent, and add 10-hydroxyl-10 successively subsequently, 9-boron oxa-phenanthrene (0.76g, 3.88mmol) under agitation in above-mentioned reactor, slowly add H with 1mol/L aqueous sodium hydroxide solution (0.2mL, 0.2mmol)
2o
2(30%, 1.5mL); 20h is stirred at 30 ~ 40 DEG C.Reaction terminates rear 1mol/L aqueous hydrochloric acid and regulates above-mentioned reaction solution to PH=2, adds water and each 30mL of ethyl acetate, is separated organic phase, and washs aqueous phase by ethyl acetate (2 × 20mL), merges organic phase.Colorless oil drop is obtained after vacuum rotary steam removes solvent after NaCl solution washing organic phase, normal hexane (10mL) is joined and fills both stirrings fully mixing rear precipitation gray powdery solid and object product 2,2-dihydroxybiphenyl in colorless oil drop reactor.Yield 87%, fusing point 108-111 DEG C.Product structure warp
1h NMR
13c NMR characterizes.Analytical results is consistent with embodiment 5.
Embodiment 7 synthesizes 2,2 '-dihydroxybiphenyl:
Add tetrahydrofuran (THF) (10mL) in the reactor and make solvent, and add 10-hydroxyl-10 successively subsequently, 9-boron oxa-phenanthrene (0.76g, 3.88mmol) under agitation in above-mentioned reactor, slowly add H with 1mol/L aqueous sodium hydroxide solution (0.2mL, 0.2mmol)
2o
2(30%, 1.5mL); 30h is stirred at 40 ~ 50 DEG C.Reaction terminates rear 1mol/L aqueous hydrochloric acid and regulates above-mentioned reaction solution to PH=2, adds water and each 30mL of ethyl acetate, is separated organic phase, and washs aqueous phase by ethyl acetate (2 × 20mL), merges organic phase.Colorless oil drop is obtained after vacuum rotary steam removes solvent after NaCl solution washing organic phase, normal hexane (10mL) is joined and fills both stirrings fully mixing rear precipitation gray powdery solid and object product 2,2-dihydroxybiphenyl in colorless oil drop reactor.Yield 81%, fusing point 105-110 DEG C.Product structure warp
1h NMR
13c NMR characterizes.Analytical results is consistent with embodiment 5.
Embodiment 8 synthesizes 2,2 '-dihydroxybiphenyl:
Add tetrahydrofuran (THF) (10mL) in the reactor and make solvent, and add 10-hydroxyl-10 successively subsequently, 9-boron oxa-phenanthrene (0.76g, 3.88mmol) under agitation in above-mentioned reactor, slowly add H with 1mol/L aqueous sodium hydroxide solution (0.6mL, 0.6mmol)
2o
2(30%, 1.5mL); 10h is stirred at 30 ~ 40 DEG C.Reaction terminates rear 1mol/L aqueous hydrochloric acid and regulates above-mentioned reaction solution to PH=2, adds water and each 30mL of ethyl acetate, is separated organic phase, and washs aqueous phase by ethyl acetate (2 × 20mL), merges organic phase.Colorless oil drop is obtained after vacuum rotary steam removes solvent after NaCl solution washing organic phase, normal hexane (10mL) is joined and fills both stirrings fully mixing rear precipitation gray powdery solid and object product 2,2-dihydroxybiphenyl in colorless oil drop reactor.Yield 75%, fusing point 109-110 DEG C.Product structure warp
1h NMR
13c NMR characterizes.Analytical results is consistent with embodiment 5.
Claims (6)
1. prepare 2 for one kind, the method for 2 '-dihydroxybiphenyl, is characterized in that, carries out as follows:
(1) add aprotic solvent, boron trichloride hexane solution, 2-xenol solution in a reservoir, mixed solution adds aluminum trichloride (anhydrous) after at room temperature stirring 10-20min, and stirring and refluxing is reacted;
(2), after reaction terminates, the reaction solution of step (1) is cooled to room temperature and adds frozen water and stir, point isolated product 10-hydroxyl-10,9-boron oxa-is luxuriant and rich with fragrance;
(3) product 10-hydroxyl-10, the 9-boron oxa-obtained in step (2) is luxuriant and rich with fragrance and sodium hydroxide solution is dissolved in tetrahydrofuran (THF) and joins in reactor, under agitation in above-mentioned reactor, slowly drips H
2o
2,dropwise stirred at ambient temperature reaction;
(4) reaction terminates rear hydrochloric acid soln regulating step (3) reaction solution to acid, and add water and ethyl acetate, be separated organic phase, vacuum rotary steam recycling design obtains target product 2,2 '-dihydroxybiphenyl.
2. preparation 2 as claimed in claim 1, the method for 2 '-dihydroxybiphenyl, is characterized in that, in step (1), described aprotic solvent is selected from the one in normal hexane, hexanaphthene or toluene etc.; The concentration of boron trichloride hexane solution is the concentration of 1mol/L ~ 10mol/L, 2-xenol solution is 1mol/L ~ 10mol/L; The mol ratio of 2-xenol and boron trichloride is 1:1 ~ 5; The mol ratio of 2-xenol and aluminum trichloride (anhydrous) is 1:0.02 ~ 0.05; Reflux temperature is 50 ~ 150
oc, return time is 0.5 ~ 20h.
3. preparation 2 as claimed in claim 2, the method for 2 '-dihydroxybiphenyl, is characterized in that, the solvent that 2-xenol solution adopts is toluene, m-xylene or hexanaphthene.
4. preparation 2 as claimed in claim 1, the method for 2 '-dihydroxybiphenyl, is characterized in that, in step (2), the add-on of described frozen water and the mol ratio of 2-xenol are 10:1 ~ 100:1; Stir 5 ~ 30min.
5. preparation 2 as claimed in claim 1, the method for 2 '-dihydroxybiphenyl, is characterized in that, in step (3), the concentration of described sodium hydroxide solution is 1mol/L ~ 10mol/L, and the mol ratio of sodium hydroxide and 10-hydroxyl-10,9-boron oxa-phenanthrene is 1:1 ~ 1:1.5; H
2o
2mass concentration be 30% ~ 50%, H
2o
2be 1:1 ~ 5:1 with the mol ratio of 10-hydroxyl-10,9-boron oxa-phenanthrene; The temperature of stirring reaction is 25 ~ 50
oc, the reaction times is 0.5 ~ 20h.
6. preparation 2 as claimed in claim 1, the method for 2 '-dihydroxybiphenyl, is characterized in that, in described step (4), the concentration of hydrochloric acid soln is 1mol/L ~ 10mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510103332.7A CN104710284A (en) | 2015-03-09 | 2015-03-09 | Method for preparing 2,2'-dihydroxy diphenyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510103332.7A CN104710284A (en) | 2015-03-09 | 2015-03-09 | Method for preparing 2,2'-dihydroxy diphenyl |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104710284A true CN104710284A (en) | 2015-06-17 |
Family
ID=53410078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510103332.7A Pending CN104710284A (en) | 2015-03-09 | 2015-03-09 | Method for preparing 2,2'-dihydroxy diphenyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104710284A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967980A (en) * | 2016-06-30 | 2016-09-28 | 河南师范大学 | 2,2'-biphenol compound synthesizing method |
| CN107903151A (en) * | 2017-11-22 | 2018-04-13 | 安庆三喜医药化工有限公司 | A kind of purification process of 2,2 ' dihydroxybiphenyls |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5821376A (en) * | 1995-06-23 | 1998-10-13 | Schill & Seilacher Gmbh & Co. | Process for the preparation of a dop-containing mixture |
-
2015
- 2015-03-09 CN CN201510103332.7A patent/CN104710284A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5821376A (en) * | 1995-06-23 | 1998-10-13 | Schill & Seilacher Gmbh & Co. | Process for the preparation of a dop-containing mixture |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967980A (en) * | 2016-06-30 | 2016-09-28 | 河南师范大学 | 2,2'-biphenol compound synthesizing method |
| CN105967980B (en) * | 2016-06-30 | 2018-11-16 | 河南师范大学 | A kind of synthetic method of 2,2 '-Biphenol compounds |
| CN107903151A (en) * | 2017-11-22 | 2018-04-13 | 安庆三喜医药化工有限公司 | A kind of purification process of 2,2 ' dihydroxybiphenyls |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104086379B (en) | The synthetic method of the clean intermediate of Da Gelie | |
| CN104892566A (en) | Preparation method of 2-(5-bromo-2-methylbenzyl)-5-(4-fluorophenyl)thiophene | |
| CN102060867A (en) | Method for preparing potassium trifluoroborate series compounds | |
| CN104710284A (en) | Method for preparing 2,2'-dihydroxy diphenyl | |
| CN102617302B (en) | Process for synthesizing trimethoxyphenyl stilbene | |
| CN101671242B (en) | Method for synthesizing trans-4-(trans-4'-alkyl cyclohexyl) cyclohexanal | |
| CN102167716A (en) | Synthesis method of clofarabine, midbody thereof and preparation method of midbody | |
| CN103073421A (en) | High-efficiency simple synthetic method for delta-chlorobutyl ester | |
| CN105061177B (en) | A kind of preparation method of 10,10-- dimethyl anthrone | |
| Rajendran et al. | A domino green synthesis of bis (indolyl) methanes catalyzed by ionic liquid [Et3NH][HSO4] | |
| CN101486730A (en) | Creatine phosphate sodium compound and method for synthesizing the same | |
| CN103566972B (en) | A kind of Ferrocene oligomer and preparation method thereof | |
| CN103272638B (en) | Chiral guanidine catalysts based on tartaric acid skeleton, preparation method and application thereof | |
| CN108586529A (en) | A kind of chipal compounds and the preparation method and application thereof containing biphenyl backbone | |
| CN102532195B (en) | Method for synthesis of chlorpyrifos | |
| CN102153462A (en) | Method for synthesizing tanshinol | |
| CN104557744A (en) | Preparation method of triazoie compound | |
| CN105237483B (en) | A kind of symmetric form pyrimidine radicals salt compounded of iodine and preparation method thereof | |
| CN102731315B (en) | Production method for N,N'dimethylcyclohexanediamine | |
| CN104028310A (en) | Preparation method for synthesizing dimethoxy bisphenol A carbonate catalyst | |
| CN105348197A (en) | Preparation method of lorcaserin hydrochloride | |
| CN109320538B (en) | Synthesis method of 3-bromo-5-aryl-2- (trimethylsilyl) -1- (N, N-dimethyl sulfonamide) pyrrole | |
| CN104529726A (en) | Preparation method of hydroxyacetophenone | |
| CN106966937A (en) | Diaryl selenide analog derivative and preparation method thereof | |
| CN106928136A (en) | A kind of Graphene palladium cobalt sequential catalyst synthesizes the method for MK intermediate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150617 |