CN103113174B - Preparation method of phenolic compounds - Google Patents
Preparation method of phenolic compounds Download PDFInfo
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- CN103113174B CN103113174B CN201310036992.9A CN201310036992A CN103113174B CN 103113174 B CN103113174 B CN 103113174B CN 201310036992 A CN201310036992 A CN 201310036992A CN 103113174 B CN103113174 B CN 103113174B
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- preparation
- boric acid
- phenolic compound
- boron ester
- compound
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- 150000002989 phenols Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 boron ester Chemical class 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000004327 boric acid Substances 0.000 claims abstract description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims abstract 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- 238000001819 mass spectrum Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 5
- 229940043279 diisopropylamine Drugs 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GRFNBEZIAWKNCO-UHFFFAOYSA-N Oc1cccnc1 Chemical compound Oc1cccnc1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229930014669 anthocyanidin Natural products 0.000 description 1
- 150000001452 anthocyanidin derivatives Chemical class 0.000 description 1
- 235000008758 anthocyanidins Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HVQSEKGARNNWON-UHFFFAOYSA-N boric acid pyrene Chemical compound OB(O)O.c1cc2ccc3cccc4ccc(c1)c2c34 HVQSEKGARNNWON-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 210000005252 bulbus oculi Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003476 thallium compounds Chemical class 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Abstract
The invention relates to a preparation method of phenolic compounds, which comprises the following steps: dissolving arylcyclic or arylheterocyclic boron ester or boric acid in organic solvent; adding secondary amine at room temperature, and reacting for 2-72 hours; and then performing centrifugal drying on the reaction solution, and separating through a chromatographic column to obtain the phenolic compounds. According to the invention, the preparation method is simple to operate and mild in reaction conditions; no expensive catalysts are required; some active groups can be reserved; fewer byproducts are generated; and different kinds of arylcyclic or arylheterocyclic boron ester or boric acid derivatives can be selected at will for the synthesis of corresponding phenols, thereby ensuring that the invention is high in universality.
Description
Technical field
The invention belongs to the preparation field of aromatics, particularly a kind of preparation method of phenolic compound.
Background technology
Phenolic compound is a kind ofly extensively present in nature and has the material of important use in the industry.Occurring in nature, the anthocyanidin that people know, Vanillin and catechol are exactly polyphenol substance.At industrial circle, aldehydes matter is the important intermediate of synthesizing a lot of organic compound, and in addition, aldehydes matter also act as vital stain, the role of dyestuff and medicine.The vital role of aldehydes matter and extensive use determine the importance of its synthesis.
The method preparing phenolic compound conventional at present mainly contains the reaction of oxidation aromatic hydrocarbons, aryl thallium salt displacement hydrolysis, halogeno-benzene hydrolysis and diazonium salt method etc.The hydrolysis of application halogeno-benzene, usually needs High Temperature High Pressure and catalyzer to exist and just can carry out; And utilizing diazonium salt legal system for phenols, the synthesis step of needs is a lot; Although the temperature of reaction that aryl thallium salt displacement hydrolysis needs is low, speed is also very fast, has used poisonous heavy metal thallium compound, be not suitable for large-scale popularization in reaction.In view of above present situation, develop the new method rapidly and efficiently preparing phenolic compound, a lot of problems in synthetic work can be solved.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of phenolic compound, and the method is easy and simple to handle, and the raw material of needs is simple, and productive rate is high, easily separated, purity is high, can at normal temperatures, adopt usual vehicle to prepare phenolic compound.
The preparation method of a kind of phenolic compound of the present invention, comprising:
The boron ester of aromatic ring or fragrant heterocycle or boric acid are dissolved in organic solvent, secondary amine is added under room temperature, react after 2-72 hour and (degree can be carried out according to the reaction of TLC display suitably shorten or extend the reaction times), be spin-dried for reaction soln, chromatographic column is separated and obtains phenolic compound, and the raw material of recovery part; Reaction formula is as shown in (III):
（III） 。
The mol ratio of the boron ester of described aromatic ring or fragrant heterocycle or boric acid and secondary amine is 1:2-50.
The boron ester of described aromatic ring or fragrant heterocycle or the structural formula of boric acid are as shown in (I):
（I）
Wherein R
1be selected from the group of A1-A20:
R
2for hydrogen or the group being selected from A21-A37, R
5be selected from group A21-A37:
The structural formula of described secondary amine is as shown in (II):
（II）
Wherein R
3with R
4take from group A21-A37 respectively:
Described organic solvent is the one in methyl alcohol, ethanol, acetone, methylene dichloride, chloroform, toluene, tetrahydrofuran (THF), second eyeball.
The reaction formula of the preparation method of phenolic compound of the present invention is:
Wherein R
1represent benzene, naphthalene, anthracene, pyrene, fluorenes, connect dinaphthyl, carbazole, quinoline, imidazoles, pyridine, the one in the aromatic ring substituents such as pyrimidine and derivative thereof, R
2, R
3, R
4and R
5for alkyl substituent, R
2can also be hydrogen.
The present invention, using the boron ester of aromatic ring or fragrant heterocycle or boric acid derivatives as raw material, using secondary amine as reactant in room temperature and common solvent, prepares corresponding phenolic compound.Preparation method is novel, simple to operate, and reaction conditions is gentle, and some active groups can retain, and by product is few, and can choose at random the boron ester of different types of aromatic ring or fragrant heterocycle or boric acid derivatives synthesizes corresponding phenol, and universality is stronger.
Beneficial effect:
(1) synthesis of the boron ester of raw material aromatic ring of the present invention or fragrant heterocycle or boric acid is simple, can obtain in a large number;
(2) some active function groups can retain in the process preparing phenol, such as aldehyde radical;
(3) reaction is except remaining raw material and reaction target product, does not almost have by product to produce;
(4) reaction conditions is gentle, does not need valuable catalyzer.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1 gives the building-up process of compound 1, embodiment 2 and embodiment 3 sets forth the building-up process of compound 2, and embodiment 4 gives the building-up process of compound 3, embodiment 5 gives the building-up process of compound 4, and embodiment 6 gives the building-up process of compound 5.
Embodiment 1
The structure of compound 1 and synthesis (R
1=
r
2=-C (CH
3)
2(CH
3)
2c-, R
3=R
4=-CH (CH
3)
2, R
5=-C
8h
17)
Take 516mg9, single port bottle put into by which alcohol ester (purchased from Beijing Sheng Weite Science and Technology Ltd.) of 9-dioctyl fluorene-2-boric acid Knit-the-brows and 505mg Diisopropylamine, add 20ml methylene dichloride wherein as solvent, react 24h under room temperature, then extraction liquid is spin-dried on a rotary evaporator.The thick product obtained is separated to obtain compound as white solid 1 through chromatographic column, productive rate 82%.
Nucleus magnetic hydrogen spectrum
1h-NMR (400MHz, CDCl
3, 25 DEG C, TMS): δ=7.58-7.57 (d, 1H), 7.54-7.52 (d, 1H), 7.29-7.27 (m, 2H), 7.24-7.19 (m, 1H), 6.81-6.80 (m, 1H), 6.79-6.77(m, 1H), 4.96 (s, 1H), 1.96-1.84 (m, 4H), 1.23-1.15 (m, 4H), 1.12-1.03 (m, 16H), 0.82-0.77 (m, 6H), 0.64-0.57(m, 4H).
Mass spectrum: MALDI-TOF406.3
Embodiment 2
Synthesis (the R of compound 2
1=
r
2=-C (CH
3)
2(CH
3)
2c-, R
3=R
4=-CH (CH
3)
2)
Take 328mg1-pyrene boric acid Knit-the-brows any alcohol ester and 1g Diisopropylamine is placed in 50ml single port bottle, add 20ml methylene dichloride as solvent reaction 24h, then extraction liquid is spin-dried on a rotary evaporator.The thick product obtained is separated to obtain pale solid compound 2 through chromatographic column, productive rate 95%.
Nucleus magnetic hydrogen spectrum
1h-NMR (400MHz, CDCl
3, 25 DEG C, TMS): δ=8.50-7.62 (m, 9H), 5.64 (s, 1H)
Mass spectrum: EI220
The preparation method of pyrene boric acid Knit-the-brows any alcohol ester:
At-78 DEG C, in the tetrahydrofuran solution of the 1-bromine pyrene of 1.2g, dropwise instill n-Butyl Lithium (9.5mmol), then the 2-isopropoxy-4,4,5 of 3.6ml is dripped gradually, 5-tetramethyl--1,3,2-dioxy boron penta ring, react 1 hour at this temperature, then be warming up to normal temperature and continue reaction 12 hours, use brine It with after dichloromethane extraction, filter after organic phase dried over mgso, be separated through chromatographic column after being spin-dried for and obtain flaxen solid, productive rate 81%.
Nucleus magnetic hydrogen spectrum:
1h NMR (500M, CDCl
3, ppm) and δ=(d, 1H), 8.526 (d, 1H), 8.223-8.107 (m, 5H), 8.057 (d, 1H), 7.992 (t, 1H), 1.494 (s, 12H)
Mass spectrum MALDI-TOF MS:m/z328
Embodiment 3
Synthesis (the R of compound 2
1=
r
2=H, R
3=R
4=-CH
2cH
3)
Take 1-pyrene boric acid (purchased from Suzhou subfamily chemical reagent company limited) and 1g diethylamine is placed in 50ml single port bottle, add 20ml ethanol as solvent reaction 72h, then extraction liquid is spin-dried on a rotary evaporator.The thick product obtained is separated to obtain pale solid compound 2 through chromatographic column, productive rate 91%.
Nucleus magnetic hydrogen spectrum
1h-NMR (400MHz, CDCl
3, 25 DEG C, TMS): δ=8.50-7.62 (m, 9H), 5.64 (s, 1H)
Mass spectrum: EI220
Embodiment 4
Synthesis (the R of compound 3
1=
r
2=-C (CH
3)
2(CH
3)
2c-, R
3=R
4=-CH (CH
3)
2)
Take 410mg9, which alcohol ester-2 (thiophene-5-aldehyde) of 9-dioctyl fluorene-7-boric acid Knit-the-brows and 1g Diisopropylamine are placed in 50ml single port bottle, add 20ml tetrahydrofuran (THF) as solvent, react 24h, be then spin-dried on a rotary evaporator by mother liquor under room temperature.The thick product obtained is separated to obtain yellow oily material 3 through chromatographic column, productive rate 83%.
Nucleus magnetic hydrogen spectrum
1h-NMR (400MHz, CDCl
3, 25 DEG C, TMS): δ=9.89 (s, 1H), 7.76 (d, 1H), 7.64-7.63 (m, 2H), 7.58-7.56 (m, 2H), 7.45 (d, 1H), 6.84-6.82 (m, 2H), 5.29 (s, 1H), 1.99-1.89 (m, 4H), 1.20-1.14 (m, 4H), 1.11-1.05 (m, 16H), 0.81-0.78 (m, 6H), 0.64 (m, 4H).
Mass spectrum: MALDI-TOF MS:m/z517.3
The preparation method of 9,9-dioctyl fluorene-7-boric acid Knit-the-brows any alcohol ester-2 (thiophene-5-aldehyde):
Take 586mg9,9-dioctyl fluorene-2, which alcohol ester (purchased from Beijing Sheng Weite Science and Technology Ltd.) of 7-hypoboric acid Knit-the-brows and 190mg5-bromothiophene-2-formaldehyde and 100mg tetra--triphenyl phosphorus palladium are placed in the there-necked flask of 100ml, except oxygen leads to nitrogen, then the tetrahydrofuran (THF) that 30ml removed oxygen is injected, and 1ml salt of wormwood (2M) aqueous solution, react after 24 hours, mother liquor is spin-dried for, mix the thick product after silica gel and obtain yellow oily material 9 through chromatographic column separation, 9-dioctyl fluorene-7-boric acid Knit-the-brows any alcohol ester-2 (thiophene-5-aldehyde), productive rate 35%.
Nucleus magnetic hydrogen spectrum:
1h-NMR (400MHz, CDCl
3, 25 DEG C, TMS): δ=9.90 (s, 1H), 7.83 (d, 1H), 7.77-7.75 (m, 3H), 7.71 (d, 1H), 7.66 (d, 1H), 7.62 (s, 1H), 7.47 (d, 1H), 2.04-1.98 (m, 4H), 1.39 (s, 12H), 1.19-1.15 (m, 4H), 1.10-1.03 (m, 16H), 0.80-0.77 (t, 6H), 0.60-0.59 (m, 4H)
Mass spectrum: MALDI-TOF MS:m/z626.
Embodiment 5
The structure of compound 4 and synthesis (R
1=
r
2=H, R
3=R
4=-CH (CH
3)
2)
Take 300mg1-naphthalene boronic acids (purchased from Suzhou Su Kailu chemistry Science and Technology Ltd.) and 1g Diisopropylamine be placed in 50ml single port bottle, add 20ml methylene dichloride as solvent reaction 24h, then reaction mother liquor be spin-dried on a rotary evaporator.The thick product obtained is separated obtain white plates crystal 4 through chromatographic column, productive rate 75%.
Nucleus magnetic hydrogen spectrum
1h-NMR (400MHz, CDCl
3, 25 DEG C, TMS): δ=7.75-7.74 (m, 2H), 7.66 (d, 1H), 7.4 (m, 1H), 7.32 (m, 1H), 7.12 (d, 1H), 7.09 (m, 1H), 5.19 (s, 1H)
Mass spectrum: EI144
Embodiment 6
The structure of compound 5 and synthesis (R
1=
r
2=H, R
3=R
4=-CH (CH
3)
2)
Take 500mg3-pyridine boronic acid (purchased from Suzhou Su Kailu chemistry Science and Technology Ltd.) and 2g Diisopropylamine be placed in 50ml single port bottle, add 25ml methylene dichloride as solvent reaction 72h, then reaction mother liquor be spin-dried on a rotary evaporator.The thick product obtained is separated obtain white crystal 4 through chromatographic column, productive rate 70%.
Nucleus magnetic hydrogen spectrum
1h-NMR (400MHz, CDCl
3, 25 DEG C, TMS): δ=8.31 (d, 1H), 8.10 (d, 1H), 7.33-7.24 (m, 2H), 1.48-1.46 (m, 1H)
Mass spectrum: EI95.
Claims (3)
1. a preparation method for phenolic compound, comprising:
The boron ester of aromatic ring or fragrant heterocycle or boric acid are dissolved in organic solvent, add secondary amine under room temperature, react and be spin-dried for reaction soln after 2-72 hour, chromatographic column is separated and obtains phenolic compound; Wherein organic solvent is the one in ethanol, methylene dichloride, tetrahydrofuran (THF);
Wherein the boron ester of aromatic ring or fragrant heterocycle or the structural formula of boric acid are as shown in (I):
Wherein R
1be selected from group:
in one;
R
2for hydrogen or the group being selected from A21-A30, A32-A37, R
5be selected from group A21-A30, A32-A37:
2. the preparation method of a kind of phenolic compound according to claim 1, is characterized in that: the mol ratio of the boron ester of described aromatic ring or fragrant heterocycle or boric acid and secondary amine is 1:2-50.
3. the preparation method of a kind of phenolic compound according to claim 1, is characterized in that: the structural formula of described secondary amine is as shown in (II):
Wherein R
3with R
4take from group A21-A30, A32-A37 respectively:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310036992.9A CN103113174B (en) | 2013-01-31 | 2013-01-31 | Preparation method of phenolic compounds |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310036992.9A CN103113174B (en) | 2013-01-31 | 2013-01-31 | Preparation method of phenolic compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103113174A CN103113174A (en) | 2013-05-22 |
| CN103113174B true CN103113174B (en) | 2015-02-04 |
Family
ID=48411589
Family Applications (1)
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| CN105085190B (en) * | 2015-08-28 | 2017-01-25 | 中节能万润股份有限公司 | Preparing method of 2,6-difluoro-4-bromophenol |
| CN110668921A (en) * | 2019-08-27 | 2020-01-10 | 温州大学 | Method for preparing alcohol and phenol by aerobic hydroxylation reaction of boric acid derivative under condition of no photocatalyst |
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| Title |
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| A Facile Oxidation of Boronic Acids and Boronic Esters;Kevin S. Webb et al.;《Tetrahedron Letters》;19951231;第36卷(第9期);第5117-5118页 * |
| A mild conversion of arylboronic acids and their pinacolyl boronate esters into phenols using hydroxylamine;Ebrahim Kianmehr et al.;《Tetrahedron Letters》;20070217;第48卷;第2713-2715页 * |
| Highly Efficient Synthesis of Phenols by Copper-Catalyzed Oxidative Hydroxylation of Arylboronic Acids at Room Temperature in Water;Jimin Xu et al.;《Oganic Letters》;20100408;第12卷(第9期);第1964-1967页 * |
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