CN103113174A - Preparation method of phenolic compounds - Google Patents
Preparation method of phenolic compounds Download PDFInfo
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- CN103113174A CN103113174A CN2013100369929A CN201310036992A CN103113174A CN 103113174 A CN103113174 A CN 103113174A CN 2013100369929 A CN2013100369929 A CN 2013100369929A CN 201310036992 A CN201310036992 A CN 201310036992A CN 103113174 A CN103113174 A CN 103113174A
- Authority
- CN
- China
- Prior art keywords
- preparation
- boric acid
- phenolic compound
- boron ester
- secondary amine
- 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
- 150000002989 phenols Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- -1 boron ester Chemical class 0.000 claims abstract description 20
- 239000004327 boric acid Substances 0.000 claims abstract description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 10
- 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 210000005252 bulbus oculi Anatomy 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 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
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 0 Cc(cc1C2(*)*)ccc1-c1c2cccc1 Chemical compound Cc(cc1C2(*)*)ccc1-c1c2cccc1 0.000 description 7
- 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 229940125904 compound 1 Drugs 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
- 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
- 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
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 150000001875 compounds Chemical class 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
- PWJYOTPKLOICJK-UHFFFAOYSA-N Cc(cc1)cc2c1c(cccc1)c1[nH]2 Chemical compound Cc(cc1)cc2c1c(cccc1)c1[nH]2 PWJYOTPKLOICJK-UHFFFAOYSA-N 0.000 description 1
- URUCEYZTJIJMLX-UHFFFAOYSA-N Cc(cc1)cc2c1c(cccc1)c1[s]2 Chemical compound Cc(cc1)cc2c1c(cccc1)c1[s]2 URUCEYZTJIJMLX-UHFFFAOYSA-N 0.000 description 1
- VAUMDUIUEPIGHM-UHFFFAOYSA-N Cc1ccc(C=O)[s]1 Chemical compound Cc1ccc(C=O)[s]1 VAUMDUIUEPIGHM-UHFFFAOYSA-N 0.000 description 1
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N Cc1ccc(cccc2)c2n1 Chemical compound Cc1ccc(cccc2)c2n1 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 1
- TWGNOYAGHYUFFR-UHFFFAOYSA-N Cc1cncnc1 Chemical compound Cc1cncnc1 TWGNOYAGHYUFFR-UHFFFAOYSA-N 0.000 description 1
- OYWUCVHMVXHBFX-UHFFFAOYSA-N Oc1cc2cccc3c2c2c1cccc2cc3 Chemical compound Oc1cc2cccc3c2c2c1cccc2cc3 OYWUCVHMVXHBFX-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
- 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
- 238000002156 mixing Methods 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
- 239000012266 salt solution Substances 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
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 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
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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 of material that extensively is present in nature and important use is arranged in 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 synthetic a lot of organic compound, and in addition, aldehydes matter is also serving as vital stain, the role of dyestuff and medicine.The vital role of aldehydes matter and extensive use have determined its synthetic importance.
The method for preparing phenolic compound commonly used mainly contains the reaction of oxidation aromatic hydrocarbons at present, 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 the standby phenols of diazonium salt legal system, the synthesis step that 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 in reaction, is not suitable for large-scale popularization.In view of above present situation, develop the new method that rapidly and efficiently prepares phenolic compound, can solve a lot of problems in synthetic work.
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 that needs is simple, and productive rate is high, easily separated, purity is high, can be at normal temperatures, adopt usual vehicle to prepare phenolic compound.
The preparation method of a kind of phenolic compound of the present invention comprises:
Boron ester or the boric acid of aromatic ring or fragrant heterocycle are dissolved in organic solvent, add secondary amine under room temperature, react (can carry out degree according to the reaction that TLC shows suitably shortens or extend the reaction times) after 2-72 hour, be spin-dried for reaction soln, the chromatographic column separation namely gets phenolic compound, and the raw material of recovery part; Reaction formula is as shown in (III):
（III）?。
The boron ester of described aromatic ring or fragrant heterocycle or the mol ratio of boric acid and secondary amine are 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):
R wherein
1Be selected from the group of A1-A20:
R
2For hydrogen or be selected from the group of A21-A37, R
5Be selected from group A21-A37:
The structural formula of described secondary amine is as shown in (II):
R wherein
3With R
4Take from respectively group A21-A37:
Described organic solvent is a kind of in methyl alcohol, ethanol, acetone, methylene dichloride, chloroform, toluene, tetrahydrofuran (THF), second eyeball.
The preparation method's of phenolic compound of the present invention reaction formula is:
R wherein
1Represent benzene, naphthalene, anthracene, pyrene, fluorenes connects dinaphthyl, carbazole, quinoline, imidazoles, pyridine, a kind of in the aromatic ring substituting group such as pyrimidine and derivative thereof, R
2, R
3, R
4And R
5Be alkyl substituent, R
2Can also be hydrogen.
The present invention with the boron ester of aromatic ring or fragrant heterocycle or boric acid derivatives as raw material, in room temperature and common solvent with secondary amine as reactant, prepare corresponding phenolic compound.The preparation method is novel, and is simple to operate, and reaction conditions is gentle, and some active groups can keep, and by product is few, and can choose at random boron ester or the synthetic corresponding phenol of boric acid derivatives of different types of aromatic ring or fragrant heterocycle, and universality is stronger.
Beneficial effect:
(1) the boron ester of raw material aromatic ring of the present invention or fragrant heterocycle or boric acid is synthetic simple, can obtain in a large number;
(2) some active function groups can keep in the process of preparation phenol, for example aldehyde radical;
(3) reaction 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, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1 has provided the building-up process of compound 1, embodiment 2 and embodiment 3 have provided respectively the building-up process of compound 2, and embodiment 4, have provided the building-up process of compound 3, embodiment 5 has provided the building-up process of compound 4, and embodiment 6 has provided the building-up process of compound 5.
Embodiment 1
The structure of compound 1 and synthetic (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, which alcohol ester (available from Beijing Sheng Weite Science and Technology Ltd.) of 9-dioctyl fluorene-2-boric acid Knit-the-brows and 505mg Diisopropylamine are put into the single port bottle, add wherein the 20ml methylene dichloride as solvent, react 24h under room temperature, then extraction liquid is spin-dried on Rotary Evaporators.The thick product that obtains separates to get white solid compound 1, productive rate 82% through chromatographic column.
Nucleus magnetic hydrogen spectrum
1H-NMR (400MHz, CDCl
3, 25 ℃, 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
Synthetic (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 and be placed in 50ml single port bottle, add the 20ml methylene dichloride as solvent reaction 24h, then extraction liquid is spin-dried on Rotary Evaporators.The thick product that obtains separates to get pale solid compound 2, productive rate 95% through chromatographic column.
Nucleus magnetic hydrogen spectrum
1H-NMR (400MHz, CDCl
3, 25 ℃, 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:
Under-78 ℃, in the tetrahydrofuran solution of the 1-bromine pyrene of 1.2g, dropwise splash into n-Butyl Lithium (9.5mmol), then drip gradually the 2-isopropoxy-4,4 of 3.6ml, 5,5-tetramethyl--1,3,2-dioxy boron penta ring, at this temperature, reaction is 1 hour, then be warming up to normal temperature and continue reaction 12 hours, with after dichloromethane extraction with the salt solution washing, organic phase is filtered after with dried over mgso, be spin-dried for to separate by chromatographic column and obtain flaxen solid, productive rate 81%.
Nucleus magnetic hydrogen spectrum:
1H NMR (500M, CDCl
3, ppm) 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
Synthetic (the R of compound 2
1=
R
2=H, R
3=R
4=-CH
2CH
3)
Take 1-pyrene boric acid (available from Suzhou subfamily chemical reagent company limited) and 1g diethylamine and be placed in 50ml single port bottle, add 20ml ethanol as solvent reaction 72h, then extraction liquid is spin-dried on Rotary Evaporators.The thick product that obtains separates to get pale solid compound 2, productive rate 91% through chromatographic column.
Nucleus magnetic hydrogen spectrum
1H-NMR (400MHz, CDCl
3, 25 ℃, TMS): δ=8.50-7.62 (m, 9H), 5.64 (s, 1H)
Mass spectrum: EI220
Embodiment 4
Synthetic (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 the 20ml tetrahydrofuran (THF) as solvent, react 24h under room temperature, then mother liquor are spin-dried on Rotary Evaporators.The thick product that obtains separates to get yellow oily material 3, productive rate 83% through chromatographic column.
Nucleus magnetic hydrogen spectrum
1H-NMR (400MHz, CDCl
3, 25 ℃, 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 (available from Beijing Sheng Weite Science and Technology Ltd.) of 7-hypoboric acid Knit-the-brows and 190mg5-bromothiophene-2-formaldehyde and 100mg four-triphenyl phosphorus palladium are placed in the there-necked flask of 100ml, except the logical nitrogen of oxygen, then inject the tetrahydrofuran (THF) that 30ml removed oxygen, and 1ml salt of wormwood (2M) aqueous solution, react after 24 hours, mother liquor is spin-dried for, mixing thick product after silica gel separates through chromatographic column and obtains yellow oily material 9,9-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 ℃, 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 synthetic (R
1=
R
2=H, R
3=R
4=-CH (CH
3)
2)
Take 300mg1-naphthalene boronic acids (available from Suzhou Su Kailu chemistry Science and Technology Ltd.) and 1g Diisopropylamine and be placed in 50ml single port bottle, add the 20ml methylene dichloride as solvent reaction 24h, then reaction mother liquor is spin-dried on Rotary Evaporators.The thick product that obtains separates to such an extent that obtain white plates crystal 4, productive rate 75% through chromatographic column.
Nucleus magnetic hydrogen spectrum
1H-NMR (400MHz, CDCl
3, 25 ℃, 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 synthetic (R
1=
R
2=H, R
3=R
4=-CH (CH
3)
2)
Take 500mg3-pyridine boric acid (available from Suzhou Su Kailu chemistry Science and Technology Ltd.) and 2g Diisopropylamine and be placed in 50ml single port bottle, add the 25ml methylene dichloride as solvent reaction 72h, then reaction mother liquor is spin-dried on Rotary Evaporators.The thick product that obtains separates to such an extent that obtain white crystal 4, productive rate 70% through chromatographic column.
Nucleus magnetic hydrogen spectrum
1H-NMR (400MHz, CDCl
3, 25 ℃, 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 (5)
1. the preparation method of a phenolic compound comprises:
Boron ester or the boric acid of aromatic ring or fragrant heterocycle 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 is namely got phenolic compound.
2. the preparation method of a kind of phenolic compound according to claim 1, it is characterized in that: the boron ester of described aromatic ring or fragrant heterocycle or the mol ratio of boric acid and secondary amine are 1:2-50.
3. the preparation method of a kind of phenolic compound according to claim 1, it is characterized in that: the boron ester of described aromatic ring or fragrant heterocycle or the structural formula of boric acid are as shown in (I):
R wherein
1Be selected from the group of A1-A20:
R
2For hydrogen or be selected from the group of A21-A37, R
5Be selected from group A21-A37:
4. the preparation method of a kind of phenolic compound according to claim 1, it is characterized in that: the structural formula of described secondary amine is as shown in (II):
R wherein
3With R
4Take from respectively group A21-A37:
5. the preparation method of a kind of phenolic compound according to claim 1 is characterized in that: described organic solvent is a kind of in methyl alcohol, ethanol, acetone, methylene dichloride, chloroform, toluene, tetrahydrofuran (THF), second eyeball.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140387A (en) * | 2013-11-29 | 2014-11-12 | 郑州泰基鸿诺药物科技有限公司 | Preparation method for N-tert-butyloxycarboryl-azetidine aromatic ether/aromatic heterocyclic ether compounds |
| CN105085190A (en) * | 2015-08-28 | 2015-11-25 | 中节能万润股份有限公司 | Preparing method of 2,6-difluoro-4-bromophenol |
| JP2016074644A (en) * | 2014-10-08 | 2016-05-12 | 田岡化学工業株式会社 | Diol compound having spirobifluorene skeleton and method for producing the same |
| CN104140387B (en) * | 2013-11-29 | 2016-11-30 | 郑州泰基鸿诺医药股份有限公司 | A kind of preparation method of N-tertbutyloxycarbonyl-azetidine aromatic ether/heteroaromatic ether compound |
| 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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| JPH1025261A (en) * | 1996-07-09 | 1998-01-27 | Chisso Corp | Production of phenol derivative |
| CN1330060A (en) * | 2000-06-26 | 2002-01-09 | 辉瑞产品公司 | Oxidizing of carbon-boron bond |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH1025261A (en) * | 1996-07-09 | 1998-01-27 | Chisso Corp | Production of phenol derivative |
| CN1330060A (en) * | 2000-06-26 | 2002-01-09 | 辉瑞产品公司 | Oxidizing of carbon-boron bond |
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| EBRAHIM KIANMEHR ET AL.: "A mild conversion of arylboronic acids and their pinacolyl boronate esters into phenols using hydroxylamine", 《TETRAHEDRON LETTERS》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140387A (en) * | 2013-11-29 | 2014-11-12 | 郑州泰基鸿诺药物科技有限公司 | Preparation method for N-tert-butyloxycarboryl-azetidine aromatic ether/aromatic heterocyclic ether compounds |
| CN104140387B (en) * | 2013-11-29 | 2016-11-30 | 郑州泰基鸿诺医药股份有限公司 | A kind of preparation method of N-tertbutyloxycarbonyl-azetidine aromatic ether/heteroaromatic ether compound |
| JP2016074644A (en) * | 2014-10-08 | 2016-05-12 | 田岡化学工業株式会社 | Diol compound having spirobifluorene skeleton and method for producing the same |
| CN105085190A (en) * | 2015-08-28 | 2015-11-25 | 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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