CN115894178A - High-efficiency catalytic preparation method of high-purity 1,1' -bi-2-naphthol - Google Patents
High-efficiency catalytic preparation method of high-purity 1,1' -bi-2-naphthol Download PDFInfo
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- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 238000004128 high performance liquid chromatography Methods 0.000 claims abstract description 59
- 229950011260 betanaphthol Drugs 0.000 claims abstract description 45
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 239000012043 crude product Substances 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 15
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- 150000004985 diamines Chemical class 0.000 claims abstract description 9
- 238000012544 monitoring process Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 12
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229940045803 cuprous chloride Drugs 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 5
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 claims description 3
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 claims description 3
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 238000010992 reflux Methods 0.000 description 9
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005691 oxidative coupling reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RDMHXWZYVFGYSF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RDMHXWZYVFGYSF-LNTINUHCSA-N 0.000 description 1
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- -1 VO(acac) 2 Copper (II) Schiff base Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a high-efficiency catalytic preparation method of high-purity 1,1' -bi-2-naphthol, which comprises the steps of stirring an organic solvent, 2-naphthol, a solid copper salt and a diamine ligand in a container to form a mixed solution, introducing oxygen-containing gas at the temperature of 40-70 ℃, controlling the flow of the oxygen-containing gas at 100-1000 ml/min, controlling the temperature for reaction, monitoring the reaction progress, and finishing the reaction when the HPLC (high performance liquid chromatography) content of the 2-naphthol is less than 1%; then adding sodium bicarbonate aqueous solution, controlling the temperature at 40-70 ℃, stirring, separating, washing, cooling, crystallizing, filtering to obtain crude product 1,1' -bi-2-naphthol, and then adopting refined solvent to recrystallize. The method has mild reaction conditions, simple and convenient operation and low equipment requirement, and is suitable for industrial production; can effectively promote the high-efficiency circulation of molecular oxygen and realize the high-efficiency preparation of 2-naphthol.
Description
Technical Field
The invention belongs to the field of fine chemical synthesis, and particularly relates to an industrially simple, convenient and feasible high-efficiency catalytic preparation method of high-purity 1,1' -bi-2-naphthol.
Background
1,1'-bi-2-naphthol (1, 1' -bi-2-naphthols, BINOL or binaphthol for short) is a typical chiral compound, has optical activity, and can be split into (R) - (+) BINOL and (S) - (-) BINOL. Which has C 2 The characteristics of asymmetric axis, multiple modification sites, highly stable hand configuration and the like, and the characteristics of molecular or ion recognition and organic electroluminescenceThe field of photoelectric engineering materials such as light, nonlinear optics and the like is widely researched, and the photoelectric engineering material has good application prospect. Meanwhile, the 1,1' -bi-2-naphthol is also an excellent chiral ligand and a chiral auxiliary reagent and is widely applied to asymmetric synthesis reaction.
The existing 1,1' -bi-2-naphthol is generally prepared by an oxidative coupling method of 2-naphthol. The previous main preparation methods have been oxidative coupling of 2-naphthol using various oxidizing agents, e.g. using FeCl 3 、K 3 Fe(CN) 6 、Mn(acac) 3 Cu (II) -amine complex AgCl and FeCl 3 -CuCl、Cu(OAC) 2 As a coupling reagent. These reactions are generally carried out in an organic, aqueous or solid phase using a stoichiometric amount of the oxidizing agent, usually in excess. However, these methods have disadvantages such as the use of expensive oxidizing agents, the production of large amounts of heavy metal wastes, wastewater, and the need for high temperatures for the reaction. In recent years, a plurality of methods for preparing 1,1' -bi-2-naphthol by catalytic oxidative coupling have been developed. Generally with CuCl, cu (OH) 2 、[Cu(NH 3 ) 4 ] 2+ 、[Cu(OH)Cl·(TMEDA)]、CuSO 4 /Al 2 O 3 、CuSO 4 /SiO 2 、FeCl 3 /Al 2 O 3 、FeCl 3 /SiO 2 、VO(acac) 2 Copper (II) Schiff base complex, fe, cu/MCM-41 (mesoporous molecular sieve aluminosilicate) and CuCl-N-alkyl imidazole complex are used as catalysts, and molecular oxygen is used as a main oxidant to realize the oxidative coupling of 2-naphthol. The methods have good use effect and high yield. In addition, there are improved catalytic oxidative coupling methods using molecular oxygen as the oxidant, with copper salts (CuCl, cu (OAc) respectively) 2 ) And a nitrogen-containing polar solvent or a specific copper compound, an anionic surfactant and an alkaline material component catalytic system to realize the oxidative coupling of the 2-naphthol. However, these methods generally require complicated catalyst preparation, complicated synthesis processes, and improvements in catalyst activity and practicality are still required.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the high-efficiency catalytic preparation method of the high-purity 1,1'-bi-2-naphthol, which has the advantages of simplicity, low cost, low equipment requirement, suitability for industrial production, high-efficiency catalytic system and capability of obtaining the 1,1' -bi-2-naphthol product with the electronic chemical grade purity of over 99.9 percent.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a high-efficiency catalytic preparation method of high-purity 1,1' -bi-2-naphthol comprises the following steps:
1) Stirring an organic solvent, 2-naphthol, a solid copper salt and a diamine ligand in a container to form a mixed solution, introducing oxygen-containing gas at the temperature of 40-70 ℃, controlling the flow rate of the oxygen-containing gas at 100-1000 ml/min, controlling the temperature for reaction, monitoring the reaction progress, and finishing the reaction when the HPLC (high performance liquid chromatography) monitoring shows that the content of the 2-naphthol is less than 1%;
2) After the reaction is finished, adding a sodium bicarbonate aqueous solution into the reaction system in the step 1), controlling the temperature at 40-70 ℃, stirring for 0.5-1 h, and then washing, cooling, filtering and drying to obtain a crude product 1,1' -bi-2-naphthol;
3) Recrystallizing the crude product 1,1'-bi-2-naphthol obtained in the step 2) to obtain a product 1,1' -bi-2-naphthol; the mass ratio of the 1,1' -bi-2-naphthol crude product to the recrystallization solvent is =1 (1-15).
The organic solvent is aliphatic alcohol solvent.
The aliphatic alcohol solvent is at least one of methanol, ethanol, isopropanol and n-butanol.
The mass ratio of the 2-naphthol to the organic solvent is =1 (1-10).
The mass ratio of the 2-naphthol, the solid copper salt and the diamine ligand is =100: (1-20): (1-20).
The solid cupric salt is at least one of cuprous chloride, cuprous bromide and cuprous iodide.
The diamine ligand is at least one of ethylenediamine, N-methyl ethylenediamine, N '-dimethyl ethylenediamine, N-dimethyl ethylenediamine, N-ethyl ethylenediamine, N-diethyl ethylenediamine and N, N' -diethyl ethylenediamine.
The oxygen-containing gas in the step 1) is at least one of oxygen, air and oxygen-nitrogen mixed gas.
The concentration of the sodium bicarbonate aqueous solution in the step 2) is 1-5 wt%, and the mass ratio of the 2-naphthol to the sodium carbonate aqueous solution is =1 (0.1-0.5).
The recrystallization solvent in the step 3) is at least one of toluene and xylene in an aromatic hydrocarbon solvent.
Compared with the prior art, the invention has the beneficial effects that:
the method has mild reaction conditions, simple and convenient operation and low equipment requirement, and is suitable for industrial production; the invention adopts diamine ligand and solid copper salt to construct a catalytic system, effectively promotes the high-efficiency circulation of molecular oxygen, and realizes the high-efficiency oxidative coupling of 2-naphthol to prepare 1,1' -bi-2-naphthol; in the treatment process of the reacted crude product, a small amount of byproducts such as polyphenol and the like generated in the reaction process are dissolved in a weak alkali aqueous solution by adding a 2% sodium bicarbonate aqueous solution into the reaction solution, so that the washing and purifying effects are achieved, and the product quality deterioration caused by the byproducts is further improved; the crude product is recrystallized to obtain a product with the purity of more than 99.9 percent, and the high-quality requirement of the electronic chemical grade purity can be met.
Drawings
FIG. 1 is a schematic diagram showing the HPLC analysis results of the product of example 1.
FIG. 2 is a diagram showing the results of HPLC analysis of the product of example 3.
FIG. 3 is a diagram showing the HPLC analysis results of the product of example 4.
FIG. 4 is a diagram showing the results of HPLC analysis of the product of example 6.
FIG. 5 is a graph showing the results of HPLC analysis of the product of comparative example 1.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the present invention is not limited to the following embodiments.
Example 1:
a high-efficiency catalytic preparation method of high-purity 1,1' -bi-2-naphthol comprises the following specific steps:
1) 40g of 2-naphthol, 200g of methanol, 1.37g of solid cuprous chloride and 1.22g of N, N' -dimethylethylenediamine ligand are added into a 500ml four-neck flask with a heating, stirring, refluxing and condensing tube device, stirred and heated to 40 ℃ to dissolve the 2-naphthol, oxygen is introduced, the flow is 300ml/min, the temperature is controlled to be 40-70 ℃ for reaction, the reaction progress is monitored, when the HPLC (high performance liquid chromatography) detects that the HPLC (high performance liquid chromatography) content of the 2-naphthol is less than 1.0 percent, the reaction is stopped, and the reaction time is 8 hours.
2) After the reaction is finished, 20g of 2wt% sodium bicarbonate aqueous solution is added, the temperature is raised to 40-70 ℃, the mixture is stirred for 30min, and the mixture is filtered, washed and dried to obtain 35.2g of 1,1' -bi-2-naphthol crude product, wherein the reaction yield is 88.0%.
3) The crude 1,1' -bi-2-naphthol product is recrystallized by using 320g of dimethylbenzene, and then the temperature is reduced, the crude 1,1' -bi-2-naphthol product is filtered, washed and dried to obtain 31g of white 1,1' -bi-2-naphthol product.
The content of the product is detected by high performance liquid chromatography, the HPLC result is 99.96%, the requirement of electronic chemical grade purity is met, and the specific HPLC analysis result is shown in figure 1.
Example 2:
the high-efficiency catalytic preparation method of the high-purity 1,1' -bi-2-naphthol comprises the following steps:
1) 40g of 2-naphthol, 200g of methanol, 0.82g of solid cuprous chloride and 0.73g of N, N' -dimethyl ethylenediamine ligand are added into a 500ml four-neck flask with a heating, stirring and reflux condenser tube device, the mixture is stirred and heated to 40 ℃ to dissolve the 2-naphthol, oxygen and nitrogen mixed gas (oxygen content is 80 percent) is introduced, the flow is 300ml/min, the temperature is controlled to be 40-60 ℃ for reaction, the reaction progress is monitored, when the HPLC content of the 2-naphthol is detected to be less than 1.0 percent by high performance liquid chromatography, the reaction is stopped, and the reaction time is 16 hours.
2) After the reaction is finished, 20g of 2wt% sodium bicarbonate aqueous solution is added, the temperature is raised to 40-70 ℃, the mixture is stirred for 30min, and the mixture is filtered, washed and dried to obtain 35.6g of 1,1' -bi-2-naphthol crude product, wherein the reaction yield is 89.0%.
3) The crude 1,1'-bi-2-naphthol product was recrystallized from 320g of toluene, cooled, filtered, washed and dried to yield 32.0g of white 1,1' -bi-2-naphthol product.
The content of the product is detected by high performance liquid chromatography, the HPLC result is 99.91 percent, and the requirement of electronic chemical grade purity is met.
Example 3:
the difference from example 1 is that different solid copper salts are used in different amounts.
The high-efficiency catalytic preparation method of the high-purity 1,1' -bi-2-naphthol comprises the following steps:
1) 40g of 2-naphthol, 200g of methanol, 3.98g of solid cuprous bromide and 2.45g of N, N' -dimethyl ethylenediamine ligand are added into a 500ml four-neck flask with a heating, stirring, thermometer and reflux condenser device, the mixture is stirred and heated to 40 ℃ to dissolve the 2-naphthol, oxygen is introduced, the flow is 300ml/min, the temperature is controlled to be 40-70 ℃ for reaction, the reaction progress is monitored, when the HPLC content of the 2-naphthol is detected to be less than 1.0 percent, the reaction is stopped, and the reaction time is 10 hours.
2) After the reaction is finished, 20g of 2wt% sodium bicarbonate aqueous solution is added, the temperature is raised to 40-50 ℃, the mixture is stirred for 30min, and 34g of 1,1' -bi-2-naphthol crude product is obtained after filtration, washing and drying, and the reaction yield is 85%.
3) The crude 1,1'-bi-2-naphthol product was recrystallized from 320g of xylene, cooled, filtered, washed and dried to give 30.2g of white 1,1' -bi-2-naphthol product.
Example 3 the use of solid cuprous bromide as catalyst gave better experimental results, but solid cuprous iodide could also be used instead.
The content of the product is detected by high performance liquid chromatography, the HPLC result is 99.90%, the requirement of electronic chemical grade purity is met, and the specific HPLC analysis result is shown in figure 2.
Example 4:
the difference from example 1 is that the diamine-based ligand and the amount thereof are different.
The high-efficiency catalytic preparation method of the high-purity 1,1' -bi-2-naphthol comprises the following steps:
1) 40g of 2-naphthol, 200g of methanol, 3.98g of solid cuprous bromide and 3.22g of N, N' -diethyl ethylenediamine ligand are added into a 500ml four-neck flask with a heating, stirring, refluxing and condensing tube device, the 2-naphthol is dissolved by stirring and heating to 40 ℃, oxygen is introduced, the flow is 300ml/min, the temperature is controlled to 40-70 ℃ for reaction, the progress of the reaction is monitored for 6 hours, and when the HPLC (high performance liquid chromatography) detects that the HPLC (high performance liquid chromatography) content of the 2-naphthol is less than 1.0 percent, the reaction is stopped, and the reaction time is 9 hours.
2) After the reaction is finished, 20g of 2wt% sodium bicarbonate aqueous solution is added, the temperature is raised to 40-70 ℃, the mixture is stirred for 30min, and then the mixture is filtered, washed and dried to obtain 35g of 1,1' -bi-2-naphthol crude product, wherein the reaction yield is 87.5%.
3) The crude 1,1'-bi-2-naphthol product was recrystallized from 320g of xylene, cooled, filtered, washed and dried to give 30.8g of white 1,1' -bi-2-naphthol product.
Example 4 the use of N, N' -diethylethylenediamine as the ligand gave better experimental results, but instead of ethylenediamine, N-methylethylenediamine, N-dimethylethylenediamine, N-ethylethylenediamine, N-diethylethylenediamine, etc. may be used.
The content of the product is detected by high performance liquid chromatography, the HPLC result is 99.92%, the requirement of electronic chemical grade purity is met, and the specific HPLC analysis result is shown in figure 3.
Example 5:
the high-efficiency catalytic preparation method of the high-purity 1,1' -bi-2-naphthol comprises the following specific steps:
1) Adding 60g of 2-naphthol, 300g of methanol, 2.06g of solid cuprous chloride and 1.83g of N, N' -dimethyl ethylenediamine ligand into a 500ml four-neck flask with a heating, stirring and reflux condenser tube device, stirring and heating to 40 ℃ to dissolve the 2-naphthol, introducing nitrogen-oxygen mixed gas (the oxygen content is 50%), controlling the flow rate to be 500ml/min, reacting at the temperature of 40-70 ℃, monitoring the reaction progress, stopping the reaction when the HPLC (high performance liquid chromatography) detects that the HPLC (high performance liquid chromatography) content of the 2-naphthol is less than 1.0%, and reacting for about 16 hours.
2) After the reaction is finished, 15g of 1wt% sodium bicarbonate water solution is added, the temperature is raised to 40-70 ℃, the mixture is stirred for 30min, filtered, washed and dried to obtain 54.6g of 1,1' -bi-2-naphthol crude product, and the reaction yield is 91%.
3) After the crude product of 1,1'-bi-2-naphthol was recrystallized from 480g of xylene, the temperature was lowered, filtered, washed and dried to obtain 49g of white 1,1' -bi-2-naphthol product.
The oxygen-containing gas used in example 5 was a nitrogen-oxygen mixed gas (oxygen content: 50%) and the experimental results were better, but it may be replaced by air, in which the higher the oxygen concentration in the oxygen-containing gas, the more intense the reaction.
The content of the product is detected by high performance liquid chromatography, the HPLC result is 99.93 percent, and the requirement of electronic chemical grade purity is met.
Example 6:
the high-efficiency catalytic preparation method of the high-purity 1,1' -bi-2-naphthol comprises the following specific steps:
1) Adding 80g of 2-naphthol, 640g of methanol, 5.49g of solid cuprous chloride and 4.89g of N, N' -dimethyl ethylenediamine ligand into a 1000ml four-neck flask with a heating, stirring and reflux condenser tube device, stirring and heating to 40 ℃ to dissolve the 2-naphthol, introducing air at the flow rate of 300ml/min, controlling the temperature to react at 40-70 ℃, monitoring the reaction progress, and stopping the reaction when the HPLC (high performance liquid chromatography) content of the 2-naphthol is detected to be less than 1.0 percent, wherein the reaction time is about 24 hours.
2) After the reaction is finished, 20g of 1wt% sodium bicarbonate aqueous solution is added, the temperature is raised to 40-70 ℃, the mixture is stirred for 30min, and then the mixture is filtered, washed and dried to obtain 72g of 1,1' -bi-2-naphthol crude product, wherein the reaction yield is 90%.
3) After the crude 1,1' -bi-2-naphthol is recrystallized by using 640g of dimethylbenzene, the temperature is reduced, the crude 1,1' -bi-2-naphthol is filtered, washed and dried to obtain 64.1g of white 1,1' -bi-2-naphthol product.
The content of the product is detected by high performance liquid chromatography, the HPLC result is 99.93%, the requirement of electronic chemical grade purity is met, and the specific HPLC analysis result is shown in figure 4.
Example 7:
the high-efficiency catalytic preparation method of the high-purity 1,1' -bi-2-naphthol comprises the following specific steps:
1) Adding 40g of 2-naphthol, 280g of n-butanol, 2.75g of solid cuprous chloride and 2.45g of N, N' -dimethylethylenediamine into a 500ml four-neck flask with a heating and stirring device, a thermometer and a reflux condenser device, stirring and heating to 40 ℃ to dissolve the 2-naphthol, introducing oxygen at the flow rate of 300ml/min, controlling the temperature to 40-70 ℃ for reaction, monitoring the reaction progress, and stopping the reaction when the HPLC (high performance liquid chromatography) detects that the HPLC (high performance liquid chromatography) content of the 2-naphthol is less than 1.0 percent, wherein the reaction time is about 10 hours.
2) After the reaction is finished, 20g of 2wt% sodium bicarbonate aqueous solution is added, the temperature is raised to 40-70 ℃, the mixture is stirred for 30min, the water phase is separated, 40g of water is added into the organic phase, the temperature is kept, the water washing is carried out, the water phase is separated, the organic phase is cooled to 25 ℃, the filtration and the drying are carried out, 36.2g of 1,1' -bi-2-naphthol crude product is obtained, and the reaction yield is 87.5%.
3) The crude 1,1'-bi-2-naphthol was recrystallized from 320g of xylene, cooled, filtered, washed and dried to obtain 32.2g of a white crude 1,1' -bi-2-naphthol.
The content of the product is detected by high performance liquid chromatography, the HPLC result is 99.90%, and the requirement of electronic chemical grade purity is met.
Example 8:
the high-efficiency catalytic preparation method of the high-purity 1,1' -bi-2-naphthol comprises the following specific steps:
1) 40g of 2-naphthol, 280g of methanol, 2.75g of solid cuprous chloride and 2.45g of N, N' -dimethyl ethylenediamine are added into a 500ml four-neck flask with a heating, stirring, thermometer and reflux condenser device, the mixture is stirred and heated to 40 ℃ to dissolve the 2-naphthol, oxygen is introduced, the flow is 300ml/min, the temperature is controlled to be 40-70 ℃ for reaction, the reaction progress is monitored, when the content of the 2-naphthol is detected to be less than or equal to 1.0 percent by high performance liquid chromatography, the reaction is stopped, and the reaction time is about 5 hours.
2) After the reaction is finished, 20g of 5wt% sodium bicarbonate aqueous solution is added, the temperature is raised to 40-70 ℃, the mixture is stirred for 30min, and 34.2g of 1,1' -bi-2-naphthol crude product is obtained after filtration, water washing and drying, and the reaction yield is 85.5%.
3) The crude 1,1'-bi-2-naphthol product was recrystallized from 480g of xylene, then cooled, filtered, washed and dried to obtain 30.5g of white 1,1' -bi-2-naphthol product.
The content of the product is detected by high performance liquid chromatography, the HPLC result is 99.94%, and the requirement of electronic chemical grade purity is met
Comparative example 1:
the high-efficiency catalytic preparation method of the high-purity 1,1' -bi-2-naphthol comprises the following specific steps:
40g of 2-naphthol, 200g of methanol, 1.37g of solid cuprous chloride and 1.22g of N, N' -dimethyl ethylenediamine ligand are added into a 500ml four-neck flask with a heating, stirring, thermometer and reflux condenser device, the mixture is stirred and heated to 40 ℃ to dissolve the 2-naphthol, oxygen is introduced, the flow is 300ml/min, the temperature is controlled to be 40-70 ℃ for reaction, the reaction progress is monitored, when the HPLC content of the 2-naphthol is detected to be less than 1.0 percent, the reaction is stopped, and the reaction time is 8 hours.
After the reaction is finished, 20g of water is added, the temperature is raised to 40-70 ℃, the mixture is stirred for 30min, filtered, washed and dried to obtain 36.6g of 1,1' -bi-2-naphthol crude product, and the reaction yield is 91.5 percent.
3) The crude 1,1'-bi-2-naphthol is recrystallized by using 320g of dimethylbenzene, and then 32.8g of white 1,1' -bi-2-naphthol product is obtained by cooling, filtering, washing and drying.
The content of the product is detected by high performance liquid chromatography, the HPLC result is 99.40%, the requirement of electronic chemical grade purity is not met, and the specific HPLC analysis result is shown in figure 5.
The difference between example 1 and comparative example 1 is that the reaction of example 1 is purified by washing with 2% aqueous sodium bicarbonate solution, while the reaction of comparative example 1 is followed by washing with water. From experimental results, the 2% sodium bicarbonate aqueous solution added in example 1 enables a small amount of byproducts such as polyphenol generated in the reaction to be dissolved and removed, so that the washing and purification effects are achieved, the HPLC content of the 1,1' -bi-2-naphthol product obtained by recrystallizing the crude product is 99.96%, and the requirement of the electronic chemical grade purity is met; the water added in the comparative example 1 has no obvious effect of removing a small amount of by-products such as polyphenol and the like, so that the HPLC content of the 1,1' -bi-2-naphthol product obtained after the crude product is recrystallized is 99.40 percent, and the purity requirement of the electronic chemical grade with the content of more than 99.9 percent is not met.
Claims (10)
1. A high-efficiency catalytic preparation method of high-purity 1,1' -bi-2-naphthol is characterized by comprising the following steps:
1) Stirring an organic solvent, 2-naphthol, a solid copper salt and a diamine ligand in a container to form a mixed solution, introducing oxygen-containing gas at the temperature of 40-70 ℃, controlling the flow rate of the oxygen-containing gas at 100-1000 ml/min, controlling the temperature for reaction, monitoring the reaction progress, and finishing the reaction when the HPLC (high performance liquid chromatography) monitoring shows that the content of the 2-naphthol is less than 1%;
2) After the reaction is finished, adding a sodium bicarbonate aqueous solution into the reaction system in the step 1), controlling the temperature at 40-70 ℃, stirring for 0.5-1 h, and then washing, cooling, filtering and drying to obtain a crude product 1,1' -bi-2-naphthol;
3) Recrystallizing the crude product 1,1'-bi-2-naphthol obtained in the step 2) to obtain a product 1,1' -bi-2-naphthol; the mass ratio of the 1,1' -bi-2-naphthol crude product to the recrystallization solvent is =1 (1-15).
2. The efficient catalytic preparation method of high-purity 1,1' -bi-2-naphthol according to claim 1, wherein the organic solvent is an aliphatic alcohol solvent.
3. The method for preparing high-purity 1,1' -bi-2-naphthol according to claim 2, wherein the aliphatic alcohol solvent is at least one of methanol, ethanol, isopropanol and n-butanol.
4. The efficient catalytic preparation method of high-purity 1,1' -bi-2-naphthol according to claim 1, wherein the mass ratio of 2-naphthol to organic solvent is =1 (1-10).
5. The efficient catalytic preparation method of high-purity 1,1' -bi-2-naphthol according to claim 4, wherein the mass ratio of 2-naphthol, solid copper salt and diamine ligand is =100: (1-20): (1-20).
6. The method for preparing high-purity 1,1' -bi-2-naphthol according to claim 1, wherein the solid copper salt is at least one of cuprous chloride, cuprous bromide and cuprous iodide.
7. The method according to claim 1, wherein the diamine-based ligand is at least one of ethylenediamine, N-methylethylenediamine, N '-dimethylethylenediamine, N-dimethylethylenediamine, N-ethylethylenediamine, N-diethylethylenediamine, and N, N' -diethylethylenediamine.
8. The efficient catalytic preparation method of high-purity 1,1' -bi-2-naphthol according to claim 1, wherein the oxygen-containing gas in step 1) is at least one of oxygen, air and oxygen-nitrogen gas mixture.
9. The high-efficiency catalytic preparation method of high-purity 1,1' -bi-2-naphthol according to claim 1, wherein the concentration of the aqueous sodium bicarbonate solution in step 2) is 1-5 wt%, and the mass ratio of 2-naphthol to the aqueous sodium carbonate solution is =1 (0.1-0.5).
10. The method for efficiently catalytically producing high-purity 1,1' -bi-2-naphthol according to claim 1, wherein the recrystallization solvent in the step 3) is at least one of toluene and xylene in an aromatic hydrocarbon solvent.
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