CN102180776B - Preparation method for 2-(4-phenoxy phenoxy)ethanol - Google Patents
Preparation method for 2-(4-phenoxy phenoxy)ethanol Download PDFInfo
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- CN102180776B CN102180776B CN 201110033462 CN201110033462A CN102180776B CN 102180776 B CN102180776 B CN 102180776B CN 201110033462 CN201110033462 CN 201110033462 CN 201110033462 A CN201110033462 A CN 201110033462A CN 102180776 B CN102180776 B CN 102180776B
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- oxyethane
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- GFDTXHCIHYNABU-UHFFFAOYSA-N 2-(4-phenoxyphenoxy)ethanol Chemical compound C1=CC(OCCO)=CC=C1OC1=CC=CC=C1 GFDTXHCIHYNABU-UHFFFAOYSA-N 0.000 title abstract 3
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000007046 ethoxylation reaction Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 claims description 46
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001953 recrystallisation Methods 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 28
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012043 crude product Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229930014550 juvenile hormone Natural products 0.000 description 4
- 239000002949 juvenile hormone Substances 0.000 description 4
- 150000003633 juvenile hormone derivatives Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- -1 4-butyl Chemical group 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012280 lithium aluminium hydride Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RGHQKFQZGLKBCF-UHFFFAOYSA-N 2-bromoethyl acetate Chemical compound CC(=O)OCCBr RGHQKFQZGLKBCF-UHFFFAOYSA-N 0.000 description 2
- 150000003862 amino acid derivatives Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000012453 solvate Substances 0.000 description 2
- 150000003527 tetrahydropyrans Chemical class 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 description 1
- CBNLNXLAIMQSTR-UHFFFAOYSA-N 5-ethyl-1h-pyrazole Chemical class CCC1=CC=NN1 CBNLNXLAIMQSTR-UHFFFAOYSA-N 0.000 description 1
- 0 C=*c(cc1)ccc1Oc1ccccc1 Chemical compound C=*c(cc1)ccc1Oc1ccccc1 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 102000003728 Peroxisome Proliferator-Activated Receptors Human genes 0.000 description 1
- 108090000029 Peroxisome Proliferator-Activated Receptors Proteins 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 230000001610 euglycemic effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002218 hypoglycaemic effect Effects 0.000 description 1
- 229930191400 juvenile hormones Natural products 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 208000001072 type 2 diabetes mellitus Diseases 0.000 description 1
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Abstract
The invention relates to a preparation method for 2-(4-phenoxy phenoxy)ethanol. The preparation method comprises the following steps of: performing ethoxylation reaction on paraphenoxy phenol and oxacyclopropane serving as raw materials under the action of an alkaline catalyst to obtain a crude product; and performing aftertreatment processes of recrystallizing, washing, drying and the like to obtain the high-quality 2-(4-phenoxy phenoxy)ethanol product. Compared with the prior art, the preparation method has the advantages of simple process, suitability for industrialization, high yield and stable quality of the product, environmental friendliness and the like.
Description
Technical field
The present invention relates to the phenol derivatives ethoxylation, belong to organic synthesis and fine chemical technology category, be specifically related to the preparation method of a kind of 2-(4-phenoxy group phenoxy group) ethanol.
Background technology
People such as William have reported that it is research (document 1:William S.Bowers, Tucson, the Ariz. of the imitated thing of the further synthesizing pyrazole neotonin of raw material that the preparation of 2-(4-phenoxy group phenoxy group) ethanol reaches with it; Takeyoshi Sugiyama, Sendai, Japan.PYRAZOLE-CONTAINING JUVENILEHORMONE MIMICS FOR PEST CONTROL, COMPOSITIONS AND USE.USP4,943,586. (Jul.24,1990 announce)).In this technology of preparing, use p-phenoxyphenol, in the acetone soln that contains salt of wormwood and 4-butyl amine iodide, with the bromoethyl acetate back flow reaction, handle residual bromoethyl acetate with a small amount of pyridine then, use the extracted with diethyl ether reactant.Extraction liquid obtains oily 2-(4-phenoxy group phenoxy group) ethyl acetate after pickling, washing, alkali cleaning, salt washing, drying and steaming desolventize.The latter with Lithium Aluminium Hydride (LAH) reduction, and successively with ethyl acetate and salt acid treatment, isolates organic phase in ether solvent.Organic phase is washed by salt solution earlier, dried over sodium sulfate, and steaming makes 2-(4-phenoxy group phenoxy group) ethanol (yield 91%) except behind the ether.Be raw material with it then, successively with the reaction of toluene sulfonyl chloride and pyrazoles (PYR alkane), make and contain the imitated thing (sterilant) of pyrazoles neotonin-2-(4-phenoxy group phenoxy group) ethyl pyrazoles (formula II)
Foreign data reported 2-(4-phenoxy group phenoxy group) ethanol with the similar preparation method of document (1), namely earlier make 2-(4-phenoxy group phenoxy group) oxyethyl group tetrahydro-pyrans by p-phenoxyphenol and the condensation of 2-(2-chloroethoxy) tetrahydro-pyrans.Then, the latter handles (acidolysis) with the tosic acid that is dissolved in the methylene dichloride in methanol solvate.Remove after the methyl alcohol, residue is dissolved in methylene dichloride, gained solution is after salt water washing, drying and steaming desolventize, the residue of getting back, the latter separates purification in column chromatography, make target product, its fusing point is that 65-66 ℃ (yield 95%) (sees document (2) Juan B.Rodri guez, Eduardo G.Gros, and Angel M.Stoka, Synthesis and Activity of JuvenileHormone Analogues (JHA), Part II, Z.Naturforsch.44b, 983-987 (1989), Buenos Aires, Argentina.).
Another method of preparation 2-(4-phenoxy group phenoxy group) ethanol that also bibliographical information arranged: in the 250ml three-necked flask, add p-phenoxyphenol 10.0g (54mmol), ethylene chlorhydrin 7.2ml (108mmol), salt of wormwood 7.42g and DMF 60ml, be heated to 125 ℃ of water-bath back flow reaction 20h under stirring, thin-layer chromatography shows and reacts completely.Reaction solution is poured in the water, used ethyl acetate extraction, organic layer washes with water 1 time, 2mol/L salt acid elution 1 time, wash with water again 1 time, anhydrous magnesium sulfate drying, underpressure distillation gets deep yellow oily thing, get pale powder 7.2g, yield 58.3%, m.p.68-70 ℃ with methanol crystallization.(see document (3) Xue Yang, Liu Lanxiang, leaf clear spring, 8 people such as Li Shuxin, novel hypoglycemic medicinal compound glycine derivative synthetic and to the effect research of PPARs, PLA's Acta Pharmaceutica Sinica the 25th the 1st phase of volume of February in 2009,5-10 and document (4) Sun Shuping, Yang Qing, a kind of amino acid derivative and its esters and solvate, their preparation method and application, application for a patent for invention Publication Specification, publication number CN 1966493A, application number 200510123853.5).
According to document announcement, 2-(4-phenoxy group phenoxy group) ethanol can be used as raw material, is mainly used in the manufacturing of fine chemical products such as medicine, agricultural chemicals.As, (see document 1 with its juvenile hormone analogue (JHA) that is raw material has been produced as sterilant, 2,5), produced novel blood sugar lowing medicinal compound-glycine derivative (seeing document 3) and as the amino acid derivative (seeing document 4) of euglycemic agent (type ii diabetes medicine).Document (5): Yamansarova.E.T.; Kukovinets, A.G.; Kukovinets, O.S.; Et al. (Institute ofOrganic Chemistry, Ufa Scientific Center, Russian Academy of Science, Ufa450054, Russia) .synthesis of analogs of juvenile hormones proceeding fromphenol derivatives.Russian Journal of Organic Chemistry (Translation of zhurnalOrganicheskoi Khimii), 37 (2), 246-255 (English).
Domestic existing Shanghai chemical Science and Technology Ltd. of great unit is producing this product, but its manufacturing technology is not appeared in the newspapers.
According to above-mentioned report ( document 1,2,3,4), there are many shortcomings in the existing technology of preparing of this product: 1. synthetic route is long, and trivial operations (needs condensation and reduction two-step reaction process and extraction, washing, distillation, a plurality of post-processing operation processes such as drying) 2. the material toxicity of use is big, dangerous (as acetone, pyridine, ether, Lithium Aluminium Hydride, methylene dichloride etc.) 3. product yield low (document 3 is though 4 adopted the condensation single stage method, but its preparation technology is numerous and diverse, and product yield only is 58.3%).Above prepared in laboratory technology is difficult to industrializing implementation.
Summary of the invention
Purpose of the present invention is exactly to provide in order to overcome the defective that above-mentioned prior art exists that a kind of preparation technology is simple, constant product quality, yield height, be easy to the preparation method of friendly 2-(4-phenoxy group phenoxy group) ethanol of industrializing implementation, environment.
Purpose of the present invention can be achieved through the following technical solutions: the preparation method of a kind of 2-(4-phenoxy group phenoxy group) ethanol is characterized in that this method comprises the steps:
(1) p-phenoxyphenol through melting is added reactor, add catalyzer simultaneously, the mol ratio of catalyzer and p-phenoxyphenol is 0.02-0.04: 1;
(2) material in reactor is being evacuated to-below the 0.09mPa, 80 ℃～90 ℃ were heated 30-60 minute, and removed institute's water content;
(3) make negative pressure in the reactor after vacuumizing, charging into nitrogen to pressure then is 0, so replaces 3 times, and to make the still internal pressure be 0;
(4) under nitrogen atmosphere, oxyethane is progressively added reactor, the control temperature of reaction is 85-105 ℃, keeps reacting kettle inner pressure in the 0.3-0.5mPa scope, the mol ratio of oxyethane and p-phenoxyphenol is 1.0-1.2: 1;
(5) after oxyethane finishes, keep temperature of reaction, make reacting kettle inner pressure be down to 0, and then insulation reaction 20-40 minute, be cooled to 75-85 ℃ after discharging, get thick product;
(6) the thick product of above ethoxylation is carried out aftertreatment, namely carry out recrystallization, alkali cleaning, washing and drying and make finished product.
The purity of described p-phenoxyphenol 〉=99%, oxyethane purity 〉=99%.
Described catalyzer is one or more mixture in inorganic alkali compound or the organo-alkali compound.
Described inorganic alkali compound comprises potassium hydroxide, sodium hydroxide, sodium methylate or sodium ethylate, and described organo-alkali compound comprises triethylamine, Tributylamine or diethylenetriamine.
The solvent that the described recrystallization of step (6) adopts is a kind of in methyl alcohol, ethanol, propyl alcohol and the butanols.
The soda-wash solution that the described alkali cleaning of step (6) is adopted is the aqueous sodium hydroxide solution of 1%-5% massfraction.
The used water of the described washing of step (6) is deionized water.
The temperature of the described drying of step (6) is 60-70 ℃.
The mother liquor that forms after the crystallization solid-liquid separation of the described recrystallization of step (6) returns crystallizer and recycles, and the enrichment mother liquor is after alcoholic solvent is reclaimed in distillation, and last raffinate can be used as boiler oil.
Compared with prior art, the present invention is raw material with p-phenoxyphenol and oxyethane, carries out ethoxylation under the basic catalyst effect, obtains thick product, through last handling processes such as recrystallization, washing, dryings, make high-quality 2-(4-phenoxy group phenoxy group) alcohol product again.The present invention have technology simple, be easy to industrializing implementation, product yield height, steady quality, environment than advantages such as close friends.
Description of drawings
Fig. 1 is technical process and the operation chart of 2-provided by the invention (4-phenoxy group phenoxy group) ethanol preparation method.
Among the figure: 1---the p-phenoxyphenol melter; 2---the oxyethane storage tank; 3---the ethoxylation still; Press with the oxyethane adding wherein with nitrogen, under catalyst action, with the p-phenoxyphenol reaction of melting heating, generate thick product; 4---postprocessing working procedures, thick product makes 2-(4-phenoxy group phenoxy group) alcohol product through recrystallization, alkali cleaning, washing and drying treatment.
Embodiment
The invention will be further described below in conjunction with accompanying drawing.
Embodiment 1
As shown in Figure 1, the preparation method of a kind of 2-(4-phenoxy group phenoxy group) ethanol, this method comprises the steps:
(1) ethoxylation
663g (3.56mol) p-phenoxyphenol through having melted and 6g (0.107mol) potassium hydroxide are added in the 2L stainless steel autoclave; (0.09mPa) heating (80-90 ℃) removed the contained moisture of material in 40 minutes in decompression then; Decompression is also fallen air in the reactor with nitrogen replacement; Progressively add 171g (3.89mol) oxyethane with the nitrogen pressure and carry out ethoxylation, the control temperature of reaction is 85 ± 5 ℃, and the still internal pressure is no more than 0.4mPa.Oxyethane finishes, and the still internal pressure is down to after 0, and insulation reaction is 30 minutes again.Temperature in the kettle is reduced to 75-80 ℃ then, discharging gets thick product 823g.The purity that HPLC records thick product is 94.2%.
(2) recrystallization purifying
With 1296g ethanol with above thick product recrystallization, isolated filter cake is after alkali cleaning (using 2%NaOH solution), washing and drying, obtain white powdery 2-(4-phenoxy group phenoxy group) alcohol product 691g, its HPLC purity is 99.4%, fusing point is 69-70 ℃, yield 84.4% (in p-phenoxyphenol), the yield that mother liquor repeats once to utilize 〉=90%.
The preparation method of a kind of 2-(4-phenoxy group phenoxy group) ethanol, this method comprises the steps:
(1) p-phenoxyphenol (purity of p-phenoxyphenol 〉=99%) through melting is added reactor;
(2) material in reactor is being evacuated to-below the 0.09mPa, 80 ℃～90 ℃ were heated 30 minutes, and removed institute's water content;
(3) with water coolant material in reactor is cooled to 60 ℃, triethylamine is added reactor, the mol ratio of triethylamine and p-phenoxyphenol is 0.02: 1;
(4) make negative pressure in the reactor after vacuumizing, charging into nitrogen to pressure then is 0, so replaces 3 times, and to make the still internal pressure be 0;
(5) under nitrogen atmosphere, oxyethane (oxyethane purity 〉=99%) is progressively added reactor, the control temperature of reaction is 85-105 ℃, keeps reacting kettle inner pressure in the 0.3-0.5mPa scope, the mol ratio of oxyethane and p-phenoxyphenol is 1: 1;
(6) after oxyethane finishes, keep temperature of reaction, make reacting kettle inner pressure be down to 0, and then insulation reaction 20-40 minute, be cooled to 75-85 ℃ after discharging, get thick product;
(7) adopt methyl alcohol to carry out recrystallization to the thick product of above ethoxylation, adopt the aqueous sodium hydroxide solution of 1% massfraction to carry out alkali cleaning, adopt the deionized water washing again as soda-wash solution then, be preferably in 60-70 ℃ of drying and make the adjacent phenyl phenoxyethyl alcohol product with structural formula I
The mother liquor that forms after the crystallization solid-liquid separation of above-mentioned recrystallization returns crystallizer and recycles, and the enrichment mother liquor is after methyl alcohol is reclaimed in distillation, and last raffinate is as boiler oil.
The preparation method of a kind of 2-(4-phenoxy group phenoxy group) ethanol, this method comprises the steps:
(1) p-phenoxyphenol through melting is added reactor, add sodium methylate simultaneously, the mol ratio of sodium methylate and p-phenoxyphenol is 0.04: 1;
(2) material in reactor is being evacuated to-below the 0.09mPa, 80 ℃～90 ℃ were heated 40 minutes, and removed institute's water content;
(3) make negative pressure in the reactor after vacuumizing, charging into nitrogen to pressure then is 0, so replaces 3 times, and to make the still internal pressure be 0;
(4) under nitrogen atmosphere, oxyethane is progressively added reactor, the control temperature of reaction is 85-105 ℃, keeps reacting kettle inner pressure in the 0.3-0.5mPa scope, the mol ratio of oxyethane and p-phenoxyphenol is 1.2: 1;
(5) after oxyethane finishes, keep temperature of reaction, make reacting kettle inner pressure be down to 0, and then insulation reaction 20-40 minute, be cooled to 75-85 ℃ after discharging, get thick product;
(6) adopt methyl alcohol to carry out recrystallization to the thick product of above ethoxylation, adopt the aqueous sodium hydroxide solution of 3% massfraction to carry out alkali cleaning, adopt the deionized water washing again as soda-wash solution then, be preferably in 60-70 ℃ of drying and make finished product.
The mother liquor that forms after the crystallization solid-liquid separation of above-mentioned recrystallization returns crystallizer and recycles, and the enrichment mother liquor is after methyl alcohol is reclaimed in distillation, and last raffinate is as boiler oil.
Claims (9)
1. 2-(4-phenoxy group phenoxy group) preparation method of ethanol is characterized in that this method comprises the steps:
(1) p-phenoxyphenol through melting is added reactor, add catalyzer simultaneously, the mol ratio of catalyzer and p-phenoxyphenol is 0.02-0.04:1;
(2) material in reactor is evacuated to-below the 0.09mPa, 80 ℃ ~ 90 ℃ were heated 30-60 minute, and removed institute's water content;
(3) make negative pressure in the reactor after vacuumizing, charging into nitrogen to pressure then is 0, so replaces 3 times, and to make the still internal pressure be 0;
(4) under nitrogen atmosphere, oxyethane is progressively added reactor, the control temperature of reaction is 85-105 ℃, keeps reacting kettle inner pressure in the 0.3-0.5mPa scope, the mol ratio of oxyethane and p-phenoxyphenol is 1.0-1.2:1;
(5) after oxyethane finishes, keep temperature of reaction, make reacting kettle inner pressure be down to 0, and then insulation reaction 20-40 minute, be cooled to 75-85 ℃ after discharging, get thick product;
(6) the thick product of above ethoxylation is carried out aftertreatment, namely carry out recrystallization, alkali cleaning, washing and drying and make finished product.
2. a kind of 2-(4-phenoxy group phenoxy group according to claim 1) preparation method of ethanol is characterized in that the purity of described p-phenoxyphenol 〉=99%, oxyethane purity 〉=99%.
3. a kind of 2-(4-phenoxy group phenoxy group according to claim 1) preparation method of ethanol is characterized in that, described catalyzer is one or more mixture in inorganic alkali compound or the organo-alkali compound.
4. the preparation method of ethanol a kind of 2-(4-phenoxy group phenoxy group according to claim 3), it is characterized in that, described inorganic alkali compound comprises potassium hydroxide or sodium hydroxide, and described organo-alkali compound comprises triethylamine, Tributylamine, diethylenetriamine, sodium methylate or sodium ethylate.
5. a kind of 2-(4-phenoxy group phenoxy group according to claim 1) preparation method of ethanol is characterized in that, the solvent that the described recrystallization of step (6) adopts is a kind of in methyl alcohol, ethanol, propyl alcohol and the butanols.
6. a kind of 2-(4-phenoxy group phenoxy group according to claim 1) preparation method of ethanol is characterized in that, the soda-wash solution that the described alkali cleaning of step (6) is adopted is the aqueous sodium hydroxide solution of 1%-5% massfraction.
7. a kind of 2-(4-phenoxy group phenoxy group according to claim 1) preparation method of ethanol is characterized in that the used water of the described washing of step (6) is deionized water.
8. a kind of 2-(4-phenoxy group phenoxy group according to claim 1) preparation method of ethanol is characterized in that the temperature of the described drying of step (6) is 60-70 ℃.
9. the preparation method of ethanol a kind of 2-(4-phenoxy group phenoxy group according to claim 1), it is characterized in that, the mother liquor that forms after the crystallization solid-liquid separation of the described recrystallization of step (6) returns crystallizer and recycles, the enrichment mother liquor is after alcoholic solvent is reclaimed in distillation, and last raffinate can be used as boiler oil.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347864A (en) * | 2001-10-15 | 2002-05-08 | 中国科学院大连化学物理研究所 | Synthesis of phenylate alcohol compounds |
| CN1760170A (en) * | 2005-11-09 | 2006-04-19 | 山西大学 | Method for producing p-nitryl phenoxycthanol |
| CN101712600A (en) * | 2008-10-07 | 2010-05-26 | 抚顺佳化聚氨酯有限公司 | Method for preparing ethylene glycol phenyl ether, propylene glycol phenyl ether and butylene glycol phenyl ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347864A (en) * | 2001-10-15 | 2002-05-08 | 中国科学院大连化学物理研究所 | Synthesis of phenylate alcohol compounds |
| CN1760170A (en) * | 2005-11-09 | 2006-04-19 | 山西大学 | Method for producing p-nitryl phenoxycthanol |
| CN101712600A (en) * | 2008-10-07 | 2010-05-26 | 抚顺佳化聚氨酯有限公司 | Method for preparing ethylene glycol phenyl ether, propylene glycol phenyl ether and butylene glycol phenyl ether |
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