CN114262263B - Preparation method of 4-iodophenol - Google Patents
Preparation method of 4-iodophenol Download PDFInfo
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- VSMDINRNYYEDRN-UHFFFAOYSA-N 4-iodophenol Chemical compound OC1=CC=C(I)C=C1 VSMDINRNYYEDRN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 20
- 239000011630 iodine Substances 0.000 claims abstract description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006266 etherification reaction Methods 0.000 claims abstract description 18
- 238000006192 iodination reaction Methods 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 238000002444 silanisation Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000006460 hydrolysis reaction Methods 0.000 claims description 31
- 230000007062 hydrolysis Effects 0.000 claims description 18
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 16
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 5
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 claims description 4
- KQIADDMXRMTWHZ-UHFFFAOYSA-N chloro-tri(propan-2-yl)silane Chemical group CC(C)[Si](Cl)(C(C)C)C(C)C KQIADDMXRMTWHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005955 Ferric phosphate Substances 0.000 claims description 3
- KWYZNESIGBQHJK-UHFFFAOYSA-N chloro-dimethyl-phenylsilane Chemical group C[Si](C)(Cl)C1=CC=CC=C1 KWYZNESIGBQHJK-UHFFFAOYSA-N 0.000 claims description 3
- 229940032958 ferric phosphate Drugs 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- MXOSTENCGSDMRE-UHFFFAOYSA-N butyl-chloro-dimethylsilane Chemical group CCCC[Si](C)(C)Cl MXOSTENCGSDMRE-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000005457 ice water Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000006884 silylation reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RKORKXFKXYYHAQ-UHFFFAOYSA-N 2-(4-iodophenoxy)acetic acid Chemical compound OC(=O)COC1=CC=C(I)C=C1 RKORKXFKXYYHAQ-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- 241000282887 Suidae Species 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- DEBPSHDHSJWLHY-UHFFFAOYSA-M potassium;methanol;iodide Chemical compound [K+].[I-].OC DEBPSHDHSJWLHY-UHFFFAOYSA-M 0.000 description 1
- 230000002035 prolonged effect Effects 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
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005475 siliconizing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 4-iodophenol, which comprises the following steps: under the action of N-alkyl imidazole, phenol and a silanization reagent perform a silicon etherification reaction; after the silicon etherification reaction is finished, adding ferric salt and iodine simple substance to carry out iodination reaction; and after the iodination reaction is finished, hydrolyzing and post-treating to obtain the 4-iodophenol. The preparation method of the 4-iodophenol provided by the invention is a one-pot method, the reaction raw materials are easy to obtain, no organic solvent is used in the whole process, the preparation method is environment-friendly and environment-friendly, the raw material utilization rate is high, the yield is high, the operation conditions of each step are mild, and the preparation method is favorable for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 4-iodophenol.
Background
4-Iodophenol is an important organic synthesis intermediate, for example, 4-iodophenol is condensed with chloroacetic acid to obtain p-iodophenoxyacetic acid, and the p-iodophenoxyacetic acid can be used as a plant growth regulator, for fattening pigs and the like.
The existing synthetic method of 4-iodophenol mainly comprises the following steps: (1) Para-aminophenol is taken as a raw material, and 4-iodophenol is produced through diazotization and replacement. (2) Slowly adding an oxidant into the phenylboronic acid and potassium iodide methanol solution, and reacting to obtain the 4-iodophenol. (3) Phenol is used as a raw material, acetyl chloride or methanesulfonyl chloride is used for protecting phenolic hydroxyl, iodine monochloride or iodine simple substance is used as an iodine reagent to carry out iodine in dichloromethane or glacial acetic acid, and then deprotection is carried out under alkaline conditions to obtain the 4-iodophenol.
The method (1) needs to prepare diazonium salt intermediates with active properties and easy decomposition, and has the advantages of complex operation, difficult control, more byproducts, low yield, high three wastes and environmental friendliness; the method (2) and the method (3) have more reaction byproducts, low yield and difficult separation and purification.
Therefore, the preparation method of the 4-iodophenol, which has high yield, simple operation and easy control, is a technical problem to be solved urgently at present.
Disclosure of Invention
In view of the above, the invention provides a preparation method of 4-iodophenol, which is simple to operate, easy to control and high in yield.
In order to achieve the above purpose, the embodiment of the invention adopts the following technical scheme:
a preparation method of 4-iodophenol comprises the following steps:
under the action of N-alkyl imidazole, phenol and a silanization reagent perform a silicon etherification reaction;
after the silicon etherification reaction is finished, directly adding ferric salt and iodine simple substance to carry out iodination reaction;
And after the iodination reaction is finished, hydrolyzing and post-treating to obtain the 4-iodophenol.
The invention aims to solve the technical problems that the existing method for synthesizing 4-iodophenol has the problems of complex operation, difficult control, more byproducts and difficult separation and purification in the preparation process. The current improvement of the synthetic method for 4-iodophenol is limited to optimizing several existing synthetic routes, but has no effect basically: the highest yield can reach about 75%, and an organic solvent is needed in the preparation process.
The invention jumps out of the synthetic thought in the prior art, creatively adopts specific N-alkyl imidazole as an acid-binding agent, promotes the silylation reaction between a silylation agent and hydroxyl in phenol to realize the protection of the hydroxyl in phenol, generates trialkyl silicon-based phenol ether and N-alkyl imidazole hydrochloride after the silylation reaction is finished, reacts with iodine simple substance under the compound action of the N-alkyl imidazole hydrochloride and ferric salt to generate 4-iodotrialkyl silicon-based phenol ether, and the 4-iodotrialkyl silicon-based phenol ether can be obtained after hydrolysis deprotection. The silicon etherification reaction and the iodination reaction do not use organic solvents, the reaction raw materials can be used as solvents, and water added in the hydrolysis step can be used as a reactant or a solvent.
In addition, the preparation method of the 4-iodophenol provided by the invention is a one-pot method, the post-treatment is not needed after the silicon etherification reaction and the iodination reaction are finished, the subsequent reaction is directly carried out, and particularly, if the post-treatment is carried out after the silicon etherification reaction is finished, the yield of the final product 4-iodophenol is greatly reduced. In addition, the reaction raw materials involved in the whole reaction are easy to obtain, and byproducts (aqueous solution containing N-alkyl imidazole hydrochloride and ferric salt) can be subjected to subsequent reaction to prepare other types of ionic liquids, so that new economic benefits are generated. The method has the advantages of high raw material utilization rate, high yield, stable process, simple operation, no use of organic solvent in the whole process and environmental friendliness. Therefore, the invention opens up a brand new reaction route for the synthesis of 4-iodophenol, not only improves the yield and the purity of the product, but also has mild operation conditions, low cost, no waste generation and environmental protection in each step, and is beneficial to industrial production.
The inventor also found through intensive researches that if imidazole or other acid binding agents are adopted to replace N-alkyl imidazole, other trivalent metal salts or divalent metal salts are adopted to replace trivalent ferric salts or other iodine agents are adopted to replace iodine simple substances, the target product 4-iodophenol can not be obtained finally, or the yield of the target product 4-iodophenol is low and can only reach about 60%.
Optionally, the silicon etherification reaction includes the following steps:
a silylating agent is added dropwise to a mixture of N-alkyl imidazole and phenol.
Optionally, the molar ratio of the phenol, the silylating agent and the N-alkyl imidazole is 1 (1-1.1): 1-1.2.
Optionally, the temperature of the silicon etherification reaction is 0-50 ℃.
Optionally, the molar ratio of the phenol, the iodine simple substance and the ferric salt is 1 (0.5-0.55): 0.35-0.5.
Optionally, the temperature of the iodination reaction is 20-50 ℃.
Optionally, the hydrolysis includes the steps of:
water was added to the system after the completion of the iodination reaction.
Optionally, the mass volume ratio of the ferric salt to the water added in the hydrolysis step is 1g (3-5) mL.
Optionally, the temperature of the hydrolysis step is 20-50 ℃.
Optionally, the hydrolysis reaction time is 20-100min.
By limiting the amount of the reaction raw materials, the reaction temperature and other parameters in each step, the reaction yield and the product purity can be further improved, the yield of the 4-iodophenol can be more than 90%, and the purity is more than 99.6%.
Optionally, the silylating agent is at least one of trimethylchlorosilane, triethylchlorosilane, tert-butyldimethylchlorosilane, phenyldimethylchlorosilane and triisopropylchlorosilane;
the N-alkyl imidazole is at least one of N-methyl imidazole, N-ethyl imidazole and N-butyl imidazole;
the ferric salt is at least one of anhydrous ferric trichloride, anhydrous ferric sulfate, anhydrous ferric nitrate and anhydrous ferric phosphate.
Optionally, the post-treatment step comprises filtering and drying;
The drying temperature is 40-60 ℃ and the drying time is 4-6h.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of 4-iodophenol, which comprises the following specific steps:
Under the protection of nitrogen, 188.0g (2.0 mol) of phenol and 196.8g (2.4 mol) of N-methylimidazole are added into a 2000mL three-port bottle, then 238.9g (2.2 mol) of trimethylchlorosilane is dropwise added, the temperature of the system is controlled to be 0-5 ℃ by using an ice water bath, after the dropwise addition, the reaction is continued at the temperature for 1h until the silicon etherification reaction is finished, 193.6g (0.8 mol) of anhydrous ferric nitrate solid and 254.0g (1.0 mol) of iodine simple substance are directly added, the temperature of the system is controlled to be 20-25 ℃ by using the water bath, after the reaction is finished for 4h until the iodination reaction is finished, 600mL of water is directly added into the system, the temperature of the water bath is controlled to be 40-45 ℃ and stirred for 30min until the hydrolysis is complete, 4-iodophenol is continuously separated out in the hydrolysis process, after the hydrolysis reaction is finished, the hydrolysis reaction is dried at 50 ℃ for 6h, and the yield of 404.9g of white-like powder 4-iodophenol is obtained, and the yield is 92.0%, and the purity is 99.64%.
1H-NMR(400MHz,CDCl3)δ(ppm)：4.68(s,1H),6.63(d,J 8.8Hz,2H),7.52(d,J 8.8Hz,2H)；
MS(EI)m/z:[M]220。
Example 2
The embodiment provides a preparation method of 4-iodophenol, which comprises the following specific steps:
under the protection of nitrogen, 188.0g (2.0 mol) of phenol and 192.0g (2.0 mol) of N-ethylimidazole are added into a 2000mL three-port bottle, 302.0g (2.0 mol) of triethylchlorosilane is dropwise added, the temperature of the system is controlled to be 45-50 ℃ by using a water bath, after the dropwise addition, the reaction is continued at the temperature for 1h until the silicon etherification reaction is finished, 110.0g (0.73 mol) of anhydrous ferric phosphate solid and 279.0g (1.1 mol) of iodine simple substance are directly added, the reaction is continued at the temperature for 4h until the iodination reaction is finished, 550mL of water is directly added into the system, the temperature of the water bath is controlled to be 100min at the temperature of 20-25 ℃ until the hydrolysis is complete, 4-iodophenol is continuously separated out in the process of the water bath, the hydrolysis reaction is dried at the temperature of 55 ℃ for 4h, and the white-like powder 4-iodophenol 402.9g is obtained, the yield is 91.6%, and the HPLC purity is 99.72%.
Example 3
The embodiment provides a preparation method of 4-iodophenol, which comprises the following specific steps:
Under the protection of nitrogen, 188.0g (2.0 mol) of phenol and 272.8g (2.2 mol) of N-butylimidazole are added into a 2000mL three-port bottle, then 360.0g (2.1 mol) of phenyl dimethyl chlorosilane is dropwise added, the temperature of the system is controlled to be 20-25 ℃, after the dropwise addition is finished, the reaction is continued for 1h at the temperature until the silicon etherification reaction is finished, 162.0g (1.0 mol) of anhydrous ferric trichloride solid and 270.0g (1.06 mol) of iodine elementary substance are directly added, then the temperature of the system is controlled to be 30-35 ℃ by a water bath, after the iodination reaction is finished, 700mL of water is directly added into the system, the temperature of the system is controlled by the water bath and is stirred for 60min at the temperature of 30-35 ℃ until the hydrolysis is complete, 4-iodophenol is continuously separated out in the hydrolysis process, after the hydrolysis reaction is finished, the HPLC is performed, the product is dried at the temperature of 45 ℃ for 5h, and the yield is 409.1%, and the purity is 99.81%.
Example 4
Under the protection of nitrogen, 188.0g (2.0 mol) of phenol and 196.8g (2.4 mol) of N-methylimidazole are added into a 2000mL three-port bottle, then 331.5g (2.2 mol) of tert-butyldimethyl chlorosilane is added in batches, the temperature of the system is controlled to be 0-5 ℃ by using an ice water bath, after the dropwise addition, the reaction is continued for 1h at the temperature until the siliconizing reaction is finished, 193.6g (0.8 mol) of anhydrous ferric nitrate solid and 254.0g (1.0 mol) of iodine elementary substance are directly added, then the temperature of the system is controlled to be 50 ℃ by using a water bath, after the reaction is finished for 4h at the temperature until the iodination reaction is finished, 600mL of water is directly added into the system, the temperature of the system is controlled by using the water bath and stirred for 30min at 20-25 ℃ until the hydrolysis is complete, 4-iodophenol is continuously separated out in the hydrolysis process, after the hydrolysis reaction is finished, the product is dried for 6h at 60 ℃ to obtain 406.6g of white-like powder, the yield is 92.4-4%, and the purity is 99.65%.
Example 5
The embodiment provides a preparation method of 4-iodophenol, which comprises the following specific steps:
Under the protection of nitrogen, 188.0g (2.0 mol) of phenol and 272.8g (2.2 mol) of N-butylimidazole are added into a 3000mL three-port bottle, then 238.9g (2.2 mol) of trimethylchlorosilane is dropwise added, the temperature of the system is controlled to be 0-5 ℃ by using an ice water bath, after the dropwise addition, the reaction is continued for 1h at the temperature until the silicon etherification reaction is finished, 320.0g (0.8 mol) of anhydrous ferric sulfate solid and 254.0g (1.0 mol) of iodine elementary substance are directly added, then the temperature of the system is controlled to be 20-25 ℃ by using a water bath, after the reaction is finished for 4h at the temperature, 1000mL of water is directly added into the system, the temperature of the water bath is controlled to be stirred for 30min at the temperature of 40 ℃ until the hydrolysis is complete, 4-iodophenol is continuously separated out in the hydrolysis process, after the hydrolysis reaction is finished, the hydrolysis reaction is dried for 6h at the temperature of 40 ℃, 413.2g of white-like powder, the yield is 93.9%, and the purity is 99.77%.
Comparative example 1
The comparative example provides a preparation method of 4-iodophenol, which comprises the following specific steps:
Under the protection of nitrogen, 188.0g (2.0 mol) of phenol and 196.8g (2.4 mol) of N-methylimidazole are added into 2000mL of a three-port bottle, then 238.9g (2.2 mol) of trimethylchlorosilane is dropwise added, the temperature of the system is controlled to be 0-5 ℃ by using an ice water bath, after the dropwise addition, the reaction is continued at the temperature for 1 hour until the silicon etherification reaction is finished, the reaction liquid (400 mL multiplied by 3) after the completion of the reaction is extracted by using methylene dichloride, the organic phases of the methylene dichloride are combined, water washing (100 mL multiplied by 2) is carried out, the organic phases of the methylene dichloride are dried to obtain methylene dichloride solution containing trimethylsiloxybenzene, 193.6g (0.8 mol) of anhydrous ferric nitrate solid, 254.0g (1.0 mol) of iodine simple substance is added into the solution, then 600mL of water is added into the system after the water bath is controlled to reflux the system until the iodination reaction is finished, the obtained concentrate is added with 600mL of water, the aqueous hydrochloric acid solution (200 mL of concentrated hydrochloric acid is dissolved in 400mL of water) is stirred at 40 ℃, the temperature of 30 ℃ until the hydrolysis reaction is finished, the hydrolysis reaction is carried out for 30 ℃ until the crystallization is finished, the water phase is washed by using 3.3 g, the water phase is washed by using a water washing machine, the water phase is washed with 3.3.3.3%, the purity is high-purity is 3.43%, and the product is obtained by HPLC is obtained, and the product is obtained.
Comparative example 2
The comparative example provides a preparation method of 4-iodophenol, which comprises the following specific steps:
under the protection of nitrogen, 188.0g (2.0 mol) of phenol and 189.6g (2.4 mol) of pyridine are added into a 2000mL three-port bottle, then 238.9g (2.2 mol) of trimethylchlorosilane is dropwise added, the temperature of the system is controlled to be 0-5 ℃ by an ice water bath, after the dropwise addition is finished, the reaction is continued at the temperature for 1h until the silicon etherification reaction is finished, 193.6g (0.8 mol) of anhydrous ferric nitrate solid and 254.0g (1.0 mol) of elemental iodine are directly added, then the temperature of the water bath is controlled to be 20-25 ℃, after the reaction is carried out for 4h to the end of the iodination reaction at the temperature, 600mL of water is directly added into the system, the temperature of the water bath is controlled to be stirred for 30min at the temperature of 40-45 ℃ until the hydrolysis is complete, 4-iodophenol is continuously separated out in the hydrolysis process, after the hydrolysis reaction is finished, the hydrolysis reaction is dried at the temperature of 50 ℃ for 6h, 272.8g of white-like powder is obtained, and the yield is 62.0%, and the purity is 94.62%.
Comparative example 3
This comparative example is similar to example 1 except that no anhydrous ferric nitrate solid was added, and no target product 4-iodophenol was detected by heating to 45-50 ℃ and extending the reaction time after the addition of elemental iodine.
Comparative example 4
This comparative example is similar to example 1 except that anhydrous cupric sulfate is used instead of anhydrous ferric nitrate solid, and after the elemental iodine is added, the temperature is raised to 45-50 ℃ and the reaction time is prolonged, and no target product 4-iodophenol is detected.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (2)
1. The preparation method of the 4-iodophenol is characterized by comprising the following steps of:
under the action of N-alkyl imidazole, phenol and a silanization reagent perform a silicon etherification reaction;
after the silicon etherification reaction is finished, directly adding ferric salt and iodine simple substance to carry out iodination reaction;
after the iodination reaction is finished, hydrolyzing and post-treating to obtain the 4-iodophenol;
The molar ratio of the phenol to the silylating agent to the N-alkyl imidazole is 1 (1-1.1), the temperature of the silicon etherification reaction is 0-50 ℃, the molar ratio of the phenol to the iodine simple substance to the ferric salt is 1 (0.5-0.55), the temperature of the iodination reaction is 20-50 ℃, the mass volume ratio of the ferric salt to the water added in the hydrolysis step is 1g (3-5) mL, the temperature of the hydrolysis step is 20-50 ℃, the hydrolysis reaction time is 20-100min, the silylating agent is at least one of trimethylchlorosilane, triethylchlorosilane, tertiary butyl dimethyl chlorosilane, phenyl dimethyl chlorosilane and triisopropylchlorosilane, the N-alkyl imidazole is at least one of N-methylimidazole, N-ethylimidazole and N-butylimidazole, the ferric salt is at least one of anhydrous ferric chloride, anhydrous ferric nitrate and anhydrous ferric phosphate.
2. The method for producing 4-iodophenol according to claim 1, wherein said post-treatment step comprises filtration and drying;
The drying temperature is 40-60 ℃ and the drying time is 4-6h.
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