CN107522615B - Synthesis method of β -iodoformate compound - Google Patents
Synthesis method of β -iodoformate compound Download PDFInfo
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- CN107522615B CN107522615B CN201710728215.9A CN201710728215A CN107522615B CN 107522615 B CN107522615 B CN 107522615B CN 201710728215 A CN201710728215 A CN 201710728215A CN 107522615 B CN107522615 B CN 107522615B
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 60
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 50
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 50
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 50
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims abstract description 48
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims abstract description 48
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 235000019253 formic acid Nutrition 0.000 claims abstract description 30
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 23
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 114
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical group [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 65
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- 239000003480 eluent Substances 0.000 claims description 60
- 239000002904 solvent Substances 0.000 claims description 59
- 239000007788 liquid Substances 0.000 claims description 54
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 49
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 42
- 238000004440 column chromatography Methods 0.000 claims description 42
- 238000009830 intercalation Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 23
- 230000002687 intercalation Effects 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000012046 mixed solvent Substances 0.000 claims description 21
- 239000000741 silica gel Substances 0.000 claims description 21
- 229910002027 silica gel Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000003208 petroleum Substances 0.000 claims description 20
- -1 styrene compound Chemical class 0.000 claims description 19
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 4
- 229940107816 ammonium iodide Drugs 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 229920001684 low density polyethylene Polymers 0.000 abstract 1
- 239000004702 low-density polyethylene Substances 0.000 abstract 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 68
- 239000000243 solution Substances 0.000 description 21
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 238000012512 characterization method Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- 239000012071 phase Substances 0.000 description 17
- 238000001704 evaporation Methods 0.000 description 16
- 239000005416 organic matter Substances 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a synthesis method of β -iodoformate compounds shown in formula II, which takes styrene compounds shown in formula I as raw materials and zinc-aluminum hydrotalcite ZnAl-BrO intercalated with bromate radicals3 ‑The method comprises the following steps of reacting LDHs (low density polyethylene) serving as an oxidant and iodide serving as a reducing agent in formic acid at 15-60 ℃ for 1-6 hours, and then carrying out aftertreatment on the obtained reaction liquid to obtain β -iodoformate compounds shown in a formula II.
Description
(I) technical field
The invention relates to a synthetic method of an organic compound, in particular to a synthetic method of β -iodoformate compounds.
(II) background of the invention
The ortho-position double-functionalization reaction of the carbon-carbon double bond is an important reaction in the field of organic chemistry, particularly β -iodoformate compounds are important reaction intermediates in organic synthesis and can be subjected to various conversions to obtain drug molecules and active natural products.
Currently, few methods for synthesizing β -bromoformate are reported at home and abroad, and mainly include (1) the synthesis of β -bromoformate compounds from elemental iodine and N, N-dimethylformamide and styrene compounds (see Prasad PK, Reddi R N, Sudalai a.chemical Communications,2015,51(51):10276.), which is low in yield and causes great environmental pollution by the elemental iodine, (2) the synthesis of β -iodoformate compounds from ammonium iodide and potassium hydrogen persulfate composite salts and styrene compounds in the presence of N, N-dimethylformamide (see Durgaiah C, Naresh M, Kumar MA, et al synthetic Communications,2016 (13)), which uses N, N-dimethylformamide, and thus the post-treatment process after the reaction is complicated, thus increasing the difficulty of product separation and analysis.
In view of the above problems, it is necessary to design a new method for synthesizing β -iodoformate compounds, which has good atomic economy, simple operation, low toxicity and environmental friendliness.
Disclosure of the invention
In order to solve the problems of high toxicity, environmental pollution, high cost and the like in the conventional method for synthesizing β -iodate compounds, the invention provides a preparation method of β -iodoformate compounds, and the synthetic method of the invention overcomes the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
takes styrene compound shown in formula I as raw material, zinc-aluminum hydrotalcite ZnAl-BrO with bromate radical intercalation3 -LDHs is an oxidant, iodide is a reducing agent, the mixture reacts in formic acid at 15-60 ℃ for 1-6 hours, the obtained reaction liquid is subjected to post-treatment to obtain β -iodoformate compounds shown in formula II, and the zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is3 -The mass of the LDHs is 0.35-0.55 g/mmol based on the mass of the styrene compound shown in the formula I; the volume usage amount of the formic acid is 4-8 mL/mmol based on the amount of the styrene compound shown in the formula I; the mass ratio of the iodide to the styrene compound represented by the formula I is 1-2: 1;
formula I or formula II:
1 3 3and R is one of H, -CH, -O-C (═ O) -CH, Br or Cl.
Further, the iodide is potassium iodide, sodium iodide, lithium iodide or ammonium iodide, preferably potassium iodide.
Further, the reaction temperature is preferably 25 ℃ and the reaction time is preferably 3 hours.
Furthermore, the zinc-aluminum hydrotalcite with the bromate intercalation ZnAl-BrO is preferably selected3 -The mass of the LDHs is 0.4g/mmol based on the amount of the styrene compound represented by the formula I.
Further, it is preferable that the mass ratio of the iodide to the styrene-based compound represented by the formula I is 1.1: 1.
further, the volume usage of the formic acid is preferably 5mL/mmol based on the amount of the substance of the styrene compound represented by the formula I.
After the reaction is finished, centrifuging the obtained reaction liquid to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, combining organic phases, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by column chromatography, collecting eluent containing the target product by taking a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the solvent from the eluent to obtain the β -iodoformate compound shown in the formula II.
Furthermore, the synthesis method provided by the invention is recommended to be specifically carried out according to the following steps:
takes styrene compound shown in formula I as raw material, zinc-aluminum hydrotalcite ZnAl-BrO with bromate radical intercalation3 -LDHs is used as an oxidant, potassium iodide is used as a reducing agent, the mixture reacts in formic acid at 25 ℃ for 3 hours, after the reaction is finished, the obtained reaction liquid is centrifuged to remove zinc-aluminum hydrotalcite solid, the obtained liquid is placed in a separating funnel, dichloromethane and deionized water are added, organic phases are combined, column chromatography silica gel is added into the obtained solution, the solvent is removed by reduced pressure distillation, the residual mixture is separated by column chromatography, a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 is used as an eluent, the eluent containing the target product is collected, and the solvent is removed by evaporation to obtain β shown in formula II-iodoformate compounds; the zinc-aluminum hydrotalcite with the bromate intercalation ZnAl-BrO3 --the mass of LDHs is 0.4g/mmol, based on the mass of the styrenic compound represented by formula I; the volume usage amount of the formic acid is 5mL/mmol based on the amount of the substances of the styrene compound shown in the formula I; the mass ratio of the potassium iodide to the styrene compound shown in the formula I is 1.1: 1.
compared with the prior art, the invention has the beneficial effects that:
(1) the formic acid used in the invention not only provides an acidic chemical reaction environment, but also is directly used as a nucleophilic reagent for addition esterification, belongs to an atomic economic reaction, and fully exerts the acidity, solubility and nucleophilicity of the formic acid.
(2) The iodine source is simple and easy to obtain, the reaction condition is mild, the environment is friendly, the operation is simple, and the yield of the target product is high.
(IV) detailed description of the preferred embodiments
The invention will be further illustrated by the following examples, without limiting the scope of the invention:
the zinc-aluminum hydrotalcite with bromate intercalation ZnAl-BrO used in the invention3 -LDHs, which can be prepared by the person skilled in the art on their own in accordance with the methods disclosed in the prior art (Wangli Plough, Zhenghang, Jianchenxing, Nizhen Ming. silicate science 2015, 43 (5): 672 and 677.). (the scope of the invention is not limited thereto)
Weighing 7.55g NaBrO3The prepared solution was added to a four-necked flask in an amount of 100mL as a base solution. 29.75g Zn (NO) are weighed out3)2∙6H2O and 18.75g Al (NO)3)3∙9H20 was prepared as 200mL of mixed salt solution. 12.00g NaOH was weighed out to prepare 200mL of lye. Slowly dripping the mixed salt solution and the alkali liquor into a four-neck flask by adopting a double-dripping method, strongly stirring at normal temperature (1000r/min), adjusting the dripping speed, keeping the pH value to be 7.0+0.2, and continuously stirring for 0.5h after dripping. Crystallizing the obtained slurry at 70 deg.C for 24h, filtering, washing, drying at 60 deg.C for 18h, and grinding to obtain ZnAl-BrO3 --LDHs。
Example 1
2mmol (0.208g) of styrene and 2.2mmol (0.3652g) of potassium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and then 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 25 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by using a column chromatography method, collecting eluent containing the product by using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the eluent to remove the solvent to obtain a pure product. The material was a pale yellow liquid in 86% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.1Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculatedfor C9H9IO2(M+H)+276.9725,found 276.9727.
Example 2
2mmol (0.366g) of 4-bromostyrene and 2.2mmol (0.3652g) of potassium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 50 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, and placing the obtained liquid in a liquid separation drainAdding dichloromethane and deionized water into a bucket, extracting the organic matters obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by column chromatography, collecting eluent containing the product by taking a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the eluent to remove the solvent to obtain the pure product. The material was a pale yellow liquid in 87% yield.
Characterization data: yellow solid, melting point: 51-53 ℃.1H NMR(500MHz,CDCl3)δ8.14(s,1H),7.54–7.52(m,2H),7.27–7.25(m,2H),5.96–5.93(m,1H),3.48(qd,J＝10.7,6.5Hz,2H)；13C NMR(126MHz,CDCl3)δ159.41,136.76,131.98,128.19,123.09,74.36,6.31；HRMS(ESI,m/s):Calculated for C9H8BrIO2(M+H)+254.8831,found 254.8829.
Example 3
2mmol (0.277g) of 4-chlorostyrene and 2.2mmol (0.3652g) of potassium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 50 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by using a column chromatography method, collecting eluent containing the product by using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the eluent to remove the solvent to obtain a pure product. The material was a light yellow liquid in 82% yield.
Characterization data: yellow solid, melting point: 52-53 ℃.1H NMR(500MHz,CDCl3)δ8.14(s,1H),7.38(dd,J＝8.3,1.4Hz,2H),7.32(d,J＝8.5Hz,2H),5.98–5.95(m,1H),3.48(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.42,136.25,134.92,129.02,127.91,74.32,6.41；HRMS(ESI,m/s):Calculated for C9H8ClIO2(M+H)+310.9336,found 310.9335.
Example 4
2mmol (0.324g) of 4-acetoxystyrene and 2.2mmol (0.3652g) of potassium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 25 ℃ for 4 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by using a column chromatography method, collecting eluent containing the product by using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the eluent to remove the solvent to obtain a pure product. The material was a pale yellow liquid in 85% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.14(s,1H),7.41–7.38(m,2H),7.14–7.11(m,2H),6.01(dd,J＝8.0,5.2Hz,1H),3.51(dd,J＝10.7,8.1Hz,1H),3.47(dd,J＝11.0,5.4Hz,1H),2.31(s,3H)；13C NMR(126MHz,CDCl3)δ169.16,159.48,151.00,135.26,127.68,121.97,74.48,21.10,6.56；HRMS(ESI,m/s):Calculated for C11H11IO4(M+H)+334.9780,found 334.9783.
Example 5
Will 2mmol (0.208g) of styrene and 2.0mmol (0.3320g) of potassium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and then 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 25 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by using a column chromatography method, collecting eluent containing the product by using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the eluent to remove the solvent to obtain a pure product. The material was a light yellow liquid in 84% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.1Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculatedfor C9H9IO2(M+H)+276.9725,found 276.9727.
Example 6
2mmol (0.208g) of styrene and 4.0mmol (0.6640g) of potassium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and then 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 25 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, removing the solvent by reduced pressure distillation, separating the residual mixture by using a column chromatography method, and separating the mixture by using stoneAnd (3) taking a mixed solvent of the oil ether and the ethyl acetate in a volume ratio of 10:1 as an eluent, collecting the eluent containing the product, and evaporating the solvent from the eluent to obtain a pure product. The material was a pale yellow liquid with 85.8% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.1Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculatedfor C9H9IO2(M+H)+276.9725,found 276.9727.
Example 7
2mmol (0.208g) of styrene and 2.2mmol (0.3652g) of potassium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and then 0.70g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 25 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by using a column chromatography method, collecting eluent containing the product by using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the eluent to remove the solvent to obtain a pure product. The material was a pale yellow liquid in 71% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.1Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculatedfor C9H9IO2(M+H)+276.9725,found 276.9727.
Example 8
2mmol (0.208g) of styrene and 2.2mmol (0.3652g) of potassium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and 1.1g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 25 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by using a column chromatography method, collecting eluent containing the product by using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the eluent to remove the solvent to obtain a pure product. The material was a pale yellow liquid in 86% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.1Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculatedfor C9H9IO2(M+H)+276.9725,found 276.9727.
Example 9
2mmol (0.208g) of styrene and 2.2mmol (0.3652g) of potassium iodide are added into a 50mL three-necked flask, 8.0mL of formic acid is added as a solvent, and 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 25 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, the obtained reaction liquid is centrifuged by a centrifugal machine 6500r/min to remove zinc and aluminumPutting the obtained liquid of the hydrotalcite solid into a separating funnel, adding dichloromethane and deionized water, extracting the organic matters obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, carrying out reduced pressure distillation to remove the solvent, separating the residual mixture by column chromatography, collecting the eluent containing the product by taking a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and distilling the eluent to remove the solvent to obtain the pure product. The material was a light yellow liquid in 80% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.1Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculatedfor C9H9IO2(M+H)+276.9725,found 276.9727.
Example 10
2mmol (0.208g) of styrene and 2.2mmol (0.3652g) of potassium iodide are added into a 50mL three-necked flask, 16mL of formic acid is added as a solvent, and then 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 25 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by using a column chromatography method, collecting eluent containing the product by using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the eluent to remove the solvent to obtain a pure product. The material was a pale yellow liquid with 85.7% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.1Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculatedfor C9H9IO2(M+H)+276.9725,found 276.9727.
Example 11
2mmol (0.208g) of styrene and 2.2mmol (0.3652g) of potassium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and then 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 15 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by using a column chromatography method, collecting eluent containing the product by using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the eluent to remove the solvent to obtain a pure product. The material was a light yellow liquid in 80% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.1Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculatedfor C9H9IO2(M+H)+276.9725,found 276.9727.
Example 12
2mmol (0.208g) of styrene and 2.2mmol (0.3652g) of potassium iodide were placed in a 50mL three-necked flaskThen 10mL of formic acid is added as a solvent, and 0.8g of bromate intercalated zinc-aluminum hydrotalcite ZnAl-BrO is added3 -LDHs, magnetically stirred at 60 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by using a column chromatography method, collecting eluent containing the product by using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the eluent to remove the solvent to obtain a pure product. The material was a pale yellow liquid in 83% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.1Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculatedfor C9H9IO2(M+H)+276.9725,found 276.9727.
Example 13
2mmol (0.208g) of styrene and 2.2mmol (0.3652g) of potassium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and then 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3LDHs, magnetically stirred at 25 ℃ for 1 hour, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by using a column chromatography method, taking a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and collecting the productThe eluent is evaporated to remove the solvent to obtain the pure product. The material was a light yellow liquid in 70% yield.
Characterization data: a yellow oily liquid.1H NMR(500 MHz,CDCl3)δ8.17(d,J＝7.1 Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7 Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculated for C9H9IO2(M+H)+276.9725,found 276.9727.
Example 14
2mmol (0.208g) of styrene and 2.2mmol (0.3652g) of potassium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and then 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 25 ℃ for 6 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by using a column chromatography method, collecting eluent containing the product by using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the eluent to remove the solvent to obtain a pure product. The material was a pale yellow liquid in 85% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.1Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculatedfor C9H9IO2(M+H)+276.9725,found 276.9727.
Example 15
2mmol (0.208g) of styrene and 2.2mmol (0.1909g) of lithium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 25 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by using a column chromatography method, collecting eluent containing the product by using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the eluent to remove the solvent to obtain a pure product. The material was a light yellow liquid in 84% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.1Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculatedfor C9H9IO2(M+H)+276.9725,found 276.9727.
Example 16
2mmol (0.208g) of styrene and 2.2mmol (0.2264g) of sodium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and then 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 25 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, and reactingExtracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by column chromatography, collecting eluent containing the product by taking a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and distilling the eluent to remove the solvent to obtain the pure product. The material was a pale yellow liquid in 85% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.1Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculatedfor C9H9IO2(M+H)+276.9725,found 276.9727.
Example 17
2mmol (0.208g) of styrene and 2.2mmol (0.3190g) of ammonium iodide are added into a 50mL three-necked flask, 10mL of formic acid is added as a solvent, and 0.8g of zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is added3 -LDHs, magnetically stirred at 25 ℃ for 3 hours, followed by TLC for completion of the reaction. After the reaction is finished, centrifuging the obtained reaction liquid by using a centrifugal machine 6500r/min to remove zinc-aluminum hydrotalcite solid, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, extracting the organic matter obtained by the reaction into a dichloromethane phase, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by using a column chromatography method, collecting eluent containing the product by using a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 as an eluent, and evaporating the eluent to remove the solvent to obtain a pure product. The material was a pale yellow liquid in 85% yield.
Characterization data: a yellow oily liquid.1H NMR(500MHz,CDCl3)δ8.17(d,J＝7.1Hz,1H),7.41–7.37(m,5H),6.02(dd,J＝7.7,5.5Hz,1H),3.52(qd,J＝10.7,6.7Hz,2H)；13C NMR(126MHz,CDCl3)δ159.56,137.78,128.99,128.77,126.44,75.10,6.87；HRMS(ESI,m/s):Calculatedfor C9H9IO2(M+H)+276.9725,found 276.9727.
Claims (8)
1. A synthesis method of β -iodoformate compounds shown in formula II is characterized by comprising the following steps:
takes styrene compound shown in formula I as raw material, zinc-aluminum hydrotalcite ZnAl-BrO with bromate radical intercalation3 -LDHs is an oxidant, iodide is a reducing agent, the mixture reacts in formic acid at 15-60 ℃ for 1-6 hours, the obtained reaction liquid is subjected to post-treatment to obtain β -iodoformate compounds shown in formula II, and the zinc-aluminum hydrotalcite ZnAl-BrO with bromate intercalation is3 -The mass of the LDHs is 0.35-0.55 g/mmol based on the mass of the styrene compound shown in the formula I; the volume usage amount of the formic acid is 4-8 mL/mmol based on the amount of the styrene compound shown in the formula I; the mass ratio of the iodide to the styrene compound represented by the formula I is 1-2: 1; the iodide is potassium iodide, sodium iodide, lithium iodide or ammonium iodide;
formula I or formula II:
R1is H, -CH3、-O-C(＝O)-CH3Br or Cl.
2. The method of claim 1, wherein: the iodide is potassium iodide.
3. The method of claim 1, wherein: the reaction temperature is 25 ℃, and the reaction time is 3 h.
4. The method of claim 1, wherein: the bromic acidZinc-aluminum hydrotalcite ZnAl-BrO with root intercalation3 -The mass of the LDHs is 0.4g/mmol based on the amount of the styrene compound represented by the formula I.
5. The method of claim 1, wherein: the mass ratio of the iodide to the styrene compound represented by the formula I is 1.1: 1.
6. the method of claim 1, wherein: the volume usage of the formic acid is 5mL/mmol based on the amount of the substance of the styrene compound shown in the formula I.
7. The method as claimed in claim 1, wherein the post-treatment of the reaction solution comprises centrifuging the obtained reaction solution after the reaction is finished to remove the solid zinc-aluminum hydrotalcite, placing the obtained liquid in a separating funnel, adding dichloromethane and deionized water, combining organic phases, adding column chromatography silica gel into the obtained solution, distilling under reduced pressure to remove the solvent, separating the residual mixture by column chromatography, collecting the eluent containing the target product by using a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 10:1 as an eluent, and distilling off the solvent by the eluent to obtain the β -iodoformate compound shown in formula II.
8. The method of claim 1, wherein: the synthesis method is specifically carried out according to the following steps:
takes styrene compound shown in formula I as raw material, zinc-aluminum hydrotalcite ZnAl-BrO with bromate radical intercalation3 -LDHs is used as an oxidant, potassium iodide is used as a reducing agent, the mixture reacts in formic acid at 25 ℃ for 3 hours, after the reaction is finished, the obtained reaction liquid is centrifuged to remove zinc-aluminum hydrotalcite solid, the obtained liquid is placed in a separating funnel, dichloromethane and deionized water are added, organic phases are combined, column chromatography silica gel is added into the obtained solution, the solvent is removed by reduced pressure distillation, the residual mixture is separated by column chromatography, a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 10:1 is used as an eluent, and the mixture containing the target compounds is collectedThe eluent is evaporated to remove the solvent to obtain β -iodoformate compounds shown in formula II, and the zinc-aluminum hydrotalcite with bromate intercalation is ZnAl-BrO3 --the mass of LDHs is 0.4g/mmol, based on the mass of the styrenic compound represented by formula I; the volume usage amount of the formic acid is 5mL/mmol based on the amount of the substances of the styrene compound shown in the formula I; the mass ratio of the potassium iodide to the styrene compound shown in the formula I is 1.1: 1.
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