CN109180474A - A method of synthesis Beta-bromo acetate compounds - Google Patents
A method of synthesis Beta-bromo acetate compounds Download PDFInfo
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- 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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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Abstract
The invention discloses a kind of preparation methods of Beta-bromo acetate compounds, using styrene compound shown in Formulas I as raw material, with the zinc-aluminum hydrotalcite ZnAl-BrO of bromate intercalation3 ‑- LDHs and alkali metal bromide are bromine source, in organic solvent, react 1~6 hour in 15~60 DEG C, obtain reaction solution after reaction, post-treated to obtain Beta-bromo acetate compounds shown in Formula II.Synthetic method of the invention has bromine source stability good, simple and easy to get, and solvent not only provides acidic chemical reaction environment, while the nucleopilic reagent as synthesis target product, and reaction condition is mild, environmental-friendly, simple operation and other advantages.
Description
(1) technical field
The present invention relates to a kind of synthetic methods of organic compound, and in particular to a kind of Beta-bromo acetate compounds
Synthetic method.
(2) background technique
Beta-bromo acetic acid esters and its derivative are a kind of important fine chemical materials and intermediate, are widely used in curing
Medicine, dyestuff, a variety of industrial chemicals such as polymer especially have vast potential for future development in study of pharmacy field.It is synthesis antidepression
The important source material of medicine fluphenazine, emetic lycorine, antibacterial agent and spectrum antibiotic can also prepare muscarine M3 receptor Gao Xuan
Selecting property antibody drug, purposes are very extensive.
Currently, the synthetic method for the related Beta-bromo acetic acid esters reported both at home and abroad is mainly the following method: 1. are dividing
In the presence of son sieve and N-bromosuccinimide, make the acetyl bromide oxygroup of alkene, prepares Beta-bromo acetate compounds (ginseng
See Chen F, Jiang XJ, Er JC, et al.Tetrahedron Letters, 2010,51 (26): 3433-3435.).2.
Use NH4Br and oxone prepares Beta-bromo acetic acid esters to the regioselectivity and stereoselectivity acetyl bromide oxygroup of alkene
Class compound is (referring to Naresh M, Swamy P, Kumar M A, et al. Cheminform, 2014,55 (29): 3926-
3933.).3.DABCO (1,4- diazabicyclo [2.2.2] octane) catalyzed alkene and N- halosuccinimides and acetic acid
Intermolecular esterification prepares Beta-bromo acetate compounds (referring to Pimenta L S, Gusevskaya E, Alberto
E.Advanced Synthesis&Catalysis,2017,359(13).)。
So far, the raw material and method for synthesizing Beta-bromo acetate compounds are existing very much, but many methods are all deposited
In certain deficiency.Therefore a kind of new, effective method is developed to synthesize β-bromine formic ether compounds be very necessary.
(3) summary of the invention
To solve in the method for synthesis Beta-bromo acetate compounds at present there is bromine source stability is poor, toxicity is big,
Condition is harsh, poor selectivity, pollute environment and it is at high cost the problems such as, the invention proposes a kind of Beta-bromo acetate compounds
Synthetic method.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A kind of synthetic method of Beta-bromo acetate compounds, the method specifically carry out in accordance with the following steps:
Styrene compound shown in Formulas I is raw material, with the zinc-aluminum hydrotalcite ZnAl-BrO of bromate intercalation3 -- LDHs and
Alkali metal bromide is bromine source, in organic solvent, reacts 1~6 hour in 15~60 DEG C, obtains reaction solution after reaction,
It is post-treated to obtain Beta-bromo acetate compounds shown in Formula II；The zinc-aluminum hydrotalcite ZnAl- of the bromate intercalation
BrO3 -The quality of-LDHs is calculated as 0.35~0.75g/mmol with the amount of the substance of styrene compound shown in Formulas I；Described
The amount of the substance of alkali metal bromide is calculated as 0.8~1.35mmol/ with the amount of the substance of styrene compound shown in Formulas I
Mmol,
Reaction formula is as follows:
In the Formulas I or Formula II,
R1For one of hydrogen, methyl, tert-butyl, acetoxyl group, bromine or chlorine；
R2For one of hydrogen, methyl, methylol, carboxyl, phenyl or methyl formate base.
Further, the R1Preferably hydrogen or methyl；The R2Preferably hydrogen, methyl or phenyl.
The zinc-aluminum hydrotalcite ZnAl-BrO for the bromate intercalation that the present invention uses3 -- LDHs, those skilled in the art can roots
According to existing literature (Wang Ligeng, Zheng Feixiang, Jiang Chenxing, Ni Zheming.Silicate journal, 2015,43 (5): 672-677.) disclosure side
Method is voluntarily prepared.(the scope of protection of the present invention is not limited to this)
Further, it is preferred that the zinc-aluminum hydrotalcite ZnAl-BrO of the bromate intercalation3 -The quality of-LDHs is with Formulas I
Shown in the amount of substance of styrene compound be calculated as 0.4g/mmol.
Further, the alkali metal bromide is potassium bromide, sodium bromide or lithium bromide, preferably potassium bromide.
Further, it is preferred that the amount of the substance of the alkali metal bromide is with styrene compound shown in Formulas I
The amount of substance be calculated as 1.1mmol/mmol.
Further, the organic solvent is acetic acid.
Further, the volume of the organic solvent be calculated as 8 with the amount of the substance of styrene compound shown in Formulas I~
12mL/mmol, preferably 10mL/mmol.
Reaction temperature of the present invention is preferably 40 DEG C, and the reaction time is preferably 4 hours.
Further, the post-processing approach of reaction solution of the present invention are as follows: after reaction, obtained reaction solution is centrifuged
Zinc-aluminum hydrotalcite solid is removed, methylene chloride and deionized water are added into gained liquid, merges organic phase, then to described
Be added column chromatography silica gel in organic phase, vacuum distillation removes solvent, remaining mixture by column chromatography separation, with petroleum ether,
The mixed solvent that ethyl acetate volume ratio is 10:1 collects the eluent containing product as eluant, eluent, and solvent is evaporated off in eluent
Obtain Beta-bromo acetate compounds shown in Formula II.
Further, it is preferred that the method for the invention sequentially includes the following steps: styrene compound shown in Formulas I
For raw material, with the zinc-aluminum hydrotalcite ZnAl-BrO of bromate intercalation3 -- LDHs and potassium bromide are bromine source, in 30 in acetic acid solvent
It is stirred at a temperature of DEG C, reacts 4 hours, after reaction, be centrifuged off zinc-aluminum hydrotalcite solid using centrifuge 6000r/min,
Gained liquid is placed in separatory funnel, and methylene chloride and deionized water is added, will react resulting organic matter and be extracted to dichloromethane
In alkane phase, column chromatography silica gel is added in acquired solution, vacuum distillation removes solvent, and remaining mixture is separated by column chromatography,
Using petroleum ether, ethyl acetate volume ratio for 10:1 mixed solvent as eluant, eluent, collect the eluent containing product, eluent
Solvent is evaporated off and obtains Beta-bromo acetate compounds shown in Formula II.The zinc-aluminum hydrotalcite ZnAl- of the bromate intercalation
BrO3 -The quality of-LDHs is calculated as 0.4g/mmol with the amount of the substance of styrene compound shown in Formulas I；The potassium bromide
The amount of substance 1.1mmol/mmol is calculated as with the amount of the substance of styrene compound shown in Formulas I；The volume of the acetic acid
10mL/mmol is calculated as with the amount of the substance of styrene compound shown in Formulas I.
Compared with prior art, the beneficial effects of the present invention are:
Pass through the zinc-aluminum hydrotalcite ZnAl-BrO of bromate intercalation3 -- LDHs, potassium bromide, the combination of acetic acid efficiently realize
The preparation of Beta-bromo acetate compounds.The method of the present invention bromine source stabilization is easy to get, and solvent has given full play to its acidity, dissolution
Property, nucleophilicity simplifies reaction process so that it with yield height, reaction condition is mild, environmental-friendly, it is easy to operate the features such as.
(4) specific embodiment
Below with reference to specific example, invention is further explained, and subordinate's example is only the preferred embodiment of the present invention,
And it is not all.
The zinc-aluminum hydrotalcite ZnAl-BrO of bromate intercalation of the present invention3 -- LDHs is specifically carried out as follows
Preparation:
Weigh 7.55gNaBrO3100mL solution is configured to be added in four-hole boiling flask as bottom liquid.Weigh 29.75g Zn
(NO3)2﹒ 6H2O and 18.75g Al (NO3)3﹒ 9H20 is configured to 200mL mixing salt solution.12.00g NaOH is weighed to be configured to
200mL lye.Saline solution and lye will be mixed using double drop methods to be slowly dropped in four-hole boiling flask simultaneously, are stirred strongly under room temperature
It is 7.0+0.2 that (1000r/min), which adjusts drop speed and keep pH value, continues to stir 0.5h after dripping.By gained slurries in 70 DEG C of crystalline substances
Change for 24 hours, filtering and washing, is ground after 60 DEG C of dry 18h, product ZnAl-BrO3 --LDHs。
Embodiment 1
2mmol (0.208g) styrene, 2.2mmol (0.262g) potassium bromide are added in 50mL three-neck flask, then plus
Enter 20mL acetic acid and make solvent, is subsequently added into the zinc-aluminum hydrotalcite ZnAl-BrO of 0.8g bromate intercalation3 -- LDHs, the magnetic at 40 DEG C
Power stirs 4 hours.After reaction, it is centrifuged off zinc-aluminum hydrotalcite solid using centrifuge 6000r/min, gained liquid is placed in
In separatory funnel, methylene chloride and deionized water is added, resulting organic matter will be reacted and be extracted in methylene chloride phase, gained is molten
Column chromatography silica gel is added in liquid, vacuum distillation removes solvent, and remaining mixture is separated by column chromatography, with petroleum ether, acetic acid
The mixed solvent that ethyl ester volume ratio is 10:1 collects the eluent containing product as eluant, eluent, and eluent is evaporated off solvent and obtains
Pure products, yield 91%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.33 (m, 5H), 6.07 (dd, J=5.0,7.8Hz, 1H),
3.73-3.50(m,2H),2.17(s,3H)；13C NMR(126MHz, CDCl3)δ170.25,139.33,128.41,128.37,
127.26,78.46,34.85,20.57； HRMS(ESI,m/s):Calculated for C10H11BrO2(M+H)+
243.0021,found 243.0025.
Embodiment 2
2mmol (0.208g) styrene, 1.6mmol (0.190g) potassium bromide are added in 50mL three-neck flask, then plus
Enter 16mL acetic acid and make solvent, is subsequently added into the zinc-aluminum hydrotalcite ZnAl-BrO of 0.7g bromate intercalation3 -- LDHs, the magnetic at 25 DEG C
Power stirs 6 hours.After reaction, it is centrifuged off zinc-aluminum hydrotalcite solid using centrifuge 6000r/min, gained liquid is placed in
In separatory funnel, methylene chloride and deionized water is added, resulting organic matter will be reacted and be extracted in methylene chloride phase, gained is molten
Column chromatography silica gel is added in liquid, vacuum distillation removes solvent, and remaining mixture is separated by column chromatography, with petroleum ether, acetic acid
The mixed solvent that ethyl ester volume ratio is 10:1 collects the eluent containing product as eluant, eluent, and eluent is evaporated off solvent and obtains
Pure products, yield 81%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.33 (m, 5H), 6.07 (dd, J=5.0,7.8Hz, 1H),
3.73-3.50(m,2H),2.17(s,3H)；13C NMR(126MHz, CDCl3)δ170.25,139.33,128.41,128.37,
127.26,78.46,34.85,20.57； HRMS(ESI,m/s):Calculated for C10H11BrO2(M+H)+
243.0021,found 243.0025.
Embodiment 3
2mmol (0.208g) styrene, 2.7mmol (0.321g) potassium bromide are added in 50mL three-neck flask, then plus
Enter 18mL acetic acid and make solvent, is subsequently added into the zinc-aluminum hydrotalcite ZnAl-BrO of 1.2g bromate intercalation3 -- LDHs, the magnetic at 60 DEG C
Power stirs 6 hours.After reaction, it is centrifuged off zinc-aluminum hydrotalcite solid using centrifuge 6000r/min, gained liquid is placed in
In separatory funnel, methylene chloride and deionized water is added, resulting organic matter will be reacted and be extracted in methylene chloride phase, gained is molten
Column chromatography silica gel is added in liquid, vacuum distillation removes solvent, and remaining mixture is separated by column chromatography, with petroleum ether, acetic acid
The mixed solvent that ethyl ester volume ratio is 10:1 collects the eluent containing product as eluant, eluent, and eluent is evaporated off solvent and obtains
Pure products, yield 89%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.33 (m, 5H), 6.07 (dd, J=5.0,7.8Hz, 1H),
3.73-3.50(m,2H),2.17(s,3H)；13C NMR(126MHz, CDCl3)δ170.25,139.33,128.41,128.37,
127.26,78.46,34.85,20.57； HRMS(ESI,m/s):Calculated for C10H11BrO2(M+H)+
243.0021,found 243.0025.
Embodiment 4
2mmol (0.208g) styrene, 2.7mmol (0.321g) potassium bromide are added in 50mL three-neck flask, then plus
Enter 20mL acetic acid and make solvent, is subsequently added into the zinc-aluminum hydrotalcite ZnAl-BrO of 1.2g bromate intercalation3 -- LDHs, the magnetic at 60 DEG C
Power stirs 6 hours.After reaction, it is centrifuged off zinc-aluminum hydrotalcite solid using centrifuge 6000r/min, gained liquid is placed in
In separatory funnel, methylene chloride and deionized water is added, resulting organic matter will be reacted and be extracted in methylene chloride phase, gained is molten
Column chromatography silica gel is added in liquid, vacuum distillation removes solvent, and remaining mixture is separated by column chromatography, with petroleum ether, acetic acid
The mixed solvent that ethyl ester volume ratio is 10:1 collects the eluent containing product as eluant, eluent, and eluent is evaporated off solvent and obtains
Pure products, yield 87%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.33 (m, 5H), 6.07 (dd, J=5.0,7.8Hz, 1H),
3.73-3.50(m,2H),2.17(s,3H)；13C NMR(126MHz, CDCl3)δ170.25,139.33,128.41,128.37,
127.26,78.46,34.85,20.57； HRMS(ESI,m/s):Calculated for C10H11BrO2(M+H)+
243.0021,found 243.0025.
Embodiment 5
2mmol (0.208g) styrene, 2.2mmol (0.226g) sodium bromide are added in 50mL three-neck flask, then plus
Enter 20mL acetic acid and make solvent, is subsequently added into the zinc-aluminum hydrotalcite ZnAl-BrO of 0.8g bromate intercalation3 -- LDHs, the magnetic at 50 DEG C
Power stirs 4 hours.After reaction, it is centrifuged off zinc-aluminum hydrotalcite solid using centrifuge 6000r/min, gained liquid is placed in
In separatory funnel, methylene chloride and deionized water is added, resulting organic matter will be reacted and be extracted in methylene chloride phase, gained is molten
Column chromatography silica gel is added in liquid, vacuum distillation removes solvent, and remaining mixture is separated by column chromatography, with petroleum ether, acetic acid
The mixed solvent that ethyl ester volume ratio is 10:1 collects the eluent containing product as eluant, eluent, and eluent is evaporated off solvent and obtains
Pure products, yield 86%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.33 (m, 5H), 6.07 (dd, J=5.0,7.8Hz, 1H),
3.73-3.50(m,2H),2.17(s,3H)；13C NMR(126 MHz,CDCl3)δ170.25,139.33,128.41,128.37,
127.26,78.46,34.85, 20.57；HRMS(ESI,m/s):Calculated for C10H11BrO2(M+H)+
243.0021, found 243.0025.
Embodiment 6
2mmol (0.208g) styrene, 2.2mmol (0.191g) lithium bromide are added in 50mL three-neck flask, then plus
Enter 20mL acetic acid and make solvent, is subsequently added into the zinc-aluminum hydrotalcite ZnAl-BrO of 0.8g bromate intercalation3 -- LDHs, the magnetic at 40 DEG C
Power stirs 2 hours.After reaction, it is centrifuged off zinc-aluminum hydrotalcite solid using centrifuge 6000r/min, gained liquid is placed in
In separatory funnel, methylene chloride and deionized water is added, resulting organic matter will be reacted and be extracted in methylene chloride phase, gained is molten
Column chromatography silica gel is added in liquid, vacuum distillation removes solvent, and remaining mixture is separated by column chromatography, with petroleum ether, acetic acid
The mixed solvent that ethyl ester volume ratio is 10:1 collects the eluent containing product as eluant, eluent, and eluent is evaporated off solvent and obtains
Pure products, yield 89%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.33 (m, 5H), 6.07 (dd, J=5.0,7.8Hz, 1H),
3.73-3.50(m,2H),2.17(s,3H)；13C NMR(126 MHz,CDCl3)δ170.25,139.33,128.41,128.37,
127.26,78.46,34.85, 20.57；HRMS(ESI,m/s):Calculated for C10H11BrO2(M+H)+
243.0021, found 243.0025.
Embodiment 7
2mmol (0.236g) 4- methyl styrene, 2.2mmol (0.262g) potassium bromide are added to 50mL three-neck flask
In, it adds 20mL acetic acid and makees solvent, be subsequently added into the zinc-aluminum hydrotalcite ZnAl-BrO of 0.8g bromate intercalation3 -- LDHs, in 40
Magnetic agitation 4 hours at DEG C.After reaction, zinc-aluminum hydrotalcite solid, gained liquid are centrifuged off using centrifuge 6000r/min
Body is placed in separatory funnel, and methylene chloride and deionized water is added, will react resulting organic matter and be extracted in methylene chloride phase,
Column chromatography silica gel is added in acquired solution, vacuum distillation removes solvent, and remaining mixture is separated by column chromatography, with petroleum
Ether, the mixed solvent that ethyl acetate volume ratio is 10:1 collect the eluent containing product, eluent is evaporated off as eluant, eluent
Solvent obtains pure products, yield 88%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.23 (d, J=8.4Hz, 2H), 7.08 (d, J=8.4Hz,
2H), 5.99 (dd, J=5.0,8.0Hz, 1H), 3.68-3.53 (m, 2H), 2.13 (s, 3H), 2.11 (s, 3H)；13C NMR
(126MHz,CDCl3)δ170.43, 138.32,136.13,128.05,127.19,78.45,35.69,21.38,21.65；
HRMS(ESI, m/s):Calculated for C11H13BrO2(M+H)+257.0177,found 257.0175.
Embodiment 8
2mmol (0.236g) Beta-methyl styrene, 2.2mmol (0.262g) potassium bromide are added to 50mL three-neck flask
In, it adds 20mL acetic acid and makees solvent, be subsequently added into the zinc-aluminum hydrotalcite ZnAl-BrO of 0.8g bromate intercalation3 -- LDHs, in 40
Magnetic agitation 4 hours at DEG C.After reaction, zinc-aluminum hydrotalcite solid, gained liquid are centrifuged off using centrifuge 6000r/min
Body is placed in separatory funnel, and methylene chloride and deionized water is added, will react resulting organic matter and be extracted in methylene chloride phase,
Column chromatography silica gel is added in acquired solution, vacuum distillation removes solvent, and remaining mixture is separated by column chromatography, with petroleum
Ether, the mixed solvent that ethyl acetate volume ratio is 10:1 collect the eluent containing product, eluent is evaporated off molten as eluant, eluent
Agent obtains pure products, yield 83%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.24 (s, 5H), 5.94 (d, J=6.6Hz, 1H), 4.85 (dd,
J=5.4,6.8Hz, 1H), 2.16 (s, 3H)), 1.63 (d, J=7.0 Hz, 3H)；13C NMR(126MHz,CDCl3)δ
170.25,138.47,129.18,128.59, 126.77,78.84,50.87,21.35,21.32；HRMS(ESI,m/s):
Calculated for C11H13BrO2(M+H)+257.0177,found 257.0173.
Embodiment 9
2mmol (0.360g) trans stilbene, 2.2mmol (0.262g) potassium bromide are added to 50mL three-neck flask
In, it adds 20mL acetic acid and makees solvent, be subsequently added into the zinc-aluminum hydrotalcite ZnAl-BrO of 0.8g bromate intercalation3 -- LDHs, in
Magnetic agitation 5 hours at 40 DEG C.After reaction, zinc-aluminum hydrotalcite solid, gained are centrifuged off using centrifuge 6000r/min
Liquid is placed in separatory funnel, and methylene chloride and deionized water is added, will react resulting organic matter and be extracted to methylene chloride phase
In, column chromatography silica gel is added in acquired solution, vacuum distillation removes solvent, and remaining mixture is separated by column chromatography, with stone
Oily ether, the mixed solvent that ethyl acetate volume ratio is 10:1 collect the eluent containing product, eluent is evaporated off as eluant, eluent
Solvent obtains pure products, yield 80%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.42-7.32 (m, 10H), 6.70 (d, J=8.0Hz, 1H),
6.08 (d, J=8.0Hz, 1H), 2.18 (s, 3H)；13C NMR(126 MHz,CDCl3)δ169.37,139.33,137.17,
129.25,129.20,128.27,128.38, 128.35,128.33,78.64,56.37,21.28；HRMS(ESI,m/s):
Calculated for C16H15BrO2(M+H)+319.0334,found 319.0337。
Claims (10)
1. a kind of synthetic method of Beta-bromo acetate compounds, it is characterised in that: the method is specifically according to following step
It is rapid to carry out:
Using styrene compound shown in Formulas I as raw material, with the zinc-aluminum hydrotalcite ZnAl-BrO of bromate intercalation3 -- LDHs and alkali
Metal bromide is bromine source, in organic solvent, reacts 1~6 hour in 15~60 DEG C, obtains reaction solution after reaction, passes through
Post-processing obtains Beta-bromo acetate compounds shown in Formula II；The zinc-aluminum hydrotalcite ZnAl- of the bromate intercalation
BrO3 -The quality of-LDHs is calculated as 0.35~0.75g/mmol with the amount of the substance of styrene compound shown in Formulas I；Described
The amount of the substance of alkali metal bromide is calculated as 0.8~1.35mmol/ with the amount of the substance of styrene compound shown in Formulas I
Mmol,
In the Formulas I or Formula II,
R1For one of hydrogen, methyl, tert-butyl, acetoxyl group, bromine or chlorine；
R2For one of hydrogen, methyl, methylol, carboxyl, phenyl or methyl formate base.
2. the method as described in claim 1, it is characterised in that: the R1For hydrogen or methyl.
3. the method as described in claim 1, it is characterised in that: the R2For hydrogen, methyl or phenyl.
4. the method as described in claim 1, it is characterised in that: the zinc-aluminum hydrotalcite ZnAl-BrO of the bromate intercalation3 --
The quality of LDHs is calculated as 0.4g/mmol with the amount of the substance of styrene compound shown in Formulas I.
5. the method as described in claim 1, it is characterised in that: the alkali metal bromide is potassium bromide, sodium bromide or bromine
Change lithium.
6. the method as described in claim 1, it is characterised in that: the amount of the substance of the alkali metal bromide is shown in Formulas I
The amount of substance of styrene compound be calculated as 1.1mmol/mmol.
7. the method as described in claim 1, it is characterised in that: the organic solvent is acetic acid.
8. the method as described in claim 1, it is characterised in that: the volume of the organic solvent is with phenylethylene shown in Formulas I
The amount of the substance of compound is calculated as 8~12mL/mmol.
9. the method as described in claim 1, it is characterised in that: the reaction temperature is 40 DEG C, and the reaction time is 4
Hour.
10. the method as described in claim 1, it is characterised in that: the post-processing approach of the reaction solution are as follows: after reaction,
Obtained reaction solution is centrifuged off zinc-aluminum hydrotalcite solid, methylene chloride and deionized water are added into gained liquid, is merged
Then column chromatography silica gel is added in organic phase into the organic phase, vacuum distillation removes solvent, and remaining mixture passes through column layer
Analysis method separation, using petroleum ether, ethyl acetate volume ratio for 10:1 mixed solvent be used as eluant, eluent, collection the elution containing product
Liquid, eluent are evaporated off solvent and obtain Beta-bromo acetate compounds shown in Formula II.
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| CN110156577A (en) * | 2019-05-22 | 2019-08-23 | 浙江工业大学 | A kind of synthetic method of Beta-bromo ether compound |
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| CN107628945A (en) * | 2017-08-23 | 2018-01-26 | 浙江工业大学 | A kind of method of synthesis β bromine formic ether compounds |
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| CN107628945A (en) * | 2017-08-23 | 2018-01-26 | 浙江工业大学 | A kind of method of synthesis β bromine formic ether compounds |
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| CN110156577A (en) * | 2019-05-22 | 2019-08-23 | 浙江工业大学 | A kind of synthetic method of Beta-bromo ether compound |
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