CN109336743A - A kind of synthetic method of Beta-bromo ether compound - Google Patents
A kind of synthetic method of Beta-bromo ether compound Download PDFInfo
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- C07C41/01—Preparation of ethers
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Abstract
The invention discloses a kind of synthetic method of Beta-bromo ether compound, the method is specifically prepared in accordance with the following steps: the zinc-aluminum hydrotalcite ZnAl-BrO using styrene compound shown in Formulas I as raw material, with bromate intercalation3 ‑- LDHs and alkali metal bromide mixing, are dissolved in organic solvent, under the action of inorganic acid, react 1~4 hour in 15~60 DEG C, after reaction, reaction solution are obtained, by isolating and purifying to obtain Beta-bromo ether compound shown in Formula II；The method of the present invention has bromine source stability good, and simple and easy to get, 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, in particular to a kind of Beta-bromo ether compound
Synthetic method.
(2) background technique
Process is important in organic synthesis to the regioselectivity electrophilic addition of alkene, the ortho position functionalization of alkene is
A kind of important synthetics, especially when reaction provides product in a manner of regio- and stereo-selectivity, wherein ortho position is halogenated
Ether is general and useful synthetic intermediate, can provide a series of functional groups, can be converted into various important compounds, portion
It point exists in the precursor of bioactive compound or bioactive compound, and is widely used in synthetic drug, agricultural
The industrial process of chemicals.
Currently, the synthetic method for the related Beta-bromo ether compound reported both at home and abroad is mainly the following method: 1.
Report uses metal salt such as LiX and NaX as halide reagent, NaIO4As catalyst, Beta-bromo ether compound is prepared.(referring to
Dewkar G K, Narina S V, Sudalai A.Organic Letters, 2003,5 (23): 4501-4.), this method
Major defect be H using a large amount of catalyst and stoichiometry2SO4, have the reaction time long, low yield, what is not environmentally waited lacks
Point.2. using Ytterbiumtriflate (Yb (OTf)3), NBS synthesize in methyl alcohol Beta-bromo ether compound (referring to Hajra S,
Bhowmick M, Karmakar A.Tetrahedron Letters, 2005,36 (33): 3073-3077.), the method yield
Low, the reaction time is long, using the NBS of stoichiometry, forms a large amount of organic and inorganic wastes, does not meet the theory of Green Chemistry.
3. in NH4In the presence of OAc using N- halosuccinimides carry out Beta-bromo ether compound preparation (referring to Das B,
Venkateswarlu K,Damodar K,et al.Journal of Molecular Catalysis A Chemical,
2007,269 (1-2): the problems such as 17-21.), the method equally deposits that the middle reaction time is long, does not meet the theory of Green Chemistry.
In view of the above problems, the halogenation synthetic method of very simple and effective and ecological close friend in organic chemistry is developed to close
It is very necessary at Beta-bromo ether compound.
(3) summary of the invention
To solve in the method for synthesis Beta-bromo ether compound at present there is method low yield, the reaction time is long, toxicity
Greatly, pollute environment and it is at high cost the problems such as, the invention proposes a kind of synthetic methods of Beta-bromo ether compound.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A kind of synthetic method of Beta-bromo ether compound, the method are specifically prepared in accordance with the following steps:
Zinc-aluminum hydrotalcite ZnAl-BrO using styrene compound shown in Formulas I as raw material, with bromate intercalation3 --
LDHs and alkali metal bromide mixing, are dissolved in organic solvent, small in 15~60 DEG C of reactions 1~4 under the action of inorganic acid
When, after reaction, reaction solution is obtained, by isolating and purifying to obtain Beta-bromo ether compound shown in Formula II；The bromine
The zinc-aluminum hydrotalcite ZnAl-BrO of acid group intercalation3 -The quality of-LDHs is with the meter of the substance of styrene compound shown in Formulas I
For 0.4~1.0g/mmol；The amount of the substance of the alkali metal bromide is with the substance of styrene compound shown in Formulas I
Amount be calculated as 1.0~2.0mmol/mmol；Reaction formula is as follows:
In the Formulas I or Formula II,
R is one of hydrogen, methyl, tert-butyl, bromine, chlorine, methoxyl group, acetoxyl group, nitro.
Further, the R is hydrogen, methyl, tert-butyl or bromine.
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 institute
The amount of the substance of the styrene compound shown is calculated as 0.8g/mmol.
Further, the alkali metal bromide is potassium bromide, sodium bromide or lithium bromide, preferably lithium 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 is calculated as 1.2mmol/mmol.
Further, the inorganic acid is 1mol/L hydrochloric acid.
Further, it is preferred that the volume of the inorganic acid is with the meter of the substance of styrene compound shown in Formulas I
For 2mL/mmol.
Further, the organic solvent is methanol.
Further, the volume of the organic solvent be calculated as 5 with the amount of the substance of styrene compound shown in Formulas I~
10mL/mmol, preferably 8mL/mmol.
Reaction temperature of the present invention is preferably 25 DEG C, and the reaction time is preferably 3 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, separates organic phase, water phase is with organic molten
Agent extracts 3~5 times, merges organic phase, and anhydrous sodium sulfate drying is added, is concentrated, after silica gel post separation, with petroleum ether, acetic acid second
The mixed solvent that ester volume ratio is 20:1 collects the eluent containing product as eluant, eluent, and eluent is evaporated off solvent and obtains formula
Beta-bromo ether compound shown in II.
Further, preferably the method for the invention is sequentially included the following steps: and is added in the reaction vessel with structural formula such as
(I) styrene compound shown in, with the zinc-aluminum hydrotalcite ZnAl-BrO of bromate intercalation3 -- LDHs and alkali metal bromide,
1mol/L hydrochloric acid stirring and dissolving is added dropwise, is reacted 3 hours in acetic acid in 25 DEG C, is centrifuged off zinc using centrifuge 6000r/min
Aluminum hydrotalcite solid, gained liquid are placed in separatory funnel, and methylene chloride and deionized water are added into reaction solution, are separated organic
Phase, water phase are extracted 3~5 times with organic solvent, merge organic phase, and anhydrous sodium sulfate drying is added, is concentrated, after silica gel post separation,
Using petroleum ether, ethyl acetate volume ratio for 20:1 mixed solvent as eluant, eluent, collect the eluent containing product, eluent
Solvent is evaporated off and obtains Beta-bromo ether compound shown in Formula II.The zinc-aluminum hydrotalcite ZnAl-BrO of the bromate intercalation3 --
The quality of LDHs is calculated as 0.8g/mmol with the amount of the substance of styrene compound shown in Formulas I；The substance of the potassium bromide
Amount 1.2mmol/mmol is calculated as with the amount of the substance of styrene compound shown in Formulas I；The volume of the hydrochloric acid is with Formulas I institute
The amount of the substance of the styrene compound shown is calculated as 2mL/mmol；The volume of the methanol is with phenylethylene shown in Formulas I
The amount for closing the substance of object is calculated as 8mL/mmol.
Compared with prior art, the beneficial effects of the present invention are:
Pass through the zinc-aluminum hydrotalcite ZnAl-BrO of bromate intercalation3 -- LDHs, lithium bromide, the combination of methanol, hydrochloric acid, efficiently
Realize the preparation of Beta-bromo ether compound.The method of the present invention has bromine source stability good, simple and easy to get, reaction condition temperature
With environmental-friendly, simple operation and other advantages.
(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, 2.4mmol (0.208g) lithium bromide are added in 50mL three-neck flask, then plus
Enter 16mL methanol as solvent, 1mol/L hydrochloric acid 4mL stirring and dissolving is added dropwise, is subsequently added into the zinc-aluminum hydrotalcite of 1.6g bromate intercalation
ZnAl-BrO3 -- LDHs, magnetic agitation 3 hours at 25 DEG C, tracks fully reacting by TLC.After reaction, using centrifugation
Machine 6000r/min is centrifuged off zinc-aluminum hydrotalcite solid, and gained liquid is placed in separatory funnel, and methylene chloride and deionization is added
Water will react resulting organic matter and be extracted in methylene chloride phase, and column chromatography silica gel is added in acquired solution, and vacuum distillation removes
Solvent, remaining mixture are separated by column chromatography, using petroleum ether, ethyl acetate volume ratio for 20:1 mixed solvent as washing
De- agent, collects the eluent containing product, and eluent is evaporated off solvent and obtains pure products, yield 88%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.34 (m, 5H), 4.78 (dd, J=4.6,7.8Hz, 1H), 3.88
(m,2H),3.20(s,3H)；13C NMR(126MHz,CDCl3)δ138.72,128.33,128.17,127.34,88.16,
56.93,40.91；HRMS(ESI,m/s):Calculated for C9H11BrO(M+H)+215.0072,found
215.0075.
Embodiment 2
2mmol (0.208g) styrene, 2.0mmol (0.174g) lithium bromide are added in 50mL three-neck flask, then plus
Enter 10mL methanol as solvent, 1mol/L hydrochloric acid 2mL stirring and dissolving is added dropwise, is subsequently added into the zinc-aluminum hydrotalcite of 0.8g bromate intercalation
ZnAl-BrO3 -- LDHs, magnetic agitation 4 hours at 60 DEG C, tracks fully reacting by TLC.After reaction, using centrifugation
Machine 6000r/min is centrifuged off zinc-aluminum hydrotalcite solid, and gained liquid is placed in separatory funnel, and methylene chloride and deionization is added
Water will react resulting organic matter and be extracted in methylene chloride phase, and column chromatography silica gel is added in acquired solution, and vacuum distillation removes
Solvent, remaining mixture are separated by column chromatography, using petroleum ether, ethyl acetate volume ratio for 20:1 mixed solvent as washing
De- agent, collects the eluent containing product, and eluent is evaporated off solvent and obtains pure products, yield 80%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.34 (m, 5H), 4.78 (dd, J=4.6,7.8Hz, 1H), 3.88
(m,2H),3.20(s,3H)；13C NMR(126MHz,CDCl3)δ138.72,128.33,128.17,127.34,88.16,
56.93,40.91；HRMS(ESI,m/s):Calculated for C9H11BrO(M+H)+215.0072,found
215.0075.
Embodiment 3
2mmol (0.208g) styrene, 4.0mmol (0.476g) potassium bromide are added in 50mL three-neck flask, then plus
Enter 20mL methanol as solvent, 1mol/L hydrochloric acid 8mL stirring and dissolving is added dropwise, is subsequently added into the zinc-aluminum hydrotalcite of 2.0g bromate intercalation
ZnAl-BrO3 -- LDHs, magnetic agitation 1 hour at 15 DEG C, tracks fully reacting by TLC.After reaction, using centrifugation
Machine 6000r/min is centrifuged off zinc-aluminum hydrotalcite solid, and gained liquid is placed in separatory funnel, and methylene chloride and deionization is added
Water will react resulting organic matter and be extracted in methylene chloride phase, and column chromatography silica gel is added in acquired solution, and vacuum distillation removes
Solvent, remaining mixture are separated by column chromatography, using petroleum ether, ethyl acetate volume ratio for 20:1 mixed solvent as washing
De- agent, collects the eluent containing product, and eluent is evaporated off solvent and obtains pure products, yield 83%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.34 (m, 5H), 4.78 (dd, J=4.6,7.8Hz, 1H), 3.88
(m,2H),3.20(s,3H)；13C NMR(126MHz,CDCl3)δ138.72,128.33,128.17,127.34,88.16,
56.93,40.91；HRMS(ESI,m/s):Calculated for C9H11BrO(M+H)+215.0072,found
215.0075.
Embodiment 4
2mmol (0.208g) styrene, 4.0mmol (0.412g) sodium bromide are added in 50mL three-neck flask, then plus
Enter 20mL methanol as solvent, 1mol/L hydrochloric acid 4mL stirring and dissolving is added dropwise, is subsequently added into the zinc-aluminum hydrotalcite of 2.0g bromate intercalation
ZnAl-BrO3 -- LDHs, magnetic agitation 4 hours at 15 DEG C, tracks fully reacting by TLC.After reaction, using centrifugation
Machine 6000r/min is centrifuged off zinc-aluminum hydrotalcite solid, and gained liquid is placed in separatory funnel, and methylene chloride and deionization is added
Water will react resulting organic matter and be extracted in methylene chloride phase, and column chromatography silica gel is added in acquired solution, and vacuum distillation removes
Solvent, remaining mixture are separated by column chromatography, using petroleum ether, ethyl acetate volume ratio for 20:1 mixed solvent as washing
De- agent, collects the eluent containing product, and eluent is evaporated off solvent and obtains pure products, yield 87%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.34 (m, 5H), 4.78 (dd, J=4.6,7.8Hz, 1H), 3.88
(m,2H),3.20(s,3H)；13C NMR(126MHz,CDCl3)δ138.72,128.33,128.17,127.34,88.16,
56.93,40.91；HRMS(ESI,m/s):Calculated for C9H11BrO(M+H)+215.0072,found
215.0075.
Embodiment 5
2mmol (0.236g) 4- methyl styrene, 2.4mmol (0.208g) lithium bromide are added to 50mL three-neck flask
In, 16mL methanol as solvent is added, 1mol/L hydrochloric acid 4mL stirring and dissolving is added dropwise, is subsequently added into the zinc of 1.6g bromate intercalation
Aluminum hydrotalcite ZnAl-BrO3 -- LDHs, magnetic agitation 3 hours at 25 DEG C, tracks fully reacting by TLC.After reaction,
It is centrifuged off zinc-aluminum hydrotalcite solid using centrifuge 6000r/min, gained liquid is placed in separatory funnel, and methylene chloride is added
And deionized water, resulting organic matter will be reacted and be extracted in methylene chloride phase, column chromatography silica gel is added in acquired solution, depressurized
Solvent is distilled off, remaining mixture is separated by column chromatography, molten for the mixing of 20:1 with petroleum ether, ethyl acetate volume ratio
Agent collects the eluent containing product as eluant, eluent, and eluent is evaporated off solvent and obtains pure products, yield 93%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.28 (s, 4H), 4.84 (dd, J=4.6,8.0Hz, 1H),
3.86-3.58(m,2H),3.18(s,3H),2.24(s,3H)；13C NMR(126MHz,CDCl3)δ137.65,133.85,
129.39,127.82,88.27,57.63,38.19,21.17；HRMS(ESI,m/s):Calculated for C10H13BrO(M
+H)+229.0228,found 229.0226.
Embodiment 6
2mmol (0.321g) 4- t-butyl styrene, 2.4mmol (0.208g) lithium bromide are added to 50mL three-neck flask
In, 16mL methanol as solvent is added, 1mol/L hydrochloric acid 4mL stirring and dissolving is added dropwise, is subsequently added into the zinc of 1.6g bromate intercalation
Aluminum hydrotalcite ZnAl-BrO3 -- LDHs, magnetic agitation 3 hours at 25 DEG C, tracks fully reacting by TLC.After reaction,
It is centrifuged off zinc-aluminum hydrotalcite solid using centrifuge 6000r/min, gained liquid is placed in separatory funnel, and methylene chloride is added
And deionized water, resulting organic matter will be reacted and be extracted in methylene chloride phase, column chromatography silica gel is added in acquired solution, depressurized
Solvent is distilled off, remaining mixture is separated by column chromatography, molten for the mixing of 20:1 with petroleum ether, ethyl acetate volume ratio
Agent collects the eluent containing product as eluant, eluent, and eluent is evaporated off solvent and obtains pure products, yield 95%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.38 (d, J=8Hz, 2H), 7.23 (d, 8Hz, 2H), 4.76
(dd, J=4.0,8.5Hz, 1H), 3.31 (s, 3H), 3.61-3.53 (m, 2H), 1.31 (s, 9H)；13C NMR(126MHz,
CDCl3)δ151.36,133.12,126.35,125.27,85.74,57.14,34.26,34.27,31.15；HRMS(ESI,m/
s):Calculated for C13H19BrO(M+H)+271.0698,found 271.0696.
Embodiment 7
2mmol (0.277g) 4- chlorostyrene, 2.4mmol (0.208g) lithium bromide are added in 50mL three-neck flask,
16mL methanol as solvent is added, 1mol/L hydrochloric acid 4mL stirring and dissolving is added dropwise, is subsequently added into the zinc-aluminium water of 1.6g bromate intercalation
Talcum ZnAl-BrO3 -- LDHs, magnetic agitation 3 hours at 25 DEG C, tracks fully reacting by TLC.After reaction, it uses
Centrifuge 6000r/min is centrifuged off zinc-aluminum hydrotalcite solid, and gained liquid is placed in separatory funnel, and methylene chloride is added and goes
Ionized water will react resulting organic matter and be extracted in methylene chloride phase, column chromatography silica gel is added in acquired solution, vacuum distillation
Solvent is removed, remaining mixture is separated by column chromatography, is made with petroleum ether, ethyl acetate volume ratio for the mixed solvent of 20:1
For eluant, eluent, the eluent containing product is collected, eluent is evaporated off solvent and obtains pure products, yield 85%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.36 (d, J=8.5Hz, 2H), 7.24 (d, J=8.5Hz, 2H),
4.76 (dd, J=4.5,7.0Hz, 1H), 3.56-3.43 (m, 2H), 3.19 (s, 3H)；13C NMR(126MHz,CDCl3)δ
137.16,133.53,128.59,128.62,86.27,57.34,36.98；HRMS(ESI,m/s):Calculated for
C9H10BrClO(M+H)+248.9682,found 248.9685.
Embodiment 8
2mmol (0.366g) 4- bromstyrol, 2.4mmol (0.208g) lithium bromide are added in 50mL three-neck flask,
16mL methanol as solvent is added, 1mol/L hydrochloric acid 4mL stirring and dissolving is added dropwise, is subsequently added into the zinc-aluminium water of 1.6g bromate intercalation
Talcum ZnAl-BrO3 -- LDHs, magnetic agitation 3 hours at 25 DEG C, tracks fully reacting by TLC.After reaction, it uses
Centrifuge 6000r/min is centrifuged off zinc-aluminum hydrotalcite solid, and gained liquid is placed in separatory funnel, and methylene chloride is added and goes
Ionized water will react resulting organic matter and be extracted in methylene chloride phase, column chromatography silica gel is added in acquired solution, vacuum distillation
Solvent is removed, remaining mixture is separated by column chromatography, is made with petroleum ether, ethyl acetate volume ratio for the mixed solvent of 15:1
For eluant, eluent, the eluent containing product is collected, eluent is evaporated off solvent and obtains pure products, yield 84%.
Characterize data:1H NMR(500MHz,CDCl3) δ 7.89 (d, J=8.5Hz, 2H), 7.27 (d, J=8.5Hz, 2H),
4.74 (dd, J=4.5,7.5Hz, 1H), 3.71-3.61 (m, 2H), 3.19 (s, 3H)；13C NMR(126MHz,CDCl3)δ
137.39,131.25,127.96,125.35,122.75,55.34,39.17；HRMS(ESI,m/s):Calculated for
C9H10Br2O(M+H)+292.9177,found 292.9179.
Claims (10)
1. a kind of preparation method of Beta-bromo ether compound, it is characterised in that: the method specifically in accordance with the following steps into
Row preparation:
Zinc-aluminum hydrotalcite ZnAl-BrO using styrene compound shown in Formulas I as raw material, with bromate intercalation3 -- LDHs and
Alkali metal bromide mixing, is dissolved in organic solvent, under the action of inorganic acid, reacts 1~4 hour in 15~60 DEG C, reaction
After, reaction solution is obtained, by isolating and purifying to obtain Beta-bromo ether compound shown in Formula II；The bromate intercalation
Zinc-aluminum hydrotalcite ZnAl-BrO3 -- quality of LDHs is calculated as 0.4 with the amount of the substance of styrene compound shown in Formulas I~
1.0g/mmol；The amount of the substance of the alkali metal bromide is calculated as with the amount of the substance of styrene compound shown in Formulas I
1.0~2.0mmol/mmol；
In the Formulas I or Formula II,
R is one of hydrogen, methyl, tert-butyl, bromine, chlorine, methoxyl group, acetoxyl group, nitro.
2. the method as described in claim 1, it is characterised in that: the R is hydrogen, methyl, tert-butyl or bromine.
3. 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 0.8g/mmol with the amount of the substance of styrene compound shown in Formulas I.
4. 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.
5. 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 1.2mmol/mmol.
6. the method as described in claim 1, it is characterised in that: the inorganic acid is 1mol/L hydrochloric acid.
7. method as claimed in claim 6, it is characterised in that: the volume of the inorganic acid is with phenylethylene shown in Formulas I
The amount for closing the substance of object is calculated as 2mL/mmol.
8. the method as described in claim 1, it is characterised in that: the organic solvent is methanol.
9. the method as described in claim 1, it is characterised in that: the volumetric usage of the organic solvent is with benzene second shown in Formulas I
The amount of the substance of vinyl compound is calculated as 5~10mL/mmol.
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, separation are added into gained liquid
Organic phase, water phase are extracted 3~5 times with organic solvent, merge organic phase, and anhydrous sodium sulfate drying, concentration, silica gel post separation is added
Afterwards, using petroleum ether, ethyl acetate volume ratio for 20:1 mixed solvent as eluant, eluent, collect the eluent containing product, wash
De- liquid is evaporated off solvent and obtains Beta-bromo ether compound 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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