CN107021950B - Preparation method of 2, 5-dibromo-3-methylthiophene - Google Patents
Preparation method of 2, 5-dibromo-3-methylthiophene Download PDFInfo
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- CN107021950B CN107021950B CN201710303876.7A CN201710303876A CN107021950B CN 107021950 B CN107021950 B CN 107021950B CN 201710303876 A CN201710303876 A CN 201710303876A CN 107021950 B CN107021950 B CN 107021950B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- IHFXZROPBCBLLG-UHFFFAOYSA-N 2,5-dibromo-3-methylthiophene Chemical compound CC=1C=C(Br)SC=1Br IHFXZROPBCBLLG-UHFFFAOYSA-N 0.000 title abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 40
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- YYJBWYBULYUKMR-UHFFFAOYSA-N 2-bromo-3-methylthiophene Chemical compound CC=1C=CSC=1Br YYJBWYBULYUKMR-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 13
- 239000012043 crude product Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- PIDRHKDECUFWTG-UHFFFAOYSA-N 3-methyl-1,3-thiazol-3-ium Chemical compound C[N+]=1C=CSC=1 PIDRHKDECUFWTG-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims 2
- 230000006837 decompression Effects 0.000 claims 1
- 229930192474 thiophene Natural products 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000007086 side reaction Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- KEFUDFMHQALCMK-UHFFFAOYSA-N 2-bromo-3-methyl-1,3-thiazol-3-ium Chemical compound C[N+]=1C=CSC=1Br KEFUDFMHQALCMK-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical class BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/28—Halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of 2, 5-dibromo-3-methylthiophene shown in formula (II), which comprises the following steps: a method for preparing 2, 5-dibromo-3-methylthiophene shown in formula (II) is characterized by comprising the following steps: 3-methylthiophene shown in formula (I) is taken as a raw material, a brominating agent potassium bromide is added, the mixture is stirred and mixed evenly in a mixed solution of acetic acid and water, and the brominating agent ZnAl-BrO is slowly added at the temperature of 10-50 DEG C3 ‑Continuously stirring and reacting for 2h by using LDHs, and carrying out aftertreatment on the obtained reaction liquid to obtain 2, 5-dibromo-3-methylthiophene shown in a formula (II); 3-methylthiophene and ZnAl-BrO shown in the formula (I)3 ‑The mass ratio of LDHs to potassium bromide is 1:1.3: 1.6-1.9; the reaction condition of the invention is mild, and the adopted brominationThe reagent is a solid substance, is cheap and easy to obtain, and is environment-friendly; the reaction operation is simple, and the post-treatment is convenient; high yield of target product and less side reaction.
Description
Technical field
The invention belongs to organic chemical synthesis fields, the in particular to preparation method of the bromo- 3 methyl thiophene of 2,5- of one kind bis-.
Background technique
2,5- bis- bromo- 3 methyl thiophenes, structural formula are as follows:
2,5- bis- bromo- 3 methyl thiophenes (2,5-Dibromo-3-methylthiophene), density 1.972g/
cm3.Material containing thiophene-structure is widely used in because it has very outstanding photoelectric properties and information storge quality
The fields such as sensor, high power capacitor, electrochromism device, conductive coating, rechargeable battery.Most of synthesis of these materials
It is all using bromo thiophene derivative as raw material.
In existing document report, majority synthesizes the bromo- 3- methyl thiazolium of 2,5- bis- as bromine source using bromine or NBS
Pheno.Bromine is kind of a unstable and readily volatilized rufous liquid, larger to the corrosion of equipment and very big to the harm of human body.
There is hydrogen bromide generation in the actual production process, not only the atom utilization of bromine is not high, but also needs to post-process etc. it
Complicated procedures of forming；Although NBS is kind of a safer brominated reagent, but its preparation process is complicated, and preparation cost is higher, and is using
In the process usually along with the use of special chemical auxiliary agent, so cannot spread in actual production process.
Although these methods are generally all prior art discloses the methods of the various preparation bromo- 3 methyl thiophenes of 2,5- bis-
Have one or more disadvantages such as: severe reaction conditions, yield is lower, and the reaction time is longer, and selectivity of product is low, operation and
Post-process intricate operation etc..
Summary of the invention
For the deficiency and disadvantage for overcoming the existing synthesis bromo- 3 methyl thiophene of 2,5- bis-, the purpose of the present invention is to provide one
The new preparation method of the kind bromo- 3 methyl thiophene of 2,5- bis-.
The present invention uses following scheme:
The preparation method of the bromo- 3 methyl thiophene of 2,5- bis- shown in a kind of formula (II), which is characterized in that the method is pressed
Following steps carry out: using 3 methyl thiophene shown in formula (I) as raw material, brominating agent potassium are added, in the mixing of acetic acid and water
It is uniformly mixed in solution, then is slowly added to bromating agent ZnAl-BrO at 10~50 DEG C3 -- LDHs continues to be stirred to react 2h,
Gained reaction solution is post-treated to obtain the bromo- 3 methyl thiophene of 2,5- bis- shown in formula (II)；3- methyl thiazolium shown in the formula (I)
Pheno, ZnAl-BrO3 -The mass ratio of the material of-LDHs and potassium bromide is 1:1.3:1.6~1.9.
Further, the volume ratio of the mixed solution of acetic acid and water is V (AcOH): V (H in the solvent2O)=9:1.
Further, 3 methyl thiophene, ZnAl-BrO shown in the preferably described formula (I)3 -The amount of-LDHs and the substance of potassium bromide
The ratio between be 1:1.3:1.8.
Further, the preferably described reaction temperature is 30 DEG C, reaction time 2.25h.
The post-processing approach of reaction solution of the present invention are as follows: after reaction, reaction solution is through distilling water washing, methylene chloride
Extraction merges organic phase, and vacuum distillation removes organic solvent, obtains crude product, finally uses ethyl alcohol recrystallization, obtains formula (II) institute
The bromo- 3 methyl thiophene of 2,5- bis- shown.
Compared with prior art disclosure, the beneficial effects of the present invention are: reaction condition is mild, bromination examination used
Agent is solid matter, cheap and easy to get, and environmentally friendly；Operation is simple, convenient post-treatment；Target product yield is high, secondary
Reaction is few.
Detailed description of the invention:
Fig. 1 is the structural formula of the bromo- 3 methyl thiophene of 2,5- bis-；
Fig. 2 is the bromo- 3 methyl thiophene gas phase figure of 2,5- bis- prepared in the embodiment of the present invention；
Fig. 3 is the mass spectrogram of the bromo- 3 methyl thiophene of 2,5- bis- prepared in the embodiment of the present invention；
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of the bromo- 3 methyl thiophene of 2,5- bis- prepared in the embodiment of the present invention.
Specific embodiment
In order to be easy to understand creation feature, technological means, purpose and effect of the invention, below with reference to embodiment
The present invention is described further and explains, but specific embodiment is not limitation of the present invention.
All raw materials are bought from domestic chemical reagents corporation, are used not by purification but directly.
Embodiment 1
By the mixed of 3 methyl thiophene (512mg, 2mmol), potassium bromide (380.8mg, 3.2mmol), acetic acid 9ml and water 1ml
Close solution sequentially add with condenser pipe, thermometer three-neck flask in, be transferred in heated at constant temperature magnetic agitation water-bath,
ZnAl-BrO is slowly added in 15min in batches3 -- LDHs (2.6g, 2.6mmol), reaction temperature are 30 DEG C, are tracked with gas phase anti-
Process is answered, after reaction, is washed using distilled water (3 × 10ml), is then extracted using methylene chloride (3 × 10ml), merged
Organic phase.It is evaporated under reduced pressure away organic solvent, obtains crude product, ethyl alcohol recrystallization is finally used, obtains the bromo- 3- methyl thiazolium of 2,5- bis-
Pheno, yield 85%.1H NMR(500MHz,CDCl3)δ:6.78(s,1H),2.17(s,3H)；MS(EI)m/z:256.2([M+H]+).
Embodiment 2
By the mixed of 3 methyl thiophene (512mg, 2mmol), potassium bromide (428.4mg, 3.6mmol), acetic acid 9ml and water 1ml
Close solution sequentially add with condenser pipe, thermometer three-neck flask in, be transferred in heated at constant temperature magnetic agitation water-bath,
ZnAl-BrO is slowly added in 15min in batches3 -- LDHs (2.6g, 2.6mmol), reaction temperature are 30 DEG C, are tracked with gas phase anti-
Process is answered, after reaction, is washed using distilled water (3 × 10ml), is then extracted using methylene chloride (3 × 10ml), merged
Organic phase.It is evaporated under reduced pressure away organic solvent, obtains crude product, ethyl alcohol recrystallization is finally used, obtains the bromo- 3- methyl thiazolium of 2,5- bis-
Pheno, yield 94%.1H NMR(500MHz,CDCl3)δ:6.78(s,1H),2.17(s,3H)；MS(EI)m/z:256.2([M+H]+).
Embodiment 3
By the mixing of 3 methyl thiophene (512mg, 2mmol), potassium bromide (429mg, 3.8mmol), acetic acid 9ml and water 1ml
Solution sequentially add with condenser pipe, thermometer three-neck flask in, be transferred in heated at constant temperature magnetic agitation water-bath,
ZnAl-BrO is slowly added in 15min in batches3 -- LDHs (2.6g, 2.6mmol), reaction temperature are 30 DEG C, are tracked with gas phase anti-
Process is answered, after reaction, is washed using distilled water (3 × 10ml), is then extracted using methylene chloride (3 × 10ml), merged
Organic phase.It is evaporated under reduced pressure away organic solvent, obtains crude product, ethyl alcohol recrystallization is finally used, obtains the bromo- 3- methyl thiazolium of 2,5- bis-
Pheno, yield 92%.1H NMR(500MHz,CDCl3)δ:6.78(s,1H),2.17(s,3H)；MS(EI)m/z:256.2([M+H]+).
Embodiment 4
By the mixed of 3 methyl thiophene (512mg, 2mmol), potassium bromide (428.4mg, 3.6mmol), acetic acid 9ml and water 1ml
Close solution sequentially add with condenser pipe, thermometer three-neck flask in, be transferred in heated at constant temperature magnetic agitation water-bath,
ZnAl-BrO is slowly added in 15min in batches3 -- LDHs (2.6g, 2.6 mmol), reaction temperature are 10 DEG C, are tracked with gas phase
Reaction process is washed using distilled water (3 × 10ml) after reaction, is then extracted using methylene chloride (3 × 10ml), is closed
And organic phase.It is evaporated under reduced pressure away organic solvent, obtains crude product, ethyl alcohol recrystallization is finally used, obtains the bromo- 3- methyl thiazolium of 2,5- bis-
Pheno, yield 54%.1H NMR(500MHz,CDCl3)δ:6.78(s,1H),2.17(s,3H)；MS(EI)m/z:256.2([M+H]+).
Embodiment 5
By the mixed of 3 methyl thiophene (512mg, 2mmol), potassium bromide (428.4mg, 3.6mmol), acetic acid 9ml and water 1ml
Close solution sequentially add with condenser pipe, thermometer three-neck flask in, be transferred in heated at constant temperature magnetic agitation water-bath,
ZnAl-BrO is slowly added in 15min in batches3 -- LDHs (2.6g, 2.6mmol), reaction temperature are 20 DEG C, are tracked with gas phase anti-
Process is answered, after reaction, is washed using distilled water (3 × 10ml), is then extracted using methylene chloride (3 × 10ml), merged
Organic phase.It is evaporated under reduced pressure away organic solvent, obtains crude product, ethyl alcohol recrystallization is finally used, obtains the bromo- 3- methyl thiazolium of 2,5- bis-
Pheno, yield 84%.1H NMR(500MHz,CDCl3)δ:6.78(s,1H),2.17(s,3H)；MS(EI)m/z:256.2([M+H]+).
Embodiment 6
By the mixed of 3 methyl thiophene (512mg, 2mmol), potassium bromide (428.4mg, 3.6mmol), acetic acid 9ml and water 1ml
Close solution sequentially add with condenser pipe, thermometer three-neck flask in, be transferred in heated at constant temperature magnetic agitation water-bath,
ZnAl-BrO is slowly added in 15min in batches3 -- LDHs (2.6g, 2.6mmol), reaction temperature are 40 DEG C, are tracked with gas phase anti-
Process is answered, after reaction, is washed using distilled water (3 × 10ml), is then extracted using methylene chloride (3 × 10ml), merged
Organic phase.It is evaporated under reduced pressure away organic solvent, obtains crude product, ethyl alcohol recrystallization is finally used, obtains the bromo- 3- methyl thiazolium of 2,5- bis-
Pheno, yield 91%.1H NMR(500MHz,CDCl3)δ:6.78(s,1H),2.17(s,3H)；MS(EI)m/z:256.2([M+H]+).
Embodiment 7
By the mixed of 3 methyl thiophene (512mg, 2mmol), potassium bromide (428.4mg, 3.6mmol), acetic acid 9ml and water 1ml
Close solution sequentially add with condenser pipe, thermometer three-neck flask in, be transferred in heated at constant temperature magnetic agitation water-bath,
ZnAl-BrO is slowly added in 15min in batches3 -- LDHs (2.6g, 2.6mmol), reaction temperature are 50 DEG C, are tracked with gas phase anti-
Process is answered, after reaction, is washed using distilled water (3 × 10ml), is then extracted using methylene chloride (3 × 10ml), merged
Organic phase.It is evaporated under reduced pressure away organic solvent, obtains crude product, ethyl alcohol recrystallization is finally used, obtains the bromo- 3- methyl thiazolium of 2,5- bis-
Pheno, yield 88%.1H NMR(500MHz,CDCl3)δ:6.78(s,1H),2.17(s,3H)；MS(EI)m/z:256.2([M+H]+)。
Claims (5)
1. the preparation method of the bromo- 3 methyl thiophene of 2,5- bis- shown in a kind of formula (II), which is characterized in that the method is by such as
Lower step carries out: using 3 methyl thiophene shown in formula (I) as raw material, brominating agent potassium is added, it is molten in the mixing of acetic acid and water
It is uniformly mixed in liquid, bromating agent ZnAl-BrO is slowly added at 10~50 DEG C3 -- LDHs continues to be stirred to react 2h, institute
Reaction solution is post-treated obtains the bromo- 3 methyl thiophene of 2,5- bis- shown in formula (II)；3- methyl thiazolium shown in the formula (I)
Pheno, ZnAl-BrO3 -The mole dosage of-LDHs and potassium bromide ratio is 1:1.3:1.6~1.9；
。
2. a kind of preparation method of the bromo- 3 methyl thiophene of 2,5- bis- according to claim 1, which is characterized in that described
The volume ratio of the mixed solution of acetic acid and water is V (AcOH): V (H2O)=9:1.
3. a kind of preparation method of the bromo- 3 methyl thiophene of 2,5- bis- according to claim 1, which is characterized in that the formula
(I) 3 methyl thiophene, ZnAl-BrO shown in3 -The ratio between amount of substance of-LDHs and potassium bromide is 1:1.3:1.8.
4. a kind of preparation method of the bromo- 3 methyl thiophene of 2,5- bis- according to claim 1, which is characterized in that described anti-
Answering temperature is 30 DEG C, reaction time 2.25h.
5. a kind of preparation method of the bromo- 3 methyl thiophene of 2,5- bis- according to claim 1, which is characterized in that described anti-
Answer the post-processing approach of liquid are as follows: after reaction, reaction solution is distilled water washing, and methylene chloride extraction merges organic phase, decompression
Organic solvent is distilled off, obtains crude product, finally uses ethyl alcohol recrystallization, obtains the bromo- 3- methyl of 2,5- bis- shown in formula (II)
Thiophene.
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| 以溴酸根插层锌铝水滑石为载体构建新溴源体系;王力耕等;《硅酸盐学报》;20150502;第43卷(第5期);参见对比文件2第673页第1栏第1段、第2栏第2段、第676页第1栏第4段 * |
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