CN101157682B - Method for preparing acetyl thiophene - Google Patents
Method for preparing acetyl thiophene Download PDFInfo
- Publication number
- CN101157682B CN101157682B CN200710156595XA CN200710156595A CN101157682B CN 101157682 B CN101157682 B CN 101157682B CN 200710156595X A CN200710156595X A CN 200710156595XA CN 200710156595 A CN200710156595 A CN 200710156595A CN 101157682 B CN101157682 B CN 101157682B
- Authority
- CN
- China
- Prior art keywords
- thiophene
- acetyl thiophene
- preparation
- palladium
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical compound CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 13
- 150000003577 thiophenes Chemical class 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 229910052763 palladium Inorganic materials 0.000 claims description 24
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000012141 concentrate Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000010898 silica gel chromatography Methods 0.000 claims description 14
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 claims description 13
- -1 vinyl ethers compound Chemical class 0.000 claims description 12
- 150000003440 styrenes Chemical class 0.000 claims description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003456 ion exchange resin Substances 0.000 claims description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims 1
- 239000012485 toluene extract Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 16
- 229920005989 resin Polymers 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 25
- 239000007788 liquid Substances 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 10
- GSFNQBFZFXUTBN-UHFFFAOYSA-N 2-chlorothiophene Chemical compound ClC1=CC=CS1 GSFNQBFZFXUTBN-UHFFFAOYSA-N 0.000 description 6
- 150000005759 2-chloropyridine Chemical class 0.000 description 5
- ROIMNSWDOJCBFR-UHFFFAOYSA-N 2-iodothiophene Chemical compound IC1=CC=CS1 ROIMNSWDOJCBFR-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- RNIDWJDZNNVFDY-UHFFFAOYSA-N 3-Acetylthiophene Chemical compound CC(=O)C=1C=CSC=1 RNIDWJDZNNVFDY-UHFFFAOYSA-N 0.000 description 2
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 2
- QUBJDMPBDURTJT-UHFFFAOYSA-N 3-chlorothiophene Chemical compound ClC=1C=CSC=1 QUBJDMPBDURTJT-UHFFFAOYSA-N 0.000 description 2
- 238000007341 Heck reaction Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 150000005760 3-chloropyridine Chemical class 0.000 description 1
- WGKRMQIQXMJVFZ-UHFFFAOYSA-N 3-iodothiophene Chemical compound IC=1C=CSC=1 WGKRMQIQXMJVFZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a preparation method of acetyl thiophene, in particular to the preparation method of acetyl thiophene with the involvement of macroporous weak base styrene type anion exchange resins, the technical proposal is that: vinyl ether compounds and halogenated thiophene are agitated in the dimethyl formamide for reaction for 1 to 20 hours with the presence of macroporous weak base styrene type anion exchange resins and the palladium acetate catalyst at 100 to 150 DEG C, so as to get the reaction product, the acetyl thiophene is obtained by separation and purification of the reaction product, the ratio of the weight of halogenated thiophene, vinyl ether compounds, palladium acetate, weak base anion exchange resins is 1: 1 to 5: 0.005 to 0.01: 1 to 2. Compared with the prior art, the main beneficial effects of the technical proposal adopted by the invention are that the resins in the reaction product can be reclaimed, the invention does not use the organic phosphine ligand and is easy for industrialization production without environmental pollution.
Description
(1) technical field
The present invention relates to a kind of method for preparing acetyl thiophene, the preparation acetyl thiophene method that particularly a kind of macroreticular weakly base styrene series anion exchange resin participates in.
(2) background technology
Acetyl thiophene is the important intermediate of important chemical material and many medicines.On the ring of thiophene heterogeneous ring compound, introduce ethanoyl; generally on 2 of ring than being easier to; mainly under the Lewis acid catalysis, directly carry out close electric acylation reaction with carboxy derivatives; and have the active intermediate of carbonium ion by some aromatic hydrocarbons is carried out electrophilic substitution, after decomposing, be converted into the indirect reaction of acyl group again.But it is just relatively more difficult to adopt aforesaid method to carry out acetylize on 3 of ring.
The Heck reaction is under phosphine part and catalyzing by metal palladium, and organic amine is as alkali, by the important method of halogenated aryl hydrocarbon and the synthetic alkenyl substituted aromatic hydroxy compound of alkene.Utilize traditional synthetic method to carry out suitability for industrialized production, be difficult to reclaim, and need organophosphorus ligand to improve reactive activity as the organic amine of alkali, big for environment pollution.Therefore, friendly new catalytic material of development environment and catalysis The Study on New Technology will be the important contents of Green Chemistry research.Along with the development of weak-base ion-exchange resin, utilize the functional cleansing preparation method of making Study on Technology of carrying out of ion exchange resin, be an important development direction of Green Chemistry synthetic technology.
(3) summary of the invention
The object of the present invention is to provide a kind of weak base anion-exchange resin that utilizes as alkali; under the catalysis of palladium metal reagent; carry out the Heck reaction by halogenated thiophene and vinyl ethers compound; make ethanoyl substituted thiophene compound, synthesis technique of the present invention is easy to suitability for industrialized production, is convenient to operation and processing; resin easily reclaims; avoid the use of organic phosphine compound, reduced production cost, solved the pollution problem that occurs in the chemical reaction process.
For reaching goal of the invention the technical solution used in the present invention be:
Use suc as formula the vinyl ether shown in (I) with suc as formula (II) or the halogenated thiophene (III) in dimethyl formamide, in the presence of suc as formula the macroreticular weakly base styrene series anion exchange resin shown in (IV), palladium catalyzer, in 100～150 ℃, stirring reaction got reaction product in 1～20 hour, reaction product obtains described acetyl thiophene through separation and purification, and described halogenated thiophene, vinyl ethers compound, palladium, the weak-base ion-exchange resin amount of substance ratio that feeds intake is 1: 1～5: 0.005～0.01: 1～2;
In the formula (I), R
1Be expressed as the alkyl of carbonatoms 4;
Formula (II) and (III) in, X is Cl, Br or I;
Formula (IV) R2, R3 are methyl or hydrogen atom independently of one another, and n represents contained number of repeat unit purpose mean value on the polymer macromolecule chain, weigh the index of polymer molecule size, are Styrene-DVBD301 type resin in the present invention.
The volumetric usage that the present invention recommends described dimethyl formamide is 1～10: 1 (ml/mmol) with the molar weight ratio of halogenated thiophene material.
The amount of substance ratio of halogenated thiophene of the present invention, vinyl ether, palladium, macroreticular weakly base styrene series anion exchange resin is preferably 1: 2: 0.005: 1.5.
Halogenated thiophene of the present invention is 2-bromothiophene, 3 bromo thiophene, 2-chlorothiophene, 3-chlorothiophene, 2-iodothiophen or 3-iodothiophen.
Vinyl ethers compound of the present invention is a n-butyl vinyl ether.
Temperature of reaction of the present invention is preferably 120～140 ℃, and the reaction times is preferably 5～8 hours.
What method of the present invention was concrete is: use 2-bromothiophene and n-butyl vinyl ether in dimethyl formamide; in palladium with in the presence of suc as formula a kind of macroreticular weakly base styrene series anion exchange resin participation shown in (IV); got reaction product in 5 hours at 140 ℃ of following stirring reactions; reaction product obtains described acetyl thiophene through separation and purification; described 2-bromothiophene; n-butyl vinyl ether; palladium; the mol ratio of weak-base ion-exchange resin is 1: 2: 0.01: 1.5, and the volume of described dimethyl formamide is 5: 1 (ml/mmol) with the ratio of the mole number of halogenated thiophene.
Separation and purification of the present invention is: with toluene extractive reaction product, with toluene extraction liquid drying, concentrate, get acetyl thiophene with silica gel column chromatography separating purification.
A kind of macroreticular weakly base styrene series anion exchange resin of the present invention is the commercially available prod, proposed model is: Styrene-DVB (D301R), Styrene-DVB (D301T), Styrene-DVB (D301G), Styrene-DVB (D392), the weak-base ion-exchange resin of Styrene-DVB (D380).
Technical scheme that the present invention adopts beneficial effect compared with the prior art is presented as that mainly the resin in the reaction product can reclaim, and does not use organophosphorus ligand, is easy to suitability for industrialized production, environmentally safe.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1: prepare the 2-acetyl thiophene by the 2-bromothiophene
With 163 milligrams of 2-bromothiophenes (1 mmole), 23 milligrams of palladium (0.01 mmole), 200 milligrams of n-butyl vinyl ether (2 mmole), Styrene-DVB (D301R) resin 0.3 gram (1.5 mmole), 5 milliliters of dimethyl formamides, place 50 ml flasks, stirring heating was 100 ℃ of reactions 10 hours.After reaction finishes, cooling.With toluene (3 * 50 milliliters) extraction, extraction liquid drying, concentrate, silica gel column chromatography separate 113 milligrams of products, yield 90%.
1H?NMR(CDCl
3)δ：2.57(s，3H)，7.14(m，1H)，7.64(m，1H)，7.71(m，1H)；
13CNMR(CDCl
3)δ：27.32，128.5，132.9，134.2，145.0，191.2。
MS(m/z)：126(M
+)。
Embodiment 2: prepare the 2-acetyl thiophene by the 2-bromothiophene
With 163 milligrams of 2-bromothiophenes (1 mmole), 12 milligrams of palladium (0.005 mmole), 150 milligrams of n-butyl vinyl ether (1.5 mmole), Styrene-DVB (D301R) resin 0.4 gram (2 mmole), 5 milliliters of dimethyl formamides, place 50 ml flasks, stirring heating was 130 ℃ of reactions 10 hours.After reaction finishes, cooling.With toluene (3 * 50 milliliters) extraction, extraction liquid drying, concentrate, silica gel column chromatography separate 110 milligrams of products, yield 88%.
Embodiment 3: prepare the 3-acetyl thiophene by 3 bromo thiophene
With 163 milligrams of 3 bromo thiophenes (1 mmole), 23 milligrams of palladium (0.01 mmole), 200 milligrams of n-butyl vinyl ether (2 mmole), Styrene-DVB (D301R) resin 0.3 gram (1.5 mmole), 10 milliliters of dimethyl formamides, place 50 ml flasks, stirring heating was 100 ℃ of reactions 10 hours.After reaction finishes, cooling.With toluene (3 * 50 milliliters) extraction, extraction liquid drying, concentrate, silica gel column chromatography separate 111 milligrams of products, yield 88%.
1H?NMR(CDCl
3)δ：2.51(s，3H)，7.31(m，1H)，7.54(m，1H)，8.04(m，1H)；
13CNMR(CDCl
3)δ：27.40，126.8，127.3，132.5，143.1，192.7。
MS(m/z)：126(M
+)。
Embodiment 4: prepare the 3-acetyl thiophene by the 3-chlorothiophene
With 119 milligrams of 3-chloropyridines (1 mmole), 23 milligrams of palladium (0.01 mmole), 200 milligrams of n-butyl vinyl ether (2 mmole), Styrene-DVB (D301R) resin 0.3 gram (1.5 mmole), 1 milliliter of dimethyl formamide, place 50 ml flasks, stirring heating was 150 ℃ of reactions 20 hours.After reaction finishes, cooling.With toluene (3 * 50 milliliters) extraction, extraction liquid drying, concentrate, silica gel column chromatography separate 101 milligrams of products, yield 80%.
Embodiment 5: prepare the 2-acetyl thiophene by the 2-chlorothiophene
With 119 milligrams of 2-chloropyridines (1 mmole), 23 milligrams of palladium (0.01 mmole), 200 milligrams of n-butyl vinyl ether (2 mmole), Styrene-DVB (D301G) resin 0.36 gram (1.5 mmole), 10 milliliters of dimethyl formamides, place 50 ml flasks, stirring heating was 130 ℃ of reactions 5 hours.After reaction finishes, cooling.With toluene (3 * 50 milliliters) extraction, extraction liquid drying, concentrate, silica gel column chromatography separate 107 milligrams of products, yield 85%.
Embodiment 6: prepare the 2-acetyl thiophene by the 2-iodothiophen
With 210 milligrams of 2-iodothiophens (1 mmole), 23 milligrams of palladium (0.01 mmole), 200 milligrams of n-butyl vinyl ether (2 mmole), Styrene-DVB (D301T) resin 0.3 gram (1.5 mmole), 5 milliliters of dimethyl formamides, place 50 ml flasks, stirring heating was 100 ℃ of reactions 10 hours.After reaction finishes, cooling.With toluene (3 * 50 milliliters) extraction, extraction liquid drying, concentrate, silica gel column chromatography separate 118 milligrams of products, yield 94%.
Embodiment 7: prepare the 2-acetyl thiophene by the 2-chlorothiophene
With 119 milligrams of 2-chloropyridines (1 mmole), 16 milligrams of palladium (0.007 mmole), 100 milligrams of n-butyl vinyl ether (1 mmole), Styrene-DVB (D301G) resin 0.36 gram (1.5 mmole), 10 milliliters of dimethyl formamides, place 50 ml flasks, stirring heating was 130 ℃ of reactions 5 hours.After reaction finishes, cooling.With with toluene (3 * 50 milliliters) extraction, the extraction liquid drying concentrates, silica gel column chromatography separate 107 milligrams of products, yield 85%.
Embodiment 8: prepare the 2-acetyl thiophene by the 2-chlorothiophene
With 119 milligrams of 2-chloropyridines (1 mmole), 20 milligrams of palladium (0.009 mmole), 500 milligrams of n-butyl vinyl ether (5 mmole), Styrene-DVB (D301G) resin 0.36 gram (1.5 mmole), 5 milliliters of dimethyl formamides, place 50 ml flasks, stirring heating was 130 ℃ of reactions 5 hours.After reaction finishes, cooling.With toluene (3 * 50 milliliters) extraction, extraction liquid drying, concentrate, silica gel column chromatography separate 101 milligrams of products, yield 80%.
Embodiment 9: prepare the 2-acetyl thiophene by the 2-bromothiophene
With 163 milligrams of 2-bromothiophenes (1 mmole), 23 milligrams of palladium (0.01 mmole), 200 milligrams of n-butyl vinyl ether (2 mmole), Styrene-DVB (D301R) resin 0.3 gram (1.5 mmole), 10 milliliters of dimethyl formamides, place 50 ml flasks, stirring heating was 100 ℃ of reactions 10 hours.After reaction finishes, cooling.With toluene (3 * 50 milliliters) extraction, extraction liquid drying, concentrate, silica gel column chromatography separate 113 milligrams of products, yield 91%.
Embodiment 10: prepare the 2-acetyl thiophene by the 2-chlorothiophene
With 119 milligrams of 2-chloropyridines (1 mmole), 20 milligrams of palladium (0.009 mmole), 500 milligrams of n-butyl vinyl ether (5 mmole), Styrene-DVB (D301G) resin 0.36 gram (1.5 mmole), 1 milliliter of dimethyl formamide, place 50 ml flasks, stirring heating was 130 ℃ of reactions 5 hours.After reaction finishes, cooling.With toluene (3 * 50 milliliters) extraction, extraction liquid drying, concentrate, silica gel column chromatography separate 101 milligrams of products, yield 80%.
Embodiment 11: prepare the 2-acetyl thiophene by the 2-chlorothiophene
With 119 milligrams of 2-chloropyridines (1 mmole), 20 milligrams of palladium (0.009 mmole), 500 milligrams of n-butyl vinyl ether (5 mmole), the Styrene-DVB of reclaiming (D301G) resin 0.36 gram (1.5 mmole), 1 milliliter of dimethyl formamide, place 50 ml flasks, stirring heating was 130 ℃ of reactions 5 hours.After reaction finishes, cooling.With toluene (3 * 50 milliliters) extraction, extraction liquid drying, concentrate, silica gel column chromatography separate 101 milligrams of products, yield 80%.
Embodiment 12: prepare the 2-acetyl thiophene by the 2-iodothiophen
With 210 milligrams of 2-iodothiophens (1 mmole), 23 milligrams of palladium (0.01 mmole), 200 milligrams of n-butyl vinyl ether (2 mmole), Styrene-DVB (D301T) resin 0.2 gram (1 mmole), 5 milliliters of dimethyl formamides, place 50 ml flasks, stirring heating was 150 ℃ of reactions 20 hours.After reaction finishes, cooling.With toluene (3 * 50 milliliters) extraction, extraction liquid drying, concentrate, silica gel column chromatography separate 118 milligrams of products, yield 83%.
Claims (7)
1. the preparation method of an acetyl thiophene, it is characterized in that described method be use suc as formula the vinyl ethers compound shown in (I) with suc as formula (II) or the halogenated thiophene (III) in dimethyl formamide, in the presence of suc as formula macroreticular weakly base styrene series anion exchange resin shown in (IV) and palladium catalyzer, in 100～150 ℃, stirring reaction got reaction product in 1～20 hour, reaction product obtains described acetyl thiophene through separation and purification, described halogenated thiophene, vinyl ethers compound, palladium, the macroreticular weakly base styrene series anion exchange resin amount of substance ratio that feeds intake is 1: 1～5: 0.005～0.01: 1～2;
In the formula (I), R
1Be expressed as carbonatoms and be 4 alkyl;
Formula (II) and (III) in, X is Cl, Br or I;
R in the formula (IV)
2, R
3Be methyl or hydrogen atom independently of one another, n represents contained number of repeat unit purpose mean value on the polymer macromolecule chain.
2. the preparation method of acetyl thiophene according to claim 1, the volumetric usage that it is characterized in that described dimethyl formamide is 1～10: 1 (ml/mmol) with the ratio of the mole number of halogenated thiophene.
3. the preparation method of acetyl thiophene according to claim 1 is characterized in that described vinyl ethers compound is a n-butyl vinyl ether.
4. the preparation method of acetyl thiophene according to claim 1 is characterized in that described temperature of reaction is 120～140 ℃, and the reaction times is 5～8 hours.
5. the preparation method of acetyl thiophene according to claim 1 is characterized in that the amount of substance ratio that feeds intake of described halogenated thiophene, vinyl ethers compound, palladium, macroreticular weakly base styrene series anion exchange resin is 1: 2: 0.005: 1.5.
6. the preparation method of acetyl thiophene according to claim 1; it is characterized in that described method is to use 2-bromothiophene and n-butyl vinyl ether in dimethyl formamide; in palladium with in the presence of suc as formula the macroreticular weakly base ion exchange resin shown in (IV); got reaction product in 5 hours at 140 ℃ of following stirring reactions; reaction product obtains described acetyl thiophene through separation and purification; described 2-bromothiophene; n-butyl vinyl ether; palladium; the amount of substance ratio of macroreticular weakly base styrene series anion exchange resin is 1: 2: 0.01: 1.5, and the volume of described dimethyl formamide is 1～5: 1 (ml/mmol) with the ratio of the mole number of 2-bromothiophene.
7. as the preparation method of the described acetyl thiophene of one of claim 1～6, it is characterized in that described separation and purification is: reaction product extracts with toluene, with the toluene extract drying, concentrates, and silica gel column chromatography separating purification gets acetyl thiophene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710156595XA CN101157682B (en) | 2007-11-09 | 2007-11-09 | Method for preparing acetyl thiophene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710156595XA CN101157682B (en) | 2007-11-09 | 2007-11-09 | Method for preparing acetyl thiophene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101157682A CN101157682A (en) | 2008-04-09 |
| CN101157682B true CN101157682B (en) | 2010-06-23 |
Family
ID=39305931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710156595XA Expired - Fee Related CN101157682B (en) | 2007-11-09 | 2007-11-09 | Method for preparing acetyl thiophene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101157682B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544432A (en) * | 2003-11-27 | 2004-11-10 | 北京石油化工学院 | 2-acetyl thiophene synthetic method using thiophene in crude benzene as material |
| CN1651427A (en) * | 2004-11-18 | 2005-08-10 | 浙江工业大学 | Preparation method of acetyl thiophene |
| CN1886396A (en) * | 2003-12-17 | 2006-12-27 | 住友精化株式会社 | Process for producing 2-acylthiophene compound |
-
2007
- 2007-11-09 CN CN200710156595XA patent/CN101157682B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544432A (en) * | 2003-11-27 | 2004-11-10 | 北京石油化工学院 | 2-acetyl thiophene synthetic method using thiophene in crude benzene as material |
| CN1886396A (en) * | 2003-12-17 | 2006-12-27 | 住友精化株式会社 | Process for producing 2-acylthiophene compound |
| CN1651427A (en) * | 2004-11-18 | 2005-08-10 | 浙江工业大学 | Preparation method of acetyl thiophene |
Non-Patent Citations (4)
| Title |
|---|
| Hisahiro Hagiwara, et al..Heterogeneous Heck reaction catalyzed by Pd/C inionicliquid.Tetrahedron Letters42 26.2001,42(26),4349-4351. |
| Hisahiro Hagiwara, et al..Heterogeneous Heck reaction catalyzed by Pd/C inionicliquid.Tetrahedron Letters42 26.2001,42(26),4349-4351. * |
| 曾朝霞.胺基功能化树脂负载钯催化剂的制备、表征及Heck芳基化反应性能的研究.中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑 12.2006,工程科技I辑(12),第7页第2段,第21-23页第2.4.3.3小节,第2.4.3.4小节,第2.4.3.6小节,第41页第3.6.3小节. |
| 曾朝霞.胺基功能化树脂负载钯催化剂的制备、表征及Heck芳基化反应性能的研究.中国优秀博硕士学位论文全文数据库(硕士)工程科技I辑 12.2006,工程科技I辑(12),第7页第2段,第21-23页第2.4.3.3小节,第2.4.3.4小节,第2.4.3.6小节,第41页第3.6.3小节. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101157682A (en) | 2008-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Silica-gel-supported dual acidic ionic liquids as efficient catalysts for the synthesis of polyoxymethylene dimethyl ethers | |
| CN107573370A (en) | The method that supported copper ion chitosan microball catalysis prepares organoboron compound and β hydroxy compounds | |
| Aoyama et al. | Silica gel-supported polyphosphoric acid (PPA/SiO2) as an efficient and reusable catalyst for conversion of carbonyl compounds into oxathioacetals and dithioacetals | |
| CN104892655B (en) | The method that alkylboronic acids ester compounds are prepared based on iron catalysis | |
| Ren et al. | Enhanced basicity of Ag2O by coordination to soft anions | |
| Liu et al. | Enantioselective Nickel‐Catalyzed Hydrosilylation of 1, 1‐Disubstituted Allenes | |
| CN103936562A (en) | Method for preparing bisphenol F | |
| CN104892614A (en) | Synthesis method of 6H-isoindolo[2, 1-alpha]indol-6-one derivative | |
| CN101157682B (en) | Method for preparing acetyl thiophene | |
| CN101381362A (en) | Preparation method of thiophen derivate chloromethylation products | |
| CN101851200A (en) | Synthetic method of 1-phenyl-1,2,3,4-tetrahydroisoquinoline | |
| Maki et al. | Arylboronic acid-catalyzed direct condensation of carboxylic acids with ureas | |
| CN101880228A (en) | Clean preparation method for butyl acetate | |
| CN110885292A (en) | β -amino alcohol compound synthesis method | |
| CN101186602B (en) | Method for synthesizing 2-methyl-2-aryl-1,3-dioxolane compound | |
| CN106380469A (en) | Synthesis method of 1-aromatic carbonyl-2-aryl-3-ester imidazolone compounds | |
| CN101016222B (en) | Method of eliminating boric acid group from alkyl biphenyl boric acid compounds | |
| CN102950025A (en) | Asymmetric hydrogenation catalyst of imine and its use | |
| CN105294581B (en) | A kind of preparation method of quinocetone | |
| Zhang | Mild and Efficient Allylation of Aldehydes with Allyltributylstannane Promoted by MgI2·(OEt) n Etherate | |
| CN101177412B (en) | Method for synthesizing acetyl substituted nitrogen heterocycle compounds | |
| CN103274958B (en) | Method for preparing amide compound through catalysis of ligand-assisted zirconium oxychloride | |
| CN101830763A (en) | Application of nickel catalyst in suzuki-miyaura coupling reaction | |
| CN1295226C (en) | Preparation method of acetyl thiophene | |
| CN102911044A (en) | Method for preparing sec-butyl acetate via n-butene addition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Linhai Limin Chemicals Co., Ltd. Assignor: Zhejiang University of Technology Contract record no.: 2010330001947 Denomination of invention: Method for preparing acetyl thiophene Granted publication date: 20100623 License type: Exclusive License Open date: 20080409 Record date: 20100926 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100623 Termination date: 20131109 |