CN101204670A - Aminopyridine resin catalyst loading Pd and application thereof - Google Patents
Aminopyridine resin catalyst loading Pd and application thereof Download PDFInfo
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Abstract
A resin containing aminopyridine-supported palladium catalyst is provided by the invention. The catalyst is acquired by carrying of PdCl2 (CH3CN) 2 by resin containing aminopyridine in N, N-dimethylfomamide, and mass content of the palladium in the resin containing aminopyridine-supported palladium catalyst is 1.0 percent-10.0 percent. The resin containing aminopyridine-supported palladium catalyst is prepared by the method: resin containing aminopyridine and PdCl2 (CH3CN) 2, weigh ratio of which is 1:0.05-0.5, is added into N, N-dimethylfomamide and stirred for 60-80h at room temperature; after the reaction finishes, the material acquired is filtered, residue filtered, washed and dried at the temperature of 60 DEG C, and the resin containing aminopyridine-supported palladium catalyst is acquired; dosage of the N, N-dimethylfomamide is 10-20ml/g resin containing aminopyridine. The resin containing aminopyridine-supported palladium catalyst of the invention is applied in Heck reaction, and has simple and easy technique, low cost, high reaction activity, little pollution and high product yield and purity, requiring no inorganic base or organic amine and organic phosphonate ligand and the resin is recyclable.
Description
(1) technical field
The present invention relates to a kind of aminopyridine resin catalyst loading Pd and the application in the Heck reaction thereof.
(2) background technology
Heck reaction under the palladium catalysis is the important method that forms the C-C key, is having broad application prospects aspect many natural products of preparation and the pharmaceutical intermediate.Reaction has advantages of high catalytic activity to palladium catalytic system to Heck, but, in this reaction system, must use inorganic base or organic amine as alkali, organic phosphine compound easily produces palladium black as the reaction part in course of reaction, be difficult to separate with reactant liquor, catalyst activity is reduced, and the inorganic base that uses or organic amine and organophosphorus ligand be difficult to reclaim, and had a strong impact on the practical application of Heck reaction.
In recent years, as support type heterogeneous catalyst technology, owing to have advantages of high catalytic activity and stereoselectivity, and stability and repeat performance preferably, the polymer loaded palladium catalyst has obtained bigger development, becomes important research direction from now on.
Aminopyridine resin has good adsorptivity to some metal ion, can be used as adsorbent and be applied in the hydrometallurgy aspects such as enrichment, extraction, be applied to the report that the Heck reaction has good catalytic performance after the aminopyridine resin supported palladium is not also arranged at present metal ion.
(3) summary of the invention
The present invention seeks to need not to use inorganic base or organic amine and organophosphorus ligand, reactivity height in order to provide a kind of, pollute few the aminopyridine loaded palladium catalyst and the application thereof that can be applicable to the Heck reaction.
The technical solution used in the present invention is:
A kind of aminopyridine resin catalyst loading Pd, by aminopyridine resin at N, load P dCl in the dinethylformamide
2(CH
3CN)
2Obtain, the palladium mass content is 1.0～10.0% in the described aminopyridine resin catalyst loading Pd.Described aminopyridine resin catalyst loading Pd is prepared by following method: be 1: 0.05～0.5 aminopyridine resin and PdCl with mass ratio
2(CH
3CN)
2Adding N in the dinethylformamide, stirred under the room temperature 60～80 hours, after reaction finishes, filtered, and filter residue gets described aminopyridine resin catalyst loading Pd through washing, 60 ℃ of dryings; Described N, dinethylformamide consumption are 10～20mL/g aminopyridine resin.
Described aminopyridine resin is 4-aminopyridine resin, 3-aminopyridine resin or 2-aminopyridine resin.
The preparation method of aminopyridine resin catalyst loading Pd of the present invention is as follows: be 1: 0.05～0.5 aminopyridine resin and PdCl with mass ratio
2(CH
3CN)
2Adding N in the dinethylformamide, stirred under the room temperature 60～80 hours, after reaction finishes, filtered, and filter residue is used N successively, dinethylformamide, distilled water, ethanol, ether washing, and 60 ℃ of dryings get described aminopyridine resin catalyst loading Pd; Described N, dinethylformamide consumption are 10～20mL/g aminopyridine resin.
Described aminopyridine resin can according to document (Xiong Chunhua, Shu Zengnian, Wang Yongjiang, the chemical industry journal, 2005,56 (7), 1267-1270) reported method makes with chloromethyl polystyrene bead body and aminopyridine.
The invention still further relates to the application of aminopyridine resin catalyst loading Pd in the Heck reaction.
Concrete, described being applied as: be 1: 1～5: 0.01～0.1 halogenated aryl hydrocarbon compounds, vinyl compound, aminopyridine resin catalyst loading Pd with the ratio of amount of substance, join in the aprotic polar solvent, in 50～180 ℃ of following stirring reactions 1～30 hour, reaction finishes afterreaction liquid and obtains functionalized aromatic compound through separation and purification, and described aprotic polar solvent consumption is 10～500mL/mmol halogenated aryl hydrocarbon compounds.
Described aprotic polar solvent is the common aprotic polar solvent that is applied to the Heck reaction, as N, and dinethylformamide, dimethyl sulfoxide (DMSO), dimethyl sulfone, 1-methyl pyrrolidone etc.; Described halogenated aryl hydrocarbon compounds is the common chloride atom of Heck reaction or all kinds of substituted arenes and the heterocyclic compound of bromine atoms or iodine atom of carrying out, as m-trifluoromethyl phenyl-bromide, 2-bromopyridine, 3-chloropyridine, 3-bromoquinoline, 5-bromo pyrimi piperidine, 2-bromo-6-methoxynaphthalene, 2-iodine 6-methoxynaphthalene, 2-bromothiophene, 3 bromo thiophene, bromobenzene, 3-bromobenzylcyanide, 4-toluene bromide, 2-bromonaphthalene, 4-bromoacetophenone, 4-bromoanisole etc.; Described vinyl compound is the common compound that contains vinyl that carries out the Hcek reaction, as vinyl-n-butyl ether, n-butyl vinyl ether, n-hexyl vinyl ethers, allyl alcohol, N-vinyl-2-Pyrrolidone, 2-hydroxyethyl vinyl ethers etc.
Preferably, described being applied as: the halogenated aryl hydrocarbon compounds, vinyl compound, the aminopyridine resin catalyst loading Pd that with the ratio of amount of substance are 1: 2: 0.1, join in the aprotic polar solvent, agitating heating was 100 ℃ of reactions 15 hours, after reaction finishes, cooling is with 50 milliliters of extractions of toluene three times, extract drying, concentrate, column chromatography for separation gets functionalized aromatic compound; Described aprotic polar solvent consumption is a 50mL/mmol halogenated aryl hydrocarbon compounds.
Aminopyridine resin catalyst loading Pd of the present invention is applied to the Heck reaction, and technology is simple to operation, and cost is low, need not to use inorganic base or organic amine and organophosphorus ligand, reactivity height, pollutes and lack product yield purity height, and the recyclable utilization of resin.
(4) specific 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: aminopyridine resin catalyst loading Pd synthetic
The 4-aminopyridine resin catalyst loading Pd is synthetic:
Get chlorinty and be 19.6%, chloromethylated polystyrene pearl body (Lishui department of chemistry of the teachers training school provides) 100g of degree of cross linking 6%DVB, at 50mL 1, swelling in the 4-dioxane, add 4-aminopyridine 94g (4-AP/Cl=1, mol ratio), 60 ℃ of reaction temperatures, reaction time 15h, filter, use dioxane, absolute ethanol washing successively, 2% (mass percent) sodium hydroxide solution soaked 10 hours, and deionized water is washed till neutrality, with acetone, ether washing, drying obtains the 4-aminopyridine resin that functional group content is 3.31mmol/g again.
1.0 gram 4-aminopyridine resin and 0.2 gram PdCl
2(CH
3CN)
2In 15 milliliters of DMF, stirred 72 hours in the room temperature lower magnetic force.Filter after the reaction end, fully wash,, get pale brown look solid 4-aminopyridine resin catalyst loading Pd, record palladium content by the atom absorption and be about 3.0% (mass percent) 60 ℃ of oven dry down with DMF, distilled water, ethanol, ether.
The 2-aminopyridine resin catalyst loading Pd is synthetic:
Get chlorinty and be 19.6%, chloromethylated polystyrene pearl body (Lishui department of chemistry of the teachers training school provides) 100g of degree of cross linking 6%DVB, at 50mL 1, swelling in the 4-dioxane, add 2-aminopyridine 94g (4-AP/Cl=1, mol ratio), 60 ℃ of reaction temperatures, reaction time 15h, filter, use dioxane, absolute ethanol washing successively, 2% sodium hydroxide solution soaked 10 hours, and deionized water is washed till neutrality, with acetone, ether washing, drying obtains the 2-aminopyridine resin that functional group content is 3.31mmol/g again.
1.0 gram 2-aminopyridine resin and 0.4 gram PdCl
2(CH
3CN)
2In 20 milliliters of DMF, stirred 72 hours in the room temperature lower magnetic force.Filter after the reaction end, fully wash,, get pale brown look solid 2-aminopyridine resin catalyst loading Pd, record palladium content by the atom absorption and be about 6.0% (mass percent) 60 ℃ of oven dry down with DMF, distilled water, ethanol, ether.
The 3-aminopyridine resin catalyst loading Pd is synthetic:
Get chlorinty and be 19.6%, chloromethylated polystyrene pearl body (Lishui department of chemistry of the teachers training school provides) 100g of degree of cross linking 6%DVB, at 50mL 1, swelling in the 4-dioxane, add 3-aminopyridine 94g (4-AP/Cl=1, mol ratio), 60 ℃ of reaction temperatures, reaction time 15h, filter, use dioxane, absolute ethanol washing successively, 2% sodium hydroxide solution soaked 10 hours, and deionized water is washed till neutrality, with acetone, ether washing, drying obtains the 3-aminopyridine resin that functional group content is 3.31mmol/g again.
1.0 gram 3-aminopyridine resin and 0.08 gram PdCl
2(CH
3CN)
2In 10 milliliters of DMF, stirred 72 hours in the room temperature lower magnetic force.Filter after the reaction end, fully wash,, get pale brown look solid 3-aminopyridine resin catalyst loading Pd, record palladium content by the atom absorption and be about 1.0% (mass percent) 60 ℃ of oven dry down with DMF, distilled water, ethanol, ether.
Embodiment 2: m-trifluoromethyl phenyl-bromide prepares the m-trifluoromethyl acetophenone
With m-trifluoromethyl phenyl-bromide 0.22 gram (1 mM), vinyl-n-butyl ether 0.2 gram (2 mM), 4-aminopyridine resin catalyst loading Pd 0.36 gram (0.1 mM), N, 100 milliliters of dinethylformamides, place 500 milliliters of there-necked flasks, agitating heating was 150 ℃ of reactions 10 hours.After reaction finishes, cooling, the watery hydrochloric acid that adds 10% (mass percent) is acidified to pH=3, stirs 30 minutes, and with 50 milliliters of extractions of toluene three times, the extract drying concentrates, and column chromatography for separation gets product 0.13 gram, yield 70%.198～202 ℃ of boiling points, purity 〉=98%, MS (m/z): 188 (M
+).
Embodiment 3: m-trifluoromethyl phenyl-bromide prepares the m-trifluoromethyl acetophenone
With m-trifluoromethyl phenyl-bromide 0.22 gram (1 mM), vinyl-n-butyl ether 0.2 gram (2 mM), 2-aminopyridine resin catalyst loading Pd 0.36 gram (0.1 mM), 100 milliliters of dimethyl sulfoxide (DMSO)s, place 500 milliliters of there-necked flasks, agitating heating was 150 ℃ of reactions 10 hours.After reaction finishes, cooling, the watery hydrochloric acid of adding 10% is acidified to pH=3, stirs 30 minutes, and with 50 milliliters of extractions of toluene three times, the extract drying concentrates, and column chromatography for separation gets product 0.12 gram, yield 66%.198～202 ℃ of boiling points, purity 〉=98%, MS (m/z): 188 (M
+).
Embodiment 4: m-trifluoromethyl phenyl-bromide prepares the m-trifluoromethyl acetophenone
With m-trifluoromethyl phenyl-bromide 0.22 gram (1 mM), vinyl-n-butyl ether 0.2 gram (2 mM), 3-aminopyridine resin catalyst loading Pd 0.36 gram (0.1 mM), 100 milliliters of dimethyl sulfones, place 500 milliliters of there-necked flasks, agitating heating was 180 ℃ of reactions 1 hour.After reaction finishes, cooling, the watery hydrochloric acid of adding 10% is acidified to pH=3, stirs 30 minutes, and with 50 milliliters of extractions of toluene three times, the extract drying concentrates, and column chromatography for separation gets product 0.1 gram, yield 56%.198～202 ℃ of boiling points, purity 〉=98%, MS (m/z): 188 (M
+).
Embodiment 5: prepare the 2-acetylpyridine by the 2-bromopyridine
With 158 milligrams of 2-bromopyridines (1 mM), 500 milligrams of n-butyl vinyl ether (5 mM), 4-aminopyridine resin catalyst loading Pd 0.036 gram (0.01 mM), 50 milliliters of 1-methyl pyrrolidones, place 200 milliliters of there-necked flasks, agitating heating was 140 ℃ of reactions 10 hours.The watery hydrochloric acid of adding 10% is acidified to pH=3, stirs 30 minutes, and with 50 milliliters of extractions of toluene three times, the extract drying is filtered, and concentrates, and column chromatography for separation gets 73 milligrams of products, yield 60%.
1HNMR(CDCl
3)ppm：2.73(s，3H)，7.49(m，1H)，7.84(m，1H)，8.04(m，1H)，8.69(d，1H)；
13C?NMR(CDCl
3)δppm：26.1，122.0，127.4,137.1，149.2,153.9，200.4。MS(m/z)：121(M
+)。
Embodiment 6: prepare the 3-acetylpyridine by the 3-chloropyridine
With 114 milligrams of 3-chloropyridines (1 mM), 500 milligrams of n-butyl vinyl ether (5 mM), 4-aminopyridine resin catalyst loading Pd 0.18 gram (0.05 mM), N, 50 milliliters of dinethylformamides place 200 milliliters of there-necked flasks, agitating heating, 50 ℃ of reactions 30 hours, reaction finishes the back cooling, and the watery hydrochloric acid of adding 10% is acidified to pH=3, stirs 30 minutes, with 50 milliliters of extractions of toluene three times, the extract drying is filtered, and concentrates, column chromatography for separation gets 64 milligrams of products, yield 53%.
Embodiment 7: prepare 3-acetyl group quinoline by the 3-bromoquinoline
With 208 milligrams of 3-bromoquinolines (1 mM), 500 milligrams of n-butyl vinyl ether (5 mM), 4-aminopyridine resin catalyst loading Pd 0.18 gram (0.05 mM), 50 milliliters of dimethyl sulfones, place 200 milliliters of there-necked flasks, agitating heating was 140 ℃ of reactions 10 hours.After reaction finishes, cooling, the watery hydrochloric acid of adding 10% is acidified to pH=3, stirs 30 minutes.With 50 milliliters of extractions of toluene three times, the extract drying is filtered, and concentrates, and column chromatography for separation gets 135 milligrams of products, yield 79%.
1HNMR(CDCl
3)ppm：2.74(s，3H)，7.63(m，1H)，7.84(m，1H)，7.95(m，1H)，8.16(d，1H)，8.70(s，1H)，9.43(s，1H)；
13C?NMR(CDCl
3)δppm：27.2，126.9，128.2，129.6，129.8，132.4，137.7，149.6,150.2，197.1。
MS(m/z)：171(M
+)。
Embodiment 8: prepare 5-acetyl group pyrimidine by the 5-bromo pyrimi piperidine
With 159 milligrams of 5-bromo pyrimi piperidines (1 mM), 128 milligrams of n-hexyl vinyl ethers (1 mM), 2-aminopyridine resin catalyst loading Pd 0.36 gram (0.1 mM), 100 milliliters of 1-methyl pyrrolidones, place 500 milliliters of there-necked flasks, agitating heating was 140 ℃ of reactions 15 hours.After reaction finishes, cooling, the watery hydrochloric acid of adding 10% is acidified to pH=3, stirs 30 minutes.With 50 milliliters of extractions of toluene three times, the extract drying is filtered, and concentrates, and column chromatography for separation gets 71 milligrams of products, yield 58%.
1HNMR(CDCl
3)ppm：2.61(s，3H)，9.46(m，1H)，9.52(m，1H)，9.64(1H，)；
13CNMR(CDCl
3)δppm：28.1，131.3，158.3，158.4，160.2，200.2。
MS(m/z)：122(M
+)。
Embodiment 9: prepare 2-(6 '-methoxyl group-2 '-naphthyl) allyl alcohol by 2-bromo-6-methoxynaphthalene
With 23.7 milligrams of 2-bromo-6-methoxynaphthalenes (0.1 mM), 29 milligrams of allyl alcohols (0.5 mM), 2-aminopyridine resin catalyst loading Pd 0.36 gram (0.1 mM), 50 milliliters of dimethyl sulfoxide (DMSO)s, place 500 milliliters of there-necked flasks, agitating heating was 110 ℃ of reactions 20 hours.After reaction finishes, cooling, with 50 milliliters of extractions of toluene three times, the extract drying concentrates, and column chromatography for separation gets 36.4 milligrams of product 2-(6 '-methoxyl group-2 '-naphthyl) allyl alcohols, yield 90%.132～133 ℃ of fusing points;
1H?NMR(CDCl
3)δppm：1.76(s，1H)，3.91(s，3H)，4.63(s，2H)，5.41(s，1H)，5.58(s，1H)，7.11～7.16(m，2H)，7.57～7.59(m，1H)，7.70～7.74(m，2H)，7.82(m，1H)；
13C?NMR(CDCl
3)δppm：158.6，147.8，134.9，130.4，129.5，127.6，125.5，125.3，119.7，113.1，106.4，65.9，60.1。
MS(m/z)：202(M
+)。
Embodiment 10: prepare 2-(6 '-methoxyl group-2 '-naphthyl) allyl alcohol by 2-iodo-6-methoxynaphthalene
With 28.4 milligrams of 2-iodo-6-methoxynaphthalenes (0.1 mM), 4-aminopyridine resin catalyst loading Pd 0.36 gram (0.1 mM), 29 milligrams of allyl alcohols (0.5 mM), 50 milliliters of 1-methyl pyrrolidones, place 500 milliliters of there-necked flasks, agitating heating was 110 ℃ of reactions 20 hours.After reaction finishes, cooling, with 50 milliliters of extractions of toluene three times, the extract drying concentrates, and column chromatography for separation gets 36.4 milligrams of product 2-(6 '-methoxyl group-2 '-naphthyl) allyl alcohols, yield 90%.
Embodiment 11: prepare the 2-acetyl thiophene by the 2-bromothiophene
With 163 milligrams of 2-bromothiophenes (1 mM), 200 milligrams of n-butyl vinyl ether (2 mM), 4-aminopyridine resin catalyst loading Pd 0.36 gram (0.1 mM), 50 milliliters of DMF, place 200 ml flasks, agitating heating was 100 ℃ of reactions 10 hours.After reaction finishes, cooling.Behind toluene extraction product, drying concentrates, and column chromatography for separation gets 100 milligrams of products, yield 80%.
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 12: prepare the 3-acetyl thiophene by 3 bromo thiophene
With 163 milligrams of 3 bromo thiophenes (1 mM), 200 milligrams of n-butyl vinyl ether (2 mM), 4-aminopyridine resin catalyst loading Pd 0.18 gram (0.05 mM), 5 milliliters of DMF, place 50 ml flasks, agitating heating was 100 ℃ of reactions 10 hours.After reaction finishes, cooling.Behind toluene extraction product, drying concentrates, and column chromatography for separation gets 111 milligrams of products, yield 88%.3 bromo thiophene
1HNMR(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 13: prepare 2-phenyl allyl alcohol by bromobenzene
With 157 milligrams of bromobenzenes (1 mM), 290 milligrams of allyl alcohols (5 mM), 4-aminopyridine resin catalyst loading Pd 0.18 gram (0.05 mM), 50 milliliters of dimethyl sulfoxide (DMSO)s, place 200 milliliters of there-necked flasks, agitating heating was 100 ℃ of reactions 5 hours.After reaction finishes, cooling, the watery hydrochloric acid of adding 10% is acidified to pH=3, stirred 30 minutes, 50 milliliters of extractions of toluene three times, the extract drying concentrates, and column chromatography for separation gets 121 milligrams of product 2-phenyl allyl alcohols, yield 90%.
1HNMR(CDCl
3)δppm：1.5(s，1H)，3.70(d，J＝6.5Hz，2H)，5.16(m，1H)，5.42(s，1H)，7.25～7.33(m，3H)，7.40～7.45(m，2H)；
13C?NMR(CDCl
3)δppm：65.14，112.65，126.13，127.97，128.55，138.58，147.42。MS(m/z)：134(M
+)。
Embodiment 14: utilize recovery 4-aminopyridine resin to make the 4-aminopyridine resin catalyst loading Pd, prepare 2-phenyl allyl alcohol by bromobenzene
Obtain 115 milligrams of product 2-phenyl allyl alcohols, yield 86% by embodiment 1 reactions steps.
Embodiment 15: prepare 2-(3 '-cyano-phenyl) allyl alcohol by the 3-bromobenzylcyanide
With 182 milligrams of 3-bromobenzylcyanides (1 mM), 290 milligrams of allyl alcohols (5 mM), 4-aminopyridine resin catalyst loading Pd 0.18 gram (0.05 mM), 100 milliliters of dimethyl sulfones, place 200 milliliters of there-necked flasks, agitating heating was 180 ℃ of reactions 30 hours.After reaction finishes, cooling, the watery hydrochloric acid of adding 10% is acidified to pH=3, stirred 30 minutes, 50 milliliters of extractions of toluene three times, the extract drying concentrates, and column chromatography for separation gets 129 milligrams of product 2-(3 '-cyano-phenyl) allyl alcohols, yield 81%.
1H?NMR(CDCl
3)δppm：1.67(s，1H)，4.53(d，J＝5.3Hz，2H)，5.47(d，J＝0.57Hz，1H)，5.53(d，J＝0.58Hz，1H)，7.44～7.76(m，4H)；
13C?NMR(CDCl
3)δppm：61.34，111.65，117.63，119.17，127.35，132.68，144.42，145.72。MS(m/z)：159(M
+)。
Embodiment 16: prepare 2-(4 '-aminomethyl phenyl) allyl alcohol by the 4-toluene bromide
With 171 milligrams of 4-toluene bromides (1 mM), 290 milligrams of allyl alcohols (5 mM), 4-aminopyridine resin catalyst loading Pd 0.18 gram (0.05 mM), 100 milliliters of dimethylacetylamides, place 200 milliliters of there-necked flasks, agitating heating was 140 ℃ of reactions 10 hours.After reaction finishes, cooling, the watery hydrochloric acid of adding 10% is acidified to pH=3, stirred 30 minutes, 50 milliliters of extractions of toluene three times, the extract drying concentrates, and column chromatography for separation gets 131 milligrams of product 2-(4 '-aminomethyl phenyl) allyl alcohols, yield 89%.
1HNMR(CDCl
3)δppm：1.51(s，1H)，2.35(s，3H)，4.54(m，2H)，5.29(dd，J＝1.3，3.1Hz，1H)，5.43(d，J＝1.3Hz，1H)，7.15～7.47(m，4H)；MS(m/z)：148(M
+)。
Embodiment 17: prepare 2-(2 '-naphthyl) allyl alcohol by the 2-bromonaphthalene
With 207 milligrams of 2-bromonaphthalenes (1 mM), 290 milligrams of allyl alcohols (5 mM), 4-aminopyridine resin catalyst loading Pd 0.18 gram (0.05 mM), 100 milliliters of sulfolane, place 200 milliliters of there-necked flasks, agitating heating was 140 ℃ of reactions 10 hours.After reaction finishes, cooling, the watery hydrochloric acid of adding 10% is acidified to pH=3, stirred 30 minutes, 50 milliliters of extractions of toluene three times, the extract drying concentrates, and column chromatography for separation gets 170 milligrams of product 2-(4 '-aminomethyl phenyl) allyl alcohols, yield 92%.
1H?NMR(CDCl
3)δppm：1.76(s，1H)，4.63(s，2H)，5.44(d，J＝1.2，Hz，1H)，5.6(s，1H)，7.42～7.86(m，7H)；MS(m/z)：184(M
+)。
Embodiment 18:1-[1-(4-acetylphenyl) vinyl]-preparation of 2-Pyrrolidone
With 199 milligrams of 4-bromoacetophenones (1 mM), 334 milligrams of N-vinyl-2-Pyrrolidones (3 mM), 4-aminopyridine resin catalyst loading Pd 0.18 gram (0.05 mM), 50 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 200 milliliters of there-necked flasks, agitating heating was 110 ℃ of reactions 15 hours.After reaction finishes, cooling, 50 milliliters of extractions of reactant liquor toluene three times, the extract drying concentrates, and column chromatography for separation gets 179 milligrams of products, yield 78%.
1H?NMR(CDCl
3)δppm：7.92～7.94(m，2H)，7.44～7.41(m，2H)，5.40(s，1H)，5.30(s，1H)，3.60(t，J＝7.0Hz，2H)，2.60(s，3H)，2.58(t，J＝7.5Hz，2H)，2.16(dd，J＝7.0，7.5Hz，2H)；
13C?NMR(CDCl
3)δppm：
198.8,174.8，143.6，140.6，137.3，128.9，126.9，110.4，49.9，32.5，27.0，19.0；MS(m/z)：229(M
+)。
Embodiment 19:1-[1-(4-methoxyphenyl) vinyl]-preparation of 2-Pyrrolidone
With 187 milligrams of 4-bromoanisoles (1 mM), 334 milligrams of N-vinyl-2-Pyrrolidones (3 mM), 4-aminopyridine resin catalyst loading Pd 0.18 gram (0.05 mM), 50 milliliters of 1-butyl-3-methylimidazole hexafluorophosphate, place 200 milliliters of there-necked flasks, agitating heating was 115 ℃ of reactions 20 hours.After reaction finishes, cooling, 50 milliliters of extractions of reactant liquor toluene three times, the extract drying concentrates, and column chromatography for separation gets 176 milligrams of products, yield 81%.
1H?NMR(CDCl
3)δppm：7.06～6.97(m，2H)，6.75～6.47(m，2H)，4.98(s，1H)，4.87(s，1H)，3.45(s，3H)，2.19(dd，J＝7.0，8.0Hz，2H)，2.10(t，J＝8.0Hz，2H)，1.76(m，2H)；
13C?NMR(CDCl
3)δppm：
172.8，160.8，143.6，127.3，127.0，126.8，114.9，114.3，107.2,55.9，41.5，32.8，19.0；MS(m/z)：217(M
+)。
The preparation of embodiment 20:1-(2-naphthyl vinyl)-2-Pyrrolidone
With 207 milligrams of 2-bromonaphthalenes (1 mM), 334 milligrams of N-vinyl-2-Pyrrolidones (3 mM), 4-aminopyridine resin catalyst loading Pd 0.18 gram (0.05 mM), 50 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 500 milliliters of there-necked flasks, agitating heating was 110 ℃ of reactions 15 hours.After reaction finishes, cooling, 50 milliliters of extractions of reactant liquor toluene three times, the extract drying concentrates, and column chromatography for separation gets 218 milligrams of products, yield 92%.
1H?NMR(CDCl
3)δppm：7.58～7.78(m，3H)，7.54～7.44(m，3H)，7.34～7.32(m，1H)，5.51(s，1H)，5.39(s，1H)，3.59(t，J＝7.0Hz，2H)，2.61(t，J＝8.0Hz，2H)，2.29(dd，J＝7.0，8.0Hz，2H)；
13C?NMR(CDCl
3)δppm：175.02，144.05，134.22,133.7，133.6，128.9，128.6，28.4，128.0，126.7，125.9，124.7，110.1，50.0，32.3，19.0；MS(m/z)：237(M
+)。
Embodiment 21: prepare 2-methyl-2-phenyl-1 by bromobenzene, 3-two oxa-s penta ring
With 157 milligrams of bromobenzenes (1 mM), 500 milligrams of 2-hydroxyethyl vinyl ethers (5 mM), 4-aminopyridine resin catalyst loading Pd 0.18 gram (0.05 mM), 20 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 500 milliliters of there-necked flasks, agitating heating was 110 ℃ of reactions 15 hours.After reaction finishes, cooling, 50 milliliters of extractions of reactant liquor toluene three times, the extract drying concentrates, and column chromatography for separation gets product 2-methyl-2-phenyl-1,140 milligrams on 3-two oxa-s penta ring, yield 85%.
1H?NMR(400?MHz，CDCl
3)δ7.47-7.51(d，J＝0.02，2H)，7.25-7.36(m，3H)，4.01-4.06(m，2H)，3.75-3.80(m，2H)，1.67(s，1H)；
13C?NMR(400?MHz，CDCl
3)δ?129.0，125.6，64.8，32.0，27.0，23.0，14.5；MSm/z?165(M
+，100)。
Claims (8)
1. aminopyridine resin catalyst loading Pd, by aminopyridine resin at N, load P dCl in the dinethylformamide
2(CH
3CN)
2Obtain, the palladium mass content is 1.0～10.0% in the described aminopyridine resin catalyst loading Pd.
2. catalyst as claimed in claim 1 is characterized in that described aminopyridine resin catalyst loading Pd is prepared by following method: be 1: 0.05～0.5 aminopyridine resin and PdCl with mass ratio
2(CH
3CN)
2Adding N in the dinethylformamide, stirred under the room temperature 60～80 hours, after reaction finishes, filtered, and filter residue gets described aminopyridine resin catalyst loading Pd through washing, 60 ℃ of dryings; Described N, dinethylformamide consumption are 10～20mL/g aminopyridine resin.
3. catalyst as claimed in claim 1 is characterized in that described washing is for using N successively, dinethylformamide, distilled water, ethanol, ether washing.
4. catalyst as claimed in claim 1 is characterized in that described aminopyridine resin is one of following: 4-aminopyridine resin, 2-aminopyridine resin, 3-aminopyridine resin.
5. as the application of the described aminopyridine resin catalyst loading Pd of one of claim 1～4 in the Heck reaction.
6. application as claimed in claim 5, it is characterized in that described being applied as: be 1: 1～5: 0.01～0.1 halogenated aryl hydrocarbon compounds, vinyl compound, aminopyridine resin catalyst loading Pd with the ratio of amount of substance, join in the aprotic polar solvent, in 50～180 ℃ of following stirring reactions 1～30 hour, reaction finishes afterreaction liquid and obtains functionalized aromatic compound through separation and purification, and described aprotic polar solvent consumption is 10～500mL/mmol halogenated aryl hydrocarbon compounds.
7. application as claimed in claim 6 is characterized in that described aprotic polar solvent is one of following: N, dinethylformamide, dimethyl sulfoxide (DMSO), dimethyl sulfone, 1-methyl pyrrolidone.
8. application as claimed in claim 6, it is characterized in that described being applied as: the halogenated aryl hydrocarbon compounds, vinyl compound, the aminopyridine resin supported palladium complex that with the ratio of amount of substance are 1: 2: 0.1, join in the aprotic polar solvent, agitating heating was 100 ℃ of reactions 15 hours, after reaction finishes, cooling is with 50 milliliters of extractions of toluene three times, extract drying, concentrate, column chromatography for separation gets functionalized aromatic compound; Described aprotic polar solvent consumption is a 50mL/mmol halogenated aryl hydrocarbon compounds.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851153A (en) * | 2010-06-12 | 2010-10-06 | 浙江工业大学 | Method for preparing 2-(6'-methoxy-2'-naphthyl) propenol by allylic oxidation |
-
2007
- 2007-12-14 CN CNA2007101611498A patent/CN101204670A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851153A (en) * | 2010-06-12 | 2010-10-06 | 浙江工业大学 | Method for preparing 2-(6'-methoxy-2'-naphthyl) propenol by allylic oxidation |
| CN101851153B (en) * | 2010-06-12 | 2013-01-16 | 浙江工业大学 | Method for preparing 2-(6'-methoxy-2'-naphthyl) propenol by allylic oxidation |
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