CN101161617A - A method for preparing 2-(6'-methoxy group-2'-naphthyl) propenol - Google Patents
A method for preparing 2-(6'-methoxy group-2'-naphthyl) propenol Download PDFInfo
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- CN101161617A CN101161617A CNA2007101568515A CN200710156851A CN101161617A CN 101161617 A CN101161617 A CN 101161617A CN A2007101568515 A CNA2007101568515 A CN A2007101568515A CN 200710156851 A CN200710156851 A CN 200710156851A CN 101161617 A CN101161617 A CN 101161617A
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- vinyl carbinol
- methoxynaphthalene
- naphthyl
- exchange resin
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Abstract
The invention provides a method for preparing 2-(6'-methoxy-2'-naphthyl) allyl alcohol shown in formula (I). The method comprises: 2-halogenated-6-mthoxynaphthalene and allyl alcohol shown in formula (II) are taken as raw materials and are stirred and reacted for 1 to 50 hours in the non-aprotic polar solvent with the existence of macroporous weak base styrene type anion-exchange resin and palladium acetate catalyst under the temperature between 50 DEG C and 150 DEG C; when the reaction is finished, the reacting liquid is separated and purified to produce the 2-(6'-methoxy-2'- naphthyl) allyl alcohol. The preparation method of the invention has a simple preparation process, high yield and easy operation, has the weak base anion-exchange resin capable of being reclaimed and reused, does not use small molecular organic amine or inorganic base, and has small pollution to the environment.
Description
(1) technical field
The present invention relates to the preparation method of a kind of 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol, the preparation method of especially a kind of 2-that in the presence of the macroreticular weakly base styrene series anion exchange resin, carries out (6 '-methoxyl group-2 '-naphthyl) vinyl carbinol.
(2) background technology
Naproxen Base (Naproxen) is a kind of non-steroidal anti-inflammatory, analgesic and analgesic, has wide demand market at home and abroad.2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol is the important intermediate of Naproxen Base (Naproxen) medicine.People such as Dustin K.James study this in U.S. Pat 5286902.But, in the synthetic route of report, set out by 2-methoxyl group-6-isopropyl naphthalene, in the high-temperature tubular reactor, behind dehydrogenation catalyst dehydrogenation generation allyl group naphthalene compound, make through the tin anhydride oxidation.With this synthetic method complicated operation, severe reaction conditions, used tin anhydride oxygenant toxicity is big, and the raw material sources difficulty of Synthetic 2-methoxyl group-6-isopropyl naphthalene, and synthetic route is longer, and yield is low, is difficult to carry out large-scale industrial production.
Utilize the Heck reaction, with ionic liquid as emerging Green Chemistry solvent, under catalyzing by metal palladium,, successfully synthesized 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol, tentatively solved the pollution problem that may occur in the chemical reaction process by halogenated aryl hydrocarbon and enol.But the Heck reaction is that organic amine is as alkali under phosphine part and catalyzing by metal palladium, react by halogenated aryl hydrocarbon and alkene, in carrying out suitability for industrialized production, need with the organic amine that is difficult to reclaim as alkali, and need organophosphorus ligand to improve reactive activity, 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, also be a kind of green synthesis techniques that application prospect is arranged.
(3) summary of the invention
The object of the invention is to provide a kind of preparation technology simple, excellent catalytic effect, utilize the Heck reaction, participate at the macroreticular weakly base styrene series anion exchange resin, no phosphine part and small molecules organic amine or mineral alkali exist down, and high reactivity ground prepares the method for 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol.
The technical solution used in the present invention is:
The preparation method of the 2-shown in a kind of formula (I) (6 '-methoxyl group-2 '-naphthyl) vinyl carbinol, described method comprises: with 2-halo-6-methoxynaphthalene shown in the formula (II) and vinyl carbinol is raw material, in aprotic polar solvent, in the presence of macroreticular weakly base styrene series anion exchange resin shown in the formula (III) and palladium catalyzer, in 50 ℃～150 ℃ following stirring reactions 1～50 hour, after reaction finished, reaction solution got 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol through separation and purification;
In the formula (II), X is chlorine or bromine or iodine;
In the formula (III), R
1, R
2Independent separately is methyl or hydrogen atom.N represents contained number of repeat unit purpose mean value on the polymer macromolecule chain, for weighing the index of polymer molecule size, is Styrene-DVB D301 type resin in the present invention.
Reaction formula is as follows:
The ratio of described 2-halo-6-methoxynaphthalene, vinyl carbinol, palladium catalyzer, macroreticular weakly base styrene series anion exchange resin amount of substance is: 1: 1～5: 0.005～0.01: 1～2, be preferably 1: 2: 0.005: 1.5.
Described macroreticular weakly base styrene series anion exchange resin can adopt commercial commodity, is recommended as one of following in the Styrene-DVB D301 type resin among the present invention: Styrene-DVB (D301 R), Styrene-DVB (D301 T), Styrene-DVB (D301 G), Styrene-DVB (D392), Styrene-DVB (D380).
Described aprotic polar solvent is this area aprotic polar solvent commonly used, adopts one of following among the present invention: dimethyl formamide, dimethyl sulfoxide (DMSO), 1-methyl-2-pyrrolidone.
Described aprotic polar solvent consumption is 10～100mL/mmol 2-halo-6-methoxynaphthalene.
Described separation purification method is as follows: the reaction solution cooling, and the toluene extraction, extraction liquid drying, concentrated, column chromatography for separation gets described 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol.
Concrete, described method is as follows: with 2-halo-6-methoxynaphthalene, vinyl carbinol, palladium catalyzer, macroreticular weakly base styrene series anion exchange resin, 1-methyl-2-pyrrolidone, place there-necked flask, stirring heating was 130 ℃ of reactions 10 hours, after reaction finishes, cooling is with toluene extraction, extraction liquid drying, concentrate, column chromatography for separation gets 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol; The ratio of described 2-halo-6-methoxynaphthalene, vinyl carbinol, palladium catalyzer, macroreticular weakly base styrene series anion exchange resin amount of substance is 1: 2: 0.005: 1.5, and 1-methyl-2-pyrrolidone consumption is 50mL/mmol 2-halo-6-methoxynaphthalene.
Preparation method of the present invention, preparation technology is simple, yield is high, and is easy to operate, and the recyclable regeneration of weak-base ion-exchange resin is used, and environmental pollution is little.
(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 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol by 2-bromo-6-methoxynaphthalene
With 2-bromo-6-methoxynaphthalene 0.24 gram (1 mmole), vinyl carbinol 0.29 gram (5 mmole), palladium 0.0012 gram (0.005 mmole), Styrene-DVB (D301 R) resin 0.3 gram (1.5 mmole), 10 milliliters of dimethyl sulfoxide (DMSO), place 200 milliliters of there-necked flasks, stirring heating was 150 ℃ of reactions 1 hour.After reaction finishes, cooling, with methylene dichloride (3 * 50 milliliters) extraction (promptly extract 3 times, each 50mL, down with), the extraction liquid drying concentrates, column chromatography for separation gets product 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol 0.182 and restrains yield 90%.132～133 ℃ of fusing points;
1H NMR (CDCl
3) δ ppm: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) δ ppm: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 2: prepare 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol by 2-iodo-6-methoxynaphthalene
With 2-iodo-6-methoxynaphthalene 0.28 gram (1 mmole), vinyl carbinol 0.12 gram (2 mmole), palladium 0.0022 gram (0.01 mmole), Styrene-DVB (D301 R) resin 0.3 gram (1.5 mmole), 100 milliliters of dimethyl formamides, place 200 milliliters of there-necked flasks, stirring heating was 50 ℃ of reactions 50 hours.After reaction finishes, cooling, with methylene dichloride (3 * 50 milliliters) extraction, the extraction liquid drying concentrates, and column chromatography for separation gets product 0.178 gram, yield 88%.
Embodiment 3: prepare 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol by 2-chloro-6-methoxynaphthalene
With 2-chloro-6-methoxynaphthalene 0.19 gram (1 mmole), vinyl carbinol 0.058 gram (1.0 mmole), palladium 0.0012 gram (0.005 mole), Styrene-DVB (D301 R) resin 0.4 gram (2 mmole), 50 milliliters of 1-methyl-2-pyrrolidones, place 200 milliliters of there-necked flasks, stirring heating was 150 ℃ of reactions 1 hour.After reaction finished, with methylene dichloride (3 * 50 milliliters) extraction, the extraction liquid drying concentrated, and column chromatography for separation gets product 0.125 gram, yield 62%.
Embodiment 4: prepare 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol by 2-chloro-6-methoxynaphthalene
With 2-chloro-6-methoxynaphthalene 0.19 gram (1 mmole), vinyl carbinol 0.12 gram (2 mmole), palladium 0.0012 gram (0.005 mmole), Styrene-DVB (D301G) resin 0.36 gram (1.5 mmole), 50 milliliters of 1-methyl-2-pyrrolidones, place 200 milliliters of there-necked flasks, stirring heating was 140 ℃ of reactions 10 hours.After reaction finished, with methylene dichloride (3 * 50 milliliters) extraction, the extraction liquid drying concentrated, and column chromatography for separation gets product 0.125 gram, yield 62%.
Embodiment 5: prepare 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol by 2-iodo-6-methoxynaphthalene
With 2-iodo-6-methoxynaphthalene 0.28 gram 1 mmole), vinyl carbinol 0.12 gram (2 mmole), palladium 0.0022 gram (0.01 mmole), Styrene-DVB (D301 R) resin 0.3 gram (1.5 mmole), 50 milliliters of dimethyl formamides, place 200 milliliters of there-necked flasks, stirring heating was 100 ℃ of reactions 12 hours.After reaction finishes, cooling, with methylene dichloride (3 * 50 milliliters) extraction, the extraction liquid drying concentrates, and column chromatography for separation gets product 0.178 gram, yield 88%.
Embodiment 6: prepare 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol by 2-iodo-6-methoxynaphthalene
With 2-iodo-6-methoxynaphthalene 0.28 gram (1 mmole), vinyl carbinol 0.12 gram (2 mmole), palladium 0.0022 gram (0.01 mmole), Styrene-DVB (D301 R) resin 0.3 gram (1.5 mmole), 10 milliliters of dimethyl formamides, place 200 milliliters of there-necked flasks, stirring heating was 130 ℃ of reactions 10 hours.After reaction finishes, cooling, with methylene dichloride (3 * 50 milliliters) extraction, the extraction liquid drying concentrates, and column chromatography for separation gets product 0.178 gram, yield 88%.
Claims (8)
1. the preparation method of the 2-shown in the formula (I) (6 '-methoxyl group-2 '-naphthyl) vinyl carbinol, it is characterized in that described method comprises: with 2-halo-6-methoxynaphthalene shown in the formula (II) and vinyl carbinol is raw material, in aprotic polar solvent, in the presence of macroreticular weakly base styrene series anion exchange resin shown in the formula (III) and palladium catalyzer, in 50～150 ℃ of following stirring reactions 1～50 hour, after reaction finished, reaction solution got 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol through separation and purification;
In the formula (II), X is chlorine, bromine or iodine;
In the formula (III), R
1, R
2Independent separately is methyl or hydrogen atom.
2. the method for claim 1 is characterized in that the ratio of described 2-halo-6-methoxynaphthalene, vinyl carbinol, palladium catalyzer, macroreticular weakly base styrene series anion exchange resin amount of substance is: 1: 1～5: 0.005～0.01: 1～2.
3. the method for claim 1 is characterized in that the ratio of described 2-halo-6-methoxynaphthalene, vinyl carbinol, palladium catalyzer, macroreticular weakly base styrene series anion exchange resin amount of substance is: 1: 2: 0.005: 1.5.
4. as the described method of one of claim 1～3, it is characterized in that described macroreticular weakly base styrene series anion exchange resin is one of following: Styrene-DVB (D301 R), Styrene-DVB (D301 T), Styrene-DVB (D301 G), Styrene-DVB (D392), Styrene-DVB (D380).
5. as the described method of one of claim 1～3, it is characterized in that described aprotic polar solvent is one of following: dimethyl formamide, dimethyl sulfoxide (DMSO), 1-methyl-2-pyrrolidone.
6. as the described method of one of claim 1～3, it is characterized in that described aprotic polar solvent consumption is 10～100mL/mmol 2-halo-6-methoxynaphthalene.
7. as the described method of one of claim 1～3, it is characterized in that described separation purification method is as follows: the reaction solution cooling, the toluene extraction, extraction liquid drying, concentrated, column chromatography for separation gets described 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol.
8. the method for claim 1, it is characterized in that described method is as follows: with 2-halo-6-methoxynaphthalene, vinyl carbinol, palladium catalyzer, macroreticular weakly base styrene series anion exchange resin, 1-methyl-2-pyrrolidone, place there-necked flask, stirring heating was 130 ℃ of reactions 10 hours, after reaction finishes, cooling is with toluene extraction, extraction liquid drying, concentrate, column chromatography for separation gets 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol; The ratio of described 2-halo-6-methoxynaphthalene, vinyl carbinol, palladium catalyzer, macroreticular weakly base styrene series anion exchange resin amount of substance is 1: 2: 0.005: 1.5, and 1-methyl-2-pyrrolidone consumption is 50mL/mmol 2-halo-6-methoxynaphthalene.
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Cited By (4)
| 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 |
| CN101967497A (en) * | 2010-07-15 | 2011-02-09 | 池州方达科技有限公司 | Preparation of 2-(6'-methoxy-2'-naphthyl) allyl alcohol by laccase method |
| CN102154299A (en) * | 2010-12-10 | 2011-08-17 | 杭州华津允上医药有限公司 | Preparation method of oral medicament active peptide from shark liver for treating diabetes |
| CN102911020A (en) * | 2012-09-12 | 2013-02-06 | 浙江工业大学 | Preparation method of 2-(6'-methoxy-2'-naphthyl)allylalcohol |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253422C (en) * | 2004-08-11 | 2006-04-26 | 浙江工业大学 | Process for preparing 2-(6'-methoxy-2'-naphthyl) allyl alcohol |
| CN1284756C (en) * | 2004-10-29 | 2006-11-15 | 浙江工业大学 | Process for preparing 2-aryl allyl alcohol |
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Cited By (5)
| 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 |
| CN101967497A (en) * | 2010-07-15 | 2011-02-09 | 池州方达科技有限公司 | Preparation of 2-(6'-methoxy-2'-naphthyl) allyl alcohol by laccase method |
| CN102154299A (en) * | 2010-12-10 | 2011-08-17 | 杭州华津允上医药有限公司 | Preparation method of oral medicament active peptide from shark liver for treating diabetes |
| CN102911020A (en) * | 2012-09-12 | 2013-02-06 | 浙江工业大学 | Preparation method of 2-(6'-methoxy-2'-naphthyl)allylalcohol |
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