JPH11222452A - 6-vinyl-2-tert-butoxynaphthalene and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful as a raw material for a medicine, an agrochemical, a functional polymer or the like. SOLUTION: This new compound is expressed by formula I. The compound of formula I is obtained by reacting activated magnesium with 6-halogeno-2-t- butoxynaphthalene, e.g. 6-bromo-2-t-butoxynaphthalene in a solvent to provide a Grignard reagent, and reacting the obtained Grignard reagent with a vinyl halide (e.g. vinyl fluoride, vinyl chloride and vinyl bromide) in the presence of a metal catalyst in an inert gas atmosphere such as nitrogen and/or argon in a solvent (e.g. an etheric solvent and an aromatic hydrocarbon-based solvent). The metal catalyst is preferably a transition metal halide such as an iron halide, a nickel halide, a palladium halide and a cobalt halide, and can be combined with a ligand [e.g. 1,2-bis(diphenylphosphino)ethane].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to 6-vinyl-2-, which is expected to be useful as a raw material for medical and agricultural chemicals, functional polymers and the like.
t-butoxynaphthalene (hereinafter abbreviated as VTBN)
And its manufacturing method. For example, para-tertiary butoxystyrene is known as a compound having a structure similar to VTBN. The compound is useful as a raw material for medical and agricultural chemicals, functional polymers, and the like, and is particularly attracting attention as a resist raw material (JP-A-59-199705,
JP-A-3-277608). VTBN can also be expected to be developed in the same field, and particularly when used as a resist material, it is expected to improve physical properties such as far-ultraviolet absorption characteristics, heat resistance, and etching resistance.

[0002]

2. Description of the Related Art VTBN provided by the present invention is a novel compound not described in any literature, and its production method and the like are not known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide VT which is expected to be useful as a raw material for medical and agricultural chemicals, functional polymers and the like.
An object of the present invention is to provide a BN and a method for manufacturing the same.

[0004]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the following formula (2) is obtained.

[0005]

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(X represents a halogen atom)
The inventors have found that VTBN can be easily obtained by reacting a Grignard reagent prepared from -halogeno-2-t-butoxynaphthalene with vinyl halide, thereby completing the present invention.

Hereinafter, the present invention will be described in detail.

The present invention provides the following formula (1)

[0009]

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6-vinyl-2-t-butoxynaphthalene represented by the formula:

The Grignard reagent used in the method of the present invention can be easily prepared by a conventional method. That is,
It can be easily prepared by, for example, reacting a metal magnesium with 6-halogeno-2-t-butoxynaphthalene represented by the formula (2) (X represents a halogen atom) in a solvent. In this preparation reaction, particularly good results are obtained when activated magnesium metal is used.
As a method for activating metal magnesium, a method of heating and stirring metal magnesium suspended in a solvent, or adding a small amount of iodine, an iodide such as methyl iodide, a bromide such as bromoethane or dibromoethane, etc. The method of stirring with stirring is effective.

In the method of the present invention, VTBN can be produced with high yield by reacting the Grignard reagent prepared by the above method with vinyl halide in the presence of a metal catalyst.

The vinyl halide used in the method of the present invention is vinyl fluoride, vinyl chloride, vinyl bromide or vinyl iodide, and these can be used alone or as a mixture. Usually, vinyl chloride and / or vinyl bromide are selected in consideration of economy and availability.

The catalyst used in the method of the present invention is a metal catalyst. In the present reaction, particularly, in the present reaction, a transition metal halide such as iron halide, nickel halide, palladium halide, cobalt halide, manganese halide and the like is used. Useful. These transition metal halides can be combined with a ligand, if desired. Examples of the ligand include 1,2-bis (diphenylphosphino) ethane and 1,3-bis (diphenylphosphino) propane. ,
1,1′-bis (diphenylphosphino) ferrocene,
Examples include bidentate ligands such as 2,2'-dipyridyl, and monodentate ligands such as triphenylphosphine and pyridine. The amount of the metal catalyst used in the method of the present invention is not particularly limited, but is usually selected to be about 10-4 to 10-1 mol per mol of the Grignard reagent.

The process of the present invention is usually carried out in a solvent under an atmosphere of an inert gas such as nitrogen and / or argon. Examples of the reaction solvent used in the method of the present invention include ether solvents, aromatic hydrocarbon solvents, and aliphatic hydrocarbon solvents. Usually, these solvents are used alone or as a mixture.

After completion of the reaction, the reaction solution is treated by adding an aqueous solution of ammonium chloride to the reaction solution according to a conventional method, and then the organic phase is separated. Subsequently, after distilling off the solvent, the target VTBN is obtained by an operation such as recrystallization.

[0017]

EXAMPLES Hereinafter, the method of the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 "Production of 6-bromo-2-t-butoxynaphthalene" In a four-necked flask having a thermometer, a reflux condenser and a stirring blade, 44.6 g (0.2 g) of 6-bromo-2-naphthol was added.
mol), concentrated sulfuric acid (0.05 g, 0.5 mmol) and methylene chloride (250 ml).
2.3 g (0.22 mol) was blown in over 3 hours.

After completion of the reaction, a 10% aqueous solution of NaOH 100
g was added, and unreacted raw materials and impurities were extracted and removed. Subsequently, the solvent was distilled off from the obtained organic phase to obtain 44.3 g of a solid. Further, the solid was recrystallized in ethanol to obtain 35.5 g of white crystals (yield: 63.6).
%). As a result of analysis by nuclear magnetic resonance analysis, mass analysis and elemental analysis, it was confirmed that the white crystals were 6-bromo-2-t-butoxynaphthalene. As a result of analysis by gas chromatography, the purity of 6-bromo-2-t-butoxynaphthalene was 99.8%.

<Results of Analysis of Product> 1H-NMR (CDCl3): δ = 1.43 (s, 9H), 7.18 to 7.95 (m,
6H) GC-MS (m / s): 278 (M +), 222 "Production of VTBN" 1.34 g (55 mmol) of metallic magnesium and tetrahydrofuran (10 ml) as a solvent were placed in a four-necked flask having a thermometer, a reflux condenser and a stirring blade replaced with a nitrogen atmosphere, and one piece of iodine was added. . After confirming that the color of iodine disappeared, 13.96 g of 6-bromo-2-t-butoxynaphthalene (50
(mmol) in 40 ml of tetrahydrofuran. After confirming the start of the reaction, an additional 45
It was added dropwise at about 1 hour at about ° C. Reflux was continued for another hour to obtain a Grignard reagent. The conversion to the Grignard reagent in this reaction was 99.0%.

After cooling the Grignard reagent obtained by the above-mentioned operation to room temperature, the supernatant is subjected to 100 m under a nitrogen atmosphere.
Transferred to 1 volume flask. Dichloro [1,1
0.14 g (0.25 mmol) of 3-bis (diphenylphosphino) propane] nickel is added, and the temperature is increased to 20 to 30 ° C.
3.44 g (55 mmo) of vinyl chloride while maintaining
l) was blown in for about 10 minutes. And then,
Stirring was continued at the same temperature for 1 hour.

After completion of the reaction, an aqueous solution of ammonium chloride was added to dissolve and remove the salts formed. Subsequently, the solvent was distilled off from the obtained organic phase to obtain 11.1 g of a solid. The solid was recrystallized in ethanol to obtain 8.3 g of white crystals (yield: 73.4%). As a result of analysis by nuclear magnetic resonance analysis, mass analysis and elemental analysis, it was confirmed that the white crystal was VTBN. Further, as a result of analyzing the white crystals by gas chromatography, the purity of VTBN was 99.0%.

<Results of Analysis of Product> 1H-NMR (CDCl3): δ = 1.45 (s, 9H), 5.33 (d, J = 13H)
z, 1H), 5.87 (d, J = 18 Hz, 1H),
6.89 (dd, J = 13 Hz and 18 Hz), 7.1
7-7.76 (m, 6H) GC-MS (m / s): 226 (M +), 170 Example 2 In Example 1, "Preparation of VTBN", 5.99 g (55 mm) of vinyl bromide was used instead of vinyl chloride.
ol), except that the method described in Example 1 was used.

As a result, the purity of VTBN was 99.2%. (Yield: 74.2%)

[0025]

As is apparent from the above description, according to the method of the present invention, VTBN can be obtained with a high yield.
In addition, VTBN obtained in the present invention is expected to be useful as a raw material for medical and agricultural chemicals, functional polymers, and the like.

[0026]

Claims (2)

[Claims] (1) The following formula (1): 6-vinyl-2-t-butoxynaphthalene represented by the formula: 2. The following formula (2): 6-halogeno represented by (X represents a halogen atom)
A method for producing 6-vinyl-2-t-butoxynaphthalene, comprising reacting a Grignard reagent prepared from 2-t-butoxynaphthalene with vinyl halide.