Method for making 8-hydroxyjulolidine compound

a technology of julolidine and compound, applied in the field of making 8-hydroxyjulolidine compound, can solve the problems of reducing energy dissipation caused, bringing out relatively higher production costs, and hazardous materials to the environment, and achieves the effect of easy preparation and higher yield of the invented method

Inactive Publication Date: 2002-08-29
ALLIED IND
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0010] The objective of this invention is to provide a simplified method for the preparation of 8-hydroxyjulolidine and its analogous compounds wherein only one single step reaction is needed.
[0011] Another objective of this invention is to provide a novel method for the preparation of 8-hydroxyjulolidine and its analogous compounds wherein preparation costs may be reduced.
[0013] Another objective of this invention is to provide a method for the preparation of 8-hydroxyjulolidine and its analogous compounds wherein yields of preparation may be improved.

Problems solved by technology

According to U.S. Pat. No. 3,873,940, U.S. Pat. No. 3,932,415, U.S. Pat. No. 4,005,092 , U.S. Pat. No. 4,471,041 U.S. Pat. No. 4,736,032 and U.S. Pat. No. 4,794,184, coumarin compounds with fused and rigid nitrogen-containing rings significantly hinder the mobility of amino groups and thus reduce the energy dissipation caused by the rotation of uncyclized amino groups.
Such an approach will bring out relatively higher production costs.
Secondly, in the step of demethylation corrosive strong acids such as hydrochloric acid, hydroiodic acid and boron tribromide are needed.
These materials are hazardous to the environment.
Thirdly, the overall yields in the above-said approaches are low (<30%) due to the need of two extra steps, prior protection of the hydroxyl group with a toxic reagent of dimethyl sulfate and removal of the protecting methyl group after the cyclization reaction.

Method used

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  • Method for making 8-hydroxyjulolidine compound
  • Method for making 8-hydroxyjulolidine compound
  • Method for making 8-hydroxyjulolidine compound

Examples

Experimental program
Comparison scheme
Effect test

embodiment 1

8-Hydroxyjulolidine

[0022] m-Aminophenol (110 mg, 1 mmol), 1-bromo-3-chloropropane (2.35 g, 1.6 ml, 15 mmol) and anhydrous Na.sub.2CO.sub.3 (212 g, 2 mmol) were placed in a 100 ml two-necked round-bottomed flask equipped with a thermometer and an addition funnel containing molecular sieves (4.ANG., 0.3 g). The top of the funnel was fitted with a condenser. Under an atmosphere of nitrogen, the mixture was heated to 70.degree. C. for 3 hours and then refluxed at 110.degree. C. for 15 hours. The resulting red mixture was cooled to room temperature and concentrated HCI solution (15 ml) was slowly added with care. After addition of CH.sub.2Cl.sub.2 (5 ml), the aqueous layer was separated. The aqueous phase was neutralized by the addition of 40% NaOH aqueous solution and extracted with CH.sub.2Cl.sub.2 (50 ml.times.4). The CH.sub.2Cl.sub.2 extracts were combined, washed with brine, dried over anhydrous MgSO.sub.4 and concentrated in reduced pressure. The crude product was subjected to sili...

embodiment 2

8-Hydroxyjuloldine

[0024] According to a procedure similar to that of Embodiment 1, a mixture of m-aminophenol(1.1 g, 10 mmol), 1-bromo-3-chloropropane (23.5 g, 16 ml, 150 mmol) and anhydrous Na.sub.2CO.sub.3 (4.27 g, 40 mmol) was heated and stirred at 70.degree. C. for 3 hours and refluxed at 110.degree. C. for 15 hours. After silica gel column chromatography 8-hydroxyjulolidine (800 mg) was obtained in 42% yield.

embodiment 3

8-Hydroxyjulolidine

[0025] According to a procedure similar to that of Embodiment 1, a mixture of m-aminophenol (11.0 g, 101 mmol), 1 -bromo-3-chloropropane (127.4 g, 80 ml, 809 mmol) and anhydrous Na.sub.2CO.sub.3 (42.4 g, 400 mmol) was heated and stirred at 70.degree. C. for 3 hours and refluxed at 110.degree. C. for 15 hours. After silica gel column chromatography, 8-hydroxyjulolidine (7.3 g) was obtained in 38% yield.

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Abstract

The present invention relates to 8-hydroxyjulolidine, its analogous compounds and their preparation methods. The invented method comprises one single step of cyclization reactions of 3-aminophenol or 1,3-dihydroxyaniline with 1,3-dihalopropane or its analogs, to prepare the desired julolidines with improved yields. The products of this invention have the following structures: wherein R1 and R2 represent independently H, halogen, hydroxyl or alkyl. The method of this invention includes the following chemical reaction: wherein X and Y represent independently halogen, acyloxyl, sulfonyloxyl or phosphoryloxyl and R1 and R2 are as defined above. This invention also discloses method for the preparation of various coumarins by additionally reacting the produced 8-hydroxyjulolidine and its analogs with appropriate reagents such as malonate and acetoacetate. This invention also discloses the products and intermediates prepared therefrom.

Description

[0001] The present invention relates to 8-hydroxyjulolidine and its analogous compounds and preparation thereof, especially to a one-step cyclization reaction of 3-aminophenol or 1,3-dihydroxyaniline with 1,3-dihalopropane or its analogs to prepare the desired julolidines. The 8-hydroxyjulolidine and its analogous compounds have the following chemical structure: 3[0002] wherein R.sup.1 and R.sup.2 represent independently hydrogen, halogen, hydroxyl group or alkyl groups.BACKGROUND OF INVENTION[0003] Coumarins are often used as lasing dyes and fluorescent probes in bioassays, because they exhibit the beneficial properties of tunable wavelengths, high quantum yields, high absorption coefficient and little overlapping in the absorption and emission spectra. According to U.S. Pat. No. 3,873,940, U.S. Pat. No. 3,932,415, U.S. Pat. No. 4,005,092 , U.S. Pat. No. 4,471,041 U.S. Pat. No. 4,736,032 and U.S. Pat. No. 4,794,184, coumarin compounds with fused and rigid nitrogen-containing rings ...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C07D455/04C07D491/16
CPCC07D455/04
Inventor CHEN, CHAO-TSENTANG, SHAO-TZULU, LINGFANG, JIM-MIN
Owner ALLIED IND
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