Mercapto-containing naphthopyran photochromic compound and its preparation method and application
A technology of naphthopyrans and photochromism, which is applied in the field of polymer chemistry, can solve problems such as premature termination of the reaction, and achieve the effect of broadening the application field and the synthesis method is simple and efficient
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Embodiment 1
[0067]
[0068] In a 1000mL three-neck flask, the compound shown in the dry formula III-1 (see US Patent US5645767 for the preparation method) (20.5g, 37.9mmol) was dissolved in 300mL of anhydrous toluene, and then mercaptoethanol (5.9g, 75.5mmol) was added , Stir at room temperature for 1 hour, then slowly add 5ml of concentrated sulfuric acid dropwise, after the concentrated sulfuric acid is added dropwise, connect the water separation condensing device, raise the temperature to 115°C for reflux reaction and water separation for 4 hours, turn off the heating and cool to room temperature, add water to wash And separate the liquid (3 × 500mL), dry the toluene layer with anhydrous sodium sulfate, spin the solvent to dry, and then purify by column chromatography (200-300 mesh silica gel), use toluene and ethyl acetate with a volume ratio of 100:1 for development agent to obtain 18.7g of pale yellow solid compound I-1. 1 H NMR (300MHz, CDCl 3 )δ8.22(s,1H),8.19(d,1H),7.65(m,4H...
Embodiment 2
[0074]
[0075] In a 1000mL three-neck flask, dissolve the dried formula III-2 (20.2g, 46.1mmol) (20.2g, 46.1mmol) in anhydrous toluene, add mercaptoethanol (7.2g, 92.1mmol), and stir at room temperature After 1 hour, slowly add 5ml of concentrated sulfuric acid dropwise. After the concentrated sulfuric acid is added dropwise, connect the water separation condensing device, raise the temperature to 115°C for reflux reaction and water separation for 4 hours, turn off the heating, and cool to room temperature. Add water to wash and separate (3×500mL), dry the toluene layer with anhydrous sodium sulfate, spin the solvent to dryness, and purify by column chromatography (200-300 mesh silica gel), use toluene and ethyl acetate with a volume ratio of 100:1 As a developer, 17.1 g of white solid compound II-1 was obtained. 1 H NMR (300MHz, CDCl 3 )δ8.15(s,1H),7.65(d,1H),7.28(d,4H),7.26(s,H),6.89(m,5H),6.58(d,2H),4.91(s,2H ),3.81(s,6H),3.67(t,2H),2.73(t,2H),2.66(s,3H),1.4(s,1H,-SH)...
Embodiment 3
[0080]
[0081] In a 1000mL three-neck flask, dissolve the dried formula III-3 (see US Patent US5645767 for the preparation method) (20.8g, 36.9mmol) in 300mL of anhydrous toluene, then add mercaptoethanol (5.8g, 73.8mmol), and stir at room temperature After 1 hour, slowly add 5ml of concentrated sulfuric acid dropwise. After the concentrated sulfuric acid is added dropwise, connect the water separation condensing device, raise the temperature to 115°C for reflux reaction and water separation for 4 hours, turn off the heating, and cool to room temperature. Add water to wash and separate (3×500mL), dry the toluene layer with anhydrous sodium sulfate, spin the solvent to dryness, and then purify by column chromatography (200-300 mesh silica gel), use toluene and ethyl acetate with a volume ratio of 100:1 As a developer, 18.1 g of white solid compound I-2 was obtained. 1 H NMR (300MHz, CDCl 3 )δ8.22(s,1H),8.18(d,1H),7.62(m,4H),7.28(d,2H),7.30(m,3H),7.10(d,2H),6.71(m,2H ),6.3...
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