Molecules 2020, 25, 592
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Bisphenol A Diacrylate. M.p. 89 °C (DSC); Tdec 431 °C (TGA); FTIR (cm , ATR) 3086 (w) Csp2–H, 2971
1
(m) 2873 (w) Csp3–H, 1750 (s) ester carbonyl, 1633(w) C=C, 1508 (s) aromatic nucleus; H‐NMR (δ,
CDCl3) 1.69 (s, 6H, methyl protons), 5.96–6.66 (ABX pattern, 6H, vinylic protons), 7.16 (AB pattern,
13
8H, aromatic protons); C‐NMR (δ, CDCl3) 31.0 (methyl carbon atoms), 42.5 (quaternary carbon
atoms), 128.0, 132.5 (vinylic carbon atoms), 120.9, 127.9, 147.9, 148.5 (aromatic carbon atoms), 164.6
(carbonyl carbon atoms).
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Tetrabromobisphenol A Diacrylate. Tdec 345 °C (TGA); FTIR (cm , ATR) 3098 (w) Csp2–H, 2971 (w), 2873
1
(w) Csp3–H, 1750 (s) ester carbonyl, 1633 (w) C=C, 1605 (m) aromatic nucleus, 1182 (s) C–O; H‐NMR
(δ, CDCl3) 1.62 (s, methyl protons), 6.09–6.78 (ABX pattern, 6H, vinylic protons), 7.40 (s, 4H, aromatic
13
protons); C‐NMR (δ, CDCl3) 29.8 (methyl carbon atoms), 43.1 (quaternary carbon atoms), 126.2,
136.1 (vinylic carbon atoms), 117.8, 130.7, 144.3, 150.4 (aromatic carbon atoms), 162.3 (carbonyl carbon
atoms).
The acrylate esters of bis‐2,5‐(hydroxymethyl)furan, bisphenol A and tetrabromobisphenol A
were converted to phosphorus derivatives by Michael addition of phosphites using a previously
described procedure [58].
2,5‐Di[(3‐dopylpropanoyl)methyl]furan (DDMF). A solution of 20.61 g (0.095 mol) of DOPO, 5.7 mL
(0.038 mol) of 1,8‐diazabicycloundec‐7‐ene and 9.01 g (0.038 mol) of bis‐2,5‐(hydroxymethyl)furan
diacrylate in 75 mL of chloroform was stirred at 65 °C for 4 h. The solution was allowed to cool to
room temperature and washed, successively with three 20‐mL portions of 5% aqueous hydrochloric
acid solution, 20 mL of 5% aqueous sodium hydroxide solution and 20 mL of saturated aqueous
sodium chloride solution. The chloroform solution was dried over anhydrous sodium sulfate and the
solvent was removed by rotary evaporation at reduced pressure. The crude product was purified by
column chromatography (silica gel; 5:3 ethyl acetate/hexane as eluent) to afford 23.45 g (92.10% yield)
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of DDMF as a white solid: m.p. 47 °C (DSC), Tdec 352 °C (TGA); FTIR (cm , ATR) 3071 (w) Csp2–H,
2923 (w) Csp3–H, 1732 (vs) ester carbonyl, 1598 (w) aromatic nucleus, 1235 (vs) C–O, 1197 (vs) P=O,
1
910 (s), 757 (s) P–O–C; H‐NMR (δ, CDCl3) 2.36 (m, 4H, methylene protons adjacent to phosphorus),
2.68 (m, 4H, methylene protons adjacent to carbonyl groups), 4.98 (s, 4H, methylene protons adjacent
to oxygen and a furan nucleus), 6.31 (s, 2H, furan aromatic protons), 7.18–7.98 (m, 16H, dopyl
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protons); C‐NMR (δ, CDCl3) 23.2, 26.3, 58.1 (methyl carbon atoms), 111.9, 120.4, 123.0, 123.9, 124.8,
125.2, 128.6, 130.1, 130.7, 133.5, 135.8, 148.5, 149.2, 164.0 (furan and dopyl carbon atoms), 171.8
+
+
+
(carbonyl carbon atoms); MS (ESI, m/z), 669.13 [M + H] , 691.11 [M + Na] , 707.08 [M + K] .
Other adducts were prepared in an analogous manner.
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2,5‐Di[(3‐diethylphosphonatopropanoyl)methyl]furan (DEMF). Tdec 181 °C (TGA); FTIR (cm , ATR) 3066
(w) Csp2–H, 2953 (w) and 2926 (w) Csp3–H, 1737 (vs) ester carbonyl, 1596 (w) aromatic nucleus, 1232
1
(vs) C–O, 1208 (vs) P=O, 907 (s), 754 (s) P–O–C; H‐NMR (δ, CDCl3) 1.26 (m, 12H, methyl protons),
2.02 (m, 4H, methylene protons adjacent to phosphorus), 2.58 (m, 4H, methylene protons adjacent to
carbonyl groups), 4.03 (m, 8H, methylene protons on ethyl groups), 4.99 (s, 4H, methylene protons
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adjacent to oxygen and a furan nucleus), 6.32 (s, 2H, furan protons); C‐NMR (δ, CDCl3) 16.4 (methyl
carbon atoms), 20.9 (methylene carbon atoms adjacent to phosphorus), 27.4, 58.3, 62.0 (methylene
carbon atoms), 111.7, 149.9 (furan carbon atoms), 171.6 (carbonyl carbon atoms); MS (ESI, m/z), 513.13
+
+
+
[M + H] , 535.07 [M + Na] , 551.09 [M + K] .
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2,5‐Di[(3‐diphenylphosphonatopropanoyl)methyl]furan (DPMF). Tdec 198 °C (TGA); FTIR (cm , ATR) 3065
(w) Csp2–H, 2930 (w) Csp3–H, 1740 (vs) ester carbonyl, 1598 (w) aromatic nucleus, 1186 (vs) C–O, 1162
1
(vs) P=O, 927 (s), 762 (s) P–O–C; H‐NMR (δ, CDCl3) 2.46 (m, 4H, methylene protons adjacent to
phosphorus), 2.85 (m, 4H, methylene protons adjacent to carbonyl groups), 5.02 (s, 4H, methylene
protons adjacent to oxygen and a furan nucleus), 6.37 (s, 2H, furan protons), 7.14 and 7.29 (m, 20H,
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phenyl protons); C‐NMR (δ, CDCl3) 21.4 (carbon atoms adjacent to phosphorus), 27.4 (carbon atoms
adjacent to carbonyl groups), 58.6 (carbon atoms adjacent to oxygen), 111.9, 149.9 (furan carbon
atoms), 120.5, 125.3, 129.8, 150.1 (phenyl carbon atoms), 171.2 (carbonyl carbon atoms); MS (ESI, m/z)
+
+
+
705.11 [M + H] , 727.07 [M + Na] , 743.05 [M + K] .