A kind of preparation method of β, γ-unsaturated carboxylic acid benzyl ester compound
A technology of benzyl carboxylate and compounds, which is applied in the field of preparation of benzyl carboxylate compounds of β, γ-unsaturated benzyl carboxylates, and achieves the effects of simple experimental operation, good substrate compatibility, and easy industrialization
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Embodiment 1
[0036] Example 1: Synthesis of Benzyl but-3-enoate (2a)
[0037]
[0038] Accurately weigh tris(dibenzylideneacetone)dipalladium (22.8 mg, 0.025 mmol) and tetrabutylammonium bromide (225.7 mg, 0.7 mmol) and add them to a 50 mL reaction kettle in turn, add tetrahydrofuran (5.0 mL ), benzyl chloride (63.3 mg, 0.5 mmol), tributylallyl tin (198.7 mg, 0.6 mmol). Then filled with carbon dioxide to 2.0 MPa. The reactor was placed in a 70 oC oil bath for 24 h. After the reaction, the reactor was slowly cooled to room temperature, and the remaining carbon dioxide was released. Finally, the solvent was removed under reduced pressure, using petroleum ether / ethyl acetate as the eluent, and separated on a silica gel column, the yield of benzyl 3-butenoate was 86%. 1 H NMR (400 MHz, CDCl 3 ) δ 3.12 (d, J = 6.8 Hz, 2H), 5.12 (s, 2H), 5.13–5.18 (m, 2H), 5.88–5.99 (m, 1H), 7.28–7.34 (m, 5H); 13 C NMR (100 MHz, CDCl 3 ) δ 39.1, 66.5, 118.7, 128.2, 128.3, 128.6, 130.2, 135.9, 171.3.
Embodiment 2
[0039] Example 2: Synthesis of 4-Fluorobenzyl but-3-enoate (2b)
[0040]
[0041] Accurately weigh palladium chloride (4.4 mg, 0.025 mmol), tetrabutylammonium bromide (225.7 mg, 0.7 mmol) and sequentially add them to a 50 mL reaction kettle, add tetrahydrofuran (5.0 mL), 1-chloromethyl -4-fluorobenzene (72.3 mg, 0.5 mmol), tributylallyl tin (198.7 mg, 0.6 mmol). Then filled with carbon dioxide to 2.0 MPa. The reactor was placed in a 70 oC oil bath for 24 h. After the reaction, the reactor was slowly cooled to room temperature, and the remaining carbon dioxide was released. Finally, the solvent was removed under reduced pressure, using petroleum ether / ethyl acetate as the eluent, and separated on a silica gel column, the yield of 3-butenoic acid-4-fluorobenzyl was 84%. 1 H NMR (400 MHz, CDCl 3) δ 3.13 (d, J = 6.8 Hz, 2H), 5.09 (s, 2H), 5.14–5.19 (m, 2H), 5.88–5.98 (m, 1H), 7.02–7.07 (m, 2H), 7.31– 7.36 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 39.1, 65.7, 115.5 (d, 2 J ...
Embodiment 3
[0042] Example 3: Synthesis of 4-Chlobenzyl but-3-enoate (2c)
[0043]
[0044] Accurately weigh palladium chloride (4.4 mg, 0.025 mmol), tetrabutylammonium chloride (194.5 mg, 0.7 mmol) and sequentially add to a 50 mL reaction kettle, add toluene (5.0 mL), 1-chloromethyl -4-Chlorobenzene (80.5 mg, 0.5 mmol), tributylallyl tin (198.7 mg, 0.6 mmol). Then filled with carbon dioxide to 2.0 MPa. The reactor was placed in a 70 oC oil bath for 24 h. After the reaction, the reactor was slowly cooled to room temperature, and the remaining carbon dioxide was released. Finally, the solvent was removed under reduced pressure, using petroleum ether / ethyl acetate as the eluent, and separated on a silica gel column. The yield of 3-butenoic acid-4-chlorobenzyl ester was 80%. 1 H NMR (400 MHz, CDCl 3 ) δ 3.13 (d, J = 6.8 Hz, 2H), 5.08 (s, 2H), 5.14–5.18 (m, 2H), 5.87–5.98 (m, 1H), 7.27 (d, J = 8.4 Hz, 2H) , 7.31 (d, J = 8.4 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 39.0, 65.6, 118.8, 1...
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