Thiourea compositions and uses thereof
A technology of mixtures and compounds, applied in the field of thiourea-palladium complexes, can solve the problems of air-sensitivity limiting synthesis and application of phosphine ligands and the like
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Embodiment 1
[0040] Synthesis of Cyclic Thiourea 1f-1k
[0041]
[0042] Diagram 1
[0043] Cyclic thiourea ligands were synthesized using two methods (Scheme 1).
[0044] Method A:
[0045] To a solution of N,N'-diaryldiamine in anhydrous toluene was added 1,1'-thiocarbonyldiimidazole (1.2 equivalents). The solution was then stirred at 100°C and the reaction was monitored by TLC. After completion, the solution was diluted with ethyl acetate and washed with dilute HCl and brine. The organic layer was concentrated under vacuum. Pure thiourea was obtained by flash chromatography or recrystallization from 95% ethanol.
[0046] Method B:
[0047] To the stirred N,N'-diaryldiamine and Na at room temperature 2 CO 3 (1.5 equiv) in dry THF was added dropwise a THF solution of thiophosgene (1.2 equiv). After stirring overnight at room temperature, water and ethyl acetate were added. The organic layer was washed with dilute HCl and brine, dried and concentrated. Pure thiourea was obtai...
Embodiment 2
[0064] Synthesis of acyclic dithiourea ligand:
[0065]
[0066] Diagram 2
[0067] At 0°C, N, N'-diaryldiamine (1.0mmol) and NEt 3 (3 eq) in THF was added dropwise to a stirred solution of thiophosgene (3.0 eq) in anhydrous THF. After stirring overnight at room temperature, the organic layer was washed with water, dried and concentrated.
[0068] For the synthesis of the acyclic bis-thiourea, the dichloride obtained above and excess secondary amine were heated at 100° C. for 24 hours in a sealed pressure tube. The solution was then diluted with EtOAc and washed with dilute HCl and brine. The organic layer was dried and concentrated. Flash chromatography gave pure bis-thiourea as a white solid.
[0069] 1l: white solid, 95% yield; m.p 225-226°C; 1 H NMR (400MHz, CDCl 3 )δ7.37-7.34 (m, 2H), 7.21-7.18 (m, 2H), 7.18-7.00 (m, 2H), 4.87-4.79 (m, 2H), 4.15-4.11 (m, 2H), 3.54- 3.35(m, 8H), 1.44-1.19(m, 48H); 13 C NMR (100MHz, CDCl 3 )δ190.0, 149.1, 142.9, 141.3, 129.8, 1...
Embodiment 3
[0073] Synthesis of cyclic bis-thiourea ligand 1o:
[0074]
[0075] Preparation of 1o::
[0076] Add diamine salt (2.0g, 9.2mmol) and Na 2 CO 3 (0.85g, 8mmol) in CH 3 To the mixture in CN (15ml) was slowly added bis(bromomethyl)mesitylene (0.72g, 2.3mmol) in CH 3CN (10ml) solution. The resulting mixture was refluxed for 24 hours. The mixture was then diluted with ethyl acetate and washed with brine, dried and concentrated. The resulting oil was dissolved in THF (30ml) and Na 2 CO 3 (1.27g, 12mmol). Sulfurphosgene (0.7ml, 9mmol) in THF (10ml) was added very slowly dropwise at room temperature. After stirring overnight, THF was removed and water (20ml) and ethyl acetate (40ml) were added. The organic layer was washed with dilute HCl and brine, dried and concentrated. Pure bis-thiourea 1o was obtained by flash chromatography (20% ethyl acetate / petroleum ether) as a white solid (150 mg, 11%).
[0077] 1o: m.p>230°C; 1 H NMR (400MHz, CDCl 3 )δ6.97(s, 1H), 6.95(s, ...
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