Preparation method of heteroatom-containing cyclohexene halide
A technology of benzylcyclohexyl and raw materials, which is applied in the field of synthesis of fine chemical intermediates, can solve the problems of cumbersome reaction process, three wastes that are difficult to handle, and difficult industrial production, etc., and achieve the effect of simple process
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Embodiment 1
[0028] Under nitrogen protection, add tetrahydropyran-4-one (10.0 g, 0.1 mol) and 50.1 g of 1,2-dichloroethane to a 250 mL three-neck reaction flask equipped with a condenser and a constant pressure low liquid funnel, Cool down to 5-10°C in an ice-salt bath with stirring, and add thionyl chloride (16.9 g, 0.15 mol) dropwise. After the dropwise addition was completed, the mixture was heated to reflux for 5.0 hours. Sample sent to detect the residue of raw materials is less than 0.5%, GC and GC-MS are not detected tetrahydropyran-4-enyl chloride, concentrated to remove excess thionyl chloride, concentrated solution (GC: 97.8%, GC-MS : 154.0) directly proceed to the next step without purification.
[0029] In the reaction flask containing the concentrated solution in the previous step, drop DBU (18.3g, 0.12mol), NaNH 2 (7.8g, 0.2mol) and 50.2g 1,2-dichloroethane. After feeding, heat to 80°C and stir for 3.0 hours. Send samples to detect that the residual intermediate is less ...
Embodiment 2
[0031] Under nitrogen protection, add tetrahydrothiopyran-4-one (11.6g, 0.1mol) and 58.1g 1,4-dioxane to a 250mL three-necked reaction flask equipped with a condenser and a constant pressure low liquid funnel, Cool down to 5-10°C in an ice-salt bath with stirring, and add oxalyl chloride (19.1 g, 0.15 mol) dropwise. After the dropwise addition was completed, the mixture was heated to reflux and stirred for 6.0 hours. Sampling detection raw material residue is less than 0.5%, GC and GC-MS all do not detect tetrahydrothiopyran-4-enyl chloride, start to concentrate and excess oxalyl chloride is taken off, concentrated solution (GC: gem dichloride 95.5%, two Oxycycline 4.1%) was carried on to the next step without purification.
[0032] In the reaction flask containing the concentrated solution in the previous step, drop into TMG (17.3g, 0.15mol), LiNH 2 (4.6 g, 0.2 mol) and 58.1 g 1,4-dioxane. After feeding, heat to reflux and stir for 8.0 hours. Send a sample to detect that ...
Embodiment 3
[0034]Under nitrogen protection, add N-benzylcyclohexyl-4-one (18.9 g, 0.1 mol), triethylamine (11.2 g, 0.11mol) and 94.6g of acetonitrile and sulfolane (mass ratio: 5:1) mixture, replaced with nitrogen three times, heated to 30-40°C under stirring and added phosphorus pentachloride (24.9g, 0.12mol) in batches. After the addition was complete, the mixture was heated at 80°C and stirred for 5.0 hours. The residue of the raw material is less than 0.5% in the sample sent by GC, and the product contains alkenyl chloride and geminal dichloride (confirmed by molecular weight in GC-MS), and the proportion of the two is 81% and 19% (only the two peaks are retained), NMR The conversion ratio of the two by hydrogen spectrum detection is 78:22. The reaction solution was directly carried to the next step without purification. (comparison experiment: when not adding triethylamine in this reaction, there is the raw material hydrochloride of obvious amount, and raw material transformation ...
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