6,11-dihydrobenzo[c][1]benzothiepin-11-ol

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6,11-Dihydrodibenzo[b,e]thiepin-11-ol (1.14 g, 5 mmol) was dissolved in dry THF (25 mL) at 0° C. Sodium hydride (0.24 g of 50% mineral oil dispersion, 5 mmol) was added portionwise at 0° C. and then refluxed for 30 min. tert-Butylbromoacetate (980 mg, 5.0 mmol) in dry THF (10 mL) was added over a period of 20 min followed by a 30 min reflux. The reaction mixture was quenched with water at 0° C. and the product extracted with ether. The combined ex-extracts were dried (MgSO4), and concentrated in vacuo. The product was redissolved in ether and added dropwise to an ether (15 mL) suspension of lithium aluminium hydride (190 mg, 5.0 mmol). The reaction was stirred 16 h at room temperature, quenched with water, cooled, and filtered through Decalit. The ether solution was washed with saturated NaCl, dried, and purified by chromatography eluting with ethyl acetate/dichloromethan (1:10) to give 850 mg (63%) of 2-(6,11-dihydrodibenzo[b,e]thiepin-11-yloxy)-ethanol. 1H NMR (300 MHz, CDCl3) δ 3.55-3.70 (m, 2H), 3.75-3.85 (m, 2H), 4.00 (bs,1H), 4.85 (bs, 1H), 5.55 (bs, 1H), 7.03-7.13 (m, 3H), 7.13-7.48 (m, 5H). was added over a period of 20 min reflux The reaction mixture was quenched with water at 0° C. the product extracted with ether were dried (MgSO4) concentrated in vacuo The product was redissolved in ether quenched with water cooled filtered through Decalit The ether solution was washed with saturated NaCl dried purified by chromatography eluting with ethyl acetate/dichloromethan (1:10)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6,11-Dihydrodibenzo[b,e]thiepin-11-ol (1.14 g, 5 mmol) was dissolved in dry THF (25 mL) at 0° C. Sodium hydride (0.24 g of 50% mineral oil dispersion, 5 mmol) was added portionwise at 0° C. and then refluxed for 30 min. tert-Butylbromoacetate (980 mg, 5.0 mmol) in dry THF (10 mL) was added over a period of 20 min followed by a 30 min reflux. The reaction mixture was quenched with water at 0° C. and the product extracted with ether. The combined extracts were dried (MgSO4), and concentrated in vacuo. The product was redissolved in ether and added dropwise to an ether (15 mL) suspension of lithium aluminium hydride (190 mg, 5.0 mmol). The reaction was stirred 16 h at room temperature, quenched with water, cooled, and filtered through Decalit. The ether solution was washed with saturated NaCl, dried, and purified by chromatography eluting with ethyl acetate/dichloromethan (1:10) to give 850 mg (63%) of 2-(6,11-dihydrodibenzo[b,e]thiepin-11-yloxy)-ethanol. 1H NMR (300 MHz, CDCl3) δ3.55-3.70 (m, 2H), 3.75-3.85 (m, 2H), 4.00 (bs, 1H), 4.85 (bs, 1H), 5.55 (bs, 1H), 7.03-7.13 (m, 3H), 7.13-7.48 (m, 5H). was added over a period of 20 min reflux The reaction mixture was quenched with water at 0° C. the product extracted with ether The combined extracts were dried (MgSO4) concentrated in vacuo The product was redissolved in ether quenched with water cooled filtered through Decalit The ether solution was washed with saturated NaCl dried purified by chromatography eluting with ethyl acetate/dichloromethan (1:10)

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 48 g (212 mmol) 6.1-dihydro-dibenzo[b,e]thiepin-11-one are dissolved in 480 ml absolute methanol and cooled to ca. −10° C. 19.2 g (507 mmol) sodium borohydride is added portion wise to this solution. The mixture is stirred for three hours at RT without further cooling. After the careful addition of 30 ml water, the suspension is concentrated under vacuum. The residue is taken up in 500 ml dichloromethane and washed twice each with 150 ml water. The organic phase is dried over sodium sulfate and the solvent is removed under vacuum. The residue is crystallized from 180 ml toluene. Colorless crystals of MP. 108° C.: Yield 41.2 g (85%). the suspension is concentrated under vacuum washed twice each with 150 ml water The organic phase is dried over sodium sulfate the solvent is removed under vacuum The residue is crystallized from 180 ml toluene Colorless crystals of MP. 108° C.

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 48 g (212 mmol) 6.1-dihydro-dibenzo[b,e]thiepin-11-one are dissolved in 480 ml absolute methanol and cooled to ca. −10° C. 19.2 g (507 mmol) sodium borohydride is added portion wise to this solution. The mixture is stirred for three hours at RT without further cooling. After the careful addition of 30 ml water, the suspension is concentrated under vacuum. The residue is taken up in 500 ml dichloromethane and washed twice each with 150 ml water. The organic phase is dried over sodium sulfate and the solvent is removed under vacuum. The residue is crystallized from 180 ml toluene. Colorless crystals of MP. 108° C.: Yield 41.2 g (85%). the suspension is concentrated under vacuum washed twice each with 150 ml water The organic phase is dried over sodium sulfate the solvent is removed under vacuum The residue is crystallized from 180 ml toluene Colorless crystals of MP. 108° C.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6,11-Dihydrodibenzo[b,e]thiepin-11-ol (1.14 g, 5 mmol) was dissolved in dry THF (25 mL) at 0° C. Sodium hydride (0.24 g of 50% mineral oil dispersion, 5 mmol) was added portionwise at 0° C. and then refluxed for 30 min. tert-Butylbromoacetate (980 mg, 5.0 mmol) in dry THF (10 mL) was added over a period of 20 min followed by a 30 min reflux. The reaction mixture was quenched with water at 0° C. and the product extracted with ether. The combined ex-extracts were dried (MgSO4), and concentrated in vacuo. The product was redissolved in ether and added dropwise to an ether (15 mL) suspension of lithium aluminium hydride (190 mg, 5.0 mmol). The reaction was stirred 16 h at room temperature, quenched with water, cooled, and filtered through Decalit. The ether solution was washed with saturated NaCl, dried, and purified by chromatography eluting with ethyl acetate/dichloromethan (1:10) to give 850 mg (63%) of 2-(6,11-dihydrodibenzo[b,e]thiepin-11-yloxy)-ethanol. 1H NMR (300 MHz, CDCl3) δ3.55-3.70 (m, 2H), 3.75-3.85 (m, 2H), 4.00 (bs, 1H), 4.85 (bs, 1H), 5.55 (bs, 1H), 7.03-7.13 (m, 3H), 7.13-7.48 (m, 5H). was added over a period of 20 min reflux The reaction mixture was quenched with water at 0° C. the product extracted with ether were dried (MgSO4) concentrated in vacuo The product was redissolved in ether quenched with water cooled filtered through Decalit The ether solution was washed with saturated NaCl dried purified by chromatography eluting with ethyl acetate/dichloromethan (1:10)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6,11-Dihydrodibenzo[b,e]thiepin-11-ol (1.14 g, 5 mmol) was dissolved in dry THF (25 mL) at 0° C. Sodium hydride (0.24 g of 50% mineral oil dispersion, 5 mmol) was added portionwise at 0° C. and then refluxed for 30 min. tert-Butylbromoacetate (980 mg, 5.0 mmol) in dry THF (10 mL) was added over a period of 20 min followed by a 30 min reflux. The reaction mixture was quenched with water at 0° C. and the product extracted with ether. The combined ex-extracts were dried (MgSO4), and concentrated in vacuo. The product was redissolved in ether and added dropwise to an ether (15 mL) suspension of lithium aluminium hydride (190 mg, 5.0 mmol). The reaction was stirred 16 h at room temperature, quenched with water, cooled, and filtered through Decalit. The ether solution was washed with saturated NaCl, dried, and purified by chromatography eluting with ethyl acetate/dichloromethan (1:10) to give 850 mg (63%) of 2-(6,11-dihydrodibenzo[b,e]thiepin-11-yloxy)-ethanol. 1H NMR (300 MHz, CDCl3) δ3.55-3.70 (m, 2H), 3.75-3.85 (m, 2H), 4.00 (bs, 1H), 4.85 (bs, 1H), 5.55 (bs, 1H), 7.03-7.13 (m, 3H), 7.13-7.48 (m, 5H). was added over a period of 20 min reflux The reaction mixture was quenched with water at 0° C. the product extracted with ether were dried (MgSO4) concentrated in vacuo The product was redissolved in ether quenched with water cooled filtered through Decalit The ether solution was washed with saturated NaCl dried purified by chromatography eluting with ethyl acetate/dichloromethan (1:10)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6,11-Dihydrodibenzo[b,e]thiepin-11-ol (1.14 g, 5 mmol) was dissolved in dry THF (25 mL) at 0° C. Sodium hydride (0.24 g of 50% mineral oil dispersion, 5 mmol) was added portionwise at 0° C. and then refluxed for 30 min. tert-Butylbromoacetate (980 mg, 5.0 mmol) in dry THF (10 mL) was added over a period of 20 min followed by a 30 min reflux. The reaction mixture was quenched with water at 0° C. and the product extracted with ether. The combined extracts were dried (MgSO4), and concentrated in vacuo. The product was redissolved in ether and added dropwise to an ether (15 mL) suspension of lithium aluminium hydride (190 mg, 5.0 mmol). The reaction was stirred 16 h at room temperature, quenched with water, cooled, and filtered through Decalit. The ether solution was washed with saturated NaCl, dried, and purified by chromatography eluting with ethyl acetate/dichloromethan (1:10) to give 850 mg (63%) of 2-(6,11-dihydrodibenzo[b,e]thiepin-11-yloxy)-ethanol. 1H NMR (300 MHz, CDCl3) δ3.55-3.70 (m, 2H), 3.75-3.85 (m, 2H), 4.00 (bs,1H), 4.85 (bs, 1H), 5.55 (bs, 1H), 7.03-7.13 (m, 3H), 7.13-7.48 (m, 5H). was added over a period of 20 min reflux The reaction mixture was quenched with water at 0° C. the product extracted with ether The combined extracts were dried (MgSO4) concentrated in vacuo The product was redissolved in ether quenched with water cooled filtered through Decalit The ether solution was washed with saturated NaCl dried purified by chromatography eluting with ethyl acetate/dichloromethan (1:10)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6,11-Dihydrodibenzo[b,e]thiepin-11-ol (1.14 g, 5 mmol) was dissolved in dry THF (25 mL) at 0° C. Sodium hydride (0.24 g of 50% mineral oil dispersion, 5 mmol) was added portionwise at 0° C. and then refluxed for 30 min. tert-Butylbromoacetate (980 mg, 5.0 mmol) in dry THF (10 mL) was added over a period of 20 min followed by a 30 min reflux. The reaction mixture was quenched with water at 0° C. and the product extracted with ether. The combined ex-extracts were dried (MgSO4), and concentrated in vacuo. The product was redissolved in ether and added dropwise to an ether (15 mL) suspension of lithium aluminium hydride (190 mg, 5.0 mmol). The reaction was stirred 16 h at room temperature, quenched with water, cooled, and filtered through Decalit. The ether solution was washed with saturated NaCl, dried, and purified by chromatography eluting with ethyl acetate/dichloromethan (1:10) to give 850 mg (63%) of 2-(6,11-dihydrodibenzo[b,e]thiepin-11-yloxy)-ethanol. 1H NMR (300 MHz, CDCl3) δ 3.55-3.70 (m, 2H), 3.75-3.85 (m, 2H), 4.00 (bs,1H), 4.85 (bs, 1H), 5.55 (bs, 1H), 7.03-7.13 (m, 3H), 7.13-7.48 (m, 5H). was added over a period of 20 min reflux The reaction mixture was quenched with water at 0° C. the product extracted with ether were dried (MgSO4) concentrated in vacuo The product was redissolved in ether quenched with water cooled filtered through Decalit The ether solution was washed with saturated NaCl dried purified by chromatography eluting with ethyl acetate/dichloromethan (1:10)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6,11-Dihydrodibenzo[b,e]thiepin-11-ol (1.14 g, 5 mmol) was dissolved in dry THF (25 mL) at 0° C. Sodium hydride (0.24 g of 50% mineral oil dispersion, 5 mmol) was added portionwise at 0° C. and then refluxed for 30 min. tert-Butylbromoacetate (980 mg, 5.0 mmol) in dry THF (10 mL) was added over a period of 20 min followed by a 30 min reflux. The reaction mixture was quenched with water at 0° C. and the product extracted with ether. The combined ex-extracts were dried (MgSO4), and concentrated in vacuo. The product was redissolved in ether and added dropwise to an ether (15 mL) suspension of lithium aluminium hydride (190 mg, 5.0 mmol). The reaction was stirred 16 h at room temperature, quenched with water, cooled, and filtered through Decalit. The ether solution was washed with saturated NaCl, dried, and purified by chromatography eluting with ethyl acetate/dichloromethan (1:10) to give 850 mg (63%) of 2-(6,11-dihydrodibenzo[b,e]thiepin-11-yloxy)-ethanol. 1H NMR (300 MHz, CDCl3) δ 3.55-3.70 (m, 2H), 3.75-3.85 (m, 2H), 4.00 (bs,1H), 4.85 (bs, 1H), 5.55 (bs, 1H), 7.03-7.13 (m, 3H), 7.13-7.48 (m, 5H). was added over a period of 20 min reflux The reaction mixture was quenched with water at 0° C. the product extracted with ether were dried (MgSO4) concentrated in vacuo The product was redissolved in ether quenched with water cooled filtered through Decalit The ether solution was washed with saturated NaCl dried purified by chromatography eluting with ethyl acetate/dichloromethan (1:10)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6,11-Dihydrodibenzo[b,e]thiepin-11-ol (1.14 g, 5 mmol) was dissolved in dry THF (25 mL) at 0° C. Sodium hydride (0.24 g of 50% mineral oil dispersion, 5 mmol) was added portionwise at 0° C. and then refluxed for 30 min. tert-Butylbromoacetate (980 mg, 5.0 mmol) in dry THF (10 mL) was added over a period of 20 min followed by a 30 min reflux. The reaction mixture was quenched with water at 0° C. and the product extracted with ether. The combined extracts were dried (MgSO4), and concentrated in vacuo. The product was redissolved in ether and added dropwise to an ether (15 mL) suspension of lithium aluminium hydride (190 mg, 5.0 mmol). The reaction was stirred 16 h at room temperature, quenched with water, cooled, and filtered through Decalit. The ether solution was washed with saturated NaCl, dried, and purified by chromatography eluting with ethyl acetate/dichloromethan (1:10) to give 850 mg (63%) of 2-(6,11-dihydrodibenzo[b,e]thiepin-11-yloxy)-ethanol. 1H NMR (300 MHz, CDCl3) δ3.55-3.70 (m, 2H), 3.75-3.85 (m, 2H), 4.00 (bs, 1H), 4.85 (bs, 1H), 5.55 (bs, 1H), 7.03-7.13 (m, 3H), 7.13-7.48 (m, 5H). was added over a period of 20 min reflux The reaction mixture was quenched with water at 0° C. the product extracted with ether The combined extracts were dried (MgSO4) concentrated in vacuo The product was redissolved in ether quenched with water cooled filtered through Decalit The ether solution was washed with saturated NaCl dried purified by chromatography eluting with ethyl acetate/dichloromethan (1:10)