18531-99-2
(S)-(-)-1,1'-Bi-2-naphthol
[1,1'-Binaphthalene]-2,2'-diol,
(S)-;(-)-2,2'-Dihydroxy-1,1'-binaphthalene;
(1S)-1,1'-Binaphthalene-2,2'-diol;
(S)-(-)-2,2'-Dihydroxy-1,1'-binaphthyl;
(S)-(-)-Bi-2-naphthol;(S)-1,1'-Bi-2,2'-naphthol;
(S)-1,1'-Binaphthyl-2,2'-diol;
(S)-2,2'-Dihydroxy-1,1'-binaphthalene;
| FeCl3· 6 H2O |
 |
(±)-2,2'-dihydroxy-1,1'-binaphthyl
| Reaction type: | oxidative coupling |
| Substance classes: | naphthol, aromatics |
| Techniques: | heating under reflux, stirring with magnetic stir bar, removal of water by azeotropic distillation, filtering, evaporating with rotary evaporator, heating with oil bath, stirring with KPG stirrer, heating with regulatable heating mantle |
Equipment |
 | two-necked flask 250 mL |  | reflux condenser | |
 | addition funnel with elongated outlet |  | round bottom flask 100 mL | |
 | heatable magnetic stirrer with magnetic stir bar |  | suction filter | |
 | suction flask |  | water separator | |
 | exsiccator with drying agent |  | oil bath |
Instruction (batch scale 10 mmol)
Equipment
250 mL two-neck flask, reflux condenser, addition funnel with pressure balance and
elongated outlet, 100 mL round bottom flask, heatable magnetic stirrer, magnetic stir bar,
Buechner funnel (Ø = 5.5 cm), suction flask, water separator, desiccator, oil bath
Substances 2-naphthol (mp 122-123 °C) 1.44 g (10.0 mmol) iron(III) chloride hexahydrate 2.70 g (10.0 mmol) toluene (bp 111 °C) about 30 mL water 120 mL
Equipment
250 mL two-neck flask, reflux condenser, addition funnel with pressure balance and
elongated outlet, 100 mL round bottom flask, heatable magnetic stirrer, magnetic stir bar,
Buechner funnel (Ø = 5.5 cm), suction flask, water separator, desiccator, oil bath
Substances 2-naphthol (mp 122-123 °C) 1.44 g (10.0 mmol) iron(III) chloride hexahydrate 2.70 g (10.0 mmol) toluene (bp 111 °C) about 30 mL water 120 mL
Reaction
The reaction apparatus consists of a 250 mL two-neck flask with magnetic stir bar, a reflux
condenser and an addition funnel with elongated outlet, which dips into the reaction solution
in the flask. An oil bath serves as heating source.
In the reaction flask 1.44 g (10.0 mmol) 2-naphthol are dissolved in 100 mL water under
stirring and heating to boiling at an oil bath temperature of 130 °C. Under strong stirring, the
solution of 2.70 g (10.0 mmol) iron(III) chloride hexahydrate in 20 mL water is slowly
transferred from the addition funnel within a period of 20 minutes directly into the reaction
solution. Then it is stirred for one further hour at an oil bath temperature of 100 °C.
Work up
From the hot reaction solution the precipitated solid is sucked off over a Buechner funnel. The
solid is rinsed with 20 mL water back into the reaction flask, stirred and heated under ref1ux
for 10 minutes, and then again sucked off. For purification and removal of residual water the
so obtained crude product is heated with 30 mL toluene under reflux and under stirring with a
magnetic stir bar in a 100 mL round bottom flask with a water separator for 2 hours. After
cooling down to room temperature, the flask is stored in the refrigerator for crystallization.
The precipitated product is sucked off and dried in the desiccator.
Yield: 0.930 g (3.25 mmol, 66%); mp 216 °C
A further crystal fraction can be obtained through evaporating the mother liquor at a rotary
evaporator to 50% of its volume and again cooling in the refrigerator.
Yield: 0.110 g (0.384 mmol, 8%); mp 212 °C
Total yield: 1.04 g (3.63 mmol, 73%); light-brown solid
The reaction apparatus consists of a 250 mL two-neck flask with magnetic stir bar, a reflux
condenser and an addition funnel with elongated outlet, which dips into the reaction solution
in the flask. An oil bath serves as heating source.
In the reaction flask 1.44 g (10.0 mmol) 2-naphthol are dissolved in 100 mL water under
stirring and heating to boiling at an oil bath temperature of 130 °C. Under strong stirring, the
solution of 2.70 g (10.0 mmol) iron(III) chloride hexahydrate in 20 mL water is slowly
transferred from the addition funnel within a period of 20 minutes directly into the reaction
solution. Then it is stirred for one further hour at an oil bath temperature of 100 °C.
Work up
From the hot reaction solution the precipitated solid is sucked off over a Buechner funnel. The
solid is rinsed with 20 mL water back into the reaction flask, stirred and heated under ref1ux
for 10 minutes, and then again sucked off. For purification and removal of residual water the
so obtained crude product is heated with 30 mL toluene under reflux and under stirring with a
magnetic stir bar in a 100 mL round bottom flask with a water separator for 2 hours. After
cooling down to room temperature, the flask is stored in the refrigerator for crystallization.
The precipitated product is sucked off and dried in the desiccator.
Yield: 0.930 g (3.25 mmol, 66%); mp 216 °C
A further crystal fraction can be obtained through evaporating the mother liquor at a rotary
evaporator to 50% of its volume and again cooling in the refrigerator.
Yield: 0.110 g (0.384 mmol, 8%); mp 212 °C
Total yield: 1.04 g (3.63 mmol, 73%); light-brown solid
| Atom economy | 51.3 | % | |
| Yield | 73 | % | |
| Target product mass | 1.04 | g | |
| Sum of input masses | 150 | g | |
| Mass efficiency | 7.1 | mg/g | |
| Mass index | 140 | g input / g product | |
| E factor | 140 | g waste / g product |
GC: pure productcolumnDB-1, L=28 m, d=0.32 mm, film=0.25 µminleton column injectioncarrier gasH2, 40 cm/soven90°C (5 min), 10°C/min --> 240°C (30 min)detectorFID, 270°Cintegrationpercent concentration calculated from relative peak area
| 1H-NMR: 2,2'-Dihydroxy-1,1'-binaphthyl | |||
| 300 MHz, CDCl3 | |||
| delta [ppm] | mult. | atoms | assignment |
| 5.05 | s | 2 H | OH |
| 7.13 | d | 2 H | 3-H |
| 7.40-7.21 | m | 6 H | 6-H, 7-H, 8-H |
| 7.85 | d | 2 H | 4-H (5-H) |
| 7.93 | d | 2 H | 5-H (4-H) |
| 13C-NMR: 2,2'-Dihydroxy-1,1'-binaphthyl | |||
| 75.5 MHz, CDCl3 | |||
| delta [ppm] | assignment | ||
| 111.0 | C1 | ||
| 117.8 | C3 | ||
| 124.0 | C6 | ||
| 124.2 | C8 | ||
| 127.5 | C7 | ||
| 128.4 | C5 | ||
| 129.6 | C4 | ||
| 131.4 | C4a | ||
| 133.5 | C8a | ||
| 152.8 | C2 | ||
| 76.5-77.5 | CDCl3 | ||
process (1).
..................................
