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Tuesday, 2 September 2014

(±)-2,2'-dihydroxy-1,1'-binaphthyl


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;

2-Naphthol
FeCl3· 6 H2O
reacts to
2,2

(±)-2,2'-dihydroxy-1,1'-binaphthyl

Inline image 1


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

Batch scale:0.01 mol

two-necked flask 250 mLtwo-necked flask 250 mLreflux condenserreflux condenser
addition funnel with elongated outletaddition funnel with elongated outletround bottom flask 100 mLround bottom flask 100 mL
heatable magnetic stirrer with magnetic stir barheatable magnetic stirrer with magnetic stir barsuction filtersuction filter
suction flasksuction flaskwater separatorwater separator
exsiccator with drying agentexsiccator with drying agentoil bathoil 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
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
Batch scale:0.01 mol


Atom economy51.3%
Yield73%
Target product mass1.04g
Sum of input masses150g
Mass efficiency7.1mg/g
Mass index140g input / g product
E factor140g waste / g product

Operating scheme
pure product chromatogram
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
Inline image 2
1H-NMR: 2,2'-Dihydroxy-1,1'-binaphthyl
300 MHz, CDCl3
delta [ppm]mult.atomsassignment
5.05s2 HOH
7.13d2 H3-H
7.40-7.21m6 H6-H, 7-H, 8-H
7.85d2 H4-H (5-H)
7.93d2 H5-H (4-H)
13C NMR
Inline image 3
13C-NMR: 2,2'-Dihydroxy-1,1'-binaphthyl
75.5 MHz, CDCl3
delta [ppm]assignment
111.0C1
117.8C3
124.0C6
124.2C8
127.5C7
128.4C5
129.6C4
131.4C4a
133.5C8a
152.8C2
76.5-77.5CDCl3

process (1).
Figure imgb0001


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