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31st October 2011 @ 04:32
Step 2 of 3 towards (S)-1,1'-binaphthyl-2,2'-disulfonic acid as for MW45-2

MNR18-1%20scheme.png

MNR18-1%20table.PNG

Hazard and Risk Assessment:
As for HIRAC-MNR17

Procedure
MNR16-1 (610 mg, 1.32 mmol) was placed in a roundbottom flask (100 ml) and heated in a heating mantle to 250°C for 90 min. The dark brown solid was dissolved in chloroform and purified by column chromatography (silica gel, 5% EtoAC/Hex).

Major spot - 0.240 g - NOT PRODUCT

1H NMR MNR18-1

Not sure what's gone wrong here. The crude product was not totally soluble and was stuck to flask. Heated for too long or too hot? Hard to control the temperature of the mantle.
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31st October 2011 @ 04:15
Step 2 of 3 towards (R)-1,1'-binaphthyl-2,2'-disulfonic acid as for MW45-2

MNR17-1%20scheme.png

MNR17-1%20table.PNG

Hazard and Risk Assessment:
HIRAC-MNR17

Procedure

MNR15-1 (680 mg, 1.48 mmol) was placed in a roundbottom flask (100 ml) and heated in a heating mantle to 250°C for 90 min. The dark brown solid was dissolved in chloroform and purified by column chromatography (silica gel, 5% EtoAC/Hex).

Major spot - 0.131 g - NOT PRODUCT

1H NMR MNR17-1

Not sure what's gone wrong here. The crude product was not totally soluble and was stuck to flask. Heated for too long or too hot? Hard to control the temperature of the mantle.
Attached Files
27th October 2011 @ 01:40
Step 1 of 3 towards (S)-1,1'-binaphthyl-2,2'-disulfonic acid as for MW45-1

MNR16-1%20scheme.png

MNR16-1%20table.PNG

Hazard and Risk Assessment:
As for MNR15:- HIRAC MNR15

Procedure

To an ice cooled solution of (S)-(+)-1,1'-Bi(2-naphthol)(0.50 g, 1.75 mmol) in dry DMF (5 mL) under argon was added sodium hydride (60% oil dispersion) (0.17 mg, 4.37 mmol). The reaction was allowed to warm to room temperature and stirred for 10 mins. The resulting yellow solid was gently heated to obtain a yellow dispersion to which N,N-dimethylthiocarbamoyl chloride (470 mg, 3.84 mmol) was added at room temperature and the resulting mixture was heated to 85°C for 1.5 h.

The yellow-brown mixture was cooled to room temperature and poured into 1% aqueous KOH solution (15 mL) where a off white solid precipitated out instantly. The solid was filtered and washed with water and dissolved in DCM, dried over magnsium sulfate, filtered and concentrated to give a light fluffy foam that slowly crystallised.

610 mg,

MNR16-1 first filter - clean product, traces of DMF

More solid precipitated out of the aqueous layer after standing for one day and was filtered and washed with water.

81 mg

MNR16-1 second filter - messy, only traces of product


Tare:- 61.818 g
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27th October 2011 @ 01:28
Step 1 of 3 towards (R)-1,1'-binaphthyl-2,2'-disulfonic acid as for MW45-1

MNR15-1%20scheme.png

MNR15-1%20table.PNG

Hazard and Risk Assessment:
HIRAC MNR15

Procedure

To an ice cooled solution of (R)-(+)-1,1'-Bi(2-naphthol)(0.50 g, 1.75 mmol) in dry DMF (5 mL) under argon was added sodium hydride (60% oil dispersion) (0.17 mg, 4.37 mmol). The reaction was allowed to warm to room temperature and stirred for 10 mins. The resulting yellow solid was gently heated to obtain a yellow dispersion to which N,N-dimethylthiocarbamoyl chloride (470 mg, 3.84 mmol) was added at room temperature and the resulting mixture was heated to 85°C for 1.5 h.

The yellow-brown mixture was cooled to room temperature and poured into 1% aqueous KOH solution (15 mL). The pale brown solid was filtered off, washed with water and dissolved in DCM. The organic layer was separated from the remaining water, washed with brine and dried over sodium sulfate. After evaporation of the solvent a pale yellow, fine crystals was obtained.

682 mg,

1H NMR MNR15-1 first filter - clean product

More solid precipitated out of the aqueous layer after standing for one day and was filtered and washed with water.

39 mg,

1H NMR MNR15-1 second filter - some product, not clean
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20th October 2011 @ 07:12
Reactions carried out in parallel with MNR11-11/12

MNR12-3%20scheme.png

MNR12-3%20table.PNG

Hazard and Risk Assessment:
As for MNR11-3

Procedure

MNR12-3
MNR10-1(50 mg, 0.11 mmol) and 1,1’-Binaphthalene-2,2’-disulfonic acid, MW54-3 (5 mg, 0.01 mmol) DCM (2 mL) was heated at reflux.

1st LCMS sample taken after 4 days

After another 24 hours (5 days in total) the reaction was quenched with saturated sodium carbonate and extracted with EtOAc (10 mL x3). The organic fractions were dried over magnesium sulfate, filtered and concentrated under reduced pressure.

Crude - 45 mg

1H NMR MNR12-3

Still large amounts of starting material.

MNR12-4
MNR10-1(50 mg, 0.11 mmol) and 1,1’-Binaphthalene-2,2’-disulfonic acid, MW54-3 (5 mg, 0.01 mmol) toluene(2 mL) was heated at reflux.

1st LCMS sample taken after 4 days

After another 24 hours (5 days in total) the reaction was quenched with saturated sodium carbonate and extracted with EtOAc (10 mL x3). The organic fractions were dried over magnesium sulfate, filtered and concentrated under reduced pressure.

Crude - 47 mg

1H NMR MNR12-3

Looks a lot better than MNR12-3, -OEt signals from starting material only in trace amounts.

This needs repeated, LCMS shows more SM than product but NMR shows very little SM
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