Notice: Undefined index: inline in /home/www/hosts/www.ourexperiment.org/docs/export/xml.php on line 68

Notice: Undefined index: inline in /home/www/hosts/www.ourexperiment.org/docs/export/xml.php on line 68
56427382Preparation of the dimethoxy Ugi-intermediate (MNR8-5)
Experiments
plus.google.com-113014781212630252105Murray Robertson

Hazard and Risk Assessment:

As for MNR8-1

Procedure:

To a stirring suspension of paraformaldehyde (3.17 g, 105.6 mmol), 2,2-diethoxyethylamine (15.4 mL, 105.6 mmol) and cyclohexanecarboxylic acid (13.5 g, 105.6 mmol) in methanol (90 mL) at 0 °C was added 2-(3,4-Dimethoxyphenyl)ethyl isocyanide MNR4-4 (20.2 g, 105.6 mmol) in methanol (10 mL) dropwise and stirred at room temperature for 48 hours.

The reaction was concentrated and dissolved in EtOAc (100 mL) then washed with water (75 mL) and brine (75 mL) then dried over magnesium sulfate, filtered and concentrated under reduced pressure to give the crude as a pale yellow oil.

Column :- 25-100 % EtOAc/Hex

Frac 3 10.2 g as a clear oil, clean product Frac 4-8 17.138 g as a clear oil, clean product Frac 9-13 15.496 g as a slightly yellow oil, mostly product

Total recovered 42.834 g, 92.2 mmol, 87 %

Clean fractions were transferred in vials of approximately 2 g per vial and flasks were rinsed into the impure flask. Total remaining to be recolumn'd 17.9 g

It was found that "azeotroping" the clean product with Et2O several times resulted in a white foamy solid under vacuum. This however collapsed on warming to room temperature under vacuum back to the clear oil.

Characterisation

[data]4932[/data][data]4930[/data]

As a 50:50 mixture of rotamers

1H NMR (500 MHz, CDCl3): d = 7.09 (t, J = 5.3 Hz, NH), 6.80 (s, 0.5H), 6.79 (s, 0.5H), 6.74-6.70 (m, 2H),6.56 (t, J = 5.4 Hz, NH) 4.73 (t, J = 5.1 Hz, 0.5H), 4.55 (t, J = 5.1 Hz, 0.5H), 4.04 (s, 1H), 3.99 (s, 1H), 3.88 (s, 1.5H), 3.88 (s, 1.5H), 3.85 (s, 3H), 3.77-3.65 (m, 2H), 3.55-3.41 (m, 6H), 2.79-2.65 (m, 2H), 2.31-2.23 (m, 1H), 1.81-1.71 (m, 2H), 1.71-1.58 (m, 3H), 1.53-1.36 (m, 2H), 1.31-1.13 (m, 9H).

[data]4928[/data][data]4930[/data]

13C NMR (125 MHz, CDCl3): d= 178.1, 177.7, 169.6, 169.3, 149.1, 149.0, 147.8, 147.6, 131.3, 131. 0, 129.0, 128.2, 120.6, 120.5, 111.9, 111.7, 111.4, 111.3, 101.3, 100.5, 64.1, 63.5, 55.9, 55.8, 54.0, 52.3, 52.1, 50.9, 41.0, 40.8, 40.6, 40.2, 40.1, 35.3, 35.2, 29.3, 29.2, 29.0, 25.7, 25.6, 25.6, 25.5, 15.3.

 

IR [data]5341[/data]

]]>
Mnr: 1-10

Hazard and Risk Assessment:

As for MNR8-1

Procedure:

To a stirring suspension of paraformaldehyde (3.17 g, 105.6 mmol), 2,2-diethoxyethylamine (15.4 mL, 105.6 mmol) and cyclohexanecarboxylic acid (13.5 g, 105.6 mmol) in methanol (90 mL) at 0 °C was added 2-(3,4-Dimethoxyphenyl)ethyl isocyanide MNR4-4 (20.2 g, 105.6 mmol) in methanol (10 mL) dropwise and stirred at room temperature for 48 hours.

The reaction was concentrated and dissolved in EtOAc (100 mL) then washed with water (75 mL) and brine (75 mL) then dried over magnesium sulfate, filtered and concentrated under reduced pressure to give the crude as a pale yellow oil.

Column :- 25-100 % EtOAc/Hex

Frac 3 10.2 g as a clear oil, clean product Frac 4-8 17.138 g as a clear oil, clean product Frac 9-13 15.496 g as a slightly yellow oil, mostly product

Total recovered 42.834 g, 92.2 mmol, 87 %

Clean fractions were transferred in vials of approximately 2 g per vial and flasks were rinsed into the impure flask. Total remaining to be recolumn'd 17.9 g

It was found that "azeotroping" the clean product with Et2O several times resulted in a white foamy solid under vacuum. This however collapsed on warming to room temperature under vacuum back to the clear oil.

Characterisation

mnr08-2_1H.pdf
mnr8-2.zip

As a 50:50 mixture of rotamers

1H NMR (500 MHz, CDCl3): d = 7.09 (t, J = 5.3 Hz, NH), 6.80 (s, 0.5H), 6.79 (s, 0.5H), 6.74-6.70 (m, 2H),6.56 (t, J = 5.4 Hz, NH) 4.73 (t, J = 5.1 Hz, 0.5H), 4.55 (t, J = 5.1 Hz, 0.5H), 4.04 (s, 1H), 3.99 (s, 1H), 3.88 (s, 1.5H), 3.88 (s, 1.5H), 3.85 (s, 3H), 3.77-3.65 (m, 2H), 3.55-3.41 (m, 6H), 2.79-2.65 (m, 2H), 2.31-2.23 (m, 1H), 1.81-1.71 (m, 2H), 1.71-1.58 (m, 3H), 1.53-1.36 (m, 2H), 1.31-1.13 (m, 9H).

mnr08-2_13C.pdf
mnr8-2.zip

13C NMR (125 MHz, CDCl3): d= 178.1, 177.7, 169.6, 169.3, 149.1, 149.0, 147.8, 147.6, 131.3, 131. 0, 129.0, 128.2, 120.6, 120.5, 111.9, 111.7, 111.4, 111.3, 101.3, 100.5, 64.1, 63.5, 55.9, 55.8, 54.0, 52.3, 52.1, 50.9, 41.0, 40.8, 40.6, 40.2, 40.1, 35.3, 35.2, 29.3, 29.2, 29.0, 25.7, 25.6, 25.6, 25.5, 15.3.

 

IR 

7d IR MNR8-5.jpg

Linked Entries
This entry is linked by:
]]>2012-05-09T04:46:25+01:002016-01-26T18:27:33+00:0061-10https://www.ourexperiment.org/data/4216.xmlhttps://www.ourexperiment.org/data/4218.xmlhttps://www.ourexperiment.org/data/4220.xmlhttps://www.ourexperiment.org/data/4222.xmlhttps://www.ourexperiment.org/data/4224.xmlhttps://www.ourexperiment.org/data/4926.xmlhttps://www.ourexperiment.org/data/4928.xmlhttps://www.ourexperiment.org/data/4930.xmlhttps://www.ourexperiment.org/data/4932.xmlhttps://www.ourexperiment.org/data/5341.xmlhttp://www.ourexperiment.org/uri/25ehttps://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.htmlhttps://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.htmlhttps://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xmlhttps://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.pnghttps://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=7382https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5642https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5643https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5644https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5645https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5646https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5647https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5648https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5649https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=6455https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=6456https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=6457https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=6458https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=6459https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=7076https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=-1
56427076Preparation of the dimethoxy Ugi-intermediate (MNR8-5)
Experiments
plus.google.com-113014781212630252105Murray Robertson

Hazard and Risk Assessment:

As for MNR8-1

Procedure:

To a stirring suspension of paraformaldehyde (3.17 g, 105.6 mmol), 2,2-diethoxyethylamine (15.4 mL, 105.6 mmol) and cyclohexanecarboxylic acid (13.5 g, 105.6 mmol) in methanol (90 mL) at 0 °C was added 2-(3,4-Dimethoxyphenyl)ethyl isocyanide MNR4-4 (20.2 g, 105.6 mmol) in methanol (10 mL) dropwise and stirred at room temperature for 48 hours.

The reaction was concentrated and dissolved in EtOAc (100 mL) then washed with water (75 mL) and brine (75 mL) then dried over magnesium sulfate, filtered and concentrated under reduced pressure to give the crude as a pale yellow oil.

Column :- 25-100 % EtOAc/Hex

Frac 3 10.2 g as a clear oil, clean product Frac 4-8 17.138 g as a clear oil, clean product Frac 9-13 15.496 g as a slightly yellow oil, mostly product

Total recovered 42.834 g, 92.2 mmol, 87 %

Clean fractions were transferred in vials of approximately 2 g per vial and flasks were rinsed into the impure flask. Total remaining to be recolumn'd 17.9 g

It was found that "azeotroping" the clean product with Et2O several times resulted in a white foamy solid under vacuum. This however collapsed on warming to room temperature under vacuum back to the clear oil.

Characterisation

[data]4932[/data][data]4930[/data]

As a 50:50 mixture of rotamers

1H NMR (500 MHz, CDCl3): d = 7.09 (t, J = 5.3 Hz, NH), 6.80 (s, 0.5H), 6.79 (s, 0.5H), 6.74-6.70 (m, 2H),6.56 (t, J = 5.4 Hz, NH) 4.73 (t, J = 5.1 Hz, 0.5H), 4.55 (t, J = 5.1 Hz, 0.5H), 4.04 (s, 1H), 3.99 (s, 1H), 3.88 (s, 1.5H), 3.88 (s, 1.5H), 3.85 (s, 3H), 3.77-3.65 (m, 2H), 3.55-3.41 (m, 6H), 2.79-2.65 (m, 2H), 2.31-2.23 (m, 1H), 1.81-1.71 (m, 2H), 1.71-1.58 (m, 3H), 1.53-1.36 (m, 2H), 1.31-1.13 (m, 9H).

[data]4928[/data][data]4930[/data]

13C NMR (125 MHz, CDCl3): d= 178.1, 177.7, 169.6, 169.3, 149.1, 149.0, 147.8, 147.6, 131.3, 131. 0, 129.0, 128.2, 120.6, 120.5, 111.9, 111.7, 111.4, 111.3, 101.3, 100.5, 64.1, 63.5, 55.9, 55.8, 54.0, 52.3, 52.1, 50.9, 41.0, 40.8, 40.6, 40.2, 40.1, 35.3, 35.2, 29.3, 29.2, 29.0, 25.7, 25.6, 25.6, 25.5, 15.3.

 

IR [data]5341[/data]

]]>
Mnr: 1-10

Hazard and Risk Assessment:

As for MNR8-1

Procedure:

To a stirring suspension of paraformaldehyde (3.17 g, 105.6 mmol), 2,2-diethoxyethylamine (15.4 mL, 105.6 mmol) and cyclohexanecarboxylic acid (13.5 g, 105.6 mmol) in methanol (90 mL) at 0 °C was added 2-(3,4-Dimethoxyphenyl)ethyl isocyanide MNR4-4 (20.2 g, 105.6 mmol) in methanol (10 mL) dropwise and stirred at room temperature for 48 hours.

The reaction was concentrated and dissolved in EtOAc (100 mL) then washed with water (75 mL) and brine (75 mL) then dried over magnesium sulfate, filtered and concentrated under reduced pressure to give the crude as a pale yellow oil.

Column :- 25-100 % EtOAc/Hex

Frac 3 10.2 g as a clear oil, clean product Frac 4-8 17.138 g as a clear oil, clean product Frac 9-13 15.496 g as a slightly yellow oil, mostly product

Total recovered 42.834 g, 92.2 mmol, 87 %

Clean fractions were transferred in vials of approximately 2 g per vial and flasks were rinsed into the impure flask. Total remaining to be recolumn'd 17.9 g

It was found that "azeotroping" the clean product with Et2O several times resulted in a white foamy solid under vacuum. This however collapsed on warming to room temperature under vacuum back to the clear oil.

Characterisation

mnr08-2_1H.pdf
mnr8-2.zip

As a 50:50 mixture of rotamers

1H NMR (500 MHz, CDCl3): d = 7.09 (t, J = 5.3 Hz, NH), 6.80 (s, 0.5H), 6.79 (s, 0.5H), 6.74-6.70 (m, 2H),6.56 (t, J = 5.4 Hz, NH) 4.73 (t, J = 5.1 Hz, 0.5H), 4.55 (t, J = 5.1 Hz, 0.5H), 4.04 (s, 1H), 3.99 (s, 1H), 3.88 (s, 1.5H), 3.88 (s, 1.5H), 3.85 (s, 3H), 3.77-3.65 (m, 2H), 3.55-3.41 (m, 6H), 2.79-2.65 (m, 2H), 2.31-2.23 (m, 1H), 1.81-1.71 (m, 2H), 1.71-1.58 (m, 3H), 1.53-1.36 (m, 2H), 1.31-1.13 (m, 9H).

mnr08-2_13C.pdf
mnr8-2.zip

13C NMR (125 MHz, CDCl3): d= 178.1, 177.7, 169.6, 169.3, 149.1, 149.0, 147.8, 147.6, 131.3, 131. 0, 129.0, 128.2, 120.6, 120.5, 111.9, 111.7, 111.4, 111.3, 101.3, 100.5, 64.1, 63.5, 55.9, 55.8, 54.0, 52.3, 52.1, 50.9, 41.0, 40.8, 40.6, 40.2, 40.1, 35.3, 35.2, 29.3, 29.2, 29.0, 25.7, 25.6, 25.6, 25.5, 15.3.

 

IR 

7d IR MNR8-5.jpg

Linked Entries
This entry is linked by:
]]>2012-05-09T04:46:25+01:002016-01-19T13:13:32+00:0063a2f33ed869377c1b0bcfafb506bcf381-10https://www.ourexperiment.org/data/4216.xmlhttps://www.ourexperiment.org/data/4218.xmlhttps://www.ourexperiment.org/data/4220.xmlhttps://www.ourexperiment.org/data/4222.xmlhttps://www.ourexperiment.org/data/4224.xmlhttps://www.ourexperiment.org/data/4926.xmlhttps://www.ourexperiment.org/data/4928.xmlhttps://www.ourexperiment.org/data/4930.xmlhttps://www.ourexperiment.org/data/4932.xmlhttps://www.ourexperiment.org/data/5341.xmlhttp://www.ourexperiment.org/uri/25ehttps://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.htmlhttps://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.htmlhttps://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xmlhttps://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.pnghttps://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=7382https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5642https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5643https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5644https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5645https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5646https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5647https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5648https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=5649https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=6455https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=6456https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=6457https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=6458https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=6459https://www.ourexperiment.org/racemic_pzq/5642/Preparation_of_the_dimethoxy_Ugiintermediate_MNR85.xml?revision=7076