802
Martin Maier
Reaction
Carboxylation
Start Date
2017-05-28 04:00
Project
PA
End Date
Status
Closed
Description
Conclusion
Compound
MW
W
Moles
(g)
(mol)
Equiv
Conc.
Vol
Density
Pur
Yield
(M)
(mL)
(g/mL)
(%)
(%)
0.740
230.018
C11H14O3 (R1)
194.227
33.060
0.170
1.000
DMAP (R2)
122.168
2.079
0.017
0.100
Pyridine (R3)
79.100
40.392
0.511
3.000
41.082
0.983
100.0
MeOCOCl (R4)
94.497
33.778
0.357
2.100
27.619
1.223
100.0
DCM (S1)
84.933
1.326
100.0
C13H16O5 (P1)
252.263
Page 1 of 4
35.700
0.142
Reported by Martin Maier
100.0
100.0
100.0
83.1
2018-11-24 23:58
802
Description
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substrate in 1 L flask from previous reaction
added DMAP
added addition funnel
evacuated and refilled with N2
added 250 mL dry DCM
added pyridine
placed in an ice-bath --> yellowish solution
dropwise added MeOCOCl
• within 20 min
• yellow suspension
• stirred with warming to RT for 18.5 h
• after several hours: orange suspension
• next day: no change
• TLC (reaction mixutre diluted with DCM, 2.5% EtOAc/DCM, UV/PAA)
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• full conversion
added 200 mL 2 M HCl and mixed thoroughly
separated layers
extracted with 2x50 mL DCM
washed with 100 mL 2 M HCl and 100 mL water
dried over MgSO4
removed solvent: 40.79 g red-orange oil that slowly solidified after cooling to RT
1H-NMR (CDCl3): product with minor impurities
added 150 mL EtOH
warmed to reflux (120 degree celsius aluminum heating block)
cooled to RT --> no solids
cooled with ice bath under vigorous stirring --> mixture solidified
separated solids and dried (rotovap, then HV): 29.6 g --> 26.4 g
removed solvent from filtrate (rotovap, then open flask over night): 19.3 g --> 13.39 g
1H-NMR(CDCl3):
• solids: clean product
• filtrate: product with some impurities
• purified filtrate by chromatography:
• combiflash: full 65 g cartridge
• celite wet load with DCM in 65 g cartridge
• EtOAc/hexane 0% to 15% (eluted at 15%)
• seprated two fractions (not full separated)
• Fr1: 9.33 g white solids
• Fr2: 0.66 g off-white oily solids
• 1H-NMR (CDCl3):
• Fr1; clean product
• Fr2: product with significant impurites
• total clean product: 37.7 g
Page 2 of 4
Reported by Martin Maier
2018-11-24 23:58
802
Sources
DMAP (R2)
Oakwood
102_Bases
2.080 g
31_Bases
42.000 mL
F7
28.000 mL
Pyridine (R3)
Acros
MeOCOCl (R4)
Acros
Page 3 of 4
Reported by Martin Maier
2018-11-24 23:58
802
History
Closed
2017-05-31 18:42
Martin Maier
Open
2017-05-31 18:42
Martin Maier
Closed
2017-05-31 18:42
Martin Maier
Open
2017-05-31 18:44
Martin Maier
Closed
2017-05-31 18:45
Martin Maier
Open
2017-05-31 18:45
Martin Maier
Closed
2017-05-31 18:46
Martin Maier
Open
2017-06-01 12:42
Martin Maier
Closed
2017-06-01 18:07
Martin Maier
Open
2017-06-22 16:33
Martin Maier
Closed
2017-06-22 16:34
Martin Maier
Page 4 of 4
Reported by Martin Maier
2018-11-24 23:58