HomeMCPWorkbenchSkills
HomeWorkbenchNotificationsMe
llms.txt · MCP GuidePrivacy Policy · Terms of Service · Supportv1.8.0
  1. Home
  2. /Reaction

Sodium hydride → Butyl 1-{11-[1-(butoxycarbonyl)cyclopentyl]-6-isocyano-6-[(4-methylphenyl)sulfonyl]undecyl}-1-cyclopentanecarboxylate

HRID 468030
Notes
Print preview

Reaction equation

HRID 468030 reaction equation
[H-].[Na+].[CH3:3][C:4]1[CH:9]=[CH:8][C:7]([S:10]([CH2:13][N+:14]#[C-:15])(=[O:12])=[O:11])=[CH:6][CH:5]=1.Br[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][C:22]1([C:27]([O:29][CH2:30][CH2:31][CH2:32][CH3:33])=[O:28])[CH2:26][CH2:25][CH2:24][CH2:23]1>[N+](CCCC)(CCCC)(CCCC)CCCC.[I-].CS(C)=O>[CH2:30]([O:29][C:27]([C:22]1([CH2:21][CH2:20][CH2:19][CH2:18][CH2:17][C:13]([N+:14]#[C-:15])([S:10]([C:7]2[CH:6]=[CH:5][C:4]([CH3:3])=[CH:9][CH:8]=2)(=[O:12])=[O:11])[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][C:22]2([C:27]([O:29][CH2:30][CH2:31][CH2:32][CH3:33])=[O:28])[CH2:26][CH2:25][CH2:24][CH2:23]2)[CH2:26][CH2:25][CH2:24][CH2:23]1)=[O:28])[CH2:31][CH2:32][CH3:33]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 3

HCID 24758Sodium hydride2×HCID 161915Tosylmethyl isocyanideHCID 21932025Butyl 1-(5-bromo-pentyl)-cyclopentanecarboxylate

Product 1

HCID 21932067Butyl 1-{11-[1-(butoxycarbonyl)cyclopentyl]-6-isocyano-6-[(4-methylphenyl)sulfonyl]undecyl}-1-cyclopentanecarboxylateYield 78.1%

Reagents, catalysts & solvents 2

HCID 67553
Tetrabutylammonium Iodide
Catalyst
HCID 679Dimethyl SulfoxideSolvent

Procedure

Under a N2 atmosphere, NaH (60% (%) in mineral oil, 7.55 g, 189 mmol) was added portion wise to a solution of TosMIC (12.48 g, 62.6 mmol) and Bu4NI (2.56 g, 6.93 mmol) in dry DMSO (200 mL) while stirring vigorously and cooling with a water bath. After 30 min, butyl 1-(5-bromo-pentyl)-cyclopentanecarboxylate (44.46 g, >90% pure by GC, 125 mmol) was added drop wise to the mixture in 20 min and after 1 h of stirring, another portion of NaH (60% (%) in mineral oil, 1.20 g, 30.0 mmol) was added. After 1 h, the reaction mixture was slowly poured into ice-cold H2O (500 mL) and the resulting mixture was extracted with Et2O (3×250 mL). The combined organic layers were washed with aqueous NaCl (10%, 250 mL) and brine (2×200 mL), dried (Na2SO4) and filtered through a layer of silica (150 g). The residue was washed with Et2O (250 mL) and the combined filtrate and washings were evaporated in vacuo. The remaining oil was purified by column chromatography (silica, heptane:EtOAc=8:1) to give butyl 1-{11-[1-(butoxycarbonyl)cyclopentyl]-6-isocyano-6-[(4-methylphenyl)sulfonyl]undecyl}-1-cyclopentanecarboxylate as a yellow oil (32.79 g). This oil (32.79 g) was dissolved in CH2Cl2 (400 mL), and cont aqueous HCl (150 mL) was added. After stirring vigorously for 4.5 h, H2O (500 mL) was added and the layers were separated. The aqueous phase was extracted with CH2Cl2 (2×100 mL) and the combined organic layers were washed with saturated H2O (200 mL), saturated aqueous NaHCO3 (500 mL) and brine (500 mL), dried (Na2SO4) and evaporated in vacuo. The remaining residue was purified by column chromatography (silica, heptane:EtOAc=6:1) to give butyl 1-{11-[1-(butoxycarbonyl)cyclopentyl]-6-oxoundecyl}-1-cyclopentanecarboxylate (24.11 g, 90% pure by 1H NMR, 69%) as a slightly yellow liquid. 1H NMR (CDCl3): δ=4.06 (t, J=6.6 Hz, 4H), 2.36 (t, J=7.4 Hz, 4H), 2.15-2.06 (m, 4H), 1.65-1.52 (m, 20H), 1.49-1.32 (m, 8H), 1.27-1.19 (m, 8H), 0.94 (t, J=7.4 Hz, 6H). 13C NMR (CDCl3): δ=210.9, 177.6 (2×), 63.8 (2×), 54.0 (2×), 42.5 (2×), 38.9 (2×), 35.8 (4×), 30.6 (2×), 29.5 (2×), 25.6 (2×), 24.7 (4×), 23.4 (2×), 19.0 (2×), 13.5 (2×). HRMS calcd for C31H54O5 (M+): 506.3971. found: 506.3981.

Workup

  1. temperaturecooling with a water bath
  2. stirringafter 1 h of stirring
  3. waitAfter 1 h
  4. extractionthe resulting mixture was extracted with Et2O (3×250 mL)
  5. washThe combined organic layers were washed with aqueous NaCl (10%, 250 mL) and brine (2×200 mL)
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered through a layer of silica (150 g)
  8. washThe residue was washed with Et2O (250 mL)
  9. customthe combined filtrate and washings were evaporated in vacuo
  10. customThe remaining oil was purified by column chromatography (silica, heptane:EtOAc=8:1)

Sources & evidence

ORD record
ord-504533165b2448169d1c133be8996b94
Source dataset
uspto-grants-2014_01
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08623915B2

Reaction notes

Loading…

On this pageParticipantsProcedureWorkupSources & evidenceReaction notes