Oxalyl chloride → HCID 22046699, compound

HRID 1830972Notes

Reaction equation

HRID 1830972 reaction equation
[N+:1]([C:4]1[C:12]([O:13][CH3:14])=[C:11]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C:10]([O:23][CH3:24])=[CH:9][C:5]=1[C:6]([OH:8])=O)([O-:3])=[O:2].C(Cl)(=O)C(Cl)=O.C(OC1[C:47](OC)=[CH:46][C:42](C(Cl)=O)=[C:41]([N+:50]([O-])=O)[C:40]=1[O:53]C)C1C=CC=CC=1.N1(CO)CCCC1>CN(C=O)C.CC#N.C(Cl)Cl>[CH2:16]([O:15][C:11]1[C:10]([O:23][CH3:24])=[CH:9][C:5]([C:6]([N:50]2[CH2:47][CH2:46][CH2:42][CH:41]2[CH2:40][OH:53])=[O:8])=[C:4]([N+:1]([O-:3])=[O:2])[C:12]=1[O:13][CH3:14])[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

8

Reactant 4

HCID 65578Oxalyl chlorideHCID 2331391PyrrolidinemethanolHCID 22046690HCID 22046690, compoundHCID 22046726HCID 22046726, compound

Product 1

HCID 22046699HCID 22046699, compoundYield 70%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 6342AcetonitrileSolvent2×HCID 6344DichloromethaneSolvent

Procedure

A catalytic amount of DMF (5 drops) was added to a stirred solution of 124 (10 g, 30.0 mmol) and oxalyl chloride (4.65 g, 36.0 mmol) in dry CH3CN (115 mL) under a nitrogen atmosphere. The reaction mixture was allowed to stir overnight and the resulting acid chloride used directly in the next part of the procedure. 4-benzyloxy-3,5-dimethoxy-2-nitro-benzoyl chloride in anhydrous CH3CN (115 mL) was added dropwise over 0.5 hours to a stirring solution of pyrrolidine methanol (3.34 g, 33.03 mmol, 1.1 eq) and TEA (7.58 g, 75.1 mmol, 2.5 eq) in anhydrous DCM (100 mL) at 0° C. under a nitrogen atmosphere and the reaction mixture was allowed to stir overnight at room temperature. The reaction mixture was washed with 1N HCl (2×100 mL), and the organic layer was washed with distilled H2O (2×100 mL), brine (2×100 mL) and dried over anhydrous MgSO4. Evaporation of the solvent yielded a brown glass (8.71 g, 20.9 mmol, 70%); 1H NMR (270 MHz, CDCl3) δ1.7-2.2 (m, 4H), 3.3-3.5 (m, 2H), 3.7-3.9 (m, 2H), 3.9 (s, 3H), 4.0 (s, 3H), 4.2-4.3 (m, 1H), 5.1 (s, 2H), 6.85 (s, 1H), 7.3-7.5 (m, 5H); 13C NMR (67.8 MHz, CDCl3) δ167.3, 156.8, 148.2, 142.3, 136.4, 136.0, 129.0, 128.5, 128.4, 104.8, 75.6, 65.7, 62.8, 61.4, 56.6, 50.2, 28.3, 24.5.

Workup

  1. stirringto stir overnight at room temperature
  2. washThe reaction mixture was washed with 1N HCl (2×100 mL)
  3. washthe organic layer was washed with distilled H2O (2×100 mL), brine (2×100 mL)
  4. dry with materialdried over anhydrous MgSO4
  5. customEvaporation of the solvent

Sources & evidence

ORD record
ord-fc91022c18194c04932b091314ecfc7c
Source dataset
uspto-grants-2006_06
Patent number
US07067511B2

Reaction notes

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