Toluene-p-sulphonic anhydride → HCID 12849000, compound

HRID 1252771Notes

Reaction equation

HRID 1252771 reaction equation
C1(C)C=CC(S([O:10][S:11]([C:14]2[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][CH:15]=2)(=[O:13])=[O:12])(=O)=O)=CC=1.C(N(CC)C(C)C)(C)C.[N:31]12[C:37](=[O:38])[CH2:36][CH:35]1[CH2:34][C:33](=O)[CH:32]2[C:40]([O:42][CH2:43][C:44]1[CH:49]=[CH:48][C:47]([N+:50]([O-:52])=[O:51])=[CH:46][CH:45]=1)=[O:41]>C(Cl)Cl>[C:17]1([CH3:20])[CH:16]=[CH:15][C:14]([S:11]([O:10][C:33]2[CH2:34][CH:35]3[N:31]([C:37](=[O:38])[CH2:36]3)[C:32]=2[C:40]([O:42][CH2:43][C:44]2[CH:49]=[CH:48][C:47]([N+:50]([O-:52])=[O:51])=[CH:46][CH:45]=2)=[O:41])(=[O:12])=[O:13])=[CH:19][CH:18]=1

Participants

5

Reactant 3

HCID 77773Toluene-p-sulphonic anhydrideHCID 81531DiisopropylethylamineHCID 12804727HCID 12804727, compound

Product 1

HCID 12849000HCID 12849000, compoundYield 61.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

p-toluenesulfonic anhydride (520 mg, 1.59 mmol) and N,N-diisopropylethylamine (300 μl, 1.72 mmol) are added to an ice-cold, stirring solution of p-nitrobenzyl 1-azabicyclo[3.2.0]heptan-3,7-dione-2-carboxylate (484 mg, 1.59 mmol) in anhydrous methylene chloride (17 ml). The resulting solution is stirred in the cold for 2 hours, then diluted with more methylene chloride, washed with water, 1μ ph 3.4 phosphate buffer and saturated aqueous sodium bicarbonate, dried with magnesium sulfate, filtered, and evaporated under vacuum. Addition of cold ethyl acetate and a few seed crystals to the oily residue induces crystallization. The product is collected, washed with cold ethyl acetate, and dried under vacuum to afford p-nitrobenzyl 3-(p-toluenesulfonyloxy)-1-azabicyclo[3.2.0]hept-2-en-7-one-2-carboxylate (446 mg, 61%) as off-white crystals: mp 99°-102° (dec.); IR (neat) 1790, 1725, 1521, 1345, and 1172 cm-1 ; UV (CH2Cl2) 272 nm; NMR (CDCl3) δ 2.40 (s, 3, ArCH3), 3.06 (dd, 1, J=3.0 and 17.2, H6β), 3.16 (dd, 1, J=9.0 and 9.0, H4a), 3.31 (dd, 1, J=9.0 and 10.0, H4b), 3.59 (dd, 1, J=5.8 and 17.2, H6α), 4.24 (m, I, H5), 5.20 and 5.32 (ABq, 2, J=14.0, CH2Ar), 7.32 and 7.77 (two d's, 4, J=8.0, p-MeC6H4), 7.51 and 8.19 (two d's, 4, J=8.0, p-NO2C6H4).

Workup

  1. washwashed with water, 1μ ph 3.4 phosphate buffer and saturated aqueous sodium bicarbonate
  2. dry with materialdried with magnesium sulfate
  3. filtrationfiltered
  4. customevaporated under vacuum
  5. additionAddition of cold ethyl acetate
  6. customcrystallization
  7. customThe product is collected
  8. washwashed with cold ethyl acetate
  9. customdried under vacuum

Sources & evidence

ORD record
ord-4e129a597ee2444194097122a6ce01d6
Source dataset
uspto-grants-1988_05
Patent number
US04745188

Reaction notes

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