Trifluoroacetic acid → HCID 89618399, compound

HRID 1502572Notes

Reaction equation

HRID 1502572 reaction equation
[OH:1]/[CH:2]=[C:3]1/[CH:4]2[CH2:22][C:21]3[C:16](=[CH:17][CH:18]=[CH:19][C:20]=3[C:23]#[C:24][Si](C)(C)C)[CH:5]2[N:6](C(OC(C)(C)C)=O)[C:7]/1=[O:8].O/C=C1/C2CC3C(=CC=CC=3C#C[Si](C)(C)C)C2NC/1=O.FC(F)(F)C(O)=O.[Na]>ClCCl>[C:23]([C:20]1[CH:19]=[CH:18][CH:17]=[C:16]2[C:21]=1[CH2:22][CH:4]1[CH:5]2[NH:6][C:7](=[O:8])/[C:3]/1=[CH:2]\[OH:1])#[CH:24]

Participants

6

Reactant 4

HCID 6422Trifluoroacetic acidHCID 5360545SodiumHCID 89618211HCID 89618211, compoundHCID 131734310HCID 131734310, compound

Product 1

HCID 89618399HCID 89618399, compoundYield 72%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of tert-butyl (3Z)-3-(dimethylaminomethylene)-2-oxo-5-(2-trimethylsilylethynyl)-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylate D2 (Example 2, Step 2, 0.13 g, 0.3 mmol) in dioxane (5 mL) was added HCl (37%, 0.321 mL). The solution was stirred 2 h at room temperature and was then diluted with water, extracted with ethyl acetate, washed with brine, dried and concentrated to give 0.130 g of a mixture of tert-butyl (3Z)-3-(hydroxymethylene)-2-oxo-5-(2-trimethylsilylethynyl)-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylate and (3Z)-3-(hydroxymethylene)-5-(2-trimethylsilylethynyl)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one. A solution of 0.13 g of a mixture of tert-butyl (3Z)-3-(hydroxymethylene)-2-oxo-5-(2-trimethylsilylethynyl)-4,8b-dihydro-3aH-indeno[1,2-b]pyrrole-1-carboxylate and (3Z)-3-(hydroxymethylene)-5-(2-trimethylsilylethynyl)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one in dichloromethane (18 mL) was added trifluoroacetic acid (2 mL) at 0° C. The solution was stirred for 1 h at 0° C. A saturated solution of sodium hydrogenocarbonate was added and the aqueous layer was extracted with dichloromethane. The combined organic layers were washed with a saturated solution of sodium hydrogenocarbonate, dried and concentrated in vacuo to give ((3Z)-5-ethynyl-3-(hydroxymethylene)-1,3a,4,8b-tetrahydroindeno[1,2-b]pyrrol-2-one C2 (70 mg, 72%). LC-MS (Method C) RT 0.67 min, ES− 224 (M−H+), ES+226 (M+H+).

Workup

  1. extractionthe aqueous layer was extracted with dichloromethane
  2. washThe combined organic layers were washed with a saturated solution of sodium hydrogenocarbonate
  3. customdried
  4. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-0b995785e518424284def4e84f0ae0ed
Source dataset
uspto-grants-2015_12
Patent number
US09210929B2

Reaction notes

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