N,N-Dimethylethylenediamine → 3-Aminocoumarin

HRID 1251303Notes

Reaction equation

HRID 1251303 reaction equation
C([C:4]1[C:5](=[O:16])[O:6][C:7]2[C:12]([CH:13]=1)=[CH:11][C:10](Cl)=[C:9](O)[CH:8]=2)(O)=O.C([N:20](C(C)C)CC)(C)C.ClCOCC1C=CC=CC=1.CN(C)CCN>C1COCC1.CN(C=O)C>[O:6]1[C:7]2[C:12](=[CH:11][CH:10]=[CH:9][CH:8]=2)[CH:13]=[C:4]([NH2:20])[C:5]1=[O:16]

Participants

7

Reactant 4

HCID 66053N,N-DimethylethylenediamineHCID 81531Diisopropylethylamine2×HCID 137983Benzyl chloromethyl etherHCID 21924856HCID 21924856, compound

Product 1

HCID 742173-AminocoumarinYield 117.9%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

241 mg 3-carboxy-6-chloro-7-hydroxy coumarin (1 mmol) dissolved in the mixture of 5 ml THF and 5 ml DMF was added 200 ul diisopropylethylamine (DIEA, 1.1 mmol) and 330 mg O—(N-succinium)-N,N,N′,N′-tetramethyl uronium tetrafluoroborate (TSTU, 1.1 mmol). After stirring at room temperature for 20 minutes under nitrogen atmosphere, the reaction mixture was added 400 ul of DIEA and 460 ul benzyl chloromethyl ether (BOM-Cl) and stirred for another 2 hours at room temperature. The resulted mixture was then pulled high vacuum for 2 hours and 1 ml THF, 480 ul 2-dimethyaminoethylamine was added into the solution afterwards. After the reaction mixture was allowed to react at room temperature for 1 hour, the crude product was pulled high vacuum again overnight and purified on a silica gel column (chloroform:methanol=95:5 as eluent). 190 mg colorless solid was obtained as product, 44% yield. 1H NMR (CDCl3, ppm): 2.32 (d, 6H), 2.56 (t, 2H), 2.16 (t, 2H), 4.76 (s,2H), 5.46 (s, 2H), 7.33 (m, 7H), 7.68 (s, 1H), 8.76 (s, 1H). MS: C22H23O5N2Cl, 430.3 calculated; 431.2 (M+1) found.

Workup

  1. stirringstirred for another 2 hours at room temperature
  2. customfor 2 hours
  3. customto react at room temperature for 1 hour
  4. customvacuum again overnight
  5. custompurified on a silica gel column (chloroform:methanol=95:5 as eluent)

Sources & evidence

ORD record
ord-4faa76d87720427eada0ac71bf516968
Source dataset
uspto-grants-2002_01
Patent number
US06342379B1

Reaction notes

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