Sodium Formate → 4-Chloro-2-formylamino-6-methyl-10,10-dioxo-10,11-dihydro-5-oxa-10lambda*6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acid isopropyl ester

HRID 2425083Notes

Reaction equation

HRID 2425083 reaction equation
[CH:1]([O-])=[O:2].[Na+].[CH:5]([O:8][C:9]([C:11]1[CH:12]=[C:13]([CH3:30])[C:14]2[O:20][C:19]3[C:21]([Cl:26])=[CH:22][C:23]([NH2:25])=[CH:24][C:18]=3[CH2:17][S:16](=[O:28])(=[O:27])[C:15]=2[CH:29]=1)=[O:10])([CH3:7])[CH3:6].COC(C1C=C(C)C2OC3C(Cl)=CC(N)=CC=3CS(=O)(=O)C=2C=1)=O>C(O)=O>[CH:5]([O:8][C:9]([C:11]1[CH:12]=[C:13]([CH3:30])[C:14]2[O:20][C:19]3[C:21]([Cl:26])=[CH:22][C:23]([NH:25][CH:1]=[O:2])=[CH:24][C:18]=3[CH2:17][S:16](=[O:28])(=[O:27])[C:15]=2[CH:29]=1)=[O:10])([CH3:7])[CH3:6]

Participants

5

Reactant 3

HCID 2723810Sodium FormateHCID 115596902-Amino-4-chloro-6-methyl-10,10-dioxo-10,11-dihydro-5-oxa-10lambda *6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acid methyl esterHCID 1317285272-Amino-4-chloro-6-methyl-10,10-dioxo-10,11-dihydro-5-oxa-10lambda*6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acid isopropyl ester

Product 1

HCID 115536024-Chloro-2-formylamino-6-methyl-10,10-dioxo-10,11-dihydro-5-oxa-10lambda*6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acid isopropyl ester

Reagents, catalysts & solvents 1

HCID 284Formic AcidSolvent

Procedure

Sodium formate (0.040 g, 0.581 mmol) was added to a suspension of 2-amino-4-chloro-6-methyl-10,10-dioxo-10,11-dihydro-5-oxa-10lambda*6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acid isopropyl ester (0.23 g, 0.581 mmol) [prepared by hydrolysis of compound of Example 1 and followed by esterification using isopropanol/H2SO4] in formic acid (20 mL) and refluxed for 1.5 h. The reaction mixture was cooled and poured into ice water (100 mL). The solid precipitated was filtered, washed with water and dried. The crude product was crystallised with ethylacetate/pet. ether 60-80° C. to obtain the title compound. Yield: 0.12 g (48%); mp: 212-215° C.; 1H NMR (DMSO-d6, 300 MHz): δ 1.30 (d, 6H, OCH(CH3)2), 2.64 (s, 3H, CH3), 5.12 (m, 1H, OCH(CH3)2), 5.25 (s, 2H, CH2, trans minor isomer), 5.32 (s, 2H, CH2, cis major isomer), 7.33 (d, 1H, Ar, trans minor isomer), 7.50 (d, 1H, Ar, trans minor isomer), 7.69 (d, 1H, Ar, cis major isomer), 7.86 (d, 1H, Ar, cis major isomer), 8.10 (s, 1H, Ar), 8.15 (s, 1H, Ar), 8.30 (s, 1H, CHO, cis major isomer), 8.80 (d, 1H, CHO, trans minor isomer), 10.40 (d, 1H, NH, trans minor isomer), 10.57 (s, 1H, NH, cis major isomer); MS: m/e (ES−) 422 (M−1); analysis: C16H18ClNO6S requires C, 53.84; H, 4.28; N, 3.30; Cl, 8.36, S, 7.56. found: C, 54.27; H, 4.45; N, 2.94; Cl, 8.76; S, 7.77%.

Workup

  1. temperaturerefluxed for 1.5 h
  2. temperatureThe reaction mixture was cooled
  3. customThe solid precipitated
  4. filtrationwas filtered
  5. washwashed with water
  6. customdried
  7. customThe crude product was crystallised with ethylacetate/pet. ether 60-80° C.

Sources & evidence

ORD record
ord-f2a6c427bab44aeb889541f7290bb8d1
Source dataset
uspto-grants-2011_06
Patent number
US07964631B2

Reaction notes

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