Methanol → HCID 178464043, compound

HRID 1382535Notes

Reaction equation

HRID 1382535 reaction equation
[CH2:1]([N:3]([CH2:31][CH3:32])[CH2:4][CH2:5][N:6]1[C:14]2[CH:13]=[CH:12][C:11]([NH:15][CH2:16][CH2:17][NH:18]C(=O)O)=[C:10]3[S:22][C:23]4[CH:28]=[C:27]([O:29]C)[CH:26]=[CH:25][C:24]=4[C:8]([C:9]=23)=[N:7]1)[CH3:2].B(Br)(Br)Br.CO>ClC(Cl)C.ClCCl>[NH2:18][CH2:17][CH2:16][NH:15][C:11]1[CH:12]=[CH:13][C:14]2[N:6]([CH2:5][CH2:4][N:3]([CH2:31][CH3:32])[CH2:1][CH3:2])[N:7]=[C:8]3[C:24]4[CH:25]=[CH:26][C:27]([OH:29])=[CH:28][C:23]=4[S:22][C:10]=1[C:9]=23

Participants

6

Reactant 3

HCID 887MethanolHCID 25134Boron tribromideHCID 21274745[2-[[2-[2-(diethylamino)ethyl]-8-methoxy-2H-[1]benzothiopyrano[4,3,2-cd]indazol-5-yl]amino]ethyl]-carbamic acid

Product 1

HCID 178464043HCID 178464043, compoundYield 154%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 63651,1-DichloroethaneSolvent

Conditions

Temperature
25 °C

Procedure

A 25° C. solution of 0.25 g (0.49 mmol) of [2-[[2-[2-(diethylamino)ethyl]-8-methoxy-2H-[1]benzothiopyrano[4,3,2-cd]indazol-5-yl]amino]ethyl]-carbamic acid; 1,1-dimethylethyl ester (6) in 7.5 mL of dichloroethane was treated dropwise with 2.45 mL (2.45 mmol) of a 1M solution of boron tribromide in dichloromethane. The mixture was stirred at 25° C. for 18 hr, treated cautiously with 3 mL of methanol, then heated at reflux for 6 hr. After cooling to 25° C., the precipitated solids were collected by filtration, washed successively with methanol and dichloromethane, and dried at 200 mm/60° C./overnight to give 0.3 g of 4, 95.2% pure by HPLC. The solids were dissolved in 10.6 mL of ethanol:H2O (4:1) and the solution was treated portionwise with 1.6 mL of a 2.6M solution of hydrogen bromide in 2-propanol. After standing overnight at 0°-5° C., the precipitated solids were collected by filtration, washed, and dried as above to give 0.28 g (90%) of 4 as a salt with 2.9 equivalents of hydrogen bromide, mp 282° C. (dec), 96.1% pure by HPLC.

Workup

  1. temperatureheated
  2. temperatureat reflux for 6 hr
  3. temperatureAfter cooling to 25° C.
  4. filtrationthe precipitated solids were collected by filtration
  5. washwashed successively with methanol and dichloromethane
  6. customdried at 200 mm/60° C./overnight

Sources & evidence

ORD record
ord-d53f2df00c424c198dff532a4b7a6b10
Source dataset
uspto-grants-1989_02
Patent number
US04806654

Reaction notes

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