Sodium Carbonate → 6'-(4-Methoxypyridin-2-yl)-2',2'-dimethyldispiro[1,3-oxazole-4,4'-chromene-3',3''-oxetan]-2-amine

HRID 594904

Reaction equation

HRID 594904 reaction equation
C(OC([N:8]([C:16]1[O:17][CH2:18][C:19]2([N:43]=1)[C:28]1([CH2:31][O:30][CH2:29]1)[C:27]([CH3:33])([CH3:32])[O:26][C:25]1[C:20]2=[CH:21][C:22](B2OC(C)(C)C(C)(C)O2)=[CH:23][CH:24]=1)C(OC(C)(C)C)=O)=O)(C)(C)C.Br[C:45]1[CH:50]=[C:49]([O:51][CH3:52])[CH:48]=[CH:47][N:46]=1.C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.O.CO.C(Cl)(Cl)Cl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:52][O:51][C:49]1[CH:48]=[CH:47][N:46]=[C:45]([C:22]2[CH:21]=[C:20]3[C:25](=[CH:24][CH:23]=2)[O:26][C:27]([CH3:32])([CH3:33])[C:28]2([CH2:29][O:30][CH2:31]2)[C:19]23[CH2:18][O:17][C:16]([NH2:8])=[N:43]2)[CH:50]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 47384842-Bromo-4-methoxypyridineHCID 86724310Di-tert-butyl[2',2'-dimethyl-6'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dispiro[1,3-oxazole-4,4'-chromene-3',3''-oxetan]-2-yl]imidodicarbonate

Product 1

HCID 867243096'-(4-Methoxypyridin-2-yl)-2',2'-dimethyldispiro[1,3-oxazole-4,4'-chromene-3',3''-oxetan]-2-amineYield 81.4%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 21584188Chloroform methanolSolventHCID 218864351,4-Dioxane--water (1/1)Solvent

Conditions

Temperature
100 °C

Procedure

A mixture of di-tert-butyl[2′,2′-dimethyl-6′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dispiro[1,3-oxazole-4,4′-chromene-3′,3″-oxetan]-2-yl]imidodicarbonate (282 mg, 0.470 mmol), 2-bromo-4-methoxypyridine (221 mg, 1.17 mmol), tetrakis(triphenylphosphine)palladium(0) (271 mg, 0.235 mmol) and Na2CO3 (149 mg, 1.41 mmol) in dioxane-water (4:1, 5.6 mL) was stirred for 8 hours at 100° C. The mixture was diluted with MeOH—CHCl3 (1:9) and washed with water, then the organic layer was dried over MgSO4 and filtered. The filtrate was concentrated at reduced pressure. To the residue were added toluene (2.8 mL) and silica gel (neutral; 846 mg), and the mixture was stirred for 3 hours at 120° C. After concentration of the reaction mixture at reduced pressure, the residue was purified with column chromatography on silica gel (CHCl3-EtOH, a linear gradient of EtOH from 0 to 20%) afforded 6′-(4-methoxypyridin-2-yl)-2′,2′-dimethyldispiro[1,3-oxazole-4,4′-chromene-3′,3″-oxetan]-2-amine (146 mg).

Workup

  1. washwashed with water
  2. dry with materialthe organic layer was dried over MgSO4
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated at reduced pressure
  5. additionTo the residue were added toluene (2.8 mL) and silica gel (neutral; 846 mg)
  6. stirringthe mixture was stirred for 3 hours at 120° C
  7. customAfter concentration of the reaction mixture at reduced pressure, the residue was purified with column chromatography on silica gel (CHCl3-EtOH

Sources & evidence

ORD record
ord-8199f9467c6b4c2ca6947f5719e882f1
Source dataset
uspto-grants-2016_01
Patent number
US09242973B2

Linked notes

Loading…