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

HRID 873757

反応式

HRID 873757 の反応式
[CH3:1][C:2]1([CH3:43])[C:30]2([CH2:33][O:32][CH2:31]2)[C:10]2([CH2:14][O:13][C:12]([N:15](C(OC(C)(C)C)=O)C(OC(C)(C)C)=O)=[N:11]2)[C:9]2[C:4](=[CH:5][CH:6]=[C:7](B3OC(C)(C)C(C)(C)O3)[CH:8]=2)[O:3]1.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:7]2[CH:8]=[C:9]3[C:4](=[CH:5][CH:6]=2)[O:3][C:2]([CH3:1])([CH3:43])[C:30]2([CH2:31][O:32][CH2:33]2)[C:10]23[CH2:14][O:13][C:12]([NH2:15])=[N:11]2)[CH:50]=1

参加物

7

反応物 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

生成物 1

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

試薬・触媒・溶媒 3

HCID 178418397HCID 178418397、化合物触媒HCID 21584188Chloroform methanol溶媒HCID 218864351,4-Dioxane--water (1/1)溶媒

反応条件

温度
100 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-828ea07df72643b789eecff679ccedaf
出典データセット
uspto-grants-2015_03
特許番号
US08975415B2

関連ノート

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