Dimethylamine → Hydrochloric Acid

HRID 1180049

反応式

HRID 1180049 の反応式
[CH3:1][N:2]([CH3:6])[CH2:3][CH2:4]O.[Li][CH2:8][CH2:9][CH2:10][CH3:11].[CH3:12][NH:13][CH3:14].[N:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.C[Si](C)(C)[O:23][C:24]1[CH:31]=[CH:30][C:27]([CH:28]=O)=[CH:26][CH:25]=1.N[C@H](C(O)=[O:48])CC1C=C2C(C=CC=C2)=CC=1.C[Si]([Cl:54])(C)C>CCCCCC.CC#N>[CH3:12][N:13]([CH3:14])[C:18]1[CH:19]=[CH:20][N:15]=[C:16]([CH2:28][C:27]2[CH:30]=[CH:31][C:24]([O:23][C:1](=[O:48])[N:2]([CH3:6])[C:3]3[CH:11]=[CH:10][CH:9]=[CH:8][CH:4]=3)=[CH:25][CH:26]=2)[CH:17]=1.[ClH:54]

参加物

11

反応物 7

HCID 674DimethylamineHCID 1049PyridineHCID 6397ChlorotrimethylsilaneHCID 79022-(Dimethylamino)ethanolHCID 70536p-((Trimethylsilyl)oxy)benzaldehydeHCID 1859152-NaphthylalanineHCID 178418339Butyllithium

生成物 2

HCID 313Hydrochloric AcidHCID 69517588Methyl-phenyl-carbamic Acid 4-(4-dimethylamino-pyridin-2-ylmethyl)-phenyl Ester

試薬・触媒・溶媒 2

HCID 6342Acetonitrile溶媒HCID 8058Hexane溶媒2 回

反応条件

温度
-78 °C

実験手順

A solution of 2-(dimethylamino)ethanol (32 mmol) in hexane (120 mL) was cooled to −5° C. and n-BuLi (64 mmol) was added. After 30 min 4-(dimethylamine=pyridine (16 mmol) was added and the red-orange mixture was stirred for further 1 h. The solution was cooled to −78° C. and 4-(trimethylsilyloxy)benzaldehyde (40 mmol) dissolved in hexane (80 mL) was added and the suspension was allowed to warm to rt over 20 min. The reaction mixture was quenched with water, and the aqueous phase was washed with CH2Cl2. The aqueous phase was evaporated to dryness, added Nal (96 mmol) and dissolved in MeCN (160 mL). Addition of trimethylsilylchloride (96 mmol) and stirring at rt for 16 h. The purple reaction mixture was evaporated to dryness and treated with an aqueous solution of Na2SO3 and pH was adjusted to 8. Extraction with CH2Cl2 gave after evaporation 560 mg (15%) slightly impure 4-(4-dimethylamino-pyridin-2-ylmethyl)phenol as yellow crystals. This was carbamoylated using general procedure 1 (CH2Cl2 was used as solvent) to give the title product as its hydrochloride after purification by preparative HPLC (Gilson) and treatment with HCl in Et2O (48%, light yellow crystals).

後処理

  1. additionwas added
  2. temperatureto warm to rt over 20 min
  3. customThe reaction mixture was quenched with water
  4. washthe aqueous phase was washed with CH2Cl2
  5. customThe aqueous phase was evaporated to dryness
  6. stirringstirring at rt for 16 h
  7. customThe purple reaction mixture was evaporated to dryness
  8. additiontreated with an aqueous solution of Na2SO3 and pH
  9. extractionExtraction with CH2Cl2
  10. customgave
  11. customafter evaporation 560 mg (15%) slightly impure 4-(4-dimethylamino-pyridin-2-ylmethyl)phenol as yellow crystals

出典と根拠

ORDレコード
ord-edf62507421a4f56b7d062d389143477
出典データセット
uspto-grants-2007_10
特許番号
US07279470B2

関連ノート

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