Benzyl Alcohol → (1R,2S)-2-(phenylmethoxycarbonylamino)cyclohexane-1-carboxylic acid

HRID 485740ノート

反応式

HRID 485740 の反応式
C(O)(=O)[C@@H:2]1[CH2:10][CH2:9][CH2:8][CH2:7][C@@H:3]1[C:4]([OH:6])=[O:5].C1(P([N:27]=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1.[CH2:30]([OH:37])[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1.CC[O:40][CH2:41]C>O.C1COCC1.C(N(CC)CC)C>[CH2:30]([O:37][C:41]([NH:27][C@H:2]1[CH2:10][CH2:9][CH2:8][CH2:7][C@H:3]1[C:4]([OH:6])=[O:5])=[O:40])[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1

参加物

8

反応物 4

HCID 244Benzyl AlcoholHCID 3283Diethyl EtherHCID 199401P,P-Diphenylphosphinic azideHCID 245564cis-1,2-Cyclohexanedicarboxylic acid

生成物 1

HCID 2733677(1R,2S)-2-(phenylmethoxycarbonylamino)cyclohexane-1-carboxylic acid

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回HCID 8471Triethylamine溶媒

反応条件

温度
30 °C

実験手順

A solution was prepared by dissolving 18.6 g. of cis-(±)-perhydrophthalic acid, 2,4-cyclolactone in 235 ml. of THF. 12.1 g. of triethyl amine were added thereto. Next, a solution of 31.6 g. of diphenylphosphoryl azide in 50 ml. of THF was added in dropwise fashion at room temperature. The reaction mixture was warmed at about 30° C. for 20 min. and then at reflux temperature for about 3 hrs. The reaction mixture was then cooled to room temperature and stirred at that temperature overnight. 12.4 ml. of benzyl alcohol were added. This reaction mixture was heated to reflux for three hours and was then poured into water. The aqueous mixture was extracted with methylene dichloride. (The pH of the aqueous layer was about 7). The organic extract was dried, and the volatile constituents removed to leave a colorless oil weighing 50.6 g. The residual oil was dissolved in ether, and the ethereal solution chromatographed over silica. Initial fractions were shown to be unreacted benzyl alcohol. The next material to be eluted was cis-(±)-2-benzyloxycarbonylaminocyclohexanecarboxylic acid, 1,3-cyclolactone. 9.5 g. of a white solid product were obtained.

後処理

  1. customA solution was prepared
  2. dissolutionby dissolving 18.6 g
  3. temperatureat reflux temperature for about 3 hrs
  4. temperatureThe reaction mixture was then cooled to room temperature
  5. temperatureThis reaction mixture was heated
  6. temperatureto reflux for three hours
  7. extractionThe aqueous mixture was extracted with methylene dichloride
  8. extractionThe organic extract
  9. customwas dried
  10. customthe volatile constituents removed
  11. customto leave a colorless oil
  12. customthe ethereal solution chromatographed over silica
  13. washThe next material to be eluted
  14. customof a white solid product were obtained

出典と根拠

ORDレコード
ord-143fbc3506ed426cbc3b71bb71d4f65f
出典データセット
uspto-grants-1985_08
特許番号
US04537964

反応ノート

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