Hydrochloric Acid → N-Tosylhydroxy-L-prolinol

HRID 1605952

反応式

HRID 1605952 の反応式
[S:1]([N:11]1[CH2:18][CH2:17][CH2:16][C@@:12]1([OH:19])[C:13](O)=[O:14])([C:4]1[CH:10]=[CH:9][C:7]([CH3:8])=[CH:6][CH:5]=1)(=[O:3])=[O:2].CC(C)=NNC(C1C=C(Cl)N=C(Cl)C=1)=O.B#B.Cl>C1COCC1.C(Cl)(Cl)Cl.O>[S:1]([N:11]1[CH2:18][CH2:17][CH2:16][C@@:12]1([OH:19])[CH2:13][OH:14])([C:4]1[CH:5]=[CH:6][C:7]([CH3:8])=[CH:9][CH:10]=1)(=[O:2])=[O:3]

参加物

8

反応物 4

HCID 313Hydrochloric AcidHCID 27511Isonicotinic acid, 2,6-dichloro-, isopropylidenehydrazideHCID 6328200DiboronHCID 54335759N-tosylhydroxy-L-proline

生成物 1

HCID 67796897N-Tosylhydroxy-L-prolinol収率 91.6%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6212Chloroform溶媒HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
0 °C

実験手順

A solution of 182.6 g (0.642 mole) N-tosylhydroxy-L-proline, made according to the procedure of P. S. Portoghese and A. A. Mikhail as reported in J. Org. Chem., 31, p 1059, 1966, in 800 ml dry THF was added over a 3 hour period to 1300 ml of 0.5 m diborane in tetrahydrofuran with stirring at 0° C. The reaction mixture solidified into a white opaque gel. This was broken up by hand, 800 ml of tetrahydrofuran was added, and the mixture was refluxed 2.5 hours with mechanical stirring. During this time, most of the solid redissolved. After 18 hours at ambient temperature, the reaction mixture was chilled, and 6N hydrochloric acid was carefully added until gas evolution ceased. One liter of water was added, and the homogeneous solution was diluted with chloroform until two phases formed. The aqueous phase was separated and extracted with additional chloroform. The combined organic phases were washed with water, dried with sodium sulfate, and evaporated in vacuo to leave a semi-solid residue (159.6 g) that gave 80.0 g (50.5%, melting point 130°-132° C), of N-tosylhydroxy-L-prolinol upon crystallization from ethyl acetate. Portoghese and Mikkail reported a melting point of 131°-133° C for the same compound made via the methyl ester of N-tosylhydroxy-L-lproline.

後処理

  1. additionwas added
  2. temperaturethe mixture was refluxed 2.5 hours with mechanical stirring
  3. dissolutionDuring this time, most of the solid redissolved
  4. temperaturethe reaction mixture was chilled
  5. customformed
  6. customThe aqueous phase was separated
  7. extractionextracted with additional chloroform
  8. washThe combined organic phases were washed with water
  9. dry with materialdried with sodium sulfate
  10. customevaporated in vacuo

出典と根拠

ORDレコード
ord-7142b4cdb3e74de7a79a3645db9f5f4b
出典データセット
uspto-grants-1976_04
特許番号
US03951980

関連ノート

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