Dichloromethane → (N,N-diethylcarbamoyl)methyl methyl (2E)but-2-ene-1,4-dionate

HRID 229494

反応式

HRID 229494 の反応式
S(O)(=O)(=O)C.[NH2:6][C@@H:7]([CH2:23][C:24]1[CH:29]=[CH:28][C:27]([OH:30])=[C:26]([OH:31])[CH:25]=1)[C:8]([O:10][CH2:11][C@H:12]([O:14][C:15]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)=[O:16])[CH3:13])=[O:9].C(OC(N[C@@H](CC1C=CC(O)=C(O)C=1)C(OC[C@H](OC(C1C=CC=CC=1)=O)C)=O)=O)(C)(C)C.ClCCl>O1CCOCC1>[NH2:6][C@@H:7]([CH2:23][C:24]1[CH:29]=[CH:28][C:27]([OH:30])=[C:26]([OH:31])[CH:25]=1)[C:8]([O:10][CH2:11][C@H:12]([O:14][C:15]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)=[O:16])[CH3:13])=[O:9]

参加物

5

反応物 3

HCID 6344DichloromethaneHCID 16125134(2R)-2-phenylcarbonyloxypropyl (2S)-2-amino-3-(3,4-dihydroxyphenyl)propanoate mesylateHCID 46899463(2R)-2-Phenylcarbonyloxypropyl(2S)-2-(tert-Butoxycarbonyl)amino-3-(3,4-dihydroxyphenyl)propanoate

生成物 1

HCID 11559525(N,N-diethylcarbamoyl)methyl methyl (2E)but-2-ene-1,4-dionate

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

実験手順

As an example of the one-pot procedure for preparing crystalline (2R)-2-phenylcarbonyloxypropyl (2S)-2-amino-3-(3,4-dihydroxyphenyl)propanoate mesylate, a solution of (2R)-2-phenylcarbonyloxypropyl (2S)-2-(tert-butoxycarbonyl)amino-3-(3,4-dihydroxyphenyl)propanoate in a solvent in which it is soluble is prepared. Examples of suitable solvents include dichloromethane and dioxane. The tert-butoxycarbonyl group is deprotected by adding an acid to provide (2R)-2-phenylcarbonyloxypropyl (2S)-2-amino-3-(3,4-dihydroxyphenyl)propanoate acid salt. Suitable acids are not limited to volatile acids. Examples of suitable acids for deprotecting the tert-butoxycarbonyl group include hydrochloric acid, methanesulfonic acid, trifluoroacetic acid, and hydrogen bromide. After deprotection, the first solvent can be removed and water added to the (2R)-2-phenylcarbonyloxypropyl (2S)-2-amino-3-(3,4-dihydroxyphenyl)propanoate acid salt. The (2R)-2-phenylcarbonyloxypropyl (2S)-2-amino-3-(3,4-dihydroxyphenyl)propanoate acid salt can be neutralized with a base such as NaHCO3 or KHCO3 to provide (2R)-2-phenylcarbonyloxypropyl (2S)-2-amino-3-(3,4-dihydroxyphenyl)propanoate. (2R)-2-Phenylcarbonyloxypropyl (2S)-2-amino-3-(3,4-dihydroxyphenyl)propanoate can then be extracted with a second solvent such as methyl tert-butylether, dichloromethane, ethylacetate, or a mixture of ethylacetate and isopropanol. Methanesulfonic acid can be added to the extracted (2R)-2-phenylcarbonyloxypropyl (2S)-2-amino-3-(3,4-dihydroxyphenyl)propanoate to convert the (2R)-2-phenylcarbonyloxypropyl (2S)-2-amino-3-(3,4-dihydroxyphenyl)propanoate to crystalline (2R)-2-phenylcarbonyloxypropyl (2S)-2-amino-3-(3,4-dihydroxyphenyl)propanoate mesylate. Crystalline (2R)-2-phenylcarbonyloxypropyl (2S)-2-amino-3-(3,4-dihydroxyphenyl)propanoate mesylate can then be isolated from the second solvent by filtration.

後処理

  1. additionby adding an acid

出典と根拠

ORDレコード
ord-d090d5a071024868a6f1117d7352b101
出典データセット
uspto-grants-2009_07
特許番号
US07563821B2

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