Water → (2S-trans)-18-Carboxy-20-(carboxymethyl)-13-ethyl-2,3-dihydro-3,7,12,17-tetramethyl-8-vinyl-21H,23H-porphine-2-propionic acid; (17S,18S)-18-(2-Carboxyethyl)-20-(carboxymethyl)-12-ethenyl-7-ethyl-3,8,13,17-tetramethyl-17,18,22,23-tetrahydroporphyrin-2-carboxylic acid

HRID 2371466Notes

Reaction equation

HRID 2371466 reaction equation
[CH3:1][CH2:2][C:3]1[C:21]2=[N:22][C:5](=[CH:6][C:7]3[NH:11][C:10]([CH:12]=[C:13]4[CH:34]([CH3:35])[CH:33]([CH2:36][CH2:37][C:38]([O:40]C)=[O:39])[C:15]([C:16]5[CH:27]([C:28]([O:30]C)=[O:29])C(=O)[C:24]6[C:17]=5[NH:18][C:19]([C:23]=6[CH3:32])=[CH:20]2)=[N:14]4)=[C:9]([CH3:42])[C:8]=3[CH:43]=[CH2:44])[C:4]=1[CH3:45].[CH3:46][O-:47].[Na+].[Na].[OH2:50]>O1CCCC1.CO>[CH3:1][CH2:2][C:3]1[C:21]2[N:22]=[C:5]([CH:6]=[C:7]3[C:8]([CH:43]=[CH2:44])=[C:9]([CH3:42])[C:10](=[CH:12][C:13]4[C@@H:34]([CH3:35])[C@H:33]([CH2:36][CH2:37][C:38]([OH:40])=[O:39])[C:15](=[C:16]([CH2:27][C:28]([OH:30])=[O:29])[C:17]5[NH:18][C:19]([CH:20]=2)=[C:23]([CH3:32])[C:24]=5[C:46]([OH:50])=[O:47])[N:14]=4)[NH:11]3)[C:4]=1[CH3:45]

Participants

7

Reactant 4

HCID 962WaterHCID 5360545SodiumHCID 10942334Sodium MethoxideHCID 178435494HCID 178435494, compound

Product 1

HCID 138978174(2S-trans)-18-Carboxy-20-(carboxymethyl)-13-ethyl-2,3-dihydro-3,7,12,17-tetramethyl-8-vinyl-21H,23H-porphine-2-propionic acid; (17S,18S)-18-(2-Carboxyethyl)-20-(carboxymethyl)-12-ethenyl-7-ethyl-3,8,13,17-tetramethyl-17,18,22,23-tetrahydroporphyrin-2-carboxylic acidYield 67%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

The procedure of Smith and Bushell (M. J. Bushell, Ph.D. Thesis, Univ. of Liverpool, U.K., 1978) was used. The starting material, 1 gm of methyl pheophorbide-a, was dissolved in dry tetrahydrofuran (THF). To this was added sodium methoxide prepared by dissolving 200 mg sodium in 40 ml methanol, and the reaction was allowed to stir at room temperature for 1 hr. The mixture was poured into water and extracted with dichloromethane. The organic layer was washed with water, dried over anhydrous sodium sulfate and evaporated. The residue was dissolved in chloroform and treated with dichloromethane and ether, and the solid obtained was chromatographed on Alumina (Grade III) and eluted with toluene/dichloromethane 1/1. The major band, chlorin-e6 tetramethyl ester was recrystallized from dichloromethane/methanol to obtain 700 mg or 67% yield of the compound of formula ##STR7## By re-utilizing the remaining starting material, an overall yield of 88.7% was obtained, and the structure was confirmed by NMR spectroscopy.

Workup

  1. customprepared
  2. extractionextracted with dichloromethane
  3. washThe organic layer was washed with water
  4. dry with materialdried over anhydrous sodium sulfate
  5. customevaporated
  6. dissolutionThe residue was dissolved in chloroform
  7. additiontreated with dichloromethane and ether
  8. customthe solid obtained
  9. customwas chromatographed on Alumina (Grade III)
  10. washeluted with toluene/dichloromethane 1/1
  11. customThe major band, chlorin-e6 tetramethyl ester was recrystallized from dichloromethane/methanol

Sources & evidence

ORD record
ord-3afa0a5b5e064ee786590aac62c219ff
Source dataset
uspto-grants-1992_03
Patent number
US05093349

Reaction notes

Loading…