Hydrochloric Acid → HCID 131724884, compound

HRID 2181776Notes

Reaction equation

HRID 2181776 reaction equation
C([C:3]1[CH:7]=[C:6]2[C:8]([C:45]3[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=3)=[C:9]3[N:13]=[C:12]([C:14]([C:39]4[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=4)=[C:15]4[NH:19][C:18](=[C:20]([C:33]5[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=5)[C:21]5[CH:22]=[CH:23][C:24](=[C:26]([C:27]6[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=6)[C:4]=1[NH:5]2)[N:25]=5)[CH:17]=[CH:16]4)[CH:11]=[CH:10]3)=[O:2].[Si]([C:55]([F:58])([F:57])[F:56])(C)(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-].Cl.C([O-])(=O)C.[Na+]>O1CCCC1.C(Cl)Cl>[F:56][C:55]([F:58])([F:57])[OH:2].[CH:48]1[CH:49]=[CH:50][C:45]([C:8]2[C:6]3[NH:5][C:4]([C:26]([C:27]4[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=4)=[C:24]4[CH:23]=[CH:22][C:21](=[C:20]([C:33]5[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=5)[C:18]5[CH:17]=[CH:16][C:15](=[C:14]([C:39]6[CH:40]=[CH:41][CH:42]=[CH:43][CH:44]=6)[C:12]6[CH:11]=[CH:10][C:9]=2[N:13]=6)[N:19]=5)[NH:25]4)=[CH:3][CH:7]=3)=[CH:46][CH:47]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 517045Sodium AcetateHCID 552549(Trifluoromethyl)trimethylsilaneHCID 2724141Tetrabutylammonium FluorideHCID 135955127HCID 135955127, compound

Product 1

HCID 131724884HCID 131724884, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Trifluoromethanol-tetraphenylporphyrin (22) was synthesized according to a modification of the procedure reported by Prakash and Olah (J. Am. Chem. Soc. 1989, 111, 393). All flasks and syringes were flame-dried and cooled under argon. To a stirring solution of formyl-tetraphenylporphyrin (21) (25 mgs, 0.039 mmol) in distilled tetrahydrofuran (15 mL) was added TMS-CF3 (1.16 μL, 0.585 mmol). The mixture was cooled to 0° under argon, and a catalytic amount of TBAF (10 μL, 0.01 mmol) was added. The reaction was monitored by TLC whereby disappearance of the green starting material (Rf=0.5) and appearance of the reddish, faster moving trifluoromethylated siloxy intermediate (Rf=0.78) signaled completion of the reaction. Hydrolysis was achieved by addition of 0.5M hydrochloric acid (until the solution takes on a bright green colour). Methylene chloride and a solution of saturated sodium acetate were then added to neutralize the product. The organic layer was separated, the solvent removed in vacuo, and the residue chromatographed on silica gel 60, 70-230 mesh, (50-100% CH2Cl2/hexanes as gradient eluent) to yield 24.7 mgs (89%) of trifaoromethanol-tetraphenylporphyrin. One faint impurity was visible by TLC, a light green spot (Rf=0.73), but did not impede isolation of the desired product (Rf=0.34) which moved much slower.

Workup

  1. customAll flasks and syringes were flame-dried
  2. temperaturecooled under argon
  3. temperatureThe mixture was cooled to 0° under argon
  4. customcompletion of the reaction
  5. customHydrolysis
  6. customThe organic layer was separated
  7. customthe solvent removed in vacuo
  8. customthe residue chromatographed on silica gel 60, 70-230 mesh, (50-100% CH2Cl2/hexanes as gradient eluent)

Sources & evidence

ORD record
ord-68ed0190c916480d804e47101a365ee8
Source dataset
uspto-grants-2005_05
Patent number
US06894161B2

Reaction notes

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