p-Toluenesulfonic acid → HCID 70465999, compound

HRID 2164294Notes

Reaction equation

HRID 2164294 reaction equation
[F:1][C:2]([F:31])([CH2:8][C@H:9]([C@@H:11]1[C@:28]2([CH3:29])[C@H:14]([C@H:15]3[C@H:25]([CH2:26][CH2:27]2)[C@:23]2([CH3:24])[C:18]([CH2:19][C@@H:20]([OH:30])[CH2:21][CH2:22]2)=[CH:17][CH2:16]3)[CH2:13][CH2:12]1)[CH3:10])[CH2:3][C:4]([OH:7])([CH3:6])[CH3:5].[CH2:32]([O:34]C(=O)C(CC(F)(F)C[C@H]([C@@H]1[C@]2(C)[C@H]([C@H]3[C@H](CC2)[C@]2(C)C(C[C@@H](OC4CCCCO4)CC2)=CC3)CC1)C)C(OCC)=O)[CH3:33].CC1C=CC(S(O)(=O)=O)=CC=1.C(OC(=O)C)(=O)C>CO.N1C=CC=CC=1>[C:32]([O:30][C@H:20]1[CH2:21][CH2:22][C@@:23]2([CH3:24])[C:18](=[CH:17][CH2:16][C@@H:15]3[C@@H:25]2[CH2:26][CH2:27][C@@:28]2([CH3:29])[C@H:14]3[CH2:13][CH2:12][C@@H:11]2[C@H:9]([CH3:10])[CH2:8][C:2]([F:31])([F:1])[CH2:3][C:4]([OH:7])([CH3:6])[CH3:5])[CH2:19]1)(=[O:34])[CH3:33]

Participants

7

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 7918Acetic AnhydrideHCID 57222703HCID 57222703, compoundHCID 57289156HCID 57289156, compound

Product 1

HCID 70465999HCID 70465999, compoundYield 96%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 1049PyridineSolvent

Procedure

The THP-ether (13) (26 mg, 0.0498 mmol) in methanol (4 ml) and THP (9) (4 ml) was treated with a catalytic amount of TsOH at room temperature for 1 hr. The usual work-up (ethyl acetate for extraction) gave the crude diol (21.4 mg). This diol was treated with acetic anhydride (1 ml) and pyridine (1 ml) at room temperature for 14 hr. The usual work-up (ethyl acetate for extraction) gave a crude product, which was applied to a column of silica gel (5 g). Elution with benzene-ethyl acetate (10:1) provided the acetate (14) (23.0 mg, 96%); mp 168°-170° C. (methanol). 1H-NMR δ: 0.82 (3H, s, 18-H3), 1.02 (3H, s, 19-H3), 1.07 (3H, d, J=6 Hz, 21-H3), 1.35 (6H, s, 26-H3 and 27-H 3), 2.03 (3H, s, acetyl), 4.55 (1H, m, 3-H), 5.36 (1H, m, 6-H). High resolution MS Calcd for C27H42F2O (M+ --CH3COOH): 420, 3202. Found: 420, 3206.

Workup

  1. extractionThe usual work-up (ethyl acetate for extraction)
  2. customgave the crude diol (21.4 mg)
  3. extractionThe usual work-up (ethyl acetate for extraction)
  4. customgave a crude product, which
  5. washElution with benzene-ethyl acetate (10:1)

Sources & evidence

ORD record
ord-e714ea3f77d54f8f8ecb18a28ab39a37
Source dataset
uspto-grants-1985_03
Patent number
US04502991

Reaction notes

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