HCID 10318376, compound → HCID 53936135, compound

HRID 1265234Notes

Reaction equation

HRID 1265234 reaction equation
[CH3:1][O:2][C:3](=[O:29])[C:4]1[CH:9]=[CH:8][C:7]([C:10]([C:12]2[C:21]([CH2:22][CH2:23][CH3:24])=[CH:20][C:19]3[C:18]([CH3:26])([CH3:25])[CH2:17][CH2:16][C:15]([CH3:28])([CH3:27])[C:14]=3[CH:13]=2)=O)=[CH:6][CH:5]=1.[Br-].[CH3:31][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[N-]=[N+]=[N-].[Na+]>C1COCC1>[CH3:1][O:2][C:3](=[O:29])[C:4]1[CH:5]=[CH:6][C:7]([CH:10]=[CH:12][C:21]2[C:22]([CH2:23][CH2:24][CH3:31])=[CH:13][C:14]3[C:15]([CH3:28])([CH3:27])[CH2:16][CH2:17][C:18]([CH3:26])([CH3:25])[C:19]=3[CH:20]=2)=[CH:8][CH:9]=1

Participants

4

Reactant 2

HCID 10318376HCID 10318376, compoundHCID 86758912HCID 86758912, compound

Product 1

HCID 53936135HCID 53936135, compoundYield 78%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

4-[(3-n-Propyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-2-naphthyl)carbonyl]benzoic acid methyl ester (2.7 mmol) in THF (25 mL) was treated with methyltriphenylphosphonium bromide/sodium azide (1.2 g, 3.1 mmol) and the solution was allowed to stir at ambient temperature for 3 h. The reaction was quenched with saturated aqueous NH4Cl and diluted with EtOAc. The organic solution was separated and washed with water and brine, dried (MgSO4), filtered, and concentrated to give a yellow oil. The crude product was crystallized (CH2Cl2/hexanes) to give 4-[(3-n-propyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-2-naphthyl)ethenyl] benzoic acid methyl ester as white crystal (78%): TLC (20% ethyl acetate: 80% hexanes) Rf 0.8; mp 120-121° C.; 1H-NMR (400 MHz, CDCl3) δ7.94 (½ABq, J=8.0 Hz, 2H, ArH), 7.33 (½ABq, J=8.0 Hz, 2H, ArH), 7.09 (s, 1H, ArH), 7.08 (s, 1H, ArH), 5.80 (s, 1H, olefinic), 5.30 (s, 1H, olefinic), 3.90 (s, 3H, OCH3), 2.24 (t, J=8.0 Hz, 2H, CH2), 1.70 (s, 4H, 2CH2), 1.39 (m, 2H, CH2), 1.30 (s, 6H, 2CH3), 1.26 (s, 6H, 2CH3), 0.73 (t, J=7.5 Hz, 3H, CH3), Anal. (C27H34O2) C, H. The ester was hydrolized using the standard conditions of Example 1 to yield 4-[(3-n-propyl-5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthyl)ethyl]benzoic acid (102). Crystallization gave white crystals (83%): TLC (10% MeOH-90% CHCl3) Rf 0.5; mp 263-265° C. 1H-NMR (400 MHz, CDCl3) δ8.00 (½ABq, J=8.0 Hz, 2H, ArH), 7.09 (s, 1H, ArH), 7.08 (s, 1H, ArH), 5.81 (s, 1H, olefinic), 5.31 (s, 1H, olefinic), 2.23 (t, J=8.0 Hz, 2H, CH2), 1.70 (s, 4H, 2CH2), 1.39 (m, 2H, CH2), 1.30 (s, 6H, 2CH3), 1.26 (s, 6H, 2CH3), 0.73 (t, J=7.5 Hz, 3H, CH3), FAB-MS m/z 377 (MH+); Anal. (C26H32O2) C, H.

Workup

  1. customThe reaction was quenched with saturated aqueous NH4Cl
  2. additiondiluted with EtOAc
  3. customThe organic solution was separated
  4. washwashed with water and brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto give a yellow oil
  9. customThe crude product was crystallized (CH2Cl2/hexanes)

Sources & evidence

ORD record
ord-77497fac1f194a65bb18321c2a4926a0
Source dataset
uspto-grants-2003_04
Patent number
US06545049B1

Reaction notes

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