Methylparaben → (RS)-methyl 4-[2-(4,4-dimethyl-thiochroman-6-yl)-heptyloxy]-benzoate

HRID 394948Notes

Reaction equation

HRID 394948 reaction equation
[CH3:1][C:2]1([CH3:20])[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([CH:12]([CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])[CH2:13][OH:14])[CH:10]=2)[S:5][CH2:4][CH2:3]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O[C:41]1[CH:50]=[CH:49][C:44]([C:45]([O:47][CH3:48])=[O:46])=[CH:43][CH:42]=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1.CCOCC>[CH3:1][C:2]1([CH3:20])[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([CH:12]([CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])[CH2:13][O:14][C:41]3[CH:50]=[CH:49][C:44]([C:45]([O:47][CH3:48])=[O:46])=[CH:43][CH:42]=3)[CH:10]=2)[S:5][CH2:4][CH2:3]1

Participants

7

Reactant 4

HCID 7456MethylparabenHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 18177890(RS)-2-(4,4-dimethyl-thiochroman-6-yl)-heptanol

Product 1

HCID 18177937(RS)-methyl 4-[2-(4,4-dimethyl-thiochroman-6-yl)-heptyloxy]-benzoateYield 76.8%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

0.25 g of (RS)-2-(4,4-dimethyl-thiochroman-6-yl)-heptanol dissolved in 15 ml THF were treated with 250 mg of triphenylphosphine, 150 mg of methyl 4-hydroxybenzoate and 0.15 ml of diethyl azodicarboxylate. The reaction mixture was heated to reflux for 6 hours. The mixture was diluted with 50 ml of ether and washed with two portions of 15 ml of water and one portion of 15 ml of sat. aq. sodium chloride solution. The organic phase was dried over MgSO4. The solvents were removed in vacuo and the resulting yellow oil was purified by flash chromatography (SiO2, 3% ethyl acetate/hexanes), giving 280 mg of (RS)-methyl 4-[2-(4,4-dimethyl-thiochroman-6-yl)-heptyloxy]-benzoate as a pale yellow oil. 1H NMR (CDCl3): 7.95 (d, J=8.9 Hz, 2H), 7.21 (d, J=1.9 Hz, 1H), 7.03 (d, J=8.1 Hz, 1H), 6.91 (dd, J=8.1, 1.9 Hz, 1H), 6.87 (d, J=8.9 Hz, 2H), 4.10-4.00 (m, 2H), 3.87 (s, 3H), 3.05-2.90 (m, 3H), 2.00-1.80 (m, 3H), 1.70-1.60 (m, 1H), 1.32 (s, 3H), 1.31 (s, 3H), 1.35-1.15 (m, 6H), 0.90-0.80 (m, 3H).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux for 6 hours
  3. washwashed with two portions of 15 ml of water and one portion of 15 ml of sat. aq. sodium chloride solution
  4. dry with materialThe organic phase was dried over MgSO4
  5. customThe solvents were removed in vacuo
  6. customthe resulting yellow oil was purified by flash chromatography (SiO2, 3% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-1a32c39b955743f9905494aec7565634
Source dataset
uspto-grants-2003_08
Patent number
US06603012B2

Reaction notes

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