Potassium Carbonate → 5-(3-Tert-butyl-5-methoxycarbonyl-benzyl)-2,2-dimethyl-5-[3-[(triphenylmethyl)thio]propyl]-[1,3]dioxane-4,6-dione

HRID 1612416Notes

Reaction equation

HRID 1612416 reaction equation
Br[CH2:2][C:3]1[CH:4]=[C:5]([CH:10]=[C:11]([C:13]([CH3:16])([CH3:15])[CH3:14])[CH:12]=1)[C:6]([O:8][CH3:9])=[O:7].[CH3:17][C:18]1([CH3:49])[O:23][C:22](=[O:24])[CH:21]([CH2:25][CH2:26][CH2:27][S:28][C:29]([C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=2)([C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C:20](=[O:48])[O:19]1.C(=O)([O-])[O-].[K+].[K+]>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.C(#N)C>[C:13]([C:11]1[CH:12]=[C:3]([CH:4]=[C:5]([C:6]([O:8][CH3:9])=[O:7])[CH:10]=1)[CH2:2][C:21]1([CH2:25][CH2:26][CH2:27][S:28][C:29]([C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=2)([C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[C:30]2[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=2)[C:22](=[O:24])[O:23][C:18]([CH3:49])([CH3:17])[O:19][C:20]1=[O:48])([CH3:16])([CH3:15])[CH3:14]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 111343192,2-Dimethyl-5-(3-((triphenylmethyl)thio]propyl]-1,3-dioxane-4,6-dione2×HCID 12144660Methyl 3-bromomethyl-5-tert-butylbenzoate

Product 1

HCID 121446615-(3-Tert-butyl-5-methoxycarbonyl-benzyl)-2,2-dimethyl-5-[3-[(triphenylmethyl)thio]propyl]-[1,3]dioxane-4,6-dione

Reagents, catalysts & solvents 2

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
60 °C

Procedure

A solution of methyl 3-bromomethyl-5-tert-butylbenzoate (10.3 g, 36.1 mmol), 2,2-dimethyl-5-[3-[(triphenylmethyl)-thio]propyl]-[1,3]dioxane-4,6-dione IX (13.8 g, 30.0 mmol), and benzyltriethylammonium chloride (6.38 g, 30 mmol) in acetonitrile (90 mL) was added potassium carbonate (4.35 g, 30 mmol) at 25° C., and the reaction mixture was stirred at 60° C. overnight (the synthesis of compound IX was previously described in International Publication No. WO 00/01668). The solvent was removed under reduced pressure and the residue was partitioned between ethyl acetate and a 10% aqueous KHSO4 solution. The organic layer was dried over MgSO4, concentrated. The crude material was recrystallized from ethyl acetate/hexane mixture to afford 5-(3-tert-butyl-5-methoxycarbonyl-benzyl)-2,2-dimethyl-5-[3-[(triphenyl-methyl)thio]propyl]-[1,3]dioxane-4,6-dione X (14.0 g, 79%) as a white solid: 1H NMR (CDCl3) δ 0.7 (s, 3H), 1.3 (s, 9H), 1.2–1.3 (m, 2H), 1.5 (s, 3H), 2.0 (m, 2H), 2.2 (m, 2H), 3.3 (s, 2H), 3.8 (s, 3H), 7.2–7.4 (m, 16H), 7.6 (s, 1H), 7.8 (s, 1H); 13C NMR (CDCl3) δ 24.8, 29.1, 29.4, 31.2, 31.4, 34.9, 40.3, 43.7, 52.3, 57.3, 66.8, 105.8, 126.0, 126.8, 128.0, 128.5, 129.6, 130.5, 132.3, 135.3, 144.8, 152.4, 167.1, 168.5.

Workup

  1. customThe solvent was removed under reduced pressure
  2. customthe residue was partitioned between ethyl acetate
  3. dry with materialThe organic layer was dried over MgSO4
  4. concentrationconcentrated
  5. customThe crude material was recrystallized from ethyl acetate/hexane mixture

Sources & evidence

ORD record
ord-bee83f066cfb44f697c454d77e93f66b
Source dataset
uspto-grants-2006_01
Patent number
US06992215B2

Reaction notes

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