Methyl Acetate → HCID 68173591, compound

HRID 538907Notes

Reaction equation

HRID 538907 reaction equation
[CH3:1][O:2][C:3](=[O:5])[CH3:4].C([O-])(O)=O.[Na+].[CH3:11][N:12]1[C:16]([SH:17])=[N:15][N:14]=[N:13]1.C[O:19][C:20](C)([CH3:22])[CH3:21].CN1[CH2:29][CH2:28][CH2:27][C:26]1=[O:30]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC>[CH3:1][O:2][C:3](=[O:5])[CH2:4][C@H:26]1[CH2:27][C@@H:28]([CH2:29][S:17][C:16]2[N:12]([CH3:11])[N:13]=[N:14][N:15]=2)[O:19][C:20]([CH3:22])([CH3:21])[O:30]1

Participants

7

Reactant 5

HCID 6584Methyl Acetate2×HCID 13387N-methyl-2-pyrrolidoneHCID 15413tert-Butyl methyl etherHCID 516892Sodium Bicarbonate2×HCID 178482017HCID 178482017, compound

Product 1

HCID 68173591HCID 68173591, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 74236Tetrabutylammonium BromideCatalyst

Conditions

Temperature
90 °C

Procedure

(4R,6S)-6-(Chloromethyl)-2,2-dimethyl-1,3-dioxan-4-yl)acetic acid methyl ester (Compound B, 47.2 g, 0.20 mol) was dissolved in 150 mL of N-methylpyrrolidone. Then NaHCO3 (23.5 g, 0.28 mol) and tetra-n-butyl ammonium bromide (0.5 g) were added. To the stirred mixture was added 1-methyl-1H-tetrazole-5-thiol (MTT, 27.8 g, 0.24 mol). The mixture was heated to 90° C. and kept at this temperature for 18 h. After cooling to 20-25° C., methyl-tert-butyl ether was added (500 mL) and saturated aqueous NaHCO3 (250 mL). Some precipitation was removed by filtration and washed with 100 mL of methyl-tert-butyl ether. The filtrate was washed with 200 mL of saturated aqueous NaHCO3. After drying over Na2SO4, the organic phase was concentrated to give 2-((4R,6S)-2,2-dimethyl-6-((1-methyl-1H-tetrazol-5-ylthio)methyl)-1,3-dioxan-4-yl)acetic acid methyl ester as a solid (Compound C, 45.2 g, yield 71%). 1H NMR (300 MHz, CDCl3) δ 4.40-4.22 (m, 2H), 3.92 (s, 3H), 3.68 (s, 3H), 3.40 (dd, 2H), 2.48 (dd, 2H), 1.74 (dt, 1H), 1.42 (s, 3H), 1.39-1.29 (m, 1H), 1.35 (s, 3H).

Workup

  1. temperatureAfter cooling to 20-25° C.
  2. customSome precipitation
  3. customwas removed by filtration
  4. washwashed with 100 mL of methyl-tert-butyl ether
  5. washThe filtrate was washed with 200 mL of saturated aqueous NaHCO3
  6. dry with materialAfter drying over Na2SO4
  7. concentrationthe organic phase was concentrated

Sources & evidence

ORD record
ord-d49a255ccc6b403bbb92903099a03d83
Source dataset
uspto-grants-2014_10
Patent number
US08865900B2

Reaction notes

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