Water → 6-Ethynyl-4,4-dimethylthiochroman

HRID 2219798Notes

Reaction equation

HRID 2219798 reaction equation
O.[OH-].[Na+].[CH3:4][C:5]1([CH3:20])[C:14]2[C:9](=[CH:10][CH:11]=[C:12]([C:15](Cl)=[CH:16]C=O)[CH:13]=2)[S:8][CH2:7][CH2:6]1>O1CCOCC1>[CH3:4][C:5]1([CH3:20])[C:14]2[C:9](=[CH:10][CH:11]=[C:12]([C:15]#[CH:16])[CH:13]=2)[S:8][CH2:7][CH2:6]1

Participants

5

Reactant 3

HCID 962WaterHCID 14798Sodium HydroxideHCID 729909543-[4,4-Dimethylthiochroman-6-yl]-3-chloro-2-propene-1-al

Product 1

HCID 109325396-Ethynyl-4,4-dimethylthiochromanYield 87.68%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

In a 250 ml 4-necked round bottom flask fitted with a mechanical stirrer and reflux condenser, water (41.3 ml) and sodium hydroxide (5.22 g, 0.1305M) are added and heated to a temperature in the range of from about 80° C. to about 90° C. The reaction mixture is stirred, and a solution of 3-[4,4-dimethylthiochroman-6-yl]-3-chloro-2-propene-1-al (3.0 gm, 0.0113 M) is added dropwise in 1,4-dioxane (52.2 ml) under vigorous stirring. The reaction mixture is maintained at a temperature in the range of from about 80° C. to about 90° C. for about 2 hours. After completion of the reaction as determined by TLC, the solvents are distilled off and the product is extracted with ether (15 ml×3). The ether layer is washed with brine (15 ml×3). The organic layer is dried over sodium sulfate, and the solvent is distilled off to get an oily residue. The resulting crude oil is distilled under high vacuum and the vapors are collected at a temperature of about 126° C./0.2 mm as the main product. The main fraction appears as red viscous oil, which upon standing crystallized. Net wt of about 2.00 g, yield of about 87.68%; m.p. in the range of from about 69° C. to about 72° C., purity of about 98% (HPLC). The IR (neat) shows the following absorptions: 3200 cm−1 (C—H-str), 2950 cm−1 (—C═C—H str), 2100 cm−1 (—C═C—). The 1H-NMR (CDCl3), TMS as internal standard shows the following signals δ 1.35 (6H, s), 1.92-1.98 (2H, m), 3.02-3.08 (3H, m), 7.13 (1H, d 8.6 Hz), 7.58 (1H, dd, J 8.6 Hz, 2 Hz), 7.99 (1H, d, J 2 Hz). The CI/MS shows m/z 202 (M+).

Workup

  1. customIn a 250 ml 4-necked round bottom flask fitted with a mechanical stirrer
  2. temperaturereflux condenser
  3. temperatureheated to a temperature in the range of from about 80° C. to about 90° C
  4. temperatureThe reaction mixture is maintained at a temperature in the range of from about 80° C. to about 90° C. for about 2 hours
  5. customAfter completion of the reaction
  6. distillationthe solvents are distilled off
  7. extractionthe product is extracted with ether (15 ml×3)
  8. washThe ether layer is washed with brine (15 ml×3)
  9. dry with materialThe organic layer is dried over sodium sulfate
  10. distillationthe solvent is distilled off
  11. customto get an oily residue
  12. distillationThe resulting crude oil is distilled under high vacuum
  13. customthe vapors are collected at a temperature of about 126° C./0.2 mm as the main product
  14. customupon standing crystallized
  15. customof from about 69° C. to about 72° C., purity of about 98% (HPLC)

Sources & evidence

ORD record
ord-aaaf6a6bdbb34a2b92827cbb45817d85
Source dataset
uspto-grants-2008_08
Patent number
US07414143B2

Reaction notes

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