Aluminium lithium hydride → 1,3-Propanedithiol, 2-ethyl-2-(mercaptomethyl)-

Temperature

-5 °C

Compound 3 was converted to the trithiol by reduction with lithium aluminum hydride. Under N2, compound 3 (1.0 g, 3.9 mmol) and LiAlH4 (0.89 g, 23.4 mmol) were added to a 50 mL three necked round bottom flask. After the reaction was cooled to −5° C., cold ethyl ether (30 mL) was added by syringe while stirring. The reaction continued stir for 3 h at −5° C., brought to room temperature and stirred overnight. Upon return, grey solids were present. The reaction was cooled then quenched by the slow addition of saturated ammonium chloride (20 mL). Solids were removed via vacuum filtration, and 2 M HCl (20 mL) was added to the mother liquor. The product, 4, was extracted into ethyl ether (3×50 mL), dried over anhydrous Na2SO4, filtered, and taken to dryness to yield a light yellow oil, which crystallized upon cooling. Yield: 584 mg, 82%. 1H NMR (CDCl3; 500 MHz) δ ppm: 0.82 (t, 3H, CH3), 1.18 (t, 3H, SH), 1.46 (q, 2H, CCH2), 2.58 (d, 6H, SCH2). 13C NMR (CDCl3; 125.8 MHz) δ ppm: 7.85 (CH3), 25.10 (CCH2), 28.80 (SCH2), 41.66 (C). ESI-MS (m/z) 181.12 (181.03 calcd for [M−H]− of [C6H14S3]).

1. stirringThe reaction continued stir for 3 h at −5° C.
2. custombrought to room temperature
3. stirringstirred overnight
4. temperatureThe reaction was cooled
5. customthen quenched by the slow addition of saturated ammonium chloride (20 mL)
6. customSolids were removed via vacuum filtration, and 2 M HCl (20 mL)
7. additionwas added to the mother liquor
8. extractionThe product, 4, was extracted into ethyl ether (3×50 mL)
9. dry with materialdried over anhydrous Na2SO4
10. filtrationfiltered
11. customto yield a light yellow oil, which
12. customcrystallized
13. temperatureupon cooling

ORD record

ord-9eb8b8a164674cbeadc9b2c6e65329d1

Source dataset

uspto-grants-2016_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09427483B2