(+-)-Cashmeran → HCID 70926131, compound

HRID 1042421Notes

Reaction equation

[CH3:1][C:2]1([CH3:15])[CH:10]2[CH:5]([C:6](=O)[CH2:7][CH2:8][CH2:9]2)[C:4]([CH3:13])([CH3:12])[CH:3]1[CH3:14].CC1(C)C2CCCC(=O)C=2C(C)(C)C1C.CC1(C)C2C(C(=O)C(=O)CC2)C(C)(C)C1C.[C:47]([NH2:50])(=[S:49])[CH3:48]>COCCOCCOC>[CH3:48][C:47]1[S:49][C:7]2[CH2:8][CH2:9][CH:10]3[CH:5]([C:4]([CH3:13])([CH3:12])[CH:3]([CH3:14])[C:2]3([CH3:15])[CH3:1])[C:6]=2[N:50]=1

Participants

Conditions

Temperature: 130 °C

Procedure

1,1,2,3,3-Pentamethyl-octahydro-inden-4-one is first prepared by the hydrogenation of 1,1,2,3,3-pentamethyl-1,2,3,5,6,7-hexahydro-inden-4-one (Cashmeran®) (commercially available at IFF). 1,1,2,3,3-Pentamethyl-hexahydro-indene-4,5-dione is subsequently prepared with 1,1,2,3,3-pentamethyl-octahydro-inden-4-one (prepared as described by Barton in Tetrahedron Letters, 1984, 25(6), pages: 603-606). A 100 mL reaction flask is charged with 1,1,2,3,3-pentamethyl-hexahydro-indene-4,5-dione (10 g, 0.04 mol), thioacetamide (3.5 g, 0.04 mol), and diglyme (50 mL). The reaction mixture is heated to 130° C. and stirred for 24 hours. The crude mass is washed once with aqueous sodium carbonate (10%, 100 mL) followed by twice with brine (30 mL). Diglyme is recovered by roto-evaporation. The crude product is further purified with liquid chromatography (Biotage® system) and then crystallized. Product 2,6,6,7,8,8-hexamethyl-5,5a,6,7,8,8a-hexahydro-4H-3-thia-1-aza-as-indacene (˜10 g) is obtained.

Workup

customA 100 mL reaction flask
washThe crude mass is washed once with aqueous sodium carbonate (10%, 100 mL)
customDiglyme is recovered by roto-evaporation
customThe crude product is further purified with liquid chromatography (Biotage® system)
customcrystallized

Sources & evidence

ORD record: ord-a3cdfc4815e24cd19e2074c3cfbca1bf
Source dataset: uspto-grants-2013_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08557876B2

Reaction notes

Loading…