Dimethyl Sulfoxide → 2-(7-Bromo-9,9-diethyl-9H-fluoren-2-yl)-1,3-benzothiazole

HRID 1188741Notes

Reaction equation

[CH2:1]([C:3]1([CH2:19][CH3:20])[C:15]2[CH:14]=[C:13]([CH:16]=O)[CH:12]=[CH:11][C:10]=2[C:9]2[C:4]1=[CH:5][C:6]([Br:18])=[CH:7][CH:8]=2)[CH3:2].[NH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=1[SH:28].CS(C)=O.O>C(O)C>[S:28]1[C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][C:22]=2[N:21]=[C:16]1[C:13]1[CH:14]=[C:15]2[C:10]([C:9]3[CH:8]=[CH:7][C:6]([Br:18])=[CH:5][C:4]=3[C:3]2([CH2:1][CH3:2])[CH2:19][CH3:20])=[CH:11][CH:12]=1

Participants

Conditions

Temperature: 195 °C

Procedure

A mixture of 9,9-diethyl-7-bromo-fluorene-2-carboxaldehyde (Example 3; 49.35 g, 0.15 mol), 2-aminothiophenol (20 mL, 0.187 mol, 1.25 eq.), and DMSO (110 mL) was heated in an oil bath to a bath temperature of 195° C., held there for 45 minutes, and then poured into water. The separated solids were collected, reslurried in 1:4 acetic acid-water (1000 mL), filtered, and washed with water and dilute sodium bicarbonate solution. These solids, 80.05 g, were then reslurried in hot ethanol (600 mL) cooled and filtered to get the product, 45.69 g, m.p. 133.6-135° C. An additional 6.6 g, m.p. 134.6-135.5° C., was obtained by chromatography of the ethanol filtrate. Total recovery 52.29 g. (80.3% yield). Mass Spec: m/z 433, 435, (M+). Analysis: Calculated for C24H20BrNS: C, 66.37%; H, 4.64%; Br, 18.40%; N, 3.23%; S 7.37%. Found: C, 66.46%; H, 4.52%; Br, 18.54%; N, 3.14%; S, 7.19%.

Workup

customThe separated solids were collected
filtrationfiltered
washwashed with water and dilute sodium bicarbonate solution
temperaturecooled
filtrationfiltered
customto get the product, 45.69 g, m.p. 133.6-135° C

Sources & evidence

ORD record: ord-c3fe79c636364aad8528796a900f1500
Source dataset: uspto-grants-2014_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08674057B1

Reaction notes

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