Dithiooxamide → 2,5-Bis(7-bromo-9,9-didecylfluoren-2-yl)-1,3-thiazolo(5,4-d)1,3-thiazole

HRID 1581868Notes

Reaction equation

HRID 1581868 reaction equation
[Br:1][C:2]1[CH:14]=[C:13]2[C:5]([C:6]3[CH:7]=[CH:8][C:9]([CH:35]=O)=[CH:10][C:11]=3[C:12]2([CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])=[CH:4][CH:3]=1.[NH2:37][C:38]([C:40]([NH2:42])=[S:41])=[S:39]>CS(C)=O>[Br:1][C:2]1[CH:14]=[C:13]2[C:5]([C:6]3[CH:7]=[CH:8][C:9]([C:35]4[S:39][C:38]5[N:37]=[C:35]([C:9]6[CH:8]=[CH:7][C:6]7[C:5]8[C:13](=[CH:14][C:2]([Br:1])=[CH:3][CH:4]=8)[C:12]([CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])([CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[C:11]=7[CH:10]=6)[S:41][C:40]=5[N:42]=4)=[CH:10][C:11]=3[C:12]2([CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 2777982DithiooxamideHCID 22723474HCID 22723474, compound

Product 1

HCID 859666662,5-Bis(7-bromo-9,9-didecylfluoren-2-yl)-1,3-thiazolo(5,4-d)1,3-thiazoleYield 15.1%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
190 °C

Procedure

A mixture of 7-bromo-9,9-didecylfluorene-2carbaldehyde (example 2; 6.6 g, 12 mmol), dithiooxamide (rubeanic acid, 0.6 g, 5 mmol) and DMSO (4 mL) was heated in an oil-bath to a bath temperature of 190° C., held 1 hour and poured onto water. The mixture was extracted into toluene (200 mL). The toluene extract was washed with water, dried and concentrated. The resulting residue was chromatographed over alumina to get a mixture of product containing the aldehyde product. The mixture was rechromatographed over silica gel, and elution with toluene gave 0.9 g (15% yield) of the product which was recrystallized from a mixture of heptane and hexanes to get pure product 0.6 g, (10% yield), m.p. 150.8-152.7° C. Mass Spec.(m/z): 1186, 1188, 1190 (M+). Anal. Calcd. for C70H96Br2N2S2: C, 70.68%; H, 8.14%; N, 2.36%; S, 5.39%; Br, 13.44%. Found: C, 70.69%; H, 8.22%; N, 2.07%; S, 5.31%; Br, 13.67%.

Workup

  1. additionpoured onto water
  2. extractionThe mixture was extracted into toluene (200 mL)
  3. extractionThe toluene extract
  4. washwas washed with water
  5. customdried
  6. concentrationconcentrated
  7. customThe resulting residue was chromatographed over alumina
  8. customto get
  9. additiona mixture of product
  10. customThe mixture was rechromatographed over silica gel, and elution with toluene

Sources & evidence

ORD record
ord-b15f85af20af4d5b97c42fd0b5a6dcc1
Source dataset
uspto-grants-2004_05
Patent number
US06730793B1

Reaction notes

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