Cyclohexanol → 2-Chlorotetracene

HRID 2215953Notes

Reaction equation

HRID 2215953 reaction equation
[Cl:1][C:2]1[CH:19]=[CH:18][C:17]2[C:16](=O)[C:15]3[C:6](=[CH:7][C:8]4[C:13]([CH:14]=3)=[CH:12][CH:11]=[CH:10][CH:9]=4)[C:5](=O)[C:4]=2[CH:3]=1.C1(O)CCCCC1>[Al](OC(CC)C)(OC(CC)C)OC(CC)C>[Cl:1][C:2]1[CH:19]=[CH:18][C:17]2[C:4](=[CH:5][C:6]3[C:15]([CH:16]=2)=[CH:14][C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[CH:7]=3)[CH:3]=1

Participants

4

Reactant 2

HCID 7966CyclohexanolHCID 219535562-Chlorotetracene-5,12-dione

Product 1

HCID 123364632-ChlorotetraceneYield 48.7%

Reagents, catalysts & solvents 1

HCID 16685157Aluminum(III) s-butoxideSolvent

Conditions

Temperature
159 °C

Procedure

A 2-necked, 500 mL round-bottomed flask was fitted with a distillation head and receiver, and charged with 2-chloro-5,12-tetracenequinone (11.5 g, 39.4 mmol), cyclohexanol (100 mL), and Al(O-sec-Bu)3 (50 mL) under nitrogen. The mixture was heated until distillate began collecting in the receiver at a pot temperature of ca. 115° C. The distillation was continued until the temperature of the dark orange mixture reached 162° C., and the solution was then heated at 159° C. for 36 h. The mixture was cooled to 50° C., an equal volume of dry THF was added, and then it was heated up to 80° C. and stirred. The hot mixture was poured onto a 10–20 μm frit to isolate a bright orange solid that was washed with water (150 mL), 5% HCl (150 mL), and additional water (150 mL). The filtrate was mixed with some additional water and conc. HCL, stirred, and allowed to sit overnight. The solid was air-dried for a couple of hours to afford 5.04 g of material. Purification by high vacuum (pressure ˜10−5 Torr) train sublimation at 130–150° C. afforded 4.0 g of fluorescent orange product. An additional crop of crude material was isolated from the filtrate above and afforded another 1.37 g after sublimation. Net yield 52%. DSC (20° C./min): 361° C. (ΔH=96 Jg−1, decomp). EIMS: 262 ([M]+, 100%), 226 ([M−HCl]+, 23%). Anal. Calcd. for C18H11Cl: C, 82.3; H, 4.22. Found: C, 82.5; H, 4.27.

Workup

  1. customA 2-necked, 500 mL round-bottomed flask was fitted with a distillation head and receiver
  2. temperatureThe mixture was heated until distillate
  3. custombegan collecting in the receiver at a pot temperature of ca. 115° C
  4. distillationThe distillation
  5. customreached 162° C.
  6. temperatureThe mixture was cooled to 50° C.
  7. additionan equal volume of dry THF was added
  8. temperatureit was heated up to 80° C.
  9. additionThe hot mixture was poured onto a 10–20 μm frit
  10. customto isolate a bright orange solid
  11. washthat was washed with water (150 mL), 5% HCl (150 mL), and additional water (150 mL)
  12. additionThe filtrate was mixed with some additional water and conc. HCL
  13. stirringstirred
  14. customThe solid was air-dried for a couple of hours

Sources & evidence

ORD record
ord-71fa1e3868154eb5b008a2ca85633d46
Source dataset
uspto-grants-2006_09
Patent number
US07109519B2

Reaction notes

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