Indene → HCID 70150899, compound

HRID 2303741Notes

Reaction equation

HRID 2303741 reaction equation
[CH2:1]1[C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[CH:3]=[CH:2]1.C([Li])CCC.[C:15]1([P:21]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)Cl)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[CH2:29]([Sn:33](Cl)([CH2:38][CH2:39][CH2:40][CH3:41])[CH2:34][CH2:35][CH2:36][CH3:37])[CH2:30][CH2:31][CH3:32]>C(OCC)C.CCCCCC>[CH2:38]([Sn:33]([C:2]1[CH:3]([P:21]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C:4]2[C:9]([CH:1]=1)=[CH:8][CH:7]=[CH:6][CH:5]=2)([CH2:29][CH2:30][CH2:31][CH3:32])[CH2:34][CH2:35][CH2:36][CH3:37])[CH2:39][CH2:40][CH3:41]

Participants

7

Reactant 4

HCID 7219IndeneHCID 15096Tributyltin ChlorideHCID 66180ChlorodiphenylphosphineHCID 178418339Butyllithium2×

Product 1

HCID 70150899HCID 70150899, compoundYield 92.5%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent2×

Conditions

Temperature
-20 °C

Procedure

10 g (0.086 moles) of indene were placed in a round-bottomed flask, diluted with 200 ml of diethyl ether and cooled to −20° C. 36 ml of a 2.36 molar solution of butyllithium (0.085 moles) in n-hexane were added to this solution, which immediately assumed a yellow colouration. The cooling bath was removed and the reaction mixture was allowed to warm up to room temperature and stirred for a further one hour. The reaction mixture was then cooled to 0° C. again and 19 g (15.9 ml, 0.086 moles) of diphenylchlorophosphine were added to form a precipitate. The cooling bath was removed again and the solution was able to warm up to room temperature, stirring being continued for a further one hour. The solution was then cooled to −20° C. again and 36 ml (0.085 moles) of butyllithium in n-hexane were added dropwise. When the addition was complete, the cooling bath was removed again and the temperature rose to room temperature; the solution was stirred for a further 1.5 hours. The suspension was then cooled to 0° C. again and 28 g (0.086 moles) of tributyltin chloride were added dropwise. The resulting suspension was heated to room temperature and stirred for a further 1.5 hours; it was then filtered through a frit and the solvent was removed under vacuum to leave 46.9 g of compound 4 (92% of the theoretical yield) in the form of a heavy yellow oil. 1H NMR (400 MHz, CDCl3): δ=7.5-7.3 (m, 6H); 7.28 (bs, 6H); 7.14 (pseudo dt, 7.3 Hz/1.0 Hz, 1H); 7.08 (t, J=7.3 Hz, 1H); 6.5 (bm, 1H); 4.24 (bs, 1H); 1.4-1.25 (m, 6H); 1.25-1.15 (m, 6H); 0.82 (t, J 7.2 Hz, 9H); 0.53 (t, J=8 Hz, 6H); −P NMR (161.9 MHz, CDCl3): δ=−20.6.

Workup

  1. customThe cooling bath was removed
  2. temperatureto warm up to room temperature
  3. temperatureThe reaction mixture was then cooled to 0° C. again
  4. customto form a precipitate
  5. customThe cooling bath was removed again
  6. temperatureto warm up to room temperature
  7. stirringstirring
  8. waitbeing continued for a further one hour
  9. temperatureThe solution was then cooled to −20° C. again
  10. additionWhen the addition
  11. customthe cooling bath was removed again
  12. customrose to room temperature
  13. stirringthe solution was stirred for a further 1.5 hours
  14. temperatureThe suspension was then cooled to 0° C. again
  15. temperatureThe resulting suspension was heated to room temperature
  16. stirringstirred for a further 1.5 hours
  17. filtrationit was then filtered through a frit
  18. customthe solvent was removed under vacuum

Sources & evidence

ORD record
ord-3733babc85f04654b595008027935fb6
Source dataset
uspto-grants-2002_08
Patent number
US06433112B1

Reaction notes

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