Hydrochloric Acid → HCID 14856505, compound

HRID 1073332Notes

Reaction equation

HRID 1073332 reaction equation
C([Li])CCC.[F:6][C:7]1[CH:19]=[CH:18][C:17]2[C:16]3[C:11](=[CH:12][C:13]([F:20])=[CH:14][CH:15]=3)[CH2:10][C:9]=2[CH:8]=1.C1(C)C=CC(S([N:30]=[N+:31]=[N-])(=O)=O)=CC=1.Cl>CCCCCC.CCOCC.CCOCC.CCCCCC>[F:6][C:7]1[CH:19]=[CH:18][C:17]2[C:16]3[C:11](=[CH:12][C:13]([F:20])=[CH:14][CH:15]=3)[C:10](=[N+:30]=[N-:31])[C:9]=2[CH:8]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 13661p-Toluenesulfonyl azideHCID 2451192,7-difluoro-9h-fluoreneHCID 178418339Butyllithium

Product 1

HCID 14856505HCID 14856505, compoundYield 37%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolventHCID 21584099Diethylether hexaneSolvent

Procedure

Under nitrogen, n-butyllithium (20 mL of a 2.5M solution in hexane, 1 eq) was added dropwise to a stirred, -20 ° C. solution of commercially available (Alfred Bader Library of Rare Chemicals) 2,7-difluorofluorene (24) (10 g, 49.5 mmoL) [which may also be prepared according to U.S. Pat. No. 4,436,745] in 250 mL of anhydrous ether. After 10 min., this mixture was transferred via a cannula using nitrogen pressure into a 0° C. solution of p-toluenesulfonylazide [prepared by the method described in Doering, et al. J. Am. Chem. Soc. (1953) 75, 5955] in 200 mL of anhydrous ether over 20 min. The reaction was allowed to warm to room temperature over 1.5 h and was then acidified with 1N aqueous hydrochloric acid and extracted with ethyl acetate (3×200 mL). The combined organics were washed with brine (3×100 mL), dried (MgSO4), and concentrated to provide 10 g of crude material which was leached with ether/hexane to provide 4 g (37%) of product (25): mp 148°-150 ° C.; IR (KBr) 2070, 1600, 1575, 845 cm-1 ; 1H NMR (CDCl3, 200 MHz) 7.77 (ddd, 2H, J=0.5, 5.0, 8.7Hz), 7.14 (ddd, 2H, J=0.5, 2.5, 8.5Hz), 7.0 (ddd, 2H, J=2.3, 8.5, 9.3Hz); MS m/z 228 (M+), 200 (base peak). Anal. Calcd. for C13H6N2F2 : C, 68.42;H, 2.65; N, 12.28. Found: C, 68.25;H, 2.78; N, 12.50.

Workup

  1. custommay also be prepared
  2. custominto a 0° C.
  3. customprepared by the method
  4. extractionextracted with ethyl acetate (3×200 mL)
  5. washThe combined organics were washed with brine (3×100 mL)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated
  8. customto provide 10 g of crude material which

Sources & evidence

ORD record
ord-467c5567aa4a4b17af886a9780ef53ee
Source dataset
uspto-grants-1990_11
Patent number
US04968809

Reaction notes

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