Potassium Hydroxide → HCID 15938648, compound

HRID 982540Notes

Reaction equation

HRID 982540 reaction equation
C[Si](C)(C)[C:3](=[O:16])[C:4]([F:15])([F:14])[CH:5]([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[CH:6]=[CH2:7].[N+](=[CH:21][CH2:22][CH2:23][CH2:24][CH3:25])=[N-].C(N(N=O)C(N[N+]([O-])=O)=N)CCCC.[OH-].[K+]>C(OCC)C>[F:14][C:4]([F:15])([C:3](=[O:16])[CH2:21][CH2:22][CH2:23][CH2:24][CH3:25])[CH:5]([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[CH:6]=[CH2:7]

Participants

6

Reactant 4

HCID 14797Potassium HydroxideHCID 13434349HCID 13434349, compoundHCID 15207452HCID 15207452, compoundHCID 135483364N-Pentyl-N'-nitro-N-nitrosoguanidine

Product 1

HCID 15938648HCID 15938648, compoundYield 24%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
0 °C

Procedure

Trimethyl-(2,2-difluoro-3-phenyl-4-pentenoyl)silane (400 mg, 1.5 mmol) was dissolved in diethyl ether (10 ml). The resulting solution was cooled to 0° C. and etheral 1-diazopentane [prepared from 1-pentyl-3-nitro-1-nitrosoguanidine (0.6 g) added slowly to a two-phase mixture of aqueous KOH (0.67 g in 2 ml of water) and ethyl ether (10 ml)] was added dropwise. The mixture was then stirred at room temperature for 12 hours, refluxed for 0.5 hours and allowed to cool to room temperature. Excess diazopentane was destroyed and the enol ether hydrolyzed by the addition of excess aqueous acetic acid. The mixture was concentrated in vacuo to give 731 mg of crude product. This material was purified by flash chromatography using 1:4 chloroform:hexane as eluant. Pure fractions were combined and concentrated to provide 99 mg (24% yield) of title product as a viscous yellow oil. 1H-NMR(CDCl3)delta(ppm): 7.32 (m, 5H), 6.16 (ddd, 10 12 and 20 Hz, 1H), 5.32 (d, 12 Hz, 1H), 5.24 (d, 20 Hz, 1H), 4.06 (dt, 10 and 16 Hz, 1H), 2.50 (dt, 7 and 17 Hz, 1H), 2.28 (dt, 5 and 17 Hz, 1H), 1.45 (m, 2H), 1.16 (m, 4H), 0.84 (t, 6 Hz, 3H). 13C-NMR(CDCl3)delta(ppm): 134.87, 132.03, 129.51, 128.70, 127.93, 120,62, 120.40, 117.25, 114.00, 53.27, 52.98, 52.67, 37.86, 30.85, 22.24, 21.93, 13.79. IR (CDCl3) cm-1 : 2925, 1739. Mass spectrum m/e (relative intensity): M+ 276.1 (1).

Workup

  1. additionwas added dropwise
  2. temperaturerefluxed for 0.5 hours
  3. temperatureto cool to room temperature
  4. customExcess diazopentane was destroyed
  5. additionthe enol ether hydrolyzed by the addition of excess aqueous acetic acid
  6. concentrationThe mixture was concentrated in vacuo
  7. customto give 731 mg of crude product
  8. customThis material was purified by flash chromatography
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-7b11e8945949444586bc07ef808201fe
Source dataset
uspto-grants-1991_02
Patent number
US04996345

Reaction notes

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