Hydrogen Bromide → HCID 13507932, compound

HRID 542993Notes

Reaction equation

HRID 542993 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.C[SiH](C)C.BrBr.S(=O)(O)[O-:18].[Na+].[K+].[Br-:23].Br.[CH2:25]1[CH2:29][O:28][CH2:27][CH2:26]1>C(#N)C.C1CCCCC1>[CH3:25][CH:26]([CH:6]1[CH:7]([Br:23])[C:2]([Cl:1])=[CH:3][CH:4]=[C:5]1[N+:8]([O-:10])=[O:9])[C:27]([O:28][CH3:29])=[O:18]

Participants

10

Reactant 7

HCID 260Hydrogen BromideHCID 74741-Chloro-4-nitrobenzeneHCID 8028Tetrahydrofuran2×HCID 24408BromineHCID 70435TrimethylsilaneHCID 253877Potassium BromideHCID 23665763Sodium Bisulfite

Product 1

HCID 13507932HCID 13507932, compound

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8078CyclohexaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 0.779 g (5.00 mmol) of 4-chloronitrobenzene and 0.930 mL (5.04 mmol) of [1-methoxy-1-propenyl)oxy]trimethylsilane (MTS) in 15 mL of anhydrous THF was added 1.348 g (4.90 mmol) of tris(dimethylamino)sulfonium trimethyldifluorosilicate (TASF) in 4 mL of THF and 2 mL of acetonitrile in 10 min at -78° C. The mixture was stirred for 45 min at -78° C. A solution of 0.250 mL (4.88 mmol) of bromine in 2 mL of cyclohexane was added, and the mixture was stirred for 15 min. After warming to room temperature, 20 mL of saturated sodium bisulfite was added. Extraction with four 50 mL portions of ether gave a product mixture from which, after separation by column chromatography, 0.233 g (14%) of the named produced was obtained. The following analytical data was obtained: IR (KBr): 1740, 1525, 1345 cm-1 ; 1HNMR: δ 7.55 (d, J=6 Hz), 7.48 (d, J=6 Hz) together 1H, 6.30 (d, m, J=6 Hz), 6.34 (d, m, J=6 Hz) together 1H), 5.00 (s, br), 4.90 (s, br) together 1H, 4.15 (d, m, J=5 Hz), 3.97 (d, m, J=5 Hz) together 1H, 3.74 (s), 3.67 (s) together 3H 2.83 (m, 1H), 1.22 (d, J=7 Hz), 1.15 (d, J=7 Hz) together 3H; HRMS: M+ --HBr,--NO2 197.0366; calculated for C10H10O2Cl 197.0369; Chemical ionization mass spectrum: M+ 323 and showed the presence of 1Cl, 1Br, and an odd number of N.

Workup

  1. stirringthe mixture was stirred for 15 min
  2. temperatureAfter warming to room temperature
  3. extractionExtraction with four 50 mL portions of ether
  4. customgave a product mixture from which
  5. customafter separation by column chromatography, 0.233 g (14%) of the
  6. customnamed produced
  7. customwas obtained
  8. customThe following analytical data was obtained

Sources & evidence

ORD record
ord-7e2c3e6b74654dc4bc45bc90c403daca
Source dataset
uspto-grants-1987_04
Patent number
US04659862

Reaction notes

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