Triphenylphosphine → HCID 86653601, compound

HRID 1892009Notes

Reaction equation

HRID 1892009 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2([CH3:20])[C:13]([C:14]([O:16][CH3:17])=[O:15])=[CH:12][CH2:11][CH:10]([CH2:18]O)[CH2:9]2)=[CH:4][C:3]=1[C:21]([F:24])([F:23])[F:22].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[NH:44]=[N+:45]=[N-:46].N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[N:44]([CH2:18][CH:10]1[CH2:9][C:8]([C:5]2[CH:6]=[CH:7][C:2]([Cl:1])=[C:3]([C:21]([F:24])([F:23])[F:22])[CH:4]=2)([CH3:20])[C:13]([C:14]([O:16][CH3:17])=[O:15])=[CH:12][CH2:11]1)=[N+:45]=[N-:46]

Participants

6

Reactant 4

HCID 11776Triphenylphosphine2×HCID 24530Hydrazoic acid2×HCID 220568ethyl N-ethoxycarbonyliminocarbamate2×HCID 86653598HCID 86653598, compound

Product 1

HCID 86653601HCID 86653601, compoundYield 51.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of methyl (4RS,6RS)-6-(4-chloro-3-(trifluoromethyl)phenyl)-4-(hydroxymethyl)-6-methylcyclohex-1-enecarboxylate (Example 7, Step 9; 38.2 mg, 0.105 mmol) in THF (0.8 mL) was treated sequentially with triphenylphosphine (83 mg, 0.316 mmol), hydrazoic acid (ca. 2M in benzene, 0.211 mL, 0.421 mmol) and diethyl azodicarboxylate (0.050 mL, 0.316 mmol). The resulting mixture was stirred at rt for 19.5 h and then an additional amount of triphenylphosphine (83 mg, 0.316 mmol), diethyl azodicarboxylate (0.050 mL, 0.316 mmol) and hydrazoic acid (ca. 2M in benzene, 0.211 mL, 0.421 mmol) were added. The resulting mixture was stirred for a total of 43 h. After this time, the mixture was concentrated under vacuum to yield a residue. The residue was purified by column chromatography on silica gel, eluting with 5-50% ethyl acetate-hexanes, to provide methyl (4RS,6RS)-4-(azidomethyl)-6-(4-chloro-3-(trifluoromethyl)-phenyl)-6-methylcyclohex-1-enecarboxylate (21 mg, 51%). Mass spectrum m/z 405.0 (M+NH4+). 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J=2.4 Hz, 1 H), 7.40 (d, J=8.4 Hz, 1 H), 7.31 (dd, J=8.4, 2.4 Hz, 1 H), 7.25 (dd, J=5.5, 2.4 Hz, 1 H), 3.65 (s, 3 H), 3.17 (d, J=5.3 Hz, 2 H), 2.45 (m, 1 H), 2.01 (m, 1 H), 1.73 (m, 1 H), 1.66 (s, 3 H), 1.58 (m, 2 H).

Workup

  1. stirringThe resulting mixture was stirred for a total of 43 h
  2. concentrationAfter this time, the mixture was concentrated under vacuum
  3. customto yield a residue
  4. customThe residue was purified by column chromatography on silica gel
  5. washeluting with 5-50% ethyl acetate-hexanes

Sources & evidence

ORD record
ord-6dbcddfb803c4611a61ed1a51143e07a
Source dataset
uspto-grants-2013_08
Patent number
US08507559B2

Reaction notes

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