Triphenylphosphine → HCID 22905239, compound

HRID 1376645Notes

Reaction equation

HRID 1376645 reaction equation
[CH2:1]([N:4]([CH2:15][CH:16]([OH:24])[CH2:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:5](=[O:14])[C:6]1[CH:11]=[C:10]([I:12])[CH:9]=[CH:8][C:7]=1O)[CH:2]=[CH2:3].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[CH2:1]([N:4]1[CH2:15][CH:16]([CH2:17][C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[O:24][C:7]2[CH:8]=[CH:9][C:10]([I:12])=[CH:11][C:6]=2[C:5]1=[O:14])[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 22904902HCID 22904902, compound

Product 1

HCID 22905239HCID 22905239, compoundYield 38.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a magnetically stirred solution of N-allyl-N-(2-hydroxy-5-iodobenzoyl)-2-hydroxy-3-phenylpropylamine (12.05 grams, 0.027 mol) in 100 mL THF was added triphenylphosphine (7.24 grams, 0.027 mol), and diethyl azodicarboxylate (4.7 grams, 0.027 mol). The mixture was heated to reflux overnight, allowed to cool to room temperature, and concentrated in vacuo. the resulting residue was dissolved in ethyl acetate (10 mL) and diluted with diethyl ether. The solids that form were filtered and the mother liquor was concentrated in vacuo. The yellow oil was purified by column chromatography (SiO2, using 15% diethyl ether/85% hexane to 1:1 diethyl ether/hexane as the eluting solvent gradient, Rf(product, 1:1 Et2O/heaxane)=0.64) to yield 4.31 grams (38%) of 2-allyl-4-benzyl-8-iodo-2,3,4,5-tetrahydro-1H-5-oxa-2-benzazepin-1-one. 1H NMR (CDCl3, dTMS) 8.10 (1H, d, 4JHH =2 Hz, C9-H), 7.69 (1H, dd, 4JHH =2 Hz, 3JHH =9 Hz, C7-H), 7.4-7.2 (5H, m, C6H5), 6.76 (1H, d, 3JHH =9 Hz, C6-H), 5.79 (1H, ddt, 3JHH =17 Hz, 3JHH =11 Hz, 3JHH =6 Hz, CH2CH=CH2), 5.2-5.0 (2H, m, CH=CH2), 5.71 (1H, m, CHOH), 4.31 (1H, ddt, 2JHH =15 Hz, 3JHH =6 Hz, 4JHH =1 Hz, NCHHCH=CH2), 4.00 (1H, ddt, 2JHH =15 Hz, 3JHH =6 Hz, 4JHH =1 Hz, NCHHCH=CH2), 3.34 (1H, dd, 2JHH =16 Hz, 3JHH =5.1 Hz, C3-H), 3.25 (1H, dd, 2JHH =16 Hz, 3JHH =4.2 Hz, C3-H), 3.09 (1H, dd, 2JHH =14 Hz, 3JHH =7 Hz, CHHPh), 2.73 (1H, dd, 2JHH =14 Hz, 3JHH =7 Hz, CHHPh). 13C NMR (CDCl3) 166.9, 152.7, 141.4, 139.6, 136.5, 132.6, 129.8, 129.1, 128.8, 127.0, 124.6, 118.4, 86.7, 84.7, 50.4, 48.9, 38.9. IR (NaCl, cm-1) 1641, 1589, 1463, 1430, 1264, 1217, 699.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux overnight
  3. concentrationconcentrated in vacuo
  4. dissolutionthe resulting residue was dissolved in ethyl acetate (10 mL)
  5. additiondiluted with diethyl ether
  6. filtrationThe solids that form were filtered
  7. concentrationthe mother liquor was concentrated in vacuo
  8. customThe yellow oil was purified by column chromatography (SiO2

Sources & evidence

ORD record
ord-66960b912675441b834f433a64c96d9f
Source dataset
uspto-grants-1997_09
Patent number
US05663166

Reaction notes

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