N-Hydroxyphthalimide → (S)-N-(2,2-Dimethyl-1,3-dioxolan-4-ylmethoxy)phthalimide

HRID 1089274Notes

Reaction equation

HRID 1089274 reaction equation
[CH3:1][C:2]1([CH3:9])[O:6][C@H:5]([CH2:7][OH:8])[CH2:4][O:3]1.O[N:11]1[C:15](=[O:16])[C:14]2=[CH:17][CH:18]=[CH:19][CH:20]=[C:13]2[C:12]1=[O:21].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[CH3:1][C:2]1([CH3:9])[O:6][C@H:5]([CH2:7][O:8][N:11]2[C:12](=[O:21])[C:13]3=[CH:20][CH:19]=[CH:18][CH:17]=[C:14]3[C:15]2=[O:16])[CH2:4][O:3]1

Participants

6

Reactant 4

HCID 10665N-HydroxyphthalimideHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 736056(R)-Solketal

Product 1

HCID 14814201(S)-N-(2,2-Dimethyl-1,3-dioxolan-4-ylmethoxy)phthalimide

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of (R)-2,2-dimethyl-1,3-dioxolane-4-methanol (7.3 g, 0.05 mol), N-hydroxyphthalimide (8.15 g, 0.05 mol) and triphenylphosphine (13.11 g, 0.05 mol) in tetrahydrofuran (200 ml) was cooled to 0° C. and stirred during the addition of diethyl azodicarboxylate (9.57 g, 0.066 mol). The dark red solution was stirred at 25° C. for 18 h when the colour had turned to pale yellow, and the solution was evaporated to dryness. The residue was extracted once with ether (200 ml) and the ether removed under reduced pressure. The residue was chromatographed in chloroform-hexane 10:1 affording (S)-N-(2,2-dimethyl-1,3-dioxolan-4-ylmethoxy)phthalimide (10.5 g, 69%) as a white solid; m.p. 99°-100° C., [α]D25 -14.6° (0.4 in MeOH); υmax (KBr) [α]D25 1790, 1730 and 1610 cm-1 ; δH (CDCl3) 1.35(3H,S,CH3), 1.4 (3H,S,CH3), 3.99(1H,q,J5.5,8.8 Hz,CH2ON/CH2OCMe2), 4.17(2H,m,1H of CH2ON+1H of CH2OCMe2), 4.32(1H,q,J5.7,10.1 Hz,CH2ON/CH2OCMe2), 4.50(1H,m,CH) and 7.75-7.87(4H,m,aromatic). Found: C, 60.53; H, 5.46; N, 5.03%. C14H15NO5 requires C, 60.64; H, 5.45; N, 5.05%.

Workup

  1. customwas evaporated to dryness
  2. extractionThe residue was extracted once with ether (200 ml)
  3. customthe ether removed under reduced pressure
  4. customThe residue was chromatographed in chloroform-hexane 10:1 affording (S)-N-(2,2-dimethyl-1,3-dioxolan-4-ylmethoxy)phthalimide (10.5 g, 69%) as a white solid

Sources & evidence

ORD record
ord-6dfa7553cef7402588712929bed22e9f
Source dataset
uspto-grants-1990_10
Patent number
US04965270

Reaction notes

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