Ammonia → HCID 68980724, compound

HRID 28344Notes

Reaction equation

HRID 28344 reaction equation
[OH:1][CH2:2][C:3]#[C:4][C:5]1[C:6](=[O:20])[NH:7][C:8](=[O:19])[N:9]([CH:18]=1)[C@@H:10]1[O:17][C@H:14]([CH2:15][OH:16])[C@@H:12]([OH:13])[CH2:11]1.[N+:21]([C:24]1[CH:29]=[CH:28][C:27](O)=[CH:26][CH:25]=1)([O-:23])=[O:22].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O.N>C1COCC1>[N+:21]([C:24]1[CH:29]=[CH:28][C:27]([O:1][CH2:2][C:3]#[C:4][C:5]2[C:6](=[O:20])[NH:7][C:8](=[O:19])[N:9]([CH:18]=2)[C@@H:10]2[O:17][C@H:14]([CH2:15][OH:16])[C@@H:12]([OH:13])[CH2:11]2)=[CH:26][CH:25]=1)([O-:23])=[O:22]

Participants

7

Reactant 5

HCID 222AmmoniaHCID 9804-NitrophenolHCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 159576762'-Deoxy-5-(3-hydroxyprop-1-yn-1-yl)uridine

Product 1

HCID 68980724HCID 68980724, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

A solution of pre-dried 5-(3-hydroxy-1-propynyl)-2′-deoxyuridine (“Nucleic Acid Compounds. 39. Efficient Conversion of 5-Iodo to 5-Alkynyl and Derived 5-Substituted Uracil Bases and Nucleosides” Robins and Barr, (1983) supra) (565 mg, 2 mmol) in 40 mL of anhydrous THF under argon was treated with 4-nitrophenol (696 mg, 5 mmol), triphenylphosphine (787 mg, 3 mmol), and diisopropyl azodicarboxylate (590 L, 3 mmol), and the reaction mixture heated at 60° C. until the solution was clear, and then 1 h longer. The mixture was allowed to cool to 23° C. and then it was evaporated onto SiO2 and purified by chromatography using MeOH/CH2Cl2 as eluent to afford 107 mg (13%) of the desired ether product: mp 112-118° C. 1H NMR((CD3)2SO) δ 11.65 (s, exchanges with D20, 1, NH), 8.29 (s, 1, H6), 8.24 (d, J=9.3 Hz, 2, m-ArH), 7.23 (d, J=9.3 Hz, 2, o-ArH), 6.09 (pseudo-t, 1, H1′), 5.17 (s, 2, propargyl-CH2), 4.22 (m, 1, H3), 3.80 (m, 1, H4′), 3.59 (m, 2,5′-CH2), 2.13 (pseudo-t, 2,2′-CH2). Low-resolution mass spectrum (DCI-NH3) on per-trimethylsilyated material, m/z 547 [M(TMS)2H+], 565 [M(TMS)2NH4+], 620 [M(TMS)3H+].

Workup

  1. custom1 h
  2. temperatureto cool to 23° C.
  3. customit was evaporated onto SiO2
  4. custompurified by chromatography
  5. customto afford 107 mg (13%) of the desired ether product

Sources & evidence

ORD record
ord-23f057ddf8f14869a199b797ef97f0e7
Source dataset
uspto-grants-2008_09
Patent number
US07419968B1

Reaction notes

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