Carbon Tetrachloride → 113274-29-6

HRID 1650329Notes

Reaction equation

HRID 1650329 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:20]([N:25]([CH3:31])[N:26]=[N:27][CH2:28][CH2:29]O)([O:22][CH2:23][CH3:24])=[O:21].C(Cl)(Cl)(Cl)[Cl:33]>CCCCC>[C:20]([N:25]([CH3:31])[N:26]=[N:27][CH2:28][CH2:29][Cl:33])([O:22][CH2:23][CH3:24])=[O:21]

Participants

5

Reactant 3

HCID 5943Carbon TetrachlorideHCID 11776TriphenylphosphineHCID 14024259HCID 14024259, compound

Product 1

HCID 354113113274-29-6

Reagents, catalysts & solvents 1

HCID 8003PentaneSolvent

Procedure

6a. A solution of triphenylphosphine (2.83 g, 1.08×10-2 mol) and 3-carboethoxy-1-(2-hydroxyethyl)-3-methyltriazene, 5a. (1.89 g, 1.08×10-2 mol) in 25 mL of carbon tetrachloride (dried over 3A molecular sieves) was refluxed overnight under nitrogen. The reaction mixture was cooled to room temperature and diluted with pentane (100 mL). After standing at 10° C. for four hours, the reaction mixture was filtered through a pad of Celite to remove precipitated triphenylphosphine oxide. The filtrate was concentrated on a rotary evaporator at 22° C., redissolved in a minimum amount of ether and chromatographed on a column of 40 g of Silica Gel 60 packed in 1:10 ether-pentane and eluted with 200 mL each of 10%, 20% and 30% ether in pentane. The first 200 mL of eluent contained 1.4 g of a yellow oil. Distillation of that oil at reduced pressure with a short path distillation apparatus produced 1.22 g (6:30×10-3 mol, 58.3%) of the desired compound, 3-carboethoxy-(2-chloroethyl)-3-methyltriazene, 6a:bp 60°-62° C. (0.003 mm); IR (CCl4) 2990, 2970, 1730, 1155, 990 cm10-1 ; UV (CH3CN) λ max 2333 (log ε 4.19); 1H NMR 9CDCl3, Me4Si) δ 1.39 (0-CH2CH3,t,J=7 Hz), 3.28 (NCH3,s), 3.88 (Cl-CH2,t,J=6 Hz), 4.12 (CH2CH-N.t,J=6Hz), 4.39 (0--CH2CH3,q,J=7 Hz); proton decoupled 13C NMR (CDCl3, Me4Si) δ 14.47 (0--CH2CH3), 29.76 (N--CH3), 41.92 (Cl--CH2), 62.50 (CH2 --N), 63.17 (0--CH2CH3), 154.27 (C50 0); (1H and 13C NMR assignments made via 13C -APT and 2D-heteronuclear correlated spectrum (2D-COSY) experiments); exact mass calcd m/z for C6H12N23O2Cl 193.0618, found 193.0629 (by EI).

Workup

  1. filtrationthe reaction mixture was filtered through a pad of Celite
  2. customto remove
  3. customprecipitated triphenylphosphine oxide
  4. concentrationThe filtrate was concentrated on a rotary evaporator at 22° C.
  5. dissolutionredissolved in a minimum amount of ether
  6. customchromatographed on a column of 40 g of Silica Gel 60
  7. washeluted with 200 mL each of 10%, 20% and 30% ether in pentane
  8. distillationDistillation of that oil at reduced pressure
  9. distillationwith a short path distillation apparatus

Sources & evidence

ORD record
ord-9cc17e760c7f46588cfc479071e83cb7
Source dataset
uspto-grants-1990_05
Patent number
US04923970

Reaction notes

Loading…