Glycerol → HCID 13458531, compound

HRID 1247891Notes

Reaction equation

HRID 1247891 reaction equation
[CH2:1]([N:4]([CH2:16][CH2:17][CH3:18])[CH:5]1[CH2:14][C:13]2[C:12]([NH2:15])=[CH:11][CH:10]=[CH:9][C:8]=2[CH2:7][CH2:6]1)[CH2:2][CH3:3].O[CH2:20][CH:21]([CH2:23]O)O.II.S(=O)(=O)(O)O.[NH4+].[OH-]>>[CH2:16]([N:4]([CH2:1][CH2:2][CH3:3])[CH:5]1[CH2:6][CH2:7][C:8]2=[CH:9][CH:10]=[C:11]3[C:12]([N:15]=[CH:23][CH:21]=[CH:20]3)=[C:13]2[CH2:14]1)[CH2:17][CH3:18]

Participants

6

Reactant 5

HCID 753GlycerolHCID 807Iodine2×HCID 1118Sulfuric AcidHCID 14923Ammonium HydroxideHCID 13424113HCID 13424113, compound

Product 1

HCID 13458531HCID 13458531, compound

Conditions

Temperature
140 °C

Procedure

A mixture of N7,N7 -dipropyl-5,6,7,8-tetrahydro-1,7-naphthalenediamine (1.95 g, 0.008 mol), described by F.L.-E. Arvidsson et al., World Patent Application 81/03491, published Dec. 10, 1981, glycerol (4.7 mL, 0.064 mol) and iodine (0.05 g) was placed in a 250 mL round bottomed flask. The mixture was stirred at 20°-22° C. and concentrated sulfuric acid (6.5 mL, 0.120 mol) was added dropwise. The reaction soon commenced and the temperature rose to 70° C. and stayed at that point until the addition was complete. The flask was heated to 140° C. in an oil bath for 30 minutes. The reaction proceeded with evolution of SO2 and some iodine vapor. Thereafter, the reaction mixture was cooled to 20°-22° C. and then rendered alkaline by the dropwise addition of concentrated NH4OH. The mixture was extracted with chloroform. Insoluble polymeric material in the extract was removed by filtering the extract through a bed of diatomaceous earth. The filtrate was evaporated to dryness. The residue was taken up in diethyl ether. The solution was passed through a column of magnesium silicate, and the column washed with diethyl ether. The combined eluate was evaporated to give the title compound as a colorless oil. Treatment of the oil with a solution of HCl in diethyl ether, followed by recrystallization of the resulting solid from methanol gave the trihydrochloride salt of the title compound having mp 249°-255° C.; Anal. Calcd for C19H26N2.3HCl; C, 58,40% H, 7.48% N, 7.16%; Found: C, 58.62%, H, 7.22% N, 7.22%; the NMR (CDCl3) of the free base exhibited δ1.04 (t, 3H), 1.06 (t, 3H), 2.05 (m, 6H), 3.25 (m, 8H), 4.22 and 4.40 (m, 1H), 7.65 (d, J=8 Hz, 1H), 7.87 (2d, J=8 Hz, 1H), 7.95 (d, J= 8 Hz, 1H), 8.88 (2d, J=8 Hz, J=1.5 Hz, 1H), 9.19 (2d, J=8 Hz, J=1.5 Hz, 1H), 11.0 (broad, 2H).

Workup

  1. customThe reaction
  2. customrose to 70° C.
  3. additionstayed at that point until the addition
  4. temperatureThereafter, the reaction mixture was cooled to 20°-22° C.
  5. extractionThe mixture was extracted with chloroform
  6. customInsoluble polymeric material in the extract was removed
  7. filtrationby filtering the
  8. extractionextract through a bed of diatomaceous earth
  9. customThe filtrate was evaporated to dryness
  10. washthe column washed with diethyl ether
  11. customThe combined eluate was evaporated

Sources & evidence

ORD record
ord-0238a3db901c471790bf209d3f91154e
Source dataset
uspto-grants-1985_06
Patent number
US04521423

Reaction notes

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