Sulfuric Acid → 4-[1-(acetoxymethyl)propyl]-N-(1,3-dithiolan-2-ylidene)aniline dihydrogen sulfate

HRID 1074449Notes

Reaction equation

HRID 1074449 reaction equation
S1CCSC1=NC1C=CC(C(CC)CO)=CC=1.C(Cl)(=O)C.[C:22]([O:25][CH2:26][CH:27]([C:30]1[CH:41]=[CH:40][C:33]([N:34]=[C:35]2[S:39][CH2:38][CH2:37][S:36]2)=[CH:32][CH:31]=1)[CH2:28][CH3:29])(=[O:24])[CH3:23].[S:42](=[O:46])(=[O:45])([OH:44])[OH:43]>C(Cl)Cl.C(OCC)C.C(N(CC)CC)C>[S:42]([OH:46])([OH:45])(=[O:44])=[O:43].[C:22]([O:25][CH2:26][CH:27]([C:30]1[CH:41]=[CH:40][C:33]([N:34]=[C:35]2[S:39][CH2:38][CH2:37][S:36]2)=[CH:32][CH:31]=1)[CH2:28][CH3:29])(=[O:24])[CH3:23]

Participants

8

Reactant 4

HCID 1118Sulfuric AcidHCID 6367Acetyl chlorideHCID 131457192-[4-(1,3-Dithiolan-2-ylideneamino)phenyl]butanolHCID 131457214-[1-(acetoxymethyl)propyl]-N-(1,3-dithiolan-2-ylidene)aniline

Product 1

HCID 204967074-[1-(acetoxymethyl)propyl]-N-(1,3-dithiolan-2-ylidene)aniline dihydrogen sulfate

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolvent2×HCID 6344DichloromethaneSolvent2×HCID 8471TriethylamineSolvent

Procedure

To a mixture of 3 g of 2-[4-(1,3-dithiolan-2-ylideneamino)phenyl]butanol and 1.25 g of triethylamine in 50 ml of dried methylene chloride was added dropwise a solution of 0.88 g of acetyl chloride in 25 ml of methylene chloride. The resulting solution was stirred at room temperature for 3 hours. It was then washed once with 0.1 N hydrochloric acid, twice with water, and once with saturated aqueous sodium chloride solution and dried over magnesium sulfate. The solid was removed to leave a crude orange oil which was purified by flash chromatography using 15 cm of silica gel and ethyl acetate/hexane as eluant. This gave a colorless oil which was 4-[1-(acetoxymethyl)propyl]-N-(1,3-dithiolan-2-ylidene)aniline. This oil was dissolved in 150 ml of diethyl ether and there was added dropwise a solution of 1.2 g of sulfuric acid in 75 ml of diethyl ether. When the addition was complete, the mixture was placed in a freezer. The precipitate which formed was separated by filtration and recrystallized from acetone/diethyl ether to give 4-[1-(acetoxymethyl)propyl]-N-(1,3-dithiolan-2-ylidene)aniline dihydrogen sulfate as white platelets melting at about 128.5°-131° C. The free base of this compound has the following structural formula ##STR4##

Workup

  1. washIt was then washed once with 0.1 N hydrochloric acid, twice with water
  2. dry with materialonce with saturated aqueous sodium chloride solution and dried over magnesium sulfate
  3. customThe solid was removed
  4. customto leave a crude orange oil which
  5. customwas purified by flash chromatography
  6. customThis gave a colorless oil which
  7. additionWhen the addition
  8. customThe precipitate which formed
  9. customwas separated by filtration
  10. customrecrystallized from acetone/diethyl ether

Sources & evidence

ORD record
ord-492bb6fb2fa041119b0dd62321355359
Source dataset
uspto-grants-1983_07
Patent number
US04391818

Reaction notes

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