Salicylaldehyde → HCID 23345887, compound

HRID 1390522Notes

Reaction equation

HRID 1390522 reaction equation
[NH2:1][CH2:2][CH:3]1[CH2:8][CH2:7][NH:6][CH2:5][CH2:4]1.C(=O)C1C(=CC=CC=1)O.C(N(CC)CC)C.[CH2:25]([S:37]([C:40]1[C:41]([N+:64]([O-:66])=[O:65])=[C:42]([CH:46]=[C:47]([S:49]([CH2:52][CH2:53][CH2:54][CH2:55][CH2:56][CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][CH2:62][CH3:63])(=[O:51])=[O:50])[CH:48]=1)[C:43]([Cl:45])=[O:44])(=[O:39])=[O:38])[CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH3:36]>O1CCCC1.C1C=CC=CC=1>[ClH:45].[NH2:1][CH2:2][CH:3]1[CH2:8][CH2:7][N:6]([C:43](=[O:44])[C:42]2[CH:46]=[C:47]([S:49]([CH2:52][CH2:53][CH2:54][CH2:55][CH2:56][CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][CH2:62][CH3:63])(=[O:51])=[O:50])[CH:48]=[C:40]([S:37]([CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH3:36])(=[O:38])=[O:39])[C:41]=2[N+:64]([O-:66])=[O:65])[CH2:5][CH2:4]1

Participants

7

Reactant 4

HCID 6998SalicylaldehydeHCID 8471TriethylamineHCID 235274-(Aminomethyl)piperidineHCID 23345879HCID 23345879, compound

Product 1

HCID 23345887HCID 23345887, compound

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To 1.14 g. (0.01 mole) of 4-aminomethylpiperidine in 25 ml. benzene were added 1.22 g. (0.01 mole) salicylaldehyde dropwise with stirring. The volume was then reduced to about 10 ml. by distilling off benzene at atmospheric pressure. The concentrated yellow solution was mixed with 30 ml. of tetrahydrofuran (THF) and 1.01 g (0.01 mole) of triethylamine were added. The mixture was stirred and cooled in a cold-water bath while a solution of 6.5 g. (0.01 mole) of 3,5-didodecylsulfonyl-2-nitrobenzoyl chloride (see Example 1) in 40 ml. THF was added dropwise. After the addition, the reaction mixture was stirred for 30 min. at ambient temperature and filtered to remove the by-product, triethylamine hydrochloride. The solid was washed with a small amount of THF and discarded. The combined filtrate-and-THF wash was treated with 4 ml. 6N HCl and stirred about 15 hr. The resulting gelled solution was boiled to reduce the volume of the acidified filtrate to about 50 ml. At this point, the hot solution was diluted slowly with 75 ml. acetonitrile and rapid stirring. The diluted mixture was stirred at ambient temperature until cool. The white solid was collected on a funnel, washed with cold acetonitrile and dried. The yield of the desired product was 4.69 g. TLC of a sample of the product on silica gel with methanol-acetone (5:20) gave only one spot.

Workup

  1. distillationby distilling off benzene at atmospheric pressure
  2. additionThe concentrated yellow solution was mixed with 30 ml
  3. temperaturecooled in a cold-water bath while a solution of 6.5 g
  4. additionAfter the addition
  5. stirringthe reaction mixture was stirred for 30 min. at ambient temperature
  6. filtrationfiltered
  7. customto remove the by-product, triethylamine hydrochloride
  8. washThe solid was washed with a small amount of THF
  9. washThe combined filtrate-and-THF wash
  10. additionwas treated with 4 ml
  11. stirring6N HCl and stirred about 15 hr
  12. additionAt this point, the hot solution was diluted slowly with 75 ml
  13. stirringThe diluted mixture was stirred at ambient temperature
  14. temperatureuntil cool
  15. customThe white solid was collected on a funnel
  16. washwashed with cold acetonitrile
  17. customdried
  18. customTLC of a sample of the product on silica gel with methanol-acetone (5:20) gave only one spot

Sources & evidence

ORD record
ord-79ebcf7112a146648821e54fef5d8f42
Source dataset
uspto-grants-1979_02
Patent number
US04139389

Reaction notes

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