4-Nitrobenzenesulfonyl chloride → HCID 12071413, compound

HRID 2084594Notes

Reaction equation

HRID 2084594 reaction equation
[CH2:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH2:4][C@H:3]([C:11]([OH:13])=[O:12])[NH:2]1.[OH-].[Na+].C(Cl)Cl.O.[N+:20]([C:23]1[CH:28]=[CH:27][C:26]([S:29](Cl)(=[O:31])=[O:30])=[CH:25][CH:24]=1)([O-:22])=[O:21]>C(Cl)Cl.C(Cl)(Cl)Cl.Cl>[N+:20]([C:23]1[CH:24]=[CH:25][C:26]([S:29]([N:2]2[C@@H:3]([C:11]([OH:13])=[O:12])[CH2:4][C:5]3[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=3)[CH2:1]2)(=[O:31])=[O:30])=[CH:27][CH:28]=1)([O-:22])=[O:21]

Participants

8

Reactant 4

HCID 74044-Nitrobenzenesulfonyl chloride2×HCID 14798Sodium Hydroxide2×HCID 712398(R)-1,2,3,4-Tetrahydro-3-isoquinolinecarboxylic acidHCID 21908982Water methylene chloride

Product 1

HCID 12071413HCID 12071413, compoundYield 37%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent2×

Procedure

(3R)-1,2,3,4-Tetrahydro-3-isoquinolinecarboxylic acid (5.32 g) and sodium hydroxide (2.40 g) are added to a mixture of methylene chloride-water (200 ml-200 ml), and thereto is added dropwise a solution of 4-nitrophenylsulfonyl chloride (6.62 g) in methylene chloride (100 ml) under ice cooling over a period of 30 minutes. The mixture is stirred under ice cooling for 3 hours, and thereto are further added sodium hydroxide (1.20 g) and a solution of 4-nitrophenylsulfonyl chloride (3.32 g) in methylene chloride (60 ml) in this order. The mixture is stirred under ice cooling for 2 hours, and further stirred at room temperature for 17 hours, and the reaction mixture is diluted with chloroform and 10% hydrochloric acid. The chloroform layer is collected and washed with water and then with an aqueous saturated saline solution, dried over sodium sulfate and then treated with active carbon. Undissolved materials are filtered off from the chloroform layer, and the solvent is distilled off under reduced pressure. The residue is purified with a silica gel column chromatography (eluent, chloroform) and recrystallized from ethyl acetate-hexane to give (3R)-N-(4-nitrophenylsulfonyl)-1,2,3,4-tetrahydro-3-isoquinolinecarboxylic acid (4.01 g) as colorless crystals.

Workup

  1. stirringThe mixture is stirred under ice cooling for 2 hours
  2. stirringfurther stirred at room temperature for 17 hours
  3. customThe chloroform layer is collected
  4. washwashed with water
  5. dry with materialwith an aqueous saturated saline solution, dried over sodium sulfate
  6. additiontreated with active carbon
  7. filtrationUndissolved materials are filtered off from the chloroform layer
  8. distillationthe solvent is distilled off under reduced pressure
  9. customThe residue is purified with a silica gel column chromatography (eluent, chloroform)
  10. customrecrystallized from ethyl acetate-hexane

Sources & evidence

ORD record
ord-9c09540dc54648b6b1fdbd86a2a8f4b8
Source dataset
uspto-grants-2004_04
Patent number
US06716983B2

Reaction notes

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