Sulfuric Acid → HCID 19040669, compound

HRID 1683766Notes

Reaction equation

HRID 1683766 reaction equation
[Cl:1][C:2]1[C:7]2[CH2:8][CH2:9][N:10]([CH3:13])[CH2:11][CH2:12][C:6]=2[C:5](N)=[CH:4][CH:3]=1.S(=O)(=O)(O)O.N([O-])=O.[Na+].[C-:24]#[N:25].[K+].C(=O)(O)[O-].[Na+].[OH-].[Na+]>C(O)(=O)C.O.C1(C)C=CC=CC=1>[Cl:1][C:2]1[C:7]2[CH2:8][CH2:9][N:10]([CH3:13])[CH2:11][CH2:12][C:6]=2[C:5]([C:24]#[N:25])=[CH:4][CH:3]=1

Participants

10

Reactant 6

HCID 1118Sulfuric AcidHCID 9032Potassium CyanideHCID 14798Sodium HydroxideHCID 516892Sodium Bicarbonate2×HCID 13338332HCID 13338332, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 19040669HCID 19040669, compoundYield 79.2%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolvent5×HCID 1140TolueneSolvent

Conditions

Temperature
5 °C

Procedure

A solution of 9-chloro-2,3,4,5-tetrahydro-3-methyl-1H-3-benzazepin-6-amine, (10 g, 47.5 mmol) in acetic acid (34 ml) and water (20 ml) was stirred, treated with sulfuric acid (7.5 ml), cooled to 5° C. and treated with a solution of sodium nitrite (3.65 g, 53 mmol) in water (7.5 ml) added below the surface over 20 minutes. The mixture was added dropwise under the surface of a stirred mixture prepared from cupric sulfate pentahydrate (14.2 g, 57 mmol) in water (35 ml), potassium cyanide (15.4 g, 240 mmol), ice (24 g), sodium bicarbonate (31.8 g, 380 mmol) in water (36 ml) and toluene (35 ml) at 50°-55° C. The mixture was stirred for 15 minutes at 50° C. and for 1 hour at 25° C., treated with a solution of sodium bicarbonate (70 g) in water (700 ml) to pH 8 and then with 10% sodium hydroxide (300 ml). The mixture was extracted with ethyl acetate and the organic phase was washed with aqueous sodium hydroxide and brine, dried with magnesium sulfate and concentrated. The residual oil was treated with ethereal hydrogen chloride to give 8.3 g (68%) of 9-chloro-2,3,4,5-tetrahydro-3-methyl-1H-3-benzazepine-6-carbonitrile; mp 288°-290° C.

Workup

  1. additionadded below the surface over 20 minutes
  2. additionThe mixture was added dropwise under the surface of a stirred mixture
  3. customat 50°-55° C
  4. extractionThe mixture was extracted with ethyl acetate
  5. washthe organic phase was washed with aqueous sodium hydroxide and brine
  6. dry with materialdried with magnesium sulfate
  7. concentrationconcentrated
  8. additionThe residual oil was treated with ethereal hydrogen chloride

Sources & evidence

ORD record
ord-3ad7c9b8f0b345ac97b48d342d1a242a
Source dataset
uspto-grants-1997_06
Patent number
US05639748

Reaction notes

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