Hydrochloric Acid → Benzenediazonium chloride

HRID 255512Notes

Reaction equation

HRID 255512 reaction equation
C(OCC)=O.[CH2:6]([N:9]1[C@H:18]2[C@@H:13]([CH2:14][CH2:15][C:16](=[O:19])[CH2:17]2)[CH2:12][CH2:11][CH2:10]1)[CH2:7][CH3:8].[K].[ClH:21].C([O-])(=O)C.[Na+].NC1C=CC=CC=1.N#N.[Cl-].[C:37]1([N+:43]#[N:44])[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1>C1COCC1.O>[Cl-:21].[C:37]1([N+:43]#[N:44])[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1.[CH2:6]([N:9]1[C@H:18]2[C@@H:13]([CH2:14][C:15](=[N:44][NH:43][C:37]3[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=3)[C:16](=[O:19])[CH2:17]2)[CH2:12][CH2:11][CH2:10]1)[CH2:7][CH3:8]

Participants

12

Reactant 8

HCID 313Hydrochloric AcidHCID 947NitrogenHCID 6115AnilineHCID 8025Ethyl formateHCID 60992Benzenediazonium chlorideHCID 517045Sodium AcetateHCID 5462222PotassiumHCID 86741432HCID 86741432, compound

Product 2

HCID 60992Benzenediazonium chlorideHCID 86741431HCID 86741431, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

Alternatively, the above reaction was carried out using a reverse addition procedure: a solution was prepared from 5.5 ml of ethyl formate, 3.3 g of trans-(±)-1-n-propyl-7-oxodecahydroquinoline and 20 ml THF. This solution was added to a solution of 3.8 g of potassium t-tutoxide in 80 ml of THF. The reaction mixture was stirred for 2 hours at about 0° C. at which time TLC indicated that all the starting ketone had reacted. The pH was adjusted to about 6 by the addition of 10% hydrochloric acid. A solution of 7.2 g of sodium acetate in 20 ml of water was added. Next, a phenyldiazonium chloride solution was prepared as above from 1.6 g aniline. The solution of the trans-(±)-1-n-propyl-6-formyl-7-oxo-decahydroquinoline was cannulated rapidly under positive N2 pressure beneath the surface of the phenyldiazonium chloride solution held at 0° C. The reaction mixture was stirred at that temperature for 2 hours and then worked up as above. Flash chromatography yielded 43.5% of the desired trans-(±)-1-n-propyl-6-phenylhydrazono-7-oxodecahydroquinoline (compared with 31.4% by normal addition).

Workup

  1. customAlternatively, the above reaction
  2. additiona reverse addition procedure
  3. customhad reacted
  4. customheld at 0° C
  5. stirringThe reaction mixture was stirred at that temperature for 2 hours

Sources & evidence

ORD record
ord-af0be6e5156d4ea59ed09a7ff4eb05b9
Source dataset
uspto-grants-1987_10
Patent number
US04698347

Reaction notes

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