Nitrogen mustard hydrochloride → 4-(3-Chlorophenyl)-1-methylpiperidine-4-carbonitrile

HRID 2416916

Reaktionsgleichung

Reaktionsgleichung von HRID 2416916
Cl.Cl[CH2:3][CH2:4][N:5]([CH3:9])[CH2:6][CH2:7]Cl.[Cl:10][C:11]1[CH:12]=[C:13]([CH:17]=[CH:18][CH:19]=1)[CH2:14][C:15]#[N:16].[OH-].[Na+]>[Br-].C([P+](CCCC)(CCCC)CCCC)CCCCCCCCCCCCCCC.O>[Cl:10][C:11]1[CH:12]=[C:13]([C:14]2([C:15]#[N:16])[CH2:7][CH2:6][N:5]([CH3:9])[CH2:4][CH2:3]2)[CH:17]=[CH:18][CH:19]=1

Komponenten

6

Edukt 3

HCID 5935Nitrogen mustard hydrochlorideHCID 14798Sodium HydroxideHCID 73722m-Chlorophenylacetonitrile

Produkt 1

HCID 108574034-(3-Chlorophenyl)-1-methylpiperidine-4-carbonitrileAusbeute 88 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 84716Hexadecyltributylphosphonium bromideKatalysatorHCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

The starting material, 4-(3-chlorophenyl)-1-methylpiperidine-4-carbonitrile was prepared as follows by the procedure of T. Cammack and P. C. Reeves, J. Heterocycl. Chem., 23, 73 (1986): a mixture of 100 g (0.52 mole) of N,N-bis(chloroethyl)methylamine hydrochloride, 80 g (0.53 mole) of 3-chlorobenzyl cyanide, 13 g of hexadecyltributyl-phosphonium bromide and 750 mL of 50% aqueous sodium hydroxide was stirred at 100° C. internal temperature for 1 hour. Water (750 mL) was added to the cooled mixture that was then extracted with 500 mL and three 100-mL portions of toluene. Removal of the solvent from the dried/solution and rapid short-path distillation of the residue (160° C. bath temperature, 0.1 mm) gave 107.2 g (88% yield) of 4-(3-chlorophenyl)-1-methylpiperidine-4-carbonitrile as a colorless oil which slowly crystallizes. 1H NMR (CDCl3): δ 7.5 (s,1H); 2.3 (m,3H); 3.0 (d,2H); 2.5 (m,2H); 2.4 (s,3H) and 2.1 (m,4H). The hydrochloride had m.p 235° C.-236° C. after crystallization from isopropyl alcohol.

Aufarbeitung

  1. customThe starting material, 4-(3-chlorophenyl)-1-methylpiperidine-4-carbonitrile was prepared
  2. extractionwas then extracted with 500 mL and three 100-mL portions of toluene
  3. customRemoval of the solvent
  4. distillationfrom the dried/solution and rapid short-path distillation of the residue (160° C. bath temperature, 0.1 mm)

Quellen und Nachweise

ORD-Eintrag
ord-0ed1e978ce6f4b2f96c5889f322707fe
Quelldatensatz
uspto-grants-2004_11
Patentnummer
US06825217B2

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