4-Chlorobenzylamine → HCID 12083039, compound

HRID 1168512Notes

Reaction equation

HRID 1168512 reaction equation
[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6][NH2:7])=[CH:4][CH:3]=1.C[Al](C)C.[N:14]1([CH2:20][C:21]2[CH:22]=[C:23]3[C:32]4[N:31]([CH:33]=2)[C:30](=[O:34])[C:29]([C:35](OCC)=[O:36])=[CH:28][C:27]=4[CH2:26][CH2:25][CH2:24]3)[CH2:19][CH2:18][O:17][CH2:16][CH2:15]1>C(Cl)Cl>[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6][NH:7][C:35]([C:29]2[C:30](=[O:34])[N:31]3[CH:33]=[C:21]([CH2:20][N:14]4[CH2:15][CH2:16][O:17][CH2:18][CH2:19]4)[CH:22]=[C:23]4[CH2:24][CH2:25][CH2:26][C:27]([CH:28]=2)=[C:32]34)=[O:36])=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 660364-ChlorobenzylamineHCID 12083038HCID 12083038, compoundHCID 16682925Trimethylaluminum

Product 1

HCID 12083039HCID 12083039, compoundYield 73%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 4-chlorobenzylamine (142 mg, delivered as a 1M methylene chloride solution) in anhydrous CH2Cl2 (3 mL), is added trimethylaluminum (482 μL, 2 M solution in heptane). After two hours at room temperature, ethyl 6-(morpholin-4-ylmethyl)-3-oxo-9,10-dihydro-3H,8H-pyrido[3,2,1-ij]quinoline-2-carboxylate (Preparation 18, 327 mg) is added as a solid in one portion. Stirring is continued for 2.5 hours before quenching with 10 mL of a 35% aqueous solution of Rochelle's salt. This biphasic, gelatinous mixture is stirred for two hours before separating the layers and extracting the aqueous layer five times with CH2Cl2. The resulting solution is concentrated in vacuo to give a bright yellow solid which is recrystallized from acetone (reflux, 62 mL/g) to afford 251 mg (73%) of the title compound as a canary yellow solid. Physical characteristics: M.p. 200-201° C.; 1H NMR (CDCl3); δ10.2, 9.07, 8.54, 7.41, 7.33, 7.28, 4.67, 3.71, 3.53, 3.02, 2.48, 2.02; 13C NMR (CDCl3): δ165.5, 157.5, 140.6, 138.6, 137.7, 134.7, 132.7, 130.9, 129.0, 128.6, 127.1, 125.2, 113.1, 109.2, 66.8, 60.4, 53.6, 42.9, 30.4, 28.7, 21.3; HRMS m/z 452.1747 (C25H26ClN3O3+H).

Workup

  1. waitis continued for 2.5 hours
  2. custombefore quenching with 10 mL of a 35% aqueous solution of Rochelle's salt
  3. stirringThis biphasic, gelatinous mixture is stirred for two hours
  4. custombefore separating the layers
  5. extractionextracting the aqueous layer five times with CH2Cl2
  6. concentrationThe resulting solution is concentrated in vacuo
  7. customto give a bright yellow solid which
  8. customis recrystallized from acetone (reflux, 62 mL/g)

Sources & evidence

ORD record
ord-c8e8f652d1b74cffa037a43f4217477d
Source dataset
uspto-grants-2003_09
Patent number
US06624159B2

Reaction notes

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