Isocyanate → HCID 14626126, compound

HRID 1638706Notes

Reaction equation

HRID 1638706 reaction equation
[NH2:1][C:2]1[C:11]2[C:6](=[CH:7][C:8]([O:14][CH3:15])=[C:9]([O:12][CH3:13])[CH:10]=2)[C:5]([CH3:16])=[N:4][C:3]=1[O:17][C:18](=[O:24])[N:19]([CH2:22][CH3:23])[CH2:20][CH3:21].C([O:28][C:29]1[N:30]=[C:31](C)[C:32]2[C:37]([C:38]=1[N+]([O-])=O)=CC(OC)=C(OC)C=2)(=O)C.[N-:47]=[C:48]=[O:49].[K+].[Br-]>C(Cl)Cl.CCO.C(OCC)(=O)C.C(Cl)(Cl)Cl>[CH2:3]([NH:47][C:48]([N:1]([C:2]1[C:11]2[C:6](=[CH:7][C:8]([O:14][CH3:15])=[C:9]([O:12][CH3:13])[CH:10]=2)[C:5]([CH3:16])=[N:4][C:3]=1[O:17][C:18](=[O:24])[N:19]([CH2:22][CH3:23])[CH2:20][CH3:21])[C:29]([NH:30][CH2:31][CH2:32][CH2:37][CH3:38])=[O:28])=[O:49])[CH2:2][CH2:11][CH3:10]

Participants

8

Reactant 4

HCID 105034IsocyanateHCID 253877Potassium BromideHCID 14626125HCID 14626125, compoundHCID 14626131HCID 14626131, compound

Product 1

HCID 14626126HCID 14626126, compound

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 6344DichloromethaneSolventHCID 21584013Chloroform ethylacetateSolvent

Procedure

To a solution of 4-amino-3-(diethylcarbamyloxy)-6,7-dimethoxy-1-methylisoquinoline (410.5 mg, 1.24 mmol) in methylene chloride (20 mL) was added n-butylisocyanate (2, 0.17 mL, 1.49 mmol, 1.2 eq.) and the solution was stirred at room temperature overnight. TLC analysis (40% ethyl acetate/chloroform) revealed the presence of a small amount of unreacted starting material. Therefore, additional isocyanate (0.17 mL, 1.49 mmol, 1.2 eq; total 0.34 mL, 2.98 mmol, 2.4 eq) was added and the mixture was stirred at room temperature overnight. Then the mixture was heated to reflux for an additional 48 hours. The crude mixture was separated on a low pressure silica gel column using ether/petroleum ether. Two products were isolated. The slower moving product is described in Example 6b. The faster moving product weighed 205 mg (31%) and had mp 138°-140° C. IR (KBr): 3360, 1700, 1650, 1610, 1500, 1420, 1142 cm-1 ; NMR (CDCl3): δ 0.85 (br t, J=7 Hz, 6H, N(CH2 -CH3)2 ], 1.10-1.70 [br m, 14H, N(CH2CH3)2 +H2C(CH2)2 -CH3 ], 2.88 (s, 3H, 1-CH3), 3.0-3.70 [m, 8H, CON(CH2CH3)2 +N[CH2 (CH2)2CH3 ]2, 3.95 (s, 3H, OCl4)3OCH3 4.02 (s, 3H, OCH3), 6.88 (s, 1H, 5- or 8-H), 7.27 (s, 1H, 5- or 8-H), 7.35 (m, 1H, CONH); MS (FAB): 532 (MH)+ ; UV (EtOH) nm: 241 (ε59060), 273 (ε4740), 286 (ε4700), 298 (ε4755), 322 (ε4390), 344 (ε4700).

Workup

  1. stirringthe mixture was stirred at room temperature overnight
  2. temperatureThen the mixture was heated
  3. temperatureto reflux for an additional 48 hours
  4. customThe crude mixture was separated on a low pressure silica gel column
  5. customTwo products were isolated

Sources & evidence

ORD record
ord-2c1ae3474b3242b0ba02e51467991d27
Source dataset
uspto-grants-1989_11
Patent number
US04880817

Reaction notes

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