Water → HCID 86724157, compound

HRID 1748836Notes

Reaction equation

HRID 1748836 reaction equation
[CH3:1]N(N=O)C(N[N+]([O-])=O)=N.[OH-].[K+].O.[CH3:14][C:15]1[CH:16]=[C:17]([CH:21]=[CH:22][C:23]=1[CH:24]1[C:33]2[C:32]([C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][N:35]=3)=[N:31][N:30]([CH3:40])[C:29]=2[CH2:28][C:27](=[O:41])[CH2:26][CH2:25]1)[C:18]([OH:20])=[O:19]>C1COCC1.CCOCC>[CH3:14][C:15]1[CH:16]=[C:17]([CH:21]=[CH:22][C:23]=1[CH:24]1[C:33]2[C:32]([C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][N:35]=3)=[N:31][N:30]([CH3:40])[C:29]=2[CH2:28][C:27](=[O:41])[CH2:26][CH2:25]1)[C:18]([O:20][CH3:1])=[O:19]

Participants

7

Reactant 4

HCID 962WaterHCID 14797Potassium HydroxideHCID 86724158HCID 86724158, compoundHCID 135436526N-Methyl-N'-nitro-N-nitrosoguanidine

Product 1

HCID 86724157HCID 86724157, compoundYield 88.4%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent4×HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

In an Erlenmeyer flask, 1-methyl-3-nitro-1-nitrosoguanidine (1.20 g, 8.16 mmol, TCI) was added portionwise to 45% KOH (10 mL)/H2O (5 mL) and Et2O (24 mL) at 0° C. The mixture was stirred until the yellow color of the ether layer did not change in intensity. The solution was poured into a separatory funnel and the aqueous layer was drained. The ether layer was poured into an Erlenmeyer flask and then decanted into another to remove some residual water. The yellow ether solution was poured slowly into a solution of 3-methyl-4-(1-methyl-7-oxo-3-(pyridin-2-yl)-1,4,5,6,7,8-hexahydrocyclohepta[c]pyrazol-4-yl)benzoic acid (0.240 g, 0.639 mmol) in THF (12 mL) cooled to about 0° C. in an ice bath. The ice bath was allowed to melt. The mixture was diluted with THF (12 mL) and a nitrogen stream was blown over the surface until the solution turned from yellow to colorless. The mixture was concentrated in vacuo to give methyl 3-methyl-4-(1-methyl-7-oxo-3-(pyridin-2-yl)-1,4,5,6,7,8-hexahydrocyclohepta[c]pyrazol-4-yl)benzoate (0.220 g, 88%): LC-MS (Table 1, Method g) Rt=2.09 min, m/z 390 (M+H)+; 1H-NMR (DMSO, Bruker 400 MHz) δ 8.30-8.24 (m, 1H), 7.71-7.64 (m, 2H), 7.62-7.57 (m, 1H), 7.45-7.41 (m, 1H), 7.08-7.01 (m, 1H), 6.73-6.69 (m, 1H), 5.30-5.26 (m, 1H), 4.28-4.17 (m, 1H), 3.96 (d, J=15.6 Hz, 1H), 3.89 (s, 3H), 3.75 (s, 3H), 2.63-2.56 (m, 4H), 2.39-2.30 (m, 2H), 2.19-2.07 (m, 1H).

Workup

  1. additionThe solution was poured into a separatory funnel
  2. customdecanted into
  3. customanother to remove some residual water
  4. concentrationThe mixture was concentrated in vacuo

Sources & evidence

ORD record
ord-95b694d9574b46d6a66d3a66e1fa8375
Source dataset
uspto-grants-2015_10
Patent number
US09150592B2

Reaction notes

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