1,2-Dimethoxyethane → 3-Nitro-4-(1,4-dioxaspiro[4.5]dec-7-en-8-yl)pyridine

HRID 2046783Notes

Reaction equation

COCCOC.C(=O)([O-])[O-].[Na+].[Na+].Cl[C:14]1[CH:19]=[CH:18][N:17]=[CH:16][C:15]=1[N+:20]([O-:22])=[O:21].CC1(C)C(C)(C)OB([C:31]2[CH2:40][CH2:39][C:34]3([O:38][CH2:37][CH2:36][O:35]3)[CH2:33][CH:32]=2)O1>C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl>[N+:20]([C:15]1[CH:16]=[N:17][CH:18]=[CH:19][C:14]=1[C:31]1[CH2:40][CH2:39][C:34]2([O:38][CH2:37][CH2:36][O:35]2)[CH2:33][CH:32]=1)([O-:22])=[O:21]

Participants

Conditions

Temperature: 110 °C

Procedure

A solution of DME (0.2 M) and 2M aq. sodium carbonate (1.7 equiv.) was purged with nitrogen for 20 min. Then 4-chloro-3-nitropyridine (1.6 equiv.), 4,4,5,5-tetramethyl-2-(1,4-dioxaspiro[4.5]dec-7-en-8-yl)-1,3,2-dioxaborolane (1.0 equiv.), Pd(dppf)Cl2-DCM (0.05 equiv.) were added and stirred in a sealed bomb at 110° C. The reaction was stirred at that temperature for 3.5 hours. The reaction was diluted with ethyl acetate, washed with water, dried over MgSO4, filtered, and concentrated. The residue was purified by column (ethyl acetate:hexanes=1:1 with 10% methanol) to give 3-nitro-4-(1,4-dioxaspiro[4.5]dec-7-en-8-yl)pyridine (83%). LC/MS (m/z): MH+=263.2, Rt=0.71.

Workup

stirringThe reaction was stirred at that temperature for 3.5 hours
washwashed with water
dry with materialdried over MgSO4
filtrationfiltered
concentrationconcentrated
customThe residue was purified by column (ethyl acetate:hexanes=1:1 with 10% methanol)

Sources & evidence

ORD record: ord-fcd3e4932ac043f0b6df4683e1e4d092
Source dataset: uspto-grants-2013_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08592455B2

Reaction notes

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