2,2,2-Trifluoroacetaldehyde hydrate → 3-ethyl-3,4-dihydro-7-nitro-4-(2,2,2-trifluoroethyl)-2H-1,4-benzoxazine

HRID 990945Notes

Reaction equation

[CH2:1]([CH:3]1[NH:8][C:7]2[CH:9]=[CH:10][C:11]([N+:13]([O-:15])=[O:14])=[CH:12][C:6]=2[O:5][CH2:4]1)[CH3:2].O.[F:17][C:18]([F:22])([F:21])[CH:19]=O.[BH3-]C#N.[Na+]>>[CH2:1]([CH:3]1[N:8]([CH2:19][C:18]([F:22])([F:21])[F:17])[C:7]2[CH:9]=[CH:10][C:11]([N+:13]([O-:15])=[O:14])=[CH:12][C:6]=2[O:5][CH2:4]1)[CH3:2]

Participants

Reactant 3

HCID 27813662,2,2-Trifluoroacetaldehyde hydrate

HCID 5003444Sodium cyanoborohydride

HCID 166589403-ethyl-3,4-dihydro-7-nitro-2H-1,4-benzoxazine

Product 1

HCID 184161343-ethyl-3,4-dihydro-7-nitro-4-(2,2,2-trifluoroethyl)-2H-1,4-benzoxazineYield 36%

Procedure

This compound was prepared by General Method 7 (EXAMPLE 5) from (±)-3-ethyl-3,4-dihydro-7-nitro-2H-1,4-benzoxazine (200 mg, 0.96 mmol), 2,2,2-trifluoroacetaldehyde monohydrate (1.12 g, 9.6 mmol) and NaBH3CN (292 mg, 4.6 mmol) to afford 100 mg (36%) of 3-ethyl-3,4-dihydro-7-nitro-4-(2,2,2-trifluoroethyl)-2H-1,4-benzoxazine, a yellow solid. Data for (±)-3-ethyl-3,4-dihydro-7-nitro-4-(2,2,2-trifluoroethyl)-2H-1,4-benzoxazine: Rf 0.69 (2:3 EtOAc:hexanes); 1H NMR (500 MHz, CDCl3) δ 7.80 (dd, 1H, J=8.9, 2.6), 7.71 (d, 1H, J=2.6), 6.72 (d, 1H, J=9.0), 4.34 (dd, 1H, J=10.9, 1.4), 4.19-4.05 (m, 1H), 4.02 (dd, 1H, J=11.0, 2.3), 3.87-3.72 (m, 1H), 1.72-1.62 (m, 2H), 1.00 (t, 34H, J=7.4).

Sources & evidence

ORD record: ord-9ccbfbe63ffa4d9ba2111190b58cc50f
Source dataset: uspto-grants-2002_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06462038B1

Reaction notes

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