Phosphorus oxychloride → HCID 86655313, compound

HRID 222060Notes

Reaction equation

[CH3:1][N:2]1[CH2:7][CH2:6][N:5]([CH2:8][CH2:9][N:10]2[C:14]3[CH2:15][CH2:16][C:17]4[C:18]5[C:19](O)=[N:20][CH:21]=[N:22][C:23]=5[S:24][C:25]=4[C:13]=3[CH:12]=[N:11]2)[CH2:4][CH2:3]1.O=P(Cl)(Cl)[Cl:29]>>[Cl:29][C:19]1[N:20]=[CH:21][N:22]=[C:23]2[C:18]=1[C:17]1[CH2:16][CH2:15][C:14]3[N:10]([CH2:9][CH2:8][N:5]4[CH2:6][CH2:7][N:2]([CH3:1])[CH2:3][CH2:4]4)[N:11]=[CH:12][C:13]=3[C:25]=1[S:24]2

Participants

Reactant 2

HCID 24813Phosphorus oxychloride

HCID 178480890HCID 178480890, compound

Product 1

HCID 86655313HCID 86655313, compoundYield 71.4%

Conditions

Temperature: 105 °C

Procedure

A suspension of 3-[2-(4-methyl-piperazin-1-yl)-ethyl]-4,5-dihydro-3H-10-thia-2,3,7,9-tetraaza-cyclopenta[a]fluorene-6-ol (2 g, 5.4 mmol) in POCl3 (18 ml, 194 mmol) was heated at 105° C. (bath temperature) for 3 h. Analytical HPLC showed no more starting material and a new peak. Excess POCl3 was removed under vacuum and the residue was neutralized with 1N NaOH, extracted with CHCl3:isopropanol (v/v, 3/1). The organic phase was washed with brine, dried over Na2SO4, concentrated to afford a brown syrup, which was purified by silica gel column (CH2Cl2/2N NH3 in MeOH=100/8). The desire product was obtained as a light yellow solid (1.5 g, 71%). 1H-NMR (CD2Cl2-d2) δ 8.66 (s, 1H), 7.60 (s, 1H), 4.19 (t, 2H, J=6.2 Hz), 3.55 (t, 2H, J=8.5 Hz), 3.10 (t, 2H, J=8.3 Hz), 2.80 (t, 2H, J=6.0 Hz), 2.52-2.39 (b, 8H), 2.25 (s, 3H); LCMS RT=1.97 min; [M+H]+=389.4.

Workup

customExcess POCl3 was removed under vacuum
extractionextracted with CHCl3
washThe organic phase was washed with brine
dry with materialdried over Na2SO4
concentrationconcentrated
customto afford a brown syrup, which
customwas purified by silica gel column (CH2Cl2/2N NH3 in MeOH=100/8)

Sources & evidence

ORD record: ord-2d2ddbeccb97471fb6d7aa1e85e9e505
Source dataset: uspto-grants-2012_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08207172B2

Reaction notes

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