Lithium borohydride → HCID 67421332, compound

HRID 1987347Notes

Reaction equation

HRID 1987347 reaction equation
[CH3:1][O:2][C:3](=[O:35])[C:4]1[CH:13]=[CH:12][C:11]([CH2:14][N:15]2[CH:20]([C:21]3[C:26]([CH3:27])=[CH:25][CH:24]=[CH:23][N:22]=3)[CH2:19][CH2:18][CH2:17][CH:16]2[C:28]2[C:33]([CH3:34])=[CH:32][CH:31]=[CH:30][N:29]=2)=[C:6]([C:7]([O:9][CH3:10])=[O:8])[CH:5]=1.[Li+].[BH4-]>C1COCC1.CO.[OH-].[Na+]>[CH3:1][O:2][C:3](=[O:35])[C:4]1[CH:13]=[CH:12][C:11]([CH2:14][N:15]2[CH:16]([C:28]3[C:33]([CH3:34])=[CH:32][CH:31]=[CH:30][N:29]=3)[CH2:17][CH2:18][CH2:19][CH:20]2[C:21]2[C:26]([CH3:27])=[CH:25][CH:24]=[CH:23][N:22]=2)=[C:6]([C:7]([O:9][CH3:10])=[O:8])[CH:5]=1.[CH3:10][O:9][C:7](=[O:8])[C:6]1[CH:5]=[C:4]([CH2:3][OH:2])[CH:13]=[CH:12][C:11]=1[CH2:14][N:15]1[CH:16]([C:28]2[C:33]([CH3:34])=[CH:32][CH:31]=[CH:30][N:29]=2)[CH2:17][CH2:18][CH2:19][CH:20]1[C:21]1[C:26]([CH3:27])=[CH:25][CH:24]=[CH:23][N:22]=1

Participants

7

Reactant 2

HCID 4148881Lithium borohydrideHCID 67422096HCID 67422096, compound

Product 2

HCID 67421332HCID 67421332, compoundYield 56%HCID 67422096HCID 67422096, compoundYield 4%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolventHCID 14798Sodium HydroxideSolvent

Procedure

To a cold (0° C.) solution of 4-(3,3″-Dimethyl-3′,4′,5′,6′-tetrahydro-2′H-[2,2′;6′,2″]terpyridin-1′-ylmethyl)-isophthalic acid dimethyl ester (0.710 g, 1.50 mmol) in THF (15 mL) and MeOH (15 mL) was added LiBH4 (720 mg, 33.1 mmol) and the mixture was allowed to warm to room temperature overnight. The mixture was diluted with 1.0 N NaOH (15 mL) and extracted with CH2Cl2 (5×40 mL). The combined organic extracts were dried (Na2SO4) and concentrated. Purification of the crude material by column chromatography on silica gel (20:1:1 CH2Cl2—CH3OH—NH4OH) provided 31 mg (4%) of 4-(3,3″-dimethyl-3′,4′,5′,6′-tetrahydro-2′H-[2,2′;6′,2″]terpyridin-1′-ylmethyl)-isophthalic acid dimethyl ester as a white foam, 155 mg (23%) of 4-3,3″-dimethyl-3′,4′,5′,6′-tetrahydro-2′H-[2,2′;6′,2″]terpyridin-1′-ylmethyl)-3-hydroxymethyl-benzoic acid methyl ester as a white foam, and 375 mg (56%) of COMPOUND 53 as a white foam. Characterization data for COMPOUND 53: 1H NMR (CDCl3) δ 1.52-1.74 (m, 3H), 2.05-2.10 (m, 1H), 2.31-2.45 (m, 8H), 2.62 (br s, 1H, OH), 3.80 (s, 3H), 3.96 (s, 2H), 4.14 (d, 2H, J=11.1 Hz), 4.46 (d, 2H, J=3 Hz), 6.82-6.87 (dd, 2H, J=4.8, 7.5 Hz), 7.10-7.17 (m, 3H), 7.25 (s, 1H), 7.62 (d, 1H, J=7.5 Hz), 8.24 (d, 2H, J=4.8 Hz); 13C NMR (CDCl3) δ 19.38, 25.62, 28.97, 50.63, 52.01, 64.91, 67.26, 122.05, 127.58, 128.07, 129.26, 131.61, 132.08, 137.64, 138.09, 143.24, 146.85, 159.86, 167.97; ES-MS m/z 446 (M+H). Anal. Calcd. For C27H31N3O3.1.3H2O: C, 69.15; H, 7.22; N, 8.96. Found: C, 69.22; H, 6.90; N, 8.87.

Workup

  1. extractionextracted with CH2Cl2 (5×40 mL)
  2. dry with materialThe combined organic extracts were dried (Na2SO4)
  3. concentrationconcentrated
  4. customPurification of the crude material by column chromatography on silica gel (20:1:1 CH2Cl2—CH3OH—NH4OH)

Sources & evidence

ORD record
ord-9bd02df3886d4639979168b0b002d986
Source dataset
uspto-grants-2009_06
Patent number
US07550484B2

Reaction notes

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