Lithium hydroxide, monohydrate → HCID 86712486, compound

HRID 1496830Notes

Reaction equation

HRID 1496830 reaction equation
O[Li].O.Cl.Cl.[NH2:6][CH:7]([C:48]([O:50]C)=[O:49])[CH2:8][CH2:9][CH2:10][CH2:11][NH:12][S:13]([C:16]1[C:29]2[C:30]3=[C:31]4[C:26](=[CH:27][CH:28]=2)[C:25]([OH:32])=[CH:24][C:23]([OH:33])=[C:22]4[CH:21]=[CH:20][C:19]3=[C:18]([S:34](=[O:47])(=[O:46])[NH:35][CH2:36][CH2:37][CH2:38][CH2:39][CH:40]([C:42]([O:44]C)=[O:43])[NH2:41])[CH:17]=1)(=[O:15])=[O:14]>O.CO>[NH2:41][CH:40]([C:42]([OH:44])=[O:43])[CH2:39][CH2:38][CH2:37][CH2:36][NH:35][S:34]([C:18]1[C:19]2[C:30]3=[C:31]4[C:22](=[CH:21][CH:20]=2)[C:23]([OH:33])=[CH:24][C:25]([OH:32])=[C:26]4[CH:27]=[CH:28][C:29]3=[C:16]([S:13](=[O:15])(=[O:14])[NH:12][CH2:11][CH2:10][CH2:9][CH2:8][CH:7]([C:48]([OH:50])=[O:49])[NH2:6])[CH:17]=1)(=[O:46])=[O:47]

Participants

5

Reactant 2

HCID 168937Lithium hydroxide, monohydrateHCID 86712487HCID 86712487, compound

Product 1

HCID 86712486HCID 86712486, compoundYield 96.2%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

A solution of LiOH.H2O (1.319 g, 31.43 mmol) in water (20 mL) was added to a solution of the dihydrochloride 6 (2.443 g, 3.250 mmol) in methanol (80 mL). The mixture was stirred vigorously at room temperature for 3 h and then concentrated by evaporation. The residue was taken up in 80 ml of water and 4 ml of conc. hydrochloric acid were added. The reaction mixture was concentrated by evaporation once again and then taken up in 100 ml of water, added to a 4 cm×40 cm column packed with acidic Dowex 50WX2-200, washed with 1.5 L of water and then eluted with 1.5 L of 1N ammonia solution. The emerald green solution of 7, which was evaporated under reduced pressure at 50° C., was dried over phosphorus pentoxide overnight to give the dark brown powder 7 (2.0350 g, 96%). The powder was stirred in 20 ml of water at 70° C. for 20 min, cooled and centrifuged. The sediment was stirred in ice-cold water, centrifuged off and dried overnight over phosphorus pentoxide (1.1907 g). Melting point: 210-212° C. (decomposition). 1H NMR (300 MHz, [D6]-DMSO): δ=8.84 (s, 1H), 8.53 (d, J=9.0 Hz, 2H), 8.46 (d, J=9.0 Hz, 2H), 8.15 (br. s, 2H, 2 NH), 7.27 (s, 1H), 3.12 (m, 2H, 2 CHN; overlapping with HOD and NH2), 2.65 (t, J=7.5 Hz, 4H, 2 CH2N), 1.57-1.35 (m, 4H, 2 CH2), 1.30-1.00 (m, 8H, 4 CH2). HRMS (ESI): m/z [M+Na]+ calculated for C28H34N4NaO10S2 673.1614; found 673.1609; m/z [M−H]+ calculated for C28H33N4O10S2 649.1638; found 649.1644.

Workup

  1. concentrationconcentrated by evaporation
  2. addition4 ml of conc. hydrochloric acid were added
  3. concentrationThe reaction mixture was concentrated by evaporation once again
  4. additionadded to a 4 cm×40 cm column
  5. washwashed with 1.5 L of water
  6. washeluted with 1.5 L of 1N ammonia solution
  7. customThe emerald green solution of 7, which was evaporated under reduced pressure at 50° C.
  8. dry with materialwas dried over phosphorus pentoxide overnight

Sources & evidence

ORD record
ord-c5e5f3e790a74903a85a36a0ec39724e
Source dataset
uspto-grants-2015_12
Patent number
US09199928B2

Reaction notes

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