1,2-Diaminocyclohexane → HCID 57504899, compound

HRID 2060767Notes

Reaction equation

HRID 2060767 reaction equation
O.O.O.O.O.[S:6]([O-:10])([O-:9])(=[O:8])=[O:7].[Cu+2:11].[Na].[O:13]=[C:14]1[O:20][C@H:19]([C@H:21]([CH2:23][OH:24])[OH:22])[C:17]([OH:18])=[C:15]1[OH:16].Br[C:26]1[CH:27]=[C:28]([C@:32]23[CH2:41][CH2:40][O:39][CH2:38][CH:37]2[CH2:36][S:35][C:34]([NH:42][C:43](=[O:49])[O:44][C:45]([CH3:48])([CH3:47])[CH3:46])=[N:33]3)[CH:29]=[CH:30][CH:31]=1.[N-:50]=[N+:51]=[N-:52].[Na+].C1(N)CCCCC1N>O.C(O)C>[S:6]([O-:10])([O-:9])(=[O:8])=[O:7].[Cu+2:11].[O:13]=[C:14]1[O:20][C@H:19]([C@H:21]([CH2:23][OH:24])[OH:22])[C:17]([OH:18])=[C:15]1[OH:16].[N:50]([C:26]1[CH:27]=[C:28]([C@:32]23[CH2:41][CH2:40][O:39][CH2:38][CH:37]2[CH2:36][S:35][C:34]([NH:42][C:43](=[O:49])[O:44][C:45]([CH3:48])([CH3:47])[CH3:46])=[N:33]3)[CH:29]=[CH:30][CH:31]=1)=[N+:51]=[N-:52]

Participants

10

Reactant 5

HCID 46101,2-DiaminocyclohexaneHCID 24463Copper sulfate pentahydrate2×HCID 33557Sodium AzideHCID 57504898HCID 57504898, compoundHCID 66586226sodium L-ascorbic acid2×

Product 3

HCID 24462Copper SulfateHCID 54670067L-Ascorbic AcidHCID 57504899HCID 57504899, compoundYield 88%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent4×

Conditions

Temperature
80 °C

Procedure

A 0.33 M solution of copper sulfate is prepared by dissolving copper (II) sulfate pentahydrate (1.0 g, 2.0 mmol) in water (12 mL). A 0.66 M solution of L-ascorbic acid is prepared by dissolving L-ascorbic acid sodium salt (1.58 g, 4.0 mmol) in water (12 mL). To a solution of tert-butyl (8aS)-8a-(3-bromophenyl)-4,4a,5,7,8,8a-hexahydropyrano[4,3-d][1,3]thiazin-2-ylcarbamate (0.500 g, 1.20 mmol) in ethanol (3.6 mL) is added sodium azide (0.228 g, 3.50 mmol), 1,2-cyclohexanediamine, N,N′-dimethyl-, trans (+/−) (0.0549 g, 0.386 mmol), 0.66 M aqueous L-ascorbic acid sodium salt (0.772 mL, 0.509 mmol), and water (0.71 mL) and the mixture is purged with nitrogen. A 0.33 M aqueous solution of copper (II) sulfate pentahydrate (0.773 mL, 0.255 mmol) is added and the reaction is heated to 80° C. for 12 min. The reaction is poured into cold water to afford a blue mixture that is extracted three times with EtOAc. The organic layer is dried over Na2SO4 to afford crude material which is purified by silica gel chromatography eluting with a linear gradient of 5% to 100% EtOAc in hexanes to give the title compound (0.400 g, 88%). ES/MS m/e: 390 (M+1).

Workup

  1. customthe mixture is purged with nitrogen
  2. customto afford a blue mixture that
  3. extractionis extracted three times with EtOAc
  4. dry with materialThe organic layer is dried over Na2SO4
  5. customto afford crude material which
  6. customis purified by silica gel chromatography
  7. washeluting with a linear gradient of 5% to 100% EtOAc in hexanes

Sources & evidence

ORD record
ord-b0fe46eecfaf474a9e434041a7bde414
Source dataset
uspto-grants-2012_10
Patent number
US08278441B2

Reaction notes

Loading…