Thiourea → 2-S-(2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl)-2-thiopseudourea hydrobromide

HRID 2408224Notes

Reaction equation

HRID 2408224 reaction equation
[C:1]([O:4][C@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@@H:6]1[Br:24])(=[O:3])[CH3:2].[NH2:25][C:26]([NH2:28])=[S:27]>CC(C)=O>[BrH:24].[C:1]([O:4][C@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@@H:6]1[S:27][C:26](=[NH:25])[NH2:28])(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 2723790ThioureaHCID 11069632alpha-D-Mannopyranosyl bromide, 2,3,4,6-tetraacetate

Product 1

HCID 228232872-S-(2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl)-2-thiopseudourea hydrobromide

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

2-S-(2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl bromide (38 g) dissolved in acetone (180 ml) with thiourea (11 g) at 25° C. Batch heated to reflux for a minimum of 2 hrs. Reaction followed by TLC (1:1 petrol/EtOAc. Starting material 0.69, plus multiple peaks below. Product is a salt and therefore is seen on baseline (uv-active)). Batch cooled to R.T. and crystallised, as a white crystalline solid, with the aid of petrol as an anti-solvent (22 g, 49%). M.p=125-127° C. (Lit6 125-128° c.). [α]D22+101 (CHCl3, C=1.1) (Lit6+103). 1HNMR (400 MHz, DMSO). δ=2.0, 2.0, 2.0, 2.0 (sx4, 3H x4, —C(O)CH3×4), 4.1 (dd, J6,612.4 Hz, J5,62.3 Hz, 1H, H-6), 4.2 (dd, J6,612.4 Hz, J5,65.3 Hz, 1H, H-6′), 4.3 (m, 1H, H-5), 5.1 (dd, J3,410 Hz, J2,33.5 Hz, 1H, H-3), 5.2 (t, J3,49.9 Hz, 1H, H-4), 5.4 (dd, J2,33.4 Hz, J1,21.6 Hz, 1H, H-2), 6.3 (d, J1.3 Hz, 1H, H-1), 9.3 (s, 4H, 2×NH2).

Workup

  1. temperatureBatch heated
  2. temperatureto reflux for a minimum of 2 hrs
  3. customReaction
  4. customcrystallised, as a white crystalline solid, with the aid of petrol as an anti-solvent (22 g, 49%)
  5. customM.p=125-127° C. (Lit6 125-128° c.)

Sources & evidence

ORD record
ord-a02270548f664c7597b1585383e57f4d
Source dataset
uspto-grants-2014_08
Patent number
US08815563B2

Reaction notes

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