Hydrochloric Acid → Thiocyanic acid, 2-chloro-5-nitrophenyl ester

HRID 1442464Notes

Reaction equation

HRID 1442464 reaction equation
[Cl:1][C:2]1[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[CH:5][C:3]=1N.Cl.N([O-])=O.[Na+].[C:17]([S-:19])#[N:18].[K+]>O>[Cl:1][C:2]1[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[CH:5][C:3]=1[S:19][C:17]#[N:18]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 226912-Chloro-5-nitroanilineHCID 516872Potassium thiocyanateHCID 23668193Sodium Nitrite

Product 1

HCID 1277678Thiocyanic acid, 2-chloro-5-nitrophenyl esterYield 42%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

2-Chloro-5-nitroaniline (90.0 g, 522 mmole) and 6 N HCl (600 mL) were stirred at room temperature until a homogeneous paste was obtained. Sodium nitrite (40.5 g, 585 mmole) in water (60 mL) was added drop by drop to this solution at 0° C. under inert atmosphere. After the addition was complete, the mixture was stirred for an additional hour. This was added in portions to a solution of KSCN (72.0 g, 738 mmole) and CuSCN (63.0 g, 522 mmole) in water (200 mL) at room temperature over a period of 2 hrs. On adding the diazonium salt to the thiocyanates, the solution turned from yellow to black with foaming. The mixture was stirred overnight and then filtered. The precipitate washed with CH2Cl2 three times. The filtrate was also washed with CH2Cl2. The combined organic extracts were washed with water and dried with MgSO4. The solvent was then removed and the crude mixture was further recrystallized in hexane to yield light yellow powder (44.7 g, 42%). mp 103° C. (lit. 102° C.). 1H NMR (250 MHz, CDCl3) δ: 8.32 (d, 1H, J=2.5 Hz), 8.10 (dd, 1H, J=8.8, 2.5 Hz), 7.66 (d, 1H, J=8.8 Hz). 13C NMR (62.5 MHz, CDCl3) δ: 147.0, 138.7, 131.1, 124.6, 124.0, 107.4. HR-MS (EI): calcd. for C7H3ClN2O2S 213.9600 [M+]. Found 213.9598.

Workup

  1. customwas obtained
  2. additionAfter the addition
  3. stirringThe mixture was stirred overnight
  4. filtrationfiltered
  5. washThe precipitate washed with CH2Cl2 three times
  6. washThe filtrate was also washed with CH2Cl2
  7. washThe combined organic extracts were washed with water
  8. dry with materialdried with MgSO4
  9. customThe solvent was then removed
  10. customthe crude mixture was further recrystallized in hexane

Sources & evidence

ORD record
ord-20b18f1048b74e298f2cf61af6f44377
Source dataset
uspto-grants-2010_02
Patent number
US07658868B2

Reaction notes

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