4,5-Dichloro-1,2,3-dithiazol-1-ium chloride → tert-Butyl (2-cyanonaphtho[2,1-d]thiazol-7-yl)carbamate

HRID 64513Notes

Reaction equation

HRID 64513 reaction equation
[NH2:1][C:2]1[C:3](Br)=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7]([NH:12][C:13](=[O:19])[O:14][C:15]([CH3:18])([CH3:17])[CH3:16])[CH:6]=[CH:5]2.[C:21]1(Cl)[C:25](Cl)=[S+:24]S[N:22]=1.[Cl-]>C(Cl)Cl.CCOC(C)=O.N1C=CC=CC=1.[Cu]I>[C:21]([C:25]1[S:24][C:3]2[C:4]3[C:9](=[CH:8][C:7]([NH:12][C:13](=[O:19])[O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[CH:6][CH:5]=3)[CH:10]=[CH:11][C:2]=2[N:1]=1)#[N:22]

Participants

7

Reactant 2

HCID 110958474,5-Dichloro-1,2,3-dithiazol-1-ium chlorideHCID 131737224tert-Butyl (6-amino-5-bromonaphthalen-2-yl)carbamate

Product 1

HCID 131737225tert-Butyl (2-cyanonaphtho[2,1-d]thiazol-7-yl)carbamateYield 28.4%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 1049PyridineSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

To a stirred solution of tert-butyl (6-amino-5-bromonaphthalen-2-yl)carbamate (540 mg, 1.6 mmol) in dry DCM, 351 mg of Appel's salt (1.68 mmol) was added. Upon completion, the reaction was diluted with EtOAc and washed with water. The organic layer was dried over Na2SO4 and evaporated. The crude material thus obtained was dissolved in 10 mL of pyridine and treated with 529 mg (2.78 mmol) of CuI. The reaction was heated in a 110° C. oil bath for 40 min, and then the solvents were removed under reduced pressure. The resulting solids were taken up in EtOAc and filtered. The filtrate was washed with 1 N HCl, the aqueous layer extracted with 2×EtOAc, and the combined organic layers dried over Na2SO4. The solvents were removed under reduced pressure, and the resulting material subjected to silica gel chromatography eluting with 15→35% EtOAc in heptanes to yield 148 mg of a yellow solid. 1H NMR (CD2Cl2) d 8.21 (d, 1H); 8.12 (d, 1H); 8.03 (d, 1H); 7.96 (d, 1H); 7.64 (dd, 1H); 6.90 (br s, 1H); 1.55 (s, 9H).

Workup

  1. washwashed with water
  2. dry with materialThe organic layer was dried over Na2SO4
  3. customevaporated
  4. customThe crude material thus obtained
  5. customthe solvents were removed under reduced pressure
  6. filtrationfiltered
  7. washThe filtrate was washed with 1 N HCl
  8. extractionthe aqueous layer extracted with 2×EtOAc
  9. dry with materialthe combined organic layers dried over Na2SO4
  10. customThe solvents were removed under reduced pressure
  11. washeluting with 15→35% EtOAc in heptanes

Sources & evidence

ORD record
ord-591f6035201642c6bdd8627cf1fc9ced
Source dataset
uspto-grants-2016_09
Patent number
US09447450B2

Reaction notes

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