Triethylamine → N-(5'-bromo-4-methoxyspiro[cyclohexane-1,2'-indene]-3'(1'H)-ylidene)-2-(trimethylsilyl)ethanesulfonamide

HRID 1503437Notes

Reaction equation

HRID 1503437 reaction equation
[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7]3([CH2:16][CH2:15][CH:14]([O:17][CH3:18])[CH2:13][CH2:12]3)[C:8]2=O)=[CH:4][CH:3]=1.[CH3:19][Si:20]([CH3:28])([CH3:27])[CH2:21][CH2:22][S:23]([NH2:26])(=[O:25])=[O:24].CCN(CC)CC>C(Cl)CCl.Cl[Ti](Cl)(Cl)Cl>[Br:1][C:2]1[CH:10]=[C:9]2[C:5](=[CH:4][CH:3]=1)[CH2:6][C:7]1([CH2:16][CH2:15][CH:14]([O:17][CH3:18])[CH2:13][CH2:12]1)[C:8]2=[N:26][S:23]([CH2:22][CH2:21][Si:20]([CH3:28])([CH3:27])[CH3:19])(=[O:25])=[O:24]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 110085532-(Trimethylsilyl)ethane-1-sulfonamideHCID 581972636'-bromo-4-methoxyspiro[cyclohexane-1,2'-inden]-1'(3'H)-one

Product 1

HCID 67043529N-(5'-bromo-4-methoxyspiro[cyclohexane-1,2'-indene]-3'(1'H)-ylidene)-2-(trimethylsilyl)ethanesulfonamideYield 91%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 111,2-DichloroethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a mixture of 6′-bromo-4-methoxyspiro[cyclohexane-1,2′-inden]-1′(3′H)-one (3) (0.9822 g, 3.18 mmol, 1.0 equiv) and 2-(trimethylsilyl)ethanesulfonamide) (SESNH2) (0.6338 g, 3.50 mmol, 1.1 equiv) in ClCH2CH2Cl (10 mL), cooled to 0° C., were successively added Et3N (0.9 mL, 6.46 mmol, 2.0 equiv) and TiCl4 (1.0 M in CH2Cl2, 3.4 mL, 3.4 mmol, 1.1 equiv). After 10 min, the ice bath was removed. The reaction mixture was stirred at room temperature for 3 h and then heated at 110° C. for 42 h. The reaction mixture was cooled to room temperature, quenched with water, and extracted with CH2Cl2. The combined organic phase was dried (Na2SO4) and evaporated. The residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate to afford 1.3685 g (91%) of N-(5′-bromo-4-methoxyspiro[cyclohexane-1,2′-indene]-3′(1′H)-ylidene)-2-(trimethylsilyl)ethanesulfonamide (8) as a solid. LC-MS tR=2.31 min in 3 min chromatography, m/z 472, 474 (MH+); 1H NMR (400 MHz, CDCl3) δ 8.78 (br s, 1H), 7.67 (dd, J=8.2, 1.8 Hz, 1H), 7.29 (d, J=8.2 Hz, 1H), 3.39 (s, 3H), 3.29-3.21 (m, 3H), 2.98 (s, 2H), 2.16-2.12 (m, 2H), 1.80-1.76 (m, 2H), 1.62-1.57 (m, 2H), 1.42-1.33 (m, 2H), 1.21-1.17 (m, 2H), 0.10 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 189.97, 151.30, 137.91, 133.35, 127.50, 121.43, 78.10, 55.80, 51.79, 51.39, 39.55, 33.97, 28.60, 9.98, −1.93.

Workup

  1. customthe ice bath was removed
  2. temperatureheated at 110° C. for 42 h
  3. temperatureThe reaction mixture was cooled to room temperature
  4. customquenched with water
  5. extractionextracted with CH2Cl2
  6. dry with materialThe combined organic phase was dried (Na2SO4)
  7. customevaporated
  8. customThe residue was purified by chromatography on silica gel
  9. washeluted with hexanes/ethyl acetate

Sources & evidence

ORD record
ord-a956bc84d3c24ac48fb23989a67ca9b2
Source dataset
uspto-grants-2015_12
Patent number
US09212153B2

Reaction notes

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