2,3,3-trimethylindole

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Freshly distilled 2,3,3-trimethylindolenine (0.53 g, 3.3 mmol) and N-(3-bromopropyl)triethylammonium chloride (1.01 g, 3.9 mmol) were mixed in the thick-wall tube and placed under an argon atmosphere. The mixture was then heated at 140° C. for 1.5 h, giving a deep red viscous product, which solidified to a glass on cooling. It was ground to a powder under acetone; product was collected by filtration, triturated 3 times with 10 mL portions of acetone and dried under vacuum to give 0.45 g (36%) of 2,3,3-trimethyl-1-(3-triethylammoniopropyl)-3H-indolium bromide chloride as a white powder. δH (200 MHz, DMSO-d6) 8.10 (1H, d, 6.7 Hz, arom.), 7.87 (1H, d, 5.8 Hz, arom.), 7.75-7.58 (2H, m, arom.), 4.56 (2H, t, 7.3 Hz, N+CH2), 3.27 (6H, q, 6.0 Hz, N+(CH2)3), 2.91 (3H, s, CH3), 2.34-2.10 (2H, m, N+CH2), 1.56 (6H, s, (CH3)2) 1.36-1.05 (11H, m, CH2, (CH3)3). giving a deep red viscous product, which on cooling product was collected by filtration triturated 3 times with 10 mL portions of acetone dried under vacuum

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 2,3,3-trimethylindolenine (1.59 g) was added 1-bromo-2-(2-methoxyethoxy)ethane (2.75 g) and dichlorobenzene (5 ml). The mixture was heated to 70° C. overnight. The volatiles were stripped and the material purified by HPLC. the material purified by HPLC

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 2,3,3-trimethylindolenine (1.64 g) was added 3,5-dinitrobenzyl iodide (3.71 g) and dichlorobenzene (15 ml). After heating to 90° C. for 6 hours the mixture was allowed to cool and the resultant precipitate removed by filtration. The solid was washed with dichlorobenzene (2×10 ml) and ether (2×50 ml). The material was dried in a vacuum oven to give the product as a yellow solid (2.69 g). to cool the resultant precipitate removed by filtration The solid was washed with dichlorobenzene (2×10 ml) and ether (2×50 ml) The material was dried in a vacuum oven

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: N-(5-carboxypentyl)-2,3,3-trimethylindolinium bromide was prepared by the process set forth in Example IA with 2,3,3-trimethylindolenine and 6-bromohexanoic acid to produce 2.43 grams (71.2 percent yield) of yellow crystals. 1H and 13C NMR spectra indicated the following:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: N-(5-carboxypentyl)-2,3,3-trimethylindolinium bromide was prepared by the process set forth in Example IA with 2,3,3-trimethylindolenine and 6-bromohexanoic acid to produce 2.43 grams (71.2 percent yield) of yellow crystals. 1H and 13C NMR spectra indicated the following:

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2-necked 50 milliliter round-bottomed flask equipped with a magnetic stirring bar and an argon inlet was charged with re-distilled (pressure 2 mm Hg, temperature 45° C.) 2,3,3-trimethylindolenine (7.95 grams, 50.0 mmol) and 3-iodopropionic acid (2.00 grams, 10 mmol). The mixture was heated to 80° C. for 12 hours, during which time the product precipitated out of solution and formed a highly viscous medium. Upon cooling, the reaction mixture was extracted three times with 200 milliliter portions of diethyl ether to remove all of the unreacted starting material. The remaining crystalline solid was then dissolved in 10 milliliters of water, extracted three times with 50 milliliter portions of diethyl ether, and extracted three times with 25 milliliter portions of CHCl3. The aqueous layer was then removed and dried under vacuum (1.0 mm Hg) for 24 hours. The resulting amorphous solid was then recrystallized from toluene/CHCl3 mixtures to produce the N-(2-carboxyethyl)-2,3,3-trimethylindolinium iodide product as 3.0 grams of a yellow solid (83.5 percent yield). 1H and 13C NMR spectra indicated the following: A 2-necked 50 milliliter round-bottomed flask equipped with a magnetic stirring bar and an argon inlet was charged precipitated out of solution formed a highly viscous medium Upon cooling the reaction mixture was extracted three times with 200 milliliter portions of diethyl ether to remove all of the The remaining crystalline solid was then dissolved in 10 milliliters of water extracted three times with 50 milliliter portions of diethyl ether extracted three times with 25 milliliter portions of CHCl3 The aqueous layer was then removed dried under vacuum (1.0 mm Hg) for 24 hours The resulting amorphous solid was then recrystallized from toluene/CHCl3

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2-necked 50 milliliter round-bottomed flask equipped with a magnetic stirring bar and an argon inlet was charged with re-distilled (pressure 2 mm Hg, temperature 45° C.) 2,3,3-trimethylindolenine (7.95 grams, 50.0 mmol) and 3-iodopropionic acid (2.00 grams, 10 mmol). The mixture was heated to 80° C. for 12 hours, during which time the product precipitated out of solution and formed a highly viscous medium. Upon cooling, the reaction mixture was extracted three times with 200 milliliter portions of diethyl ether to remove all of the unreacted starting material. The remaining crystalline solid was then dissolved in 10 milliliters of water, extracted three times with 50 milliliter portions of diethyl ether, and extracted three times with 25 milliliter portions of CHCl3. The aqueous layer was then removed and dried under vacuum (1.0 mm Hg) for 24 hours. The resulting amorphous solid was then recrystallized from toluene/CHCl3 mixtures to produce the N-(2-carboxyethyl)-2,3,3-trimethylindolinium iodide product as 3.0 grams of a yellow solid (83.5 percent yield). 1H and 13C NMR spectra indicated the following: A 2-necked 50 milliliter round-bottomed flask equipped with a magnetic stirring bar and an argon inlet was charged precipitated out of solution formed a highly viscous medium Upon cooling the reaction mixture was extracted three times with 200 milliliter portions of diethyl ether to remove all of the The remaining crystalline solid was then dissolved in 10 milliliters of water extracted three times with 50 milliliter portions of diethyl ether extracted three times with 25 milliliter portions of CHCl3 The aqueous layer was then removed dried under vacuum (1.0 mm Hg) for 24 hours The resulting amorphous solid was then recrystallized from toluene/CHCl3

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4.0 g of 2,3,3-trimethylindolenine in 25 ml of chloroform was added 5.6 g of p-methoxybenzyl bromide and the mixture was heated in an autoclave at 80° C. for 21 hours. The resulting precipitate was recovered by filtration to give 8.5 g of 1-(4-methoxybenzyl)-2,3,3-trimethylindolenium as white crystals. To these crystals was added 85 ml of 10N aqueous potassium hydroxide solution in a nitrogen atmosphere and the mixture was heated at 50° C. for 3 hours. The reaction mixture was then extracted with ether and the extract was dried over magnesium sulfate and concentrated under reduced pressure to give 5.7 g of 3,3-dimethyl-1-(4-methoxybenzyl)-2-methyleneindoline (Yield 80.6%). The resulting precipitate was recovered by filtration to give 8.5 g of 1-(4-methoxybenzyl)-2,3,3-trimethylindolenium as white crystals the mixture was heated at 50° C. for 3 hours The reaction mixture was then extracted with ether the extract was dried over magnesium sulfate concentrated under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: N-(5-carboxypentyl)-2,3,3-trimethylindolinium bromide was prepared by the process set forth in Example IA with 2,3,3-trimethylindolenine and 6-bromohexanoic acid to produce 2.43 grams (71.2 percent yield) of yellow crystals. 1H and 13C NMR spectra indicated the following:

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2-necked 50 milliliter round-bottomed flask equipped with a magnetic stirring bar and an argon inlet was charged with re-distilled (pressure 2 mm Hg, temperature 45° C.) 2,3,3-trimethylindolenine (7.95 grams, 50.0 mmol) and 3-iodopropionic acid (2.00 grams, 10 mmol). The mixture was heated to 80° C. for 12 hours, during which time the product precipitated out of solution and formed a highly viscous medium. Upon cooling, the reaction mixture was extracted three times with 200 milliliter portions of diethyl ether to remove all of the unreacted starting material. The remaining crystalline solid was then dissolved in 10 milliliters of water, extracted three times with 50 milliliter portions of diethyl ether, and extracted three times with 25 milliliter portions of CHCl3. The aqueous layer was then removed and dried under vacuum (1.0 mm Hg) for 24 hours. The resulting amorphous solid was then recrystallized from toluene/CHCl3 mixtures to produce the N-(2-carboxyethyl)-2,3,3-trimethylindolinium iodide product as 3.0 grams of a yellow solid (83.5 percent yield). 1H and 13C NMR spectra indicated the following: A 2-necked 50 milliliter round-bottomed flask equipped with a magnetic stirring bar and an argon inlet was charged precipitated out of solution formed a highly viscous medium Upon cooling the reaction mixture was extracted three times with 200 milliliter portions of diethyl ether to remove all of the The remaining crystalline solid was then dissolved in 10 milliliters of water extracted three times with 50 milliliter portions of diethyl ether extracted three times with 25 milliliter portions of CHCl3 The aqueous layer was then removed dried under vacuum (1.0 mm Hg) for 24 hours The resulting amorphous solid was then recrystallized from toluene/CHCl3

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 2-necked 50 milliliter round-bottomed flask equipped with a magnetic stirring bar and an argon inlet was charged with re-distilled (pressure 2 mm Hg, temperature 45° C.) 2,3,3-trimethylindolenine (7.95 grams, 50.0 mmol) and 3-iodopropionic acid (2.00 grams, 10 mmol). The mixture was heated to 80° C. for 12 hours, during which time the product precipitated out of solution and formed a highly viscous medium. Upon cooling, the reaction mixture was extracted three times with 200 milliliter portions of diethyl ether to remove all of the unreacted starting material. The remaining crystalline solid was then dissolved in 10 milliliters of water, extracted three times with 50 milliliter portions of diethyl ether, and extracted three times with 25 milliliter portions of CHCl3. The aqueous layer was then removed and dried under vacuum (1.0 mm Hg) for 24 hours. The resulting amorphous solid was then recrystallized from toluene/CHCl3 mixtures to produce the N-(2-carboxyethyl)-2,3,3-trimethylindolinium iodide product as 3.0 grams of a yellow solid (83.5 percent yield). 1H and 13C NMR spectra indicated the following: A 2-necked 50 milliliter round-bottomed flask equipped with a magnetic stirring bar and an argon inlet was charged precipitated out of solution formed a highly viscous medium Upon cooling the reaction mixture was extracted three times with 200 milliliter portions of diethyl ether to remove all of the The remaining crystalline solid was then dissolved in 10 milliliters of water extracted three times with 50 milliliter portions of diethyl ether extracted three times with 25 milliliter portions of CHCl3 The aqueous layer was then removed dried under vacuum (1.0 mm Hg) for 24 hours The resulting amorphous solid was then recrystallized from toluene/CHCl3