2-bromoethyl benzoate

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

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

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

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

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of 60% NaH in mineral oil (1.70 g, 42.57 mmol) in anhydrous DMF (120 mL) was added adenine (5.23 g, 38.70 mmol) under argon, and the mixture was heated at 60° C. for 1 h. 2-Bromoethylbenzoate (9.2 mL, 58.06 mmol) was added dropwise at 60° C., and the reaction was stirred at this temperature for 16 h. The mixture was then filtered to remove insoluble materiel, the filtrate was evaporated under reduced pressure and co-evaporated three times with toluene. The residue was triturated with EtOAc then filtered to give a white solid, which was immediately resuspended in a saturated ammonia solution in MeOH (400 mL). The reaction mixture was stirred for 14 h at room temperature, and then methanol was removed under reduced pressure. Recrystallization from EtOH afforded compound 2 (5.87 g, 85%): mp 236° C. (Lit. 238-239° C.); 1H NMR (DMSO-d6): 8.13 (s, 1H, H-2), 8.10 (s, 1H, H-8), 7.23 (bs, 2H, NH2), 5.05 (bs, 1H, OH), 4.19 (t, J=5.2 Hz, 2H, CH2O), 3.71 (t, J=5.2 Hz, 2H, CH2N). 13C NMR (DMSO-d6) δ: 155.79, 152.23, 149.44, 141.46, 118.55, 59.17, 45.61. MS (GT, FAB+): 136 (B+1H)+, 180 (M+1H)+, 202 (M+Na)+. The mixture was then filtered to remove insoluble materiel the filtrate was evaporated under reduced pressure The residue was triturated with EtOAc then filtered to give a white solid, which The reaction mixture was stirred for 14 h at room temperature methanol was removed under reduced pressure Recrystallization from EtOH afforded compound 2 (5.87 g, 85%) mp 236° C. (Lit. 238-239° C.)

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

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

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

Procedure: A mixture of ethyl 2-hydroxyimino-3-oxobutyrate (syn isomer, 15.7 g.), 2-bromoethyl benzoate (27.5 g.), potassium carbonate (20.7 g.), N,N-dimethylformamide (25 ml.) and ethyl acetate (25 ml.) was treated in a similar manner to that of Example A-(1) to give ethyl 2-(2-benzoyloxyethoxyimino)-3-oxobutyrate (syn isomer, 28 g.). was treated in a similar manner to that of Example A-(1)

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

Procedure: A mixture of ethyl 2-hydroxyimino-3-oxobutyrate (syn isomer, 15.7 g.), 2-bromoethyl benzoate (27.5 g.), potassium carbonate (20.7 g.), N,N-dimethylformamide (25 ml.) and ethyl acetate (25 ml.) was treated in a similar manner to that of Example A-(1) to give ethyl 2-(2-benzoyloxyethoxyimino)-3-oxobutyrate (syn isomer, 28 g.). was treated in a similar manner to that of Example A-(1)

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

Procedure: A solution of 50.0 grams (0.218 mol) of 2-bromoethyl benzoate, 17.27 grams (0.218 mol) of pyridine and 135 milliters of acetonitrile was heated at reflux for 17.75 hours and cooled. Solid crystallized and was collected, washed with acetonitrile, then with ether and dried. The yield of product was 48.5 grams (72.19% of theory); mp=162°-164° C. at reflux for 17.75 hours cooled Solid crystallized was collected washed with acetonitrile with ether and dried

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

Procedure: A solution of 50.0 grams (0.218 mol) of 2-bromoethyl benzoate, 17.27 grams (0.218 mol) of pyridine and 135 milliters of acetonitrile was heated at reflux for 17.75 hours and cooled. Solid crystallized and was collected, washed with acetonitrile, then with ether and dried. The yield of product was 48.5 grams (72.19% of theory); mp=162°-164° C. at reflux for 17.75 hours cooled Solid crystallized was collected washed with acetonitrile with ether and dried

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

Procedure: A mixture of 120.14 grams (0.80 mol) of 2-phenyl-1,3-dioxolane, 142.39 grams (0.80 mol) of N-bromosuccinimide, 1 liter of carbon tetrachloride and a catalytic amount of benzoyl peroxide was heated with stirring at reflux for 5.25 hours and then cooled. The mixture was filtered, and the filtrate was concentrated to an oil. Distillation of this oil gave 147.8 grams; (80.65% of theory) of the product; bp=104°-111° C./0.40 mm. at reflux for 5.25 hours cooled The mixture was filtered the filtrate was concentrated to an oil Distillation of this oil gave 147.8 grams