تفاعل #2306292

معادلة التفاعل

4,8,11-Tris(diethoxyphosphoryl)-1,4,8,11-tetraazacyclotetradecane

K2CO3

α,α′-dibromo-p-xylene

→

diethoxyphosphoryl-1,4,8,11-tetraazacyclotetra-decane

المردود 139.7%

المذيبات

CH3CN

ظروف التفاعل

المعالجة

1. 1
   درجة الحرارةThe solution was cooled to room temperature
2. 2
   أخرىthe solvent removed under reduced pressure
3. 3
   أخرىThe residue was partitioned between brine (50 ml) and CH2Cl2 (100 ml)
4. 4
   أخرىThe organic phase was separated
5. 5
   تجفيفdried (Na2SO4)
6. 6
   تركيزconcentrated to a minimum volume
7. 7
   ترشيحThe solid was filtered off
8. 8
   أخرىthe solvent evaporated under reduced pressure
9. 9
   أخرىto give the crude product as a pale yellow oil
10. 10
    أخرىPurification by column chromatography in silica gel (CH2Cl2\CH3OH, 25:1)

الإجراء التجريبي

To a stirred solution of 4,8,11-Tris(diethoxyphosphoryl)-1,4,8,11-tetraazacyclotetradecane (See Bridger et al. J Med. Chem. 1995, 38, 366-378) (6.1 g, 0.01 mol) and K2CO3 (1.89 g, 0.013 mol) in CH3CN (150 ml) was added α,α′-dibromo-p-xylene (13.2 g, 0.05 mol) and the reaction mixture stirred at 70° C. for 1 hour. The solution was cooled to room temperature and the solvent removed under reduced pressure. The residue was partitioned between brine (50 ml) and CH2Cl2 (100 ml). The organic phase was separated, dried (Na2SO4) and concentrated to a minimum volume. The solid was filtered off and the solvent evaporated under reduced pressure to give the crude product as a pale yellow oil. Purification by column chromatography in silica gel (CH2Cl2\CH3OH, 25:1) gave 1-[1-methylene-4-(bromomethylene)phenylene]-4,8,11-tris(diethoxyphosphoryl-1,4,8,11-tetraazacyclotetra-decane (4.7 g, 59%) as a pale yellow oil. 1H NMR (CDCl3) δ 1.21-1.37 (m, 18H), 1.66-1.74 (m, 2H), 1.82-1.91 (m, 2H), 2.30-2.35 (m, 2H), 2.58-2.63 (m, 2H), 2.99-3.16 (m, 12H), 3.48 (s, 2H), 3.95-4.07 (m, 12H), 4.48 (s, 2H), 7.21-7.35 (4H).

المصدر