تفاعل #4248

معادلة التفاعل

water

ammonia

methyl 2-(chlorosulfonyl)-4-ethoxybenzoate

water

→

Methyl 2-(aminosulfonyl)-4-ethoxybenzoate

المردود 74.4%

المذيبات

dichloromethane

dichloromethane

ظروف التفاعل

المعالجة

1. 1
   غسيلfor rinsing
2. 2
   workup.ADDITIONtetrahydrofuran (ca. 40 mL) was also added
3. 3
   أخرىseparated
4. 4
   استخلاصthe aqueous layer was extracted with dichloromethane (2×221 mL)
5. 5
   غسيلThe combined dichloromethane solutions were washed with water (221 mL)
6. 6
   غسيلthe aqueous wash
7. 7
   استخلاصwas back-extracted with dichloromethane (ca. 120 mL)
8. 8
   تجفيفThe combined dichloromethane solutions were dried (Na2SO4)
9. 9
   ترشيحfiltered
10. 10
    أخرىRotary evaporation of the solvent
11. 11
    workup.WAITleft crude product as an off-white crystalline solid (18.1 g)
12. 12
    workup.DISSOLUTIONThis was dissolved in hot methanol (ca. 200 mL)
13. 13
    درجة الحرارةcooling with the aid of an ice bath
14. 14
    أخرىthe crystals were collected
15. 15
    غسيلrinsed with ice-cold methanol and hexanes
16. 16
    أخرىdried

الإجراء التجريبي

Liquified ammonia (4.4 mL, 180 mmol) was added to a stirred solution of methyl 2-(chlorosulfonyl)-4-ethoxybenzoate (22.1 g, 79.3 mmol) in dichloromethane (221 mL) at -70° C. The reaction mixture was allowed to warm to -10° C. and was held at this temperature for 30 minutes. The mixture was then poured into water (221 mL). More water and dichloromethane were used for rinsing, and tetrahydrofuran (ca. 40 mL) was also added. The layers were shaken and separated, and the aqueous layer was extracted with dichloromethane (2×221 mL). The combined dichloromethane solutions were washed with water (221 mL), and the aqueous wash was back-extracted with dichloromethane (ca. 120 mL). The combined dichloromethane solutions were dried (Na2SO4), and filtered. Rotary evaporation of the solvent left crude product as an off-white crystalline solid (18.1 g). This was dissolved in hot methanol (ca. 200 mL) and hot filtered. The solution was boiled down to a volume corresponding to 3 mL/g methanol. After seeding and cooling with the aid of an ice bath, the crystals were collected, rinsed with ice-cold methanol and hexanes, and dried. Methyl 2-(aminosulfonyl)-4-ethoxybenzoate (15.3 g) was obtained as white crystalline needles melting at 146°-148° C. PMR (CDCl3, 200 mHz): δ7.91 (d, 1H, H ortho to CO2CH3); 7.68 (d, 1H, H ortho to SO2NH2); 7.04 (dd, 1H, H para to SO2NH2); 5.91 (broad s, 2H, NH2); 4.14 (q, 2H, OCH2CH3); 3.95 (s, 3H, CO2CH3); 1.45 (t, 3H, OCH2CH3). IR (Nujol): 3348 (m, NH); 3241 (m, NH); 1692 (s, C=O) cm-1.

المصدر