THE ACTION OF SODIUM IODIDE ON SOME ESTERS OF p-TOLUENESULFONIC ACID¹

Abstract

In 1897 it ivas observed (1) that potassium iodide (in hot alcohol or acetone) converts ethyl p-bromobenzenesulfonate to ethyl iodide. Many years later, methyl and ethyl iodides (2, 3) and ethyl a-iodopropionate (4) were prepared in good yield by the action of the same reagent (in boiling water or alcohol) on the corresponding p-toluenesulfonates. The method was next applied (5) to the preparation of diisopropylidene-6-iododesoxygalactose from the 6-tosyl derivative, with the improvement of using Finkelstein's reagent (6), namely, sodium iodide dissolved in acetone. Further research has, however, been mainly confined to study of the behavior of tosyl esters of sugar derivatives (7) towards the reagent and it has been found that a primary tosyloxy group is much more reactive than a secondary in such aldo-sugar derivatives as methyl 2,3,4,6tetratosyl-iS-D-glucoside.The reaction is usually found to proceed as an alkyl-oxygen fission (8) in accordance with the equation: ! SUMMARYThe reaction of certain esters of p-toluenesulfonic acid with sodium iodide dissolved in acetone has been studied. Their reactivities are found to be in the same relative order as those of the corresponding organic chlorides towards the same reagent.The tosyl esters of isopropyl alcohol and thymol have been obtained in crystalline condition. The less reactive esters studied may be prepared in good yield in the presence of pyridine at room temperature.Pittsburgh 13, Pa.

Dimeric Capsules by the Self‐Assembly of Triureidocalix[6]arenes through Hydrogen Bonds

“…Calixarenes 2, [8] 3 d, [8] 4 d [8] and 6 [16] were obtained by known procedures. 5,17,40,39,23,arene (3 a): A suspension of 2 (850 mg, 0.87 mmol) and NaH (450 mg, 11.25 mmol, 60 % in mineral oil) in DMF (150 mL) was stirred at 50 8C for 15 min and was treated with 1-iodooctane (3.8 mL, 21.05 mmol) at 75 8C for 3 days. The reaction mixture was partitioned between CH 2 Cl 2 and HCl (aq 10 %).…”

“…The residue was subjected to chromatography (hexane/EtOAc 9:1) and triturated (EtOH) to give 3 a as a yellow solid (534 mg, 51 % H 8.48,N 3.19;found C 73.40,H 8.87,N 3.23. 5,17,39,40,23,arene (3 b): A solution of 2 (421 mg, 0.43 mmol), K 2 CO 3 (366 mg, 2.60 mmol) and KI (ca. 20 mg) in CH 3 CN (70 mL) at 80 8C was treated with EtOCH 2 CH 2 OTs [17] (730 mg, 2.90 mmol) for 3 days.…”

“…5,17,39,40,23,arene (3 b): A solution of 2 (421 mg, 0.43 mmol), K 2 CO 3 (366 mg, 2.60 mmol) and KI (ca. 20 mg) in CH 3 CN (70 mL) at 80 8C was treated with EtOCH 2 CH 2 OTs [17] (730 mg, 2.90 mmol) for 3 days. The reaction mixture was partitioned between EtOAc (50 mL) and HCl (aq 10 %).…”

“…The residue was subjected to chromatography (hexane/EtOAc 2:1) and triturated (MeOH) to give 3 b as a pale yellow solid (196 mg, 38 % 15,H 7.32,N 3.51;found C 69.35,H 6.81,N 3.30. 5,17,39,40,23,arene (3 c): A solution of 2 (200 mg, 0.20 mmol) and K 2 CO 3 (171 mg, 1.24 mmol) in CH 3 CN (40 mL) was stirred at 70 8C for 2 h and was treated with 2-chloro-N,N-diethylacetamide (0.20 mL, 1.24 mmol) at 70 8C for 5 days. The reaction mixture was partitioned between EtOAc and HCl (aq 10 %).…”

Preparations of Anthraquinone and Naphthoquinone Derivatives and Their Cytotoxic Effects

“…5 (1,4-Dioxo-1,4-dihydronaphthalen-2-yl)methyl Thiocyanate (65) A solution of compound 59 (50 mg, 0.19 mmol) and HNO 3 (0.28 g, 2.90 mmol) in AcOH (10 ml) was stirred at room temperature for 1 h. The mixture was poured into ice-water (50 ml) and extracted with Et 2 O (50 mlϫ3). The organic extracts were washed successively with 5% aqueous NaHCO 3 and water, dried over MgSO 4 , and filtered.…”