5 2,4-Dinitrophenyl sulfide

Mercaptobenzo[6]thiophenes are readily characterized through the formation of benzo[6]thienyl 2,4-dinitrophenyl sulfides by reaction with 2,4-dinitrochlorobenzene in the presence of base. 2-506,700 and 3-mercaptobenzo[6]thiophene505 are readily oxidized to the corresponding disulfides (e.g., with nitric acid). 

Asymmetric imidations of aryl alkyl sulfides with [(tosylimino)iodo]ben-zene, catalyzed by various chiral (salen)manganese(III) complexes, have been investigated in some detail [31,32]. The influence of catalyst structure, solvent, temperature, 3°-amine AT-oxides, and the presence of molecular sieves on product yields and the enantioselectivity of imidation with 17 was evaluated. Enan-tioselectivities as high as 90 % ee and 97 % ee with methyl 2-nitrophenyl sulfide and methyl 2,4-dinitrophenyl sulfide, respectively, were achieved. 

N 14.40% crysts (from, aq acet), mp 174—75° sol in acet mod sol in glac acet ac insol in w dec in alkalies. Can be prepd from bis(2,4-dinitrophenyl) -sulfide by Cheating for 6 hrs with an excess of CtOg in glac acet ac or by heating with K2Ct20Y in 87% sulfuric acid to 120° or in 57% sulfuric acid at boiling temp. 

Bis-(2,4-dinitrophenyl) sulfide 292 1-Chloro-l,4-dinitrobenzene (100 g) is dissolved in ethanol (11), and a melt of sodium sulfide nonahydrate (65.5 g) and sulfur (9 g) is added in small portions. A violent reaction occurs, which is completed by 3 hours boiling on a sand-bath. After cooling, the product is filtered off and washed, first, with ethanol and then with warm water to remove the sodium chloride. The product (86 g) has m.p. 280° (dec.). 

Dinitrobenzenesulfenyl chloride derivative (Aryl 2,4-dinitrophenyl sulfide)... 

Day, E. A. Patton, S. Paper chromatography of 2,4-dinitrophenyl sulfide derivatives of mercaptans and mercapto-acids. Microchem. J. 1959, 3, 137-141. 

General Method of Preparation of Alkyl (Aryl)2,4-Dinitrophenyl Sulfides... 

Benzyl 2,4-Dinitrophenyl Sulfide (Identification of Benzyl Mercaptan)... 

Procedure In a test tube containing a solution of 20 mg of benzyl 2,4-dinitrophenyl sulfide in 2 ml of acetic acid, hydrogen peroxide (0.3 ml) is added and the mixture is boiled gently for 2 min. After partial cooling an additional 0.3 ml of hydrogen peroxide is added and the mixture is boiled for a further 2 min. Water is then added until a colloidal precipitate is formed, and the mixture is allowed to stand in a refrigerator for 30 min. The separated sulfone is filtered off and washed twice with 1 ml of water. Yield, 23 mg mp, 168 —170 °C. Crystallization from 2 ml of methanol yielded 14 mg of the product, mp 177 —178 °C. A second crystallization from 1.5 ml of methanol left 8 mg of product, mp 181 — 182 °C. 

C22H15F2N3O1Q 100993-11-1) see Levofloxacin 4,4 -dinilrophenyl sulfide (C 2HjN204S 1223-31-0) see Dapsone 4,4 -dinitrophenyl sulfone (C 2HgN20,jS 1156-50-9) see Dapsone diosgenin... 

B. 2,4-Dinitrobenzenesulfenyl chloride. Dry 2,4-dinitrophenyl benzyl sulfide (232 g., 0.80 mole) and 400 ml. of dry ethylene chloride are placed in a 2-1., one-necked, round-bottomed flask equipped with a stirrer (Note 3). Sulfuryl chloride (119 g., 0.88 mole) (Note 4) is added to the resulting suspension at room temperature. A mildly exothermic reaction causes the solid to dissolve quickly, usually within 1 to 2 minutes, with a temperature rise of 10-15° (Note 5). The resulting clear yellow solution is concentrated to an oil by heating under aspirator vacuum on a steam bath (Note 6). Caution Do not heat with gas or electricity because the product, like many nitro compounds, can explode if overheated.) The residual oil is cooled to 50-60°, and 3-4 volumes of dry petroleum ether (b.p. 30-60°) are added with vigorous handswirling. The oil quickly crystallizes. The mixture is cooled to room temperature and filtered to separate 2,4-dinitrobenzene-sulfenyl chloride as a yellow crystalline solid. The sulfenyl chloride is washed well with dry petroleum ether and dried at 60-80° (Note 7) weight 150-170 g. (80-90%) m.p. 95-96° (Notes 8, 9). 

Dinitrophenyl benzyl sulfide has been prepared by the reaction of benzyl chloride with 2,4-dinitrothiophenol2 or bis-(2,4-dinitrophenyl) disulfide2 and by the condensation of 2,4-dinitrochlorobenzene with benzyl mercaptan.4... 

The chlorinolysis of 2,4-dinitrophenyl benzyl sulfide gives a good yield of product which is satisfactory for most purposes without recrystallization. Only simple equipment and inexpensive materials are needed, only 2 or 3 hours of the operator s time are required, and the entire procedure can be completed within 24 homs. 

Benzyl isocyanide, 41, 14 Benzyl mercaptan for synthesis of 2,4-dinitrophenyl benzyl sulfide, 44, 48... 

A. 2,4-Dinitrophenyl benzyl sulfide. The apparatus consists of a 1-1., three-necked, round-bottomed flask equipped with a sealed... 

The 2,4-dinitrophenyl benzyl sulfide normally undergoes cleavage at room temperature without the addition of a catalyst. If the reaction does not occur spontaneously, the mixture may be warmed gently and/or one drop of dry pyridine may be added to initiate the reaction. 

Dinitrobenzenesulfenyl bromide may be similarly prepared by refluxing 2,4-dinitrophenyl benzyl sulfide with the equivalent amount of bromine in 5 parts of dry carbon tetrachloride. As it is less stable than the chloride, losing bromine if overheated, it should be concentrated on a 40° water bath under vacuum. When worked up in the same manner as the chloride, the product usually contains some is-(2,4r-dinitrophenyl) disulfide. Because the disulfide is insoluble in carbon tetrachloride, the sulfenyl bromide may be readily purified by recrystallization yield 75-80%, m.p. 102-104°. 

In this group of readily oxidised materials, individually indexed compounds are Arsenic trisulfide, 0108 Bis(2,4-dinitrophenyl) disulfide, 3449 Bis(2-nitrophenyl) disulfide, 3465 Boron trisulfide, 0172 f Carbon disulfide, 0560 Carbon sulfide, 0559 f Carbonyl sulfide, 0556... 

Dimethoxy 1 methyl 2(1//) quinoxalinone-3-proprionylcarboxylic acid hydrazide Dimethyl sulfide Dimethyl sulfoxide Deoxyribonucleic acid 5is-(2,4-dinitrophenyl) oxalate Dansyl chloride Dansyl hydrazine... 

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