Nitrophenyl Sulfide

In a 1-1. round-bottomed flask equipped with a reflux condenser are placed 157.5 g. (1 mole) of / -chloronitrobenzene, 160 g. (1 mole) of potassium xanthate (Note 1), and 450 ml. of 95% ethanol. This reaction mixture is heated under reflux on a steam bath for 48 hours. The crystalline product, which deposits from solution during the course of the reaction, is collected by filtration, crushed into small particles in a mortar, and washed twice with hot ethanol and once with hot water. The 3neld of / -nitrophenyl sulfide melting at 158-160° is 105-113 g. (76-82%). This product is pure enough for most purposes. Recrystallization from glacial acetic acid (15 ml. per gram) raises the melting point to 160-161°. 

Potassium xanthate may be prepared in the following manner With heating, 300 g. (5.36 moles) of potassium hydroxide is dissolved in 31. of absolute ethanol. The solution is then cooled in an ice bath, and the temperature is kept below 10° while carbon disulfide is added in portions with stirring imtil the solution is no longer alkaline about 456 g. (360 ml., 5.95 moles) of carbon disulfide is required. The potassium xanthate is collected by suction filtration and air-dried on large sheets of filter paper yield, 429-472 g. (50-55%). 

---

Bis(2-nitrophenyl) sulfide is transformed into the parent dibenzothiadiazepine in low yield by reduction with lithium aluminum hydride153 or electrochemicaliy.328... 

Chlorine scission of 2-chloroheptyl 4-nitrophenyl sulfide or of the 2,4-dinitro analogue in presence of lithium perchlorate formed the explosive 2-chloroheptyl perchlorate in 5-7% yield. 

The a- and /3-cyclodextrins have been found to accelerate the Smiles rearrangement of 4-nitrophenyl salicylate. The reaction of 2,4-dinitrobenzenesulfonamide with acyl chlorides in the presence of excess triethylamine has been found to produce the corresponding nitrile in good yield. Mechanistic studies have indicated that the reaction proceeds via a Smiles rearrangement of the initially formed iV-(2,4-dinitrobenzenesulfonyl)amide to form the nitrile, 2,4-dinitrophenol, and sulfur dioxide (see Scheme 12). l-Chloro-3-fluorophenothiazines have been prepared by Smiles rearrangement of 3-chloro-5-fluoro-2-formamido-2 -nitrophenyl sulfides in alcoholic... 

Some discussion has arisen concerning the products and mechanism of the formation of dibenzo[fc/]-l,4,5-thiadiazepine derivatives from di-(2-nitrophenyl) sulfide (91). In one investigation156 it was concluded that the dibenzothiadiazepine was formed by reaction of a nitroso group with an... 

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. 

An alternative method for asymmetric and metal-free sulfoxidation was explored by Kita et al. [133], In their approach, iodosylbenzene (Ph-I02) was used as oxidant in reversed micelles formed by cetyltrimethylammonium bromide (CTAB) in toluene. From the numerous chiral inductors tested, tartaric acid derivatives proved best. In the presence of 10 mol% bis(2-methoxybenzoyl)tartaric acid, methyl (4-nitrophenyl)sulfide was converted into the sulfoxide in 91% yield and with 72% enantiomeric excess [133],... 

To a single-necked, round-bottomed flask (100 mL), add 4-chlorophenyl 2-nitrophenyl sulfide 15 (2.0 g, 7.5 mmol), freshly distilled cumene (75 mL), dry triethyl phosphite (5.0 g, 30 mmol) and a magnetic stirrer bar. 

A solution of 990 g. (4.40 moles) of stannous chloride dihydrate in 975 ml. of concentrated hydrochloric acid is added to 165 g. (0.598 mole) of di-(p-nitrophenyl) sulfide [Org. Syntheses, 28, 82 (1948)]. To initiate reaction, the mixture is warmed on the steam bath to 65°. The reaction mixture is heated to 80-90° for 5 hours and then poured into an ice-cold solution of 1290 g. of sodium hydroxide dissolved in 3230 ml. of water. The precipitated solid is removed by filtration and... 

Nitrophenyl sulfide has been prepared by the reaction between />-chloronitrobcnzcnc and sodium sulfide. This is not a... 

One nitro group of 0-dinitrobenzene and its derivatives is reactive and can be replaced by a mercapto, alkylthio, or sulfo group under the influence of sodium sulfide, sodium thiolates, or sodium sulfite, respectively. For preparative purposes this reaction is, however, restricted to a few examples. o-Dinitro-benzene and sodium sulfide give bis-(0-nitrophenyl) sulfide,492 and trinitro-anisole gives the bis(methoxydinitrophenyl) sulfide.493... 

Novel heterocycles. Some novel heterocycles have been prepared by de-oxygenation of indolyl o-nitrophenyl sulfides, prepared by reaction of indoles with 2-nitrobenzenesulfenyl chloride. The reaction involves intermediate spirocycUc compounds. 

---