Diphenyl orange

Tropeolin 00 (also called orange IV, aniline yellow, or diphenyl orange) Schultz No. 97. Sodium salt of diphenylaminoazo-p-benzenesulfonic acid,... 

CUCI2 on phenyl magnesium halides also provide reasonable quantities of diphenyl. Uses include its action as a fungistat during shipment of apples and oranges, and as a heat transfer agent (dowtherms) mixed with diphenyl ether and terphenyls. 

Methyl Orange.--The first point to notice in this reaction is that the diazonium salt forms no diazoamino-compotind with the dimethylanilinc, but at once pioduces an azo-compound. This is always the case with tertiary amines, some secondary amines like diphenyl.amine and the phenols. The reaction may be regarded as typical of the formation of all azo-colounng m.atters. At least two substances are requisite in this process on the one hand. an aromatic compound containing an amino-groujD in the nucleus, and, on the other, a base or phenol... 

General procedure To a flame-dried, three-necked, 250 mL, round-bottomed flask equipped with argon inlet, addition funnel and gas bubbler was added 100 mL of dry 1,2-dimethoxyethane (DME) with 0.20 g (0.98 mmol) of triflate [R, R =Me] and 0.50 g (1.2 mmol) of diphenyl diteUuride. The reaction mixture was cooled to 50°C and a solution of potassium f-butoxide (0.15 g, 1.3 mmol) in 50 mL of dry DME was added dropwise. After the addition, stirring was continued for 15 min at -50°C, then the reaction was aUowed to warm to room temperature. DME was then removed on a rotary evaporator and the residue taken up in hexane and filtered. The resulting coloured solution was chromatographed on activated silica (hexane as eluent). Isolated yield was 0.12 g (26%), as an orange oil. 

Method a + c. The tellurium dibromide (1.0 mmol) in THF (20 mL) is treated with 0.5 N NaOH (10 mL) at room temperature with stirring, and the resnlting solntion is stirred for 1 h, the colour of the solution turning to orange. The mixtnre is dilnted with brine and extracted with ether. The extracts are dried (MgS04), evaporated nnder vacnnm and the residue purified from diphenyl ditelluride by Si02 chromatography (elntion with hexane). The pure olefin is isolated by distillation of the residne. 

Ph, R = H) and acetic anhydride-triethylamine was initially thought to be anhydro-2,3-diphenyl-4-hydroxy-l,3-thiazolium hydroxide, CijHiiNOS (114, R = R = Ph, R = H), but later studies established that the product had the molecular formula C30H24N2O2 and the constitution 116. The synthesis of the meso-ionic l,3-thiazol-4-one (114, R = R = Ph, R = H), orange-yellow needles, m.p. 113°-115°, was successfully achieved by dehydration of the acid (115, R = R = Ph, R = H) using acetic anhydride-triethylamine for a few minutes at room temperature. The acids (115, R = NR2, R = Ph, R = H) and acid anhydrides similarly yield the corresponding meso-ionic l,3-thiazol-4-ones (114, R = NRj, R = Ph, R = H). Analogous polycylic meso-ionic l,3-thiazol-4-ones have also been prepared. ... 

As early as 1963 Markl prepared the first representatives of this class of compounds via multi-step synthesis l,l-diphenyl-X -phosphorin 118 ( 1,1-diphenyl-phosphabenzene ) and 1,l-diphenyl-2,3-benzo-X -phosphorin i20 ( 1,1-diphenyl-phospha-naphthalene ). Neither compound could be obtained in crystalline form. Instead, treatment of the crystalline phosphonium salts iiP and 121 with aqueous alkali affords very reactive, air-sensitive yellow or orange powders 118 and 120). Acid treatment leads back to the phosphonium salts. 

Preparation of tetraphenylallene. (See Eq. 24.) To 200 ml of stirred liquid ammonia containing 7.28 gm (0.0255 mole) of 1,1,1-trichloro-2,2-diphenyl-ethane is added a solution of 0.0255 mole of potassium diphenylmethide in 300 ml of liquid ammonia. The mixture turns an orange-red color and then discharges immediately. After 1 hr the mixture is worked up to give 4.46 gm (75%) of l,l-dichloro-2,2-diphenylethene. 

To a stirred solution of 0.02 mole of an orange-red solution of potassium diphenylmethide in 150 ml of liquid ammonia and 50 ml of dry ethyl ether, prepared from 0.02 mole of KNH2 and 3.36 gm (0.02 mole) of diphenyl-methane, is added 2.5 gm (0.01 mole) of l,l-dichloro-2,2-diphenylethene. The reaction mixture darkens and then a precipitate forms. The reaction mixture is stirred until all the ammonia evaporates to leave a solid. The solid is recrystallized from chloroform-methanol to afford 3.1 gm (90%) of tetraphenylallene, m.p. 164°C. 

A suspension of potassium amide (0.23 mole) in liquid ammonia is prepared in a 1-1. three-necked flask equipped with an air condenser (without drying tube), a ball-sealed mechanical stirrer, and a dropping funnel. Commercial anhydrous liquid ammonia (500 ml.) is introduced into the flask from a cylinder through an inlet tube. To the stirred ammonia is added a small piece of potassium metal. After the appearance of a blue color, a few crystals (about 0.25 g.) of ferric nitrate hydrate are added, followed by small pieces of potassium (Note 1) until 9.0 g. (0.39 g.-atom) has been added. After all the potassium has been converted to the amide (Note 2), 44.6 g. (0.23 mole) of diphenyl-acetonitrile (Note 3) is added and the resulting greenish-brown solution is stirred for 5 minutes. To this is added, over 10 minutes, 30.5 g. (0.24 mole) of benzyl chloride (Note 4) in 100 ml. of anhydrous ether. The orange solution is stirred for 1 hour, and the ammonia is then evaporated on a steam bath as 300 ml. of anhydrous ether is being added. To the ether solution is added 300 ml. of water, whereupon the crude nitrile precipitates. riie ether is then removed by distillation and the crude... 

The self-condensation of 5-nitrosamino-3-phenyl-l,2,4-thiadiazole (269) proceeds differently in benzene, the products being the orange-red azoxy-thiadiazole 270 (40% yield), together with 3,5-diphenyl-... 

Determination of concentration. Two laboratories3 recommend l,3-diphenyl-2-propanone tosylhydrazone (m.p. 185-186° dec.) for determination of The concentration of RLi in THF solutions. The dianion of the tosylhydrazone has an intense orange color. 

Diphenyl selenide is a colourless, strongly refractive oil, B.pt. 167° C. at 16-5 mm. insoluble in water but miscible with alcohol or ether in all proportions. It has a faint odour, and a density of 1 3712 at 0° C., 1 3561 at 15 2° C., and 1 350 at 20° C. With cold bromine in ether solution it yields the dibromide. Diphenyl selenide, unlike dimethyl selenide, does not combine with alkyl iodides, and in this respect it resembles diphenyl sulphide.2 When heated nearly to its boiling-point with sulphur it gives diphenyl sulphide, the reaction being practically quantitative at 300° C.3 With palladium chloride it forms the complex PdCl2.2(C6H5)2Se, orange-red needles, M.pt. 181° to 182° C.4... 

Chromium tetraphenyl hydrogen carbonate, (C6H5)4Cr.HC03. 2HaO.—An aqueous solution of the tetraphenyl base is saturated with carbon dioxide and concentrated over sulphuric acid in vacuo. The residue is treated with alcohol and the product precipitated by ether. Orange crystals separate, M.pt. 110° to 1110 C., prolonged desiccation over phosphorus pentoxide causing decomposition and formation of diphenyl. 

The preparation of the oily ethyl 2,3-diphenyl-5-methyl-isoxazolidine-4-carboxylate provides another example of this reaction. As in the procedure described with styrene, 10.0 g. (50.7 mmoles) of N,a-diphenylnitrone is heated under nitrogen for 24 hours at 90-100° with 35.0 g. (38.0 ml., 307 mmoles) of ethyl crotonate. The excess olefin, b.p. 45° (12 mm.) is removed on the water pump, and the red-orange residue, while still warm, is transferred to a 50-ml. Claisen flask using acetone as a rinse. 

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