Diphenylic acid

Thallium diphenyl acid propionate forms fine silky needles from toluene, M.pt. 164° C., these being completely soluble in cold chloroform, hot alcohol, pyridine, ethyl acetate, or glacial acetic acid, fairly soluble in boiling water, and insoluble in ether or light petroleum. 

Thallium diphenyl acid valerate.— M.pt. 176° Cv forms fine white needles from toluene, having a similar solubility to the propionate. 

Thallium diphenyl acid butyrate forms waxy needles, M.pt. 170° C., when dissolved in acetone the addition of light petroleum precipitates the normal butyrate, M.pt. 230° C.. ... 

Thallium diphenyl acid n-hexoate forms feathery rosettes of needles from toluene, M.pt. 191° C. the normal salt obtained similarly to the butyrate melts at 208° C. 

Production of diamino diphenyl Acid-catalyzed process with Zeolite Y, ZSM-5, High selectivity to the formation of DADPM 63 ... 

Classification Aromatic phosphorus compd. Empirical C12H10CIO3P Formula (C6Hs0)2P(0)CI Properties Liq. sol. in inert org. soivs. hydrolyzes with water m.w. 268.64 dens. 1.296 b.p. 145-148 C flash pt. 113 C ref. index 1.5500 Toxicology Harmful causes burns TSCA listed Precaution Corrosive hydrolyzes on contact with water to form HCI and diphenyl acid... 

When benzii is heated with potassium hydroxide solution, it undergoes a molecular rearrangement with the formation of the potassium salt of benzilic acid, or diphenyl lycollic acid ... 

Substances suitable for the estimation acetanilide, sucrose, glucose, cinnamic acid, diphenyl amine, salicylic acid, vanillin, />"bromoacetanilide, toluene p-sul phonamide. 

Diphenyl. Reflux a mixture of 1 g, of diphenyl, 2 ml. of glacial acetic acid and 0 -5 ml. of fuming nitric acid for 10 minutes. Pour into 20 ml. of cold water, filter oflF the precipitate, wash it with cold water imtil free from acid, and recrystallise from alcohol. The product is 4-nitrodiphenyl, m.p. 114°,... 

Difluorodiphenyl. Bis-diazotise a solution of 46 g. of benzidine (Section IV,88) in 150 ml. of concentrated hydrochloric acid and 150 ml. of water by means of a solution of 35 g. of sodium nitrite in 60 ml. of water add about 200 g. of crushed ice during the process (compare p-Fbtorotoluene above). Filter the solution and add it to a filtered solution of 85 g. of sodium borofluoride in 150 ml. of water. Stir for several minutes, collect the precipitated bis-diazonium borofluoride by suction filtration, wash with 5 ml. of ice-cold water, and dry at 90-100°. Place the dry salt in a flask fitted with an air condenser, immerse the flask in an oil bath, and slowly raise the temperature to 150° (Fume Cupboard ). When decomposition of the salt is complete, steam distil the mixture collect the 4 4 difluoro-diphenyl which passes over and recrystallise it from ethanol. The yield is 21 g., m.p. 92-93°. 

Purely aromatic ethers e.g., diphenyl ether), which are commonly encountered, are very hmited in number. Most of the aromatic ethers are of the mixed aliphatic - aromatic type. They are not attacked by sodium nor by dilute acids or alkahs. When hquid, the physical proper-ties (b.p., d . and ) are useful constants to assist in their identification. Three important procedures are available for the characterisation of aromatic ethers. 

Diphenic acid. Phenanthrene upon oxidation in acetic acid solution at 85° with 30 per cent, hydrogen peroxide gives diphenic acid (diphenyl-2 2 -di-carboxyHc acid) no phenanthraquinone is formed under these experimental conditions. The reaction is essentially an oxidation of phenanthrene with peracetic acid. (For another method of preparation, see Section I V,74.)... 

Place 125 ml. of glacial acetic acid, 7 -5 g. of purifled red phosphorus (Section II,50,d) and 2 5 g. of iodine in a 500 ml, round-bottomed flask fitted with a reflux condenser. Allow the mixture to stand for 15-20 minutes with occasional shaking until aU the iodine has reacted, then add 2 5 ml. of water and 50 g, of benzilic acid (Section IV,127). Boil the mixture under reflux for 3 hours, and filter the hot mixture at the pump through a sintered glass funnel to remove the excess of red phosphorus. Pour the hot filtrate into a cold, weU-stirred solution of 12 g. of sodium bisulphite in 500 ml, of water the latter should be acid to litmus, pro duced, if necessary, by passing sulphur dioxide through the solution. This procedure removes the excess of iodine and precipitates the diphenyl-acetic acid as a fine white or pale yellow powder. Filter the solid with suction and dry in the air upon filter paper. The yield is 45 g., m.p. 

The cyclic carbonate of benzoin (4,5-diphenyl-l,3-dioxol-2-one, prepared from benzoin and phosgene) blocks both hydrogen atoms of primary amines after dehydration acid stable, easily crystallizable Sheehan oxazolinones are formed, which are also called Ox derivatives. The amine is quantitatively deblocked by catalytic hydrogenation in the presence of 1 equiv. of aqueous acid (J.C Sheehan, 1972, 1973 M.J. Miller, 1983). An intelligent application to syntheses of acid labile -lactams is given in the previous section (p. 161). 

Acyl halides are intermediates of the carbonylations of alkenes and organic-halides. Decarbonylation of acyl halides as a reversible process of the carbo-nylation is possible with Pd catalyst. The decarbonylation of aliphatic acid chlorides proceeds with Pd(0) catalyst, such as Pd on carbon or PdC, at around 200 °C[109,753]. The product is a mixture of isomeric internal alkenes. For example, when decanoyl chloride is heated with PdCF at 200 C in a distillation flask, rapid evolution of CO and HCl stops after I h, during which time a mixture of nonene isomers was distilled off in a high yield. The decarbonylation of phenylpropionyl chloride (883) affords styrene (53%). In addition, l,5-diphenyl-l-penten-3-one (884) is obtained as a byproduct (10%). formed by the insertion of styrene into the acyl chloride. Formation of the latter supports the formation of acylpalladium species as an intermediate of the decarbonylation. Decarbonylation of the benzoyl chloride 885 can be carried out in good yields at 360 with Pd on carbon as a catalyst, yielding the aryl chloride 886[754]. 

The reduction of acyl halides with hydrogen to form aldehydes using Pd catalyst is well known as the Rosenmund reduction[756]. Some acyl chlorides give decarbonyiation products rather than aldehydes under Rosenmund conditions. The diene 890 was obtained by decarbonyiation in an attempted Rosenmund reduction of acetyloleanolic acid chloride (889)[757], Rosenmund reduction of sterically hindered acyl chlorides such as diphenyl- and tnpheny-lacetyl chloride (891) gives the decarbonylated products 892[758],... 

Substitmed A-2-thiazoline-4-ones are much more stable (59. 386. 387. 413, 414). 2.5-Diphenyl-A-2-thiazoline-4-one (173) is obtained in 95% yield from 2.5-diphenyl-4-aminothiazole (172) by heating under reflux with 40% sulfuric acid (Scheme 89) (415). 

When styrene is refluxed with aqueous sulfuric acid two styrene dimers are formed as the major products One of these styrene dimers is 1 3 diphenyl 1 butene the other is 1 methyl 3 phenyhndan Suggest a reasonable mechanism for the formation of each of these compounds... 

Alkyl diphenyl phosphate plasticizers can exert flame-retardant action in vinyl plastics by a condensed-phase mechanism, which is probably some sort of phosphoms acid coating on the char. Triaryl phosphates appear to have a vapor-phase action (29). 

Phosphites. Tertiary phosphites are also commonly used and are particularly effective ia most mixed metal stabilizers at a use level of 0.25—1.0 phr. They can take part ia a number of different reactions duting PVC processing they can react with HCl, displace activated chlorine atoms on the polymer, provide antioxidant functionaHty, and coordinate with the metals to alter the Lewis acidity of the chloride salts. Typical examples of phosphites are triphenyl phosphite [101 -02-0], diphenyl decyl phosphite [3287-06-7], tridecyl phosphite [2929-86-4], and polyphosphites made by reaction of PCl with polyols and capping alcohols. The phosphites are often included in commercial stabilizer packages. 

Colorless dyes of the chlorinated diphenyl ether—ureasulfonic acid type (Mitin [3567-25-7] (158)) and the (polychloro-2-chloromethylsulfonamido)-diphenyl ether type (Eulan (159)) appHed at 1—3% of the fabric weight are the most widely used during the fabrication of woolens. They cannot be removed by dry cleaning and provide protection from fabric pests over the lifetime of the product. 

Nitric acid may be precipitated by nitron [2218-94-2] (4,5-dihydro-l,4-diphenyl-3,5-phenylimino-l,2,4-triazole). The yellow precipitate maybe seen at dilutions as low as 1 60,000 at 25°C or 1 80,000 at 0°C. To prevent nitrous acid from interfering with the test results, it may be removed by treating the solution with hydrazine sulfate, sodium azide, or sulfamic acid. 

The anti-inflammatory agent Oxapro2in, 2-(4,5-diphenyl-2-oxa2ole)propionic acid mono aluminum and dihydroxyalurninum salts, is made by reaction of the sodium salt with aluminum sulfate under controlled conditions (96). Again, the aluminum salts of many carboxylic acid based dmgs are less irritating, ulcerous, and/or toxic, and have a more pleasant taste than their parent acids. 

---