Benzene phosphoric acid

In some non-polar solvents such as benzene, phosphoric acid (13.1a), phosphonic acids (13.1b) and phosphinic acids (13.1c) form dimers which have stronger H bonds than the corresponding carboxylic dimers (13.Id). 

Propylation of benzene with propylene, catalyzed by supported phosphoric acid (or related catalysts such as AlCl ), gives cumene [98-82-8] in another important industrial process. Cumene (qv), through the intermediacy of cumene hydroperoxide, is used in the manufacture of phenol (qv). Resorcinol similarly can be made from y -diisopropylbenzene (6). 

Catalysts. Nearly aU. of the industrially significant aromatic alkylation processes of the past have been carried out in the Hquid phase with unsupported acid catalysts. For example, AlCl HF have been used commercially for at least one of the benzene alkylation processes to produce ethylbenzene (104), cumene (105), and detergent alkylates (80). Exceptions to this historical trend have been the use of a supported boron trifluoride for the production of ethylbenzene and of a soHd phosphoric acid (SPA) catalyst for the production of cumene (59,106). 

A Methylamino)phenol. This derivative (15) is easily soluble ia ethyl acetate, ethanol, diethyl ether, and benzene. It is also soluble ia hot water, but only spatingly soluble ia cold water. Industrial synthesis is by heating 3-(A/-methylamino)benzenesulfonic acid with sodium hydroxide at 200—220°C (179) or by the reaction of resorciaol with methylamiae ia the presence of aqueous phosphoric acid at 200°C (180). 

A Phenylamino)phenol. This phenol (17) is slightly soluble ia ethanol, diethyl ether, acetone, benzene, and water. The compound is made by heating resorciaol and aniline at 200°C ia the preseace of aqueous phosphoric acid or calcium chloride. Ia another process, 3-amiaophenol is heated with aniline hydrochloride at 210—215°C (181). 

The radioactive isotopes available for use as precursors for radioactive tracer manufacturing include barium [ C]-carbonate [1882-53-7], tritium gas, p2p] phosphoric acid or pP]-phosphoric acid [15364-02-0], p S]-sulfuric acid [13770-01 -9], and sodium [ I]-iodide [24359-64-6]. It is from these chemical forms that the corresponding radioactive tracer chemicals are synthesized. [ C]-Carbon dioxide, [ C]-benzene, and [ C]-methyl iodide require vacuum-line handling in weU-ventilated fume hoods. Tritium gas, pH]-methyl iodide, sodium borotritide, and [ I]-iodine, which are the most difficult forms of these isotopes to contain, must be handled in specialized closed systems. Sodium p S]-sulfate and sodium [ I]-iodide must be handled similarly in closed systems to avoid the Uberation of volatile p S]-sulfur oxides and [ I]-iodine. Adequate shielding must be provided when handling P P]-phosphoric acid to minimize exposure to external radiation. 

Cumene as a pure chemical intermediate is produced in modified Friedel-Crafts reaction processes that use acidic catalysts to alkylate benzene with propylene (see Alkylation Friedel-CRAFTSreactions). The majority of cumene is manufactured with a soHd phosphoric acid catalyst (7). The remainder is made with aluminum chloride catalyst (8). 

Certain /3-hydroxyoximes, unsubstituted in the ortho position of an adjacent benzene ring, cyclize when treated with phosphoric acid to give styrylbenzoxazole (equation 60). 

FIG. 23-3 Temperature and composition profiles, a) Oxidation of SOp with intercooling and two cold shots, (h) Phosgene from GO and Gfi, activated carbon in 2-in tubes, water cooled, (c) Gumene from benzene and propylene, phosphoric acid on < uartz, with four quench zones, 260°G. (d) Mild thermal cracking of a heavy oil in a tubular furnace, hack pressure of 250 psig and sever heat fluxes, Btu/(fr-h), T in °F. (e) Vertical ammonia svi,ithesizer at 300 atm, with five cold shots and an internal exchanger. (/) Vertical methanol svi,ithesizer at 300 atm, Gr O -ZnO catalyst, with six cold shots totaling 10 to 20 percent of the fresh feed. To convert psi to kPa, multiply by 6.895 atm to kPa, multiply by 101.3. 

In this process liquid propylene, containing some propane, is mixed with benzene and passed through a reaction tower containing phosphoric acid on kieselguhr as catalyst. The reaction is exothermic and the propane present acts as a quench medium. A small quantity of water is injected into the reactor to... 

One gram of 6,7-dihydro-5H-dibenz[c,e] azepine hydrochloride was dissolved in water, made alkaline with concentrated ammonia, and the resultant base extracted twice with benzene. The benzene layers were combined, dried with anhydrous potassium carbonate, and mixed with 0.261 g of allyl bromide at 25°-30°C. The reaction solution became turbid within a few minutes and showed a considerable crystalline deposit after standing 3 A days. The mixture was warmed VA hours on the steam bath in a loosely-stoppered flask, then cooled and filtered. The filtrate was washed twice with water and the benzene layer evaporated at diminished pressure. The liquid residue was dissolved in alcohol, shaken with charcoal and filtered. Addition to the filtrate of 0.3 gram of 85% phosphoric acid in alcohol gave a clear solution which, when seeded and rubbed, yielded 6-allyl-6,7-dihydro-5H-dlbenz[c,e] azepine phosphate, MP about 211°-215°C with decomposition. 

The base is extracted with ether, dried with potassium carbonate, the ether removed by distillation and the residue fractionated. The 4-(5 -diethylaminopentyl-2 -amino)-7-chloro-quinoline (BP 212° to 2l4°C/0.2 mm) is obtained. On cooling the compound solidifies crystalline. It melts, recrystallized from benzene, at BB°C. The base combines with phosphoric acid to yield a diphosphate salt. 

In the vapor-phase process, the reaction temperature and pressure are approximately 250°C and 40 atmospheres. Phosphoric acid on Kieselguhr is a commonly used catalyst. To limit polyalkylation, a mixture of propene-propane feed is used. Propylene can be as low as 40% of the feed mixture. A high benzene/propylene ratio is also used to decrease polyalkylation. A selectivity of about 97% based on benzene can be obtained. 

Aliphatic phosphoric acid and phosphonic acid amides containing lipophilic groups were prepared and used as antimicrobial surfactants. For example, 100 g ethylmethanephosphonate chloride was added to a solution of 130 g dodecyl-amine and 72 g triethylamine in 500 ml anhydrous benzene at 20-30°C to give 192 g ethylmethanephosphonate N-dodecylamide [125]. 

Acid ester phosphates with an alkyl chain up to C6 have little solubility whereas neutralized esters are soluble in water. In ethanol and isopropanol most of phosphoric acid esters and their salts are soluble. If the products are based on ethoxylated alcohols their solubility in water will increase as the degree of ethoxylation increases. The solubility in organic solvents like gasoline, benzene, perchlorethylene, and other apolar liquids recedes with an increase in the degree of ethoxylation but are increased by a higher alkyl chain. 

Benzene itself, when photolyzed in acetic and aqueous phosphoric acids, has been reported to yield photo adducts 31 and 32 respectively (Farenhorst and Bickel, 1966). Protonated prefulvene (33) is suggested... 

The prepared MAC adsorbents were tested for benzene, toluene, 0-, m-, p-xylene, methanol, ethanol, iso-propanol, and MEK. The modified content of all MACs was 5wt% with respect to AC. The specific surface areas and amounts of VOC adsorbed of MACs prepared in this study are shown in Table 1. The amounts of VOC adsorbed on 5wt%-MAC with acids and alkali show a similar tendency. However, the amount of VOC adsorbed on 5wt%-PA/AC was relatively large in spite of the decrease of specific surface area excepting in case of o-xylene, m-xylene, and MEK. This suggests that the adsorption of relatively large molecules such as 0-xylene, m-xylene, and MEK was suppressed, while that of small molecules was enhanced. It can be therefore speculated that the phosphoric acid narrowed the micropores but changed the chemical nature of surface to adsorb the organic materials strongly. 

Other bisazolides of phosphoric acid include O-phenylphosphoric diimidazolide and -ditriazolide O-phenylphosphoric diimidazolide, for instance, has been prepared from phenylphosphordichloridate and four equivalents of imidazole in benzene. 

Bromo-l-phthalimidopentane 3 was obtained in 72-82 g yield by refluxing 92 g of 1,4-dibromopentane 1, 55.5 g of potassium phthalimide 2, and 200 mL dry acetone on a steam bath for 30 h. Compound 3 (30 g) and 42 g 6-methoxy-8-aminoquinoline 4 refluxed at 130-135 °C for 6 h, extracted with benzene to separate insoluble 6-methoxy-8-aminoquinoline hydrobromide, the residue from evaporation of the benzene was refluxed with stirring with 100 mL of an alcoholic solution of 6 g hydrazine hydrate for 4 h, the solution was concentrated, made acidic to Congo red with 8 N hydrochloric acid, filtered, and washed with boiling water. The combined filtrate and washings was concentrated, made alkaline, extracted with benzene, and distilled in vacuo to give 20.5 g primaquine 6, which was treated with 19 mL 85% phosphoric acid in absolute ethanol, formed 42.5% primaquine diphosphate. 

A mixture of 10 g. of D-galactose, 10 ml. of ethyl acetoaeetate, 10 ml. of ethanol, and 5 g. of zinc chloride is heated on a steam bath during 75 minutes. The mixture is cooled, 45 ml. of water is added, and the solution is extracted with two 30-ml. portions of benzene. The aqueous layer is then extracted with nine 15-ml. portions of ethyl acetate. The united extracts are washed successively with an aqueous solution of sodium bisulfite and with an aqueous solution of sodium bicarbonate, dried with anhydrous sodium sulfate, filtered, and the filtrate evaporated to dryness, affording 4.5 g. of a sirup. This is saponified with 12.5 ml. of 10% sodium hydroxide solution, and then acidified (to Congo Red) with phosphoric acid. The aqueous solution is extracted with successive 30-ml. portions of ethyl acetate, and these are dried with anhydrous sodium sulfate, and individually evaporated to dryness. Extracts after the fourth yield a solid product m. p., 130°. Recrystallized from petroleum ether plus acetic acid, the compound has m. p. 132-134° yield, variable, ca. 2%.54... 

Equimolar quantities of 2,4-diamino-l,5-benzenediol dihydrochloride and isophthalic acid were mixed in fresh poly (phosphoric acid) using a high-shear stirrer under a slow stream of nitrogen gas. The system was heated at 40°C for 6 hours, at CG°C for 18 hours, at 120°C for 6 hours, at 160°C for 8 hours, and at 220°C for 24 hours. The resultant mixture was dark brown. The polymer was precipitated from water. After filtration and washing with water and methanol, the solid product was then dissolved in methane-sulfonic acid, filtered and precipitated by the addition of methanol. The solid was washed with concentrated ammonium hydroxide, water, methanol, methanol/benzene mixtures (with a volume ratio of 1/1), and finally benzene. The final product was dark brown. 

Alkymax A process for removing benzene from petroleum fractions. They are mixed with light olefin fractions (containing mainly propylene) and passed over a fixed-bed catalyst, which promotes benzene alkylation. The catalyst is solid phosphoric acid (SPA), made by mixing a phosphoric acid with a siliceous solid carrier, and calcining. Invented in 1980 by UOP... 

Prepare 6-methoxy-l-indanone (I) (JCS 1986(1962)) using polyphosphoric acid made by diluting 500 g of the commercial acid with 120 g 85% phosphoric acid. 2.5 g (I) in 176 ml ether and reflux one hour with 0.27 g lithium aluminum hydride. Cool and carefully add water and filter when bubbling stops (can use Celite filter aid). Dry and evaporate in vacuum and store twelve hours at -15° (under N2 if possible) to precipitate the white 6-methoxy-l-indanol (II) (recrystallize-n-hexane). 2.5 g (II) in 73 ml benzene and reflux one-half hour with 0.2 g p-toluenesulfonic acid. Cool, add water and separate the phases. Extract the aqueous phase with ether and combine with benzene phase and dry, evaporate in vacuum to get 5-methoxy-indene (III) (can distill 110-45/10). 1.53 g (III) and 1.39 g N.N-diethyl-aminoethyl-Cl.HCI in benzene (prepare the free base in benzene as described previously). Reflux four hours with 0.42 g sodamide, cool, wash with water and dry, evaporate in vacuum to get the indene analog of 6-methoxy DET as a dark liquid (can crystallize as oxalate). Alternatively, dissolve 2.51 g (III) in ether and treat (under N if possible) with 12 ml 1.6M buty-Li in hexane at 0-10°. After two hours cool to -30° and add 12 ml more of butyl-Li. Add ether suspension of 2.5 g N,N-diethylaminoethyl-CI. HCI over one-half hour and warm to room temperature. Filter, evaporate in vacuum to get the 6-methoxy-DET analog. 

Pd-catalyzed C—P bond formation on the benzene ring of quinoxaline has been reported. Phosphoric acid ester 102 was prepared from 7-bromoquinoxaline 101 and diethylphosphite via a Heck-type reaction [59],... 

Nakagome and co-workers effected the successful cyclization of N-ethyl-N-arylaminomethylenemalonates (749) in poly phosphoric acid, prepared from orthophosphoric acid and phosphorus pentoxide in polyphosphate ester (PPE), prepared from phosphorus pentoxide and anhydrous diethyl ether in chloroform in phosphoryl chloride on the action of boron trifluoride etherate on the action of acetic anhydride and concentrated sulfuric acid or on the action of phosphorus pentoxide in benzene [71GEP2033971, 71JHC357 76JAP(K) 18440]. Depending on the work-up process, l-ethyl-4-oxoquinoline-3-carboxylates (750, R1 = Et), l-ethyl-4-oxoquinoline-3-carboxylic acids (750, R2 = H) and 3-ethoxycarbonyl-4-chloroquinolinium iodides (751) were obtained. Only the cyclization of... 

Figure 2.2 Separation of aromatic compounds using isocratic elution. Conditions column, 5 pm Cis-bonded silica gel, 15 cm x 4.6 mm i.d. eluent, 0.001 M phosphoric acid in 55% aqueous acetonitrile flow rate, 1ml min-1 temperature, ambient, detection, UV 254 nm. Peaks 1, phenol, 2, 4-methylphenol 3, 2,4-dimethylphenol 4, 2,3,5-trimethylphenol 5, benzene, 6, toluene, 1, ethylbenzene, 8, propylbenzene and 9, butylbenzene.

During World War II, isopropyl benzene, more commonly and commercially known as cumene, was manufactured in large volumes for use in aviation gasoline. The combination of a benzene ring and an iso-paraffin structure made for a very high octane number at a relatively cheap cost. After the war, the primary interest in cumene was to manufacture cumene hydroperoxide. This compound was used in small amounts as a catalyst in an early process of polymerizing butadiene with styrene to make synthetic rubber. Only by accident did someone discover that mild treating of cumene hydroperoxide with phosphoric acid resulted in the formation of... 

The reachon of benzene with ethylene or propylene to form ethylbenzene or isopropylbenzene (cumene) is an industrially important transformahon, with ethylbenzene as the key building block for polystyrene and cumene as the feedstock for phenol produchon [55]. Fthylbenzene was originally produced with a Lewis acid catalyst consishng of AlCfi or a Bronsted acidic solid phosphoric acid (SPA) catalyst [56]. Both catalyst systems suffered from equipment corrosion so, in the 1980s the Mobil-Badger vapor phase alkylation process was introduced, which... 

Materials and Method. Aqueous solutions of disodium alkyl phosphates were prepared by dissolving the corresponding acids in sodium hydroxide solutions. The alkyl phosphoric acids were synthesized by the reaction of pyrophosphoric acid with the respective alcohol in benzene at room temperature for A days. Details of the purification procedures are given elsewhere(7). 

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