Derivatives Acid phthalates

MgS04, filter, evaporate, then recryst from pet ether. Also recryst from aqueous EtOH and has been distd in a vacuum. [Kergomard and Geneix Bull Soc Chim Fr 394 1958 Zweifel and Brown J Am Chem Soc 86 393 1964.] The 3,4-dinitrobenzoyl deriv has m 100-101 , the phenylcarbamoyl derivative has m 137-138 and the acid -phthalate has m 125-126 . 

Nucleophilic carboxyl group participation is much more favourable with the phthalate, maleate, glutarate, and succinate monoesters than the acetylsalicylic acid derivatives. Monophenyl phthalate hydrolyses more than 10 times as fast as aspirin. The carboxylate ion acts as a nucleophile with monophenyl phthalate but as a.general base in the case of acetylsalicylic acid, even though the leaving group... 

Cellulose acid phthalate, I, 320 Cellulose acid succinate, I, 320 Cellulose benzoate, I, 320 Cellulose carbamates, N-derivatives, I, 321... 

Optically pure (+)-l-octyn-3-ol may be obtained by recrystallization of the half acid phthalate with (+)-a-methylbenzyl amine (Aldrich Chemical Company). The half acid phthalate salt Is made by heating equal molar amounts of l-ocytn-3-ol and phthalic anhydride. This half acid phthalate derivative... 

Tritylsodium has been used in the preparation of acid phthalate derivatives of tertiary alcohols by the following procedure. " An ethereal solution of tritylsodium... 

With modification, the aforesaid method can sometimes be applied to the resolution of a neutral compound. Such a resolution is accomplished by first converting the neutral compound into a derivative which can form a salt. Resolution of dl-octanol-2 is an example of the application of this modification. The racemic mixture of the alcohol is converted by treatment with phthalic anhydride into the acid phthalate. In the next step the acid phthalate is reacted with the naturally occurring laevorotatory base, brucine. Fractional crystallisation of the resulting mixture of the brucine salts yields the separated salts. Decomposition of the separated salts with hydrochloric acid removes brucine, and the two resulting acid phthalates are then hydrolysed with alkali to get the d- and 1-forms of octanol-2. 

Aldehydes fiad the most widespread use as chemical iatermediates. The production of acetaldehyde, propionaldehyde, and butyraldehyde as precursors of the corresponding alcohols and acids are examples. The aldehydes of low molecular weight are also condensed in an aldol reaction to form derivatives which are important intermediates for the plasticizer industry (see Plasticizers). As mentioned earlier, 2-ethylhexanol, produced from butyraldehyde, is used in the manufacture of di(2-ethylhexyl) phthalate [117-87-7]. Aldehydes are also used as intermediates for the manufacture of solvents (alcohols and ethers), resins, and dyes. Isobutyraldehyde is used as an intermediate for production of primary solvents and mbber antioxidants (see Antioxidaisits). Fatty aldehydes Cg—used in nearly all perfume types and aromas (see Perfumes). Polymers and copolymers of aldehydes exist and are of commercial significance. 

Ahyl alcohol undergoes reactions typical of saturated, aUphatic alcohols. Ahyl compounds derived from ahyl alcohol and used industriahy, are widely manufactured by these reactions. For example, reactions of ahyl alcohol with acid anhydrides, esters, and acid chlorides yield ahyl esters, such as diahyl phthalates and ahyl methacrylate reaction with chloroformate yields carbonates, such as diethylene glycol bis(ahyl carbonate) addition of ahyl alcohol to epoxy groups yields products used to produce ahyl glycidyl ether (33,34). 

Phthalic anhydride and diethyl phthalate are easily converted with hydrazine into 4-hydroxyphthalazin-l(2/f)-one. Its substituted derivatives have been prepared using substituted hydrazines, substituted phthalic anhydrides, or diesters or disodium salts of substituted phthalic acids (Scheme 81). However, condensation of phenylhydrazine with phthalic anhydride gives only a small amount of the corresponding phthalazine, the main product being 2-anilinophthalimide. This can be rearranged in the presence of base into the phthalazine derivative. For the preparation of 2,3-disubstituted derivatives, 1,2-disub-stituted hydrazines are reacted with the appropriate phthalic anhydrides or phthaloyl chlorides. Derivatives of 4-amino- or 4-hydrazino-phthalazin-l(2iT)-one have been prepared either from the corresponding monothiophthalimide and 3-aminoisoindolin-3-one (1S4) or from ethyl 2-cyanobenzoate (155) and hydrazine hydrate (Scheme 82). Similarly,... 

Other derivatives can be prepared by reaction of the alcohol with an acid anhydride. For example, phthalic or 3-nitrophthalic anhydride (I mol) and the alcohol (Imol) are refluxed for half to one hour in a non-hydroxylic solvent, e.g. toluene or alcohol-free chloroform, and then cooled. The phthalate ester crystallises out, is precipitated by the addition of low boiling petroleum ether or is isolated by ev toration of the solvent. It is recrystallised from water, 50% aqueous ethanol, toluene or low boiling petroleum ether. Such an ester has a characteristic melting point and the alcohol can be recovered by acid or alkaline hydrolysis. 

Acrylic is a generic name for derivatives of acrylic acid, of which methyl methacrylate is the most important. Polymerization is controlled to produce chain length of 800 to 3,000 monomer units. A small amount of plasticizer such as dibutyl phthalate may be added before bulk polymerization to assist in deep molding. The outstanding property of polymethyl metliacrylate is 0 transparency resistance to ultraviolet radiation from fluorescent lamps and ability to be... 

Di- and mono-esters of phthalic acid, an ortho-dicarboxylic acid derivative of benzene. These compounds are widely used as industrial plasticizers to coat polyvinylchloride surfaces of plastics used in food packaging and medical devices (iv drip bags, blood storage bags, etc.) and are common environmental contaminants. Several phthalate mono-esters are peroxisome proliferator chemicals and can activate the peroxisome proliferator-activated receptor PPAR. 

The principal solvolysis reactions for PET are methanolysis with dimethyl terephthalate and ethylene glycol as products, glycolysis with a mixture of polyols and BHET as products, and hydrolysis to form terephthalic acid and ethylene glycol. The preferred route is methanolysis because the DMT is easily purified by distillation for subsequent repolymerization. However, because PET bottles are copolyesters, the products of the methanolysis of postconsumer PET are often a mixture of glycols, alcohols, and phthalate derivatives. The separation and purification of the various products make methanolysis a cosdy process. In addition to the major product DMT, methanol, ethylene glycol, diethylene glycol, and 1,4-cyclohexane dimethanol have to be recovered to make the process economical.1... 

Hercules Chemical produced an acidic organic waste derived from the manufacture of dimethyl terphthalate, which is used in the production of synthetic liber. The average dissolved organic carbon concentration was about 7100 mg/L and included acetic acid, formic acid, p-toluic acid, formaldehyde, methanol, terphthalic acid, and benzoic acid. The pH ranged from 3.5 to 4.0. The waste also contained traces (less than 0.5 mg/L) of 11 other organic compounds, including dimethyl phthalate, a listed hazardous waste. 

Organic compounds derived by replacing the hydrogen of an acid by an organic radical or group. Examples of ester plasticisers are tritolyl phosphate, dioctyl phthalate and dioctyl sebacate. ETAD... 

Examples of GC-MS data for typical total extracts from rural and urban aerosol particle samples (analyzed as silylated derivatives) (a) total ion current (TIC) trace for Oakridge, OR, rural aerosol (Jan/Feb. 1985) and (b) TIC trace for Pasadena, CA, aerosol (Feb. 1989), DEHP = diethylhexyl phthalate, lA = carbon chain length of -alkanoic acids. 

Bis(TrinitroethyI)-phtha ate or Hexanitrodi-ethyl-phthalate, H4 [COO.CH2 C (N03)3]2 ortho derivative mw 492.23, N17.07/E, OB to CO2-39.0%, crysts, sp gr 1.62, mp 125a, bp-ignites at 267°. Can be prepd by heating the acid chloride of diethylphthalate with trinitro-ethanol (Ref 2) or from the same reactants in carbon tetrachloride at 30° m the presence of Friedel-Craf s catalysts, such as AlCl3(3). 

Hepatocytes isolated from male Wistar rats (180-250 g) were treated with 0.2 mM mono(2-ethylhexyl) phthalate or 1 mM 2-ethylhexanol for 48 h (Gray et al., 1982). Both di(2-ethylhexyl) phthalate metabolites increased carnitine acetyltransferase activity about nine-fold. In studies with hepatocytes from male Sprague-Dawley rats (180-220 g), treatment with 0.2 mM mono(2-ethylhexyl) phthalate and 1.0 mM 2-ethylhexanol for 48 h resulted in induction of carnitine acetyltransferase activity about 15-fold and six-fold, respectively (Gray et al., 1983). Mono(2-ethylhexyl) phthalate was also shown to induce cyanide-insensitive palmitoyl-CoA oxidation and, by ultra-structural examination, to increase numbers of peroxisomes. Hepatocytes were isolated from Wistar-derived rats (180-220 g) and treated for 72 h with 0-0.5 mM mono(2-ethylhexyl) phthalate and some mono(2-ethylhexyl) phthalate metabolites (Mitchell etal., 1985). Treatment with mono(2-ethylhexyl) phthalate and metabolites VI and IX (see Figure 1) resulted in a concentration-dependent induction of cyanide-insensitive palmitoyl-CoA oxidation. In addition, 0-0.5 mM mono(2-ethylhexyl) phthalate and 0-1.0 mM metabolite VI produced concentration-dependent increases in lauric acid hydroxylation. Treatment with metabolites I and V resulted in only small effects on the enzymatic markers of peroxisome proliferation. In another study with hepatocytes from Wistar-derived rats (180-220 g), metabolite VI was shown by subjective ultrastructural examination to cause proliferation of peroxisomes (Elcombe Mitchell, 1986). 

Species comparisons of hepatic peroxisomal proliferation have also included studies of human and non-human primate primary hepatocyte cultures. Hepatocytes isolated from Wistar-derived rats (180-220 g), male Alderley Park guinea-pigs (400-500 g), male marmosets (350-500 g) and three human liver samples (renal transplant donors) were treated with 0-0.5 mM mono(2-ethylhexyl) phthalate for 72 h (Elcombe Mitchell, 1986). While there was a concentration-dependent induction of cyanide-insensitive palmitoyl-CoA oxidation in rat hepatocytes, no induction was observed in guinea-pig or human hepatocytes and only small non-concentration-dependent effects were observed in marmoset hepatocytes. Metabolite VI induced cyanide-insensitive palmitoyl-CoA oxidation and lauric acid hydroxylation in cultured... 

Peroxisome proliferators have also been shown to induce replicative DNA synthesis in cultured rodent hepatocytes (lARC, 1995). In contrast, several peroxisome proliferators have failed to induce replicative DNA s mthesis in human hepatocyte cultures (Doull et al., 1999). Hepatocytes were isolated from male Wistar-derived rats and from three human liver samples (liver transplantation donors) and treated with 2-ethylhexanoic acid and some other peroxisome proliferators for 72 h (Elcombe et al, 1996). While 2-ethylhexanoic acid induced replicative DNA s5mthesis in cultured rat hepatocytes, no effect was observed in human hepatocytes. Hepatocytes were isolated from male Fischer 344 rats and three humans and treated in culture with 250-2000 pM mono(2-ethylhexyl) phthalate (Hasmall et al, 1999). Increased peroxisomal (O-oxi-dation (at 250-750 pM), replicative DNA s mthesis (at 500-1000 pM), and inhibition of apoptosis (at 250-1000 pM) were observed in rat hepatocytes. None of these parameters was affected by mono(2-ethylhexyl) phthalate in human hepatocytes. 

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