3- Chloro phthalic acid

The synthetic route involves treating l-chloro-2-aminoanthraquinone with phthalic anhydride (PA), which initially affords l-chloro-2-phthalimidoanthra-quinone 95. Subsequent Ullmann reaction with copper powder in refluxing trichlorobenzene yields 2,2 -diphthalimido-l,l -dianthraquinonyl 96 through dimerization. This product is cyclized with 5% aqueous sodium hydroxide solution at 100°C, cleaving phthalic acid units, to yield 94 ... 

Requests for larger samples for field testing necessitated the examination of alternate routes to AC 94,377. One of these started with 1-amino-1-cyclohexanecarboxamide and 3-chloro-phthalic anhydride. Attempted cyclization of the intermediate phthalamic acid 4 with cold trifluoroacetic anhydride gave, albeit in low yield, the readily isolated imidazoisoindole Biological evaluation of indicated that it had very similar PGR properties to that of AC 94,377 yet was perhaps slower acting. This was attributed to the slow hydrolysis of back to AC 94,377. 

Substitution. Copper phthalocyanine is preferred as starting material. Very little is known about the position of substitution. With the exception of hexadeca-chloro CuPc, all commercial Pc substitution products, as well as the tetrasubsti-tuted derivatives synthesized from monosubstituted phthalic acids, are mixtures of isomers. Despite the 16 hydrogen atoms that can be substituted, only two different monosubstituted Pc s are possible. The number of disubstituted isomers is higher. Mono- to heptasubstituted Pc derivatives have not yet been isolated in isomerically pure form. In addition, only a limited number of isomers are accessible in pure form by synthesis. Only symmetrically substituted phthalic acids, phthalimides, or phthalodinitriles (3,6-di-, 4,5-di-, or 3,4,5,6-tetrasubstituted derivatives) yield pure isomers of octa- or hexadecasubstituted phthalocyanine derivatives. All other substituted phthalic acids give mixtures of isomers. 

Ethene, chloro (vinyl chloride) 7.8 Phthalic acid, dipentyl ester 9.1... 

Aldehyde benzoic acid, i.e., the half-aldehyde corresponding to phthalic acid, undergoes condensation with hydrazine to yield the hydrazone hydrazide (lactam-form). The lactim-form of this compound upon chlorination with phosphorus oxychloride gives the corresponding chloro derivative which on first treatment with a further mole of hydrazine and secondly with a calculated amount of hydrochloric acid affords the official compoimd. 

The phthalimide group is typically introduced by reaction of a primary amine with phthalic anhydride in chloroform at 70 °C for 4 h (85 93% yield) or phthaloyl chloride in the presence of triethylamine [Scheme 8.10]. 2-Chloro-carbonylbenzoic acid methyl ester in the presence of base [Scheme 8.11],2i-22 or N-ethoxycarbonylphthalimide - have also been used with the latter reagent being especially useful for the N-protection of a-amino acids [Scheme... 

Peroxy camphoric acid QH5COO2H, p-Nitro-, m-Chloro-peroxy-benzoic acid, Peroxy-maleic acid, Peroxy-phthalic acid CHgCSNH. 

The purpose of this experiment was to show the applicability of normal-phase gradients to LC separations. In what was described as a random selection of 10 analytes (2-phenylethylbromide, 1,4-diphenylbutane, phenetole, nitrobenzene, chloro-stilbene oxide, Sudan red 7B, 4-chIorobenzophenone, veratrole, acetophenone, phthalic acid bis-2-ethylhexylester) all peaks were well resolved with good peak shape on a silica column (2 = 254 nm). A two-ramp 100/0 (hold 2 min) 50/50 (at 8.5 min hold 5 min)0/100 (at 20min) hexane/dichloromethane gradient was used [600]. Methyl r-butyl ether was used in place of dichloromethane but resolution was not as good. 

C0, COfi-CsH,COO,C(CHs)s Peroxy acids HCOOfl, CHfiOO, C HsCOO H, Peroxy lauric acid lOOC-CE COO H CFsCOOfl Peroxy camphoric acid CfifiOO H, p-Nitro-, m-Chloro-peroxy-benzoic acid, Peroxy-maleic acid, Peroxy-phthalic acid... 

The following aromatic compounds have been detected by GLC in small amounts in Evernia prunastri (L.) Ach. benzene, toluene, isopropylbenzene, m-ethyltoluene, mesitylene, 1,2,3-trimethylbenzene, isobutylbenzene, bro-mobenzene, l,2-dimethyl-3-ethylbenzene, 1-chloro-2,4-dimethoxy-6-methylbenzene, a,p-dimethylstyrene, naphthalene, bis-(p-tolyl)-1,2-ethane, phenol, 2-chloro-3-methoxy-5-methylphenol, phthalic acid and N,N-dimethyl-p-toluenesulfonamide (Gavin and Tabacchi 1975), and a,a-dimethylstyrene,... 

Another group of halogenated fluorescein dyes is prepared by condensing chloro derivatives of phthalic anhydride with resorcinol, followed by bromination or iodination. Thus Phloxine B /78472-87-2] (Acid Red 92, Cl45410) (42) is prepared by condensing tetrachlorophthaUc anhydride with resorcinol followed by tetrabromination. Phloxine B undergoes ethylation to yield the yellowish ted acid dye Cyanosine B [6441-80-1] (43). 

Hydroxyphthalazin-l(2//)-one is obtained in a smooth reaction between phthalic anhydride and hydrazine hydrate and this is again the starting compound for many 1-substituted and/or 1,4-disubstituted phthalazines. The transformations of 1,4-dichloro-phthalazine, which is prepared in the usual manner, follow a similar pattern as shown for pyridazines in Scheme 110. On the other hand, phthalonitrile is the preferential starting compound for amino- and hydrazino-phthalazines. The most satisfactory synthesis of phthalazine is the reaction between a,a,a, a -tetrachloro-o-xylene and hydrazine sulfate in sulfuric acid (67FRP1438827), alt iough catalytic dehalogenation of 1-chloro- or 1,4-dichloro-phthalazine or oxidation of 1-hydrazinophthalazine also provides the parent compound in moderate yield. 

Benzoic m-Toluic (Benzoic acid, 3-methyl-] p-Toluic [Benzoic acid, 4-methyl-J 3,5-Dimcthylbcnzoic [Benzoic acid, 3,5-dimcthyl-] p-Chlorobenzoic [Benzoic acid, 4-chloro-] p-Bromobenzoic [Benzoic acid, 4-bromo-J Phthalic [ 1,2-Bcnzcncdicarboxylic acid] Toluene [Benzene, methyl-] (78) m-Xylene [Benzene, 1,3-dimethyl-] (82) />-Xylene [Benzene, 1,4-dimethyl-] (74) Mesitylene [Benzene, 1,3,5-trimethyl-] (82) p-Chlorotolueno [Benzene, l-ehloro-4-methyl-] (94) p-Bromotolucnc [Benzene, l-bromo-4-methyl-] (94) o-Xylene [Benzene, 1,2-dimethyl-] (64)... 

Figure 12.12 THM GC/MS curves of a Winsor Newton lemon alkyd paint (a) and of an alkyd sample taken from Fontana s work Concetto spaziale (1961) (b). Peak assignments 1, 1,3 dimethoxy 2 propanol 2, 1,2,3 trimethoxy propane 3, 3 methoxy 1,2 propandiol 4, 4 chloro benzenamine 5, 3 methoxy 2,2 bis(methoxymethyl) 1 propanol 6, 3 chloro N methyl benzenamine 7, 3 methoxy 2 methoxymethyl 1 propanol 8, 4 chloro N methyl benzenamine 9, phthalic anhydride 10, 3 chloro 4 methoxy benzenamine 11, suberic acid dimethyl ester 12, dimethyl phthalate 13, azelaic acid dimethyl ester 14, sebacic acid dimethyl ester 15, palmitic acid methyl ester 16, oleic acid methyl ester 17, stearic acid methyl ester 18, 12 hydroxy stearic acid methyl ester 19, 12 methoxy stearic acid methyl ester 20, styrene 21, 2 (2 methoxyethoxy) ethanol 22, 1,1 oxybis(2 methoxy ethane) 23, benzoic acid methyl ester 24, adipic acid dimethyl ester 25, hexadecenoic acid methyl ester 26, dihydroisopimaric acid methyl ester 27, dehydroabietic acid methyl ester 28, 4 epidehydroabietol...

Although anthraquinone is the starting point for the preparation of many derivatives, involving substitution and replacement reactions, certain compounds are obtained directly by varying the components in the above synthesis. Thus, for example, replacement of benzene with methylbenzene (toluene) leads to the formation of 2-methylanthraquinone. A particularly important variation on the phthalic anhydride route is the synthesis of 1,4-dihydroxyanthraquinone (6.6 quinizarin) using 4-chlorophenol with sulphuric acid and boric acid as catalyst (Scheme 6.3). The absence of aluminium chloride permits hydrolysis of the chloro substituent to take place. 

Operating MSR under novel process windows, the key performance parameters can be increased by a few orders of magnitude. A few examples are presented here. In the case of esterification of phthalic anhydride with methanol 53-fold higher reaction rate between 1 and 110 bar for a fixed temperature of 333 K was observed [14]. A multiphase (gas/liquid) explosive reaction of oxidation of cyclohexane under pure oxygen at elevated pressure and temperature (>200 C and 25 bar) in a transparent silicon/glass MSR increased the productivity fourfold. This reaction under conventional conditions is carried out with air [15]. Another example is for the synthesis of 3-chloro-2-hydroxypropyl pivaloate a capillary tube of 1/8 in. operated at 533 K and 35 bar, superheated pressurized processing much above the boiling point, allowedto decrease reaction time 5760-fold as compared to standard batch operation [16]. The condensation of o-phenylenediamine with acetic acid to 2-methylbenzimidazole in an MSR is an impressive example of the reduced reaction time from 9 weeks at room temperature to 30 s at 543 K and 130 bar [17]. 

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