Substitution derivatives of naphthalene

Toxicology of Opivim and its Derivatives.—Opium, its preparations and the alkaloids obtained from it, are all active poisons. They produce drowsiness, stupor, slow and stertorous respiration, contraction of the pupils, small and irregular pulse, coma, and death. The symptoms set in from 10 minutes to 3 hours, sometimes immediately, sometimes only after 18 hours. Death has. occurred in from 45 minutes to 3 days, usually in 5 to 18 hours. After 24 hours the prognosis is favorable. Death has been caused in an adult by one-half grain of acetate of morphia, while 30-grains a day have been taken by those accustomed to its use without ill effects. 

The alkaloids of opium have not the same action. In soporific action, beginning with the most powerful, they rank thus Nar-cetn, morphin, codeIn in tetanizing action thebaln, papaverin, narcotin, codeIn, morphin in toxic action thebaln, codeIn, papaverin, narcein, morphin, narcotin. 

The treatment should consist in the removal of unabsorbed poison from the stomach by emesis and the stomach-pump, and washing out of the stomach after injection into it of powdered charcoal in susiiension, or tea or coffee infusion. Cold affusions-should be used, and the patient should be kept awake. 

After death the reactions for meconic acid and narcotin permit of distinguishing whether the poisoning was by opium or its. preparations, or by morphin. 

By the replacement of the hydrogen atoms of naphthalene by other atoms or by radicals, substitution products are obtained somewhat in the same manner as in the case of benzene (see pp. 397-400). In the case of naphthalene, however, the number of 

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Tetrathiolene complexes of platinum can be prepared from the sulfur-substituted derivatives of naphthalene, tetracene and chlorinated naphthalene.1854... 

In relations (11) and (12), i is a parameter which indicates the length of the chain of normal alkanes it is equal to the number of carbon atoms in the molecule, a and Pi are constants, C2, C3 and Cp are the site fractions occupied in the molecule by the condensed aromatic carbon atoms common to two cycles, three cycles and condensed atoms in angular position. The Cas parameter represents the fraction of the sites for the substituted aromatic carbons belonging to condensed cycles, which must be taken into account for the substituted derivatives of naphthalene. Table 1 shows the values of the parameters adjusted to the experimental data of the liquid-fluid and solid-fluid equilibria as a whole. 

Grignard reagent (see Chapter 10), followed by dehydration and arom-atization (Scheme 12.2). The use of substituted benzenes in the first stage of the sequence enables variously substituted derivatives of naphthalene to be obtained. Of course, the substituents should not interfere with the Friedel-Crafts reaction with succinic anhydride. 

Derivatives of naphthalene and other polycyclic molecules— The dipole moment of the mono-substituted derivatives of naphthalene and te-tralin are given in Table CIII, and it is observed that there is an appreciable difference in the values of the moments of... 

The rifamycins belong to a class of naturally occurring highly substituted derivatives of naphthalene called... 

Naphthalene-1,8-dicarboxylic add, its nitro-substituted derivatives, and naphthalene-1,4,5,8 tetracarboxylic acid, on treatment with sulfur tetrafluoride at 0 C, undergo dehydration to form quantitatively the corresponding anhydrides [218, 221] Unsubstituted and mononitrated monoanhydndes react further at 200-250 °C to give derivatives of 1,1,3,3-tetrafluoro-l// naphtho[I,8 c,d]pyran Dinitronaphthalene-l,8-di-carboxyhc acid anhydndes and naphthalene 1,4,5,8 tetracarboxylic acid dianhydnde give the respective tetra- and octafluoroethers only in the presence of an excess of anhydrous hydrogen fluoride [221] (equabons 113 and 114)... 

The typical red shifts on ring annelation are seen in 4,5-benzo-6-azaindole (45), which like 6-azaindole show a red shift of ca. 20 m/x in acid solution. The spectra of several substituted derivatives of this pyrroloquinoline are reported also, including the [2,3-a]naphthalene compound which has a max at 405 m/x. The other Tr-conjugated derivatives all have bands at long wavelength, and are assigned the band positions indicated. The methylene malonate compound shows a four-band spectrum, with the /S band at 225 mfi. 

Bromination of (47) led to 3-azido-4-bromoisoquinoline (261). On the other hand, trifluoroacetic acid caused only the tetrazolo tautomer (262) to exist in the equilibrium of (47) with its azido partner. This is due to elimination of the unfavored o- quinoid structure (47) from the tautomeric equilibrium and formation of the more stable naphthalenic structure (262) which, consequently, is preferred over the azido form (8UOC843). To extend this equilibrium study further, NMR investigations on substituted derivatives of (47) indicated that electron-releasing groups on the isoquinoline favor the tetrazolo tautomer whereas electron-attracting substituents favor the azido tautomer. Furthermore, the tetrazole was found to be preferred in DMSO solution relative to chloroform solution (81JOC843). 

Derivatives of naphthalene and other polycyclic molecules— The dipole moment of the mono-substituted derivatives... 

Substitution Products.— The halogen derivatives of naphthalene include both substitution and addition products. The tetra- and penta-chlor substituted naphthalenes have already been referred to as furnishing proof that in naphthalene there are present two benzene nucleii (p. 771). Other halogen substituted naphthalenes are known but none need be discussed in detail. ... 

Petroleum. The presence of PCAH in petroleum is well known. Naphthalene, phenanthrene, fiuorene, pyrene, chrysene, triphenylene, perylene, several benzanthracenes, and various alkyl substituted derivatives of these compounds have been foimd in crude petroleum (7). In addition, the PCAH content of those petroleum products which have been produced by thermal cracking is much greater than in the crude oil. 

The cydopropanation of benzene, its substituted derivatives, and naphthalene with dicyanocar-bene produced stable bicyclo[4.1.0]hepta-2,4-diene-7,7-dicarbonitriles (Table 2). ... 

Patents are still appearing on further substitution reactions of naphthalene disulphonic acids by both kinetically and thermodynamically controlled processes, which have been of great commercial importance for many years. Isomer distributions for the sulphonation of other arenesulphonic acids and some alkyl derivatives have been compiled142. 

A large number of substituted polyaromatic and heteroaromatic compounds are also accessible through 5-BuLi-induced ortho lithiation reactions. These include, for example, derivatives of naphthalene, furan, thiophene, pyridine, quinoUne, and N-protected imidazoles. The smooth ortho lithiation of pyridyl (eq 25) and quinolinyl systems is notable given the weU-known tendency of organolithium compounds to undergo nucleophilic addition reactions with the pyridine nucleus. ... 

New benchrotrene derivatives have been prepared by reactions of [Cr(CO)s], etc., with oestrone and related steroids, phenalene, 2,6,15,19-tetrathia-[7.7]paracyclophane, PhjAs, and diphenic acid and related compounds. Ring-substituted derivatives of [( benzaldehyde)Cr(CO)3] have been resolved into enantiomeric forms. Reactions of carbene complexes of the type [(OQs-CrC(OMe)Ar] with alkynes have afforded derivatives of [(jy -naphthalene)-Cr(CO>3] (see Vol. 8, refs. 393, 394). 

The tendency towards a-substitution is also seen in the reactions of naphthalene derivatives containing de-activating substituents. Thus,... 

Bis(benZoxaZol-2-yl) Derivatives. Bis(benzoxazol-2-yl) derivatives (8) (Table 3) aie prepared in most cases by treatment of dicaiboxyhc acid derivatives of the central nucleus, eg, stilbene-4,4Cdicarboxyhc acid, naphthalene-l,4-dicarboxyhc acid, thiophene-2,5-dicarboxyhc acid, etc, with 2 moles of an appropriately substituted o-aminophenol, followed by a ring-closure reaction. These compounds are suitable for the brightening of plastics and synthetic fibers. 

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