Aromatic hydrocarbons adducts with

The adduct formed by two lithium atoms with polycondensed aromatic hydrocarbons crystallizes with two solvating molecules of TMEDA. The structure of the crystals derived from naphthalene (73) and anthracene (74) was elucidated by XRD. This arrangement of the unsolvated lithium atoms, in 7 -coordination fashion on the opposite sides of two contiguous rings, was found by MNDO calculations to be the most favorable one for naphthalene, anthracene and phenanthrene (75) . 

Many chlorine-substituted compounds and some aromatic hydrocarbons react with 0 T ions this type of reaction is discussed later. Adduct formation, involving a halide ion, leads to negative ions under some circumstances. There are also a few addition reactions of specialized reagents that will lead to negative ions. 

PPO is readily cleaved by reaction with alkali metal aromatic hydrocarbon adducts such as lithium-biphenyl and sodium-naphthalene." In a model reaction with the trimer 39 only two products 40 and 41 were obtained. Exhaustive cleavage of the polymer gives about a 20% yield of 41. (Scheme 14)... 

In Group 14 (IV), carbon serves as a Lewis base in a few of its compounds. In general, saturated ahphatic and aromatic hydrocarbons are stable in the presence of BF, whereas unsaturated ahphatic hydrocarbons, such as propjdene or acetylene, are polymerized. However, some hydrocarbons and their derivatives have been reported to form adducts with BF. Typical examples of adducts with unsaturated hydrocarbons are 1 1 adducts with tetracene and 3,4-benzopyrene (39), and 1 2 BF adducts with a-carotene and lycopene (40). 

An excess of crotonaldehyde or aUphatic, ahcyhc, and aromatic hydrocarbons and their derivatives is used as a solvent to produce compounds of molecular weights of 1000—5000 (25—28). After removal of unreacted components and solvent, the adduct referred to as polyester is decomposed in acidic media or by pyrolysis (29—36). Proper operation of acidic decomposition can give high yields of pure /n j ,/n7 j -2,4-hexadienoic acid, whereas the pyrolysis gives a mixture of isomers that must be converted to the pure trans,trans form. The thermal decomposition is carried out in the presence of alkaU or amine catalysts. A simultaneous codistillation of the sorbic acid as it forms and the component used as the solvent can simplify the process scheme. The catalyst remains in the reaction batch. Suitable solvents and entraining agents include most inert Hquids that bod at 200—300°C, eg, aUphatic hydrocarbons. When the polyester is spHt thermally at 170—180°C and the sorbic acid is distilled direcdy with the solvent, production and purification can be combined in a single step. The solvent can be reused after removal of the sorbic acid (34). The isomeric mixture can be converted to the thermodynamically more stable trans,trans form in the presence of iodine, alkaU, or sulfuric or hydrochloric acid (37,38). 

Sulfur dioxide acts as a dienophile ia the Diels-Alder reaction with many dienes (253,254) and this reaction is conducted on a commercial scale with butadiene. The initial adduct, sulfolene [77-79-2] is hydrogenated to a solvent, sulfolane [126-33-0] which is useful for selective extraction of aromatic hydrocarbons from... 

Tetracyanoethylene oxide [3189-43-3] (8), oxiranetetracarbonitnle, is the most notable member of the class of oxacyanocarbons (57). It is made by treating TCNE with hydrogen peroxide in acetonitrile. In reactions unprecedented for olefin oxides, it adds to olefins to form 2,2,5,5-tetracyanotetrahydrofuran [3041-31-4] in the case of ethylene, acetylenes, and aromatic hydrocarbons via cleavage of the ring C—C bond. The benzene adduct (9) is 3t ,7t -dihydro-l,l,3,3-phthalantetracarbonitrile [3041-36-9], C22HgN O. 

Aromatic hydrocarbons can be purified as their picrates using the procedures described for amines. Instead of picric acid, 1,3,5-trinitrobenzene or 2,4,7-trinitrofluorenone can also be used. In all these cases, following recrystallisation, the hydrocarbon can be isolated either as described for amines or by passing a solution of the adduct through an activated alumina column and eluting with toluene or petroleum ether. The picric acid and nitro compounds are more strongly adsorbed on the column. 

In the presence of certain ethers such as Me20, Me0CH2CH20Me or tetrahydrofuran, Na forms deep-green highly reactive paramagnetic adducts with polynuclear aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, etc. ... 

Since the nitrogen in pyridine is electron attracting it seemed reasonable to predict that the trihalopyridynes would also show the increased electrophilic character necessary to form adducts with aromatic hydrocarbons under similar conditions to those employed with the tetra-halogeno-benzynes. The availability of pentachloropyridine suggested to us and others that the reaction with w-butyl-lithium should lead to the formation of tetrachloro-4-pyridyl-lithium 82 84>. This has been achieved and adducts obtained, although this system is complicated by the ease with which pentachloropyridine undergoes nucleophilic substitution by tetrachloro-4-pyridyl lithium. Adducts of the type (45) have been isolated in modest yield both in the trichloro- and tribromo- 58) series. 

Chemical carcinogenesis by polycyclic aromatic hydrocarbons (PAHs) is a multi-step process in which each of the steps must occur if a neoplasm is to develop. Thus, exposure to PAHs alone is not necessarily sufficient for the induction of a tumor. Many of these factors are summarized below and are discussed in various chapters of this volume. Considered here will be those factors influencing the reactions of the metabolically activated forms of the PAHs with DNA and the ways in which adducts may be detected and characterized. 

Pal, K. 1984. The relationship between the levels of DNA-hydrocarbon adducts and the formation of sister-chromatid exchanges in Chinese hamster ovary cells treated with derivatives of polycyclic aromatic hydrocarbons. Mutat. Res. 129 365-372. 

Polycyclic aromatic hydrocarbons are moderately reactive as the diene component of Diels-Alder reactions. Anthracene forms adducts with a number of reactive dienophiles. The addition occurs at the center ring. There is no net loss of resonance stabilization, because the anthracene ring (resonance energy = 1.60 eV) is replaced by two benzenoid rings (total resonance energy = 2 x 0.87 = 1.74 eV).48 49... 

Nearly all the classes of compounds generally used as sensitizers can lead to complications. Aromatic hydrocarbons may interact with substrate via singlet and upper triplet states or they may self-quench, dimerize, and form adducts. Ketones with triplet states can self-quench while quinones... 

Several studies have examined the reactions of Mg+" with unsaturated molecules. Under the lower pressure conditions of FT-ICR mass spectrometry, Mg+" reacts with the polycyclic aromatic hydrocarbon, coronene, via a combination of radiative associative adduct formation (equation 16) and electron transfer (equation 17). The latter reaction is 8 times faster, consistent with it being exothermic. Adduct formation (equation 16) also readily occurs in reactions with Theoretical calculations suggest that related radiative... 

A part of the wax portion, which contained a considerable amount of oil in addition to the true wax, was further processed by fractionation by adsorption and by treatment with urea to form adducts of the latter with the n-paraffins. The wax portion was found to contain about 8% of aromatic hydrocarbons, which had been imperfectly separated from the main bulk of the aromatic hydrocarbons occurring in the extract oil portion. Of the remaining 92% of the wax portion, about 39% was determined to be n-paraffins and 53% cycloparaffins, with possibly a relatively small amount of branched paraffins. 

Deoxygenation of furan-aryne adducts. At temperatures of 50-60°, these adducts on treatment with Fe2(CO)9 in benzene form a complex with Fe(CO)4, which decomposes gradually to an aromatic hydrocarbon.1 Example ... 

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