Phenanthrenes, addition

Liquid products were characterised using GC-MS. A range of aromatic compounds were identified in which the concentrations of aJkybenzenes are greater than those of alkylindans and naphthalenes while polynuclear aromatic compounds (PACs) were only minor constituents. The prominent group of constituents eluting between n-pentadecane and n-hexadecane are mixtures of alkenes, alley (benzenes and naphthalenes. Phenanthrene addition had no significant effect on the overall liquid product distribution. 

The effect of quinoline and phenanthrene additions to a n-hexadecane feedstock has been determined for a model four-component FCC catalyst by means of a MAT reactor with analysis of all products and characterisation of the coke produced. Both additions lead to an overall loss in conversion quinoline is considered to act as a poison while phenanthrene participates strongly in coke formation and the resultant coke becomes more aromatic in nature. The cracking propensity and associated coke formation have been measured for a series of FCC catalysts with differing compositions. Increasing amounts of zeolite in a matrix lead to increasing extents of conversion but with little effect on the extent of coke production. However, a pure zeolite gave a very high coke content. 

A number of FCC catalysts was used in the present study. For comparison of the effects of quinoline and phenanthrene additions to the n-hexadecane feedstock a model catalyst of composition, zeolite US-Y (30%), silica binder (25%), Kaolin (25%) and ps do Boehmite matrix (20%) was used. Quinoline and phenanthrene additions to the n-hexadecane amounted to 1% and 10%. The catalysts used to assess the effect of composition on product yields varied from a basic matrix material through a variety of zeolitic catalysts containing 20% zeolite and 15% silica binder, the remainder being clay, to a pure zeolite catalyst. Data for all the catalysts used are presented in Table 1. In addition for the C NMR analysis a sample of coked refinery catalyst obtained from a unit processing heavy feedstock was obtained. The coke level on this catalyst was 0.9% and 30g. of this catalyst was demineralised by standard HF treatment to produce a 250 mg sample of coke concentrate containing 65% carbon. 

FIGURE 2. EFFECT OF PHENANTHRENE ADDITIONS ON YIELD OF N-HEXADECANE FEED. 

The addition product, C QHgNa, called naphthalenesodium or sodium naphthalene complex, may be regarded as a resonance hybrid. The ether is more than just a solvent that promotes the reaction. StabiUty of the complex depends on the presence of the ether, and sodium can be Hberated by evaporating the ether or by dilution using an indifferent solvent, such as ethyl ether. A number of ether-type solvents are effective in complex preparation, such as methyl ethyl ether, ethylene glycol dimethyl ether, dioxane, and THF. Trimethyl amine also promotes complex formation. This reaction proceeds with all alkah metals. Other aromatic compounds, eg, diphenyl, anthracene, and phenanthrene, also form sodium complexes (16,20). 

The high reactivity of azomethine ylides allows addition to aromatic systems (71TL481). For example, trans-aziridine (30) adds to phenanthrene to give the fran5-phenanthropyr-rolidine (31). The reversal of expected stereochemistry is again attributed to azomethine ylide interconversion being allowed by the low reactivity of the aromatic system. 

The substruetures A - D aeeount for eleven of the total of twelve double bond equivalents so that the eompound eontains one additional ring as present in anthraeene or phenanthrene skeletons. 

In order to obtain the desired photoconductive characteristics, toughness and adherence to the substrate it is usual to incorporate additives such as electron acceptors, plasticisers and primers. A typical electron acceptor is 2,4,7-trinitro-fluoronone, plasticisers include benzyltetraline and phenanthrene whilst as primers styrene-butadiene block copolymers (30-35% styrene) and styrene-maleic anhydride copolymers (5-30% maleic anhydride) are of use. 

Benzene rings can also be fused in angular fashion, as in phenanthrene, chrysene, and picene. These compounds, while reactive toward additions in the center ring, retain most of the resonance energy per electron (REPE) stabilization of benzene and naphthalene. ... 

Both phenanthrene and anthracene have a tendency to undergo addition reactions under the eonditions involved in eertain eleetrophilic substitutions. For example, in the nitration of anthracene in the presence of hydrochloric acid, an intermediate addition product can be isolated. This is a result of the relatively close balance in resonance stabilization to be regained by elimination (giving an anthracene ring) or addition (resulting in two benzenoid rings). 

Some additional derivatives containing extended 7t-systems in place of the benzene nucleus are naphthalene, anthracene (2,3-Ac) and phenanthrene (9,10-Phc). They also belong to the phthalocyanine family. For the naphthalene system two types of macrocyclcs, the 1,2-naph-thalocyanine (1,2-Nc) and the 2,3-naphthalocyanine (2,3-Nc), are known. 

Phenanthrene-9,10-dicarbonitrile (1.50 g. 6.57 mmol) and DBU (5 drops) were suspended in 1-chloronaph-thalene (15 mL) and heated to 180 C. Then, Fe(CO)5 (0.50 mL, 3.80 mmol) dissolved in 1-chloronaph-thalenc (5 mL) was added dropwise. The mixture was heated to 230 C for 4 h, cooled and, after addition of toluene, the precipitate was centrifuged. The crude product was washed with Et20, acetone, and EtOH, and then boiled with 1 M HC1 and finally with 1 M NaOH. The crude product was successively washed with H20, EtOH, Et20, and toluene. Then, it was purified by Soxhlet extraction with CHC l3 until the extracting solvent was colorless. The residue was dried in vacuo at 130 C yield 1.22 g (77%). 

The red solution of polystyryl carbanions can be kept for days without change in color or viscosity. No changes are observed on addition of further amounts of naphthalene to the red solution. These observations raise some questions. An electron transfer, say for example, between naphthalene" and phenathrene, is a reversible process and it leads eventually to an equilibrium between naphthalene , naphthalene, phenathrene-, and phenanthrene. Is the reaction involving styrene irreversible Now, the initial process of electron transfer from naphthalene to styrene that produces... 

Blackley548 measured the rates of deuteration of biphenylene, fluorene, tri-phenylene, and phenanthrene relative to o-xylene as 6.15 5.85 1.08 1.32, which is in very good agreement with the values of 8.80 7.00 - 1.14 which may be deduced from the detritiation data in Table 159, obtained using anhydrous trifluoroacetic acid. Aqueous trifluoroacetic acid (with the addition in some cases of benzene to assist solubility) was used by Rice550, who found that triptycene was 0.1 times as reactive per aromatic ring as o-xylene (cf. 0.13 derivable from Table 159) whereas the compound (XXXI) was 0.9 times as reactive as o-xylene. An exactly comparable measure is not available from Table 158, but dihydroanthracene (XXXII), which is similar, was 0.51 times as reactive as o-xylene and... 

The relative rates of bromination from the above and additional studies yielded the following relative rates with partial rate factors for the indicated position in parentheses. These rates were mostly obtained by extrapolation of observed rates to those expected in 50% aqueous acetic acid and therefore probably contain small errors benzene, 1.0 (1.0) biphenyl, 1.54 x 103(4-,4.34 x 103) naphthalene, 1.24 x 105(1 -, 1.84 x 10s 2-, 1.86 x 103) phenanthrene, 7.43 x I03(9—, 2.23 x 10s) f uoranthrene, 2.30 x 106(3 —,6.90x 106) chrysene,... 

Poly(arylene ether ketone)s can also be modified by introducing the functional groups using similar approaches to polysulfones. For example, poly(arylene ether ketone)s were sulfonated.189 In addition, o-dibenzoylbenzene moieties in the poly(arylene ether)s can be transformed to heterocycles by cyclization with small molecules. These polymers can react with hydrazine monohydrate in the presence of a mild acid in chlorobenzene or with benzylamine in a basic medium.190 Another example of the use of the o-benzyl cyclization strategy is the intramolecular ring closure of poly(arylene ketone)s containing 2,2/-dibenzoylbiphenyl units to form poly(arylene ether phenanthrenes).191... 

With this hypothesis, the calculated stability of the 9,10 addition compound of anthracene provides an explanation of the ease of attack of the 9,10 positions for addition. A similar calculation for phenanthrene shows that for this molecule too the 9,10 positions should be most reactive. 

The reaction has been applied to nonheterocyclic aromatic compounds Benzene, naphthalene, and phenanthrene have been alkylated with alkyllithium reagents, though the usual reaction with these reagents is 12-20, and Grignard reagents have been used to alkylate naphthalene. The addition-elimination mechanism apparently applies in these cases too. A protected form of benzaldehyde (protected as the benzyl imine) has been similarly alkylated at the ortho position with butyl-lithium. ... 

Increased removal of phenanthrene from soil columns spiked with the rhamnolipid mixture synthesized by Pseudomonas aeruginosa UG2 has been demonstrated, and shown to depend both on the increased desorption of the substrate and on partitioning into micelles (Noordman et al. 1998). However, the addition of the biosurfactant from the same strain of Pseudomonas aeruginosa UG2 or of sodium dodecyl sulfate had no effect on the rate of biodegradation of anthracene and phenanthrene from a chronically contaminated soil. 

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