Meta benzenes

O2NC6H4I B meta benzene, reflux. O2NC6H4C6F5 meta (85) 5... 

To have a rough idea of the potential of the method, please have a look to the syntheses below that are among those considered typical in a recent book (Scheme 1). These are a cyclization to hydroxycyclobutane via H-abstraction, a 2 + 2 alkene cycloaddition, a "meta" benzene-olefin cycloaddition, and a dye sensitized addition of singlet oxygen." Please consider whether there are facile thermal alternatives to these straightforward photochemical reactions. 

Another macrocycle that presented a 21-membered size was mPh22222 (106, Scheme 30), in which the meta-benzene spacer had been substituted by a meffl-phenolic one. Although not as high as in the mB22222-ATP system, relevant rate accelerations were also found for mPh22222... 

Remarkable also is the related case of the meta benzene-alkene cycloaddition. Here again, mixtures are formed, but at least when the alkene moiety is tethered to the benzene ring and a preferred conformation exists, regio-selective processes have been found where several new stereocentres are formed in a single step and in a rigorously controlled way—and thus are synthetically highly valued (see Scheme 2.5) [15]. 

Comparative energy diagrams for nitronium ion attachment to (a) benzene and at the (W ortho, (c) meta, and (d) para positions of (trifiuoromethyi)benzene. Eg (ortho) > (para) > Eg (meta) > (benzene). 

Nucleophilic substitution of benzene itself is not possible but the halogeno derivatives undergo nucleophilic displacement or elimination reactions (see arynes). Substituents located in the 1,2 positions are called ortho- 1,3 meta- and 1,4 para-. 

In such tables, typical chemical shifts are assigned to standard structure fragments (e.g., protons in a benzene ring). Substituents in these blocks (e.g., substituents in ortho, meta, or para positions) are assumed to make independent additive contributions to the chemical shift. These additive contributions are listed in a second series of tables. Once the tables are defined, the method is easy to implement, does not require databases, and is extremely fast. Predictions for a molecule with 50 atoms can be made in less than a second. On the other hand, it requires that the parent structure and the substituents are tabulated, and it considers no interaction... 

A is a parameter that can be varied to give the correct amount of ionic character. Another way to view the valence bond picture is that the incorporation of ionic character corrects the overemphasis that the valence bond treatment places on electron correlation. The molecular orbital wavefimction underestimates electron correlation and requires methods such as configuration interaction to correct for it. Although the presence of ionic structures in species such as H2 appears coimterintuitive to many chemists, such species are widely used to explain certain other phenomena such as the ortho/para or meta directing properties of substituted benzene compounds imder electrophilic attack. Moverover, it has been shown that the ionic structures correspond to the deformation of the atomic orbitals when daey are involved in chemical bonds. 

A brief account of aromatic substitution may be usefully given here as it will assist the student in predicting the orientation of disubstituted benzene derivatives produced in the different substitution reactions. For the nitration of nitrobenzene the substance must be heated with a mixture of fuming nitric acid and concentrated sulphuric acid the product is largely ni-dinitrobenzene (about 90 per cent.), accompanied by a little o-dinitrobenzene (about 5 per cent.) which is eliminated in the recrystallisation process. On the other hand phenol can be easily nitrated with dilute nitric acid to yield a mixture of ortho and para nitrophenols. It may be said, therefore, that orientation is meta with the... 

Disconnection b will not do as the nitio group is meta-directing and in any case nitro benzene wiU not react under FriedeTCrafts conditions. Disconnection a is fine as the MeO group is more powerfully ortho-direeting than the Me group (Ber., 1907, 3514). 

In nitration with nitronium salts in sulpholan, nitrobenzene was substituted in the following proportions 8% ortho, 90% meta and 2% paraf under the same conditions benzylidyne trifluoride yielded 8%, 88% and 4% of 0-, m- and p-nitro compound respectively Both of these aromatic compounds were stated to be io -10 times less reactive than benzene. "... 

The selectivity of an electrophile, measured by the extent to which it discriminated either between benzene and toluene, or between the meta- and ara-positions in toluene, was considered to be related to its reactivity. Thus, powerful electrophiles, of which the species operating in Friedel-Crafts alkylation reactions were considered to be examples, would be less able to distinguish between compounds and positions than a weakly electrophilic reagent. The ultimate electrophilic species would be entirely insensitive to the differences between compounds and positions, and would bring about reaction in the statistical ratio of the various sites for substitution available to it. The idea has gained wide acceptance that the electrophiles operative in reactions which have low selectivity factors Sf) or reaction constants (p+), are intrinsically more reactive than the effective electrophiles in reactions which have higher values of these parameters. However, there are several aspects of this supposed relationship which merit discussion. 

A series of meta- and para-bis (2-thiazolyI) benzenes and of meta- and para-bis(4-thiazolyl)benzenes of general formula 35 and 36 was prepared in higher yields (60-90%) from the appropriate bis-(haloacetyl)benzenes with a suitable thioamide (Scheme 18a and Table JI-8) (573, 574),... 

TABLE II-8. META- AND PARA-BIS (2-THIAZOLYL) BENZENES (35) AND AffiTA- AND PARA-BIS(4-THIAZOLYL) BENZENES (36)... 

Bis (meta or para haloacetyl) benzenes (C1CH2C0)2C6H4 condensed with thiourea yield the corresponding meta or para bis(4-thiazolyl-2-amino)phenylene (573, 574), analogous to 36 with R=NH2-By refluxing in alcohol solution m- or p-2-thiazolylphenacyl bromide (37) with thiourea, compound 111, in which R = H, Ph, P-CIC6H4, and p-OjNC H, was obtained (569). 

Dimethyl derivatives of benzene are called xylenes There are three xylene isomers the ortho (o) meta (m) and para (p) substituted derivatives... 

The prefix ortho signifies a 1 2 disubstituted benzene ring meta signifies 1 3 disubstitu tion and para signifies 1 4 disubstitution The prefixes o m and p can be used when a substance is named as a benzene derivative or when a specific base name (such as ace tophenone) is used For example... 

Because substitution m (trifluoromethyl)benzene occurs primarily at positions meta to the substituent we say that a trifluoromethyl group is a meta director... 

A methyl group is an electron releasing substituent and activates all of the ring carbons of toluene toward electrophilic attack The ortho and para positions are activated more than the meta positions The relative rates of attack at the various positions m toluene compared with a single position m benzene are as follows (for nitration at 25°C)... 

All the ring positions of (trifluoromethyl)benzene are deactivated compared with benzene The meta position is simply deactivated less than the ortho and para positions The partial rate factors for nitration of (trifluoromethyl)benzene are... 

Figure 12 11 compares the energy profile for nitration of benzene with those for attack at the ortho meta and para positions of (trifluoromethyl)benzene The presence of the electron withdrawing trifluoromethyl group raises the activation energy for attack at all the ring positions but the increase is least for attack at the meta position... 

FIGURE 12 11 Comparative energy diagrams for nitro mum ion attack on (a) ben zene and at the (b) ortho (c) meta and d) para posi tions of (trifluoromethyl) benzene fact (ortho) > fact (para) > fact (meta) >... 

Because the carbon atom attached to the ring is positively polarized a carbonyl group behaves m much the same way as a trifluoromethyl group and destabilizes all the cyclo hexadienyl cation intermediates m electrophilic aromatic substitution reactions Attack at any nng position m benzaldehyde is slower than attack m benzene The intermediates for ortho and para substitution are particularly unstable because each has a resonance structure m which there is a positive charge on the carbon that bears the electron withdrawing substituent The intermediate for meta substitution avoids this unfavorable juxtaposition of positive charges is not as unstable and gives rise to most of the product... 

When benzene undergoes disulfonation m benzenedisulfomc acid is formed The first sulfonic acid group to go on directs the second one meta to itself... 

Because the position of electrophilic attack on an aromatic nng is controlled by the direct ing effects of substituents already present the preparation of disubstituted aromatic com pounds requires that careful thought be given to the order of introduction of the two groups Compare the independent preparations of m bromoacetophenone and p bromoace tophenone from benzene Both syntheses require a Friedel-Crafts acylation step and a bromination step but the major product is determined by the order m which the two steps are carried out When the meta directing acetyl group is introduced first the final product IS m bromoacetophenone... 

Meta (Section 117) Term descnbing a 1 3 relationship be tween substituents on a benzene nng Meta director (Section 12 9) A group that when present on a benzene nng directs an incoming electrophile to a position meta to itself... 

The position of substituents is indicated by numbers, with the lowest locant possible given to substituents. When a name is based on a recognized trivial name, priority for lowest-numbered locants is given to substituents implied by the bivial name. When only two substituents are present on a benzene ring, their position may be indicated by o- ortho-), m- meta-), and p- (para-) (and alphabetized in the order given) used in place of 1,2-, 1,3-, and 1,4-, respectively. 

Aromatic. Aromatic feedstreams (C-8, C-9, C-10) derived from the steam cracking of petroleum distillates are composed of styrene, iadene, vinyltoluenes (eg, meta- and i ra-methylstyrene), and their respective alkylated analogues. A typical aromatic feedstream might contain 50% reactive olefins with the remainder being alkylated benzenes and higher aromatics. 

Diisopropjibenzenes (DIPB) are readily obtained via Eriedel-Crafts alkylation of benzene or cumene by propylene. This reaction inhquid phase has not evolved drastically since 1980 with the exception of the large variety of heterogeneous acid catalysts that are now being used, mainly zeoHtes, type HZSM-12, giving a para/meta ratio = 0.7 (4). In fact, propylene can also be replaced by isopropyl alcohol coming from the hydrogenation of acetone that... 

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