Benzene derivatives monosubstituted

A point in case is provided by the bromination of various monosubstituted benzene derivatives it was realized that substituents with atoms carrying free electron pairs bonded directly to the benzene ring (OH, NH2, etc) gave 0- and p-substituted benzene derivatives. Furthermore, in all cases except of the halogen atoms the reaction rates were higher than with unsubstituted benzene. On the other hand, substituents with double bonds in conjugation with the benzene ring (NO2, CHO, etc.) decreased reaction rates and provided m-substituted benzene derivatives. 

Let us illustrate this with the example of the bromination of monosubstituted benzene derivatives. Observations on the product distributions and relative reaction rates compared with unsubstituted benzene led chemists to conceive the notion of inductive and resonance effects that made it possible to explain" the experimental observations. On an even more quantitative basis, linear free energy relationships of the form of the Hammett equation allowed the estimation of relative rates. It has to be emphasized that inductive and resonance effects were conceived, not from theoretical calculations, but as constructs to order observations. The explanation" is built on analogy, not on any theoretical method. 

The course of aromatic substitution has been placed on a more scientific basis by the following rules of Hammick and Illingworth (jfour. Chem. Soc., 930. 2358), If a monosubstituted benzene derivative has the formula CgHsXY, where X is the atom joined to the benzene ring and Y is an atom or group of atoms attached to X, then —... 

If, on the other hand, the encounter pair were an oriented structure, positional selectivity could be retained for a different reason and in a different quantitative sense. Thus, a monosubstituted benzene derivative in which the substituent was sufficiently powerfully activating would react with the electrophile to give three different encounter pairs two of these would more readily proceed to the substitution products than to the starting materials, whilst the third might more readily break up than go to products. In the limit the first two would be giving substitution at the encounter rate and, in the absence of steric effects, products in the statistical ratio whilst the third would not. If we consider particular cases, there is nothing in the rather inadequate data available to discourage the view that, for example, in the cases of toluene or phenol, which in sulphuric acid are nitrated at or near the encounter rate, the... 

Whereas only one dehydrobenzene, benzyne, has been detected, two pyridynes are possible. Thus, the scheme we can write ab initio for the action of a nucleophile on the isomeric monosubstituted derivatives of pyridine involving 2,3- (26) and/or 3,4-pyridyne (31) is more complicated than that for the analogous reaction of the corresponding benzene derivative. The validity of this scheme can be checked using data available in the hterature on reactions of halogenopyridines with potassium amide and hthium piperidide involving pyridynes. 

Monosubstituted benzene derivatives containing an electrophilic substituent. 

Recently, a kinetic study has been made of the substitution of diazotised sulphanilic acid in the 2 position of 4-substituted phenols under first-order conditions (phenol in excess) in aqueous buffer solutions at 0 °C131a. A rough Hammett correlation existed between reaction rates and am values, with p about -3.8 however, the point for the methoxy substituent deviated by two orders of magnitude and no explanation was available for this. The unexpectedly low p-factor was attributed to the high reactivities of the aromatic substrates, so that the transition state would be nearer to the ground state than for reaction of monosubstituted benzene derivatives. 

The alkylation of benzene derivatives with methyl(vinyl)dichlorosilane (3) will be described in detail. Alkylation of monosubstituted benzenes such as toluene, chlorobenzene, and biphenyl at 75-80 C for 2 h afforded the corresponding alkylated products in 50-63% yields." ... 

Monosubstituted benzene derivatives are generally attacked in the para-position by trichlorocyclopropenium cation for toluene it was recently found39) that orthoattack also may occur as indicated by formation of 35 besides the normal product 34 ... 

Evaluation of the only appropriate Fukui function is required for investigating an intramolecular reaction, as local softness is merely scaling of Fukui function (as shown in Equation 12.7), and does not alter the intramolecular reactivity trend. For this type, one needs to evaluate the proper Fukui functions (/+ or / ) for the different potential sites of the substrate. For example, the Fukui function values for the C and O atoms of H2CO, shown above, predicts that O atom should be the preferred site for an electrophilic attack, whereas C atom will be open to a nucleophilic attack. Atomic Fukui function for electrophilic attack (fc ) for the ring carbon atoms has been used to study the directing ability of substituents in electrophilic substitution reaction of monosubstituted benzene [23]. In some cases, it was shown that relative electrophilicity (f+/f ) or nucleophilicity (/ /f+) indices provide better intramolecular reactivity trend [23]. For example, basicity of substituted anilines could be explained successfully using relative nucleophilicity index ( / /f 1) [23]. Note however that these parameters are not able to differentiate the preferred site of protonation in benzene derivatives, determined from the absolute proton affinities [24],... 

Kralj, F. and Sincic, D. Mutual solubilities of phenol, salicyaldehyde, phenol-salicyaldehyde mixture, and water with and without the presence of sodium chloride and sodium chloride plus sodium sulfate, J. Chem. Eng. Data, 25 (4) 335-338,1980. Kramer, C.R. and Henze, U. Partitioning properties of benzene derivatives. 1. Temperature dependence of the partitioning of monosubstituted benzenes and nitrobenzenes in the n-octanol/water system, Z. Phys. Chem., 271(3) 503-513,1990. Krasnoshchekova, R.Ya. and Gubergrits, M. Solubility of paraffin hydrocarbons in fresh and salt water, Neftekhlmlya, 13(6) 885-888, 1973. 

The substituent constant of the Hammett equation has been related successfully to the logarithm of the activity coefficient ratio at infinite dilution for a series of meta and para isomers of phenol. Hammett stated that a free energy relationship should exist between the equilibrium or rate behavior of a benzene derivative and a series of corresponding meta and para monosubstitut-ed benzene derivatives. The Hammett equation may be written... 

Thus, the C —H nuclei in the para position of monosubstituted benzene derivatives relax faster than those in the ortho or meta positions (Table 3.16 [151]). The reason for this behavior lies in a preferred rotation about the molecular axis passing through the substituent X and the p-carbon. During this motion, the para C —H bond does not change its direction relative to the field B0 fluctuating local fields can only arise at the p-C nucleus by rotations of the molecule perpendicular to the preferred axis. However,... 

Table 4.59. One-Bond and Longer-Range 13C — 13C Coupling Constants (Hz) of 13C-7-Labeled Monosubstituted Benzene Derivatives [133],...

Because the rate of substitution varies with position, in a benzene derivative it is more informative and frequently more useful to talk about partial rate factors than about relative rates. A partial rate factor is defined as the rate at one particular position in the benzene derivative relative to the rate of substitution at one position in benzene. Let us, for example, calculate the para and meta partial rate factors (pf and mf, respectively) for bromination of toluene with bromine in aqueous acetic acid. Toluene brominates 605 times faster than benzene under these conditions. The product is 66.8 percent p-, 0.3 percent m-, and 32.9 percent o-bromotoluene. Attack at the para position of toluene occurs 0.668 x 605 times as fast as attack at all six positions of benzene but (0.668 x 605 x 6 = 2420) times as fast as at one position of benzene. Therefore pfCH for bromination of toluene under these conditions is 2420. There are only three times as many total carbons in benzene as meta carbons in toluene. Therefore mfca3 = 0.003 x 605 x 3 = 5.5. The definitions of the partial rate factors for monosubstituted benzenes (—R) are given in Equations 7.78-7.80. 

Table IV. Correlation of Optical Hydrated Electron Production from Monosubstituted Benzene Derivatives with Hammett Substituent Constants...

This question could be answered more easily if we knew that the C6C3 units conformed with the principle of additivity. This principle can be formulated as follows. If the introduction of each of two substituents alters the free energy of activation at a particular position by amounts x and y, the presence of both substituents would alter the free energy of activation by an amount (x + y). If this relationship holds, it allows one to predict the reactivities of the individual positions in disubstituted benzene derivatives from the rate data obtained for the corresponding monosubstituted ones. The partial rate factor for a given position of a... 

The nomenclature of benzene derivatives is described in Sec. 4.6. Common names and structures to be memorized include those of toluene, styrene, phenol, aniline, and xylene. Monosubstituted benzenes are named as benzene derivatives (bromobenzene, nitrobenzene, and so on). Disubstituted benzenes are named as ortho- (1,2-), meta- (1,3-), or para- (1,4-), depending on the relative positions of the substituents on the ring. Two important groups are phenyl (C6H5-) and benzyl (C6H5CH2-). 

Kramer, C.R., Henze, U. (1990) Partitioning properties of benzene derivatives. I. Temperature dependence of the partitioning of monosubstituted benzenes and nitrobenzenes in the ra-octanol/water system. Z. Phys. Chem. (Leipzig) 271(3), 503-513. 

Regioselectivity in the formation of regioisomers is also observed in electrophilic aromatic substitution reactions. In the case of monosubstituted benzene derivatives, there are three possible regiosomeric products that form at different rates, based on the mechanism of the reaction (see Figure 13). see also Berzelius, Jons Jakob Chirality Dalton, John Davy, Humphry Molecular Structure Scheele, Carl Wohler, Friedrich. 

Holleman [55] gives the following data on the composition of the nitration products obtained in the nitration of different monosubstituted benzene derivatives with mixtures of nitric and sulphuric acids (Table 2). As appears from the data shown below, the substituent already present affects the orientation of the group which is being introduced. It is evident that nitration can be influenced by the steric factor. For exampl tert.-butylbenzene is mainly nitrated in para (72.7%) and to a much lesser extent in ortho (15.8%) positions (H. C. Brown and Nelson [88]). 

In the benzene molecule, all the carbon atoms are identical. So in monosubstituted benzene derivatives, there is no need to number the carbon atoms. Thus there is only one possible fluorobenzene structure, it makes no difference to which carbon atom the fluorine atom is attached. 

Monosubstituted benzene derivatives do not exhibit isomerism. However, when two substituents are present, there are three possible isomers depending upon the relative positions of the substituents within the ring. These relative positions are indicated by the Latin words ortho, meta or para, or their initials ... 

Aromatic compounds are the only type of i-nucleophiles involved in reactions with organoxenonium salts. While pentafluorobenzenes, CeFsZ (Z = H, F, CN, SiMej), are not reactive towards [C6F5Xe][AsF6] in MeCN at 20 °C, a series of 2,3,4,5,6-pentafIuorobiphenyls was obtained from monosubstituted benzene derivatives, CeHsZ, under these conditions. The reaction rates diminish in the sequence Z = CH3 > F > CF3 CN > NO2, which is consistent with the electrophilic nature of the process. Nevertheless, the isomer distribution in the C6F5C6H4Z products shows unambiguously the radical character of the pentafluorophenylation reaction (eq 17) 46). 

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