Chlorine atoms polarity

Replacement of Labile Chlorines. When PVC is manufactured, competing reactions to the normal head-to-tail free-radical polymerization can sometimes take place. These side reactions are few ia number yet their presence ia the finished resin can be devastating. These abnormal stmctures have weakened carbon—chlorine bonds and are more susceptible to certain displacement reactions than are the normal PVC carbon—chlorine bonds. Carboxylate and mercaptide salts of certain metals, particularly organotin, zinc, cadmium, and antimony, attack these labile chlorine sites and replace them with a more thermally stable C—O or C—S bound ligand. These electrophilic metal centers can readily coordinate with the electronegative polarized chlorine atoms found at sites similar to stmctures (3—6). 

Aromatic compounds may be chlorinated with chlorine in the presence of a catalyst such as iron, ferric chloride, or other Lewis acids. The halogenation reaction involves electrophilic displacement of the aromatic hydrogen by halogen. Introduction of a second chlorine atom into the monochloro aromatic stmcture leads to ortho and para substitution. The presence of a Lewis acid favors polarization of the chlorine molecule, thereby increasing its electrophilic character. Because the polarization does not lead to complete ionization, the reaction should be represented as shown in equation 26. 

These effects can be attributed mainly to the inductive nature of the chlorine atoms, which reduces the electron density at position 4 and increases polarization of the 3,4-double bond. The dual reactivity of the chloropteridines has been further confirmed by the preparation of new adducts and substitution products. The addition reaction competes successfully, in a preparative sense, with the substitution reaction, if the latter is slowed down by a low temperature and a non-polar solvent. Compounds (12) and (13) react with dry ammonia in benzene at 5 °C to yield the 3,4-adducts (IS), which were shown by IR spectroscopy to contain little or none of the corresponding substitution product. The adducts decompose slowly in air and almost instantaneously in water or ethanol to give the original chloropteridine and ammonia. Certain other amines behave similarly, forming adducts which can be stored for a few days at -20 °C. Treatment of (12) and (13) in acetone with hydrogen sulfide or toluene-a-thiol gives adducts of the same type. 

Selective chlorination of the 3-position of thietane 1,1-dioxide may be a consequence of hydrogen atom abstraction by a chlorine atom. Such reactions of chlorine atoms are believed to be influenced by polar effects, preferential hydrogen abstraction occurring remotely from an electron withdrawing group. The free radical chain reaction may be propagated by attack of the 3-thietanyl 1,1-dioxide radical on molecular chlorine. 

It is always important to keep in mind the relative nature of substituent effects. Thus, the effect of the chlorine atoms in the case of trichloroacetic acid is primarily to stabilize the dissociated anion. The acid is more highly dissociated than in the unsubstituted case because there is a more favorable energy difference between the parent acid and the anion. It is the energy differences, not the absolute energies, that determine the equilibrium constant for ionization. As we will discuss more fully in Chapter 4, there are other mechanisms by which substituents affect the energy of reactants and products. The detailed understanding of substituent effects will require that we separate polar effects fiom these other factors. 

Similarly, carboxylic acid and ester groups tend to direct chlorination to the / and v positions, because attack at the a position is electronically disfavored. The polar effect is attributed to the fact that the chlorine atom is an electrophilic species, and the relatively electron-poor carbon atom adjacent to an electron-withdrawing group is avoided. The effect of an electron-withdrawing substituent is to decrease the electron density at the potential radical site. Because the chlorine atom is highly reactive, the reaction would be expected to have a very early transition state, and this electrostatic effect predominates over the stabilizing substituent effect on the intermediate. The substituent effect dominates the kinetic selectivity of the reaction, and the relative stability of the radical intermediate has relatively little influence. 

In non-polar solvents, the reaction with piperidine is best represented by a two-term kinetic form indicating a mixed 2nd- and 3rd-order reaction. Also, base catalysis by tri-ri-butylamine was observed. This kinetic pattern is strongly reminiscent of the results obtained with nitro-activated benzenes.Another interesting result is that stepwise replacement of chlorine atoms by amino groups results in marked... 

Electronically, we find that strongly polarized acyl compounds react more readily than less polar ones. Thus, acid chlorides are the most reactive because the electronegative chlorine atom withdraws electrons from the carbonyl carbon, whereas amides are the least reactive. Although subtle, electrostatic potential maps of various carboxylic add derivatives indicate the differences by the relative blueness on the C-O carbons. Acyl phosphates are hard to place on this scale because they are not used in the laboratory, but in biological systems they appear to be somewhat more reactive than thioesters. 

Chloroform, CHCla, is an example of a polar molecule. It has the same bond angles as methane, CH4, and carbon tetrachloride, CCLi- Carbon, with sp3 bonding, forms four tetrahedrally oriented bonds (as in Figure 16-11). However, the cancellation of the electric dipoles of the four C—Cl bonds in CCL does not occur when one of the chlorine atoms is replaced by a hydrogen atom. There is, then, a molecular dipole remaining. The effects of such electric dipoles are important to chemists because they affect chemical properties. We shall examine one of these, solvent action. 

There is no reason to believe that the off-diagonal Q integrals which yield this increase in U over I should be equal for longitudinal and transverse polarization but neither is there at present any basis for selecting different values. Hence we assume U1 = U2 and by use of the a values given above for the chlorine atom, the value of —El is calculated to be about 30 per cent smaller than was obtained in Table VI. Since the effect of anisotropy would be expected to be about the same for all of the halogens, the qualitative conclusions drawn from the results in Table VI are not affected. It is clear that anisotropy may be important, however, and must be considered in quantitative work. 

There are three different dichlorobenzenes, CgH4Cl2, which differ in the relative positions of the chlorine atoms on the benzene ring, (a) Which of the three forms are polar ... 

Susan Solomon and James Anderson showed that CFCs produce chlorine atoms and chlorine oxide under the conditions of the ozone layer and identified the CFCs emanating from everyday objects, such as cans of hair spray, refrigerators, and air conditioners, as the primary culprits in the destruction of stratospheric ozone. The CFC molecules are not very polar, and so they do not dissolve in rain or the oceans. Instead, they rise to the stratosphere, where they are exposed to ultraviolet radiation from the Sun. They readily dissociate in the presence of this radiation and form chlorine atoms, which destroy ozone by various mechanisms, one of which is... 

Much has been learned in recent years about the 00 dimer , O2O2, produced in reaction 17. It is actually dichlorine peroxide, OOOCl its geometry is now well established from submillimeter wave spectroscopy (15). Photolysis of OOOO around 310 nm the atmospherically important wavelengths -- yields chlorine atoms and ClOO radicals (16), as given in reaction 18, rather than two OO radicals, even though QO-OQ is the weakest bond (it has a strength of about 17 Kcal/mol (17)). Thermal decomposition of QOOQ (the reverse of reaction 17) occurs very fast at room temperature, but more slowly at polar stratospheric temperatures. Hence, photolysis is the predominant destruction path for CIOOQ in the polar stratosphere and two Q atoms are produced for each ultraviolet photon absorbed. 

The C—C bond in ethane has no polarity because it connects two equivalent atoms. However, the C—C bond in chloroethane is polarized by the presence of the electronegative chlorine atom. This polarization is actually the sum of two effects. In the first of these, the C-1 atom, having been deprived of some of its electron density by the greater electronegativity of Cl, is partially compensated by drawing... 

A recent discovery shows that the lone pair electrons of the chlorine atom can also facilitate the formation of NCS frameworks. A novel family of salt-containing, mixed-metal sihcates (CU-14), Ba6Mii4Sii2034Cl3 and Ba6Fe5Sin034Cl3, was synthesized via the BaCl2 salt-inclusion reaction [6 a]. These compounds crystallize in the NCS space group Pmcli (No. 26), adopting one of the 10 polar, non-... 

Chlorine is much more electronegative than carbon, so a strong electric dipole exists between each chlorine and the carbon atom. The chlorine atoms are symmetrically arranged around the carbon so that the molecule itself is not polar, even though it has four polar covalent bonds between its atoms. 

Some simple global descriptors are molecular weight, number of atoms present in a molecule (e.g., number of chlorine atoms), number of double bonds, etc. Other descriptors represent the ramification of the molecule. Certain descriptors take into consideration the electronic charge on a certain atom, or its polarity. 

Iodo (trimethyl) platinum (IV) is a yellow crystalline product which decomposes at 190 to 195°. It is soluble in most nonpolar solvents and essentially insoluble in polar media such as water and acetone. In benzene solution, the iodo derivative is tetrameric.6 X-ray investigations have shown that in chloro-(trimethyl) platinum four platinum atoms describe a tetrahedron as do the four chlorine atoms, and the two tetrahedra are interpenetrating so as to give a cubic array of platinum and chlorine atoms. Each platinum atom is bonded to three chlorine atoms and to three terminal methyl groups. Some of the trimethylplatinum derivatives of organic chelate ligands are dimeric and in these structures the platinum is again six-coordinate.7... 

Probably the most important use of electronegativity values is in predicting bond polarities. For example, in the H-F bond, the shared electron pair will reside closer to the fluorine atom because it has an electronegativity of 4.0 while that of the hydrogen atom is 2.2. In other words, the electron pair is shared, but not equally. If we consider the HC1 molecule, the shared electron pair will reside closer to the chlorine atom, which has an electronegativity of 3.2, but the electron pair will be shared more... 

Evidently, the dissociation energies of the H—H and Cl—H bonds are very close and the triplet repulsion in the transition states of these reactions is, therefore, almost identical. Nevertheless, the quantities Eeo and re in these two reactions differ very considerably. The reason for this is that the H—H bond is nonpolar, while the Cl—H bond is polarized its AEA 92.3 kJ mol 1 (Equation [6.29]). As in the HC1 molecule, in the transition state there is evidently a strong attraction between Cl and H, which in fact induces a decrease in re and Ee0. If the Cl + H2 reaction was characterized by the same parameter re = 3.69 x 10-11m as the H + H2 reaction, an activation energy of Ee0 = 56.5 kJ mol 1 would be obtained for that reaction. The difference between the observed and expected activation energies (A ,ea = 36.7—56.5 = —19.8 kJ mol 1) must be attributed to the influence of the unequal electronegativities of the hydrogen and the chlorine atoms on Ec(, in the Cl + H2 reaction. 

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