Positive polarity

Alkyl halides and sulfonates are the most frequently used alkylating acceptor synthons. The carbonyl group is used as the classical a -synthon. O-Silylated hemithioacetals (T.H. Chan, 1976) and fomic acid orthoesters are examples for less common a -synthons. In most synthetic reactions carbon atoms with a partial positive charge (= positively polarized carbon) are involved. More reactive, "free carbocations as occurring in Friedel-Crafts type alkylations and acylations are of comparably limited synthetic value, because they tend to react non-selectively. 

One of the unshared pairs of the hydroxide oxygen is used to form a covalent bond to the positively polar ized proton of hydrogen fluoride The covalent bond betwen H and F in hydrogen fluoride breaks with the pair of electrons in this bond becoming an unshared pair of fluoride ion... 

Recall that the carbon atom of carbon dioxide bears a partial positive charge because of the electron attracting power of its attached oxygens When hydroxide ion (the Lewis base) bonds to this positively polarized carbon a pair of electrons in the carbon-oxygen double bond leaves carbon to become an unshared pair of oxygen... 

FIGURE 4 3 Adipole-dipole attractive force Two molecules of a polar sub stance associate so that the positively polarized region of one and the negatively polarized region of the other attract each other... 

Induced dipole/induced dipole forces are the only intermolecular attractive forces available to nonpolar molecules such as alkanes In addition to these forces polar molecules engage m dipole-dipole and dipole/mduced dipole attractions The dipole-dipole attractive force is easiest to visualize and is illustrated m Figure 4 3 Two molecules of a polar substance experience a mutual attraction between the positively polarized region of one molecule and the negatively polarized region of the other As its name implies the dipole/induced dipole force combines features of both the induced dipole/mduced dipole and dipole-dipole attractive forces A polar region of one mole cule alters the electron distribution m a nonpolar region of another m a direction that produces an attractive force between them... 

There is a pronounced tendency for boron to become bonded to the less substituted car bon of the double bond Thus the hydrogen atoms of diborane add to C 2 of 1 decene and boron to C 1 This is believed to be mainly a steric effect but the regioselectivity of addition does correspond to Markovmkov s rule m the sense that hydrogen is the neg atively polarized atom m a B—H bond and boron the positively polarized one... 

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... 

Unstable because of adjacent positively polarized atoms... 

Positively polarized atoms not adjacent most stable intermediate... 

With electrons flowing from ethylene to zirconium the Zr—CH3 bond weakens the carbons of ethylene become positively polarized and the methyl group migrates from zirconium to one of the carbons of ethylene Cleavage of the Zr—CH3 bond is accom panied by formation of a ct bond between zirconium and one of the carbons of ethylene m Step 3 The product of this step is a chain extended form of the active catalyst ready to accept another ethylene ligand and repeat the chain extending steps... 

Step 1 Hydride (hydrogen + two electrons) is transferred from boron to the positively polarized carbon of the carbonyl group The carbonyl oxygen bonds to boron... 

Overall the reaction is classified as an addition Water adds to the carbonyl group Hydrogen becomes bonded to the negatively polarized carbonyl oxygen hydroxyl to the positively polarized carbon... 

Section 17 2 The carbonyl carbon is sp hybridized and it and the atoms attached to It are coplanar Aldehydes and ketones are polar molecules Nucleophiles attack C=0 at carbon (positively polarized) and electrophiles especially protons attack oxygen (negatively polarized)... 

The carbonyl group withdraws rr electron density from the double bond and both the carbonyl carbon and the p carbon are positively polarized Their greater degree of charge separation makes the dipole moments of a p unsaturated carbonyl compounds signifi cantly larger than those of comparable aldehydes and ketones... 

Virtually all of the organo derivatives of CA are produced by reactions characteristic of a cycHc imide, wherein isocyanurate nitrogen (frequendy as the anion) nucleophilically attacks a positively polarized carbon of the second reactant. Cyanuric acid and ethylene oxide react neady quantitatively at 100°C to form tris(2-hydroxyethyl)isocyanurate [839-90-7] (THEIC) (48—52). Substitution of propylene oxide yields the hydroxypropyl analogue (48,49). At elevated temperatures (- 200° C). CA and alkylene oxides react in inert solvent to give A/-hydroxyalkyloxazohdones in approximately 70% yield (53). Alternatively, THEIC can be prepared by reaction of CA and 2-chloroethanol in aqueous caustic (52). THEIC can react further via its hydroxyl fiinctionahty to form esters, ethers, urethanes, phosphites, etc (54). Reaction of CA with epichlorohydrin in alkaline dioxane solution gives... 

For LT units Three impulses should be applied of positive polarity followed by three of negative between the terminals joined together and the container. 

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