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SAS SGU FALL 2012 CHEM 222 STRUCTURE, ISOMERISM {WADE: Chapter 7}

ALKENES: NOMENCLATURE,

A Carbon-Carbon double bond is an important functional group. The double bond is the site of most of the chemical reactions that alkenes undergo. Alkenes play many important roles in Biology; e.g. ethene is a plant hormone. The double bond in ethene is stronger than the C C single bond in ethane, but it not twice as strong; the bond is stronger than the bond (sigma bond energy = 347 kJ/mol; pi bond energy = 264 kj/mol). The general molecular formula for an acyclic (noncyclic) alkene is CnH2n; while for a cyclic alkene it is CnH2n-2. The total number of bonds and/or rings in an alkene is called the element (degree) of unsaturation. So, the acyclic alkene C5H10 has one (1) degree of unsaturation; while the cyclic alkene C5H8 has two degrees of unsaturation. Alkenes are unsaturated hydrocarbons. Formula for calculating element of unsaturation is: (2C+2 H), where C= number of carbons, H= number of hydrogens

{(a)Work out the element of unsaturation for the following formulas: (i) C10H16 (ii) C20H34 (iii) C40H56. (b) Determine the molecular formula for (i) a 5-carbon hydrocarbon with one bond and one ring; (ii) a 10-carbon hydrocarbon with one bond and two rings} STRUCTURE of ALKENES Recall the structure of ethene (H2C=CH2) from the hybridization lecture/handout. The bond consists of the cloud of electrons distributed above and below the plane defined by the two sp2 carbons and the four atoms bonded to them. In ethene, C2H4, three atoms are attached to each carbon atom, so three equivalent hybrid orbitals are needed. The 2s orbital is mixed with two of the 2p orbitals in sp2 hybridization. (One of the 2p orbitals with its electron is left unhybridized). Each sp2 orbital has 1/3 s character and 2/3 p character. The axes of the sp2 orbitals are co-planar giving an angle of 1200. For each carbon atom in ethene: two of the sp2 orbitals bond with two H atoms in sigma () bonds; the 3rd overlaps with the third sp2 orbital on the second carbon atom, also in a sigma () bond. Whats left is one unhybridized 2p orbital on each carbon atom. What do they do? They overlap forming a pi ( ) bond. So the double bond

between the two C atoms in ethene contains one sigma () bond and one pi ( ) bond. In order to achieve maximum orbital-orbital overlap, the two p orbitals must be parallel to each other. Therefore all six atoms of the double-bond system are in the same plane.

NOMENCLATURE of ALKENES All the IUPAC rules you learned for alkanes and alkyl halides apply to alkenes as well. 1. The longest continuous chain containing the functional group, the C = C, is numbered in the direction to give it (the functional group suffix) the lowest possible number {alternative way to name alkenes: but-1-ene, hex-2ene, etc.}

2. For a compound with two double bonds, the suffix is diene; CH2=CHCH=CH2 is 1,3butadiene. 3. When there is both a functional group and a substituent, the functional group(the C=C) gets the lowest possible number

4. If a chain has more than one substituent, the alphabet rule applies CH3CH2CH(Br)CH(Cl)CH=CHCH3 is 5-bromo-4-chloro-2-heptene 5. If counting in either direction results in the same number for the C=C group, the correct name is the one containing the lowest substituent number

6. In a cyclic alkene, the C=C is always between C1 and C2, so the 1 is not required. To assign numbers to any substituents, count around the ring in the direction (clockwise or anticlockwise) that puts the lowest number into the name.

The sp2 carbons of an alkene are called vinylic carbons. A sp3 carbon that is adjacent to a vinylic carbon is called an allylic carbon. Two groups containing a C=C are used in common names- the vinyl group (CH2=CH-) and the allyl group (CH2=CHCH2-)

The =CH2 substituent is the methylene group, so the =CH2 attached to a cyclohexane ring is methylene cyclohexane. Cis- & Trans- ISOMERISM Rotation about a double bond does not occur. Because of the high energy barrier to rotation about a C=C bond, an alkene such as 2-butene can exist in two different forms: the hydrogens bonded to the sp2 carbons can be on the same side of the double bond or on opposite sides of the double bond. The compound with the Hs on the same side of the C=C is the cis-isomer, and the compound with the Hs on opposite sides of the C=C is the trans-isomer. A pair of isomers such as cis-2-butene and trans-2-butene are called geometric (or cis-trans) isomers. Notice that the cis- and trans- isomers have the same bonds but different configurations they differ in the way the atoms are oriented in space.

The two isomers are different compounds with different physical properties (boiling points, dipole moments)

Note that if either carbon of the double bond holds two identical groups (or atoms), the molecule cannot have cis and trans forms (see below right)

The E, Z SYSTEM of NOMENCLATURE for ISOMERS The E, Z system is used to name alkenes with two (or more) substituents on one or both of the sp2 carbons. To name an isomer in the E, Z system, we first determine the relative priorities of the two groups bonded to each of the sp2 carbons. If the two highpriority groups (one from each carbon) are on the same side of the double bond, it is the Z isomer (Z is for zusammen, German for together). If the high-priority groups are on opposite side of the double bond, it is the E isomer (E is for entgegen, German for opposite).

The relative priorities of the two groups bonded to a sp2 carbon are determined using the rules below: 1. The relative priorities of the two groups depend on the atomic numbers of the atoms bonded directly to the sp2 carbons. The greater the atomic number, the higher the priority.

2. If the two groups bonded to a sp2 carbon start with the same atom (there is a tie), move outward from the point of attachment and consider the atomic numbers of the atoms attached to the tied atoms. The one with the greater atomic number belongs to the group with the higher priority.

3(a). If an atom is doubly bonded to another atom, the priority system treats it as if it were singly bonded to two of those atoms. If an atom is triply bonded to another atom, the priority system treats it as if it were singly bonded to three of those atoms.

3(b). Also, when two groups competing for the higher priority have some identical atoms, those atoms cancel each other out, and the atomic numbers of the remaining atoms are used to determine which group has higher priority. 4. If two isotopes are being compared, the isotope with the greater mass number has the higher priority

PHYSICAL PROPERTIES of ALKENES Alkenes are similar to alkanes in most of their physical properties . (i) The lower molecular mass alkenes through C4H8 are gases @ room temperature & atmospheric pressure. (ii) The boiling points of 1-butene, cis-2_butene, trans-2-butene and n-butane are all close to 00C. As with alkanes, boiling points of alkenes increase smoothly with increasing molecular mass. Also, increased branching leads to greater volatility and lower boiling points; e.g. 2methylpropene has a boiling point of -70C, lower than the boiling point of any of the unbranched alkenes. (iii) Alkenes have densities around 0.6 or 0.7 g/cm 3. (iv)Like alkanes, alkenes are relatively nonpolar but they are more polar than alkanes. They are insoluble in water but soluble in organic solvents. Alkenes are more polar than alkanes because: the more weakly held electrons in the bond are more polarizable, and vinylic bonds tend to be slightly polar (contributing to a permanent dipole moment). The dipole moments of most alkenes are quite small. Among the C4H8 isomers: 1-butene, cis-2-butene, and 2-methylpropene have dipole moments in the 0.3-0.5 D range; trans-2-butene has no dipole moment. Alkyl groups release electrons to a C=C in much the same way that they release electrons to the positively charged carbon of a carbocation. Therefore the more alkyl groups attached to the carbon atoms in the double bond, the more stable is the alkene. Among the C4H8 isomers, the data indicates that stability increases in the order 1-butene < cis-2-butene < trans-2-butene < 2methylpropene. Therefore, the more highly substituted the carbon atoms in the carbon carbon double bond are the more stable the alkene is.

Richard Jacques October 2012