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 σ bond is stronger than the π 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 π 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: ½ (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 π bond and one ring; (ii) a 10-carbon hydrocarbon with one π bond and two rings} STRUCTURE of ALKENES Recall the structure of ethene (H2C=CH2) from the hybridization lecture/handout. The π 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 (σ) bonds; the 3rd overlaps with the third sp2 orbital on the second carbon atom, also in a sigma (σ) bond. What’s left is one unhybridized 2p orbital on each carbon atom. What do they do? They overlap forming a pi ( ) bond. So the double bond

. CH2=CHCH=CH2 is 1. Therefore all six atoms of the double-bond system are in the same plane. so the “1” is not required.} 2.3butadiene. the two p orbitals must be parallel to each other.between the two C atoms in ethene contains one sigma (σ) bond and one pi ( ) bond. If a chain has more than one substituent. is numbered in the direction to give it (the functional group suffix) the lowest possible number  {alternative way to name alkenes: but-1-ene. To assign numbers to any substituents. the functional group(the C=C) gets the lowest possible number  4. hex-2ene. When there is both a functional group and a substituent. the “ alphabet” rule applies  CH3CH2CH(Br)CH(Cl)CH=CHCH3 is 5-bromo-4-chloro-2-heptene 5. In order to achieve maximum orbital-orbital overlap. etc. For a compound with two double bonds. 3. NOMENCLATURE of ALKENES All the IUPAC rules you learned for alkanes and alkyl halides apply to alkenes as well. count around the ring in the direction (clockwise or anticlockwise) that puts the lowest number into the name. the C=C is always between C1 and C2. In a cyclic alkene. 1. the suffix is “ diene”. the correct name is the one containing the lowest substituent number  6. If counting in either direction results in the same number for the C=C group. the C = C. The longest continuous chain containing the functional group.

A pair of isomers such as cis-2-butene and trans-2-butene are called geometric (or cis-trans) isomers. Cis. 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. Two groups containing a C=C are used in common names. dipole moments)  .ISOMERISM Rotation about a double bond does not occur. Notice that the cis.The sp2 carbons of an alkene are called vinylic carbons. Because of the high energy barrier to rotation about a C=C bond. so the =CH2 attached to a cyclohexane ring is methylene cyclohexane. and the compound with the H’s on opposite sides of the C=C is the trans-isomer. The compound with the H’s on the same side of the C=C is the cis-isomer.and trans.the vinyl group (CH2=CH-) and the allyl group (CH2=CHCH2-) The =CH2 substituent is the methylene group. The two isomers are different compounds with different physical properties (boiling points.isomers have the same bonds but different configurations they differ in the way the atoms are oriented in space. A sp3 carbon that is adjacent to a vinylic carbon is called an allylic carbon.& Trans.

Z SYSTEM of NOMENCLATURE for ISOMERS The E. it is the E isomer (E is for “entgegen”. The one with the greater atomic number belongs to the group with the higher priority. Z system. The relative priorities of the two groups bonded to a sp2 carbon are determined using the rules below: 1. the priority system treats it as if it were singly bonded to three of those atoms. If an atom is doubly bonded to another atom. it is the Z isomer (Z is for “zusammen”. If the two highpriority groups (one from each carbon) are on the same side of the double bond.Note that if either carbon of the double bond holds two identical groups (or atoms). If the two groups bonded to a sp2 carbon start with the same atom (there is a “tie”). If an atom is triply bonded to another atom. move outward from the point of attachment and consider the atomic numbers of the atoms attached to the “tied” atoms. German for “together”). The greater the atomic number. 3(a). To name an isomer in the E. the molecule cannot have cis and trans forms (see below right) The E. . Z system is used to name alkenes with two (or more) substituents on one or both of the sp2 carbons. the higher the priority. German for “opposite”). The relative priorities of the two groups depend on the atomic numbers of the atoms bonded directly to the sp2 carbons. If the high-priority groups are on opposite side of the double bond. 2. we first determine the “relative priorities” of the two groups bonded to each of the sp2 carbons. the priority system treats it as if it were singly bonded to two of those atoms.

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 . alkenes are relatively nonpolar but they are more polar than alkanes. Alkenes are more polar than alkanes because: the more weakly held electrons in the π bond are more polarizable. 4. Therefore. (i) The lower molecular mass alkenes through C4H8 are gases @ room temperature & atmospheric pressure. Among the C4H8 isomers. cis-2-butene. (ii) The boiling points of 1-butene. trans-2-butene has no dipole moment.3-0. 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. Richard Jacques October 2012 .g.5 D range.7 g/cm 3.3(b). cis-2_butene. those atoms cancel each other out. As with alkanes. If two isotopes are being compared. increased branching leads to greater volatility and lower boiling points. and the atomic numbers of the remaining atoms are used to determine which group has higher priority. Also. (iv)Like alkanes. boiling points of alkenes increase smoothly with increasing molecular mass. the more highly substituted the carbon atoms in the carbon – carbon double bond are the more stable the alkene is. the more stable is the alkene. Among the C4H8 isomers: 1-butene. (iii) Alkenes have densities around 0. and 2-methylpropene have dipole moments in the 0. The dipole moments of most alkenes are quite small. Therefore the more alkyl groups attached to the carbon atoms in the double bond. 2methylpropene has a boiling point of -70C. trans-2-butene and n-butane are all close to 00C. lower than the boiling point of any of the unbranched alkenes. They are insoluble in water but soluble in organic solvents. Also.6 or 0. the data indicates that stability increases in the order 1-butene < cis-2-butene < trans-2-butene < 2methylpropene. e. when two groups competing for the higher priority have some identical atoms. and vinylic bonds tend to be slightly polar (contributing to a permanent dipole moment).