• • Chemistry 201 C Organic Compounds: Alkanes and Cycloalkanes This presentation was created by Professor Carl H. Snyder Chemistry Department University of Miami Coral Gables, FL 33124 CSnyder@miami.edu Copyright 2004 by Carl H. Snyder, University of Miami. All rights reserved. Lewis Structures The Lewis Structure of Methane Lewis structures of the hydrogen atom and the carbon atom. Lewis structures show the elemental symbol and the valence electrons. Methane consists of 4 hydrogens covalently bonded to one central carbon atom. Methane, A Covalent Hydrocarbon Methane - The Molecular Model Methane in 3-dimensional perspective. Methane in a 2-dimensional representation. • •1 • • The Methyl Radical methyl radical A Radical In chemistry, a radical is any species bearing an unpaired electron. Loss of a hydrogen atom from methane produces the methyl radical, also known as the methyl free radical. Note that loss of any one of methane’s four hydrogens produces the same methyl radical. Ethane From Two Methyl Radicals Ethane - Expanded Structure, Condensed Structure, And Molecular Formula Expanded structure The combination of two methyl radicals forms ethane. Ethane can form in many other ways as well. Condensed structure Molecular formula Ethane - The Molecular Model The Ethyl Radical Ethane in 3-dimensional perspective. the ethyl radical Ethane in a 2-dimensional representation. • Loss of a hydrogen atom from ethane produces the ethyl radical, also known as the ethyl free radical. Notice that loss of any one of ethane’s six hydrogens produces the same ethyl radical. •2 • • Propane From An Ethyl Radical And A Methyl Radical Propane - Expanded Structure, Condensed Structure, And Molecular Formula Expanded structure The combination of an ethyl radical and a methyl radical produces propane. Propane can form in many other ways as well. Condensed structure Molecular formula Propane - The Molecular Model Propane in 3-dimensional perspective. Propane, a 2-dimensional representation. The First Members of The Alkane Series All compounds whose molecular formulas fit the general formula CnH(2n+2) are alkanes • Alkanes and Alkyl Groups Methane, ethane, and propane are members of a group of hydrocarbons known as the alkanes. Removing a hydrogen atom from an alkane produces an alkyl group. CH3- is the methyl group, as in methyl chloride, CH3-Cl ; CH3-CH2- is the ethyl group, as in ethyl chloride, CH3-CH2-Cl Alkyl groups are indicated generically by the symbol R-, as in R-Cl Some Terms to Remember Hydrocarbon - A compound composed exclusively of hydrogen and carbon. Saturated hydrocarbon - A compound of general formula CnH(2n+2) containing the maximum possible number of hydrogens per carbon. Alkane - The family of compounds with the general formula CnH(2n+2); the saturated hydrocarbons. Aliphatic hydrocarbons - An older term for the alkane family, derived from a Greek word for "fat" or "fatty substance" •3 • • Classes of Carbons Primary (1o) and Secondary (2o) Carbons A primary (1o) carbon is bonded to exactly one other carbon. A secondary (2o) carbon is bonded to exactly two other carbons 1o And 2o Hydrogens In Propane 1 - 1o carbon 1 - 1o carbon Classes of Hydrogens Hydrogens always take the same class as the carbons to which they are bonded. All hydrogens on a primary carbon are primary hydrogens. All hydrogens on a secondary carbon are secondary hydrogens. 1o And 2o Hydrogens In Propane 1 - 1o carbon 3 - 1o hydrogens Propane contains two 1o carbons and . . . 1 - 1o carbon 3 - 1o hydrogens Propane contains two 1o carbons and six 1o hydrogens, and . . . 1o And 2o Hydrogens In Propane 1o And 2o Hydrogens In Propane 1 - 1o carbon 1 - 1o carbon 1 - 2o carbon 1 - 1o carbon 1 - 1o carbon 1 - 2o carbon 2 - 2o hydrogens 3 - 1o hydrogens 3 - 1o hydrogens Propane contains two 1o hydrogens, and one 2o carbon and . . . • 1o carbons and six 3 - 1o hydrogens 3 - 1o hydrogens Propane contains two 1o carbons and six 1o hydrogens, and one 2o carbon and two 2 o hydrogens. •4 • • Two Different Propyl Radicals primary propyl radical Two Different Propyl Radicals primary propyl radical secondary propyl radical Removing a 1o H produces a 1o propyl radical. The Propyl Radical and the Isopropyl Radical Removing a 1o H produces a 1o propyl radical. Removing a 2o H produces a 2o propyl radical. Two Different Butanes The addition of a methyl group to the 1o carbon of a propyl radical produces a straight-chain C4H10. Two Different Butanes Isomers Different compounds that share the same molecular formula are known as isomers. The straight-chain structure and the branchedchain structure represent the two isomers of butane, C4H10. The addition of a methyl group to the 1o carbon of a propyl radical produces a straight-chain C4H10. The addition of a methyl group to the 2o carbon of an isopropyl radical produces a branched-chain C4H10. • •5 • • The Two Isomers of Butane The Tertiary Carbon And The Tertiary Hydrogen Of Isobutane A tertiary (3o) carbon is bonded to exactly three other carbons. The hydrogen on the tertiary carbon is a tertiary hydrogen. Although each structure represents one of the isomers of butane, C4H10, the straight-chain structure is known as butane, and the branched-chain structure is known as isobutane. The Tertiary Carbon And The Tertiary Hydrogen Of Isobutane The Tertiary Carbon And The Tertiary Hydrogen Of Isobutane A tertiary (3o) carbon is bonded to exactly three other carbons. The hydrogen on the tertiary carbon is a tertiary hydrogen. A tertiary (3o) carbon is bonded to exactly three other carbons. The hydrogen on the tertiary carbon is a tertiary hydrogen. 3o carbon They’re All Butane, C4H10 Each of these structures represents butane, the straight-chain, unbranched isomer. As long as you can pass from one end of the chain to the other end without encountering a branch, it’s butane. 3º H The Three Isomers of Pentane, C5H12 pentane pentane Pentane • 3o carbon isopentane isopentane Isopentane neopentane Neopentane •6 • • The Quaternary Carbon of Neopentane A quaternary (4o) carbon is bonded to exactly four other carbons. Because all of its valences are consumed in bonding to other carbons, a quaternary carbon cannot be bonded to a hydrogen. Quaternary hydrogens do not exist. quaternary carbon quaternary carbon The First 10 Alkanes We are concerned with the names of the first 10 alkanes. Those with five or more carbons begin with terms derived from Latin or Greek words for the numbers one through ten. They end with -ane to specify that we are dealing with alkanes. Alkyl Groups: The Two C3 Alkyl Groups CH3-CH2-CH2-Cl is propyl chloride CH3-CH-CH3 is isopropyl chloride | Cl • The Four C4 Alkyl Groups CH3-CH2-CH2-CH2-Cl is butyl chloride CH3-CH2-CH-CH3 is sec-butyl chloride | Cl •7 • • The Four C4 Alkyl Groups CH3-CH-CH2-Cl is isobutyl chloride | CH3 Alkane Isomers The enormous number of isomers of alkanes and alkyl groups overwhelms systems that use prefixes such as iso- and neo-. The IUPAC system can accommodate large numbers of isomers. IUPAC • The Four C4 Alkyl Groups CH3 | CH3-C-Cl is tert-butyl chloride | CH3 The IUPAC (International Union of Pure and Applied Chemistry) System IUPAC •8 • • IUPAC IUPAC IUPAC IUPAC IUPAC IUPAC • •9 • • • IUPAC IUPAC Example #1 IUPAC Example #1 IUPAC Example #1 IUPAC Example #1 IUPAC Example #2 •10 • • • IUPAC Example #2 IUPAC Example #2 IUPAC Example #2 IUPAC Example #3 IUPAC Example #3 IUPAC Example #3 •11 • • IUPAC Example #3 IUPAC Example #4 IUPAC Example #4 IUPAC Example #4 IUPAC Example #4 IUPAC Example #5 • •12 • • IUPAC Example #5 IUPAC Example #5 IUPAC Example #5 Cycloalkanes CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 Naming Cycloalkanes • Naming Cycloalkanes •13 • • • Naming Cycloalkanes Naming Cycloalkanes Cycloalkanes - Example #1 Cycloalkanes - Example #1 Cycloalkanes - Example #1 Cycloalkanes - Example #1 •14 • • Cycloalkanes - Example #2 Cycloalkanes - Example #2 Cycloalkanes - Example #3 • Cycloalkanes - Example #2 Cycloalkanes - Example #3 Cycloalkanes - Example #3 •15 • • Kinds of Isomerism Cycloalkanes - Example #3 The Rigid Ring of Cyclopropane Constitutional isomers show different sequences in the connections of their atoms - butane and isobutane are constitutional isomers. Stereoisomers show the same sequences of connections, but differ in the 3-dimensional, spacial orientation of their atoms. cis-1,2-Dimethylcyclopropane The rigid ring of cyclopropane fixes substituents on each side of the ring, allowing the kind of stereoisomerism known as geometric or cis/trans isomerism. The two CH3 groups of cis-1,2dimethylcyclopropane lie on the same side of the ring. Moving one of the CH3 groups to the other side of the ring would require breaking covalent bonds, which is a high-energy process. trans-1,2Dimethylcyclopropane The two CH3 groups of trans-1,2dimethylcyclopropane lie on opposite sides of the ring. Moving one of the CH3 groups to the other side of the ring would require breaking covalent bonds, which is a high-energy process. • Configurational Isomers If interconverting isomers (as in the case of stereoisomers) requires the breaking and reforming of covalent bonds, the isomers are known as configurational isomers. •16 • • End Organic Compounds: Alkanes and Cycloalkanes • •17