Chemistry B11 Chapters 10-13 Alkanes, Alkenes, Alkynes and Benzene Organic compounds: organic chemistry is the chemistry of carbon and only a few other elements-chiefly, hydrogen, oxygen, nitrogen, sulfur, halogens, and phosphorus (from 116 elements). Note: In the early days of chemistry, scientists though organic compounds were those produced by living organisms and they could not synthesize any organic compound by starting with only inorganic compounds. In 1828, Friedrich Wöhler synthesized the first organic compound in his laboratory (urea). N 4 Cl O heat + AgNCO 2 N-C-N 2 Ammonium Silver Urea ch loride cyan ate + AgCl Silver chloride Today, chemists obtain organic compounds in two principal ways: 1.Isolation from nature and 2. Synthesis in the laboratory. Note: Compounds made in the laboratory are identical in both chemical and physical properties to those found in nature. Why organic chemistry: we can find organic compounds everywhere around us (foods, flavors, fragrances, medicines, toiletries, cosmetics, plastic, paints, our body, and etc.). Chemist have discovered or synthesized more than 10 million of organic compounds. owever, 1.7 million inorganic compounds are discovered or synthesized (85% of all known compounds are organic compounds). Typical properties of organic compounds: 1. They contain carbon atom. 2. Bonding is almost entirely covalent (covalent compounds). 3. They have low boiling points and low melting points. 4. They are flammable (almost all burn). 5. They are soluble in nonpolar compounds and most are insoluble in water. 6. Many are gases, liquids, or solids. It is important to know: Carbon: normally forms four covalent bonds and has no unshared pairs of electrons. ydrogen: forms one covalent bond and has no unshared pairs of electrons. Nitrogen: normally forms three covalent bonds and has one unshared pair of electrons. Oxygen: normally forms two covalent bonds and has two unshared pairs of electrons. A alogen: normally forms one covalent bond and has three unshared pairs of electrons. Functional group: an atom or group of atoms within a molecule that shows a characteristic set of predictable physical and chemical behaviors. Functional groups are important in organic chemistry because:
1. They are sites predictable chemical behavior. A particular functional group, in whatever compound it is found, undergo the same types of chemical reactions. 2. Determine in large measure the physical properties of a molecule. 3. Serve as the units by which we classify organic compounds into families. 4. Serve as a basis for naming organic compounds. ydrocarbons: a large family of organic compounds and they contain only carbon and hydrogen. ydrocarbons are divided into two groups: 1. Saturated hydrocarbon: a hydrocarbon that contains only carbon-carbon single bonds (alkanes, also called Aliphatic hydrocarbons). Saturated in this context means that each carbon in the hydrocarbon has the maximum number of hydrogen atoms bonded to it. 2. Unsaturated hydrocarbon: a hydrocarbon that contains one or more carbon-carbon double bonds, triple bonds, or benzene rings. Alkanes: They are saturated hydrocarbons (they have only carbon-carbon single bonds). The molecular formula of this group is C n 2n+2 (n is the number of carbon atoms). Naming the unbranched alkanes: Chemists have adopted a set of rules established by the International Union of Pure and Applied Chemistry (IUPAC). The IUPAC name for an alkane consists of two parts: 1. A prefix that shows the number of carbon atoms (meth-, eth-, prop-, but-, pent-, hex-, hept-, oct-, non- and dec-). 2. The suffix -ane. C 4 Methane C 2 6 Ethane C 3 8 Propane C 4 10 Butane Note: we can represent the formula of an organic compound by the molecular formula or by the structural formula. Structural formulas can be represented by three ways: Expanded (Complete) structural formula, Condense structural formula, and Line-angle formula: Expanded (complete) structural formula: to represent this model, the carbon atom is shown attached to the hydrogen atoms (we show all connections).
Condensed structural formula: to represent this model, the hydrogen atoms are grouped with their carbon atom. The number of hydrogen atoms is written as subscript. C 3 -C 2 -C 2 -C 2 -C 3 or C 3 -(C 2 ) 3 -C 3 Line-angle formula: is a form of the structural formula. A line represents a carbon-carbon bond and a vertex represents a carbon atom. A line ending in space represents a C 3 group. C 3 -C 2 -C 3 Propane C 3 -C 2 -C 2 -C 2 -C 3 Pentane Substituent groups: they are the branches in organic compounds. A substituent group derived from an alkane by removal of a hydrogen atom is called an alkyl group (R-). Alkyl groups are named by dropping the -ane from the name of the parent alkane and adding the suffix -yl. C 3 - Methyl C 2 5 - Ethyl C 3 7 - Propyl Note: some substituents derived from other elements or other spices than alkanes: -F Fluoro -Cl Chloro -O ydroxyl -NO 2 Nitro Naming branched alkanes: 1. Write the alkane name of the longest continuous chain of carbon atoms (parent chain or root chain). 2. Number carbon atoms starting from the end nearest substituent. 3. Give the location and name of each substituent (alphabetical order) as a prefix to the alkane name (main chain). Use a hyphen to connect the number to the name. C 3 C 3 -C-C 2 -C 3 1 2 3 4 In this example, the longest chain is Butane. We number carbon atoms starting from the end nearest substituent (left to right). The location of subtituent is 2 and its name is methyl. Therefore, the complete name of this compound is 2-Methylbutane. Cl C 3 C 3 -C 2 -C-C-C 3 5 4 3 2 1 3-Chloro-2-methylpentane Constitutional isomers: compounds with the same molecular formula but a different connectivity of their atoms (different structural formulas). C 3 Butane: C 4 10 C 3 -C 2 -C 2 -C 3 Methylpropane: C 4 10 C 3 -C-C 3 Note: Constitutional isomers are different compounds and have different physical and chemical properties.
Cycloalkane: a saturated hydrocarbon that contains carbon atoms bonded to form a ring. A hydrocarbon that contains carbon atoms joined to form a ring is called a cyclic hydrocarbon. Cyclobutane Cyclopentane Physical properties of alkanes: 1. They are nonpolar compounds (the electronegativity difference between carbon and hydrogen is 2.5-2.1 = 0.4). 2. The only interactions between their molecules are the very week London dispersion forces. 3. They are insoluble in water (because water is polar) and they are soluble in nonpolar organic compounds. 4. They have the lower density than water (their densities is between 0.7 and 0.8 g/ml). 5. They have the low boiling points and the low melting points. 6. They can be gases (with 1 to 4 carbon atoms), liquids (with 5 to 17 carbon atoms), or solids (with 18 or more carbon atoms). Note: In general, both boiling and melting points of alkanes increase with increasing molecular weight (the number of carbon atoms). Note: In general, both boiling and melting points of alkanes decrease with increasing the number of branches (for alkanes with the same molecular weights). As branching increases, the alkane molecule becomes more compact and its surface area decreases (London dispersion forces act over a smaller surface area). Chemical properties of alkanes: in general, they have a low reactivity (inert). Their most important reactions are combustion (reaction with oxygen) and halogenation (reaction with halogens). Combustion: alkanes react with oxygen (they are oxidized). In this reaction, CO 2, 2 O, and energy (heat) are produced. C 4 + 2O 2 CO 2 + 2 2 O + energy (heat) alogenation: alkanes react with chlorine and bromine if we heat the mixture or if we expose the mixture to light (in the dark at room temperature, nothing happens). C 4 + Cl 2 heat or light If chlromethane is allowed to react with more chlorine: C 3 Cl + Cl Chloromethane C 3 Cl + Cl 2 heat or light C 2 Cl 2 + Cl Dichloromethane C 2 Cl 2 + Cl 2 heat or light CCl 3 + Cl Trichloromethane
CCl 3 + Cl 2 heat or light CCl 4 + Cl Tetrachloromethane Sources of alkanes: the two major sources of alkanes are natural gas and petroleum. Natural gas consists of approximately 90 to 95% methane, 5 to 10% ethane, and a mixture of other relatively low-boiling alkanes (propane, butane and 2-methylpropane). Petroleum is a thick, viscous, liquid mixture of thousands of compounds, most of them hydrocarbons, formed the decomposition of marine plants and animals. The fundamental separation process in refining petroleum is fractional distillation. All crude petroleum that enters a refinery goes to distillation units, where it is heated to temperatures as high as 370 to 425 C and separated into fractions. Alkene: an unsaturated hydrocarbon that contains one or more carbon-carbon double bonds. The molecular formula of this group is C n 2n (n is the number of carbon atoms). Alkenes have less hydrogen atoms than alkanes. C 2 4 C 2 =C 2 C 3 6 C 2 =C-C 3 Alkynes: an unsaturated hydrocarbon that contains one or more carbon-carbon triple bonds. The molecular formula of this group is C n 2n-2 (n is the number of carbon atoms). Alkynes have less hydrogen atoms than alkanes and alkenes. C 2 2 C C C 3 4 C C-C 3 Naming unbranched alkenes and alkynes: we use the IUPAC system of naming for alkanes. For alkenes, we replace the suffix -ane of alkanes by -ene. For alkynes, we replace the suffix -ane of alkanes by -yne. Note: Some alkenes and alkynes (particularly those of low molecular weight) are known almost exclusively by their common names (we show them here in the parenthesis). Naming branched alkenes and alkynes: 1. Name the longest carbon chain that contains the double or triple bond. 2. Number the carbon chain starting from the end nearest the double or triple bond. 3. Give the location and name of each substituent (alphabetical order) as a prefix to the alkene or alkyne name. C 3 -C=C-C 3 2-butene C C-C 2 -C 3 1-butyne C 2 -C 3 C 3 -C 2 -C=C-C 3 3-ethyl-2-pentene
Cis and trans isomers: isomers that have the same connectivity of their atoms (and the same molecular formulas) but a different arrangement of their atoms in space. Specifically, cis and trans stereoisomers result from the presence of either a ring or a carbon-carbon double bond (not a carbon-carbon triple bond). Cis and trans isomers are different compounds and have different physical and chemical properties. 3 C 3 C C 3 C = C C = C C 3 trans-2-butene cis-2-butene Note: Both boiling and melting points of the cis isomers are lower than the trans isomers (because the surface areas of cis isomers are smaller and molecules are more compact). Physical properties of alkenes and alkynes: their physical properties are similar to those of alkanes with the same carbon skeletons. Chemical properties of alkenes and alkynes: these organic compounds are more reactive than alkanes. The most characteristic reaction of alkenes (alkynes) is addition to the carboncarbon double bond (triple bond): The double bond is broken and in its place single bonds form to two new atoms or groups of atoms. We can name four important chemical reactions for them: 1. Addition of hydrogen (ydrogenation or Reduction). 2. Addition of hydrogen halides (ydrohalogenation). 3. Addition of water (ydration). 4. Addition of bromine and chlorine (alogenation). ydrogenation or Reduction (addition of hydrogen): atoms of hydrogen add to the carbons in a double or triple bond to form alkanes. A catalyst as platinum (Pt), nickel (Ni), or palladium (Pd) is added to speed up the reaction. The transition metal catalysts used in this hydrogenation are able to absorb large quantities of hydrogen onto their surfaces, probably by forming metal-hydrogen bonds. C = C + 2 C - C alogenation (addition of chlorine and bromine): chlorine and bromine react with alkenes (alkynes) at room temperature by addition of halogen atoms to the carbon atoms of the double bond (triple bond). We do not need any catalysts for this reaction (in general, we use an inert solvent, such as dichloromethane, C 2 C 2 ). Pt C = C + Cl 2 Pt C - C Cl Cl
Note: Addition of bromine is a useful qualitative test for the presence of an alkene (or an alkyne). If we dissolve bromine in carbon tetrachloride, the solution is red. In contrast, alkenes (alkynes) and dibromoalkanes are colorless. The disappearance of the red color as bromine adds to the double bond (triple bond) tells us that alkene (alkyne) is, indeed present. Note: addition of halogen to an alkene (an alkyne) is an addition reaction and two atoms of halogens are added to the carbon atoms of the double bond (triple bond). owever, addition of halogen to an alkane is a substitution reaction and only one atom of halogen is replaced by one hydrogen atom. Benzene: a molecule of benzene consists of a ring of six carbon atoms with onr hydrogen atom attached to each carbon. It has the molecular formula C 6 6. The real molecule of benzene is a resonance hybrid of the two Lewis structures (a unique feature that makes benzene chemically stable). C C C C C C C C C C C C Aromatic compounds: they are unsaturated hydrocarbons that contain one or more benzene rings in their structures. Arene: a compound containing one or more benzene-like rings. Naming aromatic compounds: 1. When one substituent group is attached to benzene, we write the name of the group in front of benzene. C 2 C 3 Cl + Ch lorobenzen e NO 2 + N itrob enzene Eth ylb enzene Note: The IUPAC system retains certain common names for several of the simpler monosubstituted alkylbenzenes: C 3 O OC 3 N 2 O C- O C-O Toluen e Phen ol A nisole A niline Ben zaldehyde Benzoic acid 2. When two or more substituents are attached to benzene, the ring is numbered give the lowest numbers to the substituents. The substituents are listed alphabetically.
Note: if we have two substituents, we can also use the prefix ortho-, meta-, and para- to show the position of the substituents (these names are common names). 1 COO Br 2-Bromobenzoic acid (o-bromoben zoic acid) 2 1 C 3 C 3 1,3-D imethylben zene (m-xylen e) 2 3 4 C 2 C 3 1 Cl 1-Ch loro-4-ethylbenzen e (p-chloroeth ylb enzene) 2 3 Note: The susbtituent group derived by loss of an from benzene is called phenyl group, C 6 5 -. Chemical properties of benzene and its derivatives: The most important characteristic reaction of aromatic compounds is substitution at a ring carbon (aromatic substitution). We can name for them these three reactions: 1.alogenation 2. Nitration 3. Sulfonation. alogenation: in the present of an iron catalyst, chlorine reacts rapidly with benzene to give chlorobenzene and Cl. FeCl + Cl 3 2 Cl + Cl Benzen e Ch lorobenzen e Nitration: when we heat benzene or one of its derivatives with a mixture of concentrated nitric and sulphuric acids, a nitro (-NO 2 ) group replaces one of the hydrogen atoms bonded to the ring. In this reaction, sulfuric acid is a catalyst and it is added to speed up the reaction. 2 SO 4 + NO 3 NO 2 + 2 O N itrob enzene