1. Organic Chemistry Review Part II

2. Functional Groups 1. Hydrocarbons 2. Derivatives of Hydrocarbons

3. Functional Groups Organic molecules may have functional groups attached. A functional group is a group of atoms of a particular arrangement that gives the entire molecule certain chemical characteristics. Functional groups are named according to the composition of the group.

4. Functional Groups Organic chemists use the letter "R" to indicate an organic molecule. The "R" can be any organic molecule.

5. Hydrocarbons The simplest organic compounds. Contain only carbon and hydrogen, Can be straight-chain, branched chain, or cyclic molecules. Carbon tends to form four bonds in a tetrahedral geometry.

6. Hydrocarbons Two classifications: 1. Aliphatics 2. Aromatics Aliphatic - hydrocarbons which do not contain an aromatic ring.

7. Hydrocarbons Aromatic - Aromatic hydrocarbons contain a set of covalently bound atoms with specific characteristics:  A delocalized conjugated π system, with the common arrangement of alternating single and double bonds

8. Aliphatics 1. Alkanes 2. Cycloalkanes 3. Alkenes 4. Alkynes

9. Alkanes IUPAC ending is …ane

10. Alkanes Saturated hydrocarbons. Are hydrocarbons which contain only single bonds. All alkanes are insoluble in water, but dissolve in organic solvents. Density, viscosity, melting point & boiling points increase as the molecular weight/size of the hydrocarbon increases.

11. Alkanes Contain single covalent bonds. Have the same structural formula: C n H 2n+2 All carbons have single bonds therefore the molecular geometry is tetrahedral.

12. Alkanes The names of alkanes start with the name of the alkane but end with the suffix –ane.

13. Alkanes Each atom in an alkane uses all its 4 valence electrons in forming single bonds with other atoms. Alkyl groups may be used as substituents for hydrogens.

14. Alkanes Alkyl groups form the branches of straight chain hydrocarbons. Can have more than one alkyl group for hydrogens. For multiple substituents of the same type, use the following prefixes:  di-  tri-  tetra-  penta-  hexa-

15. Alkanes

16. Other functional groups can be used as substituents. More than one substituent requires a prefix. Any hydrogen can be substituted by: 1.Halogens 2.Alcohols 3.Amines 4.Nitriles 5.Thiols 6.Aldehydes 7.Ketones

17. Alkanes Any carbon can be substituted by:  Carboxylic Acids  Esters  Amides  Thioesters Addition of other atoms:  Ethers  Thioethers  Disulfides

18. Cycloalkanes the prefix cyclo- and the ending …ane

19. Cycloalkanes Saturated hydrocarbons. Form one or more rings fused together. A single carbon in a ring may have two hydrogen atoms. Are insoluble in water, but dissolve in organic solvents. Have higher boiling points, melting points, and densities than alkanes.

20. Cycloalkanes All have the same general formula: C n H 2n The carbon atoms in cycloalkanes are sp 3 hybridized. Each atom in a cycloalkane uses all its 4 valence electrons in forming covalent bonds with other atoms.

21. Cycloalkanes Can have more than one alkyl group to make straight chains. For multiple alkyl groups of the same type, use prefixes.

22. Cycloalkanes Many functional groups can be used as substituents. More than one substituent requires a prefix. Any hydrogen or carbon atom can be substituted by:

23. Cycloalkanes The names follow those of the alkanes with the prefix cyclo-.

24. Cycloalkanes

27. Alkenes IUPAC ending is …ene

28. Alkenes Also known as olefins. Are unsaturated hydrocarbons and are generally very reactive. Are insoluble in water, but dissolve in organic solvents. Ethene, propene and butene are gases at room temperature. The remaining are liquids. Boiling points increases with molecular mass (chain length). The higher the molecular mass, the higher the boiling point.

29. Alkenes Are hydrocarbons which contain one or more double bonds. Double bonds are: Have the same structural formula: C n H 2n

30. Alkenes The main centers are the carbons of the double bond. The geometry of each carbon in the center is trigonal planar. This portion of the molecule is flat, with bond angles of 120 degrees.

31. Alkenes All the alkenes with 4 or more carbon atoms in them show structural isomerism.

32. Alkenes The carbon-carbon double bond does not rotate. Substituents groups on the molecule are locked on either one side of the molecule or opposite each other.

33. Alkenes The names of alkenes start with the name of the alkane but end with the suffix –ene. For alkenes above propene, the position of the double bond must be specified in the name.

34. Alkenes Can have more than one alkyl group to form branches. For more than one alkyl group, use prefixes.

35. Alkenes Many functional groups can be used as substituents. More than one substituent requires a prefix. Any hydrogen or carbon atom can be substituted by:

36. Alkenes For multiple double bonds, use the following prefixes:  di-  tri-  tetra-  penta-  hexa-

37. Alkenes A diene is a hydrocarbon chain that has two double bonds that may or may not be adjacent to each other.

38. Alkenes: Examples

40. Alkynes IUPAC ending is …yne

41. Alkynes Also known as acetylenes. Are unsaturated hydrocarbons and are generally very reactive. Are insoluble in water; but quite soluble in organic solvents of low polarity (e.g. ligroin, ether, benzene, carbon tetrachloride, etc.). Alkynes of four or fewer carbon atoms are gases. The rest are liquids. Their boiling points increase with increasing number of carbons.

42. Alkynes Are hydrocarbons which contain one or more triple bonds. Triple bonds are: Have the same structural formula: C n H 2n-2

43. Alkynes The main centers are the carbons of the triple bond. The geometry of the center is linear. This portion of the molecule is linear, with bond angles of 180 degrees.

44. Alkynes All the alkynes with 4 or more carbon atoms in them show structural isomerism.

45. Alkynes The names of alkynes start with the name of the alkane but end with the suffix –yne. For alkynes above propyne, the position of the triple bond must be specified in the name.

46. Alkynes Many functional groups can be used as substituents. Only one substituent is allowed. Any hydrogen or carbon atom can be substituted by:

47. Alkynes For multiple double bonds, use the following prefixes:  di-  tri-  tetra-  penta-  hexa-

48. Alkynes: Examples

49. Aromatics Structures that meet Huckel’s Rule

50. Aromatics Coplanar structures, with all the contributing atoms in the same plane. Are arranged in one or more rings.  Benzene rings are not a common motif. The three general requirements for a compound to be aromatic are:  The compound must be cyclic.  Each element within the ring must have a p-orbital that is perpendicular to the ring, hence the molecule is planar.  The compound must follow Hückel's Rule.

51. Aromatics The number of π delocalized electrons must follow Hückel's Rule. number of π electrons = 4n + 2 where n = 0, 1, 2, 3, and so on The number of π delocalized electrons is an even number, but not a multiple of 4 to be an aromatic compound.

52. Aromatics The most common examples of aromatic hydrocarbons are organic compounds, which contain one or more benzene rings. Benzene

53. Aromatics Benzene follows Huckel’s Rule:

54. Aromatics Each atom in benzene uses all its 4 valence electrons in forming covalent bonds with other atoms. Other functional groups can be used as substituents. More than one substituent requires a prefix.

55. Aromatics Any hydrogen or carbon atom can be substituted by:

56. Aromatics When two substituents are attached to the benzene ring: Ortho, meta, or para can be used to indicate where the two substituents are on the benzene ring. Three classifications:  ortho- (o-): position 1, 2-  meta- (m): posotion 1, 3-  para- (p): position 1, 4-

57. Aromatics

58. Aromatics: Examples o-dihydroxybenzene, m-dihydroxybenzene, p-dihydroxybenzene

59. Aromatics: Examples

63. Summary of Hydrocarbon

66. Derivatives of Hydrocarbons Are formed when there is a substitution of a functional group at one or more carbon atoms.

67. Derivatives of Hydrocarbons 1. Prefixes 2. Haloalkanes 3. Alcohols 4. Ethers 5. Amines 6. Nitriles 7. Thiols 8. Thioethers 9. Disulfides 10. Aldehydes 11. Ketones 12. Carboxylic Acids 13. Esters 14. Amides 15. Thioesters

68. Prefixes For multiple substituents of the same type, use the following prefixes: di- tri- tetra- penta- hexa-

69. Haloalkanes The alkyl halides have the general form where the R in the general form is typically an alkyl group with a halogen replacing one of the hydrogens. X is written as: F = fluoro Cl = chloro Br = bromo I = iodo

70. Haloalkanes Classify according to the number of carbons bonded directly to the alkyl halide.

71. Haloalkanes There can be multiple substitutions of halogens for hydrogens, and also variations where alkenes, alkynes or aromatics are involved.

72. C – O Bonds Organic Compounds 1. Alcohols 2. Ethers

73. Alcohols IUPAC ending is …ol

74. Alcohols Are organic compounds containing a hydroxyl group, -OH, substituted for a hydrogen atom. The center of the alcohol functional group is the oxygen. Have two lone pairs of electrons on the oxygen. This forces the molecular geometry on the alcohol oxygen to be BENT. This portion of the molecule is flat, with bond angles of 109 degrees.

75. Alcohols Are organic compounds containing a hydroxyl group, -OH, substituted for a hydrogen atom. The names of alcohols start with the name of the alkane but end with the suffix –ol. Can have more than one hydroxyl group for hydrogens, and also variations where alkenes, alkynes or aromatics are involved. Use a prefix for multiple hydroxyl groups.

76. Alcohols Are classified according to the number of carbon atoms attached directly to the carbon containing the hydroxyl group.

77. Ethers … “oxy”….IUPAC ending ….ane

78. Ethers Are compounds with the general formula: The center of the ether functional group is the oxygen. Have two lone pairs of electrons on the oxygen. This forces the molecular geometry on the ether oxygen to be BENT. This portion of the molecule is flat, with bond angles of 109 degrees.

79. Ethers: Examples

81. Summary of Alcohols & Ethers

82. C - S Bonds Organic Compounds 1. Thiols 2. Thioethers 3. Disulfides

83. Thiols IUPAC ending…thiols

84. Thiols Are sometimes called sulfides. Are organic compounds containing a sulfhydryl group, -SH, substituted for a hydrogen atom. Are the sulfur analogue of alcohols. Sulfur takes the place of oxygen in the hydroxyl group of an alcohol. Are stronger acids than alcohols. The –SH functional group itself is referred to as either a thiol group or a sulfhydryl group.

85. Thiols The center of the thiol functional group is the sulfur. Have two lone pairs of electrons on the sulfur. This forces the molecular geometry on the thiol sulfur to be BENT. The C–S–H angles approach 90°.

86. Thiols Classified according to the number of carbon atoms bonded directly to the carbon containing the thiol group. The names of thiols start with the name of the alkyl but end with the suffix –thiol.

87. Thiols Can have more than one sulfhydryl group, and also variations where alkenes, alkynes or aromatics are involved. Use a prefix for multiple thiol groups.

88. Thiols: Examples

89. Thioethers IUPAC ending….sulfide

90. Thioethers Are sometimes called sulfides. Are compounds with the general formula: The center of the thioether functional group is the sulfur. A thioether is similar to an ether except that it contains a sulfur atom in place of the oxygen.

91. Thioethers Have two lone pairs of electrons on the sulfur. This forces the molecular geometry on the thioether sulfur to be BENT. This portion of the molecule is flat, with bond angles of 90 degrees. 90 ⁰

92. Thioethers: Examples

94. Disulfides IUPAC ending…..disulfide

95. Disulfides Another class of sulfur containing molecules that have important biological implications. Have the generic formula: Are products from the oxidation of two thiols.

96. Disulfides The center of a disulfide functional group has two sulfur atoms single bonded to each other and to two different carbon atoms. Have two lone pairs of electrons on each sulfur. This forces the molecular geometry on the thioether sulfur to be BENT.

97. Disulfides Are named by naming the R groups attached to the sulfur atoms followed by the suffix - disulfide. Dimethyldisulfide

98. Disulfides: Examples

101. Carbon and Nitrogen Organic Compounds 1. Amines 2. Nitriles

102. Amines 1. IUPAC ending ….amine 2. Prefix is …amino

103. Amines Are organic compounds that contain nitrogen and are basic. The general form of an amine is: R represents an alkyl group, but either or both of the hydrogens may be replaced by other groups and still retain its class as an amine.

104. Amines The center of the amine functional group is the nitrogen. Have one lone pair of electrons on the nitrogen in addition to the single bonds. This forces the molecular geometry on the amine nitrogen to be trigonal pyramid. This portion of the molecule is not flat, with bond angles of 109 degrees.

105. Amines The common names for simple aliphatic amines consist of the alkyl group followed by the suffix -amine. The amino group (-NH 2 ) is named as a substituent in more complicated amines, such as those that incorporate other functional groups or in which the alkyl groups cannot be simply named.

106. Amines Are classified according to the number of carbon atoms bonded directly to the nitrogen atom.

107. Amines: Examples

109. Nitriles 1. IUPAC ending is …..nitrile 2. Prefix is …..cyano

110. Nitriles Are organic compounds that have a functional group. Have one lone pair of electrons on the nitrogen in addition to one triple bond with a carbon atom. This forces the molecular geometry on the cyano nitrogen to be linear.

111. Nitriles The common names for simple nitriles consist of the alkane/alkyl followed by the suffix -nitrile. The cyano group (−C≡N) is also used interchangeably.

112. Nitriles: Examples

113. Carbonyl Organic Compounds 1. Aldehydes 2. Ketones

114. Aldehydes (CHO) IUPAC ending is …al

115. Aldehydes Are compounds containing a carbonyl group with a hydrogen attached at end and an organic group of carbons at the other side. The center of the aldehyde functional group is the carbon double bond oxygen.

116. Aldehydes Have two lone pairs of electrons on the oxygen. With three atoms attached to this carbon, the molecular geometry is trigonal planar. This portion of the molecule is flat, with bond angles of 120 degrees.

117. Aldehydes IUPAC name includes the prefix from the alkyl groups and the suffix –al.

118. Aldehydes IUPAC name for cyclic aldehydes includes the prefix cyclo and the suffix carbaldehyde.

119. Aldehydes: Examples

120. Ketones IUPAC ending is …one

121. Ketones Are compounds containing a carbonyl group with two hydrocarbon groups attached to it. The center of the ketone functional group is the carbon double bond oxygen.

122. Ketones Have two lone pairs of electrons on the oxygen. With three atoms attached to this carbon, the molecular geometry is trigonal planar. This portion of the molecule is flat, with bond angles of 120 degrees.

123. Ketones IUPAC name includes the prefix from the alkyl group and the suffix -one. For more than one ketone group, use a prefix.

124. Ketones: Examples

125. Summary of Aldehydes & Ketones

126. Carboxyl Derivatives 1. Carboxylic Acids 2. Esters 3. Amides 4. Thioesters

127. Carboxyl Derivatives Are derivatives of carboxylic acids. Can be distinguished from aldehydes and ketones by the presence of a group containing an electronegative heteroatom - usually oxygen, nitrogen, or sulfur – bonded directly to the carbonyl carbon.

128. Carboxyl Derivatives Have two sides: 1. The carbonyl group attach to an alkyl group. This is called an acyl group. 2. The heteroatom-containing group, refer to as the ‘acyl X' group

129. Carboxylic Acids IUPAC ending is …oic acid

130. Carboxylic Acids Are important intermediate products for the production of esters and amides. Are hydrocarbon derivatives for which the functional group is the carboxyl group. The center of the acid functional group is the carbon double bonded to an oxygen and single bonded to a hydroxyl group.

131. Carboxylic Acids Each oxygen atom has a pair of lone electrons. With three atoms attached to this carbon, the molecular geometry is trigonal planar. This portion of the molecule is flat, with bond angles of 120 degrees. An additional molecular geometry is centered on the oxygen of the - OH group. This is bent.

132. Carboxylic Acids In the IUPAC system, the –e ending in alkane is removed from the name of the parent chain and is replaced -anoic acid for the COOH acidic bond system.

133. Carboxylic Acids Cyclic carboxylic acids that are saturated are called cycloalkane carboxylic acids. Dicarboxylic acids are known as alkanedioic acids.

134. Carboxylic Acids

135. Carboxylic Acids: Examples

137. Esters IUPAC ending …oate

138. Esters Are compounds with the general formula: The center of the ester functional group is the carbon double bonded to an oxygen and single bonded to an oxygen attached to an alkyl group.

139. Esters Each oxygen atom has a pair of lone electrons. With three atoms attached to this carbon, the molecular geometry is trigonal planar. This portion of the molecule is flat, with bond angles of 120 degrees. An additional molecular geometry is centered on the oxygen with all single bonds. This is bent.

140. Esters Complex esters are more frequently named using the systematic IUPAC name, based on the name for the alkyl group followed by the suffix – oate. Cyclic esters are called lactones.

141. Esters: Examples

144. Amides IUPAC ending is …amide

145. Amides Also known as an acid amide. Are formed when carboxylic acids react with amines. Are nitrogen-containing organic compounds with the general formula

146. Amides The center of the amide functional group is the carbon double bonded to oxygen and single bonded to nitrogen. Classified according to the number of carbons attached directly to the nitrogen atom:

147. Amides The oxygen atom has two lone pair of electrons. The nitrogen atom has one pair of lone electrons. With three atoms attached to this carbon, the molecular geometry is trigonal planar. This portion of the molecule is flat, with bond angles of 120 degrees.

148. Amides The molecular geometry centered on the nitrogen is bent and also flat as an extension of the trigonal planar geometry.

149. Amides In the IUPAC system: For primary amides, the –e is removed from the alkane name and the suffix -amide is added.

150. Amides For 2 ⁰ and 3 ⁰ amides, alkyl groups attached to the nitrogen are named as substituents. The letter N is used to indicate they are attached to the nitrogen. For more than one of the same substituent groups, use a prefix.

151. Amides

153. Amides: Example

157. Thioesters 1. IUPAC ending….-thioate or - carbothioate 2. Prefix….thio & ending….-ate or - carboxylate

158. Thioesters Are the product of esterification between a carboxylic acid and a thiol. Are compounds with the functional group: The center of the thioester functional group is the carbon double bonded to an oxygen and single bonded to sulfur attached to an alkyl group or hydrogen.

159. Thioesters The oxygen and sulfur atoms, each, have two sets of lone pairs electrons. With three atoms attached to this carbon, the molecular geometry is trigonal planar. This portion of the molecule is flat, with bond angles of 120 degrees.

160. Thioesters The molecular geometry centered on the sulfur is bent and also flat as an extension of the trigonal planar geometry.

161. Thioesters In the IUPAC system, the name consist of the alkyl group followed by the alkane with the suffix –thioate or –carbothioate Alkyl groups attached to the sulfur are named as substituents. The letter S is used to indicate they are attached to the sulfur. S-Methyl ethanethioate (IUPAC)

162. Thioesters For common names, the name consist of the alkyl group followed by the prefix “thio” before the common name with the suffix –ate or -carboxylate. Alkyl groups attached to the sulfur are named as substituents. The letter S is used to indicate they are attached to the sulfur. S-PENTACHLOROPHENYL PENTACHLORO-1,3- BUTADIENE-1-THIOCARBOXYLATE

163. Thioesters: Examples

165. Summary of Carboxyl Derivatives

166. Summary of Functional Groups