Physical Properties: Structure:
|
|
- May Carr
- 5 years ago
- Views:
Transcription
1 Nomenclature: Functional group suffix = -ol Functional group prefix = hydroxy- Primary, secondary or tertiary? Alcohols are described as primary (1 o ), secondary (2 o ) or tertiary (3 o ) depending on how many alkyl substiutents are attached to the C-OH unit. t-butanol ethanol 2-propanol 2-methyl-2-propanol 1 o 2 o 3 o Check the designations of primary, secondary and tertiary by counting the number of C atoms attached to the C with the O attached. Physical Properties: The polar nature of the O-H bond (due to the electonegativity difference of the atoms ) results in the formation of hydrogen bonds with other alcohol molecules or other H-bonding systems (e.g. water). The implications of this are: o high melting and boiling points compared to analogous alkanes o high solubility in aqueous media Structure: The alcohol functional group consists of an O atom bonded to a C atom and a H atom via s bonds. Both thec-o and the O-H bonds are polar due to the high electronegativity of the O atom. Reactivity: The image shows the electrostatic potential for methanol. The more red an area is, the higher the electron density and the more blue an area is, the lower the electron density. The alcohol O atom are a region of high electron density (red) due to the lone pairs. (red) Alcohol oxygen atoms are Lewis
2 bases. So alcohols can react as either bases or nucleophiles at the oxygen. There is low electron density (blue) on H atom of the -OH group alcohol, i.e. H + character. So alcohols are acidic (pka ~ 16). Removal of the proton generates the alkoxide. The -OH group is a poor leaving group and needs to be converted to a better leaving group before substitution can occur. Acidity: Due to the electronegativity of the O atoms, alcohols are slightly acidic (pka 16-18) The anion derived by the deprotonation of an alcohol is the alkoxide. Alkoxides are important bases in organic chemistry. Alcohols react with Na (or K) like water to give the alkoxide: Nomenclature: Functional group suffix = -halide Functional group prefix = halo- Primary, secondary or tertiary? In a similar fashion to alcohols, alkyl halides are described as primary (1 o ), secondary (2 o ) or tertiary (3 o ) depending on how many alkyl substiutents are attached to the C-X unit. chloromethane bromoethane or or methyl chloride ethyl bromide 2-bromopropane or isopropyl bromide 2-bromo-2-methylpropane or tert-butyl bromide primary secondary tertiary
3 Physical Properties: The polar bond creates a molecular dipole that raises the melting points and boiling points compared to alkanes. Structure: The alkyl halide functional group consists of an sp 3 hybridized C atom bonded to a halogen, X, via a s bond. The carbon halogen bonds are typically quite polar due to the electronegativity and polarizability of the halogen. Reactivity: The halogens (Cl, Br and I) are good leaving groups. The polarity makes the C atom electrophilic and prone to attack by nucleophiles via S N 1 or S N 2 reactions. Bases can remove b-hydrogens and cause 1,2-elimination to form alkenes via E1 or E2 reactions. Insertion of a metal (esp. Mg) creates an organometalic species. Nucleophilic substitution reactions are an important class of reactions that allow the interconversion of functional groups, for example R-OH R-Br. Nucleophilic substitution will be explored in much more detail in chapter 8. What does the term "nucleophilic substitution" imply? A nucleophile is an the electron rich species that will react with an electron poor species. A substitution implies that one group replaces another There are two fundamental events in these substitution reactions: 1. formation of the new bond to the nucleophile 2. breaking of the bond to the leaving group
4 Depending on the relative timing of these events, two different mechanisms are possible: Bond breaking to form a carbocation preceeds the formation of the new bond : S N 1 reaction Simultaneous bond formation and bond breaking : S N 2 reaction S N 1 mechanism S N 1 indicates a substitution, nucleophilic, unimolecular reaction, described by the expression rate = k [R-LG] This pathway is a multi-step process with the following characteristics: step 1: rate determining (slow) loss of the leaving group, LG, to generate a carbocation intermediate, then step 2: rapid attack of a nucleophile on the electrophilic carbocation to form a new s bond Multi-step reactions have intermediates and several transition states (TS). In an S N 1 there is loss of the leaving group generating an intermediate carbocation which then undergoes a rapid reaction with the nucleophile. General case The reaction profiles shown here are simplified and do not include the equilibria for protonation of the -OH. SN1 reaction The following issues are relevant to the S N 1 reactions of alcohols: Effect of R- Reactivity order : (CH 3 ) 3 C- > (CH 3 ) 2 CH- > CH 3 CH 2 - > CH 3 - In an S N 1 reaction, the key step is the loss of the leaving group to form the intermediate carbocation. The more stable the carbocation is, the easier it is to form, and the faster the S N 1 reaction will be. Some students fall into the trap of thinking that the system with the less stable carbocation will react fastest, but they are forgetting that it is the generation of the carbocation that is rate determining. -LG The only event in the rate determining step of the S N 1 is breaking the C-LG
5 bond. For alcohols it is important to remember that -OH is a very poor leaving. In the reactions with HX, the -OH is protonated first to give an oxonium, providing the much better leaving group, a water molecule (see scheme below). Nu Since the nucleophile is not involved in the rate determining step of an S N 1 reaction, the nature of the nucleophile is unimportant. In the reactions of alcohols with HX, the reactivity trend of HI > HBr > HCl > HF is not due to the nucleophilicity of the halide ion but the acidity of HX which is involved in generating the leaving group prior to the rate determining step. Stereochemistry In an SN1, the nucleophile attacks the planar carbocation. Since there is an equally probability of attack on either face there will be a loss of stereochemistry at the reactive center and both possible products will be observed. Since a carbocation intermediate is formed, there is the possibility of rearrangements (e.g. 1,2-hydride or 1,2-alkyl shifts) to generate a more stable carbocation (see later). This is usually indicated by a change in the position of the halide compared to that of the original -OH group, or a change in the carbon skeleton of the product when compared to the starting material.
6 SN1 MECHANISM FOR REACTION OF ALCOHOLS WITH HBr Step 1: An acid/base reaction. Protonation of the alcoholic oxygen to make a better leaving group. This step is very fast and reversible. The lone pairs on the oxygen make it a Lewis base. Step 2: Cleavage of the C-O bond allows the loss of the good leaving group, a neutral water molecule, to give a carbocation intermediate. This is the rate determining step (bond breaking is endothermic) Step 3: Attack of the nucleophilic bromide ion on the electrophilic carbocation creates the alkyl bromide. Carbocations Stability: The general stability order of simple alkyl carbocations is: (most stable) 3 o > 2 o > 1 o > methyl (least stable)
7 This is because alkyl groups are weakly electron donating due to hyperconjugation and inductive effects. Resonance effects can further stabilize carbocations when present. Structure: Alkyl carbocations are sp 2 hybridized, planar systems at the cationic C center. The p-orbital that is not utilized in the hybrids is empty and is often shown bearing the positive charge since it represents the orbital available to accept electrons. Reactivity: As they have an incomplete octet, carbocation s are excellent electrophil es and react readily with nucleophile s. Alternative ly, loss of H + can generate a
8 π bond. The electrostatic potential diagrams clearly show the cationic center in blue, this is where the nucleophile will attack. Rearrangements: Carbocations are prone to rearrangement via 1,2-hyride or 1,2-alkyl shifts if it generates a more stable carbocation Reactions involving carbocations: 1. Substitutions via the S N 1 2. Eliminations via the E1 3. Additions to alkenes and alkynes (HX, H 3 O + ) S N 2 mechanism S N 2 indicates a substitution, nucleophilic, bimolecular reaction, described by the expression rate = k [Nu][R-LG] This pathway is a concerted process (single step) as shown by the following reaction coordinate diagrams, where there is simultaneous attack of the nucleophile and displacement of the leaving group.
9 Single step reactions have no intermedia tes and single transition state (TS). In an S N 2 there is simultaneous formation of the carbonnucleophile bond and breaking of the carbonleaving group bond, hence the reaction proceeds via a TS in which the central C is partially bonded to five groups. The reaction profiles shown here are simplified and do not include the equilibria for protonation of the -OH. General case SN2 reaction The following issues are relevant to the S N 2 reactions of alcohols: Effects of R- Reactivity order : CH 3 - > CH 3 CH 2 - > (CH 3 ) 2 CH- > (CH 3 ) 3 C- For alcohols reacting with HX, methyl and 1 o systems are more likely to react via an S N 2 reaction since the carbocations are too high energy for the S N 1 pathway to occur.
10 -LG Once again the leaving group is a water molecule formed by protonation of the - OH group. -OH on its own is a poor leaving group. Nu Since the nucleophile is involved in the rate determining step, the nature of the nucleophile is very important in an S N 2 reaction. More reactive nucleophiles will favor an S N 2 reaction. Stereochemistry When the nucleophile attacks in an S N 2 reaction, it is on the opposite side to the position of the leaving group. As a result, the reaction will proceed with an inversion of configuration. S N 2 MECHANISM FOR REACTION OF ALCOHOLS WITH HBr Step 1: An acid/base reaction. Protonation of the alcoholic oxygen to make a better leaving group. This step is very fast and reversible. The lone pairs on the oxygen make it a Lewis base. Step 2: Simultaneous formation of C-Br bond and cleavage of the C-O bond allows the loss of the good leaving group, a neutral water molecule, to give a the alkyl bromide. This is the rate determining step.
11 Radical Substitution Summary Substitution of R-H by -X provides the alkyl halide, R-X and HX. Alkane R-H relative reactivity order : 3 o > 2 o > 1 o > methyl Halogen reactivity F 2 > Cl 2 > Br 2 > I 2 Only chlorination and bromination are useful in the laboratory. Reaction proceeds via a radical chain mechanism Radicals A radical is a species that contains unpaired electrons. Typically formed by a homolytic bond cleavage as represented by the fishhook curved arrows: Stability: The general stability order of simple alkyl radicals is: (most stable) 3 o > 2 o > 1 o > methyl (least stable) This is because alkyl groups are weakly electron donating due to hyperconjugation and inductive effects. Note that this is the same order as for carbocations. Resonance effects can further stabilize radicals when present.
12 Structure: Alkyl radicals are sp 2 hybridized, planar systems at the radical C center. The p-orbital that is not utilized in the hybrids contains the single electron. Reactivity: As they have an incomplete octet, radicals are excellent electrophiles and react readily with nucleophiles. Alternatively, loss of H. can generate a p bond Rearrangements: Unlike carbocations, radicals do not tend to undergo rearrangements Reactions involving radicals: Radical Substitution Mechanism Unlike the large majority of reactions that you will see in your organic chemistry course, radical mechanism require that fishhook curly arrows that represent the motion of a single electron are used. These can be a little more confusing and more difficult to master. We suggest you get to grips with normal curved arrows first. However, the mechanism for the bromination of methane is shown below, but the mechanism for chlorination or higher alkanes in the same. Note that it contains three distinct type of steps, depending on the net change in the number of radicals that are present. RADICAL CHAIN MECHANIS M FOR REACTION OF METHANE WITH Br 2
13 Step 1 (Initiation) Heat or uv light cause the weak halogen bond to undergo homolytic cleavage to generate two bromine radicals and starting the chain process. Step 2 (Propagatio n) (a) A bromine radical abstracts a hydrogen to form HBr and a methyl radical, then (b) The methyl radical abstracts a bromine atom from another molecule of Br 2 to form the methyl bromide product and another bromine radical, whic
14 h can then itself undergo reaction 2(a) creating a cycle that can repeat. Step 3 (Terminatio n) Various reactions between the possible pairs of radicals allow for the formation of ethane, Br 2 or the product, methyl bromide. These reactions remove radicals and do not perpetuate the cycle. Selectivity There are two components to understanding the selectivity of radical halogenations of alkanes: reactivity of R-H system reactivity of X. R-H The strength of the R-H varies slightly depending on whether the H is 1 o, 2 o or 3 o.
15 The following table shows the bond dissociation energy, that is the energy required to break the bond in a homolytic fashion, generating R. and H. Type R-H kj/mol kcal/mol CH 3 -H o CH 3 CH 2 -H o (CH 3 ) 2 CH-H o (CH 3 ) 3 C-H Halogen radical, X. Note how the bonds get weaker as we move down the table, so the R. also get easier to form, with 3 o being the easiest. Bromine radicals are less reactive than chlorine radicals Br. tends to be more selective in its reactions, and prefers to react with the weaker R-H bonds. The more reactive chlorine radical is less discriminating in what it reacts with. The selectivity of the radical reactions can be predicted mathematically based on a combination of an experimentally determined reactivity factor, R i, and a statistical factor, nh i. In order to use the equation shown below we need to look at our original alkane and look at each H in turn to see what product it would give if it were to be susbtituted. This is an exercise in recognizing different types of hydrogen, something that will be important later. %Pi nhi Ri Σi = % yield of product "i" = number of H of type "i" = reactivity factor for type "i" = sum for all types Reactivity factors, R i Br Cl 1 o o o What do the reactivity factors indicate? Well as an example of the conclusions we could make: Bromination is 1640 times more likely to occur at a 3 o position than 1 o Chlorination is 5.2 times more likely to occur at a 3 o position than 1 o Lets work an example, say propane, CH 3 CH 2 CH 3 How many different monochlorides can be produced by radical chlorination? 1-chloropropane and 2 -chloropropane, so we have two types of H, the 6 x 1 o in -
16 CH 3 and the 2 x 2 o in-ch 2 -. Use the diagrams below to highlight this if you are unsure. 1 o CH 2 o CH Reset propane 1-chloropropane 2-chloropropane Now for the calculations, so plugging the values into the equations we get (the reactivity factors R i are in the table above): % 1-chloropropane = 100 x (6 x 1) / (6 x x 3.9) = 100 x 6 / 13.8 = 43.5 % (experimental = 44 %) % 2-chloropropane = 100 x (2 x 3.9) / (6 x x 3.9) = 100 x 7.8 / 13.8 = 56.5 % (experimental = 56 %) What about bromination of propane? Most of the process is the same, all we have to do is change the reactivty factors. % 1-bromopropane = 100 x (6 x 1) / (6 x x 82) = 100 x 6 / 170 = 3.5 % (experimental = 4 %) % 2-bromoopropane = 100 x (2 x 82) / (6 x x 82) = 100 x 164 / 170 = 96.5 % (experimental = 96 %) Note that the results match well with experimental values and that they illustrate the high regioselectivity of the bromination reaction for the 2 o radical, whereas in the chlorination the number of 1 o H dictates the regioslectivity. There are other examples in the Self Assessment. Radical Halogenation of Alkanes Reaction type: Radical Substitution Summary: When treated with Br 2 or Cl 2, radical substitution of R-H generates the alkyl halide and HX.
17 Alkane R-H relative reactivity order : tertiary > secondary > primary > methyl. Halogen reactivity F 2 > Cl 2 > Br 2 > I 2 Only chlorination and bromination are useful in the laboratory. Bromination is selective for the R-H that gives the most stable radical. Chlorination is less selective Reaction proceeds via an radical chain mechanism which involves radical intermediates. The termination steps are of low probability due to the low concentration of the radical species meaning that the chances of them colliding is very low. RADICAL CHAIN MECHANIS M FOR REACTION OF METHANE WITH Br 2 Step 1 (Initiation) Heat or uv light cause the weak halogen bond to undergo homolytic cleavage to generate two bromine radicals and starting the chain process.
18 Step 2 (Propagatio n) (a) A bromine radical abstracts a hydrogen to form HBr and a methyl radical, then (b) The methyl radical abstracts a bromine atom from another molecule of Br 2 to form the methyl bromide product and another bromine radical, whic h can then itself undergo reaction 2(a) creating a cycle that can repeat.
19 Step 3 (Terminatio n) Various reactions between the possible pairs of radicals allow for the formation of ethane, Br 2 or the product, methyl bromide. These reactions remove radicals and do not perpetuate the cycle. More highly brominated by-products are possible if methyl bromide reacts with a bromine radical in the same fashion as methane does. Can you draw the cycle that leads to the formation of dibromomethane? Reaction of Alcohols with Hydrogen Halides Reaction type: Nucleophilic Substitution (S N 1 or S N 2) Summary:
20 When treated with HBr or HCl alcohols typically undergo a nucleophilic substitution reaction to generate an alkyl halide and water. Alcohol relative reactivity order : 3 o > 2 o > 1 o > methyl. Hydrogen halide reactivity order : HI > HBr > HCl > HF (paralleling acidity order). Reaction usually proceeds via an S N 1 mechanism which proceeds via a carbocation intermediate, that can also undergo rearrangement. Methanol and primary alcohols will proceed via an S N 2 mechanism since these have highly unfavorable carbocations. The reaction of alcohols with HCl in the presence of ZnCl 2 (catalyst) forms the basis of the Lucas test for alcohols.
21 S N 1 MECHANISM FOR REACTION OF ALCOHOLS WITH HBr Step 1: An acid/base reaction. Protonation of the alcoholic oxygen to make a better leaving group. This step is very fast and reversible. The lone pairs on the oxygen make it a Lewis base. Step 2: Cleavage of the C-O bond allows the loss of the good leaving group, a neutral water molecule, to give a carbocation intermediate. This is the rate determining step (bond breaking is endothermic) Step 3: Attack of the nucleophilic bromide ion on the electrophilic carbcation creates the alkyl bromide.
22 Reaction of Alcohols with other Halogenating agents (SOCl 2, PX 3 ) Reaction type: Nucleophilic Substitution (S N 1 or S N 2) Summary: Alcohols can also be converted to alkyl chlorides using thionyl chloride, SOCl 2, or phosphorous trichloride, PCl 3. Alkyl bromides can be prepared in a similar reaction using PBr 3. Used mostly for 1 o and 2 o ROH In each case a base is used to "mop-up" the acidic by-product. Common bases are triethylamine, Et 3 N, or pyridine, C 6 H 5 N. In each case the -OH reacts first as a nucleophile, attacking the electrophilic center of the halogenating agent. A displaced halide ion then completes the substitution displacing the leaving group. Note that it is not -OH that leaves, but a much better leaving group. The advantage of these reagents is in that the reaction is not under the strongly acidic conditions like using HCl or HBr.
But in organic terms: Oxidation: loss of H 2 ; addition of O or O 2 ; addition of X 2 (halogens).
Reactions of Alcohols Alcohols are versatile organic compounds since they undergo a wide variety of transformations the majority of which are either oxidation or reduction type reactions. Normally: Oxidation
More informationDAMIETTA UNIVERSITY. Energy Diagram of One-Step Exothermic Reaction
DAMIETTA UNIVERSITY CHEM-103: BASIC ORGANIC CHEMISTRY LECTURE 5 Dr Ali El-Agamey 1 Energy Diagram of One-Step Exothermic Reaction The vertical axis in this graph represents the potential energy. The transition
More informationWhat is the major product of the following reaction?
What is the major product of the following reaction? Predict the major product of the following reaction: 2-methylbutane + Br 2 /light energy? A) 1-bromo-2-methylbutane B) 2-bromo-2-methylbutane C) 2-bromo-3-methylbutane
More informationCHAPTER 7. Further Reactions of Haloalkanes: Unimolecular Substitution and Pathways of Elimination
CHAPTER 7 Further Reactions of Haloalkanes: Unimolecular Substitution and Pathways of Elimination 7-1 Solvolysis of Tertiary and Secondary Haloalkanes The rate of S N 2 reactions decrease dramatically
More informationQuímica Orgânica I. Organic Reactions
Química Orgânica I 2008/09 w3.ualg.pt\~abrigas QOI 0809 A6 1 Organic Reactions Addition two molecules combine Elimination one molecule splits Substitution parts from two molecules exchange Rearrangement
More informationThe Study of Chemical Reactions. Mechanism: The complete, step by step description of exactly which bonds are broken, formed, and in which order.
The Study of Chemical Reactions Mechanism: The complete, step by step description of exactly which bonds are broken, formed, and in which order. Thermodynamics: The study of the energy changes that accompany
More information75. A This is a Markovnikov addition reaction. In these reactions, the pielectrons in the alkene act as a nucleophile. The strongest electrophile will
71. B SN2 stands for substitution nucleophilic bimolecular. This means that there is a bimolecular rate-determining step. Therefore, the reaction will follow second-order kinetics based on the collision
More informationChapter 10 Radical Reactions"
Chapter 10 Radical Reactions Radicals are intermediates with an unpaired electron H. Cl. Hydrogen radical t Often called free radicals What are radicals? Chlorine radical t Formed by homolytic bond cleavage
More informationStudy of Chemical Reactions
Study of Chemical Reactions Introduction to Mechanisms There are four different types of organic reactions: Additions Eliminations Substitutions Rearrangements 149 Addition Reactions Occur when 2 reactants
More information4.15 Halogenation of Alkanes RH + X 2 RX + HX
4.15 alogenation of Alkanes R + X 2 RX + X Energetics R + X 2 RX + X explosive for F 2 exothermic for Cl 2 and Br 2 endothermic for I 2 4.16 Chlorination of Methane Chlorination of Methane carried out
More informationCHE1502. Tutorial letter 201/1/2016. General Chemistry 1B. Semester 1. Department of Chemistry CHE1502/201/1/2016
CE1502/201/1/2016 Tutorial letter 201/1/2016 General Chemistry 1B CE1502 Semester 1 Department of Chemistry This tutorial letter contains the answers to the questions in assignment 1. FIRST SEMESTER: KEY
More informationBasic Organic Chemistry Course code : CHEM (Pre-requisites : CHEM 11122)
Basic Organic Chemistry Course code : CHEM 12162 (Pre-requisites : CHEM 11122) Chapter 01 Mechanistic Aspects of S N2,S N1, E 2 & E 1 Reactions Dr. Dinesh R. Pandithavidana Office: B1 222/3 Phone: (+94)777-745-720
More informationEssential Organic Chemistry. Chapter 9
Essential Organic Chemistry Paula Yurkanis Bruice Chapter 9 Substitution and Elimination Reactions of Alkyl Halides 9.1 How Alkyl Halides React Substitution Reactions One group takes the place of another.
More informationOverview of Types of Organic Reactions and Basic Concepts of Organic Reaction Mechanisms
Overview of Types of Organic Reactions and Basic Concepts of Organic Reaction Mechanisms Dr. Solomon Derese 1 A chemical reaction is the transformation of one chemical or collection of chemicals into another
More informationPreparation of Alkyl Halides, R-X. Reaction of alkanes with Cl 2 & Br 2 (F 2 is too reactive, I 2 is unreactive): R + X X 2.
Preparation of Alkyl alides, R-X Reaction of alkanes with Cl 2 & Br 2 (F 2 is too reactive, I 2 is unreactive): UV R + X 2 R X or heat + X This mechanism involves a free radical chain reaction. A chain
More informationChapter 6 Ionic Reactions-Nucleophilic Substitution and Elimination Reactions of Alkyl Halides"
Chapter 6 Ionic Reactions-Nucleophilic Substitution and Elimination Reactions of Alkyl Halides" t Introduction" The polarity of a carbon-halogen bond leads to the carbon having a partial positive charge"
More informationAlcohols, Ethers, & Epoxides
Alcohols, Ethers, & Epoxides Alcohols Structure and Bonding Enols and Phenols Compounds having a hydroxy group on a sp 2 hybridized carbon enols and phenols undergo different reactions than alcohols. Chapter
More informationOChem 1 Mechanism Flashcards. Dr. Peter Norris, 2018
OChem 1 Mechanism Flashcards Dr. Peter Norris, 2018 Mechanism Basics Chemical change involves bonds forming and breaking; a mechanism describes those changes using curved arrows to describe the electrons
More informationOChem 1 Mechanism Flashcards. Dr. Peter Norris, 2015
OChem 1 Mechanism Flashcards Dr. Peter Norris, 2015 Mechanism Basics Chemical change involves bonds forming and breaking; a mechanism describes those changes using curved arrows to describe the electrons
More informationStructure and Preparation of Alkenes: Elimination Reactions
Structure and Preparation of Alkenes: Elimination Reactions Alkene Nomenclature First identify the longest continuous chain that includes the double bond. Replace the -ane ending of the corresponding unbranched
More information(Neither an oxidation or reduction: Addition or loss of H +, H 2 O, HX).
eactions of Alcohols Alcohols are versatile organic compounds since they undergo a wide variety of transformations the majority of which are either oxidation or reduction type reactions. xidation is a
More informationChapter 5. Nucleophilic aliphatic substitution mechanism. by G.DEEPA
Chapter 5 Nucleophilic aliphatic substitution mechanism by G.DEEPA 1 Introduction The polarity of a carbon halogen bond leads to the carbon having a partial positive charge In alkyl halides this polarity
More informationCH 3 Cl + Cl 2 CH 2 Cl 2 + HCl
Energetics 414 alogenation of Alkanes X 2 X X X 2 X X explosive for F 2 exothermic for l 2 and Br 2 endothermic for I 2 hlorination of Methane carried out at high temperature (400 ) 415 hlorination of
More informationElimination Reactions Heating an alkyl halide with a strong base causes elimination of a. molecule of HX
Elimination eactions eating an alkyl halide with a strong base causes elimination of a molecule of X 1. Potassium hydroxide dissolved in ethanol and the sodium salts of alcohols (such as sodium ethoxide)
More informationREACTIONS OF HALOALKANES - SUBSTITUTION AND ELIMINATION
REACTIONS OF HALOALKANES - SUBSTITUTION AND ELIMINATION Haloalkanes (also known as halogenoalkanes and alkyl halides) are organic compounds where one of the hydrogens of an alkane or cycloalkane has been
More informationGlendale Community College Chemistry 105 Exam. 3 Lecture Notes Chapters 6 & 7
Sevada Chamras, Ph.D. Glendale Community College Chemistry 105 Exam. 3 Lecture Notes Chapters 6 & 7 Description: Examples: 3 Major Types of Organic Halides: 1. Alkyl Halides: Chapter 6 (Part 1/2) : Alkyl
More information10. Alkyl Halides. What Is an Alkyl Halide. An organic compound containing at least one carbonhalogen
10. Alkyl Halides What Is an Alkyl Halide An organic compound containing at least one carbonhalogen bond (C-X) X (F, Cl, Br, I) replaces H Can contain many C-X bonds Properties and some uses Fire-resistant
More informationOrganic Chemistry(I) Chapter 3
Organic Chemistry(I) Chapter 3 1. Carbon-carbon bonds are not easily broken. Which bond in the following compound would be the least difficult to break homolytically? 2. Which of the following molecules
More informationOrganic Chemistry CHM 314 Dr. Laurie S. Starkey, Cal Poly Pomona Alkyl Halides: Substitution Reactions - Chapter 6 (Wade)
rganic Chemistry CM 314 Dr. Laurie S. Starkey, Cal Poly Pomona Alkyl alides: Substitution Reactions - Chapter 6 (Wade) Chapter utline I. Intro to RX (6-1 - 6-7) II. Substitution Reactions A) S N 2 (6-8,
More information10. Organohalides. Based on McMurry s Organic Chemistry, 7 th edition
10. Organohalides Based on McMurry s Organic Chemistry, 7 th edition What Is an Alkyl Halide An organic compound containing at least one carbonhalogen bond (C-X) X (F, Cl, Br, I) replaces H Can contain
More informationChapter 11, Part 1: Polar substitution reactions involving alkyl halides
hapter 11, Part 1: Polar substitution reactions involving alkyl halides Overview: The nature of alkyl halides and other groups with electrophilic sp 3 hybridized leads them to react with nucleophiles and
More informationCHE1502. Tutorial letter 203/1/2016. General Chemistry 1B. Semester 1. Department of Chemistry
E1502/203/1/2016 Tutorial letter 203/1/2016 General hemistry 1B E1502 Semester 1 Department of hemistry This tutorial letter contains the answers to the questions in assignment 3. FIRST SEMESTER: KEY T
More informationCHEM Lecture 7
CEM 494 Special Topics in Chemistry Illinois at Chicago CEM 494 - Lecture 7 Prof. Duncan Wardrop ctober 22, 2012 CEM 494 Special Topics in Chemistry Illinois at Chicago Preparation of Alkenes Elimination
More informationOrganic Chemistry. Radical Reactions
For updated version, please click on http://ocw.ump.edu.my Organic Chemistry Radical Reactions by Dr. Seema Zareen & Dr. Izan Izwan Misnon Faculty Industrial Science & Technology seema@ump.edu.my & iezwan@ump.edu.my
More informationAlcohols. Have seen many reactions to synthesize alcohols: In this chapter we will study reactions of the alcohols
Alcohols ave seen many reactions to synthesize alcohols: In this chapter we will study reactions of the alcohols Oxidation Need to understand the nomenclature of organic reduction/oxidation In general
More informationAcid-Base -Bronsted-Lowry model: -Lewis model: -The more equilibrium lies to the right = More [H 3 O + ] = Higher K a = Lower pk a = Stronger acid
Revision Hybridisation -The valence electrons of a Carbon atom sit in 1s 2 2s 2 2p 2 orbitals that are different in energy. It has 2 x 2s electrons + 2 x 2p electrons are available to form 4 covalent bonds.
More information7. Haloalkanes (text )
2009, Department of hemistry, The University of Western Ontario 7.1 7. aloalkanes (text 7.1 7.10) A. Structure and Nomenclature Like hydrogen, the halogens have a valence of one. Thus, a halogen atom can
More informationWhat are radicals? H. Cl. Chapter 10 Radical Reactions. Production of radicals. Reactions of radicals. Electronic structure of methyl radical
What are radicals? Radicals are intermediates with an unpaired electron Chapter 10 Radical Reactions H. Cl. Hydrogen radical Chlorine radical Methyl radical Often called free radicals Formed by homolytic
More informationNuggets of Knowledge for Chapter 17 Dienes and Aromaticity Chem 2320
Nuggets of Knowledge for Chapter 17 Dienes and Aromaticity Chem 2320 I. Isolated, cumulated, and conjugated dienes A diene is any compound with two or C=C's is a diene. Compounds containing more than two
More informationOrganic Mechanisms 1
Organic Mechanisms 1 Concepts The key ideas required to understand this section are: Concept Book page Chemical properties of alkanes 314 Chemical properties of alkenes 318 Bonding in alkenes 320 Bonding
More informationHomework problems Chapters 6 and Give the curved-arrow formalism for the following reaction: CH 3 OH + H 2 C CH +
omework problems hapters 6 and 7 1. Give the curved-arrow formalism for the following reaction: : 3 - : 2 : 3 2-3 3 2. In each of the following sets, arrange the compounds in order of decreasing pka and
More informationName: Unit 3 Packet: Activation Energy, Free Radical Chain Reactions, Alkane Preparations, S N 2, E 2
Name: Unit 3 Packet: Activation Energy, Free Radical Chain Reactions, Alkane Preparations, S N 2, E 2 Key Terms For Unit 3 Free Radical Chain Reaction Homolytic Cleavage Free Radical Initiation Propagation
More informationChapter 10 Free Radicals
hapter 10 Free Radicals This is an example of a free radical reaction. A radical is a species that has a free unpaired electron. There are several examples of stable radicals, the most common of which
More informationDr. Anand Gupta Mr Mahesh Kapil
Dr. Anand Gupta Mr Mahesh Kapil 09356511518 09888711209 anandu71@yahoo.com mkapil_foru@yahoo.com Preparation of Haloalkanes From Alkanes Alkenes Alcohols Carboxylic Acids (Hundsdicker Reaction) Halide
More informationOrganic Chemistry. Chapter 10
Organic Chemistry Chapter 10 10.1 Homologous Series Overview We Are Here Organic Chemistry Organic chemistry is the chemistry of carbon containing compounds. From the very simple: methane To the very complex:
More informationAlkyl Halides. Alkyl halides are a class of compounds where a halogen atom or atoms are bound to an sp 3 orbital of an alkyl group.
Alkyl Halides Alkyl halides are a class of compounds where a halogen atom or atoms are bound to an sp 3 orbital of an alkyl group. CHCl 3 (Chloroform: organic solvent) CF 2 Cl 2 (Freon-12: refrigerant
More informationREACTION AND SYNTHESIS REVIEW
REACTION AND SYNTHESIS REVIEW A STUDENT SHOULD BE ABLE TO PREDICT PRODUCTS, IDENTIFY REACTANTS, GIVE REACTION CONDITIONS, PROPOSE SYNTHESES, AND PROPOSE MECHANISMS (AS LISTED BELOW). REVIEW THE MECHANISM
More informationChapter 9. Nucleophilic Substitution and ß-Elimination
Chapter 9 Nucleophilic Substitution and ß-Elimination Nucleophilic Substitution Nucleophile: From the Greek meaning nucleus loving. A molecule or ion that donates a pair of electrons to another atom or
More informationC h a p t e r S e v e n : Haloalkanes: Nucleophilc Substitution and Elimination Reactions S N 2
C h a p t e r S e v e n : Haloalkanes: Nucleophilc Substitution and Elimination Reactions S N 2 CHM 321: Summary of Important Concepts Concepts for Chapter 7: Substitution Reactions I. Nomenclature of
More informationChapter 7 Substitution Reactions 7.1 Introduction to Substitution Reactions Substitution Reactions: two reactants exchange parts to give new products
hapter 7 Substitution eactions 7.1 Introduction to Substitution eactions Substitution eactions: two reactants exchange parts to give new products A-B + -D A-D + B- 3 2 + Br 3 2 Br + Elimination eaction:
More informationChapter 8. Substitution reactions of Alkyl Halides
Chapter 8. Substitution reactions of Alkyl Halides There are two types of possible reaction in organic compounds in which sp 3 carbon is bonded to an electronegative atom or group (ex, halides) 1. Substitution
More informationRearrangement: a single reactant rearranges its
Chapter 5: An overview of organic reactions 5.1 Kinds of organic reactions Even though there are hundreds of reactions to study, organic chemistry is governed by only a few key ideas that determine chemical
More informationOrganic Chemistry. Second Edition. Chapter 19 Aromatic Substitution Reactions. David Klein. Klein, Organic Chemistry 2e
Organic Chemistry Second Edition David Klein Chapter 19 Aromatic Substitution Reactions Copyright 2015 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry 2e 19.1 Introduction to Electrophilic
More information1. Radical Substitution on Alkanes. 2. Radical Substitution with Alkenes. 3. Electrophilic Addition
1. Radical Substitution on Alkanes Only Cl and Br are useful at the laboratory level. Alkane reactivity: tertiary > secondary > primary > methyl Numbers below products give their relative yield. Relative
More informationChapter 1 Reactions of Organic Compounds. Reactions Involving Hydrocarbons
Chapter 1 Reactions of Organic Compounds Reactions Involving Hydrocarbons Reactions of Alkanes Single bonds (C-C) are strong and very hard to break, therefore these compounds are relatively unreactive
More informationChapter 7: Alcohols, Phenols and Thiols
Chapter 7: Alcohols, Phenols and Thiols 45 -Alcohols have the general formula R-OH and are characterized by the presence of a hydroxyl group, -OH. -Phenols have a hydroxyl group attached directly to an
More informationAlcohols: Contain a hydroxy group( OH) bonded to an sp 2 or sp 3 hybridized
Lecture Notes hem 51B S. King hapter 9 Alcohols, Ethers, and Epoxides I. Introduction Alcohols, ether, and epoxides are 3 functional groups that contain σ-bonds. Alcohols: ontain a hydroxy group( ) bonded
More informationWeek 4. Even harder stuff!
Week 4 Even harder stuff! Focus: SN1 and SN2 Two organic reactions Learn about two basic pathways for how these reactions happen Focus on stereochemistry Focus: SN1 and SN2 You need a couple of things
More informationChapter 6: Organic Halogen Compounds; Substitution and Elimination Reactions
Chapter 6: Organic Halogen Compounds; Substitution and Elimination Reactions Halogen compounds are important for several reasons. Simple alkyl and aryl halides, especially chlorides and bromides, are versatile
More informationS N 1 Displacement Reactions
S N 1 Displacement Reactions Tertiary alkyl halides cannot undergo S N 2 reactions because of the severe steric hindrance blocking a backside approach of the nucleophile. They can, however, react via an
More informationALCOHOLS AND PHENOLS
ALCOHOLS AND PHENOLS ALCOHOLS AND PHENOLS Alcohols contain an OH group connected to a a saturated C (sp3) They are important solvents and synthesis intermediates Phenols contain an OH group connected to
More informationClass XI Chapter 13 Hydrocarbons Chemistry
Question 13.1: How do you account for the formation of ethane during chlorination of methane? Chlorination of methane proceeds via a free radical chain mechanism. The whole reaction takes place in the
More informationChapter 3. Alkenes And Alkynes
Chapter 3 Alkenes And Alkynes Alkenes ydrocarbons containing double bonds C C double bond the functional group center of reactivity Molecular Formula of Alkene Acyclic alkene: C n 2n Cyclic alkene: C n
More informationAn unknown molecule A has 4 signals in the 1 H NMR spectrum. Which of the following corresponds to molecule A
An unknown molecule A has 4 signals in the 1 H NMR spectrum. Which of the following corresponds to molecule A How many nonequivalent protons does the following structure have? 4 Reading from left to right,
More informationHalo Alkanes and Halo Arenes
alo Alkanes and alo Arenes Short Answer Questions: **1. Write the isomers of the compound having formula C 4 9 Br? Sol. There are five isomers of C 4 9 Br. These are: 2-bromobutane is expected to exhibit
More informationThe C-X bond gets longerand weakergoing down the periodic table.
Chapter 10: Organohalides Organic molecules containing halogen atoms (X) bonded to carbon are useful compounds in synthesis and on their own. 10.2 Structure of alkyl halides The C-X bond gets longerand
More informationOrganic Chemistry. REACTIONS Grade 12 Physical Science Mrs KL Faling
Organic Chemistry REACTIONS Grade 12 Physical Science Mrs KL Faling SUBSTITUTION REACTIONS This is a reaction where an atom or group of atoms is replaced by another atom or group of atoms Substitution
More informationdihalogenoalkane H 2, Nickel Catalyst KOH alcoholic HBr, HCl Br Cl Elimination KOH aqueous heat under reflux Nucleophilic substitution
7 AS mechanisms dihalogenoalkane poly(alkene) Br 2, 2 KO aqueous room temp Electrophilic addition heat under reflux Nucleophilic substitution high pressure atalyst polymerization alkene KMnO 4 oxidation
More informationOrganic Chemistry. Why are these compounds called Organic. What is a Hydrocarbon? Questions: P167 Read
Organic Chemistry The fact that carbon can form a wide variety of relatively stable long chain molecules results in this very important branch of Chemistry: Organics. Carbon forms strong covalent bonds
More informationAllyl radicals are especially stable due to resonance ( and double bond switch places):
Ch 10 Alkyl Halides Nomenclature Rules The parent is the longest alkyl chain or ring. The #1 C for a chain is at the end that is nearest to the first substituent. The #1 C for a ring possesses the first
More informationBSc. II 3 rd Semester. Submitted By Dr. Sangita Nohria Associate Professor PGGCG-11 Chandigarh 1
BSc. II 3 rd Semester Submitted By Dr. Sangita Nohria Associate Professor PGGCG-11 Chandigarh 1 Introduction to Alkyl Halides Alkyl halides are organic molecules containing a halogen atom bonded to an
More informationNucleophile. Reaction Intermediate. Introduction to Reaction mechanisms. Definitions 2/25/2012
Introduction to Reaction mechanisms Definition A reaction mechanism is the step by step sequence of elementary reactions by which overall chemical change occurs. It is also a detailed description of the
More informationORGANIC - CLUTCH CH. 3 - ACIDS AND BASES.
!! www.clutchprep.com CONCEPT: OVERVIEW OF CHEMICAL REACTIONS There are 4 types of common chemical reactions that we need to be familiar with in organic chemistry 1. Acid-Base Reactions: Two molecules
More informationLecture Topics: I. Electrophilic Aromatic Substitution (EAS)
Reactions of Aromatic Compounds Reading: Wade chapter 17, sections 17-1- 17-15 Study Problems: 17-44, 17-46, 17-47, 17-48, 17-51, 17-52, 17-53, 17-59, 17-61 Key Concepts and Skills: Predict and propose
More informationChem 3719 Klein Chapter Practice Problems
Chem 379 Klein Chapter Practice Problems Dr. Peter Norris, 208 Klein Chapter Problems : Review of General Chemistry. Draw viable structures for molecules with the following molecular formulae. Remember
More informationChem 251 Fall Learning Objectives
Learning Objectives Chapter 8 (last semester) 1. Write an electron-pushing mechanism for an SN2 reaction between an alkyl halide and a nucleophile. 2. Describe the rate law and relative rate of reaction
More informationChapter 4. Reactions of alkenes. Addition reactions Carbocations Selectivity of reactions
Chapter 4 Reactions of alkenes Addition reactions Carbocations Selectivity of reactions Prob 47 p192. Give the reagents that would be required (including catalyst). Ch 4 #2 Electrophilic addition Ch 4
More informationEthers can be symmetrical or not:
Chapter 14: Ethers, Epoxides, and Sulfides 175 Physical Properties Ethers can be symmetrical or not: linear or cyclic. Ethers are inert and make excellent solvents for organic reactions. Epoxides are very
More informationLesmahagow High School CfE Advanced Higher Chemistry
Lesmahagow High School AHChemistry Organic Chemistry& Instrumental Analysis Lesmahagow High School CfE Advanced Higher Chemistry Unit 2 Organic Chemistry and Instrumental Analysis Alkanes, Alkenes and
More informationReactions of Haloalkanes
Reactions of aloalkanes N Goalby chemrevise.org aloalkanes ontain a halogen atom covalently bonded to a carbon atom General formula: R-X where X is a halogen atom (F, l,, I) and R is the carbon chain.
More information12/27/2010. Chapter 15 Reactions of Aromatic Compounds
Chapter 15 Reactions of Aromatic Compounds Electrophilic Aromatic Substitution Arene (Ar-H) is the generic term for an aromatic hydrocarbon The aryl group (Ar) is derived by removal of a hydrogen atom
More informationPreparation of alkenes
Lecture 11 אלקנים הכנה ותגובות של אלקנים: הידרוגנציה, סיפוח הידרוהלוגנים )כלל מארקובניקוב(, סיפוח הלוגנים והסטראוכימיה של תוצרי הסיפוח, הידרובורציה, אפוקסידציה, אוזונוליזה. 1 Preparation of alkenes 1.
More informationOrganic Reactions Susbstitution S N. Dr. Sapna Gupta
Organic Reactions Susbstitution S N 2 Dr. Sapna Gupta Kinetics of Nucleophilic Reaction Rate law is order of reaction 0 order is when rate of reaction is unaffected by change in concentration of the reactants
More informationHALOALKANES. Structure Contain the functional group C-X where X is a halogen (F,Cl,Br or I)
aloalkanes AS3 1 ALOALKANES Structure ontain the functional group X where X is a halogen (F,l, or I) Types aloalkanes halogen is attached to an aliphatic skeleton alkyl group aloarenes halogen is attached
More informationMCAT Organic Chemistry Problem Drill 10: Aldehydes and Ketones
MCAT rganic Chemistry Problem Drill 10: Aldehydes and Ketones Question No. 1 of 10 Question 1. Which of the following is not a physical property of aldehydes and ketones? Question #01 (A) Hydrogen bonding
More informationLearning Guide for Chapter 11 - Alkenes I
Learning Guide for Chapter 11 - Alkenes I I. Introduction to alkenes - p 1 bond structure, classifying alkenes, reactivity, physical properties, occurrences and uses, spectroscopy, stabilty II. Unsaturation
More informationChapter 19: Alkenes and Alkynes
Chapter 19: Alkenes and Alkynes The vast majority of chemical compounds that we know anything about and that we synthesize in the lab or the industrial plant are organic compounds. The simplest organic
More informationCHEM Lecture 6
EM 494 Special Topics in hemistry Illinois at hicago EM 494 - Lecture 6 Prof. Duncan Wardrop October 15, 2012 Midterm Papers Factors that ontrol ydrocarbon Acidity Factors that ontrol ydrocarbon onformation
More informationTopic 6 Alkyl halide and carbonyl compounds Organic compounds containing a halogen
Topic 6 Alkyl halide and carbonyl compounds rganic compounds containing a halogen ompounds are named in standard way, eg: 3 1 3 3 2 3 2-iodo-2-methylpropane (tertiary alkyl halide) l 3 4-chlorotoluene
More informationORGANIC - BROWN 8E CH.4 - ACIDS AND BASES.
!! www.clutchprep.com CONCEPT: FREE ENERGY DIAGRAMS Atoms save energy by forming bonds. Free energy diagrams show overall changes in potential energy during reactions. Free energy diagrams give us information
More informationSubstitution and Elimination reactions
PART 3 Substitution and Elimination reactions Chapter 8. Substitution reactions of RX 9. Elimination reactions of RX 10. Substit n/elimin n of other comp ds 11. Organometallic comp ds 12. Radical reactions
More informationIntroduction to Alkenes and Alkynes
Introduction to Alkenes and Alkynes In an alkane, all covalent bonds between carbon were σ (σ bonds are defined as bonds where the electron density is symmetric about the internuclear axis) In an alkene,
More informationOrganic Chemistry. M. R. Naimi-Jamal. Faculty of Chemistry Iran University of Science & Technology
Organic Chemistry M. R. Naimi-Jamal Faculty of Chemistry Iran University of Science & Technology Chapter 7-1. Alkyl Halides Based on McMurry s Organic Chemistry, 6 th edition What Is an Alkyl Halide? An
More informationREASONING QUESTIONS FROM ORGANIC CHEMISTRY (CH. 1 & 2)
REASONING QUESTIONS FROM ORGANIC CHEMISTRY (CH. 1 & 2) 1.) Why do haloalkenes under go nucleophillic substitution whereas haloarenes under go electophillic substitution. Ans. Due to more electro negative
More information6-2 This exercise is worked out on page 220 as "Working with Concepts".
Copyright 2009 James K Whitesell 6-1 Although we can approach this exercise from a chemical perspective, one can also teach a non-chemist how to derive the answer once the name of the starting material
More informationClasses of Alkenes. Alkenes and Alkynes. Saturated compounds (alkanes): Have the maximum number of hydrogen atoms attached to each carbon atom.
Alkenes and Alkynes Saturated compounds (alkanes): ave the maximum number of hydrogen atoms attached to each carbon atom. Unsaturated compounds: ave fewer hydrogen atoms attached to the carbon chain than
More informationOrganic Chemistry Review: Topic 10 & Topic 20
Organic Structure Alkanes C C σ bond Mechanism Substitution (Incoming atom or group will displace an existing atom or group in a molecule) Examples Occurs with exposure to ultraviolet light or sunlight,
More informationBenzenes & Aromatic Compounds
Benzenes & Aromatic Compounds 1 Structure of Benzene H H C C C H C 6 H 6 H C C C H H A cyclic conjugate molecule Benzene is a colourless odourless liquid, boiling at 80 o C and melting at 5 o C. It is
More informationOrganic Chemistry SL IB CHEMISTRY SL
Organic Chemistry SL IB CHEMISTRY SL 10.1 Fundamentals of organic chemistry Understandings: A homologous series is a series of compounds of the same family, with the same general formula, which differ
More informationChapter 7 - Alkenes and Alkynes I
Andrew Rosen Chapter 7 - Alkenes and Alkynes I 7.1 - Introduction - The simplest member of the alkenes has the common name of ethylene while the simplest member of the alkyne family has the common name
More information