Reactions of Aromatic Compounds
|
|
- Anna Goodwin
- 7 years ago
- Views:
Transcription
1 Reactions of Aromatic Compounds Aromatic compounds are stabilized by this aromatic stabilization energy Due to this stabilization, normal S N 2 reactions observed with alkanes do not occur with aromatic compounds (S N 2 reactions never occur on sp 2 hybridized carbons!) In addition, the double bonds of the aromatic group do not behave similar to alkene reactions
2 Aromatic Substitution While aromatic compounds do not react through addition reactions seen earlier Br Br 2 Br 2 Br FeBr 3 Br With an appropriate catalyst, benzene will react with bromine The product is a substitution, not an addition (the bromine has substituted for a hydrogen) The product is still aromatic
3 Electrophilic Aromatic Substitution Aromatic compounds react through a unique substitution type reaction Initially an electrophile reacts with the aromatic compound to generate an arenium ion (also called sigma complex) The arenium ion has lost aromatic stabilization (one of the carbons of the ring no longer has a conjugated p orbital)
4 Electrophilic Aromatic Substitution In a second step, the arenium ion loses a proton to regenerate the aromatic stabilization The product is thus a substitution (the electrophile has substituted for a hydrogen) and is called an Electrophilic Aromatic Substitution
5 Energy Profile Transition states Transition states Potential energy Intermediate E H Starting material Products E Reaction Coordinate The rate-limiting step is therefore the formation of the arenium ion
6 The properties of this arenium ion therefore control electrophilic aromatic substitutions (just like any reaction consider the stability of the intermediate formed in the rate limiting step) 1) The rate will be faster for anything that stabilizes the arenium ion 2) The regiochemistry will be controlled by the stability of the arenium ion The properties of the arenium ion will predict the outcome of electrophilic aromatic substitution chemistry
7 Bromination To brominate an aromatic ring need to generate an electrophilic source of bromine In practice typically add a Lewis acid (e.g. FeBr 3 ) to bromine In presence of aromatic ring this electrophilic bromine source will react Br 2 FeBr 3 Br H Br
8 With unsubstituted benzene the position of reaction is arbitrary With a monosubstituted aromatic ring, however, can obtain three possible products How to predict which is favored? Controlled by stability of arenium ion intermediate
9 The stability is different depending upon placement of carbocation
10 Alkyl groups are electron donating Therefore toluene will favor electrophilic substitution at ortho/para positions (only ortho/para substitution places carbocation adjacent to alkyl group on ring) Often obtain more para than ortho due to sterics
11 In addition to orientational control, substituents affect reactivity CH 3 NO 2 As the aromatic ring acquires more electron density, the arenium ion will be more stable
12 Toluene therefore reacts faster in an electrophilic aromatic substitution than benzene The alkyl group is called an activating group (it activates the ring for a faster rate) Any substituent that increases the rate for an electrophilic aromatic substitution is called an activating substituent Substituents that lower the rate for an electrophilic aromatic substitution are called deactivating subsituents (nitro is one example of a deactivating group) These are groups that lower the electron density of the aromatic ring
13 Factors that affect Activators/Deactivators There are in general two mechanisms that can affect a substituent 1) Inductive Substituents that are more electronegative than carbon will inductively pull electron density out of the ring 2) Resonance Substituents that have a lone pair of electrons adjacent to the ring can donate electron density into the ring through resonance O CH3 O CH3 O CH3 O CH3
14 Many substituents will have both inductive and resonance effects Need to balance the effects Electronegative atoms with lone pair of electrons have opposing effects R Z Z Alkyl substituents inductively donate, no resonance effects, therefore activators Inductively withdrawing therefore deactivating Resonance donating, therefore activating when a neutral O or N is directly bonded to a benzene ring, the resonance effect dominates and the net effect is activating when a halogen is bonded to a benzene ring, the inductive effect dominates and the net effect is deactivating
15 Other Deactivating Groups There are two other main classes of deactivating groups 1) A conjugated system where both inductive and resonance effects pull electron density from the ring Z Y O N O O N Whenever Z is more electronegative than Y as seen in structure 2) A formal positive charge is placed directly adjacent to ring H 3 C CH 3 N CH3
16 Activating vs. Deactivating Ability can be compared The substituents can be compared relatively
17 Orientational Control Can Be Predicted 1) All activating groups favor ortho/para substitution 2) Deactivating groups with a lone pair of electrons adjacent to the ring favor ortho/para substitution (halogens are in this category) 3) Other deactivating groups favor meta substitution
18 With deactivating groups besides halogens, the favored substitution is meta Can be predicted by stability of arenium ion Only the meta substitution does not place a carbocation adjacent to EWG
19 All positions with a deactivating group are slower than benzene * The meta position is the LEAST disfavored Consider reaction coordinate for the first, rate-determining step
20 Multiple Substituents How to determine orientation of electrophilic aromatic substitution if there is more than one substituent? A few rules to consider: 1) The effects are cumulative 2) The stronger substituent according to the relative effects will be correspondingly more important for directing effects 3) When given a choice, a new substituent typically will not go ortho to two other substituents
21 Consider some examples: ortho/para director 3 CN Br 2 meta director FeBr 3 CH 3 CN ortho/para director ortho/para director H 3 C CN Br 2 meta director FeBr 3 H 3 C OCH 3 ortho/para director Br 2 FeBr 3 H 3 C H 3 C Br CN Br Stronger director wins Br OCH 3 Stronger director wins
22 Reactivity of aromatic ring can affect amount of reaction In reactions with strongly activated rings, polyhalogenation occurs With either phenol or aniline, the reaction will proceed until all ortho/para positions are reacted when catalyst is used
23 With these highly activated ring systems, catalyst is not necessary Reaction will only proceed with strongly activated ring systems, still need catalyst for less activated aromatic rings, but with phenol or aniline reaction of one halogen can occur with no catalyst present
24 Other Electrophiles Beside Bromine Chlorination reaction is similar to bromination Often use Lewis acid with chlorine substituents to avoid cross contamination (e.g. often use AlCl 3 for chlorination but FeBr 3 for bromination) Also with strongly activated rings obtain polychlorination products with catalyst
25 Iodination requires a stronger oxidizing reagent The reagents are a method to generate iodonium ion in situ The iodonium can then react as the electrophile
26 Fluorine is much harder to add in an electrophilic addition There is not an easy method to generate F+ Typically to add fluorine to an aromatic ring a diazonium route is used This chemistry will be dealt in more detail in chapter 19
27 Other Common Electrophiles Besides Halogens Nitration Adding a nitro group to an aromatic ring is a convenient and useful reaction Need to generate a source of nitronium ion
28 An advantage of nitration is the nitro group can be reduced to an amine Nitro Deactivating/Meta Director Amine Activating/Ortho-Para Director Allows the introduction of an amine group to the aromatic ring (almost all compounds that contain a nitrogen attached to aromatic ring occurred through a nitration) This conversion changes the electronic properties of the ring
29 Sulfonation Allows the introduction of a sulfur group (many biological/medicinal uses) The reverse step can also occur
30 The desulfonation step allows introduction of isotopes Occurs through arenium ion where compound is sulfonated, then add D+ and desulfonate to eliminate sulfur and add deuterium
31 Friedel-Crafts Alkylation In general carbon-carbon bonds can be made by reacting an aromatic ring with a carbocation This reaction is called a Friedel-Crafts alkylation
32 The key is formation of electrophilic carbon The alkyl halide reacts with the Lewis acid With tertiary and secondary alkyl halides this generates a discrete carbocation With primary alkyl halides the full carbocation is not formed
33 Any method that generates a carbocation can be used in a Friedel-Crafts alkylation Two other common methods: 1) From alkenes Often use HF as acid source since fluoride is weak nucleophile, therefore higher lifetime of carbocation to react 2) From alcohols
34 Limtations of Friedel-Crafts Alkylation 1) Reaction does not work with strongly deactivated aromatic rings Friedel-Crafts alkylations do not work with nitro, sulfonic, or acyl substituents 2) Carbocation rearrangements occur Because a carbocation is formed during this reaction, similar to any reaction involving carbocations the carbocation can rearrange to a more stable carbocation Can therefore never obtain n-alkyl substituents longer than 2 carbons
35 3) Polyalkylation often occurs with Friedel-Crafts alkylation Because an alkyl group is an activating group, the product is more reactive than the starting material Causes the product to react further To prevent polyreaction the starting material (benzene is this example) is used in excess
36 Another Option: Friedel-Crafts Acylation Instead of adding an alkyl group this reaction adds an acyl substituent First need to generate an acid chloride Thus any carboxylic acid can be converted into an acid chloride
37 The acid chloride can then be reacted in a Friedel-Crafts acylation First form an acylium ion by reacting with Lewis acid The acylium ion then reacts with aromatic ring in a typical electrophilic aromatic substitution
38 Advantages of Friedel-Crafts Acylation 1) The acyl substituent is a deactivating group Therefore this reaction can be stopped easily at one addition (no polyacylation occurs) 2) No rearrangements occur Since an isolated carbocation is not formed there is no rearrangement Due to these two advantages, the Friedel-Crafts acylation is a much more convenient reaction than the Friedel-Crafts alkylation -still will not react with strongly deactivated aromatic rings
39 High para substitution preference Due to the steric bulk of the Friedel-Crafts acylation reagent, often see a high preference for the para substitution with an ortho/para directing group *often see para preference with bulky electrophiles
40 Clemmensen Reduction The ability to reduce a carbonyl to a methylene further enhances usefullness of Friedel-Crafts acylation In a Clemmensen reduction the conversion occurs under acidic conditions Overall these two steps, Friedel-Crafts acylation followed by Clemmensen, allows the introduction of an n-alkyl substituent which would not be possible with a Friedel-Crafts alkylation
41 Wolf-Kishner Reduction Another method to reduce a carbonyl to methylene is a Wolf-Kishner reduction Main difference is that the Wolf-Kishner occurs under basic conditions Both Clemmensen and Wolf-Kishner require strong conditions, Clemmensen uses acidic while Wolf-Kishner uses basic conditions
42 Benzaldehyde Adding a formyl group requires stronger conditions than an acyl group addition Cannot isolate formyl chloride Therefore normal Friedel-Crafts acylation conditions cannot be used Need to generate in situ
43 Birch Reduction In addition to adding electrophiles to aromatic ring, the aromatic ring can be reduced by adding electrons to the system (in essence a nucleophilic addition) The electrons need to be generated in situ This electron is called a solvated electron
44 In the presence of an aromatic ring this electron will react e Addition of one electron thus generates a radical anion This strongly basic anion will abstract a proton from alcohol solution
45 The radical will then undergo the same operation a second time The final product has thus been reduced from benzene to a 1,4-cyclohexadiene The aromatic stabilization has been lost
46 Orientation of Birch Reduction What happens if there is a substituent on the aromatic ring before reduction? Which regioisomer will be obtained? Similar to every other reaction studied need to ask yourself, What is the stability of the intermediate structure? The preferred product is a result of the more stable intermediate
47 The intermediate in a Birch reduction is the radical anion formed after addition of electron With electron withdrawing substituent: O NH 3 (l), Na CH 3 OH O O O Placing negative charge adjacent to carbonyl allows resonance With electron donating substituent: OCH 3 NH 3 (l), Na CH 3 OH OCH 3 OCH 3 Want negative charge as far removed from donating group as possible
48 Reactions of Alkyl Substituents to Aromatic Ring Once alkyl groups are attached to aromatic rings they can undergo subsequent reactions Permanganate Oxidation Any carbon adjacent to an aromatic ring that contains at least one hydrogen will be oxidized with permanganate to the carboxylic acid stage
49 Benzylic Halide As seen in chapter 4, halogenation reactions can occur with either chlorine or bromine under photolytic conditions Reaction proceeds through a radical intermediate The benzylic radical is more stable due to resonance with aromatic ring CH 2
50 Remember that chlorination was more reactive, bromination though occurred selectively Cl 2, h! Cl Cl Br 2, h! Br Realize reaction does not occur on aromatic ring, do not obatin radical from sp 2 hybridized carbon
51 Nucleophilic Aromatic Substitution Another type of reaction with aromatic rings is a nucleophilic addition Instead of adding an electrophile to form an arenium ion, a nucleophile replaces a leaving group This is NOT a S N 2 reaction Initially a carbanion is formed which subsequently loses the leaving group, unlike a S N 2 reaction which is a one step reaction
52 Mechanism NO 2 Cl NaCN NO 2 Cl CN NO 2 Cl CN NO 2 Cl CN O 2 N O 2 N O 2 N O 2 N The anion is stabilized by electron withdrawing groups ortho/para to leaving group NO 2 Cl CN NO 2 CN O 2 N O 2 N To regain aromatic stabilization, the chloride leaves to give the substituted product
53 Unique factors for Nucleophilic Aromatic Substitution 1) Must have EWG s ortho/para to leaving group -the more EWG s present the faster the reaction rate (intermediate is stabilized) 2) The leaving group ability does not parallel S N 2 reactions -bond to leaving group is not broken in rate-determining step (fluorine for example is a good leaving group for nucleophilic aromatic substitution but is a horrible leaving group for S N 2 reaction) More electronegative atom has a faster rate F > Cl > Br > I (polarizability is not a factor)
54 Using Nucleophilic Aromatic Substitution for Peptide Determination React 2,4-dinitrobenzene with peptide O 2 N NO 2 F H 2 N R O N H (peptide chain) O 2 N NO 2 H N R O N H (peptide chain) Sanger reagent cleave O 2 N NO 2 H N R O OH The Sanger reagent can react with the N-terminal amine from the peptide The resultant nucleophilic aromatic substitution product can be cleaved and thus the terminal amino acid structure determined
55 Benzyne Mechanism A second nucleophilic aromatic substitution reaction is a benzyne mechanism Benzyne is an extremely unstable intermediate which will react with any nucleophile present NH 2 H Br NaNH 2, NH 3 NH2 benzyne Need strong base at moderate temperatures, but do not need EWG s on ring
56 Oxidation of Phenols Many reactions of phenols follow the same reactivity seen earlier -they are highly activating groups (ortho/para directors) for electrophilic aromatic substitution Phenols can also be oxidized to create quinones
57 Coenzyme Q All oxygen-consuming organisms use this process
58 Aromatic Substitution using Organometallic Reagents Extremely useful in forming carbon-carbon bonds with aromatic rings Allows a much wider diversity of products than available with Friedel-Crafts reactions Tremendous progress has been made using transition metal compounds to catalyze reactions To understand these reactions one key is knowing what metal is needed to catalyze the reaction and also what functional groups are needed for each specific reaction to occur
59 Organocuprates Formed by reacting organolithium compounds with cuprous iodide (CuI) These lithium dialkyl cuprate reagents (organocuprates) are also called Gilman reagents These Gilman reagents can react with alkyl halides to form new carbon-carbon bonds similar to S N 2 reactions
60 Reactions at sp 2 Hybridized Carbons Unlike S N 2 reactions, however, these organocuprates can react with sp 2 hybridized aryl or vinyl halides
61 Heck Reaction Can also accomplish reaction at alkene using a palladium catalyzed reaction (called Heck reaction) -the halide can be either aryl or vinyl -the halogen can be either bromine or iodine
62 Suzuki Coupling Couples aryl or vinyl halide with boronic acid with palladium catalyst and base Can use boronic acid [R-B(OH) 2 ] or ester [R-B(OR) 2 ] that is alkyl, vinyl or aryl
Electrophilic Aromatic Substitution Reactions
Electrophilic Aromatic Substitution Reactions, Course Notes Archive, 1 Electrophilic Aromatic Substitution Reactions An organic reaction in which an electrophile substitutes a hydrogen atom in an aromatic
More informationBenzene Benzene is best represented as a resonance hybrid:
Electrophilic Aromatic Substitution (EAS) is a substitution reaction usually involving the benzene ring; more specifically it is a reaction in which the hydrogen atom of an aromatic ring is replaced as
More information4/18/2011. 9.8 Substituent Effects in Electrophilic Substitutions. Substituent Effects in Electrophilic Substitutions
9.8 Substituent effects in the electrophilic substitution of an aromatic ring Substituents affect the reactivity of the aromatic ring Some substituents activate the ring, making it more reactive than benzene
More informationElectrophilic Aromatic Substitution
Electrophilic Aromatic Substitution Electrophilic Aromatic Substitution: a reaction in which the hydrogen atom of an aromatic ring is replaced as a result of an electrophilic attack on the aromatic ring
More informationElectrophilic Aromatic Substitution
Electrophilic Aromatic Substitution Electrophilic substitution is the typical reaction type for aromatic rings. Generalized electrophilic aromatic substitution: E E Electrophile Lewis acid: may be or neutral.
More informationREACTIONS OF AROMATIC COMPOUNDS
A STUDENT SHOULD BE ABLE TO: REACTIONS OF AROMATIC COMPOUNDS 1. Predict the product(s) of Electrophilic Aromatic Substitution (EAS), Nucleophilic Aromatic Substitution (S N Ar) and Elimination-Addition
More informationCHEM 322 Organic Chemistry II - Professor Kathleen V. Kilway. CHAPTER 14 Substitution Reactions of Aromatic Compounds
CHEM 322 Organic Chemistry II - Professor Kathleen V. Kilway "Organic Chemistry" by Maitland Jones, 4 th edition Chapter 14 Homework: 1, 2, 5, 7, 13, 19, 20, 23, 26, 27, 28, 30, 31, 34, 35, 36, 41, 46,
More informationCHEM 211 CHAPTER 16 - Homework
CHEM 211 CHAPTER 16 - Homework SHORT ANSWER Consider the Friedel-Crafts alkylation reaction below to answer the following question(s): 1. Refer to the reaction above. Draw the structure of the electrophilic
More informationAromaticity and Reactions of Benzene
Aromaticity and eactions of Benzene ark College Benzene is a unique molecule it is highly unsaturated with 6 carbons and 6 hydrogens, it is planar, and has a high degree of symmetry. These features explain
More informationChemistry Notes for class 12 Chapter 13 Amines
1 P a g e Chemistry Notes for class 12 Chapter 13 Amines Amines constitute an important class of organic compounds derived by replacing one or more hydrogen atoms ofnh 3 molecule by alkyl/aryl group(s).
More informationAcids and Bases: Molecular Structure and Acidity
Acids and Bases: Molecular Structure and Acidity Review the Acids and Bases Vocabulary List as needed. Tutorial Contents A. Introduction B. Resonance C. Atomic Radius D. Electronegativity E. Inductive
More informationQ.1 Draw out some suitable structures which fit the molecular formula C 6 H 6
Aromatic compounds GE 1 BENZENE Structure Primary analysis revealed benzene had an... empirical formula of and a molecular formula of 6 6 Q.1 Draw out some suitable structures which fit the molecular formula
More informationStudying an Organic Reaction. How do we know if a reaction can occur? And if a reaction can occur what do we know about the reaction?
Studying an Organic Reaction How do we know if a reaction can occur? And if a reaction can occur what do we know about the reaction? Information we want to know: How much heat is generated? How fast is
More informationWriting a Correct Mechanism
Chapter 2 1) Balancing Equations Writing a Correct Mechanism 2) Using Arrows to show Electron Movement 3) Mechanisms in Acidic and Basic Media 4) Electron rich Species: Nucleophile or Base? 5) Trimolecular
More informationBut 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 informationmethyl RX example primary RX example secondary RX example secondary RX example tertiary RX example
ucleophilic Substitution & Elimination hemistry 1 eginning patterns to knowfor S and E eactions - horizontal and vertical templates for practice Example 1 - two possible perspectives (deuterium and tritium
More informationElectrophilic Addition Reactions
Electrophilic Addition Reactions Electrophilic addition reactions are an important class of reactions that allow the interconversion of C=C and C C into a range of important functional groups. Conceptually,
More informationChapter 22 Carbonyl Alpha-Substitution Reactions
John E. McMurry www.cengage.com/chemistry/mcmurry Chapter 22 Carbonyl Alpha-Substitution Reactions The α Position The carbon next to the carbonyl group is designated as being in the α position Electrophilic
More informationReminder: These notes are meant to supplement, not replace, the textbook and lab manual. Electrophilic Aromatic Substitution notes
Reminder: These notes are meant to supplement, not replace, the textbook and lab manual. Electrophilic Aromatic Substitution notes History and Application: The rate of a reaction directly impacts the commercial
More informationMass Spec - Fragmentation
Mass Spec - Fragmentation An extremely useful result of EI ionization in particular is a phenomenon known as fragmentation. The radical cation that is produced when an electron is knocked out of a neutral
More informationINTDUCTIN T LEWIS ACID-BASE CEMISTY DEINITINS Lewis acids and bases are defined in terms of electron pair transfers. A Lewis base is an electron pair donor, and a Lewis acid is an electron pair acceptor.
More informationEXPERIMENT 3 (Organic Chemistry II) Nitration of Aromatic Compounds: Preparation of methyl-m-nitrobenzoate
EXPERIMENT 3 (Organic Chemistry II) Nitration of Aromatic Compounds: Preparation of methyl-m-nitrobenzoate Pahlavan/Cherif Purpose a) Study electrophilic aromatic substitution reaction (EAS) b) Study regioselectivity
More informationAROMATIC COMPOUNDS A STUDENT SHOULD BE ABLE TO:
A STUDENT SHULD BE ABLE T: ARMATIC CMPUNDS 1. Name benzene derivatives given the structures, and draw the structures given the names. This includes: Monosubstituted benzenes named as derivatives of benzene:
More informationChapter 11. Free Radical Reactions
hapter 11 Free Radical Reactions A free radical is a species containing one or more unpaired electrons Free radicals are electron-deficient species, but they are usually uncharged, so their chemistry is
More informationChapter 2 Polar Covalent Bonds; Acids and Bases
John E. McMurry http://www.cengage.com/chemistry/mcmurry Chapter 2 Polar Covalent Bonds; Acids and Bases Javier E. Horta, M.D., Ph.D. University of Massachusetts Lowell Polar Covalent Bonds: Electronegativity
More informationDetermining the Structure of an Organic Compound
Determining the Structure of an Organic Compound The analysis of the outcome of a reaction requires that we know the full structure of the products as well as the reactants In the 19 th and early 20 th
More informationNucleophilic Substitution and Elimination
Nucleophilic Substitution and Elimination 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
More informationAmines H 3 C H. CH 2 CH 3 ethylmethylamine. Nomenclature. 1 o : RNH 2, 2 o : RR'NH, 3 o : RR'R"N, 4 o (salt) RR'R"R'"N + R = alkyl or aryl
Amines omenclature 1 o :, 2 o : 'H, 3 o : '", 4 o (salt) '"'" + = alkyl or aryl ommon names For simple amines name groups attached to alphabetically; use suffix -amine. H 3 H H 2 ethylmethylamine In complicated
More informationHow to Quickly Solve Spectrometry Problems
How to Quickly Solve Spectrometry Problems You should be looking for: Mass Spectrometry (MS) Chemical Formula DBE Infrared Spectroscopy (IR) Important Functional Groups o Alcohol O-H o Carboxylic Acid
More informationConjugation is broken completely by the introduction of saturated (sp3) carbon:
Chapter 16 Conjugation, resonance, and dienes Conjugation relies on the partial overlap of p-orbitals on adjacent double or triple bonds. A common conjugated system involves 1,3-dienes, such as 1,3-butadiene.
More informationCarboxylic Acid Structure and Chemistry: Part 2
Principles of Drug Action 1, pring 2005, Carboxylic Acids Part 2 Carboxylic Acid tructure and Chemistry: Part 2 Jack Deuiter IV. eactions of the Carboxylic Acid eactions Depending on their overall structure,
More informationCarboxylic Acid Derivatives and Nitriles
Carboxylic Acid Derivatives and itriles Carboxylic Acid Derivatives: There are really only four things to worry about under this heading; acid chlorides, anhydrides, esters and amides. We ll start with
More informationResonance Structures Arrow Pushing Practice
Resonance Structures Arrow Pushing Practice The following is a collection of ions and neutral molecules for which several resonance structures can be drawn. For the ions, the charges can be delocalized
More informationChapter 10. Conjugation in Alkadienes and Allylic Systems. Class Notes. B. The allyl group is both a common name and an accepted IUPAC name
Chapter 10 Conjugation in Alkadienes and Allylic Systems Chapter 10 suggested problems: I. The allyl group Class Notes A. B. The allyl group is both a common name and an accepted IUPAC name 1. Allyl alcohol
More informationRESONANCE, USING CURVED ARROWS AND ACID-BASE REACTIONS
RESONANCE, USING CURVED ARROWS AND ACID-BASE REACTIONS A STUDENT SHOULD BE ABLE TO: 1. Properly use curved arrows to draw resonance structures: the tail and the head of every arrow must be drawn in exactly
More informationALCOHOLS: Properties & Preparation
ALLS: Properties & Preparation General formula: R-, where R is alkyl or substitued alkyl. Ar-: phenol - different properties. Nomenclature 1. ommon names: Name of alkyl group, followed by word alcohol.
More informationAcids and Bases. but we will use the term Lewis acid to denote only those acids to which a bond can be made without breaking another bond
Acids and Bases. Brønsted acids are proton donors, and Brønsted bases are proton acceptors. Examples of Brønsted acids: HCl, HBr, H 2 SO 4, HOH, H 3 O +, + NH 4, NH 3, CH 3 CO 2 H, H CH 2 COCH 3, H C CH,
More informationC 2 H 5 L L LC 2 H 5 l max = 256 nm (e = 20,000) 283 nm (e = 5,100) CH 3 H 3 C. CH 3 i. B bimesityl l max = 266 nm (e = 700)
750 CAPTER 6 TE CEITRY F BENZENE AND IT DERIVATIVE This hybridization allows one of its electron pairs to occupy a 2p orbital, which has the same size, shape, and orientation as the carbon 2p orbitals
More informationIdentification of Unknown Organic Compounds
Identification of Unknown Organic Compounds Introduction The identification and characterization of the structures of unknown substances are an important part of organic chemistry. Although it is often
More informationSN2 Ionic Substitution Reactions
SN2 Ionic Substitution Reactions Chem 14D Winter 2005 SN2 Ionic Substitution Reactions Substitution can occur in organic compounds that have an electronegative atom or group bonded to an sp 3 hybridized
More informationORGANIC CHEMISTRY I PRACTICE PROBLEMS FOR BRONSTED-LOWRY ACID-BASE CHEMISTRY
RGANIC CHEMISTRY I PRACTICE PRBLEMS FR BRNSTED-LWRY ACID-BASE CHEMISTRY 1. For each of the species below, identify the most acidic proton and provide the structure of the corresponding conjugate base.
More informationSurvival Organic Chemistry Part I: Molecular Models
Survival Organic Chemistry Part I: Molecular Models The goal in this laboratory experience is to get you so you can easily and quickly move between empirical formulas, molecular formulas, condensed formulas,
More informationBenzene and Aromatic Compounds
Benzene and Aromatic Compounds Benzene (C 6 H 6 ) is the simplest aromatic hydrocarbon (or arene). Benzene has four degrees of unsaturation, making it a highly unsaturated hydrocarbon. Whereas unsaturated
More informationChapter 11 Homework and practice questions Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations
Chapter 11 Homework and practice questions Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations SHORT ANSWER Exhibit 11-1 Circle your response in each set below. 1. Circle the least
More information13C NMR Spectroscopy
13 C NMR Spectroscopy Introduction Nuclear magnetic resonance spectroscopy (NMR) is the most powerful tool available for structural determination. A nucleus with an odd number of protons, an odd number
More informationINTERMOLECULAR FORCES
INTERMOLECULAR FORCES Intermolecular forces- forces of attraction and repulsion between molecules that hold molecules, ions, and atoms together. Intramolecular - forces of chemical bonds within a molecule
More informationSUBSTITUTION REACTION CHARACTERISTICS. Sn1: Substitution Nucleophilic, Unimolecular: Characteristics
SUBSTITUTION EATION AATEISTIS Sn2: Substitution cleophilic, Bimolecular: haracteristics 1) The 2 means Bimolecular (or 2 nd order) in the rate-determining (slow) step: rate = k [: - ] [-X] or rate = k
More informationChapter 10 Conjugation in Alkadienes and Allylic Systems
. 0 onjugated Systems hapter 0 onjugation in Alkadienes and Allylic Systems onjugated systems are those in which a π-bond is connected or conjugated (from the Latin conjugare which means to link r yoke
More informationChapter 15 Radical Reactions. Radicals are reactive species with a single unpaired electron, formed by
Chapter 15 Radical Reactions Radicals are reactive species with a single unpaired electron, formed by homolysis of a covalent bond; a radical contains an atom that does not have an octet of electrons,
More informationTypical Infrared Absorption Frequencies. Functional Class Range (nm) Intensity Assignment Range (nm) Intensity Assignment
Typical Infrared Absorption Frequencies Functional Class Range (nm) Intensity Assignment Range (nm) Intensity Assignment Alkanes 2850-3000 CH 3, CH 2 & CH 2 or 3 bands Alkenes 3020-3100 1630-1680 1900-2000
More informationEverything You Need to Know About Mechanisms. First rule: Arrows are used to indicate movement of electrons
Everything You eed to Know About Mechanisms A) The orrect Use of Arrows to Indicate Electron Movement The ability to write an organic reaction mechanism properly is key to success in organic chemistry
More informationSince we will be dealing with aqueous acid and base solution, first we must examine the behavior of water.
Acids and Bases Know the definition of Arrhenius, Bronsted-Lowry, and Lewis acid and base. Autoionization of Water Since we will be dealing with aqueous acid and base solution, first we must examine the
More informationammonium salt (acidic)
Chem 360 Jasperse Ch. 19 otes. Amines 1 eactions of Amines 1. eaction as a proton base (Section 19-5 and 19-6) amine base -X (proton acid) a X ammonium salt (acidic) Mechanism: equired (protonation) everse
More informationfor excitation to occur, there must be an exact match between the frequency of the applied radiation and the frequency of the vibration
! = 1 2"c k (m + M) m M wavenumbers! =!/c = 1/" wavelength frequency! units: cm 1 for excitation to occur, there must be an exact match between the frequency of the applied radiation and the frequency
More informationReactions of Fats and Fatty Acids
Reactions of Fats and Fatty Acids Outline Fats and Oils Fatty Acid Biosynthesis Biodiesel Homework We hear quite a lot about the place of fats and oils in human nutrition. Foods high in fat are at the
More informationFor example: (Example is from page 50 of the Thinkbook)
SOLVING COMBINED SPECTROSCOPY PROBLEMS: Lecture Supplement: page 50-53 in Thinkbook CFQ s and PP s: page 216 241 in Thinkbook Introduction: The structure of an unknown molecule can be determined using
More informationPhysicochemical Properties of Drugs
Therapeutics I Michael B. Bolger 1/3/02 bjectives: At the end of the next hour: Physicochemical Properties of Drugs 1. The student should be able to calculate the degree of ionization for an acidic or
More informationChapter 6 An Overview of Organic Reactions
John E. McMurry www.cengage.com/chemistry/mcmurry Chapter 6 An Overview of Organic Reactions Why this chapter? To understand organic and/or biochemistry, it is necessary to know: -What occurs -Why and
More informationSelf Assessment_Ochem I
UTID: 2013 Objective Test Section Identify the choice that best completes the statement or answers the question. There is only one correct answer; please carefully bubble your choice on the scantron sheet.
More informationIDENTIFICATION OF ALCOHOLS
IDENTIFICATION OF ALCOHOLS Alcohols are organic compounds that which considered as derivatives of water. One of the hydrogen atoms of water molecule (H-O-H) has been replaced by an alkyl or substituted
More informationChapter 2 Polar Covalent Bonds: Acids and Bases
John E. McMurry www.cengage.com/chemistry/mcmurry Chapter 2 Polar Covalent Bonds: Acids and Bases Modified by Dr. Daniela R. Radu Why This Chapter? Description of basic ways chemists account for chemical
More informationBrønsted-Lowry Acids and Bases
Brønsted-Lowry Acids and Bases 1 According to Brønsted and Lowry, an acid-base reaction is defined in terms of a proton transfer. By this definition, the reaction of Cl in water is: Cl(aq) + Cl (aq) +
More informationSULFONATE AND INORGANIC ESTER DERIVATIVES OF ALCOHOLS
0. ULFNATE AND INRGANIC ETER DERIVATIVE F ALCL 44 R 2 C L CR 2 carbocation Lewis acid base association X (halide ion) 2 $ R 2 C L CR 2 R R X C A C $ alkyl halide R R alkene $ $ Brønsted acid base reaction
More informationACID and BASES - a Summary
AID and BASES - a Summary Stefan Svensson 2004 Brönsted-Lowry : Acids donate protons Lewis -acid : Electron pair acceptor Bases accept protons Lewis-base: Electron pair donator. Acetic acid ättiksyra 3
More informationMolecular Models Experiment #1
Molecular Models Experiment #1 Objective: To become familiar with the 3-dimensional structure of organic molecules, especially the tetrahedral structure of alkyl carbon atoms and the planar structure of
More informationCH 3 CH 2 ONa + H 2 O. CH 3 CH 2 NH 2 + CH 3 OLi
rganic Chemistry Jasperse Acid- Practice Problems A. Identify each chemical as either an acid or a base in the following reactions, and identify conjugate relationships. -You should have one acid and one
More informationpartial positive an acid is a hydrogen ion donor, or proton donor base is a hydrogen ion acceptor, or proton acceptor acidic protons acid base
INTRDUCTIN T INIC MECANISMS PART I: FUNDAMENTALS F BRNSTED-LWRY ACID-BASE CEMISTRY YDRGEN ATMS AND PRTNS IN RGANIC MLECULES - A hydrogen atom that has lost its only electron is sometimes referred to as
More informationWillem Elbers. October 9, 2015
S N 1 and S N 2 reactivity of 3 alkyl bromides Willem Elbers ctober 9, 2015 1 Abstract n this experiment, we investigate the relative reactivities of three alkyl bromides with increasing steric bulk. We
More information3.4 BRØNSTED LOWRY ACIDS AND BASES
96 CAPTER 3 ACIDS AND BASES. TE CURVED-ARROW NOTATION and that the unshared electron pair (and negative charge) is shared equally by the two terminal carbons. C L C A C 1 allyl anion (c) Using the curved-arrow
More informationAddition Reactions of Carbon-Carbon Pi Bonds - Part 1
Addition eactions of arbon-arbon Pi Bonds - Part 1 3 δ+ 2 δ 3 3 3 + 2 3 2 3 What Is an Addition eaction? Addition reaction: Atoms or groups are added to opposite ends of a pi bond. X Y Why should I study
More informationAvg. 16.4 / 25 Stnd. Dev. 8.2
QUIZ TREE Avg. 16.4 / 25 Stnd. Dev. 8.2 xidation of Alcohols with Chromium (VI): Jones xidation 2 Alcohols are oxidized by a solution of chromium trioxide in aqueous acetone (2), in the presence of an
More informationSolving Spectroscopy Problems
Solving Spectroscopy Problems The following is a detailed summary on how to solve spectroscopy problems, key terms are highlighted in bold and the definitions are from the illustrated glossary on Dr. Hardinger
More informationEXPERIMENT 1: Survival Organic Chemistry: Molecular Models
EXPERIMENT 1: Survival Organic Chemistry: Molecular Models Introduction: The goal in this laboratory experience is for you to easily and quickly move between empirical formulas, molecular formulas, condensed
More informationChapter 8 Concepts of Chemical Bonding
Chapter 8 Concepts of Chemical Bonding Chemical Bonds Three types: Ionic Electrostatic attraction between ions Covalent Sharing of electrons Metallic Metal atoms bonded to several other atoms Ionic Bonding
More informationSaturated NaCl solution rubber tubing (2) Glass adaptor (2) thermometer adaptor heating mantle
EXPERIMENT 5 (Organic Chemistry II) Pahlavan/Cherif Dehydration of Alcohols - Dehydration of Cyclohexanol Purpose - The purpose of this lab is to produce cyclohexene through the acid catalyzed elimination
More informationCHEM 203 Exam 1. KEY Name Multiple Choice Identify the letter of the choice that best completes the statement or answers the question.
CHEM 203 Exam 1 KEY Name Multiple Choice Identify the letter of the choice that best completes the statement or answers the question. _D C 1. Which of the following elements is a large percentage of both
More informationORGANIC CHEMISTRY I PRACTICE EXERCISE Sn1 and Sn2 Reactions
ORGANIC CEMISTRY I PRACTICE EXERCISE Sn1 and Sn2 Reactions 1) Which of the following best represents the carbon-chlorine bond of methyl chloride? d d - d - d d d d - d - I II III IV V 2) Provide a detailed,
More informationBoston University Dresden Science Program ORGANIC CHEMISTRY CAS CH 203 Lecture
Boston University Dresden Science Program ORGANIC CHEMISTRY CAS CH 203 Lecture Instructor: Professor Wolf D. Habicher, Professor Claus Rüger Meeting Times Lectures: twice a week at 90 minutes each Discussions:
More information21.9 REDUCTION OF CARBOXYLIC ACID DERIVATIVES
10 APTER 1 TE EMITRY F ARBXYLI AID DERIVATIVE TUDY GUIDE LIK 1.5 Esters and ucleophiles 1.17 Give the structure of the product in the reaction of each of the following esters with isotopically labeled
More informationThe dipolar nature of acids
I. Introduction arboxylic Acid Structure and hemistry: Part 1 Jack Deuiter arboxylic acids are hydrocarbon derivatives containing a carboxyl () moiety. ecall that carbon has four valence electrons and
More informationCHM220 Nucleophilic Substitution Lab. Studying S N 1 and S N 2 Reactions: Nucloephilic Substitution at Saturated Carbon*
CHM220 Nucleophilic Substitution Lab Studying S N 1 and S N 2 Reactions: Nucloephilic Substitution at Saturated Carbon* Purpose: To convert a primary alcohol to an alkyl bromide using an S N 2 reaction
More informationThese instructions are for a classroom activity which supports OCR A Level Chemistry A.
Lesson Element Keyword activities Instructions for teachers These instructions are for a classroom activity which supports OCR A Level Chemistry A. Just a minute! To run this activity you will need a set
More informationLecture 15: Enzymes & Kinetics Mechanisms
ROLE OF THE TRANSITION STATE Lecture 15: Enzymes & Kinetics Mechanisms Consider the reaction: H-O-H + Cl - H-O δ- H Cl δ- HO - + H-Cl Reactants Transition state Products Margaret A. Daugherty Fall 2004
More informationOrganometallics Study Seminar Chapter 13: Metal-Ligand Multiple Bonds
Organometallics Study Seminar Chapter 13: Metal-Ligand Multiple Bonds Contents 1. Carbene Complexes 2. Silylene Complexes 3. Metal-Heteroatom Multiple Bonds 1. Carbene Complexes 1.1 Classes of Carbene
More informationCalifornia State Polytechnic University, Pomona. Exam Points 1. Nomenclature (1) 30
Chem 316 Final Exam Winter, 2008 Beauchamp ame: Topic Total Points Exam Points 1. omenclature (1) 30 Credit 2. Explanation of elative eactivities of Aromatic 20 Compounds or Carbonyl Compounds 3. eactions
More informationChapter 4 Lecture Notes
Chapter 4 Lecture Notes Chapter 4 Educational Goals 1. Given the formula of a molecule, the student will be able to draw the line-bond (Lewis) structure. 2. Understand and construct condensed structural
More informationLewis Dot Structures of Atoms and Ions
Why? The chemical properties of an element are based on the number of electrons in the outer shell of its atoms. We use Lewis dot structures to map these valence electrons in order to identify stable electron
More informationAustin Peay State University Department of Chemistry CHEM 1021 TESTING FOR ORGANIC FUNCTIONAL GROUPS
TESTING FOR ORGANIC FUNCTIONAL GROUPS Caution: Chromic acid is hazardous as are many of the organic substances in today s experiment. Treat all unknowns with extreme care. Many organic substances are flammable.
More informationSymmetric Stretch: allows molecule to move through space
BACKGROUND INFORMATION Infrared Spectroscopy Before introducing the subject of IR spectroscopy, we must first review some aspects of the electromagnetic spectrum. The electromagnetic spectrum is composed
More informationTheme 3: Bonding and Molecular Structure. (Chapter 8)
Theme 3: Bonding and Molecular Structure. (Chapter 8) End of Chapter questions: 5, 7, 9, 12, 15, 18, 23, 27, 28, 32, 33, 39, 43, 46, 67, 77 Chemical reaction valence electrons of atoms rearranged (lost,
More informationCHM220 Addition lab. Experiment: Reactions of alkanes, alkenes, and cycloalkenes*
CM220 Addition lab Experiment: Reactions of alkanes, alkenes, and cycloalkenes* Purpose: To investigate the physical properties, solubility, and density of some hydrocarbon. To compare the chemical reactivity
More informationConjugation is broken completely by the introduction of saturated (sp 3 ) carbon:
Conjugation. Conjugation relies on the partial overlap of p-orbitals on adjacent double or triple bonds. ne of the simplest conjugated molecules is 1,3-butadiene. Conjugation comes in three flavors, the
More information17.2 REACTIONS INVOLVING ALLYLIC AND BENZYLIC RADICALS
17. REACTINS INVLVING ALLYLIC AND BENZYLIC RADICALS 793 As Eq. 17. shows, the products derived from the reaction of water at the ring carbons are not formed. The reason is that these products are not aromatic
More informationLaboratory 22: Properties of Alcohols
Introduction Alcohols represent and important class of organic molecules. In this experiment you will study the physical and chemical properties of alcohols. Solubility in water, and organic solvents,
More informationMolecular Models in Biology
Molecular Models in Biology Objectives: After this lab a student will be able to: 1) Understand the properties of atoms that give rise to bonds. 2) Understand how and why atoms form ions. 3) Model covalent,
More informationIR Summary - All numerical values in the tables below are given in wavenumbers, cm -1
Spectroscopy Data Tables Infrared Tables (short summary of common absorption frequencies) The values given in the tables that follow are typical values. Specific bands may fall over a range of wavenumbers,
More informationMOLECULAR REPRESENTATIONS AND INFRARED SPECTROSCOPY
MLEULAR REPRESENTATINS AND INFRARED SPETRSPY A STUDENT SULD BE ABLE T: 1. Given a Lewis (dash or dot), condensed, bond-line, or wedge formula of a compound draw the other representations. 2. Give examples
More informationUnit 2 Review: Answers: Review for Organic Chemistry Unit Test
Unit 2 Review: Answers: Review for Organic Chemistry Unit Test 2. Write the IUPAC names for the following organic molecules: a) acetone: propanone d) acetylene: ethyne b) acetic acid: ethanoic acid e)
More informationChapter 12: Oxidation and Reduction.
207 Oxidation- reduction (redox) reactions Chapter 12: Oxidation and Reduction. At different times, oxidation and reduction (redox) have had different, but complimentary, definitions. Compare the following
More informationChapter 17. How are acids different from bases? Acid Physical properties. Base. Explaining the difference in properties of acids and bases
Chapter 17 Acids and Bases How are acids different from bases? Acid Physical properties Base Physical properties Tastes sour Tastes bitter Feels slippery or slimy Chemical properties Chemical properties
More information