Lecture 16 November 10, Metal-catalyzed cross-coupling reactions:

Size: px
Start display at page:

Download "Lecture 16 November 10, 2011. Metal-catalyzed cross-coupling reactions:"

Transcription

1 Metal-catalyzed cross-coupling reactions: Lecture 16 November 10, 2011 Let s move on now to talk about other metal-catalyzed cross-coupling reactions. All of these reactions involve the formation of a new carbon-carbon bond between unsaturated carbon atoms (either sp or sp2-hybridized). Sonogashira reaction: The mechanism here (briefly) is oxidative addition of the aryl iodide to the palladium (0), the alkyne and copper generate an organocuprate, this organocuprate undergoes transmetallation with palladium, and then reductive elimination gives the product. Heck reaction: This is also called the Mizoroki-Heck reaction. The general reaction scheme is shown below: and it proceeds via the following mechanism: Iodides are more reactive than bromides and chlorides (which is the typical order of reactivity, based on the strength of the carbon-halogen bond), which means that it is possible to convert an aryl iodide selectively and leave the aryl bromide untouched: The olefin is almost always electron-deficient. This is b/c the electron-deficient substituents increase the rate of oxidative addition to palladium. People have done Heck reactions with electron-rich vinyl ethers, but these usually require modification. For example, the reaction below works well: but they needed to use the weird phosphine oxide ligand to get good results. Another interesting aspect of the Heck reaction is its stereoselectivity, which produces trans-alkene products predominantly. This is because the insertion reaction is stereospecific and syn meaning that the R group and the PdX group add to the same side of the double bond. B-hydride elimination also reinforces the formation of the trans alkene. Let s do a few Heck reaction examples:

2 Here you can use the triflate as a halide-like substituent. The vinyl triflate can be formed in one step from the corresponding ketone by treating it with triflic anhydride and triethylamine: And the mechanism for this conversion is shown below: Another Heck example: And a Heck retrosynthesis example: Here, you look at a regular trans alkene, and are asked to do a retrosynthesis using a Heck reaction. There are two things that are missing from your molecule you really need a diene that is conjugated as the product of the Heck reaction. You also generally want an electron deficient moiety attached to your alkene to help it react faster. So you can put those back retrosynthetically. The extra double bond could have been removed by hydrogenation, and the electron withdrawing ester could have been removed by hydrolyzing it to a carboxylic acid and then decarboxylating it. This brings you back to intermediate A that is an excellent candidate for Heck retrosynthesis. You should also note here that your products are often dienes. These are perfectly poised to react further in a Diels-Alder reaction with a dienophile (keep this in mind when you have to do multi-step synthesis!). Heck reactions can be used to make polyphenylenevinylenes (PPVs), via the general reaction shown below: R in this case is generally a long alkyl or alkoxy chain.

3 Suzuki reaction: General reaction scheme: Here either the halide or the boronate can be aryl or vinyl (just has to be sp2 hybridized). The mechanism of the Suzuki reaction has a lot of similarities to the Heck reaction mechanism and is shown below: The first step is oxidative addition to a palladium, followed by transmetallation with boronic acid. Reductive elimination then gives the desired product. One downside to the Suzuki reaction is that you have to pre-form both a boronic acid and a halide before they can be coupled. It would be more efficient if you could directly couple compounds with C-H bonds. This is a whole other topic called C-H activation which we are not going to cover today, but it is a highly active field for those who are interested. Traditional Suzuki reactions required that both partners had to be sp2 hybridized in order for the reactions to take place. However, recent advances by people like Greg Fu have demonstrated that you can do Suzuki reactions with sp3 carbon centers as well, but you need a different catalyst system. Here is an example from a recent Greg Fu paper: This is particularly interesting because he uses nickel (instead of the traditional palladium) and he also uses a chiral ligand (shown below) to get enantioselectivity in the product. The new chiral center has enantioselectivities up to 90%. Chiral ligand: Let s do some Suzuki reaction examples: Example 1: Here you can see that the free amino group does not interfere with the Suzuki reaciton Example 2: Two things to note here first of all, that the aryl triflate works well as a halide surrogate, and secondly that this is actually reacting a protected amino acid to generate a biphenyl analogue, which could be useful synthetically.

4 Example 3: I think the interesting thing here is that the methoxy group on the ketone alpha carbon remains totally untouched by this reaction. There are many examples where the Suzuki reaction is used in a polymerization. To do a polymerization with a metal-catalyzed cross coupling, you need to have two bifunctional monomers (like we talked about last time). A polymerization example: Here they use a boronate ester to couple with the aryl bromide and for the new aryl-aryl bond in the polymer product. You can also make PPP (poly-para-phenylenes) by a Suzuki polymerization: And also polyfluorenes can be made this way: Glaser coupling reaction: This is between two terminal alkynes, and requires the presence of the copper and oxygen to generate a dialkyne product. The general reaction scheme is shown below: This is a big problem as a side product in Sonogashira reactions. You may have noticed that Sonogashira also has terminal alkynes and also requires a copper catalyst. So you need to be really careful to exclude oxygen in Sonogashira reactions, since that is the key difference between the Glaser coupling and the

5 Sonogashira reaction. A lot of times with Sonogashira reactions you will get defects from the homo- coupling of two alkyne groups. People have used the Glaser reaction for polymerization as well. Here is one example: To do this, they basically used a bis-terminawith di-alkyne linkages. alkyne and that allowed them to form the desired polymer Here is a non-polymer example of a Glaser coupling: H O 2, CuCl N N Glaser products are easy to identify because they will all have the bis-alkyne linkage. Retrosynthetic toolbox: These metal-catalyzed cross-coupling coupling reactions open up huge new opportunities in retrosynthesis (and in synthesis in general). Now any time you have a target molecule with unsaturation (alkene, benzene ring, etc) you can retrosynthetically disconnect that compound and decide that the key bond-forming reaction was a metal-catalyzed cross coupling. Here is an example: In this compound you have a double bond in conjugation with an arene, that you can disconnect retrosynthetically and say that it came from a Heck reaction. e + I And even if you didn t have a double bond there, you can retrosynthetically decide that there used to be a double bond there that got hydrogenated: + I and this gives you the option of disconnecting lots of bonds that may not have been possible otherwise. There are a number of other cross-coupling coupling reactions that we are not going to talk about, including the Negishi coupling, and the Stille coupling. Next time we will continue our discussion of conjugated polymers by talking about select applications of these polymers, predominantly in sensing schemes.

https://staff.ustc.edu.cn/~hxu 中国科学技术大学高分子科学与工程系

https://staff.ustc.edu.cn/~hxu 中国科学技术大学高分子科学与工程系 Transition-Metal-Catalyzed Coupling Reactions: Old History, New Reactions & Novel Applications 徐航勋 Email: hxu@ustc.edu.cn https://staff.ustc.edu.cn/~hxu 中国科学技术大学高分子科学与工程系 Heck (Mizoroki-Heck) Reaction

More information

Alkynes contain a C C triple bond

Alkynes contain a C C triple bond Chapter 8: Alkynes: an introduction to organic synthesis Alkynes contain a C C triple bond Acetylene: H-C C-H is the common name for ethyne, used as a torch fuel Alkyne nomenclature follows normal hydrocarbon

More information

Alkenes and Alkynes. Chapter 1.2

Alkenes and Alkynes. Chapter 1.2 Alkenes and Alkynes Chapter 1.2 Unsaturated Hydrocarbons Alkenes and alkynes are unsaturated hydrocarbons An alkene is a hydrocarbon that contains at least one carbon-carbon double bond An alkyne is a

More information

Chapter 25 The Chemistry of Life: Organic Chemistry. 25.1 Some General Characteristics of Organic Molecules

Chapter 25 The Chemistry of Life: Organic Chemistry. 25.1 Some General Characteristics of Organic Molecules Chapter 25 The Chemistry of Life: Organic Chemistry general characteristics of organic molecules introduction to hydrocarbons alkanes unsaturated hydrocarbons functional groups: alcohols and ethers compounds

More information

Transition Metal Catalyzed Coupling Reactions

Transition Metal Catalyzed Coupling Reactions Transition Metal Catalyzed Coupling Reactions Catalytic nucleophilicsubstitution reactions comprise some of the most commonly used catalytic processes in synthetic organic chemistry. The original cross-coupling

More information

Reactions of Aromatic Compounds

Reactions of Aromatic Compounds 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

More information

Identifying an Unknown Substance using Infrared Spectroscopy (IR), Carbon-13 Nuclear Magnetic Resonance ( 13 C NMR), and Proton Nuclear Magnetic

Identifying an Unknown Substance using Infrared Spectroscopy (IR), Carbon-13 Nuclear Magnetic Resonance ( 13 C NMR), and Proton Nuclear Magnetic Identifying an Unknown Substance using Infrared Spectroscopy (I), arbon-13 Nuclear Magnetic esonance ( 13 NM), and Proton Nuclear Magnetic esonance ( 1 NM) Identifying an Unknown Substance using Infrared

More information

Lecture Notes Chem 51B S. King. Chapter 18 Electrophilic Aromatic Substitution

Lecture Notes Chem 51B S. King. Chapter 18 Electrophilic Aromatic Substitution Lecture otes Chem 51B S. King Chapter 18 Electrophilic Aromatic Substitution I. Electrophilic Aromatic Substitution The most characteristic reaction of aromatic compounds is electrophilic aromatic substitution,

More information

Under acidic conditions, carbonyl compounds are protonated on O first, then weak base deprotonates at the α-c to give enol.

Under acidic conditions, carbonyl compounds are protonated on O first, then weak base deprotonates at the α-c to give enol. Substitution reactions of carbonyl compounds at the α-position Carbonyl compounds are acidic at α-c (e.g. C 2 C ); this is because of the electrophilic nature of carbonyl C= bond. The pka values of simple

More information

Chapter 8: Chemistry of Alkynes (C n H 2n-2 )

Chapter 8: Chemistry of Alkynes (C n H 2n-2 ) hapter 8: hemistry of Alkynes ( n 2n-2 ) Bonding & hybridization Both are sp-hybridized Bond angles = 180 o 1 σ + 2 π bonds Linear around lassification R R R' σ bond energy: 88 kcal/mol π bond energy:

More information

CHEMISTRY 263 Module7. Hydrogenation of Alkenes Text Sections: Homework Chapter7: Module8. Alkenes and Alkynes II: Addition reactions

CHEMISTRY 263 Module7. Hydrogenation of Alkenes Text Sections: Homework Chapter7: Module8. Alkenes and Alkynes II: Addition reactions 1 CHEMISTRY 263 Module7. Hydrogenation of Alkenes The Function of the Catalyst - Syn and anti- addition Hydrogenation of Alkynes - Syn- addition of hydrogen: Synthesis of cis-alkenes - Anti addition of

More information

Alkynes and Their Reactions

Alkynes and Their Reactions Alkynes and Their Reactions Naming Alkynes Alkynes are named in the same general way that alkenes are named. In the IUPAC system, change the ane ending of the parent alkane name to the suffix yne. Choose

More information

Carboxylic Acids When a carbonyl carbon also bears a hydroxyl group, then these compounds are appreciably acidic, and are called carboxylic acids.

Carboxylic Acids When a carbonyl carbon also bears a hydroxyl group, then these compounds are appreciably acidic, and are called carboxylic acids. Carboxylic Acids When a carbonyl carbon also bears a hydroxyl group, then these compounds are appreciably acidic, and are called carboxylic acids. R Carboxylic acids are classified according to the substituent

More information

Alkynes: An Introduction to Organic Synthesis

Alkynes: An Introduction to Organic Synthesis Alkynes: An Introduction to Organic Synthesis Alkynes Hydrocarbons that contain carbon-carbon triple bonds Acetylene, the simplest alkyne is produced industrially from methane and steam at high temperature

More information

very strong bases very strong nucleophiles

very strong bases very strong nucleophiles hapter 14: rganometallic ompounds - eagents with carbon-metal bonds 14.1: rganometallic Nomenclature (please read) 3 -Li Butyllithium Mg vinylmagnesium bromide ( 3 ) u - Li Dimethylcopper lithium 14.:

More information

4/18/2011. 9.8 Substituent Effects in Electrophilic Substitutions. Substituent Effects in Electrophilic Substitutions

4/18/2011. 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 information

Chapter 22 Carbonyl Alpha-Substitution Reactions

Chapter 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 information

MOLECULAR REPRESENTATIONS AND INFRARED SPECTROSCOPY

MOLECULAR 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 information

Stille, Suzuki, and Sonogashira Couplings Cross-Coupling reactions: catalyst R-X + R'-M

Stille, Suzuki, and Sonogashira Couplings Cross-Coupling reactions: catalyst R-X + R'-M Stille, Suzuki, and Sonogashira Couplings Cross-Coupling reactions: catalyst -X '-M -' M-X, ' are usually sp 2 hybridized X= (best), Tf, r, Cl M=Sn,, Zn, Zr, n Catalyst= Pd, sometimes Ni Example: Pd(0)

More information

Alkynes: An Introduction to Organic Synthesis. Based on McMurry s Organic Chemistry, 6 th edition, Chapter 8

Alkynes: An Introduction to Organic Synthesis. Based on McMurry s Organic Chemistry, 6 th edition, Chapter 8 Alkynes: An Introduction to Organic Synthesis Based on McMurry s Organic Chemistry, 6 th edition, Chapter 8 Alkynes! Hydrocarbons that contain carbon-carbon triple bonds! Acetylene, the simplest alkyne

More information

ALKENES, ALKYNES and AROMATIC COMPOUNDS Chapter 13

ALKENES, ALKYNES and AROMATIC COMPOUNDS Chapter 13 ALKENES, ALKYNES and AROMATIC COMPOUNDS Chapter 13 13.1 Introduction An ALKENE is a hydrocarbon with a double C bond that looks like C=C An ALKYNE is a hydrocarbon with a triple C bond that looks like

More information

Chapter 17: Reactions of Aromatic Compounds

Chapter 17: Reactions of Aromatic Compounds Chapter 17: Reactions of Aromatic Compounds Electrophilic aromatic substitution (17-1) Most common (normal) reaction of aromatics HNO 3 H 2 SO 4 NO 2 + H2O 452 Similar to alkenes, benzene (aromatics) has

More information

Chapter 14 Conjugated Compounds and Ultraviolet Spectroscopy

Chapter 14 Conjugated Compounds and Ultraviolet Spectroscopy John E. McMurry www.cengage.com/chemistry/mcmurry Chapter 14 Conjugated Compounds and Ultraviolet Spectroscopy Conjugated and Nonconjugated Dienes Compounds can have more than one double or triple bond

More information

An alkyne is a hydrocarbon that contain a Carbon carbon triple bond. Acetylene, the simplest alkyne, widely used in industry for the synthesis of

An alkyne is a hydrocarbon that contain a Carbon carbon triple bond. Acetylene, the simplest alkyne, widely used in industry for the synthesis of Alkynes An alkyne is a hydrocarbon that contain a Carbon carbon triple bond. Acetylene, the simplest alkyne, widely used in industry for the synthesis of acetaldehyde, acetic acid, vinyl chloride O O H

More information

19.2 Halogenation 4/18/2012. Is the reaction substitution, elimination, addition or pericyclic?

19.2 Halogenation 4/18/2012. Is the reaction substitution, elimination, addition or pericyclic? 19.1 Introduction to Electrophilic Aromatic Substitution In Chapter 18, we saw how aromatic C=C double bonds are less reactive than typical alkene double bonds. Consider a bromination reaction: 19.1 Introduction

More information

Chapter 2: Carbon-Carbon Bond Formation 11

Chapter 2: Carbon-Carbon Bond Formation 11 Contents Chapter 1: Introduction 1 1.1 What is Green 1 Principles of Green Chemistry 1 Planning a Green Synthesis 3 1.4 Introduction to Organic Synthesis 9 Chapter 2: Carbon-Carbon Bond Formation 11 2.1

More information

Organic Electronic Devices

Organic Electronic Devices Organic Electronic Devices Week 1: Semiconductor Synthesis and Characterization Lecture 1.3: Synthesis of Low Bandgap Polymers Bryan W. Boudouris Chemical Engineering Purdue University 1 Lecture Overview

More information

AP Chemistry Chapter 22 - Organic and Biological Molecules

AP Chemistry Chapter 22 - Organic and Biological Molecules AP Chemistry Chapter - Organic and Biological Molecules.1 Alkanes: Saturated Hydrocarbons A. Straight-chain Hydrocarbons 1. Straight-chain alkanes have the formula C n H n+. Carbons are sp hybridized The

More information

Suzuki Cross-Coupling. November Chem 4D03

Suzuki Cross-Coupling. November Chem 4D03 Suzuki Cross-Coupling November 8 2008 Chem 4D03 1 The Overall Reaction Reported in 1979 by Akira Suzuki and N. Miyaura Commonly referred to as the Suzuki cross-coupling Palladium catalyzed cross-coupling

More information

Organic Chemistry II with Dr Roche

Organic Chemistry II with Dr Roche Organic Chemistry II with Dr Roche Lecture Notes Email http://roche.camden.rutgers.edu alroche@camden.rutgers.edu Office SCI-311 Labs SCI 328/309/319 Office Phone 856-225-6166 Text (a) Organic Chemistry

More information

Alkanes, Alkenes, Alkynes. Alkanes

Alkanes, Alkenes, Alkynes. Alkanes Alkanes, Alkenes, Alkynes Alkanes Single bonds between carbon atoms General formula: C n H (2n+2) The maximum amount of hydrogen atoms are bonded so alkanes are referred to as saturated 1 IUPAC name Molecular

More information

Learning Guide for Chapter 11 - Alkynes

Learning Guide for Chapter 11 - Alkynes Learning Guide for Chapter 11 - Alkynes Introduction to s - p 1 ybridization and geometry, Reactivity, Types of s, Cyclic s, Physical properties, Spectroscopy, Acidity, Natural occurrence and uses Nomenclature

More information

Interpreting Infrared Spectra Painlessly, Quickly, and Correctly

Interpreting Infrared Spectra Painlessly, Quickly, and Correctly Interpreting Infrared Spectra Painlessly, Quickly, and Correctly Knowing how to interpret infrared (IR) spectra is of immense help to structure determination. Not only will it tell you what functional

More information

Cape Cod Community College

Cape Cod Community College Cape Cod Community College Departmental Syllabus Prepared by the Department of Natural Sciences & Applied Technology Date of Departmental Approval: October 6, 2008 Date approved by Curriculum and Programs:

More information

Unit Vocabulary: o Organic Acid o Alcohol. o Ester o Ether. o Amine o Aldehyde

Unit Vocabulary: o Organic Acid o Alcohol. o Ester o Ether. o Amine o Aldehyde Unit Vocabulary: Addition rxn Esterification Polymer Alcohol Ether Polymerization Aldehyde Fermentation Primary Alkane Functional group Saponification Alkene Halide (halocarbon) Saturated hydrocarbon Alkyne

More information

Chapter 12 Electrophilic and Nucleophilic Aromatic Substitution

Chapter 12 Electrophilic and Nucleophilic Aromatic Substitution Chapter 12 Electrophilic and Nucleophilic Aromatic Substitution CHAPTER 12 Electrophilic and Nucleophilic Aromatic Substitution Aromatic compounds may undergo substitution reactions. Electrophilic aromatic

More information

Mr. Kent s Organic Chemistry Unit Notes I Basic Concepts

Mr. Kent s Organic Chemistry Unit Notes I Basic Concepts Mr. Kent s Organic Chemistry Unit Notes I Basic Concepts A. Organic Chemistry-The study of containing compounds. 1. They occur extensively in nature because all living things are made of containing compounds.

More information

Chapter 7 - Alkenes and Alkynes I

Chapter 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

Protonation. favored H 3 O + R O O H

Protonation. favored H 3 O + R O O H arboxylic Acids arboxylic acids have one property that distinguishes them from most other organic compounds they re acidic. Now not as acidic as fuming sulfuric acid, but still pretty darned acidic. The

More information

Organometallics Study Seminar Chapter 13: Metal-Ligand Multiple Bonds

Organometallics 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 information

Organic Chemistry II / CHEM 252 Chapter 16 Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group

Organic Chemistry II / CHEM 252 Chapter 16 Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group Organic Chemistry II / CHEM 252 Chapter 16 Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group Bela Torok Department of Chemistry University of Massachusetts Boston Boston, MA 1 Nomenclature

More information

Chapter 24 Organic Chemistry

Chapter 24 Organic Chemistry Chapter 24 Organic Chemistry Student: 1. The general formula for alkenes is A. C n H 2n+2 B. C 2n H 2n C. C n H n+2 D. C n H 2n E. C n H 2n-2 2. The general formula of an alkane is A. C n H 2n B. C n H

More information

Look for absorption bands in decreasing order of importance:

Look for absorption bands in decreasing order of importance: Infrared spectra: It is important to remember that the absence of an absorption band can often provide more information about the structure of a compound than the presence of a band. Be careful to avoid

More information

Worksheet Addition reactions

Worksheet Addition reactions Worksheet Addition reactions The presence of electrons in alkenes allows addition reactions to take place. In general: In each case, the bond is broken and the e - are used to form a new bond in the product

More information

It does not react N.R.

It does not react N.R. Benzene versus yclohexene versus yclohexadiene 1 l l cyclohexene l l cyclohexadiene l Expect this to react similarly "cyclohexatriene" It does not react l N.R. benzene Benzene is resonance stabilized,

More information

Alkenes: Alkynes: Example: What are all the structural possibilities for C 3 H 4? Unsaturated hydrocarbons: Bonding Patterns of Multiple Bonds

Alkenes: Alkynes: Example: What are all the structural possibilities for C 3 H 4? Unsaturated hydrocarbons: Bonding Patterns of Multiple Bonds Chapter 3 Organic Chem: Alkenes & Alkynes Don t need to know the following reactions found on summary pages 110-112: 1. Hydroboration-Oxidation 2. Cycloaddition to Conjugated Dienes 3. Alkyne reaction

More information

Chapter 10 Conjugation in Alkadienes and Allylic Systems

Chapter 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 information

Introduction to Organic Chemistry Syllabus Day 1: Session 1 (evening session):

Introduction to Organic Chemistry Syllabus Day 1: Session 1 (evening session): Introduction to Organic Chemistry Syllabus Day 1: Session 1 (evening session): 1. Introduction to Organic Chemistry: 2. General discussion about what is chemistry? 3. What is organic chemistry? 4. What

More information

Joesphine Eshon & Prithvi Vangal 11 th November 2014

Joesphine Eshon & Prithvi Vangal 11 th November 2014 Joesphine Eshon & Prithvi Vangal 11 th November 2014 1 Introduction Cross-coupling reactions: A. Negishi* Reaction B. Heck* Reaction C. Stille Reaction D. Suzuki* Reaction E. Sonogashira Reaction F. Buchwald-Hartwig

More information

13.1 Alcohols and Phenols. Nomenclature. Nomenclature. Nomenclature. Alcohols possess a hydroxyl group ( OH). Hydroxyl groups in natural compounds.

13.1 Alcohols and Phenols. Nomenclature. Nomenclature. Nomenclature. Alcohols possess a hydroxyl group ( OH). Hydroxyl groups in natural compounds. 13.1 Alcohols and Phenols Alcohols possess a hydroxyl group ( OH). 13.1 Alcohols and Phenols Hydroxyl groups in natural compounds. Hydroxyl groups are extremely common in natural compounds. 13-1 13-2 13.1

More information

CHEM 121 Chapter 13. Name: Date:

CHEM 121 Chapter 13. Name: Date: CHEM 121 Chapter 13. Name: Date: 1. The common feature found in all unsaturated hydrocarbons is A) one or more carbon-carbon double bonds. B) one or more carbon-carbon triple bonds. C) one or more carbon-carbon

More information

Organic Chemistry Questions

Organic Chemistry Questions Organic Chemistry Questions 1 Molecules of 1-propanol and 2-propanol have different (1) percentage compositions (2) molecular masses (3) molecular formulas (4) structural formulas 2 Which compound is an

More information

Friedel Crafts Acylation

Friedel Crafts Acylation Friedel Crafts Acylation An acyl chloride or an acid anhydride is the source of the acyl group. A Lewis acid (AlCl 3 ) is required. The Mechanism for Friedel Crafts Acylation The electrophile adds to the

More information

Electrophilic Aromatic Substitution

Electrophilic 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 information

How to Quickly Solve Spectrometry Problems

How 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 information

Electrophilic Aromatic Substitution Reactions

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 information

ALCOHOLS: Properties & Preparation

ALCOHOLS: 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 information

Carboxylic Acid Derivatives and Nitriles

Carboxylic 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 information

Electrophilic Addition Reactions

Electrophilic 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 information

Benzene Benzene is best represented as a resonance hybrid:

Benzene 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 information

Carbocations are electrophiles, and can therefore be useful reagents for forming new C-C bonds in EAS processes.

Carbocations are electrophiles, and can therefore be useful reagents for forming new C-C bonds in EAS processes. 1 (Continuation of Chapter 17 ) VIII. Friedel-Crafts Alkylation Carbocations are electrophiles, and can therefore be useful reagents for forming new C-C bonds in EAS processes. Friedal and Craft demonstrated

More information

But in organic terms: Oxidation: loss of H 2 ; addition of O or O 2 ; addition of X 2 (halogens).

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 information

Survival Organic Chemistry Part I: Molecular Models

Survival 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 information

Chapter 4: Alkenes and Alkynes. Degree of unsaturation

Chapter 4: Alkenes and Alkynes. Degree of unsaturation hapter 4: Alkenes and Alkynes Unsaturated ydrocarbon: ontains one or more carbon-carbon double or triple bonds or benzene-like rings. Alkene: contains a carbon-carbon double bond and has the general formula

More information

Chapter 17 Alcohols and Phenols

Chapter 17 Alcohols and Phenols John E. McMurry http://www.cengage.com/chemistry/mcmurry Chapter 17 Alcohols and Phenols Alcohols and Phenols Alcohols contain an OH group connected to a saturated C (sp 3 ) They are important solvents

More information

ORGANIC AND BIOLOGICAL MOLECULES

ORGANIC AND BIOLOGICAL MOLECULES APTER TWENTY-TW RGANI AND BILGIAL MLEULES For Review 1. A hydrocarbon is a compound composed of only carbon and hydrogen. A saturated hydrocarbon has only carbon-carbon single bonds in the molecule. An

More information

Arene(Ar-H) is the generic term for an aromatic hydrocarbon

Arene(Ar-H) is the generic term for an aromatic hydrocarbon 4.8 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 from an arene Aromatic compounds undergo

More information

Determining the Structure of an Organic Compound

Determining 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 information

Chapter 13 Organic Chemistry

Chapter 13 Organic Chemistry Chapter 13 Organic Chemistry 13-1. Carbon Bonds 13-2. Alkanes 13-3. Petroleum Products 13-4. Structural Formulas 13-5. Isomers 13-6. Unsaturated Hydrocarbons 13-7. Benzene 13-8. Hydrocarbon Groups 13-9.

More information

Organic Chemistry II / CHEM 252 Chapter 20 Amines

Organic Chemistry II / CHEM 252 Chapter 20 Amines Organic Chemistry II / CHEM 252 Chapter 20 Amines Bela Torok Department of Chemistry University of Massachusetts Boston Boston, MA 1 Nomenclature Nomenclature Primary amines are named in systematic (IUPAC)

More information

Stability of vinyl C+ is about the same as H 3 C+. NOT ASSISTED!

Stability of vinyl C+ is about the same as H 3 C+. NOT ASSISTED! rganic hemistry Interactive Notes hapter 8: Alkynes Naming Alkynes Structure ommon Name IUPA Acetylene ethyne methyl acetylene propyne dimethyl acetylene -butyne ethyl acetylene -butyne =- as substituent

More information

Lecture 8. Friedel-Crafts reaction: Mechanism: Carbocation is the reactive electrophile. AlCl4- picks up a proton.

Lecture 8. Friedel-Crafts reaction: Mechanism: Carbocation is the reactive electrophile. AlCl4- picks up a proton. New Section 3 Page 1 2:37 PM Friedel-Crafts reaction: Mechanism: Carbocation is the reactive electrophile. AlCl4- picks up a proton. Limitations come from the mechanism: Carbocationic intermediates prone

More information

Conjugation is broken completely by the introduction of saturated (sp 3 ) carbon:

Conjugation 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 information

Chapter 7 Organometallic Reagents. Stability and Handling

Chapter 7 Organometallic Reagents. Stability and Handling Chapter 7 Organometallic Reagents Stability and Handling 1 Thermal Stability Titration of Alkyllithiums 2 Reactions of Alkyllithiums with Solvents Additives for Alkyllithiums 3 Enhanced Basicity of Alkyllithiums

More information

for excitation to occur, there must be an exact match between the frequency of the applied radiation and the frequency of the vibration

for 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 information

Monday, September 10th

Monday, September 10th Monday, September 10th Review Chapter 11 iclicker Quiz #1 Chapter 12 Chapter 13(maybe) Group assignment Keep checking the class webpage at www.bhsu.edu/danasunskis. Go to the course tab then CHEM107 Lecture

More information

CHEM 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. 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 information

Chapter Thirteen. Alkenes, Alkynes, and Aromatic Compounds

Chapter Thirteen. Alkenes, Alkynes, and Aromatic Compounds Chapter Thirteen Alkenes, Alkynes, and Aromatic Compounds Saturated: A molecule whose carbon atoms bond to the maximum number of hydrogen atoms. Unsaturated: A molecule that contains a carbon carbon multiple

More information

Unit 2 Review: Answers: Review for Organic Chemistry Unit Test

Unit 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 information

Last Time: Alkanes (C n H 2n+2 ) Last Time: Organic Compounds. Last Time: Intermolecular Forces- BP Increases w/ Increasing Size

Last Time: Alkanes (C n H 2n+2 ) Last Time: Organic Compounds. Last Time: Intermolecular Forces- BP Increases w/ Increasing Size Announcements & Agenda (0/02/07) Welcome Visitors! Please make yourselves comfortable; we will start with a quiz Mid-term grades are only based on lecture I will give you detailed grade sheets on Monday

More information

Chapter 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. 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 information

Nomenclature. IUPAC nomenclature for organic chemistry

Nomenclature. IUPAC nomenclature for organic chemistry Nomenclature IUPAC nomenclature for organic chemistry What is IUPAC nomenclature? A systematic method of naming organic chemical compounds as recommended by the International Union of Pure and Applied

More information

Conjugation is broken completely by the introduction of saturated (sp3) carbon:

Conjugation 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 information

Chapter 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 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 information

Chapter 13 Alkenes and Alkynes

Chapter 13 Alkenes and Alkynes hapter 13 Alkenes and Alkynes Types of Bonds Alkanes and haloalkanes consist of atoms held together by bonds. These can also be called sigma bonds (σ bonds) which means that the orbitals of each atom overlap

More information

Benzene does not undergo electrophilic addition. It undergoes electrophilic aromatic substitution maintaining the aromatic core

Benzene does not undergo electrophilic addition. It undergoes electrophilic aromatic substitution maintaining the aromatic core Substitution Reactions of Benzene and Its Derivatives Benzene does not undergo electrophilic addition It undergoes electrophilic aromatic substitution maintaining the aromatic core Electrophilic aromatic

More information

Benzene benzene aromatic hydrocarbons aromatic not not

Benzene benzene aromatic hydrocarbons aromatic not not Benzene 1 NT 87 90 ompound 87 has the formula 6 6, is known as benzene, and it is a hydrocarbon derived from petroleum distillates. Benzene is the parent compound for a class of compounds known as aromatic

More information

Study Guide Chapters 19-20 Alkanes, Alkenes and Alkynes

Study Guide Chapters 19-20 Alkanes, Alkenes and Alkynes Study Guide Chapters 19-20 Alkanes, Alkenes and Alkynes 1) Carbon-Carbon Bonding in Alkanes (C-C), Alkenes (C=C) and Alkynes (C C). Understand the hybridization of atomic orbitals (ground state promotion

More information

CHEM3115 Synthetic Medicinal Chemistry

CHEM3115 Synthetic Medicinal Chemistry CHEM3115 Synthetic Medicinal Chemistry Lecture 6 Dr Chris McErlean Rm 518a Ext. 13970 http://www.chem.uysd.edu.au/~mcerlean/ C.McErlean@chem.usyd.edu.au Lecture 19 Carbonyl Chemistry. Reducing reagents:

More information

IDENTIFYING STUDENTS MISCONCEPTIONS IN A-LEVEL ORGANIC CHEMISTRY

IDENTIFYING STUDENTS MISCONCEPTIONS IN A-LEVEL ORGANIC CHEMISTRY IDENTIFYING STUDENTS MISCONCEPTIONS IN A-LEVEL ORGANIC CHEMISTRY Lim Choon Huat Bryan Innova Junior College Abstract In recent years, research in science education has been focused on identifying and addressing

More information

Functional Groups and Chemical Families

Functional Groups and Chemical Families Functional Groups and Chemical Families Although there are a wide variety of organic compounds, most of them are composed of the elements from the upper right hand portion of the periodic chart: C, H,

More information

Electrophilic Reactions on Aromatic Compounds Monosubstitution. Dr. Sapna Gupta

Electrophilic Reactions on Aromatic Compounds Monosubstitution. Dr. Sapna Gupta Electrophilic Reactions on Aromatic Compounds Monosubstitution Dr. Sapna Gupta Electrophilic Aromatic Substitution Arene (Ar-H) is the generic term for an aromatic hydrocarbon The aryl group (Ar) is derived

More information

AROMATICITY. Chapter 8 REACTIONS OF BENZENE ORGANIC CHEMISTRY, 2 ND EDITION PAULA YURKANIS BRUICE

AROMATICITY. Chapter 8 REACTIONS OF BENZENE ORGANIC CHEMISTRY, 2 ND EDITION PAULA YURKANIS BRUICE ORGANIC CHEMISTRY, 2 ND EDITION PAULA YURKANIS BRUICE Chapter 8 AROMATICITY REACTIONS OF BENZENE RAED M. AL-ZOUBI, ASSISTANT PROFESSOR OF CHEMISTRY DEPARTMENT OF CHEMISTRY - N 4 L 0 JORDAN UNIVERSITY OF

More information

Alcohols (R-OH) and Alkyl halides R-X (X = F, Cl, Br, I) Alcohols. Suffix:

Alcohols (R-OH) and Alkyl halides R-X (X = F, Cl, Br, I) Alcohols. Suffix: Alcohols (R-O) and Alkyl halides R-X (X = F, Cl,, I) Alcohols Alcohols contain a R-O functional group. Primary, secondary or tertiary? O O O Nomenclature: Suffix: numbering scheme: The number locating

More information

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. CHM 210 Chemistry Homework #6 Alkanes (Ch. 10) Due: MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 1) Compounds that have the same molecular formula

More information

HOMEWORK PROBLEMS: IR SPECTROSCOPY AND 13C NMR. The peak at 1720 indicates a C=O bond (carbonyl). One possibility is acetone:

HOMEWORK PROBLEMS: IR SPECTROSCOPY AND 13C NMR. The peak at 1720 indicates a C=O bond (carbonyl). One possibility is acetone: HMEWRK PRBLEMS: IR SPECTRSCPY AND 13C NMR 1. You find a bottle on the shelf only labeled C 3 H 6. You take an IR spectrum of the compound and find major peaks at 2950, 1720, and 1400 cm -1. Draw a molecule

More information

C-C Bond Formation - Organometallic Coupling Reactions (McM 7th ed. 10.8, Lab ex 10) Alkenes (McM 7th ed ) Dienes (McM 7th ed

C-C Bond Formation - Organometallic Coupling Reactions (McM 7th ed. 10.8, Lab ex 10) Alkenes (McM 7th ed ) Dienes (McM 7th ed C-C Bond Formation - Organometallic Coupling eactions (McM 7th ed. 10.8, Lab ex 10) Alkenes (McM 7th ed. 11.8 11.9) Dienes (McM 7th ed. 14.1 14.3) C-C Bond Formation - Organometallic Coupling eactions

More information

1 Lecture 5 Resonance 1. Lone pair next to empty 2p orbital

1 Lecture 5 Resonance 1. Lone pair next to empty 2p orbital 1 Lecture 5 esonance 1. Lone pair next to empty 2p orbital sp 2 + is more common sp + is less common + needs electrons, has to overlap with a. an adjacent 2p lone pair with electrons b. an adjacent pi

More information

Topic: Intermolecular forces. 7. Which compound would you expect to have the lowest boiling point? A) NH 2 B) NH 2

Topic: Intermolecular forces. 7. Which compound would you expect to have the lowest boiling point? A) NH 2 B) NH 2 SS2009-08-24 MULTIPLE CICE QUESTIS Part 2: unktionella grp intermolekylära krafter (Answers on pages 17-18) Topic: Intermolecular forces 1. Which compound would you expect to have the lowest boiling point?

More information

Homework Chapter 21 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions mandatory problems are highlighted (up to page 16)

Homework Chapter 21 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions mandatory problems are highlighted (up to page 16) Homework Chapter 21 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions mandatory problems are highlighted (up to page 16) SHORT ANSWER IUPAC Naming Instructions: Provide proper IUPAC

More information