Chapter 19: Aldehydes and Ketones: Nucleophilic Addition Reactions NOMENCLATURE OF ALDEHYDES AND KETONES NATURAL OCCURRENCE OF ALDEHYDES

Size: px
Start display at page:

Download "Chapter 19: Aldehydes and Ketones: Nucleophilic Addition Reactions NOMENCLATURE OF ALDEHYDES AND KETONES NATURAL OCCURRENCE OF ALDEHYDES"

Transcription

1 Chapter 19: Aldehydes and Ketones: Nucleophilic Addition eactions The Carbonyl Group C carbon with a double bond to oxygen it is planar has bond angles of 120 is permanently polarized NENCLATUE F ALDEYDES AND KETNES IUPAC uses endings on the alkane name to indicate the functional group. These ones are easy! Aldehyde Ketone Br IUPAC rules select the longest chain containing the principal functional group number such that it gets the lowest possible number attach the appropriate ending add all other substituents and stereochemistry as you normally would E-7-bromo-4,4-dimethyloct-2-enal NATUAL CCUENCE F ALDEYDES Benzaldehyde occurs: almonds, defensive pheromones use: almond extract Vanillin occurs: vanilla bean, potato parings use: synthetic vanilla Geranial occurs: as alcohol in essence of rose use: perfumery C C C 3 C

2 NATUAL CCUENCE F ALDEYDES Glucose occurs: foodstuffs use: energy source/metabolism etinal occurs: Vitamin A use: vision C C 2 C NATUAL CCUENCE F KETNES Camphor occurs: in the camphor tree use: perfumery, explosives Cortisone occurs: hormone/adrenal gland use: relief of inflammation NATUAL CCUENCE F KETNES Fructose occurs: in sugar (sucrose) use: sweetener C 2 C 2 PEPAATIN F ALDEYDES PCC C 2 Cl 2 78% oneybee pheromone use: attractive substance of Queen bee C N PCC Cr 3 Cl Swern oxidation DS (CCl) 2 then Et 3 N C 2 Cl 2-60 Swern 99% as well as a selective oxidation of 1 alcohols, we could perform a selective reduction from acid derivatives: reducing conditions required in the second stage to produce the aldehyde this can be Zn / Ac or e 2 S

3 PEPAATIN F KETNES K 2 Cr S 4, 2 96% Kn 4 Ac, 2 96% XIDATINS F ALDEYDES EACTINS F ALDEYDES & KETNES Carbonyl groups are polar and have a dipole moment: 1 1 This leads naturally to their reactions with nucleophiles Nu 1 Nu 1

4 what kind of nucleophiles are we talking about? Steric effect Electronic effect Base catalysis Let us deal with mechanism first, then the substituent effect

5 Acid catalysis 2 ' K + K ' 2.2 x 10 3 C 3 1 (C 2 ) 2 C C(C 3 ) Ph 0.3 x 10-3 C 3 C x 10-3 C 3 Ph 6.6 x 10-6 Ph Ph 1.2 x 10-7 ClC 2 37 CCl x 10 4 ClC 2 ClC 2 10 CF 3 CF 3 too large to measure 2 + ' K 2.2 x 10 3 C 3 1 (C 2 ) 2 C C(C 3 ) Ph 0.3 x 10-3 C 3 C x 10-3 C 3 Ph 6.6 x 10-6 Ph Ph 1.2 x 10-7 ClC 2 37 CCl x 10 4 ClC 2 ClC 2 10 CF 3 CF 3 too large to measure K ' 2 + ' K K 2.2 x 10 3 C 3 1 (C 2 ) 2 C C(C 3 ) Ph 0.3 x 10-3 C 3 C x 10-3 C 3 Ph 6.6 x 10-6 Ph Ph 1.2 x 10-7 ClC 2 37 CCl x 10 4 ClC 2 ClC 2 10 CF 3 CF 3 too large to measure ' 2 + ' K ' some adducts are just not stable: K 2.2 x 10 3 C 3 1 (C 2 ) 2 C C(C 3 ) Ph 0.3 x 10-3 C 3 C x 10-3 C 3 Ph 6.6 x 10-6 Ph Ph 1.2 x 10-7 ClC 2 37 CCl x 10 4 ClC 2 ClC 2 10 CF 3 CF 3 too large to measure

6 CYANYDINS IN NATUE Addition of organometallic reagents to aldehydes & ketones andelonitrile a defensive secretion in the millipede Apheloria corrugata CN Amygdalin / Laetrile occurs in pits of apricots, plums, bitter almonds, lima beans, casava CN Depending on the starting material, different types of targets may be synthesized S reagent target comments gx Li primary alcohol with one added carbon ' gx ' Li secondary alcohol ' ' gx ' ' Li tertiary alcohol gx Li primary alcohol with two added carbons

7 etrosynthetic analysis for a secondary alcohol etrosynthetic analysis for a tertiary alcohol X = gbr, Li X = Br, Cl, I X = gbr, Li X = Br, Cl, I Addition of nitrogen nucleophiles to the carbonyl group i the addition phase Addition of nitrogen nucleophiles to the carbonyl group ii the elimination phase C 3 C N nucleophilic attack on carbonyl carbon C 3 N B + B protonation and deprotonation C 3 N addition compound B + C 3 N protonation of hydroxyl group 2 C 3 N loss of water 2 C 3 N deprotonation B C 3 N imine this, and the following slide, are a re-write of the text Fig 19.8 N 2 + K + N 2 + N 83% N 95% Enamines form when the reagent has only one which may be eliminated

8 we can see the difference here: 1 amine yields an imine 2 amine gives the enamine Where is this important??? phenylpyruvate Transamination L-phenylalanine deaminase N 2 P N pyridoxamine C 2 N 2 C 3 L-amino acid sythetase P = phosphate C P N C 3 pyridoxal phosphate C N 2 P imine 1 C N P + A useful extension of this type of reaction is the Wolff-Kischner eduction C C N P 2 N P imine 2 P = the rest of the cofactor solvent DS for those of you who want to know what s going on: Addition of alcohols: formation of hemiacetals and acetals B + B C C C 3 C 3 3 C 3 C 3 B protonation of the carbonyl group nucleophilic attack on carbonyl carbon deprotonation Sequence of events: protonate attack deprotonate this one can be acid or base catalyzed C 3 C 3 a hemiacetal -- one, one

9 Conversion of a hemiacetal to an acetal Glucose as a hemiacetal C 3 B + C 3 protonation of thehydroxyl group C C 3 loss of water C 3 C 3 C 3 resonance stabilized carbocation C 3 C 2 C 2 C C 3 C 3 C 3 C 3 C 3 glucose in its open chain conformation glucose cyclized as a hemiacetal new chiral centre: two diastereomers formed C 3 C 3 B C 3 C 3 nucleophilic attack on carbonyl carbon deprotonation an acetal -- two groups see text p 954 this one can be only be acid catalyzed altose is both an acetal and a hemiacetal C 2 acetal C 2 hemiacetal β and C 2 are cis α and C 2 are trans 4--(α-D-glucopyranosyl)-β-D-glucopyranose Sucrose is an acetal in both rings C 2 acetal C 2 acetal pyranose = 6-membered ring C 2 furanose = 5-membered ring see p 967 β-d-fructofuranosyl-α-d-glucopyranoside see p 969 Acetals as protecting groups The text deals with the following example Et Brg what is wrong, of course, is that the two functional groups in this molecule are incompatible so, we must protect the ketone before making the Grignard We will do a different one. Suppose you want to make the compound below Brg the logical disconnection is one of the C-C bonds on the alcohol carbon, and it makes most sense for this not to be one of the ring bonds. but, what is wrong with this? Br + Brg + Br remember, these are stable to base and Nu dry Et g dry Et 2 Brg dilute acid work-up not only hydrolyzes the g salts off, but also cleaves the acetal

10 The Wittig reaction This is the reaction of a carbanionic component with a carbonyl component to produce a new alkene. The carbanionic component is readily formed using triphenylphosphine 3 C PPh 3 nucleophilic P displaces leaving group I I TF Ph 3 P C 2 Bu Li base pulls off acidic proton α to P + I Ph 3 P C 2 + Bu + LiI Ph 3 P C 2 Wittig reagent is stabilized by resonance The huge advantage is that you know exactly where, in the molecule, the new double fond forms. An example: etrosynthetic analysis in a Wittig-based reaction Target: Ph 3 P PPh 3 the normal Wittig reagent is primary, so one would by preference choose the blue route There is one further aspect of this reaction which makes it even more synthetically useful one can control the stereochemistry of the resulting alkene to be E- or Z- Prostaglandin F 2α This target has two alkenes, which we can stereoselectively produce by simple modification of the Wittig reaction conditions C 2 for the lower side chain: Ac P C 5 11 (Et)2 Na C 2 SC 3 Ac stereoselection for E-alkene due to stabilized ylide

11 for the upper side chain: We have previously looked at conjugated dienes, now let us look at conjugated carbonyl systems: enones and enals Br Ph 3 P + (C 2 ) 4 C 2 C 2 once again, this reacts like a single functional group: TP C 5 11 TP Na C 2 SC 3 TP TP stereoselection for Z-alkene normal non-stabilized ylide both carbonyl carbon and β-carbon are electrophilic Essentially this means that this type of double bond is reactive towards electrophiles, whereas a normal double bond would not be When the addition occurs to the β-carbon, it is called conjugate addition Amines add readily: ther adducts: % KCN CN Ph Ph Ac Ph Ph 93%

12 rganometallics can add in a conjugate fashion, but they must be modified from the normal g or Li reagent: which then leads to regioselectivity: nce again, there are good synthetic possibilities. Let us go back to prostaglandins and see what we might do. C TBDS normally we use copper to effect the ichael addition of an organometallic, but many other metals can be used. In this case, Noyori found that zinc worked very well: Li e 2 Zn 2 2 TBDS = t-butyldimethylsilyl Exclusively 3,4-trans and, notice that the large group adjacent to the reacting site completely governs the face of the double bond which is attacked It turns out that the intermediate in this first addition is an enolate -- we can take advantage of that to introduce the second side chain Li - e 2ZnLi + e 2Zn TBDS -78 ºC 1h. I C 2Et PA, -78ºC to -40ºC 71% only product exclusively trans- anti C 2Et

ORGANIC - BROWN 8E CH ALDEHYDES AND KETONES.

ORGANIC - BROWN 8E CH ALDEHYDES AND KETONES. !! www.clutchprep.com CONCEPT: ALDEHYDE NOMENCLATURE Replace the suffix of the alkane -e with the suffix On the parent chain, the carbonyl is always terminal, and receive a location As substituents, they

More information

ORGANIC - CLUTCH CH ALDEHYDES AND KETONES: NUCLEOPHILIC ADDITION

ORGANIC - CLUTCH CH ALDEHYDES AND KETONES: NUCLEOPHILIC ADDITION !! www.clutchprep.com CONCEPT: ALDEHYDE NOMENCLATURE Replace the suffix of the alkane -e with the suffix On the parent chain, the carbonyl is always terminal, and receive a location As substituents, they

More information

Chapter 20: Aldehydes and Ketones

Chapter 20: Aldehydes and Ketones Chapter 20: Aldehydes and Ketones [Chapter 20 Sections: 20.1-20.7, 20.9-10.10, 20.13] 1. Nomenclature of Aldehydes and Ketones ' ketone aldehyde f both aldehydes and ketones, the parent chain is the longest

More information

Additions to the Carbonyl Groups

Additions to the Carbonyl Groups Chapter 18 Additions to the Carbonyl Groups Nucleophilic substitution (S N 2andS N 1) reaction occurs at sp3 hybridized carbons with electronegative leaving groups Why? The carbon is electrophilic! Addition

More information

Loudon Chapter 19 Review: Aldehydes and Ketones CHEM 3331, Jacquie Richardson, Fall Page 1

Loudon Chapter 19 Review: Aldehydes and Ketones CHEM 3331, Jacquie Richardson, Fall Page 1 Loudon Chapter 19 eview: Aldehydes and Ketones CEM 3331, Jacquie ichardson, Fall 2010 - Page 1 Beginning with this chapter, we re looking at a very important functional group: the carbonyl. We ve seen

More information

Chapter 16 Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group

Chapter 16 Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group Chapter 16 Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group Nomenclature of Aldehydes and Ketones Aldehydes are named by replacing the -e of the corresponding parent alkane with -al

More information

Chem 263 Nov 14, e.g.: Fill the reagents to finish the reactions (only inorganic reagents)

Chem 263 Nov 14, e.g.: Fill the reagents to finish the reactions (only inorganic reagents) hem 263 ov 14, 2013 More examples: e.g.: Fill the reagents to finish the reactions (only inorganic reagents) Br 2 hv Br a 2 r 4 S 2 or swern oxidation Mg Li 0 0 MgBr Li e.g. : Fill the reagents (any reagents

More information

Chapter 16. Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group. Physical Properties of Aldehydes and Ketones. Synthesis of Aldehydes

Chapter 16. Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group. Physical Properties of Aldehydes and Ketones. Synthesis of Aldehydes Nomenclature of Aldehydes and Ketones Chapter 16 Aldehydes and Ketones I. Aldehydes replace the -e of the parent alkane with -al The functional group needs no number Nucleophilic Addition to the Carbonyl

More information

Chapter 16 Aldehydes and Ketones I Nucleophilic Addition to the Carbonyl Group

Chapter 16 Aldehydes and Ketones I Nucleophilic Addition to the Carbonyl Group Chapter 16 Aldehydes and Ketones I Nucleophilic Addition to the Carbonyl Group Nomenclature of Aldehydes and Ketones Aldehydes are named by replacing the -e of the corresponding parent alkane with -al

More information

Carbonyl Compounds. Introduction

Carbonyl Compounds. Introduction Carbonyl Compounds Introduction 1 Introduction Two broad classes of compounds contain the carbonyl group: [1] Compounds that have only carbon and hydrogen atoms bonded to the carbonyl [2] Compounds that

More information

Chapter 20: Aldehydes and Ketones

Chapter 20: Aldehydes and Ketones hapter 20: Aldehydes and Ketones [hapter 20 Sections: 20.1-20.7, 20.9-10.10, 20.13] 1. Nomenclature of Aldehydes and Ketones ketone ' aldehyde 2. eview of the Synthesis of Aldehydes and Ketones Br Br f

More information

CHM 292 Final Exam Answer Key

CHM 292 Final Exam Answer Key CHM 292 Final Exam Answer Key 1. Predict the product(s) of the following reactions (5 points each; 35 points total). May 7, 2013 Acid catalyzed elimination to form the most highly substituted alkene possible

More information

Chem 263 Notes March 2, 2006

Chem 263 Notes March 2, 2006 Chem 263 Notes March 2, 2006 Average for the midterm is 102.5 / 150 (approx. 68%). Preparation of Aldehydes and Ketones There are several methods to prepare aldehydes and ketones. We will only deal with

More information

TOPIC 3 - ALDEHYDES AND KETONES (Chapters 12 & 16)

TOPIC 3 - ALDEHYDES AND KETONES (Chapters 12 & 16) TPIC 3 - ALDEYDES AND KETNES (Chapters 12 & 16) Lecture 15 Web12 12.1 Introduction 16.1 Introduction 16.2 Nomenclature of Aldehydes and Ketones 16.3 ysical Properties 12.2 xidation Reduction Reactions

More information

Chapter 18: Carbonyl Compounds II

Chapter 18: Carbonyl Compounds II Chapter 18: Carbonyl Compounds II Learning bjectives: 1. ecognize and assign names to aldehydes and ketones. 2. Write the mechanism for nucleophilic addition and nucleophilic addition-elimination reactions

More information

Chapter 17: Carbonyl Compounds II

Chapter 17: Carbonyl Compounds II Chapter 17: Carbonyl Compounds II Learning bjectives: 1. ecognize and assign names to aldehydes and ketones. 2. Write the mechanism for nucleophilic addition and nucleophilic addition-elimination reactions

More information

Chapter 9 Aldehydes and Ketones

Chapter 9 Aldehydes and Ketones Chapter 9 Aldehydes and Ketones 9.1 Nomenclature of Aldehydes and Ketones Aldehydes are named by replacing the -e of the corresponding parent alkane with -al The aldehyde functional group is always carbon

More information

Chapter 20: Aldehydes and Ketones

Chapter 20: Aldehydes and Ketones hem A225 Notes Page 67 I. Introduction hapter 20: Aldehydes and Ketones Aldehydes and ketones contain a carbonyl group (=) with no other heteroatoms attached. An aldehyde has at least one hydrogen attached;

More information

Ch 19 Aldehydes and Ketones

Ch 19 Aldehydes and Ketones Ch 19 Aldehydes and Ketones Aldehydes (RCHO), with the exception of formaldehyde (H 2 CO), are compounds with both an H and an organic group attached to a carbonyl. Ketones (R 2 CO) are compounds with

More information

MCAT Organic Chemistry Problem Drill 10: Aldehydes and Ketones

MCAT 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 information

Topic 9. Aldehydes & Ketones

Topic 9. Aldehydes & Ketones Chemistry 2213a Fall 2012 Western University Topic 9. Aldehydes & Ketones A. Structure and Nomenclature The carbonyl group is present in aldehydes and ketones and is the most important group in bio-organic

More information

Chapter 17 Aldehydes and Ketones

Chapter 17 Aldehydes and Ketones hapter 17 Aldehydes and Ketones arbonyl Groups polarized (1) Aldehydes and Ketones ' aldehydes ketones : and : are poor leaving groups (2) arboxylic Acid Derivatives l ' ' 2 carboxylic acid substituent

More information

Chapter 9 Aldehydes and Ketones Excluded Sections:

Chapter 9 Aldehydes and Ketones Excluded Sections: Chapter 9 Aldehydes and Ketones Excluded Sections: 9.14-9.19 Aldehydes and ketones are found in many fragrant odors of many fruits, fine perfumes, hormones etc. some examples are listed below. Aldehydes

More information

Chapter 12. Alcohols from Carbonyl Compounds Oxidation-Reduction & Organometallic Compounds. Structure

Chapter 12. Alcohols from Carbonyl Compounds Oxidation-Reduction & Organometallic Compounds. Structure Chapter 12 Alcohols from Carbonyl Compounds xidation-eduction & rganometallic Compounds Created by Professor William Tam & Dr. Phillis Chang Structure ~ 120 o ~ 120 o C ~ 120 o Carbonyl carbon: sp 2 hybridized

More information

Chapter 18: Ketones and Aldehydes. I. Introduction

Chapter 18: Ketones and Aldehydes. I. Introduction 1 Chapter 18: Ketones and Aldehydes I. Introduction We have already encountered numerous examples of this functional group (ketones, aldehydes, carboxylic acids, acid chlorides, etc). The three-dimensional

More information

Organic Chemistry, Third Edition. Janice Gorzynski Smith University of Hawai i. Chapter 21. Aldehydes and Ketones Nucleophilic Addition

Organic Chemistry, Third Edition. Janice Gorzynski Smith University of Hawai i. Chapter 21. Aldehydes and Ketones Nucleophilic Addition Organic Chemistry, Third Edition Janice Gorzynski Smith University of Hawai i Chapter 21 Aldehydes and Ketones Nucleophilic Addition Prepared by Rabi Ann Musah State University of New York at Albany Copyright

More information

1. Radical Substitution on Alkanes. 2. Radical Substitution with Alkenes. 3. Electrophilic Addition

1. 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 information

Lecture Notes Chem 51C S. King. Chapter 20 Introduction to Carbonyl Chemistry; Organometallic Reagents; Oxidation & Reduction

Lecture Notes Chem 51C S. King. Chapter 20 Introduction to Carbonyl Chemistry; Organometallic Reagents; Oxidation & Reduction Lecture Notes Chem 51C S. King Chapter 20 Introduction to Carbonyl Chemistry; rganometallic Reagents; xidation & Reduction I. The Reactivity of Carbonyl Compounds The carbonyl group is an extremely important

More information

p Bonds as Electrophiles

p Bonds as Electrophiles Chapter 7 p Bonds as Electrophiles REACTIONS OF CARBONYLS AND RELATED FUNCTIONAL GROUPS Copyright 2018 by Nelson Education Limited 1 7.2.1 Orbital structure of the carbonyl group Because oxygen is more

More information

Chemistry Final Examinations Summer 2006 answers

Chemistry Final Examinations Summer 2006 answers Chemistry 235 - Final Examinations Summer 2006 answers A GEERAL CEMISTRY answers are given from 1-20: no reaction C 3 CC 3 Ph C C C C C 3 Et 2 2 2 B. REACTIS AD REAGETS [32 MARKS] 2. A single substance

More information

Still More Carbonyl Chemistry

Still More Carbonyl Chemistry Lecture 17 Still More arbonyl hemistry ' ' A B P( 6 5 ) 3 A P( 6 5 ) 3 B March 22, 2018 eaction Theme The most common reaction of a carbonyl group is addition of a nucleophile to form a tetrahedral addition

More information

Chap 11. Carbonyl Alpha-Substitution Reactions and Condensation Reactions

Chap 11. Carbonyl Alpha-Substitution Reactions and Condensation Reactions Chap 11. Carbonyl Alpha-Substitution eactions and Condensation eactions Four fundamental reactions of carbonyl compounds 1) Nucleophilic addition (aldehydes and ketones) ) Nucleophilic acyl substitution

More information

Lecture 3: Aldehydes and ketones

Lecture 3: Aldehydes and ketones Lecture 3: Aldehydes and ketones I want to start by talking about the mechanism of hydroboration/ oxidation, which is a way to get alcohols from alkenes. This gives the anti-markovnikov product, primarily

More information

75. A This is a Markovnikov addition reaction. In these reactions, the pielectrons in the alkene act as a nucleophile. The strongest electrophile will

75. 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 information

Aldehydes and Ketones Reactions. Dr. Sapna Gupta

Aldehydes and Ketones Reactions. Dr. Sapna Gupta Aldehydes and Ketones Reactions Dr. Sapna Gupta Reactions of Aldehydes and Ketones Nucleophilic Addition A strong nucleophile attacks the carbonyl carbon, forming an alkoxide ion that is then protonated.

More information

Chapter 18 Ketones and Aldehydes

Chapter 18 Ketones and Aldehydes Chapter 18 Ketones and Aldehydes omenclature o Ketones have priority over alcohols Find the longest chain with the carbonyl in it. ame the parent and replace the e with one Say where the carbonyl is. octan-3-one

More information

Dr. Mohamed El-Newehy

Dr. Mohamed El-Newehy By Dr. Mohamed El-Newehy Chemistry Department, College of Science, King Saud University http://fac.ksu.edu.sa/melnewehy Aldehydes and Ketones 1 Structure of Aldehydes and Ketones - Aldehydes and ketones

More information

Reversible Additions to carbonyls: Weak Nucleophiles Relative Reactivity of carbonyls: Hydration of Ketones and Aldehydes

Reversible Additions to carbonyls: Weak Nucleophiles Relative Reactivity of carbonyls: Hydration of Ketones and Aldehydes Reversible Additions to carbonyls: Weak Nucleophiles Weak nucleophiles, such as water, alcohols, and amines, require acid or base catalysis to undergo addition to carbonyl compounds Relative Reactivity

More information

DAMIETTA UNIVERSITY CHEM-103: BASIC ORGANIC CHEMISTRY LECTURE

DAMIETTA UNIVERSITY CHEM-103: BASIC ORGANIC CHEMISTRY LECTURE DAMIETTA UNIVERSITY CHEM-103: BASIC ORGANIC CHEMISTRY LECTURE 6 Dr Ali El-Agamey 1 Oxidation States Easy for inorganic salts: CrO 4 2- reduced to Cr 2 O 3. KMnO 4 reduced to MnO 2. Oxidation: Gain of O,

More information

Aldehydes & Ketones I

Aldehydes & Ketones I 2302272 Org Chem II Part I Lecture 3 Aldehydes & Ketones I Instructor: Dr. Tanatorn Khotavivattana E-mail: tanatorn.k@chula.ac.th Recommended Textbook: Chapter 18 in Organic Chemistry, 8 th Edition, L.

More information

Aldehydes and Ketones

Aldehydes and Ketones Aldehydes and Ketones Preparation of Aldehydes xidation of Primary Alcohols --- 2 P 1o alcohol ydroboration of a Terminal Alkyne, followed by Tautomerization --- 1. B 3, TF 2. 2 2, K 2 terminal alkyne

More information

Aldehydes and Ketones: Nucleophilic Addition Reactions

Aldehydes and Ketones: Nucleophilic Addition Reactions Aldehydes and Ketones: Nucleophilic Addition Reactions Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones are intermediates in synthesis of pharmaceutical

More information

12. Aldehydes & Ketones (text )

12. Aldehydes & Ketones (text ) 2009, Department of Chemistry, The University of Western ntario 12.1 12. Aldehydes & Ketones (text 13.1 13.11) A. Structure and Nomenclature The carbonyl group is present in aldehydes and ketones and is

More information

Nucleophilic Addition Reactions of Carboxylic Acid Derivatives

Nucleophilic Addition Reactions of Carboxylic Acid Derivatives Lecture 5: bjectives: Nucleophilic Addition eactions of Carboxylic Acid Derivatives By the end of this lecture you will be able to: draw the mechanism of a nucleophilic addition-elimination reaction with

More information

Chem 263 March 7, 2006

Chem 263 March 7, 2006 Chem 263 March 7, 2006 Aldehydes and Ketones Aldehydes and ketones contain a carbonyl group, in which the carbon atom is doubly bonded to an oxygen atom. The carbonyl group is highly polarized, with a

More information

Topic 4 Aldehydes and Ketones

Topic 4 Aldehydes and Ketones 4-1 Topic 4 Aldehydes and Ketones 16.1 4-2 Aldehydes and Ketones ' aldehyde ketone The polarized oxygen-carbon -bond renders aldehydes and ketones electrophilic: ' The electrophilicity of the oxygen-carbon

More information

Chapter 19. Aldehydes and Ketones: Nucleophilic Addition Reactions

Chapter 19. Aldehydes and Ketones: Nucleophilic Addition Reactions Chapter 19. Aldehydes and Ketones: Nucleophilic Addition Reactions شیمی آلی 2 Dr M. Mehrdad University of Guilan, Department of Chemistry, Rasht, Iran m-mehrdad@guilan.ac.ir Based on McMurry s Organic

More information

Nuggets of Knowledge for Chapter 17 Dienes and Aromaticity Chem 2320

Nuggets 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 information

Aldehydes and Ketones 2. Based on Organic Chemistry, J. G. Smith 3rde.

Aldehydes and Ketones 2. Based on Organic Chemistry, J. G. Smith 3rde. Aldehydes and Ketones 2 Based on Organic Chemistry, J. G. Smith 3rde. The Wittig Reaction Wittig reaction, named for German chemist Georg Wittig, who was awarded the Nobel Prize in Chemistry in 1979 for

More information

Chem 263 March 28, 2006

Chem 263 March 28, 2006 Chem 263 March 28, 2006 Properties of Carboxylic Acids Since carboxylic acids are structurally related to both ketones and aldehydes, we would expect to see some similar structural properties. The carbonyl

More information

What is in Common for the Following Reactions, and How Do They Work?

What is in Common for the Following Reactions, and How Do They Work? What is in Common for the Following Reactions, and ow Do They Work? You should eventually be able to draw the mechanism for these (and other) reactions 13 Key Intermediate 1 Br-Br Na Br 2 C 3 -I Me NaMe

More information

Alcohols. Have seen many reactions to synthesize alcohols: In this chapter we will study reactions of the alcohols

Alcohols. 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 information

Stereoselective reactions of the carbonyl group

Stereoselective reactions of the carbonyl group 1 Stereoselective reactions of the carbonyl group We have seen many examples of substrate control in nucleophilic addition to the carbonyl group (Felkin-Ahn & chelation control) If molecule does not contain

More information

Background Information

Background Information ackground nformation ntroduction to Condensation eactions Condensation reactions occur between the α-carbon of one carbonyl-containing functional group and the carbonyl carbon of a second carbonyl-containing

More information

Suggested solutions for Chapter 28

Suggested solutions for Chapter 28 s for Chapter 28 28 PBLEM 1 ow would you make these four compounds? Give your disconnections, explain why you chose them and then give reagents for the. 2 2 Me S Exercises in basic one- group C X disconnections.

More information

FIRST EXAMINATION. Name: CHM 332

FIRST EXAMINATION. Name: CHM 332 ame: CM 332 FIRST EXAMIATI All answers should be written on the exam in the spaces provided. Clearly indicate your answers in the spaces provided; if I have to guess as to what or where your answer is,

More information

Chapter 19. Aldehydes and Ketones: Nucleophilic Addition Reactions

Chapter 19. Aldehydes and Ketones: Nucleophilic Addition Reactions Chapter 19. Aldehydes and Ketones: Nucleophilic Addition Reactions شیمی آلی 2 Dr M. Mehrdad University of Guilan, Department of Chemistry, Rasht, Iran m-mehrdad@guilan.ac.ir Based on McMurry s Organic

More information

When we deprotonate we generate enolates or enols. Mechanism for deprotonation: Resonance form of the anion:

When we deprotonate we generate enolates or enols. Mechanism for deprotonation: Resonance form of the anion: Lecture 5 Carbonyl Chemistry III September 26, 2013 Ketone substrates form tertiary alcohol products, and aldehyde substrates form secondary alcohol products. The second step (treatment with aqueous acid)

More information

Synthesis and Structure of Alcohols Alcohols can be considered organic analogues of water.

Synthesis and Structure of Alcohols Alcohols can be considered organic analogues of water. Synthesis and Structure of Alcohols Alcohols can be considered organic analogues of water. Alcohols are usually classified as primary, secondary and tertiary. Alcohols with the hydroxyl bound directly

More information

Exam 1 (Monday, July 6, 2015)

Exam 1 (Monday, July 6, 2015) Chem 231 Summer 2015 Assigned Homework Problems Last updated: Friday, July 24, 2015 Problems Assigned from Essential Organic Chemistry, 2 nd Edition, Paula Yurkanis Bruice, Prentice Hall, New York, NY,

More information

b.p.=100 C b.p.=65 C b.p.=-25 C µ=1.69 D µ=2.0 D µ=1.3 D

b.p.=100 C b.p.=65 C b.p.=-25 C µ=1.69 D µ=2.0 D µ=1.3 D Alcohols I eading: Wade chapter 10, sections 10-1- 10-12 Study Problems: 10-35, 10-37, 10-38, 10-39, 10-40, 10-42, 10-43 Key Concepts and Skills: Show how to convert alkenes, alkyl halides, and and carbonyl

More information

Chapter 12: Carbonyl Compounds II

Chapter 12: Carbonyl Compounds II Chapter 12: Carbonyl Compounds II Learning bjectives: 1. Recognize and assign names to aldehydes and ketones. 2. Write the mechanism for nucleophilic addition and nucleophilic addition-elimination reactions

More information

Ch 20 Carboxylic Acids and Nitriles

Ch 20 Carboxylic Acids and Nitriles Ch 20 Carboxylic Acids and Nitriles Carboxylic Acids (RCO 2 H) are compounds with an OH attached to a carbonyl. Nitriles (RC N) are compounds a carbon-nitrogen triple bond. Naming Carboxylic Acids 1. Replace

More information

Reactions at α-position

Reactions at α-position Reactions at α-position In preceding chapters on carbonyl chemistry, a common reaction mechanism observed was a nucleophile reacting at the electrophilic carbonyl carbon site NUC NUC Another reaction that

More information

Chemistry 5.07SC Biological Chemistry I Fall Semester, 2013

Chemistry 5.07SC Biological Chemistry I Fall Semester, 2013 Chemistry 5.07SC Biological Chemistry I Fall Semester, 2013 Lecture 9 Biochemical Transformations I. Carbon-carbon bond forming and cleaving reactions in Biology (see the Lexicon). Enzymes catalyze a limited

More information

THE CHEMISTRY OF THE CARBONYL GROUP

THE CHEMISTRY OF THE CARBONYL GROUP TE CEMISTY F TE CABYL GUP Professor Tim Donohoe 8 lectures, T, weeks 1-4, 2007 andout A C C You will be able to download copies of the handouts from this course at http://users.ox.ac.uk/~magd1571/teaching/teaching.htm

More information

CHE1502. Tutorial letter 203/1/2016. General Chemistry 1B. Semester 1. Department of Chemistry

CHE1502. 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 information

Carboxylic Acids and Nitriles

Carboxylic Acids and Nitriles Carboxylic Acids and Nitriles Why this Chapter? Carboxylic acids present in many industrial processes and most biological processes They are the starting materials from which other acyl derivatives are

More information

Topic 6 Alkyl halide and carbonyl compounds Organic compounds containing a halogen

Topic 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 3 1 3 3 2 3 2-iodo-2-methylpropane (tertiary alkyl halide) l 3 4-chlorotoluene (aryl

More information

Suggested solutions for Chapter 30

Suggested solutions for Chapter 30 s for Chapter 30 30 PRBLEM 1 uggest a mechanism for this synthesis of a tricyclic aromatic heterocycle. 2 Cl base A simple exercise in the synthesis of a pyridine fused to a pyrrole (or an indole with

More information

Topic 6 Alkyl halide and carbonyl compounds Organic compounds containing a halogen

Topic 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 information

New bond. ph 4.0. Fischer esterification. New bond 2 O * New bond. New bond H 2N. New C-C bond. New C-C bond. New C-C bond. O Cl.

New bond. ph 4.0. Fischer esterification. New bond 2 O * New bond. New bond H 2N. New C-C bond. New C-C bond. New C-C bond. O Cl. Iverson C 0N KRE Table: For use in synthesis problems, count carbons in products and starting materials then identify location(s) of new s, especially C-C or C=C s. With that information, use the following

More information

CHEMISTRY 263 HOME WORK

CHEMISTRY 263 HOME WORK Lecture Topics: CHEMISTRY 263 HOME WORK Module7: Hydrogenation of Alkenes Hydrogenation - syn and anti- addition - hydrogenation of alkynes - synthesis of cis-alkenes -synthesis of trans-alkenes Text sections:

More information

Ketones and Aldehydes Reading Study Problems Key Concepts and Skills Lecture Topics: Structure of Ketones and Aldehydes Structure:

Ketones and Aldehydes Reading Study Problems Key Concepts and Skills Lecture Topics: Structure of Ketones and Aldehydes Structure: Ketones and Aldehydes Reading: Wade chapter 18, sections 18-1- 18-21 Study Problems: 18-43, 18-44,18-50, 18-51, 18-52, 18-59, 18-60, 18-62, 18-64, 18-72. Key Concepts and Skills: Interpret the IR, NMR,

More information

(Neither an oxidation or reduction: Addition or loss of H +, H 2 O, HX).

(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 information

Answers To Chapter 7 Problems.

Answers To Chapter 7 Problems. Answers To Chapter Problems.. Most of the Chapter problems appear as end-of-chapter problems in later chapters.. The first reaction is an ene reaction. When light shines on in the presence of light and

More information

Module9. Nuclear Magnetic Resonance Spectroscopy Nuclear Magnetic Resonance (NMR) spectroscopy - Chemical shift - Integration of signal area

Module9. Nuclear Magnetic Resonance Spectroscopy Nuclear Magnetic Resonance (NMR) spectroscopy - Chemical shift - Integration of signal area 1 CHEMISTRY 263 HOME WORK Lecture Topics: Module7. Hydrogenation of Alkenes The Function of the Catalyst - Syn and anti- addition Hydrogenation of Alkynes - Syn- addition of hydrogen: Synthesis of cis-alkenes

More information

Ethers can be symmetrical or not:

Ethers 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 information

Alcohols, Ethers and Epoxides. Chapter Organic Chemistry, 8th Edition John McMurry

Alcohols, Ethers and Epoxides. Chapter Organic Chemistry, 8th Edition John McMurry Alcohols, Ethers and Epoxides Chapter 17-18 Organic Chemistry, 8th Edition John McMurry 1 Introduction Structure and Bonding Alcohols contain a hydroxy group (OH) bonded to an sp 3 hybridized carbon. 2

More information

acetaldehyde (ethanal)

acetaldehyde (ethanal) hem 263 Nov 2, 2010 Preparation of Ketones and Aldehydes from Alkenes zonolysis 1. 3 2. Zn acetone 1. 3 2. Zn acetone acetaldehyde (ethanal) Mechanism: 3 3 3 + - oncerted reaction 3 3 3 + ozonide (explosive)

More information

Lecture 13A 05/11/12. Amines. [Sn2; Hofmann elimination; reduction of alkyl azides, amides, nitriles, imines; reductive amination; Gabriel synthesis]

Lecture 13A 05/11/12. Amines. [Sn2; Hofmann elimination; reduction of alkyl azides, amides, nitriles, imines; reductive amination; Gabriel synthesis] Lecture 13A 05/11/12 Amines [Sn2; ofmann elimination; reduction of alkyl azides, amides, nitriles, imines; reductive amination; Gabriel synthesis] Curtius and ofmann rearrangements Both of these, in principle,

More information

Alcohol Synthesis. Dr. Sapna Gupta

Alcohol Synthesis. Dr. Sapna Gupta Alcohol Synthesis Dr. Sapna Gupta Synthesis of Alcohols Alcohols can be synthesized from several functional groups. Nucleophilic substitution of O - on alkyl halide ydration of alkenes water in acid solution

More information

Loudon Chapter 14 Review: Reactions of Alkynes Jacquie Richardson, CU Boulder Last updated 1/16/2018

Loudon Chapter 14 Review: Reactions of Alkynes Jacquie Richardson, CU Boulder Last updated 1/16/2018 An alkyne is any molecule with a triple bond between two carbon atoms. This triple bond consists of one σ bond and two π bonds: the σ bond exists on a straight line between carbon atoms, while one π bond

More information

Carbonyl Chemistry. aldehydes ketones. carboxylic acid and derivatives. Wednesday, April 29, 2009

Carbonyl Chemistry. aldehydes ketones. carboxylic acid and derivatives. Wednesday, April 29, 2009 Carbonyl Chemistry X aldehydes ketones carboxylic acid and derivatives Electrophiles (eg. + ) Nucleophiles (eg. C 3 MgBr) an enolate Base β β β α α α 1 2 3 4 Nuc- 1 2 Nuc 3 4 1,2-addition 1 2 3 4 Nuc-

More information

2.222 Practice Problems 2003

2.222 Practice Problems 2003 2.222 Practice Problems 2003 Set #1 1. Provide the missing starting compound(s), reagent/solvent, or product to correctly complete each of the following. Most people in the class have not done this type

More information

CHEM 345 Problem Set 07 Key

CHEM 345 Problem Set 07 Key CHEM 345 Problem Set 07 Key 1.) Fill in the appropriate reaction arrow. The starting material is on the left, the product is on the right. Use. Simple Ring Size. 5 and 6 are favored. 3 is not. That s it.

More information

TOPIC 3. ALDEHYDES AND KETONES (Chapters 12 and 16)

TOPIC 3. ALDEHYDES AND KETONES (Chapters 12 and 16) L TPIC 3. ALDEYDES AND KETNES (Chapters 12 and 16) BJECTIVES 1. Describe the synthesis aldehydes and ketones. 2. Describe the carbonyl group and oxidation-reductions reactions associated with alcohols

More information

Allyl radicals are especially stable due to resonance ( and double bond switch places):

Allyl 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 information

Page 1 of 9. Sessional Examination (November 2017) Max Marks: 20 Date: Time: One Hour. Model Answers

Page 1 of 9. Sessional Examination (November 2017) Max Marks: 20 Date: Time: One Hour. Model Answers Page 1 of 9 Sessional Examination (November 2017) Class: B. Pharm-II yr (III sem) Subject: Pharma Org. Chem-II Max Marks: 20 Date: 14.11.2017 Time: One Hour Model Answers Q. 1. Solve the following (ANY

More information

Chapter 8 Reactions of Alkenes

Chapter 8 Reactions of Alkenes Chapter 8 Reactions of Alkenes Electrophilic Additions o Regio vs stereoselectivity Regio where do the pieces add? Markovnikov s rule hydrogen will go to the side of the double bond with most hydrogens.

More information

Synthesis of Double Bonds

Synthesis of Double Bonds Synthesis of Double Bonds Wittig eaction!!! Georg Wittig: Nobel Prize 1979 For their development of the use of boronand phosphorous-containing compounds respectively, into important reagents in organic

More information

Lecture 15. Carbonyl Chemistry C B. March 6, Chemistry 328N

Lecture 15. Carbonyl Chemistry C B. March 6, Chemistry 328N Lecture 15 Carbonyl Chemistry - A C B A C + B March 6, 2018 Some loose ends Substitution Reactions Aryl halides do not undergo nucleophilic substitution by either S N 1 or S N 2 pathways! But.. But.this

More information

First Year Organic Chemistry THE CHEMISTRY OF THE CARBONYL GROUP: CORE CARBONYL CHEMISTRY

First Year Organic Chemistry THE CHEMISTRY OF THE CARBONYL GROUP: CORE CARBONYL CHEMISTRY First Year rganic Chemistry TE CEMISTY F TE CABNYL GUP: CE CABNYL CEMISTY Professor Tim Donohoe 8 lectures, T, weeks 1-4, 2015 Wednesdays at 9am; Fridays at 10am (Dyson Perrins) andout A You will be able

More information

CHE1502. Tutorial letter 201/1/2016. General Chemistry 1B. Semester 1. Department of Chemistry CHE1502/201/1/2016

CHE1502. 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 information

CARBONYL COMPOUNDS: OXIDATION-REDUCTION REACTION

CARBONYL COMPOUNDS: OXIDATION-REDUCTION REACTION CARBONYL COMPOUNDS: OXIDATION-REDUCTION REACTION Introduction Several functional groups contain the carbonyl group Carbonyl groups can be converted into alcohols by various reactions Structure of the Carbonyl

More information

ALCOHOLS AND PHENOLS

ALCOHOLS 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 information

Amines. Amines are organic compounds containing a nitrogen functionality. primary secondary tertiary quaternary

Amines. Amines are organic compounds containing a nitrogen functionality. primary secondary tertiary quaternary Amines Amines are organic compounds containing a nitrogen functionality Depending upon the number of alkyl, or aryl, groups attached to nitrogen determines its classification, or order 2 primary secondary

More information

B X A X. In this case the star denotes a chiral center.

B X A X. In this case the star denotes a chiral center. Lecture 13 Chirality III October 29, 2013 We can also access chiral molecules through the use of something called chiral auxiliaries, which basically is a chiral attachment that you add to your molecule

More information

Chapter 20: Carboxylic Acids and Nitriles شیمی آلی 2

Chapter 20: Carboxylic Acids and Nitriles شیمی آلی 2 Chapter 20: Carboxylic Acids and Nitriles شیمی آلی 2 Dr M. Mehrdad University of Guilan, Department of Chemistry, Rasht, Iran m-mehrdad@guilan.ac.ir Based on McMurry s Organic Chemistry, 7 th edition The

More information

Chapter 3. Alkenes And Alkynes

Chapter 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 information