OXIDATION AND REDUCTION

Size: px
Start display at page:

Download "OXIDATION AND REDUCTION"

Transcription

1 XIDATI AD EDUCTI Cl ' E " ' " "' ' ' ' ' " " Introduction ' uc Fundamental backbone of organic chemistry is the ability to alter oxidation states ydroxyl and carbonyl moiety provide an invaluable means for transforming molecules so the ability to introduce and remove them very important Course utline xidations alcohol to carbonyl alkene epoxidation and dihydroxylation C oxidation miscellaneous eductions carbonyl group hydrogenation electron transfer " ' This is not an all inclusive lecture course To list every reagent would be boring, so I have tried to be selective with the criteria being those that are more common, useful or interesting, but this is just my opinion As this is a new course, if you feel I have missed out any important examples (or too much detail on others) please tell me: g.rowlands@sussex.ac.uk Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation

2 ALCL XIDATI Alcohols can readily be oxidised to the carbonyl moiety This is an incredibly important reaction - you should realise that the carbonyl group is one of the cornerstones of C C bond formation (organometallics, neutral nucleophiles, aldol, Julia, Peterson & Wittig reactions) 1 = 1 1 Primary ( 1 = ) alcohols normally more reactive than seconary alcohols on steric grounds eed to be able to control oxidation of primary alcohols so only obtain aldehyde or acid Large number of reagents all have their advantages and disadvantages Look at some of the more common... General Fragmentation Mechanism E [] E [] E [] This fragmentation mechanism is common to most oxidations regardless of the nature of the reagent Chromium (VI) xidants (VI) 2 2 General Mechanism proton transfer (IV) "veroxidation" formation of carboxylic acids Invariably achieved in the prescence of 2 and proceeds via the hydrate 2 Jones xidation 2 S 4, 3, acetone 1 1 arsh, acidic conditions limit use of this method Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation

3 Pyridinium Chlorochromate (PCC) must avoid water Cl 1 1 Less acidic than Jones reagent (although still acidic) Pyridinium Dichromate (PDC) 2 Even milder than PCC and has useful selectivity PDC DCM PDC DMF ther xidants Manganese Dioxide Mn 2 Mild reagent Very selective only oxidises allylic, benzylic or propargylic alcohols only oxidises activated alcohol Mn 2 Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation

4 ALCL XIDATI Activated DMS eagent: DMS, activator (X) and base Transformation: C C= (primary or secondary alcohols) General Mechanism S + X S X + S base intermediate common to all activated DMS reactions 18 labelling has determined mechanism alternative activation of hydroxyl followed by displacement not occurring S + S Common Side-eactions Pummerer eaction S + S S Displacement eactions The cationic intermediate formed is an excellent leaving group Intramolecular C 2 C 2 DMS / (CCl) 2 93% S Intermolecular C 2 C 2 Cl Bn DMS / (CCl) 2 95% Bn Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation

5 Enolisation Generation of a carbonyl compound in the presence of an amine base is asking for trouble α-chiral centre can be racemised vercome by: keeping temperature low, remove base with cold acid buffer, use Pyr.S 3 system Eliminations Problem due to mild acidity of earlier steps or if suitable leaving group present when base added 1. DMS / (CCl) 2 2. Et 3 72% Me Me Me TBS S 2 P 1. DMS / + (CCl) 2 2. Et 3 P TBS TBS S 2 67 % Activators 28% Pfitzner-Moffatt (DMS / DCC then base) P C The original Pros: mild conditions, normally rt Cons: DCC urea by-product hard to remove frequently generates Pummerer side-product mildly acidic conditions lead to eliminations DMS / DCC TFA / Pyr 88 % active intermediate of Swern reaction Swern (DMS / (CCl) 2 ) Cl S Most popular, as mild and easy Pros: low temperature reduces enolisation very little Pummerer reaction Cons: Chlorination Parikh-Doering (DMS / Pyr S 3 ) Pros: very mild conditions, very little enolisation very little Pummerer eaction TBS TBS C 2 DMS / Pyr S 3 Et 3 94% TBS TBS Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation C

6 Activated DMS xidations in Synthesis TIPS 1. DMS / (CCl) 2 2. Et 3 92 % 1,2-diols are not cleaved TIPS 1. DMS / (CF 3 C) 2 2. Et 3 90 % sequential reactions possible due to the high yields and purity of products especially useful when aldehyde readily forms hydrate Me 3 Si 1. DMS / (CCl) 2 2. Et 3 Me 3 Si 3 P=CMeC 2 Et 54% overall Me 3 Si C 2 Et tertiary alcohols often do not need to be protected Me Me Me 1. DMS / (CCl) 2 2. Et 3 81% Me Me Me selective oxidations primary alcohols oxidised much faster but use of ipr 2 S and CS as activator (proceeds via same intermediate as Swern) oxidises primary alcohols at 0 C but secondary at -78 C do not understand this reaction AD it was only a communication 84CC762 that has never been followed up oxidation in the presence of allylic or benzylic alcohols DMS / (CF 3 C) 2 S S CCF 3 CCF 3 S Me Me Me Me Me Me the activity of allylic and benzylic alcohols means they undergo rapid displacement and hence a form of protection (±)-tazettine 61 % Et 3 Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation Me Me

7 lactol or lactone formation can be surpressed most oxidising agents oxidise primary alcohols faster than secondary and this can lead to problems [] [] activated DMS does not have this problem as aldehyde only formed on addition of base DMS / S S Et 3 (CCl) 2 selective oxidation of primary silyl ethers Mildly acidic nature and the nucleophilic chloride ion generated allows selective deprotection and concomitant oxidation of primary TES & TMS ethers TES 1. DMS / (CCl) 2 2. Et 3 62 % TES TES Limitations activated DMS systems will not oxidise propargylic alcohols What have we learnt? Activated DMS reactions are generally mild ffer many advantages of metallic reagents Drawbacks include a number of possible side-reactions Will not oxidise propargylic alcohols Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation

8 Dess-Martin Periodinane (DMP) (1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3-(1)-one) eagent: Ac Ac I Ac Transformation: C C= (primary or secondary alcohols) ligand exchange Ac Ac I Ac General mechanism Ac I could be intra or intermolecular Ac I 2 x Ac since introduction in 1983 become one of the most popular oxidants mild reagent operating at nearly neutral conditions (buffer with ac 3 if worried about Ac) many very sensitive molecules can be oxidised TBS 93 % DEIPS TES TES TES tbu Si tbu Me TES Preparation I C 2 + KBr M 2 S 4 65 C I Ac Ac Ac I Ac mild and extremely reactive oxidant Insoluble in most organic solvents and impact sensitive Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation

9 Use in Synthesis Selectivity first step is ligand exchange so an inherent steric selectivity exists primary alcohols oxidised faster than secondary TBS TBS TBS Me TBS DMP, pyr, DCM, 88% TBS TBS TBS Me TBS Allylic and benzylic alcohols react ~5 faster than saturated alcohols DMP, pyr, DCM, rt 2hrs >75% Advantages: no over oxidation is ever observed no enolisation no oxidation of heteroatoms (eg or S) Disadvantages: Behaves like periodate and cleaves 1,2-diols. BUT not always, no consistancy What have we learnt? DMP is a mild reagent selective oxidations are possible 1,2-diols behave unpredictably Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation

10 Tetrapropylammonium Perruthenate TPAP eagent: Pr 4 + u 4 Stoichiometric or catalytic with M Transformation: C C= (primary or secondary alcohols) C C 2 (if 2 present) General mechanism not entirely clear it is thought that TPAP is a 3e oxidant but each step is a 2e process and that radicals / S.E.T. is not involved due to steric selectivity it is thought that TPAP is a bulky reagent & oxidation occurs primarily through the intermediacy of a ruthenate ester u u 2 u 2 u u u Use in Synthesis Introduced in 1987 its mildness and practically have made it popular (coupled to its none explosive nature) should be used dry with 4Åms or get over-oxidation and cleavage of alkenes mechanism changes in presence of 2 advantages: good functional group tolerance no epimerisation of α-chiral centres or double bond isomerisation no competative β-elimination PMB TPAP / M, DCM, 4Åms 96% PMB Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation

11 selectivity for primary hydroxyl group allows lactone preparation TPAP / M, DCM / MeC, 4Åms 91% TPAP secondary alcohols oxidise far slower but they do oxidise TMS TPAP / M, DCM, 4Åms, 73% Swern xidation = 0% PCC = 0% TMS depending on sterics can get selectivity for least hindered hydroxyl group TPAP / M, DCM, 4Åms 61% lactols can be oxidised selectively (again sterics) Ac Me 2 C C 2 Me TPAP / M, MeC, 4Åms 75% Ac Me 2 C C 2 Me again we see how mild TPAP is TPAP oxidises sulfur but not other heteroatoms SMe S 2 Me TPAP / M, MeC, 4Åms 80% Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation

12 Sequential reactions due to ease of w/u and anhydrous conditions, TPAP is well suited to sequential reactions C 2 Me TPAP / M, DCM, 4Åms C 2 Me 3 P=CMeC 2 tbu 72% overall C 2 Me C 2 tbu Disadvantages: TPAP can cleave 1,2-diols like other metal oxidants TPAP, acl 93% Disadvantages: can cause retro-aldol reaction TPAP / M, DCM, 4Åms retro-aldol results in cleavage of β-hydroxyketones What have we learnt? TPAP is a mild oxidant Its bulk allows selective reactions It can be used in catalytic quantities Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation

13 Modified Chromium (VI) xidants Pyridinium Chlorochromate PCC eagent: Cl 3 Transformation: C C= (primary or secondary alcohols) General Mechanism Cl Use in Synthesis Must be dry, water hampers reaction and can result in the formation of acids (over-oxidation) PCC, 4Åms, DCM 93% Disadvantages: reagent is acidic Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation

14 Pyridinium Dichromate PDC eagent: Transformation: C C= (primary or secondary alcohols) Use in Synthesis eutral variant of PCC Addition of Si 2 to reaction aids work up and addition of pyridinium trifluroracetate increases rate DCM normal solvent DMF gives carboxylic acids PDC, DCM 92% PDC, DMF 83% C 2 Me xidation to the Acid Many variants involving chromium or manganate which proceed via the hydrated aldehyde But invariably require strongly acidic conditions so not useful in organic synthesis You can find them yourselves in March or Smith A mild alternative is: acl 2, a 2 P 4 Cl 2 Cl Cl Cl is very unpleasnt so alkene added as a scavenger What have we learnt? Chromium reagents can be used to oxidise to either aldehyde or carboxylic acid They are toxic Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation

15 Kinetic esolution by Selective xidation oyori has developed a method for resolving racemic alcohols via selective oxidation Uses hydrogen transfer (analgous to ppenauer oxidation or Meerwein-Ponndorf-Verley reduction) Ts u + + = unsaturated group Yield = % e.e. = > 90 % note you can not get better than 50% with kinetic resolution Mechanism u Ts u Ts u Ts u Ts u Ts More appealing is the desymmetrisation of meso-diols Theoretical maximum yield is 100 % 70 % 96 % e.e. What have we learnt? Stereoselective oxidations are now possible ydrogen transfer allows preparation of enantiopure compounds from racemates As both reductant and oxidant are organic this type of reaction will be appearing again Gareth owlands (g.rowlands@sussex.ac.uk) Ar402, eduction and xidation

Avg. 16.4 / 25 Stnd. Dev. 8.2

Avg. 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 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

Oxidation Reactions. Oxidation of Alcohols R OH R O. primary alcohol aldehyde carboxylic acid. secondary alcohol. ketone.

Oxidation Reactions. Oxidation of Alcohols R OH R O. primary alcohol aldehyde carboxylic acid. secondary alcohol. ketone. I xidation Reactions bjectives By the end of this section you will: 1) have an improved appreciation of some of the important selectivity issues involved in oxidation processes. 2) be aware of the wide

More information

17.5 ALLYLIC AND BENZYLIC OXIDATION

17.5 ALLYLIC AND BENZYLIC OXIDATION 17.5 ALLYLI AND BENZYLI XIDATIN 803 Nuc d d Nuc d 2 3 2 overlap of 2p orbitals X d no p-orbital overlap X d (a) (b) Figure 17.2 Transition states for N 2 reactions at (a) an allylic carbon and (b) a nonallylic

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

Mass Spec - Fragmentation

Mass 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 information

Organic Synthesis II: Selectivity & Control 8 lectures, TT 2011

Organic Synthesis II: Selectivity & Control 8 lectures, TT 2011 rganic Synthesis II: Selectivity & Control 8 lectures, TT 2011 andout 1 andouts will be available at: http://msmith.chem.ox.ac.uk/teaching.html Dr Martin Smith ffice: CL 1 st floor 30.087 Telephone: (2)

More information

Wittig Reaction - Phosphorous Ylides

Wittig Reaction - Phosphorous Ylides Wittig eaction - osphorous Ylides 3 P CC 3 3 C ylide tereoselectivity increases as the size of increases cis-olefin is derived from non-stabilized ylides Mechanism: Irreversible [22] cycloaddition P 3

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

Aldehydes can react with alcohols to form hemiacetals. 340 14. Nucleophilic substitution at C=O with loss of carbonyl oxygen

Aldehydes can react with alcohols to form hemiacetals. 340 14. Nucleophilic substitution at C=O with loss of carbonyl oxygen 340 14. Nucleophilic substitution at C= with loss of carbonyl oxygen Ph In Chapter 13 we saw this way of making a reaction go faster by raising the energy of the starting material. We also saw that the

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

Short Peptide Synthesis

Short Peptide Synthesis Short Peptide Synthesis Keith ó Proinsias 8 th February 2010 Introduction Amide bond and basic amide synthesis Solution phase peptide synthesis Protecting groups required for peptide synthesis Coupling

More information

Mitsunobu Reaction (1934-2003)

Mitsunobu Reaction (1934-2003) Mitsunobu eaction (1934-2003) utline General Information: Who discovered this? What is the basic reaction? The Mechanism: What exactly happens and how? Applications: i) Variations of the method- where

More information

Saturated NaCl solution rubber tubing (2) Glass adaptor (2) thermometer adaptor heating mantle

Saturated 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 information

Kurs: Metallorganische Reagenzien. Cericammoniumnitrate (CAN)

Kurs: Metallorganische Reagenzien. Cericammoniumnitrate (CAN) Kurs: Metallorganische eagenzien Cericammoniumnitrate (CAN) by Laura Munoz Senovilla and Arthur Fedoseev. CAN as one-electronelectron oxidant CAN as one-electron electron oxidant Based on: Salt of high-valent

More information

Identification of Unknown Organic Compounds

Identification 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 information

Chapter 5 Classification of Organic Compounds by Solubility

Chapter 5 Classification of Organic Compounds by Solubility Chapter 5 Classification of Organic Compounds by Solubility Deductions based upon interpretation of simple solubility tests can be extremely useful in organic structure determination. Both solubility and

More information

EXPERIMENT 5: DIPEPTIDE RESEARCH PROJECT

EXPERIMENT 5: DIPEPTIDE RESEARCH PROJECT EXPERIMENT 5: DIPEPTIDE RESEARCH PROJECT Pre-Lab Questions: None. 64 I. Background Information DIPEPTIDE RESEARCH PROJECT Methods developed by organic chemists for the synthesis of biopolymers have had

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

ammonium salt (acidic)

ammonium 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 information

Writing a Correct Mechanism

Writing 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 information

Experiment 6 Qualitative Tests for Alcohols, Alcohol Unknown, IR of Unknown

Experiment 6 Qualitative Tests for Alcohols, Alcohol Unknown, IR of Unknown Experiment 6 Qualitative Tests for Alcohols, Alcohol Unknown, I of Unknown In this experiment you are going to do a series of tests in order to determine whether or not an alcohol is a primary (1 ), secondary

More information

Chemistry Notes for class 12 Chapter 13 Amines

Chemistry 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 information

IDENTIFICATION OF ALCOHOLS

IDENTIFICATION 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 information

CHM220 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* 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 information

Laboratory 22: Properties of Alcohols

Laboratory 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 information

Prof. Dr. Burkhard König, Institut für Organische Chemie, Uni Regensburg 1. Enolate Chemistry

Prof. Dr. Burkhard König, Institut für Organische Chemie, Uni Regensburg 1. Enolate Chemistry Prof. Dr. Burkhard König, Institut für rganische Chemie, Uni Regensburg 1 1. Some Basics Enolate Chemistry In most cases the equilibrium lies almost completely on the side of the ketone. The ketone tautomer

More information

Double Bonds. Hydration Rxns. Hydrogenation Rxns. Halogenation. Formation of epoxides. Syn addition of 2 OH. Ozonolysis

Double Bonds. Hydration Rxns. Hydrogenation Rxns. Halogenation. Formation of epoxides. Syn addition of 2 OH. Ozonolysis Double Bonds What do we do with double bonds? We do addition reactions. In an addition reaction, something is added to both carbons involved in a double bond (or not involved in the double bond, in the

More information

2. Couple the two protected amino acids.

2. Couple the two protected amino acids. General Considerations The Strategy of Peptide Synthesis Making peptide bonds between amino acids is not difficult. The challenge is connecting amino acids in the correct sequence. andom peptide bond formation

More information

Suggested solutions for Chapter 3

Suggested solutions for Chapter 3 s for Chapter PRBLEM Assuming that the molecular ion is the base peak (00% abundance) what peaks would appear in the mass spectrum of each of these molecules: (a) C5Br (b) C60 (c) C64Br In cases (a) and

More information

CHM220 Addition lab. Experiment: Reactions of alkanes, alkenes, and cycloalkenes*

CHM220 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 information

Oxidation of Cyclohexanol to Cyclohexanone

Oxidation of Cyclohexanol to Cyclohexanone Reminder: These notes are meant to supplement, not replace, the laboratory manual. Oxidation of Cyclohexanol to Cyclohexanone History and Application: Oxidation reactions are incredibly important in the

More information

ORGANIC CHEMISTRY I PRACTICE EXERCISE Sn1 and Sn2 Reactions

ORGANIC 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 information

ALKENES AND ALKYNES REACTIONS

ALKENES AND ALKYNES REACTIONS A STUDENT SHULD BE ABLE T: ALKENES AND ALKYNES REACTINS 1. Given the starting materials and reaction conditions, predict the products of the following reactions of alkenes and alkynes. Regioselective Markovnikov

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

1 General introduction

1 General introduction General introduction Peptides and peptidomimetics _ 1 1 General introduction 1.1 Peptides and peptidomimetics umerous small and large peptides, which are sequence and length-specific polymers composed

More information

21.9 REDUCTION OF CARBOXYLIC ACID DERIVATIVES

21.9 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 information

SULFONATE AND INORGANIC ESTER DERIVATIVES OF ALCOHOLS

SULFONATE 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 information

T3P Propane Phosphonic Acid Anhydride

T3P Propane Phosphonic Acid Anhydride Technology StrengthS T3P Propane Phosphonic Acid Anhydride The coupling agent of the future Coupling and water removal are synthesis tools that stand at the cutting edge of purity and cost effective manufacture

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

Calculating Atoms, Ions, or Molecules Using Moles

Calculating Atoms, Ions, or Molecules Using Moles TEKS REVIEW 8B Calculating Atoms, Ions, or Molecules Using Moles TEKS 8B READINESS Use the mole concept to calculate the number of atoms, ions, or molecules in a sample TEKS_TXT of material. Vocabulary

More information

Name. Department of Chemistry and Biochemistry SUNY/Oneonta. Chem 322 - Organic Chemistry II Examination #2 - March 14, 2005 ANSWERS

Name. Department of Chemistry and Biochemistry SUNY/Oneonta. Chem 322 - Organic Chemistry II Examination #2 - March 14, 2005 ANSWERS Name INSTRUTINS --- Department of hemistry and Biochemistry SUNY/neonta hem 322 - rganic hemistry II Examination #2 - March 14, 2005 ANSWERS This examination has two parts. Part I is in multiple choice

More information

Guide to Solving Sophomore Organic Synthesis Problems

Guide to Solving Sophomore Organic Synthesis Problems Paul Bracher Chem 30 Synthesis eview Guide to Solving Sophomore rganic Synthesis Problems Disclaimer mission of a topic on this handout does not preclude that material from appearing on the final exam.

More information

Q.1 Draw out some suitable structures which fit the molecular formula C 6 H 6

Q.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 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

Assessment Schedule 2013 Chemistry: Demonstrate understanding of the properties of organic compounds (91391)

Assessment Schedule 2013 Chemistry: Demonstrate understanding of the properties of organic compounds (91391) NCEA Level 3 Chemistry (91391) 2013 page 1 of 8 Assessment Schedule 2013 Chemistry: Demonstrate understanding of the properties of organic compounds (91391) Evidence Statement Q Evidence Achievement Achievement

More information

Organic Functional Groups Chapter 7. Alcohols, Ethers and More

Organic Functional Groups Chapter 7. Alcohols, Ethers and More Organic Functional Groups Chapter 7 Alcohols, Ethers and More 1 What do you do when you are in Pain? What do you do when you are in a lot of pain? 2 Functional Groups A functional group is an atom, groups

More information

Chem101: General Chemistry Lecture 9 Acids and Bases

Chem101: General Chemistry Lecture 9 Acids and Bases : General Chemistry Lecture 9 Acids and Bases I. Introduction A. In chemistry, and particularly biochemistry, water is the most common solvent 1. In studying acids and bases we are going to see that water

More information

methyl RX example primary RX example secondary RX example secondary RX example tertiary RX example

methyl 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 information

Chapter 7 Substitution Reactions

Chapter 7 Substitution Reactions Chapter 7 Substitution Reactions Review of Concepts Fill in the blanks below. To verify that your answers are correct, look in your textbook at the end of Chapter 7. Each of the sentences below appears

More information

Allyl Metals. oxidative addition. transmet. + M(n) η 1 -allyl. n = 0, 1. base. X η 3 -allyl. Nuc. insertion. insertion. M(n+2)X MgX + MX2 MX 2

Allyl Metals. oxidative addition. transmet. + M(n) η 1 -allyl. n = 0, 1. base. X η 3 -allyl. Nuc. insertion. insertion. M(n+2)X MgX + MX2 MX 2 Allyl tals Virtually all transition metals can form η 3 -allyl complexes, but few are synthetically useful. Pd is most widely studied and has broad utility. Allyl complexes of h, Ir, u and Mo are becoming

More information

ALKENES AND ALKYNES REACTIONS A STUDENT WHO HAS MASTERED THE MATERIAL IN THIS SECTION SHOULD BE ABLE TO:

ALKENES AND ALKYNES REACTIONS A STUDENT WHO HAS MASTERED THE MATERIAL IN THIS SECTION SHOULD BE ABLE TO: ALKENES AND ALKYNES REACTINS A STUDENT W AS MASTERED TE MATERIAL IN TIS SECTIN SULD BE ABLE T: 1. Given the starting materials and reaction conditions, predict the products of the following reactions of

More information

Chemistry Assessment Unit AS 1

Chemistry Assessment Unit AS 1 Centre Number 71 Candidate Number ADVANCED SUBSIDIARY (AS) General Certificate of Education January 2011 Chemistry Assessment Unit AS 1 assessing Basic Concepts in Physical and Inorganic Chemistry [AC111]

More information

These instructions are for a classroom activity which supports OCR A Level Chemistry A.

These 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 information

Synthesis of Isopentyl Acetate

Synthesis of Isopentyl Acetate Experiment 8 Synthesis of Isopentyl Acetate Objectives To prepare isopentyl acetate from isopentyl alcohol and acetic acid by the Fischer esterification reaction. Introduction Esters are derivatives of

More information

17.2 REACTIONS INVOLVING ALLYLIC AND BENZYLIC RADICALS

17.2 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 information

Q.1 Carbonyl compounds are formed by oxidation of alcohols;

Q.1 Carbonyl compounds are formed by oxidation of alcohols; arbonyl compounds 814 1 ARBYL MPUDS - Aldehydes and Ketones Q.1 arbonyl compounds are formed by oxidation of alcohols; a) Which type of alcohol is oxidised to an aldehyde? b) Which type of alcohol is oxidised

More information

LABORATORY 5 DETECTION OF FUNCTIONAL GROUPS IN ORGANIC COMPOUNDS

LABORATORY 5 DETECTION OF FUNCTIONAL GROUPS IN ORGANIC COMPOUNDS LABATY 5 DETETIN F FUNTINAL GUPS IN GANI MPUNDS I. haracteristic reactions differentiating saturated aliphatic hydrocarbons from unsaturated aliphatic hydrocarbons 1. The test of bromine addition. Unsaturated

More information

Carboxylic Acid Structure and Chemistry: Part 2

Carboxylic 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 information

SYNTHETIC STUDIES ON TULEARIN MACROLIDES. M.Montserrat Martínez, Luis A. Sarandeses, José Pérez Sestelo

SYNTHETIC STUDIES ON TULEARIN MACROLIDES. M.Montserrat Martínez, Luis A. Sarandeses, José Pérez Sestelo SYNTHETIC STUDIES N TULEARIN MACRLIDES M.Montserrat Martínez, Luis A. Sarandeses, José Pérez Sestelo Departamento de Química Fundamental, Universidade da Coruña, E-15071 A Coruña, Spain E-mail: mmartinezc@udc.es

More information

IB Chemistry. DP Chemistry Review

IB Chemistry. DP Chemistry Review DP Chemistry Review Topic 1: Quantitative chemistry 1.1 The mole concept and Avogadro s constant Assessment statement Apply the mole concept to substances. Determine the number of particles and the amount

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. Free Radical Reactions

Chapter 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 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

Carbonyl Chemistry (12 Lectures)

Carbonyl Chemistry (12 Lectures) arbonyl hemistry (12 Lectures) Aim of ourse Professor Donna G. Blackmond d.blackmond@imperial.ac.uk tel. 41193 oom 639 1 To build upon elements of Dr E.. Smith s and Dr. D.. Braddocks s course. To introduce

More information

SUMMARY OF ALKENE REACTIONS

SUMMARY OF ALKENE REACTIONS SUMMARY F ALKENE REACTINS Alkenes are primarily prepared by elimination reactions of molecules that contain good leaving groups attached to sp 3 carbons. Examples of such reactions are dehydrohalogenations

More information

Austin Peay State University Department of Chemistry CHEM 1021 TESTING FOR ORGANIC FUNCTIONAL GROUPS

Austin 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 information

Resonance Structures Arrow Pushing Practice

Resonance 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 information

3.4 BRØNSTED LOWRY ACIDS AND BASES

3.4 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 information

Chemistry Diagnostic Questions

Chemistry Diagnostic Questions Chemistry Diagnostic Questions Answer these 40 multiple choice questions and then check your answers, located at the end of this document. If you correctly answered less than 25 questions, you need to

More information

Syllabus for General Organic Chemistry M07A- Fall 2013 Prof. Robert Keil

Syllabus for General Organic Chemistry M07A- Fall 2013 Prof. Robert Keil Syllabus for General Organic Chemistry M07A- Fall 2013 Prof. Robert Keil Textbook and Materials What you must buy: Organic Chemistry 4 th Ed. Janice G. Smith, McGraw Hill. (Older edition is fine) Chem

More information

EXPERIMENT 1: Survival Organic Chemistry: Molecular Models

EXPERIMENT 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 information

Name Lab #3: Solubility of Organic Compounds Objectives: Introduction: soluble insoluble partially soluble miscible immiscible

Name  Lab #3: Solubility of Organic Compounds Objectives: Introduction: soluble insoluble partially soluble miscible immiscible Lab #3: Solubility of rganic Compounds bjectives: - Understanding the relative solubility of organic compounds in various solvents. - Exploration of the effect of polar groups on a nonpolar hydrocarbon

More information

Chapter 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 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 information

23.7 ALKYLATION AND ACYLATION REACTIONS OF AMINES

23.7 ALKYLATION AND ACYLATION REACTIONS OF AMINES 3.7 ALKYLATIN AND ACYLATIN REACTIN F AMINE 1131 organic phase organic phase organic phase CH 3 (CH ) 6 CH Br CH 3 (CH ) 6 CH Br CH 3 (CH ) 6 CH CN R 4 P Br R 4 P CN R 4 P Br Na CN Na Br Na Br aqueous phase

More information

Reactions of Aldehydes and Ketones

Reactions of Aldehydes and Ketones Reactions of Aldehydes and Ketones Structure Deduction using lassification Tests 1 Determination of Structure Determining the structure of an unknown organic compound is an exercise in deductive reasoning.

More information

Lecture 15: Enzymes & Kinetics Mechanisms

Lecture 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 information

pk a Values for Selected Compounds

pk a Values for Selected Compounds Appendix A pk a Values for Selected ompounds ompound pk a ompound pk a I 10 Br 9 2 S 4 9 + 3 3 7.3 3 S 3 7 Br 4.0 4.2 3 4.3 2 N l 7 [( 3 ) 2 ] + 3.8 [ 3 2 ] + 2.5 3 + 1.7 3 S 3 1.2 + 3 N2 0.0 F 3 0.2 l

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

Boston University Dresden Science Program ORGANIC CHEMISTRY CAS CH 203 Lecture

Boston 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 information

Chapter 4 Chemical Reactions

Chapter 4 Chemical Reactions Chapter 4 Chemical Reactions I) Ions in Aqueous Solution many reactions take place in water form ions in solution aq solution = solute + solvent solute: substance being dissolved and present in lesser

More information

stoichiometry = the numerical relationships between chemical amounts in a reaction.

stoichiometry = the numerical relationships between chemical amounts in a reaction. 1 REACTIONS AND YIELD ANSWERS stoichiometry = the numerical relationships between chemical amounts in a reaction. 2C 8 H 18 (l) + 25O 2 16CO 2 (g) + 18H 2 O(g) From the equation, 16 moles of CO 2 (a greenhouse

More information

Nucleophilic Substitution and Elimination

Nucleophilic 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 information

Copyright 2010 Pearson Education, Inc. Chapter Fourteen 1

Copyright 2010 Pearson Education, Inc. Chapter Fourteen 1 An alcohol has an OH bonded to an alkyl group; a phenol has an OH bonded directly to an aromatic ring; and an ether has an O bonded to two organic groups. Chapter Fourteen 1 Ethyl alcohol, dimethyl ether,

More information

1. Oxidation number is 0 for atoms in an element. 3. In compounds, alkalis have oxidation number +1; alkaline earths have oxidation number +2.

1. Oxidation number is 0 for atoms in an element. 3. In compounds, alkalis have oxidation number +1; alkaline earths have oxidation number +2. à xidation numbers In the Lewis model of bonding, when nonidentical atoms are bonded together, an important consideration is how the bonding electrons are apportioned between the atoms. There are two different

More information

California State Polytechnic University, Pomona. Exam Points 1. Nomenclature (1) 30

California 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 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

Chemical Equations and Chemical Reactions. Chapter 8.1

Chemical Equations and Chemical Reactions. Chapter 8.1 Chemical Equations and Chemical Reactions Chapter 8.1 Objectives List observations that suggest that a chemical reaction has taken place List the requirements for a correctly written chemical equation.

More information

Chemistry B11 Chapter 4 Chemical reactions

Chemistry B11 Chapter 4 Chemical reactions Chemistry B11 Chapter 4 Chemical reactions Chemical reactions are classified into five groups: A + B AB Synthesis reactions (Combination) H + O H O AB A + B Decomposition reactions (Analysis) NaCl Na +Cl

More information

The Aldol Condensation

The Aldol Condensation The Aldol ondensation Synthesis and Analysis of 2,3,4,5-Tetraphenylcyclopentadienone Yakety Sax Bennie ill theme song TPP eactions of Aldehydes and Ketones ' 1. Nucleophilic Addition. 2. Substitution at

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

Chemical Reactions in Water Ron Robertson

Chemical Reactions in Water Ron Robertson Chemical Reactions in Water Ron Robertson r2 f:\files\courses\1110-20\2010 possible slides for web\waterchemtrans.doc Properties of Compounds in Water Electrolytes and nonelectrolytes Water soluble compounds

More information

INTDUCTIN 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 information

CHEMICAL REACTIONS. Chemistry 51 Chapter 6

CHEMICAL REACTIONS. Chemistry 51 Chapter 6 CHEMICAL REACTIONS A chemical reaction is a rearrangement of atoms in which some of the original bonds are broken and new bonds are formed to give different chemical structures. In a chemical reaction,

More information

Overview'of'Solid-Phase'Peptide'Synthesis'(SPPS)'and'Secondary'Structure'Determination'by'FTIR'

Overview'of'Solid-Phase'Peptide'Synthesis'(SPPS)'and'Secondary'Structure'Determination'by'FTIR' verviewofsolid-phasepeptidesynthesis(spps)andsecondarystructuredeterminationbyftir Introduction Proteinsareubiquitousinlivingorganismsandcells,andcanserveavarietyoffunctions.Proteinscanactas enzymes,hormones,antibiotics,receptors,orserveasstructuralsupportsintissuessuchasmuscle,hair,and

More information

Candidate Style Answer

Candidate Style Answer Candidate Style Answer Chemistry A Unit F321 Atoms, Bonds and Groups High banded response This Support Material booklet is designed to accompany the OCR GCE Chemistry A Specimen Paper F321 for teaching

More information

Chapter 2 Polar Covalent Bonds; Acids and Bases

Chapter 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 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

The dipolar nature of acids

The 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 information

partial positive an acid is a hydrogen ion donor, or proton donor base is a hydrogen ion acceptor, or proton acceptor acidic protons acid base

partial 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 information