ORGANIC CHEMISTRY 2 Prof Janina E Kamiska d

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ORGANIC CHEMISTRY 2 Prof. Janina E. Kamińska Łódź University of Technology Faculty of Biotechnology

ORGANIC CHEMISTRY 2 Prof. Janina E. Kamińska Łódź University of Technology Faculty of Biotechnology and Food Sciences Institute of General Food Chemistry ul. Stefanowskiego 4/10 Room no 209 (Consultation hours: Tue. 13: 15 -14: 00, Wed. 14: 15 -15: 00) Phone: 42 6313412 E-mail: janina. kaminska@p. lodz. pl

ORGANIC CHEMISTRY 2 sem. III. 2018/19 Lecture 15 h Tutorials 15 h Laboratory 45

ORGANIC CHEMISTRY 2 sem. III. 2018/19 Lecture 15 h Tutorials 15 h Laboratory 45 h Prof. J. E. Kamińska, dr Ewa Maciejczyk Workload outside classroom 90 h ECTS credits: 6

Textbooks John Mc. Murry, “Organic Chemistry”, 5 th ed. Brooks/Cole Publishing Co. , Pacific

Textbooks John Mc. Murry, “Organic Chemistry”, 5 th ed. Brooks/Cole Publishing Co. , Pacific Grove, California 2000 (or later editions) K. P. C. Vollhardt, N. E. Schore, “Organic Chemistry, Structure and Function”, 3 rd ed. W. H. Freeman and Co. , New York 1999 (or later editions) J. Clayden, N. Greeves, S. Warren, P. Wothers, “Organic Chemistry”, Oxford University Press 2000 (or later editions) Laboratory textbooks: J. R. Mohrig, C. Noring-Hammond, P. F. Shatz ”Techniques in Organic Chemistry” W. H. Freeman and Company 2010 J. C. Gilbert, S. F. Martin ”Experimental Organic Chemistry” 5 th ed. Brooks/Cole 2011 L. M. Harwood, C. J. Moody, J. M. Percy, “Experimental Organic Chemistry”, 2 nd ed. , Blackwell Science Ltd. , Oxford 1999

Textbooks Organic Chemistry Fundamentals of Organic Chemistry with Biological Applications

Textbooks Organic Chemistry Fundamentals of Organic Chemistry with Biological Applications

Mc. Murry in Polish

Mc. Murry in Polish

Laboratory textbook

Laboratory textbook

Final grade consist of: Written exam test 50% Laboratory grade 30% Organic chemistry 1

Final grade consist of: Written exam test 50% Laboratory grade 30% Organic chemistry 1 20%

Lectures • An overview of carbonyl group chemistry • Aldehydes and ketones – preparation

Lectures • An overview of carbonyl group chemistry • Aldehydes and ketones – preparation and chemical reactions: nucleophilic addition to carbonyl group; -substitution reactions, carbonyl condensation reactions (aldol condensation). • Carboxylic acids and their derivatives (acyl chlorides, anhydrides, esters, amides, nitriles) – preparation and chemical behaviour (nucleophilic acyl substitution, -substitution reactions). • Aliphatic and aromatic amines - preparation and chemical properties.

Biomolecules • -Amino acids – structure and properties. Isoelectric point, analytical reactions of amino

Biomolecules • -Amino acids – structure and properties. Isoelectric point, analytical reactions of amino acids. • Peptides and proteins. Peptide structure determination. Chemical synthesis of peptides. Protein structure (general). • Monosaccharides (pentoses and hexoses) – structure and properties. • Disaccharides (sucrose, lactose, maltose, cellobiose) and polysaccharides (cellulose, starch, glycogen) – structure and properties. • Lipids – structure and properties of glycerides, isoprenoids, terpenes. • Heterocyclic compounds containing oxygen, sulphur and nitrogen. Pyrimidine and purine bases – structure and properties. Nucleotides, nucleosides and nucleic acids structure.

An overview of carbonyl group chemistry

An overview of carbonyl group chemistry

CARBONYL GROUP sp 2 C=O bond length 1. 22 A sp 2 C=C bond

CARBONYL GROUP sp 2 C=O bond length 1. 22 A sp 2 C=C bond length 1. 33 A

CARBONYL GROUP ELECTRONIC STRUCTURE Lone-pair electrons π-bond + Carbon or Hydrogen

CARBONYL GROUP ELECTRONIC STRUCTURE Lone-pair electrons π-bond + Carbon or Hydrogen

CARBONYL GROUP ORBITALS

CARBONYL GROUP ORBITALS

POLARIZATION OF CARBONYL GROUP AND ITS REACTIVITY Nucleophilic oxygen reacts with acids and electrophiles

POLARIZATION OF CARBONYL GROUP AND ITS REACTIVITY Nucleophilic oxygen reacts with acids and electrophiles - + Electrophilic carbon reacts with bases and nucleophiles

TYPES OF CARBONYL COMPOUNDS ALDEHYDES Hydrogen or carbon cannot stabilize negative charge and therefore

TYPES OF CARBONYL COMPOUNDS ALDEHYDES Hydrogen or carbon cannot stabilize negative charge and therefore cannot act KETONES as leaving group

TYPES OF CARBONYL COMPOUNDS Carboxylic acid chloride Carboxylic acid ester Carboxylic acid anhydride Carboxylic

TYPES OF CARBONYL COMPOUNDS Carboxylic acid chloride Carboxylic acid ester Carboxylic acid anhydride Carboxylic acid amide Electronegative atom (oxygen, halogen, nitrogen) bonded to acyl group R-CO- can stabilize a negative charge, therefore groups –OH, -Cl, -OCOR’, -NH 2 can serve as leaving groups in substitution reactions.

TYPES OF CARBONYL COMPOUNDS Cyclic acid anhydride Cyclic ester (lactone) Cyclic amide (lactam)

TYPES OF CARBONYL COMPOUNDS Cyclic acid anhydride Cyclic ester (lactone) Cyclic amide (lactam)

POLARITY OF CARBONYL COMPOUNDS Compound Type of carbonyl group HCHO CH 3 CHO (CH

POLARITY OF CARBONYL COMPOUNDS Compound Type of carbonyl group HCHO CH 3 CHO (CH 3)2 CO Ph. COCH 3 Cyclobutanone CH 3 COOH CH 3 COCl CH 3 COOCH 3 CONH 2 CH 3 CON(CH 3)2 Aldehyde Ketone Carboxylic acid Acid chloride Ester Amide Dipole moment (D) 2. 33 2. 72 2. 88 3. 02 2. 99 1. 74 2. 72 1. 72 3. 76 3. 81

TYPES OF CARBONYL COMPOUNDS REACTIONS GENERAL MECHANISMS • Nucleophilic addition • Nucleophilic acyl substitution

TYPES OF CARBONYL COMPOUNDS REACTIONS GENERAL MECHANISMS • Nucleophilic addition • Nucleophilic acyl substitution • -Substitution • Condensation reactions

Nucleophilic addition to carbonyl group 1 st step Carbonyl carbon rehybridizes from sp 2

Nucleophilic addition to carbonyl group 1 st step Carbonyl carbon rehybridizes from sp 2 to sp 3

Nucleophilic addition to carbonyl group 2 nd step Two ways of stabilization of tetrahedral

Nucleophilic addition to carbonyl group 2 nd step Two ways of stabilization of tetrahedral intermediate

Nucleophilic addition to carbonyl group EXAMPLE 1 – addition of methylmagnesium bromide to cyclohexanone

Nucleophilic addition to carbonyl group EXAMPLE 1 – addition of methylmagnesium bromide to cyclohexanone Synthesis of tertiary alcohol from ketone

Nucleophilic addition to carbonyl group EXAMPLE 2 – cyclohexanone imine formation Net effect –

Nucleophilic addition to carbonyl group EXAMPLE 2 – cyclohexanone imine formation Net effect – replacing C=O by C=NR

Nucleophilic acyl substitution Net effect – replacing of group Y with nuclephile. -Y is

Nucleophilic acyl substitution Net effect – replacing of group Y with nuclephile. -Y is called leaving group Y = -OR (ester) -OCOR (anhydride) -Cl (acid chloride) -NH 2, -NHR, -NR 2 (amide)

Nucleophilic acyl substitution EXAMPLE – ester synthesis from acid chloride and alkoxide Net effect

Nucleophilic acyl substitution EXAMPLE – ester synthesis from acid chloride and alkoxide Net effect – replacing of Cl by OR

 -Substitution reactions -carbon -substituted carbonyl compound Intermediates

-Substitution reactions -carbon -substituted carbonyl compound Intermediates

 -Substitution reactions Net effect – extending of carbonyl compound hydrocarbon framework by –CH

-Substitution reactions Net effect – extending of carbonyl compound hydrocarbon framework by –CH 2 R fragment at -carbon

 -Substitution reactions EXAMPLE – -methylation of cyclohexanone

-Substitution reactions EXAMPLE – -methylation of cyclohexanone

Carbonyl condensation reactions New C-C bond Two aldehydes Aldol product (aldehyde + alcohol)

Carbonyl condensation reactions New C-C bond Two aldehydes Aldol product (aldehyde + alcohol)

Carbonyl condensation reactions Carbonyl condensation reaction is a combination of -substitution step and nucleophilic

Carbonyl condensation reactions Carbonyl condensation reaction is a combination of -substitution step and nucleophilic addition step acetaldehyde By condensation of acetaldehyde 3 -hydroxybutanal is prepared 3 -hydroxybutanal

Nucleophilic addition reactions of carbonyl compounds Alcohol Alkene Alcohol Cyanohydrin Imine Alkane Acetal Enamine

Nucleophilic addition reactions of carbonyl compounds Alcohol Alkene Alcohol Cyanohydrin Imine Alkane Acetal Enamine

Negatively charged nucleophiles Neutral nucleophiles Hydroxide ion Water Hydride ion An alcohol A carbanion

Negatively charged nucleophiles Neutral nucleophiles Hydroxide ion Water Hydride ion An alcohol A carbanion An alkoxide ion Cyanide ion Ammonia An amine