INSTRUCTIONS FOR. LITERATURE PROBLEM REPORT CHEM 30121, Fall 2018

Transcription

1 NSTRUCTNS FR LTERATURE PRBLEM REPRT CEM 30121, Fall 2018 Provide a reaction scheme for a fluorescent dye that features at least one reaction that you have performed and/or was covered during the lectures this semester (see below). You must use the template (provided on the next page). The fluorescent dye CANNT be commercially available. List of reactions: Elimination/dehydration (synthesis of alkenes, E1) Electrophilic aromatic substitution (Friedel-Crafts, nitration, bromination, etc) Nucleophilic substitution (S N 1/S N 2) Nucleophilic addition to the carbonyls (esterification, aldol condensation, Grignard reaction) Characteristics of fluorescent dyes spectral properties: Both excitation (λex) and emission (λem) wavelength should be provided (in most publications this information is given in tables; sometimes the tables are given in the supporting information. Emission wavelength will be larger than the excitation wavelength; these wavelengths are solvent specific; therefore, make sure that you report the solvent in which these spectral properties were obtained.

2 LTERATURE PRBLEM REPRT FRM CEM 30121, Fall 2018 Name Lab Section: Wed / Thu / Fri 1. Chemical structure & molecular formula 2. Chemical Name(s) (if available) 3. Physical Properties (color, liquid/solid, m.p./b.p., etc) and Spectral Properties (excitation and emission wavelengths, solvent) 4. Synthetic Scheme Below are the instructions for the synthetic scheme delete them, and use the space to write your answer: Show a synthetic route to the dye in the format provided below. Conditions should include reaction time, temperature, solvent, etc. Starting material: if the starting material is commercially available manufacturer, and the catalogue number must be provided. f the starting material is not commercially available (i.e., it was synthesized according to a literature procedure), that reference should be provided. starting material reagents conditions % yield A reagents conditions % yield B reagents conditions % yield... FLURESCENT DYE (chemical structure) 5. References Below are the instructions for references delete them, and use the space to write your answer: All references must be written in the following format, and must be original journal articles (not reviews, patents, books, conference proceedings, etc): Name of all the authors, Title of the paper, Journal, Year, Volume, Page Page. Example: P. L. Stotter, M. D. Friedman, D. E. Minter, Model studies of a conceptually new approach to the total synthesis of quinine, J. rg. Chem., 1985, 50,

3 LTERATURE PRBLEM REPRT FRM CEM 30121, Fall 2018 Name Lab Section: Wed / Thu / Fri 1. Chemical structure & molecular formula 2. Chemical Name(s) (if available) 3. Physical Properties (color, liquid/solid, m.p./b.p., etc) and Spectral Properties (excitation and emission wavelengths, solvent) 4. Synthetic Scheme Below are the instructions for the synthetic scheme delete them, and use the space to write your answer: Show a synthetic route to the dye in the format provided below. Conditions should include reaction time, temperature, solvent, etc. Starting material: if the starting material is commercially available manufacturer, and the catalogue number must be provided. f the starting material is not commercially available (i.e., it was synthesized according to a literature procedure), that reference should be provided. starting material reagents conditions % yield A reagents conditions % yield B reagents conditions % yield... FLURESCENT DYE (chemical structure) Jeff Bond Guest Lecture Next Tuesday, November 6 5. References Below are the instructions for references delete them, and use the space to write your answer: All references must be written in the following format, and must be original journal articles (not reviews, patents, books, conference proceedings, etc): Name of all the authors, Title of the paper, Journal, Year, Volume, Page Page. Example: P. L. Stotter, M. D. Friedman, D. E. Minter, Model studies of a conceptually new approach to the total synthesis of quinine, J. rg. Chem., 1985, 50,

4 Nucleophilic Additions to Carbonyls

5 Esterification Me (excess) 2 S 4 (conc) Me 2 Aldol condensation C 3 C 3 Na Et, 2 C 3 acetophenone p-anisaldehyde trans-p-anisalacetophenone Grignard reaction Br Mg Et 2 ( 2 initiator) (excess) MgBr PhCMe Et 2, reflux Ph 3 CMgX workup bromobenzene phenyl magnesium bromide triphenylmethanol (trityl alcohol)

6 LTS F DFFERENT REACTNS, DFFERENT REAGENTS, DFFERENT CNDTNS BUT T ALL CMES T Nu E B A

7 Esterification (Fischer esterification) & Aldol Reaction ( Borodin reaction ) Lab #5

8 REACTN RDER FR TE LAB 5 1. Start with esterification 2. Start on aldol, once esterification is refluxing Aldol experiment is not very long, but use time wisely

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11 Aldol Reaction Aldol addition or aldol condensation aldol - aldehyde/ketone and alcohol as starting materials β-hydroxy aldhyde or ketone - product

12 Condensation reaction of two or more molecules combine into a large molecule with a loss of a smaller molecule (water) Self-condensation both partners in the condensation reaction are the same DMERZATN

13 Self-Condensation of Acetone Base (cat) or Acid (cat)

14 BASE-catalyzed Aldol Condensation 3 C 3 C 3 C 2 3 C δ δ C 3 3 C 3 C

15 ACD-catalyzed Aldol Condensation - -

16 f the aldol is a 3 o -alcohol, an elimination (E1) is likely to take place - 2

17 f the aldol is a 3 o -alcohol, an elimination [E1cB (cb = conjugate base) - Base catalyzed] is likely to take place Even 2 o can eliminate - conjugated product!! -

18 2

19 base-catalyzed enolization elimination

20 Cross-Condensation Different carbonyl compounds: one will act as a nucleophile in enol/enolate form the other will be electrophile

21 Cross-Condensation N 2 N 2

22 R N 2 N 2 N 2 N 2 N 2 R

23 Carbonyl compounds that do not participate in enol formation Cl 3 C CCl 3 F 3 C CF 3 N No α-hydrogen

24 Nitroalkanes enolization & aldol reaction N N N C 3 N 2

25 3 C N 2 Na, Me δ δ N N 2 N 2 Na Me

26 Elimination is very facile, if possible C3 N 2 Na, Me N 2

27 aloform reaction Qualitative reaction for methyl-ketones (and a few compounds) C 3

28 3 2 2 C 3 base Nu 2 2

29 R R C C 3 2 2