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Youngstown State University - Department of Chemistry
CHEM 5822 – Advanced Organic Laboratory
Text:
“Advanced Practical Organic Chemistry, 3rd Ed.”, by Leonard, Lygo, and Procter.
Course Description: This course will introduce the student to modern methods of the organic laboratory. The focus
will be on laboratory techniques in synthesis, purification, and identification of organic compounds.
General Overview: In the past, I had each student will conduct a separate, distinct synthesis, within a related class of
reactions. We’ll do that with some of the reactions below, but not all of them (some of them varied too much). Variation
of results can be reasonably expected. The actual starting materials will be assigned randomly. The reaction schedule
is subject to change. Some reactions may take numerous attempts before a satisfactory result is obtained.
Some reactions may be conducted as group efforts [Bis(2,2,2-Trifluoroethyl) Phosphite, and Bis(2,2,2-Trifluoroethyl)
Phosphorochloridate] as they involve very similar techniques.
Arbuzov Reaction – Synthesis of Triethyl Phosphonoacetate.
O
O
(EtO)3P
Br
O
(EtO)2P
OEt
OEt
In the Arbuzov reaction, a neat mixture (no solvent) of an -haloester (potent lachrymator) and a trialkyl phosphite (very
o
strong stench) is heated at about 140 C (round bottom flask, stir bar, reflux condenser, in a HOOD) until the starting
materials are consumed (monitor by GC, or TLC). The product will be purified by distillation at reduced pressure. You
will use the product to conduct Horner-Wadsworth-Emmons Condensation #1. See pages 568-571 of the text for more
information.
Chem. Rev. 1981, 81, 415.
Chem. Rev. 1989, 89, 863.
Horner-Wadsworth-Emmons Condensation #1 and #2
O
O
(EtO)2P
O
(CF3CH2O)2P
O
1) NaH
OEt
O
OCH3
2) PhCHO
Ph
1) TMS2NK, 18-crown-6,
o
THF, -78 C
2) PhCHO
Ph
O
OEt
OEt
O
Ph
Ph
OCH3
O
OCH3
Each student will prepare and separate by flash chromatography a mixture of ,-unsaturated esters. The E/Z ratio will
be determined by spectroscopic methods.
Chem. Rev. 1981, 81, 415.
Chem. Rev. 1989, 89, 863.
Acc. Chem. Res. 1983, 16, 411.
Chem. Rev. 1974, 74, 87.
Still, W. C.; Gennari, C. Tetrahedron Lett. 1983, 24, 4405.
Wadsworth, W. S. Org. React. 1977, 25, 73.
Bis(2,2,2-Trifluoroethyl) Phosphite
CF3CH3OH
(CH3)3COH, CH2Cl2
PCl3
O
(CF3CH2O)2PH
Synthesis 1984, 410.
Bis(2,2,2-Trifluoroethyl) Phosphorochloridate (BITE)
O
(CF3CH2O)2PH
SO2Cl2
benzene
O
(CF3CH2O)2PCl
Org. Prep. Proced. Int. 1999, 31, 230.
LDA
O
O
OP(OCH2CF3)2
1) LDA
( )n
O
2) (CF3CH2O)2PCl
( )n
Each student will form a ketone enolate with LDA, and treat it with an electrophile. Product purification will be done by
flash chromatography.
Tetrahedron Lett. 1986, 27, 4265.
J. Org. Chem. 1987, 52, 4185.
Stock, J. R. MS Thesis, Youngstown State University, August 1998
Carbohydrate Lab
PRELAB
Before beginning any experiment, the student will prepare an outline, based on literature examples, of the procedure to
be followed. NO lab work will be allowed until the Prelab has been approved.
SPECTROSCOPIC CHARACTERIZATION
1
13
31
1
H and C NMR (and P NMR where applicable) spectra will be taken for all compounds prepared, and H NMR will
1
13
be recorded for all starting materials. The H and C NMR spectra will be assigned as fully as possible. GC-MS (if
available) will be taken on all products and some starting materials. IR spectra may be taken on some products/starting
materials.
LAB REPORTS
Each student will submit a typed lab report in ACS format. Abstract, Introduction, Results and Discussion, Experimental
Procedure, and References. The Arbuzov Reaction and Horner-Wadsworth-Emmons Condensations will be combined
into one lab report.
LAB NOTEBOOK
Each student will keep a lab notebook.
LECTURE TOPICS
The content of the lectures will include a discussion of the following:
TLC, GC-MS, NMR, syringe techniques, inert atmosphere techniques, the lab notebook, the lab report, simple and
vacuum distillations, extraction, the glassware in an organic lab, flash chromatography, ovens, base baths, rotary
evaporators, balances, the chemical literature, high and low temperature reactions, and lab safety.
GRADES
Midterm – Wednesday, March 4, 2015.
100 pts
Optional Final - Friday, May 8, 2015
10:30 AM-12:30 PM
Reports
200 pts
Lab Technique*
100 pts
A (400-360 pts.); B (359-320 pts.); C (319-280 pts.); D (279-200 pts.); F below 200 pts.
Lab Technique will be determined by evaluation of product purity, % yield, correct assignment of spectroscopic data,
including the lab notebook, and technique (organization, preparedness, assessment of lab skills, etc.).
All lab work will be completed by Friday, May 1, 2015
All lab reports will be turned in by Monday, May 4, 2015
Last Day for Withdrawing with a Grade of 'W', Thursday, March 26, 2015
STATEMENT OF SAFETY EXPECTATIONS
Safety is of utmost importance in the laboratories in the STEM College at Youngstown
State University. The first offense for a safety violation in the STEM College is a grade
of zero for that laboratory session. The second offense will result in a grade of F in
the laboratory course. In both situations, the student will be expected to leave the
laboratory.
You are expected to follow the safety instructions provided to you by the laboratory
instructor during the 1st laboratory session of each semester. Cell phones and other
electronic devices should not be used during the lab session. Additional rules may
apply depending on the specific lab hazards.
There are no exceptions to this rule.
After signing this form, submit this form to your laboratory instructor.
By signing this document, you, the student, acknowledges that you understand the
safety expectations of the YSU STEM College.
Were laboratory safety instructions conducted by the instructor?
Yes
No
Laboratory Instructor’s Name:
Course Number:
Academic Calendar year and Semester:
Student Signature:
Printed Name:
Date: