Professional Documents
Culture Documents
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11
structure determination
Structure
Methodology: Chem. Commun., 2008, 22, 2559-2561; Org. Lett. 2012, 14, 2940-2943; Org. Lett. 2014, 16, 4078.
Structure determination: J. Org. Chem., 2008, 73, 4053; Chem. Eur. J. 2013, 19, 12644-12648
Total synthesis: J. J. Davies, T. M. Krulle, J. W. Burton, Org. Lett. 2010, 12, 2738-2741; Org. Lett. 2014, 16, 4078;
J. Am. Chem. Soc., 2012, 134, 11781; S. J. Ferrara, J. W. Burton, Chem. Eur. J. 2016, 22, 11597-11600.
Burton Group Ethos etc. 3
Characterisation
Assigning spectra
Many people are very lazy when it comes to assigning NMR multiplets. Attached is a very useful
paper from Prof. Hoye describing a fail-safe method for coupling constant analysis. Also attached is
a list of common solvents and their chemical shifts.
T. R. Hoye, H. Zhao, J. Org. Chem. 2002, 67, 4014-4016.
Burton Group Ethos etc. 4
Characterisation
Solvent Impurities
You will find many extraneous peaks frequently appear in your NMR spectra – these are frequently
due to solvent from your reaction or your column. Fulmer has very usefully provided a list of
chmical shifts for the majority of common laboratory solvents:
G. R. Fulmer, A. J. M. Miller, N. H. Sherden, H. E. Gottlieb, A. Nudelman, B. M. Stoltz, J. E. Bercaw, K.
I. Goldberg, Organometallics 2010, 29, 2176-2179.
Burton Group Ethos etc. 5
Purity
You need to provide characterisation data for a homogenous (pure) compound i.e. a single entity
which is free from solvent.
Burton Group Ethos etc. 6
Purity
Purity is everything – the next reaction is most likely to work if the compound you put in is very
pure. Your yield can only be quoted on pure homogeneous material etc. etc.
Burton Group Ethos etc. 7
Characterisation
If you have made a new compound which is not in the literature then you require the following
characterisation as an absolute minimum:
1
H NMR – on a high field instrument which is going to be archived (i.e. not from the routine open-
access machines).
13
C NMR - on a high field instrument which is going to be archived (i.e. not from the routine open-
access machines)
IR
low and high resolution mass spec.
Rf
melting point, if the compound is a solid.
boiling point, if you have distilled the compound
Optical rotation, if the compound is chiral and non-racemic.
Burton Group Ethos etc. 8
Characterisation
Additionally -
In order to fully characterise your compound you may well need to have other NMR experiments
performed on your sample (routinely 1H-1H COSY, DEPT, HSQC, HMBC, NOE etc).
With all of the NMR samples which you run or are run for you by the service you will need to give
the sample a code. It is imperative that you number your samples systematically with a code which
matches the lab book page number so that after you have left the group you your spectra can be
readily retrieved from the database and matched up with the experiment in your lab book.
If you are have made a known compound the minimum characterisation required is 1H NMR, melting
point (if applicable) and optical rotation (if applicable).
Burton Group Ethos etc. Lab book 9
Burton Group Ethos etc. 10
Conducting Reactions
It is always better to do the reaction perfectly first time than sloppily and have to repeat it. Carefully
monitoring your reactions by observation and tlc will allow you to optimise the reaction more easily.
You should tlc your reaction just after you have added the last reagent and then after 5 mins, 30
mins, 1 hour etc to see how it is progressing.
Observation is everything! +
Burton Group Ethos etc. 11
■ Before set up, think how to monitor reaction (ie. TLC, UV, NMR, color)
■ Think about properties of product when planning work-up: a) acidity b) basicity c) volatility
■ Always plan ahead - how would you overcome an unsuccessful reaction or proceed in a successful case
■ Don't keep your chemistry a secret; talk to people and ask questions
■ Make the lab work for you when you are not in the lab
Burton Group Ethos etc. 13
Literature
It is imperative that you keep abreast of the organic chemistry literature.
Angewandte Chemie, JACS, JOC, Organic Letters, Chem. Commun – you should also look at
Tetrahedron, Tetrahedron Letters and Tetrahedron Asymmetry.
One of the easiest ways to organise your literature is to use an RSS Reader “The Group” will be able
to create accounts and show you how to use this facility.
Reports
Written research reports are to be handed into me in both bound copies and
electronically at the end of each term.
Additionally one side of Chem-Draw on what you have done this week and
plan to do next week should be sent to be by Friday 5 pm each week
Burton Group Ethos etc. 14
Burton Group Ethos etc. 15
Safety
You have all been through numerous safety inductions which are for your benefit.
If in doubt ask – if you don’t like the answer come and ask me
Much better to know exactly what you are doing than do something wrong which can be very
dangerous and will certainly waste resource.
You MUST talk with me if you are planning to use tert-BuLi, cyanide, azide, HF, mercury, nitric acid,
diazo compounds, or trialkyl alumimiums – this is by no means an exhaustive list.
Never ever use azide anion with dichloromethane (or any chlorinated solvent), or mix acetone with
chloroform, or any form of mercury with nitric acid.
Working Hours
Core working hours are 9-6 pm Monday to Friday – this is when you are
expected to be in the lab – (There is no safety cover after 4.30 pm).
If you stay after 6 pm (which many people do) or come in at the weekends
(which people do too) then you need to make sure that there are other people
around. As a matter of courtesy please ask me (by e-mail) when you wish to
take days off.
Burton Group Ethos etc. 16
Rack Clearing – Manjeet Monday (+clean area), Bruno (Denis? or Claire?) Tuesday & Wednesday, Tom Thursday &
Friday
Done first thing in the morning every day.
Empty completely the rack of dried glassware. This includes glassware, caps, suba-seal septa, stir bars… Make sure
everything is placed at the correct place as otherwise it might be considered as lost. If you won’t know where is goes,
ask around!
If people are away, just pick up their duties and the lab will do the same when you are away.
Burton Group Ethos etc. 18
Group Meetings
9 am on Thursday mornings in the Basement Meeting Room – CRL (duration ca. 2 hours)
No mobile phones
No yawning!
Group meetings provide a more formal opportunity for you to present your work
Problem sessions
Literature presentations
Burton Group Ethos etc. 19
Working as a team requires everyone to do their lab duties efficiently and in a timely manner
Please discuss your chemistry with everyone in the lab – good ideas will come from this
only music etc. that I would NOT be embarrassed by if I were to bring an academic
visitor into the lab is to be played.
Look out for each other in the lab – if someone needs help, then help them, if someone is doing something
unsafe then tell them
Doing practical organic chemistry is hard work, and difficult at times, but it is also enjoyable as should
working as part of a team be.
Burton Group Ethos etc. 20
■ Chemdrawshortcuts
■ nmr impurities
■ TLC
Burton Group Ethos etc. 21
Wiley
ACS
JWB presentation
ACS with serif atom labels
RSC
Burton Group Ethos etc. Reactivity and Control for Organic Synthesis this is arial 24
Regioselectivity – i.e. selectivity between different parts of the same functional group
direct addition in preference to conjugate addition ortho and para products in preference to meta product
Burton Group Ethos etc. Reactivity and Control for Organic Synthesis this is Times New Roman 25
Regioselectivity – i.e. selectivity between different parts of the same functional group
direct addition in preference to conjugate addition ortho and para products in preference to meta product
Burton Group Ethos etc. 26
■ sans serif fonts for all text (this is calibri) - serif fonts are hard to read and do not look good on screen
■ sans serif fonts for atom labels (arial / helvetica are the best)
not
Burton Group Ethos etc. 27
Nucleophilic Substitution at a saturated carbon ■ two limiting mechanistic cases – SN2 and SN1 – mechanistic
continuum between these extremes
■ SN2 – substitution, nucleophilic bimolecular ■ SN1 – substitution, nucleophilic unimolecular
■ example: MeI + NaOH → MeOH + I- ■ example:
■ concerted reaction, single transition state ■ stepwise reaction, via an intermediate - the 1st step is
no intermediate is formed rate determining (formation of C+), 2nd step is fast
Burton Group Ethos etc. 28
■ heats of hydrogenation
substitution
Br
Br
not addition
■ heats of hydrogenation
H2/Pt catalyst H2/Pt catalyst H2/Pt catalyst
o
ΔHhydrog = -120 kJmol-1 o
= 3 x -120 = -360 kJmol-1
ΔHhydrog
o
= -210 kJmol-1
ΔH hydrog
(hypothetical, 1,3,5-
cyclohexatriene)
Burton Group Ethos etc. 30
12.12
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11
structure determination
Structure
Methodology: Chem. Commun., 2008, 22, 2559-2561; Org. Lett. 2012, 14, 2940-2943; Org. Lett. 2014, 16, 4078.
Structure determination: J. Org. Chem., 2008, 73, 4053; Chem. Eur. J. 2013, 19, 12644-12648
Total synthesis: J. J. Davies, T. M. Krulle, J. W. Burton, Org. Lett. 2010, 12, 2738-2741; Org. Lett. 2014, 16, 4078;
J. Am. Chem. Soc., 2012, 134, 11781; S. J. Ferrara, J. W. Burton, Chem. Eur. J. 2016, 22, 11597-11600.