CHEM254 Experiment 3 Sodium Hypochlorite Oxidation of Alcohols 1

The attached article will serve as a starting point for this experiment.

“The design of laboratory experiments in the 1980's: A case study on the oxidation of alcohols
with household bleach” by Jerry R. Mohrig , David M. Nienhuis , Catherine F. Linck , Carol Van
Zoeren , Brian G. Fox and Peter G. Mahaffy in the Journal of Chemical Eduation, 1985, Vol. 62
(number 6), p 519-512

Maybe in the 1980s, students could sit around and wait an hour for the their reaction mixture to
“brew,” but in the twenty first century college students have places to be and things to do
(besides Organic Chemistry, that is). To this end we will explore the procedure for the addition
of bleach to a mixture of cyclohexanol and acetic acid. The authors of this JCE article describe
several “improvements” they have made to previous procedures, but do not mention if they
attempted to optimize the addition of bleach part of the experiment.

We will attempt to recreate the published procedure as closely as possible with the following
considerations.

Notes on published experimental procedure:

1. Dispose of all chemicals in waste disposal hood please.

2. We do not have a large quantity of three-necked flasks. They cost about $50 apiece. Sorry.

3. In reference to the situation mentioned in 2, devise a method to perform a controlled addition

of bleach, monitoring temperature, without allowing noxious vapors to escape from the
reaction mixture.

Orginal literature procedure for addition of bleach:

1) Add 25 mL of bleach and swirl
2) Add an additional 90 mL of bleach in a controlled manner over the course of about 15
minutes being careful to not allow the temperature to exceed 45o C.
3) Add an additional 115 mL of bleach in a controlled manner over the course of 20 - 30
minutes being careful to not allow the temperature to exceed 45o C.
4) Swirl the mixture from time to time for another 20 minutes.

N.B. In order to gather critical data – record temperature of reaction mixture before addition of
bleach and then afterwards at 5 minute intervals.

Proposals for modification:

Proposed modification 1:

Follow the previous procedure but reduce the time intervals by half.
Try to keep the temperature to under 45o C.
Record temperature of reaction mixture before addition of bleach and then afterwards at 5 minute
intervals.
CHEM254 Experiment 3 Sodium Hypochlorite Oxidation of Alcohols 2

Proposed modification 2;

Mix the bleach “straight away” and let sit for 30 minutes.
Try to keep the temperature to under 45o C.
Record temperature of reaction mixture before addition of bleach and then afterwards at 5 minute
intervals.

In lab analysis:

Obtain the IR spectrum of the product.

Data entry:

Record the yield in grams of product and your temperature data points at time = 0, 5, 10, 15, 20,
30, 35 min, … on a spreadsheet before leaving lab.

Submission for GC-FID and NMR analysis.

Hand in a sample of your product in a properly labeled vial: Your name, date, vials contents, and
your experimental procedure (original, #1, or #2).

Checklist for completing the "Prelab" section:

(refer to Laboratory Syllabus for complete directions)

Title and Purpose.

____Physical constants. (2 points) Create a table of physical constants, solubility and safety data
for the chemical compounds referred to in the procedure.

____ Structures and equations. (1 point) Write (using chemical structures) the balanced equation
for this reaction. Hint: water is a product.

___ Flowchart. (1 point) Refer to "Procedure" Your assigned procedures: orginal:

(1R,2R,3R,4R,5R,6R,7R,8R)
modification 1: (1L,2L,5L,7L,8L) or modification 2 (3L,4L,6L,9,10)
___ Calculations. (2 points)
1) Determine the number of moles of acetic acid used.
2) Determine the number of moles of NaOCl used. Use 5.25g/100 mL NaOCl in Clorox.
3) Calculate the theoretical yield (in grams) of cyclohexanone.

Article:
_____ (1 point) According to the authors, what are the three advantages of using (sodium)
hypochlorite rather than Cr(IV)?

____ Safety Question: (1 point) Consult the MSDS for Clorox <http://www.biosci.ohio-
state.edu/safety/MSDS/CLOROX%20LIQUID%20BLEACH.htm> What Emergency/First Aid Procedures
are advised if the product is splashed into one’s eyes?
CHEM254 Experiment 3 Sodium Hypochlorite Oxidation of Alcohols 3

Experimental Observations and Data:

Hand in a copy of your experimental observations and data before you leave lab.
Experimental Observations.
Refer to last semester and laboratory syllabus.

Lab Report Checklist:

Results.
____ Which experimental procedure did you use (original #1, or #2)?

____ (1 point) % yield of product Æ product mass x 100/theoretical yield. Show your
calculations.

____ (1 point) Interpret the IR spectrum of your product. Did you obtain the desired product?
How pure is it?

____ (1 point) Interpret the GC-FID chromatogram of your reaction mixture (GC-FID of
standards may be obtained on the CHEM254 MyDU website.) Did you obtain the desired
product? How pure is it?

Discussion and Conclusion.

Interpret the results of the class data. (2 points)

What are the issues that need to be addressed? (For example, is it sufficient to compare reported
yields or are there other aspects of the experiment that should be addressed?)
What conclusions can be drawn?

What should next year’s students do to continue to explore this intriguing reaction? (1 point)

Write a Journal of Organic Chemistry style abstract of this experiment including class data.
(2 points)
JOC website: http://pubs.acs.org/journal/joceah
Sample article with abstract: http://pubs.acs.org/doi/pdf/10.1021/jo101791w
The Design of Laboratory Experiments in the 1980's
A Case Study on the Oxidation of Alcohols with Household Bleach
Jerry R. Mohrig, David M. Nienhuis, Catherine F. Linck, Carol Van Zoeren, and Brian G. Fox
Carleton College, Northfield, MN 55057
Peter G. Mahaffy
The King's College, Edmonton, Alberta, Canada T5H 2M1

Chemists know that lahoratory experiences are an impor- Second. the hv~ochloritereaction offers substantial safetv
tant component of undergraduate education in chemistry. advantag& compared to chromic acid oxidation. chromium
This is stated once again in the new Criteria and Evaluation trioxide and its salts have a corrosive action on the skin and
Procedures booklet from the ACS Committee on Professional mucous membranes. For 1981, the time-weighted average
Training. However, teaching laboratories are expensive to (TWA) concentration limit of Cr(V1) compounds in the air
operateind administrators may question the necessity of so was 0.05 mg/m3 (milligrams of compound per cubic meter of
many lahoratory hours. We need to he clear on the . goals and air) (5). Fortunately, neither chromium trioxide nor sodium
strategies in our laboratory courses. dichromate dihydrate is very volatile. Within the last few years
Experiments must teach sound chemical principles, careful some Cr(V1) compounds have been indicted as carcinogens
observation, and useful experimental techniques. They should (6).Even though the atmospheric levels of Cr(V1) compounds
be designed to catch students' interest, transporting them in anv teaching situation would he very low, this must be
from passive spectators to active participants. Whenever viewed as a disidvantage. C'onrentrated sulfuric arid, ram-
possible, lahoratory work should involve the commonplace rnonly used in CrrVl) oxidations, is also hazanlnus. The only
and the fundamental. Experiments should relate to the appreciable safety concern in the hypochlorite oxidation is
common experience of students as well as to fundamental chlorine gas which must be contained effectively; more ahout
chemistry. this later.
In the iast few years undergraduate laboratory courses have The rising cost of common chemicals has prompted most
faced new rhallenees-inflation and increased e m ~ h a s i son chemistry teachers to reconsider common practices. The costs
lahoratory safety and the disposal of hazardous wastes. An of sodium dichromate and chromium trioxide have risen
ideal experiment is inexpensive and safe and produces in- dramatically in recent years. At current prices one can esti-
nocuous wastes. The use of some of the classic experiments mate a cost of $0.25 per student for the sodium dichromate
in the organic chemistry laboratory must be re-evaluated in alone in the Cr(V1) oxidation of 16 e of cvclohexanol.
the light of these criteria. Waste disposal, saiety, and cost &siderations associated
One experiment, found in virtually all organic chemistry with the Cr(V1Joxidation ~roceduresvrovided the imlwtus
laboratory programs, is the oxidation of an alcohol with for our exploration of sod& hypochl&ite as an alternative
chromium(VI). The oxidation of alcohols to ketones relates oxidant.
two of the most imnortant functional uerouos .
and is an im- The Stevens article reports the hypochlorite oxidation of'
portant reaction in organic synthesis. Chromic acid has been 10 alcohols in iso1atL.d yields of 8.%96"; wnh acetic acid as the
used in introductory chemistry labs since the 1940's. Probably solvent. We adapted this procedure for our introductory or-
the most popular experiment is the oxidation of cyclohexanol ganic chemistry lahoratory, using "swimming pool chlorine"
to cyclohexanone, using sodium dichromate in an acidic me- (12.5%hv " weieht)
- . to oxidize cvclohexanol to cvclohexanone.
dium. The oxidation occurs in reasonable yield and provides but encountered several problems. First, the large volumes
a good introduction to the use of infrared sDectroscoDv ."for of solvent (3-6 mL AcOHIgram of alcohol) and the ether used
fuhctiona~group analysis ( 1 ) . in multiple extractions made the experiment too expensive
In the summer of 1980 Stevens, Chapman, and Weller re- for classroom use. Second, "swimming pool chlorine" had a
ported that "swimming pool chlorine" reacts with secondary number of drawbacks. Storage of "swimming pool chlorine''
alcohols to give ketones in good yield (2).Brief notes, adapting causes its concentration to decrease by about 20% per month;
this method for use in the undergraduate laboratory, suhse- therefore, a titration was necessary before its use. Since we
quently appeared in THIS JOURNAL (3). found it availahle only in 5-gal containers, there was suh-
stantial waste in small to medium-sized classes. A more severe
disadvantage was the modest chlorine odor apparent.. in the
lahoratory from time to time. Although Clz concentrations
never exceeded the maximum recommended ACGIH short-
term exposure level (3 ppm) (5),the odor was quite unpleasant
a t this level.
..
What are the advantaees of usine hwochlorite rather than T o address these problems, we significantly altered the
Cr(V1) oxidation of an alcohol? First, oxidations with hypo- oxidation procedure in three ways. We found household
chlorite present no hazardous waste disposal problem. The bleach, a 5.25% (0.74 M ) solution of sodium hypochlorite
end are chloride and the desired ketone; no toxic availahle at most grocery stores, to function even better than
metal ions are present. Chromic acid oxidations pose a severe "swimming pool chlorine" as the oxidant for cyclohexanol.
waste disposal problem, because chromium in any soluble Yields were comparable to slightly better and atmospheric Clz
form cannot he put down the drain in some states. Chromi- concentrations were diminished considerahlv. The atmo-
um(III), produced in the oxidation of a secondary alcohol, is spheric Clz level was less than 0.2 ppm and was not detectable
toxic to fish and invertebrate snecies ( 4 ) . Its acute toxicitv ."
~hvsioloeicallv " in lahoratories in which 20 undereraduates
"
depends upon water hardness. i t 100 &L Ca('O3, the con'. were working. Bleach is available inexpensively in half-gallon
centration of Cr(l11)should not exceed .1.7 me,L. The chronic and gallon containers and standard brands do not reauire ti-
toxicity of Cr(I1I) to freshwater aquatic lif;? occurs a t con- t r a t i k Recently, the use of hypochlorite bleach has been
centrations as low as 4.4 &g/L. reported for the oxidaton of secondary alcohols (7).

Volume 62 Number 6 June 1985 519

 Second, we found no need for the large amounts of acetic is the oxidant (11). Alkaline aqueous solutions of sodium
acid renorted bv Stevens and others: 0.5 mL AcOH/e alcohol hypochlorite will not oxidize alcoholswithout additional
is suffi'cient. ~ k i point
s will be considered later in-the dis- catalysts; for example, RuCI3 and phase-transfer catalysis
cussion of the reaction nathwav. . . . At low nH.
have been renorted 112.131. . , molecular chlorine is
Third, we found ether extractions unnecessary when the a ma.ior component of the aqueous hypochlorite system. Alkali
acetic acid is neutralized with sodium hydroxide followed by meatlv increases the solubilitv of Cb bv convertine i t to
a steam distillation of the cyclohexanone. chlorihe and hypochlorite; th; pH ofbleach is abo; 12.5.
Class testing of this revised oxidation procedure by several Disproportionation and evolution of oxygen are slow a t room
hundred undergraduates in first-term organic chemistry temperature, so one can produce stable solutions of hypo-
laboratories showed that 50-60% vields of cvclohexanone are chlorite.
common. GLC analysis revealedthat two-thirds of the stu- Not a great dcal is knoumn ahout the mechanism of the hv-
dents ohtained cyclohexanone of >95% purity. Both Chlorox porhlorite oxidntion of alcohols. Presurnnl~lg,hypochlorous
and Hilex brands of bleach worked equally well. The oxidation acid must br present for the reaction to proceed. Kudes~nand
of 16 g of cyclohexanol by hypochlorite hleach works best; Mukherjee have pngpoinl that molecular rhlorine is the actual
using smaller amounts produces unacceptable product losses nxidant and the alkyl hypochlorite ester is an intermediate
on the semimicro 19/22 J glassware. Higher yields (>75%) (1.11. Their kinetic studies on the oxidation 18f 2-prnpannl with
were ohtained when extractions were used; dichloromethane chlorine pnwidr the most detailed mechanistjc studies
is an effective extraction solvent. We chose not to use the ex- a\,ailahle. If an alkyl h\lx~chlnritcis nn intermediate, one could
.. waste orodnct.
traction sten in order to avoid anv, oreanic envisage a simple E2 elimination lending to the ketone
Neutralization of the acetic acid is newsiary to avoid it5 co- ( 1 5 I.
distillation in thesteamdistillstionnithe product.Addition
of a it:w drops ot an acid-hase indirator makes the visualiza-
tion 1d ihe neutralization step cnlorful and straightforward.
.At current prices the chemicals fm the rntire experiment
cost about SU.:lS per student. Therefore, oxidation of a sec-
ondary alcohol with hypochlorite is somiwhat less expensive One expects that the mechanism of hv~ochloriteoxidation
than the Cr(V1) oxidation. of alcohois will he unraveled more compieiely in time, through
In addition to the cyclohexanol oxidation, we have used the the use of some of the elegant experimental techniques that
same procedures for the synthesis of camphor from borne01 have been applied to Cr(V1) oxidations.
and 2-octanone from 2-octanol. Both of these ketones are Our research has shown that the presence of molecular
natural products. Camphor has many medical and industrial oxygen, hydroquinone, or galvanoxyl does not affect the hy-
uses. Its fragrant
" and nenetratine odor is familiar to most pochlorite oxidation. Therefore, free-radical chain reactions
students. These two oxidation reactions can serve as excellent would seem to he unimportant in the oxidation.
variants for adventuresome students and teachers. Our kinetic studies on the acid dependence were done pri-
marily with 2-propanol, which allows a homogeneous reaction
mixture. Reaction aliquots were quenched with excess acidi-
fied iodide and the usual thiosulfate titration carried out.
Reagent-grade sodium hypochlorite was the oxidant. The
reactions were carried out under flooding conditions. where
the concentration of 2-propnnol was 20-.lij times great& than
that oithe hwochlorite.The reaction wasshown to he first-
order in oxidabt. The pH was held constant a t 25' with sodi-
um pyrophosphate (pH 9.9 and 7.8) and sodium acetate (pH
4.1) buffers. The reaction of hypochlorite with 2-propanol was
very slow at pH 9.9; only 6% reaction occurred in 12 h. At pH
7.8 it was 83% complete in 15 min, whereas a t pH 4.1 it was
83% complete in 5 min. Probably, any pH less than 7 will
Historical Interlude and Reactlon Mechanism provide a facile oxidation pathway. The pH dependence may
With all of the advantages of positive chlorine as an inex- reflect the need for hypochlorous acid. At pH 8.0,24% of the
pensive, safe oxidant, it is somewhat surprising that it has not ".
total chlorine is oresent as hvnochlorous acid:, a t .
DH6.5.91%
been a traditional reagent for the transformation of secondarv is present as hypochlorous acid (8).Since acid is produced in
alcohols to ketones. he oxidation of methyl ketones by means the oxidation itself, care must he taken in studying the acid/
of alkaline hypohalite, known to generations of organic rate relationship. We also confirmed earlier reports that metal
chemistry students as the haloform reaction, was first reported chlorides can catalyze the oxidation (14).
by Liehen in 1822 (8). One can only speculate why i t took until Oxidation of a secondary alcohol seems to proceed faster
than chlorination a t the a-carbon of the related ketone in a
..
1980 to annreciate the eeneralitv of the aaueous hvoochlorite -. weakly acidic environment. Both "swimming pool chlorine"
oxidation of secondary alcohols. In part, the delay may have
resulted from the nerceived lack of a convenient chlorine and hypochlorite hleach produce good yields of unchlorinated
source, since the generation and handling of chlminegas can ketones (2,3,16). The ring of cyclohexanone can be cleaved
be awkward. The svnthsic and use uf teri-l~utvl and adipic acid produced with alkaline hypohalite solutions
. hv~ochlorik.
.. (a), alt&ugh weohserved no ring cleavage under our reaction
another trnditiona.~oxidant, is both inconvenient and poten:
tiidly unsafe,. In tht: last drrade Corey (9)and others (10) have conditions.
developed the usr nf nmplexes crt'('l? with dimethyh~~lfuxide, The Experiment
dialksl sulfides, and h e x u ~ n e t h v l p l i ~ ~ ~ h r ~triumide.
r o u s Thesr
offer-a number of advantagesbk are not suitable for large-
scale use in the teaching laboratory.
Neglect nistdium hg;wchlnrite fnr oxidizing alcohols may
have also resulted from the lack of appreciationof the role cf
acid in the reaction. Many kinetic studies have been carried Caution: NaOH is caustic. Exercise care in its use. Glacial acetic
out on the oxidation of alcohols with BrzIH20, but this reac- acid is an excellent dehydrating agent and can cause burns. If either
tion has a different acidity dependence than when chlorine gets on the skin, wash it off immediately with cold water. Acetic acid

520 Journal of Chemical Education

fumes are also irritating, so the acid should he poured in the h o d . The will have to he collected to recover all of the product. Since it is
-
same is true for the bleach solution. Chlorine eas is a resoiratorvand
eye irritant. Its acceptable short term atmospheric exposure level is
somewhat water soluble, do not collect too much distillate. Cyclo-
hexanone forms the top layer in the receiving flask.
3 ppm. Cyclohexanol and cyclohexanone are moderate irritants; the Add 10 g solid sodium chloride to the distillate in order to decrease
acceptable 8-h average atmospheric exposure limit for cyclohexanol the solubility of cyclohexanonein the aqueous layer. Stir the mixture
is 50 ppm; far cyclohexanoneit is 25 ppm. The acceptable short-term until almost all of the salt dissolves. Separate the layers and purify
exposure level for cyclohexanone is 100 ppm. Small quantities of ex- the crude product by dryingit for 20min over 2 ganhydrousmagne-
cess sodium hypochloriteshould be disposed of in a fume hood by slow sium sulfate or potassium carbonate.
addition to a large volume of concentrated reducing agent (sodium
bisulfite or sodium thiosulfate). When reaction is complete, adjust Options and Comments
the pH to 7 and flush down the drain with large amounts of water If the bleach has been stored for manv months. one mav
117). want to increase the quantity by 5%; it is present in just over
' Pour 16 mL (0.15 mol) cyclohexanol into a three-necked 500-mL
10%stoichiometric excess in our procedure. Extraction with
round-hottomed flask. Add 8 mL glacial acetic acid. Place a condenser
in one neck of the flask, a 125 mL dropping funnel in another and a 30 mL of CHzClz before drying will increase product yield for
thermometer in the third opening. If the laboratory is well ventilated two reasons-it will recover more of t h e ketone t h a t is dis-
or the experiment is being carried out in a hood, the apparatus is sol\wl in the wnwr and it will facilitate filtration of the drying
complete. (Without good ventilation, put a piece of glass woolin the agent. Hou,ever, using CH,CI, adds a distillation step. Anal-
bottom of a drvine tube and Dour in -2 cm of sodium hisulfite. This ysis of the product can be accomplished by GLC or infrared
spectroscopy (1 ).
There are many interesting open-ended options possible
tube attached.) with this experiment. Numerous secondary alcohols can be
Grease the stopcock in the 125mL dropping funnel, and take it to substituted for cvclohexanol. T h e ~ r o c e d u r is
e simnle enough
the hood to put in 115mL of the hleach solution. When uourinp the "
bleach, use rubber gloves and dispense the solution wrefdly. stopper t h a t students can design their own experimental variations
the dropping funnel in the hood, then carry it hack to the bench with after looking up the physical properties of t h e secondary al-
a large beake~underneath it, and return it to your three-necked flask. cohol and the related ketone. T h e proper amount of sodium
Put a small piece of paper between the stopper and the neck of the bisulfate can be substituted for acetic acid and the neutral-
dropping funnel so the solution will drop evenly. Make available an ization step omitted. Isopropyl alcohol can be used in place
ice bath with about 250 mL of ice in case the reaction gets too hot. of sodium bisulfite to destroy t h e excess oxidant (16): any
Add about 25 mL of the bleach solution to the reaction vessel. Swirl remaining acetone can be removed easily by distillation.
the vessel to mix the reagents together. Then start adding the rest of T h e oxidation of secondary alcohols with common hypo-
the sodium hypochlorite solution, swirling the flask from time to time chlorite bleach provides a safe, environmentally sound, and
during the addition so that the reactants remain well mixed. The rate
of addition will be determined bv the tem~eratureof the solution. hut inexpensive modern synthetic method. It utilizes a varietv of
iho~~ld tnkc n., Ismgtr than 15 mm. Ideally, rhr marlmum tmmprrature laboratory techniqt~&and some t ' u n d ~ m e n t ~oxidation-
l
should not exceed 4.5'; 111-50" IS fine,howwcr. l l c r the ire bath if t he reduction rhe~nistry.The rxperiment pruvides on opportunity
rrartivn trmprrature e x c t r d ~15". I t the rrccrwn is kept too culd for the student t o review chemistry described in mbst intri-
(<40°), the product yield may he low. ductory chemistry courses. It offers some pretty colors and
After all the sodium hypochlorite has heen added, remove the uses a n oxidant known t o virtually everyone. ~ u m e r o u ex-s
dropping funnel, temporarily stopper the reaction flask and obtain perimental options are available within t h e experiment.
another 115 mL of bleach solution in the dropping funnel. Add this
to the reaction mixture, keeping the temperature at 45'. Addition of Acknowledgment
the total 230 mL of bleachshould take about 20-30min. In theearly
stages of the reaction, one can see the color of the chlorine disappear Our thanks en t o Jean Mohrie and Richard Ramette for
as it reacts. Near the end of the additian,the yellow color should linger. helpful suggestl'ons and to the many Carleton undergraduates
After addition is complete, remove the dropping funnel and stopper who performed variations of t h e experiment.'A Curricular
the neck of the flask. Swirl the mixture from time to time for another Research and Development Grant from Carleton College t o
20 min. J R M and PGM helped to support part of this work.
Literature Cited
Test for Excess Oxidant
OC1- + HSOs-
bisulfite
- CI- + HSOI-
bisulfate
I l l Mohrig, J. R., snd Neckers. D. C., "Laboratory Experiments in Organic Chemistry."
3rded..D.Vsn Nmtrand,New York, 1979,Chap.21.
(21 Stevens, R.V.,Chapman, K. T.,and Weller. H. N., J. Org. Chem.,45,2030(19S01.
(31 ialZuerek,N. M.,sndFurth,P.S.J. CHEM.EDUC.,58.824(1981): (bl Kauffman, J.
M.,andMcKee, J. R.,J.CHEM. EPuC.59.862 (1982J.
I41 "Ambient Water Quality Criteria for Chromium," U.S. Environmental Protedion
Wet a piece of starch-iodide indicator paper (if the bleach is too Agency, Criteriaand Standards Div., Washington, DC. 1980.
(51 "Threshold Limit Values for Chemical Subslancer in Workroom Air," American
concentrated, colorless iodate may form) and put a drop of aqueous conrennce of Governments1 Industrial Hygienists (ACGLHI, Cincinnati, 1981.
solution from the reaction vessel onto it. If excess oxidant remains, (61 "OccupationalExposure toChromium (VII."HEW Publ. No. INLOSHl76-129,U.S.
the blue color of the triiodide-starch complex will appear. If you get Government Printing Office, Washington, DC 1375.
a blue color. add 2 mL saturated NaHSO- solution to the reaction (71 (a1 Nwaukwa,S. 0. and Keehn,P. M., TatmhrdronLali.,23,35 119821:(bl Peckins,
R.A..andChau. F.,J.CWaM.Eouc.. 59.961 (19821.
181 Chskrsbsrtfy,S. K.,in '"Oxidation in OrganicChcmirfry."lEdilor:Trahsnovsky, W.
S.I. Academic Press, Now York. IWR, Part C, Chnp. V.
I91 (aJC0rey.E.J.,andKim,C.U.,J.Amer.Chrm.Soc.,94,758611972):IblCorey,E.J.,
and Kim,C.U. T s t r o h e d r o n L e r t . 9 ~ 9119731.
Remove the thermometer and condenser. Rinse them, as well as (101 A1 Neirabeyeh. M., Ziegleh J.-C.,Gross,B., and Cauhere. P., Synthesis, 811 119761.
the dropping funnel, immediately with water and then sodium bi- 1111 la1 Barker, I. R. L.,Chem. ind. ILondnnI. 1936 11964k (bl Perlmutter-Hayman. B..
sulfite solution. Add 2 mL thymol blue indicator solution to the re- and Weissmann. Y.. J. Amcr Chem Soc., 81.668 119691.
action mixture. Then over a 3-min period add 6 M NaOH (about 1121 Wolfe, S.,Hasan,S. K..sndCampbell.J.R., J. Chem. Soc. D. 1420 (19701.
(131 Lee, G. A., and Freedman, H. H., Tetrahedron Lett., 1641 (19761.
3040 mL) through a short-stemmed funnel until the solution is 1141 Kudesis, V. P.,and Mukhorjee,S. K.,lndion J. Chsm., l5A.513 (19771.
neutral (color change to blue). Swirl the flask gently at times during 1151 Kude6a.V. P.,andSharma,B. K..lndion J. Chem., 19A.82 (19801.
the addition of base. 1161 Steuens,R. V.,Chapmsn, K.T., Stubbs,C.A..Tam, W. W.,and Albizatl, K. F.,Tel-
rohrdron Lett., 23.4647 119821.
Distill the reaction mixture using a short-path column; cyclohex- 1171 Armour. M. A,, Browne, L. M.. and Weir, G. L., "HazsrdousChemiesla Information
anone and water will codistill. Approximately 70-80 mL of distillate and Disposal Guide."University of Alberta, Edmonton. IOSZ, p. 216.

Volume 62 Number 6 June 1985 521