Matthew Dintzner - Cyclohexanol Cycle and Synthesis of Nylon 6 6

Laboratory Experiment
pubs.acs.org/jchemeduc
The Cyclohexanol Cycle and Synthesis of Nylon 6,6: Green Chemistry

in the Undergraduate Organic Laboratory
Matthew R. Dintzner,* Charles R. Kinzie, Kimberly Pulkrabek, and Anthony F. Arena
Department of Chemistry, DePaul University, Chicago, Illinois 60614, United States
S Supporting Information
*
ABSTRACT: A one-term synthesis project that incorporates many of the principles of green
chemistry is presented for the undergraduate organic laboratory. In this multistep scheme of
reactions, students react, recycle, and ultimately convert cyclohexanol to nylon 6,6. The
individual reactions in the project employ environmentally friendly methodologies, and the
scheme minimizes impact on the environment by reducing waste, using the product of one
reaction as the starting material for the next.
KEYWORDS: Second-Year Undergraduate, Curriculum, Laboratory Instruction, Organic Chemistry,

Hands-On Learning/Manipulatives, Green Chemistry, Spectroscopy, Synthesis
alternative, environmentally friendlier methods for carrying

out reactions of traditional importance.
For many years, the laboratory curriculum contained
traditional experiments from a published lab manual.24
Although most of these experiments were very good and gave
students hands-on experience with the reactions they were
learning in the classroom, it was disappointing for students to
spend 4 or 5 h in the lab synthesizing and characterizing a
desired product, only to dump it into a waste container at the
end of the period. Thus, a new project-based approach to the
organic laboratory was developed in which the product of one
reaction was used as the starting material for the next reaction,
while also integrating reactions that were discussed in
concurrent lectures. In addition, the laboratory curriculum
was made more green by introducing newer, more environmentally friendly reaction methodologies and generating less
waste. Although a few excellent green organic chemistry lab
manuals are currently available,2527 a more comprehensive,
integrated lab experience was sought with an emphasis on green
chemistry. Thus, after several years of experimenting, a oneterm project was developed called The Cyclohexanol Cycle
and Synthesis of Nylon 6,6 (Scheme 1), which is a multistep
scheme of reactions in which students react, recycle, and
ultimately convert cyclohexanol to nylon 6,6.
The reactions in the project make use of environmentally
friendly methodologies, and the scheme is designed to
minimize impact on the environment by reducing waste,
using the product of one reaction as the starting material for the
next. Although not intended to be an exercise in total synthesis,
reen chemistry, which is based on the 12 guiding

principles outlined in Table 1, is the design of chemical
Table 1. The 12 Principles of Green Chemistry

Principlea
Number
1
2
3
4
5
6
7
8
9
10
11
12
a
Prevention
Atom Economy
Less Hazardous Chemical Syntheses
Designing Safer Chemicals
Safer Solvents and Auxiliaries
Design for Energy Efficiency
Use of Renewable Feedstocks
Reduce Derivatives
Catalysis
Design for Degradation
Real-time analysis for Pollution Prevention
Inherenetly Safer Chemistry for Accident Prevention
The principles are from ref 1.
products and processes that reduce or eliminate the use and

generation of hazardous substances.1 Green chemistry is a topic
of emerging importance and one that is well suited for
incorporation into the modern undergraduate organic laboratory curriculum.2 In recent years, a number of reports
concerning green chemistry and education have appeared in
this Journal,36 and an ever-growing number of relevant
laboratory experiments appropriate for the undergraduate
chemistry curriculum have emerged.722 In the words of
Chemical & Engineering Newss Editor-in-chief, Rudy Baum,
green has indeed gone mainstream,23 and so it has become
increasingly relevant that young chemists be exposed to
2011 American Chemical Society and
Division of Chemical Education, Inc.
Published: December 6, 2011

262
dx.doi.org/10.1021/ed2000878 | J. Chem. Educ. 2012, 89, 262264
Journal of Chemical Education
purity assessed by GCMS or 1H NMR spectroscopy at the

instructors discretion.
Scheme 1. The Cyclohexanol Cycle and Synthesis of Nylon

6,6
HAZARDS
General Laboratory safety procedures, including wearing safety
goggles and gloves, must be followed at all times. All organic
chemicals involved in this experiment are considered hazardous,
and direct physical contact with them should be avoided. All
wet-laboratory experiments must be performed in a fume hood,
and wearing a laboratory coat or apron is advised. Detailed
information about the hazards of the specific chemicals is
available in the Supporting Information.
DISCUSSION
In 1933, E. C. Wagner published in this Journal a manuscript
entitled Some Student Experiments In and Out of the
Cycloparaffin Series, in which a number of reactions of
cyclohexanol and related compounds were presented to give
students some first-hand acquaintance with a series of
compounds known in many instances only on the pages of
their textbooks.39 Although certainly innovative at the time,
most of the experiments reported by Wagner do not comply
with the green standards of present day. Wagners report did,
however, serve in part as our inspiration for the development of
The Cyclohexanol Cycle, as did the series of experiments,
called The Copper Cycle, which is part of the general
chemistry laboratory curriculum at this university. In The
Copper Cycle experiments, students carry out the series of
reactions that converts a piece of copper metal via several
different copper-containing compounds back into its original
elemental form. The prospect of developing an analogously
cyclic scheme of reactions for the organic lab was exciting, and
so The Cyclohexanol Cycle was devised.
In The Cyclohexanol Cycle, students carry out the series of
reactions that begins and ends with cyclohexanol, an
inexpensive and readily available organic compound (Scheme
1). Concurrently, students learn about these reactions in the
classroom, including dehydration of alcohols, addition to
alkenes, E2 elimination, epoxidation of alkenes, and hydride
reduction. The recovered cyclohexanol is then oxidized to
adipic acid, which is subsequently used for the synthesis of the
polymer, nylon 6,6. All of the reactions in the scheme were
adapted from the literature and many employ green methodology. For example, the dehydration of cyclohexanol (lab 1) is
catalyzed by Montmorillonite K10 clay, a naturally benign
aluminosilicate mineral that is inexpensive, safe to use, and easy
to handle (green chemistry principles 3, 5, 7, 9, and 12).40 The
bromination of cyclohexene (lab 2) is effected via in situ
generation of bromine from HBr and H2O2 (green chemistry
principles 3, 4, and 5). Laboratories 3, 4, and 6 are all
conducted in water (green chemistry principle 5) and produce
minimal waste or byproducts. Further, the cycle is designed to
minimize impact on the environment by reducing waste, using
the product of one reaction as the starting material for the next.
Indeed, minimal waste is generated throughout the project, and
the cost per student (for reagents, solvents, and supplies) is less
than $60 on standard scale or less than $12 on microscale. The
cost per student is kept low by employing simple, inexpensive
reagents from SigmaAldrich such as cyclohexanol ($0.03/
mL), Montmorillonite K10 clay ($0.05/g), zinc metal ($0.07/
g), Oxone ($0.03/g), and tungstic acid ($0.36/g).
the scheme provides students with a unique opportunity to

engage in a multistep synthesis project that employs many of
the reactions they are learning about concurrently in lecture. In
addition, the percent recovery of cyclohexanol allows for
assessment of laboratory techniques and skills. This secondterm project follows a techniques-based project carried out by
our students during the first term,28 and prepares them well for
a research-based project that they complete in the third term.29
The students find this project challenging and rewarding, and it
seems to inspire in them a sense of ownership of and
responsibility and accountability for their work. All laboratory
experiments and related assignments are posted on a dedicated
Web site and Zubricks The Organic Chem Lab Survival Manual
is used as a reference manual.30
EXPERIMENTAL OVERVIEW
Students begin the project with cyclohexanol (10 g on standard
scale; 2 g on microscale), which they first convert to
cyclohexene via Montmorillonite K10 clay-catalyzed dehydration in the first lab.31 The cyclohexene is subsequently
converted to racemic trans-1,2-dibromocyclohexane through
an addition reaction in which molecular bromine is generated
in situ under aqueous conditions in the second lab.32 In the
following reaction (lab 3), cyclohexene is recovered via zincmediated reduction in water,33 and in the fourth lab, the
cyclohexene is epoxidized with Oxone in aqueous acetone.34
Reduction of the cyclohexene oxide with LiBH4 in THF
methanol35 regenerates the cyclohexanol in the fifth lab. The
recovered cyclohexanol is then oxidized to adipic acid with
H2O2 catalyzed by tungstic acid (H2WO4) in water in the sixth
lab,36 and the adipic acid is then used as a precursor for the
synthesis of nylon 6,6 in the final lab period.37 Students may
also explore an alternate synthetic route to nylon 6,6 via the
environmentally friendly tunstate-catalyzed oxidation of cyclohexene to adipic acid (dashed arrow, Scheme 1).38 Each lab is
approximately 4 h and students work individually. Students
typically do not purify any of the intermediates, though this is
certainly an option at the instructors discretion. (On a 10-week
quarter system, there is not time.) Percent yields are calculated
for each reaction and percent recovery of cyclohexanol is
calculated for the cycle. Reaction products may be analyzed and
263
Journal of Chemical Education
(18) Dintzner, M. R.; Wucka, P. R.; Lyons, T. W. J. Chem. Educ.

2006, 83, 270.
(19) Bennett, G. D. J. Chem. Educ. 2005, 82, 1380.
(20) Haack, J. A.; Hutchison, J. E.; Kirchhoff, M. M.; Levy, I. J. J.
Chem. Educ. 2005, 82, 974.
(21) Palleros, D. R. J. Chem. Educ. 2004, 81, 1345.
(22) Pohl, N.; Clague, A.; Schwarz, K. J. Chem. Educ. 2002, 79, 727.
(23) Baum, R. M. Chem. Eng. News 2003, 81 (Sep 29), 3.
(24) In the most recent past we used: Lehman, J. W. Multiscale
Operational Organic Chemistry: A Problem-Solving Approach to the
Laboratory Course; Prentice Hall: Upper Saddle River, NJ, 2002.
(25) Doxsee, K. M.; Hutchison, J. E. Green Organic Chemistry:
Strategies, Tools, and Laboratory Experiments; Thomson, Brooks/Cole:
Belmont CA, 2004.
(26) Lancaster, M. Green Chemistry: An Introductory Text; Royal
Society of Chemistry: Cambridge, 2002.
(27) Department of Science & Technology, Govt. of India,
Monograph on Green Chemistry Laboratory Experiments. http://
www.dst.gov.in/green-chem.pdf (accessed Nov 2011).
(28) Dintzner, M. R.; Kinzie, C. R.; Pulkrabek, K. A.; Arena, A. F. J.
Chem. Educ. 2011, 88, 1434.
(29) Dintzner, M. R.; Maresh, J. J.; Kinzie, C. R.; Arena, A. F.; Speltz,
T. J. Chem. Educ. DOI: 10.1021/ed200256w.
(30) Zubrick, J. W. The Organic Chem Lab Survival Manual: A
Students Guide to Techniques, 7th ed.; John Wiley & Sons, Inc.:
Hoboken, NJ, 2008.
(31) Kantam, M. L.; Santhi, P. L.; Siddiqui, M. F. Tetrahedron Lett.
1993, 34, 1185.
(32) McKenzie, L. C.; Huffman, L. M.; Hutchison, J. E. J. Chem. Educ.
2005, 82, 306.
(33) Weinstock, J.; Lewis, S. N.; Bordwell, F. G. J. Am. Chem. Soc.
1956, 78, 6072.
(34) Broshears, W. C.; Esteb, J. J.; Richter, J.; Wilson, A. M. J. Chem.
Educ. 2004, 81, 1018.
(35) Soai, K.; Ookawa, A. J. Org. Chem. 1986, 51, 4000.
(36) Usui, Y.; Sato, K. Green Chem. 2003, 5, 373.
(37) Pavia, D. L.; Lampman, G. M.; Kriz, G. S.; Engel, R. G.
Introduction to Organic Laboratory Techniques: A Microscale Approach,
2nd ed., Saunders: Fort Worth, TX, 1995; p 414.
(38) Reed, S. M.; Hutchinson, J. E. J. Chem. Educ. 2000, 77, 1627.
(39) Wagner, E. C. J. Chem. Educ. 1933, 10, 113.
(40) Nagendrappa, G. Appl. Clay Sci. 2011, 53, 106.
CONCLUSIONS
The Cyclohexanol Cycle and Synthesis of Nylon 6,6
represents a one-term, integrated project for the undergraduate
organic laboratory that provides students with a contextual
basis for learning about the principles of doing green chemistry,
while also gaining hands-on experience with the reactions that
they are concurrently learning in the classroom. Students
develop a sense of accomplishment upon shepherding a batch
of cyclohexanol through a series of functional group transformations and using their recovered material to synthesize
nylon 6,6, a product with which they are all quite familiar.
ASSOCIATED CONTENT
* Supporting Information
S
Detailed instructions for the students; notes for instructors;

detailed information about the hazards of the specific chemicals.
This material is available via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: [email protected].
ACKNOWLEDGMENTS
We thank the National Science Foundation CCLI A&I program
(Grant No. DUE-0310624) for support in purchasing our
Bruker Avance 300 MHz NMR spectrometer and DePaul
Universitys College of Liberal Arts & Sciences for funding and
support of this work. The following DePaul undergraduate
students are acknowledged for their participation and
contributions: Stephanie Reeve, Barrett Unger, and Mark
Aparece.
REFERENCES
(1) Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and Practice;

Oxford University Press: New York, 1998.
(2) Anastas, P. T.; Levy, I. J. Green Chemistry Education: Changing the
Course of Chemistry; American Chemical Society, Oxford University
Press: New York, 2009.
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cited therein).
(4) Hjressen, D. L.; Schutt, D. L.; Boese, J. M. J. Chem. Educ. 2000,
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Laboratory Experiment

The Cyclohexanol Cycle and Synthesis of Nylon 6,6: Green Chemistry

KEYWORDS: Second-Year Undergraduate, Curriculum, Laboratory Instruction, Organic Chemistry,

alternative, environmentally friendlier methods for carrying

reen chemistry, which is based on the 12 guiding

Table 1. The 12 Principles of Green Chemistry

The principles are from ref 1.

products and processes that reduce or eliminate the use and

Published: December 6, 2011

dx.doi.org/10.1021/ed2000878 | J. Chem. Educ. 2012, 89, 262264

Journal of Chemical Education

purity assessed by GCMS or 1H NMR spectroscopy at the

Scheme 1. The Cyclohexanol Cycle and Synthesis of Nylon

the scheme provides students with a unique opportunity to

dx.doi.org/10.1021/ed2000878 | J. Chem. Educ. 2012, 89, 262264

Journal of Chemical Education

(18) Dintzner, M. R.; Wucka, P. R.; Lyons, T. W. J. Chem. Educ.

Detailed instructions for the students; notes for instructors;

(1) Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and Practice;

dx.doi.org/10.1021/ed2000878 | J. Chem. Educ. 2012, 89, 262264

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