Introducing GC/MS into the Introducing GC/MS into the Undergraduate Organic LabUndergraduate Organic Lab

Dan Blanchard, Ph.D.Dan Blanchard, Ph.D.

Kutztown UniversityKutztown University

http://faculty.kutztown.edu/blanchar/http://faculty.kutztown.edu/blanchar/

GC/MS as an Organic ToolGC/MS as an Organic Tool

Goals of Organic LabGoals of Organic Lab CharacterizationCharacterization LogisticsLogistics ChallengesChallenges ExperimentsExperiments ConclusionsConclusions

Goals of Organic Laboratory at KUGoals of Organic Laboratory at KU

1.1. Learn Laboratory TechniquesLearn Laboratory Techniques

2.2. Carry Out Organic SynthesesCarry Out Organic Syntheses

3.3. Explore Chemistry of Everyday LifeExplore Chemistry of Everyday Life

4.4. Demonstrate Concepts from LectureDemonstrate Concepts from Lecture

Most Involve Synthesis or IsolationMost Involve Synthesis or Isolation

Importance of CharacterizationImportance of Characterization

Synthesis RoutineSynthesis Routine ReactReact IsolateIsolate PurifyPurify CHARACTERIZECHARACTERIZE

Isolation RoutineIsolation Routine IsolateIsolate PurifyPurify CHARACTERIZECHARACTERIZE

CharacterizationCharacterization

Traditionally Melting RangeTraditionally Melting Range Not related to structureNot related to structure Sample purity dependenceSample purity dependence Not modern techniqeNot modern techniqe

GC/MSGC/MS Can be introduced early at basic levelCan be introduced early at basic level Can be developed across the courseCan be developed across the course Modern techniqueModern technique

GC/MS – LogisticsGC/MS – Logistics

Should students operate the instrument Should students operate the instrument in the Organic lab?in the Organic lab?

One Solution: The AutosamplerOne Solution: The Autosampler Allows for more samples and longer run Allows for more samples and longer run

timestimes Students can enter their own information.Students can enter their own information. Students should get to operate the Students should get to operate the

instrument once.instrument once.

Challenges of Introducing GC/MS Challenges of Introducing GC/MS

Introducing two Introducing two techniques at oncetechniques at once

Two graphs for one run!Two graphs for one run! Heaviest ion versus Heaviest ion versus

most abundant ionmost abundant ion Fragmentation: multiple Fragmentation: multiple

simultaneous reactionssimultaneous reactions

Identification of Volatile Flavor Identification of Volatile Flavor Components by Headspace AnalysisComponents by Headspace Analysis

Simple sample preparationSimple sample preparation Short run timesShort run times Identification is made by molar mass aloneIdentification is made by molar mass alone

limonene, ethyl butyrate, benzaldehyde, isoamyl acetatelimonene, ethyl butyrate, benzaldehyde, isoamyl acetate Drawback: Not all candies have adequate volatile Drawback: Not all candies have adequate volatile

componentscomponents

Kjonaas, R.A.; Soller, J.L.; McCoy L.A., Kjonaas, R.A.; Soller, J.L.; McCoy L.A., J. Chem. Educ.J. Chem. Educ. 19971997, , 7474, 1104-1105., 1104-1105.

Isolation of the Active Ingredients Isolation of the Active Ingredients from Cough Syrupfrom Cough Syrup

Includes acid-base Includes acid-base extractionextraction

Example of combining Example of combining traditional concept with traditional concept with GC/MSGC/MS

N

H

CH3O

CH3

NCH3

H

CH3

OH

O OH

OH

OCH3

Sherren, A. T. Presented at The American Chemical Society National Meeting, Boston, Sherren, A. T. Presented at The American Chemical Society National Meeting, Boston, MA, 1999.MA, 1999.

Fatty Acids Present in Snack FoodsFatty Acids Present in Snack Foods

Isolation of oils from potato chipsIsolation of oils from potato chips Detection of prepared FAMESDetection of prepared FAMES No MS interpretation No MS interpretation Food for discussionFood for discussion

Rubinson, J.F.; Neyer-Hilvert, J., Rubinson, J.F.; Neyer-Hilvert, J., J. Chem. Educ.J. Chem. Educ. 19971997, , 7474, 1106-1107., 1106-1107.

Grignard Synthesis of an Unknown Grignard Synthesis of an Unknown C6-C9 AlcoholC6-C9 Alcohol

R Br R MgBr

R' R"

O

R

R'

R"

OHMg0

ether

1)

2) H3O+

Unknown alkyl halide plus unknown ketoneUnknown alkyl halide plus unknown ketone Product is characterized by IR, Product is characterized by IR, 1313C NMR, GC/MSC NMR, GC/MS NO molecular ionNO molecular ion Fragmentation analysis is requiredFragmentation analysis is required

Everett, T.S., Everett, T.S., J. Chem. Educ.J. Chem. Educ. 19981998, , 7575, 86-87., 86-87.

Also AdoptedAlso Adopted

Isolation of Essential Oils from various spicesIsolation of Essential Oils from various spicesPavia, D.L.; Lampman, G.M.; Kriz, G.S.; Engel, R.G. Pavia, D.L.; Lampman, G.M.; Kriz, G.S.; Engel, R.G. Introduction to Organic Introduction to Organic

Laboratory Techniques, A Microscale Approach, Third EditionLaboratory Techniques, A Microscale Approach, Third Edition; Saunders: ; Saunders: Philadelphia, 1999; pp 487-492.Philadelphia, 1999; pp 487-492.

Chlorination Reactivity Ratios for Chlorination Reactivity Ratios for MethylcyclohexaneMethylcyclohexaneBishop, R.D., Jr., Bishop, R.D., Jr., J. Chem. Educ.J. Chem. Educ. 19951995, , 7272, 743-745, 743-745..

CH3

Also ModifiedAlso Modified

Acetylation of FerroceneAcetylation of Ferrocene

O O

OCH3 Cl

O

Fe Fe FeAlCl3

Amenta, D.S.; DeVore, T.C.; Gallaher, T.N.; Zook, C.M.; Mosbo, J.A., Amenta, D.S.; DeVore, T.C.; Gallaher, T.N.; Zook, C.M.; Mosbo, J.A.,

J. Chem. Educ.J. Chem. Educ. 19961996, , 7373, 572-575., 572-575.

Also TriedAlso Tried

Preparation of a C-4 or Preparation of a C-4 or C-5 Acetate Ester C-5 Acetate Ester

Pavia, D.L.; Lampman, G.M.; Kriz, Pavia, D.L.; Lampman, G.M.; Kriz, G.S.; Engel, R.G. G.S.; Engel, R.G. Introduction to Introduction to Organic Organic Laboratory Techniques, A Laboratory Techniques, A Microscale Approach, Third Microscale Approach, Third EditionEdition; Saunders: ; Saunders: Philadelphia, 1999; pp 472-475.Philadelphia, 1999; pp 472-475.

McGoran E.C.; Melton, C.; Taitch, McGoran E.C.; Melton, C.; Taitch, D., D., J. Chem. Educ.J. Chem. Educ. 19961996, , 7373, 88-92, 88-92

O

O

O

O

ConclusionsConclusions

There exist a wide range of experiments which There exist a wide range of experiments which already incorporate GC/MS.already incorporate GC/MS.

There are a wide range of experiments which There are a wide range of experiments which can be modified to incorporate GC/MS.can be modified to incorporate GC/MS.

GC/MS is a modern structurally-based GC/MS is a modern structurally-based characterization technique that can be characterization technique that can be introduced early in the organic course and introduced early in the organic course and developed across both semesters.developed across both semesters.

AcknowledgementsAcknowledgements

National Science Foundation, Division of National Science Foundation, Division of Undergraduate EducationUndergraduate Education

Organic lab students at KU 1999-2004Organic lab students at KU 1999-2004 Colleagues and lab instructors at KU 1999-Colleagues and lab instructors at KU 1999-

20042004

ReferencesReferencesKjonaas, R.A.; Soller, J.L.; McCoy L.A., Kjonaas, R.A.; Soller, J.L.; McCoy L.A., J. Chem. Educ.J. Chem. Educ. 19971997, , 7474, 1104-, 1104-

1105.1105.

Sherren, A. T. Presented at The American Chemical Society National Sherren, A. T. Presented at The American Chemical Society National Meeting, Boston, MA, 1999.Meeting, Boston, MA, 1999.

Rubinson, J.F.; Neyer-Hilvert, J., Rubinson, J.F.; Neyer-Hilvert, J., J. Chem. Educ.J. Chem. Educ. 19971997, , 7474, 1106-1107., 1106-1107.

Everett, T.S., Everett, T.S., J. Chem. Educ.J. Chem. Educ. 19981998, , 7575, 86-87., 86-87.

Pavia, D.L.; Lampman, G.M.; Kriz, G.S.; Engel, R.G. Pavia, D.L.; Lampman, G.M.; Kriz, G.S.; Engel, R.G. Introduction to Organic Introduction to Organic Laboratory Techniques, A Microscale Approach, Third EditionLaboratory Techniques, A Microscale Approach, Third Edition; Saunders: ; Saunders: Philadelphia, 1999; pp 487-492.Philadelphia, 1999; pp 487-492.

Amenta, D.S.; DeVore, T.C.; Gallaher, T.N.; Zook, C.M.; Mosbo, J.A., Amenta, D.S.; DeVore, T.C.; Gallaher, T.N.; Zook, C.M.; Mosbo, J.A., J. J. Chem. Educ.Chem. Educ. 19961996, , 7373, 572-575., 572-575.

Bishop, R.D., Jr., Bishop, R.D., Jr., J. Chem. Educ.J. Chem. Educ. 19951995, , 7272, 743-745., 743-745.

Pavia, D.L.; Lampman, G.M.; Kriz, G.S.; Engel, R.G. Pavia, D.L.; Lampman, G.M.; Kriz, G.S.; Engel, R.G. Introduction to Organic Introduction to Organic Laboratory Techniques, A Microscale Approach, Third EditionLaboratory Techniques, A Microscale Approach, Third Edition; Saunders: ; Saunders: Philadelphia, 1999; pp 472-475.Philadelphia, 1999; pp 472-475.

McGoran E.C.; Melton, C.; Taitch, D., McGoran E.C.; Melton, C.; Taitch, D., J. Chem. Educ.J. Chem. Educ. 19961996, , 7373, 88-92, 88-92