The Systemic Approach to Teaching and Learning Heterocyclic Chemistry [SATLHC]:

1. The Systemic Approach to Teaching and Learning Heterocyclic Chemistry [SATLHC]: Operational Steps for Building Teaching Units in Heterocyclic Chemistry A. F. M. Fahmy, J.J.Lagowski* Faculty of Science, Department of Chemistry Ain Shams University, Abbassia, Cairo, EGYPTE-mail:afmfahmy42@gmail.com *University of Texas at Austin ,USA Website:satlcentral.com Feb.2013

2. If their is no Teaching Chemistry their is no Chemistry • Good chemistry teaching excellent chemistry research

3. # Introduction # SATL-Teaching Strategy. # Difficulties in Learning Heterocyclic Chemistry. # SATL-in Building Unites [General strategy]. # Scienario of Building unite on 5-Membered Heterocycles. [Pyrrole – Furan – Thiophene] • # Conclusions.

4. INTRODUCTION: • -After the wide spread of the systematization in various activities including, tourism, economy, security, education,…etc, • and after globalization became a reality that we live. • -SATL became a must and Chemical Education Reform (CER) • has gained great importance internationally. • - SATL is a new way of teaching and learning, based on the idea that nowadays everything is related to everything globally. • -Students shouldn't learn isolated facts (by heart), but they should be able to connect concepts and facts in an internally logical context.

5. Taagepera and Noori (2000)tracked the development of student’s conceptual understanding of organic chemistry during a one-year sophomore course. They found that the students knowledge base increased as expected, but their cognitive organization of the knowledge was surprisingly weak . • The authors concluded that instructors should spend more time making effective connections, helping students to construct a knowledge space based on general principles. • Pungente, and Badger 2003 stated that the primary goal of teaching introductory organic chemistry is to take students beyond the simple cognitive levels of knowledge and comprehension using synthesis and analysis – rather than rote memory.

6. Fahmy,A.F.M.(Egypt),andLagowski,J.J.(USA)(1998) suggested an educational process based on the application of “Systemics” named (SATL). • SATL-in Heterocyclic Chemistry was experimented successfully on the third year major chemistry students at Ain Shams University( 2004). • Why Systemic Approach to Teaching and Learning ? • SATL helps students in the development of their mental framework with higher level of cognitive processes such as analysis and synthesis.

7. SATL helps learners in obtaining a deeper learning experience, improve their understanding, enhance their systemic thinking, and increasing their enthusiasm for learning chemistry, as well as other subjects. • SATL,will help students to understand interrelationships between concepts in a greater context. • SATL Helps teachers to teach and learners to learn.

8. What is the SATL? • - We mean an arrangement of concepts or issues through interacting systems in which all relationships between concepts and issues are made, clear up front, to the teacher and learner. Fig:1a LA concept concept concept concept concept Fig:1b SA concept concept concept

9. SD1 SD2 SD0 SDf • Systemic teaching strategy:[STS] • - we started teaching any unit by Systemic diagram (SD0) that has determined the starting point of the unit, and we ended with a final systemic diagram(SDf)and between both we crossover several Systemics. Fig (2): Systemic teaching strategy

10. The systemic diagrams involved in teaching are • similar except that the number of known relationships • () and the unknown (?)ones as indicated in the Fig.2. • A list of SATLCmaterials were produced in Egypt • e.g.:SATLGeneral Chemistry for secondary schools. SATLAliphatic, Aromatic, Green chemistry and Heterocyclic Chemistry for University Level. - In this presentation, various examples of systemic heterocyclic teaching materials will be illustrated.

11. Uses of SATL-in Building Unites: [ General Building Strategy ] In SATL building strategy of unites , we convert the linearly based unites in chemistry to systemically - based unites according to the following building strategy; First: The systemic aims and the operational objectives for the unit should be defined in the frame of national standards.. . Second: The Prerequisites needed for teaching the unite from previous studies (facts, concepts, laws, reaction types and skills) should be tabulated into a list. Third: Then content analysis of the linearly-based unite into facts, concepts, laws, reaction types, mental, and experimental skills.

12. H G Y X F Z E • Fourth: Draw a diagram illustrating linear relations • among the concepts of the unite [Fig.3]. .

13. H 6 ? 1 G Y ? 5  X 2 ? F 4 3 Z   E • Fifth: We put the sign () on the already knownrelationships from previous studies. Then the remaining linear relations are unknown and signed by (?). So, the diagram in Fig-3 should be modified as shown in Fig. 4: Fig4: Showing linear relations between concepts after defining the known from the unknown ones.

14. 7 H 12 ? ? G Y 1 6 ? ?  5 ? ? 11 X 8 2 ? F Z 4   3 ? ? E 10 9 (SDss0) • Sixth: The diagram Fig.4 is modified to a systemic • diagram SD0Fig.5 by adding unknown relations between the concepts from (7-12).SD0 is known as the starting point of teaching the unite. . Fig5: Showing systemic relations between concepts after defining the known from the unknown ones.

15. 7 H 12  ? G Y 1 6 ? ?  5 11 X 8  ? 2 ? F Z 4   3 ?  E 10 9 Seventh:In the scenario for teaching the unit the student study the relations (7, 8, and 9).So, he will be able to add them to SD0 diagram to give SD1 diagram.Fig.6. Fig.6.[SD1] At this stage of teaching the unite we can ask the students to build systemics showing the relations between the concepts (X, Y, Z, and E) via systemic assessment..

16. 7 H 12  ? G Y ? 1 6   5 11 X 8   2  F Z 4   3   E 10 9 • Eighth: In the next stage of the of the scenario • of teaching the unite, the student study the relations • (4, 5, 10, and 11) and then he will be able to add them • to SD1 to obtain SD2- Fig.7. Fig.7.[SD2]

17. 7 H 12   G Y 6  1   5 11 X 8   2  F Z 4   3   E 10 9 • Ninth: In the last stage of teaching the unit , the student studied the two relations (6, 12). Then adds them toSD2toobtainSD3-Fig.8where we reached to the end of the • systemic teaching of the unite. Fig.8.[SD3] SD3 can be denoted as the terminal systemic SDf of teaching the unite.

18. Tenth:The scenario of teaching any course systemically - • involves the development of a systemic diagram (SD0) that has determined the starting point of the course; • it incorporates the prerequisite materials. • The course ends with a terminal systemic (SDf) in which • all the relationships between concepts are known • (Fig. 8). • From SDO through SDfwe crossover several systemics • with known and unknown relationships (SD1, SD2, etc.). .

19. Difficulties in Learning Heterocyclic Chemistry By Traditional Methods • The students find the following difficulties in learning HC: • i) To Remember the structural formulas of heterocycles and • chemical properties related to these structures. • ii) Tounderstand the systemic effect of heteroatom on the • reactivity of both heterocycles and their substituent's. • iii) Tosynthesize systemic chemical relations between • compounds of the same or different heterocycles. • iv) Tounderstand the importance of heterocycles in their life's. • v) To Design synthesis of new target heterocycles via RSA. • vi) To connect between different heterocyclic systems.

20. SATLHC Pure Applied - Synthesis - Pharmaceuticals - E-Substitution - Food Additives - Nu-Substitution - Plant growth regulators - Addition - Insecticides - Cycloaddaition - Herbicides - Ring Opening - Corrosion Inhibitors X - Het. Int. Conversion - Super conductors. - Dyes - Photographic materials Z etc..) Het. Z Z X,Y,E,F F Het. Y Het. (Functional Groups) Z Z = N, O, S Het. Z Het. E [LATLHC] [SATLHC]

21. Uses of SATL-in Building Unites In Heterocyclic Chemistry: • A course of heterocyclic chemistry using the SATL technique was organized and taught to the 3rd year students at Ain Shams University. • SATLHCmeans survey study on the reactivity of both heterocycles and substituent's and the effect of heteroatom on their possible chemical relations.

22. G Z B-Reactivity of A-Reactivity of the Substituents the Nucleus SATL-HC C-Heteroatom: [(Z)= NH, O, S] D-Substituents:[(G) = R, - CH2 - X, - X, -CH2 - OH - NH2, - CHO, - COR, - COOH]

23. Scienario of Building unite • on 5-Membered Heterocycles • First: Draw a diagram summarizes linear comparative reactivites of the five membered heterocycles as model of heterocyclic compounds, and their possible chemical relations. [Fig.1]

24. [Fig.1]

25. The diagram Fig.1 represents the comparative reactivates of five membered heterocyclic rings, and gives the linear separated chemical relations between (Pyrrole,Furan,Thiophene), and their compounds. • Second: • The diagram Fig.1is modified to a systemic diagram SD1 • Fig.2 by adding relations between Heterocyclic derivatives. • - SD1summarizes the comparative reactivates of both heterocyclic nucleus and substituent's.

26. Fig.2

27. The systemic diagram SD1shows unknown chemical relations (1-7) between heterocyclic compounds. • These relations will be clarified later during the study of the unite [ pyrrole, furan and thiophen ]. • At this stage of teaching the unite we can ask the Students to answer the following Systemic Assessmet-1.

28. ASSESSMENT – I ON SD1 QI) Draw systemic diagrams illustrating the chemical relations between compounds in each of the following sets. [SSnQ,s]

29. A I - 1

30. QII) Complete the following systemic diagrams: A II - 2

31. Cl CHO N N H N N CH3Li / i) DMF/POCl3 ii) aq. Na2CO3 H H2/Rany Ni CH2Cl2 + - red. CO2NH4 N CHCl3/base H CH2OH HCHO (NH4)2CO3 N 130c Sealed Vessel H NaOH RMgX NBS R THF N + - Br N N i) C6H5NSO3 H H H ii)HCl + PhN2 AcONO2 Ac2O -10C i) RCONR2 ii) NaOAc SO3H N N2 Ph N H H NO2 N H COR N H Reactions of pyrrole, furan, thiophene and their compounds I-Pyrrole: (Prerequisites SD1) • Third:From Fig.1 the student can deduce the reactions of pyrrole as in • the following diagram(Fig. 3). (Fig. 3).

32. The diagram (Fig. 3) represents the reactivity of (pyrrole nucleus), and gives the linear separated chemical relations between pyrrole and its compounds. • Fourth: We can illustrate the chemical relations in • (Fig.3) systemically by modification of SD1 to SD2 (Fig.4)(Z = NH):

33. Reduction Oxid. Wolff/ Kishner red. ? CHO N (3) H Cl N i)DMF/POCl3 ii) aq.Na2CO3 R=CH3 CH2Cl2/ CH2OH N N CO2NH4 N H CH3Li H (8) HCHO ? (NH4)2CO3 R=CH3 CHCl3/ base ? base (1) 130oc RMgX heat COOH N R 200oC N H i) R`CONR2/POCl3 ii) NaOAc N + PhN2 (4) (2) H ? ? + - i) C6H5NSO3 ii) HCl (5) N N2Ph N COR` AcONO2 ? H H Ac2O,-10oc N SO3H H NBS/THF ? N NO2 (6) H Br N SD 2 H ? (7) (Fig.4) • Systemic diagram (SD2) shows; (i) known chemical relations between pyrrole and its compounds (ii) unknown chemical relations between pyrrole compounds (1-8), should be clarified during the study of pyrrole compounds.

34. KMnO4 R= CH3 aq. alkaline KMnO4 H2/Pd Oxid CHO N hydrolysis Cl Vap. Phase decarbonylation H (R= CH3) Ag2CO3/Celite N N LTA/AcOH,  NaBH4 CH2Cl2 / CH3Li i) DMF/poCl3; ii)aq Na2 CO3 CHBr2 CHCl3/ N N N base CH2OH H H H H2-Rany Ni CH2O/ R=CH3 R=CH3 150-200C hydro NBS,CHCl3 refulx NaOH N CO2NH4 Diborane H (NH4)2CO3 RMgx heat Alkylation 200c R N N CO2H + H PhN2 N H i) R`CONR2/POCl3 ii) aq. Na2CO3 + PhN2 H Wolff- kishner red. N NBS/THF i) C6H5NSO3 ii) HCl N2Ph H AcONO2 bromination SOCl2/ N Ac2O-10C COR` Br pyridne N N SO3H H H H Nitration COCl red N NO2 N H H N NH2 NaN3 H Curtius N CON3 rearang. SD 3 H R = CH3 Oxid., chromic acid • Fifth : After Study of pyrrole compounds [G = R, CH2OH, CHO, RCO, • COOH , NH2): The student can modify (SD 2 to SD 3) Fig.5 by adding chemical relations (1 – 8). Fig.5 • At this stage of teaching the unite we can ask the Students to answer the following Systemic Assessmet-2.

35. 1- , , N N N COOH CHO H H H 2- , , , N N N NO2 COOH CHO N H H H H 3- , , , N N N COONH4 N2Ph N COOH H H H H ASSESSMENT – II ON SD3 QI) Draw systemic diagrams illustrating the chemical relations between compounds of each of the following sets:[ SSnQ,s] (clockwise)

36. COOH N H aq. alk. heat 200oC KMnO4 i)DMF, POCl3 ii) aq. Na2 CO3 N N CHO H H A I - 1

37. QII) The systemic diagram represents the correct chemical relations between pyrrole and its related compounds is one of the following: [SMCQ,s] A) a: ()

38. QIII) Which of the following systemics are true and which are false: [STFQ,s] A) a: (x); b: () c: (x); d: ()

39. QIV) Choose heterocyclic compounds from column (A) and reaction conditions from column (B) to build the systemic diagram in column (C): [SMQ,s]

40. NBS/THF N Br N H H (NH4)2 CO3/ 130C Seald vessel heat Br2 200C NBS/THF COOH N N H H hydrolysis (NH4)2 CO3/ 130C Seald vessel COONH4 N COOH N heat Br2 H H 200C hydrolysis COONH4 Br N N H H QV) Rearrange the compounds in the following SD to give correct chemical relations:[ SRQ,s] A)

41. O CHO O O O O O i) DMF, POCl3 ii) aq Na2 CO3 Maleic anhydride H O O H O H2/Cat + H/H2O CH3I CH2N2/ hv O CH3 N3COOEt N O Bun Li O Li EtI 130C COOEt O Et 2,3-Pyridyne (CH3)2 C=CH2 N ZnCl2 /175C t O B O u i) R`CONR2/POCl3 i) AcONO2 ii) aq. Na2CO3 ii) pyridine Br2/dioxan i)C6H5N.SO3 -5C ii) HCl O COR` O NO2 O O Br SO3H II-Furan:Prerequisite SD1 • Sixth: From Fig.1 the student can deduce allthe reactions • of furan [Z=O] as in Fig.6. Fig.6 • The above diagram represents the reactivity of furan nucleus, and gives the linear separated chemical relations between furan and its compounds.

42. Oxidation 3 Reduction CHO O ? O O O i) DMF, POCl3 ii) aq Na2 CO3 O CH2OH O ? O O 1 CH2N2/hv H O O H Malic anhydride N O H2/Cat N3COOEt CH3I COOEt O CH3 + 130C H/H2O O Li EtI Bun Li (2,3)Pyridyne N O CH2CH3 Heat (200C) (CH3)2 C=CH2 ZnCl2 /175C CO2H O O But O i) AcONO2 ? Ac2O, SnCl4 5 2 ii) pyridine Br2/dioxan ? -5C O NO2 i) C6H5NSO3 ii) HCl ? COCH3 6 O 7 SD 4 4 ? Br O SO3H O ? • Seventh: From SD1 the student can illustrate the systemic chemical • relations in (Fig. 7) by modifying (SD1 to SD4) [Z=O] Fig. 7 • The Systemic diagram SD4 shows; (i) known chemical relation between furan and its compounds (ii) unknown chemical relations between furan compounds. (1-7)

43. Cu-Cr2O3/ -C K2Or2 O7/dil H2SO4 CHO O 250C red. NaBH4 O Oxid red O O i) DMF/ POCl3 CH2OH O ii) Na2CO3 O H O O H O H2 / Ni-Co  CH2N2 Maleic anhydride + H /H2O N O O CH3I N3COOEt CO2Et O CH3 H2/Cat 130C O Li EtI Bun Li 2,3 pyridyne N O CH2CH3 Heat (200C) (CH3)2 C=CH2 ZnCl2 /175C CO2H O O But O HNO3 i)CO2 i) AcONO2 Ac2O, SnCl4 ii) pyridine wolff Kishner ii)hydro Red. Br2 Br2/dioxan O NO2 i)C6H5N.SO3 ii) HCl O MgBr 0C O COCH3 COOH O Mg/cu ether H2SO4 Br Cu-Quinoline heat SD5 H2SO4 SO3H O Br O • Eighth: After the next stage of the study of furan compounds [G = R, X, CH2OH, CHO, RCO, COOH] the student can modify (SD4 to SD5) Fig.8 by additions chemical relations (1-7). Fig.8 • In the systemic diagram (SD5) the chemical relations between furan compounds are clarified. • - At this stage of teaching the unite we can ask the Students to answer the following • Systemic Assessmet-3

44. Br2 COOH Br COOH O O heat 200oc Cu/quinoline D Br2 / dioxan -5oC Br O O 1- 2- 3- , , , Br COOH Br O O O O CO2H , , COOH CHO O O O O , , , CCH3 Li O O O O Et ASSESSMENT – III ON SD5 QI) Draw systemic diagrams illustrating the possible chemical relations between compounds of each of following sets:[SSyQ,s] A I – 1

45. QII) Which of the following systemics are true and which are false: [STFQs] A ) a: (); b: (x) c: (); d: (x)

46. QIII: Link systemics from list (I) to one systemic in list (II): [SMQ,s]

47. CHO S S CH2Cl S S CH2O/HCl i) DMF, POCl3 ii) aq. NaOAc CH3 CH3 Li/NH3, CH3OH i)(CH3)3B S/700oC S CH3 ii)I2 CH3 Bun Li CH3 Rany Ni i)Et3B S Li O Maleic anhydride ii)I2 CH3CH = CH2 S S Et O S Benzyne 290C, 21 atm. O Br2/AcOH S Pri ether NO2BF4 CH3COCl/SnCl4 C6H5NSO3 C6 H6 , 0oC Br S NO2 S S S SO3H COCH3 III-Thiophene: (Prerequisite SD1) • Ninth:From Fig.1 the student can summarize all the reactions • of thiophene in the following diagram (Fig. 9). [Z=S] • The above diagram represents the reactivity of (thiophene nucleus), and gives the linear separated chemical relations between thiophene, and thiophene compounds.

48. ? oxidation reduction (2) CHO S + i) DMF, POCl3 ii) aq. NaOAc S S S CH2Cl red S, 200 Li/NH3, CH3OH CH2O/HCl O Red. I) (CH3)3B2 O S ii) I2 S CH3 Maleic S Li Bnu Li ahydride i)Et3B O ii)I2 Benzyne S Et CH3 CH=CH2 Cu / Quinoline 290C, 21 atm. heat CO2H S Pri S S (3) Br2/AcOH ? ether NO2BF4 (1) C6H5NSO3 CH3COCl/SnCl4 Br S ? C6 H6 , (5) S NO2 ? S SO3H (4) ? (6) COCH3 SD6 S • Tenth:The student can illustrate the chemical relations in (Fig. 10) systemically by modifying (SD1 to SD6) [Z = S ] Fig. 10 • The above systemic diagram (SD 6) shows; (i)The known chemical relations between thiophene and its compounds,(ii) The unknown chemical relations between thiophene compounds (1-6).

49. Eleventh:Afterthe next stage of the study of thiophene compounds [ G= R, X, CH2OH, CHO, RCO, COOH ] . The student can modify (SD6 to SD7) Fig.11 by addition of chemical relations (1-6). SD 7 Fig.11 • In the (SD7) all chemical relations between thiophene compounds were clarified. • - At this stage of teaching the unite we can ask the Students to answer the following • Systemic Assessmet-4

50. ASSESSMENT – IV ON SD7 QI) Draw systemic diagrams illustrating the chemical relations between compounds of each of the following sets:[SSnQ,s]