1. Comparison of “Polynaphthalenes” Prepared by Two Mechanistically Distinct Routes M1 Colloquium in Division Frontier Materials Science in 2005 Tobe Laboratory Hiroyuki Kuge

2. Contents Introuction Summary Experiments IR spectroscopy TGA MALDI-TOF MS & LDI-TOF MS 13 C CPMAS NMR spectroscopy

3. Cyclization of Enediyne cis-1,5-hexadiyne-3-ene benzene 1,4-benzenediradical Bergman cyclization

4. Polymerization by Kumada Coupling Polymerization by Bergman cyclization Polymerization of Two Routes

5. IR (KBr): 3062 (w), 3037 (m), 1506 (m), 1370 (m), 953 (m), 837 (m), 758 (s) cm -1. IR (KBr): 3298 (w), 3060 (m), 3024 (m), 2104 (vw), 1596 (m), 1476 (m), 874 (w), 754 (s) cm -1. α IR(KBr): 3054 (w), 3042 (w), 1506 (w), 1376 (m), 948 (w), 848 (w), 802 (s) 778 (s) 760 (s) cm -1. IR spectroscopy rf. IR: 赤外分光法

6. TGA TGA: 熱重量分析 Poly(o-diethynylbenzene) Poly(1,4-dibromonaphthalene)

7. Pyrolysis GC-MS of poly(1,4-dibromonaphthalene) naphthalene 80% methylnaphthalene 8.4% dimethylnaphthalene 1.6%

8. Pyrolysis GC-MS of  -ternaphthyl  naphthalene 91% methylnaphthalene 4.4%

9. Pyrolysis GC-MS of poly(o-diethynylbenzene) naphthalene 24% methylnaphthalene 20% indene 22% methylindene 24% dimethylnaphthalene 6.5%

10. MALDI-TOF MS

11. MALDI-TOF MS of poly(1,4-dibromonaphthalene) MALDI: マトリックス支援レーザー脱離イオン化法

12. MALDI-TOF MS of of  -ternaphthyl 

13. LDI-TOF MS of poly(o-diethynylbenzene) LDI: レーザー脱離イオン化法

14. CPMAS 13 C NMR of poly(1,4-dibromonaphthalene) 

15. CPMAS 13 C NMR of poly(o-diethynylbenzene) 

16. Suggest Mechanism of Radical Species B C F D E attack

17. Intermolecular Addition of Radical D + monomer D

18. The polymers prepared by two routes are structurally distinct. Spectroscopic and spectrometric data indicate that the poly(1,4- dibromonaphthalene) is a poly(1,4-naphthalene), whereas the poly(o-diethynylbenzene) contains five-membered rings. In light of these dissimilarities, this roport suggests that these latter polymers not be represented as a poly(1,4-naphthalene). Summary