Synthesis of silicon-substituted tricyclononenes

Tetrahedron Letters 52 (2011) 6091–6093

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Synthesis of silicon-substituted tricyclononenes M. V. Bermeshev a, A. V. Syromolotov a, M. L. Gringolts a, V. G. Lakhtin b, E. Sh. Finkelshtein a,⇑ a

A. V. Topchiev Institute of Petrochemical Synthesis, 29, Leninsky Prospekt, 119991 Moscow, Russia State Scientific Center of The Russian Federation, ‘State Research Institute for Chemistry and Technology of Organoelement Compounds’, 38, Shosse Entuziastov, 111123 Moscow, Russia

b

a r t i c l e

i n f o

Article history: Received 21 April 2011 Revised 22 August 2011 Accepted 2 September 2011 Available online 7 September 2011

a b s t r a c t A new series of tricyclononene derivatives with two and three silyl groups are successfully synthesized via [2r+2r+2p]-cycloaddition of silylethylenes to quadricyclane. The activity of the silylethylenes in the cycloaddition reactions was estimated. Ó 2011 Elsevier Ltd. All rights reserved.

Keywords: Tricyclononenes Norbornene derivatives Silicon-containing monomers

Tricyclononenes are prepared by thermal [2r+2r+2p] condensation1,2 of quadricyclane (Q) with substituted olefin derivatives (Scheme 1). They contain a norbornene fragment and, therefore, can be polymerized according to the different mechanisms1–3 shown in Scheme 2. Recently we showed that ethylene derivatives containing trichlorosilyl groups participated in the above thermal condensation2,4 (Scheme 3, overall yields are given). The obtained chlorosilyltricyclononenes were methylated with the formation of the corresponding mono- and bis(trimethylsilyl) tricyclononenes. The latter was able to undergo addition polymerization2,4 in contrast to inactive 5,6-bis(trimethylsilyl)norborn-2ene5 (Scheme 4). This polymer bearing two Me3Si-groups on each monomer unit demonstrated exclusively high gas transport parameters relative to light hydrocarbons of C1–C4 content.2 The realization of the abovementioned thermal condensation may serve as a basis for the synthesis of new polynorbornenes having the requisite number of pendant bulky Me3Si-groups responsible for high gas permeability. The goal of this work was to study the activities of different silyl olefins in [2+2+2] cycloaddition with Q6 to assess the scope of these organosilicon substrates which can represent the sources of the corresponding new tricyclononene monomers. Among these substrates we used a number of mono-, di-, and trisubstituted ethylenes 1–11 containing silyl substituents7 (Fig. 1). Silyl olefins 2–6 were found to be unreactive in condensation reactions at temperatures up to 140 °C. As was evident from ⇑ Corresponding author. Tel.: +7 495 955 4 379; fax: +7 495 633 8 520. E-mail address: fi[email protected] (E. Sh. Finkelshtein). 0040-4039/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.tetlet.2011.09.009

R

+

Δ

R

Q Scheme 1. Synthesis of tricyclononenes via [2r+2r+2p]-cycloaddition of ethylenes to Q.

NMR spectroscopy, the thermal condensations of the other silyl olefins (1, 7–11) were realized resulting in mono-, di-, and trisubstituted tricyclononenes8 (Schemes 3 and 5, Table 1). The resulting chlorosilyltricyclononene 12 was methylated9 with MeMgI (Scheme 5, overall yield is given). It is noteworthy that 1,1-bis(trichlorosilyl)ethylene (8), in contrast to 1,2-bis(trichlorosilyl)ethylene (7) and vinyltrichlorosilane (1), reacted with Q even at room temperature while the latter two silyl olefins (1 and 7) only reacted under heating2 ( Fig. 2). 1,2-Bis(trichlorosilyl)ethylene (7) and 1,1-bis(trichlorosilyl)ethylene (8) turned out to be more active than vinyltrichlorosilane (1) in the thermal condensation. This trend can be explained by the fact that an increase in the amount of electron-withdrawing groups (SiCl3) leads to a reduction in the electron density on the double bond and hence to a more pronounced activation. Vinylmethyldichlorosilane (2), vinyldimethylchlorosilane (3), vinyltrimethylsilane (4), vinyltriethoxysilane, (5) and vinyltriphenylsilane (6) failed to undergo condensation with Q at various temperatures. This is apparently due to the absence of activation of the double bond due to the presence of rather weak electron-withdrawing, or even the electron-donating effects of substituents. However, we managed to involve partially methylated chlorosilylethylenes 9–11 in the reaction with Q. Silanes 9 and 10 possessing

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R n

[W], [Ru] metathesis polymerization

n

[Ni], [Pd] addition polymerization

R

R

Scheme 2. Metathesis and addition polymerization of tricyclononenes.

9

R

SiCl3

R 6

7

MeMgI

R 95 oC

5

SiCl3

3

SiCl3

1

8

R = H, SiCl3

SiCl2Me

SiClMe2

1

SiMe

2

2

3

Si(OR)3

4

SiCl3

Scheme 3. The thermal condensation of vinyltrichlorosilane and 1,2-bis(trichlorosilyl)ethylene with Q.

5

6

SiCl3

Cl3Si

SiCl3 7

8

SiCl2Me SiCl3

Cl3Si

n

Cl3Si

9

SiMe3

SiClMe2

SiMe3

SiCl3

SiCl3

Cl3Si

10

11

Figure 1. Structures of the silyl olefins used in condensations with Q.

Me3Si

SiMe3

The above sequence shows that the number of electron-withdrawing groups (SiCl3) and their relative arrangement affect the reactivity of the silylalkenes in condensation reactions with Q. An increase in the amount of electron-acceptor SiCl3 groups increases the reactivity of silylalkene. A geminal arrangement of these groups also increases the reactivity due to the polarization of the double bond. Such a strong polarization effect is in good agreement with the proposed nonsynchronous mechanism of the reaction11,12 and with correlations observed for various sulfonyl- and fluoro-substituted ethylenes.13–17 The unreactivity of silyl olefins 2–6 is apparently associated with the weak or negligible electron-withdrawing properties of their substituents.

Scheme 4. Addition polymerization of bis(trimethylsilyl)-substituted tricyclononene.

different types of chlorosilyl groups reacted with Q at room temperature (Scheme 5, Fig. 2A). In the case of the silane with one fully methylated silyl group (11), the reaction proceeded only under heating (95 °C, Fig. 2B). The comparative reactivities of chlorosilylethylenes containing different numbers of Si–Cl bonds in thermal condensations with Q were estimated at 25 or 95 °C. The curves (Fig. 2) reflecting the course of the condensation as well as the results presented in Table 1 allowed arrangement of the studied chlorosilylethylenes in the following sequence of reactivity (Fig. 3). SiCl3

SiCl3

SiCl3

SiCl3

25 oC

SiMe3 MeMgI, Et2O

SiMe3

reflux, 70 h

12

16, 54%

SiCl3-nMen Cl3Si

SiCl3-nMen

SiCl3

13, n = 1, 14, n = 2, 15, n = 3

SiCl3

o

25-95 C SiCl3

Scheme 5. Synthesis of new silicon-containing tricyclononenes.

Table 1 The thermal condensation of silylethylenes with Q according to Schemes 3 and 5

a

SiPh3

R = Et or SiMe3

R=H (51%) R = SiMe3 (64%)

SiMe3 [Ni], [Pd]

SiMe3

4

Entry

Olefin

Molar ratio Q:olefin

T (°C)

Time (h)

Cycloadduct

Yield (%)

1 2 3 4 5 6

1 7 8 9 10 11

1:2 1:1.5 1.5:1 1.5:1 1.5:1 1.5:1

95 95 25 25 25 95

150 120 180 170 50a 20

Ref. 2 Ref. 4 12 13 14 15

66 85 83 95 95 64

Reaction time was 50 days.

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Figure 2. Conversion10 of chlorosilylethylenes on reaction with Q [Q: ethylene = 1.5: 1 (mol/mol)]. A: at 25 °C; B: at 95 °C.

SiCl2Me SiCl3

Cl3Si 9

SiClMe2

SiCl3 >

> SiCl3 Cl3Si 8

SiCl3

SiCl3 > Cl3Si

10

SiMe3 >

7

SiCl3 >

Cl3Si

SiCl3 11

1

Figure 3. The sequence of reactivity of silylethylenes in cycloaddition reactions with Q.

Thus, we have shown that quadricyclane takes part in the condensation reactions with various chlorosilylethylenes and have compared their reactivities in this reaction. The scope of substrates capable of condensation has been assessed, and a number of new silyl-substituted tricyclononenes as potentially active monomers for addition and metathesis polymerizations, have been prepared. Acknowledgments The authors are grateful for support from the Russian Foundation of Basic Research (Grant No. 09-03-00342-a) and the Ministry of Education and Science of the Russian Federation (GK No.16.740.11.0338). References and notes 1. Sanders, D. P.; Connor, E. F.; Grubbs, R. H.; Hung, R. J.; Osborn, B. P.; MacDonald, S. A.; Willson, C. G.; Conley, W. Macromolecules 2003, 36, 1534. 2. Gringolts, M.; Bermeshev, M.; Yampolskii, Yu.; Starannikova, L.; Shantarovich, V.; Finkelshtein, E. Macromolecules 2010, 43, 7165. 3. Saunders, R. S. Macromolecules 1995, 28, 4347. 4. Gringolts, M. L.; Bermeshev, M. V.; Makovetsky, K. L.; Finkelshtein, E. Sh. Eur. Polym. J. 2009, 45, 2142. 5. Finkelshtein, E. Sh.; Makovetsky, K. L.; Gringolts, M. L.; Rogan, Y. V.; Golenko, T. G.; Lakhtin, V. G.; Filatova, M. P. J. Mol. Cat.: A 2006, 257, 9. 6. Quadricyclane was synthesized according to: Smith, C. D. Org. Synth. 1988, 6, 962. 7. Compounds 1–6 were purchased from Sigma–Aldrich; compounds 7 and 8 were synthesized as described: Petrov, A. D.; Mironov, V. F.; Mashancker, D. Izv. Acad. Nauk, Ser. Khim. 1956, 550; compounds 9–11 were obtained according to the described procedure: Sheludyakov, V. D.; Korshunov, A. I.; Lakhtin, V. G.; Timofeev, V. S.; Slusarenko, T. F.; Nosova, V. M.; Gradova, E. V. Zh. Obsch. Chim. 1986, 56, 2743. 8. Examples of and the conditions for the thermal condensation of quadricyclane and silyl olefins are described in Refs. 2 and 4; 3,3-Bis(trichlorosilyl)-exotricyclo[4.2.1.02,5]non-7-ene (12, liquid): 1H NMR (400 MHz, CDCl3) d 5.41 (m, 2H), 2.89 (br s, 1H), 2.24 (br s, 1H), 1.99 (m, 2H), 1.71 (m, 2H), 1.87 (d, J = 9.9 Hz, 1H), 0.91 (d, J = 9.9 Hz, 1H). 13C NMR (100 MHz, CDCl3) d 135.65, 134.92 (C(7), C(8)), 44.30, 43.84, 43.63, 36.50 (C(1), C(2), C(5), C(6)), 42.01 (C(9)), 30.82, 27.37 (C(3), C(4)); 3-(Trichlorosilyl)-3-[dichloro(methyl)silyl]-4-(trichlorosilyl)exo-tricyclo[4.2.1.02,5]non-7-ene (13, liquid): 1H NMR (400 MHz, C6D6) d 5.60–5.55 (m, 2H), 3.28 (br s, 1H), 2.70 (br s, 1H), 2.93 (d, J = 8.7 Hz, 1H), 2.60 (m, 1H), 2.47 (d, J = 7.3 Hz, 1H), 2.23 (d, J = 10.5 Hz, 1H), 1.28 (d, J = 10.5 Hz, 1H),

9.

10.

11.

12. 13. 14. 15. 16. 17.

0.80 (s, 3H). 13C NMR (100 MHz, C6D6) d 136.69, 135.13 (C(7), C(8)), 45.09, 44.82, 39.45, 38.03 (C(1), C(2), C(4), C(5), C(6)), 42.33 (C(9)), 10.09 (SiCH3) [C(3) was not observed; for details on the low intensities of quaternary carbon atoms in 13 C NMR and APT see, for example, Friebolin, H. In Basic One- and TwoDimensional NMR Spectroscopy. Fourth, Completely Revised and Updated Edition. Wiley-VCH, 2005; p. 35]; 3-(Trichlorosilyl)-3-[chloro(dimethyl) silyl]-4-(trichlorosilyl)-exo-tricyclo[4.2.1.02,5]non-7-ene (14, viscous oil): 1 H NMR (400 MHz, C6D6) d 5.65–5.60 (m, 2H), 2.94 (br s, 1H), 2.74 (br s, 1H), 2.90 (d, J = 8.7 Hz, 1H), 2.63 (m, 1H), 2.44 (d, J = 7.5 Hz, 1H), 2.25 (d, J = 10.3 Hz, 1H), 1.29 (d, J = 10.3 Hz, 1H), 0.59 (s, 3H), 0.50 (s, 3H). 13C NMR (100 MHz, C6D6) d 136.62, 135.14 (C(7), C(8)), 45.33, 45.14, 44.34, 39.50, 37.62 (C(1), C(2), C(4), C(5), C(6)), 42.38 (C(9)), 6.85, 5.34 (Si(CH3)2) [C(3) was not observed]; 3(Trichlorosilyl)-3-(trimethylsilyl)-4-(trichlorosilyl)-exotricyclo[4.2.1.02,5]non-7-ene (15, semi-solid): 1H NMR (400 MHz, C6D6) d 5.68–5.61 (m, 2H), 2.84 (br s, 1H), 2.70 (br s, 1H), 2.66 (m, 1H), 2.43 (d, J = 7.5 Hz, 1H), 2.37 (d, J = 8.7 Hz, 1H), 1.83 (d, J = 9.9 Hz, 1H), 1.25 (d, J = 9.9 Hz, 1H), 0.22 (s, 9H). 13C NMR (100 MHz, C6D6) d 136.74, 134.70 (C(7), C(8)), 45.25, 44.81, 43.91, 39.57, 37.79 (C(1), C(2), C(4), C(5), C(6)), 42.03 (C(9)), 2.31 (Si(CH3)3) [C(3) was not observed]. Examples of and the conditions for methylation are described in Refs. 2 and 5; 3,3-Bis(trimethylsilyl)-exo-tricyclo[4.2.1.02,5]non-7-ene (16, liquid): Anal. Calcd for C15H28Si2: C, 68.10; H, 10.67. Found: C, 68.24; H, 11.01. IR (KBr): mmax 2930, 1250, 1025, 840 cm 1; 1H NMR (400 MHz, CDCl3) d 5.92 (m, 1H), 5.84 (m, 1H), 2.86 (br s, 1H), 2.85 (br s, 1H), 2.07 (m, 1H), 2.00 (d, J = 9.2 Hz, 1H), 1.89 (m, 1H), 1.82 (d, J = 7.1 Hz, 1H), 1.67 (m, 1H), 1.24 (d, J = 9.2 Hz, 1H), 0.07 (s, 9H), 0.06 (s, 9H). 13C NMR (100 MHz, CDCl3) d 136.07, 134.65 (C(7), C(8)), 45.74, 44.15, 42.99, 36.91 (C(1), C(2), C(5), C(6)), 42.07 (C(9)), 26.02 (C(4)), 13.84 (C(3)), 2.14, 1.30 (Si(CH3)3). MS (EI) m/z: 264 (M+, 2%), 73 (Me3Si+, 100%). Olefin conversion was determined with the help of 1H NMR spectroscopy: signals of the olefin hydrogen atoms in the initial silylethylene and the formed silyl-substituted tricyclononene were well resolved. Side reactions involving initial silylethylenes or final tricyclononenes were not observed. If the intensity of the olefin hydrogen signal in the initial silylethylene was I1 and the intensity of the olefin hydrogen signal in the formed silyl-substituted tricyclononene was I2 then olefin conversion was nI2/(2I1 + nI2) where n is the number of olefin hydrogen atoms in the initial silylethylene. Experiments were performed in sealed ampoules; CDCl3 was used as an external standard. (a) Jones, G. A.; Shephard, M. J.; Paddon-Row, M. N.; Beno, B. R.; Houk, K. N.; Redmond, K.; Carpenter, B. K. J. Am. Chem. Soc. 1999, 121, 4334; (b) Paquette, L. A.; Kesselmayer, M. A.; Kunzer, H. J. Org. Chem. 1988, 53, 5183. Domingo, L. R.; Saez, J. A.; Zaragoza, R. J.; Arn, M. J. Org. Chem. 2008, 73, 8791. De Lucchi, O.; Pasquato, L.; Modena, G. Tetrahedron Lett. 1984, 25, 3643. De Lucchi, O.; Lucchini, V.; Pasquato, L.; Zamai, M.; Modena, G. Gazz. Chim. Ital. 1984, 114, 293. De Lucchi, O.; Modena, G. Phosphorus Sulfur Relat. Elem. 1983, 14, 229. De Lucchi, O.; Lucchini, V.; Pasquato, L.; Modena, G. J. Org. Chem. 1984, 49, 596. Petrov, V. A.; Vasil’ev, N. V. Curr. Org. Synth. 2006, 3, 215.