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Phosphorus, Sulfur, and Silicon andthe Related ElementsPublication details, including instructions for authors andsubscription information:http://www.tandfonline.com/loi/gpss20

Highly Unsaturated MacrocyclicOrganosilicon CompoundsMikhail Voronkov a , Oleg Yarosh a & Larisa Zhilitskaya aa Institute of Organic Chemistry, Siberian Branch , Ac. Sci.USSR, 664033, Irkutsk, USSRPublished online: 06 Dec 2006.

To cite this article: Mikhail Voronkov , Oleg Yarosh & Larisa Zhilitskaya (1992) HighlyUnsaturated Macrocyclic Organosilicon Compounds, Phosphorus, Sulfur, and Silicon and theRelated Elements, 65:1-4, 33-42, DOI: 10.1080/10426509208055312

To link to this article: http://dx.doi.org/10.1080/10426509208055312

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Phosphorus, Sulfur, and Silicon, 1992, Vol. 65, pp. 33-42 Reprints available directly from the publisher Photocopying permitted by license only

0 1992 Gordon and Breach Science Publishers S.A. Printed in the United Kingdom

HIGHLY UNSATURATED MACROCYCLIC ORGANOSILICON COhfl?OUNDS

MIKHAIL VORONKOV, O U G YAROSH AND LARISA ZHILITSKAYA Institute of Organic Chemistry, Siberian Branch, Ac.Sci.USSR, 664033 Irkutsk, USSR

Abstract A series of 12-, 15-, 18-, 21-, 24-, 27- or 30-membered macrocyclic silahydrocarbons of general formula (MeRSiC=C)n, n= 4-10 and R = H, Me, CH,=CH were synthesized by reaction of Me,Si(CzCMg;Br),, Me(CHZ=CH)Si(CzCMg€3r),, BrMgCrCMe2SiC~CSiMe2C~C?d@r or BrMgCzCMe,SiCzCSiMe,CsCSiMe,CECSiMe,CrCM@r with MeH- SiCl,, Me,SiCl,, Me(CH,=CH)SiCl, or (ClMe,SiCrC),SiMe,. 23-Membered spiromacrocyclic polyacetylenic silahydro- carbons containing 6 silicon atoms, 8 triple bonds and central Si or Ge atoms were prepared by reaction of Me,Si(CrCSiMe,C=CMgBr), with MC1, (M = Si, Ge).

INTRODUCTION

As early as the middle of this century we suggested to call the unknown that time silahydrocarbons of general formula (H,SICZC)~ cyclosilethynes.’ The f irst cyclic silahydrocarbon of this type, pennethyltetracyclosilethyne (Me,SiC=C), was prepared by u9 in 1973 by reaction of di- methyldichlorosilane with calcium carbide in a molten salt system LiC1-KC1.2 Later some other cyclic oligomers (Me,SiC=C)n, n = 3-5 have been de~cribed.~-~

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M, VORONKOV, 0. ' YAROSH AND L. ZHILITSKAYA

In several publications the synthesis of silaacetylenic polymers by reaction of diorganyldichlorosilanes with

9 acetylene organometallic derivatives such as C2(b¶gE3r)2, C,Na2 , 'Otl ' C2Li212 has been reported. RESULTS AND DISCUSSION

During the last years by use of organomagnesium method we have prepared a number of new 12-30-membered polyacetylenic macrocyclic silahydrocarbons of general formula (MeRCrC), where n = 4-10: R = H, Me, CH2=CH, which we called cyclodiorganylsilethynes.

The reaction of bis(bromomagnesiumethynyldimethy1- sily1)acetylene with dimethyl-bis(dirnethylc~oroeily1- ethyny1)silane In tetrahydrofuran under high dilution Qave 15-membered decamethylcyclopentasilethyne, 1,1,4,4,7,7*10,- 10,13,13-decamethyl-l,4,7,10,13-pentasilacyclopentadeca-2,5- 8,11,14-pentaine (I) and 30-membered eicosamethylcyclodeca- silethyne , 1 ,1,4,4,7,7,10,10,13,13,16,16,19.19,22,22,25,25, - 28,28-elcosamethyl-1,4,7, lO, l3 ,16,19,22,casi lacyclo- triaconta-2,5,8,11,14,17,20,23,26,29-pentaIne (11).

13

Me Si-CrCMgBr + (ClMe,SiCzC),SIMe, + (Me,SiC=C), 2 1

C I, I1 C n = 5 ( I ) , l O ( I 1 ) 111

I

Me,S i-CzCMgBr

A similar reaction of dimethyl(bromomagneslumethyny1)- silane with dimethyl-bis(dimethy1chlorosilylethynyl)silane leads to 12-membered octamethylcyclotetrasilethyne (111) and 24-membered hexadecamethylcyclooctasilethyne (N) :

Me,Si(CECMgBr), + (CIMe,SiC=C)ZSiMe, -+ (Me,SiCrC),

n = 4(III), 8 ( N ) 111, Iv

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HIGHLY UNSATUFLATED MACROCYCLIC ORGANOSILICON COMPOUNDS

The reaction of bisC(bromomagnesiumethynyldimethy1- silyl)ethynyldimethylsilyllacetylene with dimethyl-bis(di- methylchloros i fy le t~1)s i lane gave 21-membered tetradeca- methylcycloheptasilethyne ( V ) :

Me2S iC=CS Me, C=CM@r I

Ill

I

C C

+ (ClMe,SiC=C )2SiMe2 + (Me2SiC=C)7 V

Me,SiCzCSiMe,CzCMgBr

The silahydrocarbons 111, IV and 18-membered dodeca- metylhexasilethyne ( V I ) were obtained by reaction of dimethyl-bis(bromomagneslumethynyl)sllane with dimethyldl- chlorosilane :

Me,Si(CrCMgBr), +- Cl,SIMe, + (Me,SICzC),

n = 4 ( I I I ) , 6 ( V I ) , 8( I V ) 111, IV, V I

The silahydrocarbon V I and 27-membered octadecamethyl- cyclononasilethyne ( V I I ) was obtained in an analogous way from bis(dlmethylbromomagnesiumethynylsi1yl)acetylene and dimethyldlchlorosilane.

Me,SiC=CMgBr I

111 C + Cl,SIMe, __j (Me,SIC=C), C I

Me,SiC&MgBr n = 6 ( I V ) , 9 ( V I I )

We have synthesized macrocyclic polyacetylenic sila- hydrocarbons containing exocyclic vinyl groups and Si-H bonds. In this manner, by reaction of dimethyl-bis(bromo- maeplesiumethyny1)silane with methyl(viny1)d~chlorosilane we

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M. VORONKOV, 0. YAROSH AND L. ZHILITSKAYA

obtained 12-membered 1 ,4,4,7,10,10, -hexamethyl-l,7 ,-divinyl- 1 ,4,7,1O-tetrasilacyclododeca-2,5,8,11 -te traine (VIII ) and 18-membered 1 ,4,4,7,10,10,13,16,16-nonamethyl-l,7,13-trl- viny1-1,4,7,10,13,16-hexasilacyclooctadeca-2,5,8,11,14,17- hexaine (IX):

Me Me I I

Me-SiCrC-SiCH=CH, ‘1 ‘2

Me,Si(C=CMgBr), t Cl,Si(CH=CH,)Me -+ C C + ’. 111 111

C I

C I

Hz C=CHSi-CrCS iMe I I

Me Me VIII

Me Me Me I I I

CH,=CH-SiCrCSIC&-Si-CH=CH, I ‘ 1 12 c Me c t

C ? Me I

Me-S i Cz Ch i CEC-S 1-Me he I Me I

CH=CH2 Ix

An analogous reaction of methyl(viny1)-bis(bromomagnesium- ethyny1)silane with methyl(viny1)dichlorosilane gave 12- membered cyclotetra(methylvinylsi1ethyne) (X):

Me ( CH,=CH ) Si ( C+CM@;Br ), t C1,Si ( CH=CH, )Me + [Me ( CH=CH, ) SiCzC l4 X

The reaction of bis(bromomagnesiumethynyldimethy1- sily1)acetylene with methyl(viny1)dichlorosilane led to 18-membered 1 ,4,4,7,7,10,13,13,16,16-decamethyl-l , 1 O-di- vInyl-l,4,7,10,13 , 16-hexasilacyclooctadeca-2,5,8,11, I 4,17- hexaine (XI) :

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HIGHLY UNSATURATED MACROCYCLIC ORGANOSILICON COMPOUNDS

Me t

Me Me I I

I

MezSiCzCllbgBr I Me I

Me-S ICzC6 iCzC-S I-CH=CH, I Ihe Ihe Me

XI

The 1 2-membered 1 , 4 , 4 , 7,10,1O-hexame thyl-1 ,7-dihydro-l, 4 , - 7,10-tetrasilacyclododeca-2,5,8,ll-tetraine (XII) was iso- lated by reaction of dimethyl-bis(bromomagnesiumethyny1)- silane with methyldichlorosilane :

Me,SI. (CrCMgBr), -t

Me Me H-Si-CsC-Si-Me

I '1 C C 111 111 C C

Me-Si-CzC-Si-H I '2 Me Me XI1

I I

I I

Further we have first synthesized spiromacrocyclic polyacetylenic silahydrocarbon 3,3,6,6,9,9,15,15,18,18,21,- 21-dodecamethy1-3,6,9,12,15,18,21-heptasi1asp~ro~11 ' ,11 ' 1- t r i co sa- 1 4 7,10,13,16,19,22-0~ t aine (XI1 ) and its 1 2- membered germa analog 3,3 , 6,6,15,15 , 18,18,21,21 -dodeca- rnethyl-3,6,9,15,18,2l-hexasila-l2-germa spiro[ll ' , I 1 * 1- trlcosa-1 , 4 , 7 , 1 0 , I 3,16,19 , 22-oc taine (XIV ) . These compounds were obtained by reaction of blst(bromornagnesiumethyny1- dimethylsily1)ethynylldimethylsilane with tetrachlorosllane and tetrachlorogermane, respectively :

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M. VORONKOV, 0. YAROSH AND Lo ZHILITSKAYA

2Me2Si (CrCSIMe,C=CMgBr), + MCll + ,Me Me, ,Me

M /3\

/CGC CGC\ ,cz

C \ S

/ C

P :he si si

/ \ / L Me Me Me Me

XIII, XIV M = Si(XIII), Ge(XIV)

The above compounds are colorless, high-melting crystalline substances stable in storage and heat- to the melting point.

The meltin& points and yields of the silahydrocarbons obtained are presented in Table 1.

TABLE I Macrocyclic acetylenlc silahydrocarbons Compound Yield, M.p. , Mass spectrum [MI+

I%) (OC)

I I1 I11 Iv V VI VII VIII Ix X XI XI1 XI11 XXQ

7.0 1.2 2.4 5.0 3.8 5.0 2.5 1.7 3.8 2.0 4.5 4.3 2.5 2.0

208 21 7 258 252 163 268 1 90 1 95 1 88 176 21 5 185 293 299

41 O( 13) 820 (28 ) 328 (43 ) 656 (23 ) 574( 17 ) 492 (1 9 1 738 (2 ) 352 (37 ) 528 (1 8) 376 (25 ) 516(32) 300 (58 ) 568(15) 610(5)

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HIGHLY UNSATURATED MACROCYCLIC ORGANOSILICON COIWOUNDS

The melting points of permethylcyclosilethynes (Me,SiC=C)n fall in the following order of changing the cycle size (n): 6 > 4 >8 >I0 >5 > 9 > 7. It is worth notlce that the lowest melting polnts correspond to odd n values. This alternation of melting points of even and odd members of the homologous series is quite common.14

It should be noted that our melting points for compounds (I) (n = 5 ) and (111) (n = 4), 208 and 258'C, respectively, differ from the literature data8 (255-257 and ZO~-ZO~OC, respectively .

The structures of all the silahydrocarbons obtained were proved by mass spectrometry (Table 1 ) and 'H, I3C and 29Si NMR spectrometry (Table 2 ) .

The 'H NMR spectra of cyclosilethynes (Me,SiCrC)n show one resonance simal of methyl groups attached to the sillcon atom. The signal is slightly shifted downfields as the cycle size increases (by 0.06 ppm in going from n = 4 to n = 10). In the 'H NMR spectra of cyclosilethynes VIII- XI1 there are two signals arisen from the methyl groups of non-equivalent SiMe,, Si(CH=CH,)Me and SiHMe fragments.

The '% resonance signal of methyl groups attached to the silicon atom is present in a range from -0.96 to + 0.87 ppm and from -1.06 to -2.21 and -3.8 ppm in the SiMe,, Si(CH=CH,)Me, and SiHMe groups, respectively. The chemical shifts of acetylenic carbons in the Me,SiCz group occur in the 1 I 1 -1 16 ppm region whereas those for the Me (CH=CH)SiC= group are observed in higher fields (104-1 11 ppm). The 132 and 136 ppm resonance signals correspond to the vinylic CH= and CH,= carbon atoms.

In the 29Si NMR spectra the resonance signal of sili- con in SlMe,, Si(CH=CH,)Me and SiHMe groups is observed In ranges from -41.0 to -41.7, from -48.5 to -49 and at -41.0 ppm, respectively.

In the 'H NMR spectra of splrocyclic compounds XI11 and XIV there are two signals at 0.34 and 0.31 ppm. The former corresponds to the methyl groups at the silicon atoms nearest to spirocyclic silicon and germanium atoms.

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TABL

E I1

I3C

and

29S

i Spectral parameters

of

the

com

poun

ds obtained

I 0.35

I11

0.30

V 0.33

VI

0.34

VIII 0

.30

0.35

6.

05

SIX

0.34

0.

39

6.0"

X 0.

37

6.06

XI

0.33

0.

39

6.07

XI1

0.32

0.

37

XI11 0

.34

0.31

XIV

0.34

0.

31

r_

e 00

u

-0.6

9

0.18

0.87

-0.8

0

0.11

-2 2

1

0.18

4.24

-0

.96

-1 .

I4

-1.0

8

114.

2

111 -

07

111.

55

-2.1

0 13

1.98

13

6.10

11

3.29

-1.0

6 13

2.70

13

5.63

Il

l.%

131.

71

136.

26

113.

24

-1.0

7 13

2.85

13

5.61

11

0.85

11

2.15

-3

.89

115.

78

-0.8

7 11

6.69

11

4.42

-0

.92

114.

09

113.

66

-41.

7

-41.

2

-41.

5

-41.

3

108.

84

-41

.O

-48.

7

108.

85

-41.

2

110.

74

-41.

0

113.

22

-40.

4 10

6.67

11

3.12

-4

0.7

105.

15

0 5

-49.

0

-48.

5 tr

N E

-48.

6 E 9 I3

-41 .O

$ -4

1.4

-66.

9

-41.

5

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HIGHLY UNSATURATED MACROCYCLIC ORGANOSILICON COMPOUNDS

The 13C resonance signal of the methyl groups attached to these silicon atoms occurs wlthln a range from -1.14 and -1.08 ppm for compounds XI11 and XIV, respectively. The I3C resonance of two methyl groups attached to other silicon atoms is observed at -0.87 and -0.92 ppm, respectively. The I3C NMR signals of acetylenlc carbons are shifted upfields on approaching the splrocycllc sillcon (116.69, 114.42, 113.22 and 106,67 ppm) and germanium atoms (114.09, 113.66, 113.12 and 105.15 ppm).

The *'SI NMR spectrum of spirocyclic compound XI11 also shows the presence of sillcon atoms of three types: central (6 = -66.9 ppm), 4 silicons nearest to the central atom (0 = -40.4ppm) and 2 silicons remote from the central silicon atom (6 = -41.4ppm). Analogously, in the 29Si NMR spectrum of XIV the latter two types of silicon atoms glve rise to the -40.7 and -41.5 ppm signals.

Mass spectra were run on a GLS-MS MAT-212 (Varian) instrument (ionizing voltage 70 eV). NMR spectra were recorded on a JEOL FX 90Q spectrometer (15% solution in CDCl,, TMS). The I 3 C resonance frequency Is 13-22.49 MHz, pulse length 16 ps. NMR spectra were recorded by the pulse technique . REFERENCES

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3. E. Kloster-Jensen and G.A. Eliassen, Angew.Chem., 97, 587 (1985).

4. H. Scikurai, Y.Nakodaira and A.Hosomi, J.Amer.Chem.Soc., 5. H. Sakurai, Y. Erlyama ant3 A. Hosoml, Chem.Lett., 595 6. T. Iwahara and R.West, J.Chem.Soc., Chem. Commun., 954

7. K.Bortolln, B. Parbhoo and S.S.D.Brown, J.Chem.Soc., 8. E. Herlgge and A. Baumegger, J.Ormnomet.Chem., 389, C39

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M. VORONKOV, 0, YAROSH AND L. ZHILITS-UYA

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Vasllyeva, Vysokomol .Soed., 13B, 61 2 (1 971 ) . 10. V.N.Shumov, Ya.M. Paushkin and A.F. Lunin, Vysokomol.

11. Ya.M. Paushkin, A.F. Lmln and V.N. Shumov and L.A.

12. P.R. Jones, T.E. Albanes, R.D. Gillespie and P.S. Jones

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14. M.G. Voronkov and V.P. Feshln, Teor.Exp.Khlm., 2, 444

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