10urnal of Scientific & Industrial Research Vo1.59, April 2000, pp 265-279

Methods of Synthesis and Properties of 1-Vinylsilatranes* +

M Nasim and PS Venkataramani

Defence Materials & Stores Research & Deve lopment Establi shme nt , DMSRDE PO, GT Road, Kanpur 208 01 3

and

G S Zaitseva Chemistry Department, M oscow State University, B-234, Vorob Evy Gory, 119899, M oscow, Russ ia

The synthesis and chemical reactivity of I-vinyl silatranes have been reviewed. Chemical reactions of I-vi nyls ilatranes such as cycloadd ition , oxidation, hydrosi lylation and derivatisation have been discussed in detail. Literature avai lable/publi shed till the end of 1998 have been covered.

1 Introduction

The chemistry of organo compounds of IYB group elements (Si, Ge, and Sn) is one of the fascinating areas having practical utilit y l-4. Compared to th e organocompounds of silicon and tin , the organogermanium compounds are comparatively less studied and are not widely used in practice. This is be­cause of relatively high cost of the starting germanium source such as germanium metal and its oxide. How­ever, during recent years, spec ific and prospective prac­tical applications of organogermanium compounds have been established in terms of its biological and pharma­cological activity3- JO.

Now-a-days intensive and useful research is being carried out in the field of organo derivatives of silicon, germanium, and tin in which the metal atom present has the coordination number differing from four. In the se­ries of pentacoordinated compounds, a special pl ace is occupied by the cyclic compounds of silicon , germanium and tin derivatives of triethanolamine and its homologue called silatranes2.11 -21, germatranes3.4.22 and stannatranes23-26, respectively. In general, these compounds are class i­fied under "metallatranes" as proposed by Yoronkov et ai. 27.2X. The chemical nomenclature is l-organyl-2,8,9-trioxa-5-aza- l-metalla (s ila, germa, or stanna) tricyclo [3.3.3.015] undecanes .

Their heterocyclic skeleton is depicted in struc­ture-I, where M stands for metal (Figure I) . Silatrane

*DMSRDE Reference No. 2528. + Author for correspondence.

itself, the simplest compound of thi s class has structure II, where R= H, M =Si.

(I)

l)2~~ __ C!h H/Hi 1 H,

\4-A1-o I

R

(11)

Figure I - (I) Depicts heterocyclic skeleton (M=metal ) and (II )

depicts si latrane (R= H, M=Si)

Metall atranes having cage structure are a class of pentacoordinated organometallic compounds formed from the reacti on of trialkanolamines such as trieth­anolamine with trifunctional si lanes, germanes or stannanes, [RM(OR)3]' These are characterized by transannular donation of electron density from nitrogen to the metal atom, thereby producing an effective pentacoordination at silicon or germanium 2Y-32

Syntheses of new si latranes are of much interest in view of their interesting biologicaI2.:n-3\ physicochemi ­caP6-39, and structural properties40-47 . Chemical investi­gations of these hypervalent silicon species are being intensively pursued4x-50 .

Silatranes are technologically important materials in view of their potential applications in rodenticides'il , insecticides34

, crop yield enhancement3'i.'i2 , medicine (wound healing, intensification of hair growth-treatment of diffe rent kind of alopecia) 2.35, agrochemicals

266 J SCI INO RES VOL.59 APRIL 2000

(microbic ides, bactericides, fungicides and anticancer agents)53-S\ polymers and compos ite materi als (curing agents for a number of synthetic resins, key in g coupling agents?.5fi.S7, textiles (water and oil repellents)\ corro­sion inhibitor2.5x.59, seri culture (s ilk produ ct ion)35.oo, conservating agent (fish conservati onf. Silatranes are of certain practi cal interest as suitable alkylatin g2, alkenylating2, arylating2 and reducing agentsh l for the preparati on of very pure organic deri vati ves of heavy metals2

.

The practical application of silat ranes are not lim­ited. The combinati on of the sil atrane moiety with organometallics should be of interest which can be used as redox potenti aP9 and also of technological importance e.g. non linear optic materi als21. Group 13 aza tranes (azaalumatranes, azagallatranes) and group 14 azatranes (azas ilatranes, azagermatranes etc) wi ll be futuristic po­tential MOCVD agents fo r metal and non-met I nitrides film precursorso2.o3 .

Recently, we initiated in ves ti gating the sy nthesis and chemical properties of functionalised silatranes4s-47.o4-69, and germatranes70-7X . A large number of fun cti onali zed silatranes having become avail able in earlier years2.11 .13 •

Our main attraction was fo r l-vinylsilatranes since in our hands these proved to be excellent precursor ma­terials for the synthes is of several new fun c; ti onli sed silatranes. Thus the paper summarizes the numerous data available on I-vinylsilatranes, highlighti ng, both their preparati ve aspects as well as reacti vity. The literature up to the end of 1998 is covered here.

2 Methods of Synthesis of 1-Vinylsilatranes

I-Vinylsilatrane, N(CH2CHP\SiCH=CH2 (1), was fir t prepared by Frye et af. 79 by transesterification of vinyltri al koxysil anes (2, 3) with triethanolami ne (4).

Later, tr ansesterification of Si- substituted tri alkoxys ilanes was widely and successfull y used for the synthesis of I-vinylsilatranes and vari ous I-substi­tuted silatranes2.".xo.x ,.

(RO)3SiCH=CH2 + N(CH2CHPH\ ~ 2,3 4

N(CH,CH,O),SiCH=CH2 + 3ROH - - .

1

R =: Me (2), R = Et (3)

It became poss ible for Samour~() to synthes ize 1-vinyl-(3,7, I O-trimethyl)s ilatrane (6) by the above method using triisopropanolamine (5) .

3 5

CH2=CHSi [OCH(CH3)CH

2J3N + 3EtOH

6

However, in this method the reactants were sub­jected to prolong heating for completion of the reacti on. Addition of catalytic amounts of sodium or potassi um alkox ide in the reaction mi xture shortened the react ion time. Thus, Voronkov et af. X2 synthesised compound 1 and its C-methyl substituted (in the afrane cycle) ana­logue by the transesterificati on of compound 2 with tri s(2-alkano lamines) in the pr sence of 10 per cent methanolic so lution of sodium methoxi.de.

(McO) ,SiC H=CH, + N(C H, CH,O H)"(CH,CHOH),.,,

2 CH, I -- N(CH,CH,O)" (C H,C HO),."SiC H=CH, + 3MeOH

CH, I

7,8 n = I (87 per celli ) (7); n = 2 (85 per celli ) (8)

Intermolecular condensation of si Iylether deri va­tives of dioxaazasilocanes (9-11) containing a phenyl group at silicon gave compound 1. Reaction proceeded only in the presence of sodium alkox ide to yield com­pound 1 in 70-80 per cent yieJdK3.

"ACH,CH2 .

RRIS( >-CH2CH20R2 + (AlKOhSiCH=CH, -->

OCH2CH2

9-11

R, RI = Me, R' = H (9); R, RI = -CH=:CHr R' = H (10), R = ­

CH=CH" RI = Ph, R' = SiM e~ (11)

It was observed that besides vin yl group, if phenyl group was present at the silicon of the cyclic ether, mi­gration of phenyl group took place under the influence

of base giving rise to product of sil atrane structu resX3 .

CH~CH, OH S i (OCH ,CH ,),NCH,CH,oSiMc~----~

Ph/ - PhS iMe~ N(CH,CH,o),SiCH:=CH,

NASIM & VENKATARAMANI: VINYLSILATRANES 267

The scope of trans esterification reaction is not lim­ited and the synthesis of various I-v inylsilatranes hav­ing different substituents in the atrane fragment as well as at alpha and beta carbon atoms of vinyl group have been accomplished using this methodology. Thus, I-(a­chloro-, ~-chloro- , ex, ~-dichloro- and ~, ~ ' di chloro)

vinylsilatranes were obtained in 85-95 per cent yieldsX4

by reacting the corresponding vinyltrialkoxysilanes with compound 4.

(RO\ SiC(X) = C (XI) (Xl ) + N(CH ICHPH»)~

N(CHlCHP »)SiC(X)=C(X I)(Xl)

12-15

X = XI= H, Xl= CI (93 per cent) (12); X = CI, XI = XI = H (90 per

cent) (13); X= XI= CI , X~ H (92 per cent) (14); X = H, XI = Xl = CI

(85 per cent) (15)

Lower yields were observed in the case of I-(beta phenyl- and beta silyl)v inylsil atranesxs.

(RO»S iCH=CHR I + N(CH2C HP H\ ~

N(CH2CH

20»SiCH=CHRI + 3ROH

16-18

R' = Ph (70.6 per cent) (16), SiMc) (83 per cent) (17), SiMelh

(70.8 per cent) (18)

In the case of I-vinylsil atranes containing sub­stituents in the atrane fragment, difficulty arises in ob­taining trialkanolamines with desired structure. The re­ac tion conditions and yield of 3-s ub stituted-l­vinylsilatranes mainly depend upon the structure of trialkanolamin e used . Thu s, 3-chloromethyl-l ­vinylsilatrane (22) was obtained in 25 per cent yield us­ing sodium rnethox ide as catalystXfi .

...-oCH,CH,Q}[ (EtO),SiCH=CH, HN(CH,CH,oH), + ~,-J:HCH,CI --+ ~H,CH,Q}(

([ CH,<;HOH 19 20 21 t~J,CI

/ {;H,CH,~ . ~ C~J,CH,O......- SiCH=CH, + JEtOH

a-r,p·(O CH,CI

22

3-Phenyl-I-vinylsilatrane (25) was obtained In

fairly high yield (79 per cent) under analogous condi­tionsxfi.

/(CH,CH,OI-l), (EtO),SiCH=CH, HN(CH,CH,OH), + Q:!' ~H - Ph ----+ N"

o CH,CHOH 3

I 23 24 Ph

......- CH,CII,O" N--CH,CH,O -jSiCIl=CH, + JEtOH 'CH,~HV

Ph 25

1-Vinyl-3-(2-vinyloxyethoxymethyl)silatrane (28) was obtained in almost quantitati ve yield by the action of compound 3 with N-[2-hydroxy-2-(2-vinyloxy­ethoxymethyl) ethylbis(2-hydrox yethyl ) amine] (27) at 20-40"C in the absence of catalystX7 •

HN(CH,CH,OH), + CH,- CH-CH,OC H,CH,OCH=CH, - - - ' 0 1 26 - - -

__ -+. N"" (CH,CH,OH),

' CH;t HOH CH,OCH,CH,OCH=CH,

27

3

A seri es of I-vinyl sil atra nes which were C­trifluoromethyl substituted in the 3-position of atrane fragment were prepared in 45-99 per cent yields by transesterification of the corresponding vinyltrialkoxy­silanes with tri s(2-oxyalkyl )amines. The reaction was carried out without solvent in the presence of 10 per cent methanolic solution of sodium methoxidexx.~' .

ACH,CI J,OH), (RO),SiCH=CH, + N

~r;:HOIl 2 or 3 R'R' R'

29-32 / Cll,CH,O,

---+. N-{;H,CH,O - SiCH=CII, + JROH ;>C-r:HO"""-Iii R2 h?

33-36

R' = R' = H. R' = CH,CF, (33); R'= R'= H, R' - CH,C,!', (34); R ' ~ R' = Me, R' - H (35); R' - Et, R' - R' = H (36)

A new class of (4S)-( -)-I-vinylsilatrane-4-carboxy­lic ac id (39) has been synthesized in 72 per cent yield by the transesterification of compound 3 with L- N, N- bi s(2-hydroxyethyl)serine (37) in the presence of pyridine. (3R,4S)-( -)-1-Vinyl-3-methyl silatrane-4-carboxy lic ac id (40) was similarly prepared in 67 .5 per cent yield by reacting with L-N, N-bis(2-hydroxy-ethyl)threonine'!2 (38).

/ (CH,CH,OH), H:C°~H (EtOj,SiCH=CH, + N ---+ !

"P'I-r:HOH R Si Hoot R GI'

CH=CH, 37,38 39, 40

R = H (37), (39); CH, (38), (40)

In the absence of pyridine, the transesterification can barely proceed under the usual reaction conditi ons.

268 J SCI IND RES VOL.59 APRIL 2000

This is probably due to the existence of the Zwitterionic form of the dihydroxy-ethylated amino acid and the protonated amine being unable to form the Si·N dative bond. It seems most likely that the catalytic mechanism of pyridine in this reaction is to restore the lone-pair of electrons of the nitrogen and thus facilitate the forma­tion of the transannular Si-N dative bond and the conse­quent silatrane ring. On the other hand, pyridine can also increase the miscibility of the reactants in the reactionn .

Till now, we have seen that the main synthetic ap­proach to th e I-v inylsilatranes has been th e transes terification of vinyltrialkoxysilanes with trialkanolamines.

There is another easily accessible vinylsilane hav­ing Si-O bond and which has been successfully investi­gated for obtaining compound 1, is vinyltriacetoxysilane (41) . Thus, compounds 1 and 6 were obtained in almost quantitative and 82 per cent yields, respectively by the reac tion of compound 41 with compound 4 or 5 using chloroform as solvent at O"C, followed by the continu­ous removal of acetic acid formed during course of the reaction with toluene. No catalyst was required for com­pletion of the reactionYJ .

(CH,COO\ SiCH=CHI + 4 or 5 ~ 1 or 6 + 3CH,COOH

41

ZeichanY4 and Voronkov el of. 12.Y5 utili sed the more easily accessible vinyltrichlorosilane (42) as the start­ing materials in place of compounds 2 or 3 and 41 for the sy nthes is of compound 1. This method is essentially based on the reaction of triethanolamine with hydrol y­s is products of co mp ound 42 , i.e., polyvinyl­sesqui sil oxane, (RSiO u ),' polyvinylsiloxanol, [RSi

I 5.

(OH)2 ]X (Y=O-I .S) and polyvinylhydros il oxa ne, y y .

(RSiHO)" in the presence of catalytic amount of metal hydrox ide l2 (preferably KOH).

(RSiO,)y + (HOCHzCH2),N ~ N(CH1CHP),SiR + H20

l/x [RSiO, ;./OH)z)x + (HOCHICHI )) N ~

N(CH2CHP))SiR + ( I.S+Y)HP

R = ·CH=CH1

Water fomled during course of the reaction was gradually eliminated by azeotropic distillation with a suitable inert solvent. The fo rmation of compound 1 and phenylsilatrane from the corresponding silanes with com­pound 4 is considerably faster (0.5 - I.Sh) unlike the alkyl derivatives which took anywhere from 4··8 h for its formation. The yield of compound 1 was al so usually

more than 90 per cent.

I/x (RSiHO), + (HOCH2CH1))N~ RSi (OCH1CH1))N + Hp + H2

R = ·CH = CH 2

In the reac tion of co mp ound 4 with polyvinylhydrosiloxane the first to react was the Si-H bond which results in the liberation of hydrogen. This was followed by the cleavage of the siloxane bond with consequent water formation. It was therefore not the completion of hydrogen evolution, but the termination of water formation that indicates the end of the react ion.

Compound 1 was also obtained by the reaction of organosilicon compounds, i.e., silicones or azasilicones having Ph and vinyl group at silicon atom with com­pound 4 or its tri s trimethyls il yl ether or cycli c sily l ether%.

CH, ~ CH /OCH,CH" / 'si 0 I N(CH,CI-!,OR),

Ph 'oCH,nr( 43 4,44

R ~ H (4), SiM", (44).

CH, ~ CH, ( OCI!,CH, /5 _/,X +

Ph OCH,CH1

.43, 45 9,45 X ~ 0 (43), NMe (45); R - H (9), SiMe, (46)

It is seen from the above reactions that compou nds 2, 3 and 41 or polyvinyl sesq ui siloxa nes and polysiloxanoles were used as starting material s in the transesterification reaction which were themselves ob­tained by alcoholysis , acetolysis or hydrolysis of com­pound 42, respectively.

Recently, another method was establ ishedY7 for the synthesis of compound 1 in which compound 42 was used directly as a starting material. In this method, com­pound 42 was reacted with the read ily accessible tri s(2-trimethylsiloxyethyl)amineYX (44) at 140-\ SO"C with the concomitant removal of (CHJ)JSiCI to gi ve compound 1 in 80 per ceilt yield.

] + 3Me,SiCi

42 44

A new conveni ent metal exchange method for the synthesis of compound 1 has been investigated, re­centlyYY. In this method, compound 3 was reacted with boratrane in the presence of catalyst using DMF at high temperature.

CH2=CHSi(OEt\ + B(OCH2CH2))N ~ CHz=CHSi (OCHzCHz),

3 1

NASIM & VENKATARAMANI: VINYLSILATRANES 269

The reactivity of RSi(OEt)J decreases in the fol­

lowing order: R= Ph> 2-furyl > vinyl> Me - 2-thienyl > chloromethyl.

I-Vinylsilatrane-3, 7, 10-trione (47) was synthe­sized almost in quantitative yield by reacting compound 41 with aminotriacetic acid in vacuum at 90-1 OO"C in the absence of solvent '()().

CH1=CHSi(OCOCH)) + (HOCOCH1\N ~

CH1=CHSi (OCOCH1»)N

47

Similarly, l-vinylsilatrane-3 , 7-dione (48) and 1-vinylsilatrane-3-one (49) were synthesized in 64 per cent yield by allowing the mixture of compound 3 with N-(2-hydroxyethyl)-aminoacetic acid tri s trimethylsilyl or N,N­bis(hydroxyethyl)aminoacetic acid tris trimethyl-s ilyl derivatives to stand at room temperature for 2-3 h or heating the mixture at 40-50"C using DMF as so lvent)()'.

/ (CH,COOSiMe ,)" CH,=CHSi(OEt), + N -7 - ........

3 (C H,CH ,OSiMe,) ,."

_ (CH,COO)" ............ n=3 (47), n=2 (48), n= 1 (49) N SiCH=CH, " /"" -"<CH,CH,O) , "

47-49

1-Vinylsilatrane-3, 7, I O-trione (47) formed a com­plex with DMF in 70 per cent yield when the reaction was performed in DMF using reactants 3 and nitriloacetic acid tri s trimethylsilyl derivative.

The 'H, DC, t5N and 2~Si NMR spectral data ob­

tained for compound 47 indicate that an increase in the number of carbonyl groups in the atrane framework en­hances charge transfer along the donor-acceptor N-Si bond. Because of the prominent electron-acceptor prop­erties of the central atom, the atranetrione (47) tend to bind electron-donor solvent, i.e. , DMF. This is accom­panied by an increase in the coordination number of sili­con in compound 47-DMF complex, increasing it to six 101

A series of trans beta substituted I-viny lsi latranes were obtained by hydrosi lylation of ethynylsi latrane in a regiospecific manner l 02

N(nhCH20hS\ /H N(CH~H20hSic."CH + R.Sll\feJ~H -- / c=c

H \SiRnMeJ~ 50 51-55

R=Ph, n = 1 (50); R=1hienyt, n= 1 (51), R=Ph, n =2 (52); R=thienyl, n=2 (53), R=Ph, n=3

(54); R=thienyl, 0=3 (55)

Likewise, l-(beta phenylethynyl)silatrane was read­ily hydrometallated with group IVB metal hydrides by

simply heating the reactants (I OO"C, 8h) in the absence of a catalyst 1m.

/Ph N(CH2CH,OhSiC~Ph + R,MH ---+ N(CH,CH,OhsiC=C\.

MR, 56 57-61 62-65

R,M=Et,Si (25 per cent) (62); (EtO),Si (49 per cent) (63); Et,Ge (96 per cent) (64); EI,Sn

(95 per cent) (65)

In the above reaction s the hydros il y lati o n/ hydrometallation takes place, reg iospecifically, to yield the beta adducts in contrast to the formation of both al­pha and beta adducts in the hydrometallation of acety­lenes not having a silatranyl moiety )()4.

3 Properties of 1-Vinylsilatranes

The electronic structure of I-substituted silatranes have been earlier investigated 2 . '1.I(J5 - 'o~. However the

chemical reactivity of these compounds has been stud­ied to a lesser extent. This is particularly applicable to I-vinyl silatranes. The presence of carbon-carbon dou­ble bond in the molecule makes it amenable to a wide variety of chemical transformations.

3. 1 Hydrolysis and Alcoholysis of 1-Vinylsilalran cs

Hydrolytic cleavage of silatrane fragment of l-Si­substituted silatranes in neutral and acidic medium pro­ceeds irreversibly.

N(CH1CHP»)SiCH=CH1 + 3Hp ~

N(CH1CHPH\ + (HO»)SiCH=CH1

The course of hydrolysis of compound 1 and I-Si­substituted si latranes were followed with the help ofUV

spectra (increase of absorption intensity,(n.sigma*l due to

the participation of electron pair of N-atom in the cleav­age product formed during the course of hydrolysis) in neutral medium (buffer KH2PO/ N~HP04' 2S"C, pH 7 .15)"°.

It was also found that I-alkenylsilatranes under these conditions are hydrolytically less stable as com­pared to alkylsilatranes, RSi(OCH,CH ) N, (R= i-PI' > _ 2 3

CH2CI > Me> CH2=CH). Based on the available data,

the authors proposed a possible reaction mechani sm of the hydrolysis. The initial formation of a four me mber intermediate by coordination of the oxygen atom of wa­ter with silicon and hydrogen bonding with the oxygen of the atrane skeleton , followed by a slow cleavage of atrane fragment (Scheme 1).

270 J SCI IND RES VOL.59 APRIL 2000

+ 11,0----+

R H20

N(CH,CH,OH), + . (HO)JSiR R=-CH=C~

Scheme 1- Mechanism or hydrolysis or sil alranes

Similarly, alcoholysis of compound 1 in acidic medium cleaved the atrane fragment l I I.

CH,=CHSi(OCH,CH,) .• N 1

R~Mc.Et

ROHlHCI ----+. HCI. N(CI-J,CH,OH), + (RO)JSiCH=CH,

However, it is possible to isolate the hydrochloride of compound 6 with the retention of the s ilatrane ring by pass ing dry hydrogen chloride in chloroform solution at room temperature or even below ll2

.

CI-I1=CI-ISi(OMeCI-ICH1) lN -+ HCI N(CI-IFHMcO\ SiCI-I=Cl-I l

6

The hydrochloride is stab le in aceton itril e but hy­drolysis in water immedi a te ly gives tris(2-oxypropyl)amine hydrochloride and polyvinylsesqui­oxane, CH

2=CHSiO

I 5•

3.2 Interaction of 1- Vinylsilatralles with Compounds

Having Element-Halogen Bond

The interaction of compound 1 with compounds containing e lement - ha logen bond (where E-X = metal halides e.g. HgC I

2, AgF, SbF

J and ICI , sulpheny l chlo­

ride, polyhaloalkanes, N,N-dichloroaryl sulphamides etc) mainly depends upon the nature of these bonds and the experimental conditions employed.

Unlike hydrolysis and alcohol ys is the reaction of compound 1 with antimony trifluoride proceeds with metal transfer to retain the atrane skeleton and cleavage of Si-O bond g iving rise to vinyltrifluorosilane and stibatrane IIJ.

N(CHzCHP\ SiCI-I=CH l + SbF) -+

CH2=CHSiF) + Sb(OCH1CH1\N

66

Muller suggested : IJ that this type of exchange re­action is due to the increased tendency of S i towards the formation of strong Si-F bond .

Silver fluoride reacts with compound 1 with cleav­age of Si-C bond. As a result, an unstable vinylsilver is

N(CH,CH,OhSiCH=CH, + AgF --+

I CH,=CHAg(,AgF) + N(CH,CH,O), SiF (r) \ 67 .

(x · ?) \

(Yellowrm7 (black) ·Ag + CH,=CH·CH=GI,

Scheme 2 - Synthesis of tluorosilatrallc

formed which further decomposes g iving ri se to Ag and butadiene according to the Scheme 2 proposed by Mullar el al.m . The primary product seems to be flu orosil atrane (67).

Transfer of vi nyl group from sil icon atom resu lted in the cleavage reac tion of compound 1 by aqueous so­lution of heavy metal salts i.e. Pb and Hg. The process occurs in the same way as given in Scheme 2 . Muller and Frey l1 4 established this trans formation in the pres­ence of H20 and ammonium flu oride.

I + HgCI, + NH,F + H,O ---> m '.N(CH,CH,OH), + CLHgCH~CH, + NH,CI + SiO, &9 per cent

I + Pb(OAc),+ NI-LF + H,O --+ CII,COOH.N(CH,CH,OH), + F,Pb(CH=CH,), 65 per cent

+ FPb(CH=CH,h + Ni-l,OCOCH, + SiO, 35 per cent

The facile transfer of vinyl group is due to the fo r­mat ion of an intermed iate, ammon ium pentafluoro­vinylsilicate, which is acti vely involved in the exchange reac ti on with the heavy metal salts".

N(CHF HP),SiCH=CH2+ 3Hp-+

N(CH1CH10 H») + (1-I0),SiCH=CI-I1

(HO»)SiCI-I=Cl-Il

+ 5NH4F -+

(N H4)/CH1=CI-ISiF\) + 3NHpl-l

(NH)/CH1=CHSiF;) + M · x -+ M ·· CI-I=CH 1 + (NH,\SiF;X

However, Nies et al. 115 observed that the epical Si­C bond of compound 1 is extraordinarily susceptible to the direct electrophilic attack by Hg(Il) in acetone-d() to form l-chlorQ-silatrane (68) and vinyl mercury ch loride.

CH2=CHSi (OCH2CH2\ N + HgC I2

-+

N(CH2CH,G),SiCI + ClHgCH=CH? - . -68

An important point to be noted here is that there is no need for prior hydrolysis and conversion of compound 1 to ammoniumpentafluoroviny ls ilicate. Relative rate measurements of the reaction showed that compound 1 is more active than I-aryl- , and I-alkyl substituted s il atranes in this kind of transformation.

NASIM & VENKATARAMANI: VINYLSILATRANES 271

It is suggested that vinyl group initially forms 7t­

complex with HgCI2, which effectively eliminates the steric hindrance otherwise posed by the groups. Once held in close proximity to Si-C bond, the Hg(II) now has much greater probability of successfully attacking in a manner similar to aliphatic ;·eaction. The silatranyl group in l-organylsilatranes possesses a strong electron donat­ing effect lO4 and readily undergoes electrophilic Si-halo­genation through the reaction of heavy metal hal ides 113. 11 5

The Si-C bond of I-vinylsilatrane is cleaved by bromine or iodine chloride to yield I-bromosi latrane or compound 68, respectively. In the presence of diethylether or THF and under the action of dioxane bromide, 1-bromosilatrane is formed together with l-(omega haloalkoxy)silatranes 11 6.

N(ClhCH,O),Si - Y + RX

XY=Br,. Y=Br (25 per cent), RX=CHFCHBr; XY=!CI, Y=CI (19 per cent), RX=CHFCm

N(CH,CH20hSi~H=CH' i · ·C) . Dr, -- N(CH,cH~OhSiDr (16-4 per cenl)

N(CH,CH,O),SiOCH,CH,OCH,CH,Br (1 4·6 per cent)

The reaction of l-vinylsilatrane with Br2 or ICI in dichloromethane or chlroform proceeds smoothly and even at - SO"C involves cleavage liO of the Si-C bond of compound 1.

Similar case was observed in the reacti on of com­pound 1 with the electrophilic reagents having S-Cl bond "?, i.e., phenylsulphenylchloride (69). However, unlike HgCI

2, phenyl-sulphenylchloride adds to com­

pound 1 with the formation of a stable adduct, 1-[2-chloro-( l-thiophenyl)]ethylsilatrane (70) at very low tem­perature 117.

N(CH,CH,o),SiCI I=CH, + PhSCI

69

, N(CH,CH,O),SifHyHl

70 PhS CI

IN(CH'CH'O),[~~th CH1] _ >_ -_IO_' C_ " ' N(CH,CH,O),SiCI + PhSCH=CH,

68

It was proved by IH NMR that adduct formation takes place only in mild condition (- IO"C). At higher temperature, it undergoes fragmentation (beta fission) via cyclic episulphonium intermediate resulting in the formation of compound 68 and phenylvinylsulphide. It is wellknown in organoelement compounds that in a bond sequence like M-C-C-Y, beta fragmentation takes place because of high electron donor of silatranyl group.

An analogous reaction proceeds by the interaction of compound 1 with sulphenylchloride acetylacetonate

and formylacetonate of trivalent chromium and cobalt llX .

- 45·C

R=Mc; M=Cr (ill) - 36 pcr cent (71), REM.; M=Co (In) - 30 per cent (72). R=H; M=

Cr(m) - 15 per cent (73)

The reaction of compound 1 with dialkylphos­phoryl- (74) and dialkylthiophosphorylsulfenyl-chloride (75) was more complex II~. It was shown that apart from the expec ted formation of compound 68 and S­vinyl thiopho sphate, CH 2=CHSP(O)(OR)2 (76) or viny ldithiophos-phate, CH,=CHSP(S)(OR)? (77), vinylsulphides (78 and 79) h~ving silatranyl group in the molecule was also isolated (Scheme 3). Two parallel processes occur simultaneously after the initial adduct formation with the -C=C- bond of compound 1 at -SO"C (i) beta scission and (ii) The migration of silatranyl group during the formation of a quasiphosphonium intennedi­ate. Kuteerev et ai. II~ suggested that this intermediate could be the precursors of the reaction products which predominates in the isolation of the mixture of products .

-50"'C

N(CII,CH,O),SiCH=CI!, ,. (RO),P(X)SCl ~

74,75

~ N(CH,ClhO),SiyH-fH, ~ rN(CH'CH,o)'S!-CIH ;.~'l (Ro},p(X)s CI ~ 1" J

R00R

a.r CI,\!, ~ C(CH,CH,o)'Si-~OR]

CH, - CH-/ ORJ

bl-RCt N(CH,CH,O), Si - x" /p

CHi"CH~/\R 78, 79

X - 0 , R- CH" i-C,H, (78), X- S, R= i-C,H, (79)

N(CH,CII,O),SiCI I

68

X II (RO}'pSCH = CH,

76,77

X - O(76), X=S (77)

Scheme 3 - Addition of dialkylphosphoryl- and dialkylthiophosphosulfenylchloride to J -v inylsilalrane

272 J SCI IND RES VOL.59 APRIL 2000

In contrast to HgCI2

, phenylsulphenylchloride, sulpheny Ichloride acety lacetonate/forrny I-acetonate of tri valent chromium and cobalt, dialkylphosphoryl- and d ia Iky I th iophos-phoryl su I pheny Ich lorides, N,N­dichloroaryl sulphamidesl ~o, ArS02NCI

2 adds to com­

pound 1.

ArSOzNCI2

+ CH1=CHSi(OCH 1CH2»)N --7

ArSOlNCICHzCHCISi (OCHzCHZl)N

Ar= Ph, p-CIC6H4, p-CH)C

6H4

In the presence of moisture the above addition prod­uc t converted to corresponding addition product, ArS02NHCH2CHCISi(OCH2CH2),N (ref. 120).

In a 1:2 molar ratio of reactants the reaction in­vo lves two chlorine a toms of N,N-dichloroaryl sulphamides. The yields of the products are nearly quan­titative l20 .

ArSOz CI2

+ 2CHz=CHSi(OCHzCHz») --7

ArS01N[CHzCHCISi(OCHP1 l »)N 12

However, Nasim et al.45.64 have established that

compounds 1 and 6 react exothermall y at room tempera­ture with electrophilic reagent, i.e., N-bromosuccinimide in the presence of small excess of water leading to the formation of corresponding bromohydrins (80 and 81), respectively, in more than 80 per cent yields.

NBSIH20 N(CH2CHRO),SiCH=CH2 I N(Cl-hCHRO),SiClfBrCH20H

80,81 R=H (8\ per cent)(80); Me (8\ per cent)(81)

Th is was somewhat surprising since it is known that reaction of N-bromosuccinimide with 1-organylsilatranes, e.g., arylsilatranes, in methanol or in dichloromethane, affords only l-bromos il at ranesI 21.

The react ion of compound 1 with alkali earth met­als, e.g., "BuLi in hexane so lution has been reported~Y .

With "BuLi, there was simultaneous substitut ion of Si­° bonds and addition to the C=C bond.

(CHF HP»)SiCH=CHz + "BuLi --7

"BuCHzCHzSi (OCHzCH2),N

( I 7 per cent)

82 +

nBuCH2CH2SiBu}

(30 per cent) 83

F,C- I

Table I - Addition of RH,'X to I -yinylsi latrane

Reaction Condition Yield of adducls,

(PhCOO)P, CHCI),

sealed tube 6 h, SO"C

per cent

S5.2

Scattered sun light, CCI~ +CHCI,. 94.5

sealed tube, 30 11 ,

room temperature

UV, CHCI), sealed tube, 3 11 , 9S. 1

room temperature

However, at -78" C, lBuLi adds only to the C=C bond with no attack on the silatrane ring.

-78"e N(CHzCHP\ SiCH=CHz + 'B uLi ~

'BuCHzCHzSi(OCHzCH) ,N ( I R per cent )

84

The addition of C-X (X=Br, I, F) to compound 1 was found to be less reactive. Reaction was initiated by benzoyl peroxide or photochemically and adducts hav­ing perhalogenalkyl group in the term inal carbon were isolated in very good to excellent yields l22 (Table I).

N(CHzCHP \ SiCH=CHz + R"" X

N(CH zCHP),S iCH(X)-CH ~RI""

85-87

R"·"=CI,C, X=Br (85), R"·" = F)C, X=I (86),

RH,' =F7C), X=I (87)

In a recent work by Voronkov el at. 123 and Geyer ef

al. l2~ the photochemical addition oftrifluoroiodomethane to compounds 1 and 42 have been desc ribed. The addi­tion of CF}I to compound 1 proceeded smoothly to give 79 per cent of the addition product in 102 h, whereas compound 42 gave a poor yield of the adduct (35 per cent) and took much longer reaction time ( 10 d).

Yoronkov el al. 123 established that the additi on of polyfluoroiodoalkanes to compound 1 and its C-subst i­tuted derivatives gave the co rrespondin g 1- (2-perfluoroorganyl- I -iodoethyl)-silatranes.

RI + CH/=CHSi (OMeCHCHz),,(OCHzCHz),.,,--7

RCHzCHISi(OMeCHCH z),.(OCHzCHzl,."N

8S-97

R=CF), n=O (95 per cent)(88); R=Cl7

, n=O (97 per cel1l )(89):

R=Cl7 , n= I (78 per cent) (90): R=Cl7

. n=3 (86 per

NASIM & VENKATARAMANI: VINYLSILATRANES 273

Table 2 - Addition of Cl1CCOOMe to I-vinylsilatrane in presence of different

initiators for 4 h

Experiment Peroxide/metal Nucleophilic t Yield no. complex initiator initiator (uC) (per cent)

I BZP2 95 65 2 Fe(CO), CH

1COOK 120 43

3 Fe(CO), DMF 4 Fe(CO), CH

1CN

5 Fe(CO), HMPT 6 Fe(CO), 7 Fe(CO), 8 Mo(CO)r.

cent)(91); R=H(CF)4' n=O (100 per cent)(92);

R=CF3(CF2) 3' n=O (100 per cent)(93); R=H(CF2) (" n=O

(79 per cent)(94); R=C6F n , n=O (91 per cent)(95);

R=H(CF2)x' n=O (100 per cent)(96) ; R=CF3(CF2)7' n=O (100 per cent)(97)

Reaction proceeded slowly (60-120 h) in the pres­ence of scattered light but under UV-irradiation the re­action completed in 2-3 h. Yields of the adducts were 78-100 per cent.

The reaction of compound 1 with various reagents have been studied, e.g., hydrometallation2. ' 2, . 127 which is

discussed subsequently and radical initiated addition of species containing N-CI, S-H, P-H, C-H, C-Br or C-I which occur with retention of the Si-C bond but reac­tions with electrophile, 69 will g ive compound 68 with cleavage of a silicon - carbon bond 117 . But radical initi­ated addition of species containing C-CI bond to com­pound 1 has not been reported in the literature prior to the work of Kamysheva et a/. 65 . Thi s is because of the less reactivity of the monomer under radical condition and that molecular mass of chi oro alkyl aryl polymeriza­tion slow down in the presence of silicon containing spe­c iesI2X.129.

It was established by Kamysheva et al.65 that the addition of C-CI species to the carbon-carbon double bond of compound 1 occurs with retention of the silatranyl fragment under conditions of peroxide and metal complex initiators. Compound 1 does not react with methyltrichloroacetate (98) in the absence of a cata­lyst. The reaction of compound 1 with compound 98 in the presence of peroxides, i.e. , benzoyl peroxide or metal complex initiator, Fe(CO\, MO(CO)6 or in certain cases using nucleophilic initiator, i.e. , Fe(CO), + CH

3COOK,

120 41 120 64 120 72 140 37 140 42 140 39

Fe(CO), + DMF, Fe(CO), + CH,CN, Fe(CO), + HMPT gave the adduct - methylester of 2 ,2,4-trichloro-4-silatranylbutyric acid (99) in 37-72 per cent yields de­pending upon the reaction conditions and catalyst em­ployed65 (Table 2) .

CCI,COOMe N(CH,CH,O),SiCH=CH, ,

98 N(CH,CH,O),Sif~CH,CCJ,COOMe

99

In all the cases only the simple addition product was formed unlike the reaction of compound 98 with trimethylvinyl silane, which gave both the addition prod­uct and the lactone depending on the single or combina­tion of initiators employed 12x

•

The exclusive formation of the addition products only is ascribed to the ability of atrane fragment play ing the role of nucleophilic initiator itself.

3.3 Interaction of 1- Vinylsilatranes with Compounds having Element-Hydrogen Bond

Only two types of compounds with E-H bond , i.e ., Hp and alcohol, react with compound 1 with cleavage of atrane fragment. All other compounds with element­hydrogen (E-H), i.e., C_H I27, Si_H2. 125. 127. 13o.m, Ge-H I27,

Sn-H I27 , P-H I33 and S_H2.X2 give rise to more or less sta­

ble adduct of compound 1.

The addition of C-H bond of chloroform to com­pound 1 initiated by benzoyl peroxide took place on heat­ing the reaction mixture at 100"C for I h in a sealed tube 127 .

N(CH2CHP)JSiCH=CH2 + H-CCI) ---7

N(CH2CHP»)SiCH lCH 2CCI )

100

274 J SCI IND RES VOL.59 APRIL 2000

On prolonged heating (6 h) at 80"C the adduct for­mation was not observed which led to the use of chloro­fonn as solvent in the reaction of trichl orobromomethane with compound 1 (Table I).

Hydrosilylation of compound 1 has been studied in detail with silicon hydrides hav ing alkyl, alkoxy, aryl , heteroaryl substituents at the si licon atom 127 . Irrespec­ti ve of hydro silane structure and experimental conditions employed, in all cases the adducts were obtained in high yields.

Only ~-adducts were obtained as a resu lt of the addit ion of silyl group at the terminal carbon atom of vinyl group of compound 1.

N(CHFHP))SiCH=CH1 + R)SiH ~

N(CH1CHP),SiCHF H1SiR,

Nas im e t a l .12S .126 hav e reported a seri es of hydrosilylated products, 2-silylethylsilatranes, in yields ranging from 75 to 90 per cent by refl uxing the reaction mixture in benzene for 4-5 h in the presence of HltCIr/ i-PrOH.

N(CH2CHR10 ))SiCH=CH1 + R1M eSiH

N(CH1CHR10))SiCI-I1CI-I1SiMcR 1

101-109

R,=H, Me; R=Et (80 per cent) (101), n-Pr (90 ' er cent) (102), n-Bu (89 percent) (103), Allyl (86 percent) (104), Ph (75 per cent) (lOS), p-CICr>H4 (79 per cent) (106), p­FC6H4

(77 per cent) (107), p-MeC6H~ (82 per cent) (108), C H CH (77 per cent) (109)

(, S 2

The reaction of 2-furyl- and 2-thienylsilanes with compound 1 evidently was more active2

.111l

• It bas been observed that ease of addition was dependent upon the number of furyl and/or thienyl groups present in the hydrosilanes. Thus, tris(2-furyl) silane added with greater ease (room temperature) than dimethyl (2-furyl) silane (needed heating).

N(CH,CH,O),SiCH=CH, + R"SiH --->. N(Cll,CH,OJ,SiCH,CI l,SiR"

110-114

R,=Me,( 0 ) (95 pcr cent) (110), Me (0 )' (89.5 per cent) ( III) ,On (82 per cent) (112), M~ (0 ) (82 per cent) (113), Me (!i..) h (88 pcr cent)

(114)

Likewise, bis(d imethylsily l)th iophene gdve a

diadduct with compound 1. The hydrosily lation reactions were catalysed by ch loroplatini c acid in THF"I.

Me'HS> N(CfI,CH'OJ,SiC.f1'CHz.Me'Si~ 2N(CH,CH,O),SiCH=CH, + S -- Y

Me,HS' N(CH,GH,O), SiCH,CH,M.,Si

Under analogous conditions but at low tempera­ture the hydrogermylat ion of compou nd 1 proceeded smoothly using Rhacac(CO)2 as catalyst 127 .

N(CI-I1CI-IP))SiCI-I=CI-I1 + I-IGeEt)~

N(CI-I1CHP))SiCH1CI-I1GcEt)

( 1 00 per cen t )

115

The corresponding hydrostannylation reaction of compounds 1 and 6 proceeded in the absence of a cata­lystl27 .

N(CI-I1CI-IRO\SiCH=CI-I1 + I-ISnBu, ~

N(CI-I1CI-IRO))SiC I-I1CH1SnBu)

116-117

R=I-I (7 1 [ler cent) (116); M e (74 per cent) (117)

Hydrometallation reaction was not observed if the vinyl group of compound 1 was substi tuted by styryl group . However, the correspondi ng ethy nyl derivative, N(CH CH,o),SiC=CPh, was readily hyd rometallated 2 _ .,

with R MH at 100"C for 8 h with the exclusive forma­}

tion of beta add uct in 96 per cent yield IO}.

Hydrosilylation of compound 1 with o li go meth ylh yd rosiloxanes hav ing te rminal trimethylsilyl groups in the presence of chloroplatinic ac id afforded the corresponding oligomers hav ing mo­lecular weights of 1000 and 2000 which can be used as surface active compounds l.l2 .

~ N(CI-I1CI-IP),SiCH1CH1SiMel (OSiMel )n­

OSiMe1CI-I1CI-I1Si (OCI-I1CI-I ),N

118

The addition of P-H bondto compound 1 is usu­ally initiated by UV-irradiation. However, compound 1 adds with dialkylphosphites more read ily in the pres­ence of sodium alkox ide than under UV-irradiation 111

.

Introduction of metlJyl groups at 3, 7 and 10 positions of

NASIM & VENKATARAMANI: VINYLSILATRANES 275

the silatrane skeleton markedly activates the double bond, thus increasing the yield of the adducts 133

, Thus, com­pound 1 fail s to react with dipropylphosphite upon UV­irradiation, Whereas compound 6 easily reacts with dime­thyl- , diethyl- and dipropylphosphites to g ive the cor­responding addition products in 96.4 per cent, 92 ,3 per cent, 68 ,1 per cent yields, respective ly,

N(CHF HRO)JSiCH=CHl + (RIO)l(O)H ~

N(CHICHRO)JSiCHICHl(O)(OR 1)1

119-122

R=H, R'=Me (60,S per cent) (119), R=Me, R '=Me (96 .4 per cent) (120), R=Me, R '=Et (92,3 per cent) (121), R=Me, R '=Pr (68, 1 per cent) (122)

With radical initiator (A IBN), diphenylphosphine forms beta adduct with compound 1. In the case of C­methyl derivatives the reacti on may occur without ini­tiators 133 ,

(CHICHMeO)..{CHICHP)J,nS iCH=CH1+ PhlH ~

N(CH1CHM eOl" (C HICHP)J.nS iCHICHlPhl

123-125

n=O (80 per cent ) (123), n= 1 (77.6 per cent ) (124),

n=3 (84,8 per cent) (125)

Similarl y, reg ioselecti ve beta adduct formati on occurs photochemicall y by thio lation of compound 1. The wide range of compounds havi ng S-H bond in vesti ­gated so far gave various sulfide deri vati vesX2 upon ad­diti o n of alkanethiol s, a lk a nedithi o ls, silatranylalkylthio ls to compound 1.

vh , 1·2 h

N(CI-hCHMcO). (CH,CH,O),..SiCH=Clh + RCH,CII,SH ---~

-+ N(CH~HMeO). (CH~H2Oh.,SiCHlCH1SCH~HlR 126-130

The presence of trimeth oxysi lyl group at alpha position to the thiol group signi ficant ly increases the time for thiolation reaction X2

,

vh, 3h(m=2), (m: !) N(CH, CHMeO), (CH,CH10),.SiClf=CH, + (MeO»)Si(CH,)"SH )

-+ N(CH1CfIMeO). (CH,CH10 lJ" SiCH1CH, S(Cl b). Si(OMe»)

131,132 0=2, m=1 (84 per cent)(131); n=O, m=2 (84 per cent) (132)

Thioacetic and thiobenzoic ac ids were less reac­tive among the thi ol groups studied so far. To some ex­tent, methyl ester ofthi oglyco li c acid was more reactive in which acceptor carbonyl group is away from the S- H L _ .• _1 ~')

N(CH,CHMeO).(CH,cH,O)' . .5iCH=CH, + MeOOCCH,SH

---+ N(CH,CHMeO),,(CH,CH,O),~SiCH,CH,SCH,cOOMc 133,134

r>=1 (85 per cent) (133); n=3 (90 per cent) (134)

N(CH,CHMeO).(CH,cH,O),~SiCH=CH, + RgSH

- N(CH,CHMeO).(CH ,CH,O),~SiCH,CH,SC(O)R 135·138

0=0, R=Me(lOh, 50 per ccot) (135), n=3, R=Mc (611, 85 per cent) (136), n=D, R=Pb ( 1011,

88 per cent) (137), n=3, R=Ph (6h, 85 per cent) (138)

One more class of compounds having S-H bond is dithioacid of phosphorus, which eas ily adds to the dou­ble bond of compound 1 to give the beta adducts" ·} .

N(CH1CH20 )3SiCH=CH2 + (RO):zll(S)SH --+ N(CH2CH20MiCH2CH2SP(S)(OR)2

139,140

R=Me (75 per cent) (139), i-Pr (71 .3 per cent) (140)

20°C, 3 d

3.4 Other Reactions with /- Vin yl- and /- Vinyl-3, 7, /0-

Trim ethylsilatranes

(i) DielsAlder Reaction

1-Yinylsil atranes undergoe (2+4)-cyclo addition react ion with cyc lopentadiene a nd hexachl orocyclo­pentadiene with great difficulty134,

x x

DC 170·180"C

N(CH,nI,Oh SiCH-cH, + I I ---+

. x x x x 141 , 142 143.144

X=H (141), X=(,I (142); X=H (80 per cent) (143), C1 (60 pcr cent) (144)

The adduct, 5-s ila trany l bicyclo(2,2. 1 )-hept-2-en (143) was obtained in 80 per cent yie ld and was a mi x­ture of endo and exo isomers as revealed by proton NMR 134, The reaction of compound 1 with maleic anhy­

dride or maleimide gave a copolymer (MW - 6000) con­ta inin g both th e s ilatran yl a nd im ido/a nh yd r id e functionalit ies , 0 homopolymerization was observed under these conditi ons 135 ,

o rl 600C, IOh N(CH,CH,O),SiCI-I-CH, + ~

o

----> [N(CH,CH>O)JSib H-CHQ J 145, 146 0 m

x~o (145), NI 1 (146)

276 J SCI IND RES VOL.59 APRIL 2000

(ii) Oxidation oft-Vinyl- and I-Vinyl-3,7,10-Trimethylsilatranes

It was reported by Hosomi et af. 121 that the Si-C bond in organosilatranes is c leaved by m­chloroperbenzoic acid (147). But recently Voronkov ef

ai.136 investigated the reaction of compound 1 with com­pound 147 and it was found that contrary to the reported Si-C cleavagel21 , the reaction of compound 1 with com­pound 147 in presence of Na2CO] (buffer) yielded, \­silatranyloxirane (148) in quantitative yield .

Perbenzoic acid also reacts similarly but the yield oftheoxirane is lower. 3,7,1 0-Trimethylsilatranylox irane (149) was synthesized by Nasim ef af. 46 in 83 per cent yield via the oxidation of the precursor compound 6 with compound 147, as described l36 above for the prepara­tion of compound 148.

N(C~HMeO)JSiCH=CH2 + m·CICJj4C(hOH -+ N(CH2CHMeO)JSi n 6 147 149 \f

(iii) Synthesis of a-silatranylacetaldehydes

Nasim et al. 45 have developed a route to alpha silatranylacetaldehydes 150, 151, start ing from the read­il y access ible compounds 1 and 6 (Sc heme 4) via muitisteps functional group transformation.

An analogo us procedure gave, 2-(3,7, 10-trimethy l)silatranylacetaldehyde(151) in quantitati ve yield as a mixture of almost equal amounts of the two diastreomers having different orientations of the methyl groups relative to the axial Si-N bond.

(AcOhSiCH:CH, ----+

-3 AcOH

NBSIH,O 1,6

Et, SnOMe 98,99

- MoOH t'

152, Is:! - EI,SnBr

148,149

R- H (150), R=Me (lSI)

N(CH,CllROhSiCH=oCIJ, 1,6

N(CH,CJ-lRO),SiCH(Br)Cl hOH 98, 99

[N(CH,CHRO),SiCH(Br)CH,OSnEt,] 152,1 53

N(CH,CliRO),S~Hl 148, \49

N(CH,CHRO),SiCH,CHO ISO, lSI

..... (I)

..... (2)

..... (3)

..... (4)

(5)

Scheme 4 - Synthesis of silatranylacetaldehydcs via muitistcps fun ctional group transformation

Compounds 150 and 151 were also obtained in high yields by rearrangement of compounds 148 and 149 us­ing triethylbromostannane as a catalyst46.

147 Et,SnBr 1,6 --> 148, 149 --- 150, lSI

Anodic oxidation of compound 1 in acetonitrile at a graphite electrode has also been reportedLl7 . Oxidati(;)O potential for compound 1 in acetonitri le at a graphite electrode was found to be I .S2Y. Correlation with Taft (s igma) constant, 15N NMR chemical shifts and 15N-2~Si

coupling constant suggested that the reaction centre was the N-atom. Cation radical of compound 1 was formed during the reaction137

.

(iv) Synthesis of Silatranyl- and 3,'1,10-Trimethylsilatranylcyclopropanes

Before beginning of the work by Nasim et al.66 on cyclopropanation of I-v inyl si latranes, there were only two examples of cyclopropylsilatranes reported in the literature, i.e., ) -cyclopropyl l3X and 1-(2-chl orocyc lo­propyl)silatranes UY

• These si latranes were synthesized by the usual method of transesteri ficat ion of correspond­ing cyclopropyltrimethoxysilanes with triethanolamine.

Nasim et al. 66 developed an easy and simple method for the synthesis of cyclopropy lsi latranes starting from compound 1 or 6. The cyclopropanation of the viny l group in compounds 1 and 6 by CH2 /Pd(OAc)2 sys­tem has been carried out to afford cyc lopropylsilatranes66

(154, 155).

CI I,N,,'Pd(OAc), N(CII,CI'lRO),SiCH=oCH, • N(CH,CHROhSi --..:::-7

154, 155 V R=H (1 54); R=Me (155)

In the absence of a catalyst, compou nd 1 and CH2N2

do not react to form the correspond ingilatranyl substi­tuted cyc lopropanes, even under UV -irradiation. ]n con­trast, vinyltriethoxy-silaneand CH2 2 r ad ily undergo a I ,3-cycloaddition to give the si lyl substituted heterocycle, i.e., 3-triethoxysilyl - l-pyrazolene which fa iled to yield the corresponding si latrane due to N2 el imination.

Conclusions

) -Vinylsilatranes are excellent synthons capable of undergo ing a var iety of reactions to provide new functional ized silatranes via Diels-Alder reaction , epoxidation, addition , cyclopropanation, halogenation, hydrometall ati on (hyd ros il ylati on, stanny lat ion and germyla-t ion) reactions. The syn thesis of newer and newer si latranes start ing from ) -vinylsilatranes would

NASIM & VENKATARAMANI: VINYLSILATRANES 277

not be limited and chirality could be generated in the silatrane molecule using enantiopure trialkanolamines.

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