Hydrosilylation reactions in synthesis of surface chemical compounds
With the combined use of a catalytic hydrosilylation reaction and sol-gel formation, immobilization of a number of unsaturated organic compounds (quinine, quinidine, cinchonine, cinchonidine, alprenolol, N-allylrhodanine, and hemin) was carried out on a silica surface. The structure of the compounds...
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| Дата: | 2001 |
|---|---|
| Автори: | , , , , |
| Формат: | Стаття |
| Мова: | Англійська |
| Опубліковано: |
Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine
2001
|
| Онлайн доступ: | https://surfacezbir.com.ua/index.php/surface/article/view/49 |
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| Назва журналу: | Surface |
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Репозитарії
Surface| _version_ | 1869291134804557824 |
|---|---|
| author | Tertykh, V. A. Yanishpolskii, V. V. Bereza-Kindzerska, L. V. Pesek, J. J. Matyska, M. T. |
| author_facet | Tertykh, V. A. Yanishpolskii, V. V. Bereza-Kindzerska, L. V. Pesek, J. J. Matyska, M. T. |
| author_institution_txt_mv | [
{
"author": "V. A. Tertykh",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "V. V. Yanishpolskii",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "L. V. Bereza-Kindzerska",
"institution": "Інститут хімії поверхні НАН України"
},
{
"author": "J. J. Pesek",
"institution": "San Jose State University"
},
{
"author": "M. T. Matyska",
"institution": "San Jose State University"
}
] |
| author_sort | Tertykh, V. A. |
| baseUrl_str | |
| collection | OJS |
| datestamp_date | 2018-11-27T09:42:39Z |
| description | With the combined use of a catalytic hydrosilylation reaction and sol-gel formation, immobilization of a number of unsaturated organic compounds (quinine, quinidine, cinchonine, cinchonidine, alprenolol, N-allylrhodanine, and hemin) was carried out on a silica surface. The structure of the compounds formed and the nature of their bonding with the surface were studied by DRIFT and NMR. spectroscopy. The concentrations of the olefins anchored to the surface layer of the silica matrix were estimated by a UV-spectroscopy method. A spectrophotometric method for the determination of =SiH group concentrations in solutions and on surfaces was developed. The method is based on the reduction of ammonium molybdate by silicon hydride groups and measuring the specific absorption at λ=710 nm of the blue solution of silicomolybdenum heteropolycomplex formed. The method allows for the determination microgram quantities of =SiH groups with a reasonable accuracy. Kinetic peculiarities of the hydrosilylation reaction between cinchonine and triethoxysilane in the presence of Speier’s catalyst have been studied in toluene and isopropyl alcohol by use of a spectrophotometric method. It was shown that the hydrosilylation reaction of functional olefin is complicated by transformation of the catalytic system and secondary processes occurring in the solvent medium, in particular the hydrolysis of =SiH groups. |
| first_indexed | 2025-09-24T17:44:38Z |
| format | Article |
| fulltext |
I
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HYDR0SILYLATION RЕACTIONS IN sYNTHЕsIs
oF SURFAСE сHЕМIсAL сoMPoUNDs
V.A. Tеrtykhl, v.v. Yanishpolskiil, L.v. Bеreza.Kindzеrskаl,
J.J. PеsеЁ' and М.T. Мatyskа2
lInsiitutе of Suфсe Сhеmistrу, Nаtionаl Аcаdеmу of Sciencеs,
Gen' Nаumov str, ]7' 03680 Kуiv-I64' UKRАINE; е-mаil: tеrtуkh@trlubliс.uа.nеt
2fun Josе Stаtе Ilnivеrsitу, Оnе Wаshington Squаre, Sаn Josе, CА 95lg2-a]01, (],S.А.
With the сombined use of a сatalytiс hydrosilylation rеaсtion and sol-gel foгmhtion,
ilization of a numbеr of unsatuгated organiс соmpounds (quinine, quinidine, сinсhoninе,
idinе, alprenolol, N.allylгhodanine, and hemin) was carriеd out on a siliсa suгfaсе. Thе
of thе сompounds formеd and the naturе of theiг bonding with thе suгfaсe wеге
by DRIFT and NMR sprсtrosсopy. Thе сonоentrations of thе olеfins anсhoгed to thе
laуеr of thс siliсa matrix wеге сstimated by a lJV.spесtrosсopy mеthod.
iс mеthod for the dеtегmination of =SiH gгouр сonсrntrations in solutions
on suгfaсes was devеlopеd' The method is basеd on thе геduсtion of ammonium
tе by siliсon hydride gгoups and mеasuring thе speсifiс absorption at 1,=710 nm of thе
solution of siliсomolybdenum heteropolyсomplех foгmed. The mrthod allows foг thе
ion miсrogram quantitiеs of =SiH groups with a reаsonable acоuгacy. Kinеtiс
ities of the hydrosilylation геaсtion bеtweеn сinсhoninе and triеthoxysilanе in thе
of Speiеr's сatalyst have bееn studiеd in toluenе and isoproрyl alсohol by usе of a
method. It was shown that thе hydrosilylation геaсtion of funсtional olеfin
iсated by tгansformation ofthе сatalytiс systеm and sесondary proсеsses oссurгing in
юlvеnt mеdium, in partiсular the hydrolуsis of =SiH grouрs.
uсtion
fu known, thе synthesis of сompounds with Si-C bonds oftеn involvеs the
ylation rеaсtion сonsisting of thе addition of unsaturatеd organiс сompounds to SiН
undеr thе influеnсе of сatalуsts and еlevatеd tеmprraturс [l]. In an еarly papеr
Chuiko et aI Iz7 it was dеmonstгatеd that suсh a rеaсtion on a siliсa suгfaсе is of
iilаг intеrеst for pгoduсing сhеmiсal modifiсations With siс bonds. The proсеss pгoсeеds
tо thе gеnеral sсhemе:
, / R.-.-fr*
H П
- g ; - H + H 2 c - с H - R + l . . . . . " ' , +
si/l\
+ Е si -сl l2- с|l2-R
69
whеге R is a suitablе organiс radiсal with v-arious funсtional groups and can bе гegardеd as a
hvdrosilvlation rеaсtionТn *ьi.ь.ь. modified siliсa matrix сontaining =SiH groups aсts as a
hеtеrogёneous hydrosilуiatr"в."iЫ'тys kind of rеaсtion where one of the interaсting speсies
is fiхеd on a solid .",гui," *u-, сТassifled .. u 'oiа]pйasе hydrosilylation Dгocеssеs [3]. Тhouф
an eшly attempt,o.й.'Jй-ййg-гм'i hydrosilylation-pr9с:ssе.s werе madе in 1952 by
G.H. Wagneг and A.N. Ёines [+], tьi systemaii. й aouiьd devеlopmеnt of suсh reaфions
and their usе fог .ь.*rcJ*oсiпсutron Ьf ,ili.u suгГaсеs beсame possible in thе last few years
as a rеsult of еffoгts йrci, *",. mountеd ;;;p of investigatots from San Jose Statе
Univrrsity, UsA t5-4sj;;;iь" ,.,"."ь '"".т'.o* Ьe InstitutеЪf Suгfaсе Chеmistry of the
N;;;i,li";demy of SЪiеnсеs of Ukrainе [3,48.70]. -H
(+)-Cinсhoninе
!|-i=сH,
Y*. тn
(\\_ o _ cн"с H с H2N H о H(с H з)2
\-) .i
(_)-Alprеnolol
(_)-Cinсhonidinе
o\-T'"H'cH=cH'
\.А'
N-AllYlrhodanine
Fig.1.Struсturalformulasoffunсtionalolеfinsusеdforimmobilizationonthesiliсasurfaсe
(+)-Quinidinr
(_).Quininе
Hemin
'70
вoodш
! rРPr
tL зсpeл
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b l
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LT
b
s a
) 4
iеs
rф
by
)ns
агs
аtе
the
Bonding of оptiсally aсtivе сompounds on a siliсa suгfaсе is of genеral intеrеst bесause
en approaсh expands the oppoгtunities foг the synthеsis ofоhiral stаtionary phases usеd
dtе separation of еnantiomеrs in biologiсal systems and сliniсal samplеs. In some сases thе
ilylation rеaсtion was utilizеd for suсh synthesеs, for examplе in thе сasе оf quinine [7l ],
[72], сalixarеne [73] and R(+)-1-(с-naphthyl)ethylamine [2s]. Тhе foгmation of
in moleсulеs with doublе bonds suсh as a numbеr сinсhoniс alkaloids (quinine,
idine, сinсhoninе, сinсhonidine), and in alprеnolol, hеmin, and N-allylrhodaninе (Fie l)
its onе to usе thе сatalytiс hydгosilylation reaсtion for thеir immоЬilization on a siliсa
[70]. In this papеr thе гesults ofsystematiс геsearсh are disсussed, inсluding the effесt
thе сomponent ratios and reaсtion сonditions, kinеtiсs of сatalytiс hydrosilylation of
olefins, and thе sidе rеaсtions taking plaсе undеr thе tеst сonditions.
rimеntaI
Quininе, quinidinе, сinсhoninе, сinсhonidine, alprenolol, N-allylrhodanine, hеmin,
.6н2o (atl from Aldriсh); tгiethorysilane (сhеmiсally pure' Kremnepolimеr),
ЬМozoи.4Hzo (analytiсally puге, Rеakhim), asсoгbiс aсid (Kyiv vitamin faсtory);
toluene, glaсial aсеtiс aсid, Hсl, Ko}I, Cao (all сhеmiсally purе, Rеakhim) and
molесular siеvеs wеrе used. Siloсhrom with a spесifiс suгfaсe area of about l00 m2g l was
as thе siliсa support. Toluеne and 2.propanol wеre subjeсtеd to additional drying by
methods bеfore usе. Watег was douЬly distillеd in a glass apparatus.
IR spесtra wеrе mrasured with a Fouгier-tгansform IR speсtrophotomеtеr by the diffi.lse
:аnсе method in the rangе 4000.600 сm.l. A Gх-27o instrumеnt еquipped with a probe- - _ e - ' -
сross polarizatior/magiс angle spinning (сPA{AS) was employеd to obtain solid-statе
rсlеaг magnetiс rеsonanсe sрrсtгa. Thе spесtra of thе funсtional olefins, the solutions
igated, and the сonсеntгations ofthе bondеd organiс compounds aftеr the dissolution of
weiфed poгtion (10 mg) of modified siliсa in 5 ml(or in 4 пrl) of 1 М potassium hydгoxidе
wеrе dеtermined by UV speсtrosсopy (Spесord Uv.иs).
Siliсas йth attaсhed :SiH groups (samplеs I and II) wеге obtainеd by геaсtion of
with a solution of triethorysilane in ethanol followed by drying at 70"C, Samplе III
pгeparеd by adding Siloсhrom to an rthanoU0.l М I{сl solution, holding the miхturе for
h at 70oC in a regulated tempeгature bath, whilе adding triеthоrysilanе, and allowing the
ion to proсess fоr 2.3 h at the samе tеmperature. Finally the produсt was washеd in
or ethanol and then dried at 70"C.
Thе dеtегmination of =SiH group сonсrntration in solution and on modified suгfaсes was
сted bу a сolorimetгiс mеthod,"developed by the authors whiсh is based on thе spесtral
igations of the reасtion produоts with ammonium molybdate or yellow siliсomolybdiо
id. For preparation of thе 2.5 o/o ammonium moфdate solution, 5 g ammonium
ybdate [(NЩ)oМolozц4Еzo7 aге dissolved in 200 ml of a 5Yo acetic aоid solution.
$or сomрlеte dissolution the mixture was heated on a watrr bath at 100"с. Thе rеagent сan be
вd for a week. For longег periods of storagе, a whitе prесipitate of molybdiс acid is usually
. Thе standard triеthorysilanе solutiоn was prepared by adding 2 ml of HSi(oCzHs)з to
9.s rnl isopropanol. Then l ml of this solution was plaсеd into a graduated glass tubе and 9 ml
disopropanol was addеd. The standaтd solution pгeparеd in this manner has l.08. l0.5 mol
iсthoxуsilanе in 1 ml of standard.
Thе solutions foг spесtгa of model reaсtion produсts in the visiblе rеgion is prоparеd as
: eithег 0.2 rrr1 of a water solution of asсoгbiс aсid (l.4.l0.2 moИL) oг 0.25 ml standaгd
horysilane solution in isopropanol (1'08.10.2 mol/L) oг l0 mg of modifiеd sitiсa with
71
1.4'10.4 moUg of bondеd :SiH groups aгe addеd to 4 пrl ammonium molфdate solution. Then
0.8, 0.75 or l ml isopropanol йoьЬr arе геspeсtively addеd. Thе mixtuгe is stirrеd, thеп it is
hеatеd on a boiling watЁг bath for 5 minutеs. lt is nЬxt сoolеd (in the оаsе of siliсa it is also
filterеd) and finally .ь" op.i"ur densitiеs оf thе rеsulting solutions are measurсd. In the сasе of
the rеaсtion with yеllow.siliоomolybdiс heteropolyaсЙ the ryoсg{че
for the analysis is the
samе' rxсept that 4 J Ьг yerь* siliсomo^lyЬdiЬ hetеropolyaсid is addеd. Siliсomoфdiс
hеteropolyaсid rlras p,.p,.а as fоllows: 0.012 rnl of triеthoiysilane was addеd to 79.988 rnl of
a 2.5 oА ammonium molфdatе solution (thе rеsulting solution consists of 2.8.10{ mol of
tгiеthoxysilane in 4 ml).
Procedtlrеforthedеterminаtionof=SiНgroupс?ntelтto!compoundsinsolution.4m]l
of ammonium moфdate solutioп is intrЬduсеd into Ъach of two graduated tubеs. Then in onе
tubе from O.O1 to 0.; ; of thе test solution is plaсеd (depеnding on thе еstimated
сonсеntгation of =SiH groups) and the volumе is brought up to 5 ml with 2-propanol. Тhе tube
with is thеn сlosеd, Ъ1'Ъj and plaсed in a rеgulatеd tempеratuге bath at 80oC for
5.l0 minutes. Thеn a strёam of running water сools1he tubе. If thе solution bесomеs сloudy
aftеr сooling, it is filtеrеd' Then thе sоlution is measured spеctгophotomеtriсally and the
сonсentrationof=SiHgroupsisdеteгmiпedfromthеcalibrationсurvеoгitisсalсulatеdbyusе
of a сalibration сurvr еquation' The сonсеntration of =SiH grouрs in the analyzеd solution was
dеtегminеd bу usе of thе formula Csilr (mol/L): Cвtiь'.S, whеre C""шь. is the сonсеntгation of
=SiH gгoups in thе final mixturе.
Proсеdurе r* iin detеrтninаtion of aSiH group сontе.nt of.compounds bondеd to thе
suфce af siliса. гrom t to 200 mg ofЪ modifiЪd siliсa is introduоed into a gгaduated tubе
(dеpоnd ingonthееst imatеdсonсешrat ionof :S iHgroups) , thеn4mlofammonium
molybdаtе solution uni-i ы isopropanol aге addrd. тhе шbe is closеd, stirred and plaсed in a
rеgulatеd tempeгaшrе bath at 80.с for 5-10 minutеs' Thrn the miхture is сooled by a stream
of running watеr, filterеJ and trrе optiсal densitу of thе bluе solution is mеasuгеd at 7l0 nm.
A blank solution i, p,Ьpu."а йtьout adding sil-iсa. The сonсеntration of :SiH groups in thе
final mixturе is detеrmined by a саlibration сuгvе or is сalсulatеd using the equation of
сalibration сuгvе. тье
"on."nйution
of =SiH groups in analyzеd wзighed portion of siliсa is
determinеd by use of thr formula с,,nйoй)=6*uo,.5.1o,/* whеrе C-шь. is thе
сonсentration of =SiH g,o,,p, in the final mixture, m is a wеight of siliсa in grams.
Proсedurе for Йnetic mеаSurеmеnts.--вЬ, tь. prе|aration of all solutions idеntiсal
оonсentгation. "f
,;;;;Ь''й--i;'.;oi mot) and cinсhoninе (3.10a mol) wеre usеd.
Dеpеnding on thе й",i*Ь*, tье" pьсшatysi is aaаеа in an a.mоunt whiсh in 1000 times
(з.10n mol) or
"ъ;;';;'.ii.''
цol) is less than HSi(oCzHs)з сonсеntration,
B.сyclodеxtгin ь tuк"n ii"*;;Ы ii.ro; *ы Thе 0.04 пrl of thе соnсеntratеd aсetiс aсid
is added for dissohtйn Ьr
"i,"ьonin..
voro'* Ьi solution is brought by solvent up to 10 ml.
Тhе triethoxy.ir*" i",.й.J
"t",
зo ый' uteг intеrmixin'of olеfin, Pt-оatalyst and
solvent.Thеsolut ionsareplaсedinathеrmostatat80oCandafteгaf ixеdintеrvaloft imеthe
tеsts of reaсtion 'i"tu,o аi,е sеtесt"с and arе ana|уzеd as it was dеsсribеd above.
Results and disсussiоn
|14-767, suсh as vaгious
Numеrous .uoty,'' foг usе in hydrosilylation reaсtions,
сompounds *d
"","jЁi:"' "ior"й"* ""ii,""'i'i""
metals (pt, кь, Pd, Ir, os, Ni, Co, Cr, Ti,
Fе), are known. тi" 'o,t effeсtive J]h; most frеquently used in praсtiсe arr all
Рt-сontaining сatalysts (in paпiсula^r, 'ь" spЪi"., Karstedt and.Lamorеaux сatalysts). It should
bе emphasizеd that-й; ;;ivity of pt оatori,й ь й..u*.d in the prеsеnсе of a number of
12
i
)
f
J
е
А
€
) r
lу
1е
t€
zrs
of
hе
bе
1 a
am
цn
thе
of
r i s
thе
iса1
s€d
mеs
ion,
aсid
r m l .
aлd
: thе
nous
r, Tt,
е all
nouid
еr of
nds (oxygеn, aldеhydеs, unsaturated kеtonеs, оyсlodеxtгins, aсеtylеniс еthеrs and
) whiсh сan Ье regardеd as со.catalysts of the hydrosilylation геaсtion.
Iп thе fiгst stagе of this woгk, an attеmpt was made to immobilize the сhosen aсtivе
by bonding to =SiH groups whiсh weгe prеviously fixеd on thе siliсa sцгfaсе. Foг
F,шposе' siliсa with 7.|25.70.4 moUg:SiЕI groups was usrd (sample II whiсh was obtained
abovе.desсribеd method). Thе сovеragе of =SiH g[oups on siliсa was deteгminеd by thе
iс method. Solid-phase сatalytiс hydrosilylation of сinchonic alkаloids was
as follows: l00 mg (3.4.104 mol) cinchonine, (or 110 mg (3.4.i0.4 mol) quininе,
шg (3.4.lO.a mol) cinchonidinе, 1l0 mg (3.4.lOa mol) quinidine), 9.66 ml fresЫy-distillеd
, and 0.04 ml fгeshly-distillеd aсеtiс aсid wеrе addеd into a glass rraotor. The solution
lrсatеd on a water bath at 80oC in order to сomplеtely dissolve thе alkatoid. Тhеn 0.3 ml
Sфеr's сatalyst (0.0l М solution ЦPtClс.6Hzo in 2-propanol) was added to thе reaсtor,
was сontrollеd at 80oC for l h. Thеrеafteг, l g Siloсhrom was addеd into thе rеaсtion
ion The соntеnts wеre well stiпed and weге hеld at 80"с for 10 h. Solid.phasе
ilvlation rеaсtions for other аlkaloids wеre сonduсtеd in a similar matrner' The modifiеd
were dried at 80oC for 2-3 h and at l00oC foг 2 h. Thеn the driеd modifiеd siliсas weге
еdly washed by a 0.5 % solution of an aсetiс acid in 2-propanol, еaсh time mеasuгing the
of alkaloids by speсtra in the UV region. The washing of thе siliсas was сonduсtеd as
as thе сharaсtегistiо pеaks of alkaloids appearеd in the spесtra of thе гinsing liquid
, it was neсrssary foг 100 to l50 ml of a solution of aсetiс aсid in 2-propanol for
ing of l g of modified siliсa). Тhe produсts were dried at 80oс for 2 h and at l00"C foг
Тhе сonсеntrations of bondеd organic сompounds wеre dеterminеd by UV speсtrosсoрy
e сaliЬrаtion сurve which was сonstruсted from standard solutions of the alkaloids in
рanol. To do this, a weiфеd portion (l0 mg) of modifiеd siliсa was transfеггеd into
ion by dissolving in 4 ml of 1 М potassium hydroxide' As the speсtra of alkaloids in
ions of 2-propanol and alkali aге idеntiсal, a оalibration сuгvе foг thе сonсentгation of
functional alkеnes on l g of the siliсa was dеfined. The rеsults obtained aге shown in
Тфle l .
I
immobilization of сhiral sеlесtoгs on a siliсa surfaсe йth boпdеd =SiH gгoups.
Bound olеfin
сinсhoninе
quinine
сinсhonidine
quinidine
Total amount of olefin
usеd (mmol)
Amount of immobilizеd
olеfin on thе siliсa
suгfaсe (mmoUg)
0.0210
0.0з44
0'0з24
0,0229
0.34
0.34
0.34
0.34
Тhus, on the basis of the data obtained it is observed that thс solid.phase hydrosilylation
lon involving surfaсe =SiH groups and funсtional olеfins рroсeеds with low yiеlds (up to
%) in rеlation to the suгfaсе sites. Thе problеms еnсountеred сan be eхplaiпed by invoking
mесhanism proposed by Lеwis |17 ' 78J foг thе hydrosilylatiоn геaоtion. It is pгesumеd that
hуdгosilylation rеaсtion is оatalyzеd by Pt-сolloid (wheгe Pt is in the zеro valenсе state)
l э
and the attack ofthe hуdrosilane preсedеs the attaсk ofthе olefin. Thе impoгtant influеnоe of
;;;; "' ""-Ъ"Ыyu
is ик"n into aссount; beсausе a Рt.сolloid is only foгmed in the presenсе
оf oхygrn. From thе p,o|o,"с mеоhanism, onе of the difiiсultiеs for сaгrying out of thе solid.
phasе сatalytiс hydrosilyйtion теaсtion, as сontrastеd with simi1ar proсrssеs in solution, сan be
Iй;j;;i;,.,i.i.t.a й!'ation ortьЬ Pt.сo]loid formеd along the siliсa surfaсе.
Hеnсe, it is possibiejo u,,u*" that diffiсuhiеs of immobilization of funсtional olеfins bу
meшts of sоlid-phase
""iыy,i"
ьyоrosilУlation rеaсtion may bе sоlved^ if the hуdгosilylation of
thе hydгosilari. unс orйn i, p"Ь*"j in solution with subsequent formation of the rеaсtion
produсt on thе surfac. ruy", Ьiы", syntheses^have bееn rеpoгtЪd|7|,137' For immobilization
of the aсtivе сompou,ii.*ol.iJ,iiйu ,u,гo." wе havе сombined into one pгoсess thе
hvdrosiMationгеaсt ion(a)andtheсommonsol.gеltransformations(D)thatrrsults ina
p,'o..* Ъ"'"ribed by the following genегal sсhеmes:
Pt-сata|yеt
(c2Hр).siн + cHz: сHп
j (сzHso)зsicH2сH2R (а)
+ HzO
: si + (с2H5o)3siсH2сH2R
I
: si_osiсH2сH2R (b)
The main еxpеrimеntal proсеdurеs usеd aссoгding to these reactions are dеsсribеd below
using thе еxample of сinchoninе bonding. 2-propano1 йra dried ovеr.4A moleсular siеves rrras
used.5mmol(for l0gsi l iсa)сinсhoninе,zо.пr l isopropanol,0.7mlaсеt iсaсidand0.05п' l
Spеiеr,s сatalyst (0.1 i; ,oliio, of H,Ptсl6'6I{2o i'' z-p'opanol) wеre addеd to a glass
reaсtor. Thе rеaсtor'was сontrollеd at 80oC ьr зо min. Thе rеaction mixtuгe was periodiсally
stiпed. Therеafter' 5 й;i tгiеthoхysilane was addrd intо thе reaсtor, and the mixturе was
hеld at 80oC for 6 h. It should be noted that thе amount of Spеiеr's сatalyst in thе геaсtion
mixturе is 100 times less on a 'ola, basis than the amount of thе hydridе-сontaining
сomponent triеthoxysilaliJ. тt,.n, 15 ml of isoгйa"or 11d^-T.9^'"*"*"m
wеrr addеd into
the rеaсtor and thе ',io;,; ** к.pt at the same tеmpeгature for 1 h. Thеrеafter, 1 ml
(0.055 mol) *u.". *u,laJ.с *a ..uйion mixturе was plaЪеd in adesiссator for 3 h at 100oс.
The driеd modified ,ili;;;;;pеatеdly *uй *i'ь isopropanol and the pгoduсt was again
dгiеd for 6 h at l00.C
Мodified si1iсas, сontaining other funсtional olefins (quininе, оuinidine, сinсhonidine,
alprеnolol, ш.urrя,ьodunine, ""j,ь.'iо
in the bondеd layеr, *"," ,щth"*ized in a similar
manner. Тhе appropпate arrlounts ofreagеnt u,.a гo' the synihеses and thе flnal amounts of
;;;;;; й;; Ьoiеitiеs obtainеd are listed in the Table 2.
The synthesi,.с.Ы , сontaining immobilizеd aсtivе сompounds, weгe charaсtеrizеd
by IR spеоtrosсopy ;lt;i;;';tffп,; J{r...""..
(DRIFT). and high-геsolution solid statе
'.с Nlr,ш.. ть" сonс"nt';;й of bondеd uй. .o*pounds wеre detеrmined bу mеans of
UV spесtros.oрy, ь"""u,e the ub.o.ption ,|."t.o oi tье ч,чrе 'funсtional
olеfins and thе
absorption spесtra
",;;;;Jstanсes
imйobilizеd on
"
jiliсa suгfacе and thеn transfегrеd
intosolutionbуtreatmentbyalkаliyeth1э.9amе.Thisallowsonrtouseofthegivenspесtгal
rеgion for quantitativе
-сiarjсiеrization
or цe lйoьilizеd substanсes. IR speсtra of modified
,t'il;й;ь*.а "i"Jй"i;;
й N-allylrhodaninе arе shown in Fig. 2.
14
Ls
n-
s*t
. r
t <
):.
t c
т:..
C
цп
l f
:...е
: еr1
iсc
2
nеnt гatios in thе sрthеsrs of modified siliсas and the final amounts of funсtionalbonded to thе mаtriх surfaсе.
Bоund olеfin olefin Solvеnt ьr тri 2-pro. Siliсa wat*__ Bo"d"d(mmol) olefin ethoxy- pйol G) (ml) groups
silane (mD (йmoi/g)
Ciпсhoninе 5
Ёс3н?oн
+ 0.7 ml
снзсooн
Quininе 5 l0 ml 5 25 10 l 0' 13
i-с3н7oH
+ 0.5 ml
Cн3сooн
Ciлсhonidinе 5 10 mt 5 25 10 l 0.i3
i-с3н7oн
+ 0.7 ml
с}i3сooн
Quinidine 2 l0 ml 2.5 8 5 0.s 0.04
l:CзHzoH
+ 0.35 ml
с}ъсooI{
lЁАJlylrhodaninе 5 l0 ml 5 25 10 l O.0l5
i-с3н7oll
+ 0.5 rnl
CHзCooH
Alpгeпolol 2 l0 ml 2.5 8 5 0.5 0.007
ЁCзHzoH
+ 0.7 ml
снзсooн
Hеmin l 4.5 ml 2.5 8 5 0.5 0.0l
нсoN(сн3),
+ l 0 m l
,.с3}I7oн
+ 0.1 rnl
It is sееn fтom the IR sрeсtra ofthе modifiеd siliсas that the absorption ofSiH bonds is
еtely absеnt (disappешanсе ofthе band at 2250 cm-| геlating to thе stгеtсhing vibrations
75
of thе :siн groups). Тhe solе еxсеption is thе speсtrum of the siliсa sample сontaining
immobilizеd N.allylrhodaninе. The lowеr dеgree of=SiH group substitution in the lattеr сase is
most рrobably deierminсd by inhibition of thе сatalyst as a result of platinum сhelation with
N-allylrhodanine.
nФ(,
g:е
Е
o
Cб
l--
1 0 0
9 0
8 0
7 0
6 0
5 0
4 0
3 0
2f,oЬТ
W a v e n u m b e r , с m . 1
*
oo
g
Еo
g
E
9 0
8 0
7 a
6 0
5 0
4 0
4 0 0 a v e n u m b e r , с m . 1
Fig. 2. D,RIFT sprсtra of сinоhoninе (1) and N-allуlrhodanine.(2) bonded to a siliсa surfaоe.
The lзC NМR spесtrum for the modified silica сontaining bonded quinine (Fig. 3) shows
thе сharасtеristiс pеaks foг thе сarbon atoms bеaring diffеrent substituents in thе quininе
76
шlg
€ i s
\ith
шlесulе, and a peak at 20 ppm сorгesponding to the сarbon atom direоtly bondеd to the
-соn atom and to thе adjaсеnt сarbon atom.
I
L'
I
t
\
r . | ' l . l - - д - - - j - l . . l . l , t . l l - . l
lв0 t60 140 |20
;Bi
e0 60 .0 аo
lt. 3. '.с NIv8. сP-МAs spесtrum of siliсa with immobilized quinine.
This speсtral information сlеarly demonstratrs that immobilization of funсtionаl olеfins
вr Ье aсhiеvеd by thе сombinеd use of hydrosilylation гeaсtions and sol-gеl tеоhnology and
frt the сonсеntration of funсtional groups bondеd to the suгface matгix in this сasе is highег
rbn thе amount of bonded bу solid.phasе сatalytiс hydrosilylation.
Studiеs of the kinetiсs of thе сatalytiс hydrosilylation геaсtion of functional olеfins and
рssiblе sесondary proсеsses weгe conduсted to dеtогminе thе rеasons hindering a grеаter
dсgтee of сompletion of the reaсtioц in order to find сonditions whiсh will improve thе yiеld.
l is partiсularly impoгtant to study suсh proсessеs in oгdeг to havе available a sеnsitivе,
пpгoduсiblе and гeliable method for thе quantitativе detегmination of =SiH groups both in
Ьdiйdual сompounds and in bonded gгoups on thе suгfaсe of solids. It has long beеn known
фat volumetriс methods [8' 79, 80], based on hydrolysis of =SiH groups in an alkaline mеdium
Ь most frеquеntly usеd for thеse purposes. In suсh a рroсеss gasеous hydrogеn is evolvеd. The
lls is сolleсtеd above meгсury in a graduated tube (as in Cегevitinov's appaгatus [79]) or thе
fпount of libеratеd hydrogen is dеtегminеd Ьy gas сhromatogгaphy [8]. oftеn' howеveг, thе
&tегmination оf =SiH groups by this mеthod is difiiсult for a largе number of samplеs bесausе
i is laЬoг intеnsivе and due to thе diffiсulty of estimating thе partial pгessurе of solvents, in
рrtiсular whеn dеtеrmining a small amoцnt of =SiH groups.
For this reason' thе appliсation of сoloгimetгiс mеthods, basеd on the use of thе
rсduсtion propегtiеs ofsiliсon hydride speсiеs, appеaг morе praсtiсal. The reasonably fast and
1 1
shows
quininе
сonvrnient spесtгophotomеtriо mеthod for the detеrmination of ratheг small amounts of =SiH
groups in сompound- *li;;.;;; i; solution o' л*,i оn a surfaоe of solids (in paгtiсular, siliсa)
Ьas invеstigatес in thе piеsent paprr' Thо mеthod is based on a rеaсtion оf siliсon hydгidе
sroups with an u*rn""ii'll йoiiйut" solution as a rеsult of whiсh a bluе siliсomolфdenum
::"d;- ;;;;;l il;;"1sъi!ity
of.suсh an-inteгaсtion of сompounds, сontaining of =SiH
sгouDs. with ammоntum molфdatе solution *u' p'opo'.d еarlieг izя1 тье reaсtion rеsults in
irrе fЪ.mation of a siliсomolybdеnum hetеropoiyaсij (srnптд) whiсh thеn is rеduсed up to
molvbdatе bluе. Additionui inгo*ution i, *oir,uьi;fi.;' othеr invеstigations [81-85] whiсh
аеsоribe studiеs oг tь"'Бnаitions of гo,mation or both yellow S}4}IPA and its геduсtion (in
paгtiсular, by asсoгbiс
"i1j
1вi.ввl to thе blue si'iсomoфdenum hetеropolyсomplф.
Thе prinсiplе oгtьь -.tьodis based on thе faоt that the hуdrogеn 9f an =SiH group сan
геduое a solution oгy"шl*-iйпA to the ьь...йro. In this appioaсh, thr reagent may be
both a уеllow *iri.o,noЬJ.*й ь.,.,op.oryu"ш unа ammonium molvbdatе solution. The
rеduсtion of a prеviously pгepшеd yеllow s}"fiй 'o iь. ьru. сomplех" irobably, proсееds by
the following sсhеme:
2 : si H + H4[si(Mo3o1o)J + 2 H?o -.----.._'> 2: siol-t + H4[si(Moр9ol.{)4]
SмI{PAformationinthecaseofintеraсtionofaсompound.сontaining=SiHgroups
with ammoniu* ,norфЬ..,oшtion uppu,.nф 'ukеs.plaсе тlh o.ц.toation of siliсon atoms
while the hуdгogеn
"'"'Ъ'й,.аo"tion
of thе aсid to thr blue сomоlex.
Thesе assumptions aге supported ьy .p..',й tйе visiьь rеgion of pгoduots of model
геaсtions (Fig. о.,.i,.-,"u.g;ot, soiшЬi'
"i
ammonium molфdate and yеllow
siliсomolybdenum heteropolyсomplеx -o. .й,* with геduсtion agеnts asсorbiс acid, a
solution of triеthoхys'i"""Тi-p'"Ьol TdФ;
siliсa with =SiH groups сhеmiсa'ly bondеd to
the surfaсе. д, i, ,""i,i;;i;ъ;. "bt.iJ,";;;rьic
aсiа.rJаuсed a solution of yellow
SМI{PA (Fig. 4, .';;j. Ь;;p""."а, in ,i.Ъ*.".. of a siliсon sourсe asсorbiс aoid doеs
not rсduсe tье a.nmo,iь-,diЬyьj"" ,"rшiч"ffi ;,.:}';. l). In сontrast, the triеthoxysilane
solution, bеing not ;;; 'd",b" ф, 9"i uГ,o .ili.on sourсe' reaсts with both solutions
(оurves 3, 4). The ';;*;;й;;b'йi"; й;;;йе reaсtion рroduсts (Fig. 4, сuгvеs 2-4)
whiсh ше in ttrе ranй;|,g!-i2o nmЪelong to thе samе сompound - bluе siliоomoфdеnum
hеteгopolycomplеx' ;й.p*;l;.ьi, ,"g,oi ;;;;;';*ed in the сasе of modifiеd siliсa as
a rеduсing ug*n. JJ.liiн g,o.,p' ;;"'',, йndеd.on .its
suгfaсе. Thr сasе оf
tгiеthoxysilan",,ь" Ё,'u,ЫoгЪt'дe.,.euсti"" pi"i""t was deteсted not only in thr сasе оf
intеraсtion of thе siliсa, сontaining ,iri.on ьyiяЪ"l.o:"у'..'*',l.yеllow shdI{PA (Fie: 4'
сurve 6), but also in iй.
"u."
of Jontaсt oгiье moаined siliсa surfaсe with aл ammoшum
molybdatе solution сгЁ-+, сurve 5). I. *,*;;;*;l_;йabsoгption bv siliсa of the теaсtiоп
produсt doеs not ndй,Ъ;-;ь. .JiiJ *ш,i-;;й; |iaоtiсarry.сolortess' but the solutions in
ihе immediate viсiniф ofihе siliсa suгfaсе ".;;;;;i;;.
It is quie probable that thе amourrt оf
solublе siliсa forms,й."."iiь. surfaсg l"'"';";;".'gh ror sшшшд foгmatiоn, аnd thс
reduсtion to thе bluе ;й"й;"'nь* i'..j"i.а oulьуЪu'гu"" siliсon hydгide spесies. ...
It was а"..й'"J.id", iь. Ь*utio;.;iй; pioduсt .of intегaсtion bеtween slшс'оfi
hуdridе.сontai"i"g ;"й;;;: ""а
й*""i'Ь,""шсl'" solution is сomp'еte in 2.5 h at гoom
tempеraturе' Th" ,;;i;;l, "Ъ'pr"ч "n".Тiойnut",
oг ь.uting thе iolutions on a bоiling
watеr bath. opti"d;;;;iti., "iiьЪ
sobtions studied at 7l0 nm arе unсhangеd over 2-5 hours.
The еxpеrim""t"l d;; ;;;inJuыiаu,"'ь.'p"йpьotomеtriс,mеthod
fЬr detегmination of
=SiH group
"on."йion
ii .o'po.,nd. .ьш ul'"i" a solution or bonded to a solid surfaсe.
'78
I
I
o
roups
Itoms
:sil{
liса)
lridе
num
:SiH
ts in
P t o
lhiсh
п (in
) ф n
iy bе
Тhе
ds by
)Н)4]
model
lеllow
сid, a
Jеd to
',еllolиr
1 doеs
rsilanе
lutions
э.3 2-4)
dеnum
Шсa as
asе оf
д;е оf
Fig. 4,
nonium
еасtion
dons itt
ount of
шd ths
i .
siliсо*
at room
, boiling
S houгs.
ation of
aсе.
1 . 2
Б t . o
€ 0.8
.3 o.o
д 0'4
o_2
Wаvс length, nm
1:.'o.:':".
оf intегaсtion p.roduсtsоf asсorbiс aсid (5'6.l0a mo|ll) (,t,2), triеthorysilane
4.loamol/L) (3,4) and modifiеd siliсa (weighеd poгtion l0 mg) *iй r.+.roJ;;';;
пdеd =SiH groups (5'Ф With ammonium moфdate solution (1, 3, 5) or with a solution ofyellow siliсomolybdenum hеtеropolyaоid Q, a, Ф; (Z) - speсtrum of a solution of thе
>w siliсomolybdеnum hеteropolyaсid; path lеngth of thе сеll ii 1 сm.
Foг сonstruсtion of thе сalibration оurve in a numbеr of gгaduated tubеs, fittеd with
.omрaсt stoppers, 4 ml ammonium moфdatе solution and varyiщ amounts of the standard
ahorysilanе solution in a range fгom 0.54.l0{ up to 3.78.l0{ mol were added. The volume
thе tubе is brought up to 5 ml by 2-pгopanol. The tubеs weгe put in a оontгolled tеmpегatцre
for 5.10 min at 80-100oC. During this time thе absoгption гeaсhes a сonstant valuе. Thеn
tubеs arе сooled undеr a flow of running water, stiггеd and mеasцrеd
rtrophоtomеtriсally. Thе optiсal dеnsity of thе bluе solutions is measured at a wavеlеngth
7l0 nm iп сell with a thiсkness of 1 сm. A сomparison solution is usrd as a сontгol йst
isting of 1 ml 2-pгopanol addеd to 4 ml of ammonium moфdatе solution. The measuгеd
s of optiсal dеnsity @) and thе aрpropriate desiгed сonсеntгation of triethorysilane in thе
solutions (Csi.н) arе used to сonstruсt a сatibration сuгvе (Fig. 5).
1 . 2
'; 1.0
ъ
? 0.E
R0 . 6
o.a
0.0
Cn.1хl0., moVL
5. Dеpеndenсе of an optiсal dеnsity (D) of ammonium molybdatе solution at }"=7l0 nm in
with a thiсkness of l сm vs. the сonсеntration ofaddеd triеthoxysilane (Csiн).
79
The reсtilineaг сharaсter of this dереtndenсе proves tЧthe.Plyti9п_s-ydуd ч:':thr
Lambеrt-Buger.Beеr law within the сч'сеnшation range for HSi(oCzHs)з from 0.l to
0.8 mmoИL. Thе limit of deteсtion is equattо 0.025 рrnoйd. The equation of thе сalibration
;;ъ;""ol.ы'ir;;";;;;й devеloгеd'in a previols sfudy [s9] is as fotlows:
p=(1946.l88 t 15.014';;н - (3.45'10.3 * 7 *.lgi), where the a,pafеnt mo1ar еxtinction
Ьй.i"nt @) ofthe =SiH groups is щual.яз2000'
In order to $ud;;йp"i'йrr,y of usiпg this mеthod fo'^ Ч.
deteгmirration Зf =liЕ
sгou's on a siliсa ,й;; й".'нg"iь"s. of tйе 9up"njT* of optiсal densф @) on thе
ЬnсЪntration oг *iriоon*ili'йfЬБup' dissoйеd in.solution wеrr сonduсtеd. These rrsults
werе obiained ьy *.".ЪiЪ"u.-*itь a given amount of bonded siliсon hydridе gгoups oг
varying arnounts "f
;й;.;*oТй"а.**pй F;;; thе Fig. 6 (e b) it саn be seenthat a
linear dеpеndenсе of ;р.t""' J"n*'ty оп to1j сoncentгation Ьг =siн gгoups in solшion is
observed in both
"u,",.-ii",",ш',
,ugg.*t thе possibility of detеrmining =SiH groups nоt oпly
in сompounds whiсh ш" и a solutioйЪш aЬo thosе й *" pшt of сoпrpоunds bоndеd to a
siliсa surfaсe a
s
?
э
сtix10.. цoUL
b
Б.я
tr
!
e
a
Fig.6 (a, b). Results of determinatio".of:IJT groups in vшious.samples of modifiеd siliсa
[l. samplе I with thr сonй. oгfi*ed =Siн gгiups l.75.los moUg (weiфеd portions . l0,
30, 60' and 100 'g)'
"
:.;;;йп ч.ь.ь. йnй' of fixed =Siн gгoups 1.|25.|0. moUg
(weiфrd portions - 2,3,- ;;i.ч], t
. 'PPl" III With th€ сontоnts of fixed =SiH groups
i.+.iЪ;ЬЬyg (weiфed portions - 5, l0, and 20 mg)].
o.g.
0.E
o.7
0.6
0.5
OI
o.з
0.?
о.!
wGrЕ!сdрttioь пв
0
п
l :
n
r"I
l€
ls
)г
a
is
lу
a
It is possible to study the kinetiс dеtails of thе сatal-ytiсlrydгosilylation геaсtion by usingreniеnt and sцffiсiеntly геliаblе analytiсal mеthod. кn"tl" ййG;;;. wеre сonduсtеd1Ь hydгosilylation rеaсtion between triethoхysilane (TЕs) and сinсhoninе in a mеdium of
;.'i}:j::Т"":::".:jТ:i"I.ll'.: t.:senсе of th; ьйй
-J"iй,
The рroсess ofion is dеsсгibed by the fоllowing gеneral sсhemе:
H2Ptс16
)зsiH + H ,C : сH -R
з0o Z|0o
Тime, min.
(H5о2o)зsiCH2сH2
сonсentгation in сhemiсally purе
isopropanol; (2) - solution of
in isopropanol; (J) - sotution of
and сinсhoninе (3.l0a mol) in
я
.Б 0'8
с
€ 0.6
б
8 0.4
o_
Б
o'2
7. Kinetiс сuryes of thе dесгease of =SiH gуouo
rpanol: (i)-нsi(oсЛs)з solution (3.l0.a mol) in
)з (3.l0.4.mol) and н2PtCl6.6н2o (3.1o? mol)
)3 (з.104 mol), H2PtCtс.6Hzo 1з.to.7 mol)
Тhе kinеtiс сurvеs for thе dесreasе ofthе сoncentration =SiH gгoups in an isopгopanol
um (сhеmiсally pure) аs a funсtion of timе aгe shown in Fig. 7.Ъor TЕS iп isopгopanol
no сhanges oссur as eйdеnсеd by сonstant values of1hе optiсal dеnsity (o1. a, a
oftime (Fig.7, оurvе l). In сontгast' a fast dесrеasе of=SiH grЬup сontent takes plaсе
time in the solution сontaining TЕ,S, isopгopanol and вьсйtysi (Fig, 7,
"..-"
z1.
trlysts сan cata|уze the hydrolysis of =SiH gloups as has beеn sugрstеd [49] on ейdеnсe
from IR-spеФrosсopy data. Thегеfore it is necessary to assumе that in сhЪmiсally pure
шoI residual аmounts of wateг iie present, and would bе suffiсient to hydrolyze =siн
i. Thе dесгеasе of =SiH group сonсеntгation with timе oсcurs also in thе сasе of thе
ilylation геaсtion between I{si(oC2II5)3 and сinсhonine in isopгopanol solution in the
Spеieт's сatalyst (Fig. 7, сuгve 3). It оan be sren that the dеcrеaie ofthе =SiH gтoup
rtion in this hydrosi$ation rеaсtion oссurs сonsidеrably sloweг as сompared й thЪ
=SiH groups in thе isopropanol/TЕS/Pt-сatalyst and isopropanoVсinсhonine/Pt-
s/TЕs systems (Fig. 7, сurvеs 2' 3). tt is quitе сonсeivable thЪt in the сouгsе of thе
losilylation proсеss thе transitional complexеs of thе Pt.сatalyst with thе olefin and TЕS
trmеd, геsulting in a slowеr proсess of hydгotysis
Тo pгеvеnt hydrolysis, the study of the kinetiсs of the dесrease of thе =SiH €roupпtration was done in a mеdium of сarеfully driеd isopгopanol (dried above Cao aй +д
sievеs and thеn distillеd). The results obtained aге shown in Fig. 8a. Foг thе system
8 l
iliса
10 ,
F,vg
){lPs
iЁ{li*оtlгtli:snrli 1}rg. 8 а, сilrvе i) thе.rrsults соil,ls.:id* *il
"ч1i:.-tаinеi1
еarlieг (Fig. 7'
r:..,rrn',е
'!)' l.hi:
.irlldкэl:д;;,;;;,' -i*.ulYg:-рs !n thе s:.jsт.'l! isоpгоlзanоUTЕS/Pt.сatаlуst
с:an bе рraстir:allу еиrтunatеd bv thе t.lsе nr*.iu,Ji*ошrсрaпоi (F'r.в 8,в' a;ц1.*,е 2)."Тhе dесгеasе
*li thе =5i}1 g,u',р *un,*un .,liь tь,,* in ,ь. .u** Jf iь* ьy,l'n'iiviatiоn гraсtiоn lэеtъvееn TЕS
and сtтrсhоnrrjе tn а, rпeсliutlr *rf сiriеd,*uрoopйiЫа,s'inu:е*igatеtl,,аs * fun*tign trf diffеrеnt
а.friФunts *f Рi."*a'talуs;*!u;-Ъ ;: "u*Ъ*
з'. *i, --* alsо*f,*r*thе яas* *f sirзluitaneous
ilitг{jdilei'ion irttо ttl*,.,*'**"i,u*ьРt.catailstan,t
p.й*tо*еxtrilr"{'Fig 8 а". сцг;e 5}' Eoththе
iiaia о' ртеviоus чl,огk' i901 and thе,rеsultsrэiэtui,,*с io our- stutlu,. iцdiсatе tirat $.сусlосlеx1rin in
;о*-ii;ii.ietii:tl i::it}r e Рt.сetа,iуst a{rсеlеretеs Г,Ydгоsli',,iatiоrr рrосess.
ii rs nес*sseтi,- rо takе intо с:оnsitlегatiоn that сaiaiyiс sуstеin 1таn*t'огmatiоns сan rеsult
in thе рrеsеп';* ot *.ut., *olесutеs in a mесliurгr ;; iй;";--"i Y*Р
a Рt.саtai,zst. Thеreforе tt
ъas сiесtcеd ,n *o,'о,..,;;;;;;.; kinеtrс
"-аi-'
и - l'*ji.,* or'oйеnе whiсh prеъ:iоuslу was
;ff;;ffiff;;:;iЖ'Ж;;;йе
йuеstigatiоns arе shоwn u,
;*
*o
$ it., * h,.nlltU Ll:Г.,е5.ibг thе кlесrеasе 1n =SiH Еrоuр сеriсеn..:,,o-o.,rn тhе mеdiurn of dгiеd
,s. l ; r l :а,R ' , , t l .аr аnd," , ; ; ; ; i . i - sotur iоn ттs iз"11-. . rn i : l \ : . , . s ' ] tutrоn TЕS {3.10.a mol)
on,j Ёt,t,tСi.,.5il,О r,з,l;:;,;;ii' l - sоlutiоn-Тi,S.i..,'. rnоi) сirrсhоninе i3"i0.a mol) and
НzPtСlg.6l{:О iз ]'0-,
"*;,)'^,''-
sоlutiоn тis ii iо- *oii, сinсhоninе (3.i04 mol)'
L{',РtС16.6}{2CI (3 l0.- *"'j. :-"
-:*:]"1j;s'"ti**..*oil, сinсhоninе (3.1сl-4 mol),
t{:РtСlс.6}tzO (,-].10., *ф
"-o
p-сусlоdеxtгi-й,, io'mо1); о. sоiutiоn TЕ,S (3.10.a mоlj
a*l й;,;i";еxirin (2,2.10-6 mol) in isoproрanоl.
Fгоm tlrе abсve геsults it apреars tirat thе сhangеs in the =Sij] g]"оuр с,onсеntгation
whiс.n wеrе obsеrvеd ",t;;.ffi;.noi
ь. e.*,,iй*j.щ i"у simр'e kinеtiс еquatiоn bесause tn
раrаlt;lwlththеhydrоsilуlatiоnрr0сеss-va.lou*,*"on*tuЦ.,ч'oo*:-'-:sandtiansfоrrnatiоnsоi
thе сataiyiс sуstrrn take рlaсе Thе =SiH g,"uр l'у*,,,tу*i, i, u rnajor sесоndary proсеss. In
alrсlthrr rеtlort [91] i'.*J,loi"t*d оut that1;,";;;;'; сi а..hvdrоsilvlвtiоn rеaсtion in аn
Щ;;J- т:*ж* r;J*i; il: '' ''--,1:Ж-{1тц1жt,Jfffi:, 'J}";Ё.i
t тiеthо.tуi sr. p гор 0xу st i
a hvdтоsii,'.[a,,o,, .*u"?io.n,j"-ii." p**: -т;'жт*j,ж:ъ"Ё; Ё"}'],fi'fiiiil.'J''i::
*lt'aт;l-liJ#i:J*.:-il1ъi":".x;:r;й:l:;Ж";;
*ulс*no",*.'1vеd fгоm оthег
сraiatУzjj" l,J .'1*".. Ье notесi that durшrg ihе first 80-i00 minutеs оf the hуdrоsilylatiоl'
iL sLlоuiti aisо
rсо.сt.it-';i,,,',,оi,,oрun.,-j mеdium (Fig. 8a, --;;; i::i:,::*:l.сant dесгrasr оf thе =SiН grоuр
с*nсеnt iа i lоn{ in i t ia ipогt iсrnоfthеkinеt iссurvеоf=SiF]grоuрl*ss) ,dссurs.Thеgrеatestгatе
t
: .
::г
l i : г .
Tttrr
:i:т .
t l ' . :
t
t
с
S
n
rs
€
;n
Llt
it
LS
tlron
sе in
s o f
s I n
п a n
rhiсh
sе of
Г the
thеn
oфег
lаtion
3rouр
i гatе
rеd
юl)
and
юl)'
bl),
nol)
tЬс reaсtion сorresponds to this poгtion ofthе сurve. Thеrеaftеr thе reaсtiоn гatе is shaгply
псased and is staЬilizеd. In an еarlier work [9l] it was statеd that the rеason foг.an
rcased ratе of геaсtiоn in the first stage is duе to the proсess of reduсtion P(Iv) + Pt(II)
Рt(0) whеre an unstablе intermediatе сomplеx of platinum tP(шI) and P(I)] havе inсrеased
iйty. Thе hydгosilylation in a toluеne medium @ig. 8b, сurvеs з.5j differs from the
ion in isopгopanol first and forеmost by ratе. It is nесеssary to pay spесial attеntion to thе
thаt different сonсеntгations of the PЬсatalyst signifiсaшly
-inhuinоe
the гatе of thе
вilylation reaсtion. Fгom the data obtained (Fie' s a, b, сuгves з, 4) it is obvious that in
сasе of thе addition of Pt-сatalyst in an amount in l00 timеs smallеr than TЕS
[гation, thе hydгosilylation proсеss proсеrds muсh faster in сompaгison to the systеm
thе h-сatalyst сontеnt is 1000 times lеss than thе tгiethoxysilanе conсеntration.
3
сomponent ratios in thе synthesеs of modified siliсas and the гesulting сonсеntrations
nal groups bonded to the matrix suгfaсе.
Wеiфt Solvеnt for
of сin. olеfin
фоninе
(mg)
Volumе Volumе Siliсa (g)
ofPt. ofTЕS
сatalyst (ml)
(ml)
Vo]umе Amount
of0,1 М ofbonded
solution groups
нсl (rr'l) (mmoVg)
l00 9.74 п11
toluеnе
+ 0.04 rnl
сII3сooн
l00 9.7l ml toluenе
+ 0.04 ml
сн3сooн
l00 9.44 m| toluenе
+ 0.04 ml
CHзCooH
0 0.22 I I 0.0012
0.0з 0.22 I 1 0.0128
0.3 0.22 1 l 0.0676
100 6.74 m| toluеnе
+ 0.04 ml
сн3сooн
9 . 71mI
ЁCзHzoH
+ 0.04 ml
сн3сooн
9.44ml
i-CзHzoH
+ 0.04 ml
сII3сooI{
0.22 0.0340
100 0.03 0.22 0.0200
100 0.3 0.22 0.0404
83
With thе сombinеd use of thе сatalytiо hydrosilylation and. sol-gel teсhnologу studies in
ordeг to deteгmine thе сonditions of thе ,рiй"i. ihat proйde maximum сovеrage of the
funсtional olefin on thе surfaсе of siliсa ..,"-.uй"а oш. д numbеr of synthеsеs utilizing
сatalytiс hydrosilylatiоn *J ,or-g"l tгansfогmation were usеd to bond сinсhoninе to the
suгfaсе of siliсa' and in so doing ihe сonсеntration ofPt-сatalyst and thе naturr of a solvеnt
were variеd. тtre sрthe*.. i.," pеrformJ
_simult*.ouф
and сoncentrations of thе
сinсhonine (0.34 mmor) qnd TЕS (l.2 mmol) wй rcpt сonstant.(it.should bе noted that thе
TЕS conсеntration wa,s Тou. tм", grrater 'й йotЪг сinсhonine). A 0.01 М solution of
н2Ptсt6.6tl2o in z-p,oЬ*oi (SpeierЪ ̂ сalal.yst)
was used. T1r toче1rе and aoetiс aсid wеrе
prеviouslу distillеd. ,;-.;;d;;; сriеJ aЬo.," йcium oxide and 4A moleсular siеves and
ih"n **, distillеd. The synthеsеs wеrr e*"",,t"d
"'
iotto*'. the сinсhoninе was dissolvеd in
toluеnе (or in 2-propanol) along with aсеtiс aсid, then the appгopriatr amount of Ъpeier's
сatalyst was added Jiь" sohtйn was plaсed in a герlatеd.trmprrature bath at 80oC for 2 h.
Then the TЕS тvas
"dd;.iь","".tio,,.uotution.'n,as
stirrео w"ll. тh" reaсtion solution was
again рlaсеd in tr," .onii-ottJi"*p.,*. b'ч;; вoiс for 10 h. After that, 1 g Siloсhrom and
1 ml 0'l М of solutio' нсi*o.
"са.o
i*o the sotшion and the mixturе was hеld at 80oC foг
2 h with periodiс ,tiм'Ъ.1ь".т"aшеd siliсas wer. а,i"с at 70.80oC fоr 2 h and at 100oC for
2 h. Then thе driеd *ojifi"d siliсas rvегr 'Ф;;й *asьеo ьy a 0,5 Yo solution of aсetiс aсid
in 2.propanol. Washini.ia's-.ч1а*.1.*'ii'h. ;й;егistiсieaks of сinсhonine disappеaгеd
from thе spectra oгtь".,i*ing liquid. Theсlean modified siliсas wеге driеd at 8OoC for 2 h and
at 100"с for 2 h. rо *e
"itй
modified ,iri"" *u' сi'solved in 4 ml 1 М solution KoH for the
detеrmination oгtьe u,io]uш;fi;.;d.inсhoninе and the spесtrum of thе alkaline solution in
thе UV region *u, ,ul.Ъ]i.iь" conсent,ati;;iй;еd gioups in moVL wеrе dеfined from
the сalibrаtion сuгv. Б, .i*аu,с solutions of сinchonine in z.propanol and the сonсrntrations
of bondеd сinсhoninе groups ь m*oyв.y";;;i;;;йьy maнй thе nеoеssary сalоulations'
''.'?::::*1'J"*жJl."Ж'lJ'':"''l'*1',*. qr.eatest'P9tll.:-:{,h. сinсhonine bonded to
the siliсa surfaсе
";;;j;;;'
й" *"аrtь"' or.iй. 'yntьois listеd in numbеr 3 (Table 3)' In
this сase toluenе **-;;;;;;soьеnt, *d й;;;.it,ution of thе Pt.catalyst is in 100 times
lеss than thе сonсешration ofthe сinсhoninе.
Tablе 4
Componentratiosinthesрthesеsofmodifiеdsiliсas,andthеfinalсonсеntrationsoffunсtional
й'-й. ьonа"d to thе matriх surfa.се.
Bound olеfin Amount of olefin Гofuent for olеfin Amount ofbondеd groups
mmol
Quinine
Cinоhonidine
Quinidinе
Hеmin
0.34 (se)N.Allylrhodaninе.' .нlp'.,'otol
0.3 4 (9,|)
0.34 (110)
0.34 (100)
0.з4 ( l10)
0.r7 (110)
9.43 ml toluene
+ 0.05 rnl сtl3сooн
9.43 rnl toluenе
+ 0.05 ml CHзCooH
9.43 rnl toluenr
+ 0.05 'nl сI{3сool{
9.48 ml toluеne
9,44 m| toluеne
+ 0.04 ml сtlзсooн
0.14 rrilHCON(CHз)z
+ 9.з4 ml toluеne
0.093
0.112
0.096
0.034
0.063
0.028
84
Using thеsе сonditions foг the gгеatеst yield of.bonded сinсhonine (Table 3, synthesis 3;
*:*;';:i:Тl,l1d.''!: .+:"й;i.oi'ь" сatalyst in 100 timеs lеss tЬяn tЬo:iТ'lJli:,":уjь,т:d:ij1"*{:ii1#l.*:iilЬ:,.l.':*Т"lН"l1Т;l:п of TЕs (l.2 mmol), thеvolume
".P;;6; Ёжi,НT:'#l,ii;ljT'*Тilli
3Y: T;"*,l; l;'у rfl уj::,'"' :l i Jj.;;;; ; ; ;;ч;;i ff Jil*,i,n", ".. The гesu й saге shown in Table o '1.^ Yrч"li" "iЪp..",r;j,Ж;ii:,iilJ':,ffi:,ж;,J};l for сinсhoninе. In thе сasе.Ьf ь.min Бliсф thе washing of thе modifiеd siliсaN,N-dimethylfoгmamidе and follor,vеJ--ьyЪ-.pЁ}"nor'
ns
Тhе bonding of funсtional
.olеfins
to аn =SiH group on a siliсa suгfaсe is aссompaniеd
li;Тii'fl:*Il'"r}::ч:fl:,::"ri:9 г.nriir, ii'ь" p'Ь".*l]."",o"","o undeг thеiс hydro silyl ati on/sol- sеl'.йы oй pi";;;ffi; il,:Ё,ff :H;::i"."#.#11':;
l"ж: Tr=-"1"J- ::: : :':*::::g i:Ёil A speсtrophot omеt гi с mеthod for thеration of =SiH groups in solution unа o" ti" ;й;;.;Ё',;#;;";:*.ilj:ъ,*:
;::'Т"'::i-'fl.li::::jj:::1'^:::т ^lrdroыivlatio" 'Ъйi"".-п ;;;.,,"v to takrEсount thе possible seсondary proсеssеs tйui tut. ptu." Ju,i,щ.;;;й]:ffi:х',;"l?:;
з "i:.:,жil,Т;Jj* lil!'|* r, ̂ :*:::':' т"ф"'';ih pъ;;Ё.. u, the typе andof сatalyst, eхpeгimеntal ."onаition' ."с-й. 1J'*; ffi;JflЁ:#""jr,il:j
*".'",',*:х:':"l*':::::-'r'T:ь с;:":i lгthe сatыyst, гeagent гatios, thе mostiаt e solvеnt) wеre dеtегminfo
:т ф;йJй;Ц1;.":*"f..Ж:.,:;' JhН:
l.',j:ffu{,}.}fl1'ffi#";:. *. ьonJ"с. Ьn.tional g.oup,-iь,il, i, ",p*J"пу
lеdgemеnt
Тhе геsеaгсh dеsсribеd in this publiсation was madе possible in part by gгantl38 of thе U.S. Civilian Rеseaгсh .nс о.u"ьp*еnt Foundation and of the Govеrnmеnt
:ж;*
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90
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| id | oai:ojs.pkp.sfu.ca:article-49 |
| institution | Surface |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2025-09-24T17:44:38Z |
| publishDate | 2001 |
| publisher | Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | surfacezbircomua/9a/79858df859201bcbdeba6cfde5b4e49a.pdf |
| spelling | oai:ojs.pkp.sfu.ca:article-492018-11-27T09:42:39Z Hydrosilylation reactions in synthesis of surface chemical compounds Hydrosilylation reactions in synthesis of surface chemical compounds Hydrosilylation reactions in synthesis of surface chemical compounds Tertykh, V. A. Yanishpolskii, V. V. Bereza-Kindzerska, L. V. Pesek, J. J. Matyska, M. T. With the combined use of a catalytic hydrosilylation reaction and sol-gel formation, immobilization of a number of unsaturated organic compounds (quinine, quinidine, cinchonine, cinchonidine, alprenolol, N-allylrhodanine, and hemin) was carried out on a silica surface. The structure of the compounds formed and the nature of their bonding with the surface were studied by DRIFT and NMR. spectroscopy. The concentrations of the olefins anchored to the surface layer of the silica matrix were estimated by a UV-spectroscopy method. A spectrophotometric method for the determination of =SiH group concentrations in solutions and on surfaces was developed. The method is based on the reduction of ammonium molybdate by silicon hydride groups and measuring the specific absorption at λ=710 nm of the blue solution of silicomolybdenum heteropolycomplex formed. The method allows for the determination microgram quantities of =SiH groups with a reasonable accuracy. Kinetic peculiarities of the hydrosilylation reaction between cinchonine and triethoxysilane in the presence of Speier’s catalyst have been studied in toluene and isopropyl alcohol by use of a spectrophotometric method. It was shown that the hydrosilylation reaction of functional olefin is complicated by transformation of the catalytic system and secondary processes occurring in the solvent medium, in particular the hydrolysis of =SiH groups. With the combined use of a catalytic hydrosilylation reaction and sol-gel formation, immobilization of a number of unsaturated organic compounds (quinine, quinidine, cinchonine, cinchonidine, alprenolol, N-allylrhodanine, and hemin) was carried out on a silica surface. The structure of the compounds formed and the nature of their bonding with the surface were studied by DRIFT and NMR. spectroscopy. The concentrations of the olefins anchored to the surface layer of the silica matrix were estimated by a UV-spectroscopy method. A spectrophotometric method for the determination of =SiH group concentrations in solutions and on surfaces was developed. The method is based on the reduction of ammonium molybdate by silicon hydride groups and measuring the specific absorption at λ=710 nm of the blue solution of silicomolybdenum heteropolycomplex formed. The method allows for the determination microgram quantities of =SiH groups with a reasonable accuracy. Kinetic peculiarities of the hydrosilylation reaction between cinchonine and triethoxysilane in the presence of Speier’s catalyst have been studied in toluene and isopropyl alcohol by use of a spectrophotometric method. It was shown that the hydrosilylation reaction of functional olefin is complicated by transformation of the catalytic system and secondary processes occurring in the solvent medium, in particular the hydrolysis of =SiH groups. With the combined use of a catalytic hydrosilylation reaction and sol-gel formation, immobilization of a number of unsaturated organic compounds (quinine, quinidine, cinchonine, cinchonidine, alprenolol, N-allylrhodanine, and hemin) was carried out on a silica surface. The structure of the compounds formed and the nature of their bonding with the surface were studied by DRIFT and NMR. spectroscopy. The concentrations of the olefins anchored to the surface layer of the silica matrix were estimated by a UV-spectroscopy method. A spectrophotometric method for the determination of =SiH group concentrations in solutions and on surfaces was developed. The method is based on the reduction of ammonium molybdate by silicon hydride groups and measuring the specific absorption at λ=710 nm of the blue solution of silicomolybdenum heteropolycomplex formed. The method allows for the determination microgram quantities of =SiH groups with a reasonable accuracy. Kinetic peculiarities of the hydrosilylation reaction between cinchonine and triethoxysilane in the presence of Speier’s catalyst have been studied in toluene and isopropyl alcohol by use of a spectrophotometric method. It was shown that the hydrosilylation reaction of functional olefin is complicated by transformation of the catalytic system and secondary processes occurring in the solvent medium, in particular the hydrolysis of =SiH groups. Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine 2001-06-10 Article Article application/pdf https://surfacezbir.com.ua/index.php/surface/article/view/49 Surface; No. 4-6 (2001): Chemistry, Physics and Technology of Surface; 69-90 Поверхность; № 4-6 (2001): Химия, физика и технология поверхности; 69-90 Поверхня; № 4-6 (2001): Хімія, фізика та технологія поверхні; 69-90 3154-8091 3154-8083 en https://surfacezbir.com.ua/index.php/surface/article/view/49/48 Авторське право (c) 2001 V.A. Tertykh, V.V. Yanishpolskii, L.V. Bereza-Kindzerska, J.J. Pesek, and M.T. Matyska |
| spellingShingle | Tertykh, V. A. Yanishpolskii, V. V. Bereza-Kindzerska, L. V. Pesek, J. J. Matyska, M. T. Hydrosilylation reactions in synthesis of surface chemical compounds |
| title | Hydrosilylation reactions in synthesis of surface chemical compounds |
| title_alt | Hydrosilylation reactions in synthesis of surface chemical compounds Hydrosilylation reactions in synthesis of surface chemical compounds |
| title_full | Hydrosilylation reactions in synthesis of surface chemical compounds |
| title_fullStr | Hydrosilylation reactions in synthesis of surface chemical compounds |
| title_full_unstemmed | Hydrosilylation reactions in synthesis of surface chemical compounds |
| title_short | Hydrosilylation reactions in synthesis of surface chemical compounds |
| title_sort | hydrosilylation reactions in synthesis of surface chemical compounds |
| url | https://surfacezbir.com.ua/index.php/surface/article/view/49 |
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