U.S. patent application number 11/166008 was filed with the patent office on 2005-10-27 for process for the formation of polyhedral oligomeric silsesquioxanes.
This patent application is currently assigned to Hybrid Plastics LLC. Invention is credited to An, Yi-Zong, Carr, Michael J., Feher, Frank J., Lichtenhan, Joseph D., Reinerth, William, Schwab, Joseph J., Terroba, Raquel.
Application Number | 20050239985 11/166008 |
Document ID | / |
Family ID | 35430404 |
Filed Date | 2005-10-27 |
United States Patent
Application |
20050239985 |
Kind Code |
A1 |
Lichtenhan, Joseph D. ; et
al. |
October 27, 2005 |
Process for the formation of polyhedral oligomeric
silsesquioxanes
Abstract
Three processes for the manufacture of polyhedral oligomeric
silsesquioxanes (POSS) which utilize the action of bases that are
capable of either attacking silicon or any compound that can react
with a protic solvent (e.g. ROH, H.sub.2O etc.) and generate
hydroxide [OH].sup.-, alkoxide [RO].sup.-, etc. The first process
utilizes such bases to effectively redistribute the silicon-oxygen
frameworks in polymeric silsesquioxanes [RSiO.sub.1.5].sub..infin.
where .infin.=1-1,000,000 or higher into POSS nanostructures of
formulas [(RSiO.sub.1.5).sub.n].sub..S- IGMA.#, homoleptic,
[(RXSiO.sub.1.5).sub.n].sub..SIGMA.#, functionalized homoleptic,
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.n].sub..SIGMA.#,
heteroleptic, and
{(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n}.sub..SIGMA.- #,
functionalized heteroleptic nanostructures. The second process
utilizes base to aid in the formation of POSS nanostructures of
formulas [(RSiO.sub.1.5).sub.n].sub..SIGMA.# homoleptic and
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.n].sub..SIGMA.#
heteroleptic and
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n].sub..SIGMA.#
functionalized heteroleptic nanostructures from silanes RSiX.sub.3
and linear or cyclic silsesquioxanes of the formula
RX.sub.2Si--(OSiRX).sub.m--OSiRX.sub.2 where m=0-10, X.dbd.OH, Cl,
Br, I, alkoxide OR, acetate OOCR, peroxide OOR, amine NR.sub.2,
isocyanate NCO, and R. The third process utilizes base to
selectively ring-open the silicon-oxygen-silicon (Si--O--Si) bonds
in POSS structures to form POSS species with incompletely condensed
nanostructures. These processes also afford stereochemical control
over X. The three processes result in new POSS species that can
undergo additional chemical manipulations to ultimately be
converted into POSS-species suitable for polymerization, grafting,
or other desirable chemical reactions.
Inventors: |
Lichtenhan, Joseph D.;
(Petal, MS) ; Schwab, Joseph J.; (Huntington
Beach, CA) ; An, Yi-Zong; (Fountain Valley, CA)
; Reinerth, William; (Westminster, CA) ; Carr,
Michael J.; (Fountain Valley, CA) ; Feher, Frank
J.; (Costa Mesa, CA) ; Terroba, Raquel;
(Fountain Valley, CA) |
Correspondence
Address: |
PILLSBURY WINTHROP SHAW PITTMAN LLP
P.O. BOX 10500
MCLEAN
VA
22102
US
|
Assignee: |
Hybrid Plastics LLC
Fountain Valley
CA
|
Family ID: |
35430404 |
Appl. No.: |
11/166008 |
Filed: |
June 24, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11166008 |
Jun 24, 2005 |
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09631892 |
Aug 4, 2000 |
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11166008 |
Jun 24, 2005 |
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10351292 |
Jan 23, 2003 |
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6933345 |
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11166008 |
Jun 24, 2005 |
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09818265 |
Mar 26, 2001 |
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6716919 |
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11166008 |
Jun 24, 2005 |
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09747762 |
Dec 21, 2000 |
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6911518 |
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60147435 |
Aug 4, 1999 |
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60351523 |
Jan 23, 2002 |
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60192083 |
Mar 24, 2000 |
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60171888 |
Dec 23, 1999 |
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Current U.S.
Class: |
528/15 |
Current CPC
Class: |
C08G 77/06 20130101;
C08G 77/08 20130101; C08G 77/04 20130101; C08G 77/045 20130101 |
Class at
Publication: |
528/015 |
International
Class: |
C08G 077/06 |
Claims
What is claimed is:
1. The process of using bases to convert polysilsesquioxane resins
into POSS nanostructures of the type: homoleptic
[(RSiO.sub.1.5).sub.n].sub..S- IGMA.#, heteroleptic
[(RSiO.sub.1.5).sub.m(RSiO.sub.1.5).sub.n].sub..SIGMA- .# and
functionalized heteroleptic
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).su- b.n].sub..SIGMA.#. Where m
and n represent the stoichiometric composition and #=the number of
silicon atoms contained within the nanostructure (aka cage
size).
2. The process of using bases to convert POSS fragments
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n].sub..SIGMA.# into POSS
nanostructures of the type homoleptic
[(RSiO.sub.1.5).sub.n].sub..SIGMA.#- , heteroleptic
[(RSiO.sub.1.5).sub.m(RSiO.sub.1.5).sub.n].sub..SIGMA.# and
functionalized heteroleptic
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n].s- ub..SIGMA.#.
3. The process of using bases to convert POSS nanostructures
homoleptic [(RSiO.sub.1.5).sub.n].sub..SIGMA.#, heteroleptic
[(RSiO.sub.1.5).sub.m(R- SiO.sub.1.5).sub.n].sub..SIGMA.# into
functionalized heteroleptic
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n].sub..SIGMA.#. POSS
nanostructures.
4-7. (canceled)
Description
RELATED APPLICATIONS
[0001] This application is: a continuation of U.S. patent
application Ser. No. 09/631,892 filed Aug. 14, 2000 (which claims
priority from U.S. Provisional Patent Application Ser. No.
60/147,435, filed Aug. 4, 1999); a continuation of U.S. patent
application Ser. No. 10/351,292, filed Jan. 23, 2003 (which claims
priority from U.S. Provisional Patent Application Ser. No.
60/351,523, filed Jan. 23, 2002), which is a continuation-in-part
of U.S. patent application Ser. No. 09/818,265, filed Mar. 26,
2001, now U.S. Pat. No. 6,716,919 (which claims priority from U.S.
Provisional Patent Application Ser. No. 60/192,083, filed Mar. 24,
2000); a continuation of U.S. patent application Ser. No.
09/747,762, filed Dec. 21, 2000 (which claims priority from U.S.
Provisional Patent Application Ser. No. 60/171,888, filed Dec. 23,
1999); and a continuation of U.S. patent application Ser. No.
10/186,318, filed Jun. 27, 2002 (which claims priority from U.S.
Provisional Patent Application Ser. No. 60/147,435, filed Jun. 27,
2001). The disclosures of the foregoing applications are
incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] This disclosure describes methods that enable the selective
manipulation of the silicon-oxygen frameworks in polyhedral
oligomeric silsesquioxane (POSS) cage molecules. It is desired to
selectively manipulate the frameworks of POSS compounds because
they are useful as chemical species that can be further converted
or incorporated into a wide variety of chemical feed-stocks useful
for the preparation of catalyst supports, monomers, polymers, and
as solubilized forms of silica that can be used to replace fumed
and precipitated silicas or in biological applications, and for
surface modification. When incorporated into a polymeric material
POSS can impart new and improved thermal, mechanical and physical
properties to common polymeric materials.
[0003] A variety of POSS frameworks can be prepared in
synthetically useful quantities via the hydrolytic condensation of
alkyl- or aryl-trichlorosilanes. In most cases, however, hydrolytic
condensation reactions of trifunctional organosilicon monomers
afford complex polymeric resins and POSS molecules that are
unsuitable for use in polymerization or grafting reactions because
they do not possess the desired type or degree of reactive
functionality. In light of the fact that many structurally
well-defined silsesquioxane resins [RSiO.sub.1.5].sub..infin. and
POSS molecules of the homoleptic formula
[RSiO.sub.1.5).sub.n].sub..SIGMA.# (where R=includes but is not
limited to aliphatic, aromatic, olefinic or alkoxy groups and
n=4-14) can be prepared in good to excellent yields from readily
available organosilicon monomers, there are enormous incentives for
developing a methodology capable of converting these POSS species
into systems bearing functionalities that are more desirable for
polymerization, grafting, catalysis, or compatibilization with
common organic resins. Examples of such desirable functionalities
include but are not limited to: silanes, silylhalides, silanols,
silylamines, organohalides, alcohols, alkoxides, amines, cyanates,
nitriles, olefins, epoxides, organoacids, esters, and strained
olefins.
[0004] Prior art in the silsesquioxane field has taught processes
for the chemical manipulation of the organic functionalities
(substituents denoted by R) contained on the silicon oxygen
frameworks of polyhedral oligomeric silsesquioxanes. While these
methods are highly useful for varying the organic functionality
(substituents) contained on POSS molecules they are not always
amenable to low-cost manufacturing nor do they offer the ability to
selectively cleave and or manipulate the silicon-oxygen frameworks
of such compounds. Thus, these methods are of no utility for
transforming the multitude of readily available and low cost
silane, silicate, polysilsesquioxane (aka T-resins or T-type
siloxanes) or POSS systems.
[0005] Prior art has reported that bases (e.g., NaOH, KOH, etc.)
could be used to both catalyze the polymerization of POSS into
lightly networked resins or to convert selected polysilsesquioxane
resins into homoleptic polyhedral oligomeric silsesquioxane
structures. Marsmann et al have more recently shown that a variety
of bases can be used to redistribute smaller homoleptic POSS cages
into larger sized homoleptic cages. (Marsmann, H. C. and Rikowski,
E., Polyhedron, 1997, 16, 3357-3361). While there is precedent in
the literature for treatment of silsesquioxanes and POSS systems
with base, the previous art does not afford the selective
manipulation of silicon-oxygen frameworks and the subsequent
controlled production of POSS fragments, homoleptic POSS
nanostructures, heteroleptic POSS nanostructures and functionalized
heteroleptic POSS nanostructures. Furthermore, the prior art does
not provide methods of producing POSS systems suitable for
functionalization and subsequent polymerization or grafting
reactions. This oversight in the prior art is reflective of the
fact that the invention of POSS-based reagents, monomers and
polymer technology has only recently been developed and
consequently post-dates this prior art. Hence POSS compositions and
processes relevant to the types of systems desired for POSS
monomer/polymer technology were not envisioned in the prior art.
Additionally the prior art does not demonstrate the action of bases
on silane, silicate, or silsesquioxane feedstocks suitable for
producing low-cost and high purity POSS systems.
[0006] In contrast to the prior art (see, e.g., Brown, J. F., Vogt,
L. H., and P. I. Prescott J., Am. Chem. Soc. 1964, 86, 1120-1125;
Marsmann, H. C. and Rilowski, E., Polyhedron, 1997, 16, 3357-3361),
the processes taught here specifically enable the development of
lower cost, high purity POSS systems bearing functionalities useful
as derivitizable chemical reagents and feedstocks.
SUMMARY OF THE INVENTION
[0007] This invention teaches three processes that enable the
manipulation and development of POSS compounds from readily
available and low-cost silicon containing feedstocks. Examples of
these low cost feedstocks include but are not limited to:
Polysilsesquioxanes [RSiO.sub.1.5].sub..infin., homoleptic
Polyhedral Oligomeric Silsesquioxanes (POSS)
[(RSiO.sub.1.5.sub.n].sub..SIGMA.#, functionalized homoleptic POSS
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n].sub..SIGMA.#,
heteroleptic POSS
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.n].sub..SIGMA.- #,
functionalized heteroleptic POSS
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).s-
ub.n(RXSiO.sub.1.0).sub.p].sub..SIGMA.#, and polyhedral oligomeric
silicates [(XSiO.sub.1.5).sub.n].sub..SIGMA.#, and POSS fragments
[(RXSiO.sub.1.5).sub.n].
Definition of Formula Representations for POSS Nanostructures
[0008] For the purposes of explaining this invention's processes
and chemical compositions the following definition for
representations of nanostructural-cage formulas is made:
[0009] Polysilsesquioxanes are materials represented by the formula
[RSiO.sub.1.5].sub..infin. where .infin.=degree of polymerization
within the material and R=organic substituent (H, cyclic or linear
aliphatic or aromatic groups that may additionally contain reactive
functionalities such as alcohols, esters, amines, ketones, olefins,
ethers or halides). Polysilsesquioxanes may be either homoleptic or
heteroleptic. Homoleptic systems contain only one type of R group
while heteroleptic systems contain more than one type of R
group.
[0010] POSS nanostructure compositions are represented by the
formula:
[(RSiO.sub.1.5).sub.n].sub..SIGMA.# for homoleptic compositions
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.n].sub..SIGMA.# for
homeoleptic compositions
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n].sub..SIGMA.# for
functionalized homeoleptic compositions
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.n(RXSiO.sub.1.0).sub.p].sub..SIGM-
A.# for functionalized heteroleptic compositions
[(XSiO.sub.1.5).sub.n].sub..SIGMA.# for homoleptic silicate
compositions
[0011] In all of the above R is the same as defined above and X
includes but is not limited to OH, Cl, Br, I, alkoxide (OR),
acetate (OOCR), peroxide (OOR), amine (NR.sub.2) isocyanate (NCO),
and R. The symbols m and n refer to the stoichiometry of the
composition. The symbol .SIGMA. indicates that the composition
forms a nanostructure and the symbol # refers to the number of
silicon atoms contained within the nanostructure. The value for #
is usually the sum of m+n. It should be noted that .SIGMA.# is not
to be confused as a multiplier for determining stoichiometry, as it
merely describes the overall nanostructural characteristics of the
POSS system (aka cage size).
[0012] POSS Fragments are defined as structural subcomponents that
can be assembled into POSS nanostructures and are represented by
formula [(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n]. Note the
symbols .SIGMA.# are absent as these fragments are not polyhedral
nanostructures. 1
Example of Polysilsesquioxane Resins [RSiO.sub.1.5].sub..infin.
[0013] 2
Example of Homoleptic POSS System [(RSiO.sub.1.5)].sub..SIGMA.#
[0014] 3
Example of a Heteroleptic POSS System
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5)- .sub.n].sub..SIGMA.#
[0015] 4
Example of a Functionalized Homoleptic POSS System
[(RSiO.sub.1.5).sub.m(R- XSiO.sub.1.0).sub.n].sub..SIGMA.#
[0016] 5
Example of a Functionalized Heteroleptic POSS System
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.n(RXSiO.sub.1.0).sub.p].sub..SIG-
MA.#
[0017] 6
Example of a Polyhedral Oligomeric Silicate System
[(XSiO.sub.1.5).sub.n].- sub..SIGMA.#
[0018] 7
[0019] Fragment Examples: RSiX.sub.3 (1), [(RXSiO.sub.0.5).sub.n]
(2), [(RXSiO.sub.1.0).sub.n] (3),
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n] (4)
General Process Variables Applicable to all Processes
[0020] As is typical with chemical processes there are a number of
variables that can be used to control the purity, selectivity, rate
and mechanism of any process. Variables influencing the process for
the conversion of polysilsesquioxanes [RSiO.sub.1.5].sub..infin.
into POSS structures [RSiO.sub.1.5).sub.n].sub..SIGMA.#,
[(RSiO.sub.1.5).sub.m(R'Si- O.sub.1.5).sub.n].sub..SIGMA.#,
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n- ].sub..SIGMA.#,
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.n(RXSiO.sub.1.0).-
sub.p].sub..SIGMA.# include but are not be limited to the
following: chemical class of base, silicon-oxygen ring size,
composition type [RSiO.sub.1.5].sub..infin. (silsesquioxane),
[(RSiO.sub.1.5).sub.n(R.sub.- 2SiO).sub.n].sub..SIGMA.#,
(silsesquioxane-siloxane),
[(RSiO.sub.1.5).sub.m(XSiO.sub.1.5).sub.n].sub..SIGMA.#
(silsesquioxane-silicate), effect of the organic substituents,
process temperature, process solvent, process temperature,
stoichiometry of base and the presence of a catalyst. Each of these
variables is briefly discussed below.
[0021] Co-Reagent Promoters
[0022] Specific chemical agents can be utilized to promote or
enhance the effectiveness of the bases utilized in the processes.
Specifically, nucleophilic base mixtures that work in combined
fashion to firstly solubilize the silsesquioxane and secondly
promote formation of the POSS nanostructure. Examples of such
systems may include but are not limited to KOR where OR is an
alkoxide, RMgX which include all common Grignard reagents, or
alkalihalides such as LiI, or any of a variety of molten or fused
salt media. In a similar fashion co-bases such as [Me.sub.3Sn][OH]
and [Me.sub.4Sb][OH] have been shown to promote chemical
transformations of POSS systems yet have not been utilized as a
co-reagent in the formation of POSS cages. Alternatively,
electrophilic promoters such as zinc compounds, (i.e. ZnI.sub.2,
ZnBr.sub.2, ZnCl.sub.2, ZnF.sub.2, etc.) aluminum compounds, (i.e.
Al.sub.2H.sub.6, LiAlH.sub.4, AlI.sub.3, AlBr.sub.3, AlCl.sub.3,
AlF.sub.3, etc.) boron compounds including (i.e. RB(OH).sub.2,
BI.sub.3, BBr.sub.3, BCl.sub.3, BF.sub.3, etc.) which are known to
play important roles in the solubilization and ring-opening
polymerization of cyclic silicones and in the ring-opening of
polyhedral oligomeric silsesquioxanes.
[0023] Chemical Bases
[0024] The purpose of the base is to cleave the
silicon-oxygen-silicon (Si--O--Si) bonds in the various
silsesquioxane structures. The exact type of base, its hydration
sphere, concentration, and solvent interactions all play important
roles in the effectiveness of the base for cleaving the
silicon-oxygen bonds. Proper understanding and control of
conditions enable the selective cleavage and/or assembly of
silsesquioxane, silicate, POSS, and POSS fragment systems in the
desired manner. The base can also assist in the assembly of POSS
fragments.
[0025] There are a wide range of bases that can be used in the
processes and these include but are not limited to: hydroxide
[OH].sup.-, organic alkoxides [RO].sup.-, carboxylates
[RCOO].sup.-, amides [RNH].sup.-, carboxamides [RC(O)NR].sup.-,
carbanions [R].sup.- carbonate [CO.sub.3].sup.-2, sulfate
[SO.sub.4].sup.-2, phosphate [PO.sub.4].sup.-3, biphosphate
[HPO.sub.4].sup.-2, phosphourus ylides [R.sub.4P].sup.-, nitrate
[NO.sub.3].sup.-, borate [B(OH).sub.4].sup.-, cyanate [OCN].sup.-,
fluoride [F].sup.-, hypochlorite [OCl].sup.-, silicate
[SiO.sub.4].sup.-4, stannate [SnO.sub.4]).sup.-4 basic metal oxides
(e.g. Al.sub.2O.sub.3, CaO, ZnO etc.), amines R.sub.3N and amine
oxides R.sub.3NO, and organomtallics (e.g. RLi, R.sub.2Zn,
R.sub.2Mg, RMgX etc.). Furthermore, the processes taught here are
not limited to the above-mentioned bases; rather any reagent can be
employed which produces a pH spanning the range from 7.1 to 14.
[0026] Alternatively mixtures of bases may also be utilized to
carryout the process. One advantage of such an approach is that
each of the bases in a given mixture can serve different functions.
For example in a mixed base system one base can be used to cleave
silicon-oxygen bonds or silicon-X bonds while a second base is used
to assemble the POSS structure. Thus synergies can exist amongst
several types of bases and these can be utilized to the advantage
and refinement of these processes.
[0027] Silicon-Oxygen Ring Size, Ring Type and Cage Sizes
[0028] The processes discussed in this disclosure are not limited
to the formation of specific sizes of POSS cages (i.e .SIGMA.# in
[(RSiO.sub.1.5).sub.n].sub..SIGMA.#). Similarly the processes
should not be limited to specific types of silsesquioxanes (i.e.
resins, cages or fragments). They can be carried out to manufacture
POSS cages containing four to eighteen or more silicon atoms in the
silicon-oxygen framework. It has been noted that the silicon-oxygen
ring size contained within such POSS systems does however affect
the rate at which cage silicon-oxygen ring opening can occur. For
example rings containing three silicon atoms and three oxygen atoms
as in Formula 1 appear to open faster than the larger rings
containing 4 silicon atoms and 4 oxygen atoms. The relative rate
for the opening of POSS silicon-oxygen rings appears to be six
member rings with three silicon atoms>eight member rings with
four silicon atoms>ten member rings with five silicon
atoms>twelve member rings with six silicon atoms. Selective ring
opening processes therefore can be controlled through the use of
the appropriate base and knowledge of this information allows the
user of these processes to control selective formation of POSS
molecules.
[0029] Effect of the Organic Substituent, Process Solvents and
Process Temperatures
[0030] The processes described in this disclosure are not limited
to POSS systems bearing specific organic groups (defined as R)
attached to the silicon atom of the silicon-oxygen ring systems.
They are amenable to silsesquioxane feedstocks bearing a wide
variety of organic groups (R=as previously defined) and
functionalities (X=as previously defined). The organic substituent
R does have a large effect on the solubility of both the final
product and the starting POSS material. Therefore, it is envisioned
that the different solubilities of the starting silsesquioxanes and
POSS products can be used to facilitate the separation and
purification of the final reaction products. We currently find no
limitation of the process with respect to the type of solvent used
and the processes have been carried out in common solvents
including but not limited to ketones, ethers, dimethylsulfoxide,
CCl.sub.4, CHCl.sub.3, CH.sub.2Cl.sub.2, fluorinated solvents,
aromatics (halogenated and nonhalogenated), aliphatic (halogenated
and nonhalogenated). Other processes can be carried out in
supercritical fluids including but not limited to CO.sub.2,
H.sub.2O, and propane. The variables of solvent type, POSS
concentration, and process temperature should be utilized in the
standard way to match the specific cage opening process to the
equipment available. Preferred solvents for the processes are THF,
MIK, and toluene. In many cases the solvent is an integral
component of the process, which to enables the base to act on the
specific silsesquioxane system, hence solvent effects greatly
influence the degree of ionization of the base used in these
processes.
[0031] Process 1: Formation of POSS Systems from Polymeric
Silsesquioxanes.
[0032] The current methods of preparing POSS molecules from the
acid catalyzed condensation of alkyltrichlorosilanes (RSiCl.sub.3)
is inefficient in that it produces mixtures of POSS cage species
homoleptic (POSS) [(RSiO.sub.1.5).sub.n].sub..SIGMA.#,
functionalized homoleptic POSS
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n].sub..SIGMA.#,
heteroleptic POSS
[(RSiO.sub.1.5).sub.m(RSiO.sub.0.5).sub.n].sub..SIGMA.#- ,
functionalized heteroleptic POSS
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).su- b.n].sub..SIGMA.# and
polymeric silsesquioxanes [RSiO.sub.1.5]).sub..infin- .. In some
cases the undesired polymeric silsesquioxanes are produced in as
much as 75% yield. It is therefore advantageous to develop a
process that can efficiently convert [RSiO.sub.1.5].sub..infin.
into desirable POSS nanostructures or into POSS fragments
[(RXSiO.sub.1.5).sub.n]. Such a process will serve to not only
reduce the amounts of hazardous waste produced in such reactions
but will also reduce the production costs for POSS systems.
[0033] The process developed utilize bases (as defined previously),
in particular hydroxide bases (e.g. sodium hydroxide, potassium
hydroxide, lithium hydroxide, benzyltrimethylammonium hydroxide,
tetramethyl ammonium hyrdoxide etc) to convert polymeric
silsesquioxanes [RSiO.sub.1.5].sub..infin. into homoleptic (POSS)
[RSiO.sub.1.5).sub.n].s- ub..SIGMA.#, functionalized homoleptic
POSS [(RSiO.sub.1.5).sub.n(RXSiO.su- b.1.0).sub.n].sub..SIGMA.#,
heteroleptic POSS [(RSiO.sub.1.5).sub.m(R'SiO.-
sub.1.5).sub.n].sub..SIGMA.#, and functionalized heteroleptic POSS
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n].sub..SIGMA.#.
[0034] In the current process polymeric silsesquioxane
[RSiO.sub.1.5].sub..infin. is dissolved or suspended in a technical
grade solvent such as acetone or methylisobutyl ketone, and
subsequent addition of an aqueous or alcoholic solution of base is
carried out with stirring. Sufficient base should be added to the
reaction mixture so as to produce a basic solution (pH 7.1-14). The
reaction mixture is stirred at room temperature for 3 hours
followed by heating to reflux for an additional 3-12 hours. During
this time the desired POSS cages generally precipitate from the
reaction medium due to their insolubility in the reaction medium.
This precipitation aids in the isolation of the desired products
and ensures that the products (such as the functionalized POSS
species) do not undergo further reaction. In some cases it is
desirable to reduce the volume of solvent by distillation or by
reduced pressure in order to increase product yields or to isolate
soluble POSS products. The desired POSS product is collected by
filtration or decantation and can be purified through exhaustive
washing with water.
[0035] We have found that hydroxide [OH].sup.- bases are highly
effective at concentrations of 1-equivalents (the preferred range
is 2-5 equivalents per silicon atom) per mole of silicon for the
conversion of aliphatic and aromatic polysilsesquioxanes
[RSiO.sub.1.5].sub..infin. into homoleptic (POSS)
[(RSiO.sub.1.5).sub.n].sub..SIGMA.#, functionalized homoleptic POSS
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n- ].sub..SIGMA.#
heteroleptic POSS [(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.-
n].sub..SIGMA.#, and functionalized heteroleptic POSS
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.n(RXSiO.sub.1.0).sub.p].sub..SIG-
MA.#. Hydroxyl-bases are particularly effective for producing
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n].sub..SIGMA.# POSS
species. We have found that milder bases such as acetate and
carbonate are more effective at converting
[RSiO.sub.1.5].sub..infin. systems bearing vinyl or allyl groups.
It is also recognized that the use of other co-reagents may be used
to promote the formation of POSS species from this process. 8
[0036] For the above scheme (Scheme 1) the polymers silsesquioxane
resin is converted into either POSS fragments or nanostructured
POSS cage species depending on the type of base and conditions
employed. The conversion of polysilsesquioxanes
[RSiO.sub.1.5].sub..infin. to POSS-species (homoleptic
[RSiO.sub.1.5).sub.n].sub..SIGMA.# and functionalized heteroleptic
[RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.n(RXS-
iO.sub.1.0)p].sub..SIGMA.#) or into POSS-fragments
[RXSiO.sub.1.5).sub.n] can be selectively controlled through
manipulation of the process variables discussed above. The process
can be conducted using a polysilsesquioxane resin which may contain
only one type of R group to produce homoleptic
[RSiO.sub.1.5).sub.n].sub..SIGMA.# products. Alternatively the
process can be carried out using polysilsesquioxane resins
containing more than one type of R group or with mixtures of
polysilsesquioxanes in which each contains different R groups to
afford heteroleptic
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.n].sub.93 # products. For
the above reaction scheme (Scheme 1) in which mixtures of
homoleptic POSS cages (i.e. R of one POSS cage .noteq.R of the
second POSS cage) are substituted for the polysilsesquioxane resin
the process effectively converts mixtures of homoleptically
substituted POSS cages into heteroleptic POSS cages (functionalized
and nonfunctionalized) that contain statistical distributions of
different R groups per cage. In most cases the POSS fragments and
various homo or heteroleptic nanostructured POSS species can be
separated from one another through crystallization, or extractions
by utilizing the above reaction products and the starting
silsesquioxane.
[0037] The purpose of the base in this process is to cleave
silicon-oxygen bonds in the starting silsesquioxane and thereby
allow for, as well as aid in the rearrangement and formation of the
various POSS fragments, homoleptic and heteroleptic species. The
strength of the base and the base-solvent-silsesquioxane
interaction are critical factors, which enable control over the
type of products formed in these reactions. For example, increasing
the basicity of the medium affords the production of POSS fragments
while less basic conditions coupled with exclusion of water promote
the formation of nonfunctionalized POSS species. Formation of
functionalized POSS systems are favored by carrying out the process
at an intermediate pH with scarce amounts of water for shorter
periods of time.
[0038] Process II: Reactions Between POSS Systems and
Silsesquioxane/Siloxane Fragments.
[0039] The process developed utilized bases (as defined previously)
to convert fragments and functionalized POSS nanostructures
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n].sub..SIGMA.# into
alternate functionalized POSS nanostructures
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).s- ub.n].sub..SIGMA.#. In the
process a POSS fragment is dissolved or suspended in acetone,
benzene or alcoholic solvents after which a solution of base is
added with stirring. In general the reaction conditions employed in
this process are milder than those used in Process I and can
utilize both hydroxide and nonhydroxide bases, while the molar
ratio of base relative to silicon is 1:10 (with 1:1 or 1:2 ration
being preferred). Scheme 2 below illustrates some examples of the
conversion of POSS fragments into POSS cages. 9
[0040] The purpose of the base in this process is to cleave
silicon-oxygen bonds in the starting POSS fragments. The base may
also aid in the assembly of POSS structures from the fragments. A
number of different bases (as defined previously) can be used to
convert POSS fragments into POSS compounds. The net reaction
results in the assembly of POSS fragments into POSS nanostructures,
having either homoleptic or heteroleptic composition. Additionally,
the resulting POSS cages may contain functional groups (i.e.
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.- n].sub..SIGMA.# and
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.n(RXSiO.sub.1-
.0).sub.p].sub..SIGMA.#).
[0041] When mixtures of POSS fragments are utilized they are
incorporated statistically into the POSS structure and their final
composition is based on the stoichiometry of the starting POSS
fragments. In some cases the statistical degree of substitution
between these groups is governed by isomorphism resulting from the
nearly identical topological shape of the R group (e.g. vinyl and
ethyl). Isomorphic governance is often observed for closely related
R groups (e.g. allyl and propyl etc.); however, on occasion the
trend is not followed due to other factors such as rate of
reaction, reagent addition, or solubility between various POSS
fragments and products. For example the reaction of 1 equivalent of
EthylundeconoateSi(OMe).sub.3 or VinylSi(OMe).sub.3 with 7
equivalents of MeSi(OMe).sub.3 results in a molecule of formula 2
of the composition
[(ViSiO.sub.1.5).sub.1(MeSiO.sub.1.5).sub.7].sub..SIGMA.8 or
[(EthylundeconoateSiO.sub.1.5).sub.1(MeSiO.sub.1.5).sub.7].sub..SIGMA.8
despite the topological dissimilarity between the R groups.
[0042] In many cases the desired homo or heteroleptic
nanostructured POSS species can be separated from one another via
crystallization, extraction or by utilizing differences in the
solubilities of the products and the starting POSS fragments.
[0043] An extension of this process is the action of base on
functionalized POSS nanonostructures (i.e.
[(RSiO.sub.1.5).sub.m(RXSiO.su- b.1.0).sub.n].sub..SIGMA.# and and
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).su-
b.n(RXSiO.sub.1.0).sub.p].sub..SIGMA.#) It should be noted that
these systems are chemically similar to a POSS fragments in terms
of their chemical composition. They are different however in their
topology and physical properties such as melting point, solubility
and volatility.
[0044] Scheme 3 illustrates actual reactions that use the
conditions described in Process II as proof that the bases and
conditions described in Process II are effective for the conversion
of functionalized POSS cages (i.e.
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n].sub..SIGMA.# and
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.n(RXSiO.sub.1.0).sub.p].sub..SIG-
MA.#) to desired POSS structures. It should also be noted that in
most cases this process results in an increase in the number of
functionalities (X) on a POSS nanostructure while at the same time
maintaining the original number of silicon atoms contained within
the starting nanostructural framework. This can be desirable for a
variety of subsequent synthetic product manipulations and
derivations. 10
[0045] The first example in Scheme 3 illustrates the selectivity
for the cleavage of 6 membered silicon-oxygen rings in the presence
of 8 membered silicon-oxygen rings by the base, to afford the
trifunctionalized POSS species. This reaction is driven by the
release of greater ring strain energy from the cleavage of the 6
membered silicon-oxygen ring vs. cleavage of the 8 membered
silicon-oxygen ring and is thermodynamically favorable. In the
second example the energy of the twisted conformation is relieved
upon cleavage to form a more open structure.
[0046] A final alternate of process II and one that is of great
utility is that it can also allow for the incorporation of POSS
fragments into existing POSS and POSS silicate nanostructures. This
is a very important and useful aspect of this process because it
allows for the expansion of both POSS and POSS silicate cage
species. This is analogous to a carbon-carbon bond forming
processes in organic systems. Hence this process can be utilized to
prepare larger POSS nanostructures as well as POSS nanostructures
having previously inaccessible sizes. Of particular importance is
the use of this process to prepare nanostructures having odd as
well as even numbers of silicon atoms. 11121314
[0047] Scheme 4 above illustrates examples of
Silsesquioxane/siloxane fragments being inserted into POSS cages.
The net reaction in the examples shown in Scheme 4 is cleavage of
an Si--O--Si bond in the POSS or POSS silicate nanostructure and
insertion of the POSS fragment. This reaction results in the
expansion of the silicon-oxygen ring in the POSS nanostructured
product. Note that the ring expansion in these reactions is in some
cases favored thermodynamically through relief of ring strain in
the silsesquioxane starting material. For example, the reaction of
1 equivalent of Vinyl(OMe).sub.3 with
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub- .6].sub..SIGMA.6 results in
POSS molecule having the composition
[((c-C.sub.6H.sub.11(SiO.sub.1.5).sub.4(c-C.sub.6H.sub.11)(HO)SiO.sub.1.0-
).sub.2(ViSiO.sub.1.0).sub.1).sub..SIGMA.7.
[0048] Mixtures of bases may also be utilized to carryout the
process. One advantage of such an approach is that the use of
different types of base in combination could serve different
functions. For example one base may be particularly useful for the
cleavage of Si--X groups while the second base may function in the
assembly of POSS fragments into POSS nanostructures. Synergistic
effects between different types of base can also be expected.
[0049] Particularly important is the use of mixtures of POSS
fragments (i.e. where R of one fragment .noteq.R of the other
fragment) or POSS fragments having more than one type of R group.
Use of mixed fragments or fragments having mixed R groups affords
heteroleptic POSS species
[(RSiO.sub.1.5).sub.m(RSiO.sub.1.5).sub.n].sub..SIGMA.# which
contain more than one type of R group. In general the POSS
nanostructured products formed contain a statistical mixture of R
which is determined by the stoichiometry of the starting fragments.
As a result, numerous isomers are possible.
[0050] Process III: Selective Opening, Functionalization and
Rearrangement of POSS Nanostructures
[0051] This processes utilizes bases (as defined previously) and
POSS nanostructures having homoleptic
[(RSiO.sub.1.5).sub.n].sub..SIGMA.# and heteroleptic
[(RSiO.sub.1.5).sub.m(R'SiO.sub.1.5).sub.n].sub..SIGMA.#
compositions. The process allows for the conversion of low cost and
easily produced unfunctionalized POSS nanostructures into more
desirable functionalized POSS systems of the type
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1- .0).sub.n].sub..SIGMA.# POSS
nanostuctures of the type
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n].sub.93 # can be used as
stand alone chemical reagents or further derivatized to provide a
diverse array of other POSS nanostructures. This process provides
an entirely new synthetic route for the preparation of very
important and useful incompletely condensed trisilanol reagents
[(RSiO.sub.1.5).sub.4(RXSiO.su- b.1.0).sub.3].sub..SIGMA.7 in
particular where X.dbd.OH.
[0052] Homoleptic POSS nanostructures
[(RSiO.sub.1.5).sub.n].sub..SIGMA.# are readily converted into POSS
nanostructures having the formula
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n].sub..SIGMA.# as well as
POSS fragments having the formula RSiX.sub.3,
[(RXSiO.sub.0.5).sub.n], [(RXSi.sub.1.0).sub.n], or
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n] through the use of
bases as shown in Scheme 5. Note that all possible geometric and
stereochemical isomers for each product are not shown. 15
[0053] Furthermore as a variation of this process it is possible to
interconvert various sizes of POSS nanostructures. For example,
with the proper addition of base
[(RSiO.sub.1.5).sub.6].sub..SIGMA.6 can be either cleaved into a
smaller POSS fragments (e.g. [RSiX.sub.3], [(RXSiO.sub.0.5).sub.n],
[(RXSiO.sub.1.0).sub.n], or
[(RSiO.sub.1.5).sub.m(RXSiO.sub.1.0).sub.n]) or functionalized into
heteroleptic POSS nanostructures of the same size (e.g.
[(RSiO.sub.1.5).sub.4(RXSiO.sub.1.0).sub.2].sub..SIGMA.6) or larger
(e.g. [(RSiO.sub.1.5).sub.4(RXSiO.sub.1.0).sub.3].sub..SIGMA.7) as
shown in Scheme 6. 16
[0054] As a variation of the above it is recognized that this
process can utilize mixtures and distributions of POSS cages as
well as polyhedral oligomeric silicate species (e.g.
[((CH.sub.3).sub.3SiO)SiO.sub.1.5].sub.- 6).sub..SIGMA.6,
[((CH.sub.3).sub.4NO)SiO.sub.1.5].sub.6).sub..SIGMA.6,
[((CH.sub.3).sub.3SiO)SiO.sub.1.5].sub.8).sub..SIGMA.8,
[((CH.sub.3).sub.4NO)SiO.sub.1.5].sub.8).sub..SIGMA.8. In such
cases the base effectively converts cages of several sizes into
functionalized and nonfunctionalized heteroleptic POSS
nanostructures as shown in Scheme 7. This represents an entirely
new synthetic route for the preparation of the very useful
incompletely condensed trisilanol reagents
[(RSiO.sub.1.5).sub.4(RXSiO.sub.1.0).sub.3].sub..SIGMA.7 in
particular where X.dbd.OH. 17
[0055] A final variation of this process is the selective action of
base on heteroleptic POSS nanostructures (see Scheme 8). POSS
nanostructures bearing more than one type of R group per cage
[(RSiO.sub.1.5).sub.m(RSiO- .sub.1.5).sub.n].sub..SIGMA.# are
readily converted through the use of base into functionalized POSS
nanostructures [(RSiO.sub.1.5).sub.m(RXSiO.-
sub.1.0).sub.n].sub..SIGMA.#. Note that all possible geometric and
stereochemical isomers are not shown. 18
[0056] The action of base in the described in the preceding
paragraph can also be controlled selectively so that silicon atoms
can be removed entirely from the silicon oxygen framework of a
polyhedral oligomeric silsesquioxane. This represents an entirely
new synthetic route for the preparation of the very useful
incompletely condensed trisilanol reagents such as
[(RSiO.sub.1.5).sub.4(RXSiO.sub.1.0).sub.3].sub..SIGMA.190 where
X.dbd.OH in particular. Note that not all stereochemical and
geometrical isomers have been shown.
[0057] Additional Material--Section B: Isomers of POSS Systems
[0058] Methods for Controlling Stereochemistry
[0059] Given the three dimensional, nanoscopic nature of POSS
systems it is important to realize that a number of isomeric forms
for any given formula may be produced by the processes taught in
this work. The stereochemistry of these isomers can be controlled
by the through methods taught in this patent however, in some cases
geometrical isomers will still exist. A number of examples are
provided to convey our acknowledgement of the presence of such
isomers and that we in no way limit our claims to any one specific
stereochemical or geometrical isomer.
[0060] Six isomers are possible for difunctional, incompletely
condensed POSS nanostructures
[(RSiO.sub.1.5).sub.4(RXSiO.sub.1.0).sub.2].sub..SIGM- A.6 as shown
in Scheme 9. 19
EXAMPLES
[0061] NMR spectra were recorded on Omega-500 (.sup.1H, 500 MHz;
.sup.13C, 125 MHz; .sup.29Si, 99 MHz). tetrahydrofuran,
methylisobutyl ketone were distilled prior to use. All other
solvents were used as purchased without purification.
Examples for Process I
The Conversion of Polysilsesquioxanes into POSS Fragments and
Nanostructures
[0062] Synthesis of
[((C.sub.6H.sub.5)SiO.sub.1.5).sub.8].sub..SIGMA.8 from
[(C.sub.6H.sub.5)SiO.sub.1.5].sub..infin. resin.
Tetramethylammonium hydroxide (2.0 mL, 5.57 mmol) was added to
[(C.sub.6H.sub.5)SiO.sub.1.5].- sub..infin. resin (13.0 g, 100.6
mmol) in toluene (100 mL) at room temperature. The reaction mixture
was heated to 80.degree. C. for 12 hours, then cooled to room
temperature, acidified with 1N HCl, and filtered to give 12.065 g
of [((C.sub.6H.sub.5)SiO.sub.1.5).sub.8].sub..S- IGMA.8 as a white
solid. Product was verified by EIMS which shows a molecular ion at
1032.5 amu along with daughter ions corresponding to loss of one,
two, and three phenyl groups, respectively, at 954.7, 877.4, and
800.6 amu. The above procedure can be modified for the continuous
and batch production. Alternately, benzene, acetone, and methyl
ethyl ketone can also be used as solvents for this reaction in
place of toluene and KOH can be used instead of tetraalkylammonium
bases. In addition, phenyltrimethoxysilane can be used in place of
phenyl resin to prepare
[((C.sub.6H.sub.5)SiO.sub.1.5).sub.8].sub..SIGMA.8.
[0063] Synthesis of
[((C.sub.6H.sub.5)SiO.sub.1.5).sub.12].sub..SIGMA.12 from
[(C.sub.6H.sub.5)SiO.sub.1.5].sub..infin. resin. Potassium
hydroxide (46.5 g, 829 mmol) was added to
[(C.sub.6H.sub.5)SiO.sub.1.5].sub..infin. resin (1000 g, 7740 mmol)
in THF (7.8 L) at roomtemperature. The reaction mixture was heated
to reflux for 2 days then cooled to room temperature and filtered
to give 443 g of [((C.sub.6H.sub.5)SiO.sub.1.5).sub.12].sub.-
.SIGMA.12 as a microcrystalline white solid. Additional
[(C.sub.6H.sub.5)SiO.sub.1.5).sub..infin. ]resin (912 g, 7059 mmol)
was added to the reaction mixture and the solution was heated to
reflux for 2 days followed by cooling to room temperature and
filtration to give 851 g of
[((C.sub.6H.sub.5)SiO.sub.1.5).sub.12].sub..SIGMA.12 as a
microcrystalline white solid. Characterization was accomplished by
EIMS which shows a molecular ion at 1548.2 amu. The above procedure
can be modified for the continuous and batch production.
Alternately, methylene chloride can also be used as a solvent for
this reaction in place of THF and tetraalkylammonium bases can be
used instead of KOH. In addition, phenyltrimethoxysilane can be
used in place of [((C.sub.6H.sub.5)SiO.sub.- 1.5] resin to prepare
[((C.sub.6H.sub.5)SiO.sub.1.5).sub.12].sub..SIGMA.12- .
[0064] Synthesis of [(c-C.sub.5H.sub.9)SiO.sub.1.5].sub..SIGMA.8
from [((c-C.sub.5H.sub.9)SiO.sub.1.5].sub..infin. resin. A 1.80
gram sample of resin was dissolved into 90 ml of acetone and 90 mg
of NaOH was added to the reaction mixture. The mixture was allowed
to stir for 3 hours at room temperature and then was heated to
reflux overnight. The solution was then cooled and filtered to
obtain 1.40 g (77% yield) of pure product. The white
microcrystalline powder was confirmed by X-ray diffraction and by
HPLC relative to authentic sample.
[0065] Synthesis of
[((CH.sub.2.dbd.CH)SiO.sub.1.5).sub.8].sub..SIGMA.8 from
[(CH.sub.2.dbd.CH)SiO.sub.1.5].sub..infin. resin and
[Si.sub.8O.sub.20][NMe.sub.4].sub..SIGMA.8. A 0.63 g sample of
resin and 2.22 g of tetramethylammonium silicate salt were
dissolved into 20 ml of ethanol and NMe.sub.4OH was added to the
reaction mixture until it became highly basic (pH.about.12). The
mixture was allowed to stir for 6 days at room temperature and then
was filtered to obtain 1.9 g of
[((CH.sub.2.dbd.CH)SiO.sub.1.5).sub.8].sub..SIGMA.8. Alternately a
distribution of cages of
[((CH.sub.2.dbd.CH)SiO.sub.1.5).sub.n].sub..SIGM- A.n, where n=8,
10, 12, 14 can be prepared in a similar manner from the reaction of
CH.sub.2.dbd.CHSi(OCH.sub.3).sub.3 in cyclohexane with NMe.sub.4OH
followed by azeotropic distillation of water and methanol. The
resulting white solid product
[(CH.sub.2.dbd.CH)SiO.sub.1.5].sub..SIG- MA.8.14 is obtained in 40%
yield and is highly desirable as it is highly soluble in common
solvents/reagents and melts at approximately 150.degree. C.
[0066] Synthesis of
[((c-C.sub.6H.sub.9)SiO.sub.1.5).sub.4((c-C.sub.6H.sub-
.11)SiO.sub.1.5).sub.4].sub..SIGMA.8: In a typical reaction, a
mixture of (cyclohex-3-enyl)trichlorosilane and
cyclohexyltrichlorosilane were added with vigorous stirring to a
solution of methanol (200 mL) and water (5 mL). The mixture was
then refluxed for 2 days. Upon cooling, volatiles were removed in
vacuum to afford a resin containing both cyclohexyl-Si and
cyclohex-3-enyl-Si groups. Base catalyzed redistribution of this
resin was accomplished by refluxing for 48 h in methyl isobutyl
ketone (25 ml) with enough
C.sub.6H.sub.5CH.sub.2N(CH.sub.3).sub.3OH to produce a strongly
basic solution (ca. 2 mL of 40% solution in MeOH). Evaporation of
the solvent (25.degree. C., 0.01 Torr) gave a white resinous solid,
which was stirred with acetone (15 mL) and filtered to afford a
mixture
[((R)SiO.sub.1.5).sub.n((R')SiO.sub.1.5).sub.n].sub..SIGMA.8
frameworks possessing both cyclohexyl and cyclohex-3-enyl groups.
Isolated yields are typically 70-80%.
[0067] Note: Excluding enantiomers, there are 22
[((R)SiO.sub.1.5).sub.n((- R')SiO.sub.1.5).sub.n].sub..SIGMA.8
frameworks with the formula
(cyclohexyl).sub.n(cyclohex-3-enyl).sub.8-nSi.sub.8O.sub.12
(0.ltoreq.n.ltoreq.8). All are presumed to be present in the
product mixture. The relative percentage of each compound is most
dependent on the relative amounts of
(cyclohex-3-enyl)trichlorosilane and cyclohexyltrichlorosilane used
in the reaction, but it may also depend on other factors. The
high-resolution .sup.29Si NMR spectrum (C.sub.6D.sub.6) of each
product mixture exhibits a series of well-resolved resonances for
framework Si atoms possessing cyclohexyl and cyclohexenyl groups.
The chemical shifts of these resonances are constant, but the
relative intensities of the resonances depend on the amount of
(cyclohex-3-enyl)SiCl.sub.3 and cyclohexylSiCl.sub.3 used in the
reaction. The product is clearly a mixture of
[((c-C.sub.6H.sub.11)Si-
O.sub.1.5).sub.n((c-C.sub.6H.sub.9)SiO.sub.1.5).sub.n].sub..SIGMA.8
frameworks. The following chemical shift assignments (in
C.sub.6D.sub.6) were made based on comparisons to pure, authentic
samples of [((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.8].sub..SIGMA.8,
[((c-C.sub.6H.sub.9)SiO.sub.1.5).sub.8].sub..SIGMA.8 and
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.n((c-C.sub.6H.sub.9)SiO.sub.1.5).su-
b.n].sub..SIGMA.8:
[0068] Si-cyclohexenyl groups with three Si-cyclohexyl nearest
neighbors: .delta.-67.40
[0069] Si-cyclohexenyl groups with two Si-cyclohexyl nearest
neighbors: .delta.-67.46
[0070] Si-cyclohexenyl groups with one Si-cyclohexyl nearest
neighbors: .delta.-67.51
[0071] Si-cyclohexenyl groups with zero Si-cyclohexyl nearest
neighbors: .delta.-67.57
[0072] Si-cyclohexyl with three Si-cyclohexenyl groups:
.delta.-67.91
[0073] Si-cyclohexyl with two Si-cyclohexenyl groups:
.delta.-67.97
[0074] Si-cyclohexyl with one Si-cyclohexenyl groups:
.delta.-68.02
[0075] Si-cyclohexyl with zero Si-cyclohexenyl groups:
.delta.-68.08
[0076] A sample prepared by reacting equimolar amounts (0.0125 mol)
of (cyclohex-3-enyl)trichlorosilane and cyclohexyltrichlorosilane
as described above exhibited all 8 resonances with relative
integrated intensities of approximately 4:17:17:5:4:21:22:10. A
.sup.13C NMR spectrum of the same sample (in CDCl.sub.3) resembles
a superposition of spectra for pure
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.8].sub..SIGMA.8 and
[((c-C.sub.6H.sub.9)SiO.sub.1.5).sub.8].sub..SIGMA.8, except that
resonances for .sup.13C nuclei close to the Si.sub.8O.sub.12
framework are much broader due to the overlap of many resonances
with slightly different chemical shifts: .delta. 127.45 (br m),
127.07, 27.47, 26.85, 26.63, 25.51, 25.08, 23.15, 22.64, 18.68.
Analogous results were observed when
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.n((c-C.sub.6H.sub.9)SiO.sub.1.-
5).sub.n].sub..SIGMA.8 mixtures were prepared using the following
ratios of (cyclohex-3-enyl)trichlorosilane and
cyclohexyltrichlorosilane:
1 Entry (cyclohex-3-enyl)SiCl.sub.3 cyclohexylSiCl.sub.3 1 2.7 g
(12.5 mmol) 2.72 g (12.5 mmol) 2 2.7 g (12.5 mmol) 8.18 g (37.5
mmol) 3 2.7 g (12.5 mmol) 10.88 g (50 mmol) 4 6.47 g (30 mmol) 9.79
g (45 mmol) 5 1.35 g (6.25 mmol) 9.52 g (44 mmol) 6 5.82 g (27
mmol) 9.79 g (45 mmol) 7 0.68 g (3.13 mmol) 9.52 g (44 mmol)
[0077] Synthesis of [(c-C.sub.6H.sub.9)SiO.sub.1.5].sub..SIGMA.8: A
charge of (cyclohex-3-enyl)trichlorosilane (10.78 g, 0.05 mol) was
added with vigorous stirring to a solution of methanol (200 mL) and
water (5 mL). The mixture was then refluxed overnight. Upon
cooling, volatiles were removed in vacuo to afford
[((c-C.sub.6H.sub.9)SiO.sub.1.5).sub.n].sub..i- nfin. resin in
quantitative yield. The .sup.29Si{.sup.1H} NMR spectrum of the
resin exhibits a broad featureless resonance characteristic of
silsesquioxane resins and no sharp resonances attributable to
discrete polyhedral silsesquioxanes (e.g.,
[((R)SiO.sub.1.5).sub.n].sub..SIGMA.n with n=6, 8, 10, 12, 14).
Base catalyzed redistribution of
[((c-C.sub.6H.sub.9)SiO.sub.1.5).sub.n].sub..infin. resin was
accomplished by refluxing for 48 h in methyl isobutyl ketone (25
ml) with enough C.sub.6H.sub.5CH.sub.2N(CH.sub.3).sub.3OH to
produce a strongly basic solution (ca. 2 mL of 40% solution in
MeOH). Evaporation of the solvent (25.degree. C., 0.01 Torr)) gave
a white resinous solid, which was stirred with acetone (15 mL) and
filtered to afford
[((c-C.sub.6H.sub.9)SiO.sub.1.5).sub.8].sub..SIGMA.8 in 80% yield
(5.33 g) as a white, microcrystalline solid. Characterization data:
.sup.1H NMR (500.2 MHz, CDCl.sub.3, 300 K) .delta. 5.76 (br s, 2H),
2.09 (br m, 4H), 1.92 (br m, 4H), 1.52 (br m, 1H), 1.08 (br m, 1H).
.sup.13C NMR (125.8 MHz, CDCl.sub.3, 300 K) .delta. 127.33, 127.08,
25.46, 25.03, 22.60, 18.60. .sup.29Si NMR (99.4 MHz,
C.sub.6D.sub.6, 300 K) .delta.-67.4. The product was also
characterized by a single crystal X-ray diffraction study.]
[0078] Synthesis of
[(((CH.sub.3).sub.2CH)SiO.sub.1.5).sub.8].sub..SIGMA.8- : Water (1
mL) was added carefully with vigorous stirring to a solution of
(CH.sub.3).sub.2CHSiCl.sub.3 (6.15 g, 34.8 mmol) in methanol (100
mL). The solution was then refluxed for 24 h. Upon cooling, the
solvent was evaporated to afford a quantitative yield of
[i-PrSiO.sub.3/2].sub.n resin as a pale yellow liquid. The
.sup.29Si{.sup.1H} NMR spectrum of the resin exhibits a broad
envelope of resonances characteristic of silsesquioxane resins and
indicates that very little, if any, discrete polyhedral
silsesquioxanes (e.g., [((CH.sub.3).sub.2CH)SiO.sub.1.5].sub.n with
n=6, 8, 10, 12, 14) are present. Base catalyzed redistribution of
the [((CH.sub.3).sub.2CH)SiO.sub.1.5].sub.n resin was accomplished
by refluxing for 6 h in methyl isobutyl ketone (25 ml) with water
(1.4 mL) and enough C.sub.6H.sub.5CH.sub.2N(CH.sub.3).sub.3OH to
produce a strongly basic solution (ca. 1 mL of 40% solution in
MeOH). The crude equilibration mixture was diluted with Et.sub.2O
(200 mL), washed several times with water, dried over anhydrous
MgSO.sub.4 and concentrated to afford
[(((CH.sub.3).sub.2CH)SiO.sub.1.5).sub.8].sub..SIGMA.8 as a white
microcrystalline powder. The yield after one equilibration is
typically 15-30%, but additional
[(((CH.sub.3).sub.2CH)SiO.sub.1.5).sub.8].sub..SIG- MA.8 can be
obtained by base-catalyzed redistribution of
[((CH.sub.3).sub.2CH)SiO.sub.1.5].sub..infin. resin present in the
mother liquors. The compound prepared in this fashion is identical
to [(((CH.sub.3).sub.2CH)SiO.sub.1.5).sub.8].sub..SIGMA.8 prepared
via the method described by Unno (Chemistry Letters 1990, 489)
Characterization data: .sup.1H NMR (500.2 MHz, CDCl.sub.3, 300 K)
.delta. 1.036 (d, J=6.9 Hz, 48H, CH.sub.3); 0.909 (sept, J=7.2 Hz,
8H, CH). .sup.13C NMR (125.8 MHz, CDCl.sub.3, 300 K) .delta. 16.78
(s, CH.sub.3); 11.54 (s, SiCH). .sup.29Si NMR (99.4 MHz,
CDCl.sub.3, 300 K) .delta. -66.3.
[0079] Synthesis of
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5].sub..SIGMA.8- :
(CH.sub.3).sub.2CHCH.sub.2SiCl.sub.3 (8.3 mL, 0.05 mol) was added
with vigorous stirring to a mixture of CH.sub.2Cl.sub.2 (200 mL)
and water (5 mL). The mixture was then refluxed overnight. Upon
cooling, the CH.sub.2Cl.sub.2 layer was decanted, dried over
CaCl.sub.2 (5 g) and evaporated to afford
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5].sub..infin- . resin in
quantitative yield. The .sup.29Si{.sup.1H} NMR spectrum of the
resin exhibits a broad featureless resonance characteristic of
silsesquioxane resins and no sharp resonances attributable to
discrete polyhedral silsesquioxanes (e.g.,
[(((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1- .5).sub.n].sub..SIGMA.n
with n=6, 8, 10, 12, 14). Base catalyzed redistribution of
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5].sub..infin. resin was
accomplished by refluxing for 48 h in methyl isobutyl ketone (25
ml) with enough C.sub.6H.sub.5CH.sub.2N(CH.sub.3).sub.3OH to
produce a strongly basic solution (ca. 2 mL of 40% solution in
MeOH). Evaporation of the solvent (25.degree. C., 0.01 Torr)) gave
a white resinous solid, which was stirred with acetone (15 mL) and
filtered to afford
[(((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub..SIGMA.8] in 30%
yield (1.64 g) as a white, microcrystalline solid. Evaporation of
the acetone solution gives more [i-BuSiO3/2].sub..infin. resin,
which undergoes further base catalyzed redistribution to produce
more
[(((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.8].sub..SIGMA.8. The
combined yield of
[(((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.8].sub..- SIGMA.8
after three resin redistribution reactions is typically greater
than 60%. Characterization data: .sup.1H NMR (500.2 MHz,
C.sub.6D.sub.6, 300 K) .delta. 2.09 (m, 8H, CH); 1.08 (d, J=6.6 Hz,
48H, CH.sub.3); 0.84 (d, J=7.0 Hz, 16H, CH.sub.2). .sup.13C NMR
(125.8 MHz, C.sub.6D.sub.6, 300 K) .delta. 25.6 (s, CH.sub.3); 24.1
(s, CH); 22.7 (s, CH.sub.2). .sup.29Si NMR (99.4 MHz,
C.sub.6D.sub.6, 300 K) .delta. -67.5.
[0080] Preparation of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.4((c-C.sub.6H.-
sub.11)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7 from
[(c-C.sub.6H.sub.11)SiO.s- ub.1.5].sub..infin. Resin:
[(c-C.sub.6H.sub.11)SiO.sub.1.5].sub..infin. resin was prepared in
two steps from C.sub.6H.sub.5SiCl.sub.3, In the first step, water
was added to a toluene solution of phenyltrichlorosilane to produce
[C.sub.6H.sub.5SiO.sub.1.5].sub..infin. resin according to the
procedure reported by Brown (J. Am. Chem. Soc., (1965), 87, 4317).
This [C.sub.6H.sub.5SiO.sub.1.5].sub..infin. resin (1.0 g) was then
dissolved in cyclohexane (50 mL) and hydrogenated to
[(c-C.sub.6H.sub.11)SiO.sub.1.5].sub..infin. resin in a Parr
minireactor (150.degree. C., 220 psi, 48 h) using 10% Pd/C (1.3 g)
as the catalyst. Filtration to remove the catalyst and evaporation
of the solvent in vacuo afforded the
[(c-C.sub.6H.sub.11)SiO.sub.1.5].sub..infin. resin as a white
solid. The .sup.1H NMR spectrum of this resin exhibits broad
featureless resonances characteristic of c-C.sub.6H.sub.11Si groups
and no resonances attributable to C.sub.6H.sub.5Si groups. The
.sup.29Si{.sup.1H} NMR spectrum exhibits a broad featureless
resonance characteristic of cyclohexyl silsesquioxane resins and no
sharp resonances attributable to discrete polyhedral
silsesquioxanes (e.g.,
[((c-C.sub.6H.sub.11)SiO.sub.1.5)].sub..SIGMA.n with n=6, 8, 10,
12, 14).
[0081] Base catalyzed redistribution of
[(c-C.sub.6H.sub.11)SiO.sub.1.5].s- ub..infin. resin (0.5 g) was
accomplished by refluxing in methyl isobutyl ketone (40 ml) with
35% aqueous NEt.sub.4OH (2 mL, 5 mmol) in MIK (40 mL) for 10 h.
After cooling, the solution was decanted and evaporated to dryness
in vacuo to afford a brownish solid. Analysis of this solid by
.sup.29Si{.sup.1H} NMR spectroscopy and HPLC indicated the
formation of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.4((c-C.sub.6H.sub.11)(OH)SiO.sub.1.-
0).sub.3].sub..SIGMA.7 in 10-15% yield.
Examples for Process II
Reactions between POSS Systems and Silsesquioxane/Siloxane
Fragments
[0082] Preparation of
[((CH.sub.3)SiO.sub.1.5).sub.7(CH.sub.3CH.sub.2OOC(C-
H.sub.2).sub.10)SiO.sub.1.5).sub.1].sub..SIGMA.8: One equivalent of
ethylundecanoate triethoxysilane and seven equivalents of
methyltrimethoxy silane (1.9 g) (were added dropwise to a refluxing
solution of acetone (40 ml) and 1 ml of water containing 0.15
equivalents, 235.6 mg) of potassium acetate. The reaction was
refluxed for 3 days cooled and the white crystalline product was
collected via filtration and was washed with MeOH to remove resin.
The product was characterized by MS and X-ray diffraction. A
similar procedure was followed for each of the following
compounds:
[0083]
[((CH.sub.3)SiO.sub.1.5).sub.6(CH.sub.3(CH.sub.2).sub.7)SiO.sub.1.5-
).sub.2].sub..SIGMA.8,
[((CH.sub.3)SiO.sub.1.5).sub.7(CH.sub.2.dbd.CH)SiO.-
sub.1.5).sub.1].sub..SIGMA.8,
[0084]
[((CH.sub.3)SiO.sub.1.5).sub.4(CH.sub.2.dbd.CH)SiO.sub.1.5).sub.4].-
sub..SIGMA.8,
[((CH.sub.3)SiO.sub.1.5).sub.6(CH.sub.2.dbd.CH)SiO.sub.1.5).-
sub.2].sub..SIGMA.8,
[0085]
[((CH.sub.3)SiO.sub.1.5).sub.7(H.sub.2N(CH.sub.2).sub.3)SiO.sub.1.5-
).sub.1].sub..SIGMA.8,
[((C.sub.6H.sub.5)SiO.sub.1.5).sub.7((CH.sub.2.dbd.-
CH)SiO.sub.1.5).sub.1].sub..SIGMA.8,
[0086]
[((CH.sub.3)SiO.sub.1.5).sub.7(H.sub.2N(CH.sub.2).sub.3)SiO.sub.1.5-
).sub.1].sub..SIGMA.8,
[((c-C.sub.5H.sub.9)SiO.sub.1.5).sub.7((CH.sub.3CH.-
sub.2OOC(CH.sub.2).sub.10)SiO.sub.1.0).sub.1].sub..SIGMA.8,
[0087]
[((c-C.sub.5H.sub.9)SiO.sub.1.5).sub.7((CH.sub.2.dbd.CH)SiO.sub.1.0-
).sub.1].sub..SIGMA.8.
[0088] Preparation of
[((c-C.sub.6H.sub.11)SiO.sub.1.5)].sub..SIGMA.6.8: A 1.23 g charge
of [((c-C.sub.6H.sub.11)(OH).sub.2SiOSi(OH).sub.2(c-C.sub.6-
H.sub.11)] was added to ethanol (50"m) followed by the addition of
5 meq of KHCO.sub.3. The reaction mixture was then allowed to react
during reflux for 3 hours then the mixture was made basic through
the addition of Bu.sub.4NOH and refluxed for 2 days. The reaction
was then allowed to cool and neutralized with the addition of
acetic acid and the volatiles removed under reduced pressure. The
residue was washed with MeOH repeatedly and dried. Yield of product
93%. The product was characterized by MS and X-ray diffraction.
[0089] Preparation of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.8].sub..SIGMA.- 8: Mixtures
of [((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.6].sub..SIGMA.6[((c-C-
.sub.6H.sub.11)SiO.sub.1.5).sub.6((c-C.sub.6H.sub.11)(OH)SiO.sub.1.0).sub.-
2].sub..SIGMA.8 and
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.4((c-C.sub.6H.su-
b.11)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7 dissolved in
methylisobutylketone and reacted with 20% aq. Et.sub.4NOH under
reflux for 4 days produce nearly
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.8].sub..S- IGMA.8.
Authenticity of product was verified relative to authentic
sample.
[0090] Preparation of [((CH.sub.3)SiO.sub.1.5)].sub..SIGMA.8: A
1.22 kg (7.5 mole) charge of (CH.sub.3Si(OCH.sub.3).sub.3 was added
to acetone (8 l) followed by the addition of 2.37 equivalents of
Me.sub.4NOH and 405 g of water. The reaction mixture was then
allowed to react during reflux for 24 hours and the product was
then collected by filtration. The product was washed repeatedly
with MeOH and dried. Yield 466.2 g of product 93%. The product was
characterized by MS and X-ray diffraction. A similar procedure can
be used to prepare [(CH.sub.2.dbd.CH)SiO.sub.1.5).s-
ub.8].sub..SIGMA.8.
[(c-C.sub.6H.sub.11)SiO.sub.1.5).sub.8].sub..SIGMA.8. Modification
of this procedure will afford continuous and batch-scale
production.
[0091] Preparation of
[(CH.sub.3CH.sub.2)SiO.sub.1.5).sub.8].sub..SIGMA.8: A similar
procedure to that above for [((CH.sub.3)SiO.sub.1.5).sub.8].sub-
..SIGMA.8 was followed in acetone to produce a
[(CH.sub.3CH.sub.2)SiO.sub.- 1.5)].sub..infin. resin which is then
taken up in THF using KOH to produce
[(CH.sub.3CH.sub.2)SiO.sub.1.5).sub.8].sub..SIGMA.8: .sup.1H NMR
(500 MHz, CDCl.sub.3): .delta.(ppm) 0.602 (q, J=7.9 Hz, 16H), 0.990
(t, J=7.9 Hz, 24H); .sup.13C NMR (125 MHz, CDCl.sub.3):
.delta.(ppm) 4.06, 6.50; .sup.29Si NMR (99.4 MHz, CDCl.sub.3):
.delta.(ppm) -65.42. Modification of this procedure will afford
continuous and batch-scale production.
[0092] Preparation of
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)SiO.sub-
.1.5).sub.n].sub..SIGMA.n n=8, 10. A similar procedure to that
above for [((CH.sub.3)SiO.sub.1.5).sub.8].sub..SIGMA.8 was followed
using KOH to produce
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)SiO.sub.1.5).sub.n].-
sub..SIGMA.n n=8, 10 in quantitative yield. .sup.1H NMR (500 MHz,
CDCl.sub.3): .delta.(ppm) 0.563 (dd, J=8.2, 15.1 Hz, 1H), 0.750
(dd, J=5.6, 15.1 Hz, 1H), 0.902 (s, 9H), 1.003 (d, J=6.6 Hz, 3H),
1.125 (dd, J=6.4, 13.9 Hz, 1H), 1.325 (br d, J=13.9 Hz, 1H), 1.826
(m, 1H); .sup.13C NMR (125 MHz, CDCl.sub.3): .delta.(ppm) 23.72,
24.57, 25.06, 25.31, 25.71, 25.75, 25.78, 26.98, 29.52, 30.22,
30.28, 31.22, 53.99, 54.02, 54.33; .sup.29Si NMR (99.4 MHz,
CDCl.sub.3): .delta.(ppm)-69.93, -67.75
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)SiO.sub.1.5).sub.12].sub..SI-
GMA.12, -67.95
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)SiO.sub.1.5).s-
ub.10].sub..SIGMA.10, -66.95
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)-
SiO.sub.1.5).sub.8].sub..SIGMA.8. EIMS: m/e 1039 (17%, M.sup.+
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)SiO.sub.1.5).sub.10].sub..SI-
GMA.10), 1207 (100%, M.sup.+
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)-
SiO.sub.1.5).sub.8].sub..SIGMA.8. Modification of this procedure
will afford continuous and batch-scale production.
[0093] Preparation of
[(CF.sub.3CH.sub.2CH.sub.2SiO.sub.1.5).sub.8].sub..S- IGMA.8. A
similar procedure to that above for [((CH.sub.3)SiO.sub.1.5).sub-
.8].sub..SIGMA.8 was followed using KOH and methanol as a solvent
to produce the following mixture of products
[(CF.sub.3CH.sub.2CH.sub.2SiO.s- ub.1.5).sub.8].sub..SIGMA.12 97.5%
[(CF.sub.3CH.sub.2CH.sub.2SiO.sub.1.5).- sub.8].sub..SIGMA.10 2.5%
.sup.1H NMR (300 MHz, THF-d.sub.8): .delta.(ppm) 0.978 (m,
CH.sub.2), 2.234 (m, CF.sub.3CH.sub.2); .sup.13C NMR (75.5 MHz,
THF-d.sub.8): .delta.(ppm) 4.99 (s, CH.sub.2), 5.42 (s, CH.sub.2),
28.14 (q, J=30.5 Hz, CF.sub.3CH.sub.2), 28.32 (q, J=30.5 Hz,
CF.sub.3CH.sub.2), 128.43 (q, J=276 Hz, CF.sub.3), 128.47 (q, J=276
Hz, CF.sub.3); .sup.29Si NMR (59.6 MHz, THF-d.sub.8):
.delta.(ppm)-68.38 (T.sub.12), -65.84 (T.sub.11), -65.59
(T.sub.12); .sup.19F {.sup.1H} NMR (376.5 MHz, THF-d.sub.8)
.delta.(ppm)-71.67, -71.66. EIMS: m/e 1715 (100%,
M.sup.+-H.sub.4CF.sub.3).
[0094] Preparation of
[(CH.sub.3(CH.sub.2).sub.16CH.sub.2SiO.sub.1.5).sub.-
n].sub..SIGMA.n where n=8,10,12. A similar procedure to that above
for [((CH.sub.3)SiO.sub.1.5).sub.8].sub..SIGMA.8 was followed to
produce the following mixture of products .sup.1H NMR (500 MHz,
CDCl.sub.3): .delta.(ppm) 0.604 (m, 2H), 0.901 (t, J=7.0 Hz, 3H),
1.280-1.405 (m, 32H); .sup.13C NMR (125 MHz, CDCl.sub.3):
.delta.(ppm) 12.02, 14.15, 22.79, 22.89, 29.49, 29.75, 29.79,
29.85, 29.90, 32.05, 32.76; .sup.29Si NMR (99.4 MHz, CDCl.sub.3):
.delta.(ppm)-70.48, -68.04
[(CH.sub.3(CH.sub.2).sub.16CH.sub.2SiO.sub.1.5).sub.12].sub..SIGMA.12,
-68.22
[(CH.sub.3(CH.sub.2).sub.16CH.sub.2SiO.sub.1.5).sub.10].sub..SIGMA-
.10, -66.31
[(CH.sub.3(CH.sub.2).sub.16CH.sub.2SiO.sub.1.5).sub.8].sub..SI-
GMA.8.
[0095] Preparation of
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.4((CH.-
sub.3).sub.2CHCH.sub.2)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7 from
(CH.sub.3).sub.2CHCH.sub.2Si(OCH.sub.3).sub.3:
Isobutyltrimethoxysilane (93.3 g, 523.3 mmol) was added dropwise to
LIOH.H.sub.2O (10.0 g, 238.3 mmol) and water (8.0 mL, 444 mmol) in
88/12 acetone/methanol (500 mL) at reflux. The reaction mixture was
heated at reflux the was acidified by quenching it into 1N HCl(aq)
(500 mL) and stirring for 2 h. The resulting solid was filtered and
washed with CH.sub.3CN (2.times.175 mL) and air dried. The product
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.4((CH.su-
b.3).sub.2CHCH.sub.2)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7 was
isolated in 94% yield at 98.8% purity. Note that the above
procedure can be adapted to both continuous and batch production
methods.
[0096] Preparation of
[(CH.sub.3CH.sub.2)SiO.sub.1.5).sub.4(CH.sub.3CH.sub-
.2)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7: A similar procedure to
that above for
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.4((CH.sub.3).sub.2CHCH.-
sub.2)(OH)SiO.sub.1.5).sub.3].sub..SIGMA.7 was followed using
acetone and LiOH to produce
[(CH.sub.3CH.sub.2)SiO.sub.1.5).sub.4(CH.sub.3CH.sub.2)(O-
H)SiO.sub.1.0).sub.3].sub..SIGMA.7 as white crystalline solid in
40-80% yield. .sup.1H NMR (500 MHz, CDCl.sub.3): .delta.(ppm) 0.582
(q, J=7.9 Hz, 6H), 0.590 (q, J=7.9 Hz, 2H), 0.598 (q, J=7.9 Hz,
6H), 0.974 (t, J=7.9 Hz, 3H), 0.974 (t, J=7.9 Hz, 9H), 0.982 (t,
J=7.9 Hz, 9H), 6.244 (br, 3H); .sup.13C NMR (125 MHz, CDCl.sub.3):
.delta.(ppm) 3.98 (1), 4.04 (3), 4.50 (3), 6.42 (3), 6.46 (4);
.sup.29Si NMR (99.4 MHz, CDCl.sub.3): .delta.(ppm)-65.85 (3),
-64.83 (1), -56.36 (3). MS (electrospray): m/e 617 (70%,
[M+Na].sup.+), 595 (100%, [M+H].sup.+). Modification of this
procedure will afford continuous and batch-scale production.
[0097] Preparation of
[((CH.sub.3)SiO.sub.1.5).sub.7(CH.sub.3CH.sub.2OOC(C-
H.sub.2).sub.10)SiO.sub.1.5).sub.1].sub..SIGMA.8: One equivalent of
Triethoxyethylundecanoate and seven equivalents of methyltrimethoxy
silane (1.9 g) (were added dropwise to a refluxing solution of
acetone (40 ml) and 1 ml of water containing 0.15 equivalents,
235.6 mg) of potassium acetate. The reaction was refluxed for 3
days cooled and the white crystalline product was collected via
filtration and was washed with MeOH to remove resin. The product
was characterized by MS and X-ray diffraction.
[0098] Preparation of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.4((c-C.sub.6H.-
sub.11)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7 from
[((c-C.sub.6H.sub.11)SiO.-
sub.1.5).sub.6((c-C.sub.6H.sub.11)(OH)SiO.sub.1.0).sub.1].sub..SIGMA.7:
35% aqueous NEt.sub.4OH (20 .mu.L, 0.05 mmol) is added to a THF
(0.5 mL) solution of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.6((c-C.sub.6H.sub.11)(O-
H)SiO.sub.1.0).sub.1].sub..SIGMA.7 (48 mg, 0.05 mmol) and mixed
well through agitation. After 1.5 h at 25.degree. C., several drops
of C.sub.6D.sub.6 were added and .sup.29Si {.sup.1H} NMR spectrum
was recorded. The spectrum matched the data for the previously
reported for basic solutions of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.4((c-C.sub.6H.su-
b.11)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7.
[0099] Preparation of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.2((c-C.sub.6H.-
sub.11)(OH)SiO.sub.1.0).sub.4].sub..SIGMA.6 from [((c-C.sub.6
H.sub.11)SiO.sub.1.5).sub.4((c-C.sub.6H.sub.11)(OH)SiO.sub.1.0).sub.2].su-
b..SIGMA.6:
C.sub.2-symmetry-[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.4((c-C.-
sub.6H.sub.11)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.6 (38 mg, 0.05
mmol) was reacted with 35% aqueous NEt.sub.4OH (20 .mu.L, 0.05
mmol) in THF (0.5 mL) and after 30 minutes at 25.degree. C.,
several drops of C.sub.6D.sub.6 were added and .sup.29Si{.sup.1H}
NMR spectrum was recorded. The spectrum matched the spectrum of
authentic
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.2((c-C.sub.6H.sub.11)(OH)SiO.sub.1.-
0).sub.4].sub..SIGMA.6 prepared by the reaction of
[((c-C.sub.6H.sub.11)Si- O.sub.1.5).sub.6].sub..SIGMA.6 with
aqueous NEt.sub.4OH.
[0100] Preparation
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.4((c-C.sub.6H.sub-
.11)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7 from
[((c-C.sub.6H.sub.11)SiO.sub-
.1.5).sub.6((c-C.sub.6H.sub.11)(OH)SiO.sub.1.0).sub.1].sub..SIGMA.7:
A solution of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.6((c-C.sub.6H.sub.11)(O-
H)SiO.sub.1.0).sub.1].sub..SIGMA.7 (0.46 mmol) and 35% aqueous
NEt.sub.4OH (0.2 mL, 0.49 mmol) was refluxed in THF (5 mL) for 5 h
then neutralized with dilute aqueous HCl. Evaporation of the
volatiles afforded a white solid, which was dissolved in Et.sub.2O
and dried over anhydrous MgSO.sub.4. Filtration and evaporation of
the solvent afforded a white microcrystalline solid in high yield.
Analysis of the product mixture by .sup.29Si NMR spectroscopy
indicated that the major product was
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.4((c-C.sub.6H.sub.11)(OH)SiO.sub.1.-
0).sub.3].sub..SIGMA.7; small amounts of
[((c-C.sub.6H.sub.11)SiO.sub.1.5)- .sub.8].sub..SIGMA.8 were also
present.
[0101] Preparation of
[((c-C.sub.5H.sub.9)SiO.sub.1.5).sub.8((CH.sub.3).su-
b.2SiO.sub.1.0).sub.8] from
[((c-C.sub.5H.sub.9)SiO.sub.1.5).sub.8].sub..S- IGMA.8: Reaction of
[((c-C.sub.5H.sub.9)SiO.sub.1.5).sub.8].sub..SIGMA.8 (2.21 g, 2.28
mmol) and octamethyltetracyclosiloxane (1.35 g, 4.56 mmol) in 2 mL
toluene with Me.sub.4NOH (9.4 mg of 25% solution in MeOH, 0.626
mmol) is allowed for 24 h at 120.degree. C. The mixture is then
quenched with 6 N HCl (1 mL), extracted with Et.sub.2O (3 mL),
evaporated to dryness to give a white pasty solid which contains a
mixture of 70%
[((c-C.sub.5H.sub.9)SiO.sub.1.5).sub.8((CH.sub.3).sub.2SiO.sub.1.0).sub.1-
].sub..SIGMA.9, polydimethylsiloxane, and 29%
[((c-C.sub.5H.sub.9)SiO.sub.- 1.5).sub.8].sub..SIGMA.8. Analysis by
.sup.29Si{.sup.1H} NMR (CDCl.sub.3) spectroscopy revealed
[((c-C.sub.5H.sub.9)SiO.sub.1.5).sub.8((CH.sub.3).s-
ub.2SiO.sub.1.0).sub.1].sub..SIGMA.9 at (.delta. -65.76, -68.30,
-68.34, 2:2:4).
[0102] Preparation of
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.8((5-n-
orbornene-2-ethyl)(CH.sub.3))SiO.sub.1.5).sub.1].sub..SIGMA.9 from
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.6((CH.sub.3).sub.2CHCH.sub.-
2)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8. An Et.sub.2O (5 mL)
solution of
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.6((CH.sub.3).sub.2CHCH.sub.-
2)(OH)SiO.sub.1.0).sub.2)].sub..SIGMA.8 (890 mg, 1.00 mmol) was
added a mixture of dichloromethyl(5-norbornene-2-ethyl)silane
(endo/exo=3/1, 282.3 mg, 1.20 mmol), Et.sub.3N (195 .mu.L, 1.4
mmol), and Et.sub.2O (5 mL) at -35.degree. C. After addition the
resulting mixture was warmed to room temperature and stirred for 20
h. The mixture was hydrolyzed and extracted with diethyl ether,
washed with brine, and dried over Na.sub.2SO.sub.4. Evaporation of
the volatiles gave
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.8((5-norbornene-2-ethyl)(CH-
.sub.3))SiO.sub.1.5).sub.1].sub..SIGMA.9 (720 mg, 0.68 mmol) as a
white powder in 68% yield. .sup.1H NMR (CDCl.sub.3) .delta. 0.10
(s, 9H), 0.12 (s, 3H), 0.48-0.68 (m, 72H), 0.84-1.05 (m, 194H),
1.06-1.36 (m, 18H), 1.40-1.50 (m, 4H), 1.80-1.94 (m, 32H),
1.95-2.03 (m, 3H), 2.55 (br s, 1H), 2.77 (br s, 3H), 2.78-2.83 (m,
4H), 5.93 (q, .sup.3J=5 Hz, .sup.3J=10 Hz, 3H), 6.04 (q, .sup.3J=5
Hz, .sup.3J=10 Hz, 1H), 6.09-6.14 (m, 4H). .sup.13C NMR
(CDCl.sub.3) .delta. -1.11, 15.86, 16.21, 22.58, 23.20, 23.83,
23.98, 24.06, 24.18, 25.76, 25.81, 25.89, 27.71, 29.50, 32.41,
33.10, 41.89, 41.97, 42.09, 42.65, 45.10, 45.20, 46.03, 49.61,
132.35, 136.29, 136.87, 136.96. .sup.29Si NMR (CDCl.sub.3) .delta.
-69.25, -69.23, -69.21, -69.15, -67.04, -21.73, -21.63.
[0103] Preparation
[((CH.sub.3)SiO.sub.1.5).sub.7(CH.sub.2.dbd.CCH.sub.3(O-
)CO(CH.sub.2).sub.3)SiO.sub.1.5).sub.1].sub..SIGMA.8: An Et.sub.2O
(80 mL) solution of Methacryloxypropyltrichlorosilane (0.69 mL,
3.31 mmol) and 1,8-bis(dimethylamino)naphthalene (2.34 g, 10.91
mmol) was added to an Et.sub.2O (20 mL) solution of
[((CH.sub.3)SiO.sub.1.5).sub.4((CH.sub.3)(O-
H)SiO.sub.1.0).sub.3].sub..SIGMA.7 (1.26 g, 2.54 mmol) at
-35.degree. C. The mixture was further stirred at room temperature
for 5 h and then concentrated under reduced pressure. The residue
was extracted with ether. The insoluble materials were filtered.
The filtrate was concentrated to give an oil-like solid. The solid
was passed through a silica gel column using hexane/Et.sub.2O
(50:1) as an eluent. Evaporation of the volatiles gave
[((CH.sub.3)SiO.sub.1.5).sub.7(CH.sub.2.dbd.CCH.sub-
.3(O)CO(CH.sub.2).sub.3)SiO.sub.1.5).sub.1].sub..SIGMA.8 (415 mg,
0.64 mmol) as a white solid in 25% yield. .sup.1H NMR (CDCl.sub.3)
.delta. 0.136 (s, 3H), 0.142 (s, 12H), 0.146 (s, 6H), 0.64-0.72 (m,
2H), 1.72-1.82 (m, 2H), 1.94 (s, 3H), 4.11 (t, J=6.78 Hz, 3H), 5.54
(t, J=1.58 Hz, 1H), 6.10 (br s, 1H). .sup.13C NMR (CDCl.sub.3)
.delta. -4.56, -4.48, 8.24, 18.31, 22.19, 66.46, 125.16, 136.53,
167.46. .sup.29Si NMR (CDCl.sub.3) .delta. -7.71, -6.00, 45.69.
Calcd for C.sub.14H.sub.32O.sub.14Si.sub.8: C, 25.91; H, 4.97.
Found: C, 25.69; H, 4.99.
[0104] Preparation of
[((CH.sub.3C.sub.6H.sub.4SiO.sub.15).sub.8((CH.sub.2-
.dbd.CCH.sub.3)(O)CO(CH.sub.2).sub.3
)(H.sub.3C)SiO.sub.1.0).sub.1].sub..S- IGMA.9: An Et.sub.2O (20 mL)
solution of a mixture of
[((CH.sub.3C.sub.6H.sub.5)SiO.sub.1.5).sub.6((CH.sub.3C.sub.6H.sub.5)(OH)-
SiO.sub.1.0).sub.2].sub..SIGMA.8/[((CH.sub.3C.sub.6H.sub.5)SiO.sub.1.5).su-
b.8].sub..SIGMA.8 (581.9 mg, 4/1, 0.40 mmol) was added a mixture of
dichloromethacryloxypropylmethylsilane (108.8 .mu.L, 0.50 mmol),
Et.sub.3N (139.4 .mu.L, 1.00 mmol), and Et.sub.2O (3 mL) at room
temperature and stirred for 20 h, was then hydrolyzed, and
extracted with diethyl ether. The extract was washed with brine,
dried over Na.sub.2SO.sub.4 and after evaporation of the volatiles
gave
[((CH.sub.3C.sub.6H.sub.4SiO.sub.1.5).sub.8((CH.sub.2.dbd.CCH.sub.3)(O)CO-
(CH.sub.2).sub.3)(H.sub.3C)SiO.sub.1.0).sub.1)].sub..SIGMA.9 (475.5
mg, 0.36 mmol) as a white solid in 89% yield. .sup.1H NMR
(CDCl.sub.3) .delta. 0.43 (s, 3H), 0.85-0.90 (m, 2H), 1.87-1.95 (m,
2H), 1.95 (s, 3H), 2.42 (s, 6H), 2.43 (s, 12H), 2.44 (s, 6H), 4.16
(t, 3J=6.8 Hz, 2H), 5.56 {br s, 1H), 6.11 (br s, 1H), 7.19-7.29 (m,
18H), 7.59-7.68 (m, 10H), 7.71-7.79 (m, 4H). .sup.13C NMR
(CDCl.sub.3) .delta. -0.92, 12.87, 18.24, 21.57, 22.12, 127.14,
127.38, 127.43, 128.49, 128.55, 128.58, 128.64, 133.94, 134.16,
134.19, 134.25, 140.23, 140.39, 140.59, 167.37. .sup.29Si NMR
(CDCl.sub.3) .delta. -78.72, -78.51, -76.98, -18.75.
[0105] Preparation of
[((CH.sub.3C.sub.6H.sub.4SiO.sub.1.5).sub.7((CH.dbd.-
CH.sub.2)(CH.sub.3).sub.2SiO.sub.1.0).sub.3].sub..SIGMA.7: A THF
(15 mL) solution of
[((CH.sub.3C.sub.6H.sub.5)SiO.sub.1.5).sub.8].sub..SIGMA.8, (572.9
mg, 0.50 mmol) was added an aqueous solution of Et.sub.4NOH (35%,
226.2 .mu.L, 0.55 mmol) at room temperature. After addition the
resulting mixture was stirred at the same temperature for 6 h. The
mixture was neutralized with 1N HCl solution and extracted with
diethyl ether. The organic layer was washed with brine, dried over
MgSO.sub.4 and volatiles evaporated to give
[((CH.sub.3C.sub.6H.sub.5)SiO.sub.1.5).sub.4((CH.sub.3-
C.sub.6H.sub.5)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7. The
[((CH.sub.3C.sub.6H.sub.5)SiO.sub.1.5).sub.4((CH.sub.3C.sub.6H.sub.5)(OH)-
SiO.sub.1.0).sub.3].sub..SIGMA.7 was dissolved in an Et.sub.2O (30
mL) and a mixture of chlorodimethylvinylsilane (505 .mu.L, 3.66
mmol), Et.sub.3N (595 .mu.L, 4.27 mmol), and Et.sub.2O (3 mL) was
added at room temperature and stirred for 7 h. The mixture was
hydrolyzed and extracted with diethyl ether washed with brine,
dried over MgSO.sub.4, and evaporated to give a solid.
Recrystallization of the solid from hexane afforded colorless
crystals of [((CH.sub.3C.sub.6H.sub.4SiO.sub.1.5).sub.-
4((CH.sub.3C.sub.6H.sub.5)(OSi(CH.sub.3).sub.2(CH.dbd.CH.sub.2))SiO.sub.1.-
0).sub.3].sub..SIGMA.7 (230 mg, 0.18 mmol) in 36% yield. .sup.1H
NMR (CDCl.sub.3) .delta. 0.38 (s, 18H), 2.33 (s, 9H), 2.34 (s, 9H),
2.39 (s, 3H), 5.90 (dd, .sup.2J=20.4 Hz, .sup.3J=3.8 Hz, 3H), 6.03
(dd, .sup.3J=14.9 Hz, .sup.3J=3.8 Hz, 3H), 6.28 (dd, .sup.2J=20.4
Hz, .sup.3J=3.8 Hz, 3H), 7.01 (d, .sup.3J=7.7 Hz, 12H), 7.19 (d,
.sup.3J=7.7 Hz, 2H), 7.27 (d, .sup.3J=7.7 Hz, 6H), 7.41 (d,
.sup.3J=7.7 Hz, 6H), 7.53 (d, .sup.3J=7.7 Hz, 2H). .sup.13C NMR
(CDCl.sub.3) .delta. 0.42, 21.51, 21.54,, 21.60, 127.51, 127.97,
128.14, 128.26, 128.55, 129.51, 132.26, 134.06, 134.11, 134.17,
138.78, 139.65, 139.77, 140.37. .sup.29Si NMR (CDCl.sub.3) .delta.
-77.81, -77.29, -77.15, -0.50.
[0106] Preparation
[(((CH.sub.3).sub.3SiO)SiO.sub.1.5).sub.6].sub..SIGMA.6 from
[(((CH.sub.3CH.sub.2).sub.4NO)SiO.sub.1.5).sub.6].sub..SIGMA.6: To
a solution of trimethylchlorosilane (140.0 mL, 1.10 mol), heptane
(500 mL), and N,N-dimethylformamide (200 mL) was added a powder of
[(((CH.sub.3CH.sub.2).sub.4NO)SiO.sub.1.5).sub.6].sub..SIGMA.6
(11.9 g, 10.0 mmol) over a period of ca. 30 min at 0.degree. C.
After addition of all the
[(((CH.sub.3CH.sub.2).sub.4NO)SiO.sub.1.5).sub.6].sub..SIGMA.6 the
mixture was stirred for an additional 30 min then allowed to warm
to room temperature overnight. An ice-water (1 L) was added and the
mixture stirred for 30 min. The organic layer was washed with water
until neutral, dried over MgSO.sub.4, and concentrated. To the
residue was added a methanol and the soluble part was removed by
filtration to leave a pure
[(((CH.sub.3).sub.3SiO)SiO.sub.1.5).sub.6].sub..SIGMA.6 (4.1 g,
4.84 mmol) as a white solid in 48% yield: .sup.1H NMR (CDCl.sub.3)
.delta. 0.17 (s, 54H). .sup.13C NMR (CDCl.sub.3) .delta. 1.18.
.sup.29Si NMR (CDCl.sub.3) .delta. 14.27, -99.31.
[0107] Preparation of
[(((CH.sub.3).sub.3SiO)SiO.sub.1.5).sub.6((CH.sub.2.-
dbd.CH)(CH.sub.3).sub.2SiO.sub.1.0).sub.4].sub..SIGMA.6: To an
Et.sub.2O (5 mL) solution of vinyldimethylchlorosilane (121.5
.mu.L, 0.88 mmol) and NEt.sub.3 (139.4 .mu.L, 1.00 mmol) was added
an Et.sub.2O solution of
[(((CH.sub.3).sub.3SiO)SiO.sub.1.5).sub.2(((CH.sub.3).sub.3SiO)(OH)SiO.su-
b.1.0).sub.4].sub..SIGMA.6 (174.7 mg, 0.20 mmol) at room
temperature. The mixture was stirred at room temperature for 4 h
and then concentrated under reduced pressure. The residue was
extracted with hexane. The insoluble materials were filtered. The
filtrate was concentrated to give a spectroscopic pure
[(((CH.sub.3).sub.3SiO)SiO.sub.1.5).sub.6((CH.sub.2.-
dbd.CH)(CH.sub.3).sub.2SiO.sub.1.0).sub.4].sub..SIGMA.6 (225.6 mg,
0.18 mmol) as a white foam solid in 92% yield: .sup.1H NMR
(CDCl.sub.3) .delta. 0.13 (s, 54H), 0.14 (s, 12H), 0.18(s, 12H),
5.73 {d, J=4.0 Hz, 2H), 5.77 (d, J=4.0 Hz, 2H), 5.91 (d, J=4.0 Hz,
2H), 5.94 (d, J=4.0 Hz, 2H), 6.11 (d, J=15.0 Hz, 2H), 6.15 (d,
J=15.0 Hz, 2H). .sup.13C NMR (CDCl.sub.3) .delta. 0.11, 1.52, 1.62,
132.00, 138.79. .sup.29Si NMR (CDCl.sub.3) .delta. 11.24, 10.17,
-1.35, -108.31, -108.70. MS (ESI): Calcd for
C.sub.34H.sub.90O.sub.17Si.sub.16Na, 1243.2. Found: 1243.6.
[0108] Preparation of
[(((CH.sub.3).sub.3SiO)SiO.sub.1.1).sub.6((C.sub.6H.-
sub.5)SiO.sub.1.5).sub.1((CH.sub.2.dbd.CCH.sub.3)(O)CO
(CH.sub.2).sub.3SiO.sub.1.5).sub.1].sub..SIGMA.8 from
[(((CH.sub.3).sub.3SiO)SiO.sub.1.5).sub.4((C.sub.6H.sub.5)(OH)SiO.sub.1.0-
).sub.1(((CH.sub.3).sub.3SiO) (OH)SiO.sub.1.0).sub.2].sub..SIGMA.7:
An Et.sub.2O (8 mL) solution of methacryloxypropyltrichlorosilane
(340.3 .mu.L, 1.63 mmol) and NEt.sub.3 (748.5 .mu.L, 5.37 mmol) was
added to an Et.sub.2O (7 mL) solution of
[(((CH.sub.3).sub.3SiO)SiO.sub.1.5).sub.4((C-
.sub.6H.sub.5)(OH)SiO.sub.1.0).sub.1(((CH.sub.3).sub.3SiO)(OH)SiO.sub.1.0)-
.sub.2].sub..SIGMA.7 (817.0 mg, 0.81 mmol) at -35.degree. C. and
the mixture was stirred at room temperature for 6 h and then
concentrated under reduced pressure. The residue was extracted with
hexane, insoluble materials were filtered, and the filtrate was
concentrated to give an oil. The oil was purified using a silica
gel column and hexane/Et.sub.2O (50:1) as an eluent. Evaporation of
the volatiles gave
[(((CH.sub.3).sub.3SiO)SiO.sub.1.5).sub.6((C.sub.6H.sub.5)SiO.sub.1.5).su-
b.1
((CH.sub.2.dbd.CCH.sub.3)(O)CO(CH.sub.2).sub.3SiO.sub.1.5).sub.1].sub.-
.SIGMA.8 (210.0 mg, 0.18 mmol) as a white solid in 25% yield.
.sup.1H NMR (CDCl.sub.3) .delta. 0.13 (s, 18H), 0.16 (s, 18H), 0.17
(s, 9H), 0.18 (s, 9H), 0.73-0.80 .mu.m, 2H), 1.77-1.85 (m, 2H),
1.93 (s, 3H), 4.11 (t, J=6.62 Hz, 2H), 5.54 (t, J=1.58 Hz, 1H),
6.09 (br s, 1H), 7.35-7.41 (m, 2H), 7.43-7.48 (m, 1H), 7.66-7.72
(m, 2H). .sup.13C NMR (CDCl.sub.3) .delta. 1.24, 7.95, 18.30,
22.11, 66.39, 125.22, 127.70, 130.22, 130.69, 134.08, 136.41,
167.37. .sup.29Si NMR (CDCl.sub.3) .delta. --109.06, -108.88,
-108.82, -78.86, -65.60, 12.55, 12.58, 12.59. Calcd for
C.sub.31H.sub.70O.sub.20Si.sub.14: C, 32.21; H, 6.10. Found: C,
31.99; H, 6.35. MS (ESI) Calcd for 1177.1 [M+Na].sup.+, 1193.1
[M+K].sup.+. Found: 1177.2 [M+Na].sup.+, 100%; 1193.2 [M+K].sup.+,
10%.
Examples for Process III
Selective Opening, Functionalization and Rearrangement of POSS
Nanostructures
[0109] Preparation of
[((CH.sub.2.dbd.CH)SiO.sub.1.5).sub.6((CH.sub.2.dbd.-
CH)(HO)SiO.sub.1.0).sub.2].sub..SIGMA.8 from
[((CH.sub.2.dbd.CH)SiO.sub.1.- 5).sub.8].sub..SIGMA.8: An aqueous
solution of NEt.sub.4OH (33%, 2 mL, 0.25 mmol) in THF (10 mL,
-35.degree. C.) was added to a stirred solution of
[((CH.sub.2.dbd.CH)SiO.sub.1.5).sub.8].sub..SIGMA.8 (2.95 g, 4.66
mmol) in 1:1:1 THF/CH.sub.2Cl.sub.2/isopropanol (300 mL), which was
chilled in a -35.degree. C. (1:1 methanol/water and N.sub.2) cold
bath. After 4.3 hours the reaction was quenched with 1M HCl (20 mL,
-35.degree. C.) and the solution was washed with 1M HCl (2.times.40
mL), water (2.times.40 mL), and sat. aq. NaCl solution (40 mL).
After drying over Na.sub.2SO.sub.4, and removal of the solvent in
vacuo (25.degree. C., 0.01 Torr) a white solid (3.01 g, 99%) was
isolated. The product
[((CH.sub.2.dbd.CH)SiO.sub.1.5).sub.6((CH.sub.2.dbd.CH)(HO)SiO.sub.1.0).s-
ub.2].sub..SIGMA.8 prepared by this procedure is spectroscopically
pure. Additional purification can be accomplished through
recrystallization from CH2Cl.sub.2/hexanes/acetic acid (25.degree.
C.). .sup.1H NMR (CDCl.sub.3, 500.2 MHz, 25.degree. C.): .delta.
6.12-5.74 (m, SiCH.dbd.CH.sub.2), 5.7 (br, SiOH). .sup.13C{.sup.1H}
NMR (CDCl.sub.3, 125.7 MHz, 25.degree. C.): .delta. 137.00, 136.87,
136.81 (s, CH.sub.2, rel. int. 1:1:2), 129.75, 129.17, 128.80 (s,
SiCH, rel. int. 1:2:1). .sup.29Si{.sup.1H} NMR (CDCl.sub.3, 99.4
MHz, 25.degree. C.): .delta. -71.39 (s, SiOH), -79.25, -80.56 (s,
SiCH, rel. int. 1:2). Mass Spectrum (ESI) m/z calcd for
C.sub.16H.sub.26O.sub.13Si.sub.8: [M+H].sup.+ 650.96, found 651.2
(20%); [M+Na].sup.+ 672.94, found 673.1 (100%). Mass Spectrum (EI)
m/z calculated for C.sub.16H.sub.26O.sub.13Si.sub.8: [M].sup.+
649.9528, found 649.9532 (4%); [M-C.sub.2H.sub.3].sup.+ 622.9,
found 623.2 (100%).
[0110] Preparation of
[((Boc-NHCH.sub.2CH.sub.2CH.sub.2)SiO.sub.1.5).sub.6-
((Boc-NHCH.sub.2CH.sub.2CH.sub.2)
(HO)SiO.sub.1.0).sub.2].sub..SIGMA.8 from
[((Boc-NHCH.sub.2CH.sub.2CH.sub.2)SiO.sub.1.5).sub.8].sub..SIGMA.8:
A solution of
[((Boc-NHCH.sub.2CH.sub.2CH.sub.2)SiO.sub.1.5).sub.8].sub..-
SIGMA.8 (0.11 mmol) in 1:1:1 CH.sub.2Cl.sub.2/THF/isopropanol
(-35.degree. C., 7.5 mL) and aq. NEt.sub.4OH (35 wt %, 50 .mu.L,
0.13 mmol) was stirred at -35.degree. C. for 2 h. Addition of
CH.sub.3CO.sub.2H (0.1 mL, -35.degree. C.), extraction with a
saturated aqueous NaCl solution (3.times.10 mL), drying over
Na.sub.2SO.sub.4, and removal of the solvent in vacuo (25.degree.
C., 0.001 Torr) afforded [((Boc-NHCH.sub.2CH.sub.2CH-
.sub.2)SiO.sub.1.5).sub.6((Boc-NHCH.sub.2CH.sub.2CH.sub.2)(HO)SiO.sub.1.0)-
.sub.2].sub..SIGMA.8 as a colorless paste in a 63% yield.
.sup.29Si{.sup.1H} NMR (CDCl.sub.3, 99.4 MHz, 25.degree. C.):
.delta. -57.798, -65.674, -67.419 (s, rel. int. 1:1:2). Mass
Spectrum (ESI) m/z calcd for
C.sub.64H.sub.130N.sub.8O.sub.29Si.sub.8: [M+Na].sup.+ 1721.7,
found 1722.1.
[0111] Preparation of
[((Cbz-Pro-NHCH.sub.2CH.sub.2CH.sub.2)SiO.sub.1.5).s-
ub.6((Cbz-Pro-NHCH.sub.2CH.sub.2CH.sub.2)
(HO)SiO.sub.1.0).sub.2].sub..SIG- MA.8 from
[((Cbz-Pro-NHCH.sub.2CH.sub.2CH.sub.2)SiO.sub.1.5).sub.8].sub..S-
IGMA.8: A solution of
[((Cbz-Pro-NHCH.sub.2CH.sub.2CH.sub.2)SiO.sub.1.5).s-
ub.8].sub..SIGMA.8 (0.11 mmol) in 1:1:1
CH.sub.2Cl.sub.2/THF/isopropanol (-35.degree. C., 7.5 mL) and aq.
NEt.sub.4OH (35 wt %, 50 .mu.L, 0.13 mmol) was stirred at
-35.degree. C. for 2 h. Addition of CH.sub.3CO.sub.2H (0.1 mL,
-35.degree. C.), extraction with a saturated aqueous NaCl solution
(3.times.10 mL), drying over Na.sub.2SO.sub.4, and removal of the
solvent in vacuo (25.degree. C., 0.001 Torr) afforded
[((Cbz-Pro-NHCH.sub.2CH.sub.2CH.sub.2)SiO.sub.1.5).sub.6((Cbz-Pro-NHCH.su-
b.2CH.sub.2CH.sub.2)(HO)SiO.sub.1.0).sub.2].sub..SIGMA.8 as a
colorless paste in 77% yield. .sup.29Si{.sup.1H} NMR (CDCl.sub.3,
99.4 MHz, 25.degree. C.): .delta. -58.4, -65.543, -67.470 (s, rel.
int. 1:1:2). Mass Spectrum (ESI) m/z calcd for
C.sub.128H.sub.170N.sub.16O.sub.37Si.su- b.8: [M+Na].sup.+ 2772.54,
found 2772.9.
[0112] Preparation of
[((MeO.sub.2CCH.sub.2CMe.sub.2CH.sub.2CH.sub.2CH.sub-
.2)SiO.sub.1.5).sub.6((MeO.sub.2CCH.sub.2CMe.sub.2CH.sub.2
CH.sub.2CH.sub.2)(HO)SiO.sub.1.0).sub.2].SIGMA..sub.8 from
[((MeO.sub.2CCH.sub.2CMe.sub.2CH.sub.2CH.sub.2CH.sub.2)SiO.sub.1.5).sub.8-
].sub..SIGMA.8: A solution of
[((MeO.sub.2CCH.sub.2CMe.sub.2CH.sub.2CH.sub-
.2CH.sub.2)SiO.sub.1.5).sub.8].sub..SIGMA.8 (0.11 mmol) in 1:1:1
CH.sub.2Cl.sub.2/THF/isopropanol (-35.degree. C., 7.5 mL) and aq.
NEt.sub.4OH (35 wt %, 50 L, 0.13 mmol) was stirred at -35.degree.
C. for 2 h. Addition of CH.sub.3CO.sub.2H (0.1 mL, -35.degree. C.),
extraction with a saturated aqueous NaCl solution (3.times.10 mL),
drying over Na.sub.2SO.sub.4, and removal of the solvent in vacuo
(25.degree. C., 0.001 Torr) afforded
[((MeO.sub.2CCH.sub.2CMe.sub.2CH.sub.2CH.sub.2CH.sub-
.2)SiO.sub.1.5).sub.6((MeO.sub.2CCH.sub.2CMe.sub.2CH.sub.2CH.sub.2CH.sub.2-
)(HO) SiO.sub.1.0).sub.2].sub..SIGMA.8 as a colorless paste in 66%
yield. .sup.29Si{.sup.1H} NMR (CDCl.sub.3, 99.4 MHz, 25.degree.
C.): .delta.-57.551, -64.981, -66.841 (s, rel. int. 1:1:2). Mass
Spectrum (ESI) m/z calculated for
C.sub.64H.sub.122O.sub.29Si.sub.8: [M+Na].sup.+ 1601.61, found
1602.0.
[0113] Preparation of
[(((CH.sub.3).sub.3SiO)SiO.sub.1.5).sub.2(((CH.sub.3-
).sub.3SiO)(OH)SiO.sub.1.0).sub.4].sub..SIGMA.6: To a THF (4 mL)
solution of [(((CH.sub.3).sub.3SiO)SiO.sub.1.5).sub.6].sub..SIGMA.6
(169.5 mg, 0.20 mmol) was added an aqueous solution of NEt.sub.4OH
(35%, 82.3 .mu.L, 0.20 mmol) at -40.degree. C. The resulting
mixture was stirred between -40 to -25.degree. C. for 40 min. The
mixture was neutralized with aqueous solution of HCl (1N, 3 mL) and
extracted with diethyl ether. The organic layer was washed with
brine, dried over MgSO.sub.4, and evaporated to give a
spectroscopic pure [(((CH.sub.3).sub.3SiO)SiO.sub.1.-
5).sub.2(((CH.sub.3).sub.3SiO)(OH)SiO.sub.1.0).sub.4].sub..SIGMA.6
(174.7 mg, 0.20 mmol) as a white wax solid in 99% yield. .sup.1H
NMR (CDCl.sub.3) .delta. 0.14 (s, 54H). .sup.13C NMR (CDCl.sub.3)
.delta. 1.24, 1.28. .sup.29Si NMR (CDCl.sub.3) .delta. 12.44,
12.19, -100.12, -109.27.
[0114] Preparation of
[(((H.sub.3C).sub.3SiO)SiO.sub.1.5).sub.6(((H.sub.3C-
).sub.3SiO)(OH)SiO.sub.1.0).sub.2(((CH.sub.2.dbd.CH)
(OH)SiO.sub.1.0).sub.1].sub..SIGMA.7: The starting polyhedral
oligomeric silicate
[(((H.sub.3C).sub.3SiO)SiO.sub.1.5).sub.6].sub..SIGMA.6 was
prepared via a procedure analogous to that published by Harrison et
al. Main Group Metals Chemistry (1997) vol 20, pp. 137-141. A
solution of Vinyltrimethoxysilane (0.04 mL, 0.26 mmol) and aqueous
NEt.sub.4OH (0.1 mL, 0.25 mmol) was prereacted for 10 minutes and
then added to a solution of
[(((H.sub.3C).sub.3SiO)SiO.sub.1.5).sub.6].sub..SIGMA.6 (198 mg,
0.23 mmol) and was stirred for 15 minutes at room temperature. The
reaction was then neutralized through the addition of dilute HCl
and the solvent was removed under reduced pressure. The residue was
then taken up in diethylether filtered and dried over anhydrous
MgSO.sub.4. Filtration and evaporation of the solvent afforded a
yellow oil (2.31 mg, 0.002 mol) in 10.2% yield. Selected
characterization data: .sup.29Si{.sup.1H} NMR (99.3 MHz,
CDCl.sub.3, 25.degree. C.) .delta. -99.8, -100.1, -108.0, -108.9.
MS (ESI, 100% MeOH): m/e 977.1 ([M+Na].sup.+.
[0115] Preparation of
[((CH.sub.3CH.sub.2)SiO.sub.1.5).sub.6((CH.sub.3CH.s-
ub.2)(HO)SiO.sub.1.0).sub.2].sub..SIGMA.8 from
[((CH.sub.3CH.sub.2)SiO.sub- .1.5).sub.8].sub..SIGMA.8: A
CH.sub.2Cl.sub.2/i-PrOH/THF(10/10/10 mL) solution of
[((CH.sub.3CH.sub.2)SiO.sub.1.5).sub.8].sub..SIGMA.8 (259.7 mg,
0.40 mmol) was added an aqueous solution of Et.sub.4NOH (35%, 493.5
.mu.L, 1.20 mmol) at -20.degree. C. After addition the resulting
mixture was stirred at the same temperature for 7 h. The mixture
was neutralized with 1N HCl solution and extracted with diethyl
ether. The organic layer was washed with brine, dried over
Na.sub.2SO.sub.4. Evaporation of the volatiles gave
spectroscopically pure [((CH.sub.3CH.sub.2)SiO.sub.1.5).su-
b.6((CH.sub.3CH.sub.2)(HO)SiO.sub.1.0).sub.2].sub..SIGMA.8 (263.5
mg, 0.39 mmol) as a white solid in 99% yield. .sup.1H NMR
(CDCl.sub.3) .delta. 0.54-0.66 (m, 16H), 0.93-1.04 (m, 24H), 5.21
(br s, 2H). .sup.13C NMR (CDCl.sub.3) .delta. 3.94, 4.36, 4.41,
6.42, 6.46, 6.50. .sup.29Si NMR (CDCl.sub.3) .delta. -66.73,
-64.95, -57.63. Calcd for C.sub.16H.sub.42O.sub.13Si.sub.8: C,
28.80; H, 6.35. Found: C, 28.78; H, 6.43.
[0116] Preparation Of
[(((CH.sub.3).sub.2CH)SiO.sub.1.5).sub.6(((CH.sub.3)-
.sub.2CH)(HO)SiO.sub.1.0).sub.2].sub..SIGMA.8 from
[(((CH.sub.3).sub.2CH)S- iO.sub.1.5).sub.8].sub..SIGMA.8:
[(((CH.sub.3).sub.2CH)SiO.sub.1.5).sub.8]- .SIGMA..sub.8 (302 mg,
0.397 mmol) was dissolved in 15 mL of solvents' mixture
(iso-propanol:CH.sub.2Cl.sub.2:THF=1:1:1). The aqueous 35% solution
of EtN.sub.4OH (0.8 mL) was added to the solution of
[(((CH.sub.3).sub.2CH)SiO.sub.1.5).sub.8].sub..SIGMA.8 at
-12.degree. C. After 7 hours, the reaction mixture was decanted,
extracted with Et.sub.2O (4.times.3 mL). The extract was dried over
anhydrous Na.sub.2SO.sub.4, then evaporated in vacuo, obtained a
yellow solid which was purified by column chromatography
(SiO.sub.2, 60% CH.sub.2Cl.sub.2 in hexanes) to afford a
spectroscopically pure powder (189 mg, 61%). .sup.1H NMR (500 MHz,
CDCl.sub.3, 25.degree. C.): .delta. 3.90 (br s, SiOH, 2H), 1.03 (br
m's, 48H), 0.91 (br m's, 8H. .sup.13C{.sup.1H} NMR (125 MHz,
CDCl.sub.3, 25.degree. C.): .delta. 16.91, 16.79, 16.64 (8:4:4 for
CH.sub.3), 11.91, 11.77, 11.38 (4:2:2 for CH), .sup.29Si{.sup.1H}
NMR (99 MHz, CDCl.sub.3, 25.degree. C.): .delta. -57.92, -65.29,
-67.70 (2:2:4). IR (25.degree. C., KBr, cm.sup.-1): 3352, 2950,
2869, 1466, 1260, 1112. MS (ESI, 100% MeOH): m/e 802.0
{[M+Na].sup.+, 100%}, 779.1 (M.sup.+, 70%). Anal. Calculated for
C.sub.24H.sub.57O.sub.13Si.sub.8 (found): C, 37.03 (36.92), H, 7.38
(7.54).
[0117] Preparation of
[((c-C.sub.6H.sub.9)SiO.sub.1.5).sub.4((c-C.sub.6H.s-
ub.9)(OH)SiO.sub.1.0).sub.2((CH.sub.2.dbd.CH)(OH)SiO.sub.1.0).sub.1].sub..-
SIGMA.7: A solution of 35% aqueous NEt.sub.4OH (0.1 mL, 0.25 mmol)
was added to a solution of
[(c-C.sub.6H.sub.9)SiO.sub.1.5].sub..SIGMA.6 (205 mg, 0.25 mmol)
and VinylSi(OMe).sub.3 in THF (2.5 mL). The solution was stirred
for 1 h then neutralized with dilute aqueous HCl. Evaporation of
the volatiles afforded a white resin, which was dissolved in
Et.sub.2O and dried over anhydrous MgSO.sub.4. Filtration and
evaporation of the solvent afforded a white solid in high mass
yield. Analysis by multinuclear NMR spectroscopy and electrospray
mass spectrometry indicated that the product mixture contained a
.about.6:1 mixture of
[((c-C.sub.6H.sub.9)SiO.sub.1.5).sub.2((c-C.sub.6H.sub.9)(OH)SiO.sub.1.0)-
.sub.4] and
[((c-C.sub.6H.sub.9)SiO.sub.1.5).sub.4((c-C.sub.6H.sub.9)(OH)S-
iO.sub.1.0).sub.2((CH.sub.2.dbd.CH)(OH)SiO.sub.1.0).sub.1].sub..SIGMA.7.
Selected characterization data: Si{.sup.1H} NMR (99.3 MHz,
CDCl.sub.3, 25.degree. C.) .delta. -60.1 (s, 2 Si, Cy--Si--OH),
-68.2 (s, 1 Si), -69.1 (s, 2 Si), -69.7 (s, 1 Si), -72.0 (s, 1 Si,
V--Si--OH). .sup.1H NMR (500 MHz, CDCl.sub.3, 25.degree. C.)
.delta. 5.90 (m, 3H, --CH.dbd.CH.sub.2); 1.65, 1.16 (m, 66H,
C.sub.5H.sub.11). .sup.13C{.sup.1H} NMR (125.8 MHz, C.sub.6D.sub.6,
25.degree. C.) .delta. 135.4 (s, .dbd.CH.sub.2); 130.4 (s,
--CH.dbd.); 27.53, 27.47, 26.82, 26.67, 26.59, 26.56 (s, CH.sub.2);
23.81, 23.59, 23.36, 23.10 (s, CH). MS (ESI, 100% MeOH): m/e 917
([M+H].sup.+, 75%); 939 ([M+Na].sup.+, 100
[0118] Reaction of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.6].sub..SIGMA.6 with
NEt.sub.4OH at room temperature: A solution of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.6].sub..SIGMA.6 (200 mg, 0.24
mmol) and 35% aqueous NEt.sub.4OH (0.1 mL, 0.25 mmol) in THF (2.5
mL) was stirred at 25.degree. C. for 4 h then neutralized with
dilute aqueous HCl. Evaporation of the volatiles afforded a white
solid, which was dissolved in Et.sub.2O and dried over anhydrous
MgSO.sub.4. Filtration and evaporation of the solvent afforded a
white solid in high mass yield. Analysis of the product mixture by
.sup.29Si NMR spectroscopy indicated that it contained mainly
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.2(c-C.sub.-
6H.sub.11)(OH)SiO.sub.1.0).sub.4].sub..SIGMA.6 (>60%) and
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.4(c-C.sub.6H.sub.11)(OH)SiO.sub.1.0-
).sub.3].sub..SIGMA.7 (>30%).
[0119] Preparation of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.6((c-C.sub.6H.-
sub.11)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8 from
[((c-C.sub.6H.sub.11)SiO.- sub.1.5).sub.8].sub..SIGMA.8: A solution
of [((c-C.sub.6H.sub.11)SiO.sub.1- .5).sub.8].sub..SIGMA.8 (250 mg,
0.23 mmol) and 35% aqueous NEt.sub.4OH (0.1 mL, 0.25 mmol) in THF
(3 mL) was stirred at room temperature for 1 h and then neutralized
with an aqueous solution of HCl. The volatiles were evaporated in
vacuo to afford a white solid, which was dissolved in Et.sub.2O and
dried over anhydrous MgSO.sub.4. Filtration and evaporation of the
solvent afforded a white microcrystalline solid in high yield.
Analysis by .sup.29Si NMR spectroscopy and electrospray MS
indicated that the product mixture contained .about.76% (by
.sup.29Si NMR)
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.6((c-C.sub.6H.sub.11)(OH)SiO.sub.1.-
0).sub.2].sub..SIGMA.8: .sup.29Si{.sup.1H} NMR (99.3 MHz,
C.sub.6D.sub.6, 25.degree. C.) .delta. -60.4, -67.2, -69.8 (s,
1:1:2), as well as smaller amounts of unreacted
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.8].sub..SIGMA.- 8 (.delta.
-68.2, .about.20%). Small .sup.29Si NMR resonances attributable to
tetrasilanol
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.6((c-C.sub.6H.sub.1-
1)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8 were also observed, as well
as prominent peaks in the electrospray mass spectrum for the
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.6((c-C.sub.6H.sub.11)(OH)SiO.sub.1.-
0).sub.2].sub..SIGMA.8 (1117.36 for the ion with H+ and 1139 for
the ion with Na+). Spectroscopic data for
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.6-
((c-C.sub.6H.sub.11)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8 matched
the data previously reported for this compound.
[0120] Preparation of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.4((c-C.sub.6H.-
sub.11)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7 from
[((c-C.sub.6H.sub.11)SiO.- sub.1.5).sub.8].sub..SIGMA.8: A solution
of [((c-C.sub.6H.sub.11)SiO.sub.1- .5).sub.8].sub..SIGMA.8 (500 mg,
0.46 mmol) and 35% aqueous NEt.sub.4OH (0.2 mL, 0.49 mmol) was
refluxed in THF (5 mL) for 4 h then neutralized with dilute aqueous
HCl. Evaporation of the volatiles afforded a white solid, which was
dissolved in Et.sub.2O and dried over anhydrous MgSO.sub.4.
Filtration and evaporation of the solvent afforded
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.4((c-C.sub.6H.sub.11)(OH)SiO.sub.1.-
0).sub.3].sub..SIGMA.7 as a white microcrystalline solid in 23%
yield. Spectroscopic data for the product matched the data
previously reported for samples of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.4((c-C.sub.6H.sub.11-
)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7 obtained via the hydrolytic
condensation of c-C.sub.6H.sub.11SiCl.sub.3.
[0121] Preparation of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.2((c-C.sub.6H.-
sub.11)(OH)SiO.sub.1.0).sub.4].sub..SIGMA.6 from
[((c-C.sub.6H.sub.11)SiO.- sub.1.5)].sub..SIGMA.8: A solution of
[((c-C.sub.6H.sub.11)SiO.sub.1.5)].s- ub..SIGMA.8 (200 mg, 0.24
mmol) and 35% aqueous NEt.sub.4OH (0.2 mL, 0.49 mmol) in THF (5 mL)
was stirred at 25.degree. C. for 1 h then neutralized with dilute
aqueous HCl. Evaporation of the volatiles afforded a white solid,
which was dissolved in Et.sub.2O and dried over anhydrous
MgSO.sub.4. Filtration and evaporation of the solvent afforded
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.2((c-C.sub.6H.sub.11)(OH)SiO.sub.1.-
0).sub.4].sub..SIGMA.6 as a white solid in 63% yield (135 mg).
.sup.29Si{.sup.1H} NMR (99.3 MHz, CDCl.sub.3, 25.degree. C.)
.delta. -59.4, -68.8 (s, 2:1). .sup.1H NMR (500 MHz, CDCl.sub.3,
25.degree. C.) .delta. 1.78 (v br m); 1.7 (v br m).
.sup.13C{.sup.1H} NMR (125.8 MHz, CDCl.sub.3, 25.degree. C.)
.delta.=27.55, 27.47, 26.86, 26.62(CH.sub.2); 23.68, 23.16 (2:1,
SiCH). MS (ESI, 100% MeOH): m/e 846 (M+H.sup.+, 48%); M+Na.sup.+,
95%); 885 (M.sup.+-H+ K, 100%).
[0122] Preparation of
[((C.sub.6H.sub.5CH.dbd.CH)SiO.sub.1.5).sub.6((C.sub-
.6H.sub.5CH.dbd.CH)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8 from
[((C.sub.6H.sub.5CH.dbd.CH)SiO.sub.1.5).sub.8].sub..SIGMA.8: A
CH.sub.2Cl.sub.2/i-PrOH/THF(4/4/4 mL) solution of
[((C.sub.6H.sub.5CH.dbd-
.CH)SiO.sub.1.5).sub.8).sub.8].sub..SIGMA.8 (124.2 mg, 0.10 mmol)
was added an aqueous solution of Et.sub.4NOH (35%, 49.4 mL, 0.12
mmol) at -35.degree. C. After addition the resulting mixture was
stirred at the same temperature for 5 h. The mixture was
neutralized with 1N HCl solution and extracted with diethyl ether.
The organic layer was washed with brine, dried over
Na.sub.2SO.sub.4, and evaporated. The residue was passed through a
silica gel column using hexane/Et.sub.2O (2:1) as an eluent.
Evaporation of the volatiles gave pure [((C.sub.6H.sub.5CH.dbd.CH-
)SiO.sub.1.5).sub.6((C.sub.6H.sub.5CH.dbd.CH)(OH)SiO.sub.1.0).sub.2].sub..-
SIGMA.8 (112.4 mg, 0.09 mmol) as a white solid in 89% yield.
.sup.1H NMR (CDCl.sub.3) .delta. 5.83 (br s, 2H), 6.31-6.45 (m,
16H), 7.21-7.59 (m, 40H). .sup.13C NMR (CDCl.sub.3) .delta. 117.41,
117.76, 117.96, 126.90, 128.43, 128.50, 128.53, 128.75, 128.83,
128.90, 137.17, 137.23, 137.29, 149.11, 149.15, 149.21. .sup.29Si
NMR (CDCl.sub.3) .delta. -78.05, -77.05, -68.66.
[0123] Preparation of
[((C.sub.6H.sub.5CH.sub.2CH.sub.2SiO.sub.1.5).sub.6(-
(C.sub.6H.sub.5CH.sub.2CH.sub.2)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8
from
[((C.sub.6H.sub.5CH.sub.2CH.sub.2)SiO.sub.1.5).sub.8].sub..SIGMA.8:
A CH.sub.2Cl.sub.2/i-PrOH/THF (5/5/5 mL) solution of
[((C.sub.6H.sub.5CH.sub.2CH.sub.2)SiO.sub.1.5).sub.8)].sub..SIGMA.8
(251.6 mg, 0.20 mmol) was added an aqueous solution of Et.sub.4NOH
(35%, 247.0 .quadrature.L, 0.60 mmol) at -35.degree. C. After
addition the resulting mixture was stiffed at the same temperature
for 4 h. The mixture was neutralized with 1N HCl solution and
extracted with diethyl ether. The organic layer was washed with
brine, dried over MgSO.sub.4, and evaporated. The residue was
passed through a silica gel column using hexane/Et.sub.2O (2:1) as
an eluent. Evaporation of the volatiles gave pure
[((C.sub.6H.sub.5CH.sub.2CH.sub.2SiO.sub.1.5).sub.6((C.sub.6H.sub.5C-
H.sub.2CH.sub.2)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8 (225.3 mg,
0.18 mmol) as a colorless oil in 88% yield. .sup.1H NMR
(CDCl.sub.3) .delta. 1.11-1.25 (m, 16H), 2.86-2.98 (m, 16H), 5.24
(br s, 2H), 7.25-7.47 (m, 40H). .sup.13C NMR (CDCl.sub.3) .delta.
13.56, 14.19, 14.30, 28.90, 28.95, 28.98, 125.74, 125.84, 127.71,
127.83, 128.29, 128.33, 128.42, 143.67, 143.75, 143.78. .sup.29Si
NMR(CDCl.sub.3) .delta. -67.75, -65.99, -58.35.
[0124] Preparation of
[((CH.sub.3C.sub.6H.sub.4SiO.sub.1.5).sub.6((CH.sub.-
3C.sub.6H.sub.5)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8 from
[((CH.sub.3C.sub.6H )SiO.sub.1.5).sub.8].sub..SIGMA.8: A procedure
similar to that used for
[((C.sub.6H.sub.5CH.sub.2CH.sub.2SiO.sub.1.5).su-
b.6((C.sub.6H.sub.5CH.sub.2CH.sub.2)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8
was used to produce
[((CH.sub.3C.sub.6H.sub.4SiO.sub.1.5).sub.6((CH.sub.3-
C.sub.6H.sub.5)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8. .sup.1H NMR
(CDCl.sub.3) .delta. 2.36 (s, 6H), 2.41 (s, 12H), 2.42 (s, 6H),
6.03 (br s, 2H), 7.08 (d, .sup.3J=7.5 Hz, 4H), 7.16 (d, .sup.3J=7.5
Hz, 8H), 7.24 (d, 3J=7.5 Hz, 4H), 7.56 (d, .sup.3J=7.5 Hz, 4H),
7.62 (d, .sup.3J=7.5 Hz, 8H), 7.72 (d, .sup.3J=7.5 Hz, 4H).
.sup.13C NMR (CDCl.sub.3) .delta. 21.50, 21.53, 21.56, 127.10,
127.29, 127.65, 128.41, 128.48, 128.53, 134.25, 140.26, 140.31,
140.56. .sup.29Si NMR (CDCl.sub.3) .delta. -78.22, -76.86, -69.05.
MS (ESI, 100% MeOH): m/z Calcd for
CH.sub.56H.sub.58O.sub.13Si.sub.8Na (100%): 1185.2. Found: 1185.4.
C.sub.56H.sub.58O.sub.13Si.sub.8H (20%): 1163.2. Found: 1163.5.
C.sub.56H.sub.58O.sub.13Si.sub.8K (20%): 1201.2. Found: 1201.3.
[0125] Preparation of
[(c-C.sub.6H.sub.11SiO.sub.1.5).sub.6((c-C.sub.6H.su-
b.11)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8 from
[(c-C.sub.6H.sub.11SiO.sub.- 1.5).sub.8].sub..SIGMA.8: A THF (100
mL) solution of [(c-C.sub.6H.sub.11SiO.sub.1.5).sub.8].sub..SIGMA.8
(5.41 g, 5.00 mmol) was added a methanol solution of Me.sub.4NOH
(25%, 1.90 mL, 4.50 mmol) at room temperature. After addition the
resulting mixture was stirred at the same temperature for 1 h. The
mixture was neutralized with 1N HCl solution and extracted with
diethyl ether. The organic layer was washed with brine, dried over
MgSO.sub.4, and evaporated. The residue was passed through a silica
gel column using hexane and CH.sub.2Cl.sub.2 as an eluent.
Evaporation of the volatiles gave pure [(c-C.sub.6H.sub.11SiO.sub-
.1.5).sub.6((c-C.sub.6H.sub.11)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8
(4.60 g, 4.18 mmol) as a white solid in 84% yield. .sup.1H NMR (500
MHz, CDCl.sub.3, 25.degree. C.): .delta. 4.30 (br s, SiOH, 2H),
1.76 (br m's, 40H), 1.23 (br m's, 40H), 0.74 (br m's, 8H).
.sup.13C{.sup.1H} NMR (125 MHz, CDCl.sub.3, 25.degree. C.): .delta.
27.55, 27.48, 26.88, 26.79, 26.58, 26.53 (CH.sub.2), 23.79, 23.69,
23.07 (4:2:2 for CH), .sup.29Si{.sup.1H} NMR (99 MHz, CDCl.sub.3,
25.degree. C.): .delta. -59.91, -67.60, -69.85 (2:2:4). IR
(25.degree. C., KBr, cm.sup.-1): 2916, 2838, 1447, 1197, 1109. MS
(70 eV, 200.degree. C., relative intensity): m/e 1015
([M-(C.sub.6H.sub.11)].sup.+, 100). Anal. Calcd for
C.sub.48H.sub.90O.sub.13Si.sub.8 (found): C, 52.42 (52.32), H, 8.25
(8.68).
[0126] Reaction of
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.8].sub..S- IGMA.8
with NEt.sub.4OH at room temperature. A solution of 35% NEt.sub.4OH
in water (0.11 mL, 0.25 mmol) was added to a THF (5 mL) solution of
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5)].sub..SIGMA.8 (0.20 g,
0.23 mmol). The solution was stirred at room temperature for 1 h
and then neutralized with an aqueous solution of HCl. The THF was
removed in vacuo to afford a white oil, which was dissolved in
Et.sub.2O, dried over anhydrous MgSO.sub.4 and filtered.
Evaporation of the solvent afforded in 85% mass yield a milky white
oil containing (by .sup.29Si NMR spectroscopy and ESI MS) unreacted
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1- .5)].sub..SIGMA.8 (9%),
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.4((C-
H.sub.3).sub.2CHCH.sub.2)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7
(29%),
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.6((CH.sub.3).sub.2CHCH.sub.-
2)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8 (13%) and
[((CH.sub.3).sub.2CHCH.su-
b.2)SiO.sub.1.5).sub.4((CH.sub.3).sub.2CHCH.sub.2)(OH)SiO.sub.1.0).sub.4].-
sub..SIGMA.8 (34%). Selected characterization data for
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.8].sub..SIGMA.2:
.sup.29Si{.sup.1H} NMR (99.3 MHz, C.sub.6D.sub.6, 25.degree. C.)
.delta. -67.6; MS (ESI, 100% MeOH): m/e 873 (M+H.sup.+, 5%). For
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.4((CH.sub.3).sub.2CHCH.sub.-
2)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7: .sup.29Si{.sup.1H} NMR
(99.3 MHz, C.sub.6D.sub.6, 25.degree. C.) .delta. -58.9, -67.1,
-68.5 (3:1:3); MS (ESI, 100% MeOH): m/e: .sub.3 791 (M+H.sup.+, 2%)
and 813 (M+Na.sup.+, 5%). For
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.6((CH.sub.3).sub.2-
CHCH.sub.2)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8: .sup.29Si{.sup.1H}
NMR (99.3 MHz, C.sub.6D.sub.6, 25.degree. C.) .delta. -59.6, -66.8,
-68.7 (1:1:2); MS (ESI, 100% MeOH): m/e 891 (M+H.sup.+, 11%) and
913 (M+Na.sup.+, 5%). For
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.4((CH-
.sub.3).sub.2CHCH.sub.2)(OH)SiO.sub.1.0).sub.4].sub..SIGMA.8:
.sup.29Si{.sup.1H} NMR (99.3 MHz, C.sub.6D.sub.6, 25.degree. C.)
.delta. (-58.4, -56.6, -66.5, -68.3, 1:1:1:1); MS (ESI, 100% MeOH):
m/e 909 (M+H.sup.+, 15%) and 931 (M+Na.sup.+, 100%).
[0127] Preparation of
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.4((CH.-
sub.3).sub.2CHCH.sub.2)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7 from
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5)].sub..SIGMA.8: A solution
of [((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5)].sub..SIGMA.8 (400 mg,
0.46 mmol) and 35% aqueous NEt.sub.4OH (0.2 mL, 0.49 mmol) was
refluxed in THF (5 mL) for 4 h then neutralized with dilute aqueous
HCl. Evaporation of the volatiles afforded a white resin, which was
dissolved in Et.sub.2O and dried over anhydrous MgSO.sub.4.
Filtration and evaporation of the solvent afforded crude
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.4((C-
H.sub.3).sub.2CHCH.sub.2)(OH)SiO.sub.1.5).sub.3].sub..SIGMA.7 as a
white resinous substance in 44% yield. Colorless crystals were
obtained by recrystallization from acetonitrile/toluene. Selected
characterization data for
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.4((CH.sub.3).sub.2-
CHCH.sub.2)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7: .sup.29Si{.sup.1H}
NMR (99.3 MHz, C.sub.6D.sub.6, 25.degree. C.) .delta. -58.5, -66.9,
-68.3 (s, 3:1:3). .sup.1H NMR (500 MHz, C.sub.6D.sub.6, 25.degree.
C.) .delta. 2.21 (m, 7H, --CH--); 1.24 (d, J=6.6 Hz, 18H,
CH.sub.3); 1.21 (d, J=6.6 Hz, 18H, CH.sub.3); 1.17 (d, J=6.6 Hz,
6H, CH.sub.3); 0.97 (d, J=7.1 Hz, 6H, CH.sub.2); 0.95 (d, J=7.1 Hz,
6H, CH.sub.2); 0.92 (d, J=7.0 Hz, 2H, CH.sub.2). .sup.13C{.sup.1H}
NMR (125.8 MHz, C.sub.6D.sub.6, 25.degree. C.) .delta.=25.7 (s,
CH.sub.3); 25.6 (s, CH.sub.3); 25.5 (s, CH.sub.3); 24.1 (s,
CH.sub.2); 24.05 (s, CH.sub.2); 24.0 (s, CH.sub.2); 23.4 (s, CH);
23.0 (s, CH); 22.6 (s, CH). MS (ESI, 100% MeOH): m/e 791.16
(M+H.sup.+, 80%); 813.08 (M+Na.sup.+, 100%). A single crystal X-ray
diffraction study was also performed.
[0128] Preparation of
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.6((CH.-
sub.3).sub.2CHCH.sub.2)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8 from
[((CH.sub.3).sub.2CHCH.sub.2)SiO.sub.1.5).sub.8].sub..SIGMA.8: A
reactor was charged with 2126 g (2.438 moles)
[((CH.sub.3).sub.2CHCH.sub.2)SiO.su- b.1.5).sub.8].sub..SIGMA.8,
and 20 L THF. A basic solution of Me.sub.4NOH (48 mL, 25 wt %, in
MeOH) and THF (4 L) was cooled to 0.degree. C. and added slowly
(3.5 hours) to the reaction followed by 1 hour of stirring. Product
formation was monitored by HPLC and upon completion was quenched
into 320 mL conc. HCl and 700 mL H.sub.2O at 0.degree. C.
Evaporation of the resulting solution gave waxy solids, that were
washed with water until a pH=7 and recrystallized using acetone and
acetonitrile to produce 1525 g (70% yld) of product at 98% purity.
.sup.1H NMR (CDCl.sub.3): 3.99 (2H, 2.times.OH, bs); 1.85 (8H,
8.times.CH, m); 0.95 (48H, 16.times.CH.sub.3, m); 0.60 (16H,
8.times.CH.sub.2, m). {.sup.1H} .sup.13C NMR (CDCl.sub.3): 25.80;
25.75; 25.65; 23.99; 23.93; 23.86; 23.07; 22.46. Note that the
above procedure can be adapted to both continuous and batch
production methods to produce the desired product higher yield and
greater purity.
[0129] Preparation of
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)SiO.sub-
.1.5).sub.6((CH.sub.3).sub.2CHCH.sub.2)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.-
8 from
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)SiO.sub.1.5)].sub..SIG-
MA.n n=8, 10: A reactor was charged with 128.0 g (96.82 mmol
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)SiO.sub.1.5)].sub..SIGMA.n
and 2080 mL THF. A basic solution 48 mL (25 wt %, in MeOH) of
Me.sub.4NOH was cooled to 0.degree. C. and added to the reaction
mixture over 45 minutes and stirred for an additional 1.5 hour.
Reaction progress was monitored by HPLC and at completion the
reaction was quenched into HCl (150 mL, 1 N) and hexane (500 mL)
with rapid stirring over a period of 1 hour. The top layer was
removed and evaporated to give 125.7 g (97%) of the colorless
liquid product. .sup.1H NMR (CDCl.sub.3): 1.83 (9.3, bm); 1.27
(9.8, bm); 1.15 (10, bm); 1.00 (23, m); 0.89 (64, s); 0.85 (7.7,
s); 0.73 (8.1, bm); 0.58 (8.0, bm). {.sup.1H} .sup.13C NMR
(CDCl.sub.3): 54.50; 54.37; 31.19; 30.22; 29.48; 25.59; 25.49;
25.30; 25.22; 25.00; 24.36; 24.29.
[0130] Preparation of
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)SiO.sub-
.1.5).sub.4((CH.sub.3).sub.2CHCH.sub.2)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.-
7 from
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)SiO.sub.1.5)].sub..SIG-
MA.n n=8, 10: A similar procedure to that reported above for
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)SiO.sub.1.5).sub.6((CH.sub.3-
).sub.2CHCH.sub.2)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8 can be using
LiOH in acetone to prepare an oily trisilanol product that contains
95% of two trisilanol species
[((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH.sub.2)SiO.sub.1-
.5).sub.4((CH.sub.3).sub.2CHCH.sub.2)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7
and [((CH.sub.3).sub.2CH.sub.2CHCH.sub.3CH .sub.2)
SiO.sub.1.5).sub.6((CH.sub.3).sub.2CHCH.sub.2)(OH)SiO.sub.1.0).sub.3].sub-
..SIGMA.9 .sup.1H NMR (500 MHz, CDCl.sub.3): .delta.(ppm) 0.562 (m,
1H), 0.755 (m, 1H), 0.908 (s, 9H), 1.002 (m, 3H), 1.137 (m, 1H),
1.303 (m, 1H), 1.831 (m, 1H), 6.240 (br, 3H); .sup.13C NMR (125
MHz, CDCl.sub.3): .delta.(ppm) 24.06, 24.51, 24.86, 25.44, 25.59,
25.65, 25.89, 29.65, 29.90, 30.64, 30.68, 31.59, 32.02, 54.28,
54.77; .sup.29Si NMR (99.4 MHz, CDCl.sub.3): .delta.(ppm)-68.66,
-68.43, -67.54, -67.32, -58.75, -57.99. EIMS: m/e 1382 (22%,
M.sup.+ (T.sub.9) -iOct-H.sub.2O), 1052 (100%, M.sup.+
(T.sub.7)-iOct-H.sub.2O).
[0131] Preparation
[((CH.sub.3CH.sub.2)SiO.sub.1.5).sub.4((CH.sub.3CH.sub.-
2)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7 from
[((CH.sub.3CH.sub.2)SiO.sub.1.- 5)].sub..SIGMA.8: A solution of 35%
NEt.sub.4OH in water (0.2 mL, 0.49 mmol) was added to a THF (5 mL)
solution of [((CH.sub.3CH.sub.2)SiO.sub.1- .5)].sub..SIGMA.8 (0.41
g, 0.46 mmol). The solution was refluxed for 7 h and then
neutralized with an aqueous solution of HCl. The THF was removed in
vacuo affording a colorless oil, which is dissolved in Et.sub.2O
and dried over MgSO.sub.4 anhydrous. Evaporation of the solvent in
vacuo and crystallization from MeOH afforded
[((CH.sub.3CH.sub.2)SiO.sub.1.5).sub.4-
((CH.sub.3CH.sub.2)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7 as a white
solid. Selected characterization data: .sup.29Si{.sup.1H} NMR (99.3
MHz, C.sub.6D.sub.6, 25.degree. C.) .delta.=-56.4, -64.8, 65.9
(3:1:3MS (ESI, 100% MeOH): m/e: 595 (M+H.sup.+, 100%); 617
(M+Na.sup.+, 60%).
[0132] Preparation
[((CH.sub.3)SiO.sub.1.5).sub.4((CH.sub.3)(OH)SiO.sub.1.-
0).sub.3].sub..SIGMA.7 from
[((CH.sub.3)SiO.sub.1.5).sub.8].sub..SIGMA.8: A THF (350 mL)
suspension of [((CH.sub.3)SiO.sub.1.5).sub.8].sub..SIGMA.8- , (8.5
g, 15.83 mmol) was added an aqueous solution of Et.sub.4NOH (35%,
6.51 mL, 15;83 mmol) at room temperature. After addition the
resulting mixture was stirred at the same temperature for 20 h. The
mixture was neutralized with 1N HCl solution and extracted with
diethyl ether. The organic layer was washed with brine, dried over
MgSO.sub.4. Evaporation of the volatiles gave a white oil-like
solid. Recrystallization of the white solid from a mixed solvent
(MeOH/H.sub.2O=2.5/1) afforded
[((CH.sub.3)SiO.sub.1.5).sub.4((CH.sub.3)(OH)SiO.sub.1.0).sub.3].sub..SIG-
MA.7 (1.35 g, 2.72 mmol) as a white powder in 17% yield. .sup.1H
NMR (CDCl.sub.3) .delta. 0.13 (s, 9H), 0.14 (s, 3H), 0.15 (s, 9H),
6.11(s, 3H). .sup.13C NMR (CDCl.sub.3) .delta. 4.50, 4.35.
.sup.29Si NMR (CDCl.sub.3).delta. -65.70, -45.16, -55.84. Calcd for
C.sub.7H.sub.24O.sub.12Si.sub.7: C, 16.92; H, 4.87. Found: C,
17.16; H, 4.89. MS (ESI, 100% MeOH): m/e: 496.96 (M+H.sup.+, 100%);
518.86 (M+Na.sup.+, 75%).
[0133] Preparation
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.4((c-C.sub.6H.sub-
.11)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7 from
[((c-C.sub.6H.sub.11)SiO.sub-
.1.5).sub.7((H)SiO.sub.1.0).sub.1].sub..SIGMA.8: A solution of
[((c-C.sub.6H.sub.11)SiO.sub.1.5).sub.7(H)SiO.sub.1.0).sub.1].sub..SIGMA.-
8(460 mg, 0.46 mmol) and 35% aqueous NEt.sub.4OH (0.2 mL, 0.49
mmol) was refluxed in THF (5 mL) for 5 h then neutralized with
dilute aqueous HCl. Evaporation of the volatiles afforded a white
solid, which was dissolved in Et.sub.2O and dried over anhydrous
MgSO.sub.4. Filtration and evaporation of the solvent afforded a
white microcrystalline solid in high yield. Analysis of the product
mixture by .sup.29Si NMR spectroscopy indicated that the major
product was [((c-C.sub.6H.sub.11)SiO.sub.1.5).su-
b.4((c-C.sub.6H.sub.11)(OH)SiO.sub.1.0).sub.3].sub..SIGMA.7; small
amounts of [((c-C.sub.6H.sub.11)SiO.sub.1.5)].sub..SIGMA.8 were
also present.
[0134] Preparation
[((c-C.sub.5H.sub.9)SiO.sub.1.5).sub.4((c-C.sub.5H.sub.-
9)(OH)SiO.sub.1.0).sub.2].sub..SIGMA.8 from
[(c-C.sub.5H.sub.9)SiO.sub.1.5- ].sub..SIGMA.8: A 12-L reactor
equipped with a mechanical stirrer, addition pump and drying tube,
was charged with 443.4 g (457.2 mmol)
[(c-C.sub.5H.sub.9)SiO.sub.1.5].sub..SIGMA.8 and 6.0 L THF. A base
solution of Me.sub.4NOH (in MeOH., 25 wt %, 212 mL) and THF (1.4 L)
was prepared and added slowly to the reaction mixture and this
mixture was stirred for 3 hours. Upon completion of the reaction a
mechanically stirred quench tank was charged with 65 mL conc. HCl
and 500 mL water was cooled to 0.degree. C. and the above reaction
mixture was quenched. Evaporation and filtration of the resulting
mixture gave
[((c-C.sub.5H.sub.9)SiO.sub.1.5).sub.4((c-C.sub.5H.sub.9)(OH)SiO.sub.1.0)-
.sub.2].sub..SIGMA.8 to produce 364 g (81%) of white solids at 98%
purity. .sup.1H NMR (CDCl.sub.3): 4.63 (2H, 2.times.OH, bs); 1.72
(16H, 8.times.CH.sub.2, m); 1.56(16H, 8.times.CH.sub.2, m);
1.46(32H, 16.times.CH.sub.2, m); 0.94(8H, 8.times.CH, m). {.sub.1H}
.sup.13C NMR (CDCl.sub.3): 27.41; 27.39; 27.36; 27.20; 27.06;
27.02; 27.00; 26.99; 22.88; 22.66; 22.16. Variations of this
preparative method can be used to design both continuous and batch
processes.
[0135] Although the present invention has been described above in
terms of specific embodiments, it is anticipated that alterations
and modifications thereof will no doubt become apparent to those
skilled in the art. It is therefore intended that the following
claims be interpreted as covering all such alterations and
modifications as fall within the true spirit and scope of the
invention.
* * * * *