TECHNICAL FIELD

The present disclosure relates to the field of chemistry in general and octakis (tetramethylammonium alkyl sulfonate) octa silsesquioxane (POSS) compounds in particular. Mare particularly, the present disclosure relates to the development and synthesis of POSS compounds/ionic liquids and methods of preparation and applications thereof. The POSS compound/ionic liquid of the present disclosure have use across varied industrial applications.

BACKGROUND OF THE DISCLOSURE
Ionic liquids (ILs), which have been recognized as a novel class of synthetic materials, have melting points below 100°C. With increasing demand for advanced materials, the development of novel ILs has been increasingly explored due to their unique properties, which include high ionic conductivity, high thermal stability, non-flammability, negligible vapor pressure, and a wide electrochemical stability window. Due to the above advantages, ILs have been applied as functional materials in many chemical and industrial fields including fuel cells and lithium batteries, as catalysis solvents, capacitors, and electrochemical sensors.

Over the past few decades, polyhedral oligomeric silsesquioxane (POSS) materials have attracted much attention due to their unique thermal, chemical, and mechanical stabilities derived from their siloxane (Si–O–Si) frameworks, which have high bond energies. Furthermore, POSSs exhibit good compatibility with organic materials because of their inorganic core with various functional organic substituents. Due to their many merits, POSS materials have been extensively used in many fields, including as drug delivery agents, liquid crystalline materials, and light-emitting materials. Given the advantages of POSSs, introducing them into ILs is a reasonable approach for creating more novel and functional ILs.

Ionic liquids play a major role in organic synthesis as solvents, co-solvents, catalysts, etc., for green and sustainable chemistry. ILs are organic salts that are typically in the molten state at temperatures below 100°C. ILs have been considered as “green” alternatives for molecular solvents, since there is lower risk of environmental release through the atmosphere due to their low vapour pressures. However, because of their water solubility, ILs may be a potent environmental hazard and therefore a danger to living organisms from microbes to humans. The risks remain throughout the whole life cycle of the ILs, from synthesis to application and from application to disposal.

Accordingly, there is a need for effective, sustainable and cost-effective ionic liquids which are insoluble in some organic solvents.

SUMMARY OF THE DISCLOSURE
The present disclosure relates to POSS compounds of Formula I

Formula I
wherein ‘R1’is selected from a group comprising ‘-O-R+’, ‘-O-(CH2)n-SO3-R+’, ‘-O-(CH2)n-SO3H’, ‘-O-SiMe2-H’, ‘-O-SiMe2-(CH2)nNMe2’ and ‘-O-SiMe2-(CH2)nNMe2+-(CH2)nSO3-’;
R+ is N(Me)4+; and
wherein n is 3 or 4.

The present disclosure also relates to the methods of making and application of the compounds of Formula I.

BRIEF DESCRIPTION OF THE ACCOMPANYING FIGURES
In order that the disclosure may be readily understood and put into practical effect, reference will now be made to exemplary embodiments as illustrated with reference to the accompanying figures. The figures together with a detailed description below, are incorporated in and form part of the specification, and serve to further illustrate the embodiments and explain various principles and advantages, in accordance with the present disclosure where:

Figure 1 depicts the synthetic scheme for the method of making POSS ammonium sulfonate salts of the present disclosure.
Figure 2(a) depicts the chemical equation for the synthesis of ionic liquid compound 1.
Figure 2(b) depicts the chemical equation for the synthesis of ionic liquid compound 2.
Figure 3 depicts the synthetic scheme for the method of making POSS octa sulfonic acid.
Figure 4 depicts the synthetic scheme for the method of making POSS betaine/zwitterion compounds of the present disclosure.
Figure 5(a) depicts the chemical equation for the synthesis of ionic liquid compound 4.
Figure 5(b) depicts the chemical equation for the synthesis of ionic liquid compound 5.
Figure 5(c) depicts the chemical equation for the synthesis of ionic liquid compound 6.
Figure 6 depicts 1H NMR spectrum of the compound 1.
Figure 7 depicts 1H NMR spectrum of the compound 2.
Figure 8 depicts 1H NMR spectrum of the compound 7.
Figure 9 depicts 1H NMR spectrum of the compound 3.
Figure 10 depicts 1H NMR spectrum of the compound 4.
Figure 11 depicts 1H NMR spectrum of the compound 5.
Figure 12 depicts 1H NMR spectrum of the compound 6.
Figure 13 depicts 1H NMR spectrum of the compound 8.
DETAILED DESCRIPTION OF THE DISCLOSURE
With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity. The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the disclosure to achieve one or more of the desired objects or results. Throughout this specification, the word “comprise”, or variations such as “comprises” or “comprising” or “containing” wherever used, will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

As used herein, the expressions “polyoctahedral silsesquioxanes”, “polyhedral oligomeric silsesquioxane”, “octakis (tetramethylammonium alkyl sulfonate) octa silsesquioxane” and ‘POSS’ are employed interchangeably.

The present disclosure addresses the drawbacks of the prior art and provides for novel and functional POSS compound(s), methods of preparation and application thereof.

In particular, the present disclosure relates to the development and synthesis of octakis (tetramethylammonium alkyl sulfonate) octa silsesquioxane (POSS) compounds/ionic liquids.

POSS are unique organic -inorganic hybrid materials. POSS compounds have a wide temperature range because of the stabilizing effect of the POSS core. In embodiments of the present disclosure, the POSS compounds of the present disclosure have a melting point of less than or equal to 25°C, and can thus be classified as ionic liquids.

Ionic liquids (ILs), molten salts below 100°C or 150°C, have attracted much attention because of their potential application to green solvents and electrolyte materials. These compounds indicate the negligible vapor pressure, high thermal stability, and high ionic conductivity. Most ILs are regarded as organic compounds because of the presence of large amount of organic components in ILs. On the other hand, ILs with relatively more inorganic components could be applied to a wide range of materials research due to their significantly higher thermos-stability derived from the inorganic components.

In embodiments of the present disclosure, the POSS compounds of the present disclosure are insoluble in some organic solvents, rendering them environment friendly.

In embodiments of the present disclosure, the compounds of the present disclosure are suitable for use as ionic liquids.

The present disclosure relates to a compound of Formula I

Formula I
wherein ‘R1’is selected from a group comprising ‘-O-R+’, ‘-O-(CH2)n-SO3-R+’, ‘-O-(CH2)n-SO3H’, ‘-O-SiMe2-H’, ‘-O-SiMe2-(CH2)nNMe2’ and ‘-O-SiMe2-(CH2)nNMe2+-(CH2)nSO3-’;
R+ is N(Me)4+; and
wherein n is 3 or 4.

In an embodiment, the present disclosure relates to compound of Formula I wherein ‘R1’ is selected from a group comprising ‘-O-NMe4+’, ‘-O-(CH2)3-SO3-NMe4+’, ‘-O-(CH2)4-SO3-NMe4+’, ‘-O-(CH2)3-SO3H’, ‘-O-(CH2)4-SO3H’, ‘-O-SiMe2-H’, ‘-O-SiMe2-(CH2)3NMe2’, ‘-O-SiMe2-(CH2)4NMe2’, ‘-O-SiMe2-(CH2)3NMe2+(CH2)3SO3-’, ‘-O-SiMe2-(CH2)4NMe2+(CH2)4SO3-’, ‘-O-SiMe2-(CH2)3NMe2+(CH2)4SO3-’ and ‘-O-SiMe2-(CH2)4NMe2+(CH2)3SO3-’ or any combination thereof.

In exemplary embodiments of the present disclosure, ‘R1’ in the compound of Formula I is selected from a group comprising ‘-O-NMe4+’, ‘-O-(CH2)3-SO3-NMe4+’, ‘-O-(CH2)3-SO3H’, ‘-O-SiMe2-H’, ‘-O-SiMe2-(CH2)3NMe2’ and ‘-O-SiMe2-(CH2)3NMe2+(C3H6) SO3-’.

The POSS compounds of the present disclosure include POSS ammonium sulfonate salts (such as but not limiting to compounds 1, 2 and 7), POSS octa sulfonic acid (such as but not limiting to compounds of Formula III) and POSS betaine compounds (such as but not limiting to compounds 3-6 and 8).

In an embodiment, the POSS compounds of the present disclosure include POSS ammonium sulfonate salts as represented by Formula II, POSS octa sulfonic acid as represented by Formula III and POSS betaine compounds as represented by Formula IV.

In a preferred embodiment of the present disclosure, the compound is:

Formula II
wherein R+ is N(Me)4+, and n is 3 or 4.

In another preferred embodiment of the present disclosure, the compound is:

Formula III
wherein n is 3 or 4.

In yet another preferred embodiment of the present disclosure, the compound is:

Formula IV
wherein n is 3 or 4.

In embodiments of the present disclosure, the compound is selected from a group comprising:
,
,
,
,
,

,

, and
.

In embodiments of the present disclosure, the compound has melting point of less than 25°C.

In an embodiment of the present disclosure, the characteristics of the compounds of the present disclosure are presented in table 1 below:

Table 1-
Compound No. Physical characteristics Melting
point
Appearance Chemical Formula Molecular Weight (Da)
Compound-1 White colour solid C32H96N8O20Si8 1137.84 130-150°C
Compound-2 Colourless gel C56H144N8O44S8Si8 2114.94 Gel form
Compound-3 White/off-white solid C24H56O44S8Si8 1529.83 140 – 160°C
Compound-4 White powder C16H56O20Si16 1017.96 230 – 250°C
Compound-5 Brown colour gel C56H144N8O20Si16 1699.16 Liquid
Compound-6 Pale-yellow liquid C80H192N8O44S8Si16 2676.27 Liquid
Compound-7 Colourless gel C64H160N8O44S8Si8 2227.16 Liquid
Compound-8 Pale-yellow liquid C88H208N8O44S8Si16
2788.48 Liquid

In embodiments of the present disclosure, the compound-2, compound-5, compound-6, compound-7 and compound-8 are liquids at temperature greater than or equal to -10°C.

In embodiments of the present disclosure, the compound-2, compound-5, compound-6, compound-7 and compound-8 are liquids at temperature ranging from -10°C to >250°C.

In embodiments of the present disclosure, the solubility of the compounds of the present disclosure in some solvents is presented in table 2 below:

POSS Compound No. Soluble Insoluble
Compound-1 Water, DMF, DMSO, and partially soluble in MeOH and Ethanol. Acetone, CH3CN, ethyl acetate, CH2Cl2, Hexane, ether and THF.
Compound-2 Water, DMF, DMSO, MeOH and Ethanol Acetone, CH3CN, ethyl acetate, CH2Cl2, Hexane, ether and THF.
Compound-3 DMF, DMSO, MeOH, THF, DMF and Partially soluble in water at 50°C. Acetone, CH3CN, ethyl acetate, CH2Cl2, Hexane and ether.
Compound-4 Acetone, CH3CN, ethyl acetate, CH2Cl2, Hexane, DMF, DMSO ether and THF. Water, MeOH and Ethanol
Compound-5 Acetone, CH3CN, ethyl acetate, CH2Cl2, Hexane, DMF, DMSO ether and THF. Water, MeOH and Ethanol
Compound-6 Acetone, CH3CN, THF, CH2Cl2, DMF, DMSO and partially soluble in water, methanol and ethanol. Hexane, Diethyl ether, ethyl acetate and
Compound-7 Water, DMF, DMSO, MeOH and Ethanol Acetone, CH3CN, ethyl acetate, CH2Cl2, Hexane, ether and THF.
Compound-8 Acetone, CH3CN, THF, CH2Cl2, DMF, DMSO and partially soluble in water, methanol and ethanol. Hexane, Diethyl ether, ethyl acetate and

The present disclosure also relates to a method of making the compounds of the present disclosure.

In an embodiment, the present disclosure provides for method of making the POSS compounds of Formula I.

In an embodiment, the present disclosure provides for method of making ionic compounds such as but not limiting to POSS ammonium sulfonate salts synthesized and POSS betaine compounds.

In an exemplary embodiment, the synthetic scheme for the method of making ionic liquid compounds viz. POSS ammonium sulfonate salts is illustrated in Figure 1.

In an exemplary embodiment, the synthetic scheme for the method of making ionic liquid compounds viz. POSS betaine/zwitterion compounds is illustrated in Figure 4.

In an embodiment, the present disclosure provides for method of making POSS octa sulfonic acid by hydrolysation of the POSS ammonium sulfonate salts with hydrochloric acid to from POSS octa sulfonic acid.

In an exemplary embodiment, the synthetic scheme for the method of making POSS octa sulfonic acid is illustrated in Figure 3.

In an embodiment, the method of making a compound of Formula I, comprises reacting tetramethylammonium hydroxide with tetraethoxysilane to obtain tetramethylammonium silicate octaanion.

In an embodiment, the method of making a compound of Formula I, comprises reacting tetramethylammonium hydroxide with tetraethoxysilane to obtain tetramethylammonium silicate octaanion followed by treating with C3-C4 alkane sultone to obtain (tetramethylammonium alkyl sulfonate) octa silsesquioxane.

In an embodiment, the method of making a compound of Formula I, comprises reacting tetramethylammonium hydroxide with tetraethoxysilane to obtain tetramethylammonium silicate octaanion followed by treating with C3-C4 alkane sultone to obtain (tetramethylammonium alkyl sulfonate) octa silsesquioxane; and hydrolyzing the (tetramethylammonium alkyl sulfonate) octa silsesquioxane to obtain tetramethylammonium silicate octa alkyl sulfonic acid/POSS sulfonic acid.

In an embodiment, the method of making a compound of Formula I, comprises reacting tetramethylammonium hydroxide with tetraethoxysilane to obtain tetramethylammonium silicate octaanion followed by treating with dimethylchlorosilane to obtain Octakis (hydridodimethylsiloxy) octasilsesquioxane.

In an embodiment, the method of making a compound of Formula I, comprises reacting tetramethylammonium hydroxide with tetraethoxysilane to obtain tetramethylammonium silicate octaanion followed by treating with dimethylchlorosilane to obtain Octakis (hydridodimethylsiloxy) octasilsesquioxane; and hydrosilylating the Octakis (hydridodimethylsiloxy) octasilsesquioxane with N,N-dimethylallylamine to obtain Octakis (N,N dimethyl alkyldimethylsiloxy) octasilsesquioxane.

In an embodiment, the method of making a compound of Formula I, comprises reacting tetramethylammonium hydroxide with tetraethoxysilane to obtain tetramethylammonium silicate octaanion followed by treating with dimethylchlorosilane to obtain Octakis (hydridodimethylsiloxy) octasilsesquioxane; hydrosilylating the Octakis (hydridodimethylsiloxy) octasilsesquioxane with N,N-dimethyl alkenylamine to obtain Octakis (N,N dimethyl alkyldimethylsiloxy) octasilsesquioxane followed by treating with C3-C4 alkane sultone to obtain dodecaoxa-octasila pentacyclo icosan-octayl) octakis (oxy))octakis(dimethylsilanediyl))octakis(propane-3,1-diyl))octakis (dimethylammoniumdiyl)) octakis(alkane-1-sulfonate).

In an exemplary embodiment of the present disclosure, tetramethylammonium silicate Octanion (compound 1) is synthesized by contacting tetramethylammonium hydroxide and tetramethoxysilane in methanol and water (preferably deionized water) to obtain the POSS Octanion compound 1 as white solid. In an exemplary embodiment of the present disclosure, opening of C3-C4 alkane sultone with the said Octanion gives the (tetramethylammonium alkyl sulfonate) octa silsesquioxane ionic liquid (compound of Formula II).

In an exemplary embodiment of the present disclosure, the POSS sulfonate ionic liquid (compound of Formula II) is treated with MeOH/HCl at a pH of about 1 to 2 to give off white precipitate of POSS sulfonic acid (compound of Formula III).

In an exemplary embodiment of the present disclosure, the tetramethylammonium silicate Octanion (compound 1) is treated with dimethylchlorosilane to give Octakis (hydridodimethylsiloxy) octasilsesquioxane (compound 4); this on hydrosilylation with N,N dimethylallylamine in presence of Pt catalyst gives Octakis (N,N dimethyl alkyldimethylsiloxy) octasilsesquioxane; which upon treating with sultone gives betain (ziwtter ion) POSS Ionic compounds (compound of Formula III) as a pale yellow thick liquid.

In an exemplary embodiment of the present disclosure, the method of making tetramethylammonium silicate octaanion comprises:
adding about 54.9 mL to about 0.52 mol. of tetramethylammonium hydroxide optionally along with about 26.66 mL to about 0.66 mol. of solvent and about 20.1 mL to about 1.1 mol. of water;
adding about 29.36 mL to about 0.66 mol of tetraethoxysilane to obtain a clear solution, and optionally concentrating the clear solution to remove solvent, to obtain tetramethylammonium silicate octaanion.

In an exemplary embodiment of the present disclosure, the method of making tetramethylammonium silicate octaanion comprises:
adding about 54.9 mL to about 0.52 mol. of tetramethylammonium hydroxide optionally along with about 26.66 mL to about 0.66 mol. of solvent and about 20.1 mL to about 1.1 mol. of water, optionally cooling the mixture obtained and/or maintaining the system under nitrogen;
adding about 29.36 mL to about 0.66 mol. of tetraethoxysilane, and optionally stirring the mixture at room temperature, to obtain a clear solution, and optionally concentrating the clear solution to remove solvent at temperature ranging from about 40°C to about 50°C, preferably about 50°C for a period ranging from about 12 h to about 16 h, preferably 2 hours, to obtain tetramethylammonium silicate octaanion.

In an embodiment, the said concentration step is carried out under reduced pressure.

In embodiments of the present disclosure, room temperature ranges from about 25°C to about 35°C, preferably about 30°C.

In an exemplary embodiment of the present disclosure, the method of making the (tetramethylammonium alkyl sulfonate) octa silsesquioxane comprises:
contacting about 50 g to about 43.93 mmol. 1 eq. of tetramethylammonium silicate octaanion with about 53.6 g to about 439.3 mmol. 10 eq. of C3-C4 alkane sultone along with about 2 vol. to about 5 vol. of solvent to obtain a mixture; and
refluxing the mixture for about 110°C to about 120°C hours, preferably about 48 hours, and optionally removing the solvent, to obtain (tetramethylammonium alkyl sulfonate) octa silsesquioxane.

In an exemplary embodiment of the present disclosure, the method of making the POSS sulfonic acid comprises:
contacting about 5 g to about 1 eq. of tetramethylammonium alkyl sulfonate with about 2 vol. to about 3 vol. of solvent, and optionally cooling the mixture to a temperature ranging from about 0°C to about 5°C, preferably about 0°C;
adding methanolic HCl drop wise to obtain pH of about 1.0 to about 2.0, preferably about 2.0, and optionally stirring for about 20 min to about 35 min, preferably for about 30 min at temperature ranging from about 0°C to about 5°C, preferably about 0°C;
the mixture obtained may optionally be further stirred for about 1.5 hours to about 2 hours at temperature ranging from about 25°C to about 30°C, to obtain the POSS sulfonic acid.

In an exemplary embodiment of the present disclosure, the method of making the Octakis (hydridodimethylsiloxy) octasilsesquioxane comprises:
contacting about 14.3 mL to about 0.33 mol. of dimethylchlorosilane with about 3 vol. to about 5 vol. of solvent to obtain a mixture, and optionally cooling the mixture;
adding about 0°C to about 10°C of tetramethylammonium silicate octaanion to the mixture, and optionally stirring the mixture for about 2 hours to about 5 hours, preferably about 4 hours;
separating the mixture into two layers and obtaining the solvent layer, and
removing solvent from the solvent layer to obtain Octakis (hydridodimethylsiloxy) octasilsesquioxane.

In an exemplary embodiment of the present disclosure, the method of making the Octakis (N,N dimethyl alkyldimethylsiloxy) octasilsesquioxane comprises:
a) contacting about 200 mg to about 0.196 mmol. of Octakis (hydridodimethylsiloxy) octasilsesquioxane with about 5 vol. to about 10 vol. of solvent, and optionally stirring, to obtain a mixture;
b) adding about 0.184 mL to about 1.568 mmol. of N, N-dimethyl alkenylamine;
c) optionally degassing the reaction chamber and refilling with N2 about three times;
d) adding about 2 mM to about 0.05 mL of Pt catalyst solution and optionally stirring for about 12 hours to about 18 hours; and
e) removing the solvent to obtain Octakis (N, N dimethyl alkyldimethylsiloxy) octasilsesquioxane.

In an exemplary embodiment of the present disclosure, the method of making the compound of Formula IV [the dodecaoxa-octasila pentacyclo icosan-octayl) octakis (oxy))octakis(dimethylsilanediyl))octakis(propane-3,1-diyl))octakis (dimethylammoniumdiyl)) octakis(alkane-1-sulfonate)] comprises:
contacting about 1 g to about 1 eq. of Octakis (N,N dimethyl alkyldimethylsiloxy) octasilsesquioxane, about 5 g to about 9 eq. of C3-C4 alkane sultone and about 3 vol. to about 5 vol. of solvent to obtain a mixture;
refluxing the mixture for about 36 hours to about 50 hours, preferably about 48 hours, and optionally removing the solvent, to obtain the compound of Formula IV.

In an embodiment, the (tetramethylammonium alkyl sulfonate) octa silsesquioxane employed in the present disclosure is (tetramethylammonium propyl sulfonate) octa silsesquioxane or (tetramethylammonium butyl sulfonate) octa silsesquioxane.

In an embodiment, the tetramethylammonium silicate octa alkyl sulfonic acid employed in the present disclosure is tetramethylammonium silicate octa propyl sulfonic acid or tetramethylammonium silicate octa butyl sulfonic acid.

In an embodiment, the Octakis (N,N dimethyl alkyldimethylsiloxy) octasilsesquioxane employed in the present disclosure is Octakis (N,N dimethyl propyldimethylsiloxy) octasilsesquioxane or Octakis (N,N dimethyl butyldimethylsiloxy) octasilsesquioxane.

In an embodiment, the dodecaoxa-octasila pentacyclo icosan-octayl) octakis (oxy))octakis(dimethylsilanediyl))octakis(propane-3,1-diyl))octakis (dimethylammoniumdiyl)) octakis(alkane-1-sulfonate) is dodecaoxa-octasila pentacyclo icosan-octayl) octakis (oxy))octakis(dimethylsilanediyl))octakis(propane-3,1-diyl))octakis (dimethylammoniumdiyl)) octakis(propane-1-sulfonate) or dodecaoxa-octasila pentacyclo icosan-octayl) octakis (oxy))octakis(dimethylsilanediyl))octakis(propane-3,1-diyl))octakis (dimethylammoniumdiyl)) octakis(butane-1-sulfonate).

In an embodiment, the C3-C4 alkane sultone employed in the present disclosure is 1,3-propane sultone or 1,4-butane sultone.

In an embodiment, the N,N-dimethyl alkenylamine employed in the present disclosure is N,N-dimethylallylamine or N,N-dimethyl-3-butenylamine.

In an embodiment of the present disclosure, the (tetramethylammonium alkyl sulfonate) octa silsesquioxane is Tetramethylammonium 3,3',3'',3''',3'''',3''''',3'''''',3'''''''-((2, 4, 6, 8, 10, 12, 14, 16, 17, 18, 19, 20 - dodecaoxa-1, 3, 5, 7, 9, 11, 13, 15 octasilapentacyclo [9.5.1.13,9.15,15.17,13 or Tetramethylammonium 4, 4', 4'', 4''', 4'''', 4''''', 4'''''', 4''''''' - ((2, 4, 6, 8, 10, 12, 14, 16, 17, 18, 19, 20 – dodecaoxa - 1, 3, 5, 7, 9, 11, 13, 15-octasilapentacyclo [9.5.1.13,9.15,15.17,13] icosan-1, 3, 5, 7, 9, 11, 13, 15-octayl)octakis(oxy)) octakis (butane-1-sulfonate).

In an embodiment of the present disclosure, the POSS sulfonic acid is 3,3',3'',3''',3'''',3''''',3'''''',3'''''''-((2,4,6,8,10,12,14,16,17,18,19,20 - dodecaoxa - 1,3,5,7,9,11,13,15-octasilapentacyclo[9.5.1.13,9.15,15.17,13] icosan-1,3,5,7,9,11,13,15-octayl) octakis(oxy)) octakis(propane-1-sulfonic acid) or 4,4',4'',4''',4'''',4''''',4'''''',4'''''''-((2,4,6,8,10,12,14,16,17,18,19,20-dodecaoxa-1,3,5,7,9,11,13,15- octasilapentacyclo [9.5.1.13,9.15,15.17,13]icosan-1,3,5,7,9,11,13,15-octayl) octakis(oxy)) octakis(propane-1-sulfonic acid).

In an exemplary embodiment, the compound of Formula IV is (3,3',3'',3''',3'''',3''''',3'''''',3'''''''-(((((2,4,6,8,10,12,14,16,17,18,19,20 - dodecaoxa - 1,3,5,7,9,11,13,15 - octasilapentacyclo [9.5.1.13,9.15,15.17,13] icosan-1,3,5,7,9,11,13,15octayl) octakis(oxy)) octakis (dimethylsilanediyl))octakis(propane-3,1-diyl)) octakis(dimethylammoniumdiyl)) octakis (propane-1-sulfonate) or 4,4',4'',4''',4'''',4''''',4'''''',4'''''''-(((((2,4,6,8,10,12,14,16,17,18,19,20-Dodecaoxa-1,3,5,7,9,11,13,15 – octasilapentacyclo [9.5.1.13,9.15,15.17,13] icosan-1,3,5,7,9,11,13,15-octayl)octakis(oxy)) octakis(dimethylsilanediyl)) octakis(propane-3,1-diyl))octakis(dimethylammoniumdiyl))octakis(butane-1-sulfonate).

In an embodiment, the hydrolysis of the (tetramethylammonium alkyl sulfonate) octa silsesquioxane is carried out at pH of about 2.0 to obtain the tetramethylammonium silicate octa alkyl sulfonic acid.

In an embodiment, the hydrosilylation in the methods of the present disclosure is carried out in presence of catalyst selected from a group comprising platinum(dvs) (Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane), H2PtCl6 (Speier's catalyst) and C16H24N3PRuF6 (Pentamethylcyclopentadienyltris (acetonitrile)ruthenium(II) hexafluorophosphate).

In embodiments of the present disclosure, the method of making the compounds of the present disclosure is carried out in presence or absence of solvent or a combination thereof.

In embodiments of the present disclosure, one or more step(s) of the method of making the compounds of the present disclosure is carried out in presence of solvent selected from a group comprising water, methanol, toluene, hexane, ethyl acetate, dichloromethane, acetone, methanolic hydrochloric acid, 2-propanol hydrochloric acid or any combination thereof.

In embodiments of the present disclosure, one or more step(s) of the method of making the compounds of the present disclosure is carried out under nitrogen atmosphere.

In embodiments of the present disclosure, one or more step(s) of the method of making the compounds of the present disclosure is carried out at a temperature ranging from about 20°C to about 120°C.

In embodiments of the present disclosure, one or more step(s) of the method of making the compounds of the present disclosure is carried out for a time period ranging from about 30 minutes to about 48 hours.

In embodiments of the present disclosure, the method of making the compounds of the present disclosure may comprise isolation and/or purification of the corresponding compound. In a non-limiting embodiment of the present disclosure, the said isolation is carried out by acts selected from a group comprising but not limiting to addition of solvent, cooling, heating, removal of solvent, drying, filtration, extraction and combination of acts thereof. In a non-limiting embodiment of the present disclosure, the said purification is carried out by water and/or solvent(s) washing.

In embodiments of the present disclosure, excess solvent is removed by technique selected from a group comprising but not limiting to concentrating solution at temperature ranging from about 45°C to about 120°C for a period of about 2 to about 4; washing with one or more solvent at temperature ranging from about 40°C to about 50°C, vacuum rotary vapour or any combination thereof.

In embodiments of the present disclosure, drying is carried out at temperature ranging from about 40°C to about 50°C.

In an embodiment, the POSS ionic liquids and compounds of the present disclosure are characterized by Nuclear magnetic resonance (NMR).

In a non-limiting embodiment, the POSS ionic liquids of the present disclosure have applications in/as explosive detector (aromatic nitro compounds), fuel cells and lithium batteries, catalysis solvents, capacitors, electrochemical sensors, etc.

In a non-limiting embodiment, the POSS octa sulfonic acid of the present disclosure has applications such as but not limiting to an alternate to acid catalysed reactions (Sulfuric acid, hydrochloric acid etc.)

The present disclosure also relates to a composition comprising any of the afore-described compounds of the present disclosure. In embodiments of the present disclosure, the composition further comprises one or more industrially acceptable excipient.

In a non-limiting embodiment, the composition of the present disclosure is provided as suitable coatings, sensors, catalysts, green solvents, antimicrobial silsesquioxanes, oil, gas, detectors, electronics, etc.

In a non-limiting embodiment, the compound(s) or the composition(s) of the present disclosure is employed in preparation of explosive detector, fuel cells, lithium batteries, solvent, catalyst, coatings, antimicrobial silsesquioxanes, sensors, capacitors, detectors, oil, gas, electronics, electronic materials, light emitting diodes, bioimaging’s, medical appliances, etc.

The present disclosure also relates to use of the ionic liquids/compounds or the compositions of the present disclosure for industrial application.

The present disclosure also pertains to method of using the compounds or composition of the present disclosure for industrial application.

In a non-limiting embodiment, the industrial application is selected from group comprising detection of explosives (such as aromatic nitro compounds, etc); catalysis; chemical reactions; use in sensors, detectors, fuel cells, lithium batteries, light emitting diodes, capacitors, electrochemical sensors, coatings, oil, gas, bioimaging’s, medical appliances, catalysts, solvents, electronics and electronic materials;, or any combination thereof.

The foregoing descriptive matter is illustrative of the disclosure and not a limitation. Descriptions of well-known/conventional methods and techniques are omitted so as to not unnecessarily obscure the embodiments herein.

Further, the invention herein provides for examples illustrating the above described embodiments, and in order to illustrate the embodiments of the present invention, certain aspects have been employed. The examples used herein for such illustration are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. While considerable emphasis has been placed herein on the particular features of this disclosure, it will be appreciated that various modifications can be made, and that many changes can be made in the preferred embodiments without departing from the principles of the disclosure. Accordingly, the following examples should not be construed as limiting the scope of the embodiments herein.

EXAMPLES
EXAMPLE 1:
Example 1(a): Experimental procedure for the synthesis of tetramethylammonium silicate octaanion (1)
To a 250-mL round bottom flask with a magnetic stir bar, 54.9 mL (0.52 mol) tetramethylammonium hydroxide (25 wt % in methanol), 26.66 mL (0.66 mol) methanol, and 20.1 mL (1.1 mol) distilled water were added. The flask was cooled in an ice bath, and the system was maintained under nitrogen. Then 29.36 mL (0.66 mol) tetraethoxysilane was added via an addition funnel. The solution turned cloudy and allowed to stir at room temperature overnight to obtain a clear solution. The clear solution obtained was concentrated to remove solvent under reduced pressure at 50°C for 2 hours to obtain a white colour solid compound 1 [tetramethylammonium silicate octaanion] in quantitative yield (36 g). The chemical equation is represented by Figure 2(a). Figure 6 depicts 1H NMR spectrum of tetramethylammonium silicate octaanion (compound 1).

Example 1(b): Experimental procedure for the synthesis of (tetramethylammonium propyl sulfonate) octa silsesquioxane (2)
Tetramethylammonium silicate octaanion (50 g, 43.93 mmol, 1 eq) and 1,3-propane sultone (53.6 g, 439.3 mmol, 10 eq) in dry toluene was refluxed for 48 hours. The reaction mixture was concentrated to remove toluene and washed with ethyl acetate and dichloromethane to remove unreacted 1,3-propane sultone. Trace amount of solvent was removed under vaccum rotary vapour to give 90 g of a colour less gel compound 2 [Tetramethylammonium 3,3',3'',3''',3'''',3''''',3'''''',3'''''''-((2, 4, 6, 8, 10, 12, 14, 16, 17, 18, 19, 20 - dodecaoxa-1, 3, 5, 7, 9, 11, 13, 15 octasilapentacyclo [9.5.1.13,9.15,15.17,13] icosan-1,3,5,7,9,11,13,15 octayl) octakis (oxy)) octakis (propane-1-sulfonate)] in a 96.8% yield. The chemical equation is represented by Figure 2(b).

Figure 7 depicts 1H NMR spectrum of the compound 2. 1H-NMR of Compound-2, D2O (400 MHz): d 2.07 – 1.90 (m, 16H), 2.90 -2.87 (m, 16H), 3.2 (s, 96H), 3.15 (t, 16H).

The compound 2 was a colour less thick liquid, having:
Chemical Formula: C56H144N8O44S8Si8
Molecular Weight: 2114.94.

Example 1(c): Experimental procedure for the synthesis of (tetramethylammonium butyl sulfonate) octa silsesquioxane (7)
Tetramethylammonium silicate octaanion (50 g, 43.93 mmol, 1 eq) and 1,4-butane sultone (53.6 g, 439.3 mmol, 10 eq) in dry toluene was refluxed for 48 hours. The reaction mixture was concentrated to remove toluene and washed with ethyl acetate and dichloromethane to remove unreacted 1,3-butane sultone. Trace amount of solvent was removed under vaccum rotary vapour to give 90 g of a colour less gel compound 7 [Tetramethylammonium 4, 4', 4'', 4''', 4'''', 4''''', 4'''''', 4''''''' - ((2, 4, 6, 8, 10, 12, 14, 16, 17, 18, 19, 20 – dodecaoxa - 1, 3, 5, 7, 9, 11, 13, 15-octasilapentacyclo [9.5.1.13,9.15,15.17,13] icosan-1, 3, 5, 7, 9, 11, 13, 15-octayl)octakis(oxy)) octakis (butane-1-sulfonate)] in a 96.8% yield.

Figure 8 depicts 1H NMR spectrum of the compound 7. 1H-NMR of compound 7, D2O (400 MHz): d 1.7 – 1.4 (m, 32H), 3.7 – 3.9 (m, 16H), 3.09 (s, 96H), 3.45 – 3.5 (m, 16H).

The compound 7 was a colour less thick liquid, having:
Chemical Formula: C64H160N8O44S8Si8
Molecular Weight: 2227.16.

EXAMPLE 2: Experimental procedure for the synthesis of POSS Sulfonic acid (3)
Compound 2 was taken in 2 vol. of methanol cooled to 0°C and drop wise methanolic HCl was added to obtain pH of up to 2 and strirred for 30 min at 0°C. Ensure that the pH of the reaction mass was pH 2. The mixture was allowed to stir at 25°C to 30°C for 2 hours and the solid obtained is washed with 1 vol. methanol suck dried for 30 min and dried under vacuum at 45°C for 6 h to yield 90% of compound 3 [3,3',3'',3''',3'''',3''''',3'''''',3'''''''-((2,4,6,8,10,12,14,16,17,18,19,20-dodecaoxa-1,3,5,7,9,11,13,15-octasilapentacyclo [9.5.1.13, 9.15,15.17,13]icosan-1,3,5,7,9,11,13,15-octayl)octakis(oxy))octakis(propane-1-sulfonic acid)] as an off white solid. The chemical equation is represented by Figure 3.

Figure 9 depicts 1H NMR spectrum of the compound 3. 1H-NMR of compound 3, D2O (400 MHz): d 1.77 – 1.99 (m, 16H), 2.79 – 2.94 (m, 16H), 3.49 – 3.73 (m, 16H).

The compound 3 was an off white solid, having:
Chemical Formula: C24H56O44S8Si8
Molecular Weight: 1529.83

EXAMPLE 3:
Example 3(a): Experimental procedure for the synthesis of Octakis (hydridodimethylsiloxy) octasilsesquioxane
To a 250-mL bottom flask with a magnetic stirrer, 100 mL hexane and 14.3 mL (0.33 mol) dimethylchlorosilane were added under nitrogen. The flask was placed in an ice bath and 40 mL of compound 1 octaanion solution was added via an addition funnel over a 1 hour period. The final mixture was stirred continuously for another 4 hours. The two layers were separated with a separator funnel. The hexane layer was dried over anhydrous sodium sulfate, gravity filtered and the solvent removed by rotary evaporation to yield a white powder. This powder was rinsed with methanol and collected by vacuum filtration. The product was dried in a vacuum at 70°C/5h to yield 3.5 g white powder of compound 4 [Octakis (hydridodimethylsiloxy) octasilsesquioxane] in a 70% yield. The chemical equation is represented by Figure 5(a). Figure 10 depicts 1H NMR spectrum of the compound 4.

Example 3(b): Experimental procedure for the synthesis of Octakis (N,N dimethyl propyldimethylsiloxy) octasilsesquioxane
Compound 4 (200 mg, 0.196 mmol) was placed in a 25 mL Schlenk flask equipped with a reflux condenser and a magnetic stirrer. Toluene (5 mL) was added to dissolve the cube, followed by N,N dimethylallylamine (0.184 mL, 1.568 mmol). The reaction flask was carefully degassed and refilled with N2 three times. Pt catalyst solution (2 mM, 0.05 mL) was added. When Pt(dvs) was used, the reaction was so exothermic that it began to reflux. The reaction began to reflux immediately due to the exothermic hydrosilylation and was stirred for overnight. Toluene was removed under vacuum rotary vapor. Compound 5 [Octakis (N,N dimethyl propyldimethylsiloxy) octasilsesquioxane] thus obtained is a brown colour gel (160 mg, 48%), soluble in methanol, THF, acetone, CH2Cl2 etc and characterization by NMR analysis showed that all the Si-H disappeared. The chemical equation is represented by Figure 5(b). Figure 11 depicts 1H NMR spectrum of the compound 5.

Example 3(c): Experimental procedure for the synthesis of dodecaoxa-octasila pentacyclo icosan-octayl) octakis (oxy))octakis(dimethylsilanediyl))octakis(propane-3,1-diyl))octakis (dimethylammoniumdiyl))octakis(propane-1-sulfonate)
Compound 5 (1 eq) and 1,3-propane sultone (10 eq) were taken in dry toluene and refluxed for 48 hours. The reaction mixture was then concentrated to remove toluene and washed with ethyl acetate and dichloromethane to remove unreacted 1,3-propane sultone. Trace amount of solvent was removed under vacuum rotary vapour to give a pale-yellow liquid compound 6 [(3,3',3'',3''',3'''',3''''',3'''''',3'''''''-(((((2,4,6,8,10,12,14,16,17,18,19,20-dodecaoxa-1,3,5,7,9,11,13,15-octasilapentacyclo [9.5.1.13,9.15,15.17,13]icosan-1,3,5,7,9,11,13,15octayl)octakis(oxy))octakis(dimethylsilanediyl)) octakis(propane-3,1-diyl))octakis(dimethylammoniumdiyl))octakis(propane-1-sulfonate)] at 90% yield. The chemical equation is represented by Figure 5(c).

Figure 12 depicts 1H NMR spectrum of the compound 6. 1H-NMR of compound 6, D2O (400 MHz): d 3.62 – 3.42 (m,16H), 2.93 (s, 48H), 2.77 – 2.89 (m, 16H), 1.99 – 2.17 (m, 16H), 1.58 – 1.75 (m, 16H), 0.94 – 1.05 (m, 16H), 0.45 (t, 16H, J = 8.33 Hz) and 0.00 (s, 48H).

The compound 6 was a pale-yellow liquid, having:
Chemical Formula: C80H192N8O44S8Si16
Molecular Weight: 2676.27

Example 3(d): Experimental procedure for the synthesis of dodecaoxa-octasila pentacyclo icosan-octayl) octakis (oxy))octakis(dimethylsilanediyl))octakis(propane-3,1-diyl))octakis (dimethylammoniumdiyl))octakis(alkane-1-sulfonate)
Compound 5 (1 eq) and 1,4-butane sultone (10 eq) were taken in dry toluene and refluxed for 48 hours. The reaction mixture was concentrated to remove toluene and washed with ethyl acetate and dichloromethane to remove unreacted 1,4-butane sultone. Trace amount of solvent was removed under vacuum rotary vapour to give a pale-yellow liquid compound 8 [4,4',4'',4'A'',4'''',4''''',4'''''',4'''''''-(((((2,4,6,8,10,12,14,16,17,18,19,20-Dodecaoxa- 1,3,5,7,9,11,13, 15-octasilapentacyclo[9.5.1.13,9.15,15.17,13] icosan-1,3,5,7,9,11,13,15-octayl)octakis(oxy)) octakis(dimethylsilanediyl))octakis(propane-3,1-diyl))octakis(dimethylammoniumdiyl)) octakis (butane-1-sulfonate)] 90% yield.

Figure 13 depicts 1H NMR spectrum of the compound 8. 1H-NMR of compound 8, D2O (400 MHz): d 3.25 – 3.39 (m,16H), 3.10 – 3.24 (m, 16H), 2.91 (s, 48H), 2.82 (t, 16H, J = 6.82 Hz), 1.97 – 2.16 (m, 16H), 1.54 – 1.75 (m, 16H), 0.95 – 1.05 (m, 16H), 0.37 (t, 16H, J = 8.58 Hz) and 0.00 (s, 48H).

The compound 8 was a pale-yellow liquid, having:
Chemical Formula: C88H208N8O44S8Si16
Molecular Weight: 2788.48

We Claim:

1. A compound of Formula I

Formula I
wherein ‘R1’is selected from a group comprising ‘-O-R+’, ‘-O-(CH2)n-SO3-R+’, ‘-O-(CH2)n-SO3H’, ‘-O-SiMe2-H’, ‘-O-SiMe2-(CH2)nNMe2’ and ‘-O-SiMe2-(CH2)nNMe2+-(CH2)nSO3-’;
R+ is N(Me)4+; and
wherein n is 3 or 4.

2. The compound as claimed in claim 1, wherein ‘R1’is selected from a group comprising ‘-O-NMe4+’, ‘-O-(CH2)3-SO3-NMe4+’, ‘-O-(CH2)3-SO3H’, ‘-O-SiMe2-H’, ‘-O-SiMe2-(CH2)3NMe2’ and ‘-O-SiMe2-(CH2)3NMe2+(C3H6) SO3-’.

3. The compound as claimed in claim 1 or 2, wherein the compound is:

Formula II
wherein R+ is N(Me)4+; and
wherein n is 3 or 4.

4. The compound as claimed in claim 1 or 2, wherein the compound is:

Formula III
wherein n is 3 or 4.

5. The compound as claimed in claim 1 or 2, wherein the compound is:

Formula IV
wherein n is 3 or 4.

6. The compound as claimed in claim 1 or 2, wherein the compound is selected from a group comprising:
,
,
,
,
,

,

, and
.

7. The compound as claimed in any of the preceding claim, wherein the compound has melting point of less than 25°C.

8. A composition comprising a compound as claimed in any of claims 1-7 optionally along with industrially acceptable excipient(s).

10. The compound as claimed in claim 1 or the composition as claimed in claim 8, wherein the composition is employed in preparation of solvent, catalyst, explosive detector, fuel cells, lithium batteries, coatings, sensors, oil, gas, or electronics.

11. A method of employing the compound or composition of any of the preceding claims, for industrial application.

12. A method of making a compound of Formula I, comprising:
- reacting tetramethylammonium hydroxide with tetraethoxysilane to obtain tetramethylammonium silicate octaanion;
or
- reacting tetramethylammonium hydroxide with tetraethoxysilane to obtain tetramethylammonium silicate octaanion followed by treating with C3-C4 alkane sultone to obtain (tetramethylammonium alkyl sulfonate) octa silsesquioxane;
or
- reacting tetramethylammonium hydroxide with tetraethoxysilane to obtain tetramethylammonium silicate octaanion followed by treating with C3-C4 alkane sultone to obtain (tetramethylammonium alkyl sulfonate) octa silsesquioxane; and hydrolyzing the (tetramethylammonium alkyl sulfonate) octa silsesquioxane to obtain octakis(propane-1-sulfonic acid);
or
- reacting tetramethylammonium hydroxide with tetraethoxysilane to obtain tetramethylammonium silicate octaanion followed by treating with dimethylchlorosilane to obtain Octakis (hydridodimethylsiloxy) octasilsesquioxane;
or
- reacting tetramethylammonium hydroxide with tetraethoxysilane to obtain tetramethylammonium silicate octaanion followed by treating with dimethylchlorosilane to obtain Octakis (hydridodimethylsiloxy) octasilsesquioxane; and hydrosilylating the Octakis (hydridodimethylsiloxy) octasilsesquioxane with N,N-dimethylallylamine to obtain Octakis (N,N dimethyl alkyldimethylsiloxy) octasilsesquioxane;
or
- reacting tetramethylammonium hydroxide with tetraethoxysilane to obtain tetramethylammonium silicate octaanion followed by treating with dimethylchlorosilane to obtain Octakis (hydridodimethylsiloxy) octasilsesquioxane; hydrosilylating the Octakis (hydridodimethylsiloxy) octasilsesquioxane with N,N-dimethyl alkenylamine to obtain Octakis (N,N dimethyl alkyldimethylsiloxy) octasilsesquioxane followed by treating with C3-C4 alkane sultone to obtain dodecaoxa-octasila pentacyclo icosan-octayl) octakis (oxy))octakis(dimethylsilanediyl)) octakis (propane-3,1-diyl)) octakis (dimethylammoniumdiyl))octakis(alkane-1-sulfonate).

13. The method as claimed in claim 12, wherein the (tetramethylammonium alkyl sulfonate) octa silsesquioxane is (tetramethylammonium propyl sulfonate) octa silsesquioxane or (tetramethylammonium butyl sulfonate) octa silsesquioxane; the tetramethylammonium silicate octa alkyl sulfonic acid is tetramethylammonium silicate octa propyl sulfonic acid or tetramethylammonium silicate octa butyl sulfonic acid; the Octakis (N,N dimethyl alkyldimethylsiloxy) octasilsesquioxane is Octakis (N,N dimethyl propyldimethylsiloxy) octasilsesquioxane or Octakis (N,N dimethyl butyldimethylsiloxy) octasilsesquioxane; and the dodecaoxa-octasila pentacyclo icosan-octayl) octakis (oxy))octakis(dimethylsilanediyl)) octakis(propane-3,1-diyl)) octakis (dimethylammoniumdiyl))octakis(alkane-1-sulfonate) is dodecaoxa-octasila pentacyclo icosan-octayl) octakis (oxy))octakis(dimethylsilanediyl))octakis(propane-3,1-diyl))octakis (dimethylammoniumdiyl))octakis(propane-1-sulfonate) or dodecaoxa-octasila pentacyclo icosan-octayl) octakis (oxy))octakis(dimethylsilanediyl)) octakis(propane-3,1-diyl)) octakis (dimethylammoniumdiyl))octakis(butane-1-sulfonate).

14. The method as claimed in claim 12, wherein the C3-C4 alkane sultone is 1,3-propane sultone or 1,4-butane sultone; and the N,N-dimethyl alkenylamine is N,N-dimethylallylamine or N,N-dimethyl-3-butenylamine.

15. The method as claimed in claim 12, wherein the hydrolysis of the (tetramethylammonium alkyl sulfonate) octa silsesquioxane is carried out at pH of about 2.0 to obtain the tetramethylammonium silicate octa alkyl sulfonic acid; and wherein the hydrosilylation is carried out in presence of catalyst selected from a group comprising platinum(dvs) (Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane), H2PtCl6 (Speier's catalyst) and C16H24N3PRuF6 (Pentamethylcyclopentadienyltris (acetonitrile)ruthenium(II) hexafluorophosphate).

16. The method as claimed in claim 12, wherein said method is carried out in presence of solvent selected from a group comprising water, methanol, toluene, hexane, ethyl acetate, dichloromethane, acetone, methanolic hydrochloric acid, 2-propanol hydrochloric acid or any combination thereof.

17. The method as claimed in claim 12, wherein one or more step(s) of the method is carried out under nitrogen atmosphere, at a temperature ranging from about 20°C to about 120°C, and/or for a time period ranging from about 30 minutes to about 48 hours.

18. The method as claimed in claim 12, wherein the method further comprises acts selected from a group comprising isolation and/or purification of the corresponding compound; wherein the said isolation is carried out by acts selected from a group comprising addition of solvent, cooling, heating, removal of solvent, drying, filtration, extraction and combination of acts thereof; and wherein the purification is carried out by water washing or solvent(s) washing or a combination thereof. ,