Monoalkyltin compounds with low polyalkyl contamination, compositions and methods thereof

Abstract

The pure composition comprises a monoalkyltin trialkoxide compound represented by the chemical formula RSn(OR')3 or a monoalkyltin triamide compound represented by the chemical formula RSn(NR'2)3, and no more than 4 mol% of a dialkyltin compound relative to the total tin amount, wherein R is a hydrocarbon group having 1 to 31 carbon atoms, and wherein R' is a hydrocarbon group having 1 to 10 carbon atoms. A method for forming the pure composition is described. The solid composition comprises a monoalkyltriamidetin compound represented by the chemical formula RSn‑(NR'COR”)3, wherein R is a hydrocarbon group having 1 to 31 carbon atoms, and wherein R' and R” are independently hydrocarbon groups having 1 to 10 carbon atoms. The composition is suitable for forming a resist composition suitable for EUV patterning, wherein the composition has high EUV absorption.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is a continuation-in-part of co-pending U.S. patent application No. 15 / 950,292 filed by Edson et al. on April 11, 2018, entitled “Monoalkyltin compounds, compositions thereof, and methods having low polyalkyl contamination”, and is a continuation-in-part of co-pending U.S. patent application No. 15 / 950,286 filed by Edson et al. on April 11, 2018, entitled “Monoalkyltin compounds, compositions thereof, and methods having low polyalkyl contamination”, both of which are incorporated herein by reference. Field of the Invention

[0003] The present invention relates to a high-purity composition of monoalkyltin triamide, monoalkyltin trialkoxide or monoalkyltin triamide and a preparation method thereof. Background of the Invention

[0005] Organometallic compounds are of interest for providing metal ions in solution processable forms. Alkyltin compounds provide radiation sensitive Sn-C bonds that can be used to photolithographically pattern structures. Processing of semiconductor materials with ever-shrinking dimensions has led to the need for more versatile materials to achieve the required patterning resolution, and alkyltin compounds are promising advanced materials for providing patterning advantages. SUMMARY OF THE INVENTION

[0007] In a first aspect, the present invention relates to a composition comprising a monoalkyltin trialkyloxide compound represented by the chemical formula RSn(OR')3 or a monoalkyltin triamine compound represented by the chemical formula RSn(NR'2)3, and no more than 4 mol% of a dialkyltin compound relative to the total amount of tin, wherein R is a hydrocarbon group having 1 to 31 carbon atoms, and wherein R' is a hydrocarbon group having 1 to 10 carbon atoms. The monoalkyltin triamine compound can be reacted with an alcohol represented by the formula HOR" in an organic solvent to form RSnOR"3, wherein R" is independently a hydrocarbon group having 1 to 10 carbon atoms to form a product composition, wherein the product composition has no more than 4 mol% of a dialkyltin compound relative to the total amount of tin.

[0008] In another aspect, the present invention relates to a composition comprising a monoalkyltriamidotin compound represented by the chemical formula RSn-(NR'COR")3, wherein R is a hydrocarbon group having 1 to 31 carbon atoms, and wherein R' and R" are independently hydrocarbon groups having 1 to 10 carbon atoms.

[0009] In another aspect, the present invention relates to a method for forming a monoalkyltin triamide compound, the method comprising: reacting an alkylating agent selected from the group consisting of RMgX, R2Zn, RZnNR'2 or a combination thereof with Sn(NR'2)4 in a solution comprising an organic solvent, wherein R is a hydrocarbon group having 1 to 31 carbon atoms, wherein X is a halogen, and wherein R' is a hydrocarbon group having 1 to 10 carbon atoms.

[0010] In other aspects, the present invention is directed to a method for selectively forming a monoalkyltin trialkoxide compound having low dialkyltin contamination, the method comprising: reacting RSn(NR'2)3 with an alcohol represented by the formula HOR" in an organic solvent to form RSnOR"3, wherein the RSn(NR'2)3 reactant has no more than about 4 mole % of dialkyltin contaminant and is the product of the method described herein, wherein R is a hydrocarbon group having 1 to 31 carbon atoms, and wherein R' and R" are independently hydrocarbon groups having 1 to 10 carbon atoms.

[0011] In another aspect, the present invention relates to a method for forming a monoalkyltriamidotin, the method comprising: reacting a monoalkyltin triamide compound represented by the chemical formula RSn(NR'2)3 with an amide (R"CONHR"') in an organic solvent, wherein R is a hydrocarbon group having 1 to 31 carbon atoms, and wherein R', R" and R"' are independently hydrocarbon groups having 1 to 8 carbon atoms; and collecting a solid product represented by the formula RSn(NR"'COR")3.

[0012] In addition, the present invention relates to a method for forming a monoalkyltin trialkoxide, the method comprising: reacting a monoalkyltriamidotin compound (RSn(NR"'COR")3) with an alkali metal alkoxide compound (QOR', wherein Q is an alkali metal atom) in an organic solvent to form a product compound represented by the chemical formula RSn(OR')3, wherein R is a hydrocarbon group having 1 to 31 carbon atoms, and wherein R', R" and R'" are independently hydrocarbon groups having 1 to 10 carbon atoms.

[0013] Furthermore, the present invention relates to a process for purifying monoalkyltintrialkoxides, which process comprises distilling a blend of monoalkyltintrialkoxides and a tetradentate non-planar complexing agent. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is t-BuSn(NMe2)3 synthesized using Grignard reagent 1 H NMR spectrum.

[0016] Figure 2 To get Figure 1The spectrum in the corresponding t-BuSn(NMe2)3 119 Sn NMR spectrum.

[0017] Figure 3 CySn(NMe2)3 (Cy = cyclohexyl) is synthesized using alkyl zinc halide reagents 1 HNMR spectrum.

[0018] Figure 4 To get Figure 3 The spectrum in the corresponding CySn(NMe2)3 119 Sn NMR spectrum.

[0019] Figure 5 CyHpSn(NMe2)3 was synthesized using dialkyl zinc reagent 1 H NMR spectrum.

[0020] Figure 6 To get Figure 5 The spectrum in the corresponding CyHpSn(NMe2)3 119 Sn NMR spectrum.

[0021] Figure 7 It is t-BuSn(NMe2)3 synthesized by using Grignard reagent and neutral base 1 H NMR spectrum.

[0022] Figure 8 To get Figure 7 The spectrum in the corresponding t-BuSn(NMe2)3 119 Sn NMR spectrum.

[0023] Fig. 9 t-BuSn(Ot-Am)3 is synthesized from t-BuSn(NMe2)3 1 H NMR spectrum.

[0024] Fig.10 To get Fig. 9 The spectrum in the corresponding t-BuSn(Ot-Am)3 119 Sn NMR spectrum.

[0025] Fig.11 The structure of tert-butyltri(N-methylacetamido)tin(IV) was determined by X-ray structure determination of the crystalline product.

[0026] Fig.12 is tert-butyltri(N-methylacetamido)tin(IV) 1 H NMR spectrum.

[0027] Fig.13is tert-butyltri(N-methylacetamido)tin(IV) 119 Sn NMR spectrum.

[0028] Fig.14 t-BuSn(Ot-Am)3 is synthesized from tert-butyltri(N-methylacetamido)tin(IV) 1 H NMR spectrum.

[0029] Fig.15 t-BuSn(Ot-Am)3 is synthesized from tert-butyltri(N-methylacetamido)tin(IV) 119 Sn NMR spectrum.

[0030] Fig.16 It is t-BuSn(NMe2)3 doped with t-Bu2Sn(NMe2)2 119 Sn NMR spectrum: The signal at 85.48 ppm corresponds to t-BuSn(NMe2)3, and the signal at 56.07 ppm corresponds to (t-Bu)2Sn(NMe2)2.

[0031] Fig.17 It comes from through Fig.16 The first fraction collected by fractionation of the sample is t-BuSn(NMe2)3 119 Sn NMR spectrum.

[0032] Fig.18 It comes from through Fig.16 The second fraction of the sample collected by fractionation is t-BuSn(NMe2)3 119 Sn NMR spectrum.

[0033] Fig.19 It comes from through Fig.16 The third fraction of the sample collected by fractionation is t-BuSn(NMe2)3 119 Sn NMR spectrum.

[0034] Fig. 20 is the baseline tBuSn(O t Am)3 119 Sn NMR spectrum.

[0035] Fig.21 is tBuSn(O t Am)3 119 Sn spectrum. DETAILED DESCRIPTION OF THE INVENTION

[0037] Methods for obtaining monoalkyltin compositions, particularly monoalkyltin triamides, monoalkyltin trialkoxides and monoalkyltin triamides, with low polyalkyltin byproducts have been found. In particular, three approaches have been developed for synthesizing monoalkyltin triamides with low polyalkyltin byproducts, which can be used in the form synthesized or in a further purified form. The selectively synthesized monoalkyltin triamides can then be used to synthesize monoalkyltin trialkoxides with corresponding low polyalkyltin byproducts. In addition, whether pure or impure, the monoalkyltin triamides can be reacted in solution to form solid monoalkyltin triamides that do not contain polyalkyl byproducts in the crystals, and the methods have been found to effectively form monoalkyltin triamides with low polyalkyltin byproducts. The synthesized monoalkyltin amides and monoalkyltin alkoxides can be further purified by fractionation to effectively reduce polyalkyl contaminants to levels that are lower than those that may have been obtained by direct synthesis. Analytical techniques can be used to evaluate the contaminant levels. In some embodiments, quantitative NMR (qNMR) shows that the byproducts can be reduced to a concentration of less than 1 mol%. The product tin composition can be used as a precursor for synthesizing a desired patterning material. For applications as a precursor for patterning materials, the reduction of polyalkyltin byproducts can be useful for the properties of the monoalkyltin product composition for use as EUV and UV photoresists or electron beam patterning resists.

[0038] Monoalkyltin triamides can be useful intermediate products in the preparation of organotin resists. Methods for preparing monoalkyltin triamides have previously employed lithium reagents to convert tin tetraamides into the desired triamides. For example, the monoalkyltin triamides can be prepared according to D.; Puff, H.; Beckerman, NJ Organomet. Chem. 1985, 293, 191 (which is incorporated herein by reference) are used to synthesize tert-butyltri(diethylamino)tin (t-BuSn(NEt2)3) using lithium reagents. However, these methods using lithium reagents may produce a mixture of monoalkyl and dialkyltin products. In addition, lithium contamination may be undesirable for semiconductor applications. Reported methods for preparing monoalkyltin triamines containing secondary alkyl groups produce a mixture rich in monoalkyl, dialkyl and trialkyltin products. As explained below, it may be desirable to reduce any polyalkyl byproducts such as dialkyltin contaminants. Although monoalkyl and dialkyl species can be separated from each other for some compounds, the separation or purification process generally increases manufacturing costs, and entrained dialkyl impurities may damage the performance of downstream photoresist products. Therefore, it may be desirable to synthesize monoalkyltin compounds with higher purity so that any subsequent purification, such as purification by fractionation (if necessary), results in even lower dialkyl or polyalkyl contamination. If the synthesized composition itself is sufficiently pure, further purification by fractional distillation can be avoided.

[0039] The use of high purity monoalkyltin compounds, especially mercapto compounds, as polymer stabilizers is described in U.S. Pat. No. 8,198,352, Deelman et al., entitled "High Purity Monoalkyltin Compounds and Uses Thereof," and U.S. Pat. No. 9,745,450, Frenkel et al., entitled "Stabilizers Containing High Purity Monoalkyltin Compounds," both of which are incorporated herein by reference. These patents describe the formation of pure monoalkyl halides as precursors for the synthesis of stabilizer compounds. The methods described herein focus on the synthesis of high purity monoalkyltin triamides, monoalkyltin trialkoxides, or monoalkyltriamidotin compounds using a unique and efficient synthetic route that can be combined with fractionation for purification.

[0040] For example, the use of alkyl metal coordination compounds in high performance radiation-based patterning compositions is described in U.S. Patent No. 9,310,684 to Meyers et al., entitled “High Resolution Patterning Compositions Based on Organic Metallic Solutions,” which is incorporated herein by reference. Refining of these organometallic compositions for patterning is described in published U.S. Patent Application No. 2016 / 0116839A1 to Meyers et al., entitled “High Resolution Patterning Compositions Based on Organic Metallic Solutions and Corresponding Methods,” and published U.S. Patent Application No. 2017 / 0102612A1 to Meyers et al., entitled “Organotin Oxide Hydroxide Patterning Compositions, Precursors, and Patterning,” both of which are incorporated herein by reference.

[0041] Radiation patterning using alkyltin compositions typically proceeds using alkyltin oxo-hydroxo moieties. The compositions synthesized herein can be effective precursors for forming alkyltin oxo-hydroxo compositions that are effective for high resolution patterning. The alkyltin precursor compositions contain groups that can be hydrolyzed with water or other suitable reagents under appropriate conditions to form an alkyltin oxo-hydroxo patterning composition, which can be represented by the formula RSnO (1.5-(x / 2)) (OH) x where 0 < x ≤ 3. The following reactions illustrate the hydrolysis and condensation reactions that can transform a composition with hydrolyzable groups (X):

[0042] RSnX3 + 3H2O → RSn(OH)3 + 3HX,

[0043] RSn(OH)3 → RSnO (1.5-(x / 2)) OH x + (x / 2)H2O.

[0044] If the hydrolysis product HX is volatile enough, in-situ hydrolysis can be carried out with water vapor during the substrate coating process, but the hydrolysis reaction can also be carried out in solution to form an alkylzinc oxo-hydroxo composition. These processing options are further described in the '612 application.

[0045] Polyalkyltin impurity compositions can affect condensation and promote photoresist outgassing during lithographic processing, which increases the likelihood of tin contamination of the equipment used for film deposition and patterning. Based on these concerns, there is a clear need to reduce or eliminate dialkyl or other polyalkyl components. Three classes of compositions are relevant to the processes described herein for reducing polyalkyltin contaminants in the final resist composition, specifically monoalkyltin triaminides, monoalkyltin trialkoxides, and monoalkyltriamidotin. As further explained below, monoalkyltin triaminide compositions can also serve as precursors for monoalkyltin trialkoxide and monoalkyltriamidotin compositions. Monoalkyltriamidotin compositions can also be convenient precursors for forming monoalkyltin trialkoxide compositions. Monoalkyltin trialkoxide compositions can be desirable components in precursor patterning composition solutions because they can be transformed by in-situ hydrolysis and condensation to form monoalkyltin oxo-hydroxo compositions with alcohol by-products that are generally volatile enough to be removed in correspondence with in-situ hydrolysis.

[0046] Monoalkyltin triamide compositions with low polyalkyl contaminants can be directly synthesized using any of the three methods described herein. Methods using Zn reagents have been specifically developed for synthesizing pure monoalkyltin triamides containing secondary alkyl groups. In addition, fractional distillation can be used to further purify at least some of the monoalkyltin triamide compositions. The synthesis of monoalkyltriamidotin compositions from monoalkyltin triamide compositions provides another approach to reducing polyalkyl contaminants. These approaches can be combined to obtain further reductions in polyalkyl contaminants.

[0047] The monoalkyltin triamine composition can generally be represented by the formula RSn(NR')3, wherein R and R' are independently: an alkyl or cycloalkyl group having 1 to 31 carbon atoms and wherein one or more carbon atoms are optionally substituted by one of a variety of heteroatom functional groups containing O, N, Si and / or halogen atoms, or an alkyl or cycloalkyl group further functionalized with a phenyl or cyano group. In some embodiments, R' may contain ≤10 carbon atoms and may be, for example, a methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl or tert-amyl group. The R group may be a linear, branched (i.e., secondary or tertiary at the metal-bonded carbon atom) or cyclic hydrocarbon group. Each R group individually and generally has 1 to 31 carbon atoms, 3 to 31 carbon atoms for groups having secondary bonded carbon atoms, and 4 to 31 carbon atoms for groups having tertiary bonded carbon atoms. In particular, branched alkyl ligands for compounds wherein the compound may be represented by R 1 R 2 R 3 Some patterned compositions of CSn(NR')3 may be ideal, where R 1 and R 2 are independently alkyl groups having 1 to 10 carbon atoms, and R 3 is hydrogen or an alkyl radical having 1 to 10 carbon atoms. As described below, this representation of the alkyl ligand R applies analogously to the general description of R 1 R 2 R 3 Other embodiments of CSn(X)3, wherein X corresponds to a trialkoxide or triaminate moiety. In some embodiments, R 1 and R 2 A cyclic alkyl moiety may be formed, and R 3 Other groups in the cyclic part may also be attached. Suitable branched alkyl ligands may be, for example, isopropyl (R 1 and R 2 is methyl, and R 3 is hydrogen), tert-butyl (R 1 , R 2 and R 3 is methyl), tert-amyl (R1 and R 2 is methyl, and R 3 -CH2CH3), sec-butyl (R 1 is methyl, R 2 is -CH2CH3, and R 3 is hydrogen), neopentyl (R 1 and R 2 is hydrogen, and R 3 For example, cyclohexyl, cyclopentyl, cyclobutyl and cyclopropyl. Examples of suitable cyclic groups include, for example, 1-adamantyl (-C(CH2)3(CH)3(CH2)3 or tricyclo (3.3.1.13,7) decane bonded to a metal at a tertiary carbon) and 2-adamantyl (-CH(CH)2(CH2)4(CH)2(CH2) or tricyclo (3.3.1.13,7) decane bonded to a metal at a secondary carbon). In other embodiments, the hydrocarbon group may include an aryl or alkenyl group, such as a benzyl or allyl group, or an alkynyl group. In other embodiments, the hydrocarbon group ligand R may include any group consisting only of C and H and containing 1 to 31 carbon atoms. For example: straight or branched alkyl (i-Pr ((CH3) 2CH-), t-Bu ((CH3) 3C-), Me (CH3-), n-Bu (CH3CH2CH2CH2-)), cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl), olefinic group (alkenyl, aryl, allyl) or alkynyl, or a combination thereof. In another embodiment, suitable R groups may include hydrocarbon groups substituted by heteroatom functional groups (including cyano, thiol, silyl, ether, ketone, ester or halogenated groups, or a combination thereof).

[0048] The alkyltin trialkoxide composition can be composed of the formula RSn(OR 0 )3, and the alkyltriamidotin composition can be represented by the formula RSn(NR"COR"')3. The R groups in the formulas of the alkyltin trialkoxides and alkyltriamidotin compositions can be the same R groups as summarized above for the alkyltin triamide compositions, and the corresponding discussion of these R groups above is as if reproduced in its entirety in this paragraph. 0 , R”, R”’ and R 0 The groups may independently be hydrocarbon groups having 1 to 10 carbon atoms, such as methyl, ethyl, etc. R" and R'" may also independently be hydrogen.

[0049] In some embodiments, the composition herein (monoalkyltin triamine compound, monoalkyltin trialkoxide or monoalkyltriamide tin) can have the dialkyltin pollutant of the amount of no more than about 4 mol % relative to tin, no more than about 3 mol % in further embodiments, no more than about 2 mol % in some embodiments, no more than about 1 mol % of dialkyltin pollutant in other embodiments, no more than about 0.5 mol % of dialkyltin pollutant in other embodiments, and no more than about 0.1 mol % in another embodiment. It will be appreciated by those of ordinary skill in the art that other ranges of dialkyltin pollutants within the above-mentioned clear and distinct ranges are considered and within the present disclosure. The level of dialkyltin pollutants can be carried out using any reasonable analytical technique usually. In some embodiments, by quantitative NMR, the amount of dialkyltin diamine compound or dialkyltin dialkoxide can be shown as close to or below 0.1 mol %. Due to potential undetermined pollutants, the quantitative of monoalkyltin compositions can be measured in several percentages, but utilizing quantitative NMR as described in the following examples, the error level of the smaller amount of dialkyltin pollutants provides reliability.

[0050] Without derivatization 1 H and 119 Sn NMR spectroscopy was used to analyze the monoalkyl Sn precursor. Purity was determined using the integrated value of the NMR peak of the monoalkyl Sn precursor relative to the internal standard. Precautions were taken to ensure that the value accurately reflected the purity of the monoalkyl Sn precursor. The sample was irradiated using a calibrated 90 degree pulse to 1 H NMR and inverse-gated 119 Sn{ 1 H}NMR experiment. In addition, for 1 H and 119 Sn{ 1 For both H}NMR experiments, the T1 relaxation values ​​of the standard and the analyte were measured using an inversion recovery experiment. The measured T1 values ​​were used to set a recycle delay time equal to 5 times the longest T1 time of the sample, which allowed the nuclei (Z = 1-e -(经过的时间 / T1) ) almost completely relaxes to equilibrium (Z = 1-e -5 =0.99326). Finally, for 119 Sn{ 1 H}NMR experiments, in order to explain the reduced intensity of spectral peaks that are not located in the center of the spectral window, the B1 profile of the NMR spectrometer is measured and interpreted by centering the spectrum between the analyte and the standard. Detection and quantification of trace Sn impurities utilizes anti-gating to improve the signal-to-noise ratio in the spectrum 119 Sn{ 1The parameter set for the H}NMR spectrum was implemented: the center and scan width of the spectrum were set to the calibration values, and the sample was irradiated using a 30 degree pulse with a cycle delay time set to 1 second. Quantitative values ​​were attributed to the low levels of Sn impurities detected using linear regression analysis. The method provided a limit of quantification of dialkyl, tetraamine and tetraalkoxide tin impurities of 0.1% relative to the monoalkyltin compound. In "Method development in quantitative NMR towards metrologically traceable organic certified reference materials used as 31 P qNMR standards (for 31 P (2015) "Development of quantitative NMR methods for traceable organic certified reference materials using qNMR standards"), "Anal. Bioanal. Chem., 407: 3115-3123 (2015); and Pauli et al. "Importance of Purity Evaluation and the Potential of Quantitative 1 HNMR as a Purity Assay 1 Quantitative NMR is further described in "The Potential of H NMR", J. Medicinal Chemistry, 57, 9220-9231 (2014), both of which are incorporated herein by reference.

[0051] Typically, the improved process for preparing monoalkyltin triamine compounds herein includes reacting a compound (also described as an alkylating agent) with a tin tetraamine compound having an alkyl supply group. Desirable results have been achieved, wherein the alkylating agent can be a Grignard reagent, a diorganozinc reagent or a monoorganozinc reagent. These synthesized products can directly generate monoalkyltin triamine compounds with low polyalkyl pollutants, which can be used to form an anti-corrosion agent or can be further purified to even further reduce the level of pollutants. In the synthetic method, the alkylating agent selectively replaces the amine group of the tin tetraamine compound with an alkyl group. In some embodiments, the reaction selectively generates monoalkyltin triamine compounds with low polyalkyltin pollutants, particularly low dialkyltin pollutants. The synthetic method improves the selectivity and yield of monoalkyltin triamine compounds by limiting the formation of dialkyltin byproducts. The method can be used for branched alkyl systems. Monoalkyltin triamine compounds with low polyalkyl pollutants can then be used to form monoalkyltin trialkoxides with low polyalkyl pollutants. As discussed further below, the formation of crystalline monoalkyltriamidotin compositions provides an alternative approach to avoiding polyalkyl contaminants by excluding the polyalkyl contaminants from the crystals.

[0052] For the reaction of forming monoalkyltin triamine compounds, tin tetraamines can be commercially available or synthesized using known techniques. For example, tetra(dimethylamino)tin Sn(NMe2)4 can be obtained from Sigma-Aldrich. For the synthesis of monoalkyltin compositions, the concentration of the tin tetraamine reactant in the solution can generally be from about 0.025M to about 5M, from about 0.05M to about 4M in further embodiments, or from about 0.1M to 2M in other embodiments. Those of ordinary skill in the art will recognize that other ranges of reactant concentrations within the above-defined ranges are considered and within the present disclosure. Typically, the relevant reaction of introducing alkyl ligands into Sn can be initiated in a reactor under an inert gas purge and in the dark by tin tetraamines in the solution. In an alternative embodiment, some or all of the tin tetraamine reactants are gradually added, in which case the above concentrations may not be directly related, because the higher concentrations in the solution gradually added may be appropriate, and the concentration in the reactor may be temporary.

[0053] The alkylating agent is typically added in an amount that is relatively close to the stoichiometric amount. In other words, the alkylating agent is added to provide a molar equivalent of one alkyl group for one tin atom. If the alkylating agent can provide multiple alkyl groups, such as a diorganozinc compound that can provide two alkyl groups per zinc atom, the stoichiometric amount of the alkylating agent is adjusted accordingly to provide about one alkyl group for each Sn. Thus, for the diorganozinc compound, about one mole of Zn is required for every two moles of Sn. The amount of the alkylating agent can be about ±25%, about ±20%, or about ±15% relative to the stoichiometric amount of the agent, or in other words, it can be the stoichiometric amount of the agent + or - a selected amount to achieve the desired process performance. One of ordinary skill in the art will recognize that other ranges of relative amounts of the alkylating agent within the above explicit ranges are contemplated and within the present disclosure.

[0054] Examples 2 and 3 use approximately stoichiometric amounts of alkylating agents, while Examples 1 and 4 use approximately 110% (or 100%+10%) of alkylating agents. The alkylating agent dissolved in an organic solvent can be gradually added to the reactor, such as dropwise or allowed to flow at a suitable rate to control the reaction. The addition rate can be adjusted to control the course of the reaction, such as over a time course of about 1 minute to about 2 hours, and in a further embodiment over a time course of about 10 minutes to about 90 minutes. Taking into account the addition rate, the concentration of the alkylating agent added to the solution can be adjusted within a reasonable value. In principle, the alkylating agent can be started in the reactor with the gradual addition of tetraamine tin. Those of ordinary skill in the art will recognize that other ranges of alkylating agents and addition times within the above-specified ranges are considered and are within the scope of the present disclosure.

[0055] The reaction of introducing the alkyl ligand to the tin atom can be carried out in a low oxygen, substantially oxygen free or oxygen free environment, and an effective inert gas purge can provide a suitable atmosphere, such as an anhydrous nitrogen purge or an argon purge. The following additives have been observed to reduce the addition of the second alkyl group to tin: pyridine, 2,6-lutidine, 2,4-lutidine, 4-dimethylaminopyridine, 2-dimethylaminopyridine, triphenylphosphine, tributylphosphine, trimethylphosphine, 1,2-dimethoxyethane, 1,4-di ... Alkane and 1,3-di Alkane. Other neutral coordination bases can work in the same way. The reaction can also optionally contain about 0.25 to about 4 moles of neutral coordination base / mole tin. The reaction can be protected from light during the reaction. The reaction can be carried out in an organic solvent, for example in an alkane (such as pentane or hexane), an aromatic hydrocarbon (such as toluene), an ether (such as diethyl ether C2H5OC2H5) or a mixture thereof. The solvent can be anhydrous to avoid reaction with water. The reaction is usually carried out for about 15 minutes to about 24 hours, in a further embodiment about 30 minutes to about 18 hours, and in another embodiment about 45 minutes to about 15 hours. The temperature during the reaction can be about -100°C to about 100°C, in a further embodiment about -75°C to about 75°C, and in another embodiment about -60°C to about 60°C. Cooling or heating can be used to control the reaction temperature within the desired range, and the control of the rate of addition of the reactants can also be used to affect the temperature evolution during the reaction process. The product monoalkyltin triamine compound is usually an oily substance that can be purified using vacuum distillation. Typical yields of about 50% to 85% have been observed.One of ordinary skill in the art will recognize that other ranges of concentrations and process conditions within the explicit ranges above are contemplated and within the present disclosure.

[0056] The alkylating agent can be a Grignard reagent, a diorganozinc reagent or a monoorganozinc reagent. The Grignard reagent can be an organomagnesium halide. Specifically, the Grignard reagent in the reaction can be RMgX, wherein X is a halogen, typically Cl, Br or I. R can be an alkyl or cycloalkyl group, and has 1 to 31 carbon atoms, and generally, a more complete description of R can be as described above for the R portion of the product composition, and the description of the R portion of the product composition above is as if it is incorporated as a whole for discussion herein. For example, an alkyl or cycloalkyl group can be branched, can contain an aromatic group, and / or can have one or more heteroatom functional groups containing such as O, N, Si and / or halogen. Grignard reagents are commercially available, or can be synthesized using known methods. Commercial sources include American Elements Company, Sigma-Aldrich and many other suppliers.

[0057] In some embodiments, the alkylating agent is a diorganozinc reagent. The diorganozinc reagent can provide two alkyl groups for tin, so the amount of the diorganozinc reagent is adjusted due to the difference in molar equivalents. Specifically, the diorganozinc reagent can be R2Zn. R can be an alkyl or cycloalkyl group having 1 to 31 carbon atoms. A more detailed description of the R group can be as described above for the R portion of the product composition, and the above discussion of the R group associated with the product monoalkyltin compound is considered part of this discussion, as if it is reproduced here. For example, the alkyl or cycloalkyl group can be branched and can have one or more heteroatom functional groups containing, for example, O, N, Si and / or halogen. The following exemplifies dicyclopentyl zinc ((C7H 13 )2Zn) reactant. Diorganozinc compounds are commercially available or can be synthesized using known techniques. Commercial sources include, for example, Alfa Aesar, Sigma-Aldrich, Rieke Metals (Nebraska, USA) and Triveni Chemicals (India). The reactants in the examples are synthesized.

[0058] In other embodiments, the alkylating agent is a monoorganozinc amine (RZnNR'2). R can be an alkyl or cycloalkyl group typically having 1 to 30 carbon atoms. A more complete description of the R group can be as described above for the R portion of the product composition, and the above discussion of the R group associated with the product monoalkyltin compound is considered to be part of this discussion, as if reproduced here. For example, the alkyl or cycloalkyl group can be branched and can have one or more carbon atoms substituted by one or more heteroatom functional groups containing such as O, N, Si and / or halogen. In some embodiments, R' is an alkyl or cycloalkyl group, which can be substituted by heteroatoms. In some embodiments, R' can have 1 to 8 carbon atoms, in some embodiments 1 to 5 carbon atoms, and in other embodiments 1 to 3 carbon atoms. R' can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl or tert-amyl. Monoorganozinc amides can be synthesized, for example, from alkylzinc halides (RZnX, X=I, Br, Cl) and lithium amide (LiNR'2), which are reagents commercially available from Sigma-Aldrich.

[0059] Monoalkyltin triamines prepared using the above method or other methods not described in detail herein can be further purified using fractionation. In order to reduce the temperature of the distillation process, the pressure can be reduced, for example, to a pressure of about 0.01 torr to about 10 torr, to a pressure of about 0.05 torr to about 5 torr in a further embodiment, and to a pressure of about 0.1 torr to about 2 torr in a further embodiment. Suitable fractionation columns with a volume suitable for the process can be used, and these are commercially available. Temperature can be controlled in a container containing the material to be purified and along the column to achieve the desired separation. The thermal conditions of an embodiment are provided in the following example 8, and these conditions can be easily extended to other compositions based on the teachings herein. If the dialkyltin triamine pollutant has a higher boiling point than the monoalkyltin triamine, the monoalkyltin triamine can be separated during the distillation process. The fraction can be taken out by removing a certain volume of liquid during each stage of the fractionation, but Example 8 shows a good separation with a reasonable yield without detectable pollutants. If the dialkyltin triamide contaminant has a lower boiling point than the monoalkyltin triamide, the dialkyltin triamide can be separated out during the distillation process by collecting and discarding the initial fraction.

[0060] Monoalkyltin trialkoxide can be prepared by reacting corresponding monoalkyltin triamine compound with alcohol in non-aqueous solvent and alkali. The low polyalkyltin pollutants in the monoalkyltin triamine compound using the treatment described herein can be carried forward to the product monoalkyltin trialkoxide, so that the product monoalkyltin trialkoxide has the low dialkyltin pollutants that are basically in the above-mentioned mole %. Suitable organic solvents include, for example, alkanes (such as pentane or hexane), aromatic hydrocarbons (such as toluene), ethers (such as ether C2H5OC2H5) or their mixtures. Alcohol is selected to provide the required alkoxylated group so that alcohol ROH is introduced as the -OR group of the part connected to tin. The list of suitable R groups is provided above, and is accordingly relevant to the alcohol. The embodiment using tertiary amyl alcohol is provided below, but other alcohols can be used similarly to provide the required -OR alkoxylated ligands. Alcohol can be provided roughly with stoichiometric amount. Due to the use of alcohol to replace three aminating groups, three molar equivalents of alcohol will be stoichiometric amount. Typically, the amount of alcohol may be at least about -5% stoichiometric equivalents, and in further embodiments may be at least about stoichiometric equivalents, and a large excess of alcohol may be used. Example 5 was conducted at +3.33% excess of the stoichiometric equivalents of alcohol, i.e., at 3.1 moles of alcohol / mole of monoalkyltin triamide.

[0061] In order to promote the purification of product alkyl tin trialkoxide, a tetradentate chelating agent can be added to coordinate with unreacted tin tetraamine compound material, thereby forming a complex that does not evaporate during distillation. For example, TREN, triethylenetetramine (trien) or other tetradentate non-planar coordination ligands can be used to coordinate with unreacted material to promote purification. The coordination ligand can be added at any time before distillation from the selected time of the reaction start, and the addition is about 0.5 mol % to about 15 mol % relative to the tin molar amount, and about 1.0 mol % to about 10 mol % in a further embodiment. It has also been found that tetradentate non-planar coordination ligands (such as TREN) can also be effectively coordinated with tin tetraalkoxide compounds and suppress its distillation. Generally, it will be ideal to suppress distillation with a tetradentate chelating agent with at least roughly stoichiometric amount for each tin tetraamine compound. Thus, for a given amount of tetraamine, the amount of tetravalent complexing agent can be about 1:1 on a molar basis, or at least about 95 mole %, in some embodiments about 98 mole % to about 200 mole %, and in other embodiments about 99 mole % to about 120 mole % of tetravalent complexing agent / mole of tin tetraamine. Thus, the tetradentate non-planar coordinating ligand can be effective in improving the purification of monoalkyltin trialkoxide from tetraamine or tetraalkoxide tin compounds. One of ordinary skill in the art will recognize that other ranges of reactant amounts within the above explicit ranges are contemplated and within the present disclosure. If desired, fractionation can be performed to further purify the monoalkyltin trialkoxide from the polyalkyl contaminant.

[0062] Although monoalkyltin triamine compounds with low polyalkyl pollutants can be effectively used to form derivatives with correspondingly low polyalkyl pollutants, even if monoalkyltin triamine compounds do not have low pollutant levels, the synthesis of monoalkyltriamide-tin from monoalkyltin triamine compounds can also be used to form products with low pollutants, because the formation of crystals of monoalkyltriamide-tin can obviously exclude polyalkyl pollutants. Therefore, the synthesis of monoalkyltriamide-tin provides a supplementary or alternative path to form a composition with low dialkyltin pollutants. Therefore, in some embodiments, monoalkyltin triamine compounds (such as reaction paths from commercial sources or with higher pollutant levels) with higher pollutants than required can be used, while still obtaining a product composition with low dialkyltin pollutants. Monoalkyltriamide-tin compounds can be used to form monoalkyltin trialkoxide compositions with low dialkyltin pollutants.

[0063] The reaction involves adding an N-alkylamide such as N-methylacetamide (CH3CONHCH3) to a monoalkyltin triamide. In general, the N-alkylamide reactant can be written as R a CONHR b, where R a and R b Independently be a hydrocarbon group with 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, etc. The crystal structure of the product compound has been determined, and the structure is provided in the following examples. In summary, the amide group in the product is bonded to tin at the nitrogen atom to form the corresponding ligand structure.

[0064] In order to control the heat generation and progress of the reaction, the N-alkylamide reactant can be gradually added, such as added in at least about 2 minutes. The monoalkyltin triamine compound can be dissolved in an organic solvent with a concentration of about 0.1M to about 8M, and in a further embodiment, the concentration of about 0.2M to about 6M is dissolved in an organic solvent. Suitable organic solvents include, for example, alkanes (such as pentane or hexane), aromatic hydrocarbons (such as toluene), ethers (such as ether C2H5OC2H5) or mixtures thereof. The reaction is exothermic, and heat does not need to be added usually. The reaction product can form crystals, and the reaction can usually continue for about 20 minutes to 24 hours. After the reaction is completed, the solvent can be removed to collect the crystals of the product. The crystals can be washed and dried. It is observed that dialkyltin compounds are excluded from the product crystals. Those of ordinary skill in the art will recognize that other ranges of reactant concentrations, addition times and reaction times within the above-mentioned clear ranges are considered and are within the present disclosure.

[0065] For the treatment of radiation-sensitive resist compositions, it may be desirable to react monoalkyl triamide tin to form monoalkyl tin trialkoxide compounds. Alkali metal alkoxides can be used to replace triamide ligands with alkoxide ligands by reacting in organic slurries. When forming monoalkyl tin trialkoxide compounds, it is dissolved in an organic solvent with a concentration of about 0.01M to 2M and about 0.04M to about 1M in a further embodiment. Alkali metal alkoxide compounds can be written as ZOR', wherein Z is an alkali metal atom, such as K, Na or Li, and-OR' is an alkoxide group, which is RSn(OR')3 product composition provides corresponding R' groups. Some alkali metal alkoxides are commercially available, for example, commercially available from Sigma-Aldrich, and these compounds are highly hygroscopic, so they can be isolated from air. Suitable organic solvents include, for example, alkanes (such as pentane or hexane), aromatic hydrocarbons (such as toluene), ethers (such as ether C2H5OC2H5) or their mixtures. The alkali metal alkoxide can be provided in a stoichiometric amount corresponding to three alkoxide groups / tin atom. The reaction can be carried out for about 15 minutes to about 48 hours. The product liquid can be distilled to purify the product. Those of ordinary skill in the art will recognize that other ranges of concentration and time within the above-mentioned clear ranges are all considered and are within the scope of the present disclosure. Example

[0066] Embodiment 1: Synthesis of t-BuSn(NMe2)3

[0067] This example relates to the synthesis of tin compounds having a tert-butyl group bonded to the tin in place of the N-methyl amide.

[0068] A 5L 3-neck round bottom flask was loaded with Sn(NMe2)4 (827.5 g, 2805 mmol, Sigma) in an argon filled glove box. Anhydrous ether (2000 mL) was added to the flask. A certain amount of t-BuMgCl (1500 mL, 2.06 M (just titrated), 3090 mmol) was added to a separate 2L 2-neck round bottom flask. The flask was stoppered and connected to a Schlenk line. The Sn(NMe2)4 solution was transferred to a 5L jacketed reactor and stirred at 240 RPM. An automatic syringe pump was used at 50 ml min -1 The t-BuMgCl solution is delivered to the jacketed reactor of 5L at a rate of 1.5%. The temperature of the mixture in the jacketed reactor is maintained at 20°C. After the t-BuMgCl solution is fully added, the reaction is stirred overnight. The resulting mixture is transferred through the filter reactor of 10L and enters into the 3-neck round-bottom flask of 5L equipped with a stirring rod. The jacketed reactor of 5L and the solid in the filter reactor are cleaned with pentane (2x 1L). The washings are collected in the 3-neck round-bottom flask of 5L equipped with a stirring rod, and volatiles are removed under vacuum. After removing volatiles, the light yellow oily suspension corresponding to the crude product is observed. The flask is taken to the glove box, and the crude product is filtered through a thick (course) pore sintered glass funnel. The filtrate is transferred to the 2-neck round-bottom flask of 2L equipped with a stirring rod, the flask is plugged and transferred to a Schlenk line. The crude product was purified by short path vacuum distillation into a 1 L receiving flask (500 mTorr, 65°C-75°C) to give 323 to 604 g of a 37-70% colorless oil identified as t-BuSn(NMe2)3. Proton NMR ( Figure 1 )and 119 Sn NMR Figure 2 ) to characterize the product, the following peaks were observed: 1 H NMR(C6D6,MHz):2.84(s,18H,-NCH3),1.24(s,9H,H3CC-); 119 Sn NMR (C6D6, 186.4 MHz: -85.69. Quantitative proton NMR and tin NMR were performed to assess the purity of the product based on standards. qNMR: 1 H, standard: 1,3,5-trimethoxybenzene, purity: 94.5 (3) mol% (94.5 ± 0.3 mol%) monoalkyltin;119 Sn, standard: MeSnPh3, purity: 93.5(2) mol% monoalkyltin.

[0069] About trace impurities 119 Sn qNMR:

[0070]

[0071] *Values ​​calculated by extrapolation from the calibration curve.

[0072] Embodiment 2: CySn(NMe2 ) Synthesis of 3 (Cy = cyclohexyl)

[0073] This example concerns the synthesis of tin compounds having a cyclohexyl group from the Zn reagent (instead of the N-methylamine group of Sn(NMe2)4).

[0074] In an argon-filled glove box, a 250mL 3-neck round-bottom flask (RBF) was filled with Sn(NMe2)4(5.61g, 19.0mmol, Sigma). Anhydrous ether (150mL) was added to the flask. Separately, w / LiNMe2(0.97g, 19.0mmol, Sigma) and anhydrous ether (20mL) were loaded into a 100mL RBF. CyZnBr (Cy=cyclohexyl, 48.5mL, 0.392M, 19.0mmol, Sigma]) was slowly added to this flask to generate CyZnNMe2. CyZnBr was slowly added to control the reaction temperature because the reaction was exothermic. A dropping funnel and a reflux condenser were connected to a 3-neck 250mL RBF on a Schlenk tube under an effective argon purge. The CyZnNMe2 solution was added to a dropping funnel and dispensed dropwise under stirring while covering a 250 mL RBF with aluminum foil to prevent light from entering. After complete addition, the reaction was stirred overnight and the solvent was removed in vacuo to give a light orange oil with precipitation. The oil was purified by vacuum distillation (58 to 62° C., 150 mTorr). The resulting product was 4.38 g (69% yield) of a colorless oil identified as CySn(NMe2)3. Proton NMR ( Figure 3 )and 119 Sn NMR Figure 4 ) characterized the product and the following peaks were observed: 1 H NMR(C6D6,500MHz):2.85(s,18H,-NCH3),1.86(m,3H,-CyH),1.69(m,2H,-CyH),1.53(m,3H,-CyH),1.24(m,3H,-CyH); 119 Sn NMR(C6D6,186.4MHz):-73.77.

[0075] Example 3. Synthesis of (CyHp)Sn(NMe2)3 (CyHp=cycloheptyl)

[0076] This example relates to the synthesis of a tin triamide with a cycloheptyl group as shown below: In this synthesis, the cycloheptyl group from the zinc reagent (CyHp)2Zn replaces the N-methylamine group of Sn(NMe2)4.

[0077]

[0078] In an argon-filled glove box, a 250 mL 3-neck round bottom flask (RBF) was charged with Sn(NMe2)4 (6.49 g, 22.0 mmol, Sigma). Anhydrous ether (150 mL) was added. The dropping funnel and reflux condenser were connected to a 3-neck 250 mL RBF on a Schlenk tube under an effective argon purge. Separately prepared (CyHp)2Zn (0.351 M, 31.3 mL, 11.0 mmol) was synthesized as follows: 2CyHpMgBr+Zn(OCH3)2. While covering the 250 mL RBF with aluminum foil to prevent light from entering, the (CyHp)2Zn solution was added to the dropping funnel under an effective argon purge and then distributed dropwise under stirring. After complete addition, the reaction was stirred overnight. The solvent was then removed in a vacuum. The reaction flask was taken to a glove box and hexane was added. By The solution was filtered and the solvent was removed in vacuo to give a colorless oil with a precipitate. The oil was purified by vacuum distillation (82 to 86° C., 180 mTorr). The resulting product was 4.01 g (52% yield) of a colorless oil identified as (CyHp)Sn(NMe2)3. Proton NMR ( Figure 5 )and 119 Sn NMR Figure 6 ) to characterize the product, the following peaks were observed: 1 HNMR(C6D6,500MHz):2.84(s,18H,-NCH3),2.01(m,2H,-CyHpH),1.82(m,1H,-CyHpH),1.69-1.23(m,10H,-CyHpH); 119 Sn NMR(C6D6,186.4MHz):-66.93.

[0079] Example 4. Preparation of t-BuSn(NMe2)3 with the addition of base

[0080] This example demonstrates the synthesis of a tin composition by the reaction of a Grignard reagent with Sn(NMe2)4 in the presence of a base.

[0081]

[0082] A 5 L 3-neck RBF was charged with Sn(NMe2)4 (539.0 g, 1.827 mol, Sigma) in an argon filled glove box. Approximately 3 L of anhydrous ether and pyridine (289.1 g, 3.66 mol) were added to the flask. Two necks of the flask were stoppered with glass stoppers and a vacuum connection tube was connected to the third. Separately, a 2 L 2-neck RBF was charged with 1 L of t-BuMgCl (Grignard reagent) (2.01 M (titrated), 2.01 mol, Sigma) measured in a volumetric flask. A 5 L jacketed Chemglass was prepared on an argon filled Schlenk tube. TM The reactor was used for high vacuum and heated reactions. The reactor was backfilled with argon and the jacket around the reactor vessel was then cooled to -30°C.

[0083] The contents of the 5 L 3-neck RBF were transferred to a Chemglass via polyethylene (PE) tubing under positive argon pressure. TM reactor. Stirring was started with an overhead stirrer and the temperature of the reaction was cooled to -15°C. On the Schlenk tube, the Grignard reagent was added through a polyethylene (PE) tube under positive argon pressure over the course of 20 to 30 minutes while maintaining the internal reaction temperature below 5°C. A dark orange color and a precipitate formed. After complete addition, the reaction was stirred overnight while protecting the reaction from light with aluminum foil and allowed to reach room temperature.

[0084] The reaction mixture was stirred at room temperature for 2 hours.The reaction mixture was stirred at room temperature for 2 hours.The reaction mixture was stirred at room temperature for 2 hours.The reaction mixture was stirred at room temperature for 3 ...3 hours.The reaction mixture was stirred at room temperature for 2 hours.The reaction mixture was stirred at room temperature for 3 hours.The reaction mixture was stirred at room temperature for 3 hours.The reaction mixture was stirred at room temperature for 3 hours.The reaction mixture was stirred at room temperature for 3 hours.The reaction mixture was stirred at room temperature for 3 hours.The reaction mixture was stirred at room temperature for 3 hours.The reaction mixture was stirred at room temperature for 3 hours.The reaction mixture was stirred at room temperature for 3 hours.The reaction mixture was stirred at room temperature for 3 hours.The reaction mixture was stirred at room temperature for 3 hours.The reaction mixture was stirred at room temperature for 3 hours.The reaction mixture was Figure 7 ( 1 H NMR) and 8( 119 Sn NMR) is similar to Figure 1 and 2 , and the product was shown to consist of monoalkyl species in equilibrium with Sn(NMe2)4. Quantitative proton NMR and tin NMR were performed with selected standards to evaluate the purity of the product. qNMR: 1 H, standard substance: 1,3,5-trimethoxybenzene, purity: 89.9 (7) mol% monoalkyltin;119 Sn, standard: MeSnPh3, purity: 93.6(4) mol% monoalkyltin.

[0085] About trace impurities 119 Sn qNMR:

[0086]

[0087] *Value calculated by extrapolation from the calibration curve

[0088] Example 5. Preparation of High Purity Monoalkyl Alkoxide t-BuSn(OtAm)3 from t-BuSn(NMe2)3

[0089] This example demonstrates the synthesis of monoalkyltin trialkoxides from the corresponding monoalkyltin triamides according to the following reaction.

[0090]

[0091] In a glove box, a 2L 2-neck RBF was prepared with ~500mL pentane and t-BuSn(NMe2)3 (329.4g, 1.07mol) from Example 4. The flask was tare on a balance and tris(2-aminoethyl)amine (3.91g, 26.7mmol) was added directly to the reaction mixture via a syringe. The amine complexes with and removes tetraamine tin during the reaction and purification. If tetraamine tin does not have to be removed from the system, the product of Example 1 can be used to synthesize additional monoalkyltin products. The reaction sequence can be continued with the materials synthesized according to Example 1. A magnetic stirring bar was added, and the reaction was then sealed and brought to a Schlenk tube. The flask was cooled in a dry ice / isopropanol bath. Separately, a 1L Schlenk flask was filled with tert-amyl alcohol (2-methyl-2-butanol) (292.2g, 3.315mol) and a small amount of pentane, which was then connected to the Schlenk tube. The alcohol / pentane solution in the Schlenk flask is transferred to a reaction flask through a sleeve pipe, the outlet of the reaction flask is purged to a mineral oil bubbler, which is connected online to the NMe2H acid trap solution for degassing. After adding alcohol completely, the reaction is allowed to reach room temperature, and stirred for 1 hour. After reacting for 1 hour, the solvent is removed in a vacuum, and the product is vacuum distilled (95 to 97° C., 500 mTorr) to obtain 435 g (93%) of a colorless oil. Fig. 9 ( 1 H NMR) and 10( 119 Sn NMR) shows the NMR spectrum of the final product t-BuSn(Ot-Am)3, and the following peaks are observed: 1HNMR(C6D6,500MHz):1.61(m,6H,-OC(CH3)2CH2),1.37(m,18H,-OC(CH3)2),1.28(s,9H,-C(CH3)3),1.01(m,9H,-OC(CH3)2CH2CH 3 ); 119 Sn NMR (C6D6, 186.4 MHz): -240.70. Quantitative proton NMR was performed to evaluate the purity level of the product. qNMR: 1 H, standard substance: 1,3,5-trimethoxybenzene, purity: 97.7(3) mol%; 119 Sn, standard: MeSnPh3, 99(1) mol% monoalkyltin.

[0092] Example 6. Preparation of tert-butyltri(N-methylacetamido)tin(IV)

[0093] This example demonstrates the synthesis of monoalkyltriamidotin compositions by the reaction of t-BuSn(NMe2)3 with N-methylacetamide.

[0094]

[0095] In a glove box, a 250 mL Schlenk round-bottom flask was filled with t-BuSn(NMe2)3 (40.13 g, 130 mmol) containing 1% t-Bu2Sn(NMe2)2. t-BuSn(NMe2)3 was synthesized by Example 1 or Example 4. 50 mL of toluene was added to the round-bottom flask, followed by the slow addition of N-methylacetamide (28.6 g, 391 mmol, Sigma) to control heat generation. All N-methylacetamide was washed into the reaction flask using another 30 mL of toluene. The flask was sealed with a ground glass stopper and transferred to a Schlenk tube. Large crystals precipitated from the solution over a period of several hours. Toluene was removed by cannula under effective argon purge. White crystals were harvested and washed twice with 100 mL of pentane using cannula addition and subsequent removal. They were vacuum dried to give 40.6 g (80%) of tert-butyltri(N-methylacetamido)tin(IV). Fig.11 The crystal structure of the solid determined by X-ray diffraction is shown. Fig.12 As shown in , the proton NMR spectrum produces the following peaks: 1 H NMR (C6D6, 500MHz): 2.52(s,9H,-NCH3), 2.01(m,2H,-CyHpH), 1.74(s,9H,-(H3C)3CSn), 1.69(s,9H,-CH3CO). like Fig.13 As shown in , the tin NMR spectrum produces the following peaks: 119Sn NMR(C6D6,186.4MHz):-346.5.

[0096] Example 7. Synthesis of t-BuSn(Ot-Am)3

[0097] This example demonstrates the synthesis of t-BuSn(Ot-Am)3 from the tert-butyltri(N-methylacetamido)tin(IV) product of Example 6.

[0098] In the glove box with argon atmosphere, the round-bottomed flask of 3L is filled with tert-butyl tris (N-methylacetamido) tin (IV) (100g, 255mmol) from Example 6, and NaOtAm (98g, 890mmol, Sigma) is added subsequently. Use magnetic stirrer and 2.5 inches long oval stirring rod to make the mixture become slurry in 1.5L pentane. The slurry thickens and becomes milky white after 30 to 60 minutes. Continue to stir for about 16h. Then the slurry is filtered through a medium porosity sintered glass funnel in the glove box, and the solid recovered is washed twice with 100mL of pentane. The solid left during the filtration forms a very thin cake, so stirring is used occasionally to promote collection.

[0099] The filtrate was transferred to a two-necked 2L flask equipped with a stirring bar, and the flask was then sealed with a ground glass stopper and a Schlenk inlet connection tube. The flask was removed from the glove box and connected to a vacuum line in a fume hood where excess solvent was stripped under vacuum. The crude product was then purified by vacuum distillation and collected in a 100 mL Schlenk storage flask. For the vacuum distillation, the oil bath was set to 150°C. The product was distilled at 300 mTorr and a temperature of 98 to 102°C to give 74 g (66%) of the product. Fig.14 As shown in , the proton NMR spectrum shows the following shifts: 1 H NMR shift [400MHz, C6D6]: 1.64 (q, 6H, -CH2), 1.39 (s, 18H, -C(CH3)2), 1.29 (s, 9H, (CH3)3CSn), 1.03 (t, 9H, -CCH3). Fig.15 As shown in 119 Sn NMR spectrum shows the following peaks: 119 Sn NMR shift [149.18 MHz, C6D6]: -241.9. Quantitative NMR was performed to assess purity according to the evaluation of standards. 1 H qNMR, standard: 1,3,5-trimethoxybenzene, purity: 97.3 (1) mol % monoalkyl.

[0100] About trace impurities 119 Sn qNMR:

[0101]

[0102] Example 8. Fractional purification

[0103] This example demonstrates the effectiveness of fractional distillation for the purification of t-BuSn(NMe2)3 by separating t-BuSn(NMe2)3 from a mixture of t-Bu2Sn(NMe2)2 and t-BuSn(NMe2)3.

[0104] In a glove box, a 3000 mL 3-neck round bottom flask (RBF) was charged with t-BuSn(NMe2)3 containing ~3.27% t-Bu2Sn(NMe2)2 (1420 g, 4.6 mol total); samples were prepared by the method described in Example 1 with varying t-BuMgCl:Sn(NMe2)4 ratios. Glass stoppers were placed in two of the necks of the RBF and the third was connected to a Schlenk tube. Separately, a 5 L Chemglass jacketed reactor was equipped with an overhead stirrer, temperature probe, and two 18 inch distillation columns stacked on top of each other. A Pro-Pak TM (ThermoScientific, 0.24in 2 ) High efficiency distillation column packing is filled with distillation column. A short-path distillation head with a temperature probe is connected to the top of the distillation column. The top of the short-path head is then connected to a 3-arm cow joint that holds three 500 mL Schlenk bombs. The reactor is evacuated and backfilled with argon three times. The t-Bu2-rich mixture is added to the reactor through a large cannula under argon. The jacketed reactor is heated to 110 to 120°C under reduced pressure (500 mTorr) to start distillation. The temperature at the bottom of the distillation column is measured to be 95 to 100°C, while the temperature at the top of the column is maintained at 58 to 60°C. Three fractions are collected and separated by 119 Sn NMR spectra were analyzed for each. Figure 16-19 is the combined sample ( Fig.16 ) and each of the three fractions (in order Figure 17-19 )of 119 Sn NMR spectrum. All three fractions showed no NMR signal of t-Bu2Sn(NMe2)2. The total yield of all fractions combined was 850 g (60%). 119 Sn NMR (C6D6, 186.4MHz): -85.45

[0105] Example 9 Vacuum distillation purification

[0106] This example shows the use of vacuum distillation for purification t- BuSn(OtAm)3 The effectiveness of preparing amine-free compositions was demonstrated by their separation from a mixture of Sn(OtAm)4 and t-BuSn(OtAm)3. Tris(2-aminoethyl)amine (TREN) was used as a purification aid.

[0107] In the glove box with argon atmosphere, 100mL round-bottom Schlenk flask was filled with t-BuSn(OtAm)3 contaminated by about 1.3% Sn(OtAm)4[25g, 55.825mmol], followed by 10mL anhydrous pentane. The mixture was stirred with a magnetic stirrer, and TREN[0.112g, 0.7686mmol] was then added using a glass pipette. The flask was sealed using a glass stopper for a 24 / 40ST joint and a Teflon valve for a side port. The flask was connected to a Schlenk tube and placed under an inert gas (nitrogen), and placed in a silicone oil bath. Stirring and heating control were achieved using a Heidolph HEI-TEC stirring plate with a Pt / 1000 temperature probe, so that the temperature control of the oil bath could be fed back. The bath was maintained at 45°C, and then excess solvent was stripped under vacuum. After verifying solvent removal using a mTorr vacuum gauge, a short path vacuum distillation apparatus was set up using a 50 mL Schlenk bomb flask as the receiving vessel. Vacuum distillation was performed at 300 mTorr absolute pressure, 150°C bath temperature, and vapor temperature in the range of 94 to 98°C.

[0108] Assuming 100% removal of Sn(O t The theoretical recovery of Am)4 was 24.66 g, and the distillate recovered was 21.70 g, giving a recovery of 88%. 119 Sn NMR spectrum Fig. 20 (baseline) and Fig.21 (purified). 119 Sn NMR shift [149.18 MHz, C6D6]: t Bu2Sn(O t Am)2: -113ppm; t BuSn(O t Am)3: -241ppm; Sn(O t Am)4: -370ppm.

[0109] The above embodiments are intended to be illustrative rather than restrictive. Other embodiments are also within the claims. In addition, although the present invention has been described with reference to specific embodiments, those skilled in the art will recognize that changes can be made in form and detail without departing from the spirit and scope of the present invention. Any incorporation by reference to the above documents is limited so as not to incorporate the subject matter contrary to the explicit disclosure herein. The extent to which a specific structure, composition and / or process is described herein with components, elements, ingredients or other divisions, it should be understood that, unless otherwise expressly stated, the disclosure herein encompasses specific embodiments, embodiments comprising specific components, elements, ingredients, other divisions or combinations thereof, and embodiments consisting primarily of such specific components, ingredients or other divisions or combinations thereof, which may include other features that do not change the basic nature of the subject matter, as indicated in the discussion.

Claims

1. A high-purity liquid composition, comprising: a monoalkyltin triamide compound represented by the chemical formula RSn(NR'2)3, and Not more than 0.5 mol % of dialkyltin compounds as impurities relative to the total tin content, wherein R is a hydrocarbon group having 1 to 31 carbon atoms, and wherein R' is a hydrocarbon group having 1 to 10 carbon atoms.

2. The composition of claim 1, wherein R is R 1 R 2 R 3 C-represented branched alkyl ligand, wherein R 1 and R 2 are independently alkyl groups having 1 to 10 carbon atoms, and R 3 is hydrogen or an alkyl group having 1 to 10 carbon atoms.

3. The composition of claim 1, wherein R comprises methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, sec-butyl, neopentyl, cyclohexyl, cyclopentyl, cyclobutyl or cyclopropyl.

4. The composition of claim 1, wherein R' comprises methyl, ethyl, isopropyl or tert-butyl.

5. The composition of claim 1, wherein R' comprises a tert-amyl group.

6. The composition of any one of claims 1 to 5 comprising no more than 0.1 mol % of a dialkyl tin compound.

7. A solution comprising the composition of claim 1 and an organic solvent.

8. The solution of claim 7, having a concentration of 0.005 M to 0.5 M, and wherein the solvent comprises an alcohol.

9. The solution of claim 7 or claim 8, wherein R comprises methyl, ethyl, isopropyl, tert-butyl, tert-amyl, sec-butyl, neopentyl, cyclohexyl, cyclopentyl, cyclobutyl or cyclopropyl, and wherein R' comprises methyl, ethyl, isopropyl, tert-butyl or tert-amyl.

10. A method for selectively forming a monoalkyltin trialkoxide compound having low dialkyltin contamination, the method comprising: The composition of any one of claims 1 to 5 is reacted with an alcohol represented by the formula HOR" in an organic solvent to form RSn(OR")3, wherein R" is independently a hydrocarbon group having 1 to 10 carbon atoms, thereby forming a product composition, wherein the product composition has no more than 0.5 mole % of dialkyl tin compound relative to the total amount of tin.

11. A method for selectively forming a monoalkyltin triamide compound having low dialkyltin contamination, the method comprising: reacting an alkylating agent selected from the group consisting of RMgX, R2Zn and RZnNR'2 or a combination thereof with Sn(NR'2)4 in a solution comprising an organic solvent to form a product composition, wherein R is a hydrocarbon group having 1 to 31 carbon atoms, wherein X is a halogen, and wherein R' is a hydrocarbon group having 1 to 10 carbon atoms, wherein the product composition has no more than 4 mol % of dialkyltin compounds relative to the total amount of tin.

12. The method of claim 11, wherein the solution has a concentration of 0.01 M to 5 M based on tin.

13. The method of claim 11, wherein the organic solvent comprises an alkane, an aromatic hydrocarbon, an ether, or a mixture thereof.

14. The method of claim 11, wherein the solution has a concentration of the alkylating agent that is ±25% relative to the stoichiometric reaction of the tin reagent and the alkylating agent.

15. The method of claim 11, wherein the reaction is carried out under an inert atmosphere by gradually adding the alkylating agent while being protected from ambient light.

16. The method of claim 11, wherein the alkylating agent is added gradually over a period of 10 to 90 minutes.

17. The method of claim 11, wherein the reaction is carried out at a temperature of -100°C to 100°C for a period of 15 minutes to 24 hours.

18. The method of claim 11, wherein the solution further comprises 0.25 to 4 molar equivalents of a neutral coordinating base relative to tin.

19. A method for selectively forming a monoalkyltin trialkoxide compound having low dialkyltin contamination, the method comprising: RSn(NR'2)3 is reacted with an alcohol represented by the formula HOR" in an organic solvent to form RSn(OR")3, wherein the RSn(NR'2)3 reactant has no more than 0.5 mol % of dialkyltin contaminants and is the product of the method of any one of claims 11-18, wherein R is a hydrocarbon group having 1 to 31 carbon atoms, and wherein R' and R" are independently hydrocarbon groups having 1 to 10 carbon atoms.

20. The method of claim 19, wherein the reaction is performed using a tetradentate chelating agent in an amount of 0.5 mol% to 15 mol% relative to the molar amount of tin.

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