Method for preparing an organotin compound

Abstract

Provided is a facile method for preparing certain organotin compounds having alkyl and alkylamino substituents. The method provides a highly pure form of organotin precursor compound, such as tris(dimethylamido)isopropyltin. Thus, the product of the method is particularly useful in the deposition of high purity tin oxide films, for example in extreme ultraviolet (EUV) lithography techniques used in the manufacture of microelectronic devices.

Description

Technical Field

[0001] The present invention belongs to the field of organotin chemistry. In particular, the present invention relates to an easy method for preparing certain organotin compounds, such as tris(dimethylamide)isopropyltin, with extremely high selectivity.

Background Art

[0002] It has been shown that certain organotin compounds are beneficial for the deposition of high-purity tin(II) oxide films in applications such as extreme ultraviolet (EUV) lithography technology used in the manufacture of certain microelectronic devices.

[0003] Organotin compounds having a combination of alkylamino groups and alkyl groups, which are beneficial as liquid precursors in the deposition of tin-containing films on microelectronic device substrates, have attracted particular interest. Therefore, an improved method for producing such organotin compounds in high-purity form for use in the deposition of high-purity tin oxide films is sought.

Summary of the Invention

[0004] Provided is an easy method for preparing certain organotin compounds having alkyl substituents and alkylamino substituents. The above method is particularly beneficial in situations where polyalkyl by-products cannot be efficiently removed by distillation because their boiling points are similar, for example, dialkyltin dialkylamides relative to monoalkyl species. The above method provides an organotin precursor compound in high-purity form, such as tris(dimethylamide)isopropyltin (CAS No. 1913978-89-8). Therefore, the product of the above method is particularly beneficial as a precursor in the deposition of tin oxide films, for example, in extreme ultraviolet (EUV) lithography technology used in the manufacture of microelectronic devices.

Brief Description of the Drawings

[0005]

Figure 1

Figure 2

[0006] As used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. As used in this specification and the appended claims, the term "or" is generally used in the sense of "and / or" unless the context clearly dictates otherwise.

[0007] The term "about" generally refers to a range of numerical values that are considered equivalent to the indicated value (e.g., having the same function or result). In many cases, the term "about" may include numbers rounded to the nearest significant figure.

[0008] A numerical range expressed using endpoints includes all the numbers contained within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0009] In a first aspect, the present invention relates to a method for preparing a composition comprising a compound of formula (I) TIFF0007684410000003.tif41170[wherein each R is independently selected from C 1 to C 5 alkyl groups, and R 1 is selected from C 1 to C 5 alkyl groups] comprising: a) a compound of formula R 1 SnX 3A compound [wherein X is selected from Cl, I, and Br], b) A compound of the formula Li(R) 2 N, and c) A compound of the formula R 2 NH, comprising combining, The compound of the formula R 2 NH is present in a molar excess relative to the compound of the formula R 1 SnX 3 A method is provided. For example, a composition comprising a compound of formula (I) can be prepared by a method comprising contacting a compound of the formula R 1 SnX 3 with a compound of the formula Li(R) 2 N and a compound of the formula R 2 NH. One or more of the steps of this method can preferably be carried out under conditions that minimize exposure of the materials and / or products to light.

[0010] C 1 ~C 5 Alkyl groups include straight-chain or branched-chain alkyl groups. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, sec-butyl, n-pentyl, isopentyl, and sec-pentyl. In this specification, each R and R 1 is independently selected from such groups, whereby compounds of formula (I) in which one or more groups are different from other groups can be defined. Preferably, R and R 1 are independently selected from C 1 ~C 3 alkyl groups.

[0011] As described above, the compound of the formula R 2 NH (i.e., a dialkylamine) is present in a molar excess relative to the compound of the formula R 1 SnX 3 In one embodiment, this molar excess is at least about 0.15 molar equivalents relative to the amount of the compound of the formula R 1 SnX 3 In another embodiment, the compound of the formula R 2 NH is dimethylamine, and R 1is isopropyl. In another embodiment, R 1 is isopropyl and X is chloro. In another embodiment, the compound of formula Li(R) 2 N is lithium dimethylamide, the compound of formula R 2 NH is dimethylamine, and the compound of formula R 1 SnX 3 is isopropyltin trichloride.

[0012] In this embodiment, examples of the compound of formula (I) include tris(dimethylamide)isopropyltin, tris(diethylamide)isopropyltin, tris(dipropylamide)isopropyltin, tris(methylethylamide)isopropyltin, tris(diisopropylamide)isopropyltin, tris(di-t-butylamide)isopropyltin, tris(di-n-butylamide)isopropyltin, tris(di-sec-butylamide)isopropyltin, tris(dineopentylamide)isopropyltin, tris(dimethylamide)methyltin, tris(diethylamide)methyltin, tris(di-n-propylamide)methyltin, tris(methylethylamide)methyltin, tris(diisopropylamide)methyltin, tris(di-t-butylamide)methyltin, tris(di-n-butylamide)methyltin, tris(di-sec-butylamide)methyltin, tris(dineopentylamide)methyltin, tris(dimethylamide)ethyltin, tris(diethylamide)ethyltin, tris(di-n-propylamide)ethyltin, tris(methylethylamide)ethyltin, tris(diisopropylamide)ethyltin, tris(di-t-butylamide)ethyltin, tris(di-n-butylamide)ethyltin, tris(di-sec-butylamide)ethyltin, tris(dineopentylamide)ethyltin, tris(dimethylamide)n-propyltin, tris(diethylamide)n-propyltin, tris(di-n-propylamide)n-propyltin, tris(methylethylamide)n-propyltin, tris(diisopropylamide)n-propyltin, tris(di-t-butylamide)n-propyltin, tris(di-n-butylamide)n-propyltin, tris(di-sec-butylamide)n-propyltin, tris(dineopentylamide)n-propyltin, tris(dimethylamide)n-butyltin, tris(diethylamide)n-butyltin, tris(dipropylamide)n-butyltin, tris(methylethylamide)n-butyltin, tris(diisopropylamide)n-butyltin, tris(di-t-butylamide)n-butyltin, tris(di-n-butylamide)n-butyltin, tris(di-sec-butylamide)n-butyltin,It contains tris(di-neopentylamide)n-butyltin etc.

[0013] The formula R 1 SnX 3 The compound of can be prepared, for example, by a redistribution reaction between iPrSnPh 3 (iPr = isopropyl and Ph = phenyl) and SnCl 4 In certain embodiments, the stoichiometry can vary between 1:1 and 3:1 (R 1 SnPh 3 :SnX 4 ) In one embodiment, the compound of the formula R 1 SnX 3 is distilled one or more times before use. In an implementation of the present invention where the compound of the formula R 1 SnX 3 is isopropyltin trichloride, distillation before use can provide a reactant that is at least about 99.9% pure.

[0014] In one embodiment, the compound of the formula R 1 SnX 3 includes isopropyltin trichloride, isopropyltin tribromide, and isopropyltin triiodide. In one embodiment, the compound of the formula R 1 SnX 3 is isopropyltin trichloride. Accordingly, the following references to isopropyltin trichloride apply equally to isopropyltin tribromide and isopropyltin triiodide, along with other compounds of the formula R 1 SnX 3 as defined herein. The compound of the formula R 1 SnX 3 may be added in the form of a solution or in the form of a slurry depending on the solvent used. For example, in a hydrocarbon solvent such as hexane, this may form a slurry, and in an ether such as tetrahydrofuran, these compounds may form a solution.

[0015] In the above method, the compound of the formula R 2 NH and the compound of the formula R 1 SnX3 is present in a molar excess relative to the compound. In certain embodiments, this molar excess is at least about 0.15, or at least about 4. In one embodiment, this molar excess can be from about 2 to about 10, such as from about 2 to about 8 or from about 2 to about 4, relative to the compound of formula R 1 SnX 3 .

[0016] In the above method, a nonpolar aprotic solvent, such as hexane, may be utilized. The above method can be carried out at a low temperature of from about -78 °C to about 10 °C. The reaction time can range from 1 to 60 hours at room temperature (i.e., from about 17 °C to about 27 °C). The reaction mixture can be filtered and then vacuum distilled to remove the solvent. A non-reactive filter aid, such as diatomaceous earth (i.e., celite), can be used, but higher purity products can be achieved without this filter aid, for example, because metal species are present in the filter aid. The crude product can be purified by short-path distillation after filtration of any residual solids.

[0017] In one embodiment, isopropyltin trichloride is distilled before use to remove impurities. For example, isopropyltin trichloride can be distilled to give a reactant that is at least about 99.9% pure.

[0018] Lithium dimethylamide may be commercially available or can be newly prepared from dimethylamine and an alkyllithium reagent.

[0019] As described above, the method of the present invention enables the synthesis of the compound of formula (I) with very high purity, with only very low levels of dialkyl impurities present. Thus, in another aspect, the present invention provides a composition comprising the compound of formula (I) TIFF0007684410000004.tif41170[wherein each R is independently selected from C 1 -C 5 alkyl groups, and R 1 is selected from C 1 -C 5 alkyl groups] . The composition contains less than about 0.5 mol% of the compound of formula (II). Provided is a composition comprising TIFF0007684410000005.tif36170.

[0020] In certain embodiments, R 1 is C 1 ~C 3 and is selected from alkyl groups such as methyl, ethyl, n-propyl, and isopropyl (iPr) groups.

[0021] In one embodiment, the composition comprising the compound of formula (I) contains less than about 0.1% of the compound of formula (II). In one embodiment, the compound of formula (II) is bis(dimethylamide)diisopropyltin and the compound of formula (I) is tris(dimethylamide)isopropyltin.

[0022] In another embodiment, the composition comprising the compound of formula (I) contains less than about 0.05% of the compound of formula (II). In one embodiment, the compound of formula (II) is bis(dimethylamide)diisopropyltin and the compound of formula (I) is tris(dimethylamide)isopropyltin.

[0023] In another embodiment, the composition comprising the compound of formula (I) contains less than about 0.04% of the compound of formula (II). In one embodiment, the compound of formula (II) is bis(dimethylamide)diisopropyltin and the compound of formula (I) is tris(dimethylamide)isopropyltin.

[0024] In another embodiment, the composition comprising the compound of formula (I) contains less than about 0.03% of the compound of formula (II). In one embodiment, the compound of formula (II) is bis(dimethylamide)diisopropyltin and the compound of formula (I) is tris(dimethylamide)isopropyltin.

[0025] In another embodiment, the composition comprising the compound of formula (I) comprises less than about 0.02% of the compound of formula (II). In one embodiment, the compound of formula (II) is bis(dimethylamide)diisopropyltin and the compound of formula (I) is tris(dimethylamide)isopropyltin).

[0026] As can be seen from the following Example L, when the compound of formula (I) is tris(dimethylamide)isopropyltin (i.e., each R is methyl and R 1 is isopropyl), the presence of the undesirable bis(dimethylamide)diisopropyltin impurity (i.e., each R is methyl and each R 1 is isopropyl, formula (II)) can reach a purity level such that it is not detected by conventional 119 Sn NMR analysis with an NMR dwell time for quantitative data collection of about 1 hour to about 10 hours, for example, using JEOL ECZ 400.

[0027] In the above method, a stoichiometric excess of the compound of formula R 1 SnX 3 compared to the compound of formula R 2 NH is believed to give the in situ intermediate Lewis base adduct having formula (A) TIFF0007684410000006.tif50170[wherein each R is independently selected from C 1 to C 5 alkyl groups, R 1 is selected from C 1 to C 5 alkyl groups, and X is selected from Cl, I, or Br] For example, each R and R 1 may be selected from C 1 to C 5 alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, sec-butyl groups. Accordingly, one embodiment of the present invention is a method for preparing a compound of formula (I) from a compound of formula (A), wherein the compound of formula (A) is a compound of formula R 2 NH and a compound of formula R 1 SnX 3formed from the reaction with the compound of, and then reacts with the compound of formula Li(R) 2 N. In this embodiment, the compound of formula R 2 NH is in excess relative to the compound of formula R 1 SnX 3 .

[0028] In a specific example of the above method, in one embodiment, an excess molar amount of dimethylamine compared to isopropyltin trichloride, which is from about 0.15 to about 10, gives an in-situ intermediate Lewis base adduct having formula (A-a) TIFF0007684410000007.tif41170 is considered to be obtained. In a similar manner, an excess molar amount of dimethylamine compared to ethyltin trichloride gives an in-situ intermediate Lewis base adduct having formula (A-d) TIFF0007684410000008.tif42170.

[0029] For example, when an excess molar amount of dimethylamine is utilized in the reaction, it has been observed that the formation of bis(dimethylamido)diisopropyltin, an undesirable dialkyl byproduct, is significantly reduced. In this regard, the reproduction of Example 1 of WO2017 / 066319 as shown in Comparative Example 1 below resulted in a product mixture of the desired tris(dimethylamido)isopropyltin and about 1.6 mole percent ( 119 determined by 119Sn NMR integration) of the undesirable bis(dimethylamido)diisopropyltin. Without wishing to be bound by any particular mechanism, it is believed that the excess dimethylamine forms the corresponding Lewis base adduct in situ, which advantageously improves the selectivity of the reaction upon reaction with lithium dimethylamide, thereby greatly improving the purity of the desired compound of formula (I), for example tris(dimethylamido)isopropyltin. Further, this effect is enhanced when care is taken to utilize reagents that are freshly prepared or purified.

[0030] As further evidence, the Lewis base adduct (A-a) TIFF0007684410000009.tif41170 was prepared, isolated, and crystallized.

[0031] The reaction of the adduct (A-a) with lithium dimethylamide gives tris(dimethylamide)isopropyltin at a contamination level as low as about 0.03%, 0.02%, 0.01%, or 0.001% with high yield and outstanding selectivity for the monoisopropyl species, and the NMR residence time for quantitative data collection was set to about 1 hour to about 10 hours using, for example, JEOL ECZ 400 in a conventional 119 Sn NMR analysis can be used to detect that it is not detected. Accordingly, in a further aspect, the present invention provides a compound of formula (A) that is useful as an intermediate in the synthesis of formula (I).

[0032] In one embodiment, the compound of formula (A) is added as a slurry in a hydrocarbon solvent to a slurry of lithium dimethylamide in a hydrocarbon solvent.

[0033] In one embodiment, lithium dimethylamide is freshly prepared from dimethylamine and an alkyllithium.

[0034] In a similar manner, the corresponding iodo-substituted tin compound of formula (A-b) and bromo-substituted tin compound of formula (A-c) TIFF0007684410000010.tif98170 can be prepared and isolated.

[0035] Accordingly, the compounds of formulas (A-a), (A-b), and (A-c) are also useful as intermediates in the synthesis of high-purity tris(dimethylamide)isopropyltin and form another aspect of the present invention.

[0036] Accordingly, in a further aspect, the present invention provides a method for preparing a composition comprising a compound of formula (I-a) TIFF0007684410000011.tif36170, comprising a compound of formula (A-a) Provided is a method comprising contacting TIFF0007684410000012.tif41170 with lithium dimethylamide. Furthermore, the present invention also relates to a compound of formula (I-d) A method for preparing a composition comprising TIFF0007684410000013.tif40170, A compound of formula (A-d) Provided is a method comprising contacting TIFF0007684410000014.tif42170 with lithium dimethylamide.

[0037] In the method of the present invention, lithium dimethylamide is either a solution or a slurry depending on the solvent or medium used. For example, lithium dimethylamide is usually a solution in tetrahydrofuran and usually in the form of a slurry in hydrocarbons. In one embodiment, the compound of formula (A-a) is a slurry in a hydrocarbon solvent such as hexane. In another embodiment, the compound of formula (A-a) is dissolved in an ether solvent such as tetrahydrofuran.

[0038] Typically, lithium dimethylamide is present in an excess molar amount, i.e., at least about 3 molar equivalents of lithium dimethylamide relative to 1 molar equivalent of the compound of formula (A-a), in order to fully react with the three chlorine atoms of the compound of formula (A-a). In one embodiment, about 3 to about 3.2 equivalents of lithium dimethylamide are used relative to the compound of formula (A). When preparing lithium dimethylamide, it may be advantageous to have an excess molar amount of dimethylamine, e.g., at least about 1.05 molar equivalents of dimethylamine (relative to an alkyllithium starting material such as n-butyllithium).

[0039] In one embodiment, the composition contains less than about 0.5 mol percent impurities, and the impurities consist of bis(dimethylamide)diisopropyltin.

[0040] The precursors for preparing the compounds of formula (A-b) and (A-c) can be prepared from the corresponding isopropyltrihalostannane compounds according to the following scheme TIFF0007684410000015.tif39170[where X is bromo or iodo]. Instead of an excess molar amount (e.g., about 3.5) of iodine or bromine, for example, (i) Mesubi, M.A.; Afolabi, M.O.; Falase, K.O. Halogen Cleavage of Cyanomethyltriphenylstannane. Inorg. Nucl. Chem. Lett. 1976, 12, 469~474, https: / / doi.org / 10.1016 / 0020-1650(76)80148-1, (ii) Bullard, R.H.; Robinson, W.B. Methylphenylstannanes. J. Am. Chem. Soc. 1927, 49, 1368~1373, https: / / doi.org / 10.1021 / ja01404a030, (iii) Shekouhian, M. Hassan. Organotin Compound - a Mechanistic Approach for Their Synthesis. J. Recent Adv. Appl. Sci. 1988, 3, 483~486, (iv) Bhattacharya, S.N.; Husain, Ishrat. Reactions of Tin-Naphthyl Bond with Halogens and Pseudohalogens. Indian J. Chem. Sect. Inorg. Phys. Theor. Anal. 1981, 20A, 1119~1121 and (v) Bhattacharya, S.N.; Raj, P.; Singh, Meenu. Studies on Synthetic and Structural Aspects of Some New Unsymmetric and Asymmetric Organotin(IV) Halides, Pseudohalides and Carboxylates and Their Complex Anions. Indian J. Chem. Sect. Inorg. Phys. Theor. Anal. 1979, 18A, 231~235, monoidochloride or moniodobromide can be utilized as described.

[0041] Thus, compounds of the following formula, such as the corresponding isopropyltin trichloride TIFF0007684410000016.tif26170[wherein X is bromo or iodo] can be contacted with dimethylamine up to 2.0, 4.0, or 6.0 molar equivalents to ensure the formation of Lewis base adducts (e.g., compounds of formula (A-b) and (A-c)), and then the solvent is removed under vacuum to obtain the compound in crystalline form. Thus, in a further embodiment, the present invention provides compounds of formula (A-a), (A-b), and (A-c) in crystalline form. In one embodiment, the crystalline form of the compound of formula (A-a) is as described in FIG. 1.

[0042] In a further aspect, the present invention relates to a compound of formula R 1 SnR 4 3 [wherein R 4 is selected from aryl, C 2 - C 8 alkenyl, and C 2 - C 8 alkynyl] is reacted with monoiodochloride or monoiodobromide, respectively, thereby providing the corresponding isopropyltin trihalide and iodobenzene, to provide a compound of formula R 1 SnX 3 [wherein X is chloro or bromo and R 1 is selected from C 1 - C 5 alkyl groups]. In this regard, aryl includes aromatic carbocyclic rings, such as phenyl and naphthyl, optionally substituted by C 1 - C 6 alkyl, halo, nitro, cyano, C 1 - C 6 alkoxy, C 1 - C 6 alkylamino, and C 1 - C 6 dialkylamino. C 2 - C 8 alkenyl groups and C 2 - C 8The alkynyl group is understood to mean a hydrocarbon of 2 to 8 carbons each having at least one double bond or triple bond, and the linking point may be a carbon having a double bond or triple bond, or one of the other carbons in the chain.

[0043] In another aspect, the present invention provides a method for preparing a compound of the formula R 1 SnX 3 wherein X is chloro, bromo, or iodo, and R 1 is selected from C 1 to C 5 alkyl groups, which method comprises contacting a compound of the formula R 1 SnR 2 3 wherein R 2 is aryl or C 2 to C 8 alkenyl, with a compound of the formula SnX 4 .

Examples

[0044] Example 1 - Synthesis and Isolation of the Bisdimethylamine Lewis Base Adduct of Isopropyltin Trichloride A 7 mm tube adapter was attached to a 100 mL round bottom flask equipped with a branched adapter for gas / vacuum injection. The flask was charged with isopropyltin trichloride (11.0 g, 41.02 mmol), followed by 60 mL of anhydrous hexane, sealed, and removed from the glove box. The flask was cooled in an ice bath and dimethylamine (9.00 g, 199.6 mmol) was slowly added to the solution over 48 minutes via a 1 / 4” PFA tube with foaming. A white solid precipitate was observed upon completion of the addition. The mixture was warmed to room temperature, stirred for 2 hours, then filtered and dried in vacuo to obtain 12.88 g (86.9%) of the desired product as a white solid. By slowly evaporating hexane from the filtrate, colorless crystals of iPrSnCl 3 (HN(CH 3 ) 2 ) 2 were obtained. 11H NMR (400 MHz, CDCl 3 , 298K): δ3.41 (s, 2H), 2.79 (s, 12H), 2.29 (sept, 1H), 1.45 (d, 6H) ppm. 13 13C { 1 1H} NMR (100 MHz, CDCl 3 289K): δ45.36, 39.60, 22.38 ppm. 119 119Sn { 1 1H} NMR (149 MHz CDCl 3 , 298K): δ - 405.8 ppm

[0045] Synthesis and Isolation of the Bis(dimethylamine) Lewis Base Adduct of Isopropyltin Triiodide A 100 mL round-bottom flask equipped with a gas / vacuum injection branched adapter with a 7 mm tube adapter was charged with isopropyltin triiodide (10.0 g, 18.43 mmol), followed by 60 mL of anhydrous hexane, sealed, and transferred from the glove box. The flask can be cooled in an ice bath, and dimethylamine (2.50 g, 55.3 mmol) can be slowly added to the solution through a 1 / 4” PFA tube to cause foaming. A white solid precipitate is observed when the addition is complete. The mixture is then warmed to room temperature, stirred for 2 hours, and can be filtered and dried under vacuum to obtain the predicted desired product.

[0046] Synthesis and Isolation of the Bis(dimethylamine) Lewis Base Adduct of Isopropyltin Tribromide A 100 mL round-bottom flask with a branched adapter for gas / vacuum injection equipped with a 7 mm tube adapter is charged with isopropyltin tribromide (10.0 g, 24.90 mmol), followed by 60 mL of anhydrous hexane, sealed, and can be transferred from the glove box. The flask can be cooled in an ice bath, and dimethylamine (3.37 g, 74.7 mmol) can be slowly added to the solution through a 1 / 4” PFA tube to cause foaming. A white solid precipitate is observed upon completion of the addition. The mixture is then warmed to room temperature, stirred for 2 hours, and can be filtered and dried under vacuum to obtain the predicted desired product.

[0047] Example 4 In an inert atmosphere glove box, a 100 mL round-bottom flask equipped with a thermowell was charged with a PTFE boiling chip, 50.0 g (127.1 mmol) of isopropyltriphenyltin, and 99.3 g (381.2 mmol) of tin(IV) chloride. A large exotherm was observed, and when the mixture was cooled to room temperature, 0.16 in 2 The flask was attached to a distillation assembly consisting of a 12” silver vacuum-coated column packed with stainless steel Pro-Pak (registered trademark), a variable reflux distillation head with a pressure equalization arm, and a 100 mL round-bottom receiving flask with a branch for gas / vacuum injection. The reaction mixture was heated to 120 °C for 3 hours and then distilled at 100 mtorr with a head temperature in the range of 29 - 45 °C and an average head temperature of 36 °C. The first fraction consisting of 8.24 g ( 119 99.9% purity by Sn NMR) and the second fraction consisting of 24.6 g ( 119 99.6% purity by Sn NMR) were recovered, and the combined yield was 32.8 g (96%, 99.7% purity). 1 H NMR (400 MHz, CDCl 3 , 298K): δ1.61 (sept,1H) 1.38 (d, 6H) ppm. 13 C { 1 H} NMR (100 MHz, CDCl 3 289K): δ40.91, 19.68 ppm. 119 Sn {1 1H NMR (149 MHz, Neat, 298K): δ -12.3 ppm

[0048] Synthesis of Examples A - I - Tris(dimethylamide)isopropyltin The title compound was synthesized according to the following procedure, and numerous experiments with varying certain parameters are summarized in Tables 1A and 1B below.

[0049] Procedure for Examples A and B A 100 mL round - bottom flask with a side arm for gas / vacuum injection was charged with lithium dimethylamide (4.26 g, 83.5 mmol) and 36 mL of hexane. A 5 mL syringe with a stopcock valve was charged with isopropyltin trichloride (7.00 g, 26.1 mmol) and any additives listed in Table 1A below. The slurry of lithium dimethylamide was cooled to -65 °C, and isopropyltin trichloride was added in a drop - wise manner over 10 minutes. Only a very small exotherm was observed, and the mixture was warmed to room temperature. The reaction mixture was stirred at room temperature for 36 hours, then filtered through a Celite layer, and all volatiles were removed in vacuo. The crude product was purified by short - path distillation under reduced pressure, 119 As determined by 119Sn NMR, 0.8% of iPr 2 Sn(NMe 2 ) 2 was obtained in 55% yield along with impurities as iPrSn(NMe 2 ) 3 . 1 1H NMR (400 MHz, d 6 -benzene, 298K): δ 2.83 (s, 18H), 1.63 (sept, 1H), 1.27 (d, 6H) ppm. 13 13C { 1 1H} NMR (100 MHz, d 6 -benzene, 289K): δ 43.6, 21.2, 14.9 ppm. 119 119Sn { 1 1H} NMR (149 MHz, Neat, 298K): δ -64.3 ppm

[0050] Procedures of Examples C, D, F, and H A 250 mL three-neck round-bottom flask equipped with a PTFE-coated stirring egg was charged with butyllithium (23.7 mL, 59.4 mmol), diluted with 25 mL of anhydrous hexane, and fitted with a 7 mm tube adapter, a branched tube adapter with a 7 mm valve, and an adapter for gas / vacuum injection. The flask was cooled to 2 °C in an ice bath, a condenser was attached between the flask and the gas / vacuum injection adapter, and dimethylamine (6.20 g, 138 mmol, 6.94 eq) was slowly added through a 1 / 4” PFA tube and bubbled. The reaction mixture was cooled to about -10 °C and a solution of isopropyltin trichloride (5.31 g, 19.8 mmol) diluted to 29 mL with hexane was slowly added via syringe pump over 47 minutes (0.61 mL / min). The reaction mixture was then warmed to room temperature over 20 minutes and stirred at room temperature for 1 hour. The reaction mixture was transferred to a glove box and filtered through a layer of celite with an intermediate porous filtering funnel. The residue was washed with 10 mL of anhydrous hexane and the solvent was evaporated from the filtrate under full vacuum. The crude yield was 5.427 g (93%), and the amount of iPr 119 detectable by Sn NMR 2 Sn(NMe 2 ) 2 was not contained. The crude product was distilled under reduced pressure (50 mtorr with a pump), 119 and according to Sn NMR, 0.02% of iPr 2 Sn(NMe 2 ) 2 along with 3.929 g (67%) of a colorless product was obtained.

[0051] Procedure of Example E A 100 mL round-bottom flask equipped with a PTFE-coated stirring egg was charged with butyllithium (23.0 mL, 57.4 mmol), diluted with 25 mL of anhydrous hexane, and fitted with a branched tube adapter with a valve. The flask was cooled to 2 °C in an ice bath, and dimethylamine (5.10 g, 113 mmol, 5.72 eq) was slowly added dropwise through a 1 / 4” PTFE tube at a rate slow enough to keep the reaction temperature below 20 °C, causing foaming. The reaction mixture was then stirred at room temperature overnight, and during this time, all volatiles present in the reaction mixture were evaporated by a nitrogen bubbler connected to the flask. The reaction mixture was diluted with 50 mL of hexane, cooled to approximately -10 °C in a salt water bath, and a solution of isopropyltin trichloride (5.30 g, 19.7 mmol) diluted to 26 mL with hexane was slowly added via a syringe pump over 43 minutes (0.605 mL / min). The reaction mixture was then slowly warmed to room temperature, stirred for 30 minutes, then transferred to a glove box and stirred for 60 hours. The reaction mixture was filtered through a Celite layer and washed with 15 mL of hexane. The volatiles of the filtrate were evaporated under reduced pressure, and the 119 As determined by Sn NMR, 1.05% of iPr 2 Sn(NMe 2 ) 2 was contained, and 4.73 g of a crude (82%) off-white oil was obtained. The material was then distilled under reduced pressure in a short-path distillation apparatus, and according to the 119 Sn NMR, 1.45% of iPr 2 Sn(NMe 2 ) 2 along with 4.019 g (69%) of a colorless oil was obtained as the product.

[0052] Procedure of Example G A 250 mL three-neck round-bottom flask equipped with a PTFE-coated stirring egg was charged with lithium dimethylamide (3.38 g, 63.3 mmol), diluted with 50 mL of anhydrous hexane, and fitted with two stoppers and a 7 mm branched tube adapter with a valve. The flask was transferred to a hood and the stopper was replaced under nitrogen purge with a PTFE thermocouple adapter having a PTFE-coated thermocouple and a condenser having a gas / vacuum injection valve at the top. The flask was cooled to about -10 °C in an ice-cooled salt water bath, and dimethylamine (2.9 g, 64 mmol, 3.24 eq) was slowly added dropwise over 16 minutes through a 1 / 4” PTFE tube to cause foaming (0.18 g / min). The reaction mixture (still about -10 °C) was treated with a solution of isopropyltin trichloride (5.32 g, 19.8 mmol) diluted to 23 mL with anhydrous hexane over 46 minutes. It was then slowly warmed to room temperature overnight. The reaction mixture was filtered through a Celite layer and washed with 15 mL of hexane. The volatiles of the filtrate were evaporated under reduced pressure, and the 119 As determined by Sn NMR, 0.5% of iPr 2 Sn(NMe 2 ) 2 was present, and 4.86 g (84%) of a crude off-white oil was obtained. The material was then distilled under reduced pressure in a short-path distillation apparatus, and according to 119 Sn NMR of the neat sample, 0.75% of iPr 2 Sn(NMe 2 ) 2 was present, and 3.277 g (56%) of a colorless oil was obtained as the product.

[0053] Procedure of Example I A 250 mL three-neck round-bottom flask equipped with a PTFE-coated stirring egg was charged with butyllithium (20.0 mL, 50.0 mmol), diluted with 25 mL of anhydrous hexane, and fitted with a 7 mm tube adapter, a branched tube adapter with a 7 mm valve, and a gas / vacuum injection adapter. The flask was cooled to -4 °C in a salt water bath, and dimethylamine (5.11 g, 113 mmol, 6.77 eq) was slowly added dropwise over 26 minutes via a 1 / 4” PTFE tube to cause foaming (approx. 0.20 g / min). Then, while maintaining the reaction mixture below 8 °C, the volatiles of the reaction mixture were evaporated under reduced pressure. When the reaction mixture had concentrated to a viscous paste, the reaction mixture was diluted with 50 mL of anhydrous hexane and cooled to approximately -10 °C in a salt water bath to prepare a slurry of iPrSnCl 3 (HNMe 2 ) 2 A 100 mL round-bottom flask with a 7 mm tube adapter with a gas / vacuum injection branch was charged with iPrSnCl 3 (HNMe 2 ) 2 (6.00 g, 16.7 mmol) in 30 mL of hexane, and a stirring egg was placed. The two flasks were connected by a 1 / 4” PTFE tube, and the iPrSnCl 3 (HNMe 2 ) 2 slurry was transferred in two aliquots. Most of the white solid residue remaining in the 100 mL flask was washed with an additional 25 mL of anhydrous hexane, and the aliquot of the reaction mixture was transferred from the 100 mL flask to complete the washing process and ensure thorough mixing. Then, the reaction mixture was slowly warmed overnight in a salt water bath. The reaction mixture, which was a slurry of white solids in a colorless solution, was transferred to a glove box, filtered through a 1 cm layer of celite, and washed with 10 mL of anhydrous hexane. The solvent and other volatiles were removed from the filtrate in vacuo, then combined, and the amount of iPr 119 determined by Sn NMR of the as-collected sample was below the detection limit of 2 Sn(NMe 2 ) 2A crude product (87%) containing 4.310 g was obtained. Subsequently, the material was distilled under reduced pressure in a short-path distillation apparatus, and the 119 According to Sn NMR, 0.03% of iPr 2 Sn(NMe 2 ) 2 Together with 3.541 g (72% yield) of a colorless oil was obtained as the product.

[0054] Synthesis of 25.0 g scale of Example K-tris(dimethylamide)isopropyltin (magnetic stirring) A 500 mL three-necked round-bottom flask equipped with a PTFE-coated stirring egg was charged with butyllithium (107.5 mL, 293.6 mmol) diluted with hexane (24.51 mL, 186.4 mmol). The flask was fitted with a stopper, a gas / vacuum injection adapter, and a Chemglass 7 mm tube adapter with a valve. The flask was cooled in a salt water bath, and a nitrogen flash concentrator was placed at the position of the gas / vacuum injection adapter of the flask. Then, dimethylamine (30.03 g, 0.661 mol, 7.14 equivalents) was slowly added to the reaction mixture with foaming. The resulting slurry was cooled to about -9 °C, and a solution of trichloro(propane-2-yl)stannane (25.00 g, 93.23 mmol) in hexane (122.6 mL, 932.3 mmol) (total volume 135 mL) was added dropwise over 51 minutes via a 250 mL addition funnel. After the addition was complete, the reaction mixture was warmed to room temperature and stirred for 16 hours. Then, the reaction mixture was filtered through a 2 cm layer of celite in an intermediate porous filtering funnel. The filter cake was washed with hexane (24.51 mL, 186.4 mmol), and the solvent of the combined filtrate was evaporated under reduced pressure (50 mtorr with a pump). The yellow oil was transferred to a pre-weighed vial to obtain a collection of 19.435 g (70.9%) of crude product. The crude product was distilled under a complete vacuum in a short-path distillation apparatus to obtain 16.945 g of a pale yellow oil (61.8% yield). The distilled product was 119 Sn, 1 H, and 13 Analyzed by C NMR, according to the 119 Sn NMR of the as-received sample, 0.07% of iPr2 Sn(NMe 2 ) 2 was shown.

[0055] Example Synthesis of 125.0 g scale of L-tris(dimethylamide)isopropyltin (magnetic stirring) A 3-liter round-bottom flask equipped with a mechanical stirring assembly was charged with butyllithium (540.0 mL, 1474 mmol) and hexane (525 mL), and then cooled in a salt water bath. Dimethylamine (120.3 g, 2.67 mol, 5.72 eq) was bubbled through the cold butyllithium solution over 273 minutes to form a viscous white slurry. To this slurry, still cooled in the salt water bath, a solution of isopropyltin trichloride (125.00 g, 466.1 mmol) in hexane (610 mL) was added over 52 minutes. The reaction mixture was then filtered through a 2 cm layer of celite in an intermediate porous filtering funnel into a 2 L round-bottom flask, and the salt residue was washed with hexane (125 mL). The solvent and other volatiles of the combined filtrate were then evaporated under vacuum to give 126.8 g (92.6%) of a crude product. The crude product was then filtered through an intermediate porous polyethylene filtering funnel to remove most of the solids present. The filtered product was transferred to a clean 250 mL flask and distilled at 100 mtorr to give 116.66 g (85.1%) of a distilled product that was free of 119 an amount of iPr 2 Sn(NMe 2 ) 2 detectable by Sn NMR.

[0056] Example M A 3-liter round-bottom flask equipped with a mechanical stirring assembly was charged with 2.74 M butyllithium (400 mL, 1096 mmol) and hexane (400 mL), and then cooled in an isopropanol / ice bath. Dimethylamine (66.3 g, 4.224 mol) was bubbled through the cold butyllithium solution to form a viscous white slurry. The lithium dimethylamide reaction mixture was then diluted with 871 mL of anhydrous tetrahydrofuran to form a low-viscosity but heterogeneous reaction mixture. To this cooled slurry was added additional dimethylamine (66.0 g, 4.204 mol) to obtain a homogeneous solution. To this solution, still cooled in an isopropanol / water bath, was added dropwise over 199 minutes a 750 mL solution of isopropyltin trichloride bis(dimethylamine) (125.00 g, 348 mmol) in anhydrous tetrahydrofuran at an internal reaction temperature between -18 °C and -13 °C. The reaction mixture was slowly warmed to room temperature over 18 hours. The solvent and other volatiles of the reaction mixture were evaporated under vacuum, diluted with 250 mL of anhydrous hexane, filtered through an intermediate fritted funnel, and then washed with a further 250 mL aliquot of anhydrous hexane. The hexane and other volatiles of the combined filtrates were then evaporated under vacuum to give 101.1 g (99%) of a crude product. The crude product was distilled at 70 - 100 mtorr to give 88.8 g (87%) of a distilled product 119 in an amount detectable by Sn NMR of iPr 2 Sn(NMe 2 ) 2 without containing. TIFF0007684410000017.tif130170*DMA = Dimethylamine **Isopropyltin trichloride ***In the case of Examples A - G, the tin starting material was prepared by an iPr 4 Sn / SnCl 4 redistribution reaction, and in the case of Example H, the tin starting material was iPrSn(phenyl) 3 prepared by a redistribution reaction, and in the case of Example I, the tin starting material was iPrSn(phenyl) 3Prepared by redistribution and then reacted with excess dimethylamine and the Lewis base adduct of formula (A) was isolated. ****In the case of Examples A, B, and G, LiNMe2 was obtained commercially as a dry solid and used as received. In Example E, LiNMe2 was synthesized, but all volatiles including any excess dimethylamine were evaporated over 16 hours. *****In Example I, the volatiles (excess DMA and hexane) were evaporated under vacuum so that no excess dimethylamine remained. ******In Example B, triethylamine was a synthetic additive in the preparation of isopropyl(tris)dimethylamine tin, and no synthetic additive was used in all other examples. TIFF0007684410000018.tif109170

[0057] Example J (reproduction of the comparative example of Example 1 of WO2017 / 066319) A 100 mL round bottom flask was charged with lithium dimethylamide (3.03 g, 59.5 mmol, Sigma Aldrich) and 25 mL of hexane. The flask was fitted with a PTFE-coated stirring egg and a thermocouple / adapter and then cooled in a dry ice / isopropanol bath (internal temperature of -73 °C). Trichloro(propan-2-yl)stannane (5.00 g, 18.6 mmol) was added to this slurry via syringe pump over 122 minutes using a syringe. The reaction mixture was then warmed to room temperature and stirred for 16 hours. The reaction mixture was filtered through a layer of celite with an intermediate porous glass frit. The filter cake was washed with 25 mL of anhydrous hexane and the volatiles of the filtrate were evaporated under a complete vacuum. The crude product was distilled under a complete vacuum to give 3.52 g (64.4%) of a colorless oil. 119 The Sn NMR spectrum showed the presence of about 1.6% iPr 2 Sn(NMe 2 ) 2 was present.

[0058] Preparation of 1-isopropyl-Sn(phenyl) 3 and SnCl4 Isopropyl-SnCl from 3 Synthesis of A two-necked, three-necked distillation flask equipped with a thermocouple was charged with 753 g (1.915 mol) of isopropyltriphenyltin and attached to an 8” Vigreux column distillation assembly. A 1 L flask was attached to the distillation outlet. The flask containing isopropyltriphenyltin was charged with 1000 g of tin(IV) chloride (3.838 mol, 2 equiv, Sigma Aldrich) over a period of about 2 hours, and a moderate exotherm was observed. Subsequently, isopropyltin trichloride was distilled at 1 torr between 65 °C and 75 °C, and the head temperature rose sharply to about 100 °C at the end of the distillation. The product (588 g) was found to be a mixture of PhSnCl 3 (15 mol%) and iPrSnCl 3 (85 mol%), and the distillation pot material was 119 According to Sn NMR, 55 mol% Ph 2 SnCl 2 and 45 mol% PhSnCl 3 composed of. The yield of iPrSnCl 3 calculated from the relative NMR integration values was 493 g (96% yield). The mixture of iPrSnCl 3 and PhSnCl 3 was further distilled at 50 - 100 mtorr at a head temperature of 40 - 43 °C using a 1’ column packed with stainless steel 0.16 in 2 Pro-Pak (registered trademark), and 119 According to Sn NMR, 461 g (90%) of iPrSnCl 3 with a purity of 99.9% was obtained. 1 H NMR (400 MHz, CDCl 3 , 298K): δ 1.61 (sept, 1H), 1.38 (d, 6H) ppm. 13 C { 1 H} NMR (100 MHz, CDCl 3 289K): δ 40.9, 19.7 ppm. 119 Sn { 1 H} NMR (149 MHz CDCl 3, 298K): d -5.9 ppm

[0059] Preparation of 2-(phenyl) 3 Isopropyl-SnCl from Sn-isopropyl and ICl 3 Synthesis A PTFE-coated stirring egg was placed in a 100 mL round-bottom flask, which was charged with isopropyltriphenyltin (10.00 g, 25.43 mmol) and 50 mL of anhydrous hexane, and iodine monochloride (12.42 g, 76.54 mmol) was added in a dropwise manner with stirring. Over the 10-minute addition, the temperature rose from 22 °C to 71 °C. The reaction mixture was then stirred at room temperature for 18 h. 119Sn NMR of a reaction aliquot showed the presence of a small amount of iPrSnPhCl 2 The reaction mixture was treated with iodine monochloride (2.063 g, 12.71 mmol) (an additional 0.5 equivalent) and then stirred at room temperature for 30 min. The solvent was then removed under 10 torr vacuum to give the crude product (22.439 g, a mixture of the desired product and iodobenzene). The product was then distilled using a 6” 14 / 20 distillation column packed with stainless steel 0.16 in 2 Pro-Pak® to give three fractions. Fraction 1 - 8.86 g, 8.4 mol% iPrSnCl 3 Fraction 2 - 7.08 g, 36.9 mol% iPrSnCl 3 Fraction 3 - 4.86 g, 93.8 mol% iPrSnCl 3 . Overall, the recovery of iPrSnCl 3 was quantitative.

[0060] Preparation of 3-Ph 3 Sn-isopropyl and I 2 Isopropyl SnI from 3 Synthesis A 40 m vial was charged with isopropyltriphenyltin (5.00 g, 12.7 mmol) and 20 mL of toluene. Iodine (10.2 g, 40.0 mmol) was added slowly in several portions, and exotherm was observed after each addition. The resulting dark red mixture was then heated at 90 °C for 16 h. The resulting solution was then distilled under vacuum using a short path apparatus to first remove the iodobenzene by-product and then the product (head temperature 100 - 105 °C, 200 - 500 mtorr) was distilled as a yellow oil in 94% yield. 1 H NMR (400 MHz, benzene-d 6 , 298K): δ 1.78 (sept, 1H), 0.61 (d, 6H) ppm. 13 C { 1 H} NMR (100 MHz, benzene-d 6 , 289K): δ 37.6, 19.8 ppm. 119 Sn { 1 H} NMR (149 MHz benzene-d 6 , 298K): δ - 434 ppm

[0061] EtSnCl 3 - Synthesis and purification Ph 3 PhSnEt (637.8 g, 1.68 mol) was charged into a 2 L four-necked round bottom flask equipped with a magnetic stir bar, a thermocouple, and a nitrogen injection adapter. In a glove box filled with nitrogen, SnCl 4 (916 g, 3.52 mol) was placed in a 500 mL addition funnel, then removed from the glove box and attached to the 2 L round bottom flask. The apparatus was placed under N 2 and SnCl 4 was added to the solid Ph 3It was added slowly directly to SnEt over 8 hours. The reaction mixture was heated to 115 °C for 1 hour and then distilled at 1 torr between 67 °C and 69 °C using a coated 8” Vigreux distillation column. The initial 2 - 3 mL fraction was collected and distillation was stopped when the head temperature reached 78 °C. A second distillation was carried out at 1 torr using an 8” column packed with glass Raschig rings at a head temperature of about 64 °C to obtain a colorless liquid with a purity exceeding 99.0% (327.16 g, 108 mol, 76.7% yield) of EtSnCl 3 was obtained. 1 H-NMR (400 MHz, C 6 D 6 , 298K): 1.43 (t, 3H); 2.27 (q, 2H) ppm; 119 Sn NMR (149 MHz, 298K): 2.03 ppm

[0062] EtSnCl 3 (HNMe 2 ) 2 - Synthesis and Characterization A 5L three-necked coated flask equipped with an overhead stirrer, a gas injection adapter, and a thermocouple was placed in a glove box filled with nitrogen. EtSnCl 3 (391 g, 1.53 mol) was placed in the flask and diluted with 3L of hexane. HNMe 2 was added to the reaction flask at a rate of about 1.0 g / min to cause foaming. Over 4 hours, HNMe 2 (149.3 g, 3.30 mol) was added with an exotherm of about 20 °C, resulting in the formation of a white precipitate. The reaction mixture was stirred at room temperature for about 18 hours, filtered through a medium porosity frit, washed with 500 mL of hexane, and dried under vacuum to obtain 477 g of a slightly sticky white solid with a purity exceeding 99.0% (90.7%). 1 H-NMR (400 MHz, CDCl 3 , 298K): 1.28 (t, 3H); 1.75 (q, 2H); 2.77 (s, 12H); 3.44 (s, 2H) ppm; 13 C-NMR (100 MHz, CDCl 3, 298K): 12.75, 29.61, 38.88 ppm; 119 Sn-NMR (149 MHz CDCl 3 , 298K): -394.5 ppm

[0063] EtSn(NMe 2 ) 3 - Synthesis and purification A 12 L four-necked flask equipped with a mechanical stirring assembly was charged with nBuLi (2.5 M, 1.73 L, 4.34 mol) diluted with 3 L of hexane. Then, the nBuLi solution was cooled to an internal temperature of 0 °C using an IPA / Liquid N 2 bath. Dimethylamine gas was added to the reaction mixture at a rate of approximately 1 g / min for 5 hours at an internal reaction temperature below 3 °C to foam it, forming a viscous white mixture. LiNMe 2 The reaction mixture was warmed to room temperature and stirred for about 72 hours. LiNMe 2 The mixture was cooled to about -2 °C using an IPA / N 2 bath, and then treated with a solution of EtSnCl 3 (HNMe 2 ) 2 (477 g, 1.38 mol) in 3 L of dimethoxyethane at an internal reaction temperature of about 1 - 2 °C in the dark (all subsequent steps were also carried out in the dark) for 2.5 hours to obtain a pale yellow solution, which was stirred at room temperature for about 18 hours. The solvent and other volatiles of the yellow reaction mixture were evaporated under vacuum to obtain a sticky off-white / yellow solid, which was a slurry in 3 L of hexane and filtered through an intermediate porous frit. Then, the hexane and other volatiles of the filtrate were evaporated under vacuum to obtain an orange oil as the crude product. The crude product was distilled using a 10” Vigreux column in a pressure range of 200 - 500 mtorr and a head temperature of 28 - 35 °C. The first 10 mL of the fraction was discarded, and the main fraction of EtSn(NMe 2 ) 3 was recovered as a colorless liquid with a purity of 99.84% (278 g, 0.99 mol, 72% yield). 1 H-NMR (400 MHz, C 6 D 6, 298K): 0.99 (q, 2H); 1.15 (t, 3H); 2.73 (s, 18H) ppm; 13 C-NMR (100 MHz, C 6 D 6 , 298K): 4.32, 10.14, 43.27 ppm; 119 Sn-NMR (149 MHz, C 6 D 6 , 298K): -38.48 ppm

[0064] Crystal structure data As described above, Figure 1 is a description of the crystal structure of the three-dimensional solid state of iPrSnCl 3 (HN(CH 3 ) 2 ) 2 The compound was subjected to X-ray crystallographic analysis and gave the following data. TIFF0007684410000019.tif191170

[0065] Furthermore, as described above, Figure 2 is a description of the crystal structure of the three-dimensional solid state of EtSnCl 3 (HN(CH 3 ) 2 ) 2 The compound was subjected to X-ray crystallographic analysis and gave the following data. TIFF0007684410000020.tif209170

[0066] Aspect In a first aspect, the present invention provides a compound of formula (I) TIFF0007684410000021.tif41170[wherein each R is independently selected from C 1 ~C 5 alkyl groups, and R 1 is selected from C 1 ~C 5 alkyl groups] comprising a composition, the composition having a concentration of less than about 0.5 mol% of a compound of formula (II) Provide a composition comprising TIFF0007684410000022.tif36170.

[0067] In a second aspect, the present invention relates to R and R 1 are independently C 1 ~C 3 Provide the composition according to the first aspect, which is selected from alkyl groups.

[0068] In a third aspect, the present invention provides that the compound of formula (I) is tris(dimethylamide)isopropyltin, tris(diethylamide)isopropyltin, tris(dipropylamide)isopropyltin, tris(methylethylamide)isopropyltin, tris(diisopropylamide)isopropyltin, tris(di-t-butylamide)isopropyltin, tris(di-n-butylamide)isopropyltin, tris(di-sec-butylamide)isopropyltin, tris(dineopentylamide)isopropyltin, tris(dimethylamide)methyltin, tris(diethylamide)methyltin, tris(di-n-propylamide)methyltin, tris(methylethylamide)methyltin, tris(diisopropylamide)methyltin, tris(di-t-butylamide)methyltin, tris(di-n-butylamide)methyltin, tris(di-sec-butylamide)methyltin, tris(dineopentylamide)methyltin, tris(dimethylamide)ethyltin, tris(diethylamide)ethyltin, tris(di-n-propylamide)ethyltin, tris(methylethylamide)ethyltin, tris(diisopropylamide)ethyltin, tris(di-t-butylamide)ethyltin, tris(di-n-butylamide)ethyltin, tris(di-sec-butylamide)ethyltin, tris(dineopentylamide)ethyltin, tris(dimethylamide)n-propyltin, tris(diethylamide)n-propyltin, tris(di-n-propylamide)n-propyltin, tris(methylethylamide)n-propyltin, tris(diisopropylamide)n-propyltin, tris(di-t-butylamide)n-propyltin, tris(di-n-butylamide)n-propyltin, tris(di-sec-butylamide)n-propyltin, tris(dineopentylamide)n-propyltin, tris(dimethylamide)n-butyltin, tris(diethylamide)n-butyltin, tris(dipropylamide)n-butyltin, tris(methylethylamide)n-butyltin, tris(diisopropylamide)n-butyltin, tris(di-t-butylamide)n-butyltin, tris(di-n-butylamide)n-butyltin,Provide the composition according to the first or second aspect, which is tris(di-sec-butylamide)n-butyltin or tris(di-neopentylamide)n-butyltin.

[0069] In a fourth aspect, the present invention provides the composition according to any one of the first to third aspects, wherein the compound of formula (I) is tris(dimethylamide)isopropyltin, tris(diethylamide)isopropyltin, tris(dipropylamide)isopropyltin, tris(methylethylamide)isopropyltin, tris(diisopropylamide)isopropyltin, tris(di-t-butylamide)isopropyltin, tris(di-n-butylamide)isopropyltin, tris(di-sec-butylamide)isopropyltin or tris(di-neopentylamide)isopropyltin.

[0070] In a fifth aspect, the present invention provides the composition according to any one of the first to fourth aspects, wherein the compound of formula (I) is tris(dimethylamide)isopropyltin and the compound of formula (II) is bis(dimethylamide)diisopropyltin.

[0071] In a sixth aspect, the present invention provides the composition according to any one of the first to fifth aspects, wherein the compound of formula (II) is present at a concentration of less than about 0.1 mol%.

[0072] In a seventh aspect, the present invention provides the composition according to any one of the first to sixth aspects, wherein the compound of formula (II) is present at a concentration of less than about 0.05 mol%.

[0073] In an eighth aspect, the present invention provides the composition according to any one of the first to seventh aspects, wherein the compound of formula (II) is present at a concentration of less than about 0.03 mol%.

[0074] In a ninth aspect, the present invention provides the compound of formula (I) TIFF0007684410000023.tif41170[wherein each R is independently C 1 ~C 5Selected from an alkyl group, R 1 is C 1 ~C 5 Selected from alkyl groups] A method for preparing a composition comprising a) A compound of the formula R 1 SnX 3 wherein X is selected from Cl, I, and Br, b) A compound of the formula Li(R) 2 N, and c) Combining a compound of the formula R 2 NH, comprising The compound of the formula R 2 NH is present in a molar excess relative to the compound of the formula R 1 SnX 3 A method is provided.

[0075] In a tenth aspect, the invention provides a method according to the ninth aspect, wherein R and R 1 are independently selected from C 1 ~C 3 alkyl groups.

[0076] In an eleventh aspect, the invention provides a method according to the ninth or tenth aspect, wherein R 1 is isopropyl and X is chloro.

[0077] In a twelfth aspect, the present invention provides that the compound of formula (I) is tris(dimethylamide)isopropyltin, tris(diethylamide)isopropyltin, tris(dipropylamide)isopropyltin, tris(methylethylamide)isopropyltin, tris(diisopropylamide)isopropyltin, tris(di-t-butyl-amide)isopropyltin, tris(di-n-butylamide)isopropyltin, tris(di-sec-butylamide)isopropyltin, tris(di-neopentylamide)isopropyltin, tris(dimethylamide)methyltin, tris(diethylamide)methyltin, tris(di-n-propylamide)methyltin, tris(methylethylamide)methyltin, tris(diisopropylamide)methyltin, tris(di-t-butylamide)methyltin, tris(di-n-butylamide)methyltin, tris(di-sec-butylamide)methyltin, tris(di-neopentylamide)methyltin, tris(dimethylamide)ethyltin, tris(diethylamide)ethyltin, tris(di-n-propylamide)ethyltin, tris(methylethylamide)ethyltin, tris(diisopropylamide)ethyltin, tris(di-t-butylamide)ethyltin, tris(di-n-butylamide)ethyltin, tris(di-sec-butylamide)ethyltin, tris(di-neopentylamide)ethyltin, tris(dimethylamide)n-propyltin, tris(diethylamide)n-propyltin, tris(di-n-propylamide)n-propyltin, tris(methylethylamide)n-propyltin, tris(diisopropylamide)n-propyltin, tris(di-t-butylamide)n-propyltin, tris(di-n-butylamide)n-propyltin, tris(di-sec-butylamide)n-propyltin, tris(di-neopentylamide)n-propyltin, tris(dimethylamide)n-butyltin, tris(diethylamide)n-butyltin, tris(dipropylamide)n-butyltin, tris(methylethylamide)n-butyltin, tris(diisopropylamide)n-butyltin, tris(di-t-butylamide)n-butyltin, tris(di-n-butylamide)n-butyltin,Provided is the method according to any one of Aspects 9 to 11, which is tris(di-sec-butylamide)n-butyltin or tris(di-neopentylamide)n-butyltin.,

[0078] In a 13th aspect, the present invention provides the method according to any one of Aspects 9 to 12, wherein the compound of formula (I) is selected from tris(dimethylamide)isopropyltin, tris(diethylamide)isopropyltin, tris(dipropylamide)isopropyltin, tris(methylethylamide)isopropyltin, tris(diisopropylamide)isopropyltin, tris(di-t-butylamide)isopropyltin, tris(di-n-butylamide)isopropyltin, tris(di-sec-butylamide)isopropyltin, and tris(di-neopentylamide)isopropyltin.,

[0079] In a 14th aspect, the present invention provides the method according to any one of Aspects 9 to 13, wherein the compound of formula R 2 NH is dimethylamine and R 1 is isopropyl.,

[0080] In a 15th aspect, the present invention provides the method according to any one of Aspects 9 to 14, wherein the compound of formula Li(R) 2 N is lithium dimethylamide, the compound of formula R 2 NH is dimethylamine, and the compound of formula R 1 SnX 3 is isopropyltin trichloride.,

[0081] In a 16th aspect, the present invention provides the method according to the 15th aspect, wherein the composition contains less than about 0.5% of bis(dimethylamide)diisopropyltin.,

[0082] In a 17th aspect, the present invention provides the method according to the 15th or 16th aspect, wherein the composition contains less than about 0.1% of bis(dimethylamide)diisopropyltin.,

[0083] In an 18th aspect, the present invention provides the method according to any one of the 15th to 17th aspects, wherein the composition contains less than about 0.05% of bis(dimethylamide)diisopropyltin.

[0084] In a 19th aspect, the present invention provides the method according to any one of the 9th to 18th aspects, wherein the compound of the formula R 2 NH is present in an amount of at least about 0.15 molar equivalents more than the compound of the formula R 1 SnX 3

[0085] In a 20th aspect, the present invention provides the method according to any one of the 9th to 19th aspects, wherein the compound of the formula (I) is prepared from the compound of the formula (A) TIFF0007684410000024.tif50170.

[0086] In a 21st aspect, the present invention provides the method according to the 20th aspect, wherein the compound of the formula (A) is prepared by reacting the compound of the formula R 2 NH with the compound of the formula R 1 SnX 3 and the compound of the formula R 2 NH is in excess with respect to the compound of the formula R 1 SnX 3

[0087] In a 22nd aspect, the present invention provides the method according to the 20th or 21st aspect, wherein the compound of the formula (I) is prepared by reacting the compound of the formula (A) with the compound of the formula Li(R) 2 N.

[0088] In a 23rd aspect, the present invention provides the method according to any one of the 20th to 22nd aspects, wherein the compound of the formula Li(R) 2 N is present in an excess molar amount of about 3 to about 3.2 molar equivalents with respect to the compound of the formula (A).

[0089] In a 24th aspect, the present invention provides that the compound of the formula (I) is the compound of the formula (I-a) TIFF0007684410000025.tif36170. The compound of formula (A) is the compound of formula (A-a) is TIFF0007684410000026.tif41170, The compound of formula Li(R) 2 The method according to any one of aspects 20 to 23, wherein the compound of N is lithium dimethylamide.

[0090] In aspect 25, the present invention provides that the compound of formula (I) is the compound of formula (I-d) is TIFF0007684410000027.tif40170, The compound of formula (A) is the compound of formula (A-d) is TIFF0007684410000028.tif42170, The compound of formula Li(R) 2 The method according to any one of aspects 20 to 23, wherein the compound of N is lithium dimethylamide.

[0091] In aspect 26, the present invention provides a compound of formula R 1 SnX 3 wherein X is chloro or bromo, and R 1 is selected from C 1 to C 5 alkyl groups] is reacted with a monoiodochloride or a monoiodobromide, respectively, to prepare the method according to any one of aspects 20 to 25, which is a compound of formula R 1 SnR 4 3 wherein R 4 is selected from aryl, C 2 to C 8 alkenyl, and C 2 to C 8 alkynyl].

[0092] In aspect 27, the present invention provides a compound of formula R 1 SnX 3 wherein X is chloro, bromo, or iodo, and R 1 is selected from C 1 to C 5 alkyl groups] is the formula R1 SnR 2 3 The compound of [wherein, R 2 is selected from aryl or C 2 ~C 8 alkenyl] is contacted with a compound of formula SnX 4 to provide the method according to any one of Aspects 20 to 25, which is prepared by the method.

[0093] In a 28th aspect, the present invention provides a compound of formula (A-a) TIFF0007684410000029.tif41170.

[0094] In a 29th aspect, the present invention provides the compound according to the 28th aspect in a crystalline form as depicted in FIG. 1.

[0095] In a 30th aspect, the present invention provides a compound of formula (A-d) TIFF0007684410000030.tif42170.

[0096] In a 31st aspect, the present invention provides the compound according to the 30th aspect in a crystalline form as depicted in FIG. 2.

[0097] In a 32nd aspect, the present invention provides a method for preparing a compound of formula R 1 SnX 3 [wherein, X is chloro or bromo, and R 1 is selected from C 1 ~C 5 alkyl group], which comprises reacting a compound of formula R 1 SnR 4 3 [wherein, R 4 is selected from aryl, C 2 ~C 8 alkenyl, and C 2 ~C 8 alkynyl] with monochloroiodide or monobromoiodide respectively.

[0098] In a 33rd aspect, the present invention provides a method for preparing a compound of formula R 1 SnX 3 wherein X is chloro, bromo, or iodo, and R 1 is selected from C 1 to C 5 alkyl groups, which comprises contacting a compound of formula R 1 SnR 2 3 wherein R 2 is selected from aryl or C 2 to C 8 alkenyl with a compound of formula SnX 4 .

[0099] Although several embodiments of the present disclosure have been described as such, those skilled in the art will readily appreciate that further other embodiments can be made and used within the scope of the appended claims. Numerous advantages of the present disclosure included in this document have been set forth in the foregoing description. However, it is understood that the present disclosure is merely illustrative in many respects. The scope of the present disclosure is, of course, defined by the language represented by the appended claims.

Claims

Claim 1 A method for preparing a composition comprising a compound of formula (I) [In the formula, each R is independently selected from C １ to C ５ alkyl groups, and R １ is selected from C １ to C ５ alkyl groups]. wherein a) A compound of formula R １ SnX ３ wherein X is selected from Cl, I, and Br b) Compound of formula Li(R) ２ N, and c) combining a compound of formula R ２ NH, and Formula R ２ A compound of NH is present in an excess molar amount relative to a compound of formula R １ SnX ３ The method. Claim 2 The compound of formula (I) is tris(dimethylamide)isopropyltin, tris(diethylamide)isopropyltin, tris(dipropylamide)isopropyltin, tris(methylethylamide)isopropyltin, tris(diisopropylamide)isopropyltin, tris(di-t-butyl-amide)isopropyltin, tris(di-n-butylamide)isopropyltin, tris(di-sec-butylamide)isopropyltin, tris(di-neopentylamide)isopropyltin, tris(dimethylamide)methyltin, tris(diethylamide)methyltin, tris(di-n-propylamide)methyltin, tris(methylethylamide)methyltin, tris(diisopropylamide)methyltin, tris(di-t-butylamide)methyltin, tris(di-n-butylamide)methyltin, tris(di-sec-butylamide)methyltin, tris(di-neopentylamide)methyltin, tris(dimethylamide)ethyltin, tris(diethylamide)ethyltin, tris(di-n-propylamide)ethyltin, tris(methylethylamide)ethyltin, tris(diisopropylamide)ethyltin, tris(di-t-butylamide)ethyltin, tris(di-n-butylamide)ethyltin, tris(di-sec-butylamide)ethyltin, tris(di-neopentylamide)ethyltin, tris(dimethylamide)n-propyltin, tris(diethylamide)n-propyltin, tris(di-n-propylamide)n-propyltin, tris(methylethylamide)n-propyltin, tris(diisopropylamide)n-propyltin, tris(di-t-butylamide)n-propyltin, tris(di-n-butylamide)n-propyltin, tris(di-sec-butylamide)n-propyltin, tris(di-neopentylamide)n-propyltin, tris(dimethylamide)n-butyltin, tris(diethylamide)n-butyltin, tris(dipropylamide)n-butyltin, tris(methylethylamide)n-butyltin, tris(diisopropylamide)n-butyltin, tris(di-t-butylamide)n-butyltin, tris(di-n-butylamide)n-butyltin,The method according to claim 1, which is tris(di-sec-butylamide)n-butyltin or tris(di-neopentylamide)n-butyltin., Claim 3 The compound of formula (I) is prepared from a compound of formula (A) The method according to claim 1, wherein the compound of formula (A) is an intermediate formed from a compound of formula R1SnX3, a compound of formula Li(R)2N, and a compound of formula R2NH Claim 4 Formula Li(R) ２ The method according to claim 3, wherein the compound of N is present in a molar excess of 3 to 3.2 molar equivalents with respect to the compound of formula (A). Claim 5 Formula R １ SnX ３ of the compound [wherein X is chloro, bromo, or iodo, and R １ is C １ to C ５ alkyl group selected from], but the compound of formula R １ SnR ２ ３ of the compound [wherein R ２ is aryl or C ２ to C ８ alkenyl selected from] is contacted with a compound of formula SnX ４ The method according to claim 1, which is prepared by the above method.

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