Method of preparing iodosilane

Abstract

To provide a method of preparing iodosilane such as H2SiI2 and HSiI3.SOLUTION: There is provided a method of preparing iodosilane via a reaction of an alkylaminosilane with a specific nucleus-substituted iodide. In one embodiment, a diiodosilane can be prepared via a reaction of a bis(diethylamino)silane with benzoyl iodide. The reaction substitutes an alkylamino group of aminosilane with an iodine group as a result. The transformation easily occurs at a room temperature under an atmospheric pressure and can be carried out in the absence of a solvent or in the presence of an aprotic solvent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention is in the field of silicon chemistry. In particular, the present invention relates to a method for preparing di- and tri-iodosilanes. [Background technology]

[0002] Halosilanes are useful as precursors in the manufacture of microelectronic devices. In particular, halosilanes such as H2SiI2 and HSiI3 are useful as precursor compounds for silicon-containing film deposition used in the manufacture of microelectronic devices. Current solution-based synthesis methodologies describe the synthesis of H2SiI2 and other selected iodosilanes from (i) arylsilanes (Keinan et al., J. Org. Chem., Vol. 52, No. 22, 1987, pp. 4846-4851; Kerrigan et al., U.S. Pat. No. 10,106,425) or (ii) halosilanes such as SiH2Cl2 (U.S. Pat. No. 10,384,944).

[0003] Keinan et al. describe a synthetic method for the formation of SiH2I2 using stoichiometric treatment of arylsilanes, phenyl-SiH3, with iodine in the presence of a catalyst such as ethyl acetate. The reaction by-products are aromatic functional groups from the arylsilane, liberated as benzene, and a complex by-product mixture resulting from ethyl acetate decomposition. Separating the reaction by-products from the desired SiH2I2 is cumbersome, complicating the process. Additionally, methods for preparing halosilanes based on arylsilanes typically produce products contaminated with iodine and / or hydrogen iodide, which are detrimental to the desired iodosilane product, and therefore antimony, silver, or copper are often used to stabilize the iodosilane product.

[0004] U.S. Patent No. 10,106,425 teaches the use of arylsilanes (CH3C6H4)SiH3 as reactants. The disclosed method is claimed as a less hazardous alternative to the Keinan process of producing benzene from phenyl-SiH3 because it produces toluene as a by-product. U.S. Patent No. 10,384,944 describes, for example, halide exchange of LiI with SiH2Cl2 to produce LiCl and SiH2I2 in a halogen exchange reaction. Summary of the Invention

[0005] In summary, the present invention provides a methodology for preparing highly desirable iodosilanes, such as HSiI and HSiI, by treating certain dialkylamidosilanes with acyl iodides. In one embodiment, diiodosilanes can be prepared from the reaction of bis(diethylamino)silane with benzoyl iodide. This reaction surprisingly results in the replacement of the alkylamino group of the aminosilane with an iodo group. This transformation occurs readily at room temperature and atmospheric pressure and can be carried out solvent-free and in the presence of aprotic solvents. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

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

[0008] Numerical ranges expressed using endpoints include all numbers subsumed within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0009] In a first aspect, the present disclosure provides a compound of formula (I): (H) x Si(I) y (I) wherein x is 1 or 2, y is 2 or 3, and the sum of x+y is 4. A method for preparing a compound having formula (A): (H) x Si(N(R 1 )(R 2 )) y (A) In the formula, (i) each R 1 and each R 2 are independently selected from a C1-C6 alkyl group, a C3-C8 alicyclic group, or hydrogen, or (ii) R 1 and R 2 form a C4-C7 nitrogen-containing saturated or aromatic ring together with the nitrogen atom to which they are attached, with the proviso that R 1 and R 2 is hydrogen; The compound formula: TIFF2025003979000001.tif23170, R 3 is selected from C1-C6 alkyl, C1-C6 substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl or substituted phenyl; to produce a compound of formula (I).

[0010] In a second aspect, the present disclosure provides a compound of formula (II): (H) z (I) y Si-Si(I) y (H) z (II) In the formula, y is 2 or 3, z is 0 or 1, and the sum of y and z is 3. The present invention provides a method for preparing a compound having the formula (B): H z ((R 1 )(R 2 )N) y Si-Si(N(R 2 )(R 1 )) y H z (B) In the formula, (i) each R 1 and each R 2 are independently selected from a C1-C6 alkyl group, a C3-C8 alicyclic group, or hydrogen, or (ii) R 1 and R 2 form a C4-C7 nitrogen-containing saturated or aromatic ring together with the nitrogen atom to which they are attached, with the proviso that R 1 and R 2 is hydrogen; The compound formula: TIFF2025003979000002.tif23170, R 3 is selected from C1-C6 alkyl, C1-C6 substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl or substituted phenyl; to produce a compound of formula (II).

[0011] It will be appreciated that in the above process, when a reactant of formula (A) is utilized, a product of formula (I) is produced, and when a reactant of formula (B) is utilized, a product of formula (II) is produced. In one embodiment, the compound of formula (I) is H2SiI2. In another embodiment, the compound of formula (I) is HSiI3.

[0012] In one embodiment, the formula: (H) x Si(N(R 1 )(R 2 )) y (A) is the following H2Si(N(CH3)2)2, H2Si(N(CH2CH3)2)2, H2Si(N(CH2CH3)(CH3))2 H2Si(N(CH2CH2CH3)2)2, H2Si(N(CH2CH2CH2CH3)2)2, H2Si(N(t-butyl)2)2, H2Si(N(H)(t-butyl))2, HSi(N(CH3)2)3, HSi(N(CH2CH3)2)3, HSi(N(CH2CH2CH3)2)3, HSi(N(CH2CH2CH2CH3)2)3, HSi(N(t-butyl)2)3, The compound is selected from the following:

[0013] As used herein, the term "substituted phenyl" refers to a phenyl group substituted 1 to 5 times with a group selected from C1-C6 alkyl, C1-C6 alkylamino, di(C1-C6 alkyl)amino, and halo. In one embodiment, halo is fluoro.

[0014] As used herein, the term "substituted C1-C6 alkyl" means a C1-C6 alkyl group substituted 1 to 5 times with a group selected from C1-C6 alkylamino, di(C1-C6 alkyl)amino, and halo.

[0015] As used herein, the term "substituted benzyl" means a benzyl group having 1 to 5 substituents on the aromatic ring selected from C1-C6 alkylamino, di(C1-C6 alkyl)amino, and halo.

[0016] The methodology of the present invention can be carried out without solvent or in the presence of an aprotic solvent that is non-reactive with the starting material or the iodosilane product. Such solvents include aliphatic, aromatic and halogenated hydrocarbon solvents that lack moieties and functional groups such as oxygen, esters, carboxyl groups and ketones. Examples include benzene, toluene, hexane, cyclohexane, pentane, dichloromethane, 1,2-dichloroethane, tetralin, decalin, mesitylene, dibromoethane, tetrachloroethylene, or chlorobenzene.

[0017] The reaction generally proceeds at room temperature and atmospheric pressure.

[0018] The process for preparing the precursor compounds of the present invention can be carried out in standard batch or continuous reactors. Those skilled in the art will recognize the size and type of reactor that can be utilized in the context of the reagents and products so produced.

[0019] The compounds of formula (I) and formula (II) are useful as precursors in the formation of silicon-containing films on microelectronic device surfaces by methods such as atomic layer deposition (see, for example, U.S. Patent Nos. 10,580,645 and 10,424,477, which are incorporated herein by reference). Also, by way of example, the compounds of formula (I) and formula (II) can be introduced into a deposition chamber for thermal CVD or thermal ALD, or for plasma-enhanced ALD or plasma-enhanced CVD. In these cases, a co-reactant gas can be introduced to deposit a SiO2 film via oxidation in an oxidizing environment with O2, O3, N2O, or a mixture thereof. Similarly, the compounds of formula (I) and formula (II) can be introduced into a deposition chamber for thermal CVD or thermal ALD, or for plasma-enhanced ALD or plasma-enhanced CVD. In these cases, a co-reactant gas can be introduced to deposit a silicon nitride film via nitridation with N2, NH3, hydrazine, or an alkylhydrazine-containing mixture. The deposited film serves as a dielectric layer in a microelectronic device. EXAMPLES

[0020] Example 1: Diiodosilane A sample of 25.0 g (143 mMol) of bis(diethylamino)silane was combined with 4 equivalents of benzoyl iodide, 133.0 g (574 mMol) and 500 mL of hexane. The reaction was allowed to proceed for 2 hours, after which 1 The desired diiodosilane product was detected by H NMR. All starting material was consumed. When benzoyl iodide was added to bis(diethylamino)silane, the observed yield was 7% (determined from concentration in hexane). When bis(diethylamino)silane was added to benzoyl iodide, the observed yield was 3.5% (determined from concentration in hexane). NMR samples were spiked with diiodosilane for confirmation and the identity of the signals was confirmed. 1 H NMR(400MHz, C6D6): δ 3.61( 1 J Si-H =141.5 Hz, H-SiI 2, 2H).

[0021] Example 2: Diiodosilane A sample of 20.0 g (115 mMol) of bis(diethylamino)silane was combined with 4 equivalents of acetyl iodide, 78.0 g (459 mMol), and 400 mL of hexane. The reaction was allowed to proceed for 10 minutes, after which 1 Traces of the desired diiodosilane product were detected by H NMR. All starting material was consumed. Attempted isolation resulted in decomposition of the product. When acetyl iodide was added to bis(diethylamino)silane, the observed isolated yield was 0%. 1 H NMR(400MHz, C6D6): δ 3.61( 1 J Si-H =141.5 Hz, H-SiI 2, 2H).

[0022] Example 3: Diiodosilane A sample of 0.68 g (3.9 mMol) of bis(diethylamino)silane was combined with 4 equivalents of 2-fluorobenzoyl iodide, 4.69 g (15.6 mMol) and 10 mL of hexane. The reaction was allowed to proceed for 10 minutes, after which 1 A 43% conversion of the desired diiodosilane product was detected by H NMR. All starting material had been consumed. After stirring for an additional 20 hours, the observed yield for the addition of 2-fluorobenzoyl iodide to bis(diethylamino)silane was 20%. 1 H NMR(400MHz, C6D6): δ 3.61( 1 J Si-H =141.5 Hz, H-SiI 2, 2H).

[0023] Example 4: Diiodosilane A sample of 0.27 g (1.6 mMol) of bis(diethylamino)silane was combined with 4 equivalents of 3,5-difluorobenzoyl iodide, 2.3 g (6.2 mMol) and 5 mL of hexane. The reaction was allowed to proceed for 10 minutes, after which 1 81% conversion of the desired diiodosilane product was detected by H NMR. All starting material had been consumed. After stirring for an additional 20 hours, the observed yield for the addition of 3,5-difluorobenzoyl iodide to bis(diethylamino)silane was 20%. 1 H NMR(400MHz, C6D6): δ 3.61( 1 J Si-H =141.5 Hz, H-SiI 2, 2H).

[0024] Example 5: Diiodosilane A 3.3 g (18.9 mMol) sample of bis(diethylamino)silane was combined with 4 equivalents of 2,2-dimethylpropanoyl iodide, 1.0 g (4.7 mMol), and 3 mL of hexane. The reaction was allowed to proceed for 10 minutes, after which 20% of the desired diiodosilane product was detected by 1H NMR. 72% of the starting material remained. After an additional 20 hours of stirring, the observed yield for the addition of 2,2-dimethylpropanoyl iodide to bis(diethylamino)silane was 0.1%. 1 H NMR(400MHz, C6D6): δ 3.61( 1 J Si-H =141.5Hz, H-SiI 2, 2H).

[0025] Aspects In a first aspect, the present disclosure provides a compound of formula (I): (H) x Si(I) y (I) wherein x is 1 or 2, y is 2 or 3, and the sum of x+y is 4. A method for preparing a compound having formula (A): (H) x Si(N(R 1 )(R 2 )) y (A) In the formula, (i) each R 1 and each R 2 are independently selected from a C1-C6 alkyl group, a C3-C8 alicyclic group, or hydrogen, or (ii) R 1 and R 2 form a C4-C7 nitrogen-containing saturated or aromatic ring together with the nitrogen atom to which they are attached, with the proviso that R 1 and R 2 is hydrogen; The compound formula: TIFF2025003979000003.tif23170, R 3is selected from C1-C6 alkyl, C1-C6 substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl or substituted phenyl; to produce a compound of formula (I).

[0026] In a second aspect, the disclosure provides the method of the first aspect, wherein the compound of formula (I) is H2SiI2.

[0027] In a third aspect, the disclosure provides the method of the first aspect, wherein the compound of formula (I) is HSiI3.

[0028] In a fourth aspect, the present disclosure provides a method for the preparation of a medicament for use in a pharmaceutical composition comprising: 1 and R 2 is selected from methyl, ethyl, propyl, sec-butyl, and t-butyl.

[0029] In a fifth aspect, the present disclosure provides a method for the preparation of a medicament for use in a pharmaceutical composition comprising: 1 and R 2 At least one of is t-butyl.

[0030] In a sixth aspect, the present disclosure provides a method for the preparation of a medicament ... use 1 and R 2 is cyclohexyl.

[0031] In a seventh aspect, the present disclosure provides a method for the preparation of a medicament for use in a pharmaceutical composition comprising: 1 and R 2 taken together with the nitrogen atom to which they are attached form a pyrrole, pyrrolidine or piperidine ring.

[0032] In an eighth aspect, the present disclosure provides a method for the preparation of a medicament ... 3 is C1-C6 alkyl.

[0033] In a ninth aspect, the present disclosure provides a method for the preparation of a medicament ... 3is phenyl.

[0034] In a tenth aspect, the present disclosure provides a method for the preparation of a medicament for use in a pharmaceutical composition comprising: 3 is substituted phenyl.

[0035] In an eleventh aspect, the present disclosure provides a method for the preparation of a medicament for use in a pharmaceutical composition comprising: 3 is 4-fluorophenyl.

[0036] In a twelfth aspect, the present disclosure provides a method for the preparation of a medicament for use in a pharmaceutical composition comprising 3 is 3,5-difluorophenyl.

[0037] In a thirteenth aspect, the present disclosure provides a method for the preparation of a compound comprising: 1 and R 2 At least one of R is ethyl; 3 is methyl or phenyl.

[0038] In a fourteenth aspect, the present disclosure provides a compound of formula (II): (H) z (I) y Si-Si(I) y (H) z (II) In the formula, y is 2 or 3, z is 0 or 1, and the sum of y and z is 3. The present invention provides a method for preparing a compound having the formula (B): H z ((R 1 )(R 2 )N) y Si-Si(N(R 2 )(R 1 )) y H z (B) In the formula, (i) each R 1 and each R 2 are independently selected from a C1-C6 alkyl group, a C3-C8 alicyclic group, or hydrogen, or (ii) R 1 and R2 form a C4-C7 nitrogen-containing saturated or aromatic ring together with the nitrogen atom to which they are attached, with the proviso that R 1 and R 2 is hydrogen; The compound formula: TIFF2025003979000004.tif23170, R 3 is selected from C1-C6 alkyl, C1-C6 substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl or substituted phenyl; to produce a compound of formula (II).

[0039] In a fifteenth aspect, the present disclosure provides a method for the preparation of a medicament for use in a pharmaceutical composition comprising: 1 and R 2 is selected from methyl, ethyl, propyl, sec-butyl, and t-butyl.

[0040] In a sixteenth aspect, the present disclosure provides a method for the preparation of a medicament for use in a pharmaceutical composition comprising: 1 or R 2 At least one of is t-butyl.

[0041] In a seventeenth aspect, the present disclosure provides a method for the preparation of a medicament for the treatment of cancer, comprising: 1 or R 2 is cyclohexyl.

[0042] In an eighteenth aspect, the present disclosure provides a method for the preparation of a medicament for use in a pharmaceutical composition comprising: 1 and R 2 taken together with the nitrogen atom to which they are attached form a pyrrole, pyrrolidine or piperidine ring.

[0043] In a nineteenth aspect, the present disclosure provides a method for the preparation of a medicament ... 3 is C1-C6 alkyl.

[0044] In a twentieth aspect, the present disclosure provides a method for the preparation of a medicament for use in a pharmaceutical composition comprising:3 is phenyl.

[0045] In a twenty-first aspect, the present disclosure provides a method for the preparation of a compound comprising: 1 and R 2 At least one of R is ethyl; 3 is methyl or phenyl.

[0046] Having thus described several exemplary embodiments of the present disclosure, one skilled in the art will readily appreciate that still other embodiments may be made and used within the scope of the appended claims. Many advantages of the present disclosure encompassed by this document have been set forth in the foregoing description. It will be understood, however, that the present disclosure is in many respects merely illustrative. Changes may be made in detail without departing from the scope of the present disclosure. The scope of the present disclosure is, of course, to be defined in the language in which the appended claims are expressed.

Claims

1. Formula (I): (H) ｘ Si(I) ｙ (I) (wherein x is 1 or 2, y is 2 or 3, and the sum of x+y is 4). A method for preparing a compound having the formula (A): (H) ｘ Si(N(R １ )(R ２ )) ｙ (A) [In the formula, (i) each R １ And each R ２ is independently １ ~C ６ Alkyl group, C ３ ~C ８ or (ii) R １ and R ２ together with the nitrogen atom to which they are attached, ４ ~C ７ forms a nitrogen-containing saturated or aromatic ring, with the proviso that R １ and R ２ provided that not more than one of The compound formula: (In the formula, R ３ is C １ ~C ６ Alkyl, C １ ~C ６ substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl or substituted phenyl; to produce a compound of formula (I).

2. The compound of formula (I) is H ２ SiI ２ The method of claim 1, wherein

3. The compound of formula (I) is HSiI ３ The method of claim 1, wherein

4. R １ and R ２ The method of claim 1, wherein is selected from methyl, ethyl, propyl, sec-butyl and t-butyl.

5. R １ and R ２ The method of claim 1 , wherein at least one of is t-butyl.

6. R １ and R ２ The method of claim 1 , wherein at least one of is cyclohexyl.

7. R １ and R ２ The method of claim 1 , wherein, together with the nitrogen atom to which they are attached, form a pyrrole, pyrrolidine or piperidine ring.

8. R ３ C １ ~C ６ The method of claim 1 , wherein the alkyl group is an alkyl group.

9. R ３ The method of claim 1 , wherein is phenyl.

10. R ３ The method of claim 1 , wherein is substituted phenyl.

11. R ３ The method of claim 10, wherein is 4-fluorophenyl.

12. R ３ The method of claim 10, wherein is 3,5-difluorophenyl.

13. R １ and R ２ At least one of R ３ The method of claim 1 , wherein is methyl or phenyl.

14. Formula (II): (H) ｚ (I) ｙ Si-Si(-) ｙ (H) ｚ (II) (In the formula, y is 2 or 3, z is 0 or 1, and the sum of y and z is 3.) A method for preparing a compound having the formula (B): H ｚ ((R １ )(R ２ )N) ｙ Si-Si(N(R ２ )(R １ )) ｙ H ｚ (B) [In the formula, (i) each R １ And each R ２ is independently １ ~C ６ Alkyl group, C ３ ~C ８ or (ii) R １ and R ２ together with the nitrogen atom to which they are attached, ４ ~C ７ forms a nitrogen-containing saturated or aromatic ring, with the proviso that R １ and R ２ provided that not more than one of The compound formula: (In the formula, R ３ is C １ ~C ６ Alkyl, C １ ~C ６ substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl or substituted phenyl; to produce a compound of formula (II).

15. R １ and R ２ The method of claim 14, wherein is selected from methyl, ethyl, propyl, sec-butyl and t-butyl.

16. R １ Or R ２ The method of claim 14, wherein at least one of is t-butyl.

17. R １ Or R ２ The method of claim 14, wherein at least one of is cyclohexyl.

18. R １ and R ２ The method of claim 14 , wherein, together with the nitrogen atom to which they are attached, form a pyrrole, pyrrolidine or piperidine ring.

19. R ３ C １ ~C ６ The method of claim 14, wherein the alkyl group is an alkyl group.

20. R ３ The method of claim 14 , wherein is phenyl.

21. R １ and R ２ At least one of R ３ The method of claim 14, wherein is methyl or phenyl.

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