TW201914956A - Selective reduction of chlorodisilanes with tri-n-butyl tin hydride - Google Patents

Abstract

A method for producing 1,1,1-trichlorodisilane including adding hexachlorodisilane to tri-n-butyl tin hydride in a solvent at a temperature of 20 DEG C or cooler.

Description

Selective reduction of chlorodioxane with tri-n-butyltin hydride

The present invention relates to a process for the selective reduction of hexachlorodioxane to produce 1,1,1-trichlorodioxane.

Reduction of hexachlorodioxane with tri-n-butyltin hydride has been reported, for example, in U. Herzog et al., J. Organometallic Chem ., 1978 (161) 165-169. However, the main products obtained in this reference differ depending on the catalyst used and are SiHCl ₃ , decane, or dioxane.

It is challenging to produce 1,1,1-3CDS with high selectivity to 1,1,1-trichlorodioxane (1,1,1-3 CDS) compared to other dioxane. Other dioxanes include trichloro. Other isomers of dioxane, as well as other chloro(di)decane and alkyl(di)decane impurities.

The problem addressed by the present invention is to provide a process for producing 1,1,1-3 CDS with a high selectivity to 1,1,1-3 CDS compared to other dioxanes, and other dioxanes including trichlorodioxane Structures, as well as other chloro(di)decane and alkyl(di)decane impurities. In particular, the present invention provides a method for producing 1,1,1-3 CDS in a 99 weight percent (wt%) selectivity compared to a 1,1,2-trichlorodioxane isomer, as opposed to The combined weight of the two chlorodiazine diisomers. Further, at the same time, the method of the present invention produces 1,1,1-3 CDS at a selectivity of 65 wt% or more compared to other chlorodioxane by-products. The selectable wt% values were determined by gas chromatography using the methods described below.

The method of the present invention is to find that 1,1,1-3 CDS can be produced at a high selectivity level by starting with tri-n-butyltin hydride in a solvent to form a mixture, and then at 20 degrees Celsius ( Add to the mixture hexachlorodioxane (HCDS) at a temperature of °C) or more.

In a first aspect, the invention is a process for producing 1,1,1-trichlorodioxane; the process comprising adding hexachlorodioxane to a solvent in a solvent at a temperature of no greater than 20 ° C In a mixture of butyltinhydride.

Unless otherwise noted, the percentages are by weight (wt%) and the temperature is °C. Chloro(di)decane refers to both chlorodecane and chlorodioxane. Alkyl(di)decane means both alkyldecane and alkyldioxane. Tri-n-butyltin hydride (Bu ₃ SnH) has CAS number 688-73-3 and is also known as tri-n-butylstannane.

The process of the invention requires a mixture of tri-n-butyltin hydride (TBTH) formed in a solvent. TBTH can be added to the solvent or added to the TBTH to form a mixture. Desirably, the solvent is a non-polar organic solvent. Preferred non-polar organic solvents include C ₄ -C ₂₀ hydrocarbons and ethers; preferably C ₆ -C ₂₀ linear or branched alkanes, C ₆ -C ₂₀ aromatics, or C ₄ -C ₂₀ ethers; Is decane, isododecane, toluene, xylene, diisopropylbenzene, Diethyl ether or dibutyl ether; preferably xylene, decane or isododecane. Mixtures of the organic solvents mentioned herein may be used. The non-polar organic solvent can be aromatic or non-aromatic.

The solvent is usually present in a concentration of from 1 to 99% by weight, based on the weight of the organic solvent and TBTH. Desirably, the solvent is present at a concentration of 10 wt% or more, preferably 20 wt% or more, and may be 30 wt% or more, 40 wt% or more, 50 wt% or More, and at the same time, preferably 90 wt% or less, preferably 80 wt% or less, preferably 70 wt% or less, and may be 60 wt% or less, 50 wt. % or less, 30 wt% or less, or even 25 wt% or less, wherein wt% is the combined weight of the solvent and TBTH.

Preferably, the mixture of the organic solvent and tri-n-butyltin hydride is substantially free of Lewis base, which means that the mixture has less than 5 wt% expressed as a percentage of the total amount of the solvent and tri-n-butyltin hydride. The Lewis base (the Lewis base does not include an ether solvent) is preferably less than 2 wt%, preferably less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0.1 wt%.

This process requires the addition of hexachlorodioxane (HCDS) to a mixture of organic solvent and TBTH. During the addition of HCDS, the temperature of the mixture is maintained at 20 ° C or colder, preferably 15 ° C or colder, 10 ° C or colder, 5 ° C or colder, 0 ° C or colder, -5 ° C or colder, -10 ° C or colder, -12 ° C or colder, -14 ° C or colder, and even -15 ° C or colder. At the same time, although the method may work better when the temperature is colder, in practice, the temperature is usually -30 ° C or warmer, -25 ° C or warmer, -20 ° C or warmer, and may be -15 ° C. Or warmer. The solvent is selected to maintain the liquid at the maintained temperature during the addition of HCDS.

Desirably, after the addition of the HCDS, maintaining the mixture at these same temperature values is completed in 0.5 hours or longer, preferably one hour or longer, more preferably two hours or more. Long, and may be 5 hours or longer, while at the same time typically 12 hours or less, preferably 8 hours or less, and may be 5 hours or less, and even 3 hours or less .

Preferably, sufficient HCDS is added to achieve a molar ratio of hexachlorodioxane (HCDS) to tri-n-butyltin hydride of from 1:3 to 1:2, preferably from 1:2.8 to 1:2.2, and More preferably, it is 1:2.7 to 1:2.3.

1,1,1-3 CDS was formed by the reaction of HCDS and TBTH during the addition of HCDS and during the time after the addition of HCDS was completed. What is desired is to purify 1,1,1-3 CDS by distillation, preferably at a pressure below 760 mm Hg.

1, 1, 1-3 CDS can be used to form a ruthenium-heteroatom film by known techniques including, for example, physical vapor deposition, atomic layer deposition (ALD), or chemical vapor deposition (CVD). The physical vapor deposition method can include sputtering. Suitable sputtering methods include direct current (DC) magnetron sputtering, ion beam sputtering, reactive sputtering, and ion assisted sputtering. In general, the deposition method comprises ALD or CVD. Preferably, the heteroatoms are selected from the group consisting of carbon, oxygen and nitrogen.

Suitable ALD methods include plasma enhanced atomic layer deposition (PEALD), space atomic layer deposition (SALD), and thermal atomic layer deposition (TALD). When the PEALD method is used, the plasma may be any of the foregoing plasmas. The plasma may optionally further contain a carrier gas such as molecular nitrogen or argon gas. The plasma is formed by a plasma forming gas which may comprise a mixture of molecular nitrogen and molecular hydrogen.

Suitable CVD methods include the following methods: simple thermal vapor deposition, plasma enhanced chemical vapor deposition (PECVD), electron cyclotron resonance (ECRCVD), atmospheric pressure chemical vapor deposition (APCVD), low pressure chemical vapor deposition (LPCVD), Ultra High Vacuum Chemical Vapor Deposition (UHVCVD), Aerosol Assisted Chemical Vapor Deposition (AACVD), Direct Liquid Injection Chemical Vapor Deposition (DLICVD), Microwave Plasma Assisted Chemical Vapor Deposition (MPCVD), Remote Plasma Reinforcement Chemical vapor deposition (RPECVD), atomic layer chemical vapor deposition (ALCVD), hot wire chemical vapor deposition (HWCVD), hybrid chemical vapor deposition (HPCVD), rapid thermal chemical vapor deposition (RTCVD), and gas Vapor phase epitaxy chemical vapor deposition (VPECVD), photo-assisted chemical vapor deposition (PACVD) and flame assisted chemical vapor deposition (FACVD). Instance

By using Bu ₃ SnH in a solvent having a Lewis base catalyst at room temperature, Comparative Example 1 showed a lower selectivity to 1,1,1-3CDS than other chlorodioxane ( J. Organomet. Chem. 1995 , 494 , 143)

Reduction of HCDS by 2 eq of Bu ₃ SnH in 38 wt% toluene at room temperature and addition of PPh ₃ as a Lewis base catalyst resulted in a combination of 5 mol% 1, 1, 1-3 CDS and 43 mol% The product distribution of other chlorodioxane. It is apparent from these molar percentage values that 1,1,1-3 CDS is a minor component in the reaction product distribution.

By using Bu ₃ SnH at room temperature and in a solvent lacking a Lewis base catalyst, Comparative Example 2 showed a lower selectivity to 1,1,1-3 CDS compared to other chlorodioxane (batch 27003) -16-I)

In a glove box, tri-n-butyltin hydride (2.15 mL, 2.33 g, 2.0 eq) and toluene (0.75 mL, 0.65 g. 37 wt%) were placed in a 250 mL 3-neck half clamp equipped with a glass thermowell. Set in a round bottom flask and keep at 23 °C. Hexachlorodioxane (HCDS, 0.69 mL, 1.1 g, 1 eq) was added dropwise to the Bu ₃ SnH solution over 6 min, then stirring was continued for 50 min. The solution was analyzed by GC-TCD and showed that the solution contained 16.5 wt% 1,1, 1-3 CDS, 53.1 wt% of the combined chlorodioxane, and contained no detectable alkyl (di)decane, wherein wt% was Relative to all monodecane and dioxane present, as determined by gas chromatography (GC) using the methods described below.

Inventive Example 1 showed high selectivity to 1,1,1-3CDS compared to other chlorodioxanes by using a low reaction temperature and in a solvent lacking a Lewisine catalyst (batch 27003-16- Q)

In a glove box, tri-n-butyltin hydride (3.75 mL, 4.06 g, 2.5 eq) and decane (1.69 mL, 1.23 g. 45 wt%) were placed in a 250 mL 3-necked half equipped with a glass thermowell. The jacket was placed in a round bottom flask and maintained at -14 °C. Hexachlorodioxane (HCDS, 0.96 mL, 1.50 g, 1 eq) was added dropwise to the Bu ₃ SnH solution over 5 min, then stirring was continued for 165 min. The solution was analyzed by GC-TCD and showed that the solution contained 43.4 wt% 1,1, 1-3 CDS, 22.5 wt% combined with other chlorodioxane, and contained no detectable alkyl (di)decane, wherein wt% was Relative to all monodecane and dioxane present, as determined by gas chromatography (GC) using the methods described below. It is worth noting that 1,1,2-trichlorodioxane was not detected, indicating a combination of greater than 99 wt% compared to the 1,1,1- and 1,1,2-trichlorodioxane isomers. The selectivity of % 1, 1, 1-3CDS. Gas chromatography selective analysis

The wt% selectivity of 1,1,1-3 CDS relative to other products was determined by gas chromatography using a thermal conductivity detector (GC-TCD). A capillary column having a length of 20 meters and an inner diameter of 0.32 mm is used, and a 0.25 micron thick stationary phase in the form of a coating is contained on the inner surface of the capillary column, wherein the stationary phase is composed of phenylmethyl decane. composition. The carrier gas is helium used at a flow rate of 105 mm per minute. The gas chromatography instrument can be an Agilent Model 890A gas chromatograph. The inlet temperature is 200 degrees Celsius (°C). The temperature profile consisted of holding (holding) at 50 ° C for two minutes, raising the temperature to 250 ° C at a rate of 15 ° C per minute, and then holding (holding) at 250 ° C for ten minutes.

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Claims (9)

A method for producing 1,1,1-trichlorodioxane; the method comprising adding hexachlorodioxane to a mixture of tri-n-butyltin hydride in a solvent at a temperature of not more than 20 °C. The method of claim 1, wherein the molar ratio of hexachlorodioxane to tri-n-butyltinhydride is from 1:3 to 1:2. The method of claim 2, wherein the solvent is an organic solvent. The method of claim 3, wherein the reaction mixture comprising tri-n-butyltin hydride is maintained at a temperature of -10 ° C or more during the addition of hexachlorodioxane. The method of claim 4, wherein the organic solvent is present in an amount of 10 to 90 wt% based on the total weight of the organic solvent and tri-n-butyltin hydride. The method of claim 5, wherein after the addition of the hexachlorodioxane, the reaction mixture is maintained at a temperature of not more than 10 ° C for 0.5 to 12 hours. The method of claim 6, wherein the organic solvent is a C ₄ -C ₂₀ hydrocarbon, an ether, or a combination thereof. The method of claim 7, wherein the reaction mixture is maintained at a temperature of -50 to 0 ° C for 0.5 to 12 hours after the addition of the hexachlorodioxane. The method of claim 1, wherein the mixture of tri-n-butyltin hydride in the solvent contains less than 5 weight percent of Lewis base, based on the total of the solvent and tri-n-butyltin hydride.