In the following text, if not otherwise stated, the following meanings are used:
CSI chlorosulfonyl isocyanate
CSOS chlorosulfonic acid
CISI bis(chlorosulfonyl)-imide
FSI fluorosulfonyl isocyanate
FSOS fluorosulfonic acid
FR flow rate
RT room temperature
Imidodisulfuryl compounds are used for a number of purposes. One example is the use of imidodisulfurylchlorid for the preparation of lithium bis(fluorosulfonypimid, which again is used as an electrolyte e.g. in lithium ionic batteries, which e,& can be used in automotive batteries, and is used as antistatic agent in touch screens.
DE 1 159 410 B discloses a method for preparation of halosulfonyl isocyanates by a reaction of halosulfonic acid with urea. The reaction is done preferably at a temperature of from 100 to 180° C. Specifically disclosed is the preparation of chlorosulfunyl isocyanate at a temperature of from 120 to 150° C.
DE 1 143 495 B discloses a method for preparation of imido-bis(sulfuryl)fluorid by a reaction of fluorosulfonic acid with urea. The reaction temperature is not stated apparently the reaction starts at room temperature and in the course of the reaction the reaction mixture is cooled from time to time.
CA 710255 A discloses a method for preparation of imido-bis(sulfurylchloride) by a reaction of chlorosulfonic acid with trichlorophosphazo-sulfuryl chloride. Methods such as disclosed in CA 710255 have the disadvantage of requiring phosphorus chemistry which is rather expensive and environmentally disadvantageous to use.
WO 20091123328 A1 discloses the preparation of CISI in a batch method, details are given the example section of instant invention.
The reaction equation of instant invention for preparation of imidodisulfurylhalides, also named imido)bis(sulfurylhalides), imidobissulfurylhalides or bis(halidosunnyl)imide, which also is applicable for similar compounds of instant invention, is depicted in Scheme 1;
with Xa and Xb being halogen.
Both starting compounds, the isocyanate and the sulfonic acid, and the product, the his imide, are toxic and corrosive. In case of Xa and Xb being Cl, the product shows a very high exothermic decomposition at elevated temperatures, making it necessary to provide adequate safety measures in production. The heat of reaction deltaH is ca. 100 J/mol, the onset of decomposition of the imidosulfurylchloride is around 180° C. with an adiabatic temperature rise to temperatures well over 400° C. The reaction of CSI with FSOS and the reaction of PSI with CSOS show similar temperatures for the onset of decomposition.
Therefore the reaction temperature in batch processes in production is not higher than 150° C. to avoid the risk of explosion. The reaction times of the batch processes ranges from ca, 8 h to 24 h.
On the other hand the isocyanate and the sulfonic acid only react at elevated temperatures. Due to these circumstance and safety considerations, in the past the imidodisulfurylhalides have been prepared only in small batches and at temperatures well below the onset of decomposition as mentioned, leading to the mentioned long reaction times.
There was a need for a method for preparation of imidodisulfurylhalides, which does not need phosphorous chemistry, has short reaction times and high yields, where the product shows high purity, and allows for safe handling of the substances and of the reaction, also on a large scale.
Unexpectedly, it is possible to react a halostnibnyl isocyanate with a halosulfonic acid at temperatures above the onset temperature of decomposition of the reaction product, the imidodisulfurylhalide without the expected decomposition of the desired imidodisulfurylhalide, the yields are high. It was unexpected to be able to conduct the reaction in a safe way. This allows for the desired short reaction times.
Furthermore the short reaction times can be realized still with a product with high purity, i.e. not showing discoloration due to decomposition or polymerization reactions usually taking place at too high temperatures.
Subject of the invention is a method for preparation of compound of formula (I);
the method comprises three consecutive steps step (StepS1), step (StepS2) and step (StepS3);
step (StepS1) comprises a reaction (ReacS1);
reaction (ReacS1) is a reaction of compound of formula (II) with compound of formula (III);
wherein
[N(R20)(R21)(R22)R23]+, and [P(R20)(R21)(R22)R23]+; R20, R.21, R22 and R23 are identical or different and independently from each other selected from the group consisting of H, C1-8 alkyl, C5-6 cycloalkyl, phenyl, benzyl, vinyl and allyl;
the reaction. (ReaeS1) is done in a continuous way;
Preferably,
especially,
[N(R20)(R21)(R22)R23]+; R20, R21 R22 and R23 are identical or different and independently from each other selected from the group censisting of H, C1-8 alkyl, C5-6 cycloalkyl, phenyl and benzyl,
more especially,
and
and
R20 and R.21 are identical or different and independently from each C1-8 alkyl;
in particular,
and
R20 and R21 are identical or different and independently from each selected from the group consisting of methyl, ethyl and n-butyl.
Especially, device (DevS1) and device (DevS.2) are coiled tubes.
Preferably, device (DevS3) is a conventional back pressure regulating device.
Preferably, device (DevS4) a device capable of separating gaseous CO2 from a liquid, any known device suitable for this purpose for can be used for this purpose, more preferably device (DevS4) is a column or a cyclone.
Reaction (ReacS1) is triggered in device (DevS1) by the heating of the mixture in the device (DevS1) to the temperature (TempS1),
Reaction (ReacS1) is quenched in device (DevS2), this is done by the cooling the reaction mixture in the device (DevS2) to the temperature (TempS2).
Preferably, temperature (TempS1) is of from 190 to 280° C., more preferably of from 200 to 260° C., even more preferably from 210 to 255° C., especially from 220 to 255° C.
Preferably, temperature (TempS2) is from 10 to 120° C. more preferably from 15 to 100° C., even more preferably from 15 to 90° C., especially from 15 to 85° C., more especially from 20 to 85° C.,
The melting point of pure CISI is ca. 35° C., therefore the lowest possible value of temperature (TempS2) is governed by the conversion of the reaction, since residual compound of formula (II) and residual compound of formula (iii) in the reaction mixture naturally lowers the melting point of the reaction mixture after the reaction and allows for lower values of temperature (TempS2).
In case of device (DevS1) and/or device (DevS2) being tubes, especially coiled tubes, due to constructional limitations or due to density fluctuations and the like hot spots or cold spots can occur in spite of efforts to avoid them. Therefore any mentioned temperatures are meant to be average temperatures in view of possible hot or cold spots.
Conventional back pressure regulating devices, which can he used for device (DevS3), work discontinually, i.e. by opening and closing they release the product stream while holding the pressure. This leads naturally to variations in the pressure. Therefore the pressure (PressS1) is meant to be an average pressure.
All parts in contact with the mixture of compound of formula (II) and compound of formula (III) and with the reaction mixture are made out of respective materials, which are resistant to the attack of the chemicals under the respective conditions, i.e. stainless steel, hastelloy, such as hastelloy B or hastelloy C, titanium, tantalium, silicon carbide, silicon nitride etc., they can also be passivized or lined with material inert to the chemicals, such as PTFE.
Compound of formula (I) can be used from device (DevS4) for any subsequent reaction without further purification, in case of a further purification, preferably, the liquid phase obtained from device (DevS4) is further purified by removing any low boiling residues, preferably this is done by using a film evaporator, more preferably a wiped film evaporator.
In the examples an equimolar premix of CSOS and CSI was fed into device (DevS1).
The examples were carried out with
The obtained CISI in each example was a colorless to yellow liquid.
The structure was confirmed by IR spectroscopy:
In the examples CSOS and CSI was fed separately into device (DevS1) and were mixed in device (DevS1) by a inline static mixing device. The examples were carried out with
The obtained CISI in each example was a colorless to yellow liquid.
The structure was confirmed by IR spectroscopy, the data is given in the description of example 1 to 14.
In the examples an equimolar premix of CSOS and CSI was fed into device (DevS1).
The examples were carried out with
The obtained CISI in each example was a colorless to yellow liquid.
The structure was confirmed by IR spectroscopy, the data is given in the description of example 1 to 14.
Due to the onset of decomposition it is not allowed to do a batch reaction at a temperature of higher than 160° C. for comparison with the continuous reaction of instant invention. The risk of explosion is too high. Therefore only batch reactions at 150° C. are allowed due to these safety restrictions.
An equimolar amount of CSI was added to CSOS at 120° C. over 3 h, then the mixture was heated in 3 h to 150° C. and stirred at 150° C. for 7 h. Conversion was only 90%. Therefore total reaction time to reach 90% conversion was 13 h. The color was yellow.
A color which is darker than yellow must be avoided under all circumstances in the batch process since it is an indication of a substantial amount of decomposition which again is an indication of an explosure being very close.
WO 2009/123328 A1 discloses in Synthesis Example 2 the preparation of CISI in a batch method. During 2 h CSI was added to CSOS at 120° C. then the mixture was stirred for 6 h at 150° C. Yield was 65.6%.
An equimolar premix of CSOS and CSI was fed into device (DevS1).
The example was carried out with
The obtained CISI was a colorless to yellow liquid.
The structure was confirmed by IR spectroscopy, the data is given in the description of example 1 to 14.
An equimolar premix of triflouro methane sulfonic acid and CSI was fed into device (DevS1),
The example was carried out with
The obtained compound of formula (I) was a colorless to yellow liquid.
The structure was confirmed by IR and NMR spectroscopy:
Furthermore the formation of the desired product by the reaction was confirmed by comparison of the heat of formation obtained by DSC measurements and high level calculated data.
DSC was measured dynamically with a heat rate of 0.4° C./min.
using the method B3LYP 6-31G.
An equimolar premix of flouro sulfonic acid and CSI was fed into device (DevS1). The examples were carried out with
The obtained compound of formula (2) was a colorless to yellow liquid.
The structure was confirmed by NMR spectroscopy:
NMR (CD3CN, 400 MHz, 24° C., ref: benzenesulfonyl fluoride) δ=57.24 ppm
The purity and yield of any of the examples 1 to 2.2 can be determined indirectly by using the respective obtained product as substrate in a reaction for the preparation of bis(fluorosulfonyl)-imide. As example for such determination of yield and purity in the following is described how the product prepared according to example 22 was used as substrate for the preparation of his[di((fluorosulfonyl)imideizinc salt in analogy to Synthesis Example 19-1 of WO 2009/123328 A1:
In a 500 ml reaction vessel, 179.3 g valeronitrile and 20.3 g CISI (0.093 mol, prepared according to example 22) were charged, followed by stirring. Into the reaction vessel, 10.6 g (0.10 mol) of anhydrous ZnF2 were added, followed by conducting a reaction at room temperature (25° C.) for 3 hours. The bis[di(fluorosulfonyl)imide]zinc salt was obtained as solution (yield 66,4%, determined by 19F-NMR and calculated based on CISI (of a content of 100%)).
Any of the products prepared according to examples 1 to 22 of instant invention had a similar purity and was obtained in similar yield.
An equimolar premix of 1-n-butyl-3-methylimidazolium trifluoromethanesulfonate and CSI was fed into device (DevS1).
The example was carried out with
The obtained compound of formula (I) was a yellow liquid
For the reaction product the following analytical data was measured.
Number | Date | Country | Kind |
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13176189.2 | Jul 2013 | EP | regional |
14162217.5 | Mar 2014 | EP | regional |
This application is the national stage entry of International Patent Application No. PCT/EP2014/064785 having a filing date of Jul. 10, 2014, which claims the filing benefit of European Patent Application No. 13176189.2, having a filing date of Jul. 11, 2013, U.S. Provisional Patent Application No. 61/844,963, having filing date of Jul. 11, 2013, and European Patent Application No. 14162217.5, having a filing date of Mar. 28, 2014, all of which are incorporated herein by reference in their entirety. The invention relates to a method for the preparation of imidodisulfuryl compounds in a continuous reaction at elevated temperatures.
Filing Document | Filing Date | Country | Kind |
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PCT/EP2014/064785 | 7/10/2014 | WO | 00 |
Number | Date | Country | |
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61844963 | Jul 2013 | US |