HK1227843A1 - Method for preparation of imidodisulfuryl compounds - Google Patents

Description

Method for preparing imidodithioacyl compounds

The application is a divisional application of an invention patent application with the application date of 2014, 7 and 10, Chinese patent application number of 201480001266.6 (international application number of PCT/EP2014/064785) and the invention name of a method for preparing imido dithioacyl compound.

Technical Field

The present invention relates to a method for producing imidodithioacyl compounds in a continuous reaction at high temperature.

Background

If not otherwise stated, the following meanings apply in the text below:

CSI chlorosulfonyl isocyanate

CSOS chlorosulfonic acid

Clsi bis (chlorosulfonyl) imide

FSI fluorosulfonyl isocyanate

FSOS fluorosulfonic acid

FR flow Rate

RT Room temperature

Imidodithioacyl compounds are useful for a variety of purposes. One example is the use of imidodisulfoyl chloride for the preparation of lithium bis (fluoromethanesulfonylimide), which is also used, for example, as an electrolyte in lithium ion batteries (such as may be used in automobiles) batteries, and as an antistatic agent in touch screens.

DE 1159410B discloses a process for preparing halosulfonylisocyanates by reacting halosulfonic acids with urea. The reaction is preferably carried out at a temperature of from 100 to 180 ℃.

This patent specifically discloses the preparation of chlorosulfonyl isocyanate at a temperature of 120 to 150 ℃.

DE 1143495B discloses a process for preparing imido-bis (sulfonyl) fluorides by reacting fluorosulfonic acid with urea. If the reaction temperature is not specified, the reaction is started at room temperature and the reaction mixture is cooled at intervals during the reaction.

CA 710255A discloses a process for the preparation of imide-bis (sulfonyl chloride) compounds by the reaction of chlorosulfonic acid with phosphorus trichloride azosulfonyl chloride. The process disclosed in CA 710255, for example, has the disadvantage of requiring a phosphorus chemical, which is rather expensive and whose use is environmentally unfriendly.

The preparation of ClSI in a batch process is disclosed in WO 2009/123328a1, the details of which are given in the examples section of the present invention.

The reaction equation of the present invention for the preparation of imidoyl dithiohalide (also known as imidoyl bis (sulfonyl halide), imidoyl bissulfonyl halide, or bis (halosulfonyl) imide, which is also useful for analogous compounds of the present invention) is described in scheme 1:

scheme 1

Wherein Xa and Xb are halogen.

The two starting compounds, isocyanate and sulfonic acid, and the product bis (imide), are toxic and corrosive. In the case of Xa and Xb being Cl, the product shows a very high exothermic decomposition at high temperatures and must therefore provide adequate safety measures in production. The heat of reaction Δ H is about 100kJ/mol, the decomposition of the imidosulfonyl chloride starts at about 180 ℃ and the adiabatic temperature is raised to a temperature above 400 ℃. The reaction of CSI with FSOS and the reaction of FSI with CSOS show similar decomposition onset temperatures.

Therefore, the reaction temperature in the batch process of production is not higher than 150 ℃ to avoid the danger of explosion. The reaction time for a batch process is in the range of about 8 hours to 24 hours.

On the other hand, the isocyanate and the sulfonic acid react only at high temperatures. Due to these circumstances and safety considerations, imidoyl dithiohalides have been prepared in the past only in small batches and at temperatures below the decomposition start temperature mentioned, leading to the long reaction times mentioned.

There is an ongoing need for processes for preparing imidoyl dithiohalides, also on a large scale; the process does not require phosphorus chemicals, has short reaction times and high yields, wherein the product exhibits high purity and enables safe handling of the reaction mass and reactions.

Unexpectedly, the halosulfonyl isocyanate can be reacted with the halosulfonic acid at a temperature higher than the decomposition initiation temperature of the reaction product, without the intended decomposition of the imido dithiohalide, in high yield. It was unexpected that the reaction could be carried out in a safe manner. This makes possible the desired short reaction times.

Furthermore, short reaction times can be achieved and still products with high purity are obtained, i.e. which do not show discoloration due to decomposition or polymerization reactions which usually occur at too high temperatures.

Disclosure of Invention

The subject of the present invention is a process for the preparation of a compound of formula (I):

the method comprises three successive steps: step (StepS1), step (StepS2) and step (StepS 3);

step (StepS1) includes reaction (ReacS 1);

reaction (ReacS1) is the reaction of a compound of formula (II) with a compound of formula (III);

wherein

X1 and X2 are identical or different and are each, independently of one another, selected from the group consisting of F, Cl, Br, I, C_1-6Perfluoroalkyl, and tolyl;

Rⁿ⁺is selected from H⁺、Li⁺、Na⁺、K⁺、Mg²⁺、Ca²⁺、Zn²⁺、Cu²⁺、Al³⁺、Ti³⁺、Fe²⁺、Fe³⁺、B³⁺、[N(R20)(R21)(R22)R23]⁺And [ P (R20) (R21) (R22) R23]⁺；

R20, R21, R22 and R23 are identical or different and are selected, independently of one another, from H, C_1-8Alkyl radical, C_5-6Cycloalkyl, phenyl, benzyl, vinyl and allyl;

n is 1, 2 or 3;

the reaction (ReacS1) was carried out in a continuous manner;

in step (StepS1), the mixture of compound of formula (II) and compound of formula (III) is passed through (DevS1), device (DevS1) is a continuous working device; heating a mixture of a compound of formula (II) and a compound of formula (III) in apparatus (DevS1) to a temperature (TempS1), temperature (TempS1) of 180 to 300 ℃, at which temperature a reaction occurs (ReacS1), thereby forming a reaction mixture;

in Step (Step2), the reaction mixture from the device (DevS1) is passed through the device (DevS2), the device (DevS2) is a device for cooling the reaction mixture;

in step (StepS3), the reaction mixture from the device (DevS2) is passed through the device (DevS3), the device (DevS3) is a device for regulating back pressure;

the reaction mixture is cooled to a temperature (TempS2) by acting on the reaction mixture of the device (DevS2) or the device (DevS3) or on the combination of the device (DevS2) and the device (DevS3), the temperature (TempS2) being 0 to 150 ℃.

Detailed Description

Preferably, the method comprises a step (StepS4), which step (StepS4) is carried out after step (StepS3), in which step (StepS4) the reaction mixture coming from the device (DevS3) is passed through the device (DevS4), the device (DevS4) being used to separate CO from the reaction mixture₂The apparatus of (1).

Preferably, X1 and X2 are the same and are selected from F, Cl, Br, C_1-6Perfluoroalkyl and tolyl groups;

more preferably, X1 and X2 are the same and are selected from F, Cl and C_1-6A perfluoroalkyl group;

more preferably, X1 and X2 are the same and are selected from F, Cl and CF₃；

In particular, X1 and X2 are the same and are Cl or CF₃；

More particularly, X1 and X2 are Cl.

Preferably, Rⁿ⁺Is selected from H⁺、Li⁺、Na⁺、K⁺、[N(R20)(R21)(R22)R23]⁺；

R20, R21, R22 and R23 are identical or different and are selected, independently of one another, from H, C_1-8Alkyl radical, C_5-6Cycloalkyl, phenyl, benzyl, vinyl and allyl;

more preferably, Rⁿ⁺Is selected from H⁺、Li⁺、Na⁺、K⁺、[N(R20)(R21)(R22)R23]⁺；

R20, R21, R22 and R23 are identical or different and are selected, independently of one another, from H, C_1-8Alkyl radical, C_5-6Cycloalkyl, phenyl and benzyl;

even more preferably, Rⁿ⁺Is selected from H⁺、Li⁺、Na⁺、K⁺、

[N(R20)(R21)(R22)R23]⁺；

R20, R21, R22 and R23 are identical or different and are selected, independently of one another, from H, C_1-8Alkyl radical, C_5-6Cycloalkyl, phenyl and benzyl;

in particular, Rⁿ⁺Is selected from H⁺、Li⁺、Na⁺、K⁺、[N(R20)(R21)(R22)R23]⁺；

R20, R21, R22 and R23 are identical or different and are selected, independently of one another, from H, C_1-8Alkyl radical, C_5-6A cycloalkyl group, a phenyl group and a benzyl group,

more particularly, it is preferred that the first and second,

Rⁿ⁺is selected from H⁺、Li⁺、Na⁺、K⁺Andand is

R20 and R21 are the same or different and are independently selected from H and C_1-8An alkyl group;

even more particularly it is possible to provide,

Rⁿ⁺is selected from H⁺、Na⁺Andand is

R20 and R21 are the same or different and are independently selected from C_1-8An alkyl group;

in particular, the amount of the solvent to be used,

Rⁿ⁺is H⁺OrAnd is

R20 and R21 are the same or different and are independently selected from C_1-4An alkyl group;

more specifically, the present invention is to provide a novel,

Rⁿ⁺is H⁺OrAnd is

R20 and R21 are identical or different and are selected, independently of one another, from methyl, ethyl and n-butyl.

When R isⁿ⁺Is H⁺The compounds of the formula (III) can also be represented in a conventional manner, i.e. as compounds of the formula (IIIconv).

Preferably, the reaction is carried out in a tubular reactor (ReacS 1). During passage through the apparatus (DevS1), the reaction gradually transformed the initially charged mixture into the reaction mixture.

Preferably, the device (DevS1) is selected from the group consisting of a tube, a microreactor, a shell and tube heat exchanger, a plate heat exchanger, and any conventional device whose purpose is to exchange heat with a mixture;

more preferably, the device is a tube;

more preferably, the device is a spiral tube.

Preferably, the device (DevS2) is selected from the group consisting of tubes, microreactors, shell and tube heat exchangers, plate heat exchangers, and any conventional device whose purpose is to exchange heat with a reaction mixture;

more preferably, the device is a tube;

even more preferably, the device is a spiral tube.

In particular, the device (DevS1) and the device (DevS2) are helical tubes.

Preferably, the device (DevS3) is a conventional back pressure regulating device.

Preferably, the device (DevS4) is capable of separating gaseous CO from liquid₂Any known device suitable for this purpose may be used for this purpose, more preferably the device (DevS4) is a column or a cyclone.

The heating in the device (DevS1) can be performed with any known device, preferably by electrical heating or by heating with a fluid heat carrier.

Cooling in the device (DevS2) may be performed using any known means, preferably using a fluid cooling medium.

Based on the scale of the reaction and thus of the apparatus in which the process is carried out, the cooling of the reaction mixture is carried out not only by acting on the reaction mixture of the apparatus (DevS2), i.e. during its passage through the apparatus (DevS2), but also by acting on the reaction mixture of the apparatus (DevS3), i.e. by means of the apparatus (DevS3) which facilitates the cooling. This is especially the case where the reaction scale is rather small, for example when the process is carried out on a laboratory scale; whereas in case the process is carried out on a production scale, cooling will usually be accomplished mainly during passage through the apparatus (DevS 2).

In another embodiment, especially at production scale, cooling may also be accomplished with expansion and pressure relief effected by means (DevS 3).

In addition, a combination of cooling during passage through the device (DevS2) with expansion effected by the device (DevS3) is possible.

Preferably, the heating in the device (DevS1) and the cooling in the device (DevS2) are achieved in the form of tubes arranged in tubes, in the form of tubes arranged in a vessel, in a shell and tube heat exchanger or plate heat exchanger or any conventional device for heat exchange with a mixture or reaction mixture;

more preferably, the heating in the device (DevS1) and the cooling in the device (DevS2) are achieved in the form of tubes disposed in a tube or tubes disposed in a container.

The reaction was initiated by heating the mixture in the apparatus (DevS1) to temperature (TempS1) in the apparatus (DevS1) (ReacS 1).

The reaction (ReacS1) was quenched in device (DevS2) by cooling the reaction mixture in device (DevS2) to temperature (TempS 2).

Preferably, the temperature (TempS1) is from 190 to 280 ℃, more preferably from 200 to 260 ℃, even more preferably from 210 to 255 ℃, in particular from 220 to 255 ℃.

Preferably, the temperature (TempS2) is from 10 to 120 ℃, more preferably from 15 to 100 ℃, even more preferably from 15 to 90 ℃, particularly from 15 to 85 ℃, more particularly from 20 to 85 ℃.

The melting point of pure ClSI is about 35 ℃, so the lowest possible value of the temperature (TempS2) depends on the reaction conversion, since the remaining compound of formula (II) and the remaining compound of formula (III) in the reaction mixture after the reaction naturally lowers the melting point of the reaction mixture and makes it possible to lower the value of the temperature (TempS 2).

The reaction (ReacS1) was carried out under pressure (Presss S1). Preferably, the pressure (PressS1) is from 10 to 1000 bar, more preferably from 20 to 600 bar, even more preferably from 50 to 500 bar, in particular from 60 to 400 bar, more in particular from 65 to 300 bar, even more in particular from 65 to 200 bar, in particular from 65 to 150 bar.

The pressure (PresSS1) in the device (DevS1) and the device (DevS2) is controlled and maintained by the device (DevS 3).

Time (Times1) is the time the mixture was heated in the device (DevS1) and reached temperature (TempS 1). During time (TimES1), a reaction occurs (ReacS 1). Thus, the time (Times1) is the residence time, and preferably the residence time of the mixture in the device (DevS 1).

Preferably, the time (TimeS1) is from 0.5 seconds to 4 hours, more preferably from 1 second to 2 hours, even more preferably from 1 minute to 1 hour, in particular from 2 minutes to 30 minutes, more in particular from 2 minutes to 20 minutes, even more in particular from 3 minutes to 17 minutes.

Time (Times2) is the time for the reaction mixture to cool to temperature (TempS 2). Cooling may be performed by the action of the device (DevS2), by the action of the device (DevS3), or by the action of both the device (DevS2) and the device (DevS 3). This cooling quenches the reaction. Thus, time (Times2) is the residence time, and is preferably the residence time of the reaction mixture in apparatus (DevS2) and apparatus (DevS 3).

Preferably, the time (TimeS2) is from 0.1 second to 2 hours, more preferably from 0.5 second to 1 hour, even more preferably from 1 second to 30 minutes, in particular from 10 seconds to 30 minutes, more in particular from 25 seconds to 25 minutes, even more in particular from 1 minute to 25 minutes.

Preferably, the time (Times2) is 0.0001 to 0.5 TimeS, more preferably 0.001 to 0.3 TimeS the time (Times 1).

Preferably, the molar amount of the compound of formula (III) is 0.5 to 1.5 times, more preferably 0.75 to 1.25 times, even more preferably 0.85 to 1.15 times the molar amount of the compound of formula (II).

The compound of formula (II) and the compound of formula (III) may be added to the device (DevS1) as a pre-mixed mixture, or may be added separately to the device (DevS1) and mixed in the device (DevS 1).

For the purpose of mixing before and in the device (DevS1), any suitable device for mixing may be used, such as conventional branched connections (e.g., T-or Y-tubes), or static mixing devices, as are known in the art.

Preferably, heating to temperature (TempS1) in device (DevS1) is only performed after the compound of formula (II) and the compound of formula (III) are present in the device (DevS1) in the form of a mixture.

The addition of the compound of formula (II) and the compound of formula (III), either separately or in a mixture, is carried out by apparatus (DevS 0).

The device (DevS0) is a pressurized device, such as a pump, that typically utilizes a fluid delivered against pressure. When the compound of formula (II) and the compound of formula (III) are added to the device (DevS1) separately, preferably the device (DevS0) has a separate device for each compound.

Preferably, the device (DevS1) and the device (DevS2) are in permanent fluid communication with each other during operation and both are under pressure (PressS 1).

Preferably, the device (DevS0) is a device that gradually increases the pressure (PressS1) against the device (DevS3) in the device (DevS1) and the device (DevS2), which pressure is necessary for carrying out the reaction (ReacS1) at the temperature (TempS 1).

More preferably, the compound of formula (II) is mixed with the compound of formula (III) at ambient pressure and ambient temperature and then added to the apparatus (DevS 1).

In the case where the device (DevS1) and/or the device (DevS2) is a pipe, particularly a spiral pipe, hot or cold spots may occur due to structural limitations or due to density fluctuations, etc., although attempts are made to avoid their occurrence. Thus, any reference to a temperature with respect to a possible hot or cold spot means an average temperature.

Conventional back pressure regulation devices that can be used for the device (DevS3) work discontinuously, i.e. these devices release the product stream while maintaining pressure by opening and closing. This naturally leads to variations in pressure. Therefore, the pressure (PressS1) means an average pressure.

The mixture of the compound of formula (II) and the compound of formula (III), and all parts in contact with the reaction mixture, are made of respective materials which are resistant to attack by chemicals under the respective conditions, i.e. stainless steel, hastelloy (such as hastelloy B or hastelloy C), titanium, tantalum, silicon carbide, silicon nitride, etc., which may also be passivated and lined with a material which is inert to chemicals, such as PTFE.

The compound of formula (I) from device (DevS4) can be used without further purification in any subsequent reaction; in the case of further purification, the liquid phase obtained from the apparatus (DevS4) is preferably further purified by removing any low-boiling residues, preferably by using a thin film evaporator, more preferably a wiped film evaporator.

Examples

conv (conversion): is the conversion determined by measuring the content of CSI (% by weight) in the reaction mixture after the reaction relative to the standard (CONT-CSI), conv being [ 100-content (CONT-CSI) ] (in%).

FR: flow rate of

nd: is not determined

p 1: pressure (PresSS1)

t 1: time (Times1)

t 2: time (Times2)

T1: temperature (TempS1)

T2: temperature (TempS2)

Examples 1 to 14

In these examples, an equimolar premix of CSOS and CSI was added to the apparatus (DevS 1).

These examples were carried out using the following apparatus:

device (DevS 0): piston pump 260D available from ISCO Teledyne

The device (DevS1) is a 1/8 inch spiral tube made of hastelloy C with an internal volume of VolS 1. For heating, a coil arrangement in the vessel is employed. The heating medium is a conventional oil.

Device Dev (S2) is a 1/8 inch tube made of hastelloy C having an internal volume of about 1.5 mL. Cooling is performed by simply contacting the tube with the air of a chamber having room temperature.

Device (DevS 3): KPB series of standard back pressure regulators available from Swagelok

Device (DevS 4): CO is separated from the reaction mixture in an open glass flask₂

C1SI obtained in each example was a colorless to yellow liquid.

The structure was confirmed by infrared spectroscopic analysis:

IR (ATR,24 scans, v units cm)^-1):

3205(m),2758(w),2652(w),1727(w),1416(s),1318(m),1273(w),1206(m),1167(s),862(s),567(s),500(s)。

Examples 15 to 17

In these embodiments, CSOS and CSI are added separately to the device (DevS1) and mixed in the device (DevS1) using an inline static mixing device.

These embodiments are performed with the following means:

device (DevS 0): piston pump 260D available from ISCO Teledyne

The device (DevS1) is a 1/8 inch spiral tube with an internal volume VolS1 made from Hastelloy C. For heating, a coil arrangement in the vessel is employed. The heating medium is a conventional oil.

Device Dev (S2) is a 1/8 inch tube made of hastelloy C having an internal volume of about 1.5 mL. Cooling is accomplished by simply contacting the tube with air in a chamber having room temperature.

Device (DevS 3): KPB series of standard back pressure regulators available from Swagelok

Device (DevS 4): CO is separated from the reaction mixture in an open glass flask₂

The ClSI obtained in each example was a colorless to yellow liquid.

The structure was confirmed by infrared spectroscopy analysis and the data are given in the description of examples 1 to 14.

Examples 18 to 21

In these examples, an equimolar premix of CSOS and CSI was added to the apparatus (DevS 1).

These examples were performed using the following apparatus:

device (DevS 0): piston pump 260D available from ISCO Teledyne

The device (DevS1) is a 1/4 inch spiral tube made of hastelloy C having an internal volume of approximately 54 ml. For heating, a coil arrangement in the vessel is used. The heating medium is a conventional oil.

Device Dev (S2) is a 1/8 inch tube made of hastelloy C having an internal volume of about 15 mL. Cooling is accomplished by simply contacting the tubes with water at a different temperature level T2.

Device (DevS 3): KPB series of standard back pressure regulators available from Swagelok

Device (DevS 4): CO is separated from the reaction mixture in an open glass flask₂

The ClSI obtained in each example was a colorless to yellow liquid.

The structure was confirmed by infrared spectroscopy analysis and the data are given in the description of examples 1 to 14.

Examples	FR	T1	t1	T2	t2	p1	conv
									[g/min]	[℃]	[min]	[℃]	[min]	[ Bar ]]	[％]
18	25	240	3.6	20	1	72	87.1
								19	16.5	240	5.5	20	1	88	94.5
20	17	230	5.3	80	1	83	91.7
								21	14.3	230	6.4	80	1	84	90.6

Comparative example

In contrast to the continuous reaction of the present invention, batch reactions at temperatures above 160 ℃ are not allowed due to the onset of decomposition. The risk of explosion is too great. Therefore, due to these safety restrictions, only batch reactions at 150 ℃ are allowed.

Equimolar amounts of CSI were added to CSOS at 120 ℃ over 3 hours, then the mixture was heated to 150 ℃ over 3 hours and stirred at 150 ℃ for 7 hours. The conversion was only 90%.

Thus, the total reaction time to achieve 90% conversion was 13 hours. The color is yellow.

In all cases in the intermittent process it must be avoided to produce a darker colour than yellow, since this is an indication of a large decomposition and in addition an indication that the explosion is very close.

The preparation of ClSI in a batch process is disclosed in synthesis example 2 of WO 2009/123328a 1. During 2 hours, CSI was added to CSOS at 120 ℃ and the mixture was then stirred at 150 ℃ for 6 hours. The yield was 65.6%.

Example 22

An equimolar premix of CSOS and CSI was added to the apparatus (DevS 1).

These examples were performed using the following apparatus:

device (DevS 0): commercially available piston pump

The device (DevS1) is a 1/2 inch spiral tube made of hastelloy C having an internal volume of about 1200 ml. For heating, jacket heating is used. The heating medium is a conventional oil.

Device Dev (S2) is a 1/4 inch tube with an internal volume of about 200mL made from hastelloy C. For cooling, jacket cooling is used. The cooling medium is conventional oil.

Device (DevS 3): a standard back pressure regulator is used as is commercially available.

Device (DevS 4): separation of CO in a standard separation unit₂。

The obtained ClSI was a colorless to yellow liquid.

The structure was confirmed by infrared spectroscopy analysis and the data are given in the description of examples 1 to 14.

Examples

FR

T1

t1

T2

t2

p1

conv

[kg/h]

[℃]

[min]

[℃]

[sec]

[ Bar ]]

[％]

22

22.8

About 230

5.3

About 50

About 30

80

96.5

Example 23

An equimolar premix of trifluoromethanesulfonic acid and CSI was added to the apparatus (DevS 1).

These examples were performed using the following apparatus:

device (DevS 0): piston pump 260D available from ISCO Teledyne

The device (DevS1) is a 1/8 inch spiral tube made of Hastelloy C with an internal volume VolS 1. For heating, a jacket heating arrangement is employed, the heating medium being a conventional oil.

Device Dev (S2) is a 1/8 inch tube made of hastelloy C having an internal volume of about 1.5 mL. Cooling is performed by simply contacting the tube with the air of a chamber having room temperature.

Device (DevS 3): KPB series of standard back pressure regulators available from Swagelok.

Device (DevS 4): CO separation from the reaction mixture in an open glass flask₂。

The compound of formula (1) obtained is a colorless to yellow liquid.

Examples

VolS1

FR

T1

t1

T2

t2

p1

conv

ml

[g/min]

[℃]

[min]

[℃]

[min]

[ Bar ]]

[％]

23

10

4

230

3.2

RT

About 1

80.4

90.8

Confirmation of structure by IR and nmr spectroscopy:

IR (ATR,24 scans, v units cm)^-1):

3279(w),1399(s), 1357(s); 1176(s)1149(s),740(s),611(s),581(s),510(s),549(s),476(s) NMR (CD3CN,400MHz,24 ℃, internal standard 1, 4-difluorobenzene) ═ 78.75ppm

Furthermore, the formation of the desired product in the reaction was confirmed by comparing the heat of formation obtained with DSC measurements with the data calculated at high levels.

Method of producing a composite material	Δ H (Unit J/g)	Δ H ° R (unit KJ/mol)
			DSC	Average value 322J/g	64kJ/mol
Turbomole/Gaussian		62kJ/mol

DSC is measured dynamically using a heating rate of 0.4 deg.C/min.

Turbomole: the program quantum mechanical calculations were performed using the following procedure:

turbo moloev 6.5(18161), Ahlrichs, m.baer, m.haeser, h.horns, and C.

Koelmel, electronic structure calculation in workstation computer: the program system is a system of turbo-objects,

chem.phys.lett.162:165 (1989); and

gaussian: gaussian 09, version

D.01,M.J.Frisch,G.W.Trucks,H.B.Schlegel,G.E.Scuseria,M.A.Robb,J.R.

Cheeseman,G.Scalmani,V.Barone,B.Mennucci,G.A.Petersson,H.Nakatsuji,M.

Caricato,X.Li,H.P.Hratchian,A.F.Izmaylov,J.Bloino,G.

Zheng,J.L.Sonnenberg,M.Hada,M.Ehara,K.Toyota,R.Fukuda,J.Hasegawa,M.

Ishida,T.Nakajima,Y.Honda,O.Kitao,H.Nakai,T.Vreven,J.A.Montgomery,Jr.,J.E.

Peralta,F.Ogliaro,M.Bearpark,J.J.Heyd,E.

Brothers,K.N.Kudin,V.N.Staroverov,R.Kobayashi,J.Normand,K.Raghavachari,A.

Rendell,J.C.Burant,S.S.Iyengar,J.Tomasi,M.Cossi,N.Rega,J.M.

Millam,M.Klene,J.E.Knox,J.B.Cross,V.Bakken,C.Adamo,J.Jaramillo,R.

Gomperts,R.E.Stratmann,O.Yazyev,A.J.Austin,R.

Cammi,C.Pomelli,J.W.Ochterski,R.L.Martin,K.Morokuma,V.G.

Zakrzewski,G.A.Voth,P.Salvador,J.J.Dannenberg,S.Dapprich,A.D.

Daniels,Farkas, J.B.Foresman, J.V.Ortiz, J.Cioslowski, and

D.J.Fox,Gaussian,Inc.,Wallingford CT,2009；

method B3LYP 6-31G was used.

Examples 24 and 25

An equimolar premix of sulfonic acid and CSI was added to the apparatus (DevS 1).

These examples were performed using the following apparatus:

device (DevS 0): piston pump 260D available from ISCO Teledyne

The device (DevS1) is a 1/8 inch spiral tube with an internal volume VolS1 made from Hastelloy C. For heating, a jacket heating arrangement is employed, the heating medium being a conventional oil.

Device Dev (S2) is a 1/8 inch tube with an internal volume of about 1.5mL made from hastelloy C. The cooling is performed by simply contacting the tube with the air of a chamber having room temperature.

Device (DevS 3): KPB series of standard back pressure regulators available from Swagelok.

Device (DevS 4): CO is separated from the reaction mixture in an open glass flask₂。

The compound of formula (2) obtained is a colorless to yellow liquid.

Examples	VolS1	FR	T1	t1	T2	t2	p1	conv
										ml	[g/min]	[℃]	[min]	[℃]	[min]	[ Bar ]]	[％]
24	10	2.4	230	6.6	RT	About 1	83.7	68.7
									25	10	5.1	230	3.1	RT	About 1	83.7	57.4

Confirmation of structure by nuclear magnetic resonance spectroscopy:

NMR (CD3CN,400MHz,24 ℃ C., internal standard: benzenesulfonyl fluoride) 57.24ppm

Application example

The purity and yield of any of examples 1 to 22 can be measured by indirectly using each obtained product as a substrate in a reaction for producing bis (fluorosulfonyl) imide. Examples of such yield and purity determinations are described below: how the product prepared according to example 22 was used as a substrate for preparing bis [ bis ((fluorosulfonyl) imide ] zinc salt in a manner similar to synthesis example 19-1 of WO 2009/123328a 1:

a500 ml reaction vessel was charged with 179.3g of valeronitrile and 20.3g of ClSI (0.093mol, prepared according to example 22), followed by stirring. To the reaction vessel was added 10.6g (0.10mol) of anhydrous ZnF₂Then, the reaction was carried out at room temperature (25 ℃ C.) for 3 hours. Bis [ di (fluorosulfonyl) imide is obtained in solution]Zinc salt (yield 66.4%, utilization¹⁹F-NMR measurement and calculation based on ClSI (100% content)).

Any of the products prepared according to the present invention examples 1 to 22 were of similar purity and were obtained in similar yields.

Example 26

An equimolar premix of 1-n-butyl-3-methylimidazole trifluoromethanesulfonate and CSI was added to the apparatus (DevS 1).

These examples were performed using the following apparatus:

device (DevS 0): piston pump 260D available from ISCO Teledyne, Inc.

The device (DevS1) is a 1/8 inch spiral tube with an internal volume VolS1 made from Hastelloy C. For heating, a jacket heating arrangement is employed, the heating medium being a conventional oil.

Device Dev (S2) is a 1/8 inch tube made of hastelloy C having an internal volume of about 1.5 mL. Cooling is performed by simply contacting the tube with the air in a chamber having room temperature.

Device (DevS 3): KPB series of standard back pressure regulators available from Swagelok

Device (DevS 4): CO is separated from the reaction mixture in an open glass flask₂。

The compound of formula (1) obtained is a yellow liquid.

Examples

VolS1

FR

T1

t1

T2

t2

p1

conv

ml

[g/min]

[℃]

[min]

[℃]

[min]

[ Bar ]]

[％]

26

5

0.51

180

0.8

RT

About 1

80

87

For the reaction product, the following analytical data were measured.

IR (ATR,24 scans, v units cm)^-1): 3122(w),2966(w),1573(w),1404(w),1353(w)1256(s),1224(m),1156(s),1029(s),836(m),746(m),636(s),622(s),584(s)574(s) NMR (CD3CN,400MHz,24 ℃, internal 1, 4-difluorobenzene) ═ 79.28 ppm.

Claims (14)

1. A process for the preparation of a compound of formula (I)

The method comprises reacting (ReacS 1);

reaction (ReacS1) is a reaction between a compound of formula (II) and a compound of formula (III);

wherein

X1 and X2 are identical or different and are each, independently of one another, selected from the group consisting of F, Cl, Br, I, C_1-6Perfluoroalkyl and tolyl groups;

Rⁿ⁺is selected from H⁺、Li⁺、Na⁺、K⁺、Mg²⁺、Ca²⁺、Zn²⁺、Cu²⁺、Al³⁺、Ti³⁺、Fe²⁺、Fe³⁺、B³⁺、[N(R20)(R21)(R22)R23]⁺And [ P (R20) (R21) (R22) R23]⁺；

R20, R21, R22 and R23 are identical or different and are selected, independently of one another, from H, C_1-8Alkyl radical, C_5-6Cycloalkyl, phenyl, benzyl, vinyl and allyl;

n is 1, 2 or 3;

the reaction (ReacS1) was carried out in a continuous manner at a temperature of 180 ℃ to 300 ℃ (TempS 1).

2. The method of claim 1, wherein the method comprises three consecutive steps: step (Step 1), Step (Step2) and Step (Step 3);

step (StepS1) comprises the reaction (ReacS 1);

the mixture of compound of formula (II) and compound of formula (III) in step (StepS1) is passed through a device (DevS1), device (DevS1) being a continuously operating device, in which device (DevS1) the mixture of compound of formula (II) and compound of formula (III) is heated to a temperature (TempS1) at which a reaction takes place (ReacS1), thereby forming a reaction mixture,

passing the reaction mixture from device (DevS1) through device (DevS2) in step (StepS2), device (DevS2) being a device for cooling the reaction mixture;

the reaction mixture from device (DevS2) passes through device (DevS3) in step (StepS3), device (DevS3) is a device for backpressure regulation;

the reaction mixture is cooled to a temperature (TempS2) by acting on the reaction mixture of device (DevS2) or device (DevS3) or a combination of device (DevS2) and device (DevS3), the temperature (TempS2) being 0 to 150 ℃.

3. The method as claimed in claim 2, wherein the method further comprises a step (StepS4) performed after step (StepS3), in which step (StepS4) the reaction mixture from device (DevS3) is passed through device (DevS4), device (DevS4) being used for separating CO from the reaction mixture₂The apparatus of (1).

4. The method of one or more of claims 1 to 3, wherein X1 and X2 are the same and are selected from F, Cl, Br, C_1-6Perfluoroalkyl groups, and tolyl groups.

5. The method as claimed in one or more of claims 1 to 4, wherein Rⁿ⁺Is selected from H⁺、Li⁺、Na⁺、K⁺、And [ N (R20) (R21) (R22) R23]⁺；

R20, R21, R22 and R23 are identical or different and are selected, independently of one another, from H, C_1-8Alkyl radical, C_5-6Cycloalkyl, phenyl, benzyl, vinyl and allyl.

6. The method as claimed in one or more of claims 2 to 5, wherein the device (DevS1) is selected from the group consisting of tubes, microreactors, shell-and-tube heat exchangers, plate heat exchangers, and any conventional device whose use is to exchange heat with a reaction mixture.

7. The method as claimed in one or more of claims 2 to 6, wherein the device (DevS2) is selected from the group consisting of tubes, microreactors, shell-and-tube heat exchangers, plate heat exchangers, and any conventional device whose use is to exchange heat with a reaction mixture.

8. A method as claimed in one or more of claims 2 to 7, wherein the device (DevS3) is a conventional back pressure regulating device.

9. The method of one or more of claims 1 to 8, wherein the temperature (TempS1) is 190 to 280 ℃.

10. The method of one or more of claims 2 to 9, wherein the temperature (TempS2) is 10 to 120 ℃.

11. The process as claimed in one or more of claims 1 to 10, wherein the reaction (ReacS1) is carried out under a pressure (PressS1), the pressure (PressS1) being from 10 to 1000 bar.

12. The method according to one or more of claims 2 to 11, wherein time (TimES1) is 0.5 seconds to 4 hours; time (Times1) is the time the mixture was heated in the device (DevS1) and reached temperature (TempS 1).

13. The method according to one or more of claims 2 to 12, wherein time (TimeS2) is from 0.1 seconds to 2 hours; time (Times2) is the time the reaction mixture was allowed to cool to temperature (TempS 2).

14. The process according to one or more of claims 1 to 13, wherein the molar amount of compound of formula (III) is from 0.5 to 1.5 times the molar amount of compound of formula (II).