JP2014176838A - Sublimation refining apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sublimation refining apparatus capable of increasing sublimation efficiency further even when not only a crude material having high thermal stability but also a crude material having low thermal stability are used as samples.SOLUTION: Provided is a sublimation refining apparatus having a sublimation pipe, a vacuum pump and piping connecting the sublimation pipe and the vacuum pump. When an end part of the sublimation pipe, further from the vacuum pump, is defined as A and a connection part of the piping and the vacuum pump is defined as C, conductance (K) from A to C is 0.01 m/sec or more.

Description

  The present invention relates to a sublimation purification apparatus.

  A sublimation purification device is a device for purifying a target substance using the property that a substance in a solid state at normal temperature is vaporized under an appropriate temperature and pressure, and is used to purify a chemical substance with high purity. ing. For example, in a light-emitting device using an organic electroluminescent material, the performance of the light-emitting device is greatly deteriorated even if a trace amount of impurities is contained in the organic electroluminescent material. Therefore, a sublimation purification apparatus is used to refine the material to a higher degree.

  There are various types of sublimation purification apparatuses such as a vertical type and a horizontal type. A sublimation purification apparatus usually includes a sublimation pipe having a sublimation section in which a purification target is installed and a collection section for collecting the sublimation purification product, a vacuum pump, and a pipe connecting the sublimation pipe and the vacuum pump. Further, a heat source for heating the sublimation part is provided. When the sublimation part is heated by the heat source, the sample is sublimated, and the vaporized material is cooled while flowing to the vacuum pump side, and solidifies when the temperature is below a certain temperature. In order to solidify and collect the target object in the collection unit, a temperature gradient is appropriately provided along the axial direction of the sublimation tube according to the type of the object to be purified.

In the sublimation purification, the yield of the purified product is improved by improving the sublimation efficiency of the sublimation purification target object (hereinafter, also referred to as “sublimation crude product” or simply “crude product”) including the purification target product. However, usually, a part of the coarse body does not sublime and remains a little. This residual ratio tends to increase when the thermal stability of the crude product is low.
An object of the present invention is to provide a sublimation purification apparatus capable of further improving the sublimation efficiency not only in the case of using a coarse body having high thermal stability but also a coarse body having low thermal stability as a sample.

The present inventors have adopted various gases generated from a rough body (for example, volatile impurities contained in the rough body, and thermal decomposition of the rough body, even if a temperature and reduced pressure conditions suitable for sublimation of the target product are employed. We focused on the phenomenon that the degree of vacuum in the sublimation tube is lower than expected due to the gas etc. generated. And it came to the thought that the fall of this degree of vacuum worsened the sublimation efficiency of a rough body, accelerated | stimulated decomposition | disassembly of the rough body, and also caused the vicious cycle of reducing sublimation efficiency further.
The present inventors have intensively studied to suppress the above-described decrease in the degree of vacuum. As a result, when using a sublimation purification device that increases the conductance from the sublimation tube to the piping to a specific level, excessive reduction in the degree of vacuum in the sublimation tube during sublimation purification is suppressed, thereby reducing sublimation residue. It has been found that sublimation purification can be performed with a higher yield.
The present invention has been further studied based on these findings and has been completed.

The above problems have been achieved by the following means.
<1> A sublimation purification apparatus having a sublimation pipe, a vacuum pump, and a pipe connecting the sublimation pipe and the vacuum pump,
The conductance K _AC from A to C is 0.01 m ³ / sec, where A is the end of the sublimation tube on the side away from the vacuum pump and C is the connection between the pipe and the vacuum pump. This is the sublimation purification apparatus.
<2> The sublimation purification apparatus according to <1>, wherein a conductance K _BC from B to C is 0.02 m ³ / sec or more, where B is a connection portion between the sublimation pipe and the pipe.
<3> is the _{K AC} is 0.02 m ³ / sec or more, sublimation purification apparatus according to <1> or <2>.
<4> is the _{K BC} is 0.03 m ³ / sec or more, the <1> to sublimation purification apparatus according to any one of <3>.
<5> The sublimation purification apparatus according to any one of <1> to <4>, wherein a terminal portion of the sublimation tube on the side away from the vacuum pump is closed.
<6> A sublimation purification method using the sublimation purification apparatus according to any one of <1> to <5> above, wherein the mass is reduced when maintained at a sublimation temperature under an inert gas atmosphere at normal pressure for 5 hours. A sublimation purification method in which a sample having a rate of 2% or more is a sublimation purification target sample.
<7> The sublimation purification method according to <6>, wherein the sublimation purification target sample has a mass reduction rate of 10% or more when kept at a sublimation temperature under an atmospheric pressure and at a normal pressure for 5 hours.

  The sublimation purification apparatus of this invention can raise the yield of a sublimation refinement | purification more by performing sublimation purification using this.

It is a partially cutaway sectional view showing typically the longitudinal section along the axial direction of a sublimation pipe about one form of the sublimation refining device of the present invention. 1 is a partially cutaway cross-sectional view schematically showing a cross section along the axial direction of a sublimation tube as viewed from above, with respect to one embodiment of the sublimation purification apparatus of the present invention. It is a schematic diagram when the sublimation refinement | purification apparatus of FIG. 1 is seen toward the axial direction of a sublimation pipe | tube from the Y side. It is a schematic diagram when the sublimation refinement | purification apparatus of FIG. 1 is seen toward the axial direction of a sublimation pipe | tube from the X side. In FIG. 4, the Y-side vacuum tube is not shown. It is a figure which shows typically the measuring method of the conductance in the sublimation refinement | purification apparatus of this invention. In addition, this drawing is a partially cutaway sectional view drawn on the basis of a longitudinal section along the axial direction of the sublimation tube. It is a figure which shows typically the sublimation purification apparatus which attached the control valve to piping. In addition, this drawing is a partially cutaway sectional view drawn on the basis of a longitudinal section along the axial direction of the sublimation tube.

  Hereinafter, the present invention will be described in detail.

  1-4, the sublimation purification apparatus of the present invention includes a sublimation pipe (13), a vacuum pump (11), and a pipe (12) connecting the sublimation pipe (13) and the vacuum pump (11). Is provided. In the sublimation purification apparatus of the present invention, the conductance from the sublimation pipe to the pipe is increased to a specific level. The sublimation purification apparatus shown in each drawing is a schematic diagram for facilitating the understanding of the present invention, and the size or relative size relationship of each member may be changed for convenience of explanation. The relationship is not shown as it is. Moreover, it is not limited to the external shape and shape shown by these drawings except the matter prescribed | regulated by this invention. For example, an embodiment in which the inner diameter of the pipe is wider than the inner diameter of the sublimation tube can be preferably used in the present invention.

  The material of the sublimation tube used in the present invention is not particularly limited as long as it can withstand the high heat generated by the heat source during sublimation. In sublimation purification, the sublimation tube is usually heated to about 200 to 600 ° C. Therefore, generally, a sublimation tube made of glass, quartz, metal or the like is used. Of these, it is preferable to use a quartz sublimation tube.

The shape of the sublimation tube used in the present invention is not particularly limited, and a commonly used shape can be adopted. However, since the inside becomes a high vacuum, the shape of the sublimation tube should be cylindrical from the viewpoint of applying pressure evenly. preferable. In the present specification, the term “cylindrical” is used to mean that a cross section perpendicular to the axial direction (hereinafter simply referred to as “cross section”) is circular or elliptical. Area of sublimation tube cross-section of the tube (tube cross-sectional area) is preferably 3～800Cm ^2, more preferably 30～500Cm ^2, further preferably 100~400cm ^2. In the apparatus of the present invention, it is preferable to use a sublimation tube having a larger cross-sectional area in the tube, in which conductance is easily affected by a decrease in vacuum due to generated gas.

In the sublimation tube used in the present invention, the length in the axial direction and the cross-sectional area in the tube satisfy [length in the axial direction (cm)] / [cross-sectional area in the tube (cm ² )] = 0.2-50. Preferably, 0.5-5 is more preferable, and 0.8-3 is more preferable.

1-4, in the sublimation pipe | tube (13) used for this invention, the terminal part (it is also called X side terminal part) of the side away from the vacuum pump (11) normally, or its vicinity. The sublimation part (14) which arrange | positions a rough body is provided, and everything from a sublimation part (14) to the piping side terminal part (connection part (it is also called Y side terminal part) with piping) of a sublimation pipe. Or a part is made into the collection part (15) which deposits the vapor | steam produced by sublimation as a solid. In addition, the collection part (15) in FIG. 1 shows the area | region in a sublimation tube.
The sublimation part is preferably present in a section located at the X-side end or in a section adjacent to this section when the sublimation tube is equally divided into 10 sections along the axial direction and divided into 10 sections.
The X-side end of the sublimation tube is preferably closed, and the Y-side end is opened and connected to the pipe (12).

  The sublimation tube used in the present invention may have an inner tube disposed therein. By providing the inner tube, the purified sublimation product can be collected on the inner wall of the inner tube, so that the purified sublimation product can be easily collected.

  There is no restriction | limiting in particular in the material of piping used for this invention. For example, those made of metal, rubber, resin, or glass can be used. It is preferably made of metal from the viewpoint of use in a high vacuum and ease of processing. Examples of the metal material include stainless steel, aluminum, iron, copper, silver, gold, and metal alloys.

The shape of the piping used in the present invention is not particularly limited, and can be appropriately selected according to the shape of the sublimation tube. Usually, a section perpendicular to the fluid flow direction (hereinafter simply referred to as “section”). ) Is a circular hose-like pipe.
The length of the pipe used in the present invention (the length in the direction in which the fluid flows, the same applies hereinafter) is appropriately determined depending on the arrangement of the sublimation pipe and the vacuum pump, but is preferably as short as possible. Specifically, it is preferably 200 cm or less, and more preferably 30 to 150 cm.
Furthermore, it is preferable to satisfy [pipe length (cm) / sublimation tube axial length (cm)] = 0.1-3, more preferably 0.3-2, It is more preferable to satisfy -1.5.
The relationship between the cross-sectional area of the pipe and the cross-sectional area of the sublimation pipe satisfies [the cross-sectional area of the pipe (cm ² ) / the cross-sectional area of the sublimation pipe (cm ² )] = 0.3-3. Is preferable, 0.5-2 is more preferable, and 0.8-1.5 is more preferable.
The piping used in the present invention preferably has a shape with as few curved portions as possible and more straight portions. The number of curved portions is preferably 0-6, more preferably 1-5, and even more preferably 2-4.
The pipe used in the present invention is preferably subjected to a treatment for smoothing the inner surface of the pipe from the viewpoint of reducing the amount of gas released from the pipe surface. Examples of the smoothing method include electrolytic polishing, chemical polishing, and buffing. What was electropolished is preferable. It is also preferable to perform a process after assembling the apparatus, such as a baking process in which the piping is heated while being evacuated.

The heating mode of the sublimation purification apparatus of the present invention is as shown in FIGS. 3 and 7 on page 75 of “Experimental Chemistry Course (continued) 2 Separation and Purification” (edited by Chemical Society of Japan, Publisher: Maruzen Co., Ltd.). Nichrome wire may be wound directly around the tube, or a sublimation tube is installed in a metal tube with good thermal conductivity as shown in Figs. 3 and 16, and a heat source is installed around the metal tube and heated. It may be in the form. Since the temperature gradient can be changed smoothly, a type in which a sublimation tube is installed in a metal tube is preferable. There is no restriction | limiting in the material of a metal tube, For example, stainless steel, aluminum, iron, copper, silver, gold | metal | money, a metal alloy is mentioned.
As a heat source for heating from the outside of the metal tube, an arbitrary one such as an electric heater can be used. The number and arrangement of the heat sources can be arbitrarily set according to the physical properties of the sample to be purified and the required degree of purification. The number of heat sources is preferably 2 or more and 10 or less, more preferably 3 or more and 8 or less, and further preferably 4 or more and 6 or less along the axial direction of the sublimation tube. These heat sources are preferably those that can be independently temperature controlled. Moreover, it can also heat by the electromagnetic induction heating of patent 4866527.
1 to 6, the sublimation tube is installed in the metal tube (16), and three heat sources (17) are arranged along the axial direction of the sublimation tube so as to surround the outside of the metal tube (16). The form is shown. In this case, the heat source is usually set to a gradually lower temperature from the X side to the Y side.

  There is no restriction | limiting in particular in the vacuum pump used for this invention, The vacuum pump normally used in sublimation refinement | purification can be employ | adopted.

The sublimation purification apparatus of this invention shows the specific conductance mentioned later. In this specification, “conductance” corresponds to the reciprocal of the flow resistance, and is an index representing the ease of fluid flow.
Conductance can be measured by a conventional method. For example, in order to calculate the conductance between any two points in the pipe, install a pressure gauge at each position, depressurize the pipe using a vacuum pump, and then move away from the vacuum pump of the sublimation pipe. A small amount of gas is flown from the end on the other side (X side end), and from the values of each pressure gauge in the state where this small amount of gas is flowing, "Revised 5th edition Chemical Engineering Handbook" (edited by the Chemical Engineering Association, published) (Where: Maruzen Co., Ltd.), Chapter 5, page 311 (5.321). The conductance measurement method will be described below in more detail with reference to the drawings.

FIG. 5 schematically shows a sublimation purification apparatus for measuring conductance in the sublimation purification apparatus of the present invention. A pressure gauge _{G A} to X side end A of sublimation tube (13), the pipe (12) and the sublimation tube and of the pressure gauge _{G B} in the connection portion B (13), the pipe (12) and vacuum pump (11) installing each pressure gauge G _C the connecting portion C between.
A vacuum pump is operated to depressurize the inside of the pipe line to a predetermined level described later, and then a certain amount of argon gas is introduced from the X-side end of the sublimation pipe through the inlet (19) as shown in FIG. , where the value indicated by the pressure gauge _{G a} and _{G C} stable, measure the pressure of the pressure gauge _G a ~G _C. All of these operations are performed at room temperature (usually 10 to 30 ° C.) (the operation is performed without operating the heat source).
Although the sublimation part is shown in FIG. 5, no coarse body is disposed in the sublimation part when measuring the conductance.
At this time, the conductance K _AC (m ³ / sec) from A to C is obtained by the following equation (1).

K _AC = p _A q / (p _A −p _C ) (1)

q: Argon gas introduction flow rate (m ³ / sec)
p _A: The value of the pressure gauge _{G A} (Pa)
p _C: the value of the pressure gauge _{G C} (Pa)

The conductance K _BC (m ³ / sec) from B to C is obtained by the following equation (2).
K _BC = p _B q / (p _B −p _C ) (2)

q: Argon gas introduction flow rate (m ³ / sec)
p _B: the value of the pressure gauge _{G B} (Pa)
p _C: the value of the pressure gauge _{G C} (Pa)

The conductance measurements in the present invention, after all the pressure of the vacuum pump is activated by a pressure gauge G _A ~G _C is stabilized with the following values 1 × 10 -2 ^Pa, (not operate the heat source) at room temperature Argon gas is introduced. In measuring the conductance, the values of p _A , p _B , and p _C are in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁰ Pa (1 Pa), and the flow rate q of argon gas is 1 × 10 ^−10. Within the range of ˜1 × 10 ⁻⁷ m ³ / sec. If the pressure (p _A , p _B , p _C ) and the flow rate q are within the above ranges, K _AC and K _BC show almost constant values.
Argon gas inlet flow rate set to be constant in the range of ^{1 × 10 -10 ~1 × 10 -7} m 3 / sec, since all the values of the pressure gauge _G A ~G _C is stabilized, respectively Record the pressure gauge value. Furthermore, the argon gas introduction flow rate is changed within the range of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻⁷ m ³ / sec, and measurement is performed in the same procedure. This is repeated 3 to 10 times, the conductance of each time is calculated, and the average value of the conductance of each time is defined as the conductance in the present invention.

In the conductance measurement according to the present invention, each pressure gauge can be installed by making a hole having a diameter of about 1 cm in a pipe or a sublimation pipe, attaching a pressure sensor, and then sealing. If a T-shaped vacuum pipe is used, it is easy to install a pressure gauge on the pipe.
Argon gas can be introduced using a mass flow meter by opening a hole having a diameter of about 1 cm at the X-side end of the sublimation tube. If a gas inlet as shown in FIG. 5 is installed in advance at the X-side end of the sublimation tube, it is easy to introduce argon gas in a sealed state.
Whether a certain sublimation purification apparatus is the sublimation purification apparatus of the present invention is determined by installing a pressure gauge as described above, providing an argon gas inlet, introducing argon gas, and calculating conductance from the value of each pressure gauge. It can be examined by measuring.

In the present invention, the “terminal portion of the sublimation tube” indicates the inside of the compartment located on the most end side when the sublimation tube is divided into 10 sections along the axial direction. When the X-side end portion (closed end portion) of the sublimation tube has a dome-like round shape, the sublimation tube is divided into 10 equal parts including that portion.
Further, in the present invention, the “connection portion between the pipe and the vacuum pump” means that the pipe is in contact with the vacuum pump when the pipe is divided into 10 sections along the fluid flow direction (evacuation direction). It is assumed that the inside of the piping side section (ie, closest to the vacuum pump) is shown.
Further, in the present invention, the “connection portion between the sublimation pipe and the pipe” means that the pipe is divided into 10 parts along the fluid flow direction (evacuation direction) and is divided into 10 sections, and is in contact with the sublimation pipe. (I.e., closest to the sublimation tube) inside the compartment on the piping side.
The overlapping part for connecting the pipe and the vacuum pump or the overlapping part for connecting the pipe and the sublimation pipe is not included in the “pipe” which is divided into 10 equal parts in the description of each connection part. To do. That is, the “pipe” divided into 10 equal parts in the above description is a part of the pipe member of the sublimation purification apparatus excluding the overlapping part with the vacuum pump or the sublimation pipe.

In sublimation purification apparatus of the present invention, the _{K AC} is 0.01 m ³ / sec or more. When K _AC is 0.01 m ³ / sec or more, the crude product efficiently sublimates in sublimation purification, the sublimation residue can be reduced, and the yield of the sublimation-purified target substance is improved. In sublimation purification apparatus of the present _{invention, K AC} is preferably 0.015 m ³ / sec or more, more preferably 0.02 m ³ / sec or more. Moreover, it is 0.1 m < ³ > / sec or less normally.
Also, the sublimation purification apparatus of the present invention, the _{K BC} is 0.02 m ³ / sec or more. When K _BC is at 0.02 m 3 ^/ sec or more, a crude product in the sublimation purification is sublimated more efficiently, it is possible to more reduce sublimation residue, improving more the yield of a target substance which is purified by sublimation To do. In sublimation purification apparatus of the present _{invention, K BC} is preferably 0.022 m ³ / sec or more, more preferably 0.03 m ³ / sec or more. Moreover, it is 0.5 m < ³ > / sec or less normally.

  As shown in FIG. 6, the sublimation purification apparatus of the present invention may be provided with a control valve (18) in the middle of the piping. The conductance can also be adjusted by changing the degree of opening and closing of the control valve (18). The conductance can also be adjusted by installing an obstacle (for example, a cylinder having an outer diameter smaller than the inner diameter of the sublimation tube) in the sublimation tube.

  Although there is no restriction | limiting in particular in the form of the sublimation purification apparatus of this invention, Usually, it is a horizontal type.

  The sublimation purification apparatus of the present invention may be in the form of sublimation while flowing gas under reduced pressure described in JP-A-2008-12479, or in the form of purification by a continuous method described in JP-T-2012-515643. 1-4, a remarkable effect is obtained in the case of the sublimation purification apparatus in which one end of the sublimation tube is closed as shown in FIGS. In the case of a sublimation purification apparatus in which one end of the sublimation tube is closed, sublimation purification can be performed with the highest degree of vacuum in the capacity of the apparatus, and the increase in sublimation temperature due to a decrease in the degree of vacuum is less likely to occur. That is, since thermal decomposition of the sublimation purification target sample accompanying an increase in sublimation temperature can be suppressed, it is particularly effective when a thermally unstable sample is used as a sublimation purification target.

The sublimation purification apparatus of the present invention is useful even when the sublimation purification target sample is unstable to heat. The stability of the sample to be sublimated and purified with respect to heat includes not only the stability of the substance itself but also the effect of a decrease in stability due to the inclusion of an arbitrary impurity. As a measure of the stability to heat, the mass reduction rate by thermal mass spectrometry can be used as a guide. That is, it can be said that a sample having a large mass reduction rate when kept at a specific temperature for a certain time under normal pressure in an inert gas (for example, nitrogen, argon, etc.) is a sample that is easily pyrolyzed. The specific temperature at the time of measurement of the mass reduction rate is the temperature of the sublimation part (sublimation temperature) at the time of sublimation purification. Therefore, the temperature at the time of measuring the mass reduction rate varies depending on the sample to be sublimated and purified. The mass reduction rate when kept at the sublimation temperature for 5 hours is taken as a measure of the stability to heat.
By using the sublimation purification apparatus of the present invention, mass reduction rate by thermal mass spectrometry (unit:%, calculation formula: 100 × {[before heating, when kept at sublimation temperature for 5 hours under normal pressure in an inert gas atmosphere) Mass]-[mass after being kept at sublimation temperature for 5 hours]} / [mass before heating]) is a sublimation purification target of a sample of 2% or more, and high sublimation purification efficiency can be achieved. Even if the sample is 5% or more, 10% or more, or 15% or more, high sublimation purification efficiency can be achieved. The mass reduction rate of the sublimation purification target sample is usually 40% or less, preferably 30% or less.

A more specific form of the sublimation purification target sample will be described below.
It is more preferable that the sublimation purification target sample (meaning the purification target product in the sublimation purification target sample here) is a compound represented by the following formula (I).

In the formula (I), D represents a donor group having a hetero atom. A represents an acceptor group having a carbonyl group or a cyano group. L ² and L ³ represent a methine group. This methine group may have a substituent.

  The compound represented by the formula (I) is a donor-acceptor type dye compound, and when melted, the donor group D is easily decomposed due to nucleophilic attack on the acceptor group A. That is, it is a compound having a melting point and a material decomposition temperature close to each other.

  Examples of the hetero atom that D has include a nitrogen atom, an oxygen atom, and a sulfur atom. The above D preferably has at least one nitrogen atom as a hetero atom.

  The compound represented by the above formula (I) is preferably a compound represented by the following formula (II).

In formula (II), Z ¹ represents a ring containing at least two carbon atoms and a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. L ¹ represents a methine group. This methine group may have a substituent. L ² , L ³ , D ¹ and n have the same meanings as L ² , L ³ , D and n in formula (I), respectively.

In formula (II), Z ¹ preferably has a ring structure which is usually used as an acidic nucleus in a merocyanine dye, and specific examples of this ring structure include the following (a) to (q).

(A) 1,3-dicarbonyl nucleus: For example, 1,3-indandione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, or 1,3-dioxane-4,6- Zeon.
(B) pyrazolinone nucleus: for example 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, or 1- (2-benzothiazoyl) -3-methyl- 2-pyrazolin-5-one.
(C) Isoxazolinone nucleus: For example, 3-phenyl-2-isoxazolin-5-one or 3-methyl-2-isoxazolin-5-one.
(D) Oxindole nucleus: for example 1-alkyl-2,3-dihydro-2-oxindole.
(E) 2,4,6-triketohexahydropyrimidine nucleus: for example barbituric acid or 2-thiobarbituric acid, or derivatives thereof. Examples of this derivative include 1-alkyl compounds such as 1-methyl and 1-ethyl; 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl; 1,3-diphenyl 1,3-diaryl compounds such as 1,3-di (p-chlorophenyl) and 1,3-di (p-ethoxycarbonylphenyl); 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl And 1,3-diheterocyclic substituents such as 1,3-di (2-pyridyl).
(F) 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and its derivatives. Examples of this derivative include 3-alkyl rhodanine such as 3-methyl rhodanine, 3-ethyl rhodanine and 3-allyl rhodanine; 3-aryl rhodanine such as 3-phenyl rhodanine; and 3- (2-pyridyl). ) 3-position heterocyclic substituted rhodanine such as rhodanine.

(G) 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazoledione) nucleus: for example 3-ethyl-2-thio-2,4-oxazolidinedione.
(H) Tianaphthenone nucleus: for example, 3 (2H) -thianaphthenone-1,1-dioxide.
(I) 2-thio-2,5-thiazolidinedione nucleus: for example 3-ethyl-2-thio-2,5-thiazolidinedione.
(J) 2,4-thiazolidinedione nucleus: for example 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, or 3-phenyl-2,4-thiazolidinedione.
(K) Thiazolin-4-one nucleus: for example, 4-thiazolinone or 2-ethyl-4-thiazolinone.
(L) 2,4-imidazolidinedione (hydantoin) nucleus: for example, 2,4-imidazolidinedione or 3-ethyl-2,4-imidazolidinedione.
(M) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example 2-thio-2,4-imidazolidinedione or 3-ethyl-2-thio-2,4-imidazolidine Zeon etc.
(N) 2-imidazolin-5-one nucleus: for example 2-propylmercapto-2-imidazolin-5-one.
(O) 3,5-pyrazolidinedione nucleus: for example 1,2-diphenyl-3,5-pyrazolidinedione or 1,2-dimethyl-3,5-pyrazolidinedione.
(P) Benzothiophen-3-one nucleus: for example, benzothiophen-3-one, oxobenzothiophen-3-one, or dioxobenzothiophen-3-one.
(Q) Indanone nucleus: For example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, or 3,3-dimethyl-1-indanone.

The ring structure represented by Z ¹ is preferably a 1,3-dicarbonyl nucleus, a pyrazolinone nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body, such as barbituric acid, 2-thiobarbi Tool acid, the same shall apply hereinafter), 2-thio-2,4-thiazolidinedione nucleus, 2-thio-2,4-oxazolidinedione nucleus, 2-thio-2,5-thiazolidinedione nucleus, 2,4-thiazolidinedione Nucleus, 2,4-imidazolidinedione nucleus, 2-thio-2,4-imidazolidinedione nucleus, 2-imidazolin-5-one nucleus, 3,5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus Or a structure of an indanone nucleus, more preferably a 1,3-dicarbonyl nucleus, a 2,4,6-triketohexahydropyrimidine nucleus, a 3,5-pyrazolidinedione nucleus, a benzo It has a thiophen-3-one nucleus or indanone nucleus structure, more preferably a 1,3-dicarbonyl nucleus, or a 2,4,6-triketohexahydropyrimidine nucleus structure, particularly preferably 1 , 3-indandione structure, or barbituric acid or 2-thiobarbituric acid or derivatives thereof.

In L ¹ , L ² , and L ³ of formula (II), when the methine group has a substituent, the substituents may be bonded to each other to form a ring (eg, a 6-membered ring such as a benzene ring). Examples of the substituent that the methine group may have include the substituent W described later. L ¹ , L ² and L ³ are preferably all unsubstituted methine groups.

  In general formula (II), n preferably represents an integer of 0 or more and 3 or less, and more preferably 0. When n is increased, the thermal decomposition temperature is lowered.

In the formula (II), D ¹ is preferably a group having —NR ^a (R ^b ). More preferably, D ¹ is an aryl group having —NR ^a (R ^b ) as a substituent (preferably a phenyl group or naphthyl group having —NR ^a (R ^b ) as ^a substituent).
R ^a and R ^b each independently represent a hydrogen atom or a substituent, and examples of the substituent represented by R ^a or R ^b include the substituent W described later. Among them, an alkyl group, an aryl group, An alkoxy group, an aryloxy group, a silyl group, or an aromatic heterocyclic group (preferably a 5-membered ring, specifically, furan, thiophene, pyrrole, or oxadiazole) is preferable.
D ¹ is preferably an aryl group (preferably a phenyl group) substituted with an amino group (—NR ^a (R ^b )) at the para position. In this case, D ¹ is preferably represented by the following formula (II-1).

In formula (II-1), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent. As this substituent, the substituent W mentioned later is mentioned. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ² and R ⁵ , and R ⁴ and R ⁶ may be bonded to each other to form a ring. Examples of the ring to be formed include ring RI described later. * In formula (II-1) represents a linking site with L ³ (L ¹ when n is 0).
R ^{1 to} R ⁴ are preferably all hydrogen atoms, or R ² and R ⁵ or R ⁴ and R ⁶ are preferably linked to form a 5-membered ring, more preferably R ^{1 to} R 4. All ⁴ are hydrogen atoms.
R ⁵ and R ⁶ are preferably an aryl group, and the aryl group may have a substituent. As the substituent that the aryl group may have, an alkyl group (for example, methyl group, ethyl group) or an aryl group (for example, phenyl group, naphthylene group, phenanthryl group, anthryl group) is preferable. R ⁵ and R ⁶ are preferably a phenyl group, an alkyl-substituted phenyl group, a phenyl-substituted phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, or a fluorenyl group (preferably a 9,9′-dimethyl-2-fluorenyl group).

When R ⁵ and R ⁶ are aryl groups, D ¹ is preferably represented by the following formula (II-2).

In formula (II-2), R ^{811 to} R ⁸¹⁴ , R ^{820 to} R ⁸²⁴ , and R ^{830 to} R ⁸³⁴ each independently represent a hydrogen atom or a substituent. Examples of the substituent include a substituent W described later, preferably an alkyl group (for example, a methyl group or an ethyl group) or an aryl group (for example, a phenyl group or a naphthyl group). It may have a substituent W (preferably an aryl group). Among ^them, preferred is a case ^{R 820} and ^{R 830} are substituents, and other ^{R 811 ~R 814, R 821 ~R} 824, R 831 ~R 834 is more preferable if a hydrogen atom.
Further, at least two of R ^{811 to} R ⁸¹⁴ , R ^{820 to} R ⁸²⁴ , and R ^{830 to} R ⁸³⁴ may be bonded to each other to form a ring. Examples of the ring to be formed include ring RI described later. As an example of the ring formation, R ⁸¹¹ and R ⁸¹² , R ⁸¹³ and R ⁸¹⁴ are bonded to form a benzene ring, and two adjacent R ^{820 to} R ⁸²⁴ (R ⁸²⁴ and R ⁸²³ , R ⁸²³ and R ⁸²⁰ , R ⁸²⁰ and R ⁸²¹ , R ⁸²¹ and R ⁸²² ) are bonded to form two adjacent benzene rings, R ^{830 to} R ⁸³⁴ (R ⁸³⁴ and R ⁸³³ , R ⁸³³ and R ⁸³⁰ , R ⁸³⁰ and R ⁸³¹ , R ⁸³¹ and R ⁸³² ) are combined to form a benzene ring, and R ⁸²² and R ⁸³⁴ , R ⁸¹² and R ⁸²⁴ , R ⁸¹⁴ and R ⁸³² are combined to form a 5-membered ring together with the N atom.
* Represents a linking site with L ³ (L ¹ when n is 0).

The compound represented by the formula (I) or (II) can be produced according to the synthesis method described in JP-A No. 2000-297068.
Specific examples of the compound represented by formula (I) or (II) are shown below, but the present invention is not limited thereto.

[Substituent W]
The substituent W is listed below.
An alkyl group (preferably having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, trifluoromethyl, etc.), Alkenyl groups (preferably having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), alkynyl groups (preferably having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), cycloalkyl groups (preferably Has 3 to 20 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), cycloalkenyl group (preferably having 5 to 20 carbon atoms, such as cyclopentenyl, cyclohexenyl, etc.), aryl group ( Preferably it has 6 to 26 carbon atoms, for example phenyl, -Naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl and the like), a heterocyclic group (preferably having 2 to 20 carbon atoms and having at least one oxygen atom, sulfur atom or nitrogen atom) A heterocyclic group such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzoimidazolyl, 2-thiazolyl, 2-oxazolyl, etc., an alkoxy group (preferably having 1 to 20 carbon atoms, for example, methoxy , Ethoxy, isopropyloxy, benzyloxy, etc.), alkenyloxy groups (preferably having 2 to 20 carbon atoms, such as vinyloxy, allyloxy, etc.), alkynyloxy groups (preferably having 2 to 20 carbon atoms, such as 2-propenyl, etc.) Oxy, 4-butynyloxy, etc.), a cycloalkyloxy group (preferably having a carbon number) -20, for example, cyclopropyloxy, cyclopentyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, etc.), an aryloxy group (preferably having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy) , 4-methoxyphenoxy, etc.), a heterocyclic oxy group (for example, imidazolyloxy, benzimidazolyloxy, thiazolyloxy, benzothiazolyloxy, triazinyloxy, purinyloxy),

An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), a cycloalkoxycarbonyl group (preferably having 4 to 20 carbon atoms such as cyclopropyloxycarbonyl, cyclopentyloxycarbonyl, etc. , Cyclohexyloxycarbonyl, etc.), aryloxycarbonyl groups (preferably having 6 to 20 carbon atoms, such as phenyloxycarbonyl, naphthyloxycarbonyl, etc.), amino groups (preferably having 0 to 20 carbon atoms, alkylamino groups, alkenyls) Including amino group, alkynylamino group, cycloalkylamino group, cycloalkenylamino group, arylamino group, heterocyclic amino group, for example, amino, N, N-dimethylamino, N, N-diethylamino, N- (Tilylamino, N-allylamino, N- (2-propynyl) amino, N-cyclohexylamino, N-cyclohexenylamino, anilino, pyridylamino, imidazolylamino, benzoimidazolylamino, thiazolylamino, benzothiazolylamino, triazinylamino, etc.) A sulfamoyl group (preferably an alkyl, cycloalkyl or aryl sulfamoyl group having 0 to 20 carbon atoms, such as N, N-dimethylsulfamoyl, N-cyclohexylsulfamoyl, N-phenylsulfamoyl, etc. ), An acyl group (preferably having 1 to 20 carbon atoms, such as acetyl, cyclohexylcarbonyl, benzoyl, etc.), an acyloxy group (preferably having 1 to 20 carbon atoms, such as acetyloxy, cyclohexylcarbonyl, etc.) Xy, benzoyloxy, etc.), carbamoyl groups (preferably carbamoyl groups having 1 to 20 carbon atoms, alkyl, cycloalkyl or aryl, such as N, N-dimethylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl, etc. ),

An acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, cyclohexylcarbonylamino, benzoylamino, etc.), a sulfonamide group (preferably a sulfoamide having 0 to 20 carbon atoms, alkyl, cycloalkyl or aryl) Group, for example, methanesulfonamide, benzenesulfonamide, N-methylmethanesulfonamide, N-cyclohexylsulfonamide, N-ethylbenzenesulfonamide, etc.), alkylthio group (preferably having 1 to 20 carbon atoms, for example, Methylthio, ethylthio, isopropylthio, benzylthio, etc.), cycloalkylthio groups (preferably having 3 to 20 carbon atoms, such as cyclopropylthio, cyclopentylthio, cyclohexylthio, 4-methylcyclohexyl) Thio), arylthio groups (preferably having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), alkyl, cycloalkyl or arylsulfonyl groups (preferably carbon In formulas 1 to 20, for example, methylsulfonyl, ethylsulfonyl, cyclohexylsulfonyl, benzenesulfonyl, etc.),

A silyl group (preferably a silyl group having 1 to 20 carbon atoms and substituted with alkyl, aryl, alkoxy and aryloxy, such as triethylsilyl, triphenylsilyl, diethylbenzylsilyl, dimethylphenylsilyl, etc.), silyloxy group ( Preferably, it is a silyloxy group having 1 to 20 carbon atoms and substituted with alkyl, aryl, alkoxy and aryloxy, such as triethylsilyloxy, triphenylsilyloxy, diethylbenzylsilyloxy, dimethylphenylsilyloxy, etc.), hydroxyl group , Cyano group, nitro group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group, sulfo group, phosphonyl group, phosphoryl group, boric acid group.

When a compound or a substituent includes an alkyl group, an alkenyl group, etc., these may be linear or branched, and may be substituted or unsubstituted. When an aryl group, a heterocyclic group, or the like is included, they may be monocyclic or condensed, and may be substituted or unsubstituted.
In the present specification, what is described only as a substituent refers to this substituent W, and when each group is only described (for example, described as “alkyl group”) The only preferred ranges in the corresponding groups of this substituent W, specific examples apply.

[Ring RI]
Examples of the ring RI include an aromatic or non-aromatic hydrocarbon ring, a heterocyclic ring, and a polycyclic condensed ring formed by further combining these. For example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, Pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenant Examples include a lysine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring, and a phenazine ring.

  The present invention will be described below in more detail based on examples, but the present invention is not limited thereto.

[Measurement of conductance of sublimation purification equipment]
In sublimation purification apparatus having the configuration shown in FIGS. 1-4, as shown in FIG. 5, the sublimation tube (13), a pressure gauge _{G A} to X side end A, the pipe (12) and the sublimation tube (13) a pressure gauge G _B to the connecting portion B between, and respectively installed with a pressure gauge G _C the connecting portion C of the pipe (12) and vacuum pump (11). Moreover, as shown in FIG. 6, the control valve (18) was provided in piping.
The sublimation tube was a cylindrical quartz glass tube, the cross-sectional area of the tube was 78.5 cm ² , and the axial length was 100 cm. Moreover, the said piping employ | adopted the hose shape with a circular cross section made from SUS (electropolishing treatment stainless steel), The cross-sectional area in the pipe | tube was 81 cm < ² >, and length was 50 cm. Using TG201C (manufactured by Ampere Co.) as the pressure gauge _G A ~G _C.

After operating the vacuum pump and confirming that all of the pressure gauges G _{A to} G _C were stable by showing 1 × 10 ⁻² Pa or less, the gas provided at the X-side end as shown in FIG. from the inlet, introducing a predetermined amount of argon gas using a mass flow controller, where the value indicated by the pressure gauge G _a ~G _C was stable, read the pressure indicated by the pressure gauge G _a ~G _C.
In the above measurement, argon gas was introduced at a flow rate of 3.3 × 10 ⁻⁹ m ³ / sec, 6.7 × 10 ⁻⁹ m ³ / sec, 1.0 × 10 ⁻⁸ m ³ / sec, .7 × ¹⁰ -8 ^{m 3} / sec set, and 3.3 × ¹⁰ -8 ^{m 3} / sec, in each of the flow rate, read the value of the pressure gauge _G a ~G _C. The obtained values were applied to the above formulas (1) and (2) to determine the conductance K _AC between _AC and the conductance K _BC between _BC . Wherein _{each K AC} and _{K BC} were the average of the _{K AC} and _{K BC} in the five flow of the argon gas.

[Test Example 1]
By adjusting the opening / closing degree of the control valve (18) shown in FIG. 6 and installing a quartz glass cylinder having a cross-sectional area of 5 to 50 cm ² and an axial length of 5 to 10 cm in the sublimation tube, the above sublimation purification The conductance of the apparatus was adjusted to the values shown in Table 1 below.
Using the sublimation purification apparatus (Examples 1-14, Comparative Examples 1-7) which shows each conductance, the following compound A synthesize | combined by the conventional method was used as the crude body sample, and the sublimation refinement | purification was performed with the following method. Compound A may contain not only by-products generated during synthesis as impurities, but also raw materials used, raw material decomposition products, solvents, water, inorganic substances, and the like.

The coarse body 100g was arrange | positioned in the sublimation part (14) as shown in FIG. After actuates the vacuum pump (11) under vacuum until all the pressure gauge _G A ~G _C is 5 × ¹⁰ -3 Pa, 325 ℃ sublimation unit (14) using a pipe heater (17) as a heat source The sublimation purification was performed so that the temperature gradually decreased toward the Y side end of the sublimation tube (13) (temperature of the Y side end in the sublimation tube: 100 ° C.). 1 to 6, the sublimation tube (13) is disposed in a brass metal tube (16), and a heat source (17) is disposed so as to surround the metal tube (16). did.
After 10 hours, the heating was stopped, the whole sublimation tube was cooled to room temperature, and then released to the atmosphere. The purified sublimation product and the sublimation residue were taken out, and the mass was measured. The results are shown in Table 1.

As shown in Table 1, the K _AC sublimation refining apparatus is set to 0.010 3 ^/ sec or more, it was found that the sublimation purification efficiency is greatly improved. Further, the _{K BC} sublimation refining apparatus is set to 0.02 m ³ / sec or more, it was found that the sublimation purification efficiency is further improved. These phenomena, by using a sublimation purification apparatus showing a conductance value defined in the present invention, suppresses the decrease in the degree of vacuum accompanying the generation of gas, and as a result, suppresses thermal decomposition that is competitive with sublimation. This is considered to be a cause.

[Test Example 2]
By adjusting the opening / closing degree of the control valve (18) shown in FIG. 6 and installing a quartz glass cylinder having a cross-sectional area of 5 to 50 cm ² and an axial length of 5 to 10 cm in the sublimation tube, the above sublimation purification The conductance of the apparatus was adjusted to the values shown in Table 2 below.
Sublimation purification was performed by the following method using the following compounds B to E synthesized by a conventional method as crude samples. Compounds B to E may include not only by-products generated during synthesis as impurities, but also raw materials used, raw material decomposition products, solvents, water, inorganic substances, and the like.

The coarse body 10g was arrange | positioned in the sublimation part (14) as shown in FIG. After actuates the vacuum pump (11) under vacuum until all the pressure gauge _G A ~G _C is 5 × ¹⁰ -3 Pa, sublimation unit using a pipe heater (17) as a heat source (14) Table 2 Sublimation purification was performed by heating to the indicated temperature and gradually decreasing the temperature toward the Y side end of the sublimation tube (13) (temperature of the Y side end in the sublimation tube: 100 ° C.). 1 to 6, the sublimation tube (13) is disposed in a brass metal tube (16), and a heat source (17) is disposed so as to surround the metal tube (16). did.
After 3 hours, the heating was stopped, the whole sublimation tube was cooled to room temperature, and then released to the atmosphere. The purified sublimation product and the sublimation residue were taken out, and the mass was measured. The results are shown in Table 2.

  As shown in Table 2, by using a sublimation purification apparatus showing conductance specified in the present invention, sublimation residue was small and excellent sublimation purification efficiency was obtained no matter which compound was used as a sublimation purification target.

[Test Example 3]
About the compounds A-E, the mass reduction rate when keeping at the sublimation temperature of each compound as described in Test Example 1 or 2 for 5 hours under a normal-pressure nitrogen atmosphere was measured using a thermogravimetric apparatus. The results are shown in Table 3.

  As described above, the results of Tables 1 and 2 show that the amount of purified sublimation and the amount of sublimation residue are compared between the comparative example not depending on the method of the present invention and the example based on the present invention. -14 and Comparative Examples 1-7, Example 15 and Comparative Example 8 for Compound B, Example 16 and Comparative Example 9 for Compound C, and Comparison of Example 17 and Comparative Example 10 for Compound D In the examples according to the present invention, the amount of purified sublimation was significantly increased, and the amount of sublimation residue was significantly decreased. Since compounds A to D are compounds with low thermal stability (Table 3), by using the sublimation purification apparatus of the present invention, sublimation purification can be efficiently performed regardless of the thermal stability of the sublimation purification target sample. It has been shown.

  There has never been a technical idea that a sublimation purification apparatus is designed using conductance values as an index, and by using this apparatus, efficient sublimation purification is realized.

DESCRIPTION OF SYMBOLS 10 Sublimation purification apparatus 11 Vacuum pump 12 Piping 13 Sublimation pipe 14 Sublimation part (crude body)
15 Collecting part 16 Metal pipe 17 Heat source 18 Control valve 19 Introduction pipe (introduction port)

Claims (7)

A sublimation purification apparatus having a sublimation tube, a vacuum pump, and a pipe connecting the sublimation tube and the vacuum pump,
The conductance K _AC from A to C is 0.01 m ³ / sec, where A is the end of the sublimation tube on the side away from the vacuum pump and C is the connection between the pipe and the vacuum pump. This is the sublimation purification apparatus. When the connecting portion between the pipe and the sublimation tube and B, conductance K _BC from B to C is 0.02 m 3 ^/ sec or more, sublimation purification apparatus according to claim 1. Wherein _{K AC} is the 0.02 m ³ / sec or more, sublimation purification apparatus according to claim 1 or 2. Wherein _{K BC} is 0.03 m ³ / sec or more, sublimation purification apparatus according to any one of claims 1 to 3.   The sublimation purification apparatus of any one of Claims 1-4 with which the terminal part on the side away from the vacuum pump of the said sublimation pipe | tube is closed.   A sublimation purification method using the sublimation purification apparatus according to any one of claims 1 to 5, wherein a mass reduction rate is 2% when maintained at a sublimation temperature under an atmospheric pressure and at a normal pressure for 5 hours. A sublimation purification method in which the above sample is used as a sublimation purification target sample.   The sublimation purification method according to claim 6, wherein the sublimation purification target sample has a mass reduction rate of 10% or more when kept at a sublimation temperature for 5 hours in an inert gas atmosphere under normal pressure.

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