JP2003107061A - Method for identifying structure in organic matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily identify the structure of an organic matter with less amount of sample by utilizing chemical decomposition and derivative formation inline in a coloring matter with a high intermolecular aggregation energy density and does not gave vapor pressure, a coloring matter that has a metal ion and the like in a molecular structure and does not have vapor pressure, an organic matter that does not have vapor pressure as in a macromolecular compound and has high molar weight, a coloring matter having a functional group that can be easily eliminated due to thermal decomposition in the molecular structure, and the like by a thermal decomposition gas chromatograph-mass spectrograph. SOLUTION: In the structure identification method of an organic matter for identifying the structure of the organic matter by the thermal decomposition gas chromatograph-mass spectrograph, the organic matter is reacted with a reagent at a temperature without causing thermal decomposition reaction in the organic matter in a thermal decomposition apparatus under the presence of a carrier gas or under the circulation of a carrier gas to generate a reactant, the reactant is thermally decomposed to generate a pyrolysate at a temperature for thermally decomposing the reactant, the structure of the reactant is identified by the gas chromatograph-mass spectrograph, and the structure of the organic matter is identified from the structure of the pyrolysate in the method for identifying the structure of the organic matter.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for easily identifying the structure of an organic substance using a gas chromatograph mass spectrometer (hereinafter abbreviated as GC-MS).

[0002]

2. Description of the Related Art GC-MS is widely used as an excellent structure identification method for organic substances because it has various advantages such as the ability to simultaneously perform separation and structure identification with a small amount of sample.

However, an organic substance having a high intermolecular cohesive energy density and no vapor pressure or an organic substance having a high molecular weight is not vaporized and cannot be analyzed by GC-MS. Therefore, as a method for analyzing such an organic substance by GC-MS, there is a method utilizing chemical decomposition or derivatization.
andbook of Derivatives fo
r Chromatography (2nd edit
Ion), John Wiley & Sons, L
td. (1993).

Further, among the various polymer compounds which are organic substances, in the structure identification of a vinyl polymer which is easily depolymerized by heat, a pyrolysis gas chromatograph mass spectrometer (hereinafter referred to as P
A method for easily identifying a structure by using y-GC-MS is described in “Introduction to Pyrolysis Gas Chromatography (199
4) Gihodo Publishing ”.

In a polymer compound obtained by polycondensation of polyester, polyamide, polyimide, etc., it is difficult to easily identify the structure using Py-GC-MS because decomposition by heat is unlikely to occur. Therefore, the method of hydrolyzing in the presence of an acid or alkali catalyst, performing fractional purification by solvent extraction, etc., and then derivatizing and then identifying the structure using GC-MS is described in “New edition Polymer Analysis Handbook,
Kinokuniya Bookstore (1995) ”.

[0006] A method of accommodating a reaction reagent such as tetramethylammonium hydroxide during thermal decomposition to identify a polyester or the like that is difficult to decompose by heat using Py-GC-MS is described in "Introduction to Thermal Decomposition Gas Chromatography (1994).
"Gihodo Publishing".

[0007]

The derivatization performed for analyzing an organic compound having a high intermolecular cohesive energy density and no vapor pressure by GC-MS is complicated in operation and requires a large amount of sample. Limited scope of application. For example, a dye or the like having a molecular weight of several hundreds or more does not have a vapor pressure even if such derivatization is performed, and it is impossible to analyze it by GC-MS.

An object of the present invention is that the intermolecular cohesive energy density is high and vapor pressure is not present even if derivatization is carried out in the usual GC-MS analysis. In the molecular structure, -SO3X, -COOX (X is H or a dye having a functional group such as an alkali metal or metal), a dye having a metal ion such as Na + or K + in the molecular structure and having no vapor pressure, and no vapor pressure of an organic polymer compound Provided is a structure identification method capable of performing a high-molecular-weight organic substance or the like using a pyrolysis gas chromatograph mass spectrometer (Py-GC-MS) with a simple analytical operation in a short time and with a small amount of sample. That is. Another object of the present invention is to use Py-GC-MS to analyze an organic substance having a functional group such as -SO3X (X is H or an alkali metal, a metal, etc.) and -NO2 which are easily desorbed by heat in the molecular structure. Another object of the present invention is to provide a structure identification method that can be easily performed in a small amount.

[0009]

The structure identifying method of an organic substance of the present invention is a structure identifying method of an organic substance for identifying the structure of an organic substance by using a pyrolysis gas chromatograph mass spectrometer, in the presence of a carrier gas or a carrier gas. In a thermal decomposition apparatus under gas flow, an organic substance and a reagent are reacted at a temperature at which the thermal decomposition reaction of the organic substance does not occur to generate a reaction product, and the reaction product is decomposed at a temperature at which the reaction product is thermally decomposed. Pyrolysis is performed to produce a pyrolyzate, the structure of the pyrolyzate is identified by using a gas chromatograph mass spectrometer, and the structure of the organic matter is identified from the structure of the identified pyrolyzate. To do.

More preferably, in the method for identifying the structure of an organic substance according to the present invention, the pyrolysis gas chromatograph mass spectrometer has an unheated sample chamber and a heated heating chamber, and the organic substance and the reagent are combined. The reaction is carried out in the heating chamber,
The thermal decomposition of the reaction product is performed by moving the reaction product from the heating chamber to the sample chamber, adjusting the heating chamber to a temperature at which the reaction product thermally decomposes, and then transferring the reaction product to the heating chamber. Do it.

[0011]

1 (a) to 1 (d), an organic substance and a reagent are reacted in a thermal decomposition apparatus to produce a reaction product, and the reaction product is thermally decomposed to produce a thermal decomposition product. FIG. 3 is an explanatory diagram of one embodiment of a step of identifying the structure of the thermal decomposition product. The present invention is not limited to only these embodiments. 1 (a) to 1 (d) are shown in FIG. 1 (a), FIG. 1 (b),
The steps are performed in the order of FIG. 1 (c) and FIG. 1 (d). Figure 1
In (a) to (d), an inert gas such as nitrogen, helium, or argon can be used as the carrier gas, and the carrier gas is circulated in the thermal decomposition apparatus 5 including the sample chamber 6 and the heating chamber 7. It may be filled or filled. The heating unit 4 heats the heating chamber 7,
What can be heated to a temperature at which a reaction occurs to generate a reaction product by heating an organic substance and a reagent and a temperature at which the reaction product is thermally decomposed, for example, a temperature that can be heated in a range of 50 to 1000 ° C. and the temperature can be controlled Can be used. The heating unit 4 can be provided inside or outside the thermal decomposition apparatus 5, and an electric furnace or the like can be used. The heating chamber 4 can change the temperature of the heating chamber 7 in the range of room temperature to 1000 ° C.

FIG. 1A shows a sample chamber 6 of the thermal decomposition apparatus 5.
It is explanatory drawing which sets the platinum cup 3 containing an organic substance and a reagent to FIG. At this time, the heating chamber 7 is adjusted to a temperature at which the thermal decomposition reaction of the organic substance and the reactant does not occur yet. Figure 1
In (a), when the platinum cup 3 containing an organic substance and a reagent is set in the sample chamber 6 of the thermal decomposition apparatus 5, the heating chamber 7
May be adjusted to a desired temperature in advance. After setting, the heating chamber 7 may be adjusted to a desired temperature.
In FIG. 1A, the temperature of the heating chamber 7 may be a temperature at which the chemical decomposition reaction or the derivatization reaction with the organic substance reagent is most efficiently performed and the thermal decomposition reaction of the organic substance does not occur yet. . The temperature of the heating chamber 7 can be changed within the range of room temperature to 1000 ° C. The temperature of the heating chamber 7 is preferably in the range of 50 ° C to 220 ° C, more preferably in the range of 55 ° C to 220 ° C, and more preferably 60.
C. to 220.degree. C., particularly preferably 65.degree. C. to 22.
The range of 0 ° C is preferred. The temperature of the heating chamber 7 can be changed by raising or lowering the temperature.

The pyrolyzer 5 comprises a carrier gas inlet 1,
It has a sample chamber 6, a heating chamber 7, a heating unit 4, and a carrier gas outlet 2, and the carrier gas outlet 2 is connected to a gas chromatograph mass spectrometer. In the thermal decomposition apparatus 5, the carrier gas can flow from the carrier gas inlet 1 to the carrier gas outlet 2. The thermal decomposition component can be sent to the gas chromatograph mass spectrometer from the carrier gas outlet 2 together with the carrier gas. As the thermal decomposition apparatus 5, a vertical type having a heating chamber 7 near the carrier gas outlet 2 and a vertical type having a heating unit 4 near the carrier gas outlet 2 below the thermal decomposition apparatus can be used.

In the thermal decomposition apparatus 5, the platinum cup 3 set in the thermal decomposition apparatus 5 can be operated such as heating and cooling without being taken out from the thermal decomposition apparatus 5, and the inside of the thermal decomposition apparatus 5 can be performed. Thus, the organic substance and the reagent can be chemically reacted by heating. It is preferable that the thermal decomposition apparatus 5 has a mechanism capable of repeatedly inserting and removing the sample into and from the heating chamber 7 in a state of being shielded from the outside. Further, it has a mechanism that can repeatedly insert and remove the sample into and from the heating chamber 7 in a state of being shielded from the external atmosphere, and if necessary, a mechanism that can make the insertion rate constant with good reproducibility, for example, free fall of the sample. It is desirable to have a mechanism that can be introduced into the heating chamber 7. As an example of such a device, a double shot pyrolyzer manufactured by Frontier Laboratories is commercially available.

In addition to platinum as a material of the cup, the platinum cup 3 is not chemically affected by organic substances, reagents and their reactants, and does not have a chemical influence, and is preferably in a temperature range of 25 ° C. to 1000 ° C. Can be used in the temperature range of 25 ° C. to 700 ° C., and further in the temperature range of 25 ° C. to 600 ° C. The platinum cup 3 may be set in the sample chamber 6 of the thermal decomposition apparatus 5 after containing an organic substance, and then a reagent may be added thereto.
Alternatively, the organic substance may be added thereto, or the organic substance and the reagent may be put and set in the sample chamber 6 of the thermal decomposition apparatus 5.
As the platinum cup 3, a commercially available platinum cup can be used, and a double-shot platinum cup manufactured by Frontier Laboratories may be used.

The sample chamber 6 is a space without the heating section 4. The temperature of the sample chamber 6 in FIG. 1A is lower than the temperature at which the chemical decomposition reaction or the derivatization reaction with the reagent of the organic substance is efficiently performed and the thermal decomposition reaction of the organic substance does not yet occur. Good.

In FIG. 1 (b), the platinum cup 3 is transferred from the sample chamber 6 to a heating chamber 7 which is adjusted to a temperature at which the thermal decomposition reaction of the organic substance does not yet occur, and the platinum cup 3 is moved in the state where the thermal decomposition reaction of the organic substance does not occur. It is explanatory drawing which reacts the organic substance of the cup 3, and a reagent, and produces | generates a reaction product. In FIG. 1B, the heating temperature and the heating time of the organic substance and the reagent in the heating chamber 7 are such that the chemical decomposition reaction and the derivatization reaction by the reagent of the organic substance are most efficiently performed, and the thermal decomposition reaction of the organic substance is performed. The temperature and heating time may be such that the temperature does not yet occur. The heating time of the organic substance and the reagent is preferably in the range of 1 to 120 minutes, more preferably 1 to 90 minutes, and particularly preferably 1 to 60 minutes. The heating temperature of the organic substance and the reagent is preferably in the range of 50 ° C to 220 ° C, more preferably 55 ° C.
℃ to 220 ℃ range, more preferably 60 ℃ to 22
A range of 0 ° C., particularly preferably a range of 65 ° C. to 220 ° C. is preferable. The heating chamber 7 can be adjusted to any temperature, and the temperature can be changed in the range of room temperature to 1000 ° C.

In FIG. 1 (c), a platinum cup 3 containing a reaction product of an organic substance and a reagent is transferred from a heating chamber 7 to a sample chamber 6, and then the heating chamber 7 is adjusted to a temperature at which a thermal decomposition reaction of the reaction product occurs. FIG. The temperature of the heating chamber 7 in FIG. 1 (c) may be any temperature as long as it causes thermal decomposition of the reaction product, preferably 5 ° C. or more higher than the temperature at which thermal decomposition of the reaction product occurs, and more preferably. The temperature may be 10 ° C. or more higher than the temperature causing thermal decomposition of the reaction product, and particularly preferably 15 ° C. or more higher than the temperature causing thermal decomposition of the reaction product, for example, 225 ° C. or more, and further Preferably in the range of 225 to 600 ° C., more preferably 230
To 550 ° C, particularly preferably 250 to 500 ° C. If the temperature of the heating chamber 7 at this time is 600 ° C. or higher, decomposition proceeds excessively, and a thermal decomposition product suitable for estimating the original structure may not be obtained, which is not preferable.
The temperature of the sample chamber 6 in FIG. 1C is lower than the temperature at which the chemical decomposition reaction or the derivatization reaction with the organic substance reagent is most efficiently performed and the thermal decomposition reaction of the organic substance and the reaction product does not occur yet. Temperature is preferred. In FIG. 1 (b), the organic substance and the reagent are heated at a temperature and a heating time at which the chemical decomposition reaction and the derivatization reaction are most efficiently performed and the thermal decomposition reaction of the organic substance and the reactant does not occur yet. After the reaction product is generated, if the heating chamber 7 is heated to a temperature at which a thermal decomposition reaction of an organic substance or a reactant is caused without continuously taking out the sample from the heating chamber 7, an undesired reaction may occur at the time of heating. It is not preferable because it exists.

In FIG. 1 (d), the platinum cup 3 is again moved from the sample chamber 6 to a heating chamber 7 adjusted to a temperature at which the reaction product is thermally decomposed, and the reaction product in the platinum cup 3 is thermally decomposed to carry out the reaction. It is explanatory drawing which sends the thermal decomposition component of a substance to a gas chromatograph mass spectrometer with a carrier gas. The temperature of the heating chamber 7 is
It may be any temperature as long as it causes thermal decomposition of the reaction product, preferably 5 ° C. or more higher than the temperature at which thermal decomposition of the reaction product occurs, and more preferably 10 ° C. or more higher than temperature at which thermal decomposition of the reaction product occurs. The temperature may be any temperature, particularly preferably a temperature higher by 15 ° C. or more than the temperature at which thermal decomposition of the reaction product occurs, for example, 225 ° C. or higher, more preferably 225 to 600 ° C., and further preferably 2
Range of 30 to 550 ° C, particularly preferably 250 to 500
The range of ° C is preferred. Then, the thermally decomposed components of the reaction product are separated using a gas chromatograph, and the mass spectrometry of the separated product is performed to identify the structure of each of the thermally decomposed products of the reaction product, and to estimate or identify the structures of the reaction product and the organic material. You can do it.

In the method for identifying the structure of an organic substance of the present invention, it is preferable that the reaction between the organic substance and the reagent is carried out in a heating chamber at 50 to 220 ° C., and the thermal decomposition of the reaction product is performed by heating at a temperature of 225 ° C. or higher. It is preferably performed in a room.

The organic substance and the reagent shown in FIG.
By causing a chemical reaction by heating, a change that easily causes thermal decomposition without impairing the characteristics of the partial structure of the organic substance is caused in the organic substance, and, for example, the intermolecular force of the organic substance can be reduced, When thermally decomposing a reaction product of an organic substance and a reagent, it is possible to suppress a reaction that hinders the structural identification selected from these recombination reaction, transfer reaction, isomerization reaction and functional group elimination reaction.

As an example of the operating method of the structure identifying method of the organic substance of the present invention, the following operations (1) to (11) can be mentioned. (1) As a thermal decomposition apparatus, a thermal decomposition apparatus having an unheated sample chamber and a heating unit is used, (2) an organic substance and a reagent are put in a platinum cup or the like to prepare a sample, and (3) the sample is a carrier. The sample is placed in the sample chamber of the thermal decomposition apparatus in the presence of gas or under carrier gas flow, and (4) the sample is most efficiently processed in the heating chamber of the thermal decomposition apparatus, such as chemical decomposition reaction or derivatization reaction, and The temperature at which the thermal decomposition reaction still does not occur,
For example, by heating in a range of 50 ° C. to 220 ° C. for a predetermined time, an organic substance and a reagent are reacted to generate a reaction product, and (5) the sample containing the reaction product is not taken out from the thermal decomposition apparatus, but is removed from the heating chamber to the sample chamber. And lowering the temperature of the sample containing the reaction,
(6) The heating chamber is heated to a temperature at which thermal decomposition of the reaction product occurs, for example, 225 ° C. or higher, (7) a sample containing the reaction product is transferred from the sample chamber to the heating chamber, and (8) thermal decomposition of the reaction product. To produce a thermal decomposition product, (9) the thermal decomposition product is sent to a gas chromatograph together with a carrier gas, and separated using a gas chromatograph, and (10) the reaction product and / or the reaction product is separated using a mass spectrometer. Mass analysis of the separated components of the thermal decomposition product is performed to identify the structure of the reaction product and / or the thermal decomposition product, and (11) the structure of the reaction product is identified from the identified thermal decomposition product.
2) Identify or presume the structure of the organic substance from the structure of the reaction product.

The structure identification method of the present invention allows simple and small-scale structure identification of organic substances having no vapor pressure even if a treatment for lowering the intermolecular cohesive energy density used as a pretreatment for general gas chromatographic analysis is performed. It can be carried out. The structure identification method of the present invention, -SO 3 _X and -COOX high intermolecular cohesive energy density is high and a molecular weight no vapor pressure organic substance, for example, in the molecular structure
(3) Structure identification of organic substances such as dyes having (X is H, alkali metal, metal, etc.) and hardly volatile dyes having metal ions such as Na ⁺ and K ⁺ in the molecular structure can be performed simply and in a small amount. You can Furthermore, the structure identification method of the present invention enables simple and small-scale structure identification of organic substances having no vapor pressure at 300 ° C. without changing the structure. Furthermore, the structure identification method of the present invention is performed at 100 ° C.
At a vapor pressure of 1 Pa or less, preferably 0.5 Pa or less, more preferably 0.1 Pa or less, more preferably 0.05 P.
The structure of an organic substance having a or less, and particularly preferably 0.01 Pa or less, can be identified easily and in a small amount. The intermolecular cohesive energy density is described in "Encyclopedia of Chemistry 2 (published by Kyoritsu Shuppan Co., Ltd., reduced edition 14th edition)". Having no vapor pressure means a slight vapor pressure, for example 1 Pa or less,
It is preferably 0.5 Pa or less, more preferably 0.1 Pa.
Below, it is more preferable to have a vapor pressure of 0.05 Pa or less, and particularly preferably 0.01 Pa or less.

In particular, in the method for identifying the structure of an organic substance of the present invention, the temperature at which the thermal decomposition reaction of the organic substance does not occur is 50 to 2
The temperature is preferably in the range of 20 ° C, and the temperature at which the reaction product is thermally decomposed is 2
It is preferably 25 ° C. or higher.

The following compounds are mentioned below as specific examples of the organic substance whose structure can be easily identified by the present invention, but the compound of the present invention is not limited thereto. C. I. Acid Yellow (7, 17, 2
3,42,59,99,121,155,176,20
7, 241); C.I. I. Direct Yellow
(28, 39, 86, 106); C.I. I. Reacti
ve Yellow (15, 17, 37); C.I. I. A
cid Red (52,183,198,211,21
5,256); C.I. I. Disperse Red 6
0; C.I. I. Acid Blue (90,279);
C. I. Direct Blue (71, 98, 19
9); C.I. I. Reactive Blue (15,3
8, 41, 71, 77); C.I. I. Direct Gr
een (26, 59, 28); C.I. I. Reactiv
e Green 12; C.I. I, Acid Black
1; C.I. I. IJ Black 168; C.I. I. F
pigments such as water-soluble dyes such as good black 2
C. I. Pigment Red (1, 2, 3, 4,
6,9,48,48: 4,49,50,51,52,5
Examples thereof include organic pigments such as 3).

The reagents which can be used in the present invention are
(A) having an action of chemically reacting with the organic substance to reduce an intermolecular force between the organic substances, and (b) having an action of chemically reacting with the organic substance to protect a functional group from which the organic substance is easily released. (C) those having an action of chemically reacting with the organic substance to suppress carbonization of the organic substance, (d) having an action of chemically reacting with the organic substance to inhibit a recombination reaction of the organic substance, (E) those having the action of chemically reacting with the organic substance to suppress the transfer reaction of the organic substance, (f) those having the action of chemically reacting with the organic substance to suppress the isomerization reaction of the organic substance, ( g) those having a function of chemically reacting with the organic substance to convert a bond which is difficult to be thermally cleaved such as an azo bond contained in the organic substance into a bond which is easily thermally cleaved. As the reagent, any reagent can be used as long as it has one or more actions of the above (a) to (g).

[0027] Specific examples of the action of lowering the intermolecular force between the organic or organic described above (a), -COOX present in the molecular structure of the organic _matter, -SO 3 _X, -P
Examples thereof include a reaction of esterifying O ₃ X (X is H or an alkali metal, a metal or the like) with an alkylating agent or the like.

Specific examples of the action of suppressing the carbonization of an organic substance by chemically reacting as described in the above (c) include a decomposition reaction of a main bond excluding a functional group, and a cleavage of a bond which lowers the molecular weight. And the like, for example, promotion of decomposition such as hydrolysis of ester bond or amide bond existing in the main chain.

As a specific example of the action of chemically reacting with the organic substance described in (b) above to protect the functional group of the organic substance that is easily desorbed, for example, protection of the functional group that is easily desorbed, for example,- Reduction of NO ₂ to amine, —SO ₃ X (X is H
Alternatively, alkali metal, metal, etc.) can be reduced to —SH.

As a specific example of the action described in the above (g), which chemically reacts with an organic substance and converts a bond which is difficult to be thermally cleaved such as an azo bond contained in the organic substance into a bond which is easily thermally cleaved. , Converting a flame-retardant bond into an easily pyrolyzable bond, for example, reducing an unsaturated bond such as -C = C-, -N = N- or performing an appropriate addition reaction to the unsaturated bond. You can

Specific examples of reagents that can be used in the present invention are shown below. However, as the reagent used in the present invention, an organic substance and a reagent are chemically reacted by heating according to the method of the present invention, so that the organic substance undergoes such a change as to easily cause thermal decomposition without impairing the characteristics of the partial structure of the organic substance. It is not limited to this as long as it can be caused. As a specific example, “Derivatization Handbook for Separation and Analysis (Translated by Hiroshi Nakamura, published by Maruzen Co., Ltd.), H
ANDBOOK OF DERIVATIVES FO
RCHROMATO GRAPHY (Second Ed
edition KarlBlau · John Halke
t, MARUZEN & WILEY) ”, which is preferably a silylating agent, an acylating agent, an esterifying agent, a hydrosilylating agent, a reducing agent, an oxidizing agent, a hydrolyzing agent, etc., which can chemically decompose or modify an organic substance into a derivative. Can be used alone or in combination of two or more.

Hexamethyldisilazane (HMDS), Dimethyldich can be used as a silylating agent.
lorosilane (DMCS), Trimethylchlorosilane (TMC
S), N-Trimethylsilylacetamide (TMSA), N, O-Bis (tr
imethylsilyl) -acetamide (BSA), N-Methyl-N-trimeth
ylsilyl-acetamide (MTMSA), N-Methyl-N-trimethylsi
lyl-trifluoroacetamide (MSTFA), N-Trimethylsilyld
imethylamine (TMSDMA), N-Trimethylsilyldiethylam
ine (TMSDEA), N, O-Bis (trimethylsilyl) trifluoroace
tamide (BSTFA), N-Trimethylsilylimidazole (TMS
I), Tetramethyldisilazane (TMDS), tert-Butyldime
thylchlorosilane (tert-BDMCS), N-Methyl-N- (tert-b
utyldimethylsilyl) -trifluoroacetamide (MTBSTFA),
Dichloromethyltetramethyldisilazane (CMTMDS), Chl
oromethyldimethylchlorosilane (CMDMCS), Bromometh
yldimethylchlorosilane (BMDMCS), Trimethylchloros
ilane-D9 (TMCS-D9), Hexamethyldisilazane-D18 (HMD
S-D18), N, O-Bis (trimethylsilyl-D9) acetamide (BSA-
D18), N-Trimethylsilylimidazole-D9 (TMSI-D9), Fl
ophemesylamine, Flophemesylchloride, Flophemesyldi
Ethylamine or the like can be used. It is also possible to dissolve these in an appropriate solvent such as acetonitrile or pyridine before use. It is also possible to use a mixture of several kinds of compounds.

As a reagent that can be used as an acylating agent, trifluoroacetic anhydride (TFAA), Heptafl
uorobutyric anhydride (HFBA), Pentafluoropropioni
c anhydride (PFPA), Trifuluoroacetyl Imidazole (T
FAI), Heptafluorobutyryl Imidazole (HFBI), Penta
fluoropropionyl Imidazole (PFPI), N-Methyl bis (tr
ifluoroacetamide) (MBTFA), PentafluorobenzylBromi
de (PFBB) or the like can be used. It is also possible to dissolve these in an appropriate solvent before use. It is also possible to use a mixture of several kinds of compounds.

As a reagent that can be used as an esterifying agent, dimethylformamide dimethylacetal (DMF-DM
A), Dimethylformamidediethylacetal (DMF-DEA), Di
methylformamide di-n-propylacetal (DMF-DNPA), Dim
ethylformamide di-n-butylacetal (DMF-DNBA), Pheny
ltrimethylammonium Hydroxide (PTAH), Tetramethyla
mmonium Hydroxide (TMAH) etc. can be used. It is also possible to dissolve these in an appropriate solvent such as methanol, ethanol, n-propanol, n-butanol and the like and use them. It is also possible to use a mixture of several kinds of compounds.

As a reagent which can be used as a hydrosilylation agent, trichlorosilane, triethylsilane,
Trimethylsilane, diphenylsilane, phenylsilane, or the like can be used. It is also possible to dissolve these in an appropriate solvent before use. It is also possible to use a mixture of several kinds of compounds.

Reagents that can be used as the reducing agent include alkali metals, alkaline earth metals, zinc, trichlorosilane, triethylsilane, trimethylsilane, diphenylsilane, phenylsilane, hydrosilanes such as polymethylhydrosiloxane, and hydrogenated boron. It is possible to use metal hydrogen complex compounds such as alkaline earth metals, alkaline earth borohydride metals, trivalent phosphorus compounds such as trialkylphosphine and triphenylphosphine, and hydrazine. These can be used with catalysts such as Pd, Pt. It is also possible to dissolve these in an appropriate solvent before use. It is also possible to use a mixture of several kinds of compounds.

As a reagent which can be used as an oxidizing agent, hydrogen peroxide solution, organic peracid, dimethylsulfoxide and the like can be used. It is also possible to dissolve these in an appropriate solvent before use. It is also possible to use a mixture of several kinds of compounds.

As reagents that can be used as a hydrolyzing agent, alkali metal hydroxides, sodium alkoxides, potassium alkoxides, amine compounds, quaternary ammonium compound hydroxides, inorganic acids such as sulfuric acid, phosphoric acid, and organic acids can be used. Solid acid catalysts such as p-toluenesulfonic acid, various carboxylic acids, and metal oxides can be used. It is also possible to dissolve these in an appropriate solvent before use. It is also possible to use a mixture of several kinds of compounds.

The temperature at which the organic substance reacts with the reagent in the thermal decomposition apparatus may be a temperature at which the reaction between the organic substance and the reagent proceeds efficiently and the cleavage of the bond of the organic substance between atoms due to heat does not occur, for example, 220 ℃ or less, further 50-220
The range of ° C is preferred. The time for reacting the organic substance and the reagent in the thermal decomposition apparatus may be any time as long as the reaction between the organic substance and the reagent can be sufficiently performed, and is preferably within 1 hour.

The pyrolysis gas chromatograph mass spectrometer may be any pyrolysis gas chromatograph mass spectrometer capable of heating organic substances and reagents in the pyrolysis apparatus, and has a sample chamber and a heating chamber which are not heated. Mass spectrometer, a pyrolysis gas chromatograph having an unheated sample chamber and a heating chamber A mechanism having a mechanism capable of moving the sample chamber and the heating chamber that are not heated in a state of being blocked from the external atmosphere in a mass spectrometer, It has a sample chamber that is not heated and a vertical heating chamber, and has a mechanism that can move the sample in a state where the sample chamber that is not heated and the vertical heating chamber are isolated from the external atmosphere. For example, a pyrolysis gas chromatograph mass spectrometer with a mechanism that allows a sample to fall into a vertical heating chamber from a sample chamber that is not heated It is possible to have. As the pyrolysis gas chromatograph mass spectrometer, a pyrolysis gas chromatograph mass spectrometer having a double shot pyrozer manufactured by Frontier Lab can be used. As the gas chromatograph and the mass spectrometer, known instruments used for analysis, for example, commercially available instruments can be used. As the gas chromatograph column, a known gas chromatograph column generally used for analysis or a commercially available gas chromatograph column can be used. The gas chromatograph may be any as long as it can separate the pyrolyzed components and enables mass spectrometry,
The column and the column temperature can be appropriately selected.

[0041]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

In the following Examples and Comparative Examples, a pyrolysis gas chromatograph mass spectrometer was equipped with a double shot pyrolyzer as a pyrolysis device (Py, manufactured by Frontier Laboratories).
-2010D type) provided with a gas chromatograph mass spectrometer (JEOL, JMS-AMII type). Double shot pyrolyzer (Py-2010D type, manufactured by Frontier Lab) similar to the thermal decomposition device shown in FIG.
Has a sample chamber in the upper part and a heating chamber in the lower part, and the platinum cup can be moved inline without taking out between the sample chamber and the heating chamber to the outside. If necessary, the platinum cup can be introduced into the heating chamber by free fall from the sample chamber. In the gas chromatograph, DB-5 (0.25 mmφ × 30 m) manufactured by Chrompack was used as a column, and the column temperature was held at 50 ° C. for 5 minutes and then 10 ° C.
Helium was used as a carrier gas by a method of raising the temperature to 300 ° C. under a temperature rising condition of / min.

[Embodiment 1] (Simular Red3)
Structural Identification of 045) Dye represented by Formula (1): Symbolal Red3045
0.3 mg (manufactured by Dainippon Ink and Chemicals, Inc.) and 6 μl of a 25 wt% methanol solution of tetramethylammonium hydroxide were placed in a double shot platinum cup.
The platinum cup was set in the sample chamber of the thermal decomposition apparatus similar to FIG. 1, and the inside of the thermal decomposition apparatus was replaced with helium gas. further,
Move the platinum cup to a heating chamber heated to 150 ℃,
After heating at 0 ° C. for 10 minutes, the platinum cup was transferred from the heating chamber to the sample chamber without taking it out from the pyrolyzer. Then, the heating chamber was heated to 350 ° C., the platinum cup was transferred from the sample chamber to the heating chamber by free fall, and the reaction product was thermally decomposed at 350 ° C. The thermal decomposition product generated at 350 ° C. was separated using a gas chromatograph, and the separated components were subjected to mass spectrometry with a mass spectrometer. The column temperature of the gas chromatograph was set to 10 after the platinum cup was moved from the sample chamber 6 to the heating chamber 7 by free fall and kept at 50 ° C. for 5 minutes.
The temperature was raised to 300 ° C. under the temperature rising condition of 300 ° C./minute, and then 300
Hold at ℃. The obtained pyrograms are shown in FIGS. 2 and 3. Nine components separated by gas chromatography (Fig. 2
And the obtained mass spectra of a1 to a9) shown in FIG. 3 are shown in FIGS.

4 to 12 were identified from the NIST database, and FIG. 4 (component a1 in FIG. 2) is the compound of formula (2), and FIG. 5 (component a2 in FIG. 2) is the compound of formula (3). , FIG. 6 (component a3 in FIG. 2) is the compound of formula (4), and FIG.
Component a4) is a compound of formula (5), FIG.
5) is a compound of formula (6), FIG. 9 (component a6 of FIG. 2) is a compound of formula (7), and FIG. 10 (component a7 of FIG. 2) is a compound of formula (8).
11 (component a8 in FIG. 2) is the compound of formula (9), FIG. 12 (component a9 in FIG. 2) is the compound of formula (10),
Could be identified. From the formulas (2) to (10), the compound of the formula (11) can be estimated. In particular, the compound represented by the formula (7) is an important decomposition product suggesting to which part of the aromatic ring the —SO ₃ X of the formula (11) is substituted. The derivative represented by the formula (11) is a dye Symu represented by the formula (1).
lar Red3045 by the (produced by Dainippon Ink and Chemicals, Inc.) for heating and tetramethylammonium hydroxide, _-SO 3 C each functional group from _-SO 3 Na
To H _3, from -OH to -OCH _3, -C from -COOH
To OOCH ₃ , from -N = N- to -NH-NH-.
_{NH (CH 3) -NH (CH} 3) - considered derivative shown next formula (11) was formed. Since the formula (11) can be estimated, the formula (1) could be easily identified.

[Comparative Example 1] Dye Symu represented by the formula (1)
lar Red 3045 (manufactured by Dainippon Ink and Chemicals, Inc.) 0.
3 mg and 6 μl of a 25 wt% methanol solution of tetramethylammonium hydroxide were placed in a double shot platinum cup. The platinum cup was set in the sample chamber of the thermal decomposition apparatus similar to FIG. 1, and the inside of the thermal decomposition apparatus was replaced with helium gas. The heating chamber is heated to 350 ° C, and the platinum cup is introduced from the sample chamber into the heating chamber by free fall to 350 ° C.
The product and the decomposition product generated in 1. were separated using a gas chromatograph, and further subjected to mass spectrometry with a mass spectrometer. The obtained pyrograms are shown in FIGS. 13 and 14.
The seven components (b1 to b7 described in FIGS. 13 and 14) separated by the gas chromatograph were analyzed by a mass spectrometer.

The mass spectrum of the component b1 of FIG. 13 is similar to the mass spectrum of FIG. 4, the mass spectrum of the component b2 of FIG. 13 is similar to the mass spectrum of FIG. 5, and the mass spectrum of the component b3 of FIG. Is similar to the mass spectrum of FIG. 6, the mass spectrum of component b4 of FIG. 13 is similar to the mass spectrum of FIG. 10, and component b of FIG.
The mass spectrum of 5 is similar to that of FIG. 11, and the mass spectrum of component b6 of FIG. 13 is shown in FIG.
Is similar to the mass spectrum of. The component b7 in FIG. 14, that is, the compound represented by the formula (7) was hardly observed. In this way, _-SO 3 C from _-SO 3 Na
It is considered that the reaction to H ₃ did not sufficiently occur. Therefore, the dye represented by the formula (1)
The structure of ed3045 could not be identified.

[Comparative Example 2] Dye Symu represented by the formula (1)
lar Red 3045 (manufactured by Dainippon Ink and Chemicals, Inc.) 0.
3 mg was placed in a double shot platinum cup. The platinum cup was set in the sample chamber of the thermal decomposition apparatus similar to FIG. 1, and the inside of the thermal decomposition apparatus was replaced with helium gas. 350 heating chamber
The mixture was heated to ℃, the platinum cup was introduced from the sample chamber into the heating chamber by free fall, the products and decomposed products produced at 350 ° C. were separated using a gas chromatograph, and mass spectrometry was further performed with a mass spectrometer. . Figure 1 shows the obtained pyrogram.
5 shows. The mass spectrum of component c1 in FIG. 15 is similar to the mass spectrum in FIG. In addition, the formula (1
No compound suggesting the partial structure of 1) was observed. From the above results, the dye Symula shown in formula (1)
The structure of r Red3045 could not be deduced.

[0048]

[Chemical 1]

[0049]

[Chemical 2]

[0050]

[Chemical 3]

[0051]

[Chemical 4]

[0052]

[Chemical 5]

[0053]

[Chemical 6]

[0054]

[Chemical 7]

[0055]

[Chemical 8]

[0056]

[Chemical 9]

[0057]

[Chemical 10]

[0058]

[Chemical 11]

[0059]

INDUSTRIAL APPLICABILITY The present invention can provide a method capable of simply identifying the structure of an organic substance by using a pyrolysis gas chromatograph mass spectrometer with a small amount of sample.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of an embodiment of a process of heating, cooling, and heating an organic substance and a reagent in a thermal decomposition apparatus.

FIG. 2 shows the dye Symula by the method shown in Example 1.
It is the pyrogram by the total ion obtained as a result of performing the Py-GC-MS analysis of rRed3045.

FIG. 3 shows the dye Symula by the method shown in Example 1.
It is the pyrogram by the fragment ion of m / z = 263 obtained as a result of performing the Py-GC-MS analysis of rRed3045. In this display method, equation (7)
The compound shown in is selectively and strongly displayed.

FIG. 4 is a mass spectrum of a1 shown in FIG.

5 is a mass spectrum of a2 shown in FIG.

FIG. 6 is a mass spectrum of a3 shown in FIG.

FIG. 7 is a mass spectrum of a4 shown in FIG.

FIG. 8 is a mass spectrum of a5 shown in FIG.

9 is a mass spectrum of a6 shown in the pyrogram FIG.

FIG. 10 is a mass spectrum of a7 shown in FIG.

FIG. 11 is a mass spectrum of a8 shown in the pyrogram FIG.

FIG. 12 is a mass spectrum of a9 shown in FIG.

FIG. 13 shows the dye Symul according to the method shown in Comparative Example 1.
9 is a pyrogram of total ions obtained as a result of analyzing ar Red3045 by Py-GC-MS.

FIG. 14 shows the dye Symul according to the method shown in Comparative Example 1.
It is the pyrogram by the fragment ion of m / z = 263 obtained as a result of carrying out the analysis by Py-GC-MS of ar Red3045. In this display method, the compound represented by the formula (7) is selectively and strongly displayed.

FIG. 15 shows the dye Symul according to the method shown in Comparative Example 2.
9 is a pyrogram of total ions obtained as a result of analyzing ar Red3045 by Py-GC-MS.

[Explanation of symbols]

1: Carrier gas inlet, 2: Carrier gas outlet, 3: Platinum cup, 4: heating part, 5: Pyrolysis device, 6: sample chamber, 7: heating chamber.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) G01N 30/72 G01N 30/72 A (72) Inventor Hataaki Yoshimoto 8-1 Goi Minami Kaigan, Ichihara City, Chiba Stock Association U-Bee Science Analysis Center F-term (reference) 2G052 AB11 AD06 AD12 AD42 EB00 GA24 GA27

Claims (4)

[Claims] 1. A method for identifying a structure of an organic substance for identifying the structure of the organic substance by using a pyrolysis gas chromatograph mass spectrometer, which comprises: Is reacted at a temperature at which a thermal decomposition reaction of the organic substance does not occur to generate a reaction product, and the reaction product is thermally decomposed to generate a thermal decomposition product at a temperature at which the reaction product thermally decomposes. A structure identification method for an organic substance, comprising: identifying the structure of the substance using a gas chromatograph mass spectrometer, and identifying the structure of the organic substance from the structure of the identified thermal decomposition product. 2. The pyrolysis gas chromatograph mass spectrometer has a sample chamber which is not heated and a heating chamber which is heated, and the reaction between the organic substance and the reagent is carried out in the heating chamber.
The thermal decomposition of the reaction product is performed by transferring the reaction product from the heating chamber to the sample chamber, adjusting the heating chamber to a temperature at which the reaction product thermally decomposes, and then transferring the reaction product to the heating chamber. The organic substance structure identification method according to claim 1, wherein the organic substance structure identification method is performed. 3. The reaction between the organic substance and the reagent is carried out in the range of 50 to 22.
The reaction is performed in the heating chamber at 0 ° C., and the thermal decomposition of the reaction product is performed by transferring the reaction product from the heating chamber to the sample chamber, adjusting the heating chamber to a temperature of 225 ° C. or higher, and then the reaction product. The method for identifying a structure of an organic substance according to claim 1 or 2, wherein the method is carried out by transferring the structure to the heating chamber. 4. The temperature at which the thermal decomposition reaction of the organic substance does not occur is 50 to 220 ° C., and the temperature at which the organic substance thermally decomposes is 225 ° C. or higher.
The method for identifying a structure of an organic substance according to any one of 1.