JPH11100365A - Aziridine compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject new compound useful as a raw material for a metallic ion masking agent and an oxidizing agent or the like. SOLUTION: This aziridine compound is represented by formula I (M<1> and M<2> are each H or a cation; L is a bivalent connecting group containing an alkylene and/or arylene), e.g. a compound represented by formula II. The compound represented by formula I is efficiently and simply produced by reacting an amino acid compound represented by the formula; H2 N-L-CO2 M<2> (e.g. glycine) with a propionic acid derivative represented by formula III (X and X' are each an eliminable group) (e.g. 2,3-dibromopropionic acid) in a molar amount of 0.1-10 times based on the amino acid compound, preferably 0.5-1.5 mol or an acrylic acid derivative represented by formula IV in the presence of a solvent (preferably water) and a base (preferably sodium hydroxide or the like) at pH 6-14, preferably pH 8-12 and -20 to +100 deg.C, preferably initially at 0 to +50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an aziridine compound and a method for producing the same. The aziridine compound itself can be used for various purposes, but it can also be used as a metal ion shielding agent, for example, medical, cosmetic preparations, soaps, detergents, cleaning compositions, material analysis, coating on metal materials, plating, and catalysts. It is useful as an intermediate for the synthesis of metal ion shielding agents in the fields of colloid chemistry, photography, liquid crystals, etc., and especially for metal ion shielding agents and oxidizing agents (eg, bleaching agents for photosensitive materials) in the field of silver halide photographic materials. Useful as a raw material.

[0002]

2. Description of the Related Art Heretofore, the following compounds have been known as such aziridine compounds.

[0003]

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[0004]

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[0005]

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The above compounds A, B and C are used to prepare a diamine compound used as a metal ion shielding agent (formula (I)
In order to synthesize the compound (I)), an operation of removing the protecting group is required for all the compounds, so that the number of reaction steps is increased and the cost of the final compound is increased. The compound represented by the formula (II) is disclosed in Japanese Patent Application Laid-Open No. 7-19943.
No. 3 and Zh. Neorg. Khim. , 1
980, 25 (6), 1692-4, Bull. So
c. Chim. France, 1964 (11), 27
It can be synthesized by the method described in 78-82. However, these methods all have long steps and a low total yield, and thus are not suitable for industrial synthesis. Furthermore, there were many by-products, and it was difficult to synthesize by an integrated method. In addition, it is difficult to introduce separate groups into the diamine moiety on the left and right sides by the method of the above-mentioned literature, and it was not possible to synthesize the diamine moiety while maintaining the optical activity of the carbon adjacent to N in the diamine moiety (usually racemic). Change).
In addition, depending on the conventional production method, the compound A,
The compound represented by the formula (II) could not be produced using B and C.

[0007]

DISCLOSURE OF THE INVENTION The present invention relates to a method of reacting an amine compound with --CH ₂ CH (COOM ¹¹ ) NH--L
^{An 1-} COOM ¹² group (wherein, M ¹¹ and M ^{12 each} represent a hydrogen atom or a cation, and L ¹ represents a linking group) efficiently and can be introduced without changing the configuration of L ¹ ; It is to provide a manufacturing method thereof. Further, the aziridine compound is reacted with an amino acid to form -C
An object of the present invention is to provide a method for obtaining a metal shielding agent having a skeleton of H ₂ CH (COOM ¹¹ ) NH-L ¹ -COOM ¹² in high yield.

[0008]

Accordingly, the present invention provides (1) an aziridine compound represented by the following formula (I). Formula (I)

[0009]

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(Wherein M ¹ and M ² represent a hydrogen atom or a cation; L represents a divalent linking group containing an alkylene group and / or an arylene group.) (2) An amino acid compound and a compound represented by the following formula ( The method for producing an aziridine compound according to (1), wherein the method is reacted with a compound represented by (III) or (IV).

[0011]

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(Wherein X and X ′ each represent a leaving group;
M ¹ has the same meaning as described above. ). The aziridine compound represented by the formula (I) described in the item (1) is reacted as it is with an amino compound R-NH ₂ (wherein R represents an alkyl group, an aryl group or a heterocyclic group) to obtain the following. It can be a compound represented by the formula (II). Formula (II)

[0013]

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(Wherein, M ¹ and M ² represent a hydrogen atom or a cation; R represents an alkyl group, an aryl group, or a heterocyclic group; L represents a divalent linkage containing an alkylene group and / or an arylene group) In the aziridine compound of the present invention, a carboxy-substituted alkyl is substituted on the nitrogen atom of the aziridine ring, and both the carboxyl group and the carboxyl group on the aziridine are not modified with a protecting group. It is characterized by being in the form of a hydrogen atom or a cation. Thereby, it can be easily dissolved in water and used as it is for the next reaction.

[0015]

Next, the aziridine compound of the present invention will be described in detail. The alkylene group represented by L in the formula (I) may be linear, branched or cyclic, and is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, more preferably 1-5 carbon atoms
And most preferably a linear alkylene group having 1 to 5 carbon atoms. For example, methylene, ethylene, n-propylene, n-butylene. In the present invention, the alkylene group or the arylene group represented by L includes those having a substituent. Accordingly, the alkylene group may have a substituent, and examples of the substituent include an aryl group (a phenyl group and a naphthyl group, preferably a phenyl group. The phenyl group further has a substituent. A heterocyclic group (eg, 2-pyridyl, 3-pyridyl, 4-pyridyl, 4-
Imidazolyl, 2-imidazolyl, 3-pyrazolyl, 4
-Pyrazolyl, 2-thiazolyl, 4-thiazolyl, 2-
Furyl, 3-furyl, 2-thienyl, 3-thienyl, 2
-Pyrrolyl, 3-pyrrolyl, 2-oxazolyl, 4-oxazolyl, 2-pyrazinyl, 2-pyrrolidinyl, 2-
Indolyl, 3-indazonyl, 2-quinolyl, 8-quinolyl, piperidino, morpholino, 2-piperidyl, 2
-Morpholinyl, 3-indazolyl, 2-purinyl, 6
-Purinyl, 2- (1,3,4-thiazolyl), 2-
(1,3,4-oxadiazolyl), 1-phthalazyl,
2-quinoxalinyl, 5-quinoxalinyl, 2-quinazolinyl, 4-quinazolinyl, 8-quinazolinyl, 3-cinnolinyl, 8-cinnolinyl, 2- (1,10-phenanthrolinyl), and 5-tetrazolyl. Preferably, 2-pyridyl, 4-imidazolyl, 2-imidazolyl, 3-pyrazolyl, 2-thiazolyl, 2-pyrrolyl,
2-oxazolyl, 4-oxazolyl, 2-pyrazinyl, 2-pyrrolidinyl, 2-indolyl, 3-indazonyl, 2-quinolyl, 8-quinolyl, piperidino, 2-
Piperidyl, 2-indolyl, 3-indazolyl, 2-
(1,3,4-thiazolyl) and 2- (1,3,4-oxadiazolyl), more preferably 4-imidazolyl, 2-imidazolyl and 2-pyridyl. These heterocyclic groups may further have a substituent. ), Carboxyl group, alkoxy group (alkoxy group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4. For example, methoxy,
It is ethoxy. ), A sulfo group, a nitro group, a phosphono group, a hydroxamic acid group, a hydroxy group, an aryloxy group (preferably having 6 to 12 carbon atoms, more preferably having 6 to 10 carbon atoms, and particularly preferably having 6 to 8 carbon atoms. is there.
An example is phenyloxy. ), A sulfamoyl group (preferably having 0 to 10 carbon atoms, more preferably having 0 to 6 carbon atoms, and particularly preferably having 0 to 4 carbon atoms.
It is. For example, sulfamoyl and methylsulfamoyl can be mentioned. ), A carbamoyl group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms, and particularly preferably having 1 to 4 carbon atoms, such as carbamoyl and methylcarbamoyl), and alkylthio. Group (an alkylthio group preferably has 1 to
8, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms. For example, methylthio and ethylthio are mentioned. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 1 carbon atoms)
And particularly preferably 6 to 8 carbon atoms. An example is phenylthio. ), A mercapto group, an acyl group (preferably having 2 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms, and particularly preferably having 2 to 4 carbon atoms. Examples include acetyl and benzoyl.) ,
An acylamino group (preferably having 1 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms, and particularly preferably having 2 to 4 carbon atoms, for example, acetylamino), a sulfonylamino group (preferably Is carbon number 1 to 1
0, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms. An example is methanesulfonylamino. ), An amino group (preferably having 0 to 20 carbon atoms, more preferably having 0 to 10 carbon atoms, and particularly preferably having 0 to 6. Examples include amino, methylamino, ethylamino, dimethylamino, and diethylamino. )). Preferred are an aryl group, a heterocyclic group, and a carboxyl group, and more preferred is a carboxyl group.

The arylene group represented by L in the formula (I) includes o-phenylene, m-phenylene, p-phenylene and the like. Preferred are o-phenylene and p-phenylene, and more preferred is o-phenylene. These arylene groups may have a substituent, and as the substituent, those mentioned as the substituent which the alkylene group represented by L may have can be applied. L may simultaneously contain an alkylene group and an arylene group, but preferably contains only an alkylene group. The structure of NL-CO ₂ M ² containing N of an aziridine skeleton preferably has a structure synthesized from a compound called a so-called amino acid, and more preferably a natural amino acid (eg, glycine, L- Alanine, L-valine, L-leucine, L-isoleucine, L-tyrosine, L-histidine, L-tryptophan, L-serine, L-threonine, L-methionine, L-aspartic acid, L-glutamic acid, L-phenylalanine ) Having a structure. The cation represented by M ¹ and M ² may be an organic cation or an inorganic cation. When two or more cations exist in one molecule, they may be different cations. As cations, for example, ammonium (eg, ammonium, tetraethylammonium), alkali metal (eg, lithium, sodium,
Potassium), alkaline earth metals (eg, calcium, magnesium, barium), pyridinium and the like. It is preferably an inorganic cation, and more preferably an alkali metal. M ¹ and M ² are more preferably cations than hydrogen atoms from the viewpoint of the stability of the compound. Specific examples of the compound represented by the formula (I) of the present invention include the following compounds, but are not limited thereto.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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Next, the method for producing the compound represented by the formula (I) will be described in detail. The compounds of formula (I) of the present invention
As shown in Scheme 1, it can be obtained by reacting an amino acid compound of formula (V) (a compound having an amino group and a carboxyl group) with a propionic acid derivative (formula (III)). It can also be obtained by reacting a compound of formula (V) with an acrylic acid derivative (formula (IV)) as in scheme 2. The compound represented by the formula (V), the propionic acid derivative and the acrylic acid derivative are known compounds, can be easily synthesized, and are also commercially available compounds. Scheme 1

[0025]

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(In the scheme, L, M ¹ and M ² each have the same meaning as that of formula (I). X and X ′ are each a leaving group (for example, a halogen atom (for example, a fluorine atom, a chlorine atom, A bromine atom, an iodine atom) and a sulfonate group (for example, a methylsulfonate group and a p-toluenesulfonate group).) Scheme 2

[0027]

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(In the scheme, L, M ¹ and M ² have the same meanings as those of the formula (I). X ′ is a leaving group such as a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, Iodine atom) and a sulfonate group (for example, a methylsulfonate group and a p-toluenesulfonate group).) The solvent used in the reactions of Schemes 1 and 2 is not particularly limited as long as it does not participate in the reaction, but water Use of an alcohol (eg, methanol, ethanol, 2-propanol, butanol, etc.) advantageously proceeds. From the viewpoint of increasing the solubility of the reaction product and suppressing by-products, the solvent is preferably a water-containing solvent, and more preferably water alone. This reaction is usually carried out at -20 to 100 ° C.
Preferably, the reaction is carried out at a temperature of not more than ℃. More preferably,
0-50 ° C. The reaction is preferably performed in the presence of a base, and examples of the base include alkalis (such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate) and tertiary amines (such as triethylamine). When water is used as the solvent, the reaction conditions are pH 6
To 14, more preferably pH 7 to 13, and particularly preferably pH 8 to 12.

The amount of the propionic acid derivative or acrylic acid derivative (formula (III) or (IV)) to be used is preferably 0.1 to 10 mol, more preferably 0.4 to 2 mol, per mol of compound (V). Mole, more preferably 0.1 mole.
It is 5-1.5 times mol. The raw materials may be added in any order. However, if heat is generated by the neutralization, the compound (V) is first neutralized with a base, and then the propionic acid derivative is added.
It is preferable to combine with (III) or the acrylic acid derivative (IV). Next, the production method of the formula (II) using the aziridine compound represented by the formula (I) and the amine compound as raw materials will be described in detail. Formula (II) is synthesized as in Scheme 3. Scheme 3

[0030]

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(In the scheme, L, M ¹ and M ² have the same meanings as those of the formula (I). R has the same meaning as that of the formula (II).) As an alkyl group represented by R Is a linear, branched or cyclic alkyl group, preferably having 1 to 1 carbon atoms.
It is a linear or branched alkyl group having 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and most preferably a linear alkyl group having 1 to 5 carbon atoms. For example, methyl, ethyl, propyl, butyl. Further, the alkyl group represented by R may have a substituent, and examples of the substituent include those exemplified as the substituent which the alkylene group represented by L in the formula (I) may have. it can. The aryl group represented by R may be a single ring or may form a condensed ring with another ring, and preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and still more preferably Aryl groups of the formulas 6 to 12. The aryl group represented by R is preferably monocyclic or bicyclic, and includes, for example, phenyl and naphthyl, and more preferably phenyl. The aryl group represented by R may have a substituent. As the substituent, for example, those mentioned as the substituents that the alkylene group represented by L in formula (I) may have can be applied. .

The heterocyclic group represented by R is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O and S atoms, and these may be monocyclic. Alternatively, a condensed ring may be formed with another ring. The hetero ring is preferably a 5- or 6-membered aromatic hetero ring, and more preferably a 5- or 6-membered aromatic hetero ring containing 1 or 2 nitrogen atoms. As specific examples of the heterocyclic ring, the specific examples of the heterocyclic group described as the substituent which the alkylene group represented by L in formula (I) may have can be applied. R is preferably an alkyl group or an aryl group, and more preferably an alkyl group. In addition, one N of the diamine skeleton in the formula (II)
It is preferable that the structure of RN containing the compound has a structure synthesized from a compound called a so-called amino acid, and more preferably a natural amino acid (eg, glycine, L-alanine, L-valine, L-leucine). , L
-Isoleucine, L-tyrosine, L-histidine, L-
Tryptophan, L-serine, L-threonine, L-methionine, L-aspartic acid, L-glutamic acid, L
-Phenylalanine) structure. That is, among the compounds represented by the formula (II), more preferred are the compounds represented by the following formula (VI). Equation (VI)

[0033]

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(Wherein L, M ¹ and M ² have the same meanings as those of the formula (II), and the preferred ranges are also the same. L ₂ has the same meaning as L in the formula (II), preferred ranges are also the same .M ³ has the same meaning as M ¹ and M ² in formula (II), preferable ranges are also the same.) Examples of the solvent to be used here, particularly limited as long as it does not participate in the reaction However, the use of water, alcohol (eg, methanol, ethanol, 2-propanol, butanol, etc.) advantageously proceeds. Preferred is a solvent containing water, and more preferred is water alone. This reaction is preferably performed at 0 to 150 ° C, more preferably 50 to 13 ° C.
It is 0 degreeC, More preferably, it is 70-120 degreeC.

The reaction is preferably carried out in the presence of a base. The base may be an alkali (such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) or 3 bases.
Secondary amine (such as triethylamine). Preferably, sodium hydroxide or potassium hydroxide,
More preferably, it is sodium hydroxide. When water is used as the solvent, the reaction condition is preferably pH 6 to 14, more preferably pH 7 to 13, and particularly preferably pH 8 to 12. The amount of the amine compound added is
It is preferably 0.5 to 5 moles, more preferably 0.8 to 3 moles, and still more preferably 0.9 to 2 moles of the aziridine compound. Wherein the compound of formula (V) used for the synthesis of _{(I) (H 2 N-} L-CO 2 M 2) and formula (II)
When the amine compounds (R-NH ₂ ) to be reacted are different, it is preferable to add each amine compound in each step of the reaction. However, in the case of the same amine compound, the entire amount of the amine compound used for the reaction may be added at one time during the synthesis of the aziridine compound (initial stage). Hereinafter, specific examples produced by the above production method will be described, but the present invention is not limited thereto.

[0036]

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[0037]

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[0038]

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[0039]

Next, the present invention will be described in more detail with reference to examples. Example 1 (Synthesis of Compound Represented by Formula (I)) Synthesis Example 1 (Synthesis of Compound 1) 25 g (0.33 mol) of glycine and 150 ml of water were added to a three-necked flask, and the mixture was placed in an ice bath while stirring well. 50
53.2 g of a 5% aqueous sodium hydroxide solution were added. After complete dissolution, 77 g (0.33 mol) of 2,3-dibromopropionic acid was gradually added while maintaining the temperature at 30 ° C. or lower. The ice bath was removed, the temperature was returned to room temperature, and the mixture was stirred overnight. ¹ H
After confirming the production of the target aziridine compound (compound 1) by nuclear magnetic resonance spectroscopy, the target sodium salt was obtained by desalting by electrodialysis and concentration under reduced pressure.
Melts gradually from around 100 ° C due to glassy powder. Exact yields are not required. 96% crude yield.

¹ H NMR (D ₂ O + NaOD, internal standard DSS) δ 1.67 (d 1H) δ 2.00-2.15 (m 2H) δ 2.75 (d 1H) δ 3.20 (d 1H)

Synthesis Example 2 (Synthesis of Compound 2) L-alanine (50 g, 0.56 mol) was placed in a three-necked flask.
And 100 ml of water, and the mixture was placed in an ice bath with good stirring, and 112.2 g of a 50% aqueous sodium hydroxide solution was added. After complete dissolution, keep the temperature at
65.1 g (0.28 mol) of dibromopropionic acid was slowly added. The ice bath was removed, the temperature was returned to room temperature, and the mixture was stirred for 2 nights. After confirming the formation of the target aziridine compound (compound 2) by ¹ H nuclear magnetic resonance spectroscopy, the product was desalted by electrodialysis and concentrated under reduced pressure to obtain the target sodium salt. Melts gradually from around 100 ° C due to glassy powder. Exact yields are not required. Crude yield 88%. ¹ H NMR (D ₂ O + NaOD, internal standard DSS) δ 1.28 (t 3H) δ 1.63 (d 1H) δ 1.90-2.20 (m 3H)

Synthesis Example 3 (Synthesis of Compound 4) 57.4 g of aspartic acid (0.42 m
ol) and 100 ml of water, and the mixture was placed in an ice bath with good stirring, and 120.8 g of a 50% aqueous sodium hydroxide solution was added. After complete dissolution, while keeping the temperature below 30 ° C,
3-dibromopropionic acid 50 g (0.216 mol)
Was slowly added. The ice bath was removed, the temperature was returned to room temperature, and the mixture was stirred for 3 nights. After confirming the formation of the target aziridine compound (compound 4) by ¹ H nuclear magnetic resonance spectroscopy, the product was desalted by electrodialysis and concentrated under reduced pressure to obtain the target sodium salt. Melts gradually from around 100 ° C due to glassy powder. Exact yields are not required. Crude yield 91
%. ¹ H NMR (D ₂ O + NaOD, internal standard DSS) δ 1.71 (dd1H) δ 1.93 (dd1H) δ 2.05-2.18 (m 1H) δ 2.39-2.65 (m 3H)

Synthesis Example 4 (Synthesis of Compound 9) 50 g (0.56 mol) of β-alanine was placed in a three-necked flask.
And 100 ml of water, and the mixture was placed in an ice bath with good stirring, and 112.2 g of a 50% aqueous sodium hydroxide solution was added. After complete dissolution, keep the temperature at
65 g (0.28 mol) of dibromopropionic acid were slowly added. The ice bath was removed, the temperature was returned to room temperature, and the mixture was stirred overnight. After confirming the formation of the target aziridine compound (compound 9) by ¹ H nuclear magnetic resonance spectroscopy, the product was desalted by electrodialysis and concentrated under reduced pressure to obtain the target sodium salt. Melts gradually from around 100 ° C due to glassy powder. Exact yields are not required. 91% crude yield. ¹ H NMR (D ₂ O + NaOD, internal DSS) δ 1.65 (d 1H) δ 1.93 (d 1H) δ 2.05 (t 1H) δ 2.35-2.70 (m 4H)

Synthesis Example 5 (Synthesis of Compound 11) 30 g of L-phenylalanine (0.18
2 mol) and 100 ml of water, and the mixture was placed in an ice bath with good stirring, and 72.6 g of a 50% aqueous sodium hydroxide solution was added. After complete melting, keeping the temperature below 20 ° C,
42.1 g (0.182) of 2,3-dibromopropionic acid
mol) was slowly added. The ice bath was removed, the temperature was returned to room temperature, and the mixture was stirred for 3 nights. After confirming the formation of the target aziridine compound (compound 11) by ¹ H nuclear magnetic resonance spectroscopy, the product was desalted by electrodialysis and concentrated under reduced pressure to obtain the sodium salt of the target product. Melts gradually from around 120 ° C due to glassy powder. Exact yields are not required. Crude yield 99%. ¹ H NMR (D ₂ O + NaOD, internal standard DSS) δ1.45-2.10 (m 3H) δ 2.32 (dd1H) δ 2.78-3.15 (m 2H) δ 7.20-7.40 (m 5H) )

Reference Example 1 (Synthesis of Compound represented by Formula (II)) Synthesis Example 6 (Synthesis of Compound II-1) 50 g (0.67 mol) of glycine and 150 ml of water were added to a three-necked flask and stirred well. 50 in an ice bath
53.2 g of a 5% aqueous sodium hydroxide solution were added. After complete dissolution, 77 g (0.33 mol) of 2,3-dibromopropionic acid was gradually added while maintaining the temperature at 30 ° C. or lower. The ice bath was removed, the temperature was returned to room temperature, and the mixture was stirred overnight. ¹ H
After confirming the formation of the aziridine compound (compound 1) by nuclear magnetic resonance spectroscopy, the reactor was placed in an oil bath and heated under reflux for 8 hours. After cooling to room temperature, the pH was adjusted to 2 by adding concentrated hydrochloric acid. The precipitated crystals were collected by filtration and dried by heating. 62 g of the desired compound II-1 was obtained. Yield 84%. mp 191-2 ° C. (decomposition) ¹ H NMR (D ₂ O + NaOD, internal standard DSS) δ 2.72 (m 2 H) δ 3.08-3.30 (m 5 H)

Comparative Synthesis Example (Comparative Example of Synthesis Example 6; Synthesis of Compound II-1 Using Compound B) In a three-necked flask, 5-cyano-1-aziridine acetic acid ethyl ester (Compound B) 50.9 g (0. 33 mol),
Glycine 24.8 g (0.33 mol) and water 150 ml
Was added, and 105.6 g of a 50% aqueous sodium hydroxide solution was added with good stirring. The reactor was placed in an oil bath and heated at reflux for 8 hours. After cooling to room temperature, the pH was adjusted to 2 by adding concentrated hydrochloric acid. After standing overnight, the precipitated crystals were collected by filtration and dried by heating. Desired compound II-1 was 10.2
g was obtained. Yield 14%. -Synthesis example 7 (synthesis of compound II-6) 50 g of L-alanine (0.56 mo
l) and 100 ml of water were added, and the mixture was placed in an ice bath while stirring well, and 112.2 g of a 50% aqueous sodium hydroxide solution was added. After complete dissolution, keep the temperature below 30 ° C and
-Dibromopropionic acid 65.1 g (0.28 mol)
Was slowly added. The ice bath was removed, the temperature was returned to room temperature, and the mixture was stirred for 2 nights. After confirming the formation of the aziridine compound (compound 2) by ¹ H nuclear magnetic resonance spectroscopy, the reactor was placed in an oil bath and heated at 90 ° C. for 8 hours. After cooling to room temperature, the pH was adjusted to 2 by adding concentrated hydrochloric acid. Desalting was performed by electrodialysis, and crystals precipitated during the process were collected by filtration and dried by heating.
70 g of the desired compound II-6 was obtained. Yield 93%. mp 170 ° C.-gradual decomposition NMR (D ₂ O + NaOD, internal standard DSS) δ 1.10-1.35 (m 6H) δ 2.55-2.75 (m 2H) δ 3.05-3.25 (m 3H) Elemental analysis value: C ₉ H ₁₆ N ₂ O ₆ .H ₂ O = 266.25, calculated HCN: 6.81 40.60 10.52 Actual value: 6.70 40.75 10.63

Synthesis Example 8 (Synthesis of Compound II-14) Aspartic acid 57.4 g (0.42 m
ol) and 100 ml of water, and the mixture was placed in an ice bath with good stirring, and 120.8 g of a 50% aqueous sodium hydroxide solution was added. After complete dissolution, while keeping the temperature below 30 ° C,
50 g (0.216 mol) of 3-dibromopropionic acid
Was slowly added. The ice bath was removed, the temperature was returned to room temperature, and the mixture was stirred for 3 nights. After confirming the formation of the aziridine compound (compound 4) by ¹ H nuclear magnetic resonance spectroscopy, the reactor was placed in an oil bath and heated under reflux for 15 hours. After cooling to room temperature, the pH was adjusted to 2 by adding concentrated hydrochloric acid. After desalting by electrodialysis, the crystals precipitated by concentration under reduced pressure were collected by filtration,
Heat and dry. 66 g of the desired compound II-14 was obtained. Yield 91%. mp 115-7 ° C (decomposition) NMR (D ₂ O + NaOD, internal standard DSS) δ 2.28-2.60 (m 4H) δ 2.60-2.78 (m 2H) δ 3.15 (t 1H) δ 3.35 (T 1H) δ 3.40 (t 1H) Elemental analysis value C ₁₁ H ₁₅ N ₂ O ₁₀ .2H ₂ O = 371.28, calculated H CN 5.16 35.59 7.55 Actual value 5.09 35.66 7.73

Synthesis Example 9 (Synthesis of Compound II-18) 50 g (0.56 mol) of β-alanine was placed in a three-necked flask.
And 100 ml of water, and the mixture was placed in an ice bath with good stirring, and 112.2 g of a 50% aqueous sodium hydroxide solution was added. After complete dissolution, keep the temperature at
65 g (0.28 mol) of dibromopropionic acid were slowly added. The ice bath was removed, the temperature was returned to room temperature, and the mixture was stirred overnight. After confirming the formation of the aziridine compound (compound 9) by ¹ H nuclear magnetic resonance spectroscopy, the reactor was placed in an oil bath and
The mixture was heated to reflux for 0 hour. After cooling to room temperature, the pH was adjusted to 2 by adding concentrated hydrochloric acid. After desalting by electrodialysis, the precipitated crystals were collected by filtration and dried by heating. Target compound II-1
8 was obtained in an amount of 62 g. Yield 88%. NMR (D ₂ O + NaOD, internal standard DSS) δ 2.40 (t 4H) δ 2.55-2.90 (m 6H) δ 3.20 (t 1H)

Synthesis Example 10 (Synthesis of Compound II-7) 50 g (0.67 mol) of glycine and 100 ml of water were added to a three-necked flask, and the mixture was placed in an ice bath while stirring well.
53.2 g of a 5% aqueous sodium hydroxide solution were added. After complete dissolution, 162 g (0.70 mol) of 2,3-dibromopropionic acid was gradually added while maintaining the temperature at 30 ° C. or lower. A 50% aqueous sodium hydroxide solution 15
9.6 g was added, the ice bath was removed, and the mixture was returned to room temperature and stirred overnight. Further, after confirming the formation of an aziridine compound (compound 1) by ¹ H nuclear magnetic resonance spectroscopy, the solution was divided into three equal parts, and one of them was placed in a three-necked flask. In this solution,
20 g (0.22 mol) of L-alanine and 18 g of a 50% aqueous sodium hydroxide solution were added, and the reactor was placed in an oil bath and heated under reflux for 8 hours. After cooling to room temperature, the pH was adjusted to 2 by adding concentrated hydrochloric acid. After desalting by electrodialysis,
The precipitated crystals were collected by filtration and dried by heating. Target compound II
47 g of -7 were obtained. Yield 83%. mp 200-1 ° C. (decomposition) NMR (D ₂ O + NaOD, internal standard DSS) δ 1.20 (d 3H) δ 2.55-2.80 (m 2H) δ 3.00-3.30 (m 4H)

[0050]

The aziridine compound represented by the formula (I) of the present invention is useful as an intermediate which can be reacted with an amine compound to produce a diamine compound represented by the formula (II) by a ring opening reaction. It is. The diamine compound (formula (II)) is used in medical, cosmetic preparations, soaps, detergents, cleaning compositions, material analysis, coating on metal materials, plating, as described in JP-A-7-199433. It can be used for compounds (for example, chelating agents) used in the field of, for example, catalysts, colloid chemistry, photography (for example, developing solutions and bleaching solutions), and liquid crystal fields. For photographic purposes, in addition to chelating agents, they can be used as bleaching agents, reducers, etc. as Fe complex salts.
The step of synthesizing the aziridine compound represented by the formula (I) from these amino acids and further synthesizing the diamine compound represented by the formula (II) is short, the elimination of the protecting group and the simple production of an intermediate product. It can be performed by a simplified operation in an integrated process without requiring separation or the like.

Claims (2)

[Claims] 1. An aziridine compound represented by the following formula (I). Formula (I) (In the formula, M ¹ and M ² represent a hydrogen atom or a cation. L represents a divalent linking group containing an alkylene group and / or an arylene group.) 2. The method for producing an aziridine compound according to claim 1, wherein the amino acid compound is reacted with a compound represented by the following formula (III) or (IV). Embedded image (Wherein X and X ′ represent a leaving group, and M ¹ has the same meaning as described above.)