JP2000072743A - Aziridination of alkenes - Google Patents

Abstract

(57) [Problem] To provide a simple and high-yield method for producing an aziridine ring. The present invention provides a method for producing a compound having an aziridine ring by reacting a compound having a carbon-carbon double bond with an N-halogeno-sulfonic acid amide-N-metal salt in the presence of iodine. About.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound having a carbon-carbon double bond and an N-halogeno-sulfonic acid amide.
The present invention relates to a method for producing a compound having an aziridine ring by reacting an N-metal salt, preferably chloramine T, in the presence of iodine. According to the method of the present invention, an aziridine derivative useful as a synthetic intermediate for various medicines and agricultural chemicals can be easily and efficiently produced.

[0002]

2. Description of the Related Art Heterocyclic compounds exist widely in nature,
Many are related to various biological activities of living things. It is also important as a basic skeleton of functional materials, and its synthesis has been vigorously researched and developed for many years. Aziridine is one of the heterocyclic compounds having a minimum ring structure. Aziridine itself (ethyleneimine) is a raw material of polyethyleneimine useful as a paper strength enhancer or a cellulosic fiber modifying agent, and aziridine-2,3-dicarboxylic acid is a compound having antibacterial activity. Also known as Further, an aziridine derivative is a compound useful as an intermediate for synthesizing important natural products such as alkaloids, amino acids, β-lactam antibiotics or biologically active substances by ring opening reaction or ring expansion.

As a method for synthesizing an aziridine ring, there is a cyclization reaction of primary or secondary amines having a substituent capable of leaving at the β-position. As an example, a method of synthesizing β-chloroamide by reacting styrene with N, N-dichloroamide as shown by the following reaction formula and synthesizing an aziridine ring by intramolecular cyclization using a base is known. Known (Seden, TP, et al., J. Chem. Soc., 876-878 (196
8)).

[0004]

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Further, as shown by the following reaction formula, an aziridine ring is produced from PhI = NTs ((N- (p-tolylsulfonyl) imino) phenyliodinane) and alkenes using a copper catalyst. Methods have also been reported (Evans, DA, et al., J. Am. Chem. Soc., 116, 2724-2753.
(1994)).

[0006]

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However, PhI = NTs used in this reaction
Is synthesized from diacetoxyiodobenzene and tosylamide, but diacetoxyiodobenzene is an expensive reagent, and the synthesized PhI = NTs are unstable in water and are difficult to handle. On the other hand, as a method of synthesizing an aziridine ring using chloramine T as a nitrogen source, a method of cyclization followed by aminohydroxylation of alkene using chloramine T and osmium catalyst as shown in the following reaction formula has been reported. (Shar
pless, KB, et al., Angew.Chem.Int.Ed.Engl., 36,2637-
2640 (1997)).

[0008]

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However, this method requires a two-step reaction process, is not simple, and uses a special catalyst called osmium, and is not an industrial production method. As a method using chloramine T as a nitrogen source, a method for producing an aziridine ring in one step from chloramine T and alkenes using a copper catalyst as shown by the following reaction formula has been reported (Komatsu, M., et a
l., Tetrahedron Lett., 39, 309-312 (1998)).

[0010]

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This method is very excellent in synthetic chemistry because chloramine T, which is inexpensive and easy to handle, serves as a nitrogen source for the aziridine ring and can be produced in one step.
The yield was not good. Aziridine derivatives are important as various industrial raw materials, but their production is not easy due to the special chemical structure of a three-membered ring containing a nitrogen atom, and an inexpensive and simple industrial production method is required. Had been.

[0012]

SUMMARY OF THE INVENTION The present invention provides a simple and high-yield process for producing an aziridine ring. The present inventors have been studying the improvement of the yield of the method for producing an aziridine ring by a one-step reaction in the presence of a copper catalyst using chloramine T as a nitrogen source as described above. The inventors have found that a remarkable improvement in yield has been found, and have completed the present invention.

[0013]

The present invention provides a compound having an aziridine ring by reacting a compound having a carbon-carbon double bond with an N-halogeno-sulfonic acid amide-N-metal salt in the presence of iodine. The present invention relates to a method for producing a compound. More specifically, the present invention relates to a method for producing aziridine or a derivative thereof using N-halogeno-sulfonic acid amide-N-metal salt, preferably chloramine T as a nitrogen source,
The present invention relates to a method for producing a compound having an aziridine ring, characterized by reacting in the presence of iodine.

The N-halogeno-sulfonic acid amide-N-metal salt used as the nitrogen source of the present invention is characterized in that the halogen atom is bonded to the nitrogen atom of the organic sulfonic acid amide and the other bond of the nitrogen atom. Is bonded to a metal atom to form a metal salt, and preferably has the following general formula (I):

[0015]

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(Wherein, R represents an organic group, X represents a halogen atom, and M represents a metal atom). R in the general formula (I) may be any organic group capable of forming an organic sulfonic acid amide, and preferred organic groups are those having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms. A monocyclic, polycyclic or condensed cyclic aryl group having at least one nitrogen atom, oxygen atom or sulfur atom in the ring, and having a ring size of 5 to 20 members, preferably 5 to 20 members A 10-membered, more preferably 5-7-membered, monocyclic, polycyclic or condensed-ring heterocyclic group which may be fused with a cycloalkyl group, a cycloalkenyl group or an aryl group, having 1 to 30 carbon atoms And preferably 1 to 20, more preferably 1 to 10 linear or branched alkyl groups. These aryl group, heterocyclic group or alkyl group may be substituted with the above-mentioned alkyl group, an alkoxy group formed from the above-mentioned alkyl group, a halogen atom, or the like.

As the halogen atom in the general formula (I),
What is necessary is just to function as a leaving group, and a chlorine atom or a bromine atom is preferable.

The metal atom in the general formula (I) may be any as long as it forms a salt with the nitrogen atom of the organic sulfonic acid amide, and is preferably an alkali metal, more preferably sodium or potassium.

Preferred N-halogeno-sulfonic amide-N-metal salts include those derived from aromatic sulfonic acids or aliphatic sulfonic acids, and more specifically, for example, chloramine T (N- Chloro-p-toluenesulfonic acid amide-N-sodium salt), N-chloro-
Benzenesulfonic acid amide-N-sodium salt, N-chloro-methanesulfonic acid amide-N-sodium salt and the like can be mentioned.

One of the starting compounds of the present invention, carbon-
The compound having a carbon double bond may be any compound having a carbon-carbon double bond that does not form an aromatic π-electron system, and may be a chain compound or a compound that forms part of a ring. You may. These compounds having a carbon-carbon double bond may have a functional group that does not adversely affect the reaction of the present invention, for example, a compound having a substituent such as an alkoxycarbonyl group or an alkoxy group. In the case where the compound has a functional group that adversely affects the reaction of the present invention, such a functional group may be protected by a suitable protecting group during the reaction.

The method of the present invention when chloramine T is used as the N-halogeno-sulfonic acid amide-N-metal salt of the present invention is represented by the following reaction formula.

[0022]

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(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic residue.) Thus, the method of the present invention comprises a carbon-carbon double bond The present invention provides a versatile method for introducing an aziridine ring at the position of the carbon-carbon double bond using a compound having the following formula: Preferred examples of the compound having a carbon-carbon double bond include, for example, styrene, E-β-methylstyrene, Z-β-methylstyrene, p-nitrostyrene, p-chlorostyrene, p-methylstyrene, Substituted styrenes such as p-methoxystyrene, cycloalkenes such as dihydronaphthalene and cyclohexene, 1-octene, E-2-octene, Z-2
Linear or branched alkenes such as -octene and 2-methyl-2-heptene;

The process of the present invention is preferably performed in the presence of an organic solvent. As the organic solvent, a water-soluble organic solvent is preferable, and acetonitrile is more preferable. The above-mentioned organic solvents can be used alone or as a mixture of two or more water-soluble organic solvents. In the method of the present invention, only the above-mentioned organic solvent can be used, but a mixed solvent system of an organic solvent and water can be used in consideration of the solubility of the raw material compound and the catalyst. The water in the solvent system may be a single water, but it is preferable to use a buffer to reduce the change in pH during the reaction. The buffer used may be any of an acidic buffer, a neutral buffer and a basic buffer, but a neutral buffer is generally preferred.

The amount of the compound having a carbon-carbon double bond to be used in the method of the present invention is 1 equivalent or more, preferably 1.5 equivalent or more, based on N-halogeno-sulfonic acid amide-N-metal salt. It is preferred to use 2 equivalents. The amount of iodine to be present in the reaction system is 1 to 50 mol%, preferably 5 to 30 mol%, more preferably 10 to 20 mol% based on the N-halogeno-sulfonic acid amide-N-metal salt. .

The reaction temperature can be selected from the range of 0 to the boiling point of the solvent, but the reaction at around room temperature is economically preferable.

The present inventors have studied the reaction conditions of the method of the present invention in further detail. These results will be described below, but the following description is for describing the method of the present invention in more detail and concretely, and even if the method of the present invention is subject to any limitation by these descriptions. Absent.

(1) Solvent In order to examine the influence of the solvent, styrene (2 equivalents) and chloramine T (1 equivalent) were used at room temperature in the presence of iodine (10 mol%) using styrene (2 equivalents) as a substrate. Tried. Acetonitrile has been found to be an effective solvent in the recently reported aziridination of chloramine T with alkenes using a copper catalyst (3). Since chloramine T 2 has low solubility in non-polar solvents, the reaction conditions were optimized mainly for acetonitrile, and other organic solvents were also slightly studied. Further, the number of equivalents of styrene and iodine to chloramine T was also examined.

The effect of the solvent of the reaction system on the yield and reactivity was examined. The results are shown in Table 1 below.
Shown in

[0030]

[Table 1]

The structure of the product was confirmed by the fact that its ¹ H-NMR spectrum agreed with the literature value. A clear difference was observed in the yield between the case where only acetonitrile was used as the solvent and the case where a one-to-one mixed solution with a neutral buffer was used (Experiment Nos. 1 and 2). This is considered to be due to the fact that chloramine T is hardly soluble in acetonitrile, resulting in a non-uniform reaction system. It is considered that the solubility of chloramine T is greatly involved in the reaction.

Next, when the pH of the buffer was searched for acidity and basicity, a decrease in the yield was observed (Experiment Nos. 2, 3, and 4). FIG. 1 shows the results of tracking the change over time in the reaction yield for each buffer.
When neutral and basic buffers are used, the initial rate does not change much, but the reaction rate using the basic buffer may be slower than that using the neutral buffer after about 30 minutes. understood. Also, it was found that the reaction was considerably slower when an acidic buffer was used than when other buffers were used. When a mixed solution of benzene, ether, methylene chloride and a neutral buffer was used as a solvent other than acetonitrile, the yield was significantly reduced (Experiment Nos. 5, 6, and 7). This is presumably because the reaction system is a complete two-layer system, so that the contact between styrene dissolved in the organic layer and chloramine T dissolved in the aqueous layer is reduced, and the reaction efficiency is considerably reduced. From the above, it can be seen that in this reaction, pH control in the reaction system and homogenization of the reaction system have a great influence on the yield.

(2) Amount of Styrene Up to this point, two equivalents of styrene have been used with respect to chloramine T. Here, however, the effect of the amount on the yield and reactivity was examined. . The results are shown in Table 2 below.

[0034]

[Table 2]

Reducing the number of equivalents of styrene reduced the yield. FIG. 2 shows the change over time of the reaction at each equivalent number, and it was found that both the reaction rate and the final yield decreased when the amount of styrene was reduced.

(3) Amount of Catalyst Up to now, 10 mol% of iodine has been used with respect to chloramine T, but the amount was examined here. FIG. 3 shows that the amount of iodine was 5 mol% to 1 with respect to chloramine T.
The change with time of the yield when the content is set to 00 mol% is shown.

When the amount of the catalyst is 5 mol%, the amount of the catalyst is 10 mol%.
The reaction was much slower than in the case of mol%, and conversely, when the amount of the catalyst was increased to 15, 20 mol%, the initial rate of the reaction was high, but the yield was lower than in the case of 10 mol%. In this case, even if the reaction time is extended, the yield does not change, and it is not considered that the aziridine produced in the reaction system is decomposed. Next, when 50 mol% of iodine was used, the tendency of aziridine to be decomposed was observed, and it was found that when an equal amount of iodine with respect to chloramine T was used, the reduction rate of aziridine was remarkable. When the amount of iodine was increased, the decomposition rate of aziridine was increased, and thus it is considered that an excessive amount of iodine was affecting.

Using the optimal conditions for the styrene aziridination reaction using an iodine catalyst and chloramine T, the aziridination of substrates other than styrene was examined. (4) Stereoselectivity The stereoselectivity in this reaction system was examined using trans (E) and cis (Z) -β-methylstyrene. The results are shown in Table 3 below.

[0039]

[Table 3]

The structure of the product was confirmed by the fact that its ¹ H-NMR spectrum agreed with the literature value. Transformer
When β-methylstyrene was used, the reaction proceeded relatively efficiently, but the product was obtained as a mixture of cis and trans forms. The yield was not good with cis-β-methylstyrene, but stericity was maintained to some extent. Transformer
When β-methylstyrene is used as a substrate, the following is considered as a reason why the steric structure is not retained. 1. Substrate isomerization in the system. 2. Isomerization during the course of the reaction. 3. Isomerization of the product in the system. First, with respect to 1, cis -β- methyl styrene in ^{1 H-NMR} of the reaction mixture could be denied because it not mixed. However, this is presumed to be based on the premise that the reaction rate of the cis form is much lower than that of the trans form. Then, for 3, 3 and 24
After the same time, the same reaction treatment was performed, and as a result, no difference was observed in the ratio of the isomers, which was denied. Therefore,
It is considered to be isomerization in the reaction process of No. 2. For cis-β-methylstyrene, the ¹ H-
Since no by-products were observed from NMR and the substrate remained, it is considered that the reaction simply progressed slowly.

(5) Reactivity of para-substituted styrene The present system was applied to styrenes having a substituent at the para-position, and the yield and reactivity were examined. The results are shown in Table 4 below.

[0042]

[Table 4]

The structure of the product was confirmed by the fact that its ¹ H-NMR spectrum agreed with the literature value. The yield was very low for the nitro-substituted product, and the reaction proceeded at a considerable yield for the chloro- and methyl-substituted products, although not as much as styrene. The reaction was very fast with the methoxy-substituted product, and a yield of 66% was obtained in about one hour. FIG. 4 shows the results of tracking the reaction for these para-substituted styrenes. Compared to styrene, p-methylstyrene was found to have a similar initial rate of reaction, whereas p-chlorostyrene was slightly slower and p-nitrostyrene was much slower. On the other hand, p-methoxystyrene was found to have a very high initial reaction rate. When p-methoxystyrene was used as a substrate, the decomposition of aziridine was observed from about one hour or more.

The initial rate of the reaction differs for each substrate, because the electron donating or withdrawing effect of the para-position substituent affects the stability of the cyclic iodonium ion which is thought to be formed in the system. It is considered something. Further, the details of the decomposition of aziridine when p-methoxystyrene is used as a substrate are not clear because a product in which aziridine has been changed has not been isolated and identified. However, it is considered that one of the causes is that the aziridine ring formed in this case is in an electron-rich state and thus unstable.

From the above, it has been clarified that in the present reaction system, the reaction proceeds at a higher rate in the electron-rich styrene than in the electron-deficient styrene. For those with a slow reaction or low yield, and for the substrate in which the product aziridine is decomposed, optimum conditions may be found by changing the amount of the catalyst, the pH of the solvent, and the like.

Up to this point, the aziridination of an aromatic-substituted alkene has been described. Next, the results of a study of the aziridination of an aliphatic-substituted alkene are shown in Table 5 below.

[0047]

[Table 5]

In Table 5 on the next page, "Method A" is a method in which the reaction was carried out at room temperature for 10 hours using a mixed solvent of acetonitrile and a neutral buffer, and "Method B" was a reaction at room temperature using only acetonitrile as a solvent. This is a method of reacting for 24 hours. When an aliphatic substituted alkene was used, "Method B", that is, the absence of water in the system gave better results. The reaction of an alkene substituted with an aromatic does not always proceed efficiently in "method A".
For example, in Experiment No. 8, the corresponding aziridine could be obtained in a high yield of 84% by "Method B". In systems where stereochemistry is involved as in Experiment Nos. 4, 5, 8, and 9, aliphatic substituted alkene undergoes stereospecific aziridination, whereas aromatic alkene has a stereo structure. It was not retained, and the result that the selectivity was not good especially with trans-β-methylstyrene was obtained.

As described above, this reaction can be applied to various alkenes, and the target aziridine derivative can be obtained efficiently by properly setting the conditions for each substrate.

[0050]

EXAMPLES Next, the method of the present invention will be described specifically with reference to examples, but the method of the present invention is not limited to these examples.

Example 1 General procedure according to "Method A": iodine (25.0 mg, 0.1 mmol, 10 mol%), chloramine-T under nitrogen atmosphere
(282 mg of trihydrate, 1.0 mmol) in an acetonitrile / neutral buffer solution (pH 6.86) (1.5 ml / 1.5 ml) mixed solution,
Alkene (2.0 mmol, 2 equivalents) as a substrate was added, and 25
Stirred at C for 10 hours. The reaction was performed by HPLC (Mightysil R
P-18 GP, eluent: MeOH / H2O = 7/3, flow rate: 1.0
ml / min, l = 254 nm, injection 1.0 ml). After completion of the reaction, methylene chloride (40 ml) was added to the reaction system, washed with water (20 ml × 2), further with a saturated aqueous sodium chloride solution (20 ml), and the organic layer was dried over potassium carbonate. After concentration, column chromatography (silica
The product was isolated and purified by gel, eluent; hexane / ethyl acetate = 8/2). When tracking the reaction using HPLC, use naphthalene (ca.
g) was added.

The buffer used for the solvent was a standard buffer solution (phthalate pH standard solution: Wako Pure Chemical Industries, Ltd.).
pH 4.01, neutral phosphate pH standard solution: pH 6.86, borate pH standard solution: pH 9.18) were used.

Example 2 Using styrene as the substrate alkene, the general procedure described in Example 1 was used to obtain N in the yields given in the above tables.
-(P-Toluenesulfonyl) -2-phenylaziridine was obtained. ¹ H-NMR was consistent with literature values.

As a by-product, a small amount of 2- (N- (p-
Toluenesulfonyl) amino) -1-phenylethanol was obtained. 2- (N- (p-toluenesulfonyl) amino) -1-
Phenylethanol: white crystals, melting point 107-108 ° C; TLC Rf 0.40 (1: 1 hexane: EtOAc); IR (KBr, cm ^-1 ) 3420 (active proton), 131
6, 1142 (S = O);

¹ H NMR (CDCl ₃ , 270 MH
z) δ; 7.73 (d, 2H, J = 8.6 Hz, ArH), 7.37-7.27
(m, 7H, ArH), 4.96 (dd, 1H, J = 7.8, 4.3 Hz, TsNH),
4.80 (ddd, 1H, J = 8.6, 3.8, 3.8 Hz, PhC H OH), 3.25
(ddd, 1H, J = 13.2, 7.8, 3.8 Hz, TsNHC H H), 3.03 (dd
d, 1H, J = 13.2, 8.7, 4.3 Hz, TsNHCH H ), 2.44 (d, 1
H, J = 3.8 Hz, OH), 2.42 (s, 3H, Ar-CH ₃ ); ¹³ C NMR (CDCl ₃ , 68 MHz) δ;
140.7, 136.5, 129.8, 128.6, 128.2, 127.0, 125.8,
72.6,50.1, 21.5; GCMS (CI) 292 (M + +1); HRMS (CI, methane) exact mass calcd for C 15 H 17 NO 3 S (M + H) + 292.1007, found 292.1008.

Elemental analysis; Calculated C ₁₅ H ₁₇ NO ₃ S; C, 61.83; H, 5.88; N, 4.81. Found: C, 61.56; H, 5.77; N, 4.75.

Example 3 General procedure according to "Method B": The solvent was changed from a mixed solution of acetonitrile / neutral buffer solution (pH 6.86) (1.5 ml / 1.5 ml) to acetonitrile (3 ml), and the reaction was carried out for 24 hours. Other than the above, the procedure was the same as in Example 1.

Example 4 Using trans-2-octene as a substrate alkene, the general procedure described in Example 3 was applied to the above-mentioned Table 5.
Trans-N- (p-toluenesulfonyl) -2-methyl-3-pentylaziridine was obtained in the yield described in (1). Trans-N- (p-toluenesulfonyl) -2-methyl-3-pentylaziridine; colorless oil, TLC Rf 0.43 (1: 1 hexane: EtOAc); IR (neat, cm ^-1 ) 1306, 1148 (S = O ); ¹ H NMR (CDCl ₃ , 270 MHz) δ; 7.83 (d, 2H, J = 8.4 Hz, ArH), 7.31 (d, 2H, J = 8.
4 Hz, ArH), 2.68 (m, 2H, CH-aziridine), 2.43 (s, 3
H, Ar-CH ₃ ), 1.60-1.54 (m, 5H, C H ₂ C ₄ H ₉ and CHC H
_{3), 1.26-1.20 (m, 6H} , CHC H 2 C H 2 C H 2 CH 3), 0.83 (t,
3H, J = 6.3 Hz, CH 2 C H 3);

¹³ C NMR (CDCl ₃ , 68 MH
z) δ; 143.7, 138.1, 129.4, 127.3, 49.7, 45.9, 3
1.2, 30.4, 26.8, 22.4,21.5, 14.7, 13.8; GCMS (CI) 282 (M + +1); elemental analysis; _C 15 _H 23 _NO 2 S Calculated; C, 64.02; H, 8.24 ; N, 4.98. Found: C, 63.65; H, 8.15; N, 5.07.

Example 5 Using cis-2-octene as a substrate alkene, the general procedure described in Example 3 was repeated to obtain cis-N- (p-toluenesulfonyl) in the yields shown in Table 5 above. -2-
Methyl-3-pentylaziridine was obtained. Cis-N- (p-toluenesulfonyl) -2-methyl-
3-pentylaziridine; colorless oil, TLC Rf 0.42 (1: 1 hexane: EtOAc); IR (neat, cm ^-1 ) 1320, 1150 (S = O); ¹ H NMR (CDCl ₃ , 270 MHz) δ; 7.82
(d, 2H, J = 8.3 Hz, ArH), 7.32 (d, 2H, J = 8.3 Hz,
ArH), 2.92 (dq, 1H, J = 6.3, 5.0 Hz, CH-aziridin
e), 2.72 (dt, 1H, J = 6.3, 7.3 Hz, CH-aziridine), 2.
44 (s, 3H, Ar- CH 3), 1.44-1.34 (m, 2H, C H 2 C
_{4 H 9), 1.21-1.19 (m} , 9H, CHC H 2 C H 2 C H 2 CH 3 and CH
_{C H 3), 0.82 (t} , 3H, J = 6.4 Hz, CH 2 C H 3);

¹³ C NMR (CDCl ₃ , 68 MH
z) δ; 144.1, 135.6, 129.5, 127.8, 45.2, 40.1, 3
1.3, 26.7, 26.3, 22.4,21.5, 13.8, 12.0; GCMS (CI) 282 (M + +1); elemental analysis; _C 15 _H 23 _NO 2 S Calculated; C, 64.02; H, 8.24 ; N, 4.98. Found: C, 63.83; H, 8.24; N, 5.10.

Example 6 According to the general procedure described in Example 3 using 2-methyl-2-heptene as an alkene substrate,
And N- (p-toluenesulfonyl) -2,
2-Dimethyl-3-butylaziridine was obtained. N- (p-toluenesulfonyl) -2,2-dimethyl-
3-butylaziridine; colorless crystal, melting point 61-63
° C, TLC Rf 0.44 (1: 1 hexane: EtOAc); IR (KBr, cm ^-1 ) 1306, 1142 (S = O); ¹ H NMR (CDCl ₃ , 270 MHz) δ; 7.82
(d, 2H, J = 8.1 Hz, ArH), 7.30 (d, 2H, J = 8.1 Hz,
ArH), 2.84 (dd, 1H, J = 7.6, 5.9 Hz, CH-aziridin
e), 2.43 (s, 3H, Ar-CH ₃ ), 1.71 (s, 3H, CH ₃ -azirid
ine), 1.41-1.13 (m, 9H , C H 2 C H 2 C H 2 CH 3 and CH 3 -a
ziridine), 0.79 (t, 3H , J = 7.1 Hz, CH 2 C H 3);

¹³ C NMR (CDCl ₃ , 68 MH
z) δ; 143.5, 138.4, 129.3, 127.3, 52.8, 51.8, 2
9.4, 27.4, 22.2, 21.5,21.4, 21.2, 13.8; GCMS (CI) 282 (M + +1); elemental analysis; _C 15 _H 23 _NO 2 S Calculated; C, 64.02; H, 8.24 ; N, 4.98. Found: C, 63.74; H, 8.14; N, 5.03.

[0064]

The present invention provides a simple and efficient method for producing an aziridine derivative.

[Brief description of the drawings]

FIG. 1 shows the effect of pH on the method of the present invention.

FIG. 2 shows the influence of the amount of raw material supplied in the method of the present invention.

FIG. 3 shows the effect of the amount of iodine added in the method of the present invention.

FIG. 4 shows the effect of the substituent at the para-position of the raw material in the method of the present invention.

Continuation of the front page (72) Inventor Hikari Yanagi 2-1 Yamadaoka, Suita-shi, Osaka Prefecture F-term (reference) 4H039 CA42 CF10

Claims (5)

[Claims] 1. A compound having a carbon-carbon double bond and N
A method for producing a compound having an aziridine ring by reacting -halogeno-sulfonic acid amide-N-metal salt in the presence of iodine. 2. N-halogeno-sulfonamide-N-
The production method according to claim 1, wherein the metal salt is derived from an aromatic sulfonic acid or an aliphatic sulfonic acid. 3. N-halogeno-sulfonic amide-N-
The method according to claim 2, wherein the metal salt is chloramine T. 4. The method according to claim 1, wherein a water-soluble organic solvent is used as the solvent. 5. The method according to claim 4, wherein the solvent is a mixed solvent of acetonitrile-buffer.