KR102396180B1 - Sulfenamide compound and method for producing the same - Google Patents

Abstract

The present invention relates to a sulfenamide compound and a method for preparing the same, and to a method for synthesizing sulfenamide through S-N bonding of a thiol and an amine using an azo reagent in the absence of a transition metal and/or a halogen reagent. By providing a novel sulfenamide compound that has been difficult to synthesize in the prior art, it can be variously applied to pharmaceuticals and material synthesis.

Description

SULFENAMIDE COMPOUND AND METHOD FOR PRODUCING THE SAME

The present invention relates to a sulfenamide compound and a method for preparing the same. Specifically, a sulfenamide derivative is synthesized through a coupling reaction between a thiol and an amine through a dialkyl azodicarboxylate in the absence of a transition metal and/or a halogen reagent, and it is a synthesis method showing a high yield.

S-N (sulfur-nitrogen) bonding has been applied in various fields such as synthesis, pharmaceutical chemistry, pesticides, and industrial applications. A representative compound having such an S-N bond, sulfonamide, is a sulfenyl-transfer agent such as sulfide, disulfide, and trisulfide, an intermediate of organic compound synthesis, It is used as an anti-radiation agent, polymer polymerization, and vulcanization accelerator in the rubber industry. In particular, sulfenamide derivatives have various biochemical activities, enabling the synthesis of various drug candidates, and thus can be applied to new drug development. In addition, since sulfonamide obtained by oxidizing sulfenamide can be used in pesticides and herbicides, it can be used in various ways to develop new materials.

Such sulfenamide derivatives should selectively induce oxidized sulfur to form a sulfur-nitrogen bond, but since it is difficult to control this, a method for synthesizing sulfenamide is rare. The synthesis of sulfenamides is generally synthesized using expensive transition metal catalysts or using toxic halogenated reagents.

Accordingly, there is a need for a method for preparing sulfenamide without using a transition metal or a halogen reagent.

Korean Patent Publication No. 10-2001-0046567

The present application relates to a sulfenamide compound for solving the problems of the prior art, and by providing a novel sulfenamide compound that was difficult to synthesize in the prior art, it can be variously applied to pharmaceuticals and material synthesis.

In addition, a second object of the present invention is to provide a method for preparing a sulfenamide compound, through a coupling reaction between a thiol and an amine via a dialkyl azodicarboxylate in the absence of a transition metal and/or a halogen reagent. A sulfenamide derivative can be synthesized in high yield. Furthermore, there is an advantage in that the reuse of dialkyl azodicarboxylate and the synthesis of a large scale are possible.

The sulfenamide compound of the present invention for achieving the above technical object provides a compound represented by the following Chemical Formula 1 or Chemical Formula 2.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, R ₁ is an optionally substituted 5-membered unsaturated or aromatic ring, an optionally substituted 6-membered unsaturated or aromatic ring, an optionally substituted 5-membered unsaturated or aromatic hetero ring, and an optionally substituted At least one ring selected from the group consisting of 6-membered unsaturated or aromatic heterocycles, or a polycyclic ring in which two or more rings selected from the group are fused, R ₂ and R ₃ are each independently H, which may be substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, or optionally substituted C ₃ -C ₂₀ ring, A ₁ is optionally substituted 5-membered unsaturated or at least one ring selected from the group consisting of an aromatic ring, an optionally substituted 6-membered unsaturated or aromatic ring, an optionally substituted 5-membered unsaturated or aromatic heterocycle and an optionally substituted 6-membered unsaturated or aromatic heterocyclic ring. Or is a polycyclic ring in which two or more rings selected from the group are fused, the hetero ring includes at least one selected from the group consisting of N, O and S, and the substitution is C ₁ -C ₆ Alkyl or C ₆ -C ₂₀ It may be substituted with aryl, but is not limited thereto.

The sulfenamide compound represented by Formula 1 may include a compound represented by Formula 3 below, but is not limited thereto.

[Formula 3]

In Formula 3, R ₂ and R ₃ are each independently H, optionally substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, or optionally substituted C ₃ -C ₂₀ a ring, wherein the substitution is substituted by C ₁ -C ₆ alkyl or C ₆ -C ₂₀ aryl, wherein X is O, S, Se, Te, and combinations thereof. It may be an element selected from, but is not limited thereto.

R ₂ and R ₃ may each independently include one selected from the group consisting of H, ethyl, benzyl, cyclopropane, cyclopentane, cyclohexane, and combinations thereof, but is not limited thereto .

The sulfenamide compound represented by Formula 2 may include a compound represented by Formula 4 below, but is not limited thereto.

[Formula 4]

In Formula 4, A ₁ is an optionally substituted 5-membered unsaturated or aromatic ring, an optionally substituted 6-membered unsaturated or aromatic ring, an optionally substituted 5-membered unsaturated or aromatic heterocyclic ring, and an optionally substituted 6- At least one ring selected from the group consisting of a membered unsaturated or aromatic heterocyclic ring, or a polycyclic ring in which two or more rings selected from the group are fused, the hetero ring is at least one selected from the group consisting of N, O and S including, wherein the substitution is substituted by C ₁ -C ₆ alkyl or C ₆ -C ₂₀ aryl, wherein X is an element selected from the group consisting of O, S, Se, Te, and combinations thereof. may be, but is not limited thereto.

,

,

,

,

또는

인 것 일 수 있으나, 이에 제한되는 것은 아니다. The A ₁ is

,

,

,

,

or

may be, but is not limited thereto.

The sulfenamide compound may be any one selected from the group consisting of the following compounds, but is not limited thereto:

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;

;

;

;

.

;

;

;

;

;

;

;

;

;

;

;

;

.

The method for preparing a sulfenamide compound of the present invention includes a compound represented by the following formula (5) or a compound represented by the following formula (6); a compound represented by the following formula (7); and a synthetic reagent; and reacting in a solvent, wherein the synthetic reagent includes a compound represented by the following formula (8).

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 5 to 8, R ₁ is an optionally substituted 5-membered unsaturated or aromatic ring, an optionally substituted 6-membered unsaturated or aromatic ring, an optionally substituted 5-membered unsaturated or aromatic hetero ring, and an optionally substituted At least one ring selected from the group consisting of 6-membered unsaturated or aromatic heterocycles, or a polycyclic ring in which two or more rings selected from the group are fused, R ₂ and R ₃ are each independently H, which may be substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, or optionally substituted C ₃ -C ₂₀ ring, A ₁ is optionally substituted 5-membered unsaturated or at least one ring selected from the group consisting of an aromatic ring, an optionally substituted 6-membered unsaturated or aromatic ring, an optionally substituted 5-membered unsaturated or aromatic heterocycle and an optionally substituted 6-membered unsaturated or aromatic heterocyclic ring. Or is a polycyclic ring in which two or more rings selected from the group are fused, R ₄ and R ₅ are each independently H, optionally substituted linear or branched C ₁ -C ₂₀ alkyl, which may be substituted C ₆ -C ₂₀ aryl, optionally substituted C ₃ -C ₂₀ ring, or optionally substituted C ₃ -C ₂₀ heterocyclic ring, wherein the hetero ring is at least one selected from the group consisting of N, O and S Including, the substitution may be one substituted by C ₁ -C ₆ alkyl or C ₆ -C ₂₀ aryl, but is not limited thereto.

R ₂ and R ₃ may each independently include one selected from the group consisting of H, ethyl, benzyl, cyclopropane, cyclopentane, cyclohexane, and combinations thereof, but is not limited thereto .

,

,

,

,

또는

인 것 일 수 있으나, 이에 제한되는 것은 아니다. The A ₁ is

,

,

,

,

or

may be, but is not limited thereto.

The compound represented by Formula 7 may include a compound represented by Formula 9 below, but is not limited thereto.

[Formula 9]

In Formula 9, X may be an element selected from the group consisting of O, S, Se, Te, and combinations thereof, but is not limited thereto.

R ₄ and R ₅ may each independently include one selected from the group consisting of phenyl, benzyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, turtlebutyl, and combinations thereof, but is limited thereto it's not going to be

The compound represented by Formula 8 may be any one selected from the group consisting of the following compounds, but is not limited thereto:

;

;

;

.

;

;

;

.

Based on 1 equivalent of the compound represented by Formula 7, the compound represented by Formula 5 or the compound represented by Formula 6 may be reacted in an amount of 4 to 10 equivalents, but is not limited thereto.

Based on 1 equivalent of the compound represented by Formula 7, the synthetic reagent may be reacted with 1 to 3 equivalents, but is not limited thereto.

The solvent includes a solvent selected from the group consisting of dimethylformamide, toluene, dichloromethane, tetrahydrofuran, chlorobenzene, acetonitrile, ethanol, acetone, isopropyl alcohol, ethyl ether, and combinations thereof. may be, but is not limited thereto.

The reaction may be carried out for 1 hour to 5 hours, but is not limited thereto.

The above-described problem solving means are merely exemplary, and should not be construed as limiting the present application. In addition to the exemplary embodiments described above, additional embodiments may exist in the drawings and detailed description.

The disclosed technology may have the following effects. However, this does not mean that a specific embodiment should include all of the following effects or only the following effects, so the scope of the disclosed technology should not be understood as being limited thereby.

According to the above-described means for solving the problems of the present application, the sulfenamide compound according to the present application provides a novel sulfenamide compound that was difficult to synthesize in the prior art, and thus can be variously applied to the synthesis of pharmaceuticals, materials, and the like.

The method for preparing a sulfenamide compound of the present application is a sulfenamide derivative through a coupling reaction between a thiol and an amine through a synthetic reagent (dialkyl azodicarboxylate) in the absence of a transition metal and/or halogen reagent in high yield can be synthesized with In particular, by using the synthetic reagent to selectively form sulfur, which is easily oxidized, through a sulfur-nitrogen bond, it can be prepared under atom-economical reaction conditions.

Conventionally, oxidation of sulfur occurs easily, and it is difficult to control this to synthesize a sulfenamide compound. However, in the method for preparing sulfenamide compounds of the present application, various sulfenamide compounds can be prepared simply by adjusting the substituents of thiols and amines using synthetic reagents.

Furthermore, without using an expensive transition metal, the synthetic reagent can be reused, thereby making it easy to reduce the cost of the process.

Moreover, the method for preparing the sulfenamide compound of the present application can be applied to various industries because it can be synthesized on a large scale.

In addition, the sulfenamide compound can be prepared without using a halogen reagent, which is a very weak reagent that can adversely affect the health and environmental pollution of the experimenter.

1A and 1B are diagrams showing the mechanism of a method for preparing a sulfenamide compound according to an embodiment of the present application.

Since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and will be described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In describing each figure, like reference numerals are used for like elements. Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another.

For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component. The term “and/or” includes a combination of a plurality of related listed items or any of a plurality of related listed items.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

Terms such as those defined in commonly used dictionaries should be interpreted as having meanings consistent with the meanings in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. shouldn't

Throughout this specification, when a member is positioned “on”, “on”, “on”, “on”, “under”, “under”, or “under” another member, this means that a member is positioned on the other member. It includes not only the case where they are in contact, but also the case where another member exists between two members.

Throughout this specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

As used herein, the terms "about," "substantially," and the like are used in a sense at or close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are presented, and to aid in the understanding of the present application. It is used to prevent an unconscionable infringer from using the mentioned disclosure in an unreasonable way. Also, throughout this specification, "step to" or "step to" does not mean "step for".

Throughout this specification, the term "combination of these" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, and the components It is meant to include one or more selected from the group consisting of.

Throughout this specification, reference to “A and/or B” means “A or B”, or “A and B”.

Throughout this specification, the term "aromatic ring" refers to a C _6-30 aromatic hydrocarbon ring group, for example, phenyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenylenyl, perylenyl , chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzochrysenyl, anthracenyl, stilbenyl, means including an aromatic ring such as pyrenyl, "aromatic heterocyclic ring" is at least one As an aromatic ring containing a hetero element, for example, pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindolyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, quinolyl group, isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, thienyl, and pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, Indole ring, quinoline ring, acridine ring, pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring, piperazine ring, carbazole ring, furan ring, thiophene ring, oxazole ring, oxadia Contains an aromatic heterocyclic group formed from a azole ring, a benzoxazole ring, a thiazole ring, a thiadiazole ring, a benzothiazole ring, a triazole ring, an imidazole ring, a benzoimidazole ring, a pyran ring, and a dibenzofuran ring means to do

Throughout this specification, the term "fused", with respect to two or more rings, means that at least one pair of adjacent atoms is included in both rings.

Throughout this specification, the term “alkyl” may include linear or branched, saturated or unsaturated C ₁ -C ₆ alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl or their It may include all possible isomers, but may not be limited thereto.

Throughout the specification of the present application, the term "halogen" is a group 17 element of the periodic table, and may include, for example, F, Cl, Br, or I, but may not be limited thereto.

Hereinafter, the sulfenamide compound of the present application and a method for preparing the same will be described in detail with reference to embodiments, examples, and drawings. However, the present application is not limited to these embodiments and examples and drawings.

The present application relates to a sulfenamide compound represented by the following formula (1) or formula (2).

In Formulas 1 and 2, R ₁ is an optionally substituted 5-membered unsaturated or aromatic ring, an optionally substituted 6-membered unsaturated or aromatic ring, an optionally substituted 5-membered unsaturated or aromatic hetero ring, and an optionally substituted At least one ring selected from the group consisting of 6-membered unsaturated or aromatic heterocycles, or a polycyclic ring in which two or more rings selected from the group are fused, R ₂ and R ₃ are each independently H, which may be substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, or optionally substituted C ₃ -C ₂₀ ring, A ₁ is optionally substituted 5-membered unsaturated or at least one ring selected from the group consisting of an aromatic ring, an optionally substituted 6-membered unsaturated or aromatic ring, an optionally substituted 5-membered unsaturated or aromatic heterocycle and an optionally substituted 6-membered unsaturated or aromatic heterocyclic ring. Or is a polycyclic ring in which two or more rings selected from the group are fused, the hetero ring includes at least one selected from the group consisting of N, O and S, and the substitution is C ₁ -C ₆ Alkyl or C ₆ -C ₂₀ It may be substituted with aryl, but is not limited thereto.

The sulfenamide compound of the present application provides a novel sulfenamide compound that has been difficult to synthesize in the prior art, and thus can be variously applied to the synthesis of pharmaceuticals, materials, and the like.

The sulfenamide compound represented by Formula 1 may include a compound represented by Formula 3 below, but is not limited thereto.

In Formula 3, R ₂ and R ₃ are each independently H, optionally substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, or optionally substituted C ₃ -C ₂₀ a ring, wherein the substitution is substituted by C ₁ -C ₆ alkyl or C ₆ -C ₂₀ aryl, wherein X is O, S, Se, Te, and combinations thereof. It may be an element selected from, but is not limited thereto.

R ₂ and R ₃ may each independently include one selected from the group consisting of H, ethyl, benzyl, cyclopropane, cyclopentane, cyclohexane, and combinations thereof, but is not limited thereto .

The sulfenamide compound represented by Formula 2 may include a compound represented by Formula 4 below, but is not limited thereto.

In Formula 4, A ₁ is an optionally substituted 5-membered unsaturated or aromatic ring, an optionally substituted 6-membered unsaturated or aromatic ring, an optionally substituted 5-membered unsaturated or aromatic heterocyclic ring, and an optionally substituted 6- At least one ring selected from the group consisting of a membered unsaturated or aromatic heterocyclic ring, or a polycyclic ring in which two or more rings selected from the group are fused, the hetero ring is at least one selected from the group consisting of N, O and S including, wherein the substitution is substituted by C ₁ -C ₆ alkyl or C ₆ -C ₂₀ aryl, wherein X is an element selected from the group consisting of O, S, Se, Te, and combinations thereof. may be, but is not limited thereto.

,

,

,

,

또는

인 것 일 수 있으나, 이에 제한되는 것은 아니다. The A ₁ is

,

,

,

,

or

may be, but is not limited thereto.

The sulfenamide compound may include any one of the following compounds, but is not limited thereto:

More preferably, the sulfenamide compound may be any one selected from the group consisting of the following compounds, but is not limited thereto:

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;

;

;

;

;

;

;

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;

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;

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;

.

The present application relates to a compound represented by the following formula (5) or a compound represented by the following formula (6); a compound represented by the following formula (7); and a synthetic reagent; and reacting the synthetic reagent in a solvent, wherein the synthetic reagent relates to a method for preparing a sulfenamide compound comprising a compound represented by the following formula (8).

In Formulas 5 to 8, R ₁ is an optionally substituted 5-membered unsaturated or aromatic ring, an optionally substituted 6-membered unsaturated or aromatic ring, an optionally substituted 5-membered unsaturated or aromatic hetero ring, and an optionally substituted At least one ring selected from the group consisting of 6-membered unsaturated or aromatic heterocycles, or a polycyclic ring in which two or more rings selected from the group are fused, R ₂ and R ₃ are each independently H, which may be substituted linear or branched C ₁ -C ₂₀ alkyl, optionally substituted C ₆ -C ₂₀ aryl, or optionally substituted C ₃ -C ₂₀ ring, A ₁ is optionally substituted 5-membered unsaturated or at least one ring selected from the group consisting of an aromatic ring, an optionally substituted 6-membered unsaturated or aromatic ring, an optionally substituted 5-membered unsaturated or aromatic heterocycle and an optionally substituted 6-membered unsaturated or aromatic heterocyclic ring. Or is a polycyclic ring in which two or more rings selected from the group are fused, R ₄ and R ₅ are each independently H, optionally substituted linear or branched C ₁ -C ₂₀ alkyl, which may be substituted C ₆ -C ₂₀ aryl, optionally substituted C ₃ -C ₂₀ ring, or optionally substituted C ₃ -C ₂₀ heterocyclic ring, wherein the hetero ring is at least one selected from the group consisting of N, O and S Including, the substitution may be one substituted by C ₁ -C ₆ alkyl or C ₆ -C ₂₀ aryl, but is not limited thereto.

1A and 1B are diagrams showing the mechanism of a method for preparing a sulfenamide compound according to an embodiment of the present application.

Referring to FIG. 1A , the hydrogen of the thiol group of the compound represented by Formula 7 reacts with the synthetic reagent (I) represented by Formula 8 to form an intermediate (II). The intermediate (II) reacts with the amine group of the compound represented by Formula 5 to synthesize a sulfenamide compound (Formula 1). At this time, the intermediate (II) is released as compound (III). The compound (III) can be regenerated as the synthetic reagent (I) represented by the above formula (8) in the presence of phenyliodine diacetate (PIDA). The regenerated synthetic reagent can be reused for synthesizing the sulfenamide compound.

Referring to FIG. 1B, the hydrogen of the thiol group of the compound represented by Formula 7 reacts with the synthetic reagent (I) represented by Formula 8 to form an intermediate (II). The intermediate (II) reacts with the amine group of the compound represented by Formula 6 to synthesize a sulfenamide compound (Formula 2). At this time, the intermediate (II) is released as compound (III). The compound (III) can be regenerated as the synthetic reagent (I) represented by the above formula (8) in the presence of phenyliodine diacetate (PIDA). The regenerated synthetic reagent can be reused for synthesizing the sulfenamide compound.

The method for preparing a sulfenamide compound of the present application provides a high yield of a sulfenamide derivative through a coupling reaction between a thiol and an amine through a synthetic reagent (dialkyl azodicarboxylate) in the absence of a transition metal and/or halogen reagent. can be synthesized with In particular, by using the synthetic reagent to selectively form sulfur, which is easily oxidized, through a sulfur-nitrogen bond, it can be prepared under atom-economical reaction conditions.

Conventionally, oxidation of sulfur occurs easily, and it is difficult to control this to synthesize a sulfenamide compound. However, in the method for preparing sulfenamide compounds of the present application, various sulfenamide compounds can be prepared simply by adjusting the substituents of thiols and amines using synthetic reagents.

Furthermore, without using an expensive transition metal, the synthetic reagent can be reused, thereby making it easy to reduce the cost of the process.

Moreover, the method for preparing the sulfenamide compound of the present application can be applied to various industries because it can be synthesized on a large scale.

In addition, the sulfenamide compound can be prepared without using a halogen reagent, which is a very weak reagent that can adversely affect the health and environmental pollution of the experimenter.

R ₂ and R ₃ may each independently include one selected from the group consisting of H, ethyl, benzyl, cyclopropane, cyclopentane, cyclohexane, and combinations thereof, but is not limited thereto .

,

,

,

,

또는

인 것 일 수 있으나, 이에 제한되는 것은 아니다. The A ₁ is

,

,

,

,

or

may be, but is not limited thereto.

The compound represented by Formula 7 may include a compound represented by Formula 9 below, but is not limited thereto.

In Formula 9, X may be an element selected from the group consisting of O, S, Se, Te, and combinations thereof, but is not limited thereto.

R ₄ and R ₅ may each independently include one selected from the group consisting of phenyl, benzyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, turtlebutyl, and combinations thereof, but is limited thereto it's not going to be

The compound represented by Formula 8 may be any one selected from the group consisting of the following compounds, but is not limited thereto:

;

;

;

.

;

;

;

.

Based on 1 equivalent of the compound represented by Formula 7, the compound represented by Formula 5 or the compound represented by Formula 6 may be reacted in an amount of 4 to 10 equivalents, but is not limited thereto.

When the compound represented by Formula 5 or the compound represented by 6 reacts in less than 4 equivalents or more than 10 equivalents based on 1 equivalent of the compound represented by Formula 7, the yield may decrease and by-products may increase.

Based on 1 equivalent of the compound represented by Formula 7, the synthetic reagent may be reacted with 1 to 3 equivalents, but is not limited thereto.

When the synthetic reagent reacts in less than 1 equivalent or more than 3 equivalents based on 1 equivalent of the compound represented by Formula 7, the yield may decrease and by-products may increase.

The solvent includes a solvent selected from the group consisting of dimethylformamide, toluene, dichloromethane, tetrahydrofuran, chlorobenzene, acetonitrile, ethanol, acetone, isopropyl alcohol, ethyl ether, and combinations thereof. may be, but is not limited thereto.

More preferably, the solvent may include a solvent selected from the group consisting of dimethylformamide, tetrahydrofuran, acetonitrile, and combinations thereof, but is not limited thereto.

The reaction may be carried out for 1 hour to 5 hours, but is not limited thereto.

If the reaction is carried out for less than 1 hour, the reactant may not be sufficiently generated, and thus the yield may be reduced. In addition, when the reaction is carried out for more than 5 hours, by-products may increase. However, the reaction time is not particularly limited, and the reaction time may be adjusted according to the substituent of the compound to be prepared. That is, if necessary, the reaction time may be outside the above-described reaction time range.

The present invention will be described in more detail through the following examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present application.

1. Examples for Optimizing Reaction Conditions

First, in Scheme 1, 1 equivalent (eq) (30 mg, 0.18 mmol) of the following compound 1a and 1 ml of DMF (dimethylformamide) as a solvent were placed in a reaction vessel. Then, 6 equivalents (eq) (111.1 mg, 1.08 mmol) of the following compound 2a dissolved in 2 ml of DMF and 1.5 equivalents (eq) (85.4 mg, 0.29 mmol) of DBAD (dibenzyl azodicarboxylate) as a synthetic reagent were reacted with the above reaction It was placed in a container and reacted with stirring at room temperature for 3 hours to prepare a sulfenamide compound (Compound 3a) (45 mg, 0.168 mmol, yield 93%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.84 (d, J = 8.0 Hz, 1H), 7.80 (d, J = 8.0 Hz, 1H), 7.40 (td, J = 7.8, 1.0 Hz, 1H), 7.28 (td, J = 7.8, 1.0 Hz, 1H), 3.55 (t, J = 4.8 Hz, 4H), 2.79 (t, J = 5.0 Hz, 4H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 175.9, 155.3, 135.1, 126.1, 124.0, 121.9, 121.1, 58.7, 28.7.

[Scheme 1]

A sulfenamide compound (compound 3a) was prepared in the same manner as in Example 1, except that 5 equivalents of the compound 2a was used (yield 88%).

In the sulfenamide compound prepared in Example 2, 12% of the disulfide compound was synthesized as a by-product.

A sulfenamide compound (Compound 3a) was prepared in the same manner as in Example 1, except that toluene was used as a solvent (yield 85%).

In the sulfenamide compound prepared in Example 3, 15% of the disulfide compound was synthesized as a by-product.

A sulfenamide compound (Compound 3a) was prepared in the same manner as in Example 1, except that DCM (dichloromethane) was used as a solvent (yield 86%).

In the sulfenamide compound prepared in Example 4, 14% of the disulfide compound was synthesized as a by-product.

A sulfenamide compound (Compound 3a) was prepared in the same manner as in Example 1, except that tetrahydrofuran (THF) was used as a solvent (yield 92%).

A sulfenamide compound (Compound 3a) was prepared in the same manner as in Example 1, except that chlorobenzene was used as a solvent (yield 85%).

In the sulfenamide compound prepared in Example 6, 15% of the disulfide compound was synthesized as a by-product.

A sulfenamide compound (Compound 3a) was prepared in the same manner as in Example 1, except that acetonitrile was used as a solvent (yield 89%).

A sulfenamide compound (Compound 3a) was prepared in the same manner as in Example 1, except that diisopropyl azodicarboxylate (DIAD) was used as a synthetic reagent (yield 91%).

A sulfenamide compound (compound 3a) was prepared in the same manner as in Example 1, except that DEAD (diethyl azodicarboxylate) was used as a synthetic reagent (yield 89%).

A sulfenamide compound (Compound 3a) was prepared in the same manner as in Example 1, except that Di-tert-butyl azodicarboxylate (DtBAD) was used as a synthetic reagent (yield 86%).

[Comparative Example 1]

A sulfenamide compound (compound 3a) was prepared in the same manner as in Example 1, except that 3 equivalents of the compound 2a were used (yield 42%).

In the sulfenamide compound prepared in Comparative Example 1, 42% of the disulfide compound was synthesized as a by-product.

[Comparative Example 2]

When the sulfenamide compound (Compound 3a) was prepared in the same manner as in Example 1, except that no synthetic reagent was used, it was confirmed that no reaction occurred.

According to the results shown in Examples 1 and 2 and Comparative Example 1, when the compound 2a was used in 3 equivalents, it was confirmed that the yield decreased and the by-products increased (Comparative Example 1). On the other hand, in the case of Example 1 using 6 equivalents of the compound 2a, the yield was as high as 93%, and no by-products were synthesized.

According to the results shown in Examples 1 and 3 to 7, when DMF, toluene, DCM, THF, chlorobenzene, or acetonitrile was used as a solvent, it can be confirmed that all yields were as high as 80% or more. In particular, when using DMF, THF or acetonitrile as a solvent, it can be confirmed that by-products are not generated.

According to the results shown in Examples 1 and 8 to 10, when DBAD, DIAD, DEAD, or DtBAD was used as a synthetic reagent, all yields were as high as 85% or more, and it was confirmed that no by-products were produced.

2.1 Synthesis result according to compound 2

A sulfenamide compound (Compound 3b) was prepared in the same manner as in Example 1, except that Compound 2b below was used instead of Compound 2a (yield 87%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.85 (d, J = 8.0 Hz, 1H), 7.81 (d, J = 8.0 Hz, 1H), 7.42 (td, J = 7.7, 1.0 Hz, 1H), 7.29 (td, J = 7.8, 1.0 Hz, 1H), 3.83 (t, J = 4.8 Hz, 4H), 3.29 (t, J = 4.5 Hz, 4H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 175.1, 155.2, 135.1, 126.1, 124.1, 122.0, 121.2, 68.0, 56.7.

[Compound 2b]

[Compound 3b]

A sulfenamide compound (Compound 3c) was prepared in the same manner as in Example 1 (yield 66%), except that Compound 2c below was used instead of Compound 2a. ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.85 (d, J = 8.0 Hz, 1H), 7.81 (d, J = 8.0 Hz, 1H), 7.42 (td, J = 7.7, 1.0 Hz, 1H), 7.29 (td, J = 7.8, 1.0 Hz, 1H), 3.83 (t, J = 4.8 Hz, 4H), 3.29 (t, J = 4.5 Hz, 4H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 175.1, 155.2, 135.1, 126.1, 124.1, 122.0, 121.2, 68.0, 56.7.

[Compound 2c]

[Compound 3c]

A sulfenamide compound (Compound 3d) was prepared in the same manner as in Example 1 (yield 68%), except that Compound 2d below was used instead of Compound 2a. ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.82 (d, J = 8.0 Hz, 1H), 7.79 (d, J = 7.5 Hz, 1H), 7.38 (td, J = 7.7, 0.8 Hz, 1H), 7.25 (td, J = 7.5, 1.0 Hz, 1H), 3.22 (t, J = 5.2 Hz, 4H), 1.74 (quin, J = 5.6 Hz, 4H), 1.52 (quin, J = 5.9 Hz, 2H). ¹³ C NMR (125 MHz, CDCl ₃ )δ 177.7, 155.4, 135.2, 125.8, 123.6, 121.7, 121.1, 58.2, 27.5, 23.1. IR: v 3061, 2935, 2849, 1470, 1428, 1271, 1021, 925, 755, 667 cm ^-1 ; HRMS (EI) calcd for C ₁₂ H ₁₄ N ₂ S ₂ [M] ⁺ : 250.0598. Found: 250.0598.

[Compound 2d]

[Compound 3d]

A sulfenamide compound (compound 3e) was prepared in the same manner as in Example 1 (yield 47%), except that the following compound 2e was used instead of the compound 2a. ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.82 (d, J = 8.0 Hz, 1H), 7.77 (d, J = 8.0 Hz, 1H), 7.38 (td, J = 7.6, 1.2 Hz, 1H), 7.24 (td, J = 7.6, 0.7 Hz, 1H), 3.32 (t, J = 5.8 Hz, 4H), 1.94 (quin, J = 3.3 Hz, 4H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 178.3, 155.2, 135.0, 125.8, 123.6, 121.6, 121.0, 55.7, 26.2.

[Compound 1e]

[Compound 3e]

A sulfenamide compound (compound 3f) was prepared in the same manner as in Example 1, except that the following compound 2f was used instead of the compound 2a (yield 42%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.81 (d, J = 8.0 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.38 (t, J = 7.7 Hz, 1H), 7.25 (t) , J = 7.7 Hz, 1H), 3.38 (t, J = 5.8 Hz, 4H), 1.77 (s, 4H), 1.65 (quin, J = 3.0 Hz, 4H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 180.3, 155.6, 135.1, 125.8, 123.5, 121.6, 121.1, 59.2, 29.9, 27.2. IR: v 3061, 2925, 2852, 1468, 1428, 1236, 1006, 755, 727, 667 cm ⁻¹ ; HRMS (EI) calcd for C ₁₃ H ₁₆ N ₂ S ₂ [M] ⁺ : 264.0755. Found: 264.0755.

[Compound 2f]

[Compound 3f]

A sulfenamide compound (compound 3g) was prepared in the same manner as in Example 1, except that the following compound 2g was used instead of the compound 2a (yield 96%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.82 (d, J = 8.0 Hz, 1H), 7.77 (d, J = 8.0 Hz, 1H), 7.38 (t, J = 7.5 Hz, 1H), 7.24 (t) , J = 7.7 Hz, 1H), 3.39 (d, J = 4.5 Hz, 1H), 3.18-3.12 (m, 2H), 1.22 (td, J = 7.0, 1.8 Hz, 3H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 178.8, 154.9, 135.0, 125.8, 123.6, 121.5, 121.1, 47.4, 15.7.

[Compound 2 g]

[Compound 3g]

A sulfenamide compound (Compound 3h) was prepared in the same manner as in Example 1, except that Compound 2h was used instead of Compound 2a (yield 88%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.86 (d, J = 8.0 Hz, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.44-7.38 (m, 5H), 7.35-7.28 (m, 2H), 4.29 (d, J = 6.0 Hz, 2H), 3.56 (t, J = 5.8 Hz, 1H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 177.4, 154.9, 138.6, 135.2, 128.9, 128.6, 128.1, 126.1, 123.9, 121.8, 121.3, 57.2.

[Compound 2h]

[Compound 3h]

A sulfenamide compound (compound 3i) was prepared in the same manner as in Example 1 (yield 88%), except for using the following compound 2i instead of the compound 2a. ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.97 (d, J = 7.5 Hz, 1H), 7.76 (d, J = 8.0 Hz, 1H), 7.40 (t, J = 7.5 Hz, 1H), 7.29 (t) , J = 7.5 Hz, 1H), 6.08 (s, 1H), 2.76-2.50 (m, 1H), 0.59 (d, J = 6.5 Hz, 4H). ¹³ C NMR (125 MHz, DMSOd6) δ 179.4, 154.6, 134.3, 126.0, 123.6, 121.6, 121.0, 33.1, 7.9.

[Compound 2i]

[Compound 3i]

A sulfenamide compound (Compound 3j) was prepared in the same manner as in Example 1 (yield 91%), except that Compound 2j was used instead of Compound 2a. ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.82 (d, J = 8.0 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.38 (t, J = 7.7 Hz, 1H), 7.25 (t) , J = 7.5 Hz, 1H), 3.64-3.59 (m, 1H), 3.39 (d, J = 2.5 Hz, 1H), 1.89-1.81 (m, 2H), 1.80-1.71 (m, 2H), 1.64- 1.54 (m, 4H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 179.5, 155.0, 135.0, 125.9, 123.6, 121.5, 121.1, 62.8, 33.3, 23.9. IR: v 3223, 2956, 2868, 1463, 1428, 1238, 1026, 1010, 755, 727 cm ⁻¹ ; HRMS (EI) calcd for C ₁₂ H ₁₄ N ₂ S ₂ [M] ⁺ : 250.0598. Found: 250.0598.

[Compound 2j]

[Compound 3j]

A sulfenamide compound (compound 3k) was prepared in the same manner as in Example 1, except that the following compound 2k was used instead of the compound 2a (yield 25%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.81 (d, J = 8.0 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.38 (td, J = 7.5, 1.0 Hz, 1H), 7.25 (td, J = 7.5, 0.8 Hz, 1H), 3.27 (d, J = 5.0 Hz, 1H), 2.91-2.86 (m, 1H), 2.08 (d, J = 10.0 Hz, 2H), 1.78-1.75 ( m, 2H), 1.62-1.59 (m, 1H), 1.31-1.14 (m, 5H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 180.1, 155.2, 135.0, 125.9, 123.6, 121.6, 121.1, 60.4, 33.8, 25.7, 25.0.

[Compound 2k]

[Compound 3k]

2.2 Synthesis result according to compound 2

A sulfenamide compound (Compound 3l) was prepared in the same manner as in Example 1, except that Compound 1b below was used instead of Compound 1a (yield 92%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.65 (dd, J = 7.5, 1.5 Hz, 1H), 7.49 (dd, J = 7.0, 1.5 Hz, 1H), 7.33-7.26 (m, 2H), 3.70 ( t, J = 5.2 Hz, 4H), 2.76 (t, J = 4.2 Hz, 4H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 165.8, 151.6, 141.9, 124.5, 124.4, 119.3, 110.3, 58.5, 29.3. IR : v 3061, 2913, 2852, 1496, 1451, 1235, 1122, 1089, 756, 743 cm ^-1 ; HRMS (EI) calcd for C ₁₁ H ₁₂ N ₂ OS ₂ [M] ⁺ : 252.0391. Found: 252.0389.

[Compound 1b]

[Compound 3l]

A sulfenamide compound (compound 3m) was prepared in the same manner as in Example 11, except that Compound 1b was used instead of Compound 1a (yield 76%). ¹ H NMR (500 MHz, CDCl ₃ ) 7.66 (dd, J = 7.2, 1.8 Hz, 1H), 7.50 (dd, J = 7.2, 1.7 Hz, 1H), 7.33-7.27 (m, 2H), 3.77 (t) , J = 4.5 Hz, 4H), 3.44 (t, J = 4.0 Hz, 4H). ¹³ C NMR (125 MHz, CDCl ₃ ) 165.3, 151.5, 141.8, 124.6, 124.5, 119.3, 110.3, 67.9, 55.9.

[compound 3m]

A sulfenamide compound (Compound 3n) was prepared in the same manner as in Example 12, except that Compound 1b was used instead of Compound 1a (yield 51%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.57 (dd, J = 6.5, 1.5 Hz, 1H), 7.41 (dd, J = 7.2, 1.2 Hz, 1H), 7.25-7.18 (m, 2H), 3.42 ( s, 4H), 2.45 (s, 4H), 2.25 (s, 3H). ¹³ C NMR (125 MHz, CDCl ₃ ) 165.6, 151.4, 141.6, 124.3, 124.2, 119.1, 110.1, 56.0, 55.6, 46.0. IR: v 3052, 2937, 2842, 2793, 1504, 1454, 1284, 1236, 1006, 744 cm ⁻¹ ; HRMS (EI) calcd for C ₁₂ H ₁₅ N ₃ OS [M] ⁺ : 249.0936. Found: 249.0932.

[Compound 3n]

A sulfenamide compound (Compound 3o) was prepared in the same manner as in Example 13, except that Compound 1b was used instead of Compound 1a (yield 51%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.64 (dd, J = 7.5, 1.5 Hz, 1H), 7.47 (dd, J = 7.2, 0.8 Hz, 1H), 7.28 (td, J = 7.5, 1.5 Hz, 1H), 7.25 (td, J = 7.6, 1.2 Hz, 1H), 3.40 (t, J = 5.5 Hz, 4H), 1.66 (quin, J = 5.8 Hz, 4H), 1.49 (quin, J = 5.8 Hz, 2H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 166.5, 151.4, 141.9, 124.3, 124.1, 119.0, 110.1, 57.4, 27.4, 22.8. IR : v 3062, 2937, 2851, 1496, 1451, 1236, 1119, 1088, 801, 742 cm ^-1 ; HRMS (EI) calcd for C ₁₂ H ₁₄ N ₂ OS [M] ⁺ : 234.0827. Found: 234.0832.

[Compound 3o]

A sulfenamide compound (Compound 3p) was prepared in the same manner as in Example 14, except that Compound 1b was used instead of Compound 1a (yield 26%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.62 (dd, J = 7.5, 1.5 Hz, 1H), 7.46 (dd, J = 7.5, 1.0 Hz, 1H), 7.28 (td, J = 7.5, 1.0 Hz, 1H), 7.24 (td, J = 7.7, 1.5 Hz, 1H), 3.38 (t, J = 6.8 Hz, 4H), 1.98 (quin, J = 3.4 Hz, 4H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 166.9, 151.6, 142.0, 124.3, 123.9, 118.9, 110.1, 55.4, 26.3. IR : v 3051, 2925, 2871, 1501, 1452, 1235, 1121, 1089, 1002, 742 cm ^-1 ; HRMS (EI) calcd for C ₁₁ H ₁₂ N ₂ OS [M] ⁺ : 220.0670. Found:220.0670.

[Compound 3p]

A sulfenamide compound (Compound 3q) was prepared in the same manner as in Example 15, except that Compound 1b was used instead of Compound 1a (yield 53%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.63 (dd, J = 8.0, 1.0 Hz, 1H), 7.46 (dd, J = 7.5, 1.0 Hz, 1H), 7.27 (td, J = 7.6, 1.2 Hz, 1H), 7.23 (td, J = 7.6, 1.2 Hz, 1H), 3.49 (s, 4H), 1.72 (s, 4H), 1.62 (quin, J = 2.8 Hz, 4H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ 168.4, 151.8, 142.2, 124.2, 123.7, 118.9, 110.1, 59.6, 30.0, 27.5. IR : v 3052, 2926, 2853, 1497, 1452, 1235, 1122, 1090, 1038, 742 cm-1; HRMS (EI) calcd for C13H16N2OS [M]+: 248.0983. Found:248.0980.

[Compound 3q]

A sulfenamide compound (Compound 3r) was prepared in the same manner as in Example 16, except that Compound 1b was used instead of Compound 1a (yield 91%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.62 (d, J = 7.5 Hz, 1H), 7.44 (d, J = 8.0 Hz, 1H), 7.27 (td, J = 7.6, 0.8 Hz, 1H), 7.22 (td, J = 7.8, 1.0 Hz, 1H), 3.42 (s, 1H), 3.42-3.18 (m, 2H), 1.21 (t, J = 7.3 Hz, 3H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 168.0, 151.9, 142.9, 124.4, 123.9, 118.7, 110.1, 47.0, 15.1.

[Compound 3r]

A sulfenamide compound (Compound 3s) was prepared in the same manner as in Example 17, except that Compound 1b was used instead of Compound 1a (yield 76%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.67 (d, J = 8.0 Hz, 1H), 7.48 (d, J = 7.5 Hz, 1H), 7.41-7.33 (m, 5H), 7.32-7.30 (m, 1H), 7.29-7.26 (m, 1H), 4.34 (d, J = 5.5 Hz, 2H), 3.64 (t, J = 5.0 Hz, 1H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 167.6, 152.0, 142.0, 138.3, 128.7, 128.6, 127.9, 124.5, 124.1, 118.8, 110.3, 56.5.

[Compound 3s]

A sulfenamide compound (compound 3t) was prepared in the same manner as in Example 18, except that Compound 1b was used instead of Compound 1a (yield 90%). ¹ H NMR (500 MHz, CDCl ₃ ) δ (500 MHz, CDCl 3 ) δ 7.63 (d, J = 7.5 Hz, 1H), 7.44 (d, J = 8.0 Hz, 1H), 7.27 (td, J = 7.7, 1.0 Hz, 1H), 7.22 (td, J = 7.6, 1.2 Hz, 1H), 4.24 (s, 1H), 3.07-3.03 (m, 1H), 0.66-0.63 (m, 2H), 0.62-0.58 (m) , 2H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 168.1, 151.9, 141.9, 124.3, 123.9, 118.6, 110.1, 33.0, 8.6. IR : v 3224, 3089, 1504, 1454, 1236, 1129, 1018, 802, 742, 624 cm ^-1 ; HRMS (EI) calcd for C ₁₀ H ₁₀ N ₂ OS [M] ⁺ :206.0514. Found: 206.0511.

[Compound 3t]

A sulfenamide compound (Compound 3u) was prepared in the same manner as in Example 19, except that Compound 1b was used instead of Compound 1a (yield 90%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.62 (d, J = 8.0 Hz, 1H), 7.44 (d, J = 8.0 Hz, 1H), 7.28 (t, J = 7.8 Hz, 1H), 7.23 (t) , J = 7.8, 1H), 3.80-3.75 (m, 1H), 3.41 (s, 1H), 1.83-1.72 (m, 4H), 1.69-1.65 (m, 2H), 1.58-1.55 (m, 2H) . ¹³ C NMR (125 MHz, CDCl ₃ ) δ 168.0, 151.9, 142.0, 124.3, 123.9, 118.7, 110.1, 61.3, 33.0, 23.8. IR : v 3239, 3052, 2958, 2870, 1501, 1453, 1236, 1127, 1093, 742 cm ^-1 ; HRMS (EI) calcd for C ₁₂ H ₁₄ N ₂ OS [M] ⁺ : 234.0827. Found: 234.0826.

[Compound 3u]

A sulfenamide compound (Compound 3v) was prepared in the same manner as in Example 20, except that Compound 1b was used instead of Compound 1a (yield 83%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.62 (d, J = 7.5 Hz, 1H), 7.45 (d, J = 8.0 Hz, 1H), 7.28 (t, J = 7.8 Hz, 1H), 7.23 (t) , J = 7.5, 1H), 3.34 (s, 1H), 3.04 (s, 1H), 2.05-2.03 (m, 2H), 1.75-1.73 (m, 2H), 1.59-1.56 (m, 1H), 1.30 -1.17 (m, 5H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 168.3, 151.9, 142.0, 124.3, 123.9, 118.8, 110.1, 58.3, 32.8, 25.9, 24.4. IR : v 3240, 3053, 2930, 2854, 1503, 1453, 1236, 1127, 1093, 742 cm ^-1 ; HRMS (EI) calcd for C ₁₃ H ₁₆ N ₂ OS [M] ⁺ : 248.0983. Found: 248.0980.

[Compound 3v]

2.3 Synthesis result according to compound 1

A sulfenamide compound (compound 3w) was prepared in the same manner as in Example 11, except that the following compound 1c was used instead of the compound 1a (yield 56%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.15 (d, J = 9.0 Hz, 2H), 7.41 (d, J = 9.0 Hz, 2H), 3.79 (t, J = 4.5 Hz, 4H), (t, J = 3.10 Hz, 4H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ (125 MHz, CDCl 3 ) δ 150.3, 145.4, 124.2, 122.7, 67.8, 56.3.

[Compound 1c]

[Compound 3w]

First, in Reaction Scheme 2, 1 equivalent (eq) of the following compound 1d, 1.5 equivalents (eq) of DBAD (dibenzyl azodicarboxylate) as a synthetic reagent, and DMF (dimethylformamide) as a solvent were placed in a reaction vessel, and 30 minutes at a temperature of 60 ° C. The reaction was stirred while stirring to prepare a sulfenamide compound (compound 3x) (yield 8%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.33 (s, 10H), 7.20 (t, J = 1.8 Hz, 1H), 7.09 (d, J = 1.7 Hz, 2H), 7.02 (s, 0.7H), 6.79 (s, 0.3H), 5.18 (d, J = 3.6 Hz, 3.4H), 5.00 (d, J = 9.9 Hz, 0.6H), 2.51 (s, 6H). ¹³ C NMR (125 MHz, CDCl ₃ ) δ 156.6, 156.3, 155.4, 155.2, 144.1, 143.9, 135.6, 135.3, 132.8, 132.4, 131.0, 130.9, 128.6, 128.5, 128.4, 127.8, 69.7, 69.6, 68.0, 67.9 , 22.1. IR : v 3062, 2360, 1732, 1498, 1381, 1287, 983, 775, 697, 588, 455 cm ^-1 ; HRMS (EI) calcd for C ₂₄ H ₂₄ N ₂ O ₄ S [M] ⁺ : 436.1457. Found: 436.1456.

[Scheme 2]

In Scheme 2, it can be seen that not only compound 3x but also compounds 4 and 5 are produced. Through the synthesis of compound 4, it can be inferred that the synthetic invention of the present invention can also be applied to the synthesis of disulfide. In addition, the mechanism of the present invention can be confirmed through the formation of the compounds 3x and 5.

In Examples 1 to 33, sulfenamide compounds were synthesized through the S-N coupling reaction of thiols and amines having various functional groups. Through this, it can be confirmed that the synthesis method according to the present invention can be used to prepare sulfenamide compounds having various functional groups. In addition, economical effects can be achieved by synthesizing a sulfenamide compound without using a transition metal and/or a halogen reagent.

3. Reuse of Synthetic Reagents

[Experimental Example 1]

PIDA (phenyliodine diacetate) and DCM (dichloromethane) were added to Compound 5, and the mixture was reacted with stirring at room temperature for 30 minutes to obtain DBAD (dibenzyl azodicarboxylate) in a yield of 97%.

[Experimental Example 2]

The DBAD obtained in Experimental Example 1 was tested in the same manner as in Scheme 2 (Example 33), and as a result, compounds 4 and 5 were synthesized in yields of 83% and 77%, respectively.

[Experimental Example 3]

Compound 5 obtained in Experimental Example 2 was obtained DBAD in the same manner as in Experimental Example 1, and as a result of the experiment in the same manner as in Scheme 2 (Example 33), compounds 4 and 5 were each 83% and It was synthesized in a yield of 77%.

As a result of Experimental Examples 1 to 3, it can be confirmed that DBAD, a synthetic reagent used in the present invention, can be regenerated using PIDA, and when the regenerated DBAD is used as a synthetic reagent, a compound with the same yield is synthesized. That is, since the synthetic reagent can be reused to synthesize the sulfenamide compound, it is easy to reduce the cost of the process.

The above description of the present application is for illustration, and those of ordinary skill in the art to which the present application pertains will understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a dispersed form, and likewise components described as distributed may also be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present application.

Claims (16)

delete delete delete delete delete delete a compound represented by the following formula (5) or a compound represented by the following formula (6);
a compound represented by the following formula (9); and
Synthetic reagent; including reacting in a solvent,
The method for preparing a sulfenamide compound, wherein the synthetic reagent includes a compound represented by the following formula (8):
[Formula 5]

[Formula 6]

[Formula 8]

[Formula 9]

In Formulas 5, 6, 8 and 9,
R ₂ and R ₃ are each independently selected from the group consisting of H, ethyl, benzyl, cyclopropane, cyclopentane, cyclohexane, and combinations thereof,
A ₁ is

,

,

,

,

and

At least one ring selected from the group consisting of, or a polycyclic ring in which two or more rings are fused,
R ₄ and R ₅ are each independently selected from the group consisting of phenyl, benzyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, turtlebutyl, and combinations thereof;
X is an element selected from the group consisting of O, S, Se, Te, and combinations thereof.
delete delete delete delete 8. The method of claim 7,
The method for preparing a sulfenamide compound, wherein the compound represented by Formula 8 is any one selected from the group consisting of the following compounds:

;

;

;

.
8. The method of claim 7,
The method for producing a sulfenamide compound, wherein the compound represented by Formula 5 or the compound represented by Formula 6 reacts in an amount of 4 to 10 equivalents based on 1 equivalent of the compound represented by Formula 9.
8. The method of claim 7,
The method for producing a sulfenamide compound, wherein 1 to 3 equivalents of the synthetic reagent are reacted based on 1 equivalent of the compound represented by Formula 9.
8. The method of claim 7,
The solvent includes a solvent selected from the group consisting of dimethylformamide, toluene, dichloromethane, tetrahydrofuran, chlorobenzene, acetonitrile, ethanol, acetone, isopropyl alcohol, ethyl ether, and combinations thereof. A method for preparing a phosphorus, sulfenamide compound.
8. The method of claim 7,
The method for producing a sulfenamide compound, wherein the reaction is carried out for 1 hour to 5 hours.

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