KR101585030B1 - Preparing method of hydrizide compounds - Google Patents

Abstract

The present invention relates to a process for producing hydrazide, and more particularly, to a process for preparing a hydrazide derivative compound by reacting a hydrazine-carbon dioxide bonding compound with an organic acid or a sulfonic acid compound.

Description

PREPARING METHOD OF HYDRIDIDE COMPOUNDS [0002]

The present invention relates to a process for preparing hydrazide derivatives, and more particularly to a process for preparing hydrazide derivative compounds by reacting a hydrazine-carbon dioxide bonding compound with an organic acid or a sulfonic acid compound.

Hydrazine (N ₂ H ₄ ) has similar chemical properties to ammonia (NH ₃ ) gas, but at room temperature it has a melting point, boiling point, and density similar to water as a transparent liquid. Hydrazine is a crosslinking agent for improving the physical properties of polymers containing a carbonyl group or containing an epoxy group (for example, polyacrylate, polycarbonate or epoxy resin) in the form of carbohydrazide or the like, , A precursor for making pesticides and medicines, an oxygen scavenger for boiler water, a fuel cell, and fuel for rockets. Such useful liquid hydrazine can cause pollution due to leaking fire and rapid reaction with surrounding metals or substances. In most cases, the hydrazine hydrate form contains a large amount of water, which limits its application.

As a method for reducing the problems of liquid hydrazine, it has been proposed to use a solid hydrazinium salt prepared by reacting liquid hydrazine with sulfuric acid or hydrochloric acid as a substitute for liquid hydrazine. However, when the reactivity is lowered and the anion removal And the like, hydrazine salts have been developed to a very limited extent, despite the wide variety of their types.

In order to solve the above problems, U.S. Patent Nos. 3,551,226 and 2,878,103 disclose the production of solid hydrazine using carbon dioxide, which is a flame-retardant gas. However, this product contains water in the solid and consists mainly of carbazic acid (HCO ₂ N ₂ H ₃ ) and hydrazinium carbazate (N ₂ H ₅ CO ₂ N ₂ H ₃ ) And the ratio of hydrazine to carbon dioxide is not constant.

On the other hand, in the case of using liquid hydrazine in an aqueous solution state, it is necessary to use an organic solvent such as ethanol or acetic acid, and after the reaction, a product is obtained through a neutralization process, a solvent removal and a product separation process. Therefore, it is accompanied by volatile organic chemicals (VOCs) by the use of solvents, and toxic waste water is inevitably generated accordingly. Also, in most cases, the reactants are used in an amount of 5 to 20% by weight of the total volume. Therefore, there is a disadvantage that the reactors and auxiliary devices must be used which are relatively large compared to the amount of the products. In addition, a process unit for separation and purification for obtaining a product therefrom is required, so that the production process becomes complicated and the manufacturing cost increases.

Hydrazide derivative compounds are representative materials synthesized using hydrazine in the liquid phase. For example, adipic dihydrazide (ADH), which is synthesized by using an organic acid as a base material, is widely used as a polymer crosslinking material and the like. When the adipic acid and hydrazine are directly reacted for the synthesis of adipic acid dihydrazide, the yield is low and a large amount of by-products are produced. Therefore, in order to efficiently conduct the reaction, i) adipic acid is reacted with an alcohol Methanol or ethanol, or the like), or ii) conversion to acyl chloride such as adipoyl chloride by reaction with SOCl ₂ or the like, and then hydrazine hydrate in a liquid phase is reacted with an alcohol in an alcohol solvent Reflux, and purified. Especially, when synthesized by the route of ii), there is a restriction to use toxic SOCl ₂ , and excessive hydrazine is necessary for the removal of Cl ^- ion generated as a byproduct. However, even in the case of synthesizing by the route of i), a step of synthesizing an ester is required, and since the synthesized ester has a large molar mass and a solvent is used, the use of adipic acid directly Economy is very low. On the other hand, in the case of a sulfonyl hydrazide used as an expensive foaming agent, for example, 4,4'-oxydibenzenesulfonohydrazide, a solvent is used to react 4,4'-oxydibenzene-1 -sulfonyl chloride Hydrazinium chloride is required to be used in an amount of 4 equivalents or more based on 1 equivalent of 4,4'-oxydibenzene-1-sulfonyl chloride, and it is required to undergo a complicated purification process, thereby increasing the unit price.

Generally, hydrazide derivative compounds are used as cross-linking agents for improving the physical properties of polymers containing carbonyl groups or containing epoxy groups (for example, polyacrylates, polycarbonates or epoxy resins), blowing agents for forming pores in polymers, Precursors for making medicines, oxygen scavengers for boiler water, fuel cells, and fuel for rockets.

In the conventional hydrazide production process, when a hydrazide derivative compound is obtained by using an organic acid (-COOH) and a sulfonic acid (-SO ₃ H) as a starting material and reacting with hydrazine hydrate, the yield is very low or the reaction proceeds well It does not. In the case of the conventional synthesis method, organic acid esters and sulfonic acid esters are prepared by using an alcohol having 1 to 6 carbon atoms in the -OH group of organic acid (-COOH) and sulfonic acid (-SO ₃ H), and reacting with hydrazine hydrate It is known that the Draize can be obtained. In this case, the alcohol is produced as a by-product, and since the solvent is used, it is difficult to react at a high concentration, and there are drawbacks such as removal of by-products, product separation and low productivity. Meanwhile, the -OH group of the organic acid (-COOH) and the sulfonic acid (-SO ₃ H) is reacted with a substance such as SOCl ₂ , converted into a substance such as acyl chloride or sulfonyl chloride, and then reacted with hydrazine hydrate to form a hydrazide compound However, excess hydrazine should be used, and a large amount of by-products such as hydrazine salts are generated. In addition, since the above-mentioned conventional methods are different from the invention of the present application, the organic acid (-COOH) and the sulfonic acid (-SO ₃ H) are converted into other compounds and then reacted with the hydrazine hydrate, The productivity is low and a large amount of by-products are produced. Therefore, not only a separation and purification process is further required but also the generation of VOCs by the used solvent is inevitably accompanied. This is closely related to the rise in production costs.

The present invention relates to a process for preparing an organic hydrazide derivative compound having excellent selectivity and yield by reacting a hydrazine-carbon dioxide bond solid compound with an organic substance having an organic acid (-COOH) and a sulfonic acid (-SO ₃ H) .

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

An aspect of the present invention is a process for preparing a compound of formula (VI), (VII), (VIII), (VIII), (IX), (XI) XII, XII or XIII, comprising: reacting a compound represented by the formula: < RTI ID = 0.0 >

(I)

;

;

(I ')

;

;

≪ RTI ID = 0.0 &

;

;

(III)

;

;

(IV)

;

;

(V)

;

;

(VI)

;

;

(VII)

;

;

(VIII)

;

;

(IX)

;

;

(X)

;

;

(XI)

;

;

(XII)

;

;

(XIII)

;

;

In the above equations,

R ₁ , R ₂ , R ₃ And R ₄ are each independently selected from the group consisting of a C _{1 -30} aliphatic hydrocarbon group which may be substituted, a C _{3 -30} aliphatic cyclic group which may be substituted, a C _{3 -30} heteroaliphatic cyclic group which may be substituted, C _{5 -30} aromatic (aromatic), which may be a cyclic group, and which may be substituted is selected from C _{5 -30} heteroaromatic group (aromatic) group consisting of a ring, or Si, O, S, Se, N, P, As A C _{1 -30} aliphatic hydrocarbon group containing at least one of F, Cl, Br or I, a C _{1 -30} aliphatic hydrocarbon group containing at least one of Si, O, S, Se, N, P, As, F, Cl, _{3 to 30} aliphatic cyclic groups, a C _{3 to 30} heteroaliphatic cyclic group containing at least one of Si, O, S, Se, N, P, As, F, Cl, Br or I, A C _{5 -30} heteroaromatic ring group containing at least one of Se, N, P, As, F, Cl, Br or I,

R ₅ and R ₆ are, each independently, hydrogen, optionally substituted C _{1 -30} aliphatic hydrocarbon groups, C _{3 -30} aliphatic hetero ring which may C _{3 -30} aliphatic cyclic group, optionally substituted with optionally substituted groups, that can be C _5-30 aromatic group, and may be substituted with optionally substituted C _{5 -30} is selected from the group consisting of a heteroaromatic ring, Si, O, S, Se, N, P, As, F, Cl, Br or I comprises at least one C _{1 -30} aliphatic hydrocarbon group containing Si, O, S, Se, N, P, As, F, Cl, Br or I is at least one C _{3 -30} aliphatic ring group A C _{3 -30} heteroaliphatic cyclic group containing at least one of Si, O, S, Se, N, P, As, F, Cl, Br or I, And a C _{5 -30} heteroaromatic ring group containing at least one of As, F, Cl, Br or I.

The process for preparing the hydrazide derivative compound according to the present invention solves the problems of the conventional solution phase processes by using hydrazine-carbon dioxide bonding compounds obtained by reacting hydrazine with carbon dioxide as a precursor to enable solid-phase or no-solvent reaction . A hydrazine-carbon dioxide bonding compound is reacted with organic substances having a functional group of a carboxyl group (-COOH) or a sulfonyl group (-SO ₃ H) in a solid state or a non-solvent state to produce a hydrazide ) Derivative can be synthesized.

The process of the present invention can use very small, small reaction vessels, can quantitatively obtain products with little by-products except for carbon dioxide and water, and can provide a solid or solvent-free reaction process, It can be simplified. Further, even when a solvent is used, by using a solvent in an amount of about 70% by weight or less based on the total product, an efficient process with a higher reaction rate and a higher selectivity is provided than when an excessive amount of solvent (80% by weight or more) can do. The method of the present invention is advantageous in that it does not require additional equipment installation, solvent separation cost, and wastewater treatment cost compared to conventional liquid-based reaction processes, thereby providing economical efficiency and reducing manufacturing cost, to be.

Particularly, the process of the present invention uses a hydrazine-carbon dioxide bonding compound as a precursor to perform a non-solvent or solid reaction with an organic substance having a functional group of a carboxyl group (-COOH) or a sulfonyl group (-SO ₃ H) 1) It is highly productive since a large number of products can be obtained in a very small reaction vessel by using no solvent or using a minimum amount of solvent, and 2) the productivity of toxic side-chain organic compounds (4) an ester compound [-C (O) -O-] synthesized from an organic acid, acylhalide: -C (O) X, X = Cl , Br, I etc.) or sulfonyl halide (-SO ₂ X; X = Cl, Br, I, etc.) are not used, and 5) VOCs due to solvent use hardly occur, and 6) The separation and purification process 7) The investment cost for production facilities and production sites is drastically reduced. 8) It provides a very economical and environmentally friendly production process. Such an effect can not be achieved when an excess amount of solvent is used as in the conventional liquid phase process, but can be achieved only when a solvent-free process is developed or used, or when the concentration of the reactant is maximized (about 30 wt% or more) This is because when the solvent is used in an excess amount, that is, when the concentration of the reactant is about 5 wt% to about 20 wt%, the selectivity is lowered under the same conditions or the conversion rate is very low due to the slow reaction rate.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is located on another member, this includes not only when a member is in contact with another member but also when another member is present between the two members.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

Throughout this specification, the term combination (s) thereof in the expression of a machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, ≪ / RTI > and < RTI ID = 0.0 > a < / RTI >

Throughout this specification, the description of "A and / or B" means "A or B, or A and B".

In the present specification, the term "aliphatic hydrocarbon group" means a saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and includes a C _{1 -30} alkyl group, a C _{2 -30} alkenyl group, a C _2-30 alkynyl group, But are not limited thereto.

In the specification of the present application, "alkyl", respectively, a substituted or unsubstituted linear or branched unsubstituted, may be one containing a C _{1 -30} alkyl, e.g., methyl, ethyl, propyl, butyl, pentyl, Including but not limited to all of the possible isomers thereof, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, But may not be limited thereto. When the C _{1 -30} alkyl group is substituted, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkyl group.

As used throughout this application, "alkenyl" refers to a linear or branched unsubstituted or substituted unsaturated hydrocarbon group having from 2 to 30 carbon atoms, such as ethenyl, vinyl, propenyl, allyl, isopropenyl , Butenyl, isobutenyl, t-butenyl, n-pentenyl, n-hexenyl, and the like.

Throughout the specification of the present application, "alkynyl" represents a linear or branched unsubstituted or substituted unsaturated hydrocarbon group having 2 to 30 carbon atoms, and includes, for example, ethynyl, propynyl, butynyl, pentynyl, Naphthyl, naphthyl, heptyl, octynyl, nonynyl, decynyl, and the like.

Throughout the specification of the present application, the term "aliphatic ring group" refers to an unsaturated or saturated carbocyclic ring group having 3 to 30 carbon atoms, which may be formed from a compound including, for example, a cycloalkane, a cycloparaffin or the like , But may not be limited thereto.

In the present specification, "cycloalkane" means a substituted or unsubstituted saturated hydrocarbon ring compound having 3 to 30 carbon atoms, and examples thereof include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, Cyclooctane, cyclononane, cyclodecane and the like.

Throughout the specification of the present application, "halogen" or "halo" includes a group VIIa element such as chlorine (Cl), bromine (Br), fluorine (F) or iodine (I).

Throughout this specification, "amine" or "amino" includes compounds wherein the nitrogen atom is covalently bonded to one or more carbon or heteroatoms.

Throughout the specification of the present application, an "aromatic ring group" is formed from a compound having 6 to 30 carbon atoms, including an aryl compound, a heteroaryl, an arylalkyl, a bonding aryl group and the like.

Throughout this specification, "aryl" means a partially or fully unsaturated, substituted or unsubstituted monocyclic or polycyclic carbon ring. C _{6 -30} aryl means an aryl group having 6 to 30 carbon ring atoms, and when C _{6 -30} aryl is substituted, the number of carbon atoms of the substituent is not included. Preferably the aryl is monoaryl or biaryl. The monoaryl preferably has from 5 to 6 carbon atoms, and the biaryl preferably has from 9 to 10 carbon atoms. Most preferably, the aryl is substituted or unsubstituted phenyl. When monoaryl, such as phenyl, is substituted, substitution can be made by various substituents at various positions, including, for example, halo, hydroxy, nitro, cyano, C ₁ -C ₄ substituted or unsubstituted linear or branched It may be substituted by a branched alkyl or C ₁ -C ₄ linear or branched alkoxy.

As used throughout this specification, "heteroaryl" is a heterocyclic aromatic group that includes Si, O, S, Se, N, P, or As as a heteroatom. C _{3 - 30} heteroaryl means a heteroaryl group having 3 to 30 carbon ring atoms, and when C _{3 - 30} heteroaryl is substituted, the number of carbon atoms of the substituent is not included. The number of heteroatoms is preferably 1-2. In heteroaryl, aryl is preferably monoaryl or biaryl, most preferably monoaryl. Heteroaryls may be substituted by various substituents at various positions and include, for example, halo, hydroxy, nitro, cyano, C ₁ -C ₄ substituted or unsubstituted linear or branched alkyl, C ₁ -C ₄ linear or Lt; / RTI > may be substituted by branched alkoxy.

Throughout this specification, "arylalkyl" means an alkyl group substituted with an aryl group. C _{6 -30} arylalkyl means an arylalkyl having an arylalkyl unit having 6 to 30 carbon atoms, and when the C _{6 -30} arylalkyl is substituted, the number of carbon atoms of the substituent is not included. Aryl in aryl-alkyl is preferably a monoaryl or biaryl, alkyl is preferably a C _{1 -3} alkyl, more preferably C ₁ alkyl. Aryl in arylalkyl can be substituted by various substituents at various positions and includes, for example, halo, hydroxy, nitro, cyano, C ₁ -C ₄ substituted or unsubstituted linear or branched alkyl, C ₁ -C ₄ Lt; / RTI > may be substituted by a linear or branched alkoxy or alkylcarbamylnitro

Throughout the specification of the present application, the term "bonded aryl group" means a cyclic ring composed of fused multiple aryl rings and includes naphthalene, phenanthrene, anthracene, benzo [a] pyrene, benzo [b] e] pyrene, acenaphthalene, acenaphthene, benzo [b] fluoransene, benzo [j] fluoransene, chrysene, fluoransenes, fluorenes and pyrenes, which are substituted or unsubstituted fused aryl groups . May be substituted by a variety of substituents at various positions, for example, halo, hydroxy, nitro, cyano, C ₁ -C ₄ substituted or unsubstituted linear or branched alkyl or C ₁ -C ₄ linear or branched, Alkoxy. ≪ / RTI >

A first aspect of the present invention is a process for the preparation of a compound represented by the following general formula (VI), (VII), (VIII), (VIII), (IX), , ≪ / RTI > synthesizing a compound represented by formula XI, XII or XIII: < EMI ID =

(I)

;

;

(I ')

;

;

≪ RTI ID = 0.0 &

;

;

(III)

;

;

(IV)

;

;

(V)

;

;

(VI)

;

;

(VII);

;

;

(VIII)

;

;

(IX)

;

;

(X)

;

;

(XI)

;

;

(XII)

;

;

(XIII)

;

;

In the above equations,

R ₁ , R ₂ , R ₃ And R ₄ are each independently selected from the group consisting of a C _{1 -30} aliphatic hydrocarbon group which may be substituted, a C _{3 -30} aliphatic cyclic group which may be substituted, a C _{3 -30} heteroaliphatic cyclic group which may be substituted, C _{5 -30} aromatic (aromatic), which may be a cyclic group, and which may be substituted is selected from C _{5 -30} heteroaromatic group (aromatic) group consisting of a ring, or Si, O, S, Se, N, P, As A C _{1 -30} aliphatic hydrocarbon group containing at least one of F, Cl, Br or I, a C _{1 -30} aliphatic hydrocarbon group containing at least one of Si, O, S, Se, N, P, As, F, Cl, _{3 to 30} aliphatic cyclic groups, a C _{3 to 30} heteroaliphatic cyclic group containing at least one of Si, O, S, Se, N, P, As, F, Cl, Br or I, A C _{5 -30} heteroaromatic ring group containing at least one of Se, N, P, As, F, Cl, Br or I,

R ₅ and R ₆ are, each independently, hydrogen, optionally substituted C _{1 -30} aliphatic hydrocarbon groups, C _{3 -30} aliphatic hetero ring which may C _{3 -30} aliphatic cyclic group, optionally substituted with optionally substituted groups, that can be C _5-30 aromatic group, and may be substituted with optionally substituted C _{5 -30} is selected from the group consisting of a heteroaromatic ring, Si, O, S, Se, N, P, As, F, Cl, Br or I comprises at least one C _{1 -30} aliphatic hydrocarbon group containing Si, O, S, Se, N, P, As, F, Cl, Br or I is at least one C _{3 -30} aliphatic ring group A C _{3 -30} heteroaliphatic cyclic group containing at least one of Si, O, S, Se, N, P, As, F, Cl, Br or I, And a C _{5 -30} heteroaromatic ring group containing at least one of As, F, Cl, Br or I.

In one embodiment of this disclosure, R < _{2 >} And R < ₄ > each independently may be selected from the group consisting of O, S, NR < ₅ > and PR < ₆ >

The present invention relates to a process for the preparation of hydrazide derivative compounds of the ADH series and the OBSH series by using hydrazine-carbon dioxide bonding compound produced by the reaction of hydrazine with carbon dioxide instead of hydrazine, The organic acid ester or the acyl halide and the sulfonic acid halide can be used as they are without using a solvent and the solvent is not used. Therefore, the simplest process is used, and since there is no purification process without using a solvent, Not only can the hydrazide derivative compounds be synthesized, but overcomes the disadvantages of the conventional hydrazide production process and has the advantages of being the most economical, environmentally friendly, and not requiring a production facility separately.

The hydrazide derivative compound according to the present invention may synthesize the compounds represented by the above formulas (VI) to (XIII) through the reaction shown in the following Reaction Schemes I to IV but may not be limited thereto. At this time, water and carbon dioxide may be generated during the reaction. In this reaction, the carbon dioxide contained in the hydrazine-carbon dioxide bonding compound is dissociated. In the reaction, no additional carbon dioxide is produced, and other by-products are hardly produced (conversion: about 100%, selectivity: 97% More than). It is therefore very environmentally friendly and economical.

[Reaction Scheme I]

;

;

[Reaction Scheme II]

;

;

[Reaction Scheme III]

;

;

[Reaction Scheme IV]

;

;

In the above schemes I to IV, R ₁ , R ₂ , R ₃ And R < ₄ > are the same as defined above.

As a non-limiting example, the hydrazide derivative compound may be prepared by reacting a carboxyl group (-COOH) or a sulfonyl group (-SO ₃ ) using a hydrazine-carbon dioxide bonding compound as a precursor without using an acid catalyst, a metal catalyst, H) can be prepared with very high yields, but not limited to, solid reacted or solventless reactions or reactant conditions at high concentrations (> 30% by weight) . For example, when the hydrazine-carbon dioxide bonding compound is present in a solid phase, the hydrazide production reaction may proceed even by grinding or contacting between the solid powders as a reactant in a solid phase without a solvent. .

In one embodiment herein, the reaction may be carried out at a temperature from about 100 < 0 > C to about 170 < 0 > C, but may not be limited thereto. The temperature may range from about 100 ° C to about 170 ° C, from about 100 ° C to about 150 ° C, from about 100 ° C to about 130 ° C, from about 100 ° C to about 110 ° C, from about 110 ° C to about 170 ° C, , About 110 ° C to about 130 ° C, about 130 ° C to about 170 ° C, about 130 ° C to about 150 ° C, or about 150 ° C to about 170 ° C.

In one embodiment of the present invention, the reaction may be performed without using a solvent, but may not be limited thereto. For example, in the above reaction, if the reactants are all solid, the reaction can proceed by grinding or contact between the solid powders, so that there is almost no need to separate or purify the product, Environmentally friendly, non-solvent dry synthesis may be possible, but may not be limited thereto. The production process of the present invention can increase the reaction rate and selectivity by performing a solventless reaction that does not use a solvent.

In one embodiment of the present invention, the reaction may be performed in the presence of a solvent, but may not be limited thereto. When the reaction is carried out in the presence of a solvent, the amount of the solvent used is about 70 wt% or less, about 60 wt% or less, about 50 wt% or less, about 40 wt% or less, about 40 wt% or less based on the total weight of the hydrazide derivative compound About 0.1 wt.% To about 60 wt.%, About 0.1 wt.% To about 50 wt.%, About 0.1 wt.% About 0.1 wt.% To about 1 wt.%, About 1 wt.%, About 1 wt.% To about 40 wt.%, About 0.1 wt.% To about 30 wt. % To about 70 wt%, about 10 wt% to about 70 wt%, about 20 wt% to about 70 wt%, about 30 wt% to about 70 wt%, about 40 wt% to about 70 wt% % To about 70 wt%, or from about 60 wt% to about 70 wt%. For example, when the solvent is used in an amount of about 70% by weight or less, the reaction rate and selectivity may be increased, but not limited thereto, compared with the conventional method using about 80% by weight to about 95% by weight of the solvent .

In one embodiment of the invention, the solvent is selected from the group consisting of an alcohol having from 1 to 15 carbon atoms, an ether having from 2 to 16 carbon atoms, an aliphatic hydrocarbon having from 5 to 15 carbon atoms, an aromatic hydrocarbon having from 6 to 15 carbon atoms, But may not be limited thereto.

In one embodiment of the present invention, when the alcohol having 1 to 15 carbon atoms is used as a solvent, the alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec- But are not limited to, pentanol, isopentanol, sec-pentanol, tert-pentanol, hexanol, heptanol, octanol, , Xylitol, mannitol, polyol, and combinations thereof, but may not be limited thereto.

In one embodiment of the present invention, when the ether having 2 to 16 carbon atoms is used as a solvent, the ether is selected from the group consisting of dimethyl ether, diethyl ether, tetrahydrofuran, dioxin, and combinations thereof , But may not be limited thereto.

When the aliphatic hydrocarbon having 5 to 15 carbon atoms is used as a solvent, the aliphatic hydrocarbon may be pentane, hexane, , Pentadecane, and combinations thereof. The term " anionic surfactant "

In one embodiment, when the aromatic hydrocarbon having 6 to 15 carbon atoms is used as a solvent, the aromatic hydrocarbon may be selected from the group consisting of benzene, toluene, phenol, benzoic acid, nitrobenzene, xylene, naphthalene, , But the present invention is not limited thereto.

By way of non-limiting example, the selectivity of the compound represented by Formula VI, VII, VIII, IX, X, XI, XII or XIII is about 50% or more, about 60% or more, about 70% or more, About 90% or more, or about 95% or more, but may not be limited thereto.

As a non-limiting example, the yield of the compound represented by Formula VI, VII, VIII, IX, X, XI, XII or XIII is about 50% or more, about 60% or more, about 70% 90% or more, or about 95% or more.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are given for the purpose of helping understanding of the present invention, but the present invention is not limited to the following Examples.

[Example]

When the compound of formula (I) or (I ') is reacted with an organic compound having a functional group of a carboxyl group (-COOH) or a sulfonyl group (-SO ₃ H), a hydrazide derivative compound is produced and byproducts are only water and carbon dioxide.

The hydrazide derivative compounds according to the present invention can be synthesized without using any solvent at the time of production and can be synthesized according to the characteristics of organic reactants having functional groups of a carboxyl group (-COOH) or a sulfonyl group (-SO ₃ H) An aliphatic hydrocarbon having 2 to 16 carbon atoms, an aliphatic hydrocarbon having 5 to 15 carbon atoms, an aromatic hydrocarbon having 6 to 15 carbon atoms, or a mixture thereof in an amount of about 70% by weight or less based on the total weight of the zein derivative compound, Can be synthesized. The yield of the hydrazide derivative compound is about 95% or more in both a solid reaction or a liquid phase reaction using a solvent.

When the concentration of the reactant is in the range of about 5 wt% to 20 wt% by using the solvent in excess, the selectivity is lowered under the same conditions, or the reaction rate is decreased and the conversion rate is very low during the same reaction time.

Example 1

7.6 g (100.0 mmole) of solid hydrazine (H ₃ N ⁺ NHCO ₂ ^- ) and 7.3 g (50.0 mmol) of adipic acid were mixed in a mortar without a solvent for 10 minutes and stirred at 100 ° C for 5 hours. In order to confirm the structure and composition of the product produced in this process, 400 MHz NMR (Nuclear Magnetic Resonance) and elemental analysis were used.

As a result of the analysis, the product was adipohydrazide (C ₆ H ₁₄ N ₄ O ₂ ), the conversion rate was 96% or more, and the yield was 95% or more. The analytical results of the above product are specified below:

Yield (8.27 g, 96% or greater);

Elemental analysis (measured value: C, 41.21; H, 7.98 ; N, 31.02 C 6 H 14 N 4 O 2 Calculated:. C, 41.37; H, 8.10; N, 32.16%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 1.43 (s, 4H, C H 2), 1.98 (s, 4H, C H 2), 4.14 (br s, 4H, N H 2 ), 8.90 (s, 2H, N H );

¹³ C NMR (100 MHz; DMSO-d ₆ ; TMS)? (Ppm) 25.4 ( C H ₂ ), 33.7 ( C H ₂ ), 171.9 (C = O).

Example 2

The reaction was carried out in the same manner as in Example 1 except that the reaction temperature and time were adjusted to 140 占 폚 and 1 hour to obtain a product. As a result of the analysis on the product, the product was adipohydrazide (C ₆ H ₁₄ N ₄ O ₂ ), the conversion rate was 98% or more and the yield was 94% or more.

Example 3

The product was obtained in the same manner as in Example 1 except that 10 g of decane was used as a solvent, stirring was carried out at 110 DEG C for 12 hours, and filtration and separation procedures were carried out. The filtration and separation processes were carried out by a known method. As a result of the analysis on the product, the product was adipohydrazide (C ₆ H ₁₄ N ₄ O ₂ ), the conversion was 97%, and the yield was 93%.

Example 4

The product was obtained in the same manner as in Example 3 except that 10 g of hexanol was used as a solvent and the mixture was stirred at 110 DEG C for 15 hours. As a result of the analysis on the product, the product was adipohydrazide (C ₆ H ₁₄ N ₄ O ₂ ), the conversion was 90%, and the yield was 81%.

Example 5

The product was obtained in the same manner as in Example 3 except that 10 g of diphenyl ether was used as a solvent and the mixture was stirred at 110 DEG C for 12 hours. As a result of analysis of the product, the product was adipohydrazide (C ₆ H ₁₄ N ₄ O ₂ ), the conversion was 96%, and the yield was 92%.

Comparative Example 1

The same procedure as in Example 1 was carried out except that 5.0 g of hydrazine hydrate was used instead of solid hydrazine to obtain a product. As a result of analysis of the product, the product was adipohydrazide (C ₆ H ₁₄ N ₄ O ₂ ), the conversion was 45%, and the yield was 40%.

Example 6

The product was obtained in the same manner as in Example 1 except that 5.4 g (50.0 mmole) of the hydrazine-carbon dioxide bonding compound [(H ₂ NNH ₂ ) ₂ CO ₂ ] in gel state was used instead of the solid hydrazine. As a result of the analysis on the product, the product was adipohydrazide (C ₆ H ₁₄ N ₄ O ₂ ) [following the path of X = 1 in Scheme I], the conversion was> 98% %.

Comparative Example 2

The product was obtained in the same manner as in Example 3, except that 2.5 g of hydrazine hydrate was used instead of solid hydrazine, 10 g of THF was used as a solvent, and the mixture was stirred at 60 캜 for 12 hours. As a result of analysis of the product, the product was adipohydrazide (C ₆ H ₁₄ N ₄ O ₂ ), the conversion was 30%, and the yield was 23% or less.

Comparative Example 3

5.0 g (100.0 mmol) of hydrazine hydrate was used in place of solid hydrazine, 10.12 g (100.0 mmol) of diethyl adipate was used instead of adipic acid, 10 g of ethanol was used as a solvent, and 5 g Lt; / RTI > and stirring for 1 hour. As a result of analysis of the product, the product was adipohydrazide (C ₆ H ₁₄ N ₄ O ₂ ), the conversion was 89%, and the yield was 83%.

Comparative Example 4

Using hydrazine hydrate 5.0 g (100.0 mmol) instead of solid hydrazine and using 8.71 g (100.0 mmol) of dimethyl adipate instead of adipic acid, using 10 g of methanol as a solvent and heating at 60 占 폚 for 5 hours The product was obtained by carrying out the same procedure as in Example 3, As a result of analysis of the product, the conversion was 87% and the yield was 81%.

Example 7

5.7 g (75.0 mmole) of solid hydrazine (H ₃ N ⁺ NHCO ₂ ^- ) and 7.3 g (50.0 mmol) of adipic acid were used, and the rest was obtained in the same manner as in Example 1. Analysis the product was N ^'1 - (6- hydrazide possess hexahydro-6-oxo-nonyl) Oh depot hydrazide [N' - was ^{1 (6-hydrazinyl-6-} oxohexanoyl) adipohydrazide], the conversion ratio was 99% And the yield was 97% or more. Below are the results of the analysis of this product:

Yield (7.67 g, 97%);

Elemental analysis (measured value:. C, 45.33; H, 7.87; N, 26.43 C 12 H 24 N 6 O 4 Calculated: C, 45.56; H, 7.65; N, 26.57%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 1.57 (m, 8H, C H 2), 2.02 (s, 8H, C H 2), 3.81 (br s, 6H, N H - N H , N H ₂ ), 8.61 (br s, 2H, N H );

¹³ C NMR (100 MHz; DMSO-d ₆ ; TMS)? (Ppm) 29.6 ( C H ₂ ), 33.2 ( C H ₂ ), 154.7, 171.8 (C = O).

Example 8

The product was obtained in the same manner as in Example 1 except that 8.1 g of 3-methylhexanedioic acid was used instead of adipic acid. As a result of the analysis, the product was 3-methylhexanedihydrazide, the selectivity was 97% or more, and the yield was 95%. The analytical results of the above product are specified below:

Yield (8.94 g, 95%);

Elemental analysis (measured value: C, 44.58; H, 8.42 ; N, 29.81 C 7 H 16 N 4 O 2 Calculated:. C, 44.67; H, 8.57; N, 29.77%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 1.02 (d, 3H, C H 3) 1.82 (m, 2H, CH 2 C H 2 CH), 1.93 (m, 1H, C H ), 2.08 (t, 2H, -CHC H 2 C (O)), 2.12 (t, 2H, -CH 2 C H 2 C (O)) 4.17 (br s, 4H, N H 2), 8.80 (s , 2H, N H );

^{13 C NMR (100 MHz; DMSO} -d 6; TMS) δ (ppm), 21.4 (C H 3), 32.2 (C H), 33.9, 36.4, 46.1 (C H 2), 172.3 (C = O).

Example 9

The product was obtained in the same manner as in Example 1 except that 10.2 g of decanedioic acid was used instead of adipic acid. As a result of analysis, the product was decanedihydrazide, the selectivity was 97% or more, and the yield was 96%. The analytical results of the above product are specified below:

Yield (11.05 g, 96%);

Elemental analysis (measured value: C, 52.05; H, 9.52 ; N, 23.96 C 10 H 22 N 4 O 2 Calculated:. C, 52.15; H, 9.63; N, 24.33%);

¹ H NMR (400 MHz; DMSO-d ₆ ; TMS)? (Ppm) 1.31 (m, 8H, C H ₂ ), 1.58 (m, 4H, C H ₂ ) _{) C H 2) 4.10 (br} s, 4H, N H 2), 8.87 (s, 2H, N H);

¹³ C NMR (100 MHz; DMSO-d ₆ ; TMS)? (Ppm) 26.4, 30.1, 41.2 ( C H ₂ ), 172.9 (C = O).

Example 10

The product was obtained in the same manner as in Example 1 except that 17.13 g of eicosanedioic acid was used instead of adipic acid. As a result of analysis, the product was eicosanedihydrazide, the selectivity was over 97%, and the yield was 95%. The analytical results of the above product are specified below:

Yield (17.6 g, 95%);

Elemental analysis (measured value: C, 64.65; H, 11.52 ; N, 15.21 For C 20 H 42 N 4 O 2 Calculated:. C, 64.82; H, 11.42; N, 15.12%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 1.31 (m, 20H, C H 2), 1.38 (m, 8H, C H 2), 1.61 (m, 4H, C H 2) , 2.43 (t, 4H, -C (O) C H 2) 4.12 (br s, 4H, N H 2), 8.89 (s, 2H, N H);

¹³ C NMR (100 MHz; DMSO-d ₆ ; TMS)? (Ppm) 26.3, 29.4, 30.6, 39.2 ( C H ₂ ), 171.2 (C = O).

Example 11

The product was obtained in the same manner as in Example 1 except that 11.61 g of hexanoic acid was used instead of adipic acid. As a result of analysis, the product was hexane hydrazide, the selectivity was more than 97%, and the yield was 95%. The analytical results of the above product are specified below:

Yield (12.35 g, 95%);

Elemental analysis (Measured: C, 54.97; H, 11.02; N, 21.31. Calculated for C ₆ H ₁₄ N ₂ O: C, 55.35; H, 10.84; N, 21.52%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 1.10 (t, 3H, C H 3), 1.35 (m, 2H, C H 2), 1.38 (m, 2H, C H 2) , 1.72 (m, 2H, C H ₂ ), 2.53 (m, 2H, -C H ₂ C (O)), 4.12 (br s, 2H, N H ₂ ), 8.56 (s, 1H, N H );

¹³ C NMR (100 MHz; DMSO-d ₆ ; TMS)? (Ppm) 16.2, 25.2, 29.1, 32.6, 39.9 ( C H ₂ ), 173.3 (C = O).

Example 12 :

The same procedure as in Example 1 was carried out except that 23.2 g of hexanoic acid was used instead of adipic acid to obtain a product. As a result of the analysis, the product was N'-hexanoylhexanehydrazide, the selectivity was 98% or more, and the yield was 96%. The analytical results of the above product are specified below:

Yield (10.96 g, 96%);

Elemental analysis (measured value: C, 63.23; H, 10.51 ; N, 12.11 C 12 H 24 N 2 O 2 Calculated:. C, 63.12; H, 10.59; N, 12.27%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 1.08 (t, 6H, C H 3), 1.32 (m, 4H, C H 2), 1.37 (m, 4H, C H 2) , 1.72 (m, 4H, C H ₂ ), 2.49 (m, 4H, -C H ₂ C (O)), 4.12 (br s, 4H, N H );

¹³ C NMR (100 MHz; DMSO-d ₆ ; TMS)? (Ppm) 15.4, 24.3, 27.1, 32.6, 39.9 ( C H ₂ ), 161.3 (C = O).

Example 13

The product was obtained by following the same procedure as in Example 1, except that 8.36 g of terephthalic acid was used instead of adipic acid. As a result of the analysis, the product was terephthalohydrazide, the selectivity was 98% or more, and the yield was 97%. The analytical results of the above product are specified below:

Yield (9.42 g, 97%);

Elemental analysis (measured value: C, 50.05; H, 5.12 ; N, 28.74 C 8 H 10 N 4 O 2 Calculated:. C, 49.48; H, 5.19; N, 28.85%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 4.34 (br s, 4H, N H 2), 8.23 (s, 4H, CH phenyl), 8.95 (s, 2H, N H);

^{13 C NMR (100 MHz; DMSO} -d 6; TMS) δ (ppm) 128.4 (C H phenyl), 137.3 (C phenyl), 168.9 (C = O).

Example 14 :

The product was obtained in the same manner as in Example 7 except that 8.36 g of terephthalic acid was used instead of adipic acid. Analysis the product was N ^'1 - (4- (hydrazine-carbonyl) benzoyl) as a terephthalate Gupta hydrazide [N' - was ^{1 (4- (hydrazinecarbonyl) benzoyl)} terephthalohydrazide], the selectivity was 97% or more , And the yield was 95%. The analytical results of the above product are specified below:

Yield (8.46 g, 95%);

Elemental analysis (measured value: C, 54.21; H, 4.42 ; N, 23.71 C 16 H 16 N 6 O 4 Calculated:. C, 53.93; H, 4.53; N, 23.58%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 4.34 (br s, 4H, N H 2), 8.33 (s, 8H, CH phenyl), 8.68 (s, 4H, N H);

¹³ C NMR (100 MHz; DMSO-d ₆ ; TMS)? (Ppm) 129.4 ( C H phenyl), 136.5 ( C phenyl), 160.6, 168.4 (C = O).

Example 15

The product was obtained by following the same procedure as in Example 1, except that 10.03 g of 2-chloroterephthalic acid was used instead of adipic acid. As a result of analysis, the product was 2-chloroterephthalohydrazide, the selectivity was 95% or more, and the yield was 93%. The analytical results of the above product are specified below:

Yield (10.61 g, 93%);

Elemental analysis (measured value: C, 42.24; H, 4.14 ; N, 24.71 C 8 H 9 ClN 4 O 2 Calcd:. C, 42.03; H, 3.97; N, 24.50%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 4.54 (br s, 4H, N H 2), 8.1-8.3 (m, 4H, CH phenyl), 8.92 (s, 2H, N H );

^{13 C NMR (100 MHz; DMSO} -d 6; TMS) δ (ppm) 126.3, 127.9, 129.1, 133.2, (C H phenyl) 137.2, 140.3 (C phenyl), 165.2, 168.9 (C = O).

Example 16

The same procedure as in Example 1 was carried out except that 9.08 g of 2-methylterephthalic acid was used instead of adipic acid, and the product was obtained. As a result of analysis, the product was 2-methylterephthalo-hydrazide, the selectivity was 98% or more, and the yield was 97%. The analytical results of the above product are specified below:

Yield (10.1 g, 97%);

Elemental analysis (measured value: C, 52.02; H, 5.74 ; N, 26.85 C 9 H 12 N 4 O 2 Calculated:. C, 51.92; H, 5.81; N, 26.91%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 2.54 (s, 3H, CH 3), 4.32 (br s, 4H, N H 2), 8.01-8.25 (m, 3H, CH phenyl ), 8.91 (s, 2H, N H);

^{13 C NMR (100 MHz; DMSO} -d 6; TMS) δ (ppm) 20.1 (CH3), 125.2, 126.9, 129.4 (C H phenyl) 138.2, 141.3 (C phenyl), 166.3, 168.1 (C = O).

Example 17

The product was obtained in the same manner as in Example 1 except that 17.21 g of 4-methylbenzenesulfonic acid was used instead of adipic acid. As a result of the analysis, the product was 4-methylbenzenesulfono-hydrazide, the selectivity was 96% or more, and the yield was 94%. The analytical results of the above product are specified below:

Yield (17.48 g, 94%);

Elemental analysis (measured value:. C, 45.35; H, 5.66; N, 15.25 S, 17.01 C 7 H 10 N 2 O 2 S Calculated: C, 45.15; H, 5.41 ; N, 15.04; S, 17.22%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 2.43 (s, 3H, CH 3), 4.16 (br s, 3H, N H, N H 2), 7.45, 7.81 (m, 4H , CH phenyl);

¹³ C NMR (100 MHz; DMSO-d ₆ ; TMS)? (Ppm) 22.1 (CH ₃ ), 129.4, 130.8 ( C H phenyl), 134.2, 138.3 ( C phenyl).

Example 18

The product was obtained in the same manner as in Example 1 except that 8.61 g of 4-methylbenzenesulfonic acid was used instead of adipic acid. As a result of analysis, the product was 4-methyl-N'-tosylbenzenesulfonohydrazide, the selectivity was 97%, and the yield was 95%. The analytical results of the above product are specified below:

Yield (8.08 g, 95%);

Elemental analysis (measured value:. C, 49.31; H, 4.48; N, 8.15 S, 19.03 C 14 H 16 N 2 O 4 S 2 Calculated: C, 49.40; H, 4.74 ; N, 8.23; S, 18.84%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 2.53 (s, 6H, CH 3), 4.03 (br s, 2H, N H), 7.45 (d, 4H, CH phenyl), 7.81 (d, 4H, CH phenyl);

¹³ C NMR (100 MHz; DMSO-d ₆ ; TMS)? (Ppm) 23.2 (CH ₃ ), 130.1, 131.6 ( C H phenyl), 135.3, 139.6 ( C phenyl).

Example 19

The same procedure as in Example 1 was carried out except that 14.22 g of 2,4,6-triisopropylbenzenesulfonic acid was used instead of adipic acid, and the product was obtained. As a result of analysis, the product was 2,4,6-triisopropylbenzenesulfonohydrazide, the selectivity was 97% or more, and the yield was 95%. The analytical results of the above product are specified below:

Yield (14.18 g, 95%);

Elemental analysis (measured value:. C, 60.23; H, 8.96; N, 9.22 S, 10.62 C 15 H 26 N 2 O 2 S Calculated: C, 60.37; H, 8.78 ; N, 9.39; S, 10.74%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 1.32 (d, 18H, CH 3), 2.92 (. Sep 3H, CH), 4.21 (br s, 3H, N H, N H 2 ), 7.43 (s, 2H, CH phenyl);

^{13 C NMR (100 MHz; DMSO} -d 6; TMS) δ (ppm) 23.7 (CH 3), 34.6 (CH), 123.2 (CH phenyl), 140.4, 151.3, 152.2 (C phenyl).

Example 20

The product was obtained in the same manner as in Example 1 except that 16.66 g of 4,4'-oxydibenzenesulfonic acid [4,4'-oxydibenzenesulfonic acid] was used instead of adipic acid. As a result of the analysis, the product was 4,4'-oxydibenzenesulfono-hydrazide, the selectivity was 98% or more, and the yield was 97%. The analytical results of the above product are specified below:

Yield (17.38 g, 97%);

Elemental analysis (measured value: C, 40.37; H, 3.69 ; N, 15.71 S, 18.03 C 12 H 14 N 4 O 5 S 2 Calculated:. C, 40.22; H, 3.94; N, 15.63; S, 17.89%);

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 4.06 (br s, 6H, N H, N H 2), 7.41 (d, 2H, CH phenyl), 7.78 (d, 2H, CH phenyl);

¹³ C NMR (100 MHz; DMSO-d ₆ ; TMS)? (Ppm) 119.4, 125.6 ( C H phenyl), 131.2, 161.3 ( C phenyl).

Example 21

The product was obtained in the same manner as in Example 20 except that 5.4 g (50.0 mmole) of the hydrazine-carbon dioxide bond [(H ₂ NNH ₂ ) ₂ CO ₂ ] in gel state was used instead of the solid hydrazine. As a result of the analysis, the product was 4,4'-oxydibenzenesulfono hydrazide, and the conversion was 99% or more, and the yield was 98% or more.

Example 22

The same procedure as in Example 20 was conducted except that 9.19 g of 4,4'-oxydibenzene-1-sulfonyl chloride was used instead of 4,4'-oxydibenzene-1-sulfonyl chloride. As a result of the analysis, the product was 4,4'-oxydibenzenesulfono-hydrazide and hydrazinium chloride, and 4,4'-oxydibenzenesulfono-hydrazide The selectivity of Drazide was over 96%, and the yield of 4,4'-oxydibenzenesulfono hydrazide after removal of hydrazinium chloride by using water was 91%.

Comparative Example 5

9.19 g of 4,4'-oxydibenzene-1-sulfonyl chloride and 5.2 g of hydrazine hydrate 100% (hydrazine content 64%) were dissolved in 20 g of water and reacted at 60 ° C for 12 hours. The compound obtained through the above reaction was 4,4'-oxydibenzenesulfono hydrazide and hydrazinium chloride. The conversion of 4,4'-oxydibenzenesulfono hydrazide was about 90%, and the selectivity The degree was about 95%. The yield of 4,4'-oxydibenzenesulfono hydrazide after complete removal of the hydrazinium chloride using water was about 79%.

Example 23

The product was obtained in the same manner as in Example 7 except that 16.66 g of 4,4'-oxydibenzenesulfonic acid was used instead of adipic acid. As a result of the analysis, the product was identified as 4- (4- (hydrazinylsulfonyl) -phenoxy) -N'- (4- (4- (hydrazinylsulfonyl) phenoxy) phenylsulfonyl) The selectivity was 97% or more, and the yield was 95% or more. The yield was 95% or more, . The analytical results of this compound are shown below. L

Yield (16.3 g, 95%);

Elemental analysis (measured value: C, 42.28; H, 3.59 ; N, 12. 17 S, 18.59 C 24 H 24 N 6 O 10 S 4 Calculated:. C, 42.10; H, 3.53; N, 12.27; S, 18.73% );

^{1 H NMR (400 MHz; DMSO} -d 6; TMS) δ (ppm) 3.74 (br s, 8H, N H, N H 2), 7.52 (d, 8H, CH phenyl), 7.83 (d, 8H, CH phenyl);

^{13 C NMR (100 MHz; DMSO} -d 6; TMS) δ (ppm) 118.3, 126.6 (C H phenyl), 132.4, 162.2 (C phenyl).

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics of the present invention. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the 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 invention .

Claims (21)

delete delete delete delete delete delete delete delete delete Carbon dioxide bonding compound represented by the following formula (I) or (I ') and a compound represented by the following formula (II) to synthesize a compound represented by the following formula (VI) or
/ RTI >
Method of preparing hydrazide derivative compound:
(I)

;
(I ')

;
≪ RTI ID = 0.0 &

;
(VI)

;
(VII)

;
In the above equations,
R ₁ represents an optionally substituted C _1-30 aliphatic hydrocarbon group, a C _3-30 aliphatic cyclic group which may be substituted, a C _3-30 heteroaliphatic cyclic group which may be substituted, C ₅ O, S, Se, N, P, As, F, Cl, and R are each independently selected from the group consisting of hydrogen, _-30 aromatic ring groups, and C _5-30 heteroaromatic ring groups that may be substituted, A C _1-30 aliphatic hydrocarbon group containing at least one Br or I, a C _3-30 aliphatic ring containing at least one Si, O, S, Se, N, P, A C _3-30 heteroaliphatic cyclic group containing at least one of Si, O, S, Se, N, P, As, F, Cl, Br or I and Si, O, S, Se, N, P , A C _5-30 heteroaromatic ring group containing at least one of As, F, Cl, Br or I.
Carbon dioxide bonding compound represented by the following formula (I) or (I ') and a compound represented by the following formula (III) to synthesize a compound represented by the following formula (VIII or IX)
/ RTI >
Method of preparing hydrazide derivative compound:
(I)

;
(I ')

;
(III)

;
(VIII)

;
(IX)

;
In the above equations,
R ₂ represents an optionally substituted C _1-30 aliphatic hydrocarbon group, a C _3-30 aliphatic cyclic group which may be substituted, a C _3-30 heteroaliphatic cyclic group which may be substituted, C ₅ O, S, Se, N, P, As, F, Cl, and R are each independently selected from the group consisting of hydrogen, _-30 aromatic ring groups, and C _5-30 heteroaromatic ring groups that may be substituted, A C _1-30 aliphatic hydrocarbon group containing at least one Br or I, a C _3-30 aliphatic ring containing at least one Si, O, S, Se, N, P, A C _3-30 heteroaliphatic cyclic group containing at least one of Si, O, S, Se, N, P, As, F, Cl, Br or I and Si, O, S, Se, N, P , A C _5-30 heteroaromatic ring group containing at least one of As, F, Cl, Br or I.
Carbon dioxide bonding compound represented by the following formula (I) or (I ') and a compound represented by the following formula (IV) to synthesize a compound represented by the following formula X or XI
/ RTI >
Method of preparing hydrazide derivative compound:
(I)

;
(I ')

;
(IV)

;
(X)

;
(XI)

;
In the above equations,
R ₃ represents an optionally substituted C _1-30 aliphatic hydrocarbon group, a C _3-30 aliphatic cyclic group which may be substituted, a C _3-30 heteroaliphatic cyclic group which may be substituted, C ₅ O, S, Se, N, P, As, F, Cl, and R are each independently selected from the group consisting of hydrogen, _-30 aromatic ring groups, and C _5-30 heteroaromatic ring groups that may be substituted, A C _1-30 aliphatic hydrocarbon group containing at least one Br or I, a C _3-30 aliphatic ring containing at least one Si, O, S, Se, N, P, A C _3-30 heteroaliphatic cyclic group containing at least one of Si, O, S, Se, N, P, As, F, Cl, Br or I and Si, O, S, Se, N, P , A C _5-30 heteroaromatic ring group containing at least one of As, F, Cl, Br or I.
Carbon dioxide bonding compound represented by the following formula (I) or (I ') and a compound represented by the following formula (V) to synthesize a compound represented by the following formula (XII) or
/ RTI >
Method of preparing hydrazide derivative compound:
(I)

;
(I ')

;
(V)

;
(XII)

;
(XIII)

;
In the above equations,
R ₄ represents a C _1-30 aliphatic hydrocarbon group which may be substituted, a C _3-30 aliphatic cyclic group which may be substituted, a C _3-30 heteroaliphatic cyclic group which may be substituted, C ₅ O, S, Se, N, P, As, F, Cl, and R are each independently selected from the group consisting of hydrogen, _-30 aromatic ring groups, and C _5-30 heteroaromatic ring groups that may be substituted, A C _1-30 aliphatic hydrocarbon group containing at least one Br or I, a C _3-30 aliphatic ring containing at least one Si, O, S, Se, N, P, A C _3-30 heteroaliphatic cyclic group containing at least one of Si, O, S, Se, N, P, As, F, Cl, Br or I and Si, O, S, Se, N, P , A C _5-30 heteroaromatic ring group containing at least one of As, F, Cl, Br or I.
14. The method according to claim 11 or 13,
R ₂ and R ₄ are each independently selected from the group consisting of O, S, NR _5, and PR ₆ ; and R ₅ and R ₆ are each independently hydrogen, _optionally substituted C _1-30 An aliphatic hydrocarbon group, a C _3-30 aliphatic cyclic group which may be substituted, a C _3-30 hetero aliphatic cyclic group which may be substituted, a C _5-30 aromatic cyclic group which may be substituted, and C _5-30 A C _1-30 aliphatic hydrocarbon group containing at least one of Si, O, S, Se, N, P, As, F, Cl, Br or I, Si, O, S , A C _3-30 aliphatic cyclic group containing at least one of Se, N, P, As, F, Cl, Br or I, Si, O, S, Se, N, P, As, the I comprises at least one C _3-30 aliphatic hetero ring group, and Si, O, S, Se, N, P, As, F, Cl, Br or I with a contains at least one C _5-30 heteroaromatic Selected from the group consisting of The method of producing a hydrazide derivative compound comprises a.
14. The method according to any one of claims 10 to 13,
Wherein the reaction is carried out without using a solvent.
14. The method according to any one of claims 10 to 13,
Wherein the reaction is carried out at a temperature ranging from 100 ° C to 170 ° C.
14. The method according to any one of claims 10 to 13,
Wherein the reaction is carried out in the presence of a solvent.
18. The method of claim 17,
Wherein the solvent is selected from the group consisting of alcohols having 1 to 15 carbon atoms, ethers having 2 to 16 carbon atoms, aliphatic hydrocarbons having 5 to 15 carbon atoms, aromatic hydrocarbons having 6 to 15 carbon atoms, and combinations thereof. A process for producing a drazide derivative compound.
18. The method of claim 17,
Wherein the amount of the solvent used is 70% by weight or less based on the total weight of the hydrazide derivative compound.
19. The method of claim 18,
The alcohol may be selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n- pentanol, isopentanol, sec- But are not limited to those selected from the group consisting of propylene glycol, octanol, nonanol, decanol, undecanol, dodecanol, pentadecanol, ethylene glycol, glycerol, erythritol, xylitol, mannitol, polyol, , Hydrazide derivative compound.
19. The method of claim 18,
Wherein the ether comprises a compound selected from the group consisting of dimethyl ether, diethyl ether, tetrahydrofuran, dioxin, and combinations thereof.