WO2016039466A1

WO2016039466A1 - New production method for azodicarbonamide

Info

Publication number: WO2016039466A1
Application number: PCT/JP2015/075926
Authority: WO
Inventors: 谷口　正俊
Original assignee: Ｉ＆Ｃ・ケムテック株式会社
Priority date: 2014-09-12
Filing date: 2015-09-11
Publication date: 2016-03-17
Also published as: JPWO2016039466A1; JP6165349B2; CN106795105B; CN106795105A

Abstract

　Provided is an economical, safe, and more environmentally-friendly production method for azodicarbonamide.　According to the present invention, in a homogeneous system or heterogeneous miscible system of water or an organic solvent or an ionic solution, and an organic solvent and/or an ionic solution and water, azodicarbonamide is produced by using hydrogen peroxide in urea and reacting active chlorine or active chlorine ions and an active bromine compound such as active bromine or active bromine ions and/or an active form derived from hydrogen peroxide, or by electrolytically oxidizing an intermediate as desired to obtain a target, and recycling and using post-reaction byproducts.

Description

New production method of azodicarbonamide

The present invention relates to a production method for obtaining azodicarbonamide using a urea active derivative and a structure.

Azodicarbonamide is a useful compound widely used as a foaming agent from the viewpoint of its decomposition behavior, physical properties, and chemical properties.

As shown in the following reaction formula (1), the most commonly practiced conventional production method involves reacting hydrazine hydrate produced from urea or ammonia with 2 moles of urea. This is a method for producing azodicarbonamide by several stages of reaction including the above (Patent Document 1). This conventional production method causes wasteful consumption of raw materials that do not contribute to the molecular structure of the target product azodicarbonamide, which causes an increase in cost. Another problem is the generation of a large amount of ammonia as a by-product and carbon dioxide that causes global warming. Furthermore, since this method uses a chlorinating agent, an oxidizing agent, a strong acid, a heavy metal catalyst, or the like, a large amount of waste water containing a large amount of salts, acids, heavy metals, ammonia nitrogen, and the like is generated as waste. Since disposal is required to dispose of these, it costs a large amount of processing costs, increases product costs, and may cause pollution. Sometimes it is possible.

In a recently published document (Patent Document 4), the structural formula of urea and the structural formula of azodicarbonamide (ADCA) are completely different by using a special apparatus in a special method called organic electrolytic synthesis from urea. Nevertheless, it is described that ADCA is suddenly generated from urea. It is illogical if it reacts with other raw materials from urea to produce various reaction intermediates and the desired ADCA is not obtained. Also in the energy yield, if the electric energy required for the direct reaction is calculated, there is a problem that a large amount of electric energy having a very low electric energy yield is wasted. Details will be given in later sections.

[The azodicarbonamide production method currently in practical use is a technology developed more than 40 years ago, and no major technological innovation has been made since then. As a technique disclosed in a relatively recent patent, a semicarbazide (represented by the formula (5)) is obtained by subjecting the amino isocyanate of the above reaction formula 1 (a compound represented by the formula (3)) to ammonia decomposition under pressure. An obtaining method has been reported (Patent Document 2). However, only one step is shortened. For this reason, it is necessary to use a large excess of liquid ammonia in a pressurized container, and there is a risk of a high-pressure reaction. Moreover, a high pressure reaction vessel is required. Furthermore, there are problems such as recovery of excess liquid ammonia and by-production of an equal amount of ammonium chloride, so that neither production rationalization nor economic innovation occurs. Overall, it is counterproductive.

The production method of chlorourea and bromourea used as raw materials or intermediates used in the present invention is described in (Patent Document 3) in addition to (Patent Document 1).

In a recently published document (Patent Document 4), the actual state of the reaction has not been elucidated at all using a special method and a special apparatus called an organic electrolytic synthesis method from urea. Various general problems and drawbacks have already been pointed out in the background section. It is a patent that the object that is completely different from the raw material can be unknown at once, special equipment, special technology is necessary, and if you do not perform continuous recycling reaction with raw materials with complicated composition, you can obtain the object I can't. Furthermore, since the raw material is used in a large excess, it is essential to recycle the raw material. Prediction of side reactions and impurities from the side reactions can be predicted, but there is no explanation for these exclusions and purification. Apart from the evaluation of the entire production method, the evaluation results of the energy consumption of only pure chemical reactions shown in this patent document are shown below. The biggest problem is that when the other energy necessary for the production is excluded and examined, since it is an electrolytic method, the energy required only for the electrolytic reaction is electric energy. Since a large amount of electric energy is consumed for the reaction, electric energy is regarded as a raw material as well as a chemical raw material. The unit of electrical energy used today is indicated in coulombs, not Faraday. When the contents of Example 1 of Patent Document (4) are verified, the amount of electricity consumed (used for the reaction) in Example (1) is represented by current × time (second unit) (coulomb). 1.5 cm ² (electrode area) × 66.7 × 10 ⁻³ (A / cm ² ) (current density) × 5.4 × 3600 seconds (5.4 hours) = 1944.97 coulombs. The yield of the target product (ADCA) is tentatively 100% and is 0.32 g. The molecular weight of azodicarbonamide (ADCA) is 116. The ADCA thus obtained is 0.32 ÷ 116 = 0.00276 mol. In order to obtain 1 mol ADCA by Chemical formula (8) in patent document, it is described that 4 electron mol is required. According to Coulomb's law, 1 mol = 96500 coulomb, and the corresponding quantity of electricity used to acquire the actual object is 266.34 coulomb × 4 = 1065.36 coulomb even if the purity is assumed to be 100%. Therefore, the electricity yield is 1065.36 coulombs (theoretical electricity consumed for the production of the target product) ÷ 1944.97 coulombs (actually consumed electricity) = 54.77%. The ADCA with 100% purity was not obtained, and when considering the loss at the time of separation, etc., the yield is considerably reduced. It is a very inefficient reaction of about 50% and can be said to be a mass of electric energy. It can be said that electric energy is wasted. It is an era when electricity costs are rising due to demand for power generation from renewable energy as a social trend. The method of this patent document has a big problem of wasting a large amount of expensive electricity for manufacturing, and cannot be said to be an economically advantageous method or a method that meets the demands of the times.

U.S. Pat. No. 2,996,631 Japanese Patent No. 2952712 International Publication Number WO2012 / 038954 International Publication Number WO2012 / 147953

An object of the present invention is to provide an epoch-making production method of azodicarbonamide that is simple, safe and has a reduced environmental burden.

In order to solve the above-mentioned problems, the present inventors have conducted intensive research on a simple and efficient method of reacting urea with an active urea derivative and an active structure of urea. As a result, in a homogeneous or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water, as a logical production method, active urea under normal pressure is analyzed. By reacting the active structure of the derivative and urea with urea, there is no need to make fine adjustments to the special organic electrolyzer, delicate operating conditions and reaction system at all times, and there is a risk of hydrogen that can explode. There is no short circuit between electrodes, there is no risk of explosion, and there is no risk of explosion. Large-scale, inexpensive industrial chemicals such as hydrogen peroxide, peroxide, ozone and other oxidizing agents and halogen acids or halogen salts. Anyone who is involved in the production of normal chemical products can easily operate without using a new device or a special device, and the plant currently in use can be used as it is. Target in industrially advantageous, large environmental load reduction effect, they found a method for producing energy-saving azodicarbonamide, and have completed the present invention.

Detailed Description of Means for Solving the Problems The present invention provides a method for producing azodicarbonamide according to the following items 1 to 13.
Item 1: Urea represented by formula (1) is represented by formula (10) in a homogeneous system or a heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water. Since the compound represented by the formula (10) is chemically very active, a de-HBr reaction is immediately generated and converted into the compound of the formula (7). A novel process for producing azodicarbonamide formula (7).

Item 2: Urea represented by the formula (1) is converted into water or an organic solvent or ionic liquid and an organic solvent or a homogeneous system or a heterogeneous mixed system of ionic liquid and water under the acidic condition (9) A compound of formula (10) is obtained by reacting a urea molecule with a bromourea active transition intermediate represented by the formula: A novel process for the preparation of azodicarbonamide formula (7), wherein the compound of formula (10) is chemically active and immediately undergoes de-HBr reaction to be converted to the compound of formula (7).

Item 3: Urea represented by the formula (1) can be converted from urea to acidic conditions in a homogeneous or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water. N-bromourea represented by the formula (8) is generated by an agent or a bromination method, and then brominated by electrophilic oxidation with an active bromo compound of NH group to which a bromo atom is bonded or a hydrogen peroxide-derived activator. A urea active transition intermediate formula (9) is obtained and at the same time urea molecules react to obtain a compound of formula (10). A novel process for the preparation of azodicarbonamide formula (7), wherein the compound of formula (10) is chemically active and immediately undergoes de-HBr reaction and is converted to the compound of formula (7).

Item 4: Urea represented by formula (1) is subjected to chlorination reaction under acidic conditions in a homogeneous or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water. The compound of formula (11) is obtained. Monochlorourea of formula (11) (including N-chlorourea Na salt) is subjected to bromination or bromination to obtain N-bromourea represented by formula (8). Next, the bromourea active transition intermediate formula (9) is obtained by electrophilic oxidation with the active bromo compound of NH group to which the bromo atom is bonded or the hydrogen peroxide-derived activator, and at the same time, the urea molecule reacts and the formula (10) A compound is obtained. A novel process for the preparation of azodicarbonamide formula (7), wherein the compound of formula (10) is chemically active and immediately undergoes de-HBr reaction and is converted to the compound of formula (7).

Item 5: Urea represented by the formula (1) can be converted from urea to acidic bromine under acidic conditions in a homogeneous or heterogeneous mixed system of water or organic solvent or ionic liquid and organic solvent or ionic liquid and water. N-bromourea represented by the formula (8) is produced by an agent or bromination method, and then electrophilic oxidation of the NH group to which the bromine atom is bonded is electrolyzed and desorbed as a proton by electrolysis, Bromourea active transition intermediate Formula (9). At the same time, urea molecules react to obtain a compound of formula (10). A novel process for the preparation of azodicarbonamide formula (7), wherein the compound of formula (10) is chemically active and immediately undergoes de-HBr reaction and is converted to the compound of formula (7).

Item 6: When an electrolytic reaction is used for urea represented by formula (1) in water or an organic solvent or ionic liquid, and an organic solvent or a homogeneous system or a heterogeneous mixed system of ionic liquid and water. Using a mixture of hydrogen bromide, bromo salt and hydrogen chloride, chloride salt as a supporting electrolyte, two-electron oxidation under acidic conditions to generate a bromo cation to produce N-bromourea represented by formula (8) Then, electrophilic oxidation of the NH group to which the bromo atom is bonded is subjected to two-electron oxidation by an electrolytic reaction and eliminated as a proton to obtain a bromourea active transition intermediate formula (9). At the same time, urea molecules react to obtain a compound of formula (10). A novel process for the preparation of azodicarbonamide formula (7), wherein the compound of formula (10) is chemically active and immediately undergoes de-HBr reaction and is converted to the compound of formula (7).

Item 7: The urea represented by the formula (1) is converted from urea to a bromine under acidic conditions in a homogeneous or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water. An N-bromourea represented by the formula (8) is produced by a chlorinating agent or a bromination method, or, if necessary, it is represented by the formula (11) from urea by a chlorinating agent or a chlorination method under acidic conditions. Chlorourea (including N-chlorourea Na salt) is produced, then N-bromourea represented by the formula (8) is produced by a brominating agent or bromination method, and then supported using an electrolytic reaction. Using a mixture of hydrogen bromide, bromo salt and hydrogen chloride, chloride salt as an electrolyte, two-electron oxidation produces a bromo cation to produce N-bromourea represented by formula (8), followed by bromine Electrophilic acid of NH group to which atom is bonded The desorbed as protons and two-electron oxidized by electrolytic reaction, the bromine urea active transition intermediate (9). At the same time, urea molecules react to obtain a compound of formula (10). A novel process for the preparation of azodicarbonamide formula (7), wherein the compound of formula (10) is chemically active and immediately undergoes de-HBr reaction and is converted to the compound of formula (7).

Item 8: Urea represented by the formula (1) is hydrogen bromide under acidic conditions in water or an organic solvent or ionic liquid, and an organic solvent or a homogeneous or heterogeneous mixture of ionic liquid and water. Then, bromine is generated by adding a peroxide such as hydrogen peroxide dropwise to a mixture of bromo salt, hydrogen chloride and chloride salt. The urea represented by the formula (1) is generated by the generated bromine, hypobromite, and hypobromite, and the N-bromourea represented by the formula (8) is generated by the two-electron oxidation by the brom cation. Then, the bromourea active transition intermediate formula (9) is obtained by electrophilic oxidation with an active bromo compound of NH group to which a bromo atom is bonded or an active substance derived from hydrogen peroxide, and at the same time, a urea molecule reacts with the formula (10 ) Is obtained. A novel process for the preparation of azodicarbonamide formula (7), wherein the compound of formula (10) is chemically active and immediately undergoes de-HBr reaction and is converted to the compound of formula (7).

Item 9: The urea represented by the formula (1) is converted into an organic bromide under acidic conditions in a homogeneous system or a heterogeneous mixed system of water, an organic solvent or an ionic liquid, and an organic solvent or an ionic liquid and water. Using an agent and a bromine-dioxane complex as an oxidizing agent and an active brominated compound generator, urea is two-electron-oxidized by a brom cation to produce N-bromourea represented by the formula (8), and then a bromine atom is bonded. Bromourea active transition intermediate formula (9) is obtained by electrophilic oxidation with an active bromine compound of NH group or an active substance derived from hydrogen peroxide, and at the same time, urea molecules react to obtain a compound of formula (10). A novel process for the preparation of azodicarbonamide formula (7), wherein the compound of formula (10) is chemically active and immediately undergoes de-HBr reaction and is converted to the compound of formula (7).

Item 10: In a homogeneous system or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water, a halogen acid salt such as hydrogen bromide or hydrogen chloride of urea is used as a raw material Then, chlorine or bromine is generated by dropping a peroxide such as hydrogen peroxide under acidic conditions. Generated and converted chlorine, hypochlorous acid, hypochlorite, bromine, hypobromite, hypobromite, chlorinated and brominated urea represented by formula (1) A novel process for producing an azodicarbonamide according to any one of Items 1 to 9

Item 11: A novel method for producing azodicarbonamide formula (7), wherein the method of the corresponding item is taken from the method of Item 1 to Item 10 using a mixture of urea and urea salt as a raw material.

Item 12: When a large excess of urea is used under acidic conditions and a peroxide such as hydrogen peroxide is used, the reaction is performed at a temperature of 20 to 80 ° C. under acidic conditions of PH = 3 or less. Item 1 is characterized in that when the intermediate is subjected to electrolytic oxidation, the reaction is carried out at a temperature between -25 to 60 ° C. during the electrolytic reaction, and the acidity, temperature and peroxide are selected according to the reaction method and conditions. 12. A novel process for producing azodicarbonamide according to items 11 to 11.

Item 13: When a halogen or a halogen compound is used with a peroxide such as hydrogen peroxide as an oxidizing agent, it is stable to water such as cerium compound, vanadium compound, selenium compound, tellurium compound, transition metal compound and aluminum fluoride. 13. A novel process for producing an azodicarbonamide formula (7) according to items 1 to 12, wherein a strong Lewis acid is used as a catalyst and an acid such as formic acid or acetic acid is used.

[Wherein M represents hydrogen and a monovalent to tetravalent metal selected from the group consisting of Li, Na, K, Mg, Ca, Mn, Fe, Ni, Cu, Ag, Zn, and Sn. X represents a chlorine atom and a bromine atom. m represents an integer of 1 to 4. ], Hydrogen peroxide, ozone, and peroxide.

[In the formula, M is hydrogen, Li, Na, K, Mg, Ca, Ti, Zr, Mn, Fe, Ni, Cu, Ag, Zn, Al, Si, Sn, or other metal ions, in formula (13) The cation portion of the represented compound represents H and ammonium ion, primary ammonium ion, secondary ammonium ion, tertiary ammonium ion, and X is a halogen anion and an organic brominating agent anion.] And iodine Molecule, bromine molecule, chlorine molecule, chlorobromine.

The present invention is an efficient production method for directly obtaining the azodicarbonamide represented by the formula (7) from the urea represented by the formula (1) in one step. Since it is carried out in a homogeneous or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water, it is a simple, safe and inexpensive production method with a low environmental load. Moreover, since the produced azodicarbonamide is precipitated as a solid, separation and purification are easy. Further, since the aqueous solution containing the compounds represented by formulas (12) to (13), hydrogen halide, or halogen and unreacted urea used in the reaction can be circulated and reused as it is, almost no waste is removed from the system. It is a manufacturing method with less environmental impact. The urea of formula (1) may be urea hydrochloride, bromate or other salts, and the hydrogen halide or halogen salt used for the halogenation is in an amount relative to the urea to be reacted. is there. Although the peroxide etc. which are used as an oxidizing agent can be used, since hydrogen peroxide becomes final water, there is no generation of by-products and waste. In addition, when an electrolysis method is used, if a gas diffusion electrode is used, hydrogen is not generated and power consumption can be suppressed.

Hereinafter, the present invention will be described in detail.
The present invention relates to a homogeneous or heterogeneous mixture of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water, with or under active conditions of urea or urea salts under acidic conditions. By performing oxidation reaction of bromide compounds and hydrogen peroxide-derived active substances, or by electrolytically oxidizing intermediates of chlorourea and bromourea, by-produced hydrogen halide and halogen salts are recycled and discarded. This is a method for producing an azodicarbonamide having no product, and is represented by the following reaction formula.

The chemical reaction is a homogeneous or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water. Urea or a salt thereof represented by formula (1) A compound represented by formula (12) under acidic conditions, a chlorinating agent or a brominating agent prepared from the compound represented by formula (13), and replicated hydrogen chloride or chloride salt and hydrogen bromide Alternatively, the hydrogen bromide salt is recycled using an oxidizing agent such as hydrogen peroxide that does not produce by-products. The compound (11) or compound (8) proceeds with an active bromide compound and a hydrogen peroxide-derived activator or by electrolyzing two molecules of urea theoretically by four-electron oxidation. The active bromide compound and the hydrogen peroxide-derived activator include compounds and chemical species known in the art, but are not limited to specific compounds and chemical species. In this reaction, under acidic conditions, hydrogen chloride, hydrogen bromide, chlorine, bromine, hypochlorous acid, hypochlorous acid and hydrogen peroxide undergo a correlation reaction with each other, resulting in a competitive reaction. These compounds also coordinate with urea to form complexes, complicating the reaction. When hydrogen peroxide or its active substance acts on the above halogen compounds under acidic conditions, an active bromine compound is produced. On the other hand, when the halogen compound acts on hydrogen peroxide and its active substance under acidic conditions, an active substance derived from hydrogen peroxide is generated. It is the compounds such as strong Lewis acid, formic acid, and acetic acid that are stable in water carrying tellurium compounds, vanadium compounds, cerium compounds, selenium compounds, transition metal compounds, aluminum fluoride, and the like that help generate each active form. . The active bromide compound and / or the hydrogen peroxide-derived activator may be any compound or chemical species that oxidizes bromourea to form a bromourea active transition intermediate, and there are many compounds and chemical species belonging to them. However, it is not particularly limited to a specific compound or chemical species.

[Wherein M represents hydrogen and a monovalent to tetravalent metal selected from the group consisting of Li, Na, K, Mg, Ca, Mn, Fe, Ni, Cu, Ag, Zn, and Sn. X represents a chlorine atom, a bromine atom, or an iodine atom. m represents an integer of 1 to 4. ], Hydrogen peroxide, ozone, and peroxide.

Examples of the compound represented by the formula (12) include hypochlorous acid, lithium hypochlorite, chlorous acid, lithium chlorite, chloric acid, lithium chlorate, perchloric acid, lithium perchlorate, Sodium hypochlorite, sodium chlorite, sodium chlorate, sodium perchlorate, potassium hypochlorite, potassium chlorite, potassium chlorate, potassium perchlorate, calcium hypochlorite, calcium chlorite , Calcium chlorate, calcium perchlorate, magnesium hypochlorite, magnesium chlorite, magnesium chlorate, magnesium perchlorate, hypobromite, lithium hypobromite, bromite, lithium bromite, Bromate, lithium bromate, perbromate, lithium perbromate, sodium hypobromite, sodium bromate, sodium bromate, sodium perbromate , Potassium hypobromite, potassium bromite, potassium bromate, potassium perbromate, calcium hypobromite, calcium bromate, calcium bromate, calcium perbromate, magnesium hypobromite, hypoiodide Acid, lithium hypoiodite, iodic acid, lithium iodate, iodic acid, lithium iodate, periodic acid, lithium periodate, sodium hypoiodite, sodium iodate, sodium iodate, periodate Sodium phosphate, potassium hypoiodite, potassium iodate, potassium periodate, calcium hypoiodite, calcium iodate, calcium iodate, calcium periodate, magnesium hypoiodite, magnesium iodate, Hypohalous acid such as magnesium iodate and magnesium periodate, halous acid, halogen acid, perhalogen acid, and salts thereof Fine hydrogen peroxide, mention may be made of ozone, a peroxide. The compound represented by the formula (12) can be used for generating an active bromide compound and / or an active form derived from hydrogen peroxide. The active bromide compound includes a compound generated in the reaction system, and examples thereof include a brom cation, a brom cation radical, a brom radical, bromine chloride, a bromine complex (for example, dioxane complex) and the like. The hydrogen peroxide-derived active substance includes compounds generated in the reaction system, such as OH cation, OH radical, OOH radical, singlet oxygen, OOH anion, OOH cation, superoxide, superoxide anion. , Superoxide anion radical, peroxy radical, hydroperoxyl radical and the like.

The compound represented by the formula (12) is preferably hypochlorous acid, hypobromite, sodium hypochlorite, sodium chlorate, potassium hypochlorite, potassium chlorate, calcium hypochlorite. , Calcium chlorate, magnesium hypochlorite, magnesium chlorate, hypobromite, sodium hypobromite, sodium bromate, potassium hypobromite, potassium bromate, calcium hypobromite, calcium bromate, Magnesium hypobromite, magnesium bromate, hypoiodic acid, sodium hypoiodite, sodium iodate, potassium hypoiodite, potassium iodate, calcium hypoiodite, calcium iodate, magnesium hypoiodite , Magnesium iodate and the like, and hydrogen peroxide, ozone, and peroxide, but are not limited to these compounds. There.

(In the formula, M represents a monovalent to tetravalent metal selected from the group consisting of hydrogen, Li, Na, K, Mg, Ca, Mn, Fe, Ni, Cu, Ag, Zn, and Sn. And H And an ammonium ion, a primary ammonium ion, a secondary ammonium ion, a tertiary ammonium ion and a halogen cation, X is a halogen anion and an organic brominating agent anion component, and a bromine molecule, a chlorine molecule, a chloro molecule. Indicates bromine.)

Examples of the halogen in X in the formula (13) include chlorine, bromine and iodine.

Examples of the compound represented by the formula (13) include hydrogen chloride, hydrogen bromide, hydrogen iodide, lithium chloride, sodium chloride, potassium chloride, calcium chloride, copper chloride, magnesium chloride, iron chloride, zinc chloride, and chloride. Nickel, tin chloride, silver chloride, lithium bromide, sodium bromide, potassium bromide, calcium bromide, copper bromide, magnesium bromide, iron bromide, manganese bromide, zinc bromide, nickel bromide, bromide Tin, silver bromide, lithium iodide, sodium iodide, potassium iodide, calcium iodide, copper iodide, magnesium iodide, iron iodide, manganese iodide, zinc iodide, nickel iodide, tin iodide, Silver iodide, ammonium chloride, monomethylammonium chloride, dimethylammonium chloride, trimethylammonium chloride, tetramethylammonium chloride, bromide Primary, secondary, alkyl groups, aryl groups, aralkyl groups, alkenyl groups, etc., which may have substituents such as ammonium, monomethylammonium bromide, dimethylammonium bromide, trimethylammonium bromide, tetramethylammonium bromide, Tertiary and quaternary ammonium salts, such as nitrogen-containing compounds, nitrogen-containing cyclic hydrogen halide salts and chlorine, bromine, chlorobromine and organic halogenating agents dibromoisocyanuric acid, N-bromosuccinimide, benzyltrimethylammonium Tribromide, boron tribromide, pyridinium bromide perbromide, 1-butyl-3-methylimidazole tribromide, triphenylphosphine dibromide, benzyltrimethyltetrachloroiodate, Zen sulfonic Crawlers bromide sodium, N- chlorosuccinimide, cash in acid chloride, N- chloro phthalimide, oxalyl chloride, methanesulfonyl chloride, and the like. The compound represented by the formula (13) can be used to generate an active bromide compound and / or an active form derived from hydrogen peroxide. It can be used to generate active bromide compounds and / or hydrogen peroxide derived activators. The active bromide compound includes a compound generated in the reaction system, and examples thereof include a brom cation, a brom cation radical, a brom radical, bromine chloride, a bromine complex (for example, dioxane complex) and the like. The hydrogen peroxide-derived active substance includes compounds generated in the reaction system, such as OH cation, OH radical, OOH radical, singlet oxygen, OOH anion, OOH cation, superoxide anion, superoxide. Anion radical, peroxy radical, hydroperoxyl radical and the like can be mentioned.

The compound represented by the formula (13) is preferably hydrogen chloride, hydrogen bromide, lithium chloride, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, zinc chloride, iron chloride, copper chloride, lithium bromide, Sodium bromide, potassium bromide, calcium bromide, magnesium bromide, zinc bromide, copper bromide, lithium iodide, sodium iodide, potassium iodide, copper iodide, ammonium chloride, ammonium bromide, chlorine, bromine , Iodine, chlorobromine, dibromoisocyanuric acid, N-bromosuccinimide and the like, but are not particularly limited to these compounds.

Examples of the halogen in X in the formula (13) include fluorine, chlorine, bromine and iodine.

In addition, examples of the hydrogen halide include hydrogen chloride, hydrogen bromide, and hydrogen iodide.

In addition, examples of the halogen include chlorine, bromine, and iodine. When oxidizing using chlorine, bromine, iodine, chlorine compounds, bromine compounds, iodine compounds, water carrying tellurium compounds, vanadium compounds, cerium compounds, selenium compounds, transition metal compounds, aluminum fluoride, etc. The use of highly stable strong Lewis acids as catalysts and the use of acids such as formic acid and acetic acid are effective. The invention is not particularly limited to this.

It is preferable that urea as a raw material is contained at a concentration of 0.5 to 50 mol / L in a homogeneous system or a heterogeneous mixed system with water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid. The concentration is preferably 2 to 30 mol / L. The invention is not particularly limited to this.

The concentration of urea is influenced by the solubility with respect to temperature and the ratio of bromine-based oxidant, but basically, the presence of a high concentration and a large amount of urea is preferable. The molar ratio of a compound such as a halogen-based oxidant to urea is preferably such that when the active intermediate transition compound bromourea cation (compound 9) is formed, its surroundings are enveloped with urea. The compound such as halogen-based oxidizing agent is 0.01 to 0.45 molar ratio, but preferably 0.05 to 0.3 molar ratio. Hydrogen peroxide, a substantial oxidant, corresponds to these numbers. However, it is not particularly limited to this.

The series of reactions of the present invention does not require separation of intermediates. If necessary, the compounds represented by the formulas (8) and (11) can be separated and stored, and can be used as raw materials for other derivatives.

The temperature of the series of reactions of the present invention is too low for converting halogen anions to halogen molecules, halogen cations, active halogen species with an oxidizing agent such as hydrogen peroxide, and for the production of hydrogen peroxide active substances. In this case, the solubility of the salt is lowered and the activity of an oxidizing agent such as hydrogen peroxide is reduced. The reaction is carried out at −200 to 100 ° C., preferably −10 to 70 ° C. It is desirable to adjust the temperature according to the reaction conditions in view of the stability and reactivity of the reaction intermediate and reaction active intermediate. However, an aqueous solution of urea has a significantly reduced freezing point. When the electrolytic method is applied to the intermediate, it is desirable to react at a low temperature in order to decompose the active intermediate and suppress side reactions from the heat generated during electrolysis. The reaction is carried out at −50 to 100 ° C., preferably −20 to 40 ° C. It is also possible to carry out the reaction at a low temperature. In addition, the reaction can be performed at a low temperature even in a homogeneous mixed system with an organic solvent or an ionic liquid. The invention is not particularly limited to this.

Examples of the organic solvent that can be used in the present invention include halogen solvents such as dichloroethane, carbon tetrachloride, and chlorobenzene, and chain or cyclic alkanes such as n-pentane, n-hexane, cyclopentane, and cyclohexane, Ethers such as tetrahydrofuran, 1,2-dimethoxyethane, dioxane, methyl-t-butyl ether and methylcyclopentyl ether, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone, methyl Examples include alcohols such as alcohol, ethyl alcohol, and isopropyl alcohol, and polar solvents such as DMF, DMSO, HEMPA, tributyl phosphate, and 1,3-dimethylimidazoline. Moreover, about an ionic liquid, you may have imidazolium which may have a substituent, quaternary ammonium, pyridinium which may have a substituent, phosphonium, and a substituent as a cation component. Pyrrolidiniums, sulfoniums, anion components such as boron tetrafluoride, phosphorus hexafluoride, trifluoroacetic acid, trifluoromethanesulfonic acid, bistrifluoromethanesulfonimide, alkylsulfonic acid, acetic acid, nitric acid, chlorine, bromine Can be mentioned. Examples of the ionic liquid include salts of these cationic components and anionic components. In particular, it is not limited to these. The use of water, an organic solvent, or an ionic liquid alone may be used. A combination of these may also be used. In the combined solvent system of the above solvent and each solvent, the solution containing urea may be a homogeneous phase or a heterogeneous phase (liquid phase separation state). When using a mixed solvent of water and an organic solvent, in the case of a heterogeneous system, the raw materials and various reagents are mainly dissolved in the aqueous layer. In addition, various reagents are mainly dissolved. In a solvent system in which urea and salts do not dissolve at all, it is important that urea and salts are dispersed in the solvent as fine particles as possible.

In this synthesis reaction, it is not necessary to react all of the added raw material urea within the reaction time. Rather, a compound represented by the formula (10) is produced when a large excess of urea is present around the active intermediate. It is easy to increase the yield. The azodicarbonamide solid produced directly in the reaction is continuously separated, and the solution containing urea, halogenating agent, and reaction accelerator is recycled, and urea, halogenating agent, and reaction accelerator are added as necessary. And it can also be set as the manufacturing method circulated, adjusting a liquid composition. Basically, the halogenating agent is a hydrogen halide or halogen salt after the reaction, but it is regenerated to a halogen with a peroxide such as hydrogen peroxide, so when using hydrogen peroxide in particular, The oxidation by-product is a small amount of water, and it is not necessary to adjust the liquid composition from the accumulation of by-products generated in minute amounts to the limit of recycling.

That is, unreacted urea recovered as a filtrate, a compound selected from the compounds represented by formulas (12) to (13), a by-product hydrogen halide or a halide salt, consumed urea and the compound Water, an organic solvent or an ionic liquid, and an organic solvent or a homogeneous system or a heterogeneous mixed system of ionic liquid and water can be used again as a reaction solution. By these treatments, the highest conversion rate of urea can be achieved, the concentration of urea or urea salt, the stirring speed of the reaction mixture in the reaction tank, the reaction temperature, the addition rate of oxidizing agents such as hydrogen peroxide, and the reaction acceleration It is possible to recycle the reaction system under conditions such as the agent concentration.

When using an electrolytic reaction or a combination, this electrolytic reaction may be constant voltage electrolysis or constant current electrolysis. Moreover, any method of a non-diaphragm, a diaphragm, and an ion exchange membrane is possible as an electrolysis method. Further, it is possible to install a gas diffusion electrode on the cathode of these electrolysis devices.

As the anode in the electrolysis of the present invention, a metal electrode, a carbon electrode, and a composite electrode thereof can be used.

As anode materials, noble metals such as gold, silver, platinum and ruthenium and minor metals such as titanium, chromium, nickel and manganese, and electrodes coated with noble metals other than noble metals such as titanium, stainless steel, iron and hastelloy And electrodes coated with precious metals on substrates other than metals such as olefin resins, engineering resins, carbon-based substrates, composite coated electrodes of metal oxides such as iridium oxide and ruthenium oxide and platinum, and coatings similar to the above with minor metals An electrode etc. are mentioned.

Also, examples of the carbon-based electrode include carbon-based electrodes such as carbon, glassy carbon, graphite, graphene, carbon sheet, carbon fiber sheet, carbon fiber cloth, diamond-like coated electrode, and composite electrodes thereof.

Preferred as the anode is an electrode in which platinum is coated on a metal substrate other than a noble metal such as platinum, titanium, titanium, stainless steel, iron, or hastelloy, and a substrate other than a metal such as an olefin resin, an engineering resin, or a carbon-based substrate. Electrode coated with platinum, composite electrode of platinum with metal oxide such as iridium oxide and ruthenium oxide, and carbon, glassy carbon, graphite, graphene, carbon sheet, carbon fiber sheet, carbon fiber cloth, diamond-like coated electrode Carbon-based electrodes such as these, and composite electrodes thereof, but are not particularly limited thereto.

The cathode is not particularly limited, and the materials exemplified as the anode electrode and general-purpose metals such as iron, copper, and aluminum, and stainless steel, hastelloy, various alloys, and composite electrodes thereof can be used.

Preferred as the cathode are platinum, stainless steel, titanium, stainless steel, hastelloy, iron, and electrodes in which platinum is coated on a metal base other than noble metal such as titanium, stainless steel, iron, hastelloy, olefin resin, engineering resin, carbon-based group Electrode with platinum coated on base material other than metal such as metal, and composite coated electrode of metal oxide such as iridium oxide and ruthenium oxide and platinum and carbon, glassy carbon, graphite, carbon sheet, carbon fiber sheet, carbon fiber Although it is carbon-type electrodes, such as cloth, these composite electrodes, etc., it is not specifically limited to these.

As the shape of the electrode, a plate shape, a cloth shape, a comb shape, a pipe shape, a nonwoven fabric shape, a shape obtained by a paper-making method, a felt shape, etc. can be used. Processed products can be used. Preferably, the anode has a shape without a gap and the cathode has a shape with a hole or a gap. However, when a gas diffusion electrode is used, there is no hydrogen generation at the cathode, so the shape of the cathode is not limited. In particular, it is not limited to these.

The electrolysis of the present invention is carried out in a state where the current density is kept constant at 1 to 20,000 mA / cm ² , preferably 10 to 5000 mA / cm ² . Alternatively, the electrode potential is set to 0.5 to 100 V vs. Ag / AgCl, preferably 1 to 70 V vs. Although it can hold | maintain with Ag / AgCl and can be electrolyzed, it is not specifically limited to these.

Also, the reaction temperature is preferably −40 to 100 ° C. The temperature is preferably −20 to 70 ° C., but is not particularly limited thereto. It is desirable to adjust the temperature according to the reaction conditions in view of the stability and reactivity of the reaction intermediate and reaction active intermediate. In a homogeneous mixed system with an organic solvent or ionic liquid, the reaction can be performed at a lower temperature.

Reactivity in this reaction, ease of formation of active intermediate, promotion of reactivity of active intermediate with urea, suppression of decomposition of active intermediate, generation of oxidized active species for formation of intermediate, 2 electrons Reactions under acidic conditions are desirable for promoting oxidation and suppressing side reactions such as Hoffman transition. The acid added for the acidic condition may be mineral products such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and organic acids such as acetic acid, propionic acid, citric acid. Moreover, the buffer solution which is a mixture with those salts may be sufficient. When hydrogen peroxide is used as the oxidizing agent, PH = 3 or less, preferably PH = 1, for the activation of hydrogen peroxide. It is important to adjust the reaction temperature of hydrogen peroxide, the addition rate, the hydrogen peroxide concentration, and the acidity of the reaction system in accordance with the reaction process in order to proceed the reaction as intended. In particular, it is not limited to these.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

The azodicarbonamide obtained in each of the following examples was identified by infrared absorption spectrum (IR) and proton nuclear magnetic resonance spectrum ( ¹ H-NMR).
^{IR (KBr): 3337,3187cm -1 (} N-H stretching), 1743,1731cm ^-1 (C = O ^stretch), 1637cm -1 (N-H bending), 1369,1331cm ^-1 (C-N stretch ).
¹ H-NMR (D6-DMSO): δ 8.02 (s, 2H, NH), 7.97 (s, 2H, NH).
In the following examples, unreacted urea was quantified by high performance liquid chromatography.
The analysis conditions by high performance liquid chromatography are as follows.
Column: ODS-3 (4.6 mmφ x 250 mm)
Mobile phase: 10 mM aqueous acetic acid flow rate: 1 ml / min
Detection wavelength: 205 nm

The conversion rate in the following examples indicates the amount of urea consumed and is calculated by the following formula.
Conversion rate (%) = [(amount of raw urea−amount of recovered urea) / (amount of raw urea)] × 100
The yield was calculated by the following formula.
Yield (%) = [(number of moles of azodicarbonamide obtained) × 2 / (number of moles of raw urea−number of moles of recovered urea)] × 100

Reference example 1
In a reaction vessel equipped with a stirrer and a thermometer, 75 g (1.25 mol) of urea is dissolved in 150 ml of water, and 321 ml (1.25 mol) of a 29% sodium hypochlorite aqueous solution is added dropwise at 10 ° C. over 1 hour with stirring. A sample is taken, potassium iodide and acetic acid (1: 1) are added, and 0.1N-sodium thiosulfate titration is immediately performed. As a result of titration analysis, it was confirmed that the yield of monochlorourea was 98.4%. When ultraviolet analysis was performed, absorption at 244 nm peculiar to monochlorourea was observed.

Reference example 2
Preparation of bromo urea solution by adding a solution in 10.7% NaOCl aqueous solution of urea hydrochloride and 38% aqueous solution of NaBr (wt%) (wt% as Cl ₂₎ (NaOCl: HCl: Urea: NaBr molar (Ratio 1: 2.2: 37.7: 0.8)
In a 250 ml round bottom flask equipped with a stir bar, dropping funnel and thermometer, 46.04 g urea (767 mmol) was dissolved in 30.6 g H ₂ O followed by 5.4 g 32% HCl ( 47.2 mmol) was added (with exotherm on cooling). A solution of urea hydrochloride was obtained. 13.5 g of 10.7% aqueous NaOCl (wt% as Cl ₂ , 20.3 mmol) was placed in the addition funnel and 4.84 g of 38% NaBr solution was placed in another addition funnel. The NaOCl solution was added to the urea hydrochloride solution, and with a delay of 1 minute, 38% NaBr aqueous solution was added to the solution. Ultraviolet analysis showed absorption at 275 nm which is characteristic of bromourea. A sample is taken, potassium iodide and acetic acid (1: 1) are added, and 0.1N-sodium thiosulfate titration is immediately performed. As a result of titration analysis, it was confirmed that the yield of monobromourea was 98.9%.

Reference example 3
Monochlorourea produced in Reference Example 1 is separated by crystals when concentrated under reduced pressure. Dissolve 31.5 g (0.33 mol) of monochlorourea in 100 ml of water, add 80 ml of 8% hydrochloric acid, add 34 g (0.33 mol) of sodium bromide, and add 30 ml of 30% hydrogen peroxide at 50 ° C. with stirring. (0.33 mol) is added dropwise over 1 hour. After completion of the dropwise addition, the reaction is terminated by stirring for another 30 minutes. When the sample was collected and subjected to ultraviolet analysis, the absorption at 275 nm characteristic of monobromourea was shown. A sample is taken, potassium iodide and acetic acid (1: 1) are added, and 0.1N-sodium thiosulfate titration is immediately performed. As a result of titration analysis, it was confirmed that the yield of monobromourea was 98.7%. Ultraviolet analysis showed absorption at 275 nm which is characteristic of bromourea. Monobromourea is an unstable substance, but can be obtained as crystals when concentrated under reduced pressure at low temperature or freeze-dried.

Example 1-1
In a 500 ml round bottom flask equipped with a magnetic stir bar, dropping funnel and thermometer, 90 g (1.5 mol) of urea was dissolved in 100 ml of water, followed by cooling to 5 ° C. under cooling at 5 ° C. 17 .1 g of 32% HCl (0.15 mol) was added with stirring. Adjust the addition amount of 32% HCl so that the pH of the solution is 1. To the solution was added 133 g of 10.7% NaOCl aqueous solution (wt% as active Cl ₂ , 0.2 mol) over 14 minutes upon cooling. After stirring for 1 hour after completion of the addition, 20.5 g of NaBr (0.2 mol) was added to the solution. After completion of the addition, the temperature of the reaction solution is raised to 35 ° C. and stirred for 1 hour, then 79.3 g (0.7 mol) of 30% hydrogen peroxide is divided into two, and the first half is added dropwise over 30 minutes. Stir for 1 hour, then drop the remaining half in 30 minutes. After completion of the dropwise addition, the reaction is terminated by stirring for 5 hours. As the reaction progresses, a yellow solid is formed and becomes suspended in the reaction solution. After completion of the reaction, the solid is separated by filtration, washed with water and dried. The obtained azodicarbonamide was identified by infrared absorption spectrum (IR) and proton nuclear magnetic resonance spectrum ( ¹ H-NMR). The yield of azodicarbonamide from the consumed urea was 95.3%.
^{IR (KBr): 3337,3187cm -1 (} N-H stretching), 1743,1731cm ^-1 (C = O ^stretch), 1637cm -1 (N-H bending), 1369,1331cm ^-1 (C-N stretch ).
¹ H-NMR (D6-DMSO): δ 8.02 (s, 2H, NH), 7.97 (s, 2H, NH).

Example 1-2
In a 500 ml round bottom flask equipped with a magnetic stir bar, dropping funnel and thermometer, 90 g (1.5 mol) of urea was dissolved in 300 ml of water, followed by cooling to 0 ° C. under cooling at 0 ° C. 22 0.5 g of 35% hydrochloric acid (0.22 mol) was added with stirring. Further, the solution was adjusted with 35% hydrochloric acid so that the pH was 1. To the solution was added 19.6 g ammonium bromide (0.2 mol) and 23.5 g NaCl (0.4 mol). After completion of the addition, the temperature of the reaction solution was raised to 40 ° C., and 140.5 g (1.24 mol) of 30% hydrogen peroxide was divided into two parts, half of which was added dropwise over 30 minutes, and stirred for 1 hour. Of hydrogen peroxide was added dropwise over 30 minutes, and the reaction was terminated by stirring for 5 hours. As the reaction progresses, a yellow solid is formed and becomes suspended in the reaction solution. After completion of the reaction, the solid is separated by filtration, washed with water and dried. The obtained azodicarbonamide was identified by infrared absorption spectrum (IR) and proton nuclear magnetic resonance spectrum ( ¹ H-NMR). The yield of azodicarbonamide from the consumed urea was 93.8%.
^{IR (KBr): 3337,3187cm -1 (} N-H stretching), 1743,1731cm ^-1 (C = O ^stretch), 1637cm -1 (N-H bending), 1369,1331cm ^-1 (C-N stretch ).
¹ H-NMR (D6-DMSO): δ 8.02 (s, 2H, NH), 7.97 (s, 2H, NH).

Example 1-3
In a 500 ml round bottom flask equipped with a magnetic stir bar, dropping funnel and thermometer, 788 g (13.1 mol) of urea was dissolved in 883 g of water, followed by 197 g of 0 ° C. cooled to 0 ° C. Of 35% HCl (1.891 mol) was added with stirring. To the solution was added 44.7 g NH ₄ Cl (836 mmol). Further, after the addition of 40 g of NH ₄ Br (408 mmol) is completed, the reaction solution is adjusted to PH = 1. The reaction solution was raised to 35 ° C., and 619 g (5.46 mol) of 30% hydrogen peroxide was divided into three parts. A third amount of 30% hydrogen peroxide was added dropwise over 30 minutes, followed by stirring for 1 hour. 1/3 of 30% hydrogen peroxide was added dropwise over 30 minutes and stirred for 1 hour. The remaining 1/3 of 30% hydrogen peroxide was added dropwise over 30 minutes and stirred for 5 hours to complete the reaction. . As the reaction progresses, a yellow solid is formed and becomes suspended in the reaction solution. After completion of the reaction, the solid is separated by filtration, washed with water and dried. The obtained azodicarbonamide was identified by infrared absorption spectrum (IR) and proton nuclear magnetic resonance spectrum ( ¹ H-NMR). The yield of azodicarbonamide from the consumed urea was 93.6%.
^{IR (KBr): 3337,3187cm -1 (} N-H stretching), 1743,1731cm ^-1 (C = O ^stretch), 1637cm -1 (N-H bending), 1369,1331cm ^-1 (C-N stretch ).
¹ H-NMR (D6-DMSO): δ 8.02 (s, 2H, NH), 7.97 (s, 2H, NH).

Example 1-4
In a 500 ml round bottom flask equipped with a magnetic stir bar, dropping funnel and thermometer, 90 g (1.5 mol) of urea was dissolved in 300 ml of water, followed by cooling to 0 ° C. under cooling at 0 ° C. 22 0.5 g of 35% hydrochloric acid (0.22 mol) was added with stirring. Furthermore, adjustment was performed with 35% hydrochloric acid so that the solution had a pH = 2. To the solution was added 19.6 g ammonium bromide (0.2 mol) and 47 g NaCl (0.8 mol). To this is added 2.3 g (0.05 mol) of formic acid. After all the additions were completed, the temperature of the reaction solution was raised to 40 ° C., 231.2 g (2.04 mol) of 30% hydrogen peroxide was divided into two portions, half of which was added dropwise over 30 minutes, and stirred for 1 hour. The remaining hydrogen peroxide was added dropwise over 30 minutes, and the reaction was terminated by stirring for 5 hours. As the reaction progresses, a yellow solid is formed and becomes suspended in the reaction solution. After completion of the reaction, the solid is separated by filtration, washed with water and dried. The obtained azodicarbonamide was identified by infrared absorption spectrum (IR) and proton nuclear magnetic resonance spectrum ( ¹ H-NMR). The yield of azodicarbonamide from the consumed urea was 94.1%.
^{IR (KBr): 3337,3187cm -1 (} N-H stretching), 1743,1731cm ^-1 (C = O ^stretch), 1637cm -1 (N-H bending), 1369,1331cm ^-1 (C-N stretch ).
¹ H-NMR (D6-DMSO): δ 8.02 (s, 2H, NH), 7.97 (s, 2H, NH).

Example 1-5
In a 500 ml round bottom flask equipped with a magnetic stir bar, dropping funnel and thermometer, 90 g (1.5 mol) of urea was dissolved in 300 ml of water, followed by cooling to 0 ° C. under cooling at 0 ° C. 22 0.5 g of 35% hydrochloric acid (0.22 mol) was added with stirring. Further, the solution was adjusted with 35% hydrochloric acid so that the pH was 1. To the solution were added 1.96 g ammonium bromide (0.02 mol) and 23.5 g NaCl (0.4 mol). To this, 0.84 g (10 mmol) of aluminum fluoride fine particles sintered and supported on SiC porous particles was added and dispersed as aluminum fluoride, and the temperature of the reaction solution was raised to 40 ° C. after the completion of all additions. 140.5 g (1.24 mol) of% hydrogen peroxide was divided into two parts, half of which was added dropwise over 30 minutes and stirred for 1 hour, and then the remaining hydrogen peroxide was added dropwise over 30 minutes and stirred for 5 hours. The reaction was terminated. As the reaction progresses, a yellow solid is formed and becomes suspended in the reaction solution. After completion of the reaction, the catalyst is filtered off, then solid ADCA is separated by filtration, washed with water and dried. The obtained azodicarbonamide was identified by infrared absorption spectrum (IR) and proton nuclear magnetic resonance spectrum ( ¹ H-NMR). The yield of azodicarbonamide from the consumed urea was 94.1%.
^{IR (KBr): 3337,3187cm -1 (} N-H stretching), 1743,1731cm ^-1 (C = O ^stretch), 1637cm -1 (N-H bending), 1369,1331cm ^-1 (C-N stretch ).
¹ H-NMR (D6-DMSO): δ 8.02 (s, 2H, NH), 7.97 (s, 2H, NH).

Examples 2-14
The reaction and treatment were carried out in the same manner as in Example 1-3 except that another halogenating agent was used instead of sodium bromide.

Examples 15-26
The first oxidant is converted from sodium hypochlorite to bromine, bromide and bromate in amounts considerably smaller than the theoretical amount, and reacted first, and then hydrogen peroxide is added to form hydrogen bromide. Except for using 2 times the amount of hydrogen peroxide corresponding to recycling reaction of bromine, bromide or bromate after converting the product to bromine or bromic acid or bromate, the same as Example 1-3 The reaction and treatment were carried out.

Examples 27-31
In Example 1-1, an oxidizing agent such as sodium hypochlorite that is the first oxidizing agent is not used, but a small amount of NaBr is added first, and the amount is equivalent to twice the number of moles of dissolved total chloranion. The hydrogen peroxide to be added is reacted and treated to separate the produced azodicarbonamide, the mother liquor and the washing solution of the azodicarbonamide isolate are combined, the consumed urea is added, and NaBr is When the amount of reduction becomes a problem due to adhesion to solids, the recycling reaction is performed while adjusting the composition by adding these. Moreover, since the amount of water increases, water is removed using a membrane or the like. Other reactions and treatments are carried out in the same manner as in Example 1-1.

Example 32
Urea (1.2 g, 20 mmol), sodium bromide (41 mg, 0.4 mmol), cooled to 5 ° C. in a beaker-type electrolytic cell equipped with ^two platinum plate electrodes (1.5 × 1.0 cm ² ). 0.34 mg of 32% HCl (0.3 mmol) and water (2.0 g) were weighed and stirred to obtain a homogeneous solution. While the electrolytic cell was immersed in an ice-water bath and cooled, electrolysis was performed for 10.7 hours while keeping the current constant at 100 mA, and 5778 coulombs of electricity was applied. After completion of the reaction, the resulting precipitate was collected by filtration, washed with water and dried, and the target azodicarbonamide (0.32 g, conversion rate 37%, yield 74%) was obtained as pale orange crystals. . When the filtrate was analyzed by high performance liquid chromatography, unreacted urea (0.746 g) was confirmed in the filtrate.

Example 33
Electrolysis was carried out in the same manner as described in Example 32 using the monobromourea produced in Reference Example 3 as a raw material instead of the urea in Example 32. When 282 mg (2 mmol) of monobromourea was used, 213 mg of azodicarbonamide was obtained. The yield is 92.0%. However, the electrolysis reaction is carried out with half the energizing time and the energizing electricity. A solid form of azodicarbonamide is formed. The suspension was filtered, washed with water and dried under reduced pressure.

Examples 34-52

Claims

In a homogeneous system or a heterogeneous mixed system of at least one solvent selected from the group consisting of water, an organic solvent, and an ionic liquid, a dehydrobromination reaction is performed from a compound represented by the formula (10) derived from urea. A method for producing an azodicarbonamide represented by the characteristic formula (7):
In a homogeneous system or heterogeneous mixed system of at least one solvent selected from the group consisting of water, an organic solvent, and an ionic liquid, the formula (9) bromourea active transition intermediate derived from urea is reacted with urea. A process for producing an azodicarbonamide according to claim 1, wherein the compound represented by formula (10) is obtained.
In a homogeneous system or heterogeneous mixed system of at least one solvent selected from the group consisting of water, an organic solvent, and an ionic liquid, N-bromourea represented by the formula (8) derived from urea is activated bromine. The azodicarbonamide according to claim 1 or 2, characterized in that a bromourea active transition intermediate of formula (9) is obtained by a two-electron oxidation by an active substance derived from a compound and / or hydrogen peroxide or by electrolysis. Manufacturing method.
In a homogeneous system or a heterogeneous mixed system of at least one solvent selected from the group consisting of water, an organic solvent, and an ionic liquid, N-chlorourea (N—) represented by the formula (11) derived from urea The method for producing an azodicarbonamide according to any one of claims 1 to 3, wherein the formula (8) is obtained by halogen substitution reaction using a brominating agent or a bromination method. .
In a homogeneous system or a heterogeneous mixed system of at least one solvent selected from the group consisting of water, an organic solvent, and an ionic liquid, N-chlorourea (N—) represented by the formula (11) derived from urea N-bromourea represented by the formula (8) is produced by brominating agent or bromination method, and then by an active bromine compound or an active substance derived from hydrogen peroxide or by electrolysis. A bromourea active transition intermediate represented by the formula (9) is obtained by electrophilic oxidation of an NH group to which a bromine atom is bonded, and at the same time a urea molecule reacts to obtain a compound of the formula (10). The azodicarbonamide formula according to any one of claims 1 to 4, characterized in that it is chemically active and immediately undergoes a de-HBr reaction to convert it to a compound of formula (7). New manufacturing method.
When using an electrolytic oxidation reaction in water or an organic solvent or ionic liquid, and an organic solvent or a homogeneous or heterogeneous mixed system of ionic liquid and water, the supporting electrolyte, brominating agent, and active brominated compound Two-electron oxidation is performed using hydrogen bromide and bromo salt as raw materials to generate a bromo cation to generate N-bromourea represented by the formula (8), and then the NH group to which the bromo atom is bonded. Electrophilic oxidation is two-electron-oxidized by an electrolytic reaction to protonate H: to form a formula (9) bromourea active transition intermediate, and at the same time, urea molecules react to produce a compound represented by formula (10). A novel process for producing an azodicarbonamide formula, wherein the compound of the formula (10) is chemically active and immediately undergoes a de-HBr reaction to be converted into the compound of the formula (7).
In a homogeneous or heterogeneous mixed system of water or organic solvent or ionic liquid, and organic solvent or ionic liquid and water, N— represented by the formula (8) from urea by a brominating agent or bromination method Producing bromourea or, if necessary, producing N-chlorourea (including N-chlorourea Na salt) of formula (11) from urea by chlorinating agent or chlorination method, N-bromourea represented by the formula (8) is produced by a brominating agent or bromination method, and then N-bromourea is used as a supporting electrolyte using an electrolysis reaction, using hydrogen bromide and bromide salt, Two-electron oxidation of the NH group to which the bromo atom is bonded is performed, and H: is eliminated as a proton to obtain a formula (9) bromourea active transition intermediate, and at the same time a urea molecule reacts to obtain a compound of the formula (10), The compound of formula (10) is Is chemically active, novel method for producing azodicarbonamide type, characterized in that occur de HBr reaction immediately converted to compounds of formula (7) (7).
In water or organic solvent or ionic liquid, and in organic solvent or homogeneous or heterogeneous mixed system of ionic liquid and water, hydrogen bromide, bromide salt is used and peroxide such as hydrogen peroxide is used. Bromine is generated by dropwise addition of urea, and the urea represented by the formula (1) is generated by the generated, converted bromine, hypobromite, and hypobromite, and the two-electron oxidation of the urea represented by the formula (8) The novel process for producing azodicarbonamide according to any one of claims 1 to 6, wherein N-bromourea represented by the formula:
Water or organic solvent or ionic liquid, and organic bromide, bromine-dioxane complex and chlorobromine as oxidizing agent, active brominated compound in homogeneous or heterogeneous mixed system of organic solvent or ionic liquid and water The azodicarbonamide according to any one of claims 1 to 7, wherein urea is two-electron-oxidized with a bromo cation to form N-bromourea represented by the formula (8) as a generator. New manufacturing method.
In a homogeneous system or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water, a halogen salt such as hydrogen bromide or hydrogen chloride of urea is used as a raw material. Bromine is generated by dropping a peroxide such as hydrogen peroxide on the surface, and generated, converted chlorine, hypochlorous acid, hypochlorite, bromine, hypobromite, hypobromite The novel process for producing azodicarbonamide according to any one of claims 1 to 8, wherein the urea represented by the formula (1) is chlorinated and then brominated.
A mixture of urea and a salt of urea is used as a raw material in a homogeneous system or a heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water. 11. A novel process for producing azodicarbonamide according to any one of 1 to 10.
Under acidic conditions, use a large excess of urea, select a temperature according to the reaction conditions at a low temperature of 80 ° C or lower, and between -10 and 60 ° C. The novel process for producing azodicarbonamide according to any one of claims 1 to 11, wherein the reaction is carried out at -20 to 40 ° C.