WO2011136231A1 - Nouveau procédé de production de bisaminophénylalkylurée - Google Patents

Nouveau procédé de production de bisaminophénylalkylurée Download PDF

Info

Publication number
WO2011136231A1
WO2011136231A1 PCT/JP2011/060182 JP2011060182W WO2011136231A1 WO 2011136231 A1 WO2011136231 A1 WO 2011136231A1 JP 2011060182 W JP2011060182 W JP 2011060182W WO 2011136231 A1 WO2011136231 A1 WO 2011136231A1
Authority
WO
WIPO (PCT)
Prior art keywords
bisaminophenylalkylurea
producing
reaction
formula
nitro compound
Prior art date
Application number
PCT/JP2011/060182
Other languages
English (en)
Japanese (ja)
Inventor
顕司 高瀬
健一 徳永
裕一 後藤
Original Assignee
日産化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to CN201180032682.9A priority Critical patent/CN102971288B/zh
Priority to JP2012512863A priority patent/JP5790645B2/ja
Publication of WO2011136231A1 publication Critical patent/WO2011136231A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/20—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
    • C07C275/24—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings

Definitions

  • the present invention relates to a novel method for producing bisaminophenylalkylurea, which is a diamine compound useful as a raw material for a polymer for producing a liquid crystal alignment film.
  • Some of the bisaminophenylalkylureas produced in the present invention are novel compounds, and therefore the present invention also relates to a process for producing such novel diamine compounds.
  • a polyimide film is often used as a liquid crystal alignment film used in a liquid crystal display element.
  • the liquid crystal alignment film of this polyimide film is a solution of a polyamic acid that is a precursor of polyimide or a solvent-soluble polyimide.
  • the solution is applied to a substrate, fired, and the resulting film is produced by a method of orientation treatment such as rubbing treatment.
  • the polyamic acid and the solvent-soluble polyimide are generally produced by a polycondensation reaction between a tetracarboxylic acid derivative such as tetracarboxylic acid dihydrate and a diamine compound (see Patent Documents 1 and 2).
  • the diamine compound which is a raw material such as polyamic acid and polyimide, is important because it affects the characteristics of the liquid crystal alignment film obtained therefrom, and thus the characteristics of the liquid crystal display element, and various amine compounds have been used conventionally. Proposed.
  • a bisaminophenylalkylurea represented by the following formula (1) has been proposed as International Publication WO2010 / 053128.
  • R 11 and R 21 are each independently an alkylene group having 1 to 3 carbon atoms.
  • Some of such bisaminophenylalkylureas are novel compounds not yet described in the literature prior to the filing of the present application.
  • a nitrophenylalkylamine halide salt and a carbonyl compound such as bis (4-nitro-substituted or unsubstituted phenyl) carbonate are subjected to a condensation reaction in a reaction solvent. It is conceivable to produce a target compound by producing a nitro compound and reducing the nitro compound in a reaction solvent.
  • Another object of the present invention is to provide a production method for obtaining a novel substance that has not been known so far in bisaminophenylalkylurea with high purity and high yield.
  • the present inventor has intensively studied to achieve the above object.
  • the starting material, nitrophenylalkylamine halogenate, and a specific carbonyl compound are subjected to a condensation reaction to produce a nitro compound.
  • a specific organic solvent is used as the reaction solvent and the reaction solvent in the case of producing the desired bisaminophenylurea by reducing the obtained nitro compound, and the above nitro compound is crystallized out.
  • the above object can be achieved by using a specific solvent as a solvent used for crystallization.
  • the present invention has the following gist.
  • a (nitrophenyl) alkylamine halide represented by the following formula (1) and a carbonyl compound represented by the following formula (2) are subjected to a condensation reaction in the presence of a base in an amide solvent.
  • R is an alkylene group having 1 to 3 carbon atoms
  • Y is a phenoxy group or 1-imidazolyl group in which a nitro group may be substituted on any carbon atom.
  • a (nitrophenyl) alkylamine halide represented by the formula (1) and a carbonyl compound represented by the formula (2) are subjected to a condensation reaction in the presence of a base in an amide solvent, A method for producing a nitro compound represented by the above formula (3), wherein lower alcohol is added to the obtained reaction mixture containing the nitro compound represented by the above formula (3) for crystallization.
  • the reaction rate is high, the volumetric efficiency is high, the by-products are low, the purity is high, and the yield is high, as will be apparent from the examples shown in contrast to the comparative examples described later.
  • the target product bisaminophenylalkylurea.
  • bisaminophenylalkylureas bis (4-aminophenylethyl) urea which is a novel compound can be obtained with high purity and high yield.
  • the starting material nitrophenylalkylamineamine halogenate
  • R is an alkylene group having 1 to 3 carbon atoms, preferably a methylene group or an ethylene group.
  • X is a halogen atom, preferably a chlorine atom or a bromine atom.
  • nitrophenyl alkylamine halide include 2- (4-nitrophenyl) ethylamine (also referred to as 4-nitrophenethylamine) hydrochloride or bromate, and (4-nitrophenyl) methylamine hydrochloride.
  • a salt hydrochloride or bromate may be mentioned.
  • Examples of the carbonyl compound represented by the above formula (2) include bis (4-nitro-substituted or unsubstituted phenyl) carbonate (also referred to as bis (4-nitro-substituted or unsubstituted phenyl) carbonate), carbonyldiimidazole, and the like.
  • the bis (4-nitro-substituted or unsubstituted phenyl) carbonate is preferably bis (4-nitrophenyl) carbonate or bis (4-phenyl) carbonate.
  • the condensation reaction rate is higher than that of a solvent such as tetrahydrofuran, ketone, or alcohol, and therefore the volumetric efficiency is extremely high.
  • the volumetric efficiency of Example 1 reaches 3.5 to 4 times that of Comparative Example 1 using tetrahydrofuran as the reaction solvent.
  • examples of the amide solvent include dimethylformamide (DMF), N, N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, hexamethylphosphoric triamide, and dimethylformamide is particularly preferable.
  • the nitrophenylalkylamine halide salt and the carbonyl compound are preferably used in an amount of 0.4 to 0.6 mol, particularly preferably 0.45 to 0.5 mol, with respect to 1 mol of the former. .
  • the amide solvent is preferably used in an amount of 0.5 to 10 times, more preferably 5.5 to 6.5 times the weight of the nitrophenylalkylamine halide.
  • various bases are preferably used as a catalyst.
  • Preferred examples of such a base include trialkylamines such as triethylamine, trimethylamine and tripropylamine; 4-NN-dimethylaminopyridine and the like. These bases are preferably used in an amount of 1.5 to 6 mol, particularly preferably 1.8 to 2.2 mol, per mol of the nitrophenylalkylamine halide.
  • the reaction temperature in the above condensation reaction is preferably in the range of 30 to 100 ° C., more preferably 55 to 65 ° C.
  • the specific condensation reaction is preferably carried out as follows. That is, in an inert atmosphere such as nitrogen, the nitrophenylalkylamine halide salt and the carbonyl compound are dissolved in dimethylformamide as a reaction solvent to form a solution, and preferably 30 to 100 with respect to the solution. At 35 ° C., particularly preferably 55 to 65 ° C., triethylamine as a catalyst is preferably added gradually over 5 minutes to 10 hours, preferably with stirring. If necessary, stirring is continued while maintaining the above temperature. Thus, the condensation reaction proceeds, and the nitro compound, which is the target product represented by the above formula (3), is produced.
  • a lower alcohol which is a poor solvent for the nitro compound is added to the obtained reaction mixture containing the nitro compound.
  • the lower alcohol an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol, is used.
  • the lower alcohol is preferably added gradually at 30 to 100 ° C., particularly preferably at 55 to 65 ° C., preferably over 5 minutes to 10 hours.
  • the lower alcohol solution of the obtained nitro compound is preferably crystallized by cooling to 0 to 10 ° C.
  • the nitro compound obtained by crystallization is preferably washed with a lower alcohol and dried as necessary.
  • a nitro compound is obtained from a lower alcohol solution of the nitro compound obtained above. Without being crystallized and isolated, it can be used as it is in the next step.
  • the nitro compound represented by the formula (3) is reduced to produce the target bisaminoalkylphenylurea represented by the formula (4).
  • Such a reduction reaction is also carried out in a solvent.
  • the reaction solvent greatly affects the rate of the reduction reaction and greatly affects the volumetric efficiency of the reaction.
  • reaction by-products with the solvent may be generated.
  • a lower alcohol is used as a reaction solvent.
  • tetrahydrofuran or the like which is a common organic solvent, is used as a reaction solvent, volume efficiency is low and a by-product that is an adduct is generated.
  • a catalyst is preferably used.
  • a metal catalyst generally used for catalytic reduction for example, nickel, palladium, platinum, rhodium, ruthenium, cobalt, copper and the like can be used.
  • a palladium catalyst it is preferable to use a palladium catalyst.
  • These catalysts can be used even in a metal state, but usually they are used by being supported on a carrier surface such as carbon, barium sulfate, silica gel, alumina, celite, etc., and nickel, cobalt, copper, etc. are used in Raney.
  • the amount of the catalyst used is not particularly limited, but is preferably 0.01 to 10% by mass with respect to the nitro compound represented by the formula (3). The amount is 8% by mass, and preferably 0.1 to 5% by mass when supported on a carrier.
  • the reducing agent is particularly preferable.
  • the reducing agent is preferably used in an amount of 1 to 15 mol, more preferably 2 to 10 mol, relative to 1 mol of the nitro compound represented by the formula (3).
  • the amount of the reaction solvent to be used is preferably 4 to 30 times by mass, preferably 7.5 to 8.5 times by mass with respect to the nitro compound.
  • the reaction temperature is preferably 40 to 60 ° C, particularly preferably 45 to 55 ° C.
  • the reaction pressure is preferably 0 to 1 MPa-G (gauge pressure), more preferably 0.1 to 0.4 MPa-G.
  • the specific reduction reaction is preferably carried out as follows.
  • a nitro compound as a starting material, a reduction catalyst, and a lower alcohol as a reaction solvent are charged into a reactor such as an autoclave, and hydrogen as a reducing agent is introduced with stirring at preferably 40 to 60 ° C. And preferably stirred for 1 to 20 hours.
  • the end point of the reaction can be determined by the amount of hydrogen absorption or by thin layer chromatography or high performance liquid chromatography.
  • the nitro compound represented by formula (3) is reduced to produce bisaminophenylalkylurea.
  • the produced bisaminophenylalkylurea may be recovered as it is, but can be preferably treated with hydrazine in order to further increase the purity.
  • Hydrazine preferably maintains a lower alcohol solution containing bisaminophenylalkylurea at 4.5 to 5.5 ° C., preferably 0 to 0.3 mol, more preferably 1 mol of bisaminophenylalkylurea. Is carried out by adding 0.15 to 0.25 mol, preferably stirring for 1 minute to 1 hour.
  • the target bisaminophenylalkylurea is recovered from the thus obtained lower alcohol solution containing the bisaminophenylalkylurea represented by the formula (4).
  • This recovery is performed by an existing method. be able to. That is, the lower alcohol solution containing bisaminophenylalkylurea is filtered and washed to remove the used catalyst and the like. A poor solvent is added to crystallize the target product from the filtrate, and bisaminophenylalkylurea is recovered by crystallization. In this case, as the poor solvent, isopropanol, butanol or the like is used.
  • various bisaminophenylalkylureas are produced as described above, and examples thereof include those represented by the following formulas (1-4) to (1-10).
  • those represented by formula (1-6), formula (1-7) and formula (1-8) are novel compounds and are provided for the first time by the present invention. is there.
  • DMF Dimethylformamide
  • DMAP 4-N, N-dimethylaminopyridine
  • THF Tetrahydrofuran
  • BNPU 1,3-bis (4-nitrophenylethyl) urea
  • BAPU 1,3-bis (4-aminophenylethyl) urea
  • Example 1 Synthesis of BNPU A 500 mL four-necked flask was charged with 13.98 g (69.0 mmol) of 4-nitrophenethylamine hydrochloride, 10.00 g (32.9 mmol) of bisnitrophenyl carbonate and 60 g of DMF, and stirred with a blade. The temperature was raised to 60 ° C., and 13.34 g (131.5 mmol) of triethylamine was appropriately reduced at 59 to 63 ° C. over 3 to 5 minutes, followed by stirring at 58 to 62 ° C. for 2 hours. The reaction yield was 94%. Subsequently, 100 g of methanol was added dropwise over 10 to 15 minutes to completely dissolve the reaction solution.
  • Example 1 The reaction in Example 1 is as follows.
  • Comparative Example 1 A 2000 mL jacketed separable flask was charged with 31.50 g (155.4 mmol) of 4-nitrophenethylamine hydrochloride, 1.81 g (14.8 mmol) of DMAP, 89.88 g (888.3 mmol) of triethylamine, and 338 g of THF. While stirring, the temperature was raised to 60 ° C., and a solution obtained by dissolving 22.51 g (74.02 mmol) of bisnitrophenyl carbonate in 225 g of THF was added dropwise at 57 to 63 ° C. over 42 minutes. Subsequently, the mixture was stirred at 58 to 62 ° C. for 4 hours.
  • Example 2 A 120 mL autoclave was charged with 6.01 g (16.8 mmol) of BNPU, 0.076 g of 10% Pd / C (50% wet), 0.60 g of activated carbon and 48 g of methanol, and the temperature was raised to 50 ° C. while stirring with a magnetic stirrer. The mixture was warmed and stirred at 50 to 55 ° C. for 11 hours under a hydrogen gas atmosphere of 0.3 MPa-G. Next, 0.17 g of hydrazine monohydrate was added to the reaction solution, filtered at 50 ° C., and then washed with 12 g of methanol to remove the catalyst and activated carbon.
  • the precipitated crystals were filtered, washed with 6 g of isopropanol, and dried under reduced pressure to obtain 2.18 g of BAPU white crystals (purity 99.2%) (yield 86.5%). It was.
  • the activated carbon was used to prevent coloring of the product, and the ion exchange resin was used to remove contained metals.
  • Comparative Example 2 A 2000 mL autoclave was charged with 18.06 g (50.3 mmol) of BNPU, 0.90 g of 5% Pd / c (50% wet), 1.80 g of activated carbon and 540 g of THF, and the temperature was raised to 40 ° C. while stirring with a blade. The mixture was stirred at 40 to 46 ° C. for 2 hours under a hydrogen gas atmosphere of 0.3 MPa-G. Next, the reaction solution was filtered at 40 ° C. and then washed with 54 g of THF to remove the catalyst and activated carbon.
  • the reaction solution was transferred to a 1000 mL four-necked flask, and 180 g of heptane was added dropwise over 10 to 15 minutes while stirring with a blade. Subsequently, the mixture was cooled to 5 ° C., and the precipitated crystals were filtered, washed with a mixed solvent of 25.2 g of THF and 10.8 g of heptane, and dried under reduced pressure to give 19.38 g of BAPU white crystals (purity 99.3%) ( Yield 85.2%) was obtained. In the metal analysis of the crystal, it was confirmed that Na, K, Al, Ca, Cr, Cu, Mg, Mn, Ni, Fe, Pd, and Zn were all less than 1 ppm.
  • Example 3 A 500 mL four-necked flask was charged with 21.07 g (104 mmol) of 4-nitrophenethylamine hydrochloride, 8.02 g (49.3 mmol) of carbonyldiimidazole and 90 g of DMF. (197.2 mmol) was added dropwise at 57-63 ° C. over 3-5 minutes. Subsequently, 1.21 g (6.6 mmol) of DMAP was added, and the mixture was stirred at 58 to 62 ° C. for 5 hours. Next, 150 g of methanol was added dropwise over 10 to 15 minutes to completely dissolve the reaction solution.
  • Example 4 In a 500 mL four-necked flask, charged with 14.08 g (69.5 mmol) of 4-nitrophenethylamine hydrochloride, 7.07 g (33.0 mmol) of diphenyl carbonate and 60 g of DMF, heated to 60 ° C. while stirring with a blade, 40.03 g of triethylamine (395.6 mmol) was added dropwise at 59-68 ° C. over 3-5 minutes. Subsequently, 0.80 g (6.6 mmol) of DMAP was added, and the mixture was stirred at 58 to 62 ° C. for 5 hours. Next, 100 g of methanol was added dropwise over 10 to 15 minutes to completely dissolve the reaction solution.
  • the bisaminophenylalkylurea produced according to the present invention can be used for various applications.
  • polyamic acid obtained by polycondensation reaction with a tetracarboxylic acid derivative such as tetracarboxylic acid dihydrate, and the polyamic acid can be used.
  • a polyimide obtained by imidizing is useful as a raw material for a polymer for producing a liquid crystal alignment film used in a liquid crystal display element. It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application 2010-105935 filed on April 30, 2010 are cited herein as disclosure of the specification of the present invention. Incorporated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production d'une bisaminophénylalkylurée au titre de composé recherché, avec un rendement élevé, tout en obtenant une efficacité volumétrique élevée et en générant peu de sous-produits. Un hydrohalogénure de (nitrophényl)alkylamine représenté par la formule (1) et un composé carbonylé de formule (2) sont soumis à une réaction de condensation dans un solvant amide en présence d'une base pour obtenir un composé nitro de formule (3). Le composé nitro ainsi obtenu est ensuite réduit dans un alcool court au titre de solvant pour obtenir une bisaminophénylalkylurée de formule (4).
PCT/JP2011/060182 2010-04-30 2011-04-26 Nouveau procédé de production de bisaminophénylalkylurée WO2011136231A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201180032682.9A CN102971288B (zh) 2010-04-30 2011-04-26 二氨基苯基烷基脲的新制造方法
JP2012512863A JP5790645B2 (ja) 2010-04-30 2011-04-26 ビスアミノフェニルアルキルウレアの新規な製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-105935 2010-04-30
JP2010105935 2010-04-30

Publications (1)

Publication Number Publication Date
WO2011136231A1 true WO2011136231A1 (fr) 2011-11-03

Family

ID=44861529

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/060182 WO2011136231A1 (fr) 2010-04-30 2011-04-26 Nouveau procédé de production de bisaminophénylalkylurée

Country Status (3)

Country Link
JP (1) JP5790645B2 (fr)
CN (1) CN102971288B (fr)
WO (1) WO2011136231A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022103258A (ja) * 2013-10-23 2022-07-07 日産化学株式会社 新規なジアミン、ポリアミック酸、及びポリイミド

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI773190B (zh) * 2021-03-12 2022-08-01 士峰科技股份有限公司 二胺化合物及其製備方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06239804A (ja) * 1993-02-16 1994-08-30 Aibaitsu Kk カルボニル基導入剤およびこれを用いたカーボネートならびに尿素誘導体の製造方法
WO2010053128A1 (fr) * 2008-11-06 2010-05-14 日産化学工業株式会社 Agent d'alignement de cristaux liquides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2180021A1 (fr) * 1994-11-04 1996-05-17 Yoichi Kawashima Nouveau derive de 1,3-dialkyluree ayant un groupe hydroxyle

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06239804A (ja) * 1993-02-16 1994-08-30 Aibaitsu Kk カルボニル基導入剤およびこれを用いたカーボネートならびに尿素誘導体の製造方法
WO2010053128A1 (fr) * 2008-11-06 2010-05-14 日産化学工業株式会社 Agent d'alignement de cristaux liquides

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CARA A. GRASSO ET AL., J. ORG. CHEM., vol. 65, no. 17, 2000, pages 5216 - 5222 *
MAN-KIT LEUNG ET AL., J. ORG. CHEM., vol. 61, no. 12, 1996, pages 4175 - 4179 *
PHILLIP A. SHELTON ET AL., CHEM. COMMUN., 2009, pages 947 - 949 *
TOHRU YOSHIDA ET AL., BULL. CHEM. SOC. JPN., vol. 60, no. 5, 1987, pages 1793 - 1799 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022103258A (ja) * 2013-10-23 2022-07-07 日産化学株式会社 新規なジアミン、ポリアミック酸、及びポリイミド

Also Published As

Publication number Publication date
JP5790645B2 (ja) 2015-10-07
JPWO2011136231A1 (ja) 2013-07-22
CN102971288A (zh) 2013-03-13
CN102971288B (zh) 2015-01-21

Similar Documents

Publication Publication Date Title
KR101135336B1 (ko) 아고멜라틴의 합성 방법
JP5156862B2 (ja) イオプロミドの新規な製造方法
CN104884427A (zh) 可用于合成苯甲酰胺化合物的化合物
KR20120034227A (ko) 폴리플루오로설폰아미도 아민의 합성에서 중간 생성물로서 유용한 폴리플루오로설폰아미도 아미드
JP5790645B2 (ja) ビスアミノフェニルアルキルウレアの新規な製造方法
CN113227075A (zh) 用于产生n,n’-双[2-(1h-咪唑-4-基)乙基]丙二酰胺的新方法
JP2702262B2 (ja) ビス（３‐アミノフェノキシ）化合物の製造方法
JP5040195B2 (ja) 反応性芳香族スルホン酸塩及びその製造方法
CN115836041A (zh) 光学活性的化合物的制造方法
KR102592383B1 (ko) 디아민 화합물 및 그 중간체의 제조 방법
CN101565382B (zh) 乙酰胺的合成方法
JP3821350B2 (ja) アミノヒドロキシ芳香族カルボン酸及び／又はその誘導体の製造方法
WO2003014067A1 (fr) Methode de production d'un compose beta-oxonitrile ou d'un sel de metal alcalin dudit compose
JPH04164057A (ja) ３―シアノ―３，５，５―トリメチルシクロヘキサノンの製造法
JP4807675B2 (ja) 高純度ピペラジン誘導体塩酸塩の製造方法
JP2002105034A (ja) ９，９ービス（３−アミノー４ーヒドロキシフェニル）フルオレンの製造方法
JP4022953B2 (ja) ２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパンの製造法
JPH04112862A (ja) ３―シアノ―３，５，５―トリメチルシクロへキサノンの製造方法
WO2011057430A1 (fr) Composés amides de n-sulfinylaminoacides chirals, leur procédé de préparation et leur utilisation
JP2022529916A (ja) 置換された２－［２－（フェニル）エチルアミノ］アルカンアミド誘導体の製造方法
JP4032825B2 (ja) ３，４−ジヒドロキシベンゾニトリルを製造する方法
KR20190032253A (ko) 디아민 화합물의 제조 방법
CN115947675A (zh) 一种雷沙吉兰中间体及其制备方法和应用
TW200427655A (en) Producing method of 3-nitro-4-alkoxybenzoic acid
JP3552714B2 (ja) インドロピロロカルバゾール誘導体の製造法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180032682.9

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11775012

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012512863

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 10054/CHENP/2012

Country of ref document: IN

122 Ep: pct application non-entry in european phase

Ref document number: 11775012

Country of ref document: EP

Kind code of ref document: A1