WO2016143748A1 - ジアミン化合物及びその中間体の製造方法 - Google Patents
ジアミン化合物及びその中間体の製造方法 Download PDFInfo
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- WO2016143748A1 WO2016143748A1 PCT/JP2016/057022 JP2016057022W WO2016143748A1 WO 2016143748 A1 WO2016143748 A1 WO 2016143748A1 JP 2016057022 W JP2016057022 W JP 2016057022W WO 2016143748 A1 WO2016143748 A1 WO 2016143748A1
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- piperidine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D211/26—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
Definitions
- the present invention relates to a diamine compound that is useful as a raw material of a polyimide polymer for producing a liquid crystal alignment film, and a novel method for producing an intermediate thereof.
- a polyimide film is used as a liquid crystal alignment film used in a liquid crystal display element, and the liquid crystal alignment film of the polyimide film is soluble in a solution of polyamic acid, which is a precursor of polyimide, or a solvent.
- a polyimide solution is applied to a substrate and baked, and the resulting film is produced by a method of orientation treatment such as rubbing treatment.
- This polyamic acid and polyimide are generally produced by a polycondensation reaction between a tetracarboxylic acid derivative such as tetracarboxylic acid dihydrate and a diamine.
- the diamine 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 from the raw material, that is, the characteristics of the liquid crystal display element.
- Various diamine compounds have been used and proposed in the past. Yes.
- the inventors of the present invention provide a polyamic acid capable of obtaining a liquid crystal alignment film having a high voltage holding ratio, excellent liquid crystal alignment, and having little residual charge accumulated by a direct current voltage, even when alignment processing is performed by a rubbing method or a photo alignment method.
- a diamine compound that is a raw material for polyimide a diamine represented by the following formula (A) was found.
- the present inventors react p-fluoronitrobenzene and 4- (aminomethyl) piperidine to produce a dinitro compound, which is subjected to tertiary butoxycarbonylation and then reduced.
- the method was devised and implemented.
- the present invention solves the above problems and has a high reaction rate, a high volumetric efficiency, a small amount of by-products, a high purity, and it is not necessary to isolate an intermediate. It aims at providing the method of manufacturing the diamine compound represented by this, and its intermediate body.
- the present inventors have found a method for producing the diamine compound represented by the above formula (A) that can achieve the above object and an intermediate thereof, and Completed.
- the present invention has the following gist.
- the reaction rate is high, the volumetric efficiency is high, the number of by-products is high, the purity is high, and it is not necessary to isolate the intermediate, and the polyimide precursor or the raw material for producing the polyimide is obtained in high yield.
- a diamine compound represented by the above formula (A) and a method for producing an intermediate thereof are provided.
- the proportion of 4- (aminomethyl) piperidine (E) and p-fluoronitrobenzene (D) used is preferably 2 to 10 moles of the latter with respect to 1 mole of the former. From the viewpoint of suppressing the formation of residual and excessive reactants, the amount is more preferably 2.0 to 2.2 mol.
- p-fluoronitrobenzene and 4- (aminomethyl) piperidine used as starting materials are commercially available.
- the benzene ring of p-fluoronitrobenzene may have one or more substituents such as a methyl group.
- the reaction type may be either a rotary type (batch type) or a flow type, but a batch type is preferable from the viewpoint of operability.
- the reaction is preferably performed in the presence of a base.
- the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, and phosphoric acid.
- Organic bases such as potassium and 1,8-diazabicyclo [5,4,0] -7-undecene can be used. Of these, alkali metal carbonates such as sodium carbonate and potassium carbonate are preferred.
- the amount of base used is 1 to 4 equivalents, preferably 1.0 to 1.5 equivalents, relative to 4- (aminomethyl) piperidine (E).
- the reaction solvent is at least one selected from the group consisting of dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP). used. Of these, N-methylpyrrolidone is particularly preferable.
- the reaction solution can be used as it is in the next Boc step after the reaction is completed, which is advantageous in production.
- the amount of the solvent used is not particularly limited, but it is preferable to use 1 to 10 times by mass of the solvent with respect to 1 part by mass of the compound represented by the formula (C).
- the amount is more preferably 3 to 5 times by mass, still more preferably 3.1 to 3.3 times by mass.
- the reaction temperature is, for example, ⁇ 10 to 200 ° C., preferably 40 to 100 ° C.
- the reaction time is 0.5 to 20 hours, preferably 1 to 15 hours.
- the reaction solution containing 4- (p-nitrophenylaminomethyl) -N- (p-nitrophenyl) piperidine (C) obtained in the above reaction is tertiary butyloxycarbonylated. This gives 4- (Np-nitrophenyl-N-tertiarybutoxycarbonylamino) methyl-N- (p-nitrophenyl) piperidine (B).
- a reaction solution containing it can be used as it is in the next step, improving reaction efficiency and yield. This is advantageous in terms of improvement of
- a tertiary butyloxycarbonylating agent such as di-tert-butyl dicarbonate (Boc 2 O) is preferably used in an amount of 1 to 5 mol, preferably 1.3 mol, per 1 mol of compound (C).
- the amount used is preferably 2.5 mol, and the amount of di-tert-butyl dicarbonate (also referred to as Boc group) introduced can be controlled by the amount used.
- tertiary butyloxycarbonylating agent examples include N-tert-butoxycarbonylimidazole, tert-butylphenyl carbonate, tert-butyl carbamate, tert-butyl chloroformate, di-tert-butyl dicarbonate, and the like. Is di-tert-butyl dicarbonate.
- a base for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, Inorganic bases such as lithium carbonate and cesium carbonate; amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, N, N-dimethyl-4-aminopyridine, imidazole, quinoline, collidine Bases such as sodium hydride, potassium hydride, sodium tert-butoxy, potassium tert-butoxy; and the like can be used.
- N, N-dimethyl-4-aminopyridine is preferable.
- the amount of the base used is preferably 0.01 to 5.0 equivalents, more preferably 0.01 to 0.10 equivalents, relative to the compound represented by the formula (C).
- the solvent for reacting 4- (p-nitrophenylaminomethyl) -N- (p-nitrophenyl) piperidine with the tertiary butyloxycarbonylating agent may be used as long as it does not react with each raw material. it can.
- aprotic polar organic solvents dimethylformamide (DMF), DMSO, DMAc, NMP, etc.
- ethers diethyl ether (Et 2 O), diisopropyl ether (i-Pr 2 O), tertiary butyl methyl ether (TBME), cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), dioxane, etc.
- aliphatic hydrocarbons pentane, hexane, heptane, petroleum ether, etc.
- aromatic hydrocarbons benzene, toluene, xylene, mesitylene) , Chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.
- halogenated hydrocarbons chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.
- lower fatty acid esters methylformamide (DMF
- solvents can be used. These solvents can be appropriately selected in consideration of the ease of reaction. Moreover, it can be used individually by 1 type or in mixture of 2 or more types. If necessary, the solvent can be dried using a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.
- the solvent ethers are preferable, and THF is particularly preferable.
- THF the compound represented by the formula (B), which is the target product
- the compound represented by the formula (B), which is the target product can be obtained in a state of being contained in the THF solution by adding water after the completion of the reaction and liquid separation. THF and water are usually mixed together to form a uniform solution.
- potassium fluoride produced as a by-product in the condensation step is dissolved in the aqueous phase, so that the salt concentration of the aqueous phase is increased. Since the compound represented by the formula (B), which is the target product, is poorly soluble in water, both of them are separated satisfactorily.
- the ratio of THF to water is preferably 0.1 to 0.5 parts by mass, more preferably 0.3 to 0.4 parts by mass with respect to 1 part by mass of THF.
- the amount of the solvent used is not particularly limited, but it is preferable to use 0.1 to 100 times by mass of the solvent with respect to 1 part by mass of the dinitro compound of the formula (C). More preferably, it is 0.5 to 30 times by mass, and further preferably 1 to 10 times by mass.
- the reaction temperature is not particularly limited, but is in the range from ⁇ 100 ° C. to the boiling point of the solvent used, preferably in the range of ⁇ 50 to 150 ° C.
- the reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.
- a THF solution containing the compound represented by the formula (B) can be obtained by adding water and liquid separation as described above.
- Examples of the reduction method include a hydrogenation reaction in the presence of a catalyst, a reduction reaction performed in the presence of protons, a reduction reaction using formic acid as a hydrogen source, a reduction reaction using hydrazine as a hydrogen source, and the like. A plurality of may be combined.
- the reduction method is preferably a hydrogenation reaction in the presence of a catalyst.
- the catalyst used for the hydrogenation reaction is preferably an activated carbon-supported metal available as a commercial product, and examples thereof include palladium-activated carbon, platinum-activated carbon, and rhodium-activated carbon. Further, palladium hydroxide, platinum oxide, Raney nickel or the like is not necessarily an activated carbon-supported metal catalyst. Palladium-activated carbon that is widely used in general is preferred because good results are obtained such as no generation of waste after the reaction and side reactions are unlikely to occur.
- the amount of the catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.1 mol with respect to 1 mol of the compound represented by the above formula (B) from the viewpoint of reactivity. 0.01 mole.
- the reaction may be carried out in the presence of activated carbon.
- the amount of the activated carbon to be used is not particularly limited, but is preferably 1 to 20% by mass and more preferably 5 to 10% by mass with respect to 100% by mass of the dinitro compound of the formula (B).
- the reaction may be carried out under pressurized hydrogen.
- it in order to avoid reduction of benzene nuclei, it is carried out in a pressure range up to 20 atm.
- the reaction is preferably carried out in the range up to 10 atm.
- a solvent does not react with each raw material, it can be used without a restriction
- aprotic polar organic solvents DMF, DMSO, DMAc, NMP, etc.
- ethers Et 2 O, i-Pr 2 O, TBME, CPME, THF, dioxane, etc.
- aliphatic hydrocarbons penentane, Hexane, heptane, petroleum ether, etc.
- aromatic hydrocarbons benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.
- halogenated hydrocarbons chloroform, dichloromethane, carbon tetrachloride, dichloroethane) Etc.
- lower fatty acid esters methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.
- solvents can be appropriately selected in consideration of the ease of reaction. Moreover, it can be used individually by 1 type or in mixture of 2 or more types. If necessary, the solvent can be dried using a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.
- the amount of solvent used is not particularly limited, but is 0.1 to 100 times by mass with respect to 1 part by mass of the dinitro compound of the formula (B).
- the amount is preferably 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.
- the reaction temperature is not particularly limited, but is in the range from ⁇ 100 ° C. to the boiling point of the solvent used, preferably ⁇ 50 to 150 ° C.
- the reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.
- ⁇ Condensation step> In a 1 L (liter) four-necked flask, 4- (aminomethyl) piperidine (15.0 g, 131.4 mmol), potassium carbonate (21.8 g, 157.7 mmol) and N-methylpyrrolidone (40.5 g) were added. The temperature was raised to 75 ° C. with stirring and feather stirring. Thereafter, p-fluoronitrobenzene (38.9 g, 275.9 mmol) and N-methylpyrrolidone (7.5 g) were added dropwise over 2 hours, and the mixture was stirred at 75 ° C. for 6 hours. After confirming the completion of the reaction by HPLC, the reaction solution was used as it was and proceeded to the next step.
- 4- (Np-aminophenyl-N-tertiarybutoxycarbonylamino) methyl-N- (p-aminophenyl) piperidine obtained in the present invention is a polyimide precursor or a polyimide raw material used for a liquid crystal alignment film or the like. Useful as a material.
- the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2015-045862 filed on March 9, 2015 are incorporated herein as the disclosure of the specification of the present invention. Is.
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Abstract
Description
このポリアミック酸やポリイミドは、一般的に、テトラカルボン酸二水物などのテトラカルボン酸誘導体と、ジアミンとの縮重合反応によって製造されている。
1.p-フルオロニトロベンゼンと、4-(アミノメチル)ピペリジンとを、ジメチルアセトアミド、1,3-ジメチル-2-イミダゾリジノン、ジメチルスルホキシド及びN-メチルピロリドンからなる群から選ばれる少なくとも1種の溶媒中で反応させる、4-(p-ニトロフェニルアミノメチル)-N-(p-ニトロフェニル)ピペリジン(C)の製造方法。
3.4-(アミノメチル)ピペリジン1モルに対して、p-フルオロニトロベンゼンを2~10モル反応させる上記1又は2に記載の製造方法。
4.前記溶媒が、N-メチルピロリドンである上記1~3のいずれかに記載の製造方法。
7.前記ターシャリーブチルオキシカルボニル化剤の使用量が式(C)で表される化合物1モルに対して1~10モルである上記5又は6に記載の製造方法。
8.前記ターシャリーブチルオキシカルボニル化をテトラヒドロフランの溶媒中行う上記5~7のいずれかに記載の製造方法。
本発明では、p-フルオロニトロベンゼン(D)と、4-(アミノメチル)ピペリジン(E)とを反応させることにより、4-(p-ニトロフェニルアミノメチル)-N-(p-ニトロフェニル)ピペリジン(C)が得られる。
中でも、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩が好ましい。特に、微粉末炭酸カリウムを用いると、反応性が向上するので好ましい。市販されている微粉末炭酸カリウムとしては、FG-F20(旭硝子社商品名)等が挙げられる。
溶媒の使用量は、特に限定されないが、式(C)で表される化合物1質量部に対し、1~10質量倍の溶媒を用いることが好ましい。より好ましくは、3~5質量倍であり、さらに好ましくは3.1~3.3質量倍である。
反応温度は、例えば、-10~200℃、好ましくは40~100℃である。反応時間は、バッチ処理の場合には、0.5~20時間、好ましくは1~15時間である。
ターシャリーブチルオキシカルボニル化剤としては、N-tert-ブトキシカルボニルイミダゾール、炭酸tert-ブチルフェニル、カルバジン酸tert-ブチル、クロロギ酸tert-ブチル、二炭酸ジ-tert-ブチル等が挙げられ、特に好ましいのは二炭酸ジ-tert-ブチルである。
塩基の使用量は、上記式(C)で表される化合物に対して、好ましくは0.01~5.0当量、より好ましくは0.01~0.10当量である。
例えば、非プロトン性極性有機溶媒(ジメチルホルムアミド(DMF)、DMSO、DMAc、NMPなど);エーテル類(ジエチルエーテル(Et2O)、ジイソプロピルエーテル(i-Pr2O)、ターシャリーブチルメチルエーテル(TBME)、シクロペンチルメチルエーテル(CPME)、テトラヒドロフラン(THF)、ジオキサンなど);脂肪族炭化水素類(ペンタン、へキサン、ヘプタン、石油エーテルなど);芳香族炭化水素類(ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン、ニトロベンゼン、テトラリンなど);ハロゲン系炭化水素類(クロロホルム、ジクロロメタン、四塩化炭素、ジクロロエタンなど);低級脂肪酸エステル類(酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル等);ニトリル類(アセトニトリル、プロピオニトリル、ブチロニトリル等);等が使用できる。これらの溶媒は、反応の起こり易さなどを考慮して適宜選択することができる。また、1種単独で又は2種以上混合して用いることができる。必要に応じて、適当な脱水剤や乾燥剤を用いて溶媒を乾燥し、非水溶媒として用いることもできる。
THFと水は、通常は、混合し合って均一な溶液となるが、本発明の製造方法においては、縮合工程で副生したフッ化カリウムが、水相に溶解することにより水相の塩濃度が高いこと、目的物である式(B)で表される化合物が水に難溶性であること等から、両者は良好に分液する。その際のTHFと水の比率としては、THF1質量部に対して、水0.1~0.5質量部が好ましく、0.3~0.4質量部がより好ましい。
反応温度は特に限定されないが、-100℃から使用する溶媒の沸点までの範囲、好ましくは、-50~150℃の範囲である。
反応時間は、通常0.05~200時間、好ましくは0.5~100時間である。
反応終了後は、上記の通り、水を加えて分液することで、式(B)で表される化合物を含むTHF溶液が得られる。
本発明では、式(B)のニトロ化合物を単離せずに、これを含む溶液をそのまま、次工程の還元反応に供することができ、この場合、反応効率の向上や収率の向上等の点で、好ましい。
触媒の使用量は特に限定されないが、反応性の点から、上記式(B)で表される化合物1モルに対して、好ましくは0.0001~0.1モル、より好ましくは0.001~0.01モルである。
例えば、非プロトン性極性有機溶媒(DMF、DMSO、DMAc、NMPなど);エーテル類(Et2O、i-Pr2O、TBME、CPME、THF、ジオキサンなど);脂肪族炭化水素類(ペンタン、へキサン、ヘプタン、石油エーテルなど);芳香族炭化水素類(ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン、ニトロベンゼン、テトラリンなど);ハロゲン系炭化水素類(クロロホルム、ジクロロメタン、四塩化炭素、ジクロロエタンなど);低級脂肪酸エステル類(酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル等);ニトリル類(アセトニトリル、プロピオニトリル、ブチロニトリル等);などが使用できる。なかでも、THF、ジオキサン、酢酸エチルが好ましい。
これらの溶媒は、反応の起こり易さなどを考慮して、適宜選択できる。また、1種単独で又は2種以上混合して用いることができる。必要に応じて、適当な脱水剤や乾燥剤を用いて溶媒を乾燥し、非水溶媒として用いることもできる。
装置:Varian NMR system 400NB(400MHz)(Varian社製)、及びJMTC-500/54/SS(500MHz)(JEOL社製)
測定溶媒:CDCl3(重水素化クロロホルム),DMSO-d6(重水素化ジメチルスルホキシド)
基準物質:TMS(テトラメチルシラン)(δ:0.0ppm,1H)及びCDCl3(δ:77.0ppm,13C)
装置 :LC-20AD(島津製作所社製)
カラム:X Bridge BEHC18 5μm,4.6×250mm Column (Waters)
検出器:SPD-M20A(島津製作所社製) (検出波長:254nm)
溶離液:MeOH / 0.2%AcOH、0.8%Et3N aq. = 70/30 [vol/vol]
1L(リットル)の四つ口フラスコに、4-(アミノメチル)ピペリジン(15.0g,131.4mmol)、炭酸カリウム(21.8g、157.7mmol)及びN-メチルピロリドン(40.5g)を仕込み、羽攪拌下に75℃にまで昇温した。その後、p-フルオロニトロベンゼン(38.9g、275.9mmol)、及びN-メチルピロリドン(7.5g)を2時間かけて滴下し、75℃にて6時間撹拌した。HPLCにて反応終了を確認した後、反応液をそのまま用いて、次工程へと進んだ。
前工程の反応液にテトラヒドロフラン(270.0g)、及びDMAP(N,N-dimethyl-4-aminopyridine)(0.80g,6.57mmol)を仕込み、Boc2O (二炭酸ジ-tert-ブチル)(57.3g,262.5mmol)を30分かけて滴下した後,1時間攪拌した。HPLCにて反応終了を確認し、その後、テトラヒドロフラン(15.0g)、及び水(90.0g)を加えて撹拌した(1時間)。次いで、分液して水層を除去し、THF溶液をそのまま用いて、次工程へ進んだ。
前記THF溶液に5質量%Pd/C(50質量%含水型)(3.0g)、及び活性炭(白鷺WP-H(6.0g))を仕込んだ。その後、水素置換を行い、50℃に昇温した後、5時間撹拌した。HPLCにて反応終了を確認した後、メンブレンフィルターによりろ過を行い、Pd/C等を除去した。その後、内容量が210.0gになるまで濃縮した。次いで、2-プロパノール(420.0g)を滴下し、5℃に冷却して、さらに、1時間撹拌した。析出した結晶を減圧濾過し、2-プロパノール(27.0g)で洗浄した後、乾燥し、粉末結晶として、4-(N-p-アミノフェニル-N-ターシャリーブトキシカルボニルアミノ)メチル-N-(p-アミノフェニル)ピペリジンを得た(収量44.3g,収率85.0%)。
1H-NMR(DMSO-d6):δ=6.83(d,2H, J=8.0), 6.65(d,2H J=8.4), 6.50(d,2H, J=8.4), 6.45(d,2H, J=8.4), 5.05(br, 2H), 4.54(br,2H), 3.41(d,2H, J=6.8), 3.29(d,2H,J=12.4), 2.36(t,2H, J=10.8), 1.64(d,2H, J=11.6), 1.42-1.19(br,12H).
なお、2015年3月9日に出願された日本特許出願2015-045862号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (11)
- 1.p-フルオロニトロベンゼンと、4-(アミノメチル)ピペリジンとを、ジメチルアセトアミド、1,3-ジメチル-2-イミダゾリジノン、ジメチルスルホキシド及びN-メチルピロリドンからなる群から選ばれる少なくとも1種の溶媒中で反応させる、4-(p-ニトロフェニルアミノメチル)-N-(p-ニトロフェニル)ピペリジン(C)の製造方法。
- 塩基の存在下に反応させる請求項1に記載の製造方法。
- 4-(アミノメチル)ピペリジン1モルに対して、p-フルオロニトロベンゼンを2~10モル反応させる請求項1又は2に記載の製造方法。
- 前記溶媒が、N-メチルピロリドンである請求項1~3のいずれかに記載の製造方法。
- 前記ターシャリーブチルオキシカルボニル化を塩基の存在下にて行う請求項5に記載の製造方法。
- 前記ターシャリーブチルオキシカルボニル化剤の使用量が式(C)で表される化合物1モルに対して1~5モルである請求項5又は6に記載の製造方法。
- 前記ターシャリーブチルオキシカルボニル化をテトラヒドロフランの溶媒中で行う請求項5~7のいずれかに記載の製造方法。
- 触媒の存在下における水素添加反応により還元する請求項9に記載の製造方法。
- 活性炭担持触媒の存在下に還元する請求項9又は10に記載の製造方法。
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