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CN102775315A - Preparation method of 3-aminophenylacetylene - Google Patents

Preparation method of 3-aminophenylacetylene Download PDF

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CN102775315A
CN102775315A CN201210268002XA CN201210268002A CN102775315A CN 102775315 A CN102775315 A CN 102775315A CN 201210268002X A CN201210268002X A CN 201210268002XA CN 201210268002 A CN201210268002 A CN 201210268002A CN 102775315 A CN102775315 A CN 102775315A
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aminophenylacetylene
acid
nitrobenzene
preparation
nitrophenyl
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刘传祥
刘利刚
王宇凯
王永
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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Abstract

本发明公开了一种间氨基苯乙炔的制备方法,即以间硝基苯甲醛为起始原料，首先在乙醇溶剂中，与丙二酸通过碱性催化剂催化进行缩合，脱羧得到间硝基肉桂酸，进而再在醋酸溶液中溴化得α,β-二溴-3-(3′-硝基苯基)丙酸，后通过弱碱脱羧及选择性脱溴，制得(Z)-1-(2-溴乙烯)-3-硝基苯，后再经强碱完全脱溴制得间炔基硝基苯，最后经铁粉还原并进一步精馏纯化即得间氨基苯乙炔。本发明的间氨基苯乙炔的制备方法，具有合成路线简单，原料易得且反应条件温和，总收率高等优点，适于工业化生产。

Figure 201210268002

The invention discloses a preparation method of m-aminophenylacetylene, that is, using m-nitrobenzaldehyde as a starting material, first condensing with malonic acid in an ethanol solvent through a basic catalyst, and decarboxylation to obtain m-nitrocinnamon acid, and then brominated in acetic acid solution to obtain α , β -dibromo-3-(3′-nitrophenyl)propionic acid, and then decarboxylated by weak base and selective debromination to obtain (Z)-1 -(2-Bromoethylene)-3-nitrobenzene, and then completely debrominated by a strong base to obtain m-alkynyl nitrobenzene, and finally reduced by iron powder and further rectified and purified to obtain m-aminophenylacetylene. The preparation method of m-aminophenylacetylene of the present invention has the advantages of simple synthesis route, easily available raw materials, mild reaction conditions, high total yield, etc., and is suitable for industrial production.

Figure 201210268002

Description

A kind of preparation method of m-aminophenyl acetylene
Technical field
The present invention relates to a kind of preparation method of m-aminophenyl acetylene, belong to organic synthesis and prepare chemical field.
Background technology
M-aminophenyl acetylene has another name called 3-acetylene aniline, is a kind of high-grade resin in fields such as synthetic Aeronautics and Astronautics, military affairs and important intermediate of synthesizing new cancer therapy drug (erlotinib) of being used for.The compound method that document is introduced m-aminophenyl acetylene mainly contains following several kinds.
One, a halogenated nitrobenzene is a starting raw material
As being raw material with a bromo nitrobenzene; Through dihydroxypropyl alkynes (or trimethyl silicane) the generation linked reaction of palladium-containing catalyst catalysis with the band protection; After hydro-reduction; Deprotection gets m-aminophenyl acetylene, and this route need be used expensive palladium reagent and protection reagent, and reaction conditions is unfavorable for industry's enlarging production than harshness.Be that raw material also exists above-mentioned unfavorable factor similarly with m-bromoaniline, an iodo oil of mirbane.（EP?2433931；PCT?2009009778；?UP20060224016； Org.?Bio.?Chem.,? 2003,? 1:?4441-4450； Beilstein?J.?Org.?Chem.,? 2011,? 7:?426-431）
Two, α, β-dihalo thing alkalescence is eliminated preparation alkynes
With α, β-two bromo-3-(3 '-nitrophenyl) propionic acid is a raw material, through alkaline condition eliminate down react m-nitrobenzene acetylene, and after reduce m-aminophenyl acetylene.Although this route looks economically feasible, the method for bibliographical information exists and eliminates the difficult control of side reaction at present, by product many and need utilize microwave promote effects limit such as the dehalogenation reaction industriallization of this route use ( Huaxue Shijie, 2011, 52: 423-426; Chem. Lett., 2005, 34: 28-29; Tetrahedron Lett., 2011, 52: 2394-2396; Tetrahedron, 2005, 61: 4043-4052).
Summary of the invention
The object of the invention is in order to solve the defective that above-mentioned prior art exists, and a kind of preparation method of m-aminophenyl acetylene is provided, and promptly adopts under the weak basic condition α, β-dihalo thing is eliminated the method for preparing alkynes, makes through the weak extinction of flame condition α, β-two bromo-3-(3 '-nitrophenyl) elimination of propionic acid generation selectivity; Then strengthening alkaline condition impels it that reaction takes place to eliminate fully to avoid production of by-products; And then the yield of raising target compound m-aminophenyl acetylene, the preparation method of this m-aminophenyl acetylene is the method that a kind of gentleness is efficient, simple to operate and industriallization is feasible.
Technical scheme of the present invention
A kind of preparation method of m-aminophenyl acetylene, its preparation process specifically comprises the steps:
(1), be starting raw material with the m-nitrobenzaldehyde, in alcohol solvent, obtain m-nitro-cinnamic acid after through basic catalyst catalyzing and condensing, depickling with propanedioic acid;
Described basic catalyst is triethylamine, piperidines or pyridine;
M-nitrobenzaldehyde and propanedioic acid condensation reaction in the above-mentioned steps; Proportion of raw materials is calculated in molar ratio; Be the midbody nitrobenzaldehyde: propanedioic acid: basic catalyst is 1:1.1 ~ 1.5:0.3 ~ 0.5, and preferred 1:1.1:0.3 is under the normal pressure; The temperature of control condensation reaction is at 80-85 ℃, and the reaction times is 8-10h;
(2), the m-nitro-cinnamic acid of step (1) gained in acetum through liquid bromine temperature control at 50-55 ℃, and the rate of addition of control liquid bromine is kept 30min-1h and is carried out bromination reaction, obtains α, β-two bromo-3-(3 '-nitrophenyl) propionic acid;
M-nitro-cinnamic acid that above-mentioned bromination reaction is used and liquid bromine calculate in molar ratio, i.e. m-nitro-cinnamic acid: the liquid bromine is 1:1.01 ~ 1.05, preferred 1:1.01;
(3), step (2) gained α, β-two bromo-3-(3 '-nitrophenyl) propionic acid in organic solvent under the reflux conditions through weak base NaHCO 3Catalyzed reaction control 8 ~ 10h makes (Z)-1-(2-bromine ethene)-3-oil of mirbane;
Above-mentioned used weak base is yellow soda ash or sodium hydrogencarbonate, preferred sodium hydrogencarbonate;
Described organic solvent is acetone, ethanol or acetonitrile;
Above-mentioned reaction process is used α, β-two bromo-3-(3 '-nitrophenyl) propionic acid, weak base NaHCO 3Calculate in molar ratio, promptly α, β-two bromo-3-(3 '-nitrophenyl) propionic acid: weak base NaHCO 3Be 1:3 ~ 4, preferred 1:3;
Above-mentioned steps is sloughed through the weak base base catalysis in (3) β position halogen bromineThe time, slough a part carbonic acid gas, but owing to weakly alkaline is not enough to make The cancellation of α position, thereforeMake i.e. (Z)-1-(2-bromine the ethene)-3-oil of mirbane of single bromo-derivative;
(4), (Z)-1-(2-bromine the ethene)-3-oil of mirbane of step (3) gained under ethanol/highly basic sodium hydroxide system, controlled temperature is at 35-40 ℃ of reaction 2-2.5h, catalysis is eliminated the unit molecule bromine and is got an alkynyl oil of mirbane;
The above-mentioned highly basic that adopts is Pottasium Hydroxide, sodium hydroxide or sodium hydrogen, preferred sodium hydroxide;
Above-mentioned (Z)-1-(2-bromine ethene)-3-oil of mirbane and highly basic NaOH calculate in molar ratio, i.e. (Z)-1-(2-bromine ethene)-3-oil of mirbane: weak base NaOH is 1:1.5 ~ 2, preferred 1:1.5;
(5), step (4) gained between alkynyl oil of mirbane through iron powder, after in the presence of ammonium chloride, reducing,, collect the cut under 91-93 ℃ (2mmHg), final m-aminophenyl acetylene again through the rectifying purifying;
Above-mentioned iron powder reducing method can adopt palladium carbon hydrogenating reduction or tin protochloride method of reducing to substitute, but preferred iron powder reducing.
In the above-mentioned preparation process, improve for making title product m-aminophenyl acetylene yield, whole preparation feedback process is carried out having under the protection of inert gas condition.
Beneficial effect of the present invention
The present invention compares with the compound method of existing preparation m-nitrobenzene acetylene, has following advantage:
The preparation method of a kind of m-aminophenyl acetylene of the present invention is a starting raw material with the m-nitrobenzaldehyde, and used raw material is easy to get and is cheap, and synthesis technique is simple, and therefore midbody separate easily and purifying have the low characteristics of production cost.
Further, the preparation method of a kind of m-aminophenyl acetylene of the present invention is because the intermediate product of gained in the preparation process α, β-two bromo-3-(3 '-nitrophenyl) propionic acid gets (Z)-1-(2-bromine ethene)-3-oil of mirbane through weak base catalysis earlier; And then highly basic condition catalysis elimination unit molecule bromine gets an alkynyl oil of mirbane; Therefore not only can realize the elimination reaction of highly selective and then suppress production of by-products; Improve the yield of principal product, and have the characteristics of preparation process reaction mild condition.
Further, the preparation method of a kind of m-aminophenyl acetylene of the present invention, because to have synthetic route simple, reaction conditions is gentle, therefore the raw material low and target product yield advantages of higher of cost that is easy to get is suitable for suitability for industrialized production.
Description of drawings
The preparing method's of Fig. 1, a kind of m-aminophenyl acetylene reaction process synoptic diagram.
Embodiment
Below through concrete embodiment and combine accompanying drawing that the present invention is further set forth, but do not limit the present invention.
Raw material and reagent (analytical pure) used in the various embodiments of the present invention are all purchased in Chemical Reagent Co., Ltd., Sinopharm Group.
It is Siemens Brucker AM 400 (400 MHz) instrument that the nuclear-magnetism of midbody and target compound detects used instrument.
Embodiment 1
A kind of preparation method of m-aminophenyl acetylene; The reaction process synoptic diagram of its preparation method is as shown in Figure 1; Promptly be starting raw material, at first in alcohol solvent, carry out condensation through the catalysis of basic catalyst pyridine with propanedioic acid with the m-nitrobenzaldehyde; Decarboxylation obtains m-nitro-cinnamic acid, so again in acetum bromination get α, β-two bromo-3-(3 '-nitrophenyl) propionic acid; The back is through decarboxylation of weak base sodium hydrogencarbonate and selective debromination; Make (Z)-1-(2-bromine ethene)-3-oil of mirbane; After make an alkynyl oil of mirbane through the complete debrominate of highly basic sodium hydroxide again, after iron powder reducing and further rectifying purifying promptly get m-aminophenyl acetylene.
The preparation method of above-mentioned a kind of m-aminophenyl acetylene specifically comprises the steps:
(1), reflux condensing tube is being housed, temperature is taken into account and is added 250mL95% ethanol and 25ml pyridine in the 1L there-necked flask of electric mixer, stirs adding 151g (1mol) m-nitrobenzaldehyde and 115g (1.1mol) propanedioic acid down; Heat temperature raising, 80 ℃ of temperature of reaction, and keep stirring 6h under this temperature; Stop heating, cool to room temperature, suction filtration; The filter cake oven dry promptly gets the m-nitro-cinnamic acid of 155g, and its yield is 80%;
The m-nitro-cinnamic acid of above-mentioned gained, through nuclear-magnetism measure (Siemens Brucker AM 400 (400MHz) data are following: 1H NMR (400MHz, DMSO): δ 8.51 (s, 1H), 8.23 (d, 1H), 8.17 (d, 1H), 7.72 (dd, 1H), 7.70 (d, 1H), 6.72 (d, 1H);
(2), reflux condensing tube is being housed, temperature is taken into account the Glacial acetic acid min. 99.5 that adds 500g in the 2L there-necked flask of electric mixer and the m-nitro-cinnamic acid of 193g (1mol) step (1) gained, is heated to 50 ℃; (161.6g 1.01mol), controls slowly dropping in this reaction system, to drip bromine; And make temperature of reaction system be no more than 60 ℃; Get red transparent liquid after adding, insulated and stirred 6h is cooled to room temperature and obtains reaction mixture;
The above-mentioned reaction mixture that obtains in the water of going into 2Kg, is filtered, filter cake is washed with 2*500ml, white solid, dry 326.5g α, β-two bromo-3-(3 '-nitrophenyl) propionic acid, its yield is 92.5%;
Above-mentioned gained α, β-two bromo-3-(3 '-nitrophenyl) propionic acid, through nuclear-magnetism measure (Siemens Brucker AM 400 (400MHz) data are following: 1H NMR (400MHz, DMSO): δ 8.59 (s, 1H), 8.19 (dd, 2H), 7.70 (t, 1H), 5.80 (d, 1H), 5.49 (d, 1H);
(3), reflux condensing tube is being housed, temperature takes into account and adds 700g acetone in the 2L there-necked flask of electric mixer, adds step (2) gained then respectively α, β-two bromo-3-(3 '-nitrophenyl) propionic acid (353g, 1mol) and sodium hydrogencarbonate (252g, 3mol), reflux; Slowly have a large amount of white solids to produce, tail off gradually along with reaction continues solid, about 8h, normal pressure steam and remove acetone; In flask, add 400g toluene and 500g water, suction filtration, anhydrate filtrating branch; With 200g washing one time, organic phase removes (Z)-1-(2-bromine ethene)-3-oil of mirbane that solvent gets 216g, yield 94.7% under reduced pressure to organic phase again;
Through nuclear-magnetism measure (Siemens Brucker AM 400 (400 MHz) data are following: 1H NMR (400MHz, CDCl 3): δ 8.55 (s, 1H), 8.17 (m, 1H), 7.98 (d, 1H), 7.56 (t, 1H), 7.14 (d, 1H), 6.64 (d, 1H);
(4), reflux condensing tube is being housed, temperature is taken into account 90% the ethanol that adds 300g in the 2L there-necked flask of electric mixer, adds sodium hydroxide (60g then; 1.5mol) dissolve 35～40 ℃ of back insulations, in the 1L beaker, join (Z)-1-(2-bromine ethene)-3-oil of mirbane (228g, 90% ethanol (300g) solution 1mol) of step (3) gained in addition; Then the ethanolic soln of (Z)-1-(2-bromine ethene)-3-oil of mirbane is dropped in the reaction system of there-necked flask of 2L fast, stir 2h, have solid to separate out at 35～40 ℃; Add 700g water and 400g methylene dichloride after being cooled to room temperature, collect organic phase, water is used the 50g dichloromethane extraction one time again; Merge organic phase, with the 200g washing, remove methylene dichloride under reduced pressure again; 137g between alkynyl oil of mirbane, its yield 93%;
Alkynyl oil of mirbane between above-mentioned gained, through nuclear-magnetism measure (Siemens Brucker AM 400 (400MHz) data are following: 1H NMR (400MHz, CDCl 3): δ 8.32 (s, 1H), 8.20 (d, 1H), 7.78 (d, 1H), 7.52 (t, 1H), 3.22 (s, 1H);
(5), reflux condensing tube is being housed, temperature is taken into account and is added 200g water, ammonium chloride (7.35g in the 2L there-necked flask of electric mixer; 5%) and reduced iron powder (168g, 3mol), be warmed up to after 75 ℃ the control drop rate and be 1ml/min add step (4) gained between alkynyl oil of mirbane (147g; Ethanol 1mol) (300g) solution, exothermic heat of reaction keeps refluxing; Drip the insulation of complete back to reaction end (TLC trace point plate), press filtration while hot, filter cake is washed with 100g water and 100g ethanol respectively; Solvent evaporated gets garnet m-aminophenyl acetylene bullion 105g, its yield 90%;
The direct rectifying purifying of the m-aminophenyl acetylene bullion of above-mentioned gained is collected the cut under 91-93 ℃ (2mmHg), get the m-aminophenyl acetylene of 99.8g, its yield 95%, purity is 99.9%.
(Siemens Brucker AM 400 (400MHz) data are following: NMR (400MHz, CDCl through nuclear-magnetism mensuration for the m-aminophenyl acetylene of above-mentioned gained 3): δ 7.11 (t, 1H), 6.92 (m, 1H), 6.83 (t, 1H), 6.62 (m, 1H), 3.69 (s, 2H), 3.06 (s, 1H).
The above content is merely the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.

Claims (9)

1.一种间氨基苯乙炔的制备方法，其特征在于包括如下步骤: 1. a preparation method of m-aminophenylacetylene, is characterized in that comprising the steps: （1）、以间硝基苯甲醛为起始原料，在乙醇溶剂中与丙二酸在碱性催化剂催化下进行缩合、脱酸得到间硝基肉桂酸； (1) Using m-nitrobenzaldehyde as a starting material, condensing and deacidifying m-nitrobenzaldehyde with malonic acid in an ethanol solvent under the catalysis of a basic catalyst to obtain m-nitrocinnamic acid; 所述的碱性催化剂为三乙胺、哌啶或吡啶； Described basic catalyst is triethylamine, piperidine or pyridine; 所述的中间硝基苯甲醛与丙二酸缩合反应，原料的配比按摩尔比计算，即中间体硝基苯甲醛：丙二酸：碱性催化剂为1：1.1~1.5：0.3~0.5； In the condensation reaction of intermediate nitrobenzaldehyde and malonic acid, the ratio of raw materials is calculated by molar ratio, that is, intermediate nitrobenzaldehyde: malonic acid: basic catalyst is 1: 1.1~1.5: 0.3~0.5; （2）、步骤（1）所得的间硝基肉桂酸在醋酸溶液中经液溴缓慢滴加，且控温在50-60℃下进行溴化反应制得α,β-二溴-3-(3′-硝基苯基)丙酸； (2), the m-nitrocinnamic acid obtained in step (1) is slowly added dropwise in the acetic acid solution through liquid bromine, and the bromination reaction is carried out at 50-60°C under temperature control to obtain α , β -dibromo-3- (3'-nitrophenyl)propionic acid; 所述的溴化反应所用的间硝基肉桂酸和液溴按摩尔比计算，即间硝基肉桂酸：液溴为1：1.01~1.05； The m-nitrocinnamic acid and liquid bromine used in the bromination reaction are calculated by molar ratio, that is, m-nitrocinnamic acid: liquid bromine is 1:1.01~1.05; （3）、步骤（2）所得的α,β-二溴-3-(3′-硝基苯基)丙酸在有机溶剂中回流条件下经弱碱NaHCO3催化反应控制8~10h制得(Z)-1-(2-溴乙烯)-3-硝基苯； (3) The α , β -dibromo-3-(3′-nitrophenyl)propionic acid obtained in step (2) is prepared by controlling the catalyzed reaction of weak base NaHCO 3 for 8~10h under the condition of reflux in an organic solvent (Z)-1-(2-bromoethylene)-3-nitrobenzene; 所述的有机溶剂为丙酮、乙醇或乙腈； Described organic solvent is acetone, ethanol or acetonitrile; 上述反应过程所用的α,β-二溴-3-(3′-硝基苯基)丙酸、弱碱NaHCO3按摩尔比计算，即α,β-二溴-3-(3′-硝基苯基)丙酸：弱碱NaHCO3为1：3~4； The α , β -dibromo-3-(3′-nitrophenyl)propionic acid and weak base NaHCO3 used in the above reaction process are calculated on a molar basis, that is, α , β -dibromo-3-(3′-nitrophenyl) phenyl)propionic acid: Weak base NaHCO 3 is 1:3~4; （4）、步骤（3）所得的(Z)-1-(2-溴乙烯)-3-硝基苯在乙醇/强碱氢氧化钠体系下，控制温度在35-40℃反应2-2.5h,催化消除单分子溴得间炔基硝基苯； (4) The (Z)-1-(2-bromoethylene)-3-nitrobenzene obtained in step (3) is reacted at 35-40°C for 2-2.5 minutes under the system of ethanol/strong alkali sodium hydroxide h, catalytic elimination of unimolecular bromine to obtain m-alkynyl nitrobenzene; 上述 (Z)-1-(2-溴乙烯)-3-硝基苯与强碱NaOH按摩尔比计算，即(Z)-1-(2-溴乙烯)-3-硝基苯：弱碱NaOH为1：1.5~2； The above (Z)-1-(2-bromoethylene)-3-nitrobenzene and strong base NaOH are calculated by molar ratio, that is, (Z)-1-(2-bromoethylene)-3-nitrobenzene: weak base NaOH is 1:1.5~2; （5）、步骤（4）所得的间炔基硝基苯经铁粉，在氯化铵存在下进行还原后，再经精馏纯化收集91-93℃，即2mmHg下的馏分，最终得间氨基苯乙炔。 (5), the m-alkynyl nitrobenzene obtained in step (4) is reduced by iron powder in the presence of ammonium chloride, and then purified by rectification to collect the distillate at 91-93°C, that is, at 2mmHg, to finally obtain m- Aminophenylacetylene. 2.如权利要求1所述的一种间氨基苯乙炔的制备方法，其特征在于步骤（1）中所述的中间硝基苯甲醛与丙二酸缩合反应，原料的配比按摩尔比计算，即中间体硝基苯甲醛：丙二酸：碱性催化剂为1:1.1:0.3; 2. a kind of preparation method of m-aminophenylacetylene as claimed in claim 1 is characterized in that the intermediate nitrobenzaldehyde and malonic acid condensation reaction described in step (1), the proportioning of raw material is calculated by molar ratio , that is, the intermediate nitrobenzaldehyde: malonic acid: basic catalyst is 1:1.1:0.3; 所述的缩合反应控制温度在80-85℃，时间为8-10h。 The temperature of the condensation reaction is controlled at 80-85° C. and the time is 8-10 hours. 3.如权利要求2所述的一种间氨基苯乙炔的制备方法，其特征在于步骤（2）中所述的溴化反应所用的间硝基肉桂酸和液溴按摩尔比计算，即间硝基肉桂酸：液溴为1:1.01。 3. the preparation method of a kind of m-aminophenylacetylene as claimed in claim 2 is characterized in that the m-nitrocinnamic acid used in the bromination reaction described in step (2) and liquid bromine are calculated by molar ratio, that is, m Nitrocinnamic acid: liquid bromine is 1:1.01. 4.如权利要求3所述的一种间氨基苯乙炔的制备方法，其特征在于步骤（3）所述的反应过程所用的α,β-二溴-3-(3′-硝基苯基)丙酸、弱碱NaHCO3按摩尔比计算，即α,β-二溴-3-(3′-硝基苯基)丙酸：弱碱NaHCO3为1:3。 4. A method for preparing m-aminophenylacetylene as claimed in claim 3, characterized in that the α , β -dibromo-3-(3'-nitrophenyl used in the reaction process described in step (3) ) propionic acid and weak base NaHCO 3 are calculated by molar ratio, that is, α , β -dibromo-3-(3′-nitrophenyl) propionic acid: weak base NaHCO 3 is 1:3. 5.如权利要求4所述的一种间氨基苯乙炔的制备方法，其特征在于步骤（4）所述的(Z)-1-(2-溴乙烯)-3-硝基苯与强碱NaOH按摩尔比计算，即(Z)-1-(2-溴乙烯)-3-硝基苯：弱碱NaOH为1:1.5。 5. the preparation method of a kind of m-aminophenylacetylene as claimed in claim 4 is characterized in that (Z)-1-(2-bromoethylene)-3-nitrobenzene and strong base described in step (4) NaOH is calculated by molar ratio, that is, (Z)-1-(2-bromoethylene)-3-nitrobenzene: weak base NaOH is 1:1.5. 6.如权利要求5所述的一种间氨基苯乙炔的制备方法，其特征在于步骤（3）中所述的弱碱碳酸氢钠用碳酸钠替代。 6. The preparation method of a kind of m-aminophenylacetylene as claimed in claim 5, characterized in that the weak base sodium bicarbonate described in step (3) is replaced by sodium carbonate. 7.如权利要求6所述的一种间氨基苯乙炔的制备方法，其特征在于步骤（4）中所述的强碱氢氧化钠用氢氧化钾或钠氢替代。 7. A method for preparing m-aminophenylacetylene as claimed in claim 6, characterized in that the strong base sodium hydroxide described in step (4) is replaced by potassium hydroxide or sodium hydrogen. 8.如权利要求7所述的一种间氨基苯乙炔的制备方法，其特征在于步骤（5）中所述的铁粉还原的方法采用钯碳加氢还原或氯化亚锡还原方法替代。 8. A method for preparing m-aminophenylacetylene as claimed in claim 7, characterized in that the iron powder reduction method described in step (5) is replaced by palladium carbon hydrogenation reduction or stannous chloride reduction method. 9.如权利要求1～8任一权利要求所述的一种间氨基苯乙炔的制备方法，其特征在于整个制备反应过程在有惰性气体保护条件下进行。 9. A method for preparing m-aminophenylacetylene according to any one of claims 1 to 8, characterized in that the entire preparation reaction process is carried out under the protection of an inert gas.
CN201210268002XA 2012-07-31 2012-07-31 Preparation method of 3-aminophenylacetylene Pending CN102775315A (en)

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CN107175134A (en) * 2017-05-31 2017-09-19 成都西岭源药业有限公司 It is a kind of to be used to prepare 3-aminophenylacetylene or the composition of its salt and application thereof
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CN109569730A (en) * 2018-11-27 2019-04-05 江苏师范大学 A kind of catalyst and its application
CN112645826A (en) * 2020-12-21 2021-04-13 浙江师范大学 Preparation method of ethynylaniline
CN116102440A (en) * 2023-02-06 2023-05-12 上海琼燕医药科技有限公司 Preparation method of 1- (3, 4-diaminophenyl) ethanone

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CN103724211A (en) * 2013-12-12 2014-04-16 重庆威尔德·浩瑞医药化工有限公司 Preparation method for m-aminophenylacetylene
CN107175134A (en) * 2017-05-31 2017-09-19 成都西岭源药业有限公司 It is a kind of to be used to prepare 3-aminophenylacetylene or the composition of its salt and application thereof
CN107175134B (en) * 2017-05-31 2018-03-23 成都西岭源药业有限公司 It is a kind of to be used to prepare 3-aminophenylacetylene or the composition of its salt and application thereof
CN108440309A (en) * 2018-04-09 2018-08-24 上海倍殊生物科技有限公司 A kind of preparation method of 3-aminophenylacetylene
CN108440309B (en) * 2018-04-09 2021-01-15 上海倍殊生物科技有限公司 Preparation method of m-aminophenylacetylene
CN109569730A (en) * 2018-11-27 2019-04-05 江苏师范大学 A kind of catalyst and its application
CN112645826A (en) * 2020-12-21 2021-04-13 浙江师范大学 Preparation method of ethynylaniline
CN116102440A (en) * 2023-02-06 2023-05-12 上海琼燕医药科技有限公司 Preparation method of 1- (3, 4-diaminophenyl) ethanone

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Application publication date: 20121114