CN109593045A - A kind of preparation method of 11- aminoundecanoic acid - Google Patents
A kind of preparation method of 11- aminoundecanoic acid Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/10—Formation of amino groups in compounds containing carboxyl groups with simultaneously increasing the number of carbon atoms in the carbon skeleton
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- C07—ORGANIC CHEMISTRY
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- C07C253/00—Preparation of carboxylic acid nitriles
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
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Abstract
The present invention provides a kind of preparation methods of 11- aminoundecanoic acid, this method comprises the following steps: 1) 9 hydroxynonanoic acid or 9 hydroxynonanoic acid ester being dissolved in solvent, preparation 9- oxo n-nonanoic acid or 9- oxo pelargonate are selectively oxidized in the presence of oxidant；2) the 9- oxo n-nonanoic acid or 9- oxo pelargonate and cyan-acetic ester are dissolved in solvent, carry out knoevenagel condensation reaction and obtains III compound of formula；3) product obtained in step 2) is continued into hydrolysis, 11 carbon -2- enedioic acid of 2- cyano is obtained after acidification；4) product obtained in step 3) is subjected to selective decarboxylic reaction and obtains Formula V compound 10- cyano -10- alkene capric acid；5) catalyst is added into 10- cyano -10- alkene capric acid obtained in step 4), is successively replaced with nitrogen, hydrogen, carry out hydrogenation reduction, obtain 11- aminoundecanoic acid after crude product refining.
Description
Technical field
The present invention relates to nylon material fields, the specially preparation method of nylon 11 material monomer 11- aminoundecanoic acid.
Background technique
11- aminoundecanoic acid is the monomer of a kind of multiduty organic intermediate and nylon-11, and nylon-11 has intensity
The features such as height, heatproof is wear-resisting, and chemical stability is good, and electrical insulation capability is excellent, especially at low temperature, impact resistant strength are high, than
Heavy and light, water imbibition is low, easily processed into type, in addition, harmless to the human body；It is widely used in auto industry, ordnance industry, cable
The fields such as industry, town gas engineering, electrical equipment industry, powdery paints, modified composite material.The key problem in technology of nylon 11 is list
The preparation of body 11- aminoundecanoic acid, and the quality of monomer directly affects the quality of its polymer and the yield of product, therefore,
It is most important to develop a kind of reasonable 11- aminoundecanoic acid preparation process.
Some researchs are done to 11- aminoundecanoic acid in the prior art, such as Chinese patent application discloses
CN101289409A and CN102702525A discloses the preparation method of 11- aminoundecanoic acid, and castor oil reacts generation with methanol
Castor oil methyl esters, then obtain undecenoic acid and enanthaldehyde through cracking, vacuum fractionation is added under the conditions of undecenoic acid is existing for the hydrogen peroxide
Hydrobromic acid occurs Markovnikov addition reaction and generates 11- bromination undecanoic acid, and nucleophilic displacement of fluorine then occurs with ammonium hydroxide and obtains product 11- amino
Undecanoic acid.
Chinese patent application discloses CN104499081A, CN104499082A and CN104562340A and discloses amino 11
The ammonium hydroxide of bromoundecane acid and 15wt% is added in reactor by sour preparation method, and stirring is reacted at room temperature, then will
Reaction product heating distillation, and ammonia is absorbed with cold water, the temperature for heating distillation is 60 DEG C, until bubble-free generates, that is, is stopped
Distillation, is then cooled down and is filtered, and filter cake is washed with deionized water until no bromide ion, is detected using silver nitrate solution, will
Product is dried in vacuo to obtain product 11- aminoundecanoic acid.
There are many deficiencies for the existing production method of 11- aminoundecanoic acid, wherein cracking category high energy consumption technique, needs high temperature
Condition, and cracking is not thorough, side reaction is more, and easy coking, product yield is low, since intermediate 10 hendecenoic acid double bond is easily sent out
Raw dystopy causes separation difficult, and bromination process uses hydrobromic acid environment easy to pollute, and 11- bromination undecanoic acid reacts with ammonia water the time
Long, for the quality and yield for improving product 11- aminoundecanoic acid, ammonium hydroxide usually requires big excess, and therefore, post-processing needs to recycle
A large amount of ammonium hydroxide, lead to that the production cost increases.In general, the technological reaction time is long, and design library part editor and reuse is complicated, high production cost,
The three wastes are more, therefore urgently develop the new process of 11- aminoundecanoic acid.
Patent application publication US 2016/0002147 report use olefin metathesis reaction, with unsaturated fatty acid with
The intermediate of acrylonitrile raw material, generation obtains 11- aminoundecanoic acid by hydrogenating reduction.
The patent application publication WO2012/095575A1 of French Arkema reports 11- aminoundecanoic acid preparation method,
Nitrile compounds are generated by unsaturated fat acid oxidase, hydrogenating reduction obtains product 11- aminoundecanoic acid.
The method of above-mentioned two patent reports is higher to catalyst requirement, and reaction condition is very harsh, is unsuitable for industrializing
Production.
Summary of the invention
Technical problem
The object of the present invention is to provide a kind of 11- aminoundecanoic acid preparation methods, and the method overcome traditional handicraft reactions
The deficiency that time is long, condition is harsh, by-product is more, product is not readily separated.
Technical solution
The present invention provides a kind of preparation methods of 11- aminoundecanoic acid, and this method comprises the following steps:
1) compound of formula I 9 hydroxynonanoic acid or 9 hydroxynonanoic acid ester are dissolved in solvent, are selected under oxidant effect
Selecting property aoxidizes II compound 9- oxo n-nonanoic acid of preparation formula or 9- oxo pelargonate；
2) the 9- oxo n-nonanoic acid or 9- oxo pelargonate and cyan-acetic ester are dissolved in solvent, under the action of catalyst
Knoevenagel condensation reaction is carried out, III compound of formula is obtained；
3) make III compound of formula obtained in step 2) basic catalyst effect under reaction is hydrolyzed, after be added
Acid is acidified to obtain 11 carbon -2- enedioic acid of formula IV compound 2- cyano；
4) 11 carbon -2- enedioic acid of 2- cyano obtained in step 3) is subjected to selective decarboxylic reaction and obtains Formula V chemical combination
Object 10- cyano -10- alkene capric acid；
5) catalyst is added into 10- cyano -10- alkene capric acid obtained in step 4), is successively replaced with nitrogen, hydrogen,
Carry out hydrogenation reduction, after obtain 11- aminoundecanoic acid,
Wherein, R1For the H or C of linear chain or branched chain1-C10Alkyl；The C of preferably H or linear chain or branched chain1-C6Alkyl, more
Preferably H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl or amyl；And R2For the C of linear chain or branched chain1-
C10Alkyl, the preferably C of linear chain or branched chain1-C6Alkyl, more preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl group,
Tert-butyl or amyl.
Wherein, in step 1):
The oxidant is manganese dioxide, copper oxide or zinc oxide, oxidant and 9 hydroxynonanoic acid or 9 hydroxynonanoic acid ester
Molar ratio be 1.0~2.0, preferably 1.0~1.2；
The solvent can dissolve 9 hydroxynonanoic acid or 9 hydroxynonanoic acid ester, be not particularly limited, and the example includes
But it is not limited to, ethyl acetate, tetrahydrofuran, n,N-Dimethylformamide or dioxane；
Reaction temperature is 20 DEG C~80 DEG C, preferably 25 DEG C~50 DEG C；Reaction time is 5~12h, preferably 8~10h；
The 9 hydroxynonanoic acid ester is 9 hydroxynonanoic acid methyl esters, 9 hydroxynonanoic acid ethyl ester, 9 hydroxynonanoic acid propyl ester, 9- hydroxyl
N-nonanoic acid isopropyl ester or 9 hydroxynonanoic acid butyl ester；
In step 2):
The catalyst of the knoevenagel condensation reaction is alkali, and the example includes, but are not limited to triethylamine, N, N- bis-
Wopropyl ethyl amine, N-methylmorpholine, tetramethylethylenediamine, potassium hydroxide, sodium hydroxide or piperidines, the knoevenagel contracting
It closes the catalyst of reaction and the molar ratio of 9- oxo n-nonanoic acid or 9- oxo pelargonate is 0.1~3.0, preferably 0.1~2.0, especially
Preferably, when the alkali is organic base, the molar ratio of the catalyst and 9- oxo n-nonanoic acid or 9- oxo pelargonate is 0.1~
0.5；
The additional amount of the cyan-acetic ester is so that 9- oxo n-nonanoic acid or 9- oxo pelargonate and cyan-acetic ester rub
You are than being 0.8~1.5:1.0；
The solvent is not particularly limited, and can dissolve the cyano olefin(e) acid, and the example includes, but are not limited to two
Six ring of oxygen, ethyl acetate, tetrahydrofuran；
The knoevenagel condensation reaction reaction temperature is 25 DEG C~50 DEG C, reacts 10~12h；
The cyan-acetic ester is malonic methyl ester nitrile, cyan-acetic ester, cyanoacetic acid propyl ester or cyanoacetic acid isopropyl
Ester；
In step 3):
The basic catalyst of the hydrolysis is the aqueous solution of lithium hydroxide, sodium hydroxide, potassium hydroxide, catalyst
Dosage is that the molar ratio of catalyst and 9- oxo n-nonanoic acid or 9- oxo pelargonate is 1.0~2.5:1.0；Acidification acid used is this
Field is commonly sour, includes, but are not limited to hydrochloric acid, nitric acid, sulfuric acid；
In step 4):
The selective decarboxylic reaction of the 11 carbon -2- enedioic acid of 2- cyano can or there is no carrying out under catalyst,
The catalyst is the concentrated sulfuric acid or alkali (such as sodium hydroxide, lithium hydroxide or potassium hydroxide)；It is the concentrated sulfuric acid in the catalyst
When, dosage is catalytic amount, for example, 1wt ‰~1% of 11 carbon -2- enedioic acid amount of 2- cyano；When catalyst is alkali, urge
The molar ratio of agent and 11 carbon -2- enedioic acid of 2- cyano is 1.0~2.5:1.0, and reaction temperature is 100~120 DEG C, when reaction
Between be 3~5h；The solvent used in step 4) can be dioxane, N,N-dimethylformamide and dimethyl sulfoxide.
In step 5):
The catalyst of the hydrogenation reduction can be Raney's nickel, platinum carbon or palladium carbon, the catalysis of the hydrogenation reduction
The dosage of agent and the mass ratio of 11 carbon -2- enedioic acid of 2- cyano are 0.001~0.1, preferably 0.001~0.05；Described plus hydrogen
The system of reduction reaction keeps 1.0~6.0Mpa of hydrogen partial pressure, and 1~5h is reacted at 100~120 DEG C.
Beneficial effect
The features such as 11- aminoundecanoic acid preparation method provided by the present invention has process route short, simple to operation, keeps away
Exempt from the operating units such as Pintsch process, seriously polluted bromination, the ammonification of high energy consumption, belongs to environmentally protective technique, condensation reaction catalysis
Agent dosage is few, not only reduces production cost, and post-processing is simple, easy to operate, is suitable for industrialized production.
Specific embodiment
Below will by embodiment, the present invention is further elaborated, facilitate understand the content of present invention, not to this
The real protection scope of invention constitutes any type of restriction, and the present invention includes but is not limited to following related content:
Embodiment 1
The preparation of 9- oxo methyl pelargonate
By 9 hydroxynonanoic acid methyl esters (37.6g, 0.2mol) and MnO2(17.4g, 0.2mol) is placed in reaction kettle, is added
200ml ethyl acetate opens stirring, and 180 revs/min, temperature 50 C monitors reaction process in real time, is down to room temperature after 8h, filters,
It is evaporated under reduced pressure out solvent, obtains 35.3g off-white powder product (m/z:186) after refinement treatment.
The preparation of cyano olefin(e) acid
By 9- oxo methyl pelargonate (18.6g, 0.1mol), malonic methyl ester nitrile (9.9g, 0.1mol) and triethylamine
(3.5g, 35.0mmol) is placed in reaction kettle, is added 100ml dioxane (Isosorbide-5-Nitrae-dioxane), is opened and is stirred, and 180 revs/min,
Temperature 50 C monitors reaction process in real time, is down to room temperature after 12h, and the 10wt% sodium hydrate aqueous solution that 80ml is added carries out water
Solution, 1N hydrochloric acid acidification, obtains the light yellow cyano olefin(e) acid product of 21.2g after purification.
The preparation of decarboxylation intermediate
10g cyano olefin(e) acid is placed in autoclave, 50ml dioxane is added, the concentrated sulfuric acid of catalytic amount opens stirring,
180 revs/min, 100 DEG C of temperature, decarboxylic reaction is carried out, TLC monitors reaction process, is down to room temperature, separating catalyst, crude product after 3h
It is directly used in next step.
The preparation of 11- aminoundecanoic acid
Into the reaction system after above-mentioned decarboxylation be added 5wt% Raney's nickel (Raney Ni) catalyst (RTH-3110 type,
The general Chemical Co., Ltd. in Dalian), closed reaction kettle is successively replaced with nitrogen, hydrogen, keeps hydrogen partial pressure 3Mpa, and unlatching is stirred
It mixes, 180 revs/min, temperature programming reacts 5h, be then down to room temperature, slow pressure release, reaction solution is filtered to remove catalysis to 100 DEG C
Agent is evaporated under reduced pressure out dioxane, obtains 11- aminoundecanoic acid 6.3g after crude product washing refinement treatment, and appearance is white powder,
Purity 98.0%, 189 DEG C of fusing point (lit.), (m/z:201).
Embodiment 2
The preparation of 9- oxo methyl pelargonate
By 9 hydroxynonanoic acid methyl esters (37.6g, 0.2mol) and MnO2(17.4g, 0.2mol) is placed in reaction kettle, is added
200ml ethyl acetate opens stirring, 180 revs/min, 25 DEG C of temperature, monitors reaction process in real time, be down to room temperature after 10h, filter,
It is evaporated under reduced pressure out solvent, obtains 33.1g off-white powder product (m/z:186) after refinement treatment.
The preparation of cyano olefin(e) acid
9- oxo methyl pelargonate (18.6g, 0.1mol) and malonic methyl ester nitrile (9.9g, 0.1mol) are placed in reaction kettle
In, 100ml dioxane and the 10wt% potassium hydroxide aqueous solution of 115ml is added, opens and stirs, 180 revs/min, 25 DEG C of temperature,
It monitors reaction process in real time, is down to room temperature after 10h, be evaporated under reduced pressure out dioxane, the acidification of 1N hydrochloric acid, ethyl acetate extraction take off
It is molten, 20.5g yellow cyano olefin(e) acid product is obtained after purification.
The preparation of decarboxylation intermediate
10g cyano olefin(e) acid is placed in autoclave, 50ml dioxane is added, opens and stirs, 180 revs/min, temperature 100
DEG C, decarboxylic reaction is carried out, TLC monitors reaction process, and room temperature is down to after 5h, and crude product is directly used in next step.
The preparation of 11- aminoundecanoic acid
Raney's nickel catalyst (ZL-N311 type, the Anshan crowd's power of 5wt% are added into the reaction system after above-mentioned decarboxylation
Catalyst plant), closed reaction kettle is successively replaced with nitrogen, hydrogen, keeps hydrogen partial pressure 3Mpa, opened and stir, and 180 revs/min,
Temperature programming reacts 5h, is then down to room temperature, slow pressure release, reaction solution Filtration of catalyst is evaporated under reduced pressure out to 100 DEG C
Dioxane, crude product obtain 11- aminoundecanoic acid 5.7g after washing refinement treatment, and appearance is white powder, and purity 99.2% melts
Put 190 DEG C (lit.), (m/z:201).
Embodiment 3
The preparation of 9- oxo methyl pelargonate
9 hydroxynonanoic acid methyl esters (37.6g, 0.2mol) and CuO (15.9g, 0.2mol) are placed in reaction kettle, are added
200ml tetrahydrofuran opens stirring, and 180 revs/min, temperature 50 C monitors reaction process in real time, is down to room temperature after 10h, filters,
It is evaporated under reduced pressure out solvent, obtains 30.1g off-white powder product (m/z:186) after refinement treatment.
The preparation of cyano olefin(e) acid
9- oxo methyl pelargonate (18.6g, 0.1mol) and malonic methyl ester nitrile (9.9g, 0.1mol) are placed in reaction kettle
In, 100ml dioxane and the 10wt% sodium hydrate aqueous solution of 80ml is added, opens and stirs, 180 revs/min, 25 DEG C of temperature,
It monitors reaction process in real time, is down to room temperature after 10h, be evaporated under reduced pressure out dioxane, the acidification of 1N hydrochloric acid, ethyl acetate extraction take off
It is molten, 21.3g white cyano olefin(e) acid product is obtained after purification.
The preparation of decarboxylation intermediate
10g cyano olefin(e) acid is placed in autoclave, 100ml dioxane is added, the concentrated sulfuric acid of catalytic amount opens stirring,
180 revs/min, 100 DEG C of temperature, decarboxylic reaction is carried out, TLC monitors reaction process, is down to room temperature, separating catalyst, crude product after 3h
It is directly used in next step.
The preparation of 11- aminoundecanoic acid
Raney's nickel catalyst (ZL-N211 type, the Anshan crowd's power of 5wt% are added into the reaction system after above-mentioned decarboxylation
Catalyst plant), closed reaction kettle is successively replaced with nitrogen, hydrogen, and system keeps hydrogen partial pressure 3Mpa, opens stirring, 160-
180 revs/min, program temperature reacts 5h to 100 DEG C, is then down to room temperature, slow pressure release, reaction solution Filtration of catalyst, decompression
Dioxane is distilled out, obtains 11- aminoundecanoic acid 6.3g after crude product washing refinement treatment, product is white powder, purity
98.0%, 190 DEG C of fusing point (lit.).
Embodiment 4
The preparation of 9- oxo methyl pelargonate
9 hydroxynonanoic acid methyl esters (37.6g, 0.2mol) and CuO (17.5g, 0.2mol) are placed in reaction kettle, are added
200ml tetrahydrofuran opens stirring, 180 revs/min, 25 DEG C of temperature, monitors reaction process in real time, be down to room temperature after 10h, filter,
It is evaporated under reduced pressure out solvent, obtains 31.9g off-white powder product (m/z:186) after refinement treatment.
The preparation of cyano olefin(e) acid
By 9- oxo methyl pelargonate (18.6g, 0.1mol), malonic methyl ester nitrile (9.9g, 0.1mol) and piperidines (4.3g,
It 50.0mmol) is placed in reaction kettle, solvent 100ml dioxane is added, open stirring, 160 revs/min, temperature 50 C is supervised in real time
Reaction process is controlled, is down to room temperature after 10h, the 10wt% sodium hydrate aqueous solution that 80ml is added is hydrolyzed, the acidification of 1N hydrochloric acid, essence
The light yellow cyano olefin(e) acid product of 20.5g is obtained after system.
The preparation of decarboxylation intermediate
10g cyano olefin(e) acid is placed in autoclave, 100ml dioxane is added, opens and stirs, 180 revs/min, temperature 100
DEG C, decarboxylic reaction is carried out, TLC monitors reaction process, and room temperature is down to after 5h, and crude product is directly used in next step.
The preparation of 11- aminoundecanoic acid
Pd/C catalyst (Pd content 10%, the upper triumphant green wood of Hisoon of 1wt% are added into the reaction system after above-mentioned decarboxylation
Expect Science and Technology Ltd.), closed reaction kettle is successively replaced with nitrogen, hydrogen, and system keeps hydrogen partial pressure 2Mpa, stirring is opened,
180 revs/min, program temperature reacts 3h to 100 DEG C, is then down to room temperature, slow pressure release, reaction solution Filtration of catalyst, decompression
Dioxane is distilled out, obtains 11- aminoundecanoic acid 5.9g after crude product washing refinement treatment, product is white powder, purity
99.2%, 189 DEG C of fusing point (lit.), (m/z:201).
Embodiment 5
The preparation of 9- oxo methyl pelargonate
By 9 hydroxynonanoic acid methyl esters (37.6g, 0.2mol) and MnO2(17.4g, 0.2mol) is placed in reaction kettle, is added
200ml tetrahydrofuran opens stirring, and 180 revs/min, temperature 50 C monitors reaction process in real time, is down to room temperature after 8h, filters,
It is evaporated under reduced pressure out solvent, obtains 34.4g off-white powder product (m/z:186) after refinement treatment.
The preparation of cyano olefin(e) acid
By 9- oxo methyl pelargonate (18.6g, 0.1mol), malonic methyl ester nitrile (9.9g, 0.1mol) and N, N- diisopropyl
Base ethamine (DIPEA) (3.2g, 25.0mmol) is placed in reaction kettle, and 100ml dioxane is added and opens stirring, 180 turns/
Point, temperature 50 C monitors reaction process in real time, is down to room temperature after 12h, and the 10wt%NaOH aqueous solution that 80ml is added carries out water
Solution, 1N hydrochloric acid acidification, obtains the light yellow cyano olefin(e) acid product of 21.3g after purification.
The preparation of decarboxylation intermediate
10g cyano olefin(e) acid is placed in autoclave, 100ml dioxane is added, opens and stirs, 180 revs/min, temperature 100
DEG C, decarboxylic reaction is carried out, TLC monitors reaction process, and room temperature is down to after 5h, and crude product is directly used in next step.
The preparation of 11- aminoundecanoic acid
Into the reaction system after above-mentioned decarboxylation, (Pd content 10%, upper Hisoon are triumphant new for the Pd/C catalyst of addition 0.5wt%
Material Science and Technology Ltd.), closed reaction kettle is successively replaced with nitrogen, hydrogen, and system keeps hydrogen partial pressure 3Mpa, and unlatching is stirred
It mixes, 180 revs/min, program temperature reacts 1h, is then down to room temperature to 100 DEG C, slow pressure release, reaction solution Filtration of catalyst,
It is evaporated under reduced pressure out dioxane, obtains 11- aminoundecanoic acid 4.9g after crude product washing refinement treatment, product is white powder, pure
Degree 98.1%, 189 DEG C of fusing point (lit.), (m/z:201).
Embodiment 6
The preparation of 9- oxo methyl pelargonate
9 hydroxynonanoic acid methyl esters (37.6g, 0.2mol) and CuO (17.5g, 0.2mol) are placed in reaction kettle, are added
200ml dioxane opens stirring, 180 revs/min, 25 DEG C of temperature, monitors reaction process in real time, be down to room temperature after 10h, filter,
It is evaporated under reduced pressure out solvent, obtains 30.2g off-white powder product (m/z:186) after refinement treatment.
The preparation of cyano olefin(e) acid
By 9- oxo methyl pelargonate (18.6g, 0.1mol), malonic methyl ester nitrile (9.9g, 0.1mol) and tetramethyl second two
Amine (TMEDA) (2.3g, 20.0mmol) is placed in reaction kettle, and 100ml dioxane is added, and is opened and is stirred, and 180 revs/min, temperature
It 50 DEG C, monitors reaction process in real time, is down to room temperature after 12h, the 10wt%NaOH aqueous solution that 80ml is added is hydrolyzed, 1N hydrochloric acid
Acidification obtains 20.8g yellow cyano olefin(e) acid product after purification.
The preparation of decarboxylation intermediate
10g cyano olefin(e) acid is placed in autoclave, 100ml dioxane is added, opens and stirs, 180 revs/min, temperature 100
DEG C, decarboxylic reaction is carried out, TLC monitors reaction process, and room temperature is down to after 5h, and crude product is directly used in next step.
The preparation of 11- aminoundecanoic acid
Raney's nickel catalyst (ZL-N211 type, the Anshan crowd's power of 1wt% are added into the reaction system after above-mentioned decarboxylation
Catalyst plant), closed reaction kettle is successively replaced with nitrogen, hydrogen, and system keeps hydrogen partial pressure 3Mpa, opens stirring, 160-
180 revs/min, program temperature reacts 5h to 100 DEG C, is then down to room temperature, slow pressure release, reaction solution Filtration of catalyst, decompression
Dioxane is distilled out, obtains 11- aminoundecanoic acid 5.7g after crude product washing refinement treatment, product is white powder, purity
99.1%, 190 DEG C of fusing point (lit.).
By the type and equivalent of catalyst used in the knoevenagel condensation reaction in embodiment 1 to 6, yield is total
It ties in the following table 1.
Table 1: influence of the condensation catalyst dosage to reaction
Yield described in table 1 is only the yield of condensation step.
As described above, the present invention provides a kind of preparation method of 11- aminoundecanoic acid, have reaction condition it is mild, at
The features such as this is low, simple to operation has broader practice prospect and industrial production potential compared with prior art.
Claims (10)
1. a kind of preparation method of 11- aminoundecanoic acid, the preparation method include the following steps:
1) compound of formula I 9 hydroxynonanoic acid or 9 hydroxynonanoic acid ester are dissolved in solvent, carry out selectivity under oxidant effect
Aoxidize II compound 9- oxo n-nonanoic acid of preparation formula or 9- oxo pelargonate；
2) the 9- oxo n-nonanoic acid or 9- oxo pelargonate and cyan-acetic ester are dissolved in solvent, are carried out under the action of catalyst
Knoevenagel condensation reaction obtains III compound of formula；
3) make III compound of formula obtained in step 2) that reaction be hydrolyzed under basic catalyst effect, after be added it is sour into
Row acidification obtains 11 carbon -2- enedioic acid of formula IV compound 2- cyano；
4) 11 carbon -2- enedioic acid of 2- cyano obtained in step 3) is subjected to selective decarboxylic reaction and obtains Formula V compound 10-
Cyano -10- alkene capric acid；
5) catalyst is added into 10- cyano -10- alkene capric acid obtained in step 4), is successively replaced, is carried out with nitrogen, hydrogen
Hydrogenation reduction obtains Formula IV compound 11- aminoundecanoic acid,
Wherein, R1For the H or C of linear chain or branched chain1-C10Alkyl and R2For the C of linear chain or branched chain1-C10Alkyl.
2. preparation method according to claim 1, wherein R1For the H or C of linear chain or branched chain1-C6Alkyl.
3. preparation method according to claim 1, wherein the catalyst of the knoevenagel condensation reaction is selected from three
Ethamine, N, one of N- diisopropylethylamine, N-methylmorpholine, tetramethylethylenediamine, piperidines, potassium hydroxide and sodium hydroxide
Or it is a variety of.
4. preparation method according to claim 1, wherein R2For the C of linear chain or branched chain1-C6Alkyl.
5. preparation method according to claim 1, wherein the solvent of the knoevenagel condensation reaction is selected from dioxy
One of six rings, ethyl acetate, tetrahydrofuran and N,N-dimethylformamide are a variety of.
6. preparation method according to any one of claims 1 to 5, wherein
In step 1):
The oxidant is manganese dioxide, copper oxide or zinc oxide；The oxidant and 9 hydroxynonanoic acid or 9 hydroxynonanoic acid ester
Molar ratio be 1.0~2.0；
In step 2):
The molar ratio of the catalyst of the knoevenagel condensation reaction and 9- oxo n-nonanoic acid or 9- oxo pelargonate is 0.1~
3.0；
The additional amount of the cyan-acetic ester is the molar ratio so that 9- oxo n-nonanoic acid or 9- oxo pelargonate and cyan-acetic ester
For 0.8~1.5:1.0；
In step 3):
The basic catalyst of the hydrolysis is the aqueous solution of lithium hydroxide, sodium hydroxide or potassium hydroxide, the use of catalyst
Amount is that the molar ratio of catalyst and 9- oxo n-nonanoic acid or 9- oxo pelargonate is 1.0~2.5:1.0；
In step 4):
The selective decarboxylic reaction of the 11 carbon -2- enedioic acid of 2- cyano is or there is no carrying out under catalyst, the catalysis
Agent is the concentrated sulfuric acid or alkali；
In step 5):
The hydrogenation reduction catalyst be Raney's nickel, platinum carbon or palladium carbon, the dosage of the hydrogenation reduction catalyst with
The mass ratio of 11 carbon -2- enedioic acid of 2- cyano is 0.001~0.1.
7. preparation method according to claim 6, wherein in step 4), the alkali be sodium hydroxide, lithium hydroxide or
Potassium hydroxide.
8. preparation method according to any one of claims 1 to 5, wherein in step 5), the hydrogenating reduction is anti-
The system answered keeps 1.0~6.0Mpa of hydrogen partial pressure.
9. preparation method according to any one of claims 1 to 5, wherein in step 1), the oxidant and 9-
The molar ratio of hydroxynonanoic acid or 9 hydroxynonanoic acid ester is 1.0~1.2.
10. preparation method according to any one of claims 1 to 5, wherein in step 5), the hydrogenating reduction
The dosage of catalysts and the mass ratio of 11 carbon -2- enedioic acid of 2- cyano are 0.001~0.05.
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| CN115448850A (en) * | 2022-09-19 | 2022-12-09 | 中国五环工程有限公司 | Process system and method for preparing 11-aminoundecanoic acid from 11-bromoundecanoic acid |
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