CN105801423A - Synthetic method of 2-amino-2-(3-amino-5-cyanocyclohexane)acetic acid - Google Patents
Synthetic method of 2-amino-2-(3-amino-5-cyanocyclohexane)acetic acid Download PDFInfo
- Publication number
- CN105801423A CN105801423A CN201610200582.7A CN201610200582A CN105801423A CN 105801423 A CN105801423 A CN 105801423A CN 201610200582 A CN201610200582 A CN 201610200582A CN 105801423 A CN105801423 A CN 105801423A
- Authority
- CN
- China
- Prior art keywords
- amino
- temperature
- filtrate
- passed
- acetic acid
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a synthetic method of 2-amino-2-(3-amino-5-cyanocyclohexane)acetic acid and belongs to the field of organic chemical synthesis.The method comprises the steps that naphthaline is subjected to a redox reaction to generate 1,5-diaminonaphthalene at first, a catalyst nickel and the like are added under the high-temperature condition for a reaction to generate 1,5-diamidodecalin, then, the 1,5-diamidodecalin and sodium cyanide generate 1,5-diamidodecalin-2,7-dinitrile under the effect of a catalyst palladium on carbon, and finally the 2-amino-2-(3-amino-5-cyanocyclohexane)acetic acid is generated under the open-loop condition.The synthetic method has the advantages of being mild in reaction condition and high in yield.
Description
Technical field
The invention discloses a kind of 2-amino-2-(3-amino-5-cyano cyclohexyl) acetic acid synthetic method, belong to and organise
Learn synthesis field.
Background technology
Acetic acid, is also acetic acid, glacial acetic acid, chemical formula CH3COOH, is a kind of organic acid, for vinegar main component.Pure
Anhydrous acetic acid (glacial acetic acid) be colourless hygroscopic solid, freezing point is 16.6 DEG C (62), is clear crystal after solidification, its
In faintly acid and erosion property is strong, steam effect irritant to eye and nose in aqueous solution.
Synthesis for 2-amino-2-(3-amino-5-cyano cyclohexyl) acetic acid at present have not been reported, and existing
Synthetic technology makes its synthetic ratio low, and reaction condition is violent.
Summary of the invention
The present invention provides a kind of 2-amino-2-(3-amino-5-cyano cyclohexyl) that a kind of reaction condition is gentle, yield is high
Acetic acid synthetic method.
For reaching above-mentioned purpose, 2-amino-2-of the present invention (3-amino-5-cyano cyclohexyl) acetic acid synthetic method is:
The building-up process of 2-amino-2-(the 3-amino-5-cyano cyclohexyl) acetic acid that the present invention relates to comprises the following steps:
(1) take the naphthalene of 50～100g to be placed in there-necked flask, add the manganese dioxide of 0.5～1g to it, and to its be passed through 100～
The hydrogen of 150mL, controls its amount 60～70mL/min being passed through, and after being passed through, it is carried out heat temperature raising, controls temperature
It is 200～250 DEG C, reacts 1～2h；
(2) after question response completes, the hydrogen peroxide adding 20～30mL to it, and it is cooled to 40～50 DEG C, reaction 40～
50min, while heating, and is stirred it, and controlling mixing speed is 100～120r/min, after question response terminates, right
It carries out sucking filtration, obtains filtrate；
(3) carry out mixing being placed in reactor with methanol 5:1 in mass ratio by above-mentioned filtrate, and add 0.5～1.0g to it
Nickel, and be filled with hydrogen to it, after getting rid of the air in reactor, then to its be filled with hydrogen make its pressure to 7～8MPa, and
Heating it, liter high-temperature is to 190～250 DEG C, after reaction 2～3h so that it is naturally cool to room temperature；
(4) until above-mentioned be cooled to room temperature after, to its filter, remove filtrate, collect filtrate, the filtrate of collection is pressed with Cyanogran.
After mass ratio 10:1 mixes, and add palladium catalyst/charcoal to it, and it carried out heat temperature raising, control temperature be 120～
150 DEG C, after reaction 3～4h, stand so that it is naturally cool to room temperature, obtain 1,5-diaminourea decahydronaphthalene-2,7-dintrile；
(5) by hydrogen peroxide that above-mentioned prepared 1,5-diaminourea decahydronaphthalene-2,7-dintrile and mass fraction are 35% by volume
10:1 carries out mixing and is placed in a container, then the ozone being passed through container volume 2/3 to it, heats it, controls temperature
Being 30～35 DEG C, the time is 40～50min, while adding, is slowly added to 1 to it, 5-diaminourea decahydronaphthalene-2,7-dintrile
Mass fraction is the boron trifluoride of 30～40%, after question response terminates so that it is naturally cools to room temperature, and filters it, filters
Liquid is 2-amino-2-(3-amino-5-cyano cyclohexyl) acetic acid.
Specific embodiments
First take the naphthalene of 50～100g to be placed in there-necked flask, add the manganese dioxide of 0.5～1g to it, and be passed through to it
The hydrogen of 100～150mL, controls its amount 60～70mL/min being passed through, after being passed through, it is carried out heat temperature raising, control
Temperature processed is 200～250 DEG C, reacts 1～2h；After question response completes, add the hydrogen peroxide of 20～30mL to it, and it is lowered the temperature
To 40～50 DEG C, reacting 40～50min, while heating, and be stirred it, controlling mixing speed is 100～120r/
Min, after question response terminates, carries out sucking filtration to it, obtains filtrate；Carry out mixing rearmounted with methanol 5:1 in mass ratio by above-mentioned filtrate
In reactor, and add the nickel of 0.5～1.0g to it, and be filled with hydrogen to it, after getting rid of the air in reactor, then to
It is filled with hydrogen make its pressure to 7～8MPa, and to its heat, rise high-temperature to 190～250 DEG C, reaction 2～3h after so that it is
Naturally cool to room temperature；Until above-mentioned be cooled to room temperature after, to its filter, remove filtrate, collect filtrate, by collect filtrate with
Cyanogran. is after 10:1 mixes in mass ratio, and adds palladium catalyst/charcoal to it, and it is carried out heat temperature raising, controls temperature
Degree is 120～150 DEG C, after reaction 3～4h, stands so that it is naturally cool to room temperature, obtains 1,5-diaminourea decahydronaphthalene-2,7-bis-
Nitrile；By the hydrogen peroxide 10:1 by volume that above-mentioned prepared 1,5-diaminourea decahydronaphthalene-2,7-dintrile and mass fraction are 35%
Carry out mixing to be placed in a container, then the ozone being passed through container volume 2/3 to it, it is heated, controlling temperature is 30
～35 DEG C, the time is 40～50min, while adding, is slowly added to 1 to it, 5-diaminourea decahydronaphthalene-2,7-dintrile quality
Mark is the boron trifluoride of 30～40%, after question response terminates so that it is naturally cools to room temperature, and filters it, and filtrate is i.e.
For 2-amino-2-(3-amino-5-cyano cyclohexyl) acetic acid.
Example 1
First the naphthalene taking 100g is placed in there-necked flask, adds the manganese dioxide of 1g to it, and is passed through the hydrogen of 150mL to it,
Controlling its amount 70mL/min being passed through, after being passed through, it is carried out heat temperature raising, controlling temperature is 250 DEG C, reacts 2h；
After question response completes, add the hydrogen peroxide of 30mL to it, and it is cooled to 50 DEG C, react 50min, while heating, and
Being stirred it, control mixing speed is 120r/min, after question response terminates, it is carried out sucking filtration, obtains filtrate；By above-mentioned filter
Liquid carries out mixing being placed in reactor with methanol 5:1 in mass ratio, and adds the nickel of 1.0g to it, and is filled with hydrogen to it,
After getting rid of the air in reactor, then it is filled with hydrogen to it and makes its pressure to 8MPa, and it is heated, rise high-temperature to 250
DEG C, after reaction 2～3h so that it is naturally cool to room temperature；Until above-mentioned be cooled to room temperature after, to its filter, remove filtrate, collect
Filtrate, by the filtrate of collection and Cyanogran. after 10:1 mixes in mass ratio, and adds palladium catalyst/charcoal to it, and to it
Carrying out heat temperature raising, controlling temperature is 150 DEG C, after reaction 3h, stands so that it is naturally cool to room temperature, obtain 1,5-diaminourea ten
Hydrogen naphthalene-2,7-dintrile；By hydrogen peroxide that above-mentioned prepared 1,5-diaminourea decahydronaphthalene-2,7-dintrile and mass fraction are 35% by
Volume ratio 10:1 carries out mixing and is placed in a container, then the ozone being passed through container volume 2/3 to it, heats it, control
Temperature processed is 35 DEG C, and the time is 50min, while adding, is slowly added to 1 to it, 5-diaminourea decahydronaphthalene-2,7-dintrile matter
Amount mark is the boron trifluoride of 40%, after question response terminates so that it is naturally cooling to room temperature, and filter it, filtrate is
2-amino-2-(3-amino-5-cyano cyclohexyl) acetic acid.Reaction condition is gentle, yield is high.
Example 2
First the naphthalene taking 50g is placed in there-necked flask, adds the manganese dioxide of 0.5g to it, and is passed through the hydrogen of 100mL to it,
Controlling its amount 60mL/min being passed through, after being passed through, it is carried out heat temperature raising, controlling temperature is 200 DEG C, reacts 1h；
After question response completes, add the hydrogen peroxide of 20～30mL to it, and it is cooled to 40 DEG C, react 40min, same heat
Time, and it is stirred, control mixing speed is 100r/min, after question response terminates, it is carried out sucking filtration, obtains filtrate；Will
Above-mentioned filtrate carries out mixing being placed in reactor with methanol 5:1 in mass ratio, and adds the nickel of 0.5g to it, and is filled with to it
Hydrogen, after getting rid of the air in reactor, then to its be filled with hydrogen make its pressure to 7MPa, and to its heat, rise high-temperature
To 190 DEG C, after reaction 2h so that it is naturally cool to room temperature；Until above-mentioned be cooled to room temperature after, to its filter, remove filtrate, receive
Collection filtrate is by the filtrate of collection and Cyanogran. after 10:1 mixes in mass ratio and to its addition palladium catalyst/charcoal and right
It carries out heat temperature raising, and controlling temperature is 120 DEG C, after reaction 3h, stands so that it is naturally cool to room temperature, obtain 1,5-diaminourea
Decahydronaphthalene-2,7-dintrile；It is the hydrogen peroxide of 35% by above-mentioned prepared 1,5-diaminourea decahydronaphthalene-2,7-dintrile and mass fraction
10:1 carries out mixing and is placed in a container by volume, then the ozone being passed through container volume 2/3 to it, heats it,
Controlling temperature is 30～35 DEG C, and the time is 40min, while adding, is slowly added to 1 to it, 5-diaminourea decahydronaphthalene-2,7-
Dintrile mass fraction is the boron trifluoride of 30%, after question response terminates so that it is naturally cools to room temperature, and filters it, filters
Liquid is 2-amino-2-(3-amino-5-cyano cyclohexyl) acetic acid.Reaction condition is gentle, yield is high.
Example 3
First the naphthalene taking 70g is placed in there-necked flask, adds the manganese dioxide of 0.7g to it, and is passed through the hydrogen of 120mL to it,
Controlling its amount 65mL/min being passed through, after being passed through, it is carried out heat temperature raising, controlling temperature is 220 DEG C, reacts 1h；
After question response completes, add the hydrogen peroxide of 20～30mL to it, and it is cooled to 45 DEG C, react 45min, same heat
Time, and it is stirred, control mixing speed is 110r/min, after question response terminates, it is carried out sucking filtration, obtains filtrate；Will
Above-mentioned filtrate carries out mixing being placed in reactor with methanol 5:1 in mass ratio, and adds the nickel of 0.7g to it, and is filled with to it
Hydrogen, after getting rid of the air in reactor, then to its be filled with hydrogen make its pressure to 7MPa, and to its heat, rise high-temperature
To 200 DEG C, after reaction 2h so that it is naturally cool to room temperature；Until above-mentioned be cooled to room temperature after, to its filter, remove filtrate, receive
Collection filtrate is by the filtrate of collection and Cyanogran. after 10:1 mixes in mass ratio and to its addition palladium catalyst/charcoal and right
It carries out heat temperature raising, and controlling temperature is 130 DEG C, after reaction 3h, stands so that it is naturally cool to room temperature, obtain 1,5-diaminourea
Decahydronaphthalene-2,7-dintrile；It is the hydrogen peroxide of 35% by above-mentioned prepared 1,5-diaminourea decahydronaphthalene-2,7-dintrile and mass fraction
10:1 carries out mixing and is placed in a container by volume, then the ozone being passed through container volume 2/3 to it, heats it,
Controlling temperature is 35 DEG C, and the time is 45min, while adding, is slowly added to 1 to it, 5-diaminourea decahydronaphthalene-2,7-dintrile
Mass fraction is the boron trifluoride of 35%, after question response terminates so that it is naturally cools to room temperature, and filters it, and filtrate is i.e.
For 2-amino-2-(3-amino-5-cyano cyclohexyl) acetic acid.Reaction condition is gentle, yield is high.
Claims (1)
1. 2-amino-2-(3-amino-5-cyano cyclohexyl) acetic acid synthetic method, it is characterised in that concrete synthesis step
For:
(1) take the naphthalene of 50～100g to be placed in there-necked flask, add the manganese dioxide of 0.5～1g to it, and to its be passed through 100～
The hydrogen of 150mL, controls its amount 60～70mL/min being passed through, and after being passed through, it is carried out heat temperature raising, controls temperature
It is 200～250 DEG C, reacts 1～2h；
(2) after question response completes, the hydrogen peroxide adding 20～30mL to it, and it is cooled to 40～50 DEG C, reaction 40～
50min, while heating, and is stirred it, and controlling mixing speed is 100～120r/min, after question response terminates, right
It carries out sucking filtration, obtains filtrate；
(3) carry out mixing being placed in reactor with methanol 5:1 in mass ratio by above-mentioned filtrate, and add 0.5～1.0g to it
Nickel, and be filled with hydrogen to it, after getting rid of the air in reactor, then to its be filled with hydrogen make its pressure to 7～8MPa, and
Heating it, liter high-temperature is to 190～250 DEG C, after reaction 2～3h so that it is naturally cool to room temperature；
(4) until above-mentioned be cooled to room temperature after, to its filter, remove filtrate, collect filtrate, the filtrate of collection is pressed with Cyanogran.
After mass ratio 10:1 mixes, and add palladium catalyst/charcoal to it, and it carried out heat temperature raising, control temperature be 120～
150 DEG C, after reaction 3～4h, stand so that it is naturally cool to room temperature, obtain 1,5-diaminourea decahydronaphthalene-2,7-dintrile；
(5) by hydrogen peroxide that above-mentioned prepared 1,5-diaminourea decahydronaphthalene-2,7-dintrile and mass fraction are 35% by volume
10:1 carries out mixing and is placed in a container, then the ozone being passed through container volume 2/3 to it, heats it, controls temperature
Being 30～35 DEG C, the time is 40～50min, while adding, is slowly added to 1 to it, 5-diaminourea decahydronaphthalene-2,7-dintrile
Mass fraction is the boron trifluoride of 30～40%, after question response terminates so that it is naturally cools to room temperature, and filters it, filters
Liquid is 2-amino-2-(3-amino-5-cyano cyclohexyl) acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610200582.7A CN105801423A (en) | 2016-03-31 | 2016-03-31 | Synthetic method of 2-amino-2-(3-amino-5-cyanocyclohexane)acetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610200582.7A CN105801423A (en) | 2016-03-31 | 2016-03-31 | Synthetic method of 2-amino-2-(3-amino-5-cyanocyclohexane)acetic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105801423A true CN105801423A (en) | 2016-07-27 |
Family
ID=56460051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610200582.7A Pending CN105801423A (en) | 2016-03-31 | 2016-03-31 | Synthetic method of 2-amino-2-(3-amino-5-cyanocyclohexane)acetic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105801423A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60122190A (en) * | 1983-12-06 | 1985-06-29 | Toho Chem Ind Co Ltd | Desensitizer composition |
| CN103319351A (en) * | 2012-03-23 | 2013-09-25 | 东莞市同舟化工有限公司 | Method for preparing 1,5-diamino-decahydronaphthalene by catalytic hydrogenation of 1,5-diaminonaphthalene |
| CN103420851A (en) * | 2013-08-23 | 2013-12-04 | 湘潭大学 | Method for preparing 1,5-diaminonaphthalene through naphthalene in one step and application of catalysts |
-
2016
- 2016-03-31 CN CN201610200582.7A patent/CN105801423A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60122190A (en) * | 1983-12-06 | 1985-06-29 | Toho Chem Ind Co Ltd | Desensitizer composition |
| CN103319351A (en) * | 2012-03-23 | 2013-09-25 | 东莞市同舟化工有限公司 | Method for preparing 1,5-diamino-decahydronaphthalene by catalytic hydrogenation of 1,5-diaminonaphthalene |
| CN103420851A (en) * | 2013-08-23 | 2013-12-04 | 湘潭大学 | Method for preparing 1,5-diaminonaphthalene through naphthalene in one step and application of catalysts |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2020045341A (en) | Continuous flow carboxylation reaction | |
| CN106632267B (en) | A kind of synthetic method of voriconazole | |
| CN105664955B (en) | A kind of preparation method of the metal co-doped carbon quantum dot of copper zinc | |
| CN104910032B (en) | A kind of preparation method of anilino-acetate | |
| CN105601588A (en) | Method for synthesizing N-hydroxyethylpiperazine and piperazine by means of co-production | |
| CN105367431B (en) | 3 N of one kind, the preparation method of N dimethylamino ethyl acrylates | |
| CN105801423A (en) | Synthetic method of 2-amino-2-(3-amino-5-cyanocyclohexane)acetic acid | |
| CN104370746B (en) | A kind of cost-effective preparation method to nitrobenzyl alcohol | |
| CN103450131A (en) | Preparation method of dehydroacetic acid and sodium salt thereof | |
| CN106187787B (en) | A kind of preparation method of 2- amino -4- chlorodiphenyl ether | |
| CN104592044B (en) | The low temperature synthetic method of 2,6-Dichloro-4-nitroaniline | |
| CN102942532A (en) | Preparation method of 1,4,7,10-tetraazadodecane | |
| CN104788307B (en) | A kind of purification process of sorbic acid | |
| CN106316956A (en) | Industrial production method for pyrazole | |
| CN102757394B (en) | Preparation method of 2,4,6-tri(N,N-diethoxyl)amino-1,3,5-triazine | |
| CN105130956A (en) | Preparation method of rupatadine fumarate | |
| CN105198855B (en) | A kind of synthetic method of 3,3,3 trifluoro propene carbonic ester | |
| CN102557901B (en) | A preparation method of 6-chlorocaproic aldehyde | |
| CN101704788B (en) | Improved preparation process of 2-Butyl-1,3-diazapira[4,4]nonane-1-en-4-one | |
| CN105271406B (en) | A kind of preparation method of sodium metavanadate | |
| CN109705027B (en) | 1, 2-di (pyridyl) -3, 4-di (4-pyridylvinyl-3-fluorobenzene) cyclobutane and preparation method thereof | |
| CN103601669B (en) | A kind of synthetic method of 1-tertbutyloxycarbonyl-2-methyl-4-piperidones | |
| CN106748830B (en) | A kind of preparation method of 3- amino-4-fluorophenol | |
| CN104119261B (en) | A kind of preparation method of L-Glutimic acid | |
| CN104785249A (en) | Nano Pd/C catalyst and method for preparing ursodeoxycholic acid by using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160727 |