CN106810467A - Diamine compounds list Boc guard methods - Google Patents
Diamine compounds list Boc guard methods Download PDFInfo
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- CN106810467A CN106810467A CN201710001543.9A CN201710001543A CN106810467A CN 106810467 A CN106810467 A CN 106810467A CN 201710001543 A CN201710001543 A CN 201710001543A CN 106810467 A CN106810467 A CN 106810467A
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- diamine
- boc
- diamine compounds
- nitrine
- guard methods
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- 0 CC(C)(C)OC(*1CC*CC1)=O Chemical compound CC(C)(C)OC(*1CC*CC1)=O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
- C07D295/205—Radicals derived from carbonic acid
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of diamine compounds list Boc guard methods, comprise the following steps：Nitrine t-butyl formate reacts in organic solvent with diamine compounds at 0 30 DEG C, obtains the diamine compounds of single Boc protections.The present invention provides a kind of new method that diamine compounds are carried out with Boc protections, and reagent is protected using nitrine t-butyl formate as Boc, can effectively improve reaction selectivity.And accessory substance is nitrogen, is directly escaped from reaction system.Present method avoids the shortcoming that accessory substance isobutene is generated when using Boc acid anhydrides as raw material.Thoroughly solve the problems, such as that reaction system is sticky, purification difficult, reaction efficiency is high, post processing is simple, is suitable for industrialized production.
Description
Technical field
The present invention relates to compound protection technique field, more particularly to a kind of diamine compounds list Boc guard methods.
Background technology
The compound such as the ethylenediamine of single Boc (tertbutyloxycarbonyl) protection, propane diamine, butanediamine and piperazine, homopiperazine is
The important organic intermediate of one class, is widely used in the dendrimer synthesis of drug molecule and Material Field.
The compound of this kind of single Boc protections generally uses Boc acid anhydrides carries out reaction preparation, the method master with corresponding diamines
Have the following disadvantages：(1) due to the polymerization of accessory substance isobutene in production process, cause reaction system extremely sticky, it is necessary to
Substantial amounts of solvent is added to improve mixing effect, solvent usage amount is big, production efficiency is low.Isobutene polymer glues very much simultaneously
It is thick, it is serious to product absorption, it is impossible to high efficiency filter, cause product to lose serious, actual recovery is generally relatively low.(2) Boc acid anhydrides is lived
Property it is higher, selectivity is lacked to the protection of diamine compounds, cause to have substantial amounts of double protection impurity generations, it is necessary to increase diamines
Inventory could improve mono-protected selectivity.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of diamine compounds list Boc guard methods, making
With nitrine t-butyl formate as Boc protect reagent, reaction efficiency is high, post processing is simple, thoroughly solve reaction system it is sticky,
The problem of purification difficult, is suitable for industrialized production.
A kind of diamine compounds list Boc guard methods of the invention, comprise the following steps：
Nitrine t-butyl formate reacts 3-6h in solvent with diamine compounds at 0-30 DEG C, obtains single Boc protections
Diamine compounds.
Further, the preparation method of nitrine t-butyl formate is comprised the following steps：
Tert-butyl carbazate is mixed with acetic acid in water, natrium nitrosum is then added dropwise thereto at -5 DEG C -15 DEG C
The aqueous solution, reaction 2-4h after obtain nitrine t-butyl formate.
Further, the preparation method of nitrine t-butyl formate is further comprising the steps of：
Organic solvent extractive reaction liquid is used, organic phase is washed out, dried, filtered, collect filtrate, obtain nitrine formic acid uncle
The organic solvent solution of butyl ester.Organic solvent is the one kind in isopropyl ether, ether, methyl tertiary butyl ether(MTBE), dichloromethane and chloroform
Or it is several.
Further, diamine compounds are aliphatic diamine or alicyclic diamine.
Further, aliphatic diamine is ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine or heptamethylene diamine.
Further, nitrine t-butyl formate is as follows with the reaction equation of aliphatic diamine：
Wherein, n represents the number of carbon atom in aliphatic diamine, n=1,2,3,4,5,6.
Further, alicyclic diamine is piperazine or homopiperazine.
Further, nitrine t-butyl formate is as follows with the reaction equation of piperazine：
Further, nitrine t-butyl formate is as follows with the reaction equation of homopiperazine：
Further, solvent is in isopropyl ether, ethanol, water, ether, methyl tertiary butyl ether(MTBE), dichloromethane and chloroform
Plant or several.
Further, nitrine t-butyl formate and the mol ratio of diamine compounds are 1:1.5-4.
Further, the organic solvent solution of nitrine t-butyl formate is added drop-wise in diamine compounds and is reacted,
Time for adding is 0.8-1.2h.Organic solvent is the one kind in isopropyl ether, ether, methyl tertiary butyl ether(MTBE), dichloromethane and chloroform
Or it is several.
By such scheme, the present invention at least has advantages below：
The invention provides a kind of new method that diamine compounds are carried out with Boc protections, the tertiary fourth of nitrine formic acid is used
Ester protects reagent as Boc, can effectively improve reaction selectivity；And, byproduct of reaction is nitrogen, directly from reaction system
Middle effusion, it is not easy to cause system sticky, and only need less solvent can just make system be well mixed.Additionally, of the invention
Method avoid using Boc acid anhydrides diamine compounds are carried out Boc protect generation accessory substance isobutene shortcoming.Using this
The method of invention carries out Boc protections to diamine compounds, and its product purity is high, and yield is high, and the present invention thoroughly solves reactant
It is sticky, purification difficult problem, reaction efficiency is high, post processing is simple, is suitable for industrialized production.
Described above is only the general introduction of technical solution of the present invention, in order to better understand technological means of the invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is the nuclear-magnetism test result of the ethylenediamine of single Boc protections prepared by the embodiment of the present invention 1；
Fig. 2 is the nuclear-magnetism test result of the propane diamine of single Boc protections prepared by the embodiment of the present invention 2；
Fig. 3 is the nuclear-magnetism test result of the butanediamine of single Boc protections prepared by the embodiment of the present invention 3；
Fig. 4 is the nuclear-magnetism test result of the piperazine product of single Boc protections prepared by the embodiment of the present invention 3.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiment of the invention is described in further detail.Hereinafter implement
Example is not limited to the scope of the present invention for illustrating the present invention.
Embodiment 1
To tert-butyl carbazate 300g (2.27mol, 1eq) and acetic acid 900mL is added in 5L reaction bulbs, it is subsequently adding
1.8L water dilutes, and ice salt bath is cooled to 0 DEG C.It is added dropwise 900mL's natrium nitrosums (172.3g, 2.53mol, 1.12eq) thereto again
The aqueous solution, by temperature control below 2 DEG C, time for adding about 1 hour.Drip off follow-up continuous insulation reaction 1.5 hours.By reaction solution
Extracted twice with 600mL isopropyl ethers, organic phase is washed twice with 200mL successively, and with 300mL saturated sodium bicarbonate washings
Mutually extremely in alkalescence, then washed once with 200ml saturated common salts, filtrate is collected in anhydrous sodium sulfate drying, filtering, obtains nitrine first
The isopropyl ethereal solution of tert-butyl acrylate, is directly used in next step reaction.
Ethylenediamine 204g (3.4mol, 1.5eq) is mixed with 200mL isopropyl ethers, frozen water is cooled to 10 DEG C, then thereto
The isopropyl ethereal solution of nitrine t-butyl formate is added dropwise, rear insulation reaction 3h is dripped off, TLC detection reactions terminate.Reaction solution is used successively
200mL water and 100mL saturated aqueous common salts washed once, and dry organic phase, and the ethylenediamine that single Boc protections are obtained after concentration is thick
Product, using colourless transparent liquid is obtained after oil pump vacuum distillation, the ethylenediamine of as list Boc protections, its yield is 272.0g, GC
Purity 98.2%, two-step reaction total recovery is 74.9%.Fig. 1 is the nuclear-magnetism test result of the product.
Embodiment 2
To tert-butyl carbazate 300g (2.27mol, 1eq) and acetic acid 900mL is added in 5L reaction bulbs, it is subsequently adding
1.8L water dilutes, and ice salt bath is cooled to 0 DEG C.It is added dropwise 900mL's natrium nitrosums (172.3g, 2.53mol, 1.12eq) thereto again
The aqueous solution, by temperature control below 2 DEG C, time for adding about 1 hour.Drip off follow-up continuous insulation reaction 1.5 hours.By reaction solution
Extracted twice with 600mL isopropyl ethers, organic phase is washed twice with 200mL successively, and with 300mL saturated sodium bicarbonate washings
Mutually extremely in alkalescence, then washed once with 200ml saturated common salts, filtrate is collected in anhydrous sodium sulfate drying, filtering, obtains nitrine first
The isopropyl ethereal solution of tert-butyl acrylate, is directly used in next step reaction.
Propane diamine 251.6g (3.4mol, 1.5eq) is mixed with 200mL isopropyl ethers, frozen water is cooled to 10 DEG C, then to it
The middle isopropyl ethereal solution that nitrine t-butyl formate is added dropwise, drips off rear insulation reaction 3h, and TLC detection reactions terminate.Reaction solution is successively
Be washed once with 200mL water and 100mL saturated aqueous common salts, and dry organic phase, the propane diamine that single Boc protections are obtained after concentration is thick
Product, using colourless transparent liquid is obtained after oil pump vacuum distillation, the propane diamine of as list Boc protections, its yield is 306.2g, GC
Purity 98.4%, two-step reaction total recovery 77.5%.Fig. 2 is the nuclear-magnetism test result of product manufactured in the present embodiment.
Embodiment 3
To tert-butyl carbazate 300g (2.27mol, 1eq) and acetic acid 900mL is added in 5L reaction bulbs, it is subsequently adding
1.8L water dilutes, and ice salt bath is cooled to 0 DEG C.It is added dropwise 900mL's natrium nitrosums (172.3g, 2.53mol, 1.12eq) thereto again
The aqueous solution, by temperature control below 2 DEG C, time for adding about 1 hour.Drip off follow-up continuous insulation reaction 1.5 hours.By reaction solution
Extracted twice with 600mL isopropyl ethers, organic phase is washed twice with 200mL successively, and with 300mL saturated sodium bicarbonate washings
Mutually extremely in alkalescence, then washed once with 200ml saturated common salts, filtrate is collected in anhydrous sodium sulfate drying, filtering, obtains nitrine first
The isopropyl ethereal solution of tert-butyl acrylate, is directly used in next step reaction.
Butanediamine 299.2g (3.4mol, 1.5eq) is mixed with 200mL isopropyl ethers, frozen water is cooled to 10 DEG C, then to it
The middle isopropyl ethereal solution that nitrine t-butyl formate is added dropwise, drips off rear insulation reaction 3h, and TLC detection reactions terminate.Reaction solution is successively
Be washed once with 200mL water and 100mL saturated aqueous common salts, and dry organic phase, the butanediamine that single Boc protections are obtained after concentration is thick
Product, using colourless transparent liquid is obtained after oil pump vacuum distillation, the butanediamine of as list Boc protections, its yield is 342.2g, GC
Purity 98.6%, two-step reaction total recovery 80.2%.Fig. 3 is the nuclear-magnetism test result figure of the product.
Embodiment 4
To tert-butyl carbazate 300g (2.27mol, 1eq) and acetic acid 900mL is added in 5L reaction bulbs, it is subsequently adding
1.8L water dilutes, and ice salt bath is cooled to 0 DEG C.It is added dropwise 900mL's natrium nitrosums (172.3g, 2.53mol, 1.12eq) thereto again
The aqueous solution, by temperature control in 15 DEG C, time for adding about 1 hour.Drip off follow-up continuous insulation reaction 1.5 hours.Reaction solution is used
600mL isopropyl ethers are extracted twice, and organic phase is washed twice with 200mL successively, and with 300mL saturated sodium bicarbonate washings phases
Extremely in alkalescence, then washed once with 200ml saturated common salts, filtrate is collected in anhydrous sodium sulfate drying, filtering, obtains nitrine formic acid
The isopropyl ethereal solution of the tert-butyl ester, is directly used in next step reaction.
After piperazine 292.4g (3.4mol, 1.5eq), 200mL ethanol and 50mL water are mixed, frozen water is cooled to 15 DEG C, so
The isopropyl ethereal solution of nitrine t-butyl formate is added dropwise thereto afterwards, rear insulation reaction 4h is dripped off, TLC detection reactions terminate.Reaction
Liquid concentration after add 200mL water stirring to pulps, filtering, take filtrate with 200mL dichloromethane extract three times, merge organic phase after according to
Secondary 200mL water and 100mL saturated aqueous common salts washed once, and dry organic phase, and the piperazine that single Boc protections are obtained after concentration is thick
Product.250mL petroleum ethers and it is stirred to being added in crude product, then with cryosel water cooling wash-off solid, filtering and drying to obtain to list
The piperazine of Boc protections, its yield is 282.7g, GC purity 97.9%, two-step reaction total recovery 66.9%.Fig. 4 is the present embodiment
The nuclear-magnetism test result figure of the product of preparation.
Embodiment 5
To tert-butyl carbazate 300g (2.27mol, 1eq) and acetic acid 900mL is added in 5L reaction bulbs, it is subsequently adding
1.8L water dilutes, and ice salt bath is cooled to 0 DEG C.It is added dropwise 900mL's natrium nitrosums (172.3g, 2.53mol, 1.12eq) thereto again
The aqueous solution, by temperature control in -5 DEG C, time for adding about 1 hour.Drip off follow-up continuous insulation reaction 1.5 hours.Reaction solution is used
600mL isopropyl ethers are extracted twice, and organic phase is washed twice with 200mL successively, and with 300mL saturated sodium bicarbonate washings phases
Extremely in alkalescence, then washed once with 200ml saturated common salts, filtrate is collected in anhydrous sodium sulfate drying, filtering, obtains nitrine formic acid
The isopropyl ethereal solution of the tert-butyl ester, is directly used in next step reaction.
After homopiperazine 340.0g (3.4mol, 1.5eq), 200mL ethanol and 50mL water are mixed, frozen water is cooled to 15 DEG C,
Then the isopropyl ethereal solution of nitrine t-butyl formate is added dropwise thereto, rear insulation reaction 4h is dripped off, TLC detection reactions terminates.Instead
Answer liquid that 200mL water stirring to pulps are added after concentrating, filtering takes filtrate and extracted three times with 200mL dichloromethane, after merging organic phase
Be washed once with 200mL water and 100mL saturated aqueous common salts successively, and dry organic phase, the piperazine high of single Boc protections is obtained after concentration
Piperazine crude product.250mL petroleum ethers and it is stirred to being added in crude product, then with cryosel water cooling wash-off solid, filtering and drying to obtain
To the homopiperazine of single Boc protections, its yield is 313.2g, GC purity 97.2%, two-step reaction total recovery 68.9%.
The above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill
For the those of ordinary skill in art field, on the premise of the technology of the present invention principle is not departed from, can also make it is some improvement and
Modification, these are improved and modification also should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of diamine compounds list Boc guard methods, it is characterised in that comprise the following steps：
Nitrine t-butyl formate reacts in solvent with diamine compounds at 0-30 DEG C, obtains the Diamines of single Boc protections
Compound.
2. diamine compounds list Boc guard methods according to claim 1, it is characterised in that the nitrine formic acid uncle
The preparation method of butyl ester is comprised the following steps：
Tert-butyl carbazate is mixed with acetic acid in water, the water of natrium nitrosum is then added dropwise thereto at -5 DEG C -15 DEG C
Solution, obtains nitrine t-butyl formate after reaction.
3. diamine compounds list Boc guard methods according to claim 1 and 2, it is characterised in that：The Diamines
Compound is aliphatic diamine or alicyclic diamine.
4. diamine compounds list Boc guard methods according to claim 3, it is characterised in that：The aliphatic diamine
It is ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine or heptamethylene diamine.
5. diamine compounds list Boc guard methods according to claim 3, it is characterised in that：The alicyclic diamine
It is piperazine or homopiperazine.
6. diamine compounds list Boc guard methods according to claim 1 and 2, it is characterised in that：The solvent is different
One or more in propyl ether, ethanol, water, ether, methyl tertiary butyl ether(MTBE), dichloromethane and chloroform.
7. diamine compounds list Boc guard methods according to claim 1 and 2, it is characterised in that：The nitrine formic acid
The tert-butyl ester is 1 with the mol ratio of diamine compounds:1.5-4.
8. diamine compounds list Boc guard methods according to claim 1 and 2, it is characterised in that：By the nitrine first
Tert-butyl acrylate is reacted in being added drop-wise to diamine compounds.
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| CN201710001543.9A CN106810467A (en) | 2017-01-03 | 2017-01-03 | Diamine compounds list Boc guard methods |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113493398A (en) * | 2021-08-11 | 2021-10-12 | 中车长春轨道客车股份有限公司 | Preparation method of N-Boc-trans-cyclohexanediamine |
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2017
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| WO2010115629A2 (en) * | 2009-04-08 | 2010-10-14 | Deutsches Krebsforschungszentrum | Amatoxin-armed therapeutic cell surface binding components designed for tumour therapy |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113493398A (en) * | 2021-08-11 | 2021-10-12 | 中车长春轨道客车股份有限公司 | Preparation method of N-Boc-trans-cyclohexanediamine |
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Application publication date: 20170609 |