CN109354575A - A kind of synthetic method of three (3,6- dioxaheptyl) amine - Google Patents
A kind of synthetic method of three (3,6- dioxaheptyl) amine Download PDFInfo
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- CN109354575A CN109354575A CN201811535974.4A CN201811535974A CN109354575A CN 109354575 A CN109354575 A CN 109354575A CN 201811535974 A CN201811535974 A CN 201811535974A CN 109354575 A CN109354575 A CN 109354575A
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- dioxaheptyl
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- ester
- methyl ether
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- -1 3,6- dioxaheptyl Chemical group 0.000 title claims abstract description 33
- 150000001412 amines Chemical class 0.000 title claims abstract description 32
- 238000010189 synthetic method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 150000002148 esters Chemical class 0.000 claims abstract description 15
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004327 boric acid Substances 0.000 claims abstract description 9
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 9
- XTIGGAHUZJWQMD-UHFFFAOYSA-N 1-chloro-2-methoxyethane Chemical group COCCCl XTIGGAHUZJWQMD-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 6
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 5
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 238000000746 purification Methods 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000010792 warming Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000005070 sampling Methods 0.000 description 9
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical compound OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000005311 nuclear magnetism Effects 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 238000007689 inspection Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XGLVDUUYFKXKPL-UHFFFAOYSA-N 2-(2-methoxyethoxy)-n,n-bis[2-(2-methoxyethoxy)ethyl]ethanamine Chemical compound COCCOCCN(CCOCCOC)CCOCCOC XGLVDUUYFKXKPL-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- JIQXRLOYKOJECL-UHFFFAOYSA-N 1-(2-chloroethoxy)-2-methoxyethane Chemical compound COCCOCCCl JIQXRLOYKOJECL-UHFFFAOYSA-N 0.000 description 1
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 description 1
- 125000006012 2-chloroethoxy group Chemical group 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- CBHOOMGKXCMKIR-UHFFFAOYSA-N azane;methanol Chemical compound N.OC CBHOOMGKXCMKIR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- QQBPIHBUCMDKFG-UHFFFAOYSA-N phenazopyridine hydrochloride Chemical compound Cl.NC1=NC(N)=CC=C1N=NC1=CC=CC=C1 QQBPIHBUCMDKFG-UHFFFAOYSA-N 0.000 description 1
- JMVWCCOXRGFPJZ-UHFFFAOYSA-N propoxyboronic acid Chemical compound CCCOB(O)O JMVWCCOXRGFPJZ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
Abstract
The invention discloses a kind of synthetic methods of three (3,6- dioxaheptyl) amine, belong to technical field of organic synthesis.Ester is first exchanged into using triethanolamine and three ester of boric acid, three (3,6- dioxaheptyl) amine are obtained after then reacting under the conditions of alkali and phase transfer catalyst with 2- haloethyl methyl ether.This method can be completed in same reaction kettle, realize the high efficiency of operation, and reaction obtains product purity height, and purification is easy, and provide reference for industrialization amplification.
Description
Technical field
The present invention relates to a kind of synthetic methods of tertiary amine, and in particular to a kind of synthesis side of three (3,6- dioxaheptyl) amine
Method belongs to technical field of organic synthesis.
Background technique
Three (3,6- dioxaheptyl) amine, English name Tris (2- (2-methoxyethoxy) ethyl) amine, CAS:
70384-51-9 is widely used in surfactant and phase transfer catalyst field.
It is existing the preparation method comprises the following steps: 1) use diethylene glycol monomethyl ether, reacted first with SOCl2/Pyridene, hydroxyl become
At chlorine, three (3,6- dioxaheptyl) amine of synthesis, reference: J.Gen.Chem.USSR are then reacted with ammonia methanol again
(Engl.Transl.),1970,40,1598-1602,Zhurnal Obshchei Khimii,1970,40,1611-1616.So
And document does not provide the information such as yield and product purity.
2) diethylene glycol monomethyl ether is used, directly under Raney Ni catalytic hydrogenation, reacts synthesis three at 185 DEG C with ammonia
(3,6- dioxaheptyl) amine, reference: Journal of Organic Chemistry, 1985,50,3717-3721.The method
In, other than obtaining product, have two (3,6- dioxaheptyl) amine of pronounced amount.
3) using three (2- chloroethyl) amine hydrochlorates and 2-methyl cellosolve sodium in 2-methyl cellosolve, at 125 DEG C
Reaction obtains three (3,6- dioxaheptyl) amine, yield 70%, reference: US4322369A after processing.Raw material sources in this method
It is inconvenient.
4) use diethylene glycol monomethyl ether for raw material in the presence of solvent-free, with skeleton Cu-Ni Catalyzed by Pt/M Bimetallic Nano,
130-150 DEG C of logical hydrogen leads to ammonia under atmospheric agitation, three (3,6- dioxaheptyl) amine is synthesized, with reference to CN101948394A.This method
Using composite catalyst, reaction temperature is reduced, yield improves, but is related to handling hydrogen under high temperature and pressure, and there are one
Determine risk.
5) it is reacted using diethylene glycol monomethyl ether with thionyl chloride and generates 1- (2- chloroethoxy) -2- Ethyl Methyl Ether, with
Ammonium hydroxide reacts to obtain 2- (2- methoxy ethoxy) ethamine；Under the conditions of acid binding agent, by 1- (2- chloroethoxy) -2- methoxyl group second
Alkane is added dropwise to 2- (2- methoxy ethoxy) ethamine reaction three (3,6- dioxaheptyl) amine of preparation, with reference to CN 108069836A.
In this method, reaction step is more, and complicated operation.
In the above synthetic method, it is not easy to obtain there are raw material, reaction step is long, it is related to reduction amination etc. under high temperature and pressure,
It still needs to carry out continual exploitation to synthetic method.
Summary of the invention
In order to overcome the above technical defects, the present invention is first exchanged into ester using triethanolamine and three ester of boric acid, then in alkali
With reacted under the conditions of phase transfer catalyst with 2- haloethyl methyl ether after obtain three (3,6- dioxaheptyl) amine.This method can be
It is completed in same reaction kettle, realizes the high efficiency of operation, reaction obtains product purity height, and purification is easy, reaction yield
90% or more, reference is provided for industrialization amplification.
A kind of synthetic method of three (3,6- dioxaheptyl) amine, which comprises the steps of: step 1: will
Triethanolamine and three ester of boric acid are first exchanged into ester.First step reaction equation is as follows:
Step 2: obtaining three (3,6- bis- after then reacting under the conditions of alkali and phase transfer catalyst with 2- haloethyl methyl ether
Oxa- heptyl) amine.Second step reaction equation is as follows:
Further, in the above-mentioned technical solutions, it is different to be selected from trimethylborate, triethyl borate, boric acid three for three ester of boric acid
Propyl ester and tri-n-butyl borate.The equivalent of three ester of boric acid is that ester is preferably directly carried out in excessive trimethylborate greater than 1 equivalent
After exchange, transesterification product will be obtained after the distillation of excessive trimethylborate.
Further, in the above-mentioned technical solutions, inorganic base is selected from sodium hydroxide or potassium hydroxide.
Further, in the above-mentioned technical solutions, 2- haloethyl methyl ether is selected from 2- chloroethyl methyl ether or 2- Bromoethyl methyl ether,
It is preferred that 2- chloroethyl methyl ether.When 2- haloethyl methyl ether uses 2- Bromoethyl methyl ether, need to be added more equivalents, meeting in reaction process
There is elimination phenomenon.
Further, in the above-mentioned technical solutions, phase transfer catalyst be selected from n-Bu4NBr, n-Bu4NCl or other can be with
Play the catalyst of similar effect.
Further, in the above-mentioned technical solutions, inorganic base, phase transfer catalyst, exchange ester molar ratio are 3-5:0.1-
0.45:1。
Further, in the above-mentioned technical solutions, first step reaction temperature is reflux, and second step reaction temperature is 60-120
DEG C, reaction carries out in sulfolane solvent.Product obtains 99% or more product of purity after passing through rectifying, puts in tens multikilograms
When big, yield is slightly reduced.
Invention beneficial effect
The present invention is by that the nitrogen-atoms in raw material can be got up with boron complexing, reacted first and after boric acid transesterification
The nitrogen-atoms and 2- haloethyl methyl ether avoided in triethanolamine in journey forms quaternary salt, and second step after reaction, passes through heating
Alkalinity increases afterwards, boron atom is smoothly replaced, product is dissociated again.Above-mentioned reaction can be complete in same reaction kettle
At realizing the high efficiency of operation, reaction obtains product purity height, and purification is easy, also carries out in tens multikilograms
Smooth verifying.
Specific embodiment
Embodiment 1
Step 1: the synthesis of triethanolamine borate
Into reaction flask, investment trimethylborate 62.7g (0.6mol), triethanolamine 74.6g (0.5mol) and toluene
300g is to slowly warm up to reflux 1 hour at room temperature, and then side reaction becomes normal pressure and steams fraction (65~100 DEG C), sampling GC inspection
It surveys, is concentrated under reduced pressure into does not slip liquid after the reaction was completed, recrystallized from acetonitrile, filtering is added, drying obtains 68g white solid, HPLC:
98.8%, yield: 86.6%.1H NMR (400MHz, CDCl3): 3.65 (t, J=5.5Hz, 6H), 3.04 (t, J=5.5Hz,
6H)。
Into reaction flask, investment triethyl borate 102.2g (0.7mol), triethanolamine 74.6g (0.5mol) and toluene
300g is to slowly warm up to reflux 1 hour at room temperature, and then side reaction becomes normal pressure and steams fraction (75~110 DEG C), sampling GC inspection
It surveys, is concentrated under reduced pressure into does not slip liquid after the reaction was completed, recrystallized from acetonitrile, filtering is added, drying obtains 67.4g white solid, nuclear-magnetism
Purity: 98.3%, yield: 85.9%.
Into reaction flask, investment triisopropyl borate ester 150.4g (0.8mol), triethanolamine 74.6g (0.5mol) and toluene
300g is to slowly warm up to reflux 1 hour at room temperature, and then side reaction becomes normal pressure and steams fraction (65~100 DEG C), sampling GC inspection
It surveys, is concentrated under reduced pressure into does not slip liquid after the reaction was completed, recrystallized from acetonitrile, filtering is added, drying obtains 65.1g white solid, nuclear-magnetism
Purity: 98.9%, yield: 82.9%.
Embodiment 2
Step 2: the synthesis of three (3,6- dioxaheptyl) amine
Into reaction flask put into 2- chloroethyl methyl ether 75.6g (0.8mol), triethanolamine borate 31.4g (0.2mol),
Tetrabutylammonium bromide 6.4g (0.02mol) and sulfolane 350g, is warming up to 60 DEG C, starts that sodium hydroxide 28g is added portionwise
(0.7mol), be warming up to 120 DEG C react 3~4 hours, sampling GC detection, by rectifying obtain yellow oily liquid three (3,
6- dioxaheptyl) amine 59.5g, nuclear-magnetism purity: 99.1%, yield: 91.9%.1HNMR (400MHz, CD3OD): 3.60 (m,
6H),3.54(m,12H),3.30(s,9H),2.81(m,6H)。
2- Bromoethyl methyl ether 139g (1mol), triethanolamine borate 31.4g (0.2mol), four fourths are put into reaction flask
Ammonium chloride 5.6g (0.02mol) and sulfolane 350g, is warming up to 60 DEG C, starts that sodium hydroxide 32g (0.8mol) is added portionwise,
It is reacted 3~4 hours with being warming up to 120 DEG C, sampling GC detection obtains (3, the 6- dioxas of yellow oily liquid three by rectifying
Heptyl) amine 59.9g, nuclear-magnetism purity: 99.3%, yield: 92.7%.
2- Bromoethyl methyl ether 139g (1mol), triethanolamine borate 31.4g (0.2mol), four fourths are put into reaction flask
Base ammonium bromide 6.4g (0.02mol) and sulfolane 350g, is warming up to 60 DEG C, starts that potassium hydroxide 44.9g is added portionwise
(0.8mol), be warming up to 120 DEG C react 3~4 hours, sampling GC detection, by rectifying obtain yellow oily liquid three (3,
6- dioxaheptyl) amine 58.7g, nuclear-magnetism purity: 99.4%, yield: 90.7%.
Into reaction flask put into 2- chloroethyl methyl ether 75.6g (0.8mol), triethanolamine borate 31.4g (0.2mol),
Tetrabutylammonium chloride 5.8g (0.02mol) and sulfolane 350g, is warming up to 60 DEG C, starts that potassium hydroxide 39.2g is added portionwise
(0.7mol), be warming up to 120 DEG C react 3~4 hours, sampling GC detection, by rectifying obtain yellow oily liquid three (3,
6- dioxaheptyl) amine 60.9g, nuclear-magnetism purity: 99.2%, yield: 94.1%.
Embodiment 3
Step 1: the synthesis of triethanolamine borate
Under nitrogen protection, trimethylborate 5.15Kg (49.5mol, 1.1eq), triethanolamine are put into 30L reaction kettle
6.7Kg (45mol, 1eq) and toluene 18Kg is to slowly warm up to reflux 1 hour at room temperature, and then side reaction change normal pressure steams fraction
(65~100 DEG C), sampling GC detection, are concentrated under reduced pressure into do not slip liquid after the reaction was completed, and acetonitrile is added and carries out solvent replacement, adds
12.3Kg recrystallized from acetonitrile, gradient cooling, filtering, drying obtain 6.2Kg white solid, nuclear-magnetism purity: 99.0%, yield:
87.7%.
Step 2: the synthesis of three (3,6- dioxaheptyl) amine
Under nitrogen protection, 2- chloroethyl methyl ether 14.92Kg (157.8mol, 4eq) is put into 50L stainless steel cauldron,
Triethanolamine borate 6.2Kg (39.46mol, 1eq), tetrabutylammonium bromide 1.2Kg and dimethyl sulfoxide 28Kg, are warming up to 60
DEG C, start that potassium hydroxide 7.75Kg (138mol, 3.5eq) is added portionwise, is reacted 5~6 hours with being warming up to 120 DEG C, sampling
GC detection obtains yellow oily liquid three (3,6- dioxaheptyl) amine 11.01Kg, HNMR purity by rectifying: 99.4%, it receives
Rate: 86.3%.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
- The synthetic method of one kind three 1. (3,6- dioxaheptyl) amine, which comprises the steps of:Step 1: triethanolamine and three ester of boric acid are first exchanged into ester, reaction equation are as follows:Step 2: obtaining three (3,6- dioxas after then reacting under the conditions of alkali and phase transfer catalyst with 2- haloethyl methyl ether Heptyl) amine.Second step reaction equation is as follows:
- 2. the synthetic method of three (3,6- dioxaheptyl) amine according to claim 1, it is characterised in that: in the first step, Three ester of boric acid is selected from trimethylborate, triethyl borate, triisopropyl borate ester and tri-n-butyl borate.
- 3. the synthetic method of three (3,6- dioxaheptyl) amine according to claim 1, it is characterised in that: in the first step, Three ester of boric acid is selected from trimethylborate；Operation is, after directly carrying out transesterification in excessive trimethylborate, incited somebody to action Transesterification product is obtained after amount trimethylborate distillation.
- 4. the synthetic method of three (3,6- dioxaheptyl) amine according to claim 1, it is characterised in that: in second step, The inorganic base is selected from sodium hydroxide or potassium hydroxide.
- 5. the synthetic method of three (3,6- dioxaheptyl) amine according to claim 1, it is characterised in that: in second step, The 2- haloethyl methyl ether is selected from 2- chloroethyl methyl ether or 2- Bromoethyl methyl ether.
- 6. the synthetic method of three (3,6- dioxaheptyl) amine according to claim 1, it is characterised in that: in second step, The 2- haloethyl methyl ether is selected from 2- chloroethyl methyl ether.
- 7. the synthetic method of three (3,6- dioxaheptyl) amine according to claim 1, it is characterised in that: in second step, The phase transfer catalyst, which is selected from n-Bu4NBr, n-Bu4NCl or other, can play the catalyst of similar effect.
- 8. the synthetic method of three (3,6- dioxaheptyl) amine according to claim 1, it is characterised in that: in second step, Inorganic base, phase transfer catalyst, exchange ester molar ratio are 3-5:0.1-0.45:1.
- 9. the synthetic method of three (3,6- dioxaheptyl) amine according to claim 1, it is characterised in that: first step reaction Temperature is reflux, and second step reaction temperature is 60-120 DEG C, and reaction carries out in sulfolane solvent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811535974.4A CN109354575B (en) | 2018-12-15 | 2018-12-15 | Synthesis method of tri (3, 6-dioxaheptyl) amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| WO2016100123A1 (en) * | 2014-12-19 | 2016-06-23 | The Procter & Gamble Company | Ionic liquid systems |
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Application publication date: 20190219 Assignee: Xi'an Tuochao Biotechnology Co.,Ltd. Assignor: PLUS SCIENCE & TECHNOLOGY (SHANGHAI) CO.,LTD. Contract record no.: X2024980004789 Denomination of invention: A synthesis method of tris (3,6-dioxane) amine Granted publication date: 20210319 License type: Common License Record date: 20240423 |