CN108558614A - 1,2- bis-（2-（2,6- dimethyl phenoxies）Ethyoxyl）The preparation method of ethane - Google Patents
1,2- bis-（2-（2,6- dimethyl phenoxies）Ethyoxyl）The preparation method of ethane Download PDFInfo
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- CN108558614A CN108558614A CN201810566690.5A CN201810566690A CN108558614A CN 108558614 A CN108558614 A CN 108558614A CN 201810566690 A CN201810566690 A CN 201810566690A CN 108558614 A CN108558614 A CN 108558614A
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- ethyoxyl
- ethane
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- triethylene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
Abstract
The invention discloses 1,2 two (2 (2,6 dimethyl phenoxy) ethyoxyl) ethane preparation methods, include the following steps：(1) 20 DEG C is stirred, 2,6 xylenols and triethylene-glycol addition N, in N dimethylformamides, adds dicyclohexylcarbodiimide, 150 DEG C of reaction 36h that reaction solution is poured into water standing for 24 hours, brown solid is obtained by filtration；(2) brown solid is dissolved in ether, is warming up to 35 DEG C, filters off insoluble matter while hot, is cooled to 15 DEG C, and cool down 48h, and filtering solution obtains white powdery solids, 2 two (2 (2,6 dimethyl phenoxy) ethyoxyl) ethane.Present invention is mainly used for the synthesis of 1,2 two (2 (2,6 dimethyl phenoxy) ethyoxyl) ethane.
Description
Technical field
The invention belongs to energetic material fields, and in particular to 1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane
Preparation method.
Background technology
1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane is a kind of important chemicals, it and it derivative
Object can be used for many fields.Wherein using its as the crown ether of structural unit be not only Coordinative Chemistry, analytical chemistry, organic chemistry and
The important research content of bioinorganic chemistry, and suffer from close connection with life science, information science, material science etc.
System.And the calixarenes developed on the basis of crown ether is then by rich pi-electron, the adjustable three-dimensional lumen of size and annular array oxygen original
Son, not only can complex ion but also can inclusion neutral molecule.More importantly, the readily selected sex modification of upper lower edge of calixarenes, it can
Largely there is " pre-organized structure " (Pre- for " structure platform " (Platform orbuilding block) synthesis with it
Organized structure) host molecule.
2004, Chupakhin etc. selected 2,6- xylenols and triethylene-glycol p-methyl benzenesulfonic acid ester is raw material,
Compound 1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane have been synthesized under potassium hydroxide catalysed.
(O.N.Chupakhin,G.L.Rusinov,N.A.Itsikson.New 1,2,4-triazine-containing
podands:synthesis and properties,Russian Chemical Bulletin,International
Edition,53(10),2308-2313,2004).The synthetic route of Chupakhin methods is as follows：
Chupakhin methods are raw material using triethylene-glycol p-methyl benzenesulfonic acid ester, and triethylene-glycol is to toluene sulphur
Acid esters will be prepared by triethylene glycol and the condensation of p-methyl benzenesulfonic acid acyl chlorides, increase reaction step；Chupakhin methods can generate greatly
By-product p-methyl benzenesulfonic acid potassium is measured, the latter does not allow disposable, increases the pollution of reaction；The use of sodium hydroxide is catalytic reaction
Agent increases pollution；Chupakhin methods post-processing operation is complicated, needs just obtain final product by column chromatography for separation,
Total recovery is relatively low, and only 60%.
Invention content
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, a kind of reaction step is provided
Less, post-processing approach is clear, the feature of environmental protection is high, higher 1,2-, bis- (2- (2, the 6- dimethyl phenoxy) ethyoxyl) second of reaction yield
Alkane preparation method.
The synthetic route of the present invention with 2,6- xylenols and triethylene-glycol for raw material, it is sub- with dicyclohexyl carbon two
Amine is catalyst, and n,N-Dimethylformamide is solvent, carries out etherification reaction and obtains product 1, bis- (2- of 2- using post-processing
(2,6- dimethyl phenoxies) ethyoxyl) ethane.
The preparation method of 1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane of the present invention, 1,2- bis- (2- (2,
6- dimethyl phenoxies) ethyoxyl) ethane structural formula such as shown in (I)：
With 2,6- xylenols and triethylene-glycol for raw material, structural formula as shown in (II) and (III), wraps respectively
Include following steps：
(1) under 20 DEG C~30 DEG C stirrings of temperature, 2,6- xylenols and triethylene-glycol are added to N, N- bis-
In methylformamide, then dicyclohexylcarbodiimide is added thereto, is 130 DEG C~160 DEG C reaction for 24 hours~48h in temperature, it will
Reaction solution, which is poured into water, stands for 24 hours~48h, and brown solid 1 is obtained by filtration；Wherein, triethylene-glycol, 2,6- dimethoxys
Phenol, dicyclohexylcarbodiimide mass ratio be 1:1.79~2.00:3.00~3.50；
(2) brown solid is dissolved in ether, is warming up to 30 DEG C~35 DEG C, filters off insoluble matter while hot, be cooled to -15 DEG C~-
10 DEG C, cool down for 24 hours~72h, and filtering solution obtains white powdery solids 1, (2- (2, the 6- dimethyl phenoxy) ethoxies of 2- bis-
Base) ethane.The preparation method of currently preferred 1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane, including it is following
Step：
Under (1) 20 DEG C of stirring, 2,6- xylenols and triethylene-glycol are added in n,N-Dimethylformamide,
Dicyclohexylcarbodiimide is added thereto again, is 150 DEG C of reaction 36h in temperature, reaction solution is poured into water standing for 24 hours,
Brown solid 1 is obtained by filtration, wherein triethylene-glycol, 2,6- syringol, dicyclohexylcarbodiimide mass ratio
It is 1:1.80:3.20；
(2) brown solid is dissolved in ether, is warming up to 35 DEG C, filters off insoluble matter while hot, be cooled to -15 DEG C, cool down 48h,
Filtering solution obtains white powdery solids 1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane.
Advantages of the present invention：
(1) reaction step of the present invention is simple, and triethylene-glycol and 2,6- xylenols is directly used to be condensed to yield production
Object, and documents replace triethylene-glycol p-methyl benzenesulfonic acid ester using 2,6- xylenols to obtain product, and two contract
Triethylene glycol p-methyl benzenesulfonic acid ester will be prepared by triethylene-glycol and the condensation of p-methyl benzenesulfonic acid acyl chlorides；
(2) present invention is using more environmentally friendly catalyst dicyclohexylcarbodiimide, and documents use sodium hydroxide,
With certain pollution；The by-product that the present invention generates is dicyclohexyl carbon diamines, is easily processed, and documents can generate greatly
Measure by-product p-methyl benzenesulfonic acid potassium, it is not easy to handle；
(3) the clear simplicity of post-processing approach of the present invention, after being poured into water crystallization, Diethyl ether recrystallization, purity reach 98% with
On, and documents need just obtain final product by column chromatography for separation, post-processing is complicated；The preparation method of the present invention is received
Rate is higher, and the total recovery of reaction can reach 78.24%, and the yield in documents is 60%.
Specific implementation mode
The present invention is described in further details with reference to embodiment.
Embodiment 1
Under 20 DEG C of stirrings of temperature, by 3.60g 2,15mlN, N- bis- is added in 6- xylenols and 2g triethylene-glycols
In methylformamide, dicyclohexylcarbodiimide 6.40g is added to it, is warming up to 150 DEG C, after reacting 36h, reaction solution is fallen
Enter and stood in 1L water for 24 hours, brown solid is obtained by filtration.
Brown solid is dissolved in 5ml ether, is warming up to 35 DEG C, filters off insoluble matter, is cooled to -15 DEG C, and cool down 48h, and filtering is molten
Liquid, obtains 1.87g white powdery solids 1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane, yield 78.24%,
Purity 98.31%, 67 DEG C~68 DEG C of fusing point.
Structural Identification：
IR(KBr)ν:3450,3017,2942,2914,2880,2750,2729,2393,2239,2100,2007,1957
1939,1867,1797,1676,1638,1591,1556,1478,1433,1378,1358,1348,1288,1258,1242,
1235,1198,1162,1123,1090,1061,982,973,953,914,898,845,811,775,751,670,573,
544,523,479,463cm-l.
1H NMR(CDCl3-d6):δ7.24(4H,t),6.92(2H,d),3.95(4H,t),3.86(4H,s),3.79(4H,
t),2.82(12H,t)；
13C NMR(CDCl3-d6)δ155.83,130.95,128.80,123.82,71.31,67.44,65.87,16.28；
Elemental analysis：Molecular formula C22H30O4
Theoretical value：C,73.71；H,8.44；O,17.85.
Measured value：C,73.39；H,8.47；O,18.14.
Above structure appraising datum confirms that the substance that this step obtains is strictly (the 2- (2,6- dimethyl phenoxy) of 1,2- bis-
Ethyoxyl) ethane.
Embodiment 2
Under 20 DEG C of stirrings of temperature, by 3.95g 2,15mlN, N- bis- is added in 6- xylenols and 2g triethylene-glycols
In methylformamide, dicyclohexylcarbodiimide 6.40g is added to it, is warming up to 150 DEG C, after reacting 36h, air-distillation goes out N,
Dinethylformamide obtains crocus troubled liquor.
Brown solid is dissolved in 5ml ether, is warming up to 35 DEG C, filters off insoluble matter, is cooled to -15 DEG C, and cool down 48h, and filtering is molten
Liquid, obtains 1.87g white powdery solids 1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane, yield 79.08%,
Purity 98.25%, 67 DEG C~68 DEG C of fusing point.
Embodiment 3
Under 20 DEG C of stirrings of temperature, by 3.60g 2,15mlN, N- bis- is added in 6- xylenols and 2g triethylene-glycols
In methylformamide, dicyclohexylcarbodiimide 6.40g is added to it, is warming up to 150 DEG C, after reacting 36h, air-distillation goes out N,
Dinethylformamide obtains crocus troubled liquor.
Brown solid is dissolved in 10ml ether, is warming up to 35 DEG C, filters off insoluble matter, is cooled to -15 DEG C, and cool down 48h, and filtering is molten
Liquid, obtains 1.80g white powdery solids 1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane, yield 75.31%,
Purity 98.84%, 67 DEG C~68 DEG C of fusing point.
Embodiment 4
Under 20 DEG C of stirrings of temperature, by 3.60g 2,150mlN, N- is added in 6- xylenols and 2g triethylene-glycols
In dimethylformamide, dicyclohexylcarbodiimide 6.40g is added to it, is warming up to 150 DEG C, after reacting 48h, air-distillation goes out
N,N-Dimethylformamide obtains crocus troubled liquor.
Brown solid is dissolved in 10ml ether, is warming up to 35 DEG C, filters off insoluble matter, is cooled to -15 DEG C, and cool down 48h, and filtering is molten
Liquid, obtains 1.89g white powdery solids 1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane, yield 79.08%,
Purity 98.24%, 67 DEG C~68 DEG C of fusing point.
Embodiment 5
Under 20 DEG C of stirrings of temperature, by 3.60g 2,150mlN, N- is added in 6- xylenols and 2g triethylene-glycols
In dimethylformamide, dicyclohexylcarbodiimide 6.40g is added to it, is warming up to 140 DEG C, after reacting 48h, air-distillation goes out
N,N-Dimethylformamide obtains crocus troubled liquor.
Brown solid is dissolved in 10ml ether, is warming up to 35 DEG C, filters off insoluble matter, is cooled to -15 DEG C, and cool down 48h, and filtering is molten
Liquid, obtains 1.80g white powdery solids 1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane, yield 78.24%,
Purity 75.31%, 67 DEG C~68 DEG C of fusing point.
Claims (2)
- The preparation method of 1.1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane, 1,2- bis- (2- (2,6- dimethyl benzenes Oxygroup) ethyoxyl) ethane structural formula such as shown in (I)：With 2,6- xylenols and triethylene-glycol for raw material, such as (II) and (III) is shown respectively for structural formula, including with Lower step：(1) under 20 DEG C~30 DEG C stirrings of temperature, 2,6- xylenols and triethylene-glycol are added to N, N- dimethyl In formamide, then dicyclohexylcarbodiimide is added thereto, is 130 DEG C~160 DEG C reaction for 24 hours~48h in temperature, will react Solution, which is poured into water, stands 12h~36h, and brown solid is obtained by filtration；Wherein, triethylene-glycol, 2,6- syringol, The mass ratio of dicyclohexylcarbodiimide is 1:1.79~2.00:3.00~3.50；(2) brown solid is dissolved in ether, is warming up to 30 DEG C~35 DEG C, filters off insoluble matter while hot, is cooled to -15 DEG C~-10 DEG C, Cool down for 24 hours~72h, and filtering solution obtains white powdery solids 1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) second Alkane.
- 2. the preparation method of 1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane according to claim 1, packet Include following steps：Under (1) 20 DEG C of stirring, 2,6- xylenols and triethylene-glycol are added in n,N-Dimethylformamide, then to Dicyclohexylcarbodiimide is wherein added, being 150 DEG C in temperature reacts for 24 hours, reaction solution is poured into water standing for 24 hours, filtering Obtain brown solid, wherein triethylene-glycol, 2,6- syringol, dicyclohexylcarbodiimide mass ratio be 1: 1.80:3.20；(2) brown solid is dissolved in ether, is warming up to 35 DEG C, filters off insoluble matter while hot, be cooled to -15 DEG C, cool down 48h, filtering Solution obtains white powdery solids 1,2- bis- (2- (2,6- dimethyl phenoxy) ethyoxyl) ethane.
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| CN107011128A (en) * | 2017-04-28 | 2017-08-04 | 西安近代化学研究所 | One kind 1,2 two（2‑（2,6 dimethoxy phenoxy groups）Ethyoxyl）The preparation method of ethane |
| CN107903152A (en) * | 2017-11-24 | 2018-04-13 | 西安近代化学研究所 | One kind 1,2 two（2‑（4 dimethoxy phenoxy groups）Ethyoxyl）The synthetic method of ethane |
| CN107935822A (en) * | 2017-11-24 | 2018-04-20 | 西安近代化学研究所 | 1,2 two（2‑（4 methoxyphenoxies）Ethyoxyl）The preparation method of ethane |
| CN108002988A (en) * | 2017-11-24 | 2018-05-08 | 西安近代化学研究所 | 1,2- bis-（2-（2,6- dimethoxy phenoxy groups）Ethyoxyl）The preparation method of ethane |
-
2018
- 2018-06-05 CN CN201810566690.5A patent/CN108558614A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6011042A (en) * | 1997-10-10 | 2000-01-04 | Enzon, Inc. | Acyl polymeric derivatives of aromatic hydroxyl-containing compounds |
| CN106946664A (en) * | 2017-03-16 | 2017-07-14 | 西安近代化学研究所 | One kind 1,2 two（2‑（2,6 dimethoxy phenoxy groups）Ethyoxyl）The synthetic method of ethane |
| CN107011128A (en) * | 2017-04-28 | 2017-08-04 | 西安近代化学研究所 | One kind 1,2 two（2‑（2,6 dimethoxy phenoxy groups）Ethyoxyl）The preparation method of ethane |
| CN107903152A (en) * | 2017-11-24 | 2018-04-13 | 西安近代化学研究所 | One kind 1,2 two（2‑（4 dimethoxy phenoxy groups）Ethyoxyl）The synthetic method of ethane |
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| CN108002988A (en) * | 2017-11-24 | 2018-05-08 | 西安近代化学研究所 | 1,2- bis-（2-（2,6- dimethoxy phenoxy groups）Ethyoxyl）The preparation method of ethane |
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