CN107903152A - One kind 1,2 two（2‑（4 dimethoxy phenoxy groups）Ethyoxyl）The synthetic method of ethane - Google Patents
One kind 1,2 two（2‑（4 dimethoxy phenoxy groups）Ethyoxyl）The synthetic method of ethane Download PDFInfo
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- CN107903152A CN107903152A CN201711189941.4A CN201711189941A CN107903152A CN 107903152 A CN107903152 A CN 107903152A CN 201711189941 A CN201711189941 A CN 201711189941A CN 107903152 A CN107903152 A CN 107903152A
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- ethane
- ethyoxyl
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- metoxyphenols
- dichloroethanes
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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
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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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
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
Abstract
The invention discloses a kind of 1,2 two (2 (4 methoxyphenoxy) ethyoxyl) ethane synthetic methods, are to solve to overcome the problems such as reaction time existing in the prior art is long, post processing is complicated.For the present invention with 4 metoxyphenols and 1,2 (dichloroethanes base) ethane are raw material, are comprised the following steps：(1) 20 DEG C is stirred, 4 metoxyphenols and 1,2 (dichloroethanes base) ethane addition N, in N dimethylformamides, is hydrogenated with potassium oxide, 150 DEG C of reaction 12h, reaction solution is poured into water, and obtains brown turbid solution 1；(2) brown liquid 1 is cooled to 15 DEG C, 4h is kept, filtering, obtains white flaky solid, ether is added to white flaky solid, 35 DEG C are warming up to, is filtered while hot, is cooled to 15 DEG C, keep 4h, filtering, obtains white powdery solids 1,2 two (2 (4 dimethoxy phenoxy group) ethyoxyl) ethane.Present invention is mainly used for the synthesis of 1,2 two (2 (4 dimethoxy phenoxy group) ethyoxyl) ethane.
Description
Technical field
The present invention relates to the synthetic method of one kind 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane.Belong to organic
Synthesis.
Background technology
The ability that solid propellant keeps its chemical property not occur to exceed permission excursion within storage period is referred to as
Chemical stability.The compounds containing itrate group such as common nitrocellulose, nitroglycerine are biradical and modified double base propellants
In main energetic component, its nitric acid ester bond is easy to be broken (150.5~167.2kJ/mol of bond energy), produces thermal decomposition, release big
The gas and heat of amount, the nitrogen oxides discharged, and accelerate nitrate to decompose, self-catalyzed reaction is formed, causes propellant power
Performance, combustibility decline are learned, or even the serious accidents such as burning, explosion occur.Therefore, the propellant containing itrate group component
It can also decompose under storage requirement, cause propellant stability to decline.In order to delay propellant to thermally decompose, improve stable
Property, propellant containing nitrate esters adds stabilization agent, for absorbing acid, nitrogen oxides and its free radical of nitrate decomposition generation,
So as to suppress or delay the Autocatalytic decomposition of nitrate to react.
At present, common chemical stabilization agent has anil and phenol analog derivative etc., its representation compound is N, and N '-
Dimethyl-N, N '-acardite (C2), resorcinol (Res), diphenylamines (DPA), 2- nitrodiphenylamines (2-NDPA), N- methyl
Paranitroanilinum (MNA) etc..With the development of nitrate esters high-energy propellant, the country proposes that developing tactics type high-energy solid promotes
The requirement of agent.Found in the development process of tactics type high-energy solid propellant, have been used for existing high-energy solid propellant (such as NEPE
Type propellant) stabilization agent such as N- methyl paranitroanilines (MNA) reactivity it is stronger, it can be promoted with tactics type high-energy solid
The curing agent (isocyanates) that agent uses reacts, so as to limit the application of MNA.It is, thus, sought for one kind can expire
The stability of sufficient high-energy solid propellant, no partial crystallization transport phenomena occur, and the not new stabilization agent with curing agent reaction.
1999, it was raw material that Pursiainen etc., which selects 4- metoxyphenols and 1,2- (dichloroethanes base) ethane, hydrogen-oxygen
Change and synthesized compound 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane under potassium catalysis, and be applied to carry out
Explore.(Markku L,Kirsi R,Jouni P.Synthesis of podands bearing aromatic end
groups andcomplex formation with tropyliumtetra-uoroborate in1,2-
dichloroethane,Journal of Physical Organic,1999,12:557-563.).The conjunction of Pursiainen methods
It is as follows into route：
The reaction time of Pursiainen methods is longer, post-processes complex, the table that Pursiainen is provided in article
Sign data have the problem of larger, and the H number shown in wherein 1H NMR is 30, and the number of actual this compound H is 24,
The yield of Pursiainen methods is 96%.
The content of the invention
The technical problems to be solved by the invention are to overcome the deficiencies in the prior art, there is provided a kind of yield raising,
Reaction time is short, post-processes simple 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane synthetic method.
The present invention synthetic route with 4- metoxyphenols and 1,2- (dichloroethanes base) ethane for raw material, with potassium hydroxide
For catalyst, n,N-Dimethylformamide is solvent, and etherification reaction is carried out with 1,2- (dichloroethanes base) ethane, is located later in warp
Reason, obtains product 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane.
The synthetic method of 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane of the present invention, 1,2- bis- (2- (4-
Dimethoxy phenoxy group) ethyoxyl) ethane structural formula such as shown in (I)：
With 4- metoxyphenols and 1,2- (dichloroethanes base) ethane for raw material, its structural formula is respectively such as (II) and (III) institute
Show, comprise the following steps：
(1) under 20 DEG C~30 DEG C stirrings of temperature, 4- metoxyphenols and 1,2- (dichloroethanes base) ethane are added to
N, N-
In dimethylformamide, then potassium hydroxide is added thereto, be 135 DEG C~153 DEG C reaction 10h~16h in temperature,
Will reaction
Liquid is poured into water, and obtains brown turbid solution 1；Wherein, 1,2- (dichloroethanes base) ethane, 4- metoxyphenols, hydrogen
The molar ratio of potassium oxide is 1:2~2.3:2.2~2.5；
(2) above-mentioned brown turbid solution 1 is cooled to -15 DEG C~-10 DEG C, keeps 3h~5h, filtering solution, obtains white tablets
Shape solid,
Ether is added to white flaky solid, is warming up to 30 DEG C~35 DEG C, filters off insoluble matter, is cooled to -15 DEG C~-10 DEG C, is protected
3h~4h is held, filtering solution, obtains white powdery solids 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane.
The synthetic method of currently preferred 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane, including it is following
Step：
Under (1) 20 DEG C of stirring, 4- metoxyphenols and 1,2- (dichloroethanes base) ethane are added to N, N- dimethyl methyls
In acid amides, then potassium hydroxide is added thereto, 150 DEG C of reaction 12h, reaction solution is poured into water, obtains brown turbid solution 1, its
In, 1,2- (dichloroethanes base) ethane, 4- metoxyphenols, the molar ratio of potassium hydroxide are 1:2.1:2.2；
(2) -15 DEG C are cooled to above-mentioned brown turbid solution 1, keep 4h, filtering solution, obtains white flaky solid, Xiang Bai
Color chip solid adds ether, is warming up to 35 DEG C, filters off insoluble matter, is cooled to -15 DEG C, keeps 4h, filtering solution, obtains white
Pulverulent solids 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane.
Advantages of the present invention：
The reaction time of the present invention is 12h, and the scope that documents go out the reaction time is 16-24h；The post processing of the present invention
Simply, it is only necessary to which crystal can be separated out by being poured into water reaction solution, and documents need to extract using dichloromethane, and will
Washed with sodium hydroxide solution and sodium chloride solution；The yield of the present invention is 98%, and the yield of documents is 96%, is improved
Reaction yield.
Embodiment
The present invention is described in further details with reference to embodiment.
Embodiment 1
Under 20 DEG C of stirrings of temperature, by 13.66g (110mmol) 4- metoxyphenols and 9.30g (50mmol) 1,2- (two
Chloroethene alkyl) ethane adds 100mlN, in dinethylformamide, add potassium hydroxide 6.72g (120mmol) to it, 150 DEG C
12h is reacted, reaction solution is poured into water, obtains brown turbid solution 1；
- 15 DEG C are cooled to above-mentioned brown turbid solution 1, keeps 4h, filtering solution, obtains white flaky solid, to white
Chip solid adds ether, is warming up to 35 DEG C, filters off insoluble matter, is cooled to -15 DEG C, keeps 4h, filtering solution, obtains 17.92g
White powdery solids 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane.Yield 98.35%, purity 98.11%,
67~68 DEG C of fusing point.
Structural Identification：
IR(KBr)ν:3444,3057,3014,2959,2931,2902,2871,2838,2786,2700,2590,2545,
2474,2345,2125,2050,1986,1905,1866,1740,1626,1509,1453,1385,1332,
1287,1250,
1229,1189,1132,1116,1072,1055,1031,948,927,883,821,731,593,522,449,
423cm-l.
1H NMR(CDCl3-d6):δ6.85(4H,t),6.80(4H,d),4.07(4H,t),3.83(4H,s),3.75(6H,
t),3.74(4H,t)；
13C NMR(CDCl3-d6)δ153.96,152.98,115.69,114.61,70.87,69.94,68.15,
55.70；.
Said structure appraising datum confirms that the material that this step obtains is strictly (the 2- (4- dimethoxys phenoxy group) of 1,2- bis-
Ethyoxyl) ethane.
Embodiment 2
Under 20 DEG C of stirrings of temperature, by 13.66g (110mmol) 4- metoxyphenols and 9.30g (50mmol) 1,2- (two
Chloroethene alkyl) ethane adds 100mlN, in dinethylformamide, add potassium hydroxide 6.72g (120mmol) to it, 130 DEG C
12h is reacted, reaction solution is poured into water, obtains brown turbid solution 1；
- 15 DEG C are cooled to above-mentioned brown turbid solution 1, keeps 4h, filtering solution, obtains white flaky solid, to white
Chip solid adds ether, is warming up to 35 DEG C, filters off insoluble matter, is cooled to -15 DEG C, keeps 4h, filtering solution, obtains 17.63g
White powdery solids 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane.Yield 96.76%, purity 98.06%,
67~68 DEG C of fusing point.
Embodiment 3
Under 20 DEG C of stirrings of temperature, by 13.66g (110mmol) 4- metoxyphenols and 9.30g (50mmol) 1,2- (two
Chloroethene alkyl) ethane adds 100mlN, in dinethylformamide, add potassium hydroxide 6.16g (110mmol) to it, 150 DEG C
12h is reacted, reaction solution is poured into water, obtains brown turbid solution 1；
- 15 DEG C are cooled to above-mentioned brown turbid solution 1, keeps 4h, filtering solution, obtains white flaky solid, to white
Chip solid adds ether, is warming up to 35 DEG C, filters off insoluble matter, is cooled to -15 DEG C, keeps 4h, filtering solution, obtains 17.25g
White powdery solids 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane.Yield 94.68%, purity 98.13%,
67~68 DEG C of fusing point.
Embodiment 4
Under 20 DEG C of stirrings of temperature, by 13.66g (110mmol) 4- metoxyphenols and 9.30g (50mmol) 1,2- (two
Chloroethene alkyl) ethane adds 100mlN, in dinethylformamide, add potassium hydroxide 6.72g (120mmol) to it, 150 DEG C
12h is reacted, reaction solution is poured into water, obtains brown turbid solution 1；
- 10 DEG C are cooled to above-mentioned brown turbid solution 1, keeps 4h, filtering solution, obtains white flaky solid, to white
Chip solid adds ether, is warming up to 35 DEG C, filters off insoluble matter, is cooled to -10 DEG C, keeps 4h, filtering solution, obtains 17.99g
White powdery solids 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane.Yield 98.74%, purity 95.82%,
67~68 DEG C of fusing point.
Embodiment 5
Under 20 DEG C of stirrings of temperature, by 13.66g (110mmol) 4- metoxyphenols and 9.30g (50mmol) 1,2- (two
Chloroethene alkyl) ethane adds 100mlN, in dinethylformamide, add potassium hydroxide 6.72g (120mmol) to it, 150 DEG C
16h is reacted, reaction solution is poured into water, obtains brown turbid solution 1；
- 15 DEG C are cooled to above-mentioned brown turbid solution 1, keeps 4h, filtering solution, obtains white flaky solid, to white
Chip solid adds ether, is warming up to 35 DEG C, filters off insoluble matter, is cooled to -15 DEG C, keeps 4h, filtering solution, obtains 17.99g
White powdery solids 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane.Yield 98.74%, purity 98.15%,
67~68 DEG C of fusing point.
Claims (2)
1. one kind 1, the synthetic method of 2- bis- (2- (4- methoxyphenoxies) ethyoxyl) ethane, 1,2- bis- (2- (4- methoxybenzenes
Epoxide) ethyoxyl) ethane structural formula such as shown in (I)：
With 4- metoxyphenols and 1,2- (dichloroethanes base) ethane for raw material, such as (II) and (III) is shown respectively for its structural formula,
Comprise the following steps：
(1) under 20 DEG C~30 DEG C stirrings of temperature, 4- metoxyphenols and 1,2- (dichloroethanes base) ethane are added to N, N-
In dimethylformamide, then potassium hydroxide is added thereto, be 135 DEG C~153 DEG C reaction 10h~16h in temperature, by reaction solution
It is poured into water, obtains brown turbid solution 1；Wherein, 1,2- (dichloroethanes base) ethane, 4- metoxyphenols, potassium hydroxide rub
You are than being 1:2~2.3:2.2~2.5；
(2) above-mentioned brown turbid solution 1 is cooled to -15 DEG C~-10 DEG C, keeps 3h~5h, filtering solution, obtains white plates and consolidate
Body, adds ether to white flaky solid, is warming up to 30 DEG C~35 DEG C, filter off insoluble matter, be cooled to -15 DEG C~-10 DEG C, keep
3h~4h, filtering solution, obtains white powdery solids 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane.
2. the synthetic method of 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane according to claim 1, bag
Include following steps：
Under (1) 20 DEG C of stirring, 4- metoxyphenols and 1,2- (dichloroethanes base) ethane are added to n,N-Dimethylformamide
In, then potassium hydroxide is added thereto, 150 DEG C of reaction 12h, reaction solution is poured into water, obtains brown turbid solution 1, wherein, 1,
2- (dichloroethanes base) ethane, 4- metoxyphenols, the molar ratio of potassium hydroxide are 1:2.1:2.2；
(2) -15 DEG C are cooled to above-mentioned brown turbid solution 1, keep 4h, filtering solution, obtains white flaky solid, to white tablets
Shape solid adds ether, is warming up to 35 DEG C, filters off insoluble matter, is cooled to -15 DEG C, keeps 4h, filtering solution, obtains white powder
Shape solid 1,2- bis- (2- (4- dimethoxys phenoxy group) ethyoxyl) ethane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108558614A (en) * | 2018-06-05 | 2018-09-21 | 西安近代化学研究所 | 1,2- bis-（2-（2,6- dimethyl phenoxies）Ethyoxyl）The preparation method of ethane |
| CN108558617A (en) * | 2018-06-05 | 2018-09-21 | 西安近代化学研究所 | 1,2- bis-（2-（4- methylphenoxies）Ethyoxyl）The preparation method of 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558614A (en) * | 2018-06-05 | 2018-09-21 | 西安近代化学研究所 | 1,2- bis-（2-（2,6- dimethyl phenoxies）Ethyoxyl）The preparation method of ethane |
| CN108558617A (en) * | 2018-06-05 | 2018-09-21 | 西安近代化学研究所 | 1,2- bis-（2-（4- methylphenoxies）Ethyoxyl）The preparation method of ethane |
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Application publication date: 20180413 |