CN102992968A - 2,3-dimethoxy-1-propyl alcohol and preparation method thereof - Google Patents
2,3-dimethoxy-1-propyl alcohol and preparation method thereof Download PDFInfo
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- CN102992968A CN102992968A CN2012102904213A CN201210290421A CN102992968A CN 102992968 A CN102992968 A CN 102992968A CN 2012102904213 A CN2012102904213 A CN 2012102904213A CN 201210290421 A CN201210290421 A CN 201210290421A CN 102992968 A CN102992968 A CN 102992968A
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- dimethoxy
- propyl alcohol
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Abstract
The invention relates to synthesis of an organic chemical product with the chemical name of 2,3-dimethoxy-1-propyl alcohol. The 2,3-dimethoxy-1-propyl alcohol is synthesized through the following step: mixing carbinol and epoxy chloropropane which form a reaction system, and a catalyst of room-temperature ion liquid N,N,N-trimethyl-N-sulfosuccinic ammonium bisulfate at a mole ratio of (1-7):1:(0.01-0.1), wherein the reaction temperature is 30-220 DEG C, the initial pressure of the reaction system is 0-6.0MPa, and the reaction time is 2-12 hours. The room-temperature ion liquid N,N,N-trimethyl-N-sulfosuccinic ammonium bisulfate is synthesized according to a method disclosed by Chinese patent ZL200710151000.1. The selectivity of a product provided by the invention reaches up to 100%. Under a certain reaction condition, the yield of 2,3-dimethoxy-1-propyl alcohol reaches up to more than 99%, the reaction product is clean and can be separated from the system easily, and the catalyst can be regenerated for use.
Description
Technical field:
The present invention relates to the synthetic of a kind of novel organic chemical product, use specifically ionic liquid at room temperature N, N, N-trimethylammonium-N-sulphur butyl monoammonium sulfate prepare the synthesis route of 2,3-dimethoxy-1-propyl alcohol as raw material take methyl alcohol, epoxy chloropropane as catalyzer.
Technical background:
At present, the industrial technology develop rapidlys such as aviation, traffic, military affairs, more and more harsher to the performance index requirement of petroleum products.Because the limitation of natural constituents can not meet the demands only according to complete processing in the oil, so need to add the additive with different performance.Many oil fuel can not only improve the oil product storage security and also improve incendivity after adding additive, increase the speed of burning, also can promote environment.
The petroleum products additive mainly contains antioxidant, octane promoter, antithrombotics, viscosity modifier, metal passivator, sanitising agent and dispersion agent etc., over one hundred kind of commodity of not lower 20 large classes.Now both at home and abroad extensive exploitation composite additive, can bring into play its over-all properties, can reduce consumption again, give accumulating and use brought convenient (king nine, Fang Jianhua, Dong Ling. petroleum products additive rudimentary knowledge [M]. Beijing: Sinopec press, 2009.).China starts late in the research of petroleum products additive, with developed country a certain distance is arranged, but recent researches enthusiasm is surging, and tempo is very fast.
2,3-dimethoxy-1-propyl alcohol (2,3-Dimethoxy-1-propanol), contain two methoxyl groups and a hydroxyl in the middle of its molecular formula, oxygen level higher (40%), the relatively condition of oxygenated additive in the fuel oil additive; And itself be alcohol, can add in the petroleum products as solubilizing agent.Therefore, 2,3-dimethoxy-1-propyl alcohol will have far-reaching influence to petroleum products as additive.The present invention is take methyl alcohol, epoxy chloropropane as raw material, at ionic liquid at room temperature N, and N, under the catalysis of N-trimethylammonium-N-sulphur butyl monoammonium sulfate, the reaction original pressure is normal pressure, but synthetic 2, the 3-dimethoxy of highly selective-1-propyl alcohol.Reaction process easy clean and safety non-toxic meet the requirements of the times of nowadays energy-conserving and environment-protective.
Summary of the invention:
The present invention uses methyl alcohol and epoxy chloropropane as raw material, and methyl alcohol is simple and easy to, and epoxy chloropropane can be made by biomass glycerol, has broken away from restriction and the impact of petroleum industry, meet the Green Chemistry requirement.Use ionic liquid at room temperature N, N, N-trimethylammonium-N-sulphur butyl monoammonium sulfate are as catalyzer, and it is good with the stock liquid intermiscibility, and reaction effect is good, the selectivity height.
Technical scheme of the present invention is:
A kind of compound, its chemical name are 2,3-dimethoxy-1-propyl alcohol, and structural formula is:
A kind of 2, the preparation method of 3-dimethoxy-1-propyl alcohol may further comprise the steps:
Reaction system is comprised of methyl alcohol and epoxy chloropropane, catalyzer is ionic liquid at room temperature N, N, N-trimethylammonium-N-sulphur butyl monoammonium sulfate, the three mixes in encloses container, and mol ratio is methyl alcohol: epoxy chloropropane: ionic liquid=1 ~ 7:1:0.01 ~ 0.1, temperature of reaction are 30 ~ 220 ℃, the reactive system original pressure is 0 ~ 6.0MPa, and the reaction times is 2 ~ 12h.
Ionic liquid at room temperature N recited above, N, N-trimethylammonium-N-sulphur butyl monoammonium sulfate, synthetic according to the method for Chinese patent ZL200710151000.1.
Beneficial effect of the present invention is: the epoxy chloropropane that uses the restriction of the common material benzenemethanol that is easy to get and non-oil sector, epoxy chloropropane can be that raw material is made by biological diesel oil byproduct glycerin, the dependence to oil can be reduced, the development of Biomass Energy Industry can be promoted again.Catalyzer adopts the ionic liquid of safety non-toxic, can fully mix with raw material, and catalytic performance is higher, and selectivity of product can be up to 100%.Under certain reaction conditions, the yield of 2,3-dimethoxy-1-propyl alcohol can be up to more than 99%, and reaction product is pure and be easy to separate from system, the catalyzer use of can regenerating.
Description of drawings
Fig. 1 is the gas-matter coupling spectrogram of products obtained therefrom among the embodiment 1;
Fig. 2 is the infrared spectrogram contrast of products obtained therefrom among 1,3-dimethoxy-2-propyl alcohol and the embodiment 1;
Fig. 3 is the carbon-13 nmr spectra of products obtained therefrom among the embodiment 1;
Fig. 4 is the proton nmr spectra of products obtained therefrom among the embodiment 1;
Fig. 5 is the two dimensional NMR spectrogram of products obtained therefrom among the embodiment 1.
Embodiment:
The catalyzer that the present invention uses is ionic liquid at room temperature N, N, and N-trimethylammonium-N-sulphur butyl monoammonium sulfate is synthetic according to the method for Chinese patent ZL200710151000.1.
Embodiment 1:
With material benzenemethanol 14mL, epoxy chloropropane 6.73mL, catalyst ion liquid N, N, N-trimethylammonium-N-sulphur butyl monoammonium sulfate 0.25g(three mol ratio is methyl alcohol/epoxy chloropropane/catalyzer=4/1/0.01) together put in the reactor, after fully mixing with magnetic agitation, system's original pressure is normal pressure, be warming up to 120 ℃ of reaction beginning timing, the time is 10 hours.Reaction is by cooling, and liquid sample adopts gas-chromatography to analyze.The yield of 2,3-dimethoxy-1-propyl alcohol reaches 90.17%, and its selectivity to epoxy chloropropane is 100%, and the epoxy chloropropane transformation efficiency reaches 90.17%.
To product 2,3-dimethoxy-1-propyl alcohol carries out spectrogram checking explanation, and particular content is as follows:
(1) mass spectrogram characterizes:
Product is detected with gas chromatograph-mass spectrometer, and the spectrogram result as shown in Figure 1.Its molecular fragment peak and structure are listed in the table 1.As can be seen from Figure 1, in Fig. 1, the m/z maximum value appears at 88 places, but by 88-75=13,13 is not the numerical value of rational m/z, so peak, m/z=88 place is not molecular ion peak; Other group can have with the structure of 2,3-dimethoxy-1-propyl alcohol corresponding well.
Molecular fragment structure corresponding to each peak in the table 1 gas chromatography mass spectrometry spectrogram
(2) infrared spectrum characterizes:
Adopt with the mode of known reference material (1,3-dimethoxy-2-propyl alcohol) contrast and carry out structure verification.Its contrast infrared spectrogram is listed in Fig. 2:
On the infrared spectrogram of 1,3-dimethoxy-2-propyl alcohol, can detect hydroxyl-OH, hydrocarbon key C-H, methoxyl group-O-CH
3, ehter bond C-O-C, the C-O vibration absorption peak of secondary hydroxyl-CHOH-.The O-H of hydroxyl ... the stretching vibration absorption peak of O appears at 3440cm
-1, peak shape is wider and intensity is high; And 2982cm
-1And 2892cm
-1The peak be in (3000cm in the C-H stretching vibration absorption band of saturated hydrocarbyl
-1~ 2845cm
-1); 2820cm
-1Place's absorption peak sharp-pointed and medium tenacity belongs to the vibration absorption peak of methyl in the methoxyl group; 1455cm
-1Be in the formation vibration absorption band (1470cm of alkyl
-1～1370cm
-1), and at 1450cm
-1Near the appearance at peak is the proof that has methyl in the compound; 1109cm
-1The strong absorption peak at place is the stretching vibration absorption peak of ehter bond C-O-C key, is the unique characteristic absorption band of aliphatic ether herein.It is worth mentioning that the hydroxyl of 1,3-dimethoxy-2-propyl alcohol belongs to secondary hydroxyl, is embodied in 1100cm
-1The vicinity goes out the peak, and absorption peak herein is the stretching vibration absorption peak of secondary alcohol C-O key, and the stretching vibration absorption peak of itself and ehter bond overlaps as we can see from the figure.
Can see that through contrast the infrared spectra of the infrared spectra of 2,3-dimethoxy-1-propyl alcohol and 1,3-dimethoxy-2-propyl alcohol has similar significantly.Just the part peak position slightly is offset, and has equally hydroxyl absorption peak 3415cm
-1, hydrocarbon key absorption peak 2929cm
-1, 2896cm
-1, the vibration absorption peak 2827cm of methoxyl group
-1, ehter bond absorption peak 1123cm
-1Difference is 1073cm
-1C-O vibration absorption peak (1050cm for primary hydroxyl
-1Near), illustrate that the hydroxyl of this material is positioned on the primary carbon.
By with the contrast of 1,3-dimethoxy-2-propyl alcohol infrared spectrogram, can find out that the two structural similitude just exists hydroxyl and methoxyl group to exchange and the skew that goes out the peak position that brings.Further proved the exactness of 2,3-dimethoxy-1-propyl alcohol.
(3) nuclear magnetic spectrogram characterizes:
Can find out that from carbon-13 nmr spectra (Fig. 3) carbon of the total Four types of compound is not difficult to find two methoxyl group-OCH by observing molecular formula (1)
3(i.e. 1 ' and 5 ' carbon), residing chemical environment is similar, probably causes not being detected because cover.Carbon atom and belong to as follows:
NMR(δppm)：73.62(4’)；70.29(3’)；59.42(1’、5’)；48.10(2’)
From proton nmr spectra (Fig. 4) as can be known, demonstrate altogether five groups of proton peak from δ (4.0 ~ 3.1) ppm zone, each peak respectively with its molecule in each proton mutually corresponding, the hydrogen atom in the molecular formula is carried out label, shown in molecular formula (2).The ratio of respectively organizing the peak area at peak from low field to High-Field in the spectrogram is 1:2:2:3:1.
The ownership of each hydrogen atom is as follows in its molecule:
1H?NMR(δppm)：3.90(m，1H，3’，C-H)；3.57~3.48(m，2H，2’，C-H)；3.43(d，2H，4’，C-H)；3.32(s，3H，1’、6’，C-H)；3.20(d，1H，5’，O-H)
In Fig. 5, shown correlation circumstance hydrocarbon in the compound.Comprehensive proton nmr spectra, carbon-13 nmr spectra and two-dimentional spectrogram, the structure of this compound and 2,3-dimethoxy-1-propyl alcohol are consistent.
In addition, we have carried out the mensuration of specific rotation to unknown materials, and after measured, its specific rotation is 0.
By above characterization method, we can confirm that resulting product is 2,3-dimethoxy-1-propyl alcohol.
Embodiment 2:
Reaction is carried out in autoclave, reaction conditions such as embodiment 1.Difference is proportioning raw materials methyl alcohol/epoxy chloropropane/catalyzer=6/1/0.01.It is 100% to the selectivity of epoxy chloropropane that the yield of 2,3-dimethoxy-1-propyl alcohol reaches 98.96%, 2,3-dimethoxy-1-propyl alcohol, and the epoxy chloropropane transformation efficiency reaches 98.96%.
Embodiment 3:
With material benzenemethanol 17.5mL, epoxy chloropropane 6.73mL, catalyst ion liquid N, N, N-trimethylammonium-N-sulphur butyl monoammonium sulfate 0.25g(three mol ratio is methyl alcohol/epoxy chloropropane/catalyzer=5/1/0.01) together put in the reactor, after fully mixing with magnetic agitation, system's original pressure is normal pressure, be warming up to 120 ℃ of reaction beginning timing, the time is 10 hours.Reaction is by cooling, and liquid sample adopts gas-chromatography to analyze.The yield of 2,3-dimethoxy-1-propyl alcohol reaches 99.75%, and its selectivity to epoxy chloropropane is 100%, and the epoxy chloropropane transformation efficiency reaches 99.75%.
Embodiment 4:
Reaction is carried out in autoclave, reaction conditions such as embodiment 3.Difference is that the reaction times changes 6 hours into.The yield of 2,3-dimethoxy-1-propyl alcohol reaches 96.47%, and its selectivity to epoxy chloropropane is 100%, and the epoxy chloropropane transformation efficiency reaches 96.47%.
Embodiment 5:
Reaction is carried out in autoclave, reaction conditions such as embodiment 1.Difference is that temperature of reaction changes 6 hours into, and reaction is at room temperature carried out.The yield of 2,3-dimethoxy-1-propyl alcohol reaches 26.48%, and its selectivity to epoxy chloropropane is 100%, and the epoxy chloropropane transformation efficiency reaches 26.48%.
Embodiment 6:
Reaction is carried out in autoclave, reaction conditions such as embodiment 3.Difference is that temperature of reaction changes 60 ℃ into.The yield of 2,3-dimethoxy-1-propyl alcohol reaches 27.45%, and its selectivity to epoxy chloropropane is 100%, and the epoxy chloropropane transformation efficiency reaches 27.45%.
Embodiment 7:
Reaction is carried out in autoclave, reaction conditions such as embodiment 3.Difference is material molar ratio methyl alcohol/epoxy chloropropane/catalyzer=5/1/0.05.The yield of 2,3-dimethoxy-1-propyl alcohol reaches 95.52%, and its selectivity to epoxy chloropropane is 100%, and the epoxy chloropropane transformation efficiency reaches 95.52%.
Embodiment 8:
Reaction is carried out in autoclave, reaction conditions such as embodiment 3.Difference is material molar ratio methyl alcohol/epoxy chloropropane/catalyzer=5/1/0.1.The yield of 2,3-dimethoxy-1-propyl alcohol reaches 92.32%, and its selectivity to epoxy chloropropane is 100%, and the epoxy chloropropane transformation efficiency reaches 92.32%.
Claims (3)
1. compound, it is characterized by chemical name is 2,3-dimethoxy-1-propyl alcohol, structural formula is:
2. as claimed in claim 12, the preparation method of 3-dimethoxy-1-propyl alcohol, it is characterized by and may further comprise the steps: reaction system is comprised of methyl alcohol and epoxy chloropropane, catalyzer is ionic liquid at room temperature, the three mixes in encloses container, and mol ratio is methyl alcohol: epoxy chloropropane: ionic liquid=1 ~ 7:1:0.01 ~ 0.1, temperature of reaction are 30 ~ 220 ℃, the reactive system original pressure is 0 ~ 6.0MPa, and the reaction times is 2 ~ 12h.
3. as claimed in claim 22, the preparation method of 3-dimethoxy-1-propyl alcohol, it is characterized by ionic liquid at room temperature recited above is N, N, N-trimethylammonium-N-sulphur butyl monoammonium sulfate.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101528715A (en) * | 2006-10-25 | 2009-09-09 | 埃科特莱茵药品有限公司 | 2-phenyl-6-aminocarbonyl-pyrimidine derivatives |
| WO2009111443A2 (en) * | 2008-03-03 | 2009-09-11 | Honeywell International Inc. | Heat transfer system comprising brazed aluminum, method, heat transfer fluid, and additive package |
| WO2009114443A2 (en) * | 2008-03-11 | 2009-09-17 | Gm Global Technology Operations, Inc. | Control strategy for transitions between homogeneous-charge compression-ignition and spark-ignition combustion modes |
| CN102149786A (en) * | 2008-07-11 | 2011-08-10 | 霍尼韦尔国际公司 | Heat transfer fluid, additive package, system and method |
| CN102149785A (en) * | 2008-07-11 | 2011-08-10 | 霍尼韦尔国际公司 | Heat transfer system, fluid, and method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101528715A (en) * | 2006-10-25 | 2009-09-09 | 埃科特莱茵药品有限公司 | 2-phenyl-6-aminocarbonyl-pyrimidine derivatives |
| WO2009111443A2 (en) * | 2008-03-03 | 2009-09-11 | Honeywell International Inc. | Heat transfer system comprising brazed aluminum, method, heat transfer fluid, and additive package |
| WO2009114443A2 (en) * | 2008-03-11 | 2009-09-17 | Gm Global Technology Operations, Inc. | Control strategy for transitions between homogeneous-charge compression-ignition and spark-ignition combustion modes |
| CN102149786A (en) * | 2008-07-11 | 2011-08-10 | 霍尼韦尔国际公司 | Heat transfer fluid, additive package, system and method |
| CN102149785A (en) * | 2008-07-11 | 2011-08-10 | 霍尼韦尔国际公司 | Heat transfer system, fluid, and method |
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