CN102161623B - Synthesis method of alkylhydroxyethylimide - Google Patents
Synthesis method of alkylhydroxyethylimide Download PDFInfo
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- CN102161623B CN102161623B CN 201010113055 CN201010113055A CN102161623B CN 102161623 B CN102161623 B CN 102161623B CN 201010113055 CN201010113055 CN 201010113055 CN 201010113055 A CN201010113055 A CN 201010113055A CN 102161623 B CN102161623 B CN 102161623B
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Abstract
The invention discloses a synthesis method of alkylhydroxyethylimide. The method comprises the following steps: in a reaction kettle, Lewis acid is used as catalyst, the compound shown in the formula II reacts with ethylene oxide, the reaction product is transferred to a rectifying kettle to perform vacuum distillation, and fraction is collected under 0.8-1.0KPa to obtain the compound shown in the formula I, wherein the R1 and R2 in the formula are C1-4 linear alkyl, C1-4 branched alkyl, H or hydroxyethyl. By adopting the synthesis method of alkylhydroxyethylimide, the product purity is high and the operation is simple; and the method is more suitable for industrial production. The formula I and the formula II are shown in the specification.
Description
Technical field
The present invention relates to the synthetic method of alkyl hydroxyethyl imines.
Background technology
Formula I compounds all is to produce with the amination of alcohol or the alkylation of hydramine at present, and yield is low, cost is high, and separate impurities purification etc. are difficulty.Recently report forms hydramine with amine and oxyethane open loop, with alcohols (methyl alcohol, ethanol) etc. do medium (Japanese Patent. clear 61-100 500).Be easy to reactant oxyethane generation ethylene glycol and ether thereof etc. because containing hydroxyl, thereby reduced yield.Therefore, must select for use the medium amount be oxyethane 1-10 doubly, reach the purpose that suppresses by product.In like manner, generate superpolymer such as polyethers in order to prevent the reaction of hydroxyl and oxyethane in the resultant of reaction, then must strengthen the consumption of material amine, with the mol ratio of oxyethane be 3: just 1 can obtain high yield, cost certainly will be wanted height like this.On postprocessing working procedures, this compounds is to heat and oxygen sensitive, in still-process normal adopt nitrogen protection (Japanese Patent. clear 62-1 61 749).
Formula I
Summary of the invention
The purpose of this invention is to provide that a kind of working method is simple, cost is low, the synthetic method of product purity height, alkyl hydroxyethyl imines that yield is high.
The synthetic method of alkyl hydroxyethyl imines provided by the present invention comprises the steps:
In reactor, be catalyzer with Lewis acid, compound shown in the formula II and reacting ethylene oxide change reaction product in rectifying still rectification under vacuum, collect the cut of pressure 0.8～1.0KPa, obtain the compound shown in the formula I;
Formula I formula II
R in the formula
1And R
2For carbonatoms is the straight chained alkyl of 1-4, branched-chain alkyl, H or the hydroxyethyl that carbonatoms is 1-4.
The synthetic method of alkyl hydroxyethyl imines of the present invention, wherein, the mol ratio of compound and described oxyethane shown in the described formula II is 1.0: (1.0～4.0).
The synthetic method of alkyl hydroxyethyl imines of the present invention, wherein, the temperature in the described reactor is 30-150 ℃.
The synthetic method of alkyl hydroxyethyl imines of the present invention, wherein, described oxyethane discontinuous feeds in the described reactor, makes that pressure is no more than 0.7MPa in the described reactor.
The synthetic method of alkyl hydroxyethyl imines of the present invention wherein, adds stablizer in the described rectifying still, and described stablizer is mineral acid or inorganic salt.
The synthetic method of alkyl hydroxyethyl imines of the present invention, wherein, described inorganic salt are ammonium sulfate, ammonium sulphite, nickelous nitrate or borax; Described mineral acid is sulfuric acid, hydrochloric acid, phosphoric acid or boric acid.
The synthetic method of alkyl hydroxyethyl imines of the present invention, wherein, described Lewis acid is iron trichloride, zinc dichloride, aluminum chloride, titanium tetrachloride or boric acid.
The synthetic method of alkyl hydroxyethyl imines of the present invention, wherein, the temperature in the described reactor is 40-110 ℃.
The synthetic method of alkyl hydroxyethyl imines of the present invention, wherein, described oxyethane discontinuous feeds in the described reactor, makes that pressure is no more than 0.4MPa in the described reactor.
The synthetic method of alkyl hydroxyethyl imines of the present invention, wherein, the mol ratio of compound and described oxyethane shown in the described formula II is 1.0: (1.0～2.5).
The synthetic method of alkyl hydroxyethyl imines of the present invention is selected appropriate catalyst for use, and solubilizing agent does not directly feed reacting ethylene oxide in amine, and side reaction is few, the product purity height.The synthetic method of alkyl hydroxyethyl imines of the present invention, the intact back of compound shown in the formula II and reacting ethylene oxide straight run distillation need not to feed nitrogen, has simplified operating process, is more suitable for suitability for industrialized production.
Embodiment
Synthesizing of embodiment 1, tertiary butyl diethanolamine
In the 500ml reactor, add 0.3g zinc chloride and 0.1mol TERTIARY BUTYL AMINE, build kettle cover, slowly be warmed up to 50 ℃, the beginning intermittent type feeds oxyethane, the pressure of reactor reaches 0.15MPa and stops to feed oxyethane, and the pressure of reactor is lower than 0.15MPa and feeds oxyethane again, and the pressure that remains in the reactor is no more than 0.15MPa, the feeding time is 3 hours, feeds 0.22mol oxyethane altogether.After feeding the oxyethane end, reactor continues insulation one hour, (gas chromatographic detection raw material TERTIARY BUTYL AMINE content＜1% is and reacts completely) reacts completely, reaction product is pressed in the rectifying still that contains the 0.3g borax, rectification under vacuum, temperature control is collected the cut of pressure 0.8～1K Pa (gauge pressure) about 162 ℃, get finished product 154g.
(TMS is interior mark to Bruke AVANCE 400 UltraShield type nuclear magnetic resonance analyser, CDCl
3Be solvent) the detection finished product;
1HNMR δ 1.082 (s, 9H, (CH
3)
3C), 2.698 (t, 4H ,-N (CH
2CH
2OH)
2), 3.568 (t, 4H (CH
2CH
2OH)
2-), 3.742 (2H, O-H).
Nicolet-20SX FT-IR type infrared spectrophotometer, membrane process; V:3380,2980,2830,1480,1360cm
-1
In TERTIARY BUTYL AMINE, yield 95.6%; Purity 99.54% (GC).
Synthesizing of embodiment 2, tertiary butyl diethanolamine
In 500ml, press and add 0.3g aluminum chloride and 0.1mol TERTIARY BUTYL AMINE in the reactor, build kettle cover, slowly be warmed up to 50 ℃, the beginning intermittent type feeds bad oxidative ethane, the pressure of reactor reaches 0.25MPa and stops to feed oxyethane, and the pressure of reactor is lower than 0.25MPa and feeds oxyethane again, and the pressure that remains in the reactor is no more than 0.25MPa, the feeding time is 2 hours, feeds 0.25mol oxyethane altogether.After feeding the oxyethane end, reactor continues insulation one hour, (raw material TERTIARY BUTYL AMINE content in the gas chromatographic detection still＜1% is and reacts completely) reacts completely, reaction product is pressed in the rectifying still that contains the 0.4g nickelous nitrate, rectification under vacuum, temperature control is collected the cut of pressure 0.8～1KPa (gauge pressure) about 158 ℃, get finished product 154g.
(TMS is interior mark to Bruke AVANCE 400 UltraShield type nuclear magnetic resonance analyser, CDCl
3Be solvent) the detection finished product;
1HNMR δ 1.082 (s, 9H, (CH
3)
3C), 2.698 (t, 4H ,-N (CH
2CH
2OH)
2), 3.568 (t, 4H (CH
2CH
2OH)
2-), 3.742 (2H, O-H).
Nicolet-20SX FT-IR type infrared spectrophotometer, membrane process; V:3380,2980,2830,1480,1360cm
-1
In TERTIARY BUTYL AMINE, product yield 96.3%, purity 99.29% (GC).
Embodiment 3, N, N-diethylethanolamine synthetic
In 500ml, press and add 0.3g aluminum chloride and 0.1mol diethylamine in the reactor, build kettle cover, slowly be warmed up to 40 ℃, the beginning intermittent type feeds oxyethane, the pressure of reactor reaches 0.15MPa and stops to feed oxyethane, and the pressure of reactor is lower than 0.15MPa and feeds oxyethane again, and the pressure that remains in the reactor is no more than 0.15MPa, the feeding time is 1 hour, feeds 0.12mol oxyethane altogether.After feeding the oxyethane end, reactor continues insulation one hour, (raw material diethylamine content in the gas chromatographic detection still＜1% is and reacts completely) reacts completely, reaction product is pressed in the rectifying still that contains 0.3g boric acid, rectification under vacuum, temperature control is collected the cut of pressure 0.8～1KPa (gauge pressure) at 118 ℃, gets colourless transparent liquid 114g.
(TMS is interior mark to Bruke AVANCE 400 UltraShield type nuclear magnetic resonance analyser, CDCl
3Be solvent) the detection finished product;
1HNMR δ 0.985 (t, 3H, CH
3CH
2), 2.648 (q, 2H ,-N (CH
2CH
3)
2), 2.858 (t, 2H, CH
2CH
2OH), 3.526 (t, 2H CH
2CH
2OH), 3.644 (1H, O-H).
Nicolet-20SX FT-IR type infrared spectrophotometer, membrane process; V:3370,2980,2850,2830,1480,1390,1060cm
-1
In diethylamine, product yield 95.8%, purity 99.63% (GC).
Embodiment 4, N, N_ diisopropyl ethanolamine synthetic
In 500ml, press and add 0.5g boric acid and 0.1mol diisopropylamine in the reactor, build kettle cover, slowly be warmed up to 100 ℃, the beginning intermittent type feeds oxyethane, the pressure of reactor reaches 0.4MPa and stops to feed oxyethane, and the pressure of reactor is lower than 0.4MPa and feeds oxyethane again, and the pressure that remains in the reactor is no more than 0.4MPa, the feeding time is 3 hours, feeds 0.1mol oxyethane altogether.After feeding the oxyethane end, reactor continues insulation one hour, (raw material di-isopropyl amine content in the gas chromatographic detection still＜1% is and reacts completely) reacts completely, reaction product is pressed in the rectifying still that contains 0.5g ammonium sulfate, rectification under vacuum, temperature control is collected the cut of pressure 0.8～1KPa (gauge pressure) at 142 ℃, gets colourless oil liquid 140g.
(TMS is interior mark to Bruke AVANCE 400 UltraShield type nuclear magnetic resonance analyser, CDCl
3Be solvent) the detection finished product;
1HNMR δ 1.125 (d, 3H, (CH
3)
2CH), 2.878 (hept, 1H ,-CH (CH
3)
2), 2.958 (t, 2H, CH
2CH
2OH), 3.546 (t, 2H CH
2CH
2OH), 3.886 (1H, O-H).
Nicolet-20SX FT-IR type infrared spectrophotometer, membrane process; V:3380,2980,2850,2800,1480,1380,1040cm
-1
In Diisopropylamine, product yield 96.5%, purity 99.06% (GC).
Above embodiment is described preferred implementation of the present invention; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that the common engineering technical personnel in this area make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (5)
1. the synthetic method of an alkyl hydroxyethyl imines comprises the steps:
In reactor, be catalyzer with Lewis acid, compound shown in the formula II and reacting ethylene oxide are transferred to rectification under vacuum in the rectifying still with reaction product, collect the cut of pressure 0.8～1.0KPa, obtain the compound shown in the formula I;
R1 and R2 are that carbonatoms is the straight chained alkyl of 1-4, branched-chain alkyl, H or the hydroxyethyl that carbonatoms is 1-4 in the formula;
Wherein, add suitable stablizer in described rectifying still, described stablizer is mineral acid or inorganic salt; Temperature in the described reactor is 40-110 ℃; Temperature in the described rectifying still is 118-162 ℃; Described oxyethane discontinuous feeds in the described reactor, makes that pressure is 0.25-0.7MPa in the described reactor; Before changing over to described reaction product in the rectifying still, after feeding oxyethane finished, reactor continued insulation one hour, reacts completely, and compounds content＜1% is and reacts completely shown in the gas chromatographic detection raw material formula II.
2. synthetic method according to claim 1, it is characterized in that: the mol ratio of compound and described oxyethane shown in the described formula II is 1.0:(1.0～4.0).
3. synthetic method according to claim 2, it is characterized in that: described inorganic salt are ammonium sulfate, ammonium sulphite, nickelous nitrate or borax; Described mineral acid is boric acid.
4. synthetic method according to claim 3 is characterized in that: described Lewis acid is iron(ic) chloride, zinc chloride, aluminum chloride, titanium tetrachloride or boric acid.
5. synthetic method according to claim 4, it is characterized in that: the mol ratio of compound and described oxyethane shown in the described formula II is 1.0:(1.0～2.5).
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| CN107304169A (en) * | 2016-04-21 | 2017-10-31 | 佳化化学股份有限公司 | The method that water-soluble nitrogen-containing compound or its aqueous solution react production product with cyclic ethers |
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Denomination of invention: Synthesis of alkyl hydroxyethyl imine Effective date of registration: 20220629 Granted publication date: 20130911 Pledgee: Shandong Penglai Rural Commercial Bank Co.,Ltd. Pledgor: PENGLAI HONGWEI CHEMICAL Co.,Ltd. Registration number: Y2022980009324 |
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