CN103030573A - Preparation method of ethoxyamine - Google Patents
Preparation method of ethoxyamine Download PDFInfo
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- CN103030573A CN103030573A CN2012105067371A CN201210506737A CN103030573A CN 103030573 A CN103030573 A CN 103030573A CN 2012105067371 A CN2012105067371 A CN 2012105067371A CN 201210506737 A CN201210506737 A CN 201210506737A CN 103030573 A CN103030573 A CN 103030573A
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Abstract
The invention discloses a preparation method of ethoxyamine, which comprises the following steps: 1) synthesis of hydroxylamino sodium sulfite; 2) ethylation reaction; 3) hydrolysis reaction; and 4) alkalization and distillation to obtain the ethoxyamine. Sodium nitrate, sodium bisulfite and sulfur dioxide are used as initial raw materials to synthesize the ethoxyamine; and due to the addition of a phase-transfer catalyst, the invention implements high yield on the premise of ensuring accessible and cheap raw materials and simple and reasonable technological conditions, and thus, is suitable for industrial production.
Description
Technical field
The invention belongs to the organic synthesis field, be specifically related to a kind of preparation method of amine ethoxylate.
Background technology
Cyclohexene ketone weedicide has been the new herbicides of exploitation and industrialization since the eighties in last century, and selectivity is strong, and is safer to crop, is mainly used in preventing and kill off annual gramineous weed.Amine ethoxylate and hydrochloride thereof are the main intermediate of synthetic cyclohexene ketone weedicide cycloxydim, sethoxydim, tralkoxydim etc. as oxyethyl group amination reagent.In addition, because the hydrogen on the amine is more active, amine ethoxylate can replace halogen, and replaces the two keys of carbon oxygen and become carbon-to-nitrogen double bon, so amine ethoxylate also has important application in organic synthesis fields such as synthesis of hydroxy ureas.
The route that adopts in the industrialization at present exists that cost of material is higher, severe reaction conditions, in the industrial shortcoming such as enforcement that is difficult to, is difficult to suitability for industrialized production.
Summary of the invention
Technical problem to be solved by this invention is: provide that a kind of raw materials cost is low, reaction conditions is gentle, be easy to industrialized amine ethoxylate preparation method.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of amine ethoxylate, and its preparation process is:
1) synthetic (the Raschig reaction) of azanol sodium sulfite salt
Sodium Nitrite is soluble in water, 20 ~ 25 ℃ of hierarchy of control temperature, the aqueous solution of dropping sodium bisulfite dropwises, reaction solution is cooled to-10～-5 ℃, pass into sulfur dioxide gas under stirring, control gas passes into speed, makes reacting liquid temperature be controlled at-5 ~ 0 ℃, when reaction solution pH=2.0 ~ 2.5, stop logical sulfur dioxide gas, reaction finishes, and obtains the azanol sodium sulfite salt;
2) ethylation reaction
In the solution of step 1) gained azanol sodium sulfite salt, drip 35 ~ 40Wt.% aqueous sodium hydroxide solution, conditioned reaction liquid pH=11.0 ~ 12.0, add again phase-transfer catalyst, be warming up to 80～85 ℃, drip simultaneously ethyl sulfate and 35 ~ 40Wt.% aqueous sodium hydroxide solution, make system keep pH=11.0 ~ 12.0, dropwise, keep 80～85 ℃ and continue reaction 5.5 ~ 6h;
3) hydrolysis reaction
In step 2) drip the vitriol oil in the gained reaction solution, regulate pH=0 ~ 0.5, then be heated to backflow, back flow reaction 4 ~ 4.5h, stopped reaction is distilled to driedly, obtains the mixture of amine ethoxylate vitriol and sodium sulfate;
4) alkalization and distillation
With the mixture water dissolution of amine ethoxylate vitriol and sodium sulfate, then use 35 ~ 40Wt.% aqueous sodium hydroxide solution, regulate pH=11.0 ~ 12.0, keep 45 ~ 60min, the distillation that heats up obtains amine ethoxylate.
The preparation process of described amine ethoxylate, its reaction equation is:
The mol ratio of the Sodium Nitrite step 1) and sodium bisulfite is 1:1.3 ~ 1.5.
The mol ratio of the azanol sodium sulfite salt step 2) and ethyl sulfate is 1:1.1 ~ 1.2.
Described phase-transfer catalyst is polyoxyethylene glycol or Polyethylene glycol dimethyl ether, and the phase-transfer catalyst consumption accounts for 1.5 ~ 2% of ethyl sulfate quality.
Beneficial effect of the present invention: the synthetic amine ethoxylate take Sodium Nitrite, sodium bisulfite and sulfurous gas as starting raw material, simultaneously because the adding of phase-transfer catalyst, guaranteed that raw material is easy to get under the prerequisite of inexpensive, processing condition advantages of simple, realized higher yield, be fit to suitability for industrialized production.
Embodiment
Embodiment 1
1) synthetic (the Raschig reaction) of azanol sodium sulfite salt
27.9g (0.4mol) Sodium Nitrite is dissolved in the 50mL water, 20 ~ 25 ℃ of hierarchy of control temperature, the aqueous solution (the 54.1g sodium bisulfite is dissolved in 100mL water) of dropping sodium bisulfite dropwises, reaction solution is cooled to-10 ~-5 ℃, pass into sulfur dioxide gas under stirring, control gas passes into speed, makes reacting liquid temperature be controlled at-5 ~ 0 ℃, when reaction solution pH=2.0 ~ 2.5, stop logical sulfur dioxide gas, reaction finishes, and obtains the azanol sodium sulfite salt;
2) ethylation reaction
In the solution of step 1) gained azanol sodium sulfite salt, drip the 35Wt.% aqueous sodium hydroxide solution, conditioned reaction liquid pH=11.0 ~ 12.0, add again the 0.1g polyoxyethylene glycol, be warming up to 80～85 ℃, drip simultaneously ethyl sulfate (60.0mL, 0.44mol) and the 35Wt.% aqueous sodium hydroxide solution, make system keep pH=11.0 ~ 12.0, dropwise, keep 80～85 ℃ and continue reaction 5.5h;
3) hydrolysis reaction
In step 2) drip the vitriol oil in the gained reaction solution, regulate pH=0 ~ 0.5, then be heated to backflow, back flow reaction 4 ~ 4.5h, stopped reaction is distilled to driedly, obtains the mixture (white solid) of amine ethoxylate vitriol and sodium sulfate;
4) alkalization and distillation
Mixture water dissolution with amine ethoxylate vitriol and sodium sulfate, then use the 35Wt.% aqueous sodium hydroxide solution, regulate pH=11.0 ~ 12.0, keep 45min, the distillation that heats up stops to collect when the top temperature arrives 80 ℃, obtain the liquid of the strong amine flavor of water white transparency tool, be amine ethoxylate 19.0g, gas chromatographic analysis content: 99.4%, yield 65% (in Sodium Nitrite).
Embodiment 2
1) the azanol sodium sulfite salt is synthetic
27.9g (0.4mol) Sodium Nitrite is dissolved in the 50mL water, 20 ~ 25 ℃ of hierarchy of control temperature, the aqueous solution (the 62.4g sodium bisulfite is dissolved in 120mL water) of dropping sodium bisulfite dropwises, reaction solution is cooled to-10 ~-5 ℃, pass into sulfur dioxide gas under stirring, control gas passes into speed, makes reacting liquid temperature be controlled at-5 ~ 0 ℃, when reaction solution pH=2.0 ~ 2.5, stop logical sulfur dioxide gas, reaction finishes, and obtains the azanol sodium sulfite salt;
2) ethylation reaction
In the solution of step 1) gained azanol sodium sulfite salt, drip 35 ~ 40Wt.% aqueous sodium hydroxide solution, conditioned reaction liquid pH=11.0 ~ 12.0, the Polyethylene glycol dimethyl ether that adds again 1.5g is warming up to 80～85 ℃, drips simultaneously ethyl sulfate (79.1mL, 0.48mol) and 35 ~ 40Wt.% aqueous sodium hydroxide solution, make system keep pH=11.0 ~ 12.0, dropwise, keep 80～85 ℃ and continue reaction 6h;
3) hydrolysis reaction
In step 2) drip the vitriol oil in the gained reaction solution, regulate pH=0 ~ 0.5, then be heated to backflow, back flow reaction 4.5h, stopped reaction is distilled to driedly, obtains the mixture (white solid) of amine ethoxylate vitriol and sodium sulfate;
4) alkalization and distillation
Mixture water dissolution with amine ethoxylate vitriol and sodium sulfate, then use 35 ~ 40Wt.% aqueous sodium hydroxide solution, regulate pH=11.0 ~ 12.0, keep 50min, the distillation that heats up stops to collect when the top temperature arrives 80 ℃, obtain the liquid of the strong amine flavor of water white transparency tool, be amine ethoxylate 18.9g, gas chromatographic analysis content 〉=98%, yield 75.7% (in Sodium Nitrite).
1H?NMR(CDCl
3，400MHz)δ:1.17(t，3H，J=7.2Hz，-CH3)，3.68～3.73(q，2H，-CH
2-)，5.40(s，2H，-NH
2)；IR?v:3405，2979，1643，1453，1382，1111，1038，916cm
-1；MS(70eV)m/z(%)：62(M+1，5),61(M+，100)，46(39)，44（43），43（57）。
Claims (4)
1. the preparation method of an amine ethoxylate, its preparation process is as follows:
1) the azanol sodium sulfite salt is synthetic:
Sodium Nitrite is soluble in water, 20 ~ 25 ℃ of hierarchy of control temperature, the aqueous solution of dropping sodium bisulfite dropwises, reaction solution is cooled to-10～-5 ℃, pass into sulfur dioxide gas under stirring, control gas passes into speed, makes reacting liquid temperature be controlled at-5 ~ 0 ℃, when reaction solution pH=2.0 ~ 2.5, stop logical sulfur dioxide gas, reaction finishes, and obtains the azanol sodium sulfite salt;
2) ethylation reaction
In the solution of step 1) gained azanol sodium sulfite salt, drip 35 ~ 40Wt.% aqueous sodium hydroxide solution, conditioned reaction liquid pH=11.0 ~ 12.0, add again phase-transfer catalyst, be warming up to 80～85 ℃, drip simultaneously ethyl sulfate and 35 ~ 40Wt.% aqueous sodium hydroxide solution, make system keep pH=11.0 ~ 12.0, dropwise, keep 80～85 ℃ and continue reaction 5.5 ~ 6h;
3) hydrolysis reaction
In step 2) drip the vitriol oil in the gained reaction solution, regulate pH=0 ~ 0.5, then be heated to backflow, back flow reaction 4 ~ 4.5h, stopped reaction is distilled to driedly, obtains the mixture of amine ethoxylate vitriol and sodium sulfate;
4) alkalization and distillation
With the mixture water dissolution of amine ethoxylate vitriol and sodium sulfate, then use 35 ~ 40Wt.% aqueous sodium hydroxide solution, regulate pH=11.0 ~ 12.0, keep 45 ~ 60min, the distillation that heats up obtains amine ethoxylate.
2. the preparation method of a kind of amine ethoxylate according to claim 1 is characterized in that: step 1) described in Sodium Nitrite and the mol ratio of sodium bisulfite be 1:1.3 ~ 1.5.
3. the preparation method of a kind of amine ethoxylate according to claim 1 is characterized in that: step 2) described in the azanol sodium sulfite salt and the mol ratio of ethyl sulfate be 1:1.1 ~ 1.2.
4. the preparation method of a kind of amine ethoxylate according to claim 1, it is characterized in that: described phase-transfer catalyst is polyoxyethylene glycol or Polyethylene glycol dimethyl ether, and the phase-transfer catalyst consumption accounts for 1.5 ~ 2% of ethyl sulfate quality.
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| CN2012105067371A CN103030573A (en) | 2012-12-01 | 2012-12-01 | Preparation method of ethoxyamine |
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| CN2012105067371A CN103030573A (en) | 2012-12-01 | 2012-12-01 | Preparation method of ethoxyamine |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB930389A (en) * | 1959-10-21 | 1963-07-03 | Hoechst Ag | Process for the manufacture of o-alkyl-hydroxylamines |
| US5008455A (en) * | 1984-10-24 | 1991-04-16 | Nippon Soda Co., Ltd. | Method for the production of hydroxylamine derivatives |
| JPH07252205A (en) * | 1994-03-15 | 1995-10-03 | Nippon Soda Co Ltd | Method for producing oxyamine compounds |
-
2012
- 2012-12-01 CN CN2012105067371A patent/CN103030573A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB930389A (en) * | 1959-10-21 | 1963-07-03 | Hoechst Ag | Process for the manufacture of o-alkyl-hydroxylamines |
| US5008455A (en) * | 1984-10-24 | 1991-04-16 | Nippon Soda Co., Ltd. | Method for the production of hydroxylamine derivatives |
| JPH07252205A (en) * | 1994-03-15 | 1995-10-03 | Nippon Soda Co Ltd | Method for producing oxyamine compounds |
Non-Patent Citations (3)
| Title |
|---|
| 夏岚等: "烷氧基胺的应用及合成工艺浅析", 《安徽化工》, vol. 34, no. 4, 31 August 2008 (2008-08-31), pages 25 - 27 * |
| 季永新: "甲氧胺盐酸盐的合成", 《试验与研究》, 30 September 2001 (2001-09-30), pages 200 - 202 * |
| 翁建全等: "乙氧基胺的合成工艺", 《浙江工业大学学报》, vol. 35, no. 2, 30 April 2007 (2007-04-30) * |
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Application publication date: 20130410 |