CN104645876B - 1,1,1-tri-(methylol) ethane is for connecting base three sub-surface promoting agent and preparation method thereof - Google Patents
1,1,1-tri-(methylol) ethane is for connecting base three sub-surface promoting agent and preparation method thereof Download PDFInfo
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- CN104645876B CN104645876B CN201410585810.8A CN201410585810A CN104645876B CN 104645876 B CN104645876 B CN 104645876B CN 201410585810 A CN201410585810 A CN 201410585810A CN 104645876 B CN104645876 B CN 104645876B
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Abstract
Take 1,1,1-tri-(methylol) ethane as the preparation method of the three sub-surface promoting agents connecting base, its structural formula is as follows:
Description
Technical field
The present invention relates to a kind of preparation method of three sub-surface promoting agents.
Background technology
The research of anionic gemini surfactant is existing for many years, and little to the report of negatively charged ion three sub-surface promoting agent.2004; after three (2-aminoethyl) amine, the reaction of long-chain acylated with acid chloride; three sub-anionic carboxylic acid salt surfactants are synthesized with after Lithium Aluminium Hydride reducing amide with after anhydride reaction; this achievement in research is published in JournalofSurfactantsAndDetergents (2004,7:67-73).2008, with glycerine, epoxy chloropropane, lauryl alcohol, chlorsulfonic acid etc. for main raw material, through etherificate, open loop, sulfating reaction, three sulfuric acid ester type anion surfactants are synthesized, this achievement in research is published in (Southern Yangtze University, 2008.7) in Master's thesis.At present, little to the research report of three sub-surface promoting agents both at home and abroad, due to the property that three sub-surface promoting agents have, attract a lot of researchers and constantly carry out more research.We synthesize, and a kind of what have no report is the three sub-surface promoting agents connecting base with 1,1,1-tri-(methylol) ethane, and the synthesis of this product adds the kind of three sub-surface promoting agents, simultaneously for the research of this aspect provides some references.
Summary of the invention
The object of the invention is the preparation method in order to provide with 1,1,1-tri-(methylol) ethane the three sub-surface promoting agents being connection base.This tensio-active agent has good surfactivity, wettability, foaming and foam stability.This preparation method's raw material is easy to get, and easy being easy to of operation controls, and product is easily separated.
Synthesized by the present invention is be connect three sub-surface promoting agents of base with 1,1,1-tri-(methylol) ethane.Its structural formula is:
n=5、7、9
The concrete synthetic method of three sub-surface promoting agents comprises following three steps:
(1) synthesis of alpha-brominated carboxylic acid
Under nitrogen protection; in the dry there-necked flask of the 100mL that reflux condensing tube, dropping funnel, rotor and emission-control equipment are housed; add lipid acid and be slowly heated to solid thawing; then slowly thionyl chloride is dripped under stirring at 55-60 DEG C; lipid acid acid is 1.0:1.3 with the mol ratio of thionyl chloride, mixes post-heating to 80 DEG C, reaction 1 ~ 2h; till not having waste gas to release, reduce pressure away excessive thionyl chloride.Then under agitation slowly drip bromine (about 4h dropwises) in 80 DEG C, under remaining on 80 DEG C of conditions, continue reaction 12h.Poured in frozen water by reaction solution after reaction terminates, then add extraction into ethyl acetate, use anhydrous magnesium sulfate drying 5-6h after organic phase distilled water wash, underpressure distillation removing low boiling component obtains crude product.Crude product can be collected through underpressure distillation and obtain the alpha-brominated carboxylic acid of clear yellow viscous liquid.
(2) esterification
Under nitrogen protection, sodium hydride is added in the 100mL there-necked flask of drying, the tetrahydrofuran (THF) that 5mL is dried, after stirred at ambient temperature 10min, then in there-necked flask, 1 is dripped, 1, the tetrahydrofuran (THF) mixed solution of 1-tri-(methylol) ethane and 10mL drying, 1, 1, the mol ratio of 1-tri-(methylol) ethane and sodium hydride is 1.0:3.3, at room temperature continue stirring reaction 1h, reaction unit is moved in ice-water bath, the tetrahydrofuran (THF) mixed solution of the alpha-brominated acid of fast drop and 5mL drying in reaction flask, the mol ratio of alpha-brominated acid and sodium hydride is 1.0:1.0, continue to stir 0.5h under ice-water bath, then reaction unit is moved in oil bath and be warming up to 65 DEG C, backflow 23-25h, question response liquid is cooled to room temperature, add distilled water to rock in reaction solution and make it mix, revolve steaming removing tetrahydrofuran solvent and obtain remaining liq, surplus solution pH to 1 ~ 2 are regulated with dilute hydrochloric acid, be extracted with ethyl acetate, merge organic phase and use anhydrous magnesium sulfate drying 5-6h, filter, except desolventizing, obtain clear yellow viscous liquid intermediate compound I.Obtained clear yellow viscous liquid intermediate compound I joined in 100mL there-necked flask, then add 15mL methyl alcohol, the vitriol oil makes catalyzer, is heated to 65 DEG C under stirring, and reaction stopped after reaction 14-16h, reaction flask moves in ice-water bath, adds NaHCO
3solid neutralisation of sulphuric acid, revolve and steam the excessive methyl alcohol of removing, add distilled water, be extracted with ethyl acetate, merge organic phase dried over mgso 3-4h, filtration, except desolventizing, gained crude on silica gel column chromatography for separation, eluent is V (ethyl acetate): V (sherwood oil), collects after merging same composition concentrated, can obtain colorless viscous liquid intermediate II.
(3) ester hydrolysis reaction
Intermediate is added in 100mL there-necked flask
, then add the tetrahydrofuran (THF) of 10mL drying, add the aqueous sodium hydroxide solution of a certain amount of 30%, after back flow reaction 5-8h, except desolventizing, in crude product, add distilled water, and use washed with dichloromethane water layer, underpressure distillation, except after anhydrating, is placed in refrigerator crystallization, centrifugation, solid, in 60 DEG C of vacuum-drying 5-7h, obtains white solid, and namely 1,1,1-tri-(methylol) ethane is for connecting base three sub-surface promoting agent.
Below the building-up process (for n=7) of the present invention three sub-surface promoting agent:
(1) synthesis of alpha-brominated capric acid
(2) esterification
(3) ester hydrolysis reaction
Compared with prior art, the present invention has following beneficial effect:
(1) tensio-active agent of the present invention is connect three sub-surface promoting agents of base with 1,1,1-tri-(methylol) ethane, and the three sub-surface promoting agents at present with this structure there is not yet bibliographical information.
(2) this product has water-soluble, wettability, foaming and foam stability preferably.
(3) building-up process of the present invention, has the synthesis of alpha-brominated carboxylic acid, esterification and ester hydrolysis reaction to form.Easy being easy to of operation controls, and aftertreatment is simple, and product is easy to separating-purifying.
Embodiment is as follows:
The synthesis (for n=7) of embodiment 1 three sub-surface promoting agent
(1) synthesis of alpha-brominated capric acid
Under nitrogen protection; in the dry there-necked flask of the 100mL that reflux condensing tube, dropping funnel, rotor and emission-control equipment are housed; 17.215g (0.1mol) capric acid; slowly be heated to solid melt, slowly drip 9.3mL (0.13mol) thionyl chloride under then stirring at 55-60 DEG C, the mol ratio of capric acid and thionyl chloride is 1.0:1.3; mix post-heating to 80 DEG C; reaction 1.5h, till not having waste gas to release, reduce pressure away excessive thionyl chloride.Then under agitation slowly drip 23.970g (0.15mol) bromine (about 4h dropwises) in 80 DEG C, under remaining on 80 DEG C of conditions, continue reaction 12h.After reaction terminates, reaction solution is poured in 40mL frozen water, add (45mL × 3) ethyl acetate again, point water-yielding stratum, organic phase is with distilled water wash (30mL × 3) and use anhydrous magnesium sulfate drying 5-6h, and then underpressure distillation removes low boiling component and obtains crude product.Crude product can be collected through underpressure distillation (boiling point 160 DEG C) and obtain the alpha-brominated capric acid of clear yellow viscous liquid, yield 86.1%.
(2) esterification
Under nitrogen protection, 0.528g (13.2mmol) sodium hydride is added in the 100mL there-necked flask of drying, the tetrahydrofuran (THF) that 5mL is dried, after stirred at ambient temperature 10min, then in there-necked flask, 0.240g (2.0mmol) 1 is dripped, 1, the tetrahydrofuran (THF) mixed solution of 1-tri-(methylol) ethane and 10mL drying, 1, 1, the mol ratio of 1-tri-(methylol) ethane and sodium hydride is 1.0:3.3, at room temperature continue to stir 1h, reaction unit is moved in ice-water bath, the tetrahydrofuran (THF) mixed solution of fast drop 1.658g (6.6mmol) alpha-brominated capric acid and 5mL drying in reaction flask, the mol ratio of alpha-brominated capric acid and sodium hydride is 1.0:1.0, continue to stir 0.5h under ice-water bath, then reaction unit is moved in oil bath and be warming up to 65 DEG C, after backflow 24h, question response liquid is cooled to room temperature, add 15mL distilled water to rock in reaction solution and make it mix, revolve steaming removing tetrahydrofuran solvent and obtain remaining liq, dilute hydrochloric acid with 5% regulates surplus solution pH to 1 ~ 2, be extracted with ethyl acetate (20mL × 3), merge organic phase and use anhydrous magnesium sulfate drying 5-6h, filter, except desolventizing, obtain clear yellow viscous liquid intermediate compound I 1.224g, yield 97%.Obtained clear yellow viscous liquid intermediate compound I added in 100mL there-necked flask, then add 15mL methyl alcohol and the 38.2mg vitriol oil, be heated to 65 DEG C under stirring, reaction stopped after reaction 15h, reaction flask moves in ice-water bath, adds 69.8mgNaHCO
3solid neutralisation of sulphuric acid, revolve and steam the excessive methyl alcohol of removing, add 20mL distilled water, be extracted with ethyl acetate (20mL × 3), merge organic phase dried over mgso 3-4h, filtration, except desolventizing, gained crude on silica gel column chromatography for separation, eluent is V (ethyl acetate): V (sherwood oil)=5:95, collects after merging same composition concentrated, can obtain colorless viscous liquid intermediate II 0.741g, yield is 55.1%.
(3) ester hydrolysis reaction
By 0.672g (1.0mmol) intermediate
join in 100mL there-necked flask, then add the tetrahydrofuran (THF) of 10mL drying, add the aqueous sodium hydroxide solution of a certain amount of 30%, after back flow reaction 6h, except desolventizing, in crude product, add 20mL distilled water, and with washed with dichloromethane (10mL × 3) water layer, underpressure distillation is except after anhydrating, be placed in refrigerator crystallization, centrifugation, solid is in 60 DEG C of vacuum-drying 5h, obtain white solid 0.566g, yield 81.3%.
The infrared spectra (for n=7) of embodiment 2 three sub-surface promoting agent
The three sub-surface promoting agents be obtained by reacting with capric acid are example, and adopt coating method, do infrared analysis with Fourier infrared spectrum determinator to product, data are as follows:
2956.7cm
-1, 2923.80cm
-1, 2854.40cm
-1place is-CH
3,-CH
2-symmetric and anti-symmetric stretching vibration absorption peak, 1581.40cm
-1, 1424.80cm
-1place is the charateristic avsorption band of carboxylate salt, 1109.2cm
-1place is the stretching vibration absorption peak of C-O-C key, 723.5cm
-1for long-chain-CH
2-stretching vibration vibration absorption peak.
Embodiment 3 three sub-surface promoting agent
1hNMR (for n=7)
With CDCl
3for solvent is to three sub-surface promoting agents
1h-NMR analyzes, and data are as follows:
1HNMR(600MHz,CDCl
3,ppm)
δ：0.88(t,
J=7.2,9H,CH
3),1.02(s,3H,CH
3),1.26-1.31(m,36H,(CH
2)
6),1.37-1.45(m,6H,CH
2),1.70-1.81(m,6H,CH
2),3.26(d，
J=8.4Hz,3H,CH
2),3.65(d,
J=8.4Hz,3H,CH
2),3.81-3.83(m,3H,CH)。
Claims (1)
1. be the preparation method of three sub-surface promoting agents connecting base with 1,1,1-tri-(methylol) ethane, the structural formula that to it is characterized in that with 1,1,1-tri-(methylol) ethane be the three sub-surface promoting agents connecting base is:
Above-mentioned is that the preparation method of three sub-surface promoting agents connecting base is prepared according to the following steps with 1,1,1-tri-(methylol) ethane:
(1) synthesis of alpha-brominated carboxylic acid
Under nitrogen protection, in the dry there-necked flask of the 100mL that reflux condensing tube, dropping funnel, rotor and emission-control equipment are housed, add lipid acid and be slowly heated to solid thawing, then slowly thionyl chloride is dripped under stirring at 55-60 DEG C, the mol ratio of lipid acid and thionyl chloride is 1.0:1.3, mixes post-heating to 80 DEG C, reaction 1 ~ 2h, till not having waste gas to release, the thionyl chloride that decompression removing is excessive; Then under agitation slowly drip bromine in 80 DEG C, under remaining on 80 DEG C of conditions, continue reaction 12h; Poured in frozen water by reaction solution after reaction terminates, then add extraction into ethyl acetate, use anhydrous magnesium sulfate drying 5-6h after organic phase distilled water wash, underpressure distillation removing low boiling component obtains crude product; Crude product can be collected through underpressure distillation and obtain the alpha-brominated carboxylic acid of clear yellow viscous liquid;
(2) esterification
Under nitrogen protection, sodium hydride is added in the 100mL there-necked flask of drying, the tetrahydrofuran (THF) that 5mL is dried, after stirred at ambient temperature 10min, then in there-necked flask, 1 is dripped, 1, the tetrahydrofuran (THF) mixed solution of 1-tri-(methylol) ethane and 10mL drying, 1, 1, the mol ratio of 1-tri-(methylol) ethane and sodium hydride is 1.0:3.3, at room temperature continue stirring reaction 1h, reaction unit is moved in ice-water bath, the tetrahydrofuran (THF) mixed solution of the alpha-brominated carboxylic acid of fast drop and 5mL drying in reaction flask, the mol ratio of alpha-brominated carboxylic acid and sodium hydride is 1.0:1.0, continue to stir 0.5h under ice-water bath, then reaction unit is moved in oil bath and be warming up to 65 DEG C, backflow 23-25h, question response liquid is cooled to room temperature, add distilled water to rock in reaction solution and make it mix, revolve steaming removing tetrahydrofuran solvent and obtain remaining liq, surplus solution pH to 1 ~ 2 are regulated with dilute hydrochloric acid, be extracted with ethyl acetate, merge organic phase and use anhydrous magnesium sulfate drying 5-6h, filter, except desolventizing, obtain clear yellow viscous liquid intermediate compound I, obtained clear yellow viscous liquid intermediate compound I joined in 100mL there-necked flask, then add 15mL methyl alcohol, the vitriol oil makes catalyzer, is heated to 65 DEG C under stirring, and reaction stopped after reaction 14-16h, reaction flask moves in ice-water bath, adds NaHCO
3solid neutralisation of sulphuric acid, revolve and steam the excessive methyl alcohol of removing, add distilled water, be extracted with ethyl acetate, merge organic phase dried over mgso 3-4h, filtration, except desolventizing, gained crude on silica gel column chromatography for separation, eluent is V
second acetoacetic ester: V
sherwood oil=5:95, collects after merging same composition concentrated, can obtain colorless viscous liquid intermediate II,
(3) ester hydrolysis reaction
In 100mL there-necked flask, add intermediate II, then add the tetrahydrofuran (THF) of 10mL drying, add the aqueous sodium hydroxide solution of a certain amount of 30%, after back flow reaction 5-8h, except desolventizing, in crude product, add distilled water, and use washed with dichloromethane water layer, underpressure distillation, except after anhydrating, is placed in refrigerator crystallization, centrifugation, solid, in 60 DEG C of vacuum-drying 5-7h, obtains white solid, and namely 1,1,1-tri-(methylol) ethane is for connecting base three sub-surface promoting agent.
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