CN103787834B - A kind of preparation method of 3-methyl-3-butene-1-alcohol - Google Patents
A kind of preparation method of 3-methyl-3-butene-1-alcohol Download PDFInfo
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- CN103787834B CN103787834B CN201310693927.3A CN201310693927A CN103787834B CN 103787834 B CN103787834 B CN 103787834B CN 201310693927 A CN201310693927 A CN 201310693927A CN 103787834 B CN103787834 B CN 103787834B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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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
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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Abstract
The preparation method of a kind of 3-methyl-3-butene-1-alcohol provided by the invention, comprises the following steps: under ultrasonic wave exists, the addition reaction in alkali aqueous solution of acetone and formaldehyde, obtains 4-hydroxy-2-butanone; Under strong acidic ion resin catalyzer exists, 4-hydroxy-2-butanone and isobutene reaction obtain intermediate 1; Intermediate 1 and methylenation reagents react, and obtain intermediate 2; Under deprotection catalyzer exists, intermediate 2 deprotection reaction, to obtain final product.The method technique is simple, with low cost, and by product is few, selectivity good, yield is high.
Description
Technical field
The invention belongs to the synthesis field of unsaturated alcohol, specifically a kind of preparation method of 3-methyl-3-butene-1-alcohol.
Background technology
3-methyl-3-butene-1-alcohol is a kind of important organic intermediate, and this alcohol isomerization can synthesize 3-M2BOL, as the raw material of pyrethroid under catalyzer and certain temperature and pressure condition; In addition, this alcohol can as the initiator of synthesizing polyether, under the effect of basic catalyst, form initiated polymerization spike, thus initiation epoxy alkane ring opening polymerization, synthesis unsaturated polyether, synthesized unsaturated polyether can be used as the raw material of synthesis ether type polycarboxylic acid water reducer.
The preparation method of 3-methyl-3-butene-1-alcohol, usually based on Prins condensation reaction method, is divided into the Prins thermal condensation reaction method of catalyst-free and has the Prins condensation reaction method of catalyzer.
Patent CN102206136A discloses a kind of Prins thermal condensation reaction method of catalyst-free, passes in autoclave by solvent, formaldehyde, iso-butylene, 100-300 DEG C, under the processing condition of 5-50MPa, 2-12h, synthesized 3-methyl-3-butene-1-alcohol; Patent CN102060667B also discloses a kind of Prins condensation reaction method of catalyst-free, in advance paraformaldehyde and iso-butylene are mixed slurry, then first depolymerization passes into reactor, 200-300 DEG C, under the processing condition of 9-15MPa, 50-150min, synthesized 3-methyl-3-butene-1-alcohol; Patent US4079088A disclose a kind of with 3-methyl-2-amylene-1,5-glycol and iso-butylene for raw material, under 200-450 DEG C of condition, the method for synthesis 3-methyl-3-butene-1-alcohol.
It is solvent with toluene that patent US3960972A discloses a kind of, with aromatic series phenols for catalyzer, 175-250 DEG C, in still Equilibrium pressure, 15min-8h processing condition under, catalysis formaldehyde or paraformaldehyde and iso-butylene through Prins condensation reaction, the method for synthesis 3-methyl-3-butene-1-alcohol.(study on the synthesis [D] of methyl butenol is prepared in Pu Linsi (Prins) condensation to Geng Yanxia etc., Shanghai: East China University of Science, 2006) method having the Prins condensation reaction of catalyzer to prepare 3-methyl-3-butene-1-alcohol is concluded and studied, find that the effect of slightly acidic or weakly alkaline phosphate metal salt is best, with it for catalyzer, methyl alcohol or the trimethyl carbinol are solvent, 160-250 DEG C, under the processing condition of 4-13MPa, 3-6h, catalyzing iso-butane alkene and formaldehyde, through Prins condensation reaction, have synthesized 3-methyl-3-butene-1-alcohol.
Prins condensation reaction method, because synthesis step is few, aftertreatment simple, is therefore 3-methyl-3-butene-1-alcohol preparation method the most frequently used at present.But the reaction conditions of the method is comparatively harsh, needs High Temperature High Pressure, therefore cause the input ratio of its equipment investment and security protection aspect larger.
Summary of the invention
Goal of the invention: the preparation method that the invention provides the 3-methyl-3-butene-1-alcohol that a kind of by product is few, yield is high.
Technical scheme: the preparation method of a kind of 3-methyl-3-butene-1-alcohol provided by the invention, comprises the following steps:
(1) under ultrasonic wave exists, the addition reaction in alkali aqueous solution of acetone and formaldehyde, obtains 4-hydroxy-2-butanone;
(2) under strong acidic ion resin catalyzer exists, 4-hydroxy-2-butanone and isobutene reaction obtain intermediate 1;
(3) intermediate 1 and methylenation reagents react, and obtain intermediate 2;
(4) under deprotection catalyzer exists, intermediate 2 deprotection reaction, to obtain final product.
Reaction formula is as follows:
Wherein, in step (1), described alkali is selected from NaOH, KOH, Na
2cO
3and K
2cO
3in one or more; The concentration of alkali aqueous solution is 0.1-1mol/L; The mol ratio of formaldehyde, acetone and alkali is 1:(1-5): (0.01-0.1).
Wherein, in step (1), temperature of reaction is 20-30 DEG C, and the reaction times is 15-120min; Ultrasonic frequency is 18-60KHz, and power is 150-480W.
Wherein, in step (2), described strong acidic ion resin catalyzer is selected from one or more in sulfonated styrol resin and perfluorinated sulfonic resin, preferably 001 × 7 (732) Hydrogen, NKC-9, Amberlyst series and Nafion serial in one or more.This strong acidic ion resin catalyzer, filters after the completion of reaction and can reuse; When catalytic efficiency reduces, catalyzer can be soaked in 98% vitriol oil, reflux about 8h at 100 DEG C, filters, cleans, dries and can reuse.
Wherein, in step (2), iso-butylene be (1.1-3) with the mol ratio of formaldehyde: 1, the amount ratio of catalyzer and formaldehyde is 10-100g:1mol; Temperature of reaction is 20-80 DEG C, and the reaction times is 3-10h.
Wherein, in step (2), reaction solvent is alkane, one or more in preferred normal butane, Skellysolve A, normal hexane, sherwood oil and hexanaphthene; The amount ratio of reaction solvent and formaldehyde is (100-1000) mL:1mol.
Wherein, in step (3), described methylenation reagents is Ph
3p=CH
2,
or CH
2(ZnI)
2, preferred CH
2(ZnI).
Wherein, in step (3), the mol ratio of methylenation reagents and formaldehyde is (1-3): 1; Temperature of reaction is 0-80 DEG C, and the reaction times is 20-120min.
Wherein, in step (3), reaction solvent is selected from one or more in ether, THF, dioxane and methyl tertiary butyl ether; The amount ratio of reaction solvent and formaldehyde is (100-500) mL:1mol.
Wherein, in step (4), described deprotection catalyzer is selected from one or more in the metal chloride of IIIB subgroup and IVB subgroup, preferred ScCl
3, YCl
3, LuCl
3, CeCl
3, LaCl
3, NdCl
3, PrCl
3, SmCl
3and TiCl
4in one or more.
Wherein, in step (4), the mol ratio of deprotection catalyzer and formaldehyde is (1-3): 1; Temperature of reaction is 0-50 DEG C, and the reaction times is 1-60min.
Wherein, in step (4), reaction solvent is selected from CH
2cl
2, CHCl
3, CCl
4and CH
3one or more in CN; The amount ratio of reaction solvent and formaldehyde is (100-1000) mL:1mol.
Beneficial effect: preparation method's technique of 3-methyl-3-butene-1-alcohol provided by the invention is simple, with low cost, by product is few, selectivity good, yield is high.
Specifically, the present invention has following outstanding advantage relative to prior art:
(1) existing aldehyde ketone addition reaction usually after the reaction product easily further dehydration generate beta-unsaturated ketone, cause separation difficulty; And the aldehyde ketone addition reaction in step of the present invention (1) completes under ultrasonic wave exists in conjunction with basic catalyst, in aqueous phase, complete the addition reaction of aldehyde ketone, avoid the problem easily occurring beta-unsaturated ketone in existing aldehyde ketone addition process.
(2) the present invention adopts is that the method for ether is protected hydroxyl by conversion of hydroxyl, can effectively play a protective role, and reaction conditions is gentle.
Embodiment
Describe the present invention in detail below by example, these examples are only illustrative, and do not represent the restriction scope of application of the present invention, in embodiment, medicine used or reagent all can be bought by usual channel.Utilize the purity of GC to target alcohol to characterize in embodiment, utilize the water ratio of the Karl_Fischer method in GB/T606-2003 to sample to measure, utilize NMR to characterize target alcohol.
Embodiment 1
By the NaOH (being mixed with the aqueous solution of 0.1mol/L) of 1mol formaldehyde, 1mol acetone, 0.01mol, join with in churned mechanically single port flask, then be positioned over by flask in thermostatic ultrasonic instrument, ultrasonic apparatus frequency is 18KHz, power is 150w, 20 DEG C of reaction 120min.After reaction terminates, system is neutralized to neutrality, transfers to rectification under vacuum in decompression rectification device, collect boiling point at the cut of 70-71 DEG C (1.6KPa), be 4-hydroxy-2-butanone.
Join in the there-necked flask with mechanical stirring, reflux condensate device, thermometer by 4-hydroxy-2-butanone, iso-butylene 2mol, NKC-9 sulfonate resin 20g, normal hexane 200mL, hierarchy of control temperature is 50 DEG C, the reaction times is 4h.After reaction terminates, filtering recovering catalyst, filtrate uses sodium carbonate neutralization filtrate to neutral, proceeds to rectification under vacuum, collects boiling point at the cut of 73-76 DEG C (1.6KPa), is intermediate 1.
By intermediate 1,1molCH
2(ZnI)
2, 200mL ether joins with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 0 DEG C of reaction 120min.After reaction terminates, with extremely neutral with system in the HCl of 1mol/L, proceed to vacuum distillation apparatus, collect boiling point at the cut of 45-48 DEG C (1.6KPa), be intermediate 2.
By intermediate 2,1molYCl
3, 100mLCH
2cl
2join with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 20 DEG C of reaction 10min.After reaction terminates, first at room temperature vacuum rotary steam, then filters out deprotection catalyzer under nitrogen protection; filtrate is proceeded to decompression rectification device, collects boiling point at the cut of 35-38 DEG C (1.6KPa), obtain 62.18g3-methyl-3-butene-1-alcohol; productive rate 72.3%
Test purity more than 99% through GC, the water ratio <0.5% utilizing Karl_Fischer method to test, is characterized by 3-methyl-3-butene-1-alcohol through nuclear-magnetism.
1HNMR(400MHz,CDCl
3):δ1.75(s,3H,-CH
3),2.15(s,1H,-OH),2.27-2.30(t,2H,J=5.0Hz，-CH
2-),3.69-3.72(t,J=5.1Hz，2H,-CH
2-),4.82(d,J=30.3Hz,2H,CH
2=).
Embodiment 2
By the KOH (being mixed with the aqueous solution of 0.5mol/L) of 1mol formaldehyde, 3mol acetone, 0.02mol, join with in churned mechanically single port flask, then be positioned over by flask in thermostatic ultrasonic instrument, ultrasonic apparatus frequency is 60KHz, power is 480w, 30 DEG C of reaction 15min.After reaction terminates, system is neutralized to neutrality, transfers to rectification under vacuum in decompression rectification device, collect boiling point at the cut of 70-71 DEG C (1.6KPa), be 4-hydroxy-2-butanone.
Join in the there-necked flask with mechanical stirring, reflux condensate device, thermometer by 4-hydroxy-2-butanone, iso-butylene 1.1mol, Amberlyst15 sulfonate resin 50g, normal hexane 500mL, hierarchy of control temperature is 60 DEG C, the reaction times is 6h.After reaction terminates, filtering recovering catalyst, filtrate uses sodium carbonate neutralization filtrate to neutral, proceeds to rectification under vacuum, collects boiling point at the cut of 73-76 DEG C (1.6KPa), is intermediate 1.
By intermediate 1,1.5molCH
2(ZnI)
2, 400mLTHF joins with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 50 DEG C of reaction 20min.After reaction terminates, with the NH of 1mol/L
4extremely neutral with system in Cl, proceed to vacuum distillation apparatus, collect boiling point at the cut of 45-48 DEG C (1.6KPa), be intermediate 2.
By intermediate 2,1.5molTiCl
4, 500mLCHCl
3join with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 30 DEG C of reaction 20min.After reaction terminates, first at room temperature vacuum rotary steam, then filters out deprotection catalyzer under nitrogen protection; filtrate is proceeded to decompression rectification device, collects boiling point at the cut of 35-38 DEG C (1.6KPa), obtain 70.09g3-methyl-3-butene-1-alcohol; productive rate 81.5%
Test purity more than 99% through GC, the water ratio <0.5% utilizing Karl_Fischer method to test, is characterized by 3-methyl-3-butene-1-alcohol through nuclear-magnetism.
Embodiment 3
By the Na of 1mol formaldehyde, 4mol acetone, 0.10mol
2cO
3(being mixed with the aqueous solution of 1mol/L), join with in churned mechanically single port flask, be then positioned over by flask in thermostatic ultrasonic instrument, ultrasonic apparatus frequency is 45KHz, power is 360w, 25 DEG C of reaction 60min.After reaction terminates, system is neutralized to neutrality, transfers to rectification under vacuum in decompression rectification device, collect boiling point at the cut of 70-71 DEG C (1.6KPa), be 4-hydroxy-2-butanone.
Join in the there-necked flask with mechanical stirring, reflux condensate device, thermometer by 4-hydroxy-2-butanone, iso-butylene 3mol, 001 × 7 (732) Hydrogen sulfonate resin 70g, hexanaphthene 500mL, hierarchy of control temperature is 80 DEG C, the reaction times is 8h.After reaction terminates, filtering recovering catalyst, filtrate uses sodium carbonate neutralization filtrate to neutral, proceeds to rectification under vacuum, collects boiling point at the cut of 73-76 DEG C (1.6KPa), is intermediate 1.
By intermediate 1,2molCH
2(ZnI)
2, 300mL dioxane joins with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 50 DEG C of reaction 60min.After reaction terminates, with the NH of 1mol/L
4extremely neutral with system in Cl, proceed to vacuum distillation apparatus, collect boiling point at the cut of 45-48 DEG C (1.6KPa), be intermediate 2.
By intermediate 2,3molCeCl
3, 700mLCH
3cN joins with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 40 DEG C of reaction 40min.After reaction terminates, first at room temperature vacuum rotary steam, then filters out deprotection catalyzer under nitrogen protection; filtrate is proceeded to decompression rectification device, collects boiling point at the cut of 35-38 DEG C (1.6KPa), obtain 70.78g3-methyl-3-butene-1-alcohol; productive rate 82.3%
Test purity more than 99% through GC, the water ratio <0.5% utilizing Karl_Fischer method to test, is characterized by 3-methyl-3-butene-1-alcohol through nuclear-magnetism.
Embodiment 4
By the K of 1mol formaldehyde, 4mol acetone, 0.05mol
2cO
3(being mixed with the aqueous solution of 0.2mol/L), join with in churned mechanically single port flask, be then positioned over by flask in thermostatic ultrasonic instrument, ultrasonic apparatus frequency is 25KHz, power is 260w, 25 DEG C of reaction 100min.After reaction terminates, system is neutralized to neutrality, transfers to rectification under vacuum in decompression rectification device, collect boiling point at the cut of 70-71 DEG C (1.6KPa), be 4-hydroxy-2-butanone.
Join in the there-necked flask with mechanical stirring, reflux condensate device, thermometer by 4-hydroxy-2-butanone, iso-butylene 1.5mol, NafionNR50 resin 90g, normal heptane 800mL, hierarchy of control temperature is 70 DEG C, the reaction times is 10h.After reaction terminates, filtering recovering catalyst, filtrate uses sodium carbonate neutralization filtrate to neutral, proceeds to rectification under vacuum, collects boiling point at the cut of 73-76 DEG C (1.6KPa), is intermediate 1.
By intermediate 1,3molCH
2(ZnI)
2, 500mL methyl tertiary butyl ether joins with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 80 DEG C of reaction 100min.After reaction terminates, with the NH of 1mol/L
4extremely neutral with system in Cl, proceed to vacuum distillation apparatus, collect boiling point at the cut of 45-48 DEG C (1.6KPa), be intermediate 2.
By intermediate 2,2molScCl
3, 800mLCCl
4join with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 45 DEG C of reaction 30min.After reaction terminates, first at room temperature vacuum rotary steam, then filters out deprotection catalyzer under nitrogen protection; filtrate is proceeded to decompression rectification device, collects boiling point at the cut of 35-38 DEG C (1.6KPa), obtain 3-methyl-3-butene-1-alcohol; productive rate 80.3%
Test purity more than 99% through GC, the water ratio <0.5% utilizing Karl_Fischer method to test, is characterized by 3-methyl-3-butene-1-alcohol through nuclear-magnetism.
Embodiment 5
By the Na of 1mol formaldehyde, 4mol acetone, 0.08mol
2cO
3(being mixed with the aqueous solution of 0.4mol/L), join with in churned mechanically single port flask, be then positioned over by flask in thermostatic ultrasonic instrument, ultrasonic apparatus frequency is 18KHz, power is 160w, 25 DEG C of reaction 120min.After reaction terminates, system is neutralized to neutrality, transfers to rectification under vacuum in decompression rectification device, collect boiling point at the cut of 70-71 DEG C (1.6KPa), be 4-hydroxy-2-butanone.
Join in the there-necked flask with mechanical stirring, reflux condensate device, thermometer by 4-hydroxy-2-butanone, iso-butylene 2.5mol, NafionSAC-13 resin 70g, normal butane 500mL, hierarchy of control temperature is 40 DEG C, the reaction times is 8h.After reaction terminates, filtering recovering catalyst, filtrate uses sodium carbonate neutralization filtrate to neutral, proceeds to rectification under vacuum, collects boiling point at the cut of 73-76 DEG C (1.6KPa), is intermediate 1.
By intermediate 1,2.5molCH
2(ZnI)
2, 100mLTHF joins with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 70 DEG C of reaction 110min.After reaction terminates, with the NH of 1mol/L
4extremely neutral with system in Cl, proceed to vacuum distillation apparatus, collect boiling point at the cut of 45-48 DEG C (1.6KPa), be intermediate 2.
By intermediate 2,1.5molNdCl
3, 600mLCH
2cl
2join with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 10 DEG C of reaction 20min.After reaction terminates, first at room temperature vacuum rotary steam, then filters out deprotection catalyzer under nitrogen protection; filtrate is proceeded to decompression rectification device, collects boiling point at the cut of 35-38 DEG C (1.6KPa), obtain 3-methyl-3-butene-1-alcohol; productive rate 74.2%
Test purity more than 99% through GC, the water ratio <0.5% utilizing Karl_Fischer method to test, is characterized by 3-methyl-3-butene-1-alcohol through nuclear-magnetism.
Embodiment 6
By the K of 1mol formaldehyde, 4mol acetone, 0.01mol
2cO
3(being mixed with the aqueous solution of 0.8mol/L), join with in churned mechanically single port flask, be then positioned over by flask in thermostatic ultrasonic instrument, ultrasonic apparatus frequency is 30KHz, power is 280w, 25 DEG C of reaction 30min.After reaction terminates, system is neutralized to neutrality, transfers to rectification under vacuum in decompression rectification device, collect boiling point at the cut of 70-71 DEG C (1.6KPa), be 4-hydroxy-2-butanone.
Join in the there-necked flask with mechanical stirring, reflux condensate device, thermometer by 4-hydroxy-2-butanone, iso-butylene 1.3mol, 001 × 7 (732) Hydrogen sulfonate resin 90g, Skellysolve A 400mL, hierarchy of control temperature is 60 DEG C, the reaction times is 3h.After reaction terminates, filtering recovering catalyst, filtrate uses sodium carbonate neutralization filtrate to neutral, proceeds to rectification under vacuum, collects boiling point at the cut of 73-76 DEG C (1.6KPa), is intermediate 1.
By intermediate 1,1.1molCH
2(ZnI)
2, 300mL dioxane joins with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 50 DEG C of reaction 60min.After reaction terminates, with the NH of 1mol/L
4extremely neutral with system in Cl, proceed to vacuum distillation apparatus, collect boiling point at the cut of 45-48 DEG C (1.6KPa), be intermediate 2.
By intermediate 2,1.1molLuCl
3, 700mLCHCl
3join with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 0 DEG C of reaction 60min.After reaction terminates, first at room temperature vacuum rotary steam, then filters out deprotection catalyzer under nitrogen protection; filtrate is proceeded to decompression rectification device, collects boiling point at the cut of 35-38 DEG C (1.6KPa), obtain 3-methyl-3-butene-1-alcohol; productive rate 78.9%
Test purity more than 99% through GC, the water ratio <0.5% utilizing Karl_Fischer method to test, is characterized by 3-methyl-3-butene-1-alcohol through nuclear-magnetism.
Embodiment 7
By the KOH (being mixed with the aqueous solution of 0.4mol/L) of 1mol formaldehyde, 4mol acetone, 0.02mol, join with in churned mechanically single port flask, then be positioned over by flask in thermostatic ultrasonic instrument, ultrasonic apparatus frequency is 20KHz, power is 220w, 25 DEG C of reaction 30min.After reaction terminates, system is neutralized to neutrality, transfers to rectification under vacuum in decompression rectification device, collect boiling point at the cut of 70-71 DEG C (1.6KPa), be 4-hydroxy-2-butanone.
Join in the there-necked flask with mechanical stirring, reflux condensate device, thermometer by 4-hydroxy-2-butanone, iso-butylene 1.8mol, NKC-9 resin 10g, sherwood oil 100mL, hierarchy of control temperature is 60 DEG C, the reaction times is 5h.After reaction terminates, filtering recovering catalyst, filtrate uses sodium carbonate neutralization filtrate to neutral, proceeds to rectification under vacuum, collects boiling point at the cut of 73-76 DEG C (1.6KPa), is intermediate 1.
By intermediate 1,2.8molCH
2(ZnI)
2, 400mLTHF joins with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 70 DEG C of reaction 30min.After reaction terminates, with the NH of 1mol/L
4extremely neutral with system in Cl, proceed to vacuum distillation apparatus, collect boiling point at the cut of 45-48 DEG C (1.6KPa), be intermediate 2.
By intermediate 2,1.3molPrCl
3, 700mLCH
3cN joins with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 40 DEG C of reaction 10min.After reaction terminates, first at room temperature vacuum rotary steam, then filters out deprotection catalyzer under nitrogen protection; filtrate is proceeded to decompression rectification device, collects boiling point at the cut of 35-38 DEG C (1.6KPa), obtain 3-methyl-3-butene-1-alcohol; productive rate 71.1%
Test purity more than 99% through GC, the water ratio <0.5% utilizing Karl_Fischer method to test, is characterized by 3-methyl-3-butene-1-alcohol through nuclear-magnetism.
Embodiment 8
By the NaOH (being mixed with the aqueous solution of 0.6mol/L) of 1mol formaldehyde, 5mol acetone, 0.007mol, join with in churned mechanically single port flask, then be positioned over by flask in thermostatic ultrasonic instrument, ultrasonic apparatus frequency is 50KHz, power is 440w, 25 DEG C of reaction 15min.After reaction terminates, system is neutralized to neutrality, transfers to rectification under vacuum in decompression rectification device, collect boiling point at the cut of 70-71 DEG C (1.6KPa), be 4-hydroxy-2-butanone.
Join in the there-necked flask with mechanical stirring, reflux condensate device, thermometer by 4-hydroxy-2-butanone, iso-butylene 1.1mol, Amberlyst15 resin 100g, hexanaphthene 1000mL, hierarchy of control temperature is 80 DEG C, the reaction times is 4h.After reaction terminates, filtering recovering catalyst, filtrate uses sodium carbonate neutralization filtrate to neutral, proceeds to rectification under vacuum, collects boiling point at the cut of 73-76 DEG C (1.6KPa), is intermediate 1.
By intermediate 1,1.5molCH
2(ZnI)
2, 500mL ether joins with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 40 DEG C of reaction 50min.After reaction terminates, with the NH of 1mol/L
4extremely neutral with system in Cl, proceed to vacuum distillation apparatus, collect boiling point at the cut of 45-48 DEG C (1.6KPa), be intermediate 2.
By intermediate 2,3molSmCl
3, 1000mLCH
2cl
2join with N
2in the four-hole bottle of protection, mechanical stirring, condensing reflux, thermometer, 50 DEG C of reaction 10min.After reaction terminates, first at room temperature vacuum rotary steam, then filters out deprotection catalyzer under nitrogen protection; filtrate is proceeded to decompression rectification device, collects boiling point at the cut of 35-38 DEG C (1.6KPa), obtain 3-methyl-3-butene-1-alcohol; productive rate 82.4%
Test purity more than 99% through GC, the water ratio <0.5% utilizing Karl_Fischer method to test, is characterized by 3-methyl-3-butene-1-alcohol through nuclear-magnetism.
Embodiment 9
Substantially the same manner as Example 8, difference is only: adopt LaCl
3substitute SmCl
3.Productive rate 79.5%.
Embodiment 10
Substantially the same manner as Example 8, difference is only: adopt Ph
3p=CH
2substitute CH
2(ZnI)
2.Productive rate 80.1%.
Embodiment 11
Substantially the same manner as Example 8, difference is only: adopt
substitute CH
2(ZnI)
2.Productive rate 77.5%.
Embodiment 12
Substantially the same manner as Example 8, difference is only: adopt
substitute CH
2(ZnI)
2.Productive rate 82.0%.
Embodiment 13
Substantially the same manner as Example 8, difference is only: adopt
substitute CH
2(ZnI)
2.Productive rate 76.1%.
Claims (7)
1. a preparation method for 3-methyl-3-butene-1-alcohol, is characterized in that: comprise the following steps:
(1) under ultrasonic wave exists, the addition reaction in alkali aqueous solution of acetone and formaldehyde, obtains 4-hydroxy-2-butanone;
(2) under strong acidic ion resin catalyzer exists, 4-hydroxy-2-butanone and isobutene reaction obtain intermediate 1; Described strong acidic ion resin catalyzer is selected from one or more in sulfonated styrol resin and perfluorinated sulfonic resin;
(3) intermediate 1 and methylenation reagents react, and obtain intermediate 2; Described methylenation reagents is Ph
3p=CH
2,
or CH
2(ZnI)
2;
(4) under deprotection catalyzer exists, intermediate 2 deprotection reaction, to obtain final product.
2. the preparation method of a kind of 3-methyl-3-butene-1-alcohol according to claim 1, is characterized in that: in step (1), described alkali is selected from NaOH, KOH, Na
2cO
3and K
2cO
3in one or more; The concentration of alkali aqueous solution is 0.1-1mol/L; The mol ratio of formaldehyde, acetone and alkali is 1:(1-5): (0.01-0.1).
3. the preparation method of a kind of 3-methyl-3-butene-1-alcohol according to claim 1, it is characterized in that: in step (1), temperature of reaction is 20-30 DEG C, and the reaction times is 15-120min; Ultrasonic frequency is 18-60KHz, and power is 150-480W.
4. the preparation method of a kind of 3-methyl-3-butene-1-alcohol according to claim 1, it is characterized in that: in step (2), iso-butylene be (1.1-3) with the mol ratio of formaldehyde: 1, the amount ratio of catalyzer and formaldehyde is 10-100g:1mol; Temperature of reaction is 20-80 DEG C, and the reaction times is 3-10h.
5. the preparation method of a kind of 3-methyl-3-butene-1-alcohol according to claim 1, is characterized in that: in step (3), the mol ratio of methylenation reagents and formaldehyde is (1-3): 1; Temperature of reaction is 0-80 DEG C, and the reaction times is 20-120min.
6. the preparation method of a kind of 3-methyl-3-butene-1-alcohol according to claim 1, it is characterized in that: in step (4), described deprotection catalyzer is selected from one or more in the metal chloride of IIIB subgroup and IVB subgroup.
7. the preparation method of a kind of 3-methyl-3-butene-1-alcohol according to claim 1, is characterized in that: in step (4), the mol ratio of deprotection catalyzer and formaldehyde is (1-3): 1; Temperature of reaction is 0-50 DEG C, and the reaction times is 1-60min.
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