CN107827733A - A kind of preparation method of cyclenes yl carboxylic acid - Google Patents
A kind of preparation method of cyclenes yl carboxylic acid Download PDFInfo
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- CN107827733A CN107827733A CN201711136784.0A CN201711136784A CN107827733A CN 107827733 A CN107827733 A CN 107827733A CN 201711136784 A CN201711136784 A CN 201711136784A CN 107827733 A CN107827733 A CN 107827733A
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- cyclenes
- carboxylic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of cyclenes yl carboxylic acid, the preparation method of the cyclenes yl carboxylic acid shown in described molecular formula I includes：In pressure vessel, using aqueous phase as solvent, 1.0 ~ 5.0MPa of nitrogen pressurization gauge pressure inert environments, under conditions of 120 ~ 300 DEG C, as the insatiable hunger aliphatic acid and 1 shown in molecular formula II, 3 butadiene carry out polymerisation 1 ~ 3 hour, then Synthesis liquid immigration rectifying still is subjected to rectifying under conditions of negative pressure, obtain the cyclenes yl carboxylic acid shown in molecular formula I, generally, the present invention has reaction speed fast, reaction time is short, reacted in aqueous phase, it is easy to purify cyclenes yl carboxylic acid, it is simple to operate, continuous production can be carried out, effectively improve product quality, the advantages of with high use value.
Description
Technical field
The invention belongs to chemicals to synthesize field, is related to a kind of preparation method of cyclenes yl carboxylic acid.
Background technology
Cyclohexenyl group carboxylic acid is important industrial chemicals and medicine intermediate, if cyclohexenyl group formic acid is synthesis clotting factor
The initiation material of Xa inhibitor.Diels-Alder reaction is a kind of organic reaction, double using conjugated diene and substituted olefine
The synthetically prepared substitution hexatomic ring of alkene（Cyclohexene）Compound, it is widely used in the synthesis, separation, discriminating of organic compound.Profit
Preparing cyclic olefins with Diels-Alder reaction has a high conversion rate, and selectivity is strong, the features such as stereocpecificity.Close
It is numerous in the domestic and international patent report of diene synthesis reaction prepare compound.For example, CN104693016A, isoprene and propylene
The method that aldehyde prepares p-tolyl aldehyde；The synthetic method of CN101570460 carbocyclic compounds；A kind of ethene of CN105585413A
The synthetic method of base ENB；JP2001348345 Method for Producing Diels-Alder reaction
Product reports the method by cyclopentadiene and ethylene synthase ENB；United States Patent
No.5.095.082； Sjardijnet,al.US.4.810.752；United states Patent 3671551.Report
Addition reaction of laurene epoxides and methacrylaldehyde etc., existing report use high pressure or anti-in Louis acid catalysis low temperature more
Should, common drawback is that the reaction time is longer, using organic solvent, follow-up refined complicated more difficult serialization.The purpose of the present invention is just
It is to overcome above-mentioned technological deficiency and provide a kind of preparation method of cyclenes yl carboxylic acid.
The content of the invention
It is an object of the invention to provide a kind of preparation method of cyclenes yl carboxylic acid, reaction speed is fast, and reaction time is short,
Reacted in aqueous phase, be easy to purify cyclenes yl carboxylic acid, it is simple to operate, continuous production can be carried out, is effectively carried
High yield quality, there is high use value.
The object of the present invention is achieved like this：A kind of preparation method of cyclenes yl carboxylic acid, shown in described molecular formula I
The preparation method of cyclenes yl carboxylic acid includes：In pressure vessel, using aqueous phase as solvent, 1.0 ~ 5.0MPa's of nitrogen pressurization gauge pressure is lazy
Property environment, under conditions of 120 ~ 300 DEG C, as the insatiable hunger aliphatic acid and 1 shown in molecular formula II, 3 butadiene carry out polymerisation 1 ~ 3
Hour, Synthesis liquid immigration rectifying still is then subjected to rectifying under conditions of negative pressure, obtains the cyclenes yl carboxylic acid shown in molecular formula I
Ⅰ
Ⅱ
It is the alkyl containing 1 ~ 3 carbon that formula I, which neutralizes R1 in formula II,.
Conduction oil or fused salt chuck are provided with described pressure vessel.
Described pressure vessel is two-part tubular reactor of the caliber with elevated pressures in 0.5 ~ 10mm.
Described pressure vessel is the autoclave for being built-in with cooling coil.
Mixer is provided with autoclave, described mixer rotating speed is 400 ~ 3000r/min.
Described rectifying still theoretical cam curve is 25 ~ 50 pieces.
Polymerization inhibitor is added with described unrighted acid, described polymerization inhibitor is hydroquinones.
Pressure in described rectifying still is 0.01 ~ 0.1Mpa of absolute pressure.
The mass ratio of insatiable hunger aliphatic acid shown in described water and molecular formula II is 0.5 ~ 10:1,1,3 butadiene and molecule
The mol ratio of insatiable hunger aliphatic acid shown in formula II is 1.05 ~ 2.05:1.
Insatiable hunger content of fatty acid >=97% shown in described molecular formula II, described 1,3 butadiene content >=99%.
The beneficial effect comprise that：Using aqueous phase as solvent, reaction progress is rapid in aqueous phase and selects
Selecting property is high, reduces side reaction, maintains system to have higher pressure using nitrogen, makes 1 in gas phase, 3 butadiene concentrations
Relatively low level is maintained, is advantageous to improve the selectivity of reaction, and can effectively reduce the shape of the peroxide of 1.3 butadiene
Into, and then implode caused by the end-group polymer of maximum suppression butadiene, reaction is quickly carried out at relatively high temperatures and have higher
Conversion ratio, reduce the autohemagglutination of butadiene, using and reacting for aqueous phase solvent carries out rapidly under higher temperature pressure, make do not having
There is catalyst（Lewis acid）Under conditions of still show higher regioselectivity, to Synthesis liquid carry out rectifying, separation simultaneously
Cyclenes yl carboxylic acid is purified, the industrial production of serialization can be realized.
Generally, the present invention is fast with reaction speed, and reaction time is short, is reacted in aqueous phase, is easy to cycloalkenyl group
Carboxylic acid is purified, simple to operate, can be carried out continuous production, be effectively improved product quality, and valency is used with high
The advantages of value.
Embodiment
In specific implementation, unsaturated carboxylic acid conversion ratio is defined as：
×100%
×100%
Below to embodiments of the invention further instruction.
Embodiment 1 to 4 uses pressure autoclave type reactor
Unsaturated carboxylic acid is by taking acrylic acid as an example, reaction generation product 3- cyclohexene -1- formic acid.2- butenoic acids, 2- penetenoic acids etc. are no
Saturated carboxylic acid reaction refers to embodiment parameter.
Reaction equation is as follows：
React and carried out in the stainless steel pressure kettle for being equipped with high-speed stirred and cooling coil, chuck heat-conducting oil heating, coil pipe is with cooling
Water.Reactor adds the deionized water that will be prepared in proportion after negative pressure, and acrylic acid and hydroquinones add reactor, import nitrogen and protect
Gauge pressure 0.5MPa pressure-activated stirring is held, rotating speed is in 800-1200r/min.Conduction oil is warming up to temperature of charge to 130-180
DEG C, 1.3 butadiene are at the uniform velocity pressed into nitrogen, by adjusting charging rate and coil pipe cooling water maintenance reaction temperature in 150-260
℃.Cool after reaction 1-2.5 hours, reaction pressure gauge pressure 1.5MPa-3.5MPa sampling analyses, sample analysis uses gas-chromatography
Method（Continuous production is such as realized, two reactors can be connected and reaction time, reaction ginseng are controlled according to kettle volume and feed rate
Number refers to following pipe reaction example）.Material is pressed into rectifying tower reactor afterwards, about 30 pieces of tower reactor theoretical cam curve, passes through double tower point
Light component is not sloughed, purifies finished product.Negative pressure is kept in absolute pressure 100Pa-10kPa, reflux ratio 4-7, sampling analysis after purification,
Analysis uses gas chromatography.Obtain cyclohexene carboxylate content >=99%.
Embodiment 5 to 8 uses two-part tubular reactor
Reactant unsaturated carboxylic acid is by taking acrylic acid as an example, reaction generation product 3- cyclohexene -1- formic acid.2- butenoic acids, 2- amylenes
The reaction of the unsaturated carboxylic acids such as acid refers to embodiment parameter.
By acrylic acid and water in proportion in batching kettle（In advance through nitrogen displacement）Mixing, then by the material mixed with
The tubular type that 1.3- butadiene inputs the caliber 0.5-10mm to heat up through nitrogen displacement and via conduction oil with high-pressure pump respectively is anti-
Device is answered, first stage reactor temperature control is at 120 ~ 180 DEG C, and second stage reactor temperature control is at 160 ~ 260 DEG C.By feed rate control
Reaction time processed.Reaction time was controlled at 1 ~ 2.5 hour.Reacting rear material uses gas-chromatography through cooling down sampling analysis, analysis
Method.Material refines through two sections of rectifying stills（Rectifying condition is the same as embodiment 1 ~ 4）Arrive finished product content >=99%.（Front in reaction temperature
For the temperature of first paragraph tubular reactor, back is the temperature of second segment tubular reactor）
Generally, the present invention is fast with reaction speed, and reaction time is short, is reacted in aqueous phase, is easy to cyclenes yl carboxylic acid
Purified, it is simple to operate, continuous production can be carried out, effectively improves product quality, there is high use value
Advantage.
Claims (10)
- A kind of 1. preparation method of cyclenes yl carboxylic acid, it is characterised in that：The preparation of cyclenes yl carboxylic acid shown in described molecular formula I Method includes：In pressure vessel, in aqueous phase, 1.0 ~ 5.0MPa of nitrogen pressurization gauge pressure inert environments, 120 ~ 300 DEG C of condition Under, as the insatiable hunger aliphatic acid and 1 shown in molecular formula II, 3 butadiene carry out polymerisation 1 ~ 3 hour, then move into Synthesis liquid Rectifying still carries out rectifying under conditions of negative pressure, obtains the cyclenes yl carboxylic acid shown in molecular formula IⅠⅡIt is the alkyl containing 1 ~ 3 carbon that formula I, which neutralizes R1 in formula II,.
- A kind of 2. preparation method of cyclenes yl carboxylic acid according to claim 1, it is characterised in that：On described pressure vessel It is provided with conduction oil or fused salt chuck.
- A kind of 3. preparation method of cyclenes yl carboxylic acid according to claim 1 or 2, it is characterised in that：Described pressure is held Device is two-part tubular reactor of the caliber with elevated pressures in 0.5 ~ 10mm.
- A kind of 4. preparation method of cyclenes yl carboxylic acid according to claim 1 or 2, it is characterised in that：Described pressure is held Device is the autoclave for being built-in with cooling coil.
- A kind of 5. preparation method of cyclenes yl carboxylic acid according to claim 1 or 2, it is characterised in that：Set in autoclave There is mixer, described mixer rotating speed is 400 ~ 3000r/min.
- A kind of 6. preparation method of cyclenes yl carboxylic acid according to claim 1, it is characterised in that：Described rectifying still is theoretical The number of plates is 25 ~ 50 pieces.
- A kind of 7. preparation method of cyclenes yl carboxylic acid according to claim 1, it is characterised in that：Described unsaturated fat Polymerization inhibitor is added with acid, described polymerization inhibitor is hydroquinones.
- A kind of 8. preparation method of cyclenes yl carboxylic acid according to claim 1, it is characterised in that：In described rectifying still Pressure is 0.01 ~ 0.1Mpa of absolute pressure.
- A kind of 9. preparation method of cyclenes yl carboxylic acid according to claim 1, it is characterised in that：Described water and molecular formula The mass ratio of insatiable hunger aliphatic acid shown in II is 0.5 ~ 10:Insatiable hunger aliphatic acid shown in 1,1,3 butadiene and molecular formula II rubs You are than being 1.05 ~ 2.05:1.
- A kind of 10. preparation method of cyclenes yl carboxylic acid according to claim 1, it is characterised in that：Described molecular formula II Shown insatiable hunger content of fatty acid >=97%, described 1,3 butadiene content >=99%.
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| CN201711136784.0A CN107827733A (en) | 2017-11-16 | 2017-11-16 | A kind of preparation method of cyclenes yl carboxylic acid |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4810752A (en) * | 1987-09-24 | 1989-03-07 | The West Company | Halobutyl thermoplastic elastomer |
| US20040073068A1 (en) * | 2002-09-27 | 2004-04-15 | Korea Kumho Petrochemical Co., Ltd. | Method for preparing cyclohexyl phenyl ketone from 1,3- butadiene and acrylic acid |
-
2017
- 2017-11-16 CN CN201711136784.0A patent/CN107827733A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4810752A (en) * | 1987-09-24 | 1989-03-07 | The West Company | Halobutyl thermoplastic elastomer |
| US20040073068A1 (en) * | 2002-09-27 | 2004-04-15 | Korea Kumho Petrochemical Co., Ltd. | Method for preparing cyclohexyl phenyl ketone from 1,3- butadiene and acrylic acid |
Non-Patent Citations (1)
| Title |
|---|
| 李长多等: "溶剂对Diels-Alder 反应的影响", 《化工技术与开发》 * |
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Inventor after: Wang Shusheng Inventor after: Sun Weihua Inventor after: Chen Quansheng Inventor after: Li Debiao Inventor after: Han Zhiqiang Inventor before: Wang Shusheng Inventor before: Sun Weihua Inventor before: Chen Quansheng Inventor before: Li Debiao |