CN103524479A - Preparation method of 2-alkyl-4,7-dihydro-1,3-2-propyl-1,3-dioxocyclo-5-pentene - Google Patents
Preparation method of 2-alkyl-4,7-dihydro-1,3-2-propyl-1,3-dioxocyclo-5-pentene Download PDFInfo
- Publication number
- CN103524479A CN103524479A CN201210233697.8A CN201210233697A CN103524479A CN 103524479 A CN103524479 A CN 103524479A CN 201210233697 A CN201210233697 A CN 201210233697A CN 103524479 A CN103524479 A CN 103524479A
- Authority
- CN
- China
- Prior art keywords
- preparation
- dihydro
- exchange resin
- alkyl
- cation exchange
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
- C07D321/02—Seven-membered rings
- C07D321/04—Seven-membered rings not condensed with other rings
- C07D321/06—1,3-Dioxepines; Hydrogenated 1,3-dioxepines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of 2-alkyl-4,7-dihydro-1,3-2-propyl-1,3-dioxocyclo-5-pentene. The preparation method comprises the following steps: (1) in the presence of a water-carrying agent and hydrogen-type cation exchange resin, performing heating reflux on aldehyde with a general formula of RCHO and cis-dibutene-1,4-diol to obtain a mixture containing a compound as shown by a formula I, wherein R is alkyl of C2-C4; and (2) performing solid-liquid separation on the mixture obtained in the step (1), and distilling the obtained liquid phase to separate out the 2-alkyl-4,7-dihydro-1,3-2-propyl-1,3-dioxocyclo-5-pentene. According to the preparation method disclosed by the invention, the hydrogen-type cation exchange resin is adopted as a catalyst, so that side reactions are reduced, the yield of the 2-alkyl-4,7-dihydro-1,3-2-propyl-1,3-dioxocyclo-5-pentene product is increased, the process is simplified, acid wastewater can not be generated, and the preparation method is environment-friendly. Besides, the water-carrying agent with low toxicity is preferably adopted, so that harms to the health of operators are reduced.
Description
Technical field
The present invention relates to a kind of vitamins B
6the preparation method of synthetic intermediate, particularly, relates to a kind of 2-alkyl-4,7-dihydro-1, the preparation method of 3 dioxy seven rings.
Background technology
Vitamins B
6to maintain the essential class low-molecular-weight organic compound of HUMAN HEALTH.Its participates in the metabolism of body amino acid and protein, has and maintains growing and regulating the effect of various physiological functions of human normal.Vitamins B
6can maintain the balance of sodium, potassium in body, regulate body fluid, participate in manufacturing red corpuscle.Therefore, vitamins B
6be used as treatment human body and animal vitamins B
6the assisting therapy of deficiency disease or other diseases.
At present, the production of vitamin B6 adopts “ oxazole method conventionally " be prepared, basic reactions steps is Diels-Alder addition, aromizing, hydrolysis.2-alkyl-4,7-dihydro-1,3-dioxy seven ring Shi “ oxazole methods " one of important intermediate.
2-alkyl-4,7-dihydro-1, traditional preparation method of 3-dioxy seven rings forms by aldehyde compound and the condensation of cis-2-butene-Isosorbide-5-Nitrae glycol, and chemical equation is shown below:
Wherein, the alkyl that R is C2-C4.
In traditional preparation method, using the strong acid such as sulfuric acid, hydrochloric acid, phosphoric acid as catalyzer, product 2-alkyl-4,7-dihydro-1, the yield of 3-dioxy seven rings is lower.In addition, in production process, these catalyzer easily cause side reaction in reaction to occur, and produce burnt shape thing, are unfavorable for production operation.In addition, the use of strong acid is except to equipment heavy corrosion, and in auxiliary processes such as the later stage need to neutralize, otherwise the discharge meeting of waste water is to environment.Moreover, in traditional preparation method, conventionally adopt benzene as band aqua.Benzene is a kind of colourless transparent liquid at normal temperatures, and has strong aromatic odour.Because benzene is poisonous, and it is a kind of carcinogenic substance.A large amount of uses is unfavorable for operator's health and environment protection.
Therefore, product 2-alkyl-4 need to do not affected, 7-dihydro-1, under the condition of the character of 3-dioxy seven rings, its preparation method is made improvements, to overcome, adopt traditional method to prepare 2-alkyl-4,7-dihydro-1, the lower problem of 3-dioxy seven ring product yield will drop to minimum to the pollution of environment simultaneously.
Summary of the invention
The object of the invention is to overcome 2-alkyl-4 prepared by traditional method, 7-dihydro-1, the lower problem of yield of 3-dioxy seven rings, and a kind of vitamins B with higher yields is provided
6synthetic intermediate 2-alkyl-4,7-dihydro-1, the preparation method of 3-dioxy seven rings.
The present inventor finds, use conventional methods preparation 2-alkyl-4,7 dihydro-1, easily there is side reaction and cause the yield of product to decline in 3 dioxy seven rings, infer that reason is: polymerization, molecule inner dewatering reaction easily occur reactant cis-2-butene-Isosorbide-5-Nitrae glycol under the effect of strong acid, and oxidizing reaction also easily occurs aldehyde compound under strong acid condition, therefore, can cause its yield to decline.In addition,, while using strong acid as catalyst, also need after reaction, to acid-bearing wastewater, carry out neutralizing treatment.
To achieve these goals, the invention provides a kind of 2-alkyl-4,7 dihydro-1, the preparation method of 3 dioxy seven rings, the method comprises:
(1) under the condition with aqua and hydrogen type cation exchange resin existence, the aldehyde that is RCHO by general formula and cis-2 butene-1s, 4-glycol carries out reflux, obtains the mixture containing compound shown in formula I, wherein, the alkyl that R is C2-C4;
(2) mixture step (1) being obtained carries out solid-liquid separation, and the liquid phase obtaining is distilled, and with separation, obtains 2-alkyl-4,7 dihydro-1,3 dioxy seven rings.
Preparation method provided by the invention adopts hydrogen type cation exchange resin to make catalyzer, has reduced the generation of side reaction, has improved the yield of product, simplified technique, and because can not produce acid-bearing wastewater, and avoided the neutralizing treatment process to follow-up waste water in traditional method, environmentally friendly.Under preferable case, adopt compound that toxicity is lower as, be selected from one or more in alkane, hexanaphthene, toluene and the sherwood oil of C6-C8 as band aqua, not only be conducive to 2-alkyl-4,7 dihydro-1, the raising of the yield of 3 dioxy seven rings, can also reduce the infringement to operator ' s health, and corrosion-free to equipment.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
According to 2-of the present invention alkyl-4,7 dihydro-1, the preparation method of 3 dioxy seven rings comprises:
(1) under the condition with aqua and hydrogen type cation exchange resin existence, the aldehyde that is RCHO by general formula and cis-2 butene-1s, 4-glycol carries out reflux, obtains the mixture containing compound shown in formula I, wherein, the alkyl that R is C2-C4;
(2) mixture step (1) being obtained carries out solid-liquid separation, and the liquid phase obtaining is distilled, and with separation, obtains 2-alkyl-4,7 dihydro-1,3 dioxy seven rings.
Preparation in accordance with the present invention, general formula is that the aldehyde of RCHO is for the synthesis of compound shown in formula I, wherein, R is the alkyl of C2-C4, particularly, described aldehyde compound is preferably any one in propionic aldehyde, butyraldehyde, isobutyric aldehyde, valeral, 3-methyl butyraldehyde, 2 methyl butyraldehyde and 2,2-dimethyl propionic aldehyde.
Preparation in accordance with the present invention, described hydrogen type cation exchange resin can be various hydrogen type cation exchange resins.The preferred strong acid type hydrogen type cation exchange resin of the present invention.Described strong acid type hydrogen type cation exchange resin can be strong acid type Hydrogen styrene type cation exchange resin and/or strong acid type Hydrogen vinylformic acid Zeo-karb.The preferred described hydrogen type cation exchange resin of the present invention is strong acid type Hydrogen styrene type cation exchange resin.
Preparation in accordance with the present invention, described hydrogen type cation exchange resin can be gel-type ion-exchange resin and/or large hole shape ion exchange resin.The present invention is not particularly limited for the basic resin of described macroreticular ion exchange resin and gel-type ion-exchange resin.In the preferred case, described macroporous type hydrogen type cation exchange resin is polystyrene macroreticular ion exchange resin, and described gel-type hydrogen type cation exchange resin is polystyrene gel-type ion-exchange resin.
Preparation in accordance with the present invention, the ion-exchange group of described hydrogen type cation exchange resin can suitably be selected according to concrete working conditions, be not particularly limited, particularly, be preferably-SO of the ion-exchange group of described strong acid type hydrogen type cation exchange resin
3h group.
The weight of the quantity of the operating capacity=ion-exchange group of ion exchange resin (mmole)/ion exchange resin (gram).
In the present invention, the operating capacity of described hydrogen type cation exchange resin is according to the mole number of the contained ion-exchange group of the ion exchange resin of the unit volume of measuring under the condition of GB/T8144-2008 defined.
The present invention is not particularly limited the operating capacity of described hydrogen type cation exchange resin.For example, the operating capacity of described strong acid type hydrogen type cation exchange resin can be for being not less than 0.9 mmole/milliliter, more preferably 1-3 mmole/milliliter.The ion exchange resin of operating capacity in above-mentioned scope can be commercially available, for example: be purchased the CT-500 type strongly acidic cation-exchange from industry Ninth Heaven Chemical Co., Ltd., its operating capacity is 1.7 mmole/milliliters.The D001 type large porous strong acid type hydrogen type cation exchange resin of commercially available Jiangsu Su Qing engineering of water treatment Group Co.,Ltd for example, its operating capacity is 1.8 mmole/milliliters.
Preparation in accordance with the present invention, the consumption of hydrogen type cation exchange resin can be adjusted according to the size of the operating capacity of described hydrogen type cation exchange resin, in the preferred case, it with respect to operating capacity, is the strong acid type hydrogen type cation exchange resin of 1-3 mmole/milliliter, described cis-2 butene-1s, the mass ratio of 4-glycol and hydrogen type cation exchange resin is 1:0.05-0.5, more preferably 1:0.1-0.3.
Preparation in accordance with the present invention, in order further to promote the carrying out of reaction, in the preferred case, described cis-2 butene-1s, 4-glycol, aldehyde and can be 1:0.9-2:1-3, more preferably 1:1-1.5:1-2 with the mass ratio of aqua.
Preparation in accordance with the present invention, described band aqua is to form azeotrope and water-fast organic solvent with water, in the preferred case, one or more in the described alkane, hexanaphthene, toluene and the sherwood oil that are C6-C8 with aqua, wherein, the alkane of described C6-C8 is preferably one or more in hexane, heptane and octane.
Preparation in accordance with the present invention, is used different band aquas, described reflux asynchronism(-nization), as long as guarantee preparing 2-alkyl-4,7 dihydro-1, constantly go out the moisture of generation in the process of 3 dioxy seven rings.In the preferred case, adopting under the described condition with aqua, the described reflux time is 4-24h, and preferably 4-12h, while separating until anhydrous, reacts and finish.
Preparation in accordance with the present invention, in step (2), the method also comprises carries out solid-liquid separation by the mixture that contains hydrogen type cation exchange resin.The method of described solid-liquid separation can be the method for the solid-liquid separation of various routines known in the field, for example, and the methods such as filtration, centrifugation.
Preparation in accordance with the present invention, in order to raise the efficiency, described hydrogen type cation exchange resin can carry out recycling after manipulation of regeneration.By the method for hydrogen type cation exchange resin regeneration, be conventionally known to one of skill in the art, for example, at 0-30 ℃, with acidic solution, soak described resin, or with acidic solution, at flow velocity, be, under 1-100 ml/min condition, resin is carried out to leaching regeneration, make resin revert to Hydrogen.Described acidic solution can be selected aqueous hydrochloric acid and/or aqueous sulfuric acid, and the concentration of described acidic aqueous solution can be 1-10 % by weight; By the temperature of acidic solution immersion and/or drip washing, can be 0-30 ℃, the time of immersion and/or drip washing can be 1-300 minute.
Preparation in accordance with the present invention, in step (2), the method is also included in distills described liquid phase with separation and obtains 2-alkyl-4, and band aqua and unreacted material, before 3 dioxy seven rings, are reclaimed in 7 dihydro-1 from described liquid phase.
Preparation in accordance with the present invention, in step (2), described distillation is underpressure distillation, as long as the condition that the liquid phase obtaining is carried out to underpressure distillation guarantees from reaction gained mixture fully separation and obtains 2-alkyl-4,7 dihydro-1,3 dioxies seven rings, under preferable case, the pressure of described underpressure distillation (absolute pressure) is≤30kPa, 1-30kPa for example, and temperature is≤130 ℃, 50-130 ℃ for example, more preferably, pressure is 1-10kPa, and temperature is 50-100 ℃.
Preparation in accordance with the present invention, in step (2), from described liquid phase, reclaim the recovery method that the method with aqua and unreacted material is various routines known in the field, preferably described liquid phase is distilled under condition of normal pressure, reclaim band aqua and unreacted material, to recycle.
Below will to the present invention, be further described in detail by specific embodiment.
In following embodiment, described hydrogen type cation exchange resin is the CT500 type strong acid ion exchange resin being purchased from industry Ninth Heaven Chemical Co., Ltd., operating capacity is 1.7 mmole/milliliters, and pretreatment process is with reference to GB/T5746-1996 " ion exchange resin pretreatment process ".
The renovation process of resin comprises the steps:
(1) at 25-30 ℃, with 3 times of aqueous hydrochloric acids to 10 % by weight of resin volume, soak resins, carry out ion-exchange, then take deionized water wash resin to the pH of wash water be neutral;
(2) after suction filtration, wet resin is remained in sealed vessel, to keep its water content constant, and measure its water content according to national standard method (GB/T5757-2008);
(3) or at 45 ℃ be dried two hours, be placed on sealed vessel standby.
In the present invention, adopt gas-chromatography to carry out each analysis forming in product, by proofreading and correct normalization method, undertaken quantitatively, all can carrying out with reference to prior art, calculate on this basis the evaluation indexes such as the transformation efficiency of reactant, the yield of product and selectivity.
Yield formula is shown below:
In formula, m, M are respectively product 2-alkyl-4,7 dihydro-1, quality and the molecular weight of 3-dioxy seven rings; M1, M1 are respectively cis-2 butene-1s, feed intake quality and the molecular weight of 4-glycol; η is 2-alkyl-4,7 dihydro-1, the yield of 3-dioxy seven rings.
Embodiment 1
The present embodiment is used for illustrating 2-provided by the invention sec.-propyl-4,7-dihydro-1, the preparation method of 3-dioxy seven rings.
200g cis-2-butene-Isosorbide-5-Nitrae-glycol, 300g isobutyric aldehyde, 200g sherwood oil (60-90 ℃) are put into three mouthfuls of round-bottomed flasks that 1000ml is equipped with thermometer, reflux exchanger, water trap, then add 30gCT500 type strong acid type hydrogen type cation exchange resin.Reflux 8h, under normal pressure (0.1MPa), through water trap dehydration, sherwood oil is back in three mouthfuls of round-bottomed flasks and recycles, until anhydrous, takes out of, finishes reaction.The mixture obtaining is carried out to filtering separation, strong acid type hydrogen type cation exchange resin is leached to recycle (after using 5 times, carrying out can reusing after manipulation of regeneration) next time.Then sherwood oil and the unreacted isobutyric aldehyde in normal pressure (0.1MPa) Distillation recovery filtrate.When reaching 110 ℃, liquid temperature switches receiving flask, then at pressure, be to carry out underpressure distillation at 1-10kPa, temperature 50-100 ℃, pick out the thing that boils before part, again switch the receiving flask reconfiguration thing that just boiling, obtain resultant of reaction 268.2g, through gas chromatographic detection, wherein, 2-sec.-propyl-4,7-dihydro-1, the content of 3-dioxy seven rings is 99.4 % by weight.According to detected result, calculate and reclaim 2-sec.-propyl-4 in band aqua, the front thing that boils, 7-dihydro-1, the quality of 3-dioxy seven rings is 36.1g, total recovery counts 93.8% with cis-2-butene-Isosorbide-5-Nitrae-glycol.
Comparative example 1
This comparative example is used for illustrating that available technology adopting sulfuric acid catalysis prepares 2-sec.-propyl-4,7-dihydro-1, the method for 3-dioxy seven rings.
By 200g cis-2-butene-Isosorbide-5-Nitrae-glycol, 300g isobutyric aldehyde, 200g benzene, put into three mouthfuls of round-bottomed flasks that 1000ml is equipped with thermometer, reflux exchanger, water trap, then to add 3.8ml concentration be the sulfuric acid of 98 % by weight.Reflux 8h, under normal pressure (0.1MPa), through water trap dehydration, benzene is back in three mouthfuls of round-bottomed flasks and recycles, until anhydrous, takes out of, finishes reaction.Then benzene and the unreacted isobutyric aldehyde in normal pressure (0.1MPa) Distillation recovery filtrate.When liquid temperature reaches 110 ℃, switch receiving flask, then at pressure, be to carry out underpressure distillation at 1-10kPa, temperature 50-100 ℃, pick out the thing that boils before part, again switch the receiving flask reconfiguration thing that just boiling, obtain resultant of reaction 230.7g, through gas chromatographic detection 2-sec.-propyl-4 wherein, 7-dihydro-1, the content of 3-dioxy seven rings is 97.9 % by weight.According to detected result, calculate and reclaim 2-sec.-propyl-4 in band aqua, the front thing that boils, 7-dihydro-1, the quality of 3-dioxy seven rings is 35.7g, total recovery counts 81% with cis-2-butene-Isosorbide-5-Nitrae-glycol.After reaction, to carry out neutralizing treatment to waste liquid.
Comparative example 2
This comparative example is used for illustrating that available technology adopting hydrochloric acid catalysis prepares 2-sec.-propyl-4,7-dihydro-1, the method for 3-dioxy seven rings.
By 200g cis-2-butene-Isosorbide-5-Nitrae-glycol, 300g isobutyric aldehyde, 200g benzene, put into three mouthfuls of round-bottomed flasks that 1000ml is equipped with thermometer, reflux exchanger, water trap, then to add 10ml concentration be the hydrochloric acid of 30 % by weight.Reflux 8h, under normal pressure (0.1MPa), through water trap dehydration, benzene is back in three mouthfuls of round-bottomed flasks and recycles, until anhydrous, takes out of, finishes reaction.Then benzene and the unreacted isobutyric aldehyde in normal pressure (0.1MPa) Distillation recovery filtrate.When liquid temperature reaches 110 ℃, switch receiving flask, then at pressure, be to carry out underpressure distillation at 1-10kPa, temperature 50-100 ℃, pick out the thing that boils before part, again switch the receiving flask reconfiguration thing that just boiling, obtain resultant of reaction 240.2g, through gas chromatographic detection 2-sec.-propyl-4 wherein, 7-dihydro-1, the content of 3-dioxy seven rings is 98.5 % by weight.According to detected result, calculate and reclaim 2-sec.-propyl-4 in band aqua, the front thing that boils, 7-dihydro-1, the quality of 3-dioxy seven rings is 30.9g, total recovery counts 82.9% with cis-2-butene-Isosorbide-5-Nitrae-glycol.After reaction, to carry out neutralizing treatment to waste liquid.
Embodiment 2
The present embodiment is used for illustrating 2-provided by the invention normal-butyl-4,7-dihydro-1, the preparation method of 3-dioxy seven rings.
By 200g cis-2-butene-Isosorbide-5-Nitrae-glycol, 200g valeraldehyde, 400g toluene, put into three mouthfuls of round-bottomed flasks that 1000ml is equipped with thermometer, reflux exchanger, water trap, then add 60g CT500 type strong acid type hydrogen type cation exchange resin.Reflux 7h through water trap dehydration, recycles in refluxing toluene to three mouthful round-bottomed flask under normal pressure (0.1MPa), until anhydrous, takes out of, finishes reaction.The mixture obtaining is carried out to filtering separation, strong acid type hydrogen type cation exchange resin is leached to recycle (after using 5 times, carrying out can reusing after manipulation of regeneration) next time.Then toluene and the unreacted valeraldehyde in normal pressure (0.1MPa) Distillation recovery filtrate.When liquid temperature reaches 120 ℃, switch receiving flask, then at pressure, be to carry out underpressure distillation at 1-10kPa, temperature 50-100 ℃, pick out the thing that boils before part, again switch the receiving flask reconfiguration thing that just boiling, obtain resultant of reaction 281.4g, through gas chromatographic detection 2-normal-butyl-4 wherein, 7-dihydro-1, the content of 3-dioxy seven rings is 99.2 % by weight.According to detected result, calculate and reclaim 2-normal-butyl-4 in band aqua, the front thing that boils, 7-dihydro-1, the quality of 3-dioxy seven rings is 45.3g, total recovery counts 91.5% with cis-2-butene-Isosorbide-5-Nitrae-glycol.
Embodiment 3
The present embodiment is used for illustrating 2-provided by the invention n-propyl-4,7-dihydro-1, the preparation method of 3-dioxy seven rings.
By 200g cis-2-butene-1,4-glycol, 250g butyraldehyde-n, 300g hexanaphthene, put into three mouthfuls of round-bottomed flasks that 1000ml is equipped with thermometer, reflux exchanger, water trap, then the CT500 type strong acid type hydrogen type cation exchange resin that adds 20g to reclaim from embodiment 2.Reflux 9h, under normal pressure (0.1MPa), through water trap dehydration, hexanaphthene is back in three mouthfuls of round-bottomed flasks and recycles, until anhydrous, takes out of, finishes reaction.The mixture obtaining is carried out to filtering separation, strong acid type hydrogen type cation exchange resin is leached to recycle (after using 5 times, after manipulation of regeneration, can reuse) next time.Then hexanaphthene and the unreacted butyraldehyde-n in normal pressure (0.1MPa) Distillation recovery filtrate.When liquid temperature reaches 110 ℃, switch receiving flask, then at pressure, be to carry out underpressure distillation at 1-10kPa, temperature 50-100 ℃, pick out the thing that boils before part, again switch the receiving flask reconfiguration thing that just boiling, obtain resultant of reaction 263.7g, through gas chromatographic detection 2-n-propyl-4 wherein, 7-dihydro-1, the content of 3-dioxy seven rings is 99 % by weight.According to detected result, calculate and reclaim 2-n-propyl-4 in band aqua, the front thing that boils, 7-dihydro-1, the quality of 3-dioxy seven rings is 43.9g, total recovery counts 94.5% with cis-2-butene-Isosorbide-5-Nitrae-glycol.
Embodiment 4
The present embodiment is used for illustrating 2-provided by the invention ethyl-4,7-dihydro-1, the preparation method of 3-dioxy seven rings.
By 200g cis-2-butene-Isosorbide-5-Nitrae-glycol, 360g propionic aldehyde, 500g normal hexane, put into three mouthfuls of round-bottomed flasks that 1000ml is equipped with thermometer, reflux exchanger, water trap, then add 90g CT500 type strong acid type hydrogen type cation exchange resin.Reflux 11h, under normal pressure (0.1MPa), through water trap dehydration, normal hexane is back in three mouthfuls of round-bottomed flasks and recycles, until anhydrous, takes out of, finishes reaction.The mixture obtaining is carried out to filtering separation, strong acid type hydrogen type cation exchange resin is leached to recycle (after using 5 times, carrying out can reusing after manipulation of regeneration) next time.Then normal hexane and the unreacted propionic aldehyde in normal pressure (0.1MPa) Distillation recovery filtrate.When liquid temperature reaches 100 ℃, switch receiving flask, then at pressure, be to carry out underpressure distillation at 1-10kPa, temperature 50-100 ℃, pick out the thing that boils before part, again switch the receiving flask reconfiguration thing that just boiling, obtain resultant of reaction 231.5g, through gas chromatographic detection 2-ethyl-4 wherein, 7-dihydro-1,3-dioxy seven ring contents are 98.9 % by weight.According to detected result, calculate and reclaim 2-ethyl-4 in band aqua, the front thing that boils, 7-dihydro-1, the quality of 3-dioxy seven rings is 27.1g, total recovery counts 88% with cis-2-butene-Isosorbide-5-Nitrae-glycol.
Embodiment 5
The present embodiment is used for illustrating 2-provided by the invention n-propyl-4,7-dihydro-1, the preparation method of 3-dioxy seven rings.
By 200g cis-2-butene-Isosorbide-5-Nitrae-glycol, 180g butyraldehyde-n, 600g hexanaphthene, put into three mouthfuls of round-bottomed flasks that 1000ml is equipped with thermometer, reflux exchanger, water trap, then add 16g CT500 type strong acid type hydrogen type cation exchange resin.Reflux 9h dewaters through water trap under normal pressure (0.1MPa), and hexanaphthene is back in three mouthfuls of round-bottomed flasks and recycles, until anhydrous, takes out of, finishes reaction, finishes reaction.The mixture obtaining is carried out to filtering separation, strong acid type hydrogen type cation exchange resin is leached to recycle (after using 5 times, after manipulation of regeneration, can reuse) next time.Then hexanaphthene and the unreacted butyraldehyde-n in normal pressure (0.1MPa) Distillation recovery filtrate.When liquid temperature reaches 110 ℃, switch receiving flask, then at pressure, be to carry out underpressure distillation at 1-10kPa, temperature 50-100 ℃, pick out the thing that boils before part, again switch the receiving flask reconfiguration thing that just boiling, obtain resultant of reaction 255.8g, through gas chromatographic detection 2-n-propyl-4 wherein, 7-dihydro-1, the content of 3-dioxy seven rings is 98.8 % by weight.According to detected result, calculate and reclaim 2-n-propyl-4 in band aqua, the front thing that boils, 7-dihydro-1, the quality of 3-dioxy seven rings is 39.3g, total recovery counts 90.5% with cis-2-butene-Isosorbide-5-Nitrae-glycol.
Embodiment 6
The present embodiment is used for illustrating 2-provided by the invention sec.-propyl-4,7-dihydro-1, the preparation method of 3-dioxy seven rings.
By 200g cis-2-butene-1,4-glycol, 320g isobutyric aldehyde, 560g sherwood oil (60-90 ℃), put into three mouthfuls of round-bottomed flasks that 1000ml is equipped with thermometer, reflux condensing tube, water trap, then add the CT500 type strong acid type hydrogen type cation exchange resin of 80g.Reflux 7h, under normal pressure (0.1MPa), through water trap dehydration, sherwood oil is back in three mouthfuls of round-bottomed flasks and recycles, until anhydrous, takes out of, finishes reaction.The mixture obtaining is carried out to filtering separation, strong acid type hydrogen type cation exchange resin is leached to recycle (after using 5 times, after manipulation of regeneration, can reuse) next time.Then sherwood oil and the unreacted isobutyric aldehyde in normal pressure (0.1MPa) Distillation recovery filtrate.When liquid temperature reaches 110 ℃, switch receiving flask, then at pressure, be to carry out underpressure distillation at 1-10kPa, temperature 50-100 ℃, pick out the thing that boils before part, again switch the receiving flask reconfiguration thing that just boiling, obtain resultant of reaction 240.7g, through gas chromatographic detection 2-sec.-propyl-4 wherein, 7-dihydro-1, content 98.3 % by weight of 3-dioxy seven rings.According to detected result, calculate and reclaim band aqua, front middle 2-sec.-propyl-4 of boiling, 7-dihydro-1, the quality of 3-dioxy seven rings is 45.7g, total recovery counts 87.5% with cis-2-butene-Isosorbide-5-Nitrae-glycol.
Claims (8)
1. 2-alkyl-4,7 dihydro-1, the preparation method of 3 dioxies seven rings, the method comprises:
(1) under the condition with aqua and hydrogen type cation exchange resin existence, the aldehyde that is RCHO by general formula and cis-2 butene-1s, 4-glycol carries out reflux, obtains the mixture containing compound shown in formula I, wherein, the alkyl that R is C2-C4;
(2) mixture step (1) being obtained carries out solid-liquid separation, and the liquid phase obtaining is distilled, and with separation, obtains 2-alkyl-4,7 dihydro-1,3 dioxy seven rings.
2. preparation method according to claim 1, wherein, described hydrogen type cation exchange resin is strong acid type hydrogen type cation exchange resin, the ion-exchange group of the exchange ion having of described strong acid type hydrogen type cation exchange resin is-SO
3h, operating capacity, for being not less than 0.9 mmole/milliliter, is preferably 1-3 mmole/milliliter.
3. preparation method according to claim 1 and 2, wherein, in step (1), cis-2-butene-1,4-glycol, aldehyde, hydrogen type cation exchange resin and be 1:0.9-2:0.05-0.5:1-3 with the mass ratio of aqua, be preferably 1:1-1.5:0.1-0.3:1-2.
4. preparation method according to claim 1, wherein, in step (1), the described reflux time is 4-24h, is preferably 4-12h.
5. according to the preparation method described in claim 1 or 3, wherein, one or more in the described alkane, hexanaphthene, toluene and the sherwood oil that are C6-C8 with aqua.
6. preparation method according to claim 5, wherein, the alkane of described C6-C8 is one or more in hexane, heptane and octane.
7. preparation method according to claim 1, wherein, in step (2), the method is also included in distills described liquid phase with separation and obtains 2-alkyl-4, band aqua and unreacted material before 3 dioxy seven rings, are reclaimed in 7 dihydro-1 from described liquid phase.
8. according to the preparation method described in claim 1 or 7, wherein, in step (2), described distillation is underpressure distillation, and pressure is≤30kPa that temperature is≤130 ℃; Preferred pressure is 1-10kPa, and temperature is 50-100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210233697.8A CN103524479A (en) | 2012-07-06 | 2012-07-06 | Preparation method of 2-alkyl-4,7-dihydro-1,3-2-propyl-1,3-dioxocyclo-5-pentene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210233697.8A CN103524479A (en) | 2012-07-06 | 2012-07-06 | Preparation method of 2-alkyl-4,7-dihydro-1,3-2-propyl-1,3-dioxocyclo-5-pentene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103524479A true CN103524479A (en) | 2014-01-22 |
Family
ID=49926880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210233697.8A Pending CN103524479A (en) | 2012-07-06 | 2012-07-06 | Preparation method of 2-alkyl-4,7-dihydro-1,3-2-propyl-1,3-dioxocyclo-5-pentene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103524479A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256335A (en) * | 2019-05-16 | 2019-09-20 | 湖北惠生药业有限公司 | A kind of vitamin B6Synthesis technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10231294A (en) * | 1996-12-20 | 1998-09-02 | Ichikawa Gosei Kagaku Kk | Production of 4,7-dihydro-1,3-dioxepin |
| US6166225A (en) * | 1998-02-17 | 2000-12-26 | Daicel Chemical Industries, Ltd. | Processes for producing dialdehyde monoacetals |
| CN101402600A (en) * | 2008-11-17 | 2009-04-08 | 江西天新药业有限公司 | Process for producing vitamin B6 |
-
2012
- 2012-07-06 CN CN201210233697.8A patent/CN103524479A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10231294A (en) * | 1996-12-20 | 1998-09-02 | Ichikawa Gosei Kagaku Kk | Production of 4,7-dihydro-1,3-dioxepin |
| US6166225A (en) * | 1998-02-17 | 2000-12-26 | Daicel Chemical Industries, Ltd. | Processes for producing dialdehyde monoacetals |
| CN101402600A (en) * | 2008-11-17 | 2009-04-08 | 江西天新药业有限公司 | Process for producing vitamin B6 |
Non-Patent Citations (1)
| Title |
|---|
| 李文骁等: "2-正丙基-4，7-二氢-1，3-二氧庚英的合成研究", 《精细化工原料及中间体》, no. 2, 31 December 2006 (2006-12-31), pages 20 - 21 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256335A (en) * | 2019-05-16 | 2019-09-20 | 湖北惠生药业有限公司 | A kind of vitamin B6Synthesis technology |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110452136A (en) | A method of preparing taurine | |
| CN101318880B (en) | Green synthesis process for bornyl alcohol | |
| JPH021142B2 (en) | ||
| CN103936562A (en) | Method for preparing bisphenol F | |
| CN102036942B (en) | Method of separating phenolic compounds in salified form | |
| CN103524479A (en) | Preparation method of 2-alkyl-4,7-dihydro-1,3-2-propyl-1,3-dioxocyclo-5-pentene | |
| CN112574006A (en) | Preparation method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol | |
| CN105061363A (en) | Device and method for separating N-methylpyrrolidine, water and tetrahydrofuran | |
| CN112574229B (en) | Method for preparing isosorbide by dehydrating sorbitol and preparation method of copolymer-based catalyst thereof | |
| CN110240543B (en) | Preparation method of 4-bromo-3-methyl-2-buten-1-ol acetate | |
| CN102863337A (en) | Synthesis method of 1,6-hexanediol diacrylate | |
| CN102584709B (en) | A kind of preparation technology of the Eprosartan intermediate aryl imidazole aldehyde of improvement | |
| CN104098438B (en) | A kind of method of Separation and Recovery Pentyl alcohol from pimelinketone by-product lightweight oil | |
| CN102942592B (en) | Method for synthesizing 4, 4'-biphenyl double dichloride phosphine | |
| CN106928057A (en) | The method of one kind synthesis maleic acid two (2 ethyl hexyl) ester | |
| CN102863422B (en) | Preparation method of 2-isopropylthioxanthone | |
| CN103408413B (en) | Method for preparing deuterated chloroform by using hexachloroacetone as intermediate | |
| CN108047063B (en) | A kind of preparation method of methyl triethyl ammonium chloride | |
| CN206502759U (en) | A kind of catalytic reaction rectification prepares the device of dibutyl phthalate | |
| CN107365335B (en) | Preparation method of 1,2,5, 6-di-isopropylidene-3-O-benzyl- α -D-furan glucoside | |
| CN101161621B (en) | A method for preparing trifluoromethyl acetophenone compound | |
| CN105777550B (en) | The method that one kind being continuously synthesizing to 2,4- dinitroanisol | |
| CN109809972A (en) | A kind of method that green prepares pinacoline | |
| CN104945234B (en) | The preparation method of the methoxy benzophenone of 2,2 ' dihydroxy 4 | |
| CN109851517A (en) | A kind of preparation method of Diacetone Acrylamide and catalyst for this method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140122 |