阅读说明：本技术 一种异戊氧基乙酸烯丙酯香料的合成方法 (A kind of synthetic method of allyl amyl glycolate fragrance ) 是由 王天义 汪洋 张政 汪炎 董金龙 于 2019-09-03 设计创作，主要内容包括：本发明公开了一种异戊氧基乙酸烯丙酯香料的合成方法,代替了Williamson反应,采用重氮乙酸乙酯与异戊醇在催化剂Rh<Sub>2</Sub>(OAc)<Sub>4</Sub>催化作用下进行O-H插入反应合成了异戊氧基乙酸乙酯,大大缩短了反应时间；另外制备的固体酸催化剂Yb-MoO<Sub>3</Sub>/Al<Sub>2</Sub>O<Sub>3</Sub>-ZrO<Sub>2</Sub>具有容易与液相反应体系分离、不腐蚀设备、后处理简单的优点,克服了现有液体酸对设备腐蚀和含酸废水污染环境的问题,而且选择性高,在较低温度下即可进行,节省了能耗,减少了副反应的发生,能大大提高生产效率,制备的异戊氧基乙酸烯丙酯香料收率高达98.4％,且其热稳定性好,活性组分不易流失,使其重复使用性能良好,是一类很有应用潜力的新型绿色催化材料。(The invention discloses a kind of synthetic methods of allyl amyl glycolate fragrance, react instead of Williamson, using ethyl diazoacetate and isoamyl alcohol in catalyst Rh 2 (OAc) 4 O-H intercalation reaction is carried out under catalytic action and has synthesized amyl glycolate ethyl ester, substantially reduces the reaction time；In addition the solid acid catalyst Yb-MoO prepared 3 /Al 2 O 3 ‑ZrO 2 Have the advantages that be easy separated with liquid-phase reaction system, do not corrode equipment, post-process it is simple, overcome the problem of existing liquid acid is to equipment corrosion and acid-bearing wastewater pollution environment, and selectivity is high, it can carry out at a lower temperature, save energy consumption, reduce the generation of side reaction, production efficiency can be greatly improved, the allyl amyl glycolate fragrance yield of preparation is up to 98.4%, and its thermal stability is good, active component not easily runs off, and keeps its repeat performance good, is a kind of novel green catalysis material for having very much application potential.)

1. a kind of synthetic method of allyl amyl glycolate fragrance, it is characterised in that: specifically includes the following steps:

The synthesis of the first step, amyl glycolate

1.5-2mol isoamyl alcohol, catalyst and 200ml solvent dichloroethanes are added in reaction flask, is passed through nitrogen protection, heats up To 85-90 DEG C, the dichloroethane solution for the ethyl diazoacetate that 280-380ml mass concentration is 30-40% is added dropwise dropwise, in 1- It is added dropwise in 1.5h, the reaction was continued after being added dropwise, and 2-3h is reduced to room temperature after reaction, and vacuum distillation removes solvent Dichloroethanes and extra isoamyl alcohol, the sodium hydroxide solution that 200ml mass fraction is 15% is added into crude product, and stirring adds Heat reflux 3-5h is cooled to room temperature after reaction, and the hydrochloric acid for being added 30% adjusts the pH of reaction solution as acidity, and liquid separation removes Water layer, oil reservoir uses saturated common salt water washing 3 times, through drying to obtain amyl glycolate after liquid separation；

The synthesis of second step, allyl amyl glycolate fragrance

In the three-necked flask equipped with blender, thermometer and water segregator, amyl glycolate, allyl alcohol, acid catalyst is added And toluene, it is heated to 60-65 DEG C, acid catalyst is recovered by filtration after reaction in insulation reaction 2h, using soaked in absolute ethyl alcohol After 30min drying can reuse, reacting coarse product through vacuum distillation remove toluene, then distillation under pressure collect 116-119 DEG C/ The fraction of 26kPa to get arrive allyl amyl glycolate fragrance.

2. a kind of synthetic method of allyl amyl glycolate fragrance according to claim 1, it is characterised in that: first The step catalyst is Rh₂(OAc)₄, the additional amount of catalyst is 5mmol.

3. a kind of synthetic method of allyl amyl glycolate fragrance according to claim 1, it is characterised in that: first In step, the acidity specifically: the hydrochloric acid for being added 30% adjusts the pH of reaction solution as 2.5-3.0.

4. a kind of synthetic method of allyl amyl glycolate fragrance according to claim 1, it is characterised in that: second In step, the molar ratio of amyl glycolate and allyl alcohol is 1:1.5-1.8mol.

5. a kind of synthetic method of allyl amyl glycolate fragrance according to claim 1, it is characterised in that: second In step, the acid catalyst is Yb-MoO₃/Al₂O₃-ZrO₂, the additional amount of acid catalyst is amyl glycolate mole 0.5%-7%.

6. a kind of synthetic method of allyl amyl glycolate fragrance according to claim 5, it is characterised in that: acid is urged Agent Yb-MoO₃/Al₂O₃-ZrO₂Wherein the mass ratio of element Yb:Mo:Al:Zr is 0.5-0.7:4.5-5.8:3.0-3.5: 5.4-8.2。

7. a kind of synthetic method of allyl amyl glycolate fragrance according to claim 5, it is characterised in that: acid is urged Agent is Yb-MoO₃/Al₂O₃-ZrO₂The preparation method comprises the following steps:

The eight hydration zirconyl chloride solutions that 100ml mass concentration is 20-30% are prepared, sequentially add 10g hydroxide while stirring Aluminium, 10-12g ammonium molybdate add 1.35-2g Yb (NO after stirring 10-15min is completely dissolved₃)₃·5H₂O, stirring and dissolving Afterwards, the ammonium hydroxide by above-mentioned preparation solution together with 8mol/L is added in the ammonia spirit of 300ml pH=9.00 simultaneously, is added dropwise Journey keeps the pH of solution to be maintained between 8.95-9.10, after completion of dropwise addition, continues to stir 20-30min, be aged at room temperature for 24 hours, It filters, adopts and solid is washed with deionized into cleaning solution without chloride ion presence, dry 8-10h, is finally putting into gas at 105 DEG C 2h is roasted at 800 DEG C in atmosphere protection batch-type furnace, taking-up is cooled to room temperature and obtains acid catalyst Yb-MoO₃/Al₂O₃-ZrO₂。

8. a kind of synthetic method of allyl amyl glycolate fragrance according to claim 7, it is characterised in that: inspection is washed Washing chloride ion method in liquid is to be detected using the silver nitrate solution of 0.1mol/L.

9. a kind of synthetic method of allyl amyl glycolate fragrance according to claim 7, it is characterised in that: described Atmosphere protection batch-type furnace is to be protected using nitrogen.

Technical field

The invention belongs to fragrance technical fields, and in particular to a kind of synthetic method of allyl amyl glycolate fragrance.

Background technique

The fluffy ester of allyl amyl glycolate popular name lattice is a kind of important synthetic perfume, has the strong fluffy fragrance of lattice With fruity fragrance, it is widely used in the flavoring of the various products such as perfume, cosmetics, perfumed soap, air freshener, detergent.

Traditional synthesis allyl amyl glycolate method are as follows: it synthesizes main reaction in two steps: passing through first Williamson reaction prepares amyl glycolate or cyclohexyloxy, and yield is 80% or so, then with sulfuric acid, high chlorine Acid, p-methyl benzenesulfonic acid etc. make catalyst, obtain target product through esterification with propenyl；Amyl glycolate is synthesized in this Mesosome just becomes the key for preparing allyl amyl glycolate, and synthesis alkoxy acetic acid is firstly the need of preparing sodium alcoholate, mesh Preceding report mainly has 3 kinds of methods: 1. preparing sodium alkoxide using metallic sodium as reaction reagent, it is desired to which anhydrous system, technology difficulty is big, danger Dangerous height, industrialized production relatively difficult to achieve；2. using NaH as reaction reagent, it is desired to reaction system is anhydrous, low temperature, using a large amount of Organic solvent, trivial operations, cost of material are high；3. using NaOH as reaction reagent, cost is relatively low, but water entrainer, alcohol need to be added Sodium yield is low, and the reaction time is long.

In addition acid catalyst sulfuric acid used in step of esterification etc. is cheap as traditional esterifications catalyst, catalysis Effect is preferably used till today, but its severe corrosion to equipment, and acid-bearing wastewater pollutes environment.

Summary of the invention

The purpose of the present invention is to provide a kind of synthetic method of allyl amyl glycolate fragrance, instead of Williamson reaction, using ethyl diazoacetate and isoamyl alcohol in catalyst Rh₂(OAc)₄O-H insertion is carried out under catalytic action Reaction has synthesized amyl glycolate ethyl ester, substantially reduces the reaction time.

The purpose of the present invention can be achieved through the following technical solutions:

A kind of synthetic method of allyl amyl glycolate fragrance, specifically includes the following steps:

The synthesis of the first step, amyl glycolate

1.5-2mol isoamyl alcohol, catalyst and 200ml solvent dichloroethanes are added in reaction flask, is passed through nitrogen protection, It is warming up to 85-90 DEG C, the dichloroethane solution for the ethyl diazoacetate that 280-380ml mass concentration is 30-40% is added dropwise dropwise, It is added dropwise in 1-1.5h, the reaction was continued after being added dropwise, and 2-3h is reduced to room temperature after reaction, and vacuum distillation removes The sodium hydroxide solution that 200ml mass fraction is 15% is added into crude product, stirs for solvent dichloroethanes and extra isoamyl alcohol It mixing and is heated to reflux 3-5h, after reaction, be cooled to room temperature, the pH that 30% hydrochloric acid adjusting reaction solution is added is acid, liquid separation, Water layer is removed, oil reservoir uses saturated common salt water washing 3 times, through drying to obtain amyl glycolate after liquid separation；

The synthesis of second step, allyl amyl glycolate fragrance

In the three-necked flask equipped with blender, thermometer and water segregator, amyl glycolate, allyl alcohol, acid is added and urges Agent and toluene are heated to 60-65 DEG C, and acid catalyst is recovered by filtration after reaction in insulation reaction 2h, using dehydrated alcohol It dries and can reuse after impregnating 30min, reacting coarse product removes toluene through vacuum distillation, and then 116- is collected in distillation under pressure The fraction of 119 DEG C/26kPa to get arrive allyl amyl glycolate fragrance.

Further, catalyst described in the first step is Rh₂(OAc)₄, the additional amount of catalyst is 5mmol.

Further, in the first step, the acidity specifically: the hydrochloric acid for being added 30% adjusts the pH of reaction solution as 2.5- 3.0。

Further, in second step, the molar ratio of amyl glycolate and allyl alcohol is 1:1.5-1.8mol.

Further, in second step, the acid catalyst is Yb-MoO₃/Al₂O₃-ZrO₂, the additional amount of acid catalyst is The 0.5%-7% of amyl glycolate mole.

Further, acid catalyst Yb-MoO₃/Al₂O₃-ZrO₂Wherein the mass ratio of element Yb:Mo:Al:Zr is 0.5-0.7: 4.5-5.8:3.0-3.5:5.4-8.2.

Further, acid catalyst Yb-MoO₃/Al₂O₃-ZrO₂The preparation method comprises the following steps:

The eight hydration zirconyl chloride solutions that 100ml mass concentration is 20-30% are prepared, sequentially add 10g hydrogen while stirring Aluminium oxide, 10-12g ammonium molybdate add 1.35-2g Yb (NO after stirring 10-15min is completely dissolved₃)₃·5H₂O is stirred molten Xie Hou, the ammonium hydroxide by above-mentioned preparation solution together with 8mol/L are added in the ammonia spirit of 300ml pH=9.00 simultaneously, are added dropwise Process keeps the pH of solution to be maintained between 8.95-9.10, after completion of dropwise addition, continues to stir 20-30min, be aged at room temperature For 24 hours, it filters, adopts and solid is washed with deionized into cleaning solution without chloride ion presence, dry 8-10h, finally puts at 105 DEG C Enter and roast 2h in atmosphere protection batch-type furnace at 800 DEG C, taking-up is cooled to room temperature and obtains acid catalyst Yb-MoO₃/Al₂O₃- ZrO₂。

Further, examining chloride ion method in cleaning solution is to be detected using the silver nitrate solution of 0.1mol/L.

Further, the atmosphere protection batch-type furnace is to be protected using nitrogen.

Beneficial effects of the present invention:

It is anti-instead of Williamson the present invention provides a kind of synthetic method of allyl amyl glycolate fragrance It answers, using ethyl diazoacetate and isoamyl alcohol in catalyst Rh₂(OAc)₄Progress O-H intercalation reaction has synthesized different under catalytic action Amoxy ethyl acetate substantially reduces the reaction time, and the amyl glycolate yield being prepared is 97.7%；

In addition the solid acid catalyst Yb-MoO prepared₃/Al₂O₃-ZrO₂It is separated with liquid-phase reaction system, no with easy Corrode equipment, post-process simple advantage, overcomes the problem of existing liquid acid is to equipment corrosion and acid-bearing wastewater pollution environment, And selectivity is high, can carry out at a lower temperature, save energy consumption, reduce the generation of side reaction, can greatly improve life Efficiency is produced, the allyl amyl glycolate fragrance yield of preparation is up to 98.4%；And its thermal stability is good, active component is not easy It is lost, keeps its repeat performance good, be a kind of novel green catalysis material for having very much application potential.

Specific embodiment

The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common Technical staff's all other embodiment obtained without creative efforts belongs to the model that the present invention protects It encloses.

In following embodiments, acid catalyst the preparation method comprises the following steps:

The eight hydration zirconyl chloride solutions that 100ml mass concentration is 20-30% are prepared, sequentially add 10g hydrogen while stirring Aluminium oxide, 10-12g ammonium molybdate add 1.35-2g Yb (NO after stirring 10-15min is completely dissolved₃)₃·5H₂O is stirred molten Xie Hou, the ammonium hydroxide by above-mentioned preparation solution together with 8mol/L are added in the ammonia spirit of 300ml pH=9.00 simultaneously, are added dropwise Process keeps the pH of solution to be maintained between 8.95-9.10, after completion of dropwise addition, continues to stir 20-30min, be aged at room temperature For 24 hours, filter, adopt be washed with deionized solid into cleaning solution without chloride ion exist (using the silver nitrate solution of 0.1mol/L Detection), dry 8-10h, is finally putting into atmosphere protection batch-type furnace (nitrogen protection) and roasts 2h at 800 DEG C, take at 105 DEG C It is cooled to room temperature out and obtains acid catalyst Yb-MoO₃/Al₂O₃-ZrO₂, wherein the mass ratio of Yb:Mo:Al:Zr is 0.5-0.7: 4.5-5.8:3.0-3.5:5.4-8.2.