Method for synthesizing piperonal

Abstract

The invention relates to a method for synthesizing piperonal, which comprises the
following steps of: adding 3,4-methylenedioxy benzene acid, nitric acid, sulfate, sodium
nitrite and water into a reaction kettle by one step; after introducing oxygen gas, sealing
the reaction kettle and obtaining acid filtrate, a piperonal product and recovered gas
comprising nitrogen oxide and the oxygen gas after reacting; introducing the oxygen gas
and the obtained recovered gas comprising the nitrogen oxide and the oxygen gas into
the reaction kettle filled with the 3,4-methylenedioxy benzene acid and the acid filtrate,
sealing the reaction kettle and obtaining the acid filtrate, the piperonal product and the
recovered gas comprising the nitrogen oxide and the oxygen gas after reacting; and
carrying out the operation repeatedly. The invention has the advantages of low cost, no
pollution and simple operation.

CN101774999A
China

Download PDF Find Prior Art

Similar
Other languages
Chinese
Inventor
高志贤
郗宏娟
王建国
张素红
庆绍军
邱诗铭
董凌曜
胡蕴青

Worldwide applications
2010 CN

Application CN 201010100189 events

2010-01-20
Application filed by 中国科学院山西煤炭化学研究所
2010-01-20
Priority to CN 201010100189
2010-07-14
Publication of CN101774999A

Info
Cited by (5)
Legal events
Similar documents
 Priority and Related Applications
External links
Espacenet
Global Dossier
Discuss

Description

A kind of method of synthesizing piperonal

Technical field

The present invention relates to a kind ofly with 3,4-methylene-dioxy phenylglycollic

acid is the method for raw material synthesizing piperonal.

Background technology

Piperonal is a kind of important fine chemicals, has been widely used in fields such as
spices, medicine, agricultural chemicals, plating.

Nitric acid oxidation decarboxylation 3,4-methylene-dioxy phenylglycollic acid solid

prepares the piperonal process and is known by the people.At present, known
implementation process has: with about 2.6mmol massfraction is 3.1% nitric acid and
about 2.6mmol 3,4-methylene-dioxy phenylglycollic acid reacts after mixing, and
product is dark oily liquids, and reacts when the nitric acid massfraction slightly is
reduced to 2.3% and but carry out hardly; About 1.177mol concentrated nitric acid is
added drop-wise to about 1.5mol 3, reacts in the nitric acid of 4-methylene-dioxy
phenylglycollic acid and hydrochloric acid, Sodium Nitrite, trace, the mixed solution of
water; Under protection of inert gas, the 0.15mol concentrated nitric acid is added
dropwise to 0.23mol 3, react (Perfumer in the mixed solution of 4-methylene-dioxy
phenylglycollic acid, sulfuric acid and organic solvent; Flavorist, 14,13 (1989),
US5095128, JP7258246).

Yet above process has following several respects deficiency: (1) nitric acid consumption
is bigger, and about every mole 3,4-methylene-dioxy phenylglycollic acid needs 0.65 ~
1.00 mole nitric acid; (2) reaction finishes a large amount of nitrogen oxides pollution
gases that the back generates; (3) complicated operation needs the strict rate of addition
of controlling concentration of nitric acid or concentrated nitric acid.

Summary of the invention

The invention provides a kind of low cost, piperonal synthetic method pollution-free,
simple to operate, wherein oxygen can intermittent type or is fed reactor continuously.

Preparation method of the present invention comprises the steps:

(1) with 3, the disposable adding reactor of 4-methylene-dioxy phenylglycollic acid,

nitric acid, sulfuric acid, Sodium Nitrite and water; Sealed reactor behind the aerating
oxygen, start and stir, reaction solution is heated to 30-100 ℃, behind the reaction 0.1-
24.0h, reaction solution is cooled to room temperature, obtain gas, liquid and solid, with
liquid and solids constituent from after obtain acid filtrate and piperonal product, with
the recovery gas that obtains after the carbon dioxide separation in the gaseous product
forming by oxynitride and oxygen;

Wherein, 3,4-methylene-dioxy phenylglycollic acid: nitric acid: sulfuric acid: Sodium

Nitrite: the mol ratio of oxygen is 1: 0.01-1.50: 0-3.00: 0-0.20: 0.01-3.00, the add-on of
water is that to make the concentration of nitric acid be that 0.05-1.00mol/L is as the
criterion;

(2) the recovery gas of being made up of oxynitride and oxygen that oxygen and (1)
step is obtained is passed into and is equipped with 3,4-methylene-dioxy
phenylglycollic acid and (1) step obtain in the reactor of acid filtrate, sealed reactor,
start and stir, reaction solution is heated to 30-100 ℃, behind the reaction 0.1-24.0h,
reaction solution is cooled to room temperature, obtain gas, liquid and solid, with liquid
and solids constituent from after obtain acid filtrate and piperonal product, with the
recovery gas that obtains after the carbon dioxide separation in the gaseous product
forming by oxynitride and oxygen;

In this reaction process, 3,4-methylene-dioxy phenylglycollic acid: oxynitride: the mol

ratio of oxygen is 1: 0.01-2.00: 0.01-3.00;

(3) repeat the operation of the 2nd step.

Acid filtrate and piperonal product by HPLC analytical reaction gained can obtain
piperonal productive rate and reaction preference.Divided by 3,4-methylene-dioxy
phenylglycollic acid transformation efficiency calculates reaction preference with the
piperonal productive rate.

Advantage of the present invention is as follows: (1) is real oxygenant with the oxygen
of cheapness, and will react the acid filtrate and the oxides of nitrogen gas that generate
and reuse, and has not only reduced cost, and has realized the zero release of pollutent;
(2) all can begin smoothly at bigger concentration of nitric acid scope internal reaction,
and only need the disposable adding reactor of material is got final product, save the
process of strict control concentration of nitric acid and concentrated nitric acid rate of
addition, operate fairly simple.

Embodiment

Below, exemplify embodiment and specify the present invention, but scope of the
present invention is not limited thereto.

Embodiment 1

By 3,4-methylene-dioxy phenylglycollic acid: nitric acid: sulfuric acid: the mol ratio of
Sodium Nitrite is 1: 0.45: 1.00: 0.05, the water add-on is that to make concentration of
nitric acid be that 0.24mol/L is as the criterion, with 3, the disposable adding reactor of
4-methylene-dioxy phenylglycollic acid, nitric acid, sulfuric acid, Sodium Nitrite and
water.Then, by 3, the mol ratio of 4-methylene-dioxy phenylglycollic acid and oxygen
is 1: 0.5, aerating oxygen, and sealed reactor.Start and stir, reaction solution is heated to
58 ℃, behind the reaction 1.0h, reaction solution is cooled to room temperature, obtain
gas, liquid and solid, with liquid and solids constituent from after obtain acid filtrate and
piperonal product, will obtain reclaiming gas (comprising oxynitride and oxygen) after
the carbon dioxide separation in the gaseous product.By the acid filtrate and the
piperonal product of HPLC analytical reaction gained, can obtain the piperonal
productive rate is 95.2%, and reaction preference is 97.0%.

By 3,4-methylene-dioxy phenylglycollic acid, the mol ratio of oxynitride and oxygen is

1: 0.45: 0.5, the recovery gas that oxygen and (1) step are obtained is passed into and is
equipped with 3,4-methylene-dioxy phenylglycollic acid and (1) step obtain in the
reactor of acid filtrate, sealed reactor, start and stir, reaction solution is heated to 58 ℃,
behind the reaction 1.5h, reaction solution is cooled to room temperature, obtain gas,
liquid and solid, with liquid and solids constituent from after obtain acid filtrate and
piperonal product, will obtain reclaiming gas (comprising oxynitride and oxygen) after
the carbon dioxide separation in the gaseous product.By the acid filtrate and the
piperonal product of HPLC analytical reaction gained, can obtain the piperonal
productive rate is 96.3%, and reaction preference is 98.2%.

Repeat the operation of the 2nd step.After reaction finished, by the acid filtrate and the
piperonal product of HPLC analytical reaction gained, can obtain the piperonal
productive rate was 94.9%, and reaction preference is 97.8%.

Embodiment 2

By 3,4-methylene-dioxy phenylglycollic acid: the mol ratio of nitric acid is 1: 1.50, and
concentration of nitric acid is 1.00mol/L, with 3, and the disposable adding reactor of 4-
methylene-dioxy phenylglycollic acid and salpeter solution.Then, by 3, the mol ratio of
4-methylene-dioxy phenylglycollic acid and oxygen is 1: 0.01, aerating oxygen, and
sealed reactor.Start and stir, reaction solution is heated to 58 ℃, behind the reaction
0.8h, reaction solution is cooled to room temperature, obtain gas, liquid and solid, with
liquid and solids constituent from after obtain acid filtrate and piperonal product, will
obtain reclaiming gas (comprising oxynitride and oxygen) after the carbon dioxide
separation in the gaseous product.By the acid filtrate and the piperonal product of HPLC
analytical reaction gained, can obtain the piperonal productive rate is 85.8%, and
reaction preference is 87.2%.

By 3,4-methylene-dioxy phenylglycollic acid, the mol ratio of oxynitride and oxygen is

1: 1.00: 0.01, the recovery gas that oxygen and (1) step are obtained is passed into and is
equipped with 3,4-methylene-dioxy phenylglycollic acid and (1) step obtain in the
reactor of acid filtrate, sealed reactor, start and stir, reaction solution is heated to 58 ℃,
behind the reaction 1.0h, reaction solution is cooled to room temperature, obtain gas,
liquid and solid, with liquid and solids constituent from after obtain acid filtrate and
piperonal product, will obtain reclaiming gas (comprising oxynitride and oxygen) after
the carbon dioxide separation in the gaseous product.By the acid filtrate and the
piperonal product of HPLC analytical reaction gained, can obtain the piperonal
productive rate is 95.0%, and reaction preference is 95.5%.

Repeat the operation of the 2nd step.After reaction finished, by the acid filtrate and the
piperonal product of HPLC analytical reaction gained, can obtain the piperonal
productive rate was 93.2%, and reaction preference is 95.0%.
Embodiment 3

By 3,4-methylene-dioxy phenylglycollic acid: nitric acid: sulfuric acid: the mol ratio of
Sodium Nitrite is 1: 0.01: 3.00: 0.20, the water add-on is that to make concentration of
nitric acid be that 0.05mol/L is as the criterion, with 3, the disposable adding reactor of
4-methylene-dioxy phenylglycollic acid, nitric acid, sulfuric acid, Sodium Nitrite and
water.Then, by 3, the mol ratio of 4-methylene-dioxy phenylglycollic acid and oxygen
is 1: 3.0, aerating oxygen, and sealed reactor.Start and stir, reaction solution is heated to
30 ℃, behind the reaction 24.0h, reaction solution is cooled to room temperature, obtain
gas, liquid and solid, with liquid and solids constituent from after obtain acid filtrate and
piperonal product, will obtain reclaiming gas (comprising oxynitride and oxygen) after
the carbon dioxide separation in the gaseous product.By the acid filtrate and the
piperonal product of HPLC analytical reaction gained, can obtain the piperonal
productive rate is 95.2%, and reaction preference is 99.2%.

By 3,4-methylene-dioxy phenylglycollic acid, the mol ratio of oxynitride and oxygen is

1: 0.01: 3.0, the recovery gas that oxygen and (1) step are obtained is passed into and is
equipped with 3,4-methylene-dioxy phenylglycollic acid and (1) step obtain in the
reactor of acid filtrate, sealed reactor, start and stir, reaction solution is heated to 30 ℃,
behind the reaction 24.0h, reaction solution is cooled to room temperature, obtain gas,
liquid and solid, with liquid and solids constituent from after obtain acid filtrate and
piperonal product, will obtain reclaiming gas (comprising oxynitride and oxygen) after
the carbon dioxide separation in the gaseous product.By the acid filtrate and the
piperonal product of HPLC analytical reaction gained, can obtain the piperonal
productive rate is 85.2%, and reaction preference is 99.6%.

Repeat the operation of the 2nd step.After reaction finished, by the acid filtrate and the
piperonal product of HPLC analytical reaction gained, can obtain the piperonal
productive rate was 81.6%, and reaction preference is 99.0%.

Embodiment 4

By 3,4-methylene-dioxy phenylglycollic acid: nitric acid: sulfuric acid: the mol ratio of
Sodium Nitrite is 1: 1.0: 0.2: 0.05, the water add-on is that to make concentration of
nitric acid be that 0.50mol/L is as the criterion, with 3, and the disposable adding reactor
of 4-methylene-dioxy phenylglycollic acid, nitric acid, sulfuric acid, Sodium Nitrite and
water.Then, by 3, the mol ratio of 4-methylene-dioxy phenylglycollic acid and oxygen
is 1: 1.0, aerating oxygen, and sealed reactor.Start and stir, reaction solution is heated to
100 ℃, behind the reaction 0.1h, reaction solution is cooled to room temperature, obtain
gas, liquid and solid, with liquid and solids constituent from after obtain acid filtrate and
piperonal product, will obtain reclaiming gas (comprising oxynitride and oxygen) after
the carbon dioxide separation in the gaseous product.By the acid filtrate and the
piperonal product of HPLC analytical reaction gained, can obtain the piperonal
productive rate is 86.4%, and reaction preference is 88.3%.

By 3,4-methylene-dioxy phenylglycollic acid, the mol ratio of oxynitride and oxygen is

1: 2.00: 1.0, the recovery gas that oxygen and (1) step are obtained is passed into and is
equipped with 3,4-methylene-dioxy phenylglycollic acid and (1) step obtain in the
reactor of acid filtrate, sealed reactor, start and stir, reaction solution is heated to 100 ℃,
behind the reaction 0.1h, reaction solution is cooled to room temperature, obtain gas,
liquid and solid, with liquid and solids constituent from after obtain acid filtrate and
piperonal product, will obtain reclaiming gas (comprising oxynitride and oxygen) after
the carbon dioxide separation in the gaseous product.By the acid filtrate and the
piperonal product of HPLC analytical reaction gained, can obtain the piperonal
productive rate is 92.4%, and reaction preference is 93.5%.

Repeat the operation of the 2nd step.After reaction finished, by the acid filtrate and the
piperonal product of HPLC analytical reaction gained, can obtain the piperonal
productive rate was 91.2%, and reaction preference is 92.0%.