CN100500653C

CN100500653C - Method for synthesizing 2-pyrrole methyl formate

Info

Publication number: CN100500653C
Application number: CN 200710061824
Authority: CN
Inventors: 孙予罕; 魏伟; 范素兵; 王秀芝; 赵宁; 李军平; 肖福魁
Original assignee: Shanxi Institute of Coal Chemistry of CAS
Current assignee: Shanxi Institute of Coal Chemistry of CAS
Priority date: 2007-04-25
Filing date: 2007-04-25
Publication date: 2009-06-17
Anticipated expiration: 2027-04-25
Also published as: CN101054359A

Abstract

The present invention relates to synthetic method of methyl pyrrole-2-carboxylate, which includes adding dimethyl carbonate and pyrrole into reactor by mole ratio of 1to10, then adding catalyst which account for 1 to 4wt% of total mass of both raw materials, reacting 1 to 6h under 200 to 300 DEG C. The present invention has the advantages of simple technique, environment friendly, mild reaction condition, catalyst preparing simply and low cost, and has very good industry application prospect.

Description

A kind of synthetic method of 2-pyrrole methyl formate

Technical field

The invention belongs to a kind of method of reacting Synthetic 2-pyrrole methyl formate by methylcarbonate and pyrroles.

Background technology

" green material " methylcarbonate is methylating at present, all plays a part very importantly in transesterify and the carbonylation reaction, and the methylcarbonate methoxycarbonyl turns into less report also.The pyrroles is because its N atom is very active; under the basic catalyst effect, always generate 1-pyrrole methyl formate (a) during the methoxy carbonylation in a large number; and 2-pyrrole methyl formate (b) output seldom or does not substantially have, and the catalyzer that has certain function by use makes that directly obtaining the 2-pyrrole methyl formate becomes possibility.

2-pyrrole methyl formate compound is widely used in biology, medical science, fields such as chemical industry, the chemical synthesis process of having reported at present is by the pyrroles Yu Geshi of elder generation reagent react, and then with powder solid CO ₂Reaction obtains acid, and then carries out esterification and obtain, and perhaps by pyrroles elder generation Synthetic 2-pyrrole aldehyde, obtain acid with the silver salt oxidation, and then esterification obtains.But above synthetic method all needs multistep synthetic, and yield is lower, therefore develops this green methoxycarbonyl reaction process very important that seem.

Summary of the invention

The purpose of this invention is to provide a kind of simple and convenient method that can prepare the 2-pyrrole methyl formate step by pyrroles and dimethyl carbonate.

Reaction formula of the present invention is:

With methylcarbonate and pyrroles is raw material, does not add any organic solvent in reaction process, and reaction process adopts isothermal operation, working load catalyzer, the green chemical industry technology of one-step synthesis 2-pyrrole methyl formate in the certain reaction temperature range.

Concrete synthetic method of the present invention comprises the steps:

With methylcarbonate and pyrroles methylcarbonate in molar ratio: pyrroles=1～10 adds reactor, adds catalyzer then, and the catalyzer add-on is 1～4wt% of two kinds of raw material total masses, under 200～300 ℃ of temperature, reacts 1～6 hour.

Aforesaid catalyzer is KI, K ₂CO ₃, Ag/ZnO, period 4 subgroup metallic element (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) oxide compound and load K catalyzer thereof.KI, K ₂CO ₃With the oxide compound of period 4 subgroup metallic element be the commercial goods, K salt supported catalyst by dipping method make (concrete grammar is referring to " gas chemical industry ", 2006,31 (1), 39), wherein the charge capacity of sylvite is that 1～200wt% of carrier (is designated as 1wt%K/M _mO _n～200wt%K/M _mO _n, M is a period 4 subgroup metallic element), Ag/ZnO then (is designated as Ag by the coprecipitation method preparation _xZn _yO, x and y are the percentage composition of the amount of metallics in the catalyzer).

Compare with traditional building-up process, the present invention has the following advantages:

(1) raw material green non-pollution is a kind of process for cleanly preparing;

(2) building-up process is simple, and a step can obtain product, concise production process;

(3) Preparation of Catalyst is simple, and can etching apparatus.

Embodiment

The present invention illustrates with following embodiment, but the present invention is not limited to following examples, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.

Embodiment 1

A certain amount of carrier (this example is ZnO) is joined K ₂CO ₃The aqueous solution in and flooded 12 hours, afterwards 110 ℃ of down bakings 12 hours; 600 ℃ of following roastings 3 hours, naturally cooling obtained the 17wt%K/ZnO supported catalyst again, sealed standby.

In the 150ml autoclave, add the catalyzer 17wt%K/ZnO that 6.7g pyrroles, 18.2g methylcarbonate, 0.5g prepare successively, the good seal reactor, slowly be warming up to 250 ℃ by temperature controller control heating, and use magnetic stirring apparatus to carry out whole process and stir, reacted 3 hours, after cooling with tap water immediately after reaction finishes, unload still, the liquid sample of gained is analyzed with Tianjin, island capillary chromatography, and 2-pyrrole methyl formate yield is 37.7%, and selectivity is 717%.

Embodiment 2

With embodiment 1, at first prepare catalyzer 102wt%K/ZnO, in reactor, add 6.0g pyrroles, 18.2g methylcarbonate, 0.5g100wt%K/ZnO then, 200 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 50.2%, and selectivity is 80.1%.

Embodiment 3

With embodiment 1, at first prepare catalyzer 200wt%K/ZnO, in reactor, add 6.71g pyrroles, 18.18g methylcarbonate, 0.5g200wt%K/ZnO then, 250 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 54.8%, and selectivity is 83.6%.

Embodiment 4

With embodiment 1, at first make catalyzer 30%K/Fe ₂O ₃, in reactor, add 6.7g pyrroles, 18.2g methylcarbonate, 0.5g30%K/Fe then ₂O ₃, 200 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 32.8%, selectivity is 91.0%.

Embodiment 5

With embodiment 1, at first make catalyzer 30%K/Co ₂O ₃, in reactor, add 6.8g pyrroles, 18.2g methylcarbonate, 0.5g30%K/Co then ₂O ₃, 200 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 65.6%, selectivity is 94.9%.

Embodiment 6

With embodiment 1, at first make catalyzer 30%K/NiO, in reactor, add 6.7g pyrroles, 18.1g methylcarbonate, 0.5g 30%K/NiO then, 200 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 63.3%, and selectivity is 97.2%.

Embodiment 7

With embodiment 1, in reactor, add 6.7g pyrroles, 18.2g methylcarbonate, 0.50g V ₂O ₅, 200 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 28.6%, selectivity is 69.5%.

Embodiment 8

With embodiment 1, in reactor, add 6.7g pyrroles, 18.2g methylcarbonate, 0.5g Co ₂O ₃, 200 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 33.4%, selectivity is 93.5%.

Embodiment 9

With embodiment 1, add 3.3g pyrroles, 20.0g methylcarbonate, 0.4gZnO in the reactor, 250 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 13.9%, selectivity is 26.4%.

Embodiment 10

With embodiment 1, add 6.7g pyrroles, 18.1g methylcarbonate, 0.5gMnO in the reactor ₂, 200 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 60.6%, selectivity is 94.5%.

Embodiment 11

With embodiment 1, add 2.5g pyrroles, 27.2g methylcarbonate, 0.5gK in the reactor ₂CO ₃, 250 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 19.6%, selectivity is 48.3%.

Embodiment 12

With embodiment 1, add 10.0g pyrroles, 27.0g methylcarbonate, 0.5g K in the reactor ₂CO ₃, 280 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 34.1%, selectivity is 41.9%.

Embodiment 13

With embodiment 1, add 10.0g pyrroles, 26.8g methylcarbonate, 0.5g K in the reactor ₂CO ₃, 200 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 7.0%, selectivity is 23.2%.

Embodiment 14

With embodiment 1, add 8.2g pyrroles, 11.5g methylcarbonate, 0.5gKI in the reactor, 200 ℃ of temperature of reaction, in 6 hours reaction times, 2-pyrrole methyl formate yield is 11.5%, selectivity is 35.0%.

Embodiment 15

With embodiment 1, add 6.7g pyrroles, 18.2g methylcarbonate, 1.00g KI in the reactor, 200 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 12.9%, selectivity is 38.3%.

Embodiment 16

With a certain amount of AgNO ₃And Zn (NO ₃) ₂Use water dissolution, drip Na then while stirring ₂CO ₃Solution makes and its pH=9 left standstill 3 hours, filters, and washing obtained Ag in 4 hours 400 ℃ of following roastings then _0.1Zn _0.9The O catalyzer.

In reactor, add 6.7g pyrroles, 18.2g methylcarbonate, 0.5g Ag _0.1Zn _0.9O, 250 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 30.7%, selectivity is 59.7%.

Embodiment 17

With embodiment 16, at first prepare catalyst A g _0.1Zn _0.9O adds 5.8g pyrroles, 18.0g methylcarbonate, 0.5g Ag then in reactor _0.1Zn _0.9O, 200 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 42.7%, selectivity is 91.5%.

Embodiment 18

With embodiment 16, at first prepare catalyst A g _0.25Zn _0.75O adds 6.7g pyrroles, 18.2g methylcarbonate, 0.5g Ag then in reactor _0.25Zn _0.75O, 200 ℃ of temperature of reaction, in 3 hours reaction times, 2-pyrrole methyl formate yield is 61.5%, selectivity is 96.6%.

Claims

1, a kind of synthetic method of 2-pyrrole methyl formate is characterized in that comprising the steps:

With methylcarbonate and pyrroles methylcarbonate in molar ratio: pyrroles=1～10 adds reactor, adds catalyzer then, and the catalyzer add-on is 1～4wt% of two kinds of raw material total masses, under 200～300 ℃ of temperature, reacts 1～6 hour;

Described catalyzer is KI, K ₂CO ₃, Ag/ZnO, period 4 subgroup metallic element oxide compound or its load K catalyzer;

Described period 4 subgroup metallic element is V, Mn, Fe, Co, Ni or Zn.