CN101279931A

CN101279931A - Production process of CNC

Info

Publication number: CN101279931A
Application number: CNA2008100249451A
Authority: CN
Inventors: 吴重言; 吴言富; 吉士和
Original assignee: KESHENG GROUP CO Ltd JIANGSU PROV
Current assignee: JIANGSU KESHENG CROP TECHNOLOGY CO., LTD.
Priority date: 2008-05-21
Filing date: 2008-05-21
Publication date: 2008-10-08
Anticipated expiration: 2028-05-21
Also published as: CN101279931B

Abstract

The invention discloses a CNC processing technique. Toluene, tertiary butyl alcohol and KOH are mixed and then acrylonitrile is added under the protection of nitrogen; when the temperature rises to 22-38 DEG C, cycloheptyl-dialdehyde-5-alkene is added drop by drop for 2-6h; after that, the mixture reacts for 1-2.5h under constant temperature and when the PH value of the reaction solution reaches 6-10, cycloheptyl-dialdehyde-5-alkene is sampled to measure the peak of the gas phase chromatography and when the peak is less than or equal to 0.5%, the reaction is stopped and then filtrated; at this time, the mol ratio of the materials cycloheptyl-dialdehyde-5-alkene: acrylonitrile: toluene: KOH: tertiary butyl alcohol is 1:1.78-1.79:7.38-7.40:0.0765-0.0780:0.055-0.060. The method reduces byproducts and shortens processing period; the inherent quality of the CNC is improved, and the quality of the intermediate compound from the cracked CNC as well as the yield are remarkably improved.

Description

The production technique of a kind of CNC

Technical field

The invention belongs to the synthetic field of pesticide intermediate, be specifically related to a kind of [2,2]-encircle the production technique of dialdehyde in heptan-2-β-propionitrile-5-alkene.

Background technology

At present, the production of the former medicine of China's Provado has many operational paths, and is wherein in the majority with the cyclopentadiene route.[2,2]-ring dialdehyde in heptan-2-β-propionitrile-5-alkene (being called for short CNC) is the synthetic intermediate of giving a tongue-lashing the former medicine of worm quinoline of cyclopentadiene route, it is the reactant that is obtained under KOH and trimethyl carbinol katalysis by ring dialdehyde in heptan-5-alkene (NC) intermediate and vinyl cyanide (AN), CNC is the red-brown transparent oily liquid, meets high temperature and easily decomposes.

But CNC is because its production process is complicated, again not to the effective detection technique of its quality, therefore, the quality of the CNC of explained hereafter in the past can not get effective control, and production process easily fluctuates, and the production cycle is long, and the side reaction thing is more, remove in the CNC mixed solution not only difficulty but also time-consuming of solid impurity, what directly influence next procedure goes out rate and quality.

Summary of the invention

The objective of the invention is quality for shortcoming such as, by product many, Impurity removal difficulty long and CNC and not have problem than effective detection technique at the CNC production cycle, by readjusting technical data, stably manufactured process, thereby providing a kind of can reduce polymkeric substance that side reaction generates, cut down the consumption of raw materials, shorten the production cycle, be convenient to remove in the CNC mixed solution solid impurity to promote the production technique of CNC inner quality.

Purpose of the present invention can reach by following measure:

The production technique of a kind of CNC; with toluene; after the trimethyl carbinol and KOH mix; under protection of nitrogen gas, add vinyl cyanide; when rising to 22～38 ℃, temperature drips ring dialdehyde in heptan-5-alkene; the dropping time is 2～6 hours; drip and finish back insulation reaction 1～2.5 hour; when the pH of reaction solution value reaches 6～10; the gas-chromatography peak of ring dialdehyde in heptan-5-alkene is surveyed in sampling; stopped reaction and filtering when ring dialdehyde-5-alkene peak in heptan≤0.5%, wherein the mol ratio between each raw material is ring dialdehyde in heptan-5-alkene: vinyl cyanide: toluene: KOH: the trimethyl carbinol=1: 1.78～1.79: 7.38～7.40: 0.0765～0.0780: 0.055～0.060.

The temperature that vinyl cyanide adds fashionable toluene is preferably 22～27 ℃; The temperature of solvent is preferably 29～31 ℃ when dripping ring dialdehyde in heptan-5-alkene; The dropping time of ring dialdehyde in heptan-5-alkene is determined according to the amount of NC, is preferably 2.5～3.5 hours.

The concrete reaction equation of CNC synthetic is as follows:

In CNC synthetic, whether drip NC peak, end back easily determined, determining the inner quality of reaction product, big and the NC of each raw material consumption generally need be incubated more than 7 hours or 7 hours in existing technology, measures the NC peak, and its material color is scarlet and muddiness, residue is clamminess and is difficult for suction filtration, existing simultaneously reaction conditions easily forms the AN autohemagglutination down, causes AN and NC reaction not exclusively, and level of residue is big in the reactant.Intermediate FPN after the CNC cracking (2-subunit-4-cyano group butyraldehyde) yield is low.

In order to solve in the low test of FPN yield, we attempt to carry out the inner quality contrast with NC peak minute, found that the NC peak just presents a low value after finishing dripping, and the material color are transparent, and polymkeric substance obviously reduces.At this phenomenon, we carry out tracking test with this, the result comes in and goes out and expects the ground discovery with after the soaking time shortening and cooperating specific raw material consumption, the transparency that has produced material on the contrary obviously increases, level of residue obviously reduces, the obvious result such as reductions of the CNC viscosity behind the precipitation simultaneously, and be that raw material is when carrying out cracking production FPN with CNC, the yield of FPN obviously improves, and CNC cracked chemical equation is as follows:

By adjustment to CNC production technology parameter, stable production process, the side reaction resultant significantly reduces, and raw material consumption obviously descends; Shortened soaking time, the production cycle obviously shortens; When solid impurity was removed in the CNC mixed solution, filtration saved time, CNC liquid transparent color and luster; The inner quality of CNC gets a promotion, and intermediate quality after its cracking and yield are not only stable but also improve; Because the shortening of soaking time has reduced the polymkeric substance of AN in the solution, not only energy-conservation but also reduce discharging, reduced the expense of administering waste residue.

Embodiment

Embodiment 1

In exsiccant 5000L reactor, drop into 3500Kg and handled qualified toluene (content 〉=90%, moisture content≤0.02%), logical nitrogen, open and stir, drop into the 22Kg anhydrous tertiary butanol successively, the KOH of 18Kg, treat that the toluene temperature puts into 470Kg AN at 25 ℃, begin to drip NC (rolling over hundred 605Kg) at 30 ℃, the dropping time is 3 hours 5 minutes, and temperature is controlled at 30 ℃, drip and finish back insulation 1.5 hours, obtain the red-brown transparent liquid, sampling records gas-chromatography peak 0.2% (external standard method, the 2m stainless steel 5%OV-255 post of NC, 120 ℃～140 ℃ of column temperatures, vaporize 170 ℃～190 ℃, detect 200 ℃, down together), suction filtration, washing, precipitation, get 1012Kg CNC, get 500Kg CNC and drop into cracking in the still, get the FPN (content is 95.6%) of 192Kg.

Embodiment 2

In the exsiccant reactor, drop into 3403Kg and handled qualified toluene (content 〉=90%, moisture content≤0.02%), logical nitrogen, open and stir, drop into the 21.6Kg anhydrous tertiary butanol successively, 21.6Kg KOH, treat that the toluene temperature puts into 473Kg AN at 26 ℃, begin to drip NC (rolling over hundred 600Kg) at 31 ℃, the dropping time is 3 hours, and temperature is controlled at 31 ℃, drips to finish back insulation 1 hour, obtain the red-brown transparent liquid, sampling records NC peak 0.3%, suction filtration, washing, precipitation gets 1006Kg CNC, get 450KgCNC and drop into cracking in the still, get the FPN (content is 95.1%) of 176Kg.

Comparative Examples 1

In the exsiccant reactor, drop into 6125Kg and handled qualified toluene (content 〉=90%, moisture content≤0.02%), logical nitrogen, open and stir, drop into the 24Kg anhydrous tertiary butanol successively, 25.4Kg KOH, treat that the toluene temperature puts into 473Kg AN at 26 ℃, begin to drip NC (rolling over hundred 626Kg) at 31 ℃, the dropping time is 3 hours, temperature is controlled at 31 ℃, drip and finish back insulation 7 hours, obtain the scarlet troubled liquor, sampling records NC peak 0.5%, and residue is clamminess and is difficult for suction filtration and level of residue has more 40% than embodiment 2 during suction filtration, washing, precipitation gets 991Kg CNC, get 450Kg CNC and drop in the still cracking under with the condition of embodiment 2, the FPN (content is 94.7%) of 141Kg.

This shows that not only the raw material consumption is few for the method for embodiment 2, the productive rate height, and also the inner quality of the CNC that finally obtains also is significantly increased.

Claims

1; the production technique of a kind of CNC; it is characterized in that toluene; after the trimethyl carbinol and KOH mix; under protection of nitrogen gas, add vinyl cyanide; when rising to 22～38 ℃, temperature drips ring dialdehyde in heptan-5-alkene; the dropping time is 2～6 hours; drip and finish back insulation reaction 1～2.5 hour; when the pH of reaction solution value reaches 6～10; the gas-chromatography peak of ring dialdehyde in heptan-5-alkene is surveyed in sampling; stopped reaction and filtering when ring dialdehyde-5-alkene peak in heptan≤0.5%, wherein the mol ratio between each raw material is ring dialdehyde in heptan-5-alkene: vinyl cyanide: toluene: KOH: the trimethyl carbinol=1: 1.78～1.79: 7.38～7.40: 0.0765～0.0780: 0.055～0.060.

2, technology according to claim 1 is characterized in that the temperature that vinyl cyanide adds fashionable toluene is 22～27 ℃.

3, technology according to claim 1, the temperature when it is characterized in that dripping ring dialdehyde in heptan-5-alkene is 29～31 ℃.

4, technology according to claim 1, the dropping time that it is characterized in that encircling dialdehyde in heptan-5-alkene is 2.5～3.5 hours.