CN100453527C

CN100453527C - Process for preparing 4-fluorobenzylamine with nano nickel as catalyst

Info

Publication number: CN100453527C
Application number: CNB2004100149949A
Authority: CN
Inventors: 张炳庚
Original assignee: Individual
Current assignee: Individual
Priority date: 2004-05-25
Filing date: 2004-05-25
Publication date: 2009-01-21
Anticipated expiration: 2024-05-25
Also published as: CN1704397A

Abstract

The present invention discloses a method for preparing para-fluorobenzenemethanamine by a nickel catalyst by using p-fluorobenzaldehyde, hydrogen gas, absolute methanol and liquid ammonia as raw materials Under the condition that other reaction conditions are identical thoroughly, the yield of the para-fluorobenzenemethanamine prepared by adopting the present invention is more than 95% through a contrast by experiments, and the purity is more than 99%; the yield of the para-fluorobenzenemethanamine prepared by adopting a raneys nickel catalyst is only from 75 to 79%, and the purity is below 97%.

Description

A kind of is the method for Preparation of Catalyst NSC 158269 with nanometer nickel

Technical field:

The present invention relates to a kind of preparation method of NSC 158269.

Background technology:

NSC 158269 is a kind of medicine intermediate, also is a kind of organic synthesis raw material.The existing preparation method of NSC 158269 be by p-Fluorobenzenecarboxaldehyde, methyl alcohol, liquefied ammonia with Raney's nickel as catalyzer, p-Fluorobenzenecarboxaldehyde hydrogenation is made, the manufacturing technique requirent height of this method, used pressure big (4-5Mpa), temperature of reaction height (more than 170 ℃), hydrogen utilization ratio is little, long reaction time (about 5 hours), cost height, product yield low (below 80%), catalyst levels big (being about more than 5% of p-Fluorobenzenecarboxaldehyde consumption), product purity low (below 97%).

Summary of the invention:

The object of the present invention is to provide a kind of is the method for Preparation of Catalyst NSC 158269 with nanometer nickel.

The present invention is a raw material with p-Fluorobenzenecarboxaldehyde, hydrogen, anhydrous methanol, liquefied ammonia, as catalyzer, by proper temperature and pressure, makes p-Fluorobenzenecarboxaldehyde hydrogenation with nanometer nickel, and its reaction equation is:

Preparation process of the present invention is as follows:

Step 1: p-Fluorobenzenecarboxaldehyde, methyl alcohol, nano nickel catalyst are dropped in the autoclave, feed an amount of liquefied ammonia, its weight percent that feeds intake is: p-Fluorobenzenecarboxaldehyde: methyl alcohol: liquefied ammonia=1: (0.5～2): (0.1～0.2), nano nickel catalyst input amount are the 0.1%-1.0% of p-Fluorobenzenecarboxaldehyde consumption:

Step 2: under whipped state, be warming up to 50 ℃-120 ℃, and in reactor, feed pressure hydrogen with steam heating;

Step 3: react fully, to not inhaling till the hydrogen, reaction stops back insulation 0.5～1 hour, after the cooling of question response mixture, reaction mixture is pressed into essence puts in the still, separates nano nickel catalyst with the essence method of putting, and promptly gets the crude product of the NSC 158269 that comprises methyl alcohol;

Step 4: the NSC 158269 crude product that step 3 is obtained drops into rectifying in the rectifying still, deamination and reclaim methyl alcohol, 100 ℃ of dehydrations before 80 ℃, collect the target compound NSC 158269 for 186 ℃-190 ℃, the content of NSC 158269 is greater than 99%, and the consumption of pressing p-Fluorobenzenecarboxaldehyde calculates, and product yield is more than 95%.

The present invention is the improvement to the existing preparation technology of NSC 158269, raw materials used and existing preparation method is identical, p-Fluorobenzenecarboxaldehyde, hydrogen, anhydrous methanol, liquefied ammonia are that market is commonly used easily purchases chemical, and nano nickel catalyst is the patented product of Nanjing University of Technology, and this school has nanometer nickel to sell.Adopt nano nickel catalyst to substitute Raney's nickel catalyst, through the test contrast, under the identical situation of other reaction conditions, adopt nanocatalyst, all more than 95%, purity is more than 99% for the yield of product, and adopting the yield of Raney's nickel catalyst to have only 75～79%, purity is below 97%.Through measuring and calculating, adopt the cost of 1 ton of NSC 158269 of the every production of nano nickel catalyst will reduce about 30%, shown obvious superiority.Technology advanced person of the present invention, simple to operate, catalyst levels is few, and speed of response is fast, and cost is low, the yield height, quality is good.

Embodiment:

Illustrate the specific embodiment of the present invention below.

Embodiment 1:

Preparation process of the present invention is as follows:

Step 1: with content is that 99% p-Fluorobenzenecarboxaldehyde 300Kg, anhydrous methanol 150Kg, nano nickel catalyst 0.6Kg drop in the 1000L autoclave, feeds liquefied ammonia 30Kg, and its weight ratio that feeds intake is: p-Fluorobenzenecarboxaldehyde: methyl alcohol: liquefied ammonia=1: 0.5: 0.10; The consumption of nano nickel catalyst is 0.2% of a p-Fluorobenzenecarboxaldehyde consumption.

Step 2: be warming up to about 70 ℃ with steam heating under whipped state, feed pressure hydrogen then in reactor, pressure is 1Mpa-3Mpa;

Step 3: react fully till do not inhale hydrogen, the reaction times is about 4 hours, and reaction stops back insulation about 1 hour, is pressed into essence after the cooling of question response mixture and puts in the still, separates nano nickel catalyst with the essence method of putting, and just must comprise the crude product of the NSC 158269 of methyl alcohol;

Step 4: the NSC 158269 crude product that step 3 is obtained drops into rectifying in the rectifying still, deamination and reclaim methyl alcohol, 100 ℃ of dehydrations before 80 ℃, collect NSC 158269 for 186 ℃-190 ℃, content greater than 99% product 285Kg, press the calculating of p-Fluorobenzenecarboxaldehyde consumption, product yield is 95%.

Embodiment 2:

Step 1: with content is that 99% p-Fluorobenzenecarboxaldehyde 300Kg, anhydrous methanol 300Kg, nano nickel catalyst 1.8Kg drop in the 1000L autoclave, feeds liquefied ammonia 45Kg, and its weight ratio that feeds intake is: p-Fluorobenzenecarboxaldehyde: methyl alcohol: liquefied ammonia=1: 1: 0.15; The consumption of nano nickel catalyst is 0.6% of a p-Fluorobenzenecarboxaldehyde consumption.

Step 2: stir and be warming up to about 100 ℃, feed pressure hydrogen then in reactor, pressure is 1Mpa-3Mpa;

Step 3: react fully till do not inhale hydrogen, the reaction times is about 3 hours, and reaction stops back insulation 1 hour, is pressed into essence after the cooling of question response mixture and puts in the still, separates nano nickel catalyst with the essence method of putting, and just must contain the crude product of the NSC 158269 of methyl alcohol;

Step 4: the NSC 158269 crude product that step 3 is obtained drops into rectifying in the rectifying still, deamination and reclaim methyl alcohol, 100 ℃ of dehydrations before 80 ℃, collect NSC 158269 for 186 ℃-190 ℃, content greater than 99% product 291Kg, press the calculating of p-Fluorobenzenecarboxaldehyde consumption, product yield is 97%.

Embodiment 3:

Step 1: with content is that 99% p-Fluorobenzenecarboxaldehyde 300Kg, anhydrous methanol 600Kg, nano nickel catalyst 3Kg drop in the 1000L autoclave, feeds liquefied ammonia 60Kg, and its weight ratio that feeds intake is: p-Fluorobenzenecarboxaldehyde: methyl alcohol: liquefied ammonia=1: 2: 0.2; The consumption of nano nickel catalyst is 1% of a p-Fluorobenzenecarboxaldehyde consumption.

Step 2: stir and be warming up to 120 ℃, feed pressure hydrogen then in reactor, pressure is 1Mpa-3Mpa;

Step 3: react fully till do not inhale hydrogen, the reaction times is about 1 hour, and reaction stops back insulation about 1 hour, is pressed into essence after the cooling of question response mixture and puts in the still, separates nano nickel catalyst with the essence method of putting, and just must comprise the crude product of the NSC 158269 of methyl alcohol;

Step 4: the NSC 158269 crude product that step 3 is obtained drops into rectifying in the rectifying still, deamination and reclaim methyl alcohol, 100 ℃ of dehydrations before 80 ℃, collect NSC 158269 for 186 ℃-190 ℃, content greater than 99% product 297Kg, press the calculating of p-Fluorobenzenecarboxaldehyde consumption, product yield is 99%.

Claims

1, a kind of is the method for Preparation of Catalyst NSC 158269 with nanometer nickel, is raw material with p-Fluorobenzenecarboxaldehyde, hydrogen, anhydrous methanol, liquefied ammonia, is catalyzer with nanometer nickel, by proper temperature and pressure, makes p-Fluorobenzenecarboxaldehyde hydrogenation, and its reaction equation is:

Its preparation process is as follows:

Step 1: p-Fluorobenzenecarboxaldehyde, methyl alcohol, nano nickel catalyst are dropped in the autoclave, feed an amount of liquefied ammonia, its weight ratio that feeds intake is: p-Fluorobenzenecarboxaldehyde: methyl alcohol: liquefied ammonia=1: (0.5～2): (0.1～0.2), the input amount of nano nickel catalyst are 0.1%～1.0% of p-Fluorobenzenecarboxaldehyde consumption;

Step 2: under whipped state, be warming up to 50 ℃～120 ℃, and in reactor, feed pressure hydrogen;

Step 3: react fully till do not inhale hydrogen, reaction stops back insulation 0.5～1 hour, is pressed into essence after the cooling of question response mixture and puts in the still, separates nano nickel catalyst with the essence method of putting, and promptly gets the crude product of the NSC 158269 that comprises methyl alcohol;

Step 4: the NSC 158269 crude product that step 3 is obtained drops into rectifying in the rectifying still, deamination and reclaim methyl alcohol, 100 ℃ of dehydrations before 80 ℃, collect NSC 158269 for 186 ℃-190 ℃, the content of NSC 158269 is greater than 99%, and the consumption of pressing p-Fluorobenzenecarboxaldehyde calculates, and product yield is more than 95%.