CN114874166B - Method for safely synthesizing 5-hydroxymethyl furnitrile under low temperature condition - Google Patents

Method for safely synthesizing 5-hydroxymethyl furnitrile under low temperature condition Download PDF

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CN114874166B
CN114874166B CN202210666634.5A CN202210666634A CN114874166B CN 114874166 B CN114874166 B CN 114874166B CN 202210666634 A CN202210666634 A CN 202210666634A CN 114874166 B CN114874166 B CN 114874166B
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catalyst
hydroxymethyl
hydroxymethylfurfural
low temperature
furnitrile
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CN114874166A (en
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王延吉
高璇
李志会
张东升
赵新强
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Hebei University of Technology
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D307/00Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
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    • Y02P20/584Recycling of catalysts

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Abstract

The invention relates to a method for safely synthesizing 5-hydroxymethyl furfuryl nitrile under a low temperature condition. The method comprises the following steps: by reacting 5-hydroxymethylfurfural with free NH 2 Adding an OH aqueous solution, a catalyst and a solvent into a reactor, and reacting for 1-120 min at the temperature of 20-80 ℃ under normal pressure to obtain a product of 5-hydroxymethyl furfuryl nitrile; the catalyst is HY and HZSM-5、Amberlyst‑15、ZnCl 2 、Cu(OAc) 2 The catalyst is not treated before being used. The method has no potential safety hazard caused by the existence of oxygen in the ammoxidation method, can generate 5-hydroxymethyl furnitrile without using a catalyst, and is safe and green at low reaction temperature.

Description

Method for safely synthesizing 5-hydroxymethyl furnitrile under low temperature condition
Technical Field
The invention belongs to the field of biomass conversion preparation chemicals, and particularly relates to a method for safely synthesizing 5-hydroxymethyl furonitrile at a low temperature.
Background
Hydroxynitriles are an important class of chemical intermediates that, due to their reactive hydroxyl and cyano groups, are capable of undergoing a series of reactions such as hydrogenation, hydrolysis, dehydrogenation, ring opening, and the like, to derive a number of fine chemical products for use as pharmaceutical, pesticide, and fuel aids, and the like (Nat. Commun.,2018,9 (1): 933). The 5-hydroxymethyl furfuryl nitrile is an intermediate product generated in the reaction process of preparing amide, iminoester and the like by ammoxidation of a platform compound of 5-hydroxymethyl furaldehyde, the 5-hydroxymethyl furfuryl amine can be obtained by hydrogenation, and the 5-hydroxymethyl furfuryl amide can be obtained by hydrolysis.
5-hydroxymethylfuronitrile is mainly prepared by ammoxidation of 5-hydroxymethylfurfural. Li and the like are 0.25mmol of 5-hydroxymethyl furfural, beta-MnO 2 0.1g,NH 3 200uL,DMF 10mL,O 2 Under the conditions of 0.5mpa and 100 ℃ for 1 hour, the 5-hydroxymethyl furfuryl nitrile (Chin.J.chem.2017, 35 (6): 1-7) with the yield of 25% is obtained. Slowly adding 0.25mmol of 5-hydroxymethylfurfural, 95mg of Fe-OMS-2,0.7mmol of ammonium oxalate and 2mL of benzonitrile into a 20mL stainless steel reaction kettle with polytetrafluoroethylene lining, and filling 0.4MPa O 2 Heating to 105 deg.C, reacting at the temperature for 12h to obtain 5-hydroxymethyl furfuryl nitrile (CN 107814782A [ P ] with 98% yield].2018-03-20). Synthesis of 5-hydroxymethylfurfuronitrile by ammoxidation of 5-hydroxymethylfuraldehyde to O 2 As a raw material, the potential safety hazards such as inflammability and explosiveness exist, so that a method for safely synthesizing 5-hydroxymethyl furnitrile under mild conditions is urgently needed to be developed.
In the former stage, a series of aliphatic nitrile, aromatic nitrile and heterocyclic nitrile (RSC adv.2019,9 (31): 17131-17688) are synthesized by taking acidic ionic liquid with multiple functions such as catalyst, cosolvent and phase separation as a circulating agent and aldehyde and ionic liquid hydroxylamine salt as raw materials. However, when 5-hydroxymethylfuronitrile is synthesized by using 5-hydroxymethylfuraldehyde as a raw material, the 5-hydroxymethylfuraldehyde is subjected to polycondensation or even carbonization reaction in the presence of a strong acid ionic liquid due to active hydroxyl contained in the 5-hydroxymethylfuraldehyde molecule, and the 5-hydroxymethylfuronitrile cannot be obtained. Therefore, a green and safe 5-hydroxymethyl furonitrile synthesis method needs to be developed.
Disclosure of Invention
The invention aims to provide a method for safely synthesizing 5-hydroxymethyl furfurnitrile under a low temperature condition, aiming at the safety problem that oxygen is inflammable and explosive in the process of synthesizing 5-hydroxymethyl furfurnitrile by ammoxidation of 5-hydroxymethyl furaldehyde. The method adopts 5-hydroxymethyl furfural and free hydroxylamine aqueous solution as raw materials, and can synthesize 5-hydroxymethyl furfuronitrile under the condition of no catalyst and low temperature. The method has no potential safety hazard caused by the existence of oxygen in the ammoxidation method, can generate 5-hydroxymethyl furnitrile without using a catalyst, and is safe and green at low reaction temperature.
The technical scheme of the invention is as follows:
a method for safely synthesizing 5-hydroxymethyl furnitrile under low temperature condition, which comprises the following steps:
5-hydroxymethylfurfural, NH 2 Adding an OH aqueous solution, a catalyst and a solvent into a reactor, and reacting for 1-120 min at the temperature of 20-80 ℃ under normal pressure to obtain a product of 5-hydroxymethyl furfuryl nitrile;
wherein, the molar ratio of the materials is as follows: 5-hydroxymethylfurfural: NH (NH) 2 Oh=1: 1 to 2; adding 5-15 mL of solvent into each 1mmol of 5-hydroxymethylfurfural; adding 0-0.1 g of catalyst into each 1mmol of 5-hydroxymethylfurfural; wherein, when the amount of the catalyst is 0, it means that the catalyst is not added;
said NH 2 The concentration of the OH aqueous solution is 30-60 wt.%.
The catalyst is HY, HZSM-5, amberlyst-15, znCl 2 、Cu(OAc) 2 The catalyst is not treated before being used.
The solvent is water, absolute methanol, absolute ethanol or acetonitrile.
The material is matched withThe ratio is preferably 5-hydroxymethylfurfural: NH (NH) 2 Oh=1: 1 to 1.5; every 1mmol of 5-hydroxymethylfurfural is added with 0.05-0.07 g of catalyst.
The preferable reaction temperature is 20-55 ℃.
The preferable reaction time is 3-30 min.
The invention has the substantial characteristics that:
under the low temperature condition, the 5-hydroxymethylfurfural is safely converted into 5-hydroxymethylfuronitrile. The process can synthesize 5-hydroxymethyl furfurnitrile under the condition of no catalyst, and the yield of the 5-hydroxymethyl furnitrile can be improved by adding the catalyst. Compared with the ammoxidation method, the method has better safety and greenness.
The beneficial effects of the invention are as follows:
(1) The method realizes the synthesis of 5-hydroxymethyl furnitrile by low-temperature reaction without catalyst for the first time, the conversion rate of 5-hydroxymethyl furaldehyde can reach 97.9%, and the highest yield of 5-hydroxymethyl furnitrile can reach 41.0%.
(2) The existence of the dehydration catalyst can effectively improve the yield of the 5-hydroxymethyl furnitrile, wherein ZnCl 2 The catalytic performance is optimal, the conversion rate of the 5-hydroxymethylfurfural can reach 100%, and the yield of the 5-hydroxymethylfuronitrile is 65.6%.
(3) Compared with the ammoxidation method for synthesizing the 5-hydroxymethyl furfurnitrile, the method can generate the 5-hydroxymethyl furnitrile at room temperature, has mild reaction conditions, does not use oxygen, overcomes the risk of inflammability and explosiveness of a system under the condition of molecular oxygen aggregation, and has intrinsic safety.
Detailed Description
The essential features and significant effects of the invention can be seen from the examples which follow, without however limiting the invention in any way, and those skilled in the art can make numerous insubstantial improvements and adaptations in accordance with the teachings of the invention. The invention is further illustrated by the following detailed description.
The reaction formula for safely synthesizing the 5-hydroxymethyl furfurnitrile at low temperature by using the 5-hydroxymethyl furfuraldehyde and the hydroxylamine is shown as the following formula:
example 1
5-hydroxymethylfurfural (1 mmol), free NH 2 An aqueous OH solution (50% by mass, containing 1.5 mmol) which showed very little water content in the aqueous free hydroxylamine solution containing 1.5mmol, was negligible compared to 10mL of solvent added, and solvent water (10 mL) were added to a three-necked flask, and the reaction was stirred at 55℃for 30min without catalyst. After the reaction, the sample was taken and analyzed by gas chromatography, and as a result, the conversion of 5-hydroxymethylfurfural was 97.9%, and the yield of 5-hydroxymethylfuronitrile was 41.0%.
Example 2
The other steps were the same as in example 1 except that the reaction temperature was 20℃and the conversion of 5-hydroxymethylfurfural was 92.3% and the yield of 5-hydroxymethylfuronitrile was 36.0%.
Example 3
The other steps were the same as in example 1 except that the reaction temperature was 80℃and the conversion of 5-hydroxymethylfurfural was 96.6% and the yield of 5-hydroxymethylfuronitrile was 36.0%.
Example 4
Other steps are the same as in example 1, except that NH was added 2 The OH aqueous solution was 1mmol, and as a result, the conversion of 5-hydroxymethylfurfural was 93.1%, and the yield of 5-hydroxymethylfuronitrile was 35.2%.
Example 5
Other steps are the same as in example 1, except that NH was added 2 The OH aqueous solution was 2mmol, and as a result, the conversion of 5-hydroxymethylfurfural was 98.6%, and the yield of 5-hydroxymethylfuronitrile was 38.3%.
Example 6
The other steps were the same as in example 1 except that the reaction time was 1min, and the conversion of 5-hydroxymethylfurfural was 73.7% and the yield of 5-hydroxymethylfuronitrile was 33.3%.
Example 7
The other steps were the same as in example 1 except that the reaction time was 3 minutes, and the conversion of 5-hydroxymethylfurfural was 95.2% and the yield of 5-hydroxymethylfuronitrile was 39.0%.
Example 8
The other steps were the same as in example 1 except that the reaction time was 60 minutes, and the conversion of 5-hydroxymethylfurfural was 97.9% and the yield of 5-hydroxymethylfuronitrile was 40.5%.
Example 9
The other steps were the same as in example 1 except that the reaction time was 120min, and the conversion of 5-hydroxymethylfurfural was 97.8% and the yield of 5-hydroxymethylfuronitrile was 36.1%.
Example 10
The other steps were the same as in example 1 except that 0.05g of HY molecular sieve catalyst was added, and the reaction result was that the conversion of 5-hydroxymethylfurfural was 97.1% and the yield of 5-hydroxymethylfuronitrile was 42.2%.
Example 11
The other steps were the same as in example 1 except that 0.05g of HZSM-5 molecular sieve catalyst was added, and as a result, the conversion of 5-hydroxymethylfurfural was 93.0%, and the yield of 5-hydroxymethylfuronitrile was 43.8%.
Example 12
The other steps were the same as in example 1 except that Amberlyst-15 resin catalyst was added in an amount of 0.05g, and the result of the reaction was that the conversion of 5-hydroxymethylfurfural was 96.9% and the yield of 5-hydroxymethylfuronitrile was 42.0%.
Example 13
The other steps are the same as in example 1, except that Cu (OAc) is added 2 0.05g of catalyst, and the reaction result was that the conversion of 5-hydroxymethylfurfural was 86.8% and the yield of 5-hydroxymethylfuronitrile was 51.5%.
Example 14
Other steps are the same as in example 1, except that ZnCl is added 2 0.05g of catalyst, and as a result, the conversion of 5-hydroxymethylfurfural was 91.0% and the yield of 5-hydroxymethylfuronitrile was 63.6%.
Example 15
The other steps were the same as in example 1 except that acetonitrile (10 mL) was used as the solvent, and the conversion of 5-hydroxymethylfurfural was 35.5% and the yield of 5-hydroxymethylfuronitrile was 18.4%.
Example 16
The other steps were the same as in example 1 except that absolute ethanol (10 mL) was added as a solvent, and the conversion of 5-hydroxymethylfurfural was 96.5% and the yield of 5-hydroxymethylfuronitrile was 35.1%.
Example 17
The other steps were the same as in example 1 except that anhydrous methanol (10 mL) was added as a solvent, and the conversion of 5-hydroxymethylfurfural was 98.4% and the yield of 5-hydroxymethylfuronitrile was 50.4%.
Example 18
Other steps are the same as in example 17, except that ZnCl is added 2 0.05g of catalyst, and the reaction result was that the conversion of 5-hydroxymethylfurfural was 100% and the yield of 5-hydroxymethylfuronitrile was 65.6%.
Example 19
Other steps are the same as in example 17, except that ZnCl is added 2 0.07g of catalyst, the conversion of 5-hydroxymethylfurfural was 95.2%, and the yield of 5-hydroxymethylfuronitrile was 59.6%.
Example 20
Other steps are the same as in example 17, except that ZnCl is added 2 0.1g of catalyst, the conversion of 5-hydroxymethylfurfural was 96.6%, and the yield of 5-hydroxymethylfuronitrile was 55.9%.
According to the above examples, 5-hydroxymethylfurfural can react with hydroxylamine to produce 5-hydroxymethylfuronitrile without a catalyst. The reaction solvent affects the reaction performance, and the yield of the 5-hydroxymethyl furfurnitrile in the absolute methanol is better than that in solvent water. The catalyst is added into the reaction system to improve the yield of the 5-hydroxymethyl furnitrile, wherein ZnCl 2 The catalyst has the highest catalytic activity. 1mmol of 5-hydroxymethylfurfural and NH 2 OH 1.5mmol, absolute methanol 10mL, znCl 2 Under the conditions of 0.05g and 55 ℃ for 30min, the conversion rate of 5-hydroxymethylfurfural is 100 percent, and the yield of 5-hydroxymethylfuronitrile is 65.6 percent. In the reactionIn the method, oxygen is not needed, the risk of inflammability and explosiveness in the traditional ammonia oxidation method is solved, and the method has intrinsic safety. The invention can realize green and safe synthesis of 5-hydroxymethyl furfurnitrile from 5-hydroxymethyl furaldehyde and hydroxylamine under low temperature condition, provides a better thought for industrial application of 5-hydroxymethyl furaldehyde as a biological platform compound, and provides a cheaper raw material source for synthesis of bio-based caprolactam.
The invention is not a matter of the known technology.

Claims (3)

1. A method for safely synthesizing 5-hydroxymethyl furfuronitrile under a low temperature condition is characterized by comprising the following steps:
by reacting 5-hydroxymethylfurfural with free NH 2 Adding an OH aqueous solution, a catalyst and a solvent into a reactor, and reacting for 1-120 min at normal pressure and room temperature to 80 ℃ to obtain a product of 5-hydroxymethyl furfuryl nitrile;
wherein, the molar ratio of the materials is as follows: 5-hydroxymethylfurfural: NH (NH) 2 Oh=1: 1-2; adding 5-15 mL of solvent into each 1mmol of 5-hydroxymethylfurfural; adding 0-0.1 g of catalyst into each 1mmol of 5-hydroxymethylfurfural; wherein, when the amount of the catalyst is 0, it means that the catalyst is not added;
said free NH 2 The concentration of the OH aqueous solution is 30-60 wt.%;
the catalyst is HY, HZSM-5, amberlyst-15, znCl 2 、Cu(OAc) 2 One of the following;
the solvent is water, absolute methanol or absolute ethanol.
2. The method for safely synthesizing 5-hydroxymethylfuronitrile at low temperature according to claim 1, wherein the molar ratio of the materials is 5-hydroxymethylfurfural: NH (NH) 2 Oh=1: 1-1.5; every 1mmol of 5-hydroxymethylfurfural is added with 0.05-0.07 g of catalyst.
3. The method for safely synthesizing 5-hydroxymethyl furnitrile under the low temperature condition according to claim 1, which is characterized in that the reaction temperature is room temperature to 55 ℃; the reaction time is 3-30 min.
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