CN109867284B - Reagent capable of releasing carbon monoxide on site and preparation and application thereof - Google Patents
Reagent capable of releasing carbon monoxide on site and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a reagent capable of releasing carbon monoxide on site and preparation and application thereof, and the key points of the invention are as follows: formic ether is dissolved in a certain amount of solvent, then a catalytic amount of organic base is added, the mixture is uniformly mixed at 0 to 25 ℃, and the mixture is placed in a bottle for standby. When it is used, it can be taken out in an equal proportion and injected into the reaction system. Heating to 70-130 deg.c to release CO for reaction. The release process is mild, controllable, efficient and stable as shown by the embodiment and the application example. The mixed system of the invention is stable at room temperature, convenient for storage and treatment, and does not generate potential safety hazard. By adopting the method, the CO generation rate can be adjusted through concentration and temperature, and the requirements of different conditions can be met.
Description
Technical Field
The invention belongs to the field of laboratory or industrial gas preparation, and particularly relates to a reagent capable of releasing carbon monoxide on site, and preparation and application thereof.
Background
Carbon monoxide is an important chemical raw material and is widely used in industrial production. In industry, carbon monoxide is produced on a large scale by coke gasification, and the method is low in price and convenient for large-scale production. However, this method requires a relatively complicated separation process to remove by-products such as carbon dioxide, oxygen and water. In addition, the method can be used for preparing carbon monoxide by adopting a formic acid dehydration method in industry, and the method needs to use a large amount of sulfuric acid, has large pollution and is not environment-friendly.
In addition to industrial production, carbon monoxide is also frequently used in laboratories. As a classical one-carbon synthon, CO plays a key role in the carbonyl insertion reaction and provides an important idea for the synthesis of carbonyl compounds (document I: wang, G.; mcCreanor, N.G.; shaw, M.H.; whittingham, W.G.; bower, J.F.J.Am.Chem.Soc.2016,138,13501. Document II: fang, X.; li, H.; jacksell, R.; beller, M.J.Am chem.Soc.2014,136,16039. III: jacksell, R.; fang, X.; beller, M.Angew.m., int.Ed.2013,52, 14089.). Since the amount of carbon monoxide used in the laboratory is not large, the industrial process is not suitable for the production. If the laboratory needs to use carbon monoxide, a CO steel cylinder is often used as a gas source. However, because the dosage of CO in a laboratory is small, and CO has the characteristics of high toxicity and high combustibility, the wide use of CO steel cylinders is limited, and great potential safety hazards are brought. Therefore, the method for safely and conveniently using CO is developed for a laboratory, and has great significance.
Disclosure of Invention
The invention provides a reagent capable of releasing carbon monoxide on site, and preparation and application thereof.
An agent capable of releasing carbon monoxide on site comprises the following components in parts by weight:
1.0-3.0 parts of carbonyl source;
0.001-0.1 part of catalyst;
the carbonyl source is formic ether, and the structure is shown as the formula (I):
r is a group including but not limited to C 1 ～C 10 Alkyl or C 2 ～C 10 Alkenyl and the like;
the catalyst is organic alkali, and the structural formula is shown as (II) or (III):
in formulae (II) to (III), R 1 ～R 5 Is hydrogen or alkyl, etc., and m and n are integers between 0 and 4.
Preferably, the reagent further comprises a solvent, and the amount of the solvent is 5-15 times of the mass of the carbonyl source. As a further preference, the solvent includes one or more of benzene, toluene, xylene, trimethylbenzene, chlorobenzene, acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, ether solvents, and the like.
The invention also provides a preparation method of the reagent capable of releasing carbon monoxide on site, which comprises the step of uniformly mixing the carbonyl source, the catalyst and the solvent at 0-25 ℃ to obtain the reagent.
The invention also provides application of the reagent capable of releasing carbon monoxide on site, which is characterized in that the reagent is mixed with a reaction system and heated to 70-130 ℃, and CO is released to participate in the reaction.
The invention also provides application of another reagent capable of releasing carbon monoxide on site, which comprises the following steps:
heating the reagent to 70-130 ℃, introducing the generated gas into a reaction system requiring carbon monoxide to participate in the reaction, and reacting to obtain a product.
The formic ether is dissolved in a certain amount of solvent, then a catalytic amount of organic base is added, and the mixture is uniformly mixed at 0-25 ℃ and placed in a bottle for standby. When it is used, it can be taken out in an equal proportion and injected into the reaction system. Then heating to 70-130 deg.C, releasing CO to participate in reaction. In the case of n-butyl formate, it is dissolved in deuterated benzene, and a catalytic amount of 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (TBD) is added and reacted at 110 ℃. The reaction was monitored by NMR, and as a result, as shown in FIG. 1, hydrogen (H) of n-butyl formate was found a ) Slowly decreases and completely disappears after 6 hours; while the hydrogen on the intermediate A goes through the process from more to less and completely disappears after 8 hours. Indicating that the CO is slowly released during the process.
Meanwhile, n-butyl formate (100 mmol) was dissolved in toluene (100 mL), and a catalytic amount of 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (2.5%, 2.5 mmol) was added, and the mixture was left at room temperature for 4 months and then taken out for use, and the reaction yield was substantially unchanged. The system is very stable and can meet the daily requirements of laboratories.
Compared with the prior art, the invention has the beneficial effects that:
(1) The raw materials for generating CO are common reagents in a laboratory, and CO can be generated mildly, controllably, efficiently and stably under the laboratory condition without a CO steel cylinder;
(2) The mixed system is stable at room temperature, is convenient to store and treat, and has no potential safety hazard;
(3) By adopting the method, the CO generation rate can be adjusted through concentration and temperature, and the requirements of different conditions can be met.
Drawings
FIG. 1 is a NMR spectrum of a carbon monoxide releasing agent of the present invention over time.
Detailed Description
Example 1
10.2g of n-butyl formate (100 mmol), 0.348g of 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (TBD, 2.5 mmol) and toluene (100 mL) were mixed at room temperature to obtain a homogeneous solution A, and the solution A was left at room temperature for 120 days and examined to find that no CO gas was generated.
Heating the solution A to 80 ℃, uniformly generating gas, collecting the generated gas, wherein the gas releasing time is 8h, the detection result is CO, the purity is 95%, and the gas generation amount is 2.12L.
Example 2
13.0g of n-hexyl formate (100 mmol), 0.348g of 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (TBD, 2.5 mmol) and xylene (100 mL) were mixed at room temperature to obtain a homogeneous solution B, and the solution B was left at room temperature for 60 days and examined to find that no CO gas was generated.
Heating the solution B to 100 ℃, uniformly generating gas, collecting the generated gas, wherein the gas releasing time is 5h, the detection result is CO, the purity is 94%, and the gas generation amount is 2.20L.
Example 3
8.81g of propyl formate (100 mmol), 0.348g of 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (TBD, 2.5 mmol) and tetrahydrofuran (100 mL) were mixed at room temperature to obtain a homogeneous solution C, and the solution C was left at room temperature for 30 days and examined to find that no CO gas was generated.
Heating the solution C to 70 ℃, uniformly generating gas, collecting the generated gas, and detecting that the gas release time is 10h, the purity is 93 percent, and the gas generation amount is 1.96L.
Application example 1
To a 15mL stopcock were added p-methyliodobenzene (218mg, 1mmol), pd in that order 2 (dba) 3 (46mg, 5% mmol), 1.2mL (1.2 equiv.) of a CO-generating solution, 1, 8-diazabicycloundece-7-ene (DBU, 182mg,1.2 mmol), and 3.8mL of toluene were bottled. It was sealed and reacted at 80 ℃ for 8h. Cooling, adding water (10 mL), extracting twice with ethyl acetate (5 mL), combining organic phases, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, removing solvent by rotary extraction, and performing column chromatography to obtain the product.
A colorless liquid, 150mg,78% yield; 1 H NMR(400MHz,CDCl 3 )δ7.92(d,J＝8.0Hz,2H),7.21(d,J＝8.0Hz,2H),4.29(t,J＝6.0Hz,2H),2.39(s,3H),1.73(dd,J＝1.0,5.0Hz,2H),1.50–1.43(m,2H),0.96(t,J＝7.0Hz,3H)； 13 C NMR(100MHz,CDCl 3 )δ166.8,143.4,129.5,129.0,127.8,64.6,30.8,21.6,19.3,13.8；IR(neat)3480,1641,740cm -1 ；HRMS(EI-TOF)calcd forC 12 H 16 O 2 192.1150,found 192.1152.
application example 2
In a 15mL stopcock, iodobenzene (204mg, 1mmol), pdCl were added in that order 2 (18mg, 10 mmol), and bottled CO generation liquid A1.5mL (1.5 equiv.), triethylamine (152mg, 1.5mmol), and 3.5mL of toluene. It was blocked and reacted at 130 ℃ for 4h. Cooling, adding water (10 m)L), extracting twice with ethyl acetate (5 mL), combining organic phases, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, removing the solvent by rotation, and performing column chromatography to obtain the product.
A colorless liquid, 142mg,80% yield; 1 H NMR(400MHz,CDCl 3 )δ8.08–7.97(m,2H),7.57–7.50(m,1H),7.42(dd,J＝10.0,5.0Hz,2H),4.31(t,J＝6.0Hz,2H),1.78–1.71(m,2H),1.47(dd,J＝15.0,7.0Hz,2H),0.97(t,J＝7.0Hz,3H)； 13 C NMR(100MHz,CDCl 3 )δ166.7,132.8,130.5,129.5,128.3,64.8,30.7,19.3,13.8；IR(neat)3477,1640,740cm -1 ；HRMS(EI-TOF)calcdfor C 11 H 14 O 2 178.0994,found 178.0995.
application example 3
To a 15mL stopcock were added iodobenzene (204mg, 1mmol), pd (OAc) in that order 2 (11.2 mg,5% mmol), 2.0mL (2.0 equiv.) of a bottled CO generation solution C, n-butylamine (219mg, 3mmol), triethylamine (202mg, 2.0 mmol), and 3.0mL of tetrahydrofuran. It was sealed and reacted at 100 ℃ for 6h. Cooling, adding water (10 mL), extracting twice with ethyl acetate (5 mL), combining organic phases, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, removing solvent by rotary extraction, and performing column chromatography to obtain the product.
White solid, 152mg,86% yield; 1 H NMR(400MHz,CDCl 3 )δ7.75–7.71(m,2H),7.49–7.43(m,1H),7.39(t,J＝7.0Hz,2H),6.27(br,1H),3.46–3.40(m,2H),1.60–1.55(m,2H),1.38(dd,J＝15.0,7.0Hz,2H),0.93(t,J＝7.0Hz,3H)； 13 C NMR(100MHz,CDCl 3 )δ167.6,134.7,131.3,128.5,126.8,39.8,31.7,20.1,13.8；IR(neat)3462,1640,701cm -1 ；HRMS(EI-TOF)calcdfor C 11 H 15 NO 177.1154,found 177.1155.
application example 4
To a 15mL stoppered tube were added N-benzyl-2-iodobenzylamine (323mg, 1mmol), pd (PPh) in that order 3 ) 4 (29mg, 2.5 mmol), 1.3mL (1.3 equiv.) of CO-generating solution B in a bottle, N-ethyldiisopropylamine (168mg, 1.3 mmol), and 3.7mL of xylene. It was sealed and reacted at 110 ℃ for 5h. Cooling, adding water (10 mL), extracting twice with ethyl acetate (5 mL), combining organic phases, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, removing the solvent by spinning, and performing column chromatography to obtain the product.
White solid, 168mg,75% yield; 1 H NMR(400MHz,CDCl 3 )δ7.87(d,J＝7.0Hz,1H),7.48(dd,J＝11.0,4.0Hz,1H),7.43(t,J＝7.0Hz,1H),7.35(d,J＝7.0Hz,1H),7.33–7.30(m,1H),7.29(d,J＝3.0Hz,3H),7.26(d,J＝7.0Hz,1H),4.78(s,2H),4.23(s,2H)； 13 C NMR(100MHz,CDCl 3 )δ168.4,141.2,137.0,132.6,131.3,128.8,128.1,128.0,127.6,123.8,122.8,49.4,46.3；IR(neat)3466,1679,737cm -1 ；HRMS(EI-TOF)calcd for C 15 H 13 NO 223.0997,found 223.0998.
application example 5
To a 15mL stopcock were added p-methyliodobenzene (218mg, 1mmol), pd in that order 2 (dba) 3 (46mg, 5 mmol), bottled CO-generating solution A2.0mL (2.0 equiv.), 1-hexyne (246mg, 3mmol), 1, 8-diazabicycloundecen-7-ene (DBU, 182mg, 1.2mmol), and 3.0mL of toluene. It was sealed and reacted at 80 ℃ for 12h. Cooling, adding water (10 mL), extracting twice with ethyl acetate (5 mL), combining organic phases, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, removing the solvent by spinning, and performing column chromatography to obtain the product.
Yellow liquid, 150mg,75% yield; 1 H NMR(400MHz,CDCl 3 )δ8.01(d,J＝8.0Hz,2H),7.25(d,J＝8.0Hz,2H),2.48(t,J＝7.0Hz,2H),2.41(s,3H),1.67–1.62(m,2H),1.52–1.46(m,2H),0.94(t,J＝7.0Hz,3H)； 13 C NMR(100MHz,CDCl 3 )δ178.0,144.9,134.6,129.7,129.2,96.3,79.7,29.8,22.1,21.8,18.9,13.5；IR(neat)3466,1642,740cm -1 ；HRMS(EI-TOF)calcd forC 14 H 16 O 200.1201,found 200.1202.
Claims (4)
1. use of an agent capable of releasing carbon monoxide in situ, comprising the steps of:
in a 15mL sealed tube, 1mmol of iodobenzene and PdCl are sequentially added 2 10 mmol, bottling CO generating liquid A1.5mL, triethylamine 1.5mmol, and 3.5mL toluene, sealing, reacting at 130 deg.C for 4h, cooling, adding water 10mL, extracting with ethyl acetate 5mL twice, combining organic phases, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, removing solvent by rotation, and performing column chromatography to obtain product;
the preparation process of the CO generation liquid A is as follows:
10.2g of n-butyl formate (100 mmol), 0.348g of 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (2.5 mmol) and toluene (100 mL) were mixed at room temperature to obtain a homogeneous solution A.
2. Use of an agent for the in situ release of carbon monoxide, comprising the steps of:
in a 15mL sealed tube, 1mmol of iodobenzene, pd (OAc) were added in this order 2 5mmol, 2.0mL of bottled CO generating solution C, 3mmol of n-butylamine, 2.0mmol of triethylamine and 3.0mL of tetrahydrofuran, sealing, reacting at 100 ℃ for 6h, cooling, adding 10mL of water, extracting twice with 5mL of ethyl acetate, combining organic phases, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, removing solvent by rotation, and performing column chromatography to obtain a product;
the preparation process of the CO generation liquid C is as follows:
8.81g of propyl formate, 0.348g of 1,5, 7-triazabicyclo (4.4.0) dec-5-ene and 100mL of tetrahydrofuran were mixed uniformly at room temperature to obtain a uniform solution C.
3. Use of an agent for the in situ release of carbon monoxide, comprising the steps of:
in a 15mL sealed tube, 1mmol of N-benzyl-2-iodobenzylamine 3 ) 4 2.5mmol, bottled CO generating solution B1.3mL, N-ethyldiisopropylamine 1.3mmol, and 3.7mL xylene; sealing the reaction kettle, and reacting at 110 ℃ for 5 hours; cooling, adding 10mL of water and 5mL of ethyl acetate, extracting twice, combining organic phases, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, removing the solvent by rotation, and performing column chromatography to obtain a product;
the preparation process of the CO generation liquid B is as follows:
13.0g of n-hexyl formate, 0.348g of 1,5, 7-triazabicyclo (4.4.0) dec-5-ene and 100mL of xylene were mixed at room temperature to obtain a homogeneous solution B.
4. Use of an agent for the in situ release of carbon monoxide, comprising the steps of:
in a 15mL sealed tube, 1mmol of p-methyl iodobenzene 2 (dba) 3 5mmol, bottled CO-generating liquid A2.0mL, 1-hexyne 3mmol,1, 8-diazabicycloundece-7-ene 1.2mmol, and 3.0mL of toluene; sealing the reaction kettle, and reacting at 80 ℃ for 12 hours; cooling, adding 10mL of water and 5mL of ethyl acetate, extracting twice, combining organic phases, washing with saturated sodium chloride, drying with anhydrous sodium sulfate, removing the solvent by rotation, and performing column chromatography to obtain a product;
the preparation process of the CO generation liquid A is as follows:
10.2g of n-butyl formate (100 mmol), 0.348g of 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (2.5 mmol) and toluene (100 mL) were mixed at room temperature to obtain a homogeneous solution A.
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