GB2216035A - Process and catalyst for the preparation of formamide and N-substituted derivatives thereof - Google Patents
Process and catalyst for the preparation of formamide and N-substituted derivatives thereof Download PDFInfo
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- GB2216035A GB2216035A GB8807805A GB8807805A GB2216035A GB 2216035 A GB2216035 A GB 2216035A GB 8807805 A GB8807805 A GB 8807805A GB 8807805 A GB8807805 A GB 8807805A GB 2216035 A GB2216035 A GB 2216035A
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- Prior art keywords
- component
- catalyst system
- compound
- alkali
- formamide
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- 238000000034 method Methods 0.000 title claims abstract description 40
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 30
- -1 alcohol compound Chemical class 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 20
- 239000000010 aprotic solvent Substances 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 4
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- XFTIKWYXFSNCQF-UHFFFAOYSA-N N,N-dipropylformamide Chemical compound CCCN(C=O)CCC XFTIKWYXFSNCQF-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 125000001174 sulfone group Chemical group 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- IHBVNOOZVSDNLI-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethanol;1-methoxy-2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethane Chemical compound OCCOCCOCCOCCO.COCCOCCOCCOCCOC IHBVNOOZVSDNLI-UHFFFAOYSA-N 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000002904 solvent Substances 0.000 description 16
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 14
- 239000007795 chemical reaction product Substances 0.000 description 10
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000003948 formamides Chemical class 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IOFLMSIJHXBFRK-UHFFFAOYSA-N N-phenylformamide Chemical compound O=CNC1=CC=CC=C1.O=CNC1=CC=CC=C1 IOFLMSIJHXBFRK-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WZKHBEGQWSEAJI-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound OCCOCCO.COCCOCCOC WZKHBEGQWSEAJI-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0202—Alcohols or phenols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0204—Ethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/121—Metal hydrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A process for the preparation of formamide and N-substituted derivatives comprises contacting a compound having the structure H-NR<1>R<2> with CO at increased pressure in the presence of a catalyst system comprising at least: (a) a compound selected from the group consisting of an alkali or alkaline-earth metal, alkali or alkaline-earth metal hydride or an alkali or alkaline-earth metal alcoholate, and (b) an alcohol compound; the molar ratio between (a) and (b) ranging from 2:1 to 1:5.
Description
PROCESS FOR THE PREPARATION OF FORMAMIDE
AND N-SUBSTITUTED DERIVATIVES THEREOF
The invention relates to a process for the preparation of formamide and N-substituted derivatives thereof. The invention also relates to a catalyst system.
British Patent Specification 690,131, discloses a process in which primary or secondary alkyl amines are reacted at an elevated temperature with carbon monoxide or gases containing carbon monoxide under pressure in the presence of alkali or alkaline-earth alcoholates as catalyst. As is indicated a methanolic solution of an alkali or alkaline-earth metiiylate, especially sodium methylate, has proved suitable as catalyst. Moreover, in all the examples methanol is used in excess with respect to the sodium methylate, the molar ratio varying between from 44:1 (example 1) to 7.2:1 (example 4).
Such a process has two important disadvantages.
Methanol, when used in great excess, leads to the production of large quantities of the by-product methyl formate, as can be seen from the comparative examples hereinafter. Secondly, when the reaction products are to be isolated by means of distillation, the methanol, when used in great excess, should be distilled off as it has a boiling point lower than that of the reaction products. On a large scale production this means that the methanol has to be recycled, which involves a vast amount of energy and additional apparatus costs.
On the other hand British Patent Specification 718,759 discloses a process for the production of substituted formamides by the reaction of primary or secondary amines and carbon monoxide at elevated temperature and under increased pressure in the presence of carbonyl-forming metals having an atomic weight between 52 and 59 or their compounds which consists in carrying out the reaction in the presence of water. The special advantage of this process is said to be that formamides can be obtained without the formation of by-products. However, this process requires the use of temperatures between 100 and 300 OC and pressures between 50 and 350 atmospheres.The examples show, that the preferred pressure is 200 atmospheres and the preferred temperature range is from 150 to 240 OC A further disadvantage of this process is that in order to isolate the reaction products by distillation, water first has to pass over.
Due to the still growing demand for cheaper formamides which are widely used as solvents and basic chemicals on an increasingly large scale for a variety of industrial processes, there has been a continuous research in the past decades to find an improved production process which does not suffer from the above-mentioned disadvantages.
It has now surprisingly been found that formamide and
N-substituted formamides are prepared in high yields, substantially withoutby-products and at moderate temperatures and pressures. Further, when the reaction products are to be isolated by means of distillation, said distillation may be carried out substantially without the need of removing the solvent first, so without the need for recycling the distilled solvent.
Therefore, the invention provides a process for the preparation of formamide and N-substituted derivatives thereof, which process comprises carbonylating a compound having the structure H-NR1R2, wherein R1 and R2 are each independently selected from hydrogen, a hydrocarbon group optionally substituted by one or more additional primary or secondary amino groups, or wherein R and R, together with the nitrogen atom to which they are attached, form a heterocyclic group optionally containing one or more additional primary or secondary amino groups, in the liquid phase with carbon monoxide or a carbon monoxide-containing fluid at increased pressure in the presence of a catalyst system comprising at least: component (a) - a compound selected from the group
consisting of alkali and alkaline-earth
metals, alkali and alkaline-earth metal
hydrides and alkali and alkaline-earth
metal alcoholates; component (b) - an alcohol compound, the molar ratio between component (a) and component (b) varying in the range of from 2:1 to 1:5.
Preferably component (a) comprises an alkali metal, more preferably metallic sodium, an alkali metal hydride, more preferably sodium hydride, or an alkali metal alcoholate, more preferably sodium alcoholate.
In the process according to the present invention the alcohol compound as component (b) may be selected within a wide range of alcohols, including for example alkanols, cycloalkanols, aralkylalcohols, polyols etc., these alcohol compounds optionally being substituted by further hydrocarbon groups or functional substituents. Preferably component (b) comprises an alkanol or cycloalkanol optionally substituted by reaction-inert substituents. More preferably component (b) comprises methanol or tert-amyl alcohol.
As mentioned above, the molar ratio between components (a) and (b) of the catalyst system is critical in order to prevent the formation of by-products and in order to avoid recycling a too great excess of alcohol compound. Therefore the molar ratio between components (a) and(b) preferably varies from 2:1 to 1:2, most preferably the molar ratio is approximately 1:1.
Suitable compounds to be carbonylated according to the present process are those containing at least one hydrogen atom attached to the nitrogen atom of an ammonia or amine compound, as indicated by the structure H-NR1R2. Therefore as well ammonia and primary and secondary amines may be used. The substituents of the amine compounds (R1 and R2) are not critical and may be the same or different and represent a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having from 1 to 20 carbon atoms, which may be optionally substituted by groups having not an active (acidic) hydrogen atom, except by one or more additional primary or secondary amino groups.The groups R and R may 1 representaryl group, whereas 1 and 2 also representaryl groups, whereas R and R2, together with the nitrogen atom to which they are attached, may also form a heterocyclic system, which may be aromatic. This heterocyclic system may also be substituted by additional amino groups. The additional amino groups in the groups R R2 and R may also be converted into amide groups by the carbonylating reaction, resulting in di- or poly-amides.
Advantageously a compound having the structure H-NR1R2is used, wherein R1 and R2 each are independently selected from hydrogen, an alkyl or cycloalkyl group having from 1 to 10 carbon atoms, or an aromatic group. Preferably R1 and R2 each are independently selected from hydrogen, an alkyl group having up to four carbon atoms or a phenyl group. Most preferably the amine compound is diethyl amine or aniline.
It is noted that although R and R preferably should not be substituted by a group containing an acidic hydrogen atom (except additional amino groups) in order to prevent the occurence of competitive reactions, such acidic hydrogen atom containing groups may altogether be present in R1 and/or R2, if such competitive reactions are desired.
The other starting material is carbon monoxide or a carbon monoxide-containing fluid. Therefore mixtures of carbon monoxide, hydrogen and an inert gas such as carbon dioxide, helium, argon, nitrogen etc. may also be used. Preferably a syngas mixture, optionally diluted with an inert gas, is used. By using a syngas mixture, i.e. a mixture of carbon monoxide and hydrogen, the carbon monoxide is consumed to form the formamide compound, thereby leaving pure hydrogen gas.
It will be appreciated that the molar ratio between the carbon monoxide component and the compound having structure
H-NR1R2 is not critical. However, preferably the molar ratio between carbon monoxide and the compound having structure H-NR1R2 varies between from 1:10 to 10:1.
The molar ratio between the catalyst system, comprising components (a) and (b) and the reactants can vary between wide limits and preferably varies for example between from 1:2 to 1:1000.
It is essential that the formamide producing reaction according to the present invention is carried out in the liquid phase. Therefore, in case the starting material with structure H-NR1R2 is a liquid or the primary reaction product obtained is a liquid, the reaction may be carried out without an additional liquid solvent. However, an inert liquid solvent may be used advantageously. Especially in the case that gaseous starting materials are used and/or gaseous reaction products are formed, a reaction-inert liquid solvent preferably is used. As such preferably an aprotic solvent is used. It is essential, that the aprotic solvent, when used, has a boiling point higher than that of the formamide compound produced. Only under this condition, the reaction product may be isolated by means of distillation without having to recycle the solvent.As aprotic solvent any solvent may be used which is compatible with the reaction components and/or reaction products.
Thus the aprotic solvent used in the present process may be selected from a wide range of solvents provided that they satisfy the above-mentioned condition. Suitable aprotic solvents are for example ethers, polyethers, sulphones and dialkyl formamides. Particularly suitable are the group of polyethers such as for instance the dimethyl ether of diethylene glycol (diglyme) or of tetraethylene glycol(tetraglyme). Another preferred group of solvents is the dialkylformamide group. When, for instance, diethyl amine is used as starting compound, diethyl formamide or dipropyl formamide may be used advantageously as solvent.
The amount of solvent used is not critical. However, preferably the amount of solvent used is sufficient to accommodate the catalyst system and the reaction components under the reaction conditions.
It is noted, that the term "aprotic" referred to in the specification and the claims is used to indicate that the respective substance does not contain acidic hydrogen.
The process according to the present invention may be carried out at a reaction temperature and pressure which are not critical and may vary within wide ranges. It is preferred to carry out the process at a temperature in the range of from 25 to 150 C and at a pressure of in the range of from 10 to 100 bar, although temperatures and pressures above or below said range may also be used. For example, suitable reaction conditions for some specific reactions were found to be a temperature of approximately 80 C and a pressure of approximately 40 bar.
It is noted, that the manner of charging the different reaction components and catalyst components and optionally the aprotic solvent is not critical. For example, the alcohol compound (b) and the alkali or alkaline-earth compound (a) may be introduced separately, simultaneously and as such or in a solvent, or may be premixed with each other and optionally with the solvent and then charged into the reactor. The reaction components may be introduced before or after the catalyst system.
The process according to the invention may be carried out batchwise, continuously or semi-continuously. The reaction mixtures obtained may be subjected to suitable catalyst and product recovery processes comprising one or more steps, such as precipitation, solvent extraction, distillation, fractionation or adsorption. Preferably the reaction product is recovered by means of distillation.
According to another aspect the invention relates to a catalyst system for the preparation of formamide and
N-substituted derivatives thereof by carbonylating a compound having the following structure H-NR1R2, wherein Rland R2 are defined as in claim 1, the catalyst system at least comprising the following components: component (a) - a compound selected from the group
consisting of alkali and alkaline-earth
metals, alkali and alkaline-earth metal
hydrides and alkali and alkaline-earth metal
alcoholates, component (b) - an alcohol compound, the molar ratio between component (a) and component (b) varying in the range of from 2:1 to 1:5.
Preferably component (a) comprises an alkali metal, more preferably metallic sodium, an alkali metal hydride, more preferably sodium hydride, or an alkali metal alcoholate, more preferably sodium alcoholate. The alcohol component (b) more preferably comprises an alkanol or cycloalkanol optionally substituted by reaction-inert substituents. Most preferably component (b) is methanol or tert-amyl alcohol. The molar ratio between component (a) and component (b) is preferably from 2:1 to 1:2, most preferably approximately 1:1. The components (a) and (b) are optionally mixed with an aprotic solvent.
The present invention will further be illustrated by reference to the following examples and comparative examples. The experiments were all carried out in a 300 ml magnetically stirred Hastelloy C autoclave ("Hastelloy" is a trademark). The reaction mixtures obtained were analysed by means of standard gas-liquid chromatography techniques.
The term "yield" used in the examples is defined herein as conversion x selectivity.
Example 1
The autoclave was charged with 40 ml tetraglyme together with 20 ml of diethyl amine. Next, 50 mmols of sodium hydride were added, followed by 200 mmols of tert-amyl alcohol. The reactor was flushed with carbon monoxide to remove air and then sealed, charged with carbon monoxide until a pressure of 40 bar was obtained. Then the reactor was heated to 80 C. After a reaction period of 5 hr the autoclave was allowed to cool down, then depressurized and opened for analysis. The yield of the N,N-diethyl formamide thus formed was 73t.
Example 2
In the same way as described in example 1, an experiment was carried out now using 50 mmols of tert-amyl alcohol instead of the 200 mmols used in example 1. Analysis of the N,N-diethyl formamide thus obtained resulted in a yield of 95%.
Example 3
In the same way as described in example 1, an experiment was carried out, now using 50 mmols of methanol instead of 200 mmols of tert-amyl alcohol. Further the reaction period was reduced to 2 hr. The N,N-diethyl formamide thus obtained was produced in a yield of 97%.
Example 4
In the same way as described in example 2, an experiment was carried out, now using 50 mmols of metallic sodium instead of 50 mmols of NaH. Analysis of the reaction mixture showed that the N,N-diethyl formamide was produced in a yield of 94%.
Example 5
In the same way as described in example 1 an experiment was carried out, now using 40 ml of dipropyl formamide as the solvent instead of 40 ml of tetraglyme. The desired product N,N-diethyl formamide was produced in a yield of 83% Example 6
The autoclave was charged with 50 ml of tetraglyme together with 20 ml of aniline. Subsequently 50 mmols of NaH were added and then 50 mmols of methanol. Then the reactor was flushed with carbon monoxide to remove air and subsequently sealed and pressurized with CO to a pressure of 40 bar. After heating to a temperature of 80 C and a reaction period of 5 hr, the autoclave was allowed to cool down to ambient temperature and opened for analysis of the reaction mixture. The N-phenyl formamide (formanilide) thus obtained was produced in a yield of 44%.
Comparative Example A
In the same way as described in example 2, an experiment was carried out, except that this time no alcohol compound (b) was added. Analysis of the reaction mixture thus obtained showed that substantially no desired reaction product was formed.Thus, the absence of the alcohol component (b) in the catalyst system results in a dramatic decrease in the yield of the desired product.
Comparative Example B
In the same way as described in example 3, an experiment was carried out, except that now 100 mmols of sodium methylate were used instead of 50 mmols of NaH and 50 mmols of methanol. The reaction mixture was allowed to react during 5 hr. The analysis showed, that substantially no
N,N-diethyl formamide was produced. It is concluded, that even when sodium methyl ate is used in combination with an aprotic solvent, still an alcohol compound (b) is necessary.
Comparative Example C
The autoclave was charged with 40 ml of methanol (0.99 mol), 100 mmols of sodium methylate and 20 ml of diethylamine. Then the reactor was flushed with carbon monoxide to remove air, sealed and pressurized with CO to a pressure of 40 bar, and subsequently heated to a temperature of 80 OC. After a reaction period of half an hour, the reactor was allowed to cool down to ambient temperature and opened for analysis of the reaction mixture. N,N-diethyl formamide was produced in a yield of 91%. However, in this case also 3.6 molar % of methyl formate was produced as by-product.
Comparative Example D
The autoclave was charged with 40 ml of methanol (0.99 mol), 50 mmols of sodium methylate and 20 ml of aniline.
Then the reactor was flushed with carbon monoxide to remove air, sealed and pressurized with CO to a pressure of 40 bar.
The reactor was heated to a temperature of 80 OC during 5 hr. Then the autoclave was allowed to cool down to ambient temperature, depressurized and opened. The reaction mixture thus obtained was analysed and showed the production of
N-phenyl formamide (formanilide) in a yield of 94%.
However, in this case also 20 molar % of methyl formate was produced as by-product. Thus it is shown that by using a ten-fold excess (comparative example C) or twenty-fold excess (comparative example D) of methanol with respect to sodium methylate, a substantial amount of the by-product methyl formate is formed.
Claims (27)
1. A process for the preparation of formamide and Nsubstituted derivatives thereof, which process comprises carbonylating a compound having the structure H-NR 1R2, wherein R1 and R2 are each independently selected from hydrogen, a hydrocarbon group optionally substituted by one or more additional primary or secondary amino groups, or wherein R1 and R2, together with the nitrogen atom to which they are attached, form a heterocyclic group optionally containing one or more additional primary or secondary amino groups, in the liquid phase with carbon monoxide or a carbon monoxide-containing fluid at increased pressure in the presence of a catalyst system comprising at least: component (a) - a compound selected from the group
consisting of alkali and alkaline-earth
metals, alkali and alkaline-earth metal
hydrides and alkali and alkaline-earth
metal alcoholates, component (b) - an alcohol compound, the molar ratio between component (a) and component(b) varying in the range of from 2:1 to 1:5.
2. A process as claimed in claim 1, in which component (a) comprises an alkali metal, alkali metal hydride or alkali metal alcoholate.
3. A process as claimed in claim 2, in which component (a) comprises metallic sodium, sodium hydride or sodium alcoholate.
4. A process as claimed in any one of the preceding claims in which component (b) comprises an alkanol or cycloalkanol optionally substituted by reaction-inert substituents.
5. A process as claimed in claim 4 in which component (b) is methanol or tert-amyl alcohol.
6. A process as claimed in anyone of the preceding claims in which the molar ratio between component (a) and component (b) is from 2:1 to 1:2, preferably approximately 1:1.
7. A process as claimed in anyone of the preceding claims in which a compound having the structure H-NR1R2 is used, wherein R1 and R2 each are independently selected from hydrogen, an alkyl or cycloalkylgroup having from 1 to 10 carbon atoms, or an aromatic group.
8. A process as claimed in claim 7 in which R1 and R2 each are independently selected from hydrogen, an alkyl group having up to four carbon atoms or a phenyl group.
9. A process as claimed in claim 8 in which the amine compound is diethyl amine or aniline.
10. A process as claimed in any one of the preceding claims in which a syngas mixture, optionally diluted with an inert gas, is used.
11. A process as claimed in any one of the preceding claims in which the molar ratio between carbon monoxide and the compound having structure H-NR1R2 varies between from 1:10 to 10:1.
12. A process as claimed in any one of the preceding claims in which the molar ratio between the catalyst system and the reactants varies between from 1:2 to 1:1000.
13. A process as claimed in any one of the preceding claims which is carried out in the presence of an aprotic solvent having a boiling point higher than that of the formamide compound produced.
14. A process as claimed in claim 13 in which as aprotic solvent is used an ether, polyether, sulphone or dialkyl formamide.
15. A process as claimed in claim 14 in which as aprotic solvent is used the dimethyl ether of tetraethylene glycol (tetraglyme) or dipropyl formamide.
16. A process as claimed in any one of the preceding claims which is carried out at a temperature in the range of from 25 to 150 OC and at a pressure in the range of from 10 to 100 bar.
17. A process as claimed in anyone of the preceding claims which is carried out at a temperature of approximately 80 C and at a pressure of approximately 40 bar.
18. Formamide and N-substituted derivatives thereof, whenever obtained by a process as claimed in any one of the preceding claims.
19. Catalyst system for the preparation of formamide and
N-substituted derivatives thereof by carbonylating a compound having the following structure H-NR1R2, wherein R1 and R2 are defined as in claim 1, the catalyst system at least comprising the following components: component (a) - a compound selected from the group
consisting of alkali and alkaline-earth
metals, alkali and alkaline-earth metal
hydrides and alkali and alkaline-earth metal
alcoholates, component (b) - an alcohol compound, the molar ratio between component (a) and component(b) varying in the range of from 2:1 to 1:5.
20. A catalyst system as claimed in claim 19, in which component (a) comprises an alkali metal, alkali metal hydride or alkali metal alcoholate.
21. Catalyst system as claimed in claim 20 in which component (a) comprises metallic sodium, sodium hydride or sodium alcoholate.
22. Catalyst system as claimed in any one of the claims 19-21 in which component (b) is an alkanol or cycloalkanol optionally substituted by reaction-inert substituents.
23. Catalyst system as claimed in claim 22 in which component (b) is methanol or tert-amyl alcohol.
24. Catalyst system as claimed in any one of the claims 19-23 in which the molar ratio between component (a) and component (b) is from 2:1 to 1:2, preferably approximately 1:1.
25. Catalyst system as claimed in any one of the claims 19-24 in which the components (a) and (b) are mixed with an aprotic solvent.
26. Catalyst system as claimed in claim 19, substantially as hereinbefore described with reference to the examples.
27. Process as claimed in claim 1, substantially as hereinbefore described with reference to the examples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8807805A GB2216035A (en) | 1988-03-31 | 1988-03-31 | Process and catalyst for the preparation of formamide and N-substituted derivatives thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8807805A GB2216035A (en) | 1988-03-31 | 1988-03-31 | Process and catalyst for the preparation of formamide and N-substituted derivatives thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8807805D0 GB8807805D0 (en) | 1988-05-05 |
| GB2216035A true GB2216035A (en) | 1989-10-04 |
Family
ID=10634494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8807805A Withdrawn GB2216035A (en) | 1988-03-31 | 1988-03-31 | Process and catalyst for the preparation of formamide and N-substituted derivatives thereof |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2216035A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6441234B1 (en) | 1999-01-18 | 2002-08-27 | Abbott Laboratories | Production of formamide using sodium diformylamide |
-
1988
- 1988-03-31 GB GB8807805A patent/GB2216035A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6441234B1 (en) | 1999-01-18 | 2002-08-27 | Abbott Laboratories | Production of formamide using sodium diformylamide |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8807805D0 (en) | 1988-05-05 |
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