Method for producing carbon monoxide and method for producing a synthetic fuel

Abstract

The invention relates to a method for producing carbon monoxide by decarbonylation of a compound A, B or C, wherein compound A has the structural formula: R5-C6(R1-4)-[N(CHO)-C6(R1-4')]n-R5', compound B has the structural formula: R5-[C6(R1-4)-N(CHO)-C6(R1-4')]n-R5', and compound C has the structural formula: R5-[C6(R1-4)-N(CHO)-C6(R1-4')-X]n-R5', wherein R1, R2, R3, R4, R1', R2', R3' and R4' independently of one another are H, D, F, an alkyl group or an aryl group, wherein X is an aliphatic bridge, is an aromatic bridge, has an ether group, has an ester group, has an amide group or has a urethane group, and n is in a range from 1 to 100,000. The invention also relates to a method for producing a synthetic fuel, in which method the carbon monoxide is reduced using hydrogen.

Description

[0001]2023PF12464 Foreign version 1 Description Process for producing carbon monoxide and process for producing a synthetic fuel The invention relates to a process for producing carbon monoxide and a process for producing a synthetic fuel using the carbon monoxide. In the production of renewable synthetic fuels, such as hydrocarbons or methanol, carbon monoxide and hydrogen are used. The hydrogen is produced by electrolysis of water. The carbon monoxide can be produced, for example, by a reverse water gas shift reaction (rWGS): CO2 + H2 <--> CO + H2O. In order to produce the carbon monoxide in this reaction with a good yield, however, a temperature of higher than 800°C is required and it is necessary to separate the water, which is complex.As an alternative to the water gas shift reaction, carbon monoxide can be released from an amide, such as formamide. Formamide can be produced, for example, by first reacting ammonia with carbon dioxide and water to form a bicarbonate: (1) NH3 + CO2 + H2O -> [NH4]. + ][HCO3-] and then the bicarbonate is hydrogenated to a formate: (2) [NH4 + ][HCO3-] + H2-> [NH4 + ][HCO2-] + H2O. The formate can dehydrate to formamide: (3) [NH4 +][HCO2-] -> HCONH2+ H2O. Carbon monoxide can be released from the formamide: (4) HCONH2-> NH3+ CO, whereby the ammonia is re-formed. Reactions (1) to (4) together represent the reverse water gas shift reaction CO2+ H2-> CO + H2O. 2023PF12464 Foreign Version 2 Another alternative to the water gas shift reaction is the first step of producing formic acid from carbon dioxide and hydrogen: (5) CO2+ H2-> HCOOH. Subsequently, the reaction of ammonia with formic acid leads to the formation of formamide: (6) HCOOH + NH3-> HCONH2+ H2O, whereby carbon monoxide is also released according to (4). The disadvantage of reaction (4) is that hydrogen cyanide and polymers are formed as undesirable by-products. Formic acid can also be decomposed directly on acidic catalysts by the reaction HCOOH -> CO + H2O.The object of the invention is therefore to create a process that enables the release of carbon monoxide with a high yield. The process according to the invention for producing carbon monoxide is carried out by decarbonylating a compound A, B, or C, wherein compound A has the structural formula: OH. , the B has the structural formula: has: 2023PF12464 foreign version 3 5' , where R1, R2, R3, R4, R1', R2', R3' and R4' are independently H, D, F, an alkyl radical or an aryl radical, where X is an aliphatic bridge, an aromatic bridge, an ether group, an ester group, an amide group or a urethane group, where n is in a range from 1 to 100,000. It has surprisingly been found that with formamides of the compounds A, B and C, the decarbonylation takes place in high yield. The compounds A, B and C thus act as a storage medium for carbon monoxide. If X has the alkyl radical or the aryl radical, the solubility of the compound C in non-polar solvents can be increased. If X has the ether group, the ester group, the amide group or the urethane group, the solubility of the compound C in polar solvents can be increased. Decarbonylation proceeds analogously to reaction (4) to form an amine. Preferably, n=1.Alternatively, n>1 is preferred, with n=2 in particular. For example, n can be in a range from 1 to 100 or 1 to 20 or greater than 100. The larger n, the greater the ratio of the number of atoms of the amide groups to the number of atoms of the remaining atoms in compounds A, B, or C. This allows more mass of carbon monoxide to be stored per unit mass of the amide. The alkyl radical for R1, R2, R3, R4, R1', R2', R3', and R4' is preferably unbranched or branched. The unbranched alkyl radical preferably has 1 to 5 carbon atoms. For example, the unbranched alkyl radical can be methyl, ethyl, 2023PF12464 Foreign Version 4, or n-propyl. The branched alkyl radical preferably has 1 to 10 carbon atoms. For example, the branched alkyl radical can be i-propyl or t-butyl. The aryl radical for R1, R2, R3, R4, R1', R2', R3', and R4' is preferably substituted, in particular with F, alkyl radicals, and / or aryl radicals, or unsubstituted.For example, the aryl radical can be a substituted or unsubstituted phenyl ring. In particular, the aryl radical can be pt-butylphenyl. The aliphatic bridge preferably has between 1 and 20 carbon atoms. The aliphatic bridge can be branched or unbranched. The aliphatic bridge can be saturated or unsaturated. The aromatic bridge preferably has between 1 and 30 carbon atoms. The aromatics contained in the aromatic bridge can be substituted, in particular with F, alkyl radicals and / or aryl radicals, or unsubstituted. The aromatic bridge can be partially or fully unsaturated. The aromatic bridge can, for example, have a substituted or unsubstituted phenyl ring. In the case where X has the ether group, X preferably has the empirical formula (CH2). a O b, where a is in a range from 0 to 20 and b is in a range from 1 to a+1. Peroxide groups are preferably excluded in the ether group. In the case that X has the ester group, X preferably has the following structural formula: O ( CH 2 ) b , where a+b lies in one. 2023PF12464 Foreign version 5 In the case that X has the amide group, X preferably has the following structural formula: O ( CH 2 ) b , where a+b lies in one. In the case that X has the urethane group, X preferably has the following structural formula: O ( CH 2 ) a (CH 2 ) b , where a+b lies in one. It is preferred that R5 and R5' are independently H, D, F, an alkyl radical, or an aryl radical. The alkyl radical for R5 and R5' is preferably unbranched or branched. The unbranched alkyl radical preferably has from 1 to 5 carbon atoms. For example, the unbranched alkyl radical can be methyl, ethyl, or n-propyl. The branched alkyl radical preferably has from 1 to 10 carbon atoms. For example, the branched alkyl radical can be i-propyl or t-butyl. The aryl radical for R5 and R5' is preferably substituted, in particular with F, alkyl radicals, or aryl radicals, or unsubstituted. For example, the aryl radical can be a substituted or unsubstituted phenyl ring. In particular, the aryl radical can be pt-butylphenyl. It is preferred that compound A is selected from the group: Compound A1: O H , 2023PF12464 Foreign version 6 where n=1 and R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' are independently H or D, compound A2: O H , where n=1 and R4' independent are H or t-butyl, and compound A3, O H , where n=2 and R3', R4' and R5' The decarbonylation is preferably carried out without the presence of a catalyst. The decarbonylation can be carried out, for example, with the addition of heat. Alternatively, without a catalyst, the decarbonylation can be carried out in the presence of a catalyst K having the structural formula: + M –– N R7, where R6 is an aryl radical, R7 is H, D, an aryl radical or an alkyl radical, where M + is from the group Li + , N / a + , K + , Rb + and Cs + , in particular wherein the K +complexed by a crown ether. It has been found that a high yield of carbon monoxide can be achieved with these 2023PF12464 Foreign Version 7 catalysts. K + and Cs + , because particularly high yields can be achieved with these ions. A further improvement in yield can be achieved if the K +complexed with crown ether. The decarbonylation can also be carried out in the presence of a strong base as a catalyst. The strong base can, for example, comprise a tert-butyl oxide, in particular sodium tert-butyl oxide or potassium tert-butyl oxide, and / or KOH. Another catalyst for decarbonylation can be ROM, where M is selected from the group: Na, K, Rb, and Cs, where R is selected from the group H, D, alkyl, allyl, aryl, benzyl, and vinyl. Examples of these are MeONa, MeOK, and MeORb. Another catalyst for decarbonylation can be R2NM, where M is selected from the group: Na, K, Rb, and Cs, where R is selected from the group H, D, alkyl, allyl, aryl, benzyl, and vinyl. Examples of these are Me2NK and ME2NCs. R2NM results in a faster reaction rate than ROM. K + gives better yields and faster reaction rates than Na + . Rb + and Cs +gives better yields and faster reaction rates than K + , where K + but better industrial applicability than Rb + and Cs + The amount of catalyst n K compared to the amount of compound A, B or C n A , n B or n C ^ is preferably chosen so that a ratio ^ in a ^ ಲ ∗^ ^^ೌ^ range of 0.05% to 5%, especially 0.1% to 2%, a ^ ratio ^ in a range of 0.05% to 5%, ^ ಳ ∗^ ^^ೌ^ ^ especially 0.1% to 2%, and a ratio ^ in ^ ^ ∗^ ^^ೌ^ a range of 0.05% to 5%, in particular 0.1% to 2%, where n meanis an arithmetic mean of n (i.e., an arithmetic mean of the chain length of compound A, B, or C). 2023PF12464 Foreign Version 8 The aryl radical for R6 is preferably a substituted or unsubstituted phenyl ring with the structural formula: R 12 , where R8, R9, R 10 , R 11 , R 12 from each other H, D, F, an alkyl radical or a preferred are R8, R9, R 10 , R 11 and R 12 independently of one another are H or D or particularly preferably R8, R9, R 10 and R 11 independently H or D and R 12 is t-butyl. The aryl radical for R7 is preferably a substituted or unsubstituted phenyl ring with the structural formula: R 12 ' , where R8', R9', R 10 ', each being H, D, F, an alkyl radical or a Particularly preferred are R8', R9', R 10 ', R 11 ' and R 12' independently of one another are H or D or particularly preferably R8', R9', R 10 ' and R 11 ' independently H or D and R 12 ' is t-butyl. It is particularly preferred that R 12 and / or R 12 ' is a branched alkyl radical, especially i-propyl or t-butyl. As a result, the catalyst is distributed particularly well in the compound A, B or C when both the catalyst and the compound A, B or C are in a solid state. It is particularly preferred that R6 and R7 are identical. It is particularly preferred that the catalyst K is selected from the group: K1: + K – N , 2023PF12464 Foreign version 9 where R6 and R7 are identical as well as R8, R9, R 10 , R 11 and R 12 are independently H or D, K2: + Cs – N , where R6 and R7 are identical and R8, R9, R 10 , R 11 and R 12are independently H or D, K3: + K – N , in which R6 and R7R9, R 10 and R 11 independent R 12 t-Butyl, K4: + Cs – N , where R6 and R7, R9, R 10 and R 11 independent R 12 t-Butyl. Compounds K1, K2, K3, and K4 are particularly preferred because the purity of the reaction mass remains very high in the cyclic process involving carbonylation and decarbonylation. The alkyl radical for R7 is preferably unbranched or branched. The unbranched alkyl radical preferably has 1 to 5 carbon atoms. For example, the unbranched alkyl radical can be methyl, ethyl, or n-propyl. The branched alkyl radical preferably has 1 to 10 carbon atoms. For example, the branched alkyl radical can be i-propyl or t-butyl. It is particularly preferred that R6 and / or R7 has the structural formula: 2023PF12464 Foreign Version 10 R 12 , where R 12H, D, F, an aryl radical. Particularly preferred is The crown ether is preferably 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (Kryptofix® 222). It is preferred that the decarbonylation be carried out with the addition of heat. This allows the yields of carbon monoxide to be increased and the reaction time of the decarbonylation to be shortened, or the reaction rate and thus the release rate of carbon monoxide to be controlled. Alternatively, it is preferred that the decarbonylation be carried out without the addition of heat. This results in good energy efficiency. It is preferred that the decarbonylation of compound A, B, or C be carried out in a solvent. This is particularly relevant when n=1 or when compound A1 is decarbonylated. The solvent can be, for example, tetrahydrofuran (THF). It is preferred that the decarbonylation of compound A, B or C is carried out in a melt of compound A, B or C.This is relevant, for example, when n=1 or when compound A1 is decarbonylated. It is preferred that the decarbonylation of compound A, B or C is carried out in a solid state of compound A, B or C. This is relevant, for example, when n>1 or when n=2 or when compound A3 is decarbonylated. 2023PF12464 Foreign Version 11 In a particularly preferred embodiment of the process, N,N-diphenylformamide is synthesized as compound A, which is obtained from triethylammonium formate azeotrope. Furthermore, it is preferred that diphenylamine and triethylammonium formate azeotrope are mixed and the mixture is fractionally distilled under reduced pressure, whereby N,N-diphenylformamide is obtained as compound A in the solid phase. In the process according to the invention for producing a synthetic fuel, the carbon monoxide is reacted using hydrogen.The synthetic fuel may comprise a hydrocarbon and / or an alcohol, in particular methanol and / or ethanol. Exemplary processes for producing the synthetic fuel are Fischer-Tropsch synthesis, involve synthesis gas fermentation, and / or involve methanol synthesis according to the following reaction equation: CO + 2 H2⇌ CH3OH. Preparation of Compounds A, B, and C. It is preferred that compound A is prepared starting from compound D: H and / or wherein the compound E is prepared:. 2023PF12464 Foreign version 12 and / or which is produced by the connection F: H 5' . The A is the Compound D of compounds B reverts to compound E, and decarbonylation of compounds C reverts to compound F. Compound A1 is accessible from compound D1, where n=1 and R1, R2, R3, R4, R5, R1', R2', R3', R4', and R5' are independently H or D. Compound A2 is accessible from compound D2, where n=1 and R1, R2, R3, R4, R1', R2', R3', and R4' are independently H or D, and R5 and R5' are t-butyl. Compound A3 is accessible from compound D3, where n=2 and R1, R2, R3, R4, R5, R1', R2', R3', R4', and R5' are independently H or D. Compounds D1, D2, and D3 are commercially available. Polyaniline is also commercially available. Polyaniline can be produced by oxidative polymerization of aniline. The chain length of the polyaniline can be adjusted, in particular, by adjusting the ratio of the amount of oxidizing agent to the amount of aniline.Derivatives of polyaniline are also accessible via oxidative polymerization. 2023PF12464 Foreign Version 13 It is preferred that compound A is prepared by reacting compound D with formic acid and / or compound B is prepared by reacting compound E with formic acid and / or compound C is prepared by reacting compound F with formic acid. It is particularly preferred that the formic acid is prepared from a reaction of hydrogen with carbon dioxide. As a result, the amide also acts as a hydrogen storage medium. N,N-diphenylformamide (A1) can be prepared, for example, by mixing diphenylamine (100 g, 0.591 mol) and formic acid (108 g, 2.35 mol) in a 250 ml round-bottom flask. After stirring for 3 days, a clear solution of A1 is obtained (98% conversion by 1H NMR).The excess formic acid and the condensed water were recovered by flask distillation at 50°C (91.4 g of colorless 82% formic acid, 92% recovery). The remaining white solid was ground and slurried with aqueous HCl (200 mL, 0.5 M), filtered, and rinsed with water (3 × 200 mL). The product was dried for 18 hours at 50°C under high vacuum to yield 110 g (95%) of a white solid. Further investigations have shown that the compound N,N-diphenylformamide (A1) can be prepared and supplied in a particularly preferred manner directly from triethylammonium formate azeotrope, which makes the thermodynamics of the reaction sequence significantly more favorable than formylation using formic acid. Using this improved synthesis route for the compound N,N-diphenylformamide (A1), formylation is also possible with triethylammonium formate. This eliminates the need to isolate the formic acid.Amines can be used to scrub CO2, a process known as amine scrubbing. During amine scrubbing, the CO2 is chemically absorbed by the amines in a scrubbing solution. The saturated amines or the solution are then heated to 100–140 degrees Celsius, during which a large portion of the CO2 2023PF12464 Foreign Version 14 becomes gaseous again and is then separated within the separation system. The reduction of a carbonate with hydrogen is well known; that is, when triethylammonium formate is used for formylation, the corresponding formate is obtained directly. This is a crucial and particularly advantageous step for completing the reaction sequence. Using this synthesis route, it has been shown that diarylamines can be azeotropically formylated with triethylammonium formate at 150 °C under reduced pressure.The synthesis of N,N-diphenylformamide (A1), for example, on a 30 g laboratory scale, with recycling of the triethylammonium formate complex 5:2 (azeotrope), is preferably carried out as follows: Diphenylamine (30 g, 0.177 mol) and triethylammonium formate azeotrope (46.7 g, 0.108 mol, corresponding to 0.540 mol of pure FA, formic acid) were placed in a 100 mL round-bottom flask and connected to a fractional distillation apparatus. The mixture was stirred for 2 days at 150 °C under reduced pressure (150-200 mmHg) to obtain a pale yellow solution. During the reaction, a receiver Schlenk tube maintained at -40 °C collected water (low layer) and NEt3 (upper layer) resulting from the reaction. After completion of the formylation reaction, the excess triethylammonium formate azeotrope was recovered as pure reagent by bulb-to-Schlenk distillation at 100 °C (29.3 g, 94% recovery).The white solid remaining in the flask was ground and identified by 1H NMR as diphenylformamide (34.3 g, 97%), which contained only 3% diphenylamine as the sole impurity. Thus, a highly advantageous synthetic route for the production of N,N-diphenylformamide (A1) is demonstrated, which avoids or circumvents the thermodynamically unfavorable preparation of pure formic acid. Considering CO hydrogenation in the presence of bases such as triethylamine, triethylammonium formate is obtained as a distillable azeotrope in good yields. The excess azeotrope can be easily recycled at the end of the reaction.In a further alternative, it is preferred that compound A is prepared by reacting compound D with carbon dioxide to form a carbonate and / or a bicarbonate, and then hydrogenating the carbonate and / or the bicarbonate with hydrogen to form compound A, and / or wherein compound B is prepared by reacting compound E with carbon dioxide to form a carbonate and / or a bicarbonate, and then hydrogenating the carbonate and / or the bicarbonate with hydrogen to form compound B, and / or wherein compound C is prepared by reacting compound F with carbon dioxide to form a carbonate and / or a bicarbonate, and then hydrogenating the carbonate and / or the bicarbonate with hydrogen to form compound C.Thus, the amide acts as a hydrogen storage medium. Compound E can be prepared by oxidative polymerization of a monomer M1: NH . Sang-Bum Kim, Ken. of Poly(diphenylamine-4,4'-diyl) and Related Random Copolymers by Organometallic Polycondensation. Electrical, Electrochemical, and Optical Properties” in Macromolecules 1998, 31, 988-993. Analogously, compound F can be prepared by oxidative polymerization of a monomer M2: 2023PF12464 Foreign version 16 All mentioned of compounds A, B, C, D, E and / or F can be carried out under anhydrous and / or oxygen-free conditions. For the purposes of the invention, other aromatic systems include furans, thiophenes, pyrroles, oxazoles, thiazoles, imidazoles, isoxazoles, isothiazoles, pyrazoles, pyridines, pyrazines, pyrimidine, 1,3,6-triazines, alpha- or gamma pyrones, benzo[b]furan, benzo[b]thiophene, indoles, 2H-isoindoles, Benzothiazoles, 2-Benzothiophenes, 1H-Benzimidazoles, 1H-Benzotriazoles, 1H-Indazoles, 1,3-Benzoxazoles, 2-Benzofuranes, 7H-Purines, Quinolines, Iso-Quinolines, Quinazolines, Quinoxalines, Phthalazines, 1,2,4-Benzotriazines, Pyrido[2,3-d]pyrimidine, Pyrido[3,2-d]pyrimidines, pteridines, acridines, phenazines, benzo[g]ptheridines, 9H-carbazoles or bipyridine derivatives.In particular, it is conceivable to carbonylate polypyrrole, polypyrrole derivatives, poly(indole-co-thiophene), poly(indole-co-thiophene) derivatives, poly[(pyrrole-2,5-diyl)-co-(4-hydroxylbenzylidene)], poly[(pyrrole-2,5-diyl)-co-(4-hydroxylbenzylidene)] derivatives, polyindole, or polyindole derivatives to formamides and to decarbonylate these formamides. Catalyst Preparation: The catalysts Li. +[NR6R7-] can be prepared by deprotonation of HNR6R7 with n-BuLi. In one example, lithium diphenylamide was prepared by adding 1.2 equivalents of n-BuLi (5 mL, 1.12 M) dropwise to a solution of diphenylamine (846 mg, 5.00 mmol) in n-hexane (25 mL). The reaction mixture was stirred until a white precipitate formed. After 1.5 hours of stirring, the resulting suspension was filtered through GF / B (Whatman® glass microfiber filter, grade GF / B), washed with n-pentane (3 × 10 mL), and dried under HV (high vacuum) to yield 840 mg (96%) of a white solid. The catalysts Na +[NR6R7-] can be prepared by deprotonation of HNR6R7 with sodium hydride. In one example, sodium diphenylamide was prepared by dissolving diphenylamine (1692 mg, 10.00 mmol) and sodium hydride (240 mg, 10.0 mmol) each in THF (10 mL). The sodium hydride solution was added dropwise to the diphenylamine solution to form a light yellow solution. After stirring overnight, the reaction mixture was filtered through GF / B and the solution was dried overnight in HV. The resulting solid was washed with n-pentane (3 × 5 mL) and dried in HV to afford a white solid (1797 mg, 94%). Catalysts K +[NR6R7-] can be prepared by deprotonation of HNR6R7 with benzylpotassium. In one example, potassium diphenylamide (K1) was prepared by dissolving benzylpotassium (8.083 g, 62.07 mmol) and diphenylamine (10.51 g, 62.11 mmol) each in THF (50 mL). Both solutions were pre-chilled in the freezer. The orange benzylpotassium solution was added dropwise to the diphenylamine solution to form a yellowish solution. After stirring for 1.5 h, the reaction mixture was filtered through GF / B, and the yellowish solution was dried overnight in HV. The resulting solid was washed with n-pentane (3 × 25 mL) and dried in HV to afford 13.19 g (97%) of a yellow solid. In another example, potassium bis(4-(t-butyl)phenyl)amide (K3) was prepared by dissolving benzylpotassium (1.388 g, 10.66 mmol) and bis(4-(t-butyl)phenyl)amine (3.007 g, 10.68 mmol) each in THF (10 mL). Both solutions were pre-chilled in the freezer.The orange benzylpotassium solution was added dropwise to the bis(4-(t-butyl)phenyl)amine solution, resulting in a yellowish solution. After stirring for 2 hours, the reaction mixture was filtered through GF / B, and the yellowish solution was dried overnight in HV. The resulting solid was washed with n-pentane (3 x 5 mL) and dried in HV to yield 2.946 g of yellow solid (86%). The catalysts were crown ether K. + [NR6R7-], where the K + - Cation is complexed by the crown ether, can be prepared by adding the crown ether to a solution of the uncomplexed catalyst K +[NR6R7-]. In one example, Kryptofix® 222 potassium diphenylamide (K@K22 diphenylamide) was prepared by dissolving potassium diphenylamide (186 mg, 0.897 mmol) and Kryptofix® 222 (336 mg, 0.893 mmol) each in THF (3 mL). The Kryptofix® 222 solution was added dropwise to the potassium diphenylamide solution. After stirring for 20 minutes, the reaction mixture was filtered through GF / B, and the resulting solid was dried overnight in HV. The resulting solid was washed with n-pentane (3 × 3 mL) and dried in HV to afford 279 mg (54%) of the pale yellow solid. In another example, Kryptofix® 222 potassium bis(4-(t-butyl)phenyl)amide was prepared by dissolving potassium bis(4-(t-butyl)phenyl)amide (184 mg, 0.575 mmol) and Kryptofix® 222 (217 mg, 0.577 mmol) each in THF (3 mL). The Kryptofix® 222 solution was added dropwise to the potassium bis(4-(t-butyl)phenyl)amide solution to form a yellowish solution.After stirring for 2 hours, the reaction mixture was filtered through GF / B, and the yellowish solution was dried overnight in HV. The resulting solid was washed with n-pentane (3 × 3 mL) and dried in HV to yield 384 mg (96%) of a pale yellow solid. The catalysts Cs. +[NR6R7-] can be prepared by reducing HNR6R7 with cesium. In one example, cesium diphenylamide (K2) was prepared by adding diphenylamine (508 mg, 3.00 mmol) to cesium (412 mg, 3.10 mmol) in 5 mL of THF. The mixture immediately turned dark orange, and a gas (presumably hydrogen) was released. The reaction mixture was stirred overnight at room temperature. The completion of the reaction was indicated by the cessation of gas evolution. The resulting mixture was filtered to remove the solid, and then n-pentane was slowly added to the mixture until all the precipitate dissolved in the solution and the solution became clear. The pale yellow solid was filtered through GF / B, washed with n-pentane (3×5 ml) and dried in HV to obtain 885 mg (98%) of a yellow solid.In another example, cesium bis(4-(t-butyl)phenyl)amide (K4) was prepared by adding bis(4-(t-butyl)phenyl)amine (844 mg, 3.00 mmol) to cesium (412 mg, 3.10 mmol) in 5 mL of THF. The mixture immediately turned dark orange and evolved a gas (presumably hydrogen). The reaction mixture was stirred overnight at room temperature. The completion of the reaction was indicated by the cessation of gas evolution. The resulting mixture was filtered to remove the solid, and then n-pentane was slowly added to the mixture until all the precipitate dissolved in the solution and the solution became clear. The pale yellow solid was filtered over GF / B, washed with n-pentane (3 × 5 mL), and dried in HV to afford 1153 mg (93%) of a yellow solid. All reactions for the preparation of the catalysts can be carried out under anhydrous and / or oxygen-free conditions.Decarbonylation Study General procedure for the decarbonylation of N,N-diphenylformamide (A1) under constant volume: N,N-diphenylformamide (79 mg, 0.4 mmol) was dissolved in THF-D8 (0.3 ml) and transferred into a Young's NMR tube (total volume of 1 cm). 3 ) with a screw-on Teflon cap. Metal N,N-diphenylamide (0.4 mmol) was dissolved in THF (1 ml). 10 μl of this solution was taken and added to the N,N-diphenylformamide solution in the Young's NMR tube. The reaction was monitored hourly for 66 hours at 25 °C using 1H-NMR analysis. The results are shown in Figure 1, where the conversion c of the amide to the amine and carbon monoxide is plotted against time. While Ph2NLi yielded approximately 3% conversion, Ph2NNa and Ph2NK showed 70% and 95% conversion, respectively, after 68 hours. The cesium amide K2 exhibits even faster kinetics in the initial phase of the reaction, but the conversion stagnates at 88%, suggesting equilibrium with the reverse reaction (i.e., carbonylation of diphenylamine). The potassium Kryptofix® 222 complex exhibits a similarly high initial activity, achieving a conversion of approximately 95%. General procedure for the decarbonylation of N,N-diphenylformamide (A1) to carbon monoxide and diphenylamine under solvent-free conditions: Under an inert atmosphere, clean N,N-diphenylformamide (1972 mg, 10.00 mmol) and a metal N,N-diphenylamide (1 mol%) were added to a 25 ml Schlenk flask.The reaction mixture was connected to an oil bubbler and heated to 70 °C for 3 hours, forming a melt of the mixture. During this time, gas evolution (CO) was observed. The water displacement method was used to determine and measure the volume of the gaseous products. Figure 2, in which the conversion c of the amide to the amine and carbon monoxide is plotted against time, shows similar decarbonylation rates as in Figure 1 and an almost quantitative conversion when the catalysts K1 (both with the uncomplexed K) and K2 (with the uncomplexed K) were used. + -cation as well as with the K complexed with Kryptofix® 222 +-cation) and K2 can be used. General procedure for the decarbonylation of N,N'-(1,4-phenylene)bis(N-phenylformamide) (A3) to carbon monoxide and N,N′-diphenyl-p-phenylenediamine under solvent-free conditions: Under an inert atmosphere, pure N,N'-(1,4-phenylene)bis(N-phenylformamide) (1790 mg, 5 mmol) and metal bis(4-(tert-butyl)phenyl)amide (1 mol%) were mixed very well with grinding for 5 minutes and then transferred to a 25 mL Schlenk flask. The reaction mixture was connected to a reflux condenser, which had previously been connected to an oil bubbler, and heated to the desired temperature for 6 hours. During this time, gas evolution (CO) was observed. The water displacement method was used to determine and measure the volume of the gaseous products.Figure 3, in which the conversion c of the amide to the amine and carbon monoxide is plotted against time, shows the results for K3 (without crown ether). A solid mixture of A3 and K3 is stable at room temperature. Almost quantitative conversion is achieved at 90 °C when catalysts K3 (both with the uncomplexed K) and K3 are used. + -cation as well as with the K complexed with Kryptofix® 222 + -cation) and K4. N,N-Diphenylformamide (1972 mg, 10.00 mmol) and the catalyst (1 mol%) were added to a 25 mL Schlenk flask. The reaction mixture was heated to 70 °C for 3 hours, and gas evolution was monitored. At the end of the reaction (when gas evolution ceased), the mixture was cooled to room temperature, solidified, and precipitated using 1H NMR analysis was used to determine the amount of decomposition. The results are presented in the table below: Catalyst c / % Rate tBuOK 100 Best rate in this table tBuONa 100 Similar to KOH HOK 100 Similar to tBuONa HONa 0 No reaction The decarbonylation can be carried out under anhydrous and / or oxygen-free conditions. 2023PF12464 Foreign Version 22 Screening of common primary and secondary, linear and cyclic alkyl and aryl formamides identified diphenylformamide (A1) as a particularly promising lead structure for the decarbonylation reaction. This can be synthesized either at room temperature by reacting PH2NH with formic acid on a 100 g scale or at 150 °C under reduced pressure using a 3:1 excess of the more economical triethylammonium formate azeotrope. The excess azeotrope can be easily recycled at the end of the reaction.Thus, the process for producing carbon monoxide by decarbonylation of the compound diphenylformamide (A1) is particularly interesting, since the demonstrated synthesis route for diphenylformamide (A1) via the use of a triethylammonium formate azeotrope offers significant economic advantages. In a particularly preferred embodiment of the process, diarylamines are efficiently formylated azeotropically at room temperature with formic acid or at 150 °C under reduced pressure with triethylammonium formate. Furthermore, kinetic studies of the catalytic effects of metallic cesium and potassium on the decomposition of diphenylformamide to CO were conducted. As part of the development work, the catalytic effect of the molten metals cesium and potassium on the decomposition of diphenylformamide to carbon monoxide at 80 °C was investigated.The decomposition rates are comparable to those achieved with the corresponding preformed alkali metal diphenylamide catalysts. Eliminating the catalyst synthesis has beneficial economic implications. However, several challenges remain: The resulting carbon monoxide is not highly pure due to hydrogen impurities (approximately 2.5 mol% or 0.2 wt% when using 5 mol% metals) arising from the in-situ generation of alkali metal diphenylamide. It has been shown that the simple use of metallic catalysts, particularly cesium or potassium, and their effectiveness offers significant economic advantages in carrying out the reaction. This is particularly interesting in cases where high-purity carbon monoxide (CO) is not required.Particular attention was paid to investigating the decarbonylation kinetics of diphenylformamide under solvent-free conditions, as demonstrated below using metallic cesium and potassium as examples: Diphenylformamide (DPFA, 1.97 g, 10.00 mmol) and catalyst (1 or 5 mol% metallic cesium or potassium) were mixed in a 10 ml Schlenk flask. Heating to 80°C resulted in a biphasic mixture, with liquid DPFA and liquid metal forming. Gas evolution was monitored during the reaction using the water displacement method. At the end of the reaction, the mixture was cooled to room temperature and analyzed by NMR (nuclear magnetic resonance). The NMR spectra of the solid residue identified the diphenylamine with traces of alkali metal diphenylamide.Table 1 details the decarbonylation kinetics of 1.97 g of diphenylformamide in the melt at 80°C, catalyzed by 1 or 5 mol% of metallic potassium, using an example. The decarbonylation reaction with metallic potassium as catalyst follows the reaction equation: OK 2. 2023PF12464 Foreign version 24 Table 1: Entry Amount of potassium 3.9 mg.1 mol % 19.5 mg.5 mol % t V conv. t V conv. m in sec (mL) (%) min sec (mL) (%)1 0 0 0 0 0 0 0 0 2 4 0 0 0 4 0 0 0 3 14 0 0 0 14 0 5 2 4 18 0 5 2 16 0 10 4 5 20 6 10 4 17 0 15 6 6 21 48 15 6 18 0 20 8 7 23 31 20 8 19 0 25 10 8 25 15 25 10 20 0 30 12 9 26 40 30 12 21 30 40 16 10 27 10 32 12.8 23 0 50 20 11 27 30 34 13.6 23 37 54 21.6 12 27 54 36 14.4 24 25 60 24 13 28 12 38 15.2 24 58 64 25.6 14 28 30 40 16 25 15 66 26.4 15 28 50 42 16.8 25 30 68 27.2 16 29 7 44 17.6 25 44 70 28 17 29 24 46 18.4 25 58 72 28.8 18 29 42 48 19.2 26 10 74 29.6 19 30 0 50 20 26 22 76 30.4 20 30 17 52 20.8 26 37 78 31.2 21 30 30 54 21.6 26 50 80 32 22 30 44 56 22.4 27 5 82 32.8 23 30 58 58 23.2 27 17 84 33.6 24 31 10 60 24 27 31 86 34.4 25 31 24 62 24.8 27 44 88 35.2 26 31 37 64 25.6 28 0 90 36 27 31 49 66 26.4 28 11 92 36.8 28 32 0 68 27.2 28 23 94 37.6 29 32 13 70 28 28 33 96 38.4 30 32 26 72 28.8 28 46 98 39.2 31 32 39 74 29.6 28 56 100 40 32 32 47 76 30.4 29 6 102 40.8 33 32 59 78 31.2 29 17 104 41.6 34 33 3 80 32 29 26 106 42.4 35 33 14 82 32.8 29 36 108 43.2 36 33 26 84 33.6 29 45 110 44 37 33 36 86 34.4 29 55 112 44.8 38 33 46 88 35.2 30 5 114 45.6 39 33 55 90 36 30 15 116 46.4 40 34 7 92 36.8 30 35 118 47.2 41 34 16 94 37.6 30 42 120 48 42 34 26 96 38.4 30 52 122 48.8 43 34 36 98 39.2 31 2 124 49.6 44 34 44 100 40 31 13 126 50.4 45 34 55 102 40.8 31 22 128 51.2 2023PF12464 Foreign version 25 46 35 6 104 41.6 31 30 130 52 47 35 18 106 42.4 31 36 132 52.8 48 35 33 108 43.2 31 42 134 53.6 49 35 49 110 44 31 48 136 54.4 50 35 59 112 44.8 31 57 138 55.2 51 36 8 114 45.6 32 5 140 56 52 36 19 116 46.4 32 16 142 56.8 53 36 29 118 47.2 32 26 144 57.6 54 36 44 120 48 32 35 146 58.4 55 36 59 122 48.8 32 44 148 59.2 56 37 14 124 49.6 32 54 150 60 57 37 28 126 50.4 33 3 152 60.8 58 37 41 128 51.2 33 14 154 61.6 59 37 51 130 52 33 25 156 62.4 60 38 5 132 52.8 33 34 158 63.2 61 38 12 134 53.6 33 40 160 64 62 38 25 136 54.4 33 51 162 64.8 63 38 38 138 55.2 34 1 164 65.6 64 38 52 140 56 34 10 166 66.4 65 39 6 142 56.8 34 20 168 67.2 66 39 19 144 57.6 34 28 170 68 67 39 33 146 58.4 34 35 172 68.8 68 39 45 148 59.2 34 44 174 69.6 69 39 59 150 60 34 55 176 70.4 70 40 17 152 60.8 35 4 178 71.2 71 40 30 154 61.6 35 10 180 72 72 40 43 156 62.4 35 18 182 72.8 73 40 57 158 63.2 35 27 184 73.6 74 41 10 160 64 35 35 186 74.4 75 41 25 162 64.8 35 44 188 75.2 76 41 41 164 65.6 35 52 190 76 77 41 57 166 66.4 36 0 192 76.8 78 42 10 168 67.2 36 9 194 77.6 79 42 24 170 68 36 17 196 78.4 80 42 40 172 68.8 36 25 198 79.2 81 42 52 174 69.6 36 34 200 80 82 43 5 176 70.4 36 43 202 80.8 83 43 22 178 71.2 36 53 204 81.6 84 43 35 180 72 37 6 206 82.4 85 43 53 182 72.8 37 17 208 83.2 86 44 10 184 73.6 37 30 210 84 87 44 27 186 74.4 37 44 212 84.8 88 44 45 188 75.2 37 56 214 85.6 89 44 59 190 76 38 12 216 86.4 90 45 21 192 76.8 38 26 218 87.2 91 45 31 194 77.6 38 41 220 88 92 46 0 196 78.4 38 57 222 88.8 93 46 20 198 79.2 39 19 224 89.6 94 46 39 200 80 39 41 226 90.4 95 47 2 202 80.8 40 5 228 91.2 96 47 25 204 81.6 40 35 230 92 97 47 53 206 82.4 41 10 232 92.8 2023PF12464 Foreign version 26 98 48 12 208 83.2 41 42 234 93.6 99 48 43 210 84 42 21 236 94.4 100 49 13 212 84.8 43 27 238 95.2 101 49 44 214 85.6 44 28 240 96 102 50 19 216 86.4 46 40 242 96.8 103 50 54 218 87.2 51 14 244 97.6 104 51 28 220 88 58 31 246 98.4 105 52 12 222 88.8 64 12 248 99.2 106 52 58 224 89.6 70 0 250 100 107 53 51 226 90.4 80 0 250 100 108 54 43 228 91.2 109 55 32 230 92 110 56 53 232 92.8 111 58 10 234 93.6 112 59 35 236 94.4 113 61 17 238 95.2 114 63 24 240 96 115 65 55 242 96.8 116 69 55 244 97.6 117 77 28 246 98.4 118 88 25 248 99.2 119 100 0 250 100 120 110 0 250 100 The corresponding time course of the respective measurement curve is shown graphically in Figure 4. This illustrates the kinetics of the conversion reaction by decarbonylation of diphenylformamide in the melt at 80°C at a constant CO pressure of 770 mmHg, catalyzed by potassium metal.The conversions are based on the volume of recovered carbon monoxide (CO). Accordingly, Table 2 shows the decarbonylation kinetics of 1.97 g of diphenylformamide in the melt at 80°C, catalyzed by 1 or 5 mol% metallic cesium in a single measurement sequence. The decarbonylation reaction with metallic cesium as catalyst follows the reaction equation: 2023PF12464 Foreign Version 27 . Entry Amount of Cs 13.3 mg.1 mol % 66.5 mg.5 mol % t V conv. t V conv. m in sec (mL) (%) min sec (mL) (%)1 0 0 0 0 0 0 0 0 2 2 15 5 2 3 0 5 2 3 2 40 10 4 3 30 10 4 4 3 17 15 6 4 0 15 6 5 3 50 20 8 4 26 20 8 6 4 31 25 10 4 54 25 10 7 5 10 30 12 5 19 30 12 8 6 11 40 16 5 55 40 16 9 7 9 50 20 6 28 50 20 10 8 6 60 24 7 3 60 24 11 9 5 70 28 7 29 70 28 12 10 4 80 32 7 57 80 32 13 10 59 90 36 8 27 90 36 14 11 39 100 40 8 52 100 40 15 12 21 110 44 9 18 110 44 16 13 0 120 48 9 45 120 48 17 13 38 130 52 10 8 130 52 18 14 14 14 140 56 10 28 140 56 19 14 51 150 60 10 46 150 60 20 15 34 160 64 11 5 160 64 21 16 23 170 68 11 26 170 68 22 17 18 180 72 11 48 180 72 23 18 27 190 76 12 14 190 76 24 19 47 200 80 12 46 200 80 25 19 59 202 80.8 13 24 210 84 26 20 18 204 81.6 14 14 220 88 2023PF12464 Foreign version 28 27 20 39 206 82.4 15 12 228 91.2 28 21 2 208 83.2 15 30 230 92 29 21 21 210 84 15 48 232 92.8 30 21 44 212 84.8 16 13 234 93.6 31 22 21 214 85.6 16 40 236 94.4 32 22 56 216 86.4 17 16 238 95.2 33 23 22 218 87.2 17 53 240 96 34 23 51 220 88 18 50 242 96.8 35 24 29 222 88.8 19 51 244 97.6 36 25 5 224 89.6 21 36 246 98.4 37 25 46 226 90.4 24 7 248 99.2 38 26 32 228 91.2 27 20 250 100 39 27 17 230 92 30 0 250 100 40 28 16 232 92.8 41 29 18 234 93.6 42 30 22 236 94.4 43 31 33 238 95.2 44 33 6 240 96 45 35 21 242 96.8 46 37 41 244 97.6 47 41 34 246 98.4 48 47 14 248 99.2 49 55 16 250 100 50 60 0 250 100 The corresponding time course of the respective measurement curve is shown graphically in Figure 5. It illustrates the kinetics of the conversion reaction by decarbonylation of diphenylformamide in the melt at 80°C at a constant CO pressure of 770 mmHg, catalyzed by cesium metal. The conversions are based on the volume of recovered CO.

Claims

2023PF12464 Foreign version 29 claims 1. A process for producing carbon monoxide by decarbonylation of a compound A, B or C, wherein compound A has the structural formula: OH , the B has the structural formula: has: O H 5' , wherein R1, R2, R3, R4, R1', R2', R3' and R4' are independently H, D, F, an alkyl radical or an aryl radical, wherein X is an aliphatic bridge, an aromatic bridge, an ether group, an ester group, an amide group or a urethane group, wherein n is in a range of 1 to 100,000.

2. The process according to claim 1, wherein R5 and R5' are independently H, D, F, an alkyl radical or an aryl radical. 2023PF12464 Foreign Version 30 3. The process according to claim 1 or 2, wherein the decarbonylation is carried out without the presence of a catalyst.

4. The process according to claim 3, wherein the decarbonylation is carried out with the addition of heat.

5. The process according to claim 1 or 2, wherein the decarbonylation is carried out in the presence of a catalyst K having the structural formula: + M –– N R7, where R6 is an aryl radical, R7 is H, D, an aryl radical or an alkyl radical, where M + is selected from the group Li + , N / a + , K + , Rb + and Cs + , in particular wherein the K +is complexed by a crown ether.

6. The process according to claim 5, wherein the decarbonylation is carried out with the addition of heat.

7. The process according to claim 5, wherein the decarbonylation is carried out without the addition of heat.

8. The process according to any one of claims 1 to 7, wherein the decarbonylation of compound A, B or C is carried out in a solvent.

9. The process according to any one of claims 1 to 7, wherein the decarbonylation of compound A, B or C is carried out in a melt of compound A, B or C.

10. The process according to any one of claims 1 to 7, wherein the decarbonylation of compound A, B or C is carried out in a solid state of compound A, B or C. 2023PF12464 Foreign version 31 11. Process according to one of claims 1 to 10, wherein the compound A is prepared starting from the compound D: H and / or wherein the compound E: H and / or wherein the compound is prepared starting from F: H 5' .

12. A process according to claim 11, wherein compound A is prepared by reacting compound D with formic acid and / or compound B is prepared by reacting compound E with formic acid and / or compound C is prepared by reacting compound F with formic acid.

13. A process according to claim 11, wherein compound A is prepared by reacting compound D with carbon dioxide to form a carbonate and / or a bicarbonate, and by subsequent 2023PF12464 Foreign Version 32 Hydrogenation of the carbonate and / or the bicarbonate with hydrogen to form compound A, and / or wherein compound B is prepared by reacting compound E with carbon dioxide to form a carbonate and / or a bicarbonate, and then hydrogenating the carbonate and / or the bicarbonate with hydrogen to form compound B, and / or wherein compound C is prepared by reacting compound F with carbon dioxide to form a carbonate and / or a bicarbonate, and then hydrogenating the carbonate and / or the bicarbonate with hydrogen to form compound C.

14. The process according to claim 11, wherein N,N-diphenylformamide is synthesized as compound A, which is obtained from triethylammonium formate azeotrope. 15.A process according to claim 14, wherein diphenylamine and triethylammonium formate azeotrope are mixed, and the mixture is fractionally distilled under reduced pressure to recover N,N-diphenylformamide in the solid phase.

16. A process for producing a synthetic fuel, wherein the carbon monoxide produced by a process according to any one of claims 1 to 13 is reduced using hydrogen.

17. A process according to claim 16, wherein the synthetic fuel comprises a hydrocarbon and / or an alcohol, in particular methanol and / or ethanol.

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