CA2131594A1 - Preparation of n-vinyl compounds - Google Patents
Preparation of n-vinyl compoundsInfo
- Publication number
- CA2131594A1 CA2131594A1 CA002131594A CA2131594A CA2131594A1 CA 2131594 A1 CA2131594 A1 CA 2131594A1 CA 002131594 A CA002131594 A CA 002131594A CA 2131594 A CA2131594 A CA 2131594A CA 2131594 A1 CA2131594 A1 CA 2131594A1
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- Prior art keywords
- preparation
- acetylene
- vinyl compound
- compounds
- reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/40—2,5-Pyrrolidine-diones
- C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyrrole Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Preparation Of N-Vinyl Compounds Abstract of the disclosure:
A process for the preparation of N-vinyl compounds of the general formula I
(I).
in which R1 and R2 independently denote hydrogen, C1-C20 alkyl, C5-C8 cycloalkyl, C7-C18 aralkyl, C6-C18 aryl or C1-C20 acyl, where one of the radicals R1 and R2 must be other than hydrogen, or the grouping R1-NR2 is a constituent part of a saturated, unsaturated or aromatic heterocyclic five-membered to seven-membered ring, which can additionally contain up to two further hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur or up to two keto functions and may additionally be benzanellated, by the reaction of NH compounds of the general formula II
A process for the preparation of N-vinyl compounds of the general formula I
(I).
in which R1 and R2 independently denote hydrogen, C1-C20 alkyl, C5-C8 cycloalkyl, C7-C18 aralkyl, C6-C18 aryl or C1-C20 acyl, where one of the radicals R1 and R2 must be other than hydrogen, or the grouping R1-NR2 is a constituent part of a saturated, unsaturated or aromatic heterocyclic five-membered to seven-membered ring, which can additionally contain up to two further hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur or up to two keto functions and may additionally be benzanellated, by the reaction of NH compounds of the general formula II
Description
l BASFAKTlENGEsELLscHAFT o.z.ooSo/44337 . ..
'~131~4 Preparation Of N-Vinyl Compounds . - - :
The present invention relates to an improved process for the preparation of N-vinyl compounds of the general formula I
Rl~
N--CH = CH2 ( 1), in which R1 and R2 independently denote hydrogen, C1-C20alkyl, c5-c8cycloalkyl, C~-C~8aralkyl, C~-C~8aryl or c,-c20acyl, where one of the radicals R1 and R2 must be other than hydrogen, or the grouping Rl-NR2 is a constituent part of a saturated, 0 unsaturated or aromatic heterocyclic five-membered to seven-membered ring, which can additionally contain up to two further hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur or up to two keto functions and may additionally be benzanellated, ..
I~ by the reaction of NH compounds of the general formula Il /N--H ~11), .
R2 .. :
20 with acetylene at temperatures ranging from 50 to 250C and pressures of from 1 to 30bar in the presence of compounds of the platinum metals acting as catalysts.
N-vinyl compounds are of interest as monomers for the preparation of polymers 2~ useful in diverse fielcis. Such polymers are employed, for example, as agents for clarifying drinks, as film formers in hair-setting agents or as dye transfer inhibitors in detergsnt5.
EPI-A 512,656 (1 ) discloses a process for the preparation of vinyl derivatives of ,0 Broensted-acids, ie hydrogen-active compounds, for example, secondary aromatic amines, primary aliphatic amines, amides or imides, by reacticn with acetylene in the gas phase at from 40 to 250C under pressure in the presence of zerovalent ruthenium on a support material as catalyst, in which the acetylene is diluted with nitrogen in a ratio by volume of ca 0.07:1 and in which the consumption of the ~ acetylene during the reaction is not controlled. In this manner, eg, N-vinylsuccinimide, N-vinyl-2-pyrrolidone or N-vinyi--caprolactam ars prepared. ~ . .
~ . .
BASFAKTIENGEsELiscHAFT 0 z oo50/44337 2~3~39'~
In the reference Orf~anometallics Vol. 2 (1983), pp. 1689-1691 (2) M. Rotem and Y. Shvo reveal the use of specific ruthenium carbonyls, such as Ru3(CO)12, as catalyst intermediates when adding aliphatic or aromatic carboxylic acids to di- or mono-substituted acetylenes with the formation of vinyl esters. The ruthenium s carbonyls are used in this case without support materials, and the reaction takes place in toluene at ~ 45c under pressure. It may be mentioned, in passing, thatruthenium(lII) chloride is completely inactive when used in this reaction.
It was the object of the invention to provide a more effective and more economical .0 process giving a better space-time yield and affording the possibility of better control of the conversion of the acetylene.
Accordingly, we have found ehe process defined above, wherein the acetylene is diluted in the reactor with an inert gas in a ratio by volume of from 6:1 to 0.5:1 and acetylene is forced in at the rate at which it is consumed.
It is known to the person skilled in the art that operating with acetylene underpressure, in particular at elevated temperatures, involves a safety risk, since acetylene can explosively decompose. For this reason it has hitherto been 20 considered desirable to strongly dilute the acetylene used in such systems with an inert medium such as nitrogen as described in (1). Thus it was all the more surprising to find that in the present invention the acetylene needs to be diluted with only small amounts of an inert gas in order to overcome the risk of explosion.
The possibility of controlling the acetylene consumption also increases the safety 2- of the process.
Suitable inert gases for diluting the acetylene are primarily argon, carbon monoxide, propane, and especially nitrogen.
0 The acetylene is diluted with the inert gas preferably in a ratio by volume of from 5:1 to 1:1, in particular from 4:1 to 2:1. The dimension mostly used to determine the volumes of the gases in this case is their partial pressure in the reactor.
Suitable catalysts are compounds of zero- to octa-valent platinum metals, ie J0 compounds of ruthenium, rhodium, palladium, osmium, iridium, and platinum. The preferred platinum metals are palladium, osmium, and in particular ruthenium. Weparticularly prefer palladium(II), osmium(III), and ruthenium(III) compounds such as PdC12, Oscl3, Ru(lll) acetylacetonate, and in particular RuC;13. It iS possible to use platinum metals of other valence stages, if desired, for example zerovalent 40 ruthenium carbonyls such as Ru3(CO)12.
BASF~I(TIE~GESELLSCHAFT O Z ooso/44~37 --` 213~94 The catalysts can be applied to support materials such as activated charcoal, silica gel, aluminum oxide or ion exchanger resins, but it is preferred to use unsupported catalysts.
s The catalysts are advantageously used in conventional amounts, ie approximately from 0.05 to 10 mol%, preferably from 0.2 to 5 mol%, based on one equivalent of NH in the compounds ll.
The reaction is advantageously carried out in an inert organic solvent. Suitablesolvents for this purpose are primarily higher-boiling aliphatic or aromatic hydrocarbons such as toluene or xylenes, higher-boiling aliphatic or aromatic halohydrocarbons such as chlorobenzene or dichlorobenzenes, or amides such as N-methylpyrrolidone or dimethylformamide. These solvents are usually used in an amount of from 50 to 800wt%, in particular from 100 to 500wt~/o, based on the weight of the NH compound ll used.
The reaction of the NH compounds ll with acetylene (C2H2) is usually caused to take place in a sealed pressure-proof reactor ( autoclave). The process is preferably carried out at temperatures ranging from 100 to 200~, in particular20 from 140 to 1 80C and at pressures of from 10 to 25 b~r, in particular frorn 15 to 22 bar. The reaction time required under these conditions is approximately 3 to 30 hours and is usually from 5 to 25 hours.
Purification of the reaction mixture takes place in the simplest case advantage-2~ ously by distillation of the crude vinylation product. The catalyst employed can be reused.
Suitable-straight-chain or branched-chain C~-C20alkyl radicals which can be represented by R1 and R2 are, for example, methyl, ethyl, n-propyl, isopropyl, n-.0 butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, isoamyl, sec-amyl, tert-amyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylh0xyl, n-nonyl, isononyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-pentadecyl, n hexa-decyl, n-heptadecyl, n-octadecyl and n-eicosyl. Of these, c1-C4 alkyl radicals are preferred.
.~
Suitablo c5-c8cycloalkyl radicals which can be representéd by R1 and R2 are primarily C5-C8 cycloalkyl such as cyclopentyl and cyclohexyl, as well as cycloheptyl, cyclooctyl, rnethylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl and dimethylcyclohexyl.
'~131~4 Preparation Of N-Vinyl Compounds . - - :
The present invention relates to an improved process for the preparation of N-vinyl compounds of the general formula I
Rl~
N--CH = CH2 ( 1), in which R1 and R2 independently denote hydrogen, C1-C20alkyl, c5-c8cycloalkyl, C~-C~8aralkyl, C~-C~8aryl or c,-c20acyl, where one of the radicals R1 and R2 must be other than hydrogen, or the grouping Rl-NR2 is a constituent part of a saturated, 0 unsaturated or aromatic heterocyclic five-membered to seven-membered ring, which can additionally contain up to two further hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur or up to two keto functions and may additionally be benzanellated, ..
I~ by the reaction of NH compounds of the general formula Il /N--H ~11), .
R2 .. :
20 with acetylene at temperatures ranging from 50 to 250C and pressures of from 1 to 30bar in the presence of compounds of the platinum metals acting as catalysts.
N-vinyl compounds are of interest as monomers for the preparation of polymers 2~ useful in diverse fielcis. Such polymers are employed, for example, as agents for clarifying drinks, as film formers in hair-setting agents or as dye transfer inhibitors in detergsnt5.
EPI-A 512,656 (1 ) discloses a process for the preparation of vinyl derivatives of ,0 Broensted-acids, ie hydrogen-active compounds, for example, secondary aromatic amines, primary aliphatic amines, amides or imides, by reacticn with acetylene in the gas phase at from 40 to 250C under pressure in the presence of zerovalent ruthenium on a support material as catalyst, in which the acetylene is diluted with nitrogen in a ratio by volume of ca 0.07:1 and in which the consumption of the ~ acetylene during the reaction is not controlled. In this manner, eg, N-vinylsuccinimide, N-vinyl-2-pyrrolidone or N-vinyi--caprolactam ars prepared. ~ . .
~ . .
BASFAKTIENGEsELiscHAFT 0 z oo50/44337 2~3~39'~
In the reference Orf~anometallics Vol. 2 (1983), pp. 1689-1691 (2) M. Rotem and Y. Shvo reveal the use of specific ruthenium carbonyls, such as Ru3(CO)12, as catalyst intermediates when adding aliphatic or aromatic carboxylic acids to di- or mono-substituted acetylenes with the formation of vinyl esters. The ruthenium s carbonyls are used in this case without support materials, and the reaction takes place in toluene at ~ 45c under pressure. It may be mentioned, in passing, thatruthenium(lII) chloride is completely inactive when used in this reaction.
It was the object of the invention to provide a more effective and more economical .0 process giving a better space-time yield and affording the possibility of better control of the conversion of the acetylene.
Accordingly, we have found ehe process defined above, wherein the acetylene is diluted in the reactor with an inert gas in a ratio by volume of from 6:1 to 0.5:1 and acetylene is forced in at the rate at which it is consumed.
It is known to the person skilled in the art that operating with acetylene underpressure, in particular at elevated temperatures, involves a safety risk, since acetylene can explosively decompose. For this reason it has hitherto been 20 considered desirable to strongly dilute the acetylene used in such systems with an inert medium such as nitrogen as described in (1). Thus it was all the more surprising to find that in the present invention the acetylene needs to be diluted with only small amounts of an inert gas in order to overcome the risk of explosion.
The possibility of controlling the acetylene consumption also increases the safety 2- of the process.
Suitable inert gases for diluting the acetylene are primarily argon, carbon monoxide, propane, and especially nitrogen.
0 The acetylene is diluted with the inert gas preferably in a ratio by volume of from 5:1 to 1:1, in particular from 4:1 to 2:1. The dimension mostly used to determine the volumes of the gases in this case is their partial pressure in the reactor.
Suitable catalysts are compounds of zero- to octa-valent platinum metals, ie J0 compounds of ruthenium, rhodium, palladium, osmium, iridium, and platinum. The preferred platinum metals are palladium, osmium, and in particular ruthenium. Weparticularly prefer palladium(II), osmium(III), and ruthenium(III) compounds such as PdC12, Oscl3, Ru(lll) acetylacetonate, and in particular RuC;13. It iS possible to use platinum metals of other valence stages, if desired, for example zerovalent 40 ruthenium carbonyls such as Ru3(CO)12.
BASF~I(TIE~GESELLSCHAFT O Z ooso/44~37 --` 213~94 The catalysts can be applied to support materials such as activated charcoal, silica gel, aluminum oxide or ion exchanger resins, but it is preferred to use unsupported catalysts.
s The catalysts are advantageously used in conventional amounts, ie approximately from 0.05 to 10 mol%, preferably from 0.2 to 5 mol%, based on one equivalent of NH in the compounds ll.
The reaction is advantageously carried out in an inert organic solvent. Suitablesolvents for this purpose are primarily higher-boiling aliphatic or aromatic hydrocarbons such as toluene or xylenes, higher-boiling aliphatic or aromatic halohydrocarbons such as chlorobenzene or dichlorobenzenes, or amides such as N-methylpyrrolidone or dimethylformamide. These solvents are usually used in an amount of from 50 to 800wt%, in particular from 100 to 500wt~/o, based on the weight of the NH compound ll used.
The reaction of the NH compounds ll with acetylene (C2H2) is usually caused to take place in a sealed pressure-proof reactor ( autoclave). The process is preferably carried out at temperatures ranging from 100 to 200~, in particular20 from 140 to 1 80C and at pressures of from 10 to 25 b~r, in particular frorn 15 to 22 bar. The reaction time required under these conditions is approximately 3 to 30 hours and is usually from 5 to 25 hours.
Purification of the reaction mixture takes place in the simplest case advantage-2~ ously by distillation of the crude vinylation product. The catalyst employed can be reused.
Suitable-straight-chain or branched-chain C~-C20alkyl radicals which can be represented by R1 and R2 are, for example, methyl, ethyl, n-propyl, isopropyl, n-.0 butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, isoamyl, sec-amyl, tert-amyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylh0xyl, n-nonyl, isononyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-pentadecyl, n hexa-decyl, n-heptadecyl, n-octadecyl and n-eicosyl. Of these, c1-C4 alkyl radicals are preferred.
.~
Suitablo c5-c8cycloalkyl radicals which can be representéd by R1 and R2 are primarily C5-C8 cycloalkyl such as cyclopentyl and cyclohexyl, as well as cycloheptyl, cyclooctyl, rnethylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl and dimethylcyclohexyl.
3 ::
BAsFAKrlENGEsELLscHAFT 2 1 3 1 ~ 9 ~ o Z ooS0/44 337 Suitable C7-C~8aralkyl radicals which can be represented by Rl and R2 are, for example, naphthylmethyl, diphenylmethyl or methylbenzyl, but especially c7-c~8 phenylalkyl such as 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 2-phenylprop-2-yl, 4-phenylbutyl, 2,2-dimethyl-2-phenylethyl, 5-s phenylamyl, 1 O-phenyldecyl, 1 2-phenyldodecyl or, primarily, benzyl.
Suitable c6-c~8 aryl radicals which can be represented by Rl and R2 are primarily mono- or di- nuclear residues, which can carry a further one to three cl-C4 alkyl groups as substituents. Particularly suitable examples of said radicals are unsubstituted phenyl, o-, m-, and p-tolyl, p-ethylphenyl, cumyl, p-tert-butylphenyl and - and ~- naphthyl.
Suitable C~-C20acyl radicals are primarily those in which the carbonyl group is directly adjacent to the Natom, so that amide, lactam, or imide structures are ~s present. Examples of C~-C20 acyl radicals are formyl, acetyl, propionyl, and butyryl.
In a preferred embodiment, those N-vinyl compounds I are prepared by the process of the invention in which the grouping R1-NR2 is a constituent part of asaturated, unsaturated or aromatic heterocyclic five-membered to seven-20 membered ring, which can contain a furgher nitrogen atom or an oxygen atom orup to two keto functions and which may additionally be benzanellated.
Suitable NH compounds ll to be converted are, for example:
25 - open-chain aliphatic primary or, preferably, secondary amines such as dimethylamine, cliethylamine or di-n-butylamine - cyc!oalkyl-substituted amines such as cyclohexylamine 30 - aryl- and aralkyl-substituted amines such as aniline, n-methylaniline, o-, m-, orp-toluidine, - or ~-naphthylamina, and benzylamine - open-chain carboxylic acid amides such as formarnide, N-methylformamide, acetamide, or propionamide ,~
- lactams such as 2-pyrrolidone, ô-butyrolactam or F-caprolactam - open-chain or preferably cyclic dicarboxylic acid imides such as succinimide, maleic acid imide or phthalimide ~0 - saturated or partially unsaturated heterocyclic nitrogen compounds such as :~
BAsFAKT~ENGEsELLscHAFT 2 1 3 1 ~ 9 ~ o.z.ooso/44337 , pyrrolidine, 2- or 3-pyrroline, piperidine, morpholine, indoline or isoindoline - aromatic nitrogen heterocyclics such as imidazole, pyrrole, pyrazole, 1,2,3-or 1 ,2,4-triazole, indole, isoindole, benzimidazole or 1 H-azepine.
It is possible to use NH compounds Il containing a plurality of NH groups, eg, aliphatic diamines such as N,N-dialkyl-~-diaminoalkanes or saturated hetero-cyclics such as imidazolodine or pyrazane.
Particularly preferred NH compounds Il to be converted are 2-pyrrolidone, imidazole, and -caprolactam.
There is usually used, per NH group in the compounds II, from 0.95 to 1.1 mol, preferably from 1.0 to 1.05mol, of acetylene, which is easy to control using the.. procedure of the invention.
The process of the invention for the vinyla~ion of the NH compounds ll can be applied to a large number of different NH compounds without any problem. The N-vinyl compounds I can be obtained in very good yields and ara essentially free 20 from contamination. Side-reactions such as saponification of carbonamide groupings or polymerization which otherwise frequently occur are not found to take place in the process of the invention.
2~ Examples 1 to 7 A mixture of ~ yrams of NH compound, k grams of solvent, and c mmol of platinum metal compound used as catalyst were placed in a high-pressure autoclave having a~ capacity of 300mL. After purging with nitrogen, the autoclave was heated and nitrogen and acetylene were forced in under a pressure of 5 bar until an overall pressure of 20bar (ratio by volume of C2H2 to N2 3:1) was attained.
Acetylene was th~n pumpcd in at the rato at which it was consumed. On completion of the reac~ion, the relevant N-vinyl compound was obtained by distillation of the crude product. Details are listed in the Table below.
BASFAKTlEN~EsELLscHAFT O-Z. oo50/44337 ~- 2131~94 ;
Ex. NH compound Amount Catalyst Amount Temp. Solvent Amount Reaction time Yieid a lg] Ç lg] lC] lg] lh] l~]
1 2-pyrrolidone75 RuCI3 6.5 150 toluene 75 24 87 2 2 -pyrrolidone 30 Ru(acac)3 5.3 160 toluene 120 14 77 5 3 2--pyrrolidone 100 RuCI3 9.6 150 20 82 4 2 - pyrrolidone 30 OsCI3 1.7 150toluene 120 18 44 5 imidazole 30 RuCI3 1.3 150 toluene 120 24 64 6 succinimide 30 RuCI3 9.5 150 NMP 120 7 72 7 2-pyrrolidone75 Ru(açac)3*) 2.5 160 toluene 75 24 85 acac = acetylacetonate, NMP = N-methylpyrrolidone *) 5 mmol of pyridine added
BAsFAKrlENGEsELLscHAFT 2 1 3 1 ~ 9 ~ o Z ooS0/44 337 Suitable C7-C~8aralkyl radicals which can be represented by Rl and R2 are, for example, naphthylmethyl, diphenylmethyl or methylbenzyl, but especially c7-c~8 phenylalkyl such as 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 2-phenylprop-2-yl, 4-phenylbutyl, 2,2-dimethyl-2-phenylethyl, 5-s phenylamyl, 1 O-phenyldecyl, 1 2-phenyldodecyl or, primarily, benzyl.
Suitable c6-c~8 aryl radicals which can be represented by Rl and R2 are primarily mono- or di- nuclear residues, which can carry a further one to three cl-C4 alkyl groups as substituents. Particularly suitable examples of said radicals are unsubstituted phenyl, o-, m-, and p-tolyl, p-ethylphenyl, cumyl, p-tert-butylphenyl and - and ~- naphthyl.
Suitable C~-C20acyl radicals are primarily those in which the carbonyl group is directly adjacent to the Natom, so that amide, lactam, or imide structures are ~s present. Examples of C~-C20 acyl radicals are formyl, acetyl, propionyl, and butyryl.
In a preferred embodiment, those N-vinyl compounds I are prepared by the process of the invention in which the grouping R1-NR2 is a constituent part of asaturated, unsaturated or aromatic heterocyclic five-membered to seven-20 membered ring, which can contain a furgher nitrogen atom or an oxygen atom orup to two keto functions and which may additionally be benzanellated.
Suitable NH compounds ll to be converted are, for example:
25 - open-chain aliphatic primary or, preferably, secondary amines such as dimethylamine, cliethylamine or di-n-butylamine - cyc!oalkyl-substituted amines such as cyclohexylamine 30 - aryl- and aralkyl-substituted amines such as aniline, n-methylaniline, o-, m-, orp-toluidine, - or ~-naphthylamina, and benzylamine - open-chain carboxylic acid amides such as formarnide, N-methylformamide, acetamide, or propionamide ,~
- lactams such as 2-pyrrolidone, ô-butyrolactam or F-caprolactam - open-chain or preferably cyclic dicarboxylic acid imides such as succinimide, maleic acid imide or phthalimide ~0 - saturated or partially unsaturated heterocyclic nitrogen compounds such as :~
BAsFAKT~ENGEsELLscHAFT 2 1 3 1 ~ 9 ~ o.z.ooso/44337 , pyrrolidine, 2- or 3-pyrroline, piperidine, morpholine, indoline or isoindoline - aromatic nitrogen heterocyclics such as imidazole, pyrrole, pyrazole, 1,2,3-or 1 ,2,4-triazole, indole, isoindole, benzimidazole or 1 H-azepine.
It is possible to use NH compounds Il containing a plurality of NH groups, eg, aliphatic diamines such as N,N-dialkyl-~-diaminoalkanes or saturated hetero-cyclics such as imidazolodine or pyrazane.
Particularly preferred NH compounds Il to be converted are 2-pyrrolidone, imidazole, and -caprolactam.
There is usually used, per NH group in the compounds II, from 0.95 to 1.1 mol, preferably from 1.0 to 1.05mol, of acetylene, which is easy to control using the.. procedure of the invention.
The process of the invention for the vinyla~ion of the NH compounds ll can be applied to a large number of different NH compounds without any problem. The N-vinyl compounds I can be obtained in very good yields and ara essentially free 20 from contamination. Side-reactions such as saponification of carbonamide groupings or polymerization which otherwise frequently occur are not found to take place in the process of the invention.
2~ Examples 1 to 7 A mixture of ~ yrams of NH compound, k grams of solvent, and c mmol of platinum metal compound used as catalyst were placed in a high-pressure autoclave having a~ capacity of 300mL. After purging with nitrogen, the autoclave was heated and nitrogen and acetylene were forced in under a pressure of 5 bar until an overall pressure of 20bar (ratio by volume of C2H2 to N2 3:1) was attained.
Acetylene was th~n pumpcd in at the rato at which it was consumed. On completion of the reac~ion, the relevant N-vinyl compound was obtained by distillation of the crude product. Details are listed in the Table below.
BASFAKTlEN~EsELLscHAFT O-Z. oo50/44337 ~- 2131~94 ;
Ex. NH compound Amount Catalyst Amount Temp. Solvent Amount Reaction time Yieid a lg] Ç lg] lC] lg] lh] l~]
1 2-pyrrolidone75 RuCI3 6.5 150 toluene 75 24 87 2 2 -pyrrolidone 30 Ru(acac)3 5.3 160 toluene 120 14 77 5 3 2--pyrrolidone 100 RuCI3 9.6 150 20 82 4 2 - pyrrolidone 30 OsCI3 1.7 150toluene 120 18 44 5 imidazole 30 RuCI3 1.3 150 toluene 120 24 64 6 succinimide 30 RuCI3 9.5 150 NMP 120 7 72 7 2-pyrrolidone75 Ru(açac)3*) 2.5 160 toluene 75 24 85 acac = acetylacetonate, NMP = N-methylpyrrolidone *) 5 mmol of pyridine added
Claims (9)
1. A process for the preparation of an N-vinyl compound of the general formula I
(I), in which R1 and R2 independently denote hydrogen, C1-C20 alkyl, C5-C8 cycloalkyl, C7-C18 aralkyl, C6-C18 aryl or C1-C20 acyl, where one of the radicals R1 and R2 must be other than hydrogen, or the grouping R1-NR2 is a constituent part of a saturated, unsaturated or aromatic heterocyclic five-membered to seven-membered ring, which can additionally contain up to two further hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur or up to two keto functions and may additionally be benzanellated, by the reaction of NH compounds of the general formula II
(II), with acetylene at temperatures ranging from 50° to 250°C and pressures of from 1 to 30 bar in the presence of compounds of the platinum metals acting as catalysts, wherein the acetylene is diluted in the reactor with an inert gas in a ratio by volume of from 6:1 to 0.5:1 and acetylene is forced in at the rate at which it is consumed.
(I), in which R1 and R2 independently denote hydrogen, C1-C20 alkyl, C5-C8 cycloalkyl, C7-C18 aralkyl, C6-C18 aryl or C1-C20 acyl, where one of the radicals R1 and R2 must be other than hydrogen, or the grouping R1-NR2 is a constituent part of a saturated, unsaturated or aromatic heterocyclic five-membered to seven-membered ring, which can additionally contain up to two further hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur or up to two keto functions and may additionally be benzanellated, by the reaction of NH compounds of the general formula II
(II), with acetylene at temperatures ranging from 50° to 250°C and pressures of from 1 to 30 bar in the presence of compounds of the platinum metals acting as catalysts, wherein the acetylene is diluted in the reactor with an inert gas in a ratio by volume of from 6:1 to 0.5:1 and acetylene is forced in at the rate at which it is consumed.
2. A process for the preparation of an N-vinyl compound I as defined in claim 1, wherein the acetylene is diluted in the reactor with nitrogen in a ratio of from 5:1 to 1:1 by volume.
3. A process for the preparation of an N-vinyl compound I as defined in claim 1, wherein a palladium(II), osmium(II), or ruthenium(III) compound is usedas catalyst.
4. A process for the preparation of an N-vinyl compound I as defined in claim 1, wherein the catalyst used is unsupported.
5. A process for the preparation of an N-vinyl compound I as defined in claim 1, wherein the reaction is carried out in an inert organic solvent.
6. A process for the preparation of an N-vinyl compound I as defined in claim 1, wherein the reaction is carried out at temperatures ranging from 140° to 180°C.
7. A process for the preparation of an N-vinyl compound I as defined in claim 1, wherein the reaction is carried out at pressures of from 15 to 22 bar.
8. A process for the preparation of an N-vinyl compound I as defined in claim 1, wherein the grouping R1-NR2 forms a constituent part of a saturated, unsaturated or aromatic heterocyclic five-membered to seven-membered ring, which can contain a further nitrogen atom or an oxygen atom or up to two keto functions and may additionally be benzanellated.
9. A process for the preparation of an N-vinyl compound I as defined in claim 8 which involves the reaction of 2-pyrrolidone, imidazole, or .epsilon.-caprolactam.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4333237A DE4333237A1 (en) | 1993-09-30 | 1993-09-30 | Process for the preparation of N-vinyl compounds |
| DEP4333237.4 | 1993-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2131594A1 true CA2131594A1 (en) | 1995-03-31 |
Family
ID=6498999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002131594A Abandoned CA2131594A1 (en) | 1993-09-30 | 1994-09-07 | Preparation of n-vinyl compounds |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0646571B1 (en) |
| JP (1) | JP3545062B2 (en) |
| CA (1) | CA2131594A1 (en) |
| DE (2) | DE4333237A1 (en) |
| ES (1) | ES2102114T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114829339A (en) * | 2019-12-20 | 2022-07-29 | 巴斯夫欧洲公司 | Synthesis of N-vinyl compounds by reacting cyclic NH-compounds with acetylene in the presence of a homogeneous catalyst |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19816479B4 (en) * | 1998-04-14 | 2005-02-03 | Müller, Thomas, Dr. | Process for the preparation of enamines, imines, indoles and diamines from alkynes and their further processing by catalytic hydrogenation |
| DE19836814A1 (en) * | 1998-08-14 | 2000-02-17 | Basf Ag | Process for the preparation of imines and enamines and optionally their further hydrogenation to amines |
| DE19838666B4 (en) * | 1998-08-26 | 2005-02-24 | Müller, Thomas, Dr. | Heterogeneous process for the preparation of enamines, imines, indoles and diamines from alkynes and further processing of the products obtained by catalytic hydrogenation |
| DE19924050A1 (en) * | 1999-05-26 | 2000-11-30 | Basf Ag | Process for the preparation of alkene compounds |
| DE102004038109A1 (en) | 2004-08-05 | 2006-03-16 | Basf Ag | Stabilizers for NVP synthesis |
| DE102004056819A1 (en) * | 2004-11-24 | 2006-06-01 | Studiengesellschaft Kohle Mbh | Process for the addition of amides, ureas, lactams and carbamates to alkynes |
| DE102006028000A1 (en) * | 2006-06-14 | 2007-12-20 | Basf Ag | Process for the alkenylation of carboxylic acid amides |
| EP4341244A1 (en) | 2021-05-19 | 2024-03-27 | Basf Se | Synthesis of n-vinyl compounds by reacting nh-compounds with acetylene in presence of homogeneous phosphine catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1018396B (en) * | 1955-06-16 | 1957-10-31 | Basf Ag | Process for converting gaseous or vaporous substances |
| US4873336A (en) * | 1988-03-28 | 1989-10-10 | Gaf Corporation | Process for the preparation of N-vinyl lactams |
| GB9110110D0 (en) * | 1991-05-10 | 1991-07-03 | Shell Int Research | Process for the preparation of vinyl derivatives |
-
1993
- 1993-09-30 DE DE4333237A patent/DE4333237A1/en not_active Withdrawn
-
1994
- 1994-09-07 CA CA002131594A patent/CA2131594A1/en not_active Abandoned
- 1994-09-21 EP EP94114890A patent/EP0646571B1/en not_active Expired - Lifetime
- 1994-09-21 ES ES94114890T patent/ES2102114T3/en not_active Expired - Lifetime
- 1994-09-21 DE DE59403103T patent/DE59403103D1/en not_active Expired - Lifetime
- 1994-09-29 JP JP23567094A patent/JP3545062B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114829339A (en) * | 2019-12-20 | 2022-07-29 | 巴斯夫欧洲公司 | Synthesis of N-vinyl compounds by reacting cyclic NH-compounds with acetylene in the presence of a homogeneous catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0646571A1 (en) | 1995-04-05 |
| JPH07179404A (en) | 1995-07-18 |
| EP0646571B1 (en) | 1997-06-11 |
| ES2102114T3 (en) | 1997-07-16 |
| DE4333237A1 (en) | 1995-04-06 |
| DE59403103D1 (en) | 1997-07-17 |
| JP3545062B2 (en) | 2004-07-21 |
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