Synthesis of N-vinyl compounds by reacting cyclic NH-compounds with acetylene in the presence of a homogeneous catalyst

Abstract

A process for preparing N-vinyl compounds by homogeneous catalysis, wherein acetylene is reacted with a cyclic compound in the liquid phase in the presence of a ruthenium complex (RuCat) containing at least one phosphine as a ligand, the cyclic compound containing a nitrogen with a replaceable hydrogen group as a ring member (cyclic compound C).

Description

[0001] The present invention relates to a process for preparing N-vinyl compounds by homogeneous catalysis, wherein acetylene is reacted with a cyclic compound comprising a hydrogen-substituted nitrogen as a ring member in the liquid phase in the presence of a ruthenium complex comprising at least one phosphine as a ligand.

[0002] From EP 512 656 it is known to prepare vinyl compounds by reacting acetylene with Brønsted acids in the presence of heterogeneously supported catalysts comprising ruthenium.

[0003] EP-A 646571 discloses the homogeneously catalyzed reaction of acetylene with ammonia or primary or secondary amino compounds at 1 to 30 bar; 20 bar is used in the examples. Various catalysts are disclosed, and catalysts based on ruthenium are mentioned in particular.

[0004] WO 2006 / 056166 discloses the reaction of substituted alkynes with lactams, ureas or carbamates catalyzed by homogeneous catalysts. Acetylene is not included. Since the substituted alkynes used are liquid, the reaction is carried out at normal pressure.

[0005] DE 19816479 describes a process for the synthesis of N-vinyl compounds by homogeneous catalysis. Alkynes are reacted with ammonia or primary or secondary amino compounds in the liquid phase. Acetylene is mentioned, but it is not used in the examples. Many suitable transition metal complexes are listed, but no ruthenium / phosphine complexes are used to react with acetylene.

[0006] Since acetylene is gaseous, reactions with acetylene are usually carried out under pressure. It is economical to keep the pressure as low as possible.

[0007] It is an object of the present invention to provide a process for the synthesis of N-vinyl compounds, in particular cyclic N-vinyl compounds, which process can be carried out at low pressure and in which the N-vinyl compounds are obtained in high yields and selectivities.

[0008] Thus, the above method was found.

[0009] Cyclic compounds

[0010] The cyclic compound is preferably a compound with a 5-8 membered ring system, which comprises a cyclic compound having at least one nitrogen as a ring member (cyclic compound C), wherein the nitrogen has a replaceable hydrogen group. Preferably, the cyclic compound C has one or two nitrogen ring members with one or two replaceable hydrogen groups, more preferably one hydrogen group.

[0011] In a particularly preferred embodiment, the cyclic compound C is a cyclic amide, a cyclic urea or thiourea or a cyclic carbamate or thiocarbamate.

[0012] Cyclic amides contain the amide group -NH-C(=O)-CH2- as an element of the ring system.

[0013] Cyclic ureas contain the urea group -NH-C=(O)-NH- as an element of the ring system.

[0014] Cyclic thioureas contain the thiourea group -NH-C=(S)-NH- as an element of the ring system.

[0015] Cyclic carbamates contain the carbamate group -NH-C(=O)-O- as an element of the ring system.

[0016] Cyclic thiocarbamates contain the thiocarbamate group -NH-C(=S)-O- or -NH-C(=O)-S- as an element of the ring system.

[0017] The other carbon atoms of the ring system may be substituted or unsubstituted. The substituents of the carbon atoms may be, for example, carbonyl (=O), aliphatic or aromatic hydrocarbon groups, which may contain heteroatoms, in particular oxygen in the form of ether groups, and two adjacent carbon atoms may be part of other ring systems, for example alicyclic or aromatic ring systems.

[0018] In a most preferred embodiment, the cyclic compound C is a cyclic amide.

[0019] The molecular weight of the cyclic compound C is generally at most 1000 g / mol, preferably at most 500 g / mol.

[0020] Preferred cyclic amides are: 2-pyrrolidone, 2-piperidone, caprolactam, 8-octanolactam, 2,3-dihydro-1H-isoindol-1-one, 2(1H)-quinoxalinone, 4(3H)-quinazolinone, 2,5-piperazinedione, 2-thiazolidinone, 2-azabicyclo[2.2.1]hept-5-en-3-one.

[0021] Preferred cyclic ureas are: 2-imidazolidinone, 4-methyl-2-imidazolidinone, 1,3-dihydro-2H-imidazol-2-one, 1,3-dihydro-2H-benzimidazol-2-one, 1,3-dihydro-1-methyl-2H-benzimidazol-2-one, 2,4-imidazolidinedione, 5-methyl-2,4-imidazolidinedione, 5,5-dimethyl-2,4-imidazolidinedione, 5-methyl-2,4(1H,3H)-pyrimidinedione.

[0022] Preferred cyclic carbamates are: 2-oxazolidinone, 4-methyl-2-oxazolidinone, 5-methyl-2-oxazolidinone, tetrahydro-2H-1,3-oxazin-2-one, 2(3H)-benzoxazolone.

[0023] In the process of the invention, cyclic compounds C comprising hydrogen-substituted nitrogen as ring member are reacted with acetylene in the presence of at least one homogeneous Ru metal catalyst having at least one phosphine as ligand (RuCat); hereinafter also referred to as vinylation catalyst.

[0024] The vinylation catalyst RuCat of the process of the present invention can be used in the form of a preformed Ru metal complex comprising a Ru metal compound and one or more ligands. Alternatively, the catalytic system is formed in situ in the reaction mixture by combining a Ru metal compound (also referred to herein as a precatalyst) with one or more suitable ligands to form a catalytically active metal complex in the reaction mixture.

[0025] Preferred procatalysts are selected from neutral metal complexes, oxides and salts of ruthenium. Examples of ruthenium compounds that can be used as procatalysts are [Ru(p-cymene)Cl2]2, [Ru(benzene)Cl2] n , [Ru(CO)2Cl2]n, [Ru(CO)3Cl2]2, [Ru(COD)(allyl)], [RuCl3·H2O], [Ru(acetylacetone)3], [Ru(DMSO)4Cl2], [Ru(PPh3)3Cl2], [Ru(cyclopentadienyl)(PPh3)2Cl], [Ru(cyclopentadienyl)(CO)2Cl], [Ru(cyclopentadienyl)(CO)2H], [Ru(cyclopentadienyl)(CO)2]2, [Ru(pentamethyl [Ru(pentamethylcyclopentadienyl)(CO)2Cl], [Ru(pentamethylcyclopentadienyl)(CO)2H], [Ru(pentamethylcyclopentadienyl)(CO)2]2, [Ru(indenyl)(CO)2Cl], [Ru(indenyl)(CO)2H], [Ru(indenyl)(CO)2]2, bis(indenyl), [Ru(2,2'-bipyridine)2(Cl)2·H2O], [Ru(COD)(Cl)2H]2, [Ru(pentamethylcyclopentadienyl)(COD)Cl], [Ru3(CO) 12 ] and [Ru(tetraphenylhydroxycyclopentadienyl)(CO)2H].

[0026] For the vinylation according to the process of the invention, any complex ligand known in the art may be used, in particular those known to be useful in ruthenium-catalyzed hydrogenations.

[0027] Suitable ligands for the catalytic system for the vinylation according to the process of the invention are, for example, the monodentate, bidentate, tridentate and tetradentate phosphines of the formulae I and II shown below,

[0028]

[0029] in:

[0030] n is 0 or 1;

[0031] R 4 To R 12 are independently unsubstituted or at least monosubstituted C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C3-C4-C6 ... 10 Heterocyclic, C5-C 14 an aromatic group or a C5-C ... 10 Heteroaryl,

[0032] Wherein the substituent is selected from: F, Cl, Br, OH, CN, NH2 and C1-C 10 alkyl;

[0033] A is:

[0034] i) a bridging group selected from unsubstituted or at least monosubstituted N, O, P, C1-C6 alkane, C3-C 10 Cycloalkane, C3-C4-C6 ... 10 Heterocycloalkanes, C5-C 14 Aromatic and C5-C6 heteroaromatic containing at least one heteroatom selected from N, O and S, wherein the substituents are selected from C1-C4 alkyl, phenyl, F, Cl, Br, OH, OR 16 、NH2、NHR 16 or N(R 16 )2,

[0035] Where R 16 Selected from C1-C 10 Alkyl and C5-C 10 Aryl; or

[0036] ii) a bridging group of formula (VI) or (VII):

[0037]

[0038] R 13 , R 14 Independently selected from C1-C 10 Alkyl, F, Cl, Br, OH, OR 15 、NH2、NHR 15 and N(R 15 )2,

[0039] Where R 15 Selected from C1-C 10 Alkyl and C5-C 10 Aryl;

[0040] X 1 , X 2 are independently NH, O or S;

[0041] X 3 For bond, NH, NR 16 , O, S or CR 17 R 18 ;

[0042] R 16 is unsubstituted or at least monosubstituted C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C3-C4-C6 ... 10 Heterocyclic, C5-C 14 aryl or a C5-C10 heteroaryl group containing at least one heteroatom selected from N, O and S,

[0043] Wherein the substituent is selected from: F, Cl, Br, OH, CN, NH2 and C1-C 10 alkyl;

[0044] R 17 , R 18 are independently unsubstituted or at least monosubstituted C1-C 10 Alkyl, C1-C 10 Alkoxy, C3-C 10 Cycloalkyl, C3-C 10 Cycloalkoxy, a C3-C4-cycloalkyl group containing at least one heteroatom selected from N, O and S 10 Heterocyclic, C5-C 14 Aryl, C5-C 14 an aryloxy group or a C5-C 10 Heteroaryl,

[0045] Wherein the substituent is selected from: F, Cl, Br, OH, CN, NH2 and C1-C 10 alkyl;

[0046] Y 1 , Y 2 , Y 3 are, independently of one another, a bond, an unsubstituted or at least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene,

[0047] Wherein the substituent is selected from: F, Cl, Br, OH, OR 15 、CN、NH2、NHR 15 、N(R 15 )2 and C1-C 10 alkyl,

[0048] Where R 15 Selected from C1-C 10 Alkyl and C5-C 10 Aryl.

[0049] A is a bridging group. A is selected from unsubstituted or at least monosubstituted C1-C6 alkanes, C3-C 10 Cycloalkanes, C3-C 10 Heterocycloalkanes, C5-C 14 In the case of aromatic and C5-C6 heteroaromatic groups, for the case (n=0), the two hydrogen atoms of the bridging group are replaced by the adjacent substituent Y 1 and Y 2 For the case (n=1), the three hydrogen atoms of the bridging group are replaced by the adjacent substituent Y 1 , Y 2 and Y 3 The three keys are replaced.

[0050] For the case where A is P (phosphorus), for the case (n = 0), phosphorus and the adjacent substituent Y 1 and Y 2 Two bonds are formed with phosphorus and one bond is formed with a substituent selected from C1-C4 alkyl and phenyl. For the case (n=1), phosphorus is bonded to the adjacent substituent Y 1 , Y 2 and Y 3 Three bonds are formed.

[0051] For the case where A is N (nitrogen), for the case (n = 0), the nitrogen and the adjacent substituent Y 1 and Y 2 Two bonds are formed with the nitrogen and one bond is formed with a substituent selected from C1-C4 alkyl and phenyl. For the case (n=1), the nitrogen is bonded to the adjacent substituent Y 1 , Y 2 and Y 3 Three bonds are formed.

[0052] When A is O (oxygen), n = 0. Oxygen and the adjacent substituent Y 1 and Y 2 Two bonds are formed.

[0053] Preference is given to complex catalysts comprising at least one element selected from ruthenium and iridium.

[0054] In a preferred embodiment, the process according to the invention is carried out in the presence of at least one coordination catalyst comprising Ru and at least one phosphorus donor ligand of the general formula (II), wherein:

[0055] n is 0 or 1;

[0056] R 7 To R 12are independently unsubstituted C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C3-C4-C6 ... 10 Heterocyclic, C5-C 14 an aromatic group or a C5-C ... 10 heteroaryl;

[0057] A is:

[0058] i) a bridging group selected from unsubstituted C1-C6 alkanes, C3-C 10 Cycloalkane, containing at least one C3-C 10 Heterocycloalkanes, C5-C 14 Aromatic and C5-C6 heteroaromatic containing at least one heteroatom selected from N, O and S; or

[0059] ii) a bridging group of formula (VI) or (VII):

[0060]

[0061] R 13 , R 14 Independently selected from C1-C 10 Alkyl, F, Cl, Br, OH, OR 15 、NH2、NHR 15 and N(R 15 )2,

[0062] Where R 15 Selected from C1-C 10 Alkyl and C5-C 10 Aryl;

[0063] X 1 , X 2 are independently NH, O or S;

[0064] X 3 For bond, NH, NR 16 , O, S or CR 17 R 18 ;

[0065] R 16 For unsubstituted C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C3-C4-C6 ... 10 Heterocyclic, C5-C 14 an aromatic group or a C5-C ... 10 heteroaryl;

[0066] R 17 , R 18 are independently unsubstituted C1-C 10 Alkyl, C1-C 10 Alkoxy, C3-C 10 Cycloalkyl, C3-C 10 Cycloalkoxy, a C3-C4-cycloalkyl group containing at least one heteroatom selected from N, O and S 10 Heterocyclic, C5-C 14 Aryl, C5-C 14 an aryloxy group or a C5-C 10 heteroaryl;

[0067] Y 1 , Y 2 , Y 3 Independently of one another is a bond, an unsubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene.

[0068] In a further preferred embodiment, the process according to the invention is carried out in the presence of at least one coordination catalyst comprising Ru and at least one phosphorus-donating ligand of the general formula (VIII),

[0069]

[0070] in:

[0071] R 7 To R 10 are independently unsubstituted or at least monosubstituted C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C3-C4-C6 ... 10 Heterocyclic, C5-C 14 an aromatic group or a C5-C ... 10 Heteroaryl,

[0072] Wherein the substituent is selected from: F, Cl, Br, OH, CN, NH2 and C1-C 10 alkyl;

[0073] A is:

[0074] i) a bridging group selected from unsubstituted or at least monosubstituted N, O, P, C1-C6 alkane, C3-C 10 Cycloalkane, C3-C4-C6 ... 10 Heterocycloalkanes, C5-C 14aromatic and C5-C6 heteroaromatic containing at least one heteroatom selected from N, O and S,

[0075] The substituent is selected from: C1-C4 alkyl, phenyl, F, Cl, Br, OH, OR 15 、NH2、NHR 15 or N(R 15 )2,

[0076] Where R 15 Selected from C1-C 10 Alkyl and C5-C 10 Aryl; or

[0077] ii) a bridging group of formula (VI) or (VII):

[0078]

[0079] i) a bridging group selected from unsubstituted or at least monosubstituted N, O, P, C1-C6 alkanes,

[0080] C3-C 10 Cycloalkane, C3-C4-C6 ... 10 Heterocycloalkanes, C5-C 14 Aromatic and C5-C6 heteroaromatic containing at least one heteroatom selected from N, O and S, wherein the substituents are selected from: C1-C4 alkyl, phenyl, F, Cl, Br, OH, OR 15 、NH2、NHR 15 or N(R 15 )2,

[0081] Where R 15 Selected from C1-C 10 Alkyl and C5-C 10 Aryl; or

[0082] ii) a bridging group of formula (VI) or (VII):

[0083] m, q are independently 0, 1, 2, 3 or 4;

[0084] R 13 , R 14 Independently selected from C1-C 10 Alkyl, F, Cl, Br, OH, OR 15 、NH2、NHR 15 and N(R 15 )2,

[0085] Where R 15 Selected from C1-C 10 Alkyl and C5-C 10Aryl;

[0086] X 1 , X 2 are independently NH, O or S,

[0087] X 3 For bond, NH, NR 16 , O, S or CR 17 R 18 ;

[0088] R 16 is unsubstituted or at least monosubstituted C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C3-C4-C6 ... 10 Heterocyclic, C5-C 14 an aromatic group or a C5-C ... 10 Heteroaryl,

[0089] Wherein the substituent is selected from: F, Cl, Br, OH, CN, NH2 and C1-C 10 alkyl;

[0090] R 17 , R 18 are independently unsubstituted or at least monosubstituted C1-C 10 Alkyl, C1-C 10 Alkoxy, C3-C 10 Cycloalkyl, C3-C 10 Cycloalkoxy, a C3-C4-cycloalkyl group containing at least one heteroatom selected from N, O and S 10 Heterocyclic, C5-C 14 Aryl, C5-C 14 an aryloxy group or a C5-C 10 Heteroaryl,

[0091] Wherein the substituent is selected from: F, Cl, Br, OH, CN, NH2 and C1-C 10 alkyl;

[0092] Y 1 , Y 2 are independently of one another a bond, an unsubstituted or at least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene,

[0093] Wherein the substituent is selected from: F, Cl, Br, OH, OR 15 、CN、NH2、NHR 15 、N(R 15 )2 and C1-C 10alkyl,

[0094] Where R 15 Selected from C1-C 10 Alkyl and C5-C 10 Aryl.

[0095] In another preferred embodiment, the process according to the invention is carried out in the presence of at least one coordination catalyst comprising at least one element selected from Groups 8, 9 and 10 of the Periodic Table of the Elements and at least one phosphorus donor ligand of the general formula (IX):

[0096]

[0097] in:

[0098] R 7 To R 12 are independently unsubstituted or at least monosubstituted C1-C 10 Alkyl, containing at least one heteroatom selected from N, O and S C3-C 10 Heterocyclic, C5-C 14 an aromatic group or a C5-C ... 10 Heteroaryl,

[0099] Wherein the substituent is selected from: F, Cl, Br, OH, CN, NH2 and C1-C 10 alkyl;

[0100] A is a bridging group selected from unsubstituted or at least monosubstituted N, P, C1-C6 alkane, C3-C 10 Cycloalkane, C3-C4-C6 ... 10 Heterocycloalkanes, C5-C 14 Aromatic and C5-C6 heteroaromatic containing at least one heteroatom selected from N, O and S, wherein the substituents are selected from: C1-C4 alkyl, phenyl, F, Cl, Br, OH, OR 15 、NH2、NHR 15 or N(R 15 )2,

[0101] Where R 15 Selected from C1-C 10 Alkyl and C5-C 10 Aryl;

[0102] Y 1 , Y 2 , Y 3 are independently of one another a bond, an unsubstituted or at least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene or hexamethylene,

[0103] Wherein the substituent is selected from: F, Cl, Br, OH, OR 15 、CN、NH2、NHR 15 、N(R 15 )2 and C1-C 10 alkyl,

[0104] Where R 15 Selected from C1-C 10 Alkyl and C5-C 10 Aryl.

[0105] In another preferred embodiment, the process of the invention is carried out in the presence of at least one coordination catalyst comprising at least one element selected from Groups 8, 9 and 10 of the Periodic Table of the Elements and at least one phosphorus donor ligand of the general formula (VIII), wherein:

[0106] R 7 To R 10 are independently methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl or mesityl;

[0107] A is:

[0108] i) a bridging group selected from methane, ethane, propane, butane, cyclohexane, benzene, naphthalene and anthracene; or

[0109] ii) a bridging group of formula (X) or (XI):

[0110]

[0111] X 1 , X 2 are independently NH, O or S;

[0112] X 3 is a bond, NH, O, S or CR 17 R 18 ;

[0113] R 17 , R 18 are independently unsubstituted C1-C 10 alkyl;

[0114] Y 1 , Y 2 are independently a bond, a methylene group or an ethylene group.

[0115] In a particularly preferred embodiment, the process according to the invention is carried out in the presence of at least one coordination catalyst comprising at least one element selected from Groups 8, 9 and 10 of the Periodic Table of the Elements and at least one phosphorus donor ligand of the general formula (XII) or (XIII),

[0116]

[0117] Among them, for m, q, R 7 , R 8 , R 9 , R 10 , R 13 , R 14 , X 1 , X 2 and X 3 , the definitions and preferences listed above apply.

[0118] In an embodiment, the process of the present invention is carried out in the presence of at least one Ru metal coordination catalyst, and the monodentate ligand of formula I is preferably one in which R 5a , R 5b and R 6 are each phenyl or alkyl optionally substituted with 1 or 2 C1-C4 alkyl groups, and wherein R 7 , R 8 and R 9 Each is a C5-C8 cycloalkyl or a C2-C 10 Alkyl groups, especially straight chain unbranched normal C2-C 10 Those of alkyl groups. 5a To R 6 Can be different or the same. Preferably, the group R 5a To R 6 are identical and are selected from the substituents described herein, in particular from those indicated as preferred. Examples of preferred monodentate ligands IV are triphenylphosphine (TPP), triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine and tricyclohexylphosphine.

[0119] In another embodiment, the process of the present invention is carried out in the presence of at least one Ru metal coordination catalyst and at least one phosphorus donor ligand selected from the following group: 1,2-bis(diphenylphosphino)ethane (dppe), 1,2-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)butane (dppb), 2,3-bis(dicyclohexylphosphino)ethane (dcpe), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), bis(2-diphenylphosphinoethyl)phenylphosphine and 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos).

[0120] In another particularly preferred embodiment, the process of the invention is carried out in the presence of a coordination catalyst comprising ruthenium and at least one phosphorus donor ligand selected from 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), bis(2-diphenylphosphinoethyl)phenylphosphine and 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos).

[0121] In another particularly preferred embodiment, the process of the invention is carried out in the presence of a coordination catalyst comprising iridium and at least one phosphorus donor ligand selected from 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), bis(2-diphenylphosphinoethyl)phenylphosphine and 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos).

[0122] In the context of the present invention, C1-C 10 Alkyl is understood to mean branched, unbranched, saturated and unsaturated groups. Alkyl groups having 1 to 6 carbon atoms (C1-C6 alkyl) are preferred. Alkyl groups having 1 to 4 carbon atoms (C1-C4 alkyl) are more preferred.

[0123] Examples of saturated alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl.

[0124] Examples of unsaturated alkyl (alkenyl, alkynyl) groups are vinyl, allyl, butenyl, ethynyl and propynyl.

[0125] C1-C 10 The alkyl group may be unsubstituted or substituted with one or more substituents selected from the group consisting of F, Cl, Br, hydroxyl (OH), C1-C 10 Alkoxy, C5-C 10 Aryloxy, C5-C 10 Alkaryloxy, containing at least one heteroatom selected from N, O, S, oxo, C5-C 10 Heteroaryloxy, oxo, C3-C 10 Cycloalkyl, phenyl, C5-C6 containing at least one heteroatom selected from N, O, S 10 Heteroaryl, a C5-C 10 Heterocyclyl, naphthyl, amino, C1-C 10 Alkylamino, C5-C 10 Arylamino, a C5-C 10 Heteroarylamino, C1-C 10 Dialkylamino, C 10 -C 12 Diarylamino, C 10 -C20 Alkyl aryl amino, C1-C 10 Acyl, C1-C 10 Acyloxy, NO2, C1-C 10 Carboxyl, carbamoyl, carboxamide, cyano, sulfonyl, sulfonylamino, sulfinyl, sulfinylamino, mercapto, C1-C 10 Alkylmercapto, C5-C 10 Arylthio or C1-C 10 Alkylsulfonyl.

[0126] C1-C 10 The above definition of alkyl applies correspondingly to C1-C 30 Alkyl and C1-C6 alkane.

[0127] In the case of the present invention, C3-C 10 Cycloalkyl is understood to mean saturated, unsaturated, monocyclic and polycyclic groups. 10 Examples of cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl. Cycloalkyl may be unsubstituted or substituted with one or more C1-C12 radicals as described above. 10 The alkyl group is substituted with a substituent as defined above.

[0128] By adding the ligand to the above precursor, an active vinylation catalyst can be generated in situ in the reaction mixture. The molar ratio of transition metal to ligand is 2:1 to 1:50, preferably 1:1 to 1:10, and most preferably 1:2 to 1:5.

[0129] In addition to one or more ligands selected from the above-mentioned ligand group, the catalytic system of the inventive method can also comprise at least one other ligand selected from the following group: halides, amides, carboxylates, acetylacetonates, aryl sulfonates or alkyl sulfonates, hydrides, CO, olefins, dienes, cycloolefins, nitriles, aromatic and heteroaromatic compounds, ethers, PF3, phospholene, phosphazenes, and monodentate, bidentate and multidentate phosphinates, phosphites, phosphoramidites and phosphite ligands. Preferably, the catalyst also comprises CO as a ligand.

[0130] The active catalyst RuCat can also be preformed in a dedicated synthesis step. Suitable preformed catalysts may be [Ru(PPh3)3(CO)(H)Cl], [Ru(PPh3)3(CO)Cl2], [Ru(PPh3)3(CO)(H)2], [Ru(binap)(Cl)2], [Ru(PMe3)4(H)2], [Ru(PEt3)4(H)2], [Ru(Pn-Pr3)4(H)2], [Ru(Pn-Bu3)4( H)2], [Ru(Pn-octyl3)4(H)2], [Ru(Pn-Bu3)4(H)2], [Ru(Pn-octyl3)4(H)2], [Ru(PPh3)3(CO)(H)Cl] and [Ru(PPh3)3(CO)(H)2], preferably [Ru(PEt3)4(H)2], [Ru(Pn-Bu3)4(H)2] and [Ru(Pn-octyl3)4(H)2].

[0131] In one embodiment of the present invention, the process of the present invention is characterized in that the homogeneous transition RuCat is selected from [Ru(PPh3)3(CO)(H)Cl], [Ru(PPh3)3(CO)Cl2], [Ru(PPh3)3(CO)(H)2], [Ru(binap)(Cl)2], [Ru(PMe3)4(H)2], [Ru(PEt3)4(H)2], [Ru(Pn-Pr3)4(H)2], [Ru(Pn -Bu3)4(H)2], [Ru(Pn-octyl3)4(H)2], [Ru(Pn-Bu3)4(H)2], [Ru(Pnoctyl3)4(H)2], [Ru(PPh3)3(CO)(H)Cl] and [Ru(PPh3)3(CO)(H)2], preferably [Ru(PPh3)3(CO)(H)Cl], [Ru(PPh3)3(CO)Cl2] and [Ru(PPh3)3(CO)(H)2.

[0132] If a preformed active catalyst is used, it may also be beneficial to add additional ligand of formula I or II to the reaction mixture.

[0133] In the process of the present invention, the amount of RuCat used based on the cyclic compound C can vary within a wide range. RuCat is usually used in a substoichiometric amount relative to the cyclic compound C. Usually, the amount of RuCat does not exceed 50 mol%, often does not exceed 20 mol%, in particular does not exceed 10 mol% or does not exceed 5 mol%, based on the amount of the cyclic compound C. Preferably, 0.001-50 mol%, often 0.001-20 mol%, in particular 0.005-5 mol% of RuCat is used in the process of the present invention, based on the amount of the cyclic compound C. Preferably, 0.01-5 mol% of RuCat is used. All RuCat amounts shown are calculated as Ru metal and are based on the amount of the cyclic compound C.

[0134] In one embodiment of the present invention, the process according to the invention is characterized in that homogeneous RuCat is used in an amount of 0.001 to 20 mol %, calculated as Ru metal and based on the amount of cyclic compound C used in the process.

[0135] The reaction of the cyclic compound C with acetylene can be carried out in principle according to all methods known to the person skilled in the art which are suitable for the reaction of cyclic compounds C with acetylene.

[0136] The acetylene used for the reduction reaction can be used in pure form or, if desired, in a mixture with other gases, preferably inert gases such as nitrogen or argon. Preference is given to using acetylene in undiluted form.

[0137] Acetylene may be applied discontinuously or continuously, for example by bubbling acetylene gas through the reaction mixture.

[0138] The reaction is usually carried out under a cold-pressed acetylene pressure of 0.1 to 10 bar, preferably 1 to 5 bar, more preferably 1 to 1.5 bar.

[0139] In one embodiment of the present invention, the process according to the invention is characterized in that the reaction between the cyclic compound C and acetylene is carried out at a pressure of 1 to 15 bar.

[0140] The reaction can be carried out mainly continuously, semi-continuously or discontinuously. A continuous process is preferred.

[0141] The vinylation reaction of the present invention is carried out in the liquid phase. This can be achieved by adding one or more solvents, which are preferably selected from aliphatic and aromatic hydrocarbons, linear and cyclic ethers, linear and cyclic amides, sulfoxides, nitriles and halogenated hydrocarbons. Preferred solvents are toluene, DMF and diethylene glycol dimethyl ether. The liquid phase can also be formed by the liquid cyclic compound C without any additional solvent.

[0142] One or more bases, for example nitrogen bases such as trialkylamines or pyridines, preferably N,N-dimethylaminopyridine, can also be added to the liquid phase, preferably in an amount of 0.5 to 20 equivalents, depending on the amount of catalyst RuCat used.

[0143] The reaction can be carried out in all reactors known to the person skilled in the art for such reactions, so they will choose the reactor accordingly. Suitable reactors are described and reviewed in the relevant prior art, for example K. Henkel, "Reactor Types and Their Industrial Applications", Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, Chapter 3.3: "Reactors for gas-liquid reactions".

[0144] The process of the present invention can be carried out in a wide temperature range. Preferably, the reaction is carried out at a temperature of 20-200°C, more preferably 50-180°C, especially 100-170°C. Example

[0145] A) General procedure for Examples 1, 9, 10, 11, 12, 14, 18, 21, 22, 23, 25, 27, 29, 30, 31, 32, 33, 38, 40, 42: In a glove box under argon atmosphere, CodRu(met)2 (0,001-0.06 mmol), cyclic compound C (1 mmol), toluene (5.0-10.0 mL) or dichloromethane (10 mL, entry 9) or dimethylformamide (5 mL, entries 20, 36, 37, 40, 41) and tri-n-butylphosphine (0,005-0,18 mmol) or trioctylphosphine (0.1 mmol, entry 12) or tricyclohexylphosphine (0.1 mmol, entry 13) were added to an autoclave (Premex, Hastelloy) of about 40 mL. After closing the reaction vessel, the system was purged with acetylene (3 times). Finally, the autoclave was pressurized with acetylene (15 minutes at 1.5 bar at room temperature) and heated at 100-140°C. The mixture was then stirred at the specified temperature for 14-18 hours. Note: At this temperature, the internal pressure rose to 3-4 bar. The reaction was then cooled on a water bath and carefully decompressed. The crude mixture was collected in a round-bottom flask and concentrated under vacuum. Subsequently, it was dissolved in 1 mL of CH2Cl2 and coated on silica. The product was isolated by column chromatography (petroleum ether / ethyl acetate 8 / 2—the system ratio was slightly different for different products). When the reaction was carried out in DMF, the product was extracted from the aqueous solution of the reaction mixture with dichloromethane, and the organic layer was washed with water at least 5 times (entries 40, 41) or collected in a round-bottom flask and concentrated under vacuum, followed by column chromatography (petroleum ether / ethyl acetate, entries 20, 36, 37).

[0146] B) General procedure for Examples 13, 15, 16, 17, 19, 20, 26, 28, 34, 35, 36, 37, 39, 41: In a glove box under argon atmosphere, CodRu(met)2 (0.02 0.06 mmol), cyclic compound C (1 mmol), toluene (5.0 mL, entries 15, 17, 18, 19, 21, 22, 33, 35, 43, 47, 49) or dimethylformamide (5-8 mL, entries 42, 44, 45), DMAP (0.04-0.12 mmol) and tri-n-butylphosphine (0.06-0.18 mmol) were added to an autoclave (Premex, Hastelloy) of about 40 mL. After closing the reaction vessel, the system was purged with acetylene (3 times). Finally, the autoclave is pressurized with acetylene (15 minutes at room temperature at 1.5 bar) and heated at 100-150°C. Then, the mixture is stirred at a specified temperature for 14-18 hours. Note: at this temperature, the internal pressure rises to 4-6 bar. Then, the reaction is cooled on a water bath and carefully decompressed. The crude mixture is collected in a round-bottomed flask and concentrated under vacuum. Subsequently, it is dissolved in 1mL CH2Cl2 and coated on silica. The product is isolated by column chromatography (petroleum ether / ethyl acetate 8 / 2-for different products, the system ratio is slightly different).

[0147] C) General procedure for comparative examples 2 and 3: In a glove box under argon atmosphere, 5% ruthenium on activated carbon (100 mg), 2-pyrrolidone (13, 1 mmol, 1.116 g) and diglyme (entry 13) or toluene (entry 14) (8.0 mL) were added to an autoclave of about 40 mL (Premex, Hastelloy). After closing the reaction vessel, the system was purged with acetylene (3 times). Finally, the autoclave was pressurized with acetylene (15 minutes at 1.5 bar at room temperature) and heated at 170°C. The mixture was then stirred at the specified temperature for 14 hours. Note: At this temperature, the internal pressure rose to 5 bar (diglyme) / 7 bar (toluene). The reaction was then cooled on a water bath and carefully decompressed. The crude mixture was collected in a round-bottom flask and concentrated under vacuum. The crude mixture was analyzed by GC and / or NMR. The product was not isolated. Comparative Examples 2 and 3 show that the use of heterogeneous Ru catalysts produces only small amounts of the desired product.

[0148] D) General procedure for comparative example 4: In a glove box under an argon atmosphere, 5% ruthenium (10 mg), 2-pyrrolidone (1 mmol, 0,085 g) and toluene (10.0 mL) were added to an autoclave (Premex, Hastelloy) of about 40 mL. After closing the reaction vessel, the system was purged with acetylene (3 times). Finally, the autoclave was pressurized with acetylene (1.5 bar for 15 minutes at room temperature) and heated at 170°C. The mixture was then stirred at the specified temperature for 14 hours. Note: At this temperature, the internal pressure rose to 7 bar. The reaction was then cooled in a water bath and carefully decompressed. The crude mixture was collected in a round-bottom flask and concentrated under vacuum. The crude mixture was analyzed by GC and / or NMR. The product was not separated. Comparative example 4 shows that the use of a heterogeneous Ru catalyst produces only a small amount of the desired product.

[0149] E) General procedure for comparative examples 5, 6, 7 and 8: In a glove box under argon atmosphere, 2 mol % of ruthenium catalyst (RuCl3·3H2O—entry 5; Ru(AcAc)3—entry 6; Ru3(CO) 12 —entry 7; codRumet2—entry 8), 2-pyrrolidone (1 mmol, 0,085 g) and toluene (5.0 mL). After closing the reaction vessel, the system is purged with acetylene (3 times). Finally, the autoclave is pressurized with acetylene (1.5 bar for 15 minutes at room temperature) and heated at 100°C. The mixture is then stirred at the specified temperature for 16-19 hours. Note: At this temperature, the internal pressure rises to 3-4 bar. The reaction is then cooled in a water bath and carefully decompressed. The crude mixture is collected in a round-bottom flask and concentrated under vacuum. The crude mixture is analyzed by GC. The product is not isolated. Comparative Examples 5, 6, 7 and 8 show that only traces of the desired product are formed under the same conditions using only ruthenium complexes without phosphine ligands.

[0150] F) General procedure for comparative example 43: In a glove box under an argon atmosphere, 20 mol% tri-n-butylphosphine (0.2 mmol, 0,042 g), 2-pyrrolidone (1 mmol, 0,085 g) and toluene (10.0 mL) were added to an autoclave (Premex) of about 40 mL. After closing the reaction vessel, the system was purged with acetylene (3 times). Finally, the autoclave was pressurized with acetylene (15 minutes at 1.5 bar at room temperature) and heated at 100° C. The mixture was then stirred at the specified temperature for 16 hours. Note: At this temperature, the internal pressure rose to 3-4 bar. The reaction was then cooled in a water bath and carefully decompressed. The crude mixture was collected in a round-bottom flask and concentrated under vacuum. The crude mixture was analyzed by GC. No product was formed. Comparative example 43 shows that under these conditions, the use of only phosphine ligands without ruthenium complexes does not give a product.

[0151] G) General procedure for Example 24: In a glove box under argon atmosphere, anhydrous ruthenium(III) chloride (0.03 mmol, entry 26) or ruthenium(III) chloride hydrate (0.03-0.09 mmol, entries 27, 29, 30, 31), 5-methyl-1,3-oxazolidin-2-one (1 mmol, 0,101 g), toluene (5.0 mL) and tri-n-butylphosphine (0,06-0.12 mmol, entries 26, 27, 29, 30) or triphenylphosphine (0.1 mmol, entry 31) were added to an autoclave of about 40 mL (Premex, Hastelloy). After closing the reaction vessel, the system was purged with acetylene (3 times). Finally, the autoclave was pressurized with acetylene (15 minutes at 1.5 bar at room temperature) and heated at 100°C. The mixture was then stirred at the indicated temperature for 14-16 hours. Note: At this temperature, the internal pressure rises to 3-4 bar. The reaction is then cooled on a water bath and carefully decompressed. The crude mixture is collected in a round bottom flask and concentrated under vacuum. The crude mixture is analyzed by GC and / or NMR. The product is not isolated.

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Claims

1. A process for preparing N-vinyl compounds by homogeneous catalysis, wherein acetylene is reacted with a cyclic compound C which comprises a nitrogen having a replaceable hydrogen group as a ring member in the liquid phase in the presence of a ruthenium complex which comprises at least one phosphine as a ligand, wherein the cyclic compound C is a cyclic amide, a cyclic urea or thiourea or a cyclic carbamate or thiocarbamate, and The phosphine is triphenylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine or tricyclohexylphosphine.

2. The method according to claim 1, wherein the cyclic compound C is a cyclic amide.

3. The method according to claim 1, wherein the phosphine is triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine or tricyclohexylphosphine.

4. The method according to claim 1, wherein the ruthenium complex is prepared separately or in situ during the reaction of the cyclic compound with acetylene.

5. The method according to claim 2, wherein the ruthenium complex is prepared separately or in situ during the reaction of the cyclic compound with acetylene.

6. The method according to claim 3, wherein the ruthenium complex is prepared separately or in situ during the reaction of the cyclic compound with acetylene.

7. A method according to any one of claims 4 to 6, wherein 1 to 10 mol of phosphine / mol of ruthenium is used to prepare the ruthenium complex.

8. The method according to any one of claims 1 to 6, wherein the ruthenium complex is used in an amount of 0.01 to 5 mol %, based on the amount of the cyclic compound.

9. The method according to claim 7, wherein the ruthenium complex is used in an amount of 0.01 to 5 mol% based on the amount of the cyclic compound.

10. The method according to any one of claims 1 to 6, wherein the reaction of the cyclic compound C and acetylene is carried out in the presence of an N-base.

11. The method according to claim 9, wherein the reaction of the cyclic compound C and acetylene is carried out in the presence of an N-base.

12. The method of any one of claims 1-6, wherein the liquid phase comprises a solvent.

13. The method of claim 11, wherein the liquid phase comprises a solvent.

14. The process according to any one of claims 1 to 6, wherein acetylene is fed into the reaction at a pressure of 1 to 2 bar at 20°C.

15. The process according to claim 13, wherein acetylene is fed into the reaction at a pressure of 1-2 bar at 20°C.

16. The method according to any one of claims 1 to 6, wherein the reaction is carried out at a temperature of 50-200°C.

17. The method according to claim 15, wherein the reaction is carried out at a temperature of 50-200°C.

18. The process according to any one of claims 1 to 6, wherein the pressure during the reaction is at most 10 bar.

19. The process according to claim 17, wherein the pressure during the reaction is at most 10 bar.

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