Novel vinylphosphines and photoinitiators obtainable therefrom

Abstract

The present invention relates to an efficient process for preparing alkyl and vinyl phosphines, which are used as starting materials for new bisacylphosphine oxides, bisacylphosphinic acids, salts thereof and derivatives thereof, each having a vinyl functional group bonded to a phosphorus atom, and to a general process for preparing vinyl phosphines.

Description

Technical Field

[0001] The present invention relates to an efficient process for preparing alkyl and vinyl phosphines, which are used as starting materials for new bisacylphosphine oxides, bisacylphosphinic acids, salts thereof and derivatives thereof, each having a vinyl functional group bonded to a phosphorus atom, and to a general process for preparing vinyl phosphines. Background Art

[0002] Photoinitiators carrying other functional substituents, such as monoacylphosphine oxides and bisacylphosphine oxides, have attracted a great deal of commercial attention, since photoinitiators that are tunable with respect to the wavelength at which photoinduced cleavage occurs or that can be linked to other additives, such as sensitizers, stabilizers or surfactants, in order to avoid migration, for example, in food packaging, are highly desirable.

[0003] Furthermore, water solubility has become a property of increasing interest for photoinitiators to address the urgent need for environmentally friendly production of coatings, adhesives, inks and paint materials such as water-based UV-inkjet inks as well as to expand their applicability to new areas of interest such as the fabrication of hydrogels for tissue engineering.

[0004] However, the synthesis of monoacylphosphines and bisacylphosphines and their salts and derivatives as common intermediates for the corresponding oxides or phosphinic acids usually requires the use of highly reactive phosphines, such as phosphine (PH3), primary phosphines RPH2 or secondary phosphines R2PH, but their structural diversity to accomplish the above tasks is usually low.

[0005] Processes for preparing mono- and bisacylphosphine oxides and their precursors are known, for example, from WO 2006 / 056541 A, WO 2010 / 121387 A and WO 2011 / 003772 A.

[0006] EP 1 135 399 A discloses a process for preparing monoacylphosphines and bisacylphosphines and their respective oxides and sulfides. The process comprises the following steps: where appropriate, in the presence of a catalyst, reacting a substituted monohalophosphine (R2PCl) or dihalophosphine (RPCl2) with an alkali metal or a combination of magnesium and lithium, further reacting the obtained metallated phosphine with a carboxylic acid halide, and finally oxidizing the obtained monoacylphosphine or bisacylphosphine using a sulfur or oxygen transfer oxidant.

[0007] It is also known from WO 05 / 014605 A to prepare substituted acyl phosphines by a process comprising the following steps: first, reacting a monohalogenated phosphine (R2PCl) or a dihalogenated phosphine (RPCl2) with an alkali metal in a solvent in the presence of a proton source, and then reacting the phosphine thus obtained with a carboxylic acid halide.

[0008] WO2006 / 074983A discloses a method for preparing bisacylphosphines, which comprises firstly catalytically reducing a monohalogenated phosphine (R2PCl) or a dihalogenated phosphine (RPCl2) with hydrogen in an aprotic solvent in the presence of a tertiary aliphatic amine or an aromatic amine at a temperature of 20 to 200° C. under pressure to obtain the corresponding halogen-free phosphine, and then reacting the phosphine with a carboxylic acid halide to obtain a monoacylphosphine or a bisacylphosphine.

[0009] Typically, the desired primary phosphine RPH2 or secondary phosphine R2PH is prepared by reacting the corresponding phosphane halide or diphosphane halide or their respective oxides with lithium aluminum hydride. Alkylphosphines or dialkylphosphines are thereby obtained in very moderate yields.

[0010] Primary or secondary vinyl phosphines can be obtained by reaction of vinyl magnesium halides and halogenated phosphines as disclosed in US 3,048,638 or Fedorov, SV; Krivdin, LB; Rusakov, YY; Chernysheva, NA; Mikhailenko, VL, Magnetic Resonance in Chemistry, 2010, S48 or by reduction of vinyl phosphonates via AlHCl2 (see Cabioch, JL; Denis, JM, J. Orgmet. Chem., 1989, 227).

[0011] Primary and secondary phosphines can also be prepared by reacting phosphine (PH3) with olefins in the presence of an acid or an acidic catalyst, as disclosed in, for example, Hoff, MC; Hill, P., Journal of Organic Chemistry, 1959, 356, US 4,922,025, EP 057 924A, US 5,536,880, US 5,892,120 or by free radical addition of olefins to phosphine (PH3), as disclosed, for example, in Stiles, AR; Rust, FF; Vaughan, WE, JACS, 1952, 3282, US 4163760 or by thermal addition of functionalized olefins to phosphine (PH3) (see WO 2004 / 094440).

[0012] However, the common characteristics of all the methods listed above are the harsh reaction conditions, low yields and poor selectivity, which make these methods very unattractive commercially.

[0013] It will be apparent to a person skilled in the art that the above synthetic routes allow only limited variations, particularly for organic non-carbonyl residues directly bound to phosphorus, when commercial availability is taken into account.

[0014] Recently, attempts to overcome this limitation have been successful: WO 2014 / 053455 A1 discloses new monoacylphosphine oxides and bisacylphosphine oxides containing other functional groups, in particular those that allow crosslinking via acrylic acid side functional groups. These functional groups are introduced by adding electron-deficient olefins to monoacylphosphine and bisacylphosphine or their corresponding salts.

[0015] However, there is still a need for highly photoactive photoinitiators having substituents which allow crosslinking and / or modification of known substitution patterns and for general methods for their preparation. Summary of the invention

[0016] Therefore, the present invention encompasses compounds of formula (I):

[0017]

[0018] in

[0019] n is an integer, preferably an integer of 1 to 6, more preferably 1, 2, 3 or 4, more preferably 1 or 2, and most preferably 1.

[0020] m is 1 or 2

[0021] If n is 1, then R 1 is hydrogen, alkyl, alkenyl, alkynyl or aryl

[0022] If n>1, then R 1 is an alkane-n-yl, an alkene-n-yl, an alkyne-n-yl or an aryl-n-yl

[0023] R 2 is hydrogen, alkyl, alkenyl, alkynyl or aryl

[0024] R 3 is alkyl, alkenyl, alkynyl, unsubstituted or substituted with up to three identical or different substituents. 14 Aryl, substituents selected from the group consisting of fluorine, C1-C8 alkyl, C1-C8 haloalkyl and phenyl, or -(O - )(Cat + ), where -(O - )(Cat + ) as a whole represents hydroxyl or Cat + Represents 1 / p equivalent of p-valent cation

[0025] R 4is an alkyl, alkenyl, alkynyl, aryl or heterocyclic group,

[0026] in

[0027] For R 1 , the above alkyl, alkenyl, alkynyl, alkane-n-yl, alkene-n-yl, alkyne-n-yl substituents, and for R 2 and R 3 , the above alkyl, alkenyl and alkynyl substituents

[0028] Not interrupted by a divalent residue selected from the group consisting of unsubstituted aryl diyl groups, interrupted once, twice or more than twice by a divalent residue selected from the group consisting of unsubstituted aryl diyl groups

[0029] and additionally or alternatively,

[0030] unsubstituted by a substituent selected from the group consisting of unsubstituted aryl and halogen, preferably a substituent selected from the group consisting of unsubstituted aryldiyl, substituted once, twice or more than twice by said substituent

[0031] And among them

[0032] For R 4 , the above alkyl, alkenyl and alkynyl substituents

[0033] Not interrupted by, interrupted once, twice or more than twice by non-contiguous functional groups selected from the group consisting of:

[0034] -O-, -NR 5 -, -CO-, -OCO-, -O(CO)O-, NR 5 (CO)-、-NR 5 (CO)O-、O(CO)NR 5 -、-NR 5 (CO)NR 5 -,

[0035] and additionally or alternatively

[0036] is not interrupted by a divalent residue selected from the group consisting of a heterocyclic diyl group and an aryl diyl group, is interrupted once, twice or more than twice by said divalent residue,

[0037] and additionally or alternatively

[0038] unsubstituted, substituted once, twice or more than twice by a substituent selected from the group consisting of:

[0039] Hydroxyl, protected hydroxyl, protected formyl, halogen, cyano, C6-C 14 Aryl; heterocyclic group, C1-C8 alkoxy, C6- C 14 Aryloxy, C 6- C 14 Arylthio, C1-C8 alkylthio, -COOM, -SO3M, -PO3M2, -PO(N(R 5 )2)2、-N(R 5 )2.-PO(OR 6 )2、SO2N(R 5 )2.-NR 5 S02R 6 、-N(R 5 )2-、-N + (R 5 )3An - 、-CON(R 5 2. -COR 5 、-(CO)OR 5 、-O(CO)OR 6 NR 5 (CO)R 5 、-NR 5 (CO)OR 5 、O(CO)N(R 5 )2.-NR 5 (CO)N(R 5 )2、-Si(OR 6 ) y (R 6 ) 3-y 、-OSi(OR 6 ) y (R 6 ) 3-y , where y = 1, 2 or 3

[0040] When used, in all formulas

[0041] R 5 independently selected from the group consisting of: hydrogen, C1-C8 alkyl, C6-C 14 aryl, and heterocyclic or N(R 5 )2 as a whole is a N-containing heterocyclic ring,

[0042] R 6 Independently selected from the group consisting of: C1-C8 alkyl, C 6- C 14 aryl, and heterocyclic or N(R 6 )2 as a whole is a heterocyclic ring containing N

[0043] M is hydrogen, or 1 / q equivalent of a q-valent metal ion, or an ammonium ion, a guanidine ion, a guanidine ion substituted with one or more N, or a primary, secondary, tertiary or quaternary organic ammonium ion. Specifically, the formula [N(C1-C 18 alkyl) s H t ] + Those of wherein s is 1, 2, 3 or 4, and t is (4-s), or heterocyclylium, and

[0044] An - It is 1 / r equivalent of r-valent anion. DETAILED DESCRIPTION

[0045] The scope of the present invention encompasses the substituent definitions, parameters and illustrations stated above and below in all combinations with one another in a general sense or within areas of preference or preferred embodiments, ie also any combination between specific areas and areas of preference.

[0046] Whenever used herein, the terms "including", "for example", "such as" and "like" mean "including but not limited to" or "such as but not limited to", respectively.

[0047] As used herein and unless otherwise specifically indicated, aryl refers to a carbocyclic aromatic substituent, wherein the carbocyclic aromatic substituent is unsubstituted or substituted with up to 5 identical or different substituents per ring. For example and preferably, the substituent is selected from the group consisting of fluorine, bromine, chlorine, iodine, nitro, cyano, formyl or protected formyl, hydroxy or protected hydroxy, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxy, C1-C8 haloalkoxy, C1-C8 alkyl ... 6- C 14 Aryl, specifically phenyl and naphthyl, di(C1-C8 alkyl)amino, (C1-C8 alkyl)amino, CO(C1-C8 alkyl), OCO(C1-C8 alkyl), NHCO(C1-C8 alkyl), N(C1-C8 alkyl)CO(C1-C8 alkyl), CO(C1-C8 alkyl), 6- C 14 Aryl), OCO(C6-C 14 Aryl), NHCO(C6-C 14 Aryl), N(C1-C8 alkyl)CO(C6-C 14 Aryl), COO-(C1-C8 alkyl), COO-(C6-C 14 aryl), CON(C1-C8 alkyl)2 or CONH(C1-C8 alkyl), CO2M, CONH2, SO2NH2, SO2N(C1-C8 alkyl)2, SO3M and PO3M2.

[0048] In a preferred embodiment, the carbocyclic aromatic substituents are unsubstituted or substituted with up to 3 identical or different substituents per ring selected from the group consisting of fluorine, chlorine, cyano, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxy, C1-C8 haloalkoxy, C6-C8 alkyl ... 14 Aryl, specifically phenyl.

[0049] In a more preferred embodiment, the carbocyclic aromatic substituent is unsubstituted or substituted with up to 3 identical or different substituents per ring selected from the group consisting of fluorine, C1-C8 alkyl, C1-C8 fluoroalkyl and phenyl, which in an even more preferred embodiment are not located in the ortho position.

[0050] The definitions provided above, including their preferred aspects, also apply analogously to aryloxy, arylthio, aryldiyl and aryl-n-yl substituents. Preferred aryl substituents are C6-C 14 The aryl substituent is more preferably phenyl, naphthyl, phenanthrenyl and anthracenyl.

[0051] Preferred aryl diradical substituents are C6-C 14 The aryl diyl substituent is more preferably 1,2-phenylene, 1,3-phenylene or 1,4-phenylene. 14 The number of carbon atoms in the respective carbocyclic aromatic ring systems is 6 to 14. The possible and preferred substitution types described above are likewise applicable.

[0052] As used herein and unless specifically indicated otherwise, heterocyclyl refers to heterocyclic aliphatic, aromatic or mixed aliphatic and aromatic substituents wherein there are no backbone atoms, 1, 2 or 3 backbone atoms in each ring, but at least one backbone atom in the entire ring system is a heteroatom selected from the group consisting of phosphorus, nitrogen, sulfur and oxygen, preferably nitrogen, sulfur and oxygen, wherein these heterocyclic aliphatic, aromatic or mixed aliphatic and aromatic substituents are unsubstituted or substituted with the same or different substituents per ring up to possible limitations, wherein the substituents are selected from the same groups as provided above for carbocyclic aromatic substituents (including preferred areas).

[0053] Preferred heterocyclyl substituents and heteroaryl substituents are pyridyl, oxazolyl, thiophenyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, furanyl, indolyl, pyridazinyl, pyrazinyl, imidazolyl, pyrimidinyl and quinolinyl, respectively, which are unsubstituted or substituted with 1, 2 or 3 substituents selected from the group consisting of hydroxyl, protected hydroxyl, chloro, fluoro, C1-C8 alkyl, C1-C8 fluoroalkyl, C1-C8 alkoxy, C1-C8 fluoroalkoxy and phenyl. It is known to those skilled in the art (for example) that heteroaryl substituents having a hydroxyl group adjacent to, for example, nitrogen are often described or represented as keto compounds (e.g., for 2-hydroxypyridine, pyridone). These tautomeric forms should also be covered by the above definition.

[0054] The definitions provided above (including their areas of preference) also apply analogously to the heterocyclyl onium and heteroaryl onium cations and divalent heterocyclyldiyl and heteroaryldiyl substituents.

[0055] Preferred heterocyclyl onium cations are N-(C1-C8 alkyl)imidazolium or pyridinium cations.

[0056] As used herein and unless otherwise specifically indicated, a protected formyl group is a formyl substituent that is protected by conversion to an aminal, acetal, or mixed aminal acetal, wherein the aminal, acetal, and mixed aminal acetal are acyclic or cyclic.

[0057] For example and preferably, the protected formyl group is 1,1-(2,4-dioxolanediyl).

[0058] As used herein and unless otherwise specifically indicated, a protected hydroxyl is a hydroxyl group that is protected by conversion to a ketal, acetal, or mixed aminal acetal, wherein the aminal, acetal, or mixed aminal acetal is acyclic or cyclic. A specific example of a protected hydroxyl is tetrahydropyranyl (O-THP).

[0059] As used herein and unless specifically indicated otherwise, alkyl, alkanediyl, alkenyl, alkenediyl, alkynyl, alkane-n-yl, alkene-n-yl, alkyne-n-yl, alkoxy and alkylthio groups are linear, partially or entirely cyclic, branched or unbranched, and, if not specifically mentioned otherwise, are not interrupted or substituted by any functional group.

[0060] Terminology C1-C 18 Alkyl means except C1-C 18In addition to the carbon atoms of the optional substituents of the alkyl substituent, the linear, partially or completely cyclic, branched or unbranched substituents contain 1 to 18 carbon atoms. The same applies analogously to alkanediyl, alkenyl, alkenediyl, alkynyl, alkane-n-yl, alkene-n-yl, alkyne-n-yl, alkoxy and alkylthio groups having the indicated number of carbon atoms and other substituents having the indicated number of carbon atoms.

[0061] For the avoidance of doubt, the term alkenyl refers to a substituent containing at least one carbon-carbon double bond, and also containing more than one double bond, regardless of its position in the linear, partially or fully cyclic, branched or unbranched substituent. The same applies to alkene-n-yl.

[0062] For the avoidance of doubt, the term alkynyl refers to a substituent containing at least one carbon-carbon triple bond, and more than one double bond, regardless of its position in the linear, partially or fully cyclic, branched or unbranched substituent. The same applies to alkyne-n-yl.

[0063] Specific examples of C1-C4 alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl. Other examples of C1-C8 alkyl groups are n-pentyl, isopentyl, cyclohexyl, n-hexyl, n-heptyl, n-octyl, and isooctyl. 18 Other examples of alkyl groups are norbornyl, adamantyl, n-decyl, n-dodecyl, n-hexadecyl, n-octadecyl.

[0064] Specific examples of C1-C8 alkanediyl substituents are methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene, 1,2-propylene, 1,3-propylene, 1,1-butylene, 1,2-butylene, 2,3-butylene and 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,1-cyclohexylene, 1,4-cyclohexylene, 1,2-cyclohexylene and 1,8-octylene.

[0065] Specific examples of C1-C4 alkoxy substituents are methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy and tert-butoxy. Another example of C1-C8 alkoxy is cyclohexyloxy.

[0066] C2-C 18 Specific examples of alkenyl and C2-C8 alkenyl substituents include vinyl, allyl, 3-propenyl and buten-2-yl.

[0067] C2-C 18 Specific examples of the alkynyl and C2-C8 alkynyl substituents include ethynyl.

[0068] As used above, C1-C8 haloalkyl and C1-C8 haloalkoxy are C1-C8 alkyl and C1-C8 alkoxy substituents which are substituted once, more than once or completely by halogen atoms. Substituents which are partially or completely substituted by fluorine are referred to as C1-C8 fluoroalkyl and C1-C8 fluoroalkoxy, respectively.

[0069] Specific examples of the C1-C8 haloalkyl substituent are fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, chloromethyl, fluoromethyl, bromomethyl, 2-bromoethyl, 2-chloroethyl, nonafluorobutyl and n-perfluorooctyl.

[0070] Preferred compounds of formula (I) are those wherein

[0071] n is 1

[0072] m is 1 or 2

[0073] R 1 is hydrogen, alkyl or aryl

[0074] R 2 is hydrogen, alkyl or aryl

[0075] R 3 is alkenyl, unsubstituted or phenyl substituted 1, 2 or 3 times by substituents selected from the group consisting of C1-C4 alkyl or C1-C4 haloalkyl, or -(O - )(Cat + ), where -(O - )(Cat + ) as a whole means -OH or Cat + Represents 1 / p equivalent of p-valent cation

[0076] R 4 Those for aromatic groups

[0077] in

[0078] For R 1 and R 2 , the above alkyl substituent, or

[0079] For R 3 , the above alkenyl substituents

[0080] unsubstituted by a substituent selected from the group consisting of unsubstituted aryl, substituted once, twice or more than twice by said substituent.

[0081] More preferred compounds of formula (I) are those wherein

[0082] n is 1

[0083] m is 2

[0084] R 1 is hydrogen, C1-C6 alkyl or phenyl

[0085] R 2 is hydrogen, C1-C6-alkyl or phenyl

[0086] R 3 is alkenyl, or -(O - )(Cat + ), where -(O - )(Cat + ) as a whole means -OH or Cat + Represents 1 / p equivalent of p-valent cation

[0087] R 4 C 6- C 14 Those with aromatic

[0088] in

[0089] For R 1 and R 2 , the above alkyl substituent, or

[0090] For R 3 , the above alkenyl substituents

[0091] Not substituted by a substituent selected from the group consisting of unsubstituted aryl, substituted once, twice or more than twice by said substituent

[0092] Preferred compounds of formula (I) include those of formula (II):

[0093]

[0094] in

[0095] m is 1 or 2, and

[0096] v is (3-m)

[0097] And R 1 , R 2 and R 4 It has the meaning including the preferred embodiments as described above.

[0098] For the avoidance of doubt, and in order to explain how to obtain Formula (II) from Formula (I), it should be noted that in Formula (I), n needs to be 1, and if m is 1, then R 3 The following alkenyl substituents are required: 1 C=CHR 2 ].

[0099] Preferred compounds of formula (I) also include those of formula (III):

[0100]

[0101] in

[0102] -(O - )(Cat + ) as a whole means -OH or Cat + Represents 1 / p equivalent of p-valent cation

[0103] And R 1 , R 2 and R 4 It has the meaning including the preferred embodiments as described above.

[0104] In another preferred embodiment, -(O - )(Cat + ) as a whole means -OH, or Cat + represents lithium, sodium, potassium, ammonium, guanidine, the formula [N(C1-C4-alkyl) s H t ] + A quaternary ammonium wherein s is 1, 2, 3 or 4 and t is (4-s), a guanidinium or heterocyclylium wherein N is substituted 1, 2, 3 or 4 times by s (C1-C4-alkyl).

[0105] In a more preferred embodiment, -(O - )(Cat + ) as a whole means -OH or Cat + Selected from the group consisting of: hydrogen, lithium, sodium, potassium, a compound of the formula [N(C1-C4 alkyl)4] + Quaternary ammonium and tetra-N-methylguanidine or di-N(C1-C8 alkyl)imidazolium.

[0106] Substituent -[R 1 C=CHR 2 Examples of ] include ethenyl (vinyl), 1-phenyl-vinyl-1-yl, 1,2-diphenylvinyl-1-yl and 3-hexen-3-yl, among which 1-phenyl-vinyl-1-yl, 1,2-diphenylvinyl-1-yl and 3-hexen-3-yl are preferably in Z-configuration.

[0107] Substituent R 4Examples include phenyl, p-tert-butylphenyl, 3-benzonitrile, 4-benzonitrile, 4-methylphenyl, 3-methylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl (4,2,6-trimethylphenyl), 4-methoxyphenyl, 3-methoxyphenyl, 2,6-dimethoxyphenyl, 2,4-dimethoxyphenyl, p-chlorophenyl, 3,4-dichlorophenyl, 4-bromophenyl, 3-bromophenyl, 4-iodophenyl, 3-iodophenyl, 3,4-dibromophenyl, 4-nitrophenyl, 3-nitrophenyl, p-trifluoromethyl, p-ethoxycarbonylphenyl, p-methoxycarbonylphenyl and p-isopropylphenyl, among which phenyl is more preferred.

[0108] Specific compounds of formula (I) include:

[0109] Bis(2,4,6-trimethylbenzoyl)-vinyl-phosphine oxide (also known as vinyl-bis(s-trimethylbenzoyl)phosphine oxide), bis(2,4,6-trimethylbenzoyl)-(1-phenylvinyl-1-yl)-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-(3-hexen-3-yl)-phosphine oxide, (2,4,6-trimethylbenzoyl)-vinyl-phosphinic acid, (2,4,6-trimethylbenzoyl)-vinyl-phosphinic acid sodium salt, (2,4,6-trimethylbenzoyl)-vinyl-phosphinic acid tetra-(n-butyl)ammonium salt, (2,4,6-trimethylbenzoyl)-vinyl-phosphinic acid 1,1,3, 3-Tetra-N-methyl-guanidine salt, bis-(benzoyl)-vinyl-phosphine oxide, bis(benzoyl)-(1-phenylvinyl-1-yl)-phosphine oxide, bis(benzoyl)-(3-hexen-3-yl)-phosphine oxide, (benzoyl)-vinyl-phosphinic acid, (benzoyl)-vinyl-phosphinic acid sodium salt, (benzoyl)-vinyl-phosphinic acid tetra-(n-butyl)ammonium salt, (benzoyl)-vinyl-phosphinic acid 1,1,3,3-tetra-N-methyl-guanidine salt, 1-phenylvinyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide and 1-methylvinyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0110] The compounds of formula (I) can be prepared by the following process which is also covered by the present invention:

[0111] Preparation method A:

[0112] For example, the compound of formula (I) can be prepared by a process comprising the following steps:

[0113] a) reacting a compound of formula (IV) with m equivalents of a compound of formula (V),

[0114]

[0115] in

[0116] w is 1 or 2, and

[0117] n、R 1 and R 2 has the same meaning as defined above for formula (I), including preferred embodiments, and

[0118] R 7 Having R as defined above for formula (I) 3 The same meaning, including preferred embodiments, but excluding -(O - )(Cat + )

[0119] where if w is 1, then m is 1, and if w is 2, then m is either 1 or 2

[0120]

[0121] in

[0122] R 4 has the same meaning as defined above for formula (I), including preferred embodiments, and

[0123] LG represents a leaving group, preferably chlorine, bromine or iodine, C1-C8 alkylsulfonyloxy or C1-C8 alkoxy, more preferably chlorine

[0124] And wherein the reaction with the compound of formula (V) in step a) is preferably carried out under the following conditions:

[0125] in the presence of at least one Lewis acid as defined below and including the preferred embodiments, or

[0126] In the presence of at least one base

[0127] To obtain a compound of formula (VI)

[0128]

[0129] b) oxidizing the compound of formula (IV) to the compound of formula (I).

[0130] For step a), suitable bases include all bases which have a higher basicity than the phosphine used and which preferably include ammonia, primary, secondary or tertiary amines such as triethylamine, triethanolamine and DBN, N-heteroaromatic compounds such as unsubstituted or substituted pyridine or quinoline, alcoholates such as lithium, sodium and potassium methoxides, ethoxides and tert-butoxides, amides such as lithium diisopropylamide, hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide and carbonates such as lithium carbonate, sodium carbonate and potassium carbonate.

[0131] The amount of the base may be in the range of 0.1 to 100 mol equivalents relative to the compound of formula (V), preferably in the range of 0.5 to 5 mol equivalents, more preferably in the range of 0.9 to 1.2 mol equivalents, and even more preferably in the range of 1.00 to 1.05 mol equivalents relative to the compound of formula (V) used.

[0132] Salts formed from the base during the reaction may be removed, for example, by settling and decanting, filtration or centrifugation, preferably filtration is desired or required at all.

[0133] Typical and preferred reaction pressure ranges for carrying out the process are from 50 hPa to 10 MPa, preferably from 900 hPa to 0.5 MPa, such as for example at ambient pressure.

[0134] The oxidation in step b) may be carried out in any manner known to those skilled in the art and includes oxidation with molecular oxygen, hydrogen peroxide, sodium hypochlorite, sodium or potassium percarbonate, monoperoxodisulfate or monoperoxodisulfate, peracids such as peracetic acid and 3-chloroperbenzoic acid, hydroperoxides such as tert-butyl hydroperoxide, permanganates such as potassium permanganate, chromates or dichromates such as potassium dichromate and aqueous solutions of all of the above.

[0135] Where R 3 Indicates -(O - )(Cat + ) and -(O - )(Cat + ) does not represent -OH, preferably in the presence of a cation Cat + The oxidation in step b) is carried out under the condition of

[0136] Steps a) and b) can be carried out as a one-pot synthesis or in separate steps and continuously or batchwise.

[0137] Preferably, steps a) and b) are carried out in a solvent. Suitable solvents include

[0138] Aromatic and halogenated aromatics such as benzene, toluene, o-, m- and p-xylene, mesitylene, chlorobenzene and dichlorobenzene,

[0139] Aliphatic hydrocarbons such as pentane, hexane, cyclohexane, methylcyclohexane, and

[0140] Halogenated aliphatic hydrocarbons or alkenes such as methyl chloride, dichloromethane, chloroform, trichloroethane and tetrachloromethane

[0141] or a mixture of the above solvents.

[0142] Wherein in step a), at least one base is used or, generally for step b), it is additionally possible to use

[0143] Ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethoxyethane and higher glycol ethers (glycolether);

[0144] Amides, such as dimethylformamide,

[0145] Sulfones, such as tetraethylene sulfone,

[0146] Esters, such as ethyl acetate

[0147] Or a mixture of the above solvents or a mixture with the above solvents.

[0148] In step b), water can also be used, where R 3 Indicates -(O - )(Cat + ), -(O - )(Cat + ) as a whole means -OH, or Cat + It represents 1 / p equivalent of p-valent cation.

[0149] The reaction time of each step is generally in the range of 1 min to 72 hours, preferably 5 min to 24 hours.

[0150] The amount of solvent is not critical at all and is limited only by commercial aspects, since they have to be removed if the compound of formula (I) or the intermediate of formula (VI) is ultimately to be isolated.

[0151] In order to facilitate the reaction, mixing energy is introduced into the reaction mixture, for example, by means of standard stirrers, agitators and / or static mixing elements.

[0152] Typical and preferred reaction temperatures for carrying out the process are in the range of -30°C to 120°C, preferably -10 to 80°C.

[0153] It is obvious to a person skilled in the art that when the desired reaction temperature is above the boiling point of the solvent used at 1013 hPa, the reaction is carried out under sufficient pressure. Preparation method A) is particularly suitable for preparing compounds of formula (II) and (III) as defined above by reacting a compound of formula (VII) with m equivalents of a compound of formula (V) to obtain a compound of formula (VIII):

[0154]

[0155] in

[0156] z is 1 or 2, and

[0157] R 1 and R2 has the same meaning as defined above for formula (I), including preferred embodiments, and

[0158]

[0159] in

[0160] R 4 and LG have the same meanings as defined above, and

[0161] where if z is 1, then m is 1 or 2, and if z is 2, then m is 1

[0162]

[0163] in

[0164] z is 1 or 2, and

[0165] If z is 1, then m is 1 or 2, or

[0166] If z is 2, then m is 1

[0167] R 1 , R 2 and R 3 has the same meaning as defined above for formula (I), including preferred embodiments, and

[0168] and

[0169] b) oxidizing the compound of formula (VIII) to

[0170] A compound of formula (III) (if z is 1), wherein R 3 Indicates -(O - )(Cat + ) and -(O - )(Cat + ) does not represent -OH, preferably, in the presence of a cation Cat + Oxidation is carried out under the condition of

[0171] A compound of formula (II) (if z is 2).

[0172] The compounds of formula (VI) and (VIII) are novel and the invention also covers the intermediates for preparing the compounds of formula (I) and those of formula (II) and (III).

[0173] Specific compounds of formula (VI) include:

[0174] Bis(2,4,6-trimethylbenzoyl)-vinyl-phosphine (also known as vinyl-bis(mesitylbenzoyl)phosphine), bis(2,4,6-trimethylbenzoyl)-(1-phenylvinyl-1-yl)-phosphine, bis(2,4,6-trimethylbenzoyl)-(3-hexen-3-yl)-phosphine, (2,4,6-trimethylbenzoyl)-vinyl-phosphine, bis-(benzoyl)-vinyl-phosphine, bis(benzoyl)-(1-phenylvinyl-1-yl)-phosphine, bis(benzoyl)-(3-hexen-3-yl)-phosphine, (benzoyl)-vinyl-phosphine, 1-phenylvinyl-bis(2,4,6-trimethylbenzoyl)phosphine and 1-methylvinyl-bis(2,4,6-trimethylbenzoyl)phosphine.

[0175] Preparation method B

[0176] In another embodiment, alternatively, the compound of formula (I) (wherein R 3 Indicates -(O - )(Cat + )):

[0177] aa) reacting a compound of formula (IX) with a compound of formula (X) (aldehyde) to obtain a compound of formula (XI)

[0178]

[0179] in

[0180] n、R 1 and R 2 Has the same meaning as defined above, including preferred embodiments

[0181]

[0182] Where R 4 has the same meaning as defined above for formula (I), including preferred embodiments

[0183]

[0184] and

[0185] bb) oxidizing the alcohol function of the compound of formula (XI) to a compound of formula (I) wherein R 3 Indicates -(O - )(Cat + ), where -(O - )(Cat + ) as a whole does not represent -OH, preferably, in the presence of cation Cat + Oxidation is performed under the condition of

[0186] Step aa) may be carried out in water.

[0187] To promote the reaction, mixing energy is introduced into the reaction mixture, for example, by means of standard stirrers, agitators and / or static mixing elements.

[0188] Typical and preferred reaction temperatures for carrying out the process according to step aa) are in the range of -30 to 120 °C, preferably -10 to 80 °C.

[0189] It is obvious to the person skilled in the art that when the desired reaction temperature is above the boiling point of the solvent used at 1013 hPa, the reaction is carried out under sufficient pressure.

[0190] In principle, the oxidation of the alcohol function in step bb) can be carried out in any manner known to the person skilled in the art and includes reaction with N-chlorosuccinimide or elemental chlorine in the presence of dialkyl sulfides such as dimethyl sulfide and amines such as triethylamine (Cory-Kim oxidation).

[0191] Such oxidations are disclosed, for example, in EJ Corey, CU Kim, Journal of the American Chemical Society 1972, 94, 7586-7587 and O. Berger, L. Gavara, J.-L. Montchamp, Organic Letters 2012, 14, 3404-3407).

[0192] Oxidation can also be carried out by:

[0193] The so-called Swern oxidation using oxalyl chloride as oxidant, dimethyl sulfoxide as catalyst and amines as base, as disclosed in K. Omura, D. Swern, Tetrahedron 1978, 34, 1651-1660

[0194] The so-called Pfitzner-Moffatt oxidation using dicyclohexylcarbodiimide as oxidant and dimethyl sulfoxide as catalyst, as disclosed in KEPfitzner, JG Moffatt, Journal of the American Chemical Society 1963, 85, 3027-3027

[0195] Use of a hypervalent iodine reagent, such as Dess-Martin periodinane (see DB Dess, JC Martin, The Journal of Organic Chemistry 1983, 48, 4155-4156)

[0196] The so-called Ley-Griffith oxidation using N-methylmorpholine-N-oxide as stoichiometric oxidant and tetrapropylammonium perruthenate (TPAP) as catalyst, WP Griffith, SV Ley, GP Whitcombe, AD White, Journal of the Chemical Society, Chemical Communications 1987, 1625-1627

[0197] The so-called Oppenauer oxidation using acetone and aluminium ethoxide, as disclosed in RV Oppenauer, Recueil des Travaux Chimiques des Pays-Bas 1937, 56, 137-144. Using chromium(VI) compounds, such as chromium trioxide or pyridinium chlorochromate.

[0198] In order to prepare other compounds of formula (I), in order to change the R 3 Indicates -(O - )(Cat + ) of those compounds of formula (I) can also be exchanged using all methods known to those skilled in the art. These methods include ion exchange, for example, using weak or strong acid ion exchangers, adding salts to take advantage of the different solubility of the corresponding salt couples, or when -(O - )(Cat + ) as a whole represents -OH, a base containing the desired cation is simply added.

[0199] Compounds of the formulae (IV), (VII) and (IX) are hitherto unknown or commercially unavailable since their preparation procedures are cumbersome and therefore commercially unattractive.

[0200] Therefore, the present invention also includes a process for preparing compounds of formula (XIIa) and (XIIb)

[0201]

[0202] in

[0203] n、R 1 and R 2 has the same meaning as defined above for formula (I), including preferred embodiments, and R 7 Having R as defined above for formula (I) 3 The same meaning, including preferred embodiments, but excluding -(O - )(Cat+ )

[0204] and

[0205] Pn is a nitrogen group element selected from the group consisting of phosphorus, arsenic, and antimony, preferably phosphorus or arsenic, and more preferably phosphorus.

[0206] f is 0, 1, or 2, and

[0207] R 8 and R 9 are independently hydrogen or alkyl

[0208] The method comprises the following steps:

[0209] aaa) reacting a compound of the formula with a compound of formula (XIV) in the presence of at least one, preferably one, Lewis acid

[0210] Formula (XIIIa) (in order to obtain a compound of formula XXIIa) or

[0211] Formula (XIIIb) (in order to obtain a compound of formula XXIIb) or

[0212]

[0213] Where n, R 1 and R 2 has the same meaning as defined above for formula (I), including preferred embodiments, and R 8 and R 9 has the same meaning as defined above for formula (XIIa) and (XIIb)

[0214]

[0215] Where Pn, R 7 and f have the same meanings as above.

[0216] In a preferred embodiment, the compound of formula (XIIIa) or (XIIIb) is reacted with phosphine (PH3), arsenic (AsH3) or antimony (SbH3), preferably phosphine (PH3) or arsenic (AsH3), and even more preferably phosphine (PH3), in the presence of at least one, preferably one, Lewis acid.

[0217] In a specific embodiment, the compound of formula (VII) as defined above is prepared by

[0218]

[0219] The compound of formula (XIIIa2) is reacted with arsine (PH3) in the presence of at least one, preferably one, Lewis acid.

[0220]

[0221] The term "present" for at least one Lewis acid should encompass the fact that the Lewis acid generally forms Lewis adducts with the phosphine used and at least partially or mostly or completely also with the product phosphine.

[0222] Specific compounds of formula (XIIIa) and (XIIIa2) include acetylene, phenylacetylene, 1,2-diphenylacetylene and 3-hexyne.

[0223] Specific compounds of formula (XIIIb) include ethylene, propylene, isobutylene, 1-butene, 2-butene, vinylbenzene, cyclohexene, 1-hexene, 2-hexene, 3,3-dimethyl-1-butene, cyclopentadiene, styrene, trans-stilbene, divinylbenzene, preferably isobutylene. Specific compounds of formula (XIIa) include vinylphosphine, divinylphosphine, trivinylphosphine, 1-phenylvinylphosphine, bis-(1-phenylvinyl)phosphine, tri(1-phenylvinyl)phosphine, 3-hexene-3-ylphosphine and bis(3-hexene-3-yl)phosphine.

[0224] Specific compounds of formula (XIIb) include tert-butylphosphine, tert-butylarsine, tert-butylantimony, (1-hexyl)-phosphine, (2-hexyl)-phosphine, (3-hexyl)-phosphine, 3,3-dimethylbutylphosphine, 3,3-dimethylbut-2-ylphosphine, cyclopentylphosphine, cyclohexylphosphine, 1,2-diphenylethylphosphine and 1-phenylethylphosphine.

[0225] Besides vinylphosphine, divinylphosphine and trivinylphosphine compounds or the formula (XIIa) are novel and therefore also comprised by the present invention.

[0226] They are not only suitable as precursors for compounds of formula (I), (IV), (VII) and (IX), but are also useful as precursors for other phosphorus- or arsenic-containing chemicals, such as ligands for catalytic conversions, precursor materials for agricultural and pharmaceutical products.

[0227] The compound of formula (XIIb) can be used as a phosphorus-containing and substituent R in the preparation of the compound of formula (I). 7 The starting materials of formula (IV) are desirable compounds for use in the electronics industry.

[0228] The main discovery of the present invention is that tert-butylphosphine and tert-butylarsine, in particular tert-butylphosphine, can be produced with excellent purity and selectivity compared to all currently known processes. In particular, the product shows no detectable impurities such as sulfur, which are disadvantageous for use in the electronics industry.

[0229] The process according to the invention for preparing compounds of the formula (XIIa) or (XIIb) is carried out in the presence of at least one, preferably one, Lewis acid.

[0230] In the context of the present invention, the term "Lewis acid" is to be understood as meaning the conventional definition of those compounds which have an electron vacancy, such as e.g. As explained in Chemie-Lexikon, 8th edition, Franck'sche Verlagshandlung 1983, volume 3, HL.

[0231] In a preferred embodiment, at least one Lewis acid is selected from the group consisting of methylaluminoxane (MAO) and a compound represented by formula (XV)

[0232] Met L (g) X (h-g) (XV)

[0233] in

[0234] h is 2, 3, 4 or 5

[0235] g is 0 or an integer up to h, preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0

[0236] If h is 2, Met is Sn, or in another embodiment, Sn, Fe, Mn and Zn

[0237] If h is 3, Met is an element selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Fe, B, Al, Ga, In, As

[0238] If h is 4, Met is an element selected from the group consisting of: V, Ti, Zr, Hf, Sn

[0239] If h is 5, Met is an element selected from the group consisting of: V, P, As, Sb, Bi

[0240] X is independently selected from the group consisting of fluorine, chlorine, bromine, iodine, azide, isocyanate, thiocyanate, isothiocyanate or cyanide, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine

[0241] R L Represents C1-C 18 Alkyl, cyclopentadienyl, C1-C 18 Halogenated alkyl, C1-C 18 Alkoxy, C1-C 18 Halogenated alkoxy, C6-C 14 Aryl, C7-C 18 Arylalkyl, C6-C 14 Aryloxy, C7-C 18 Arylalkoxy, -O(HC=O), -O(C=O)-(C1-C 18 alkyl), -O(C=O)-(C6-C 14 Aryl) and -O(C=O)-(C7-C 18 Arylalkyl) or

[0242] Two R's L Together they represent C4-C 18 Alkanediyl, C4-C 18 Halogenated alkanediyl, C4-C 18 Alkanedioxy, C4-C 18 Halogenated alkyldioxy, C6-C 14 Aryldiyl, C7-C 18 Arylalkanediyl, C6-C 14 Aryldioxy, C7-C 18 Arylalkanedioxy, -O(C=O)-(C1-C 18 alkyl)-(C=O)O-, -O(C=O)-(C6-C 14 -aryl)-(C=O)O- and -O(C=O)-(C7-C 18 Arylalkyl)-(C=O)O- or oxy(=O)

[0243] In one embodiment, g is 0.

[0244] For this embodiment, examples of such compounds include

[0245] h = 2 tin dichloride, or in another embodiment, tin dichloride, zinc dichloride, ferrous chloride and manganese dichloride

[0246] h=3aluminum chloride, aluminum tribromide, boron trifluoride, boron trichloride, boron tribromide, gallium trichloride, gallium tribromide, gallium triiodide, indium trifluoride, indium tribromide or indium triiodide, scandium trichloride, iron trichloride, arsenic trifluoride, bismuth trichloride.

[0247] h=4 titanium tetrachloride, titanium tetrabromide, vanadium tetrachloride, tin tetrachloride, zirconium tetrachloride, hafnium tetrachloride, titanium trichloride bromide, titanium dichloride dibromide, vanadium trichloride bromide and tin trifluoride chloride.

[0248] h = 5 Antimony pentachloride, antimony pentafluoride, arsenic pentafluoride, antimony pentafluoride chloride and arsenic tetrachloride fluoride

[0249] Preferred compounds are zinc dichloride, ferrous chloride, manganese dichloride, aluminum chloride and boron trifluoride, among which aluminum chloride and boron trifluoride are preferred, and aluminum chloride is more preferred.

[0250] In one embodiment, g is 1, 2 or 3.

[0251] For this embodiment, examples of these compounds include

[0252] h=3 methylaluminum dibromide, methylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dichloride, butylaluminum dibromide, butylaluminum dichloride, dimethylaluminum bromide, dimethylaluminum chloride, diethylaluminum bromide, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, methoxyaluminum dichloride, ethoxyaluminum dichloride, 2,6-di-tert-butylphenoxyaluminum dichloride, methoxymethylaluminum chloride, 2,6-di-tert-butylphenoxymethylaluminum chloride, isopropoxygallium dichloride and phenoxymethylindium fluoride, acetoxyaluminum dichloride, benzoylaluminum dibromide, benzoylgallium difluoride, methylacetoxyaluminum chloride and isopropoxyindium trichloride, triethylaluminum, and in one embodiment, additionally triphenylboron.

[0253] h=4-cyclopentadienyltitanium trichloride, biscyclopentadienyltitanium dichloride, cyclopentadienylzirconium trichloride and biscyclopentadienylzirconium dichloride

[0254] h=5 tetraphenylantimony chloride, triphenylantimony dichloride and vanadium trichloride.

[0255] In one embodiment, two or more Lewis acids are used, for example, two or three.

[0256] Typically and preferably, the method is carried out by first mixing a compound of formula (XIV) and at least one Lewis acid in a diluent and then adding the desired amount of a compound of formula (XIIIa) or (XIIIb). In one embodiment, the formation of the Lewis adduct formed by the reaction of the compound of formula (XIV) and at least one Lewis acid is assisted by mechanical mixing, for example for 1 to 120 minutes.

[0257] The present invention also encompasses the above-described preparation of Lewis adducts comprising the step of mixing a compound of formula (XIV) and at least one Lewis acid in a diluent, including all preferred embodiments disclosed above for the Lewis acid, the compound of formula (IV) and the diluent. In addition, the present invention also encompasses the use of Lewis adducts and their solutions for the preparation of compounds of formula (XIIIa) or (XIIIb). Suitable diluents include and are preferably those that do not or hardly react under conditions of forming new covalent bonds with the compound of formula (XIV), (XIIIa) or (XIIIb), and the diluent also does not form a Lewis adduct with the at least one Lewis acid that is more stable than the Lewis adducts typically formed by the reaction of the compound of formula (XIV) and the at least one Lewis acid.

[0258] These diluents include

[0259] Aromatic and halogenated aromatics, such as benzene, toluene, o-, m- and p-xylene, mesitylene, chlorobenzene and dichlorobenzene,

[0260] Aliphatic hydrocarbons such as pentane, hexane, cyclohexane, methylcyclohexane and

[0261] Halogenated aliphatic hydrocarbons or alkenes, such as methyl chloride, dichloromethane, chloroform, trichloroethane, and tetrachloromethane

[0262] and a mixture of the above solvents, wherein

[0263] · Benzene, toluene, o-xylene, m-xylene, p-xylene and mesitylene are preferred, and toluene is particularly preferred.

[0264] The main discovery of the present invention is that the 1:1 Lewis adducts formed between, in particular, boron trifluoride, boron trichloride, boron tribromide, boron triiodide, aluminum chloride, aluminum tribromide, triethylaluminum, gallium trichloride, gallium tribromide, gallium triiodide, indium trifluoride, indium tribromide, indium triiodide, titanium tetrachloride, titanium tetrabromide and compounds of formula (XIV), in particular that the Lewis adducts with arsine (PH3) are stable, storable, easy to handle and very soluble despite being highly reactive, in particular as solutions in aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, and therefore in particular, are useful for carrying out the process as described above. Therefore, the present invention also covers the above-mentioned Lewis adducts and their solutions in aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, preferably in toluene.

[0265] The preferred Lewis adduct is a 1:1 Lewis adduct of aluminum chloride and arsine (PH3) and its solution in toluene.

[0266] The reaction time of the process in step aaa) is generally in the range of 2 min to 168 hours, preferably 30 min to 72 hours.

[0267] The amount of diluent is not critical at all and is limited only by commercial aspects, since it has to be removed if the compound of the formula (XIIa) or (XIIb) is ultimately isolated.

[0268] To promote the reaction, mixing energy is introduced into the reaction mixture, for example, by means of standard stirrers, agitators and / or static mixing elements.

[0269] Although not required, mixing may also be supported by the use of a high force dispersing device such as, for example, an ultrasonic sonotrode or a high pressure homogenizer.

[0270] The process can be carried out batchwise or continuously.

[0271] Typical and preferred reaction temperatures for carrying out the process range from -30 to 120°C, preferably from -10 to 80°C, and even more preferably from 0 to 40°C.

[0272] It is obvious to the person skilled in the art that when the desired reaction temperature is above the boiling point of the diluent used at 1013 hPa, the reaction is carried out under sufficient pressure.

[0273] Typical and preferred reaction pressure ranges for carrying out the process are from 50 hPa to 10 MPa, preferably from 500 hPa to 1 MPa.

[0274] When arsine (PH3) is used as the compound of formula (XIV), the preferred reaction pressure range for carrying out the process is 800 hPa to 10 MPa, preferably 1000 hPa to 6 MPa, more preferably 1000 hPa to 0.5 MPa.

[0275] In one embodiment, the reaction is conducted with substantial exclusion of oxygen, ie, an oxygen partial pressure of less than 10 hPa, preferably less than 5 hPa, and more preferably less than 0.15 hPa.

[0276] In one embodiment, the reaction is carried out under an inert gas, ie a gas which does not or hardly reacts with the reactants under the reaction conditions used.

[0277] During the reaction, compounds of formula (XIIa) or (XIIb) are formed, depending on the type of Lewis acid used or the product (also partially, substantially or completely in the form of Lewis adducts thereof with at least one Lewis acid used). These Lewis adducts can be used directly in subsequent steps, such as those described in preparation method A, or, when separation is required or desired, decomposed to release the compounds of formula (XIIa) or (XIIb) in pure form. Decomposition can be carried out, for example, by thermal treatment, wherein the compounds of formula (XIIa) or (XIIb) are separated, for example, by distillation from the Lewis adducts, or by adding water or alcohols such as methanol, ethanol, isopropanol or tert-butyl alcohol, or by adding organic compounds (the Lewis adducts formed by the organic compounds with the Lewis acid used are more stable than those formed with the compounds of formula (XIIa) or (XIIb)). These organic compounds include ethers, nitriles and amines.

[0278] The molar ratio of the compound of formula (XIIIa) or (XIIIb) to the compound of formula (XIV) used in the reaction is based on the -[R 1 C=CHR 2 ]、-[R 1 R 8 C-CHR 9 R 2 ]The number of groups.

[0279] It is known to those skilled in the art that, based on the molar ratio and type of the compound of formula (XIIIa) or (XIIIb) used, different -[R 1 C=CHR 2 ]、-[R 1 R 8 C-CHR 9 R 2 ] a reaction mixture of a compound of formula (XIIa) or (XIIb) having a number of ] groups.

[0280] The molar ratio of the compound of formula (III) and the Lewis acid used in the reaction is generally 0.75 to 1.5 mol of Lewis acid per mol of the compound of formula (XIIIa) or (XIIIb), preferably 0.85 to 1.2 mol, more preferably 0.90 to 1.15 mol.

[0281] The desired compound of formula (IX) as described above can be prepared by the following steps:

[0282]

[0283] aaaa) oxidizes certain compounds of formula (XIIa), wherein

[0284] Pn is phosphorus, and

[0285] f 2

[0286] That is, those of formula (XIIa2)

[0287]

[0288] The oxidation in step aaaa) can be carried out as described above for step a) in preparation method A). Therefore, the same reagents and operating conditions (including preferred embodiments) described herein should also apply to this oxidation.

[0289] Specific examples of compounds of formula (XIIa2) include vinyl-phosphinic acid, hexen-3-yl-phosphinic acid, specifically, Z-hexen-3-yl-phosphinic acid, bis(1-phenylvinyl)phosphinic acid and (1-phenylvinyl)phosphinic acid, specifically bis-Z-(1-phenylvinyl)phosphinic acid and Z-(1-phenylvinyl)phosphinic acid.

[0290] Advantages

[0291] Compared to those compounds known from the prior art, the novel compounds of the formula (I), in particular those of the formulae (II) and (III), show high reactivity under UV and / or visible radiation and allow crosslinking via their built-in unsaturations which are directly bonded to the phosphorus.

[0292] Their preparation can be easily achieved by the process according to the invention disclosed above and based on currently readily available starting materials.

[0293] application

[0294] For the reasons provided above, compounds of formula (I) are particularly useful as photoinitiators.

[0295] Therefore, one further aspect of the present invention relates to a photocurable composition comprising

[0296] I) at least one ethylenically unsaturated compound, and

[0297] II)) at least one compound of formula (I) as defined above, including the preferred embodiments.

[0298] Suitable ethylenically unsaturated compounds contain one or more olefinic double bonds and include (meth)acrylates such as alkyl esters, such as methyl, ethyl, 2-chloroethyl, N-dimethylaminoethyl, n-butyl, isobutyl, pentyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, isobornyl, phenyl, benzyl and o-, m- and p-hydroxyphenyl esters, hydroxyalkyl esters such as 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 3,4-dihydroxybutyl or glycerol or [1,2,3-propanetriol] esters, epoxyalkyl esters such as glycidyl, 2,3-epoxybutyl, 3,4-epoxybutyl esters, 2,3-epoxycyclohexyl esters, 10,11-epoxyundecanyl esters, (meth)acrylamide, N-substituted (meth)acrylamide such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-cyclohexylmethacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide, acrylamide, N-ethyl-N-phenylmethacrylamide, N-(4-hydroxyphenyl)acrylamide and N-(4-hydroxyphenyl)methacrylamide, IBMAA (N-isobutoxymethylacrylamide), (meth)acrylonitrile, unsaturated acid anhydrides such as itaconic anhydride, maleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride, unsaturated esters such as maleic esters, phthalic esters, itaconic esters, methylene succinates, styrenes such as methyl styrene, o-, m- or p-chloromethyl styrene and o-, m- and p-hydroxystyrene, divinylbenzene, vinyl ethers such as isobutyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propylene glycol, The invention also includes but is not limited to butyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether and phenyl vinyl ether, ethylene and allyl esters such as vinyl acetate, vinyl acrylate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate, divinyl succinate, diallyl terephthalate, triallyl phosphate, vinyl chloride and vinylidene chloride, isocyanurates such as triallyl isocyanurate and tris(2-acryloylethyl)isocyanurate, N-vinyl heterocyclic compounds such as N-vinylpyrrolidone or substituted N-vinylpyrrolidone, N-vinylcaprolactam or substituted N-vinylcaprolactam, N-vinylcarbazole, N-vinylpyridine.

[0299] Other examples include diacrylates such as 1,6-hexanediol diacrylate (HDDA), ethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate, and bisphenol A diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, butanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate. esters, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol triitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol modified triacrylates, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates and methacrylates, glycerol diacrylate and glycerol triacrylate, 1,4-cyclohexane diacrylate, diacrylates and dimethacrylates of polyethylene glycols having a molecular weight of 200 to 2,500, alkoxylated alcohols such as glycerol ethoxylate triacrylate (glycerol ethoxylatetriacrylate), glyceryl propoxy ether triacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxy ether triacrylate, pentaerythritol ethoxylate tetraacrylate, pentaerythritol propoxy ether triacrylate, pentaerythritol propoxy ether tetraacrylate, neopentyl glycol ethoxylate diacrylate, neopentyl glycol propoxy ether diacrylate, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, unsaturated fatty acids such as linolenic acid or oleic acid.

[0300] Further examples of high molecular weight ethylenically unsaturated compounds include esters of ethylenically unsaturated monofunctional or polyfunctional carboxylic acids and polyols or polyepoxides and polymers having ethylenically unsaturated groups in the main chain or in or as side groups, such as, for example, unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers having (meth)acrylic groups in the side chains and mixtures of one or more of these polymers.

[0301] Other suitable ethylenically unsaturated compounds include acrylates modified by reaction with primary or secondary amines, as described, for example, in US Pat. No. 3,844,916, EP Pat. No. 280,222, US Pat. No. 5,482,649 or US Pat. No. 5,734,002. These amine-modified acrylates are also known as amine acrylates. Amine acrylates are available, for example, under the names EBECRYL 80, EBECRYL 81, EBECRYL 83, EBECRYL 7100 from UCB Chemicals, under the names Laromer PO 83F, Laromer PO 84F, Laromer PO 94F from BASF SE, under the names PHOTOMER 4775F, PHOTOMER 4967F from Cognis, or under the names CN501, CN503, CN550 from Cray Valley and GENOMER 5275 from Rahn.

[0302] When water is present, the at least one ethylenically unsaturated compound may be dissolved or emulsified in water.

[0303] In these compositions, the concentration of water is, for example, 5 to 80% by weight, preferably 30 to 60% by weight.

[0304] Other components which may additionally be present in the photocurable composition or absent are:

[0305] ·water

[0306] Organic polar diluents or solvents such as ethers, such as ethylene glycol dimethyl ether and polyethylene glycol ethers

[0307] Organic or inorganic pigments

[0308] UV-absorbent

[0309] Inorganic fillers

[0310] Heat stabilizer

[0311] Isocyanates and / or polyisocyanates

[0312] ·Flattening agent

[0313] Matting agent,

[0314] Defoaming agent

[0315] Friction reducers such as silicone-containing friction reducers,

[0316] Surfactants

[0317] Resins such as formaldehyde resins, polyurethane resins, polyacrylates, cellulose resins and sucrose benzoate

[0318] Other photoinitiators, including but not limited to Norrish Type I initiators such as 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one (Irgacure 127), 2-hydroxy-1-[4-(2-hydroxyethoxy)-phenyl]-phenyl]-2-methylpropan-1-one (Irgacure 2959), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (Irgacure 1173), 2,2-dimethoxy-2-phenylacetophenone and oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone] (Esacure KIP 150 from Lamberti) and mono- or bis-acylphosphine oxides.

[0319] The amounts of ethylenically unsaturated component, compound of formula (I), and optional other ingredients will vary depending upon the type of composition, the particular equipment used to apply it, and the application.

[0320] Typically, however, the amount of photoinitiator in the composition is in the range of 0.05 to 12 wt.-%, preferably 2 to 10 wt.-%, more preferably 4 to 9 wt.-%.

[0321] The present invention also relates to a process for preparing a cured composition by exposing the photocurable composition according to the invention to electromagnetic radiation, preferably UV or blue radiation.

[0322] Suitable sources of electromagnetic radiation include UV lamps, such as low-pressure, medium-pressure, high-pressure and ultra-high-pressure mercury lamps, which may be undoped or doped with, for example, gallium iodide, thallium iodide or other metal halides; green, blue, violet-blue LEDs or UV-LEDs; LED lamps, concentrated direct or indirect sunlight; xenon or xenon-mercury arc lamps, such as continuous output xenon short-arc or long-arc lamps, flash lamps, such as xenon or xenon-mercury flash lamps; microwave-excited metal vapor lamps; excimer lamps, superatinic fluorescent tubes; fluorescent lamps; and rare gas incandescent lamps.

[0323] Preferred sources are lamps such as low-pressure, medium-pressure, high-pressure and ultra-high-pressure mercury lamps, which may be undoped or doped with, for example, gallium iodide, thallium iodide or other metal halides; green, blue, violet-blue or UV-LEDs, xenon or xenon-mercury arc lamps such as continuous output xenon short-arc or long-arc lamps.

[0324] The compositions according to the invention can be used for various purposes, for example, in overprint coatings such as printing inks, for example, screen printing inks, inks for offset or flexographic printing, inkjet inks, inks for sheet-fed printing, electrophotographic inks, gravure printing inks, as clear coatings, white coatings or colored pigmented coatings, for example, for wood or metal, as powder coatings, as paints, especially for paper, wood, metal or plastic products, as daylight-curable paints for marking structures and roads, paints for buildings, constructions, vehicles, aircraft, etc., in photocopying processes, in holographic recording materials, in image recording processes or in the production of printing plates which can be developed using organic solvents or using alkaline aqueous media, for the production of masks for screen printing, as dental printing inks. The composition can be used as a filler compound, as an adhesive, as a pressure-sensitive adhesive, as a laminating resin, as both an etch-resistant or permanent protective liquid film and a dry film, as a photostructured dielectric and as a solder mask for electronic circuits, as a protective agent in the production of color filters for any type of display screen or in the production of plasma displays and electroluminescent displays in the production of structures, in the production of optical switches, gratings (interference gratings), in the production of three-dimensional articles by integral curing (photocuring in a transparent mold) or according to stereolithography, in the production of composite materials, in the coating or sealing of electronic components or as a coating for optical fibers. The composition is also suitable for the production of optical lenses such as contact lenses or Fresnel lenses and the production of medical devices, auxiliary devices or implants. The composition can also be used to prepare a gel having thermotropic properties.

[0325] The compounds of formula (I) are also suitable for the preparation and related use of light-curable adhesives; for example, pressure-sensitive adhesives, laminating adhesives, hot-melt adhesives, moisture-curing adhesives, silane-reactive adhesives or silane-reactive sealants, etc. The adhesive can be a hot-melt adhesive as well as a water-based or solvent-based adhesive, a solvent-free liquid adhesive or a 2-part reactive adhesive.

[0326] The compounds of the formula (I) can also be used as free-radical photoinitiators or as photoinitiating systems for radiation-curable powder coatings.

[0327] As mentioned above, curing according to the invention can be carried out by irradiation with electromagnetic radiation. However, depending on the composition of the formulation to be cured, thermal curing before, during or after irradiation may be advantageous.

[0328] Thermal curing is carried out by methods known to those skilled in the art. Typically, curing is carried out in an oven, for example, a circulating air oven, on a hot plate or by irradiation with an IR lamp. Depending on the binder system used, unassisted curing at room temperature is also possible. The curing temperature is typically between room temperature and 150° C., for example, between 25 and 150° C. or between 50 and 150° C. For powder coatings or coil coatings, the curing temperature may be even higher, for example, up to 350° C.

[0329] The present invention is further explained below by way of examples, but is not limited thereto.

[0330] Example:

[0331] Example 1): Synthesis of Cl3Al-PH3 adducts and other Lewis acid-PH3 adducts in solution

[0332] In a 500 mL round bottom flask with a gas inlet and outlet, AlCl (99.998%, from Alfa Aesar, 50.0 g, 375 mmol) was suspended in toluene (about 250 mL). Under vigorous stirring, the flask was exposed to the pressure of PH until the pressure gauge read 1800 hPa. Once the ClAl-PH adduct is formed, the pressure is reduced and the procedure must be repeated until a clear solution is obtained, and there is no undissolved AlCl in the container. The reaction mixture is stirred for another 30 min at PH and then purged to quench the system. In order to remove excess PH from the solution, the flask was flushed with argon for 15 min under vigorous stirring. Toluene was added to the flask to obtain a total volume of 375 mL, and thus a 1.0 M ClAl-PH adduct stock solution was obtained.

[0333] 31 P-NMR (101 MHz, toluene): δ = -168.7 (q, 1 J PH =374.5Hz)ppm.

[0334] Lewis adducts of PH3 with boron trichloride, boron tribromide, boron triiodide, aluminum chloride, aluminum tribromide, triethylaluminum, gallium trichloride, gallium tribromide, gallium triiodide, indium triiodide, titanium tetrachloride, and titanium tetrabromide were prepared by a strictly similar procedure as described above.

[0335] Cl3B-PH3: 31 P-NMR (101 MHz, toluene): δ = -110.2 (q, 1 J PH =421Hz)ppm.

[0336] Br3B-PH3: 31 P-NMR (101 MHz, toluene): δ = -101.4 (q,1 J PH =431Hz)ppm.

[0337] I3B-PH3: 31 P-NMR (101 MHz, toluene): δ = -92.0 (q, 1 J PH =429Hz)ppm.

[0338] Br3Al-PH3: 31 P-NMR (101 MHz, toluene): δ = -164.4 (q, 1 J PH =372Hz)ppm.

[0339] Et3Al-PH3: 31 P-NMR (101 MHz, toluene): δ = -214.0 (q, 1 J PH =249Hz)ppm.

[0340] Cl3Ga-PH3: 31 P-NMR (101 MHz, toluene): δ = -156.2 (q, 1 J PH =390Hz)ppm.

[0341] Br3Ga-PH3: 31 P-NMR (101 MHz, toluene): δ = -160.2 (q, 1 J PH =375Hz)ppm.

[0342] I3Ga-PH3: 31 P-NMR (101 MHz, toluene): δ = -165.5 (q, 1 J PH =365Hz)ppm.

[0343] I3In-PH3: 31 P-NMR (101 MHz, toluene): δ = -190.9 (q, 1 J PH =332Hz)ppm.

[0344] Br3Ti-PH3: 31 P-NMR (101 MHz, toluene): δ = -219.1 (q, 1 J PH =218Hz)ppm.

[0345] Example 2): Separation of Cl3Al-PH3 adduct

[0346] In a 20 mL Schlenk tube, AlCl (6.67 g, 50 mmol) was suspended in toluene (7.5 mL) and reacted as described in Example 1. The suspension was then filtered through a Teflon cannula and the filtrate was cooled to -30° C. The colorless crystalline solid was collected on a glass frit and dried in an argon stream to provide ClAl-PH adduct as a white powder.

[0347] Example 3): Preparation of vinyl phosphine

[0348] Under an inert atmosphere, acetylene gas was added to a stirred solution (0.5 M) of the Cl3Al-PH3 adduct prepared according to Example 1) in toluene at 0°C until the pressure gauge read 1500 hPa (i.e., 500 hPa overpressure of acetylene was added). After 15 min, the transparent solution turned into a white suspension. After 1 h, the acetylene pressure was released and the reaction mixture was hydrolyzed by slowly adding water (5 mL, degassed with N2) at 0°C. The reaction mixture was stirred at 20°C for 1 h, the organic phase was separated and the aqueous phase was extracted with toluene (3×5 mL).

[0349] 31 P-NMR (101 MHz, toluene): δ = -136.4 (tdt, 1 J PH =198.0Hz, 3 J PH,trans =28.2Hz, J PH =13.9Hz).

[0350] Example 4): Preparation of divinylphosphine

[0351] A stirred solution (0.5 M) of the Cl3Al-PH3 adduct prepared according to Example 1) in toluene was exposed to an overpressure of 0.5 bar of acetylene at 20°C. After 15 min, the clear solution turned into a white suspension. After 24 h, a pale yellow turbid suspension was obtained, the acetylene pressure was released, and the reaction mixture was hydrolyzed by slowly adding water (5 mL, degassed with N2) at 0°C. In addition to a certain amount of insoluble white polymer, 31 The P-NMR spectrum showed weak signals belonging to monovinylphosphine (15%) and divinylphosphine (85%).

[0352] 31 P-NMR (101 MHz, toluene): δ = -63.6 (dttt, 1 J PH =211.4Hz, 3 J PH,trans =28.7Hz, 3 JPH,cis =14.1Hz, 2 J PH =13.7Hz)ppm.

[0353] Example 5): Preparation of vinylphosphinic acid

[0354] To a stirred toluene solution of the vinylphosphine prepared according to Example 3 (2.5 mmol) in toluene and acetate buffer (pH=7, 5 mL) was added peracetic acid (1.4 mL, 35 w-%, 6.3 mmol, 1.25 equiv) at 0°C over 30 min. 31 P-NMR spectrum showed complete conversion. Similar product concentrations were present in the organic phase as well as in the aqueous phase.

[0355] 31 P-NMR (101 MHz, toluene): δ = 23.0 (ddt, 1 J PH =563.3Hz, J PH,trans =49.8Hz, 3 J PH =26.4Hz).

[0356] Example 6): Preparation of vinyl-bis(2,4,6-trimethylbenzoyl)phosphine

[0357] In a 50 mL Schlenk tube, AlCl3 (1.47 g, 11.0 mmol, 1.1 eq.) was suspended in toluene (20 mL). This was converted into the Cl3Al-PH3 adduct as described in Example 1 above. Subsequently, the Schlenk tube was pressurized with 0.5 bar acetylene at 0°C for 2 h under vigorous stirring. 31 P-NMR spectrum confirmed the complete conversion of Cl3Al-PH3 adduct. 2,4,6-Trimethylbenzoyl chloride (benzoyl chloride) (3.32 mL, 20.0 mmol, 1.0 equiv) was added to the stirred solution within 5 min, and the resulting orange suspension was stirred at 20 ° C for 24 h. The solution was removed from the orange suspension with a Teflon sleeve equipped with a glass fiber filter, and the solid was washed with toluene (3×5 mL). Single crystals of the aluminum complex AlCl2[vinyl-bis(2,4,6-trimethylbenzoyl)phosphine]2][AlCl4] were obtained by gas phase diffusion of n-hexane into dichlorobenzene solution.

[0358] The light yellow solid was suspended in toluene (15 mL) and hydrolyzed by adding water (5 mL, degassed with N2). The organic phase was separated and the aqueous phase was extracted with toluene (3×3 mL). The combined organic phase was filtered through a syringe filter and the solvent was removed under reduced pressure. The resulting yellow solid was recrystallized from refluxing methanol to obtain vinyl-bis(2,4,6-trimethylbenzoyl)phosphine (2.60 g, 7.38 mmol, 74%) as a yellow crystalline solid.

[0359] 1 H-NMR (300MHz, C6D6): δ=6.69-6.57(m,1H,P-CH), 6.56(s,4H,Mes-H), 5.63-5.43(m,2H,CH=CH2), 2.25(s,12H,o-Mes-CH3), 2.01(s,6H,p-Mes-CH3)ppm.

[0360] 13 C{ 1 H}-NMR (75MHz, C6D6): δ=216.1(d, 1 J PC =43.9Hz,C=O),139.5(d, 3 J PC =28.0Hz,o-Mes), 139.3(s,p-Mes), 134.7(d, 2 J PC =29.5Hz, CH=CH2), 133.8(s,ipso-Mes), 129.1(s,m-Mes), 127.4(d, 1 J PC =7.8Hz, CH=CH2), 21.1(s,p-CH3), 20.1(d, 4 J PC =5.4Hz,o-CH3)ppm.

[0361] 31 P-NMR (121MHz, C6D6): δ = 42.9 (dd, 3 J PH,trans =39.7Hz, 3 J PH,cis =15.7Hz)ppm.

[0362] Analysis, found: C, 74.7; H, 7.2; N, 0.1. 22 H 25 Calculated values ​​for O2P: C, 75.0; H, 7.2; N, 0.

[0363] Mp 82-86°C (from methanol).

[0364] Example 7): Preparation of vinyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide

[0365] To a stirred solution of vinyl-bis(2,4,6-trimethylbenzoyl)phosphine (4.23 g, 12.0 mmol, 1.0 equiv) prepared according to Example 6 in toluene (10 mL) was added peracetic acid (2.9 mL, 35 w-%, 15 mmol, 1.25 equiv) at 0 ° C. in 15 min in the dark. The pale yellow solution was stirred at 20 ° C. for 30 min. The aqueous phase was separated and discarded. The organic phase was washed with saturated Na2CO3 aqueous solution (3×10 mL), dried with MgSO4 and the solvent was removed under reduced pressure. The residue was recrystallized from refluxing toluene (15 mL) to obtain vinyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide (3.35 g, 9.10 mmol, 76%) as a pale yellow solid.

[0366] 1 H-NMR (300MHz, CDCl3): δ=6.86(s,4H,Mes-H), 6.58-6.29(m,3H,CH=CH2), 2.28(s,18H,Mes-CH3)ppm.

[0367] 13 C{ 1 H}-NMR (75MHz, CDCl3): δ=215.9(d, 1 J PC =61.7Hz C=O), 141.3(s,p-Mes), 138.5(s,CH=CH2), 136.0(d, 2 J PC =42.0Hz,ipso-Mes), 135.6(s,o-Mes), 129.2(s,m-Mes), 126.6(d, 1 J PC =74.4Hz, CH=CH2), 21.4(s,p-CH3), 19.9(s,o-CH3)ppm.

[0368] 31 P-NMR (121MHz, C6D6): δ=9.7(ddd, 3 J PH,trans =39.7Hz,J PH =27.9Hz,J PH =23.3Hz)ppm.

[0369] Analysis, found: C, 71.4; H, 6.7; N, 0.1. 22 H 25Calculated values ​​for O3P: C, 71.7; H, 6.8; N, 0.

[0370] Mp 158-160°C (decomposition, from toluene).

[0371] Example 8): 1-phenylvinyl-bis(2,4,6-trimethylbenzoyl)phosphine and 1-methylvinyl-bis(2,4,6- 1-phenylvinyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide and the corresponding phosphine oxide Preparation of Vinyl-Bis(2,4,6-Trimethylbenzoyl)Phosphine Oxide

[0372] To a stirred solution of the Cl3Al-PH3 adduct prepared according to Example 1) in toluene (10.0 mL, 1 M, 10 mmol, 1.0 equiv) was added phenylacetylene (1.2 mL, 11 mmol, 1.1 equiv) at 0°C. The resulting suspension was stirred at 20°C for 4 h. Subsequently, triethylamine (4.2 mL, 30 mmol, 1.5 equiv) and 2,4,6-trimethylbenzoyl chloride (3.32 mL, 20.0 mmol, 1.0 equiv) were added, and the resulting orange suspension was stirred at 80°C for 10 h. The suspension was filtered and the volatiles were removed from the filtrate under reduced pressure to provide 1-phenylvinyl-bis(2,4,6-trimethylbenzoyl)phosphine as a yellow solid.

[0373] 31 P{ 1 H}-NMR (121 MHz, toluene): δ=59.6 ppm.

[0374] Methylvinyl-bis(2,4,6-trimethylbenzoyl)phosphine was prepared in a strictly analogous manner by pressurizing a flask containing the Cl3Al-PH3 adduct with propyne.

[0375] 31 P{ 1 H}-NMR (121 MHz, toluene): δ=68.3 ppm.

[0376] The oxidation of the two phosphines to their corresponding phosphine oxides was carried out in a manner strictly analogous to Example 7).

[0377] 1-phenylvinyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide:

[0378] 31 P{ 1 H}-NMR (121 MHz, toluene): δ=10.0 ppm.

[0379] 1-Methylvinyl-bis(2,4,6-trimethylbenzoyl)phosphine

[0380] 31 P{ 1 H}-NMR (121 MHz, toluene): δ=11.1 ppm.

[0381] Example 9): Preparation of (1-phenylvinyl) phosphine and bis(1-phenylvinyl) phosphine Phosphonic acid and bis(1-phenylvinyl)phosphinic acid

[0382] To a stirred solution of the Cl3Al-PH3 adduct prepared according to Example 1) in toluene (25.0 mL, 1 M, 25 mmol, 1.25 eq) was added a solution of phenylacetylene (2.15 mL, 20 mmol, 1.0 eq) in toluene (15 mL) at 0° C. over 30 min. The light orange emulsion was stirred at 20° C. for 18 h and hydrolyzed with water (degassed with N2, 5 mL). 31 The integration of signal in the P-NMR spectrum shows the product distribution of 85% (1-phenyl vinyl) phosphine to 15% bis (1-phenyl vinyl) phosphine. At 0 ℃, H is added to the mixture O (5.1mL, 30w-%, 50mmol, 1.25 equivalents), and the mixture is stirred for 6h at 20 ℃. The organic phase is separated, and the aqueous phase is extracted with toluene (3 × 5mL). Use MgSO Dry the organic phase merged and remove the solvent under reduced pressure to obtain phosphinic acid (2.09g,>75%) as a light yellow oil.

[0383] Notice: The analytical data presented below do not include the phosphinate aromatic region due to overlapping signals. 1 H- and 13 C-NMR signal.

[0384] (1-Phenylvinyl)phosphine:

[0385] 31 P-NMR (121 MHz, toluene): δ = -122.2 (tdd, 1 J PH =198.9Hz, 3 J PH,trans =25.9Hz, 3 J PH,cis =11.9Hz)ppm.

[0386] Bis(1-phenylvinyl)phosphine:

[0387] 31 P-NMR (121 MHz, toluene): δ = -37.3 (dtt, 1 J PH =218.4Hz, 3 J PH,trans =23.4Hz, 3 J PH,cis =10.3Hz)ppm.

[0388] (1-phenylvinyl)phosphinic acid:

[0389] 1H-NMR (300MHz, CDCl3): δ=12.48 (br.d, 2 J PH =25.6Hz,1H,OH),7.32(d, 1 J PH =571.4Hz,1H,PH),6.18(d, 3 J PH =46.3Hz,1H,trans-CH2), 6.16(d, 3 J PH =24.5Hz,1H,cis-CH2)ppm.

[0390] 13 C{ 1 H}-NMR (75MHz, CDCl3): δ=135.3(d, 1 J PC =12.6Hz,PC),129.5(d, 2 J PC =12.8Hz,CH2)ppm.

[0391] 31 P-NMR (121MHz, CDCl3): δ = 25.8 (ddd, 1 J PH =571.4Hz, 3 J PH,trans =46.3Hz, 3 J PH,cis =24.5Hz)ppm.

[0392] Bis(1-phenylvinyl)phosphinic acid:

[0393] 1 H-NMR (300MHz, CDCl3): δ=12.48 (br.d, 2 J PH =25.6Hz,1H,OH),6.26(dd, 3 J PH =20.1Hz, 2 J HH =1.2Hz,1H,cis-CH2), 5.99(dd, 3 J PH =40.6Hz, 2 J HH =1.4Hz,1H,trans-CH2)ppm.

[0394] 13 C{ 1H}-NMR (75MHz, CDCl3): δ=136.7(d, 1 J PC =13.2Hz,PC), 131.8(d, 2 J PC =7.6Hz,CH2)ppm.

[0395] 31 P-NMR (121MHz, CDCl3): δ=30.4(tt, 3 J PH,trans =40.4Hz, 3 J PH,cis =19.9Hz)ppm.

[0396] Example 10): Preparation of tri(1-phenylvinyl)phosphine

[0397] At 0 ° C, within 5 min, phenylacetylene (3.55 mL, 33 mmol, 3.3 equiv.) was added to a stirred solution of the Cl3Al-PH3 adduct prepared according to Example 1) in toluene. The yellow emulsion was stirred at 20 ° C for 24 h and at 60 ° C for 3 h. It was hydrolyzed with water (degassed with N2, 3 mL) and stirred at 20 ° C for 30 min. The organic phase was separated and the aqueous phase was extracted with toluene (3×3 mL). The combined organic phases were filtered through a syringe filter and the solvent was removed under reduced pressure. The light yellow solid was recrystallized from refluxing MeOH (about 50 mL) to produce phosphine (2.62 g, 7.70 mml, 77%) as a light yellow crystalline solid. Single crystals suitable for X-ray diffraction were obtained from refluxing MeOH.

[0398] 1 H-NMR (300MHz, C6D6): δ=7.72-7.62(m,6H,o-Ph-H), 7.15-7.07(m,6H,m-Ph-H), 7.07-7.00(m,3H,p-Ph-H), 5.89(dd, 3 J PH =12.7Hz, 2 J HH =1.5Hz,3H,trans-CH), 5.58(dd, 3 J PH =5.6Hz, 2 J HH =1.5Hz,3H,cis-CH)ppm.

[0399] 13 C{ 1 H}-NMR (75MHz, C6D6): δ=145.7(d, 2J PC =15.9Hz,ipso-Ph),142.1(d, 1 J PC =23.5Hz,PC),128.7(d, 4 J PC =1.0Hz,m-Ph),128.1(d, 5 J PC =1.7Hz,p-Ph),127.2(d, 3 J PC =11.8Hz,o-Ph),126.2(d, 2 J PC =3.2Hz,CH2)ppm.

[0400] 31 P-NMR (121MHz, C6D6): δ=-3.1(dd, 3 J PH,trans =12.7Hz, 3 J PH,cis =5.6Hz)ppm.

[0401] Analysis, found: C, 84.7; H, 6.3; N, 0.1. 24 H 21 Calculated values ​​for P: C, 84.7; H, 6.2; N, 0.

[0402] Mp 75-78°C (from methanol).

[0403] Example 11): Preparation of (Z)-(1,2-diphenylvinyl)phosphine

[0404] At 20 ° C, under vigorous stirring, within 30 min, a solution of diphenylacetylene (3.21 g, 18 mmol, 1 equivalent) in toluene (20 mL) was added to a solution of Cl3Al-PH3 in toluene (20.0 mL, 1 M, 20 mmol, 1.1 equivalent) prepared according to Example 1), and the resulting light white suspension was stirred at 20 ° C for 3.5 h. At 0 ° C, the aluminum complex was hydrolyzed by adding phosphate buffer (pH = 7, 0.1 M, 5 mL). After the reaction mixture was stirred at 20 ° C for 30 min, the organic phase was separated and the volatile substances were removed under reduced pressure to obtain a light yellow solid. 31 Integration of the signals in the P-NMR spectrum showed a mixture of 95% of the primary phosphine (Z)-(1,2-diphenylvinyl)phosphine and 5% of the secondary phosphine bis((Z)-(1,2-diphenylvinyl))phosphine. Recrystallization from refluxing methanol gave pure (Z)-(1,2-diphenylvinyl)phosphine (2.50 g, 11.8 mmol, 65%) as a white crystalline solid. Single crystals suitable for X-ray diffraction were obtained from refluxing methanol.

[0405] 1 H-NMR (300MHz, C6D6): δ=7.46-7.37 (m, 4H, Ph-H), 7.26-7.01 (m, 7H, Ph-H and C=CH), 3.82 (dd, 1 J PH =206.8Hz, 4 J HH =1.4Hz,2H,PH)ppm.

[0406] 13 C{ 1 H}-NMR (75MHz, C6D6): δ=146.1(d,J PC =5.1Hz,C),138.9(d, 2 J PC =12.7Hz, PCCH), 138.7 (s, C), 134.4 (d, 1 J PC =20.1Hz, PC), 132.0 (s, CH), 129.5 (d, J PC =6.0Hz,CH),128.6(d,J PC =15.2Hz,CH),127.6(d,J PC =5.5Hz,CH),127.3(d,J PC =3.6Hz,CH)ppm.

[0407] 31 P-NMR (121MHz, C6D6): δ=-133.7(td, 1 J PH =206.7Hz, 3 J PH =13.7Hz)ppm.

[0408] Analysis, found: C, 79.5; H, 6.2; N, 0.1. 14 H 13 Calculated values ​​for P: C, 79.2; H, 6.2; N, 0.

[0409] Mp 49-51°C (from methanol).

[0410] Example 12): Preparation of bis((Z)-(1,2-diphenylvinyl))phosphine

[0411] To a flask containing diphenylacetylene (4.00 g, 22.5 mmol, 2.25 eq.) was added a solution of Cl3Al-PH3 in toluene (10.0 mL, 1 M, 10 mmol, 1.0 eq.) prepared according to Example 1). The yellow emulsion was stirred at 20 ° C for 4 h and at 60 ° C for 28 h. It was hydrolyzed with water (degassed with N2, 3 mL) and stirred at 20 ° C for 30 min. The organic phase was separated and the aqueous phase was extracted with toluene (3×3 mL). The combined organic phases were filtered through a syringe filter, the solvent was removed under reduced pressure and the residue was recrystallized from refluxing n-hexane to obtain bis((Z)-(1,2-diphenylvinyl))phosphine (3.80 g, 9.7 mmol, 77%) as a light yellow crystalline solid.

[0412] 1 H-NMR (300MHz, CD2Cl2): δ=7.42-7.11(m,10H,Ph), 6.99(br.d, 3 J PH,trans =17.5,2H,C=CH), 6.96-6.91(m,4H,p-Ph), 5.27(dt, 1 J PH ,228.3Hz,J HH =0.9Hz,1H,PH)ppm.

[0413] 13 C{ 1 H}-NMR (75MHz, CD2Cl2): δ=144.3(d,J PC =3.5Hz,C),141.3(d, 2 J PC =17.4Hz,PCCH),139.1(d, 1 J PC =22.9Hz,PC),138.5(d,J PC =1.5Hz,C),129.9(d,J PC =5.9Hz,CH),128.4(d,J PC =16.6Hz,CH),128.0(d,J PC =2.9Hz,CH), 127.6(d,J PC =50.4Hz,CH)ppm.

[0414] 31 P-NMR (121MHz, C6D6): δ=-75.2(dt, 1 J PH =226.9Hz, 3 J PH,trans =17.5Hz)ppm.

[0415] Analysis, found: C, 85.4; H, 6.1; N, 0.1. 28 H 23 Calculated values ​​for P: C, 86.1; H, 5.9; N, 0.

[0416] Mp 70-73°C (from n-hexane).

[0417] Example 13): Bis((Z)-3-hexen-3-yl)phosphine, (Z)-3-hexen-3-yl)phosphine and (Z)-3-hexen-3-ylphosphine Preparation of Phosphonic Acid

[0418] At 20°C, under vigorous stirring, within 45 min, a solution of 3-hexyne (2.16 mL, 19 mmol, 1 eq) in toluene (15 mL) was added to a solution of Cl3Al-PH3 in toluene (1 M, 20.0 mL, 20 mmol, 1.05 eq) prepared according to Example 1), and the resulting light white suspension was stirred at 20°C for 1 h. At 0°C, phosphate buffer (pH = 7, 0.1 M, 5 mL) was added, and the reaction mixture was stirred at 20°C for 1 h, and then the organic phase was transferred to a Schlenk flask via a Teflon cannula. 31 Integration of the signals in the P-NMR spectrum determined that the solution contained a mixture of 93% of the primary phosphine (Z)-3-hexen-3-yl)phosphine and 7% of the secondary phosphine bis((Z)-3-hexen-3-yl)phosphine. Vacuum distillation provided pure bis((Z)-3-hexen-3-yl)phosphine (200 mg, 1.01 mmol, 5%) as a colorless oil in the residue.

[0419] To the distillate pure (Z)-3-hexen-3-yl)phosphine was added H2O2 (5.8 mL, 30 w-%, 57 mmol, 1.5 eq.). The mixture was stirred at 0°C for 30 min, then the organic phase was separated and the aqueous phase was extracted with toluene (3×5 mL). Volatiles were removed from the combined organic phases under reduced pressure to afford (Z)-3-hexen-3-ylphosphinic acid (2.11 g, 14.2 mmol, 75%) as a colorless oil.

[0420] (Z)-3-Hexen-3-ylphosphine:

[0421] 31 P-NMR (101 MHz, toluene): δ = -150.1 (td, 1 J PH =197.2Hz, 3 J PH,trans =18.7Hz)ppm.

[0422] Bis((Z)-3-hexen-3-yl)phosphine:

[0423] 1H-NMR (300 MHz, C6D6): δ = 5.82 (dtt, 3 J PH = 19.6 Hz, 3 J HH = 7.2, 4 J HH = 1.5 Hz, 2H, C=CH), 4.16 (d, 1 J PH = 214.9 Hz, 1H, PH), 2.50 - 2.21 (m, 4H, CH-CH2), 2.24 - 1.95 (m, 4H, C-CH2), 1.04 (t, 3 J HH = 7.4 Hz, 6H, C-CH2-CH3), 0.95 (t, 3 J HH = 7.5 Hz, 6H, CH-CH2-CH3) ppm.

[0424] 13 C{ 1 H}-NMR (75 MHz, C6D6): δ = 140.2 (d, 2 J PC = 21.7 Hz, C=CH), 136.1 (d, 1 J PC = 16.4 Hz, C=CH), 32.9 (d, 2 J PC = 2.3 Hz, C=CH2), 25.0 (d, 3 J PC = 18.8 Hz, CH=CH2), 14.6 (s, CH-CH2-CH3), 14.2 (d, 3 J PC = 1.4 Hz, C-CH2-CH3) ppm.

[0425] 31 P-NMR (121 MHz, C6D6): δ = -86.2 (dtt, 1 J PH = 214.8 Hz, 3 J PH,trans = 19.6 Hz, 3 J PH = 4.9 Hz) ppm.

[0426] (Z)-3-Hexen-3-ylphosphinic acid:

[0427] 1 H-NMR (300 MHz, CDCl3): δ = 12.57 (br.s, 1H, OH), 7.44 (d,1 J PH =553.0Hz,1H,PH),6.11(dt, 3 J PH =43.1, 3 J HH =7.8Hz,1H,CCH), 2.50-2.32(m,2H,CCH2), 2.32-2.16(m,2H,CCHCH2), 1.08(t, 3 J HH =7.4Hz,3H,CCHCH2CH3), 1.02(t, 3 J HH =7.5Hz,3H,CCH2CH3)ppm.

[0428] 13 C{ 1 H}-NMR (75MHz, CDCl3): δ=146.9(d, 2 J PC =13.3,CH), 133.0(d, 1 J PC =125.4Hz,CP), 25.7(d, 3 J PC =12.8Hz,CCHCH2),22.6(d, 2 J PC =12.7Hz,CCH2),14.0(d, 3 J PC =5.1Hz,CCH2CH3),13.9(d, 4 J PC =2.2Hz,CCHCH2CH3)ppm.

[0429] 31 P-NMR (121MHz, CDCl3): δ=23.1(dm, 1 J PH =553.8Hz)ppm.

[0430] Analysis, found: C, 49.1; H, 8.8; N, 0.8. C6H 13 Calculated values ​​for O2P: C, 48.7; H, 8.8; N, 0.

[0431] Example 14): Preparation of tert-butylphosphine tBuPH2

[0432] A solution of Cl3Al-PH3 in toluene (1M, 50.0 mL, 50 mmol, 1 equivalent) prepared according to Example 1) was loaded into a 200 mL stainless steel autoclave purged with argon. Subsequently, isobutylene (3 g, 50 mmol, 1 equivalent) was condensed into the autoclave at 0°C. The autoclave was sealed, the contents were stirred by magnetic stirring and heated to 70°C for 8 h. The pressure was released and the autoclave was flushed with argon for 15 min at -80°C through a cold trap. No residual isobutylene condensed in the cold trap. 31 P-NMR showed a triplet of decets at δ = -61.7 ppm, which was probably due to the Cl3Al-tBuPH2 adduct. Upon addition of triethylamine (10 mL, 72 mmol, 1.44 eq), tert-butylphosphine was released from the adduct and distilled into a cold trap at -80°C (4.0 g, 44 mmol, 88%).

[0433] 31 P-NMR (121MHz, CDCl3): δ=-78.7 (tdec, 1 J PH =189.5Hz, 3 J PH =11.3Hz)ppm.

[0434] Example 15): Preparation of various primary phosphines

[0435] Equimolar amounts of Cl3Al-PH3 (1 M) prepared according to Example 1) and olefin (1 eq.) in toluene were mixed in a Schlenk tube. The mixture was stirred at 70°C and heated to 40°C by 31 The reaction was monitored by P-NMR spectroscopy. Subsequently, phosphate buffer (pH=7, 0.1 m, 5 mL) was added to the tube to release the phosphines from their aluminum complexes.

[0436] Reaction times and analytical data are given in Table 1:

[0437]

[0438] Table 1: Substrates, reaction times and phosphines obtained from the reaction of Cl3Al-PH3 with various olefins 31 Overview of P-NMR spectral data.

Claims

1. A process for preparing compounds of formula (XIIa2) and (XIIb), cyclopentylphosphine or cyclohexylphosphine, in n is 1, R 1 is hydrogen, alkyl or aryl, R 2 is hydrogen, alkyl or aryl, For R 1 and R 2 , the above alkyl substituents ● is not substituted by a substituent selected from the group consisting of unsubstituted aryl, or is substituted once, twice or more than twice by said substituent, f is 2 and hence R 7 does not exist, Pn is phosphorus, And R 8 and R 9 are independently hydrogen or alkyl, The method comprises the following steps: aaa) ● a compound of formula (XIIIa) (in order to obtain a compound of formula XIIa2) or ● a compound of formula (XIIIb) (in order to obtain a compound of formula XIIb) or ●Cyclopentene or cyclohexene Reaction with at least one 1:1 Lewis adduct selected from those formed between aluminum chloride and phosphine (PH3).

2. The method according to claim 1, wherein in formula (XIIa2) and (XIIb) n is 1 R 1 is hydrogen, C1-C6 alkyl or phenyl R 2 is hydrogen, C1-C6 alkyl or phenyl in For R 1 and R 2 , the above alkyl substituents ● is not substituted with a substituent selected from the group consisting of unsubstituted aryl, or is substituted once, twice, or more than twice with said substituent.

3. The method according to claim 1 or 2, wherein the compound of formula (XIIIa) is selected from the group consisting of acetylene, phenylacetylene, 1,2-diphenylacetylene and 3-hexyne.

4. The method according to claim 1 or 2, wherein the compound of formula (XIIa2) is selected from the group consisting of vinyl phosphine, 1-phenylvinyl phosphine and 3-hexen-3-yl phosphine.

5. The method according to claim 1 or 2, wherein the compound of formula (XIIIb) is selected from the group consisting of ethylene, propylene, isobutylene, 1-butene, 2-butene, vinylbenzene, 1-hexene, 2-hexene, 3,3-dimethyl-1-butene, styrene, trans-stilbene and divinylbenzene.

6. The method according to claim 1 or 2, wherein the compound of formula (XIIb) is selected from the group consisting of tert-butylphosphine, (1-hexyl)-phosphine, (2-hexyl)-phosphine, (3-hexyl)-phosphine, 3,3-dimethylbutylphosphine, 3,3-dimethylbut-2-ylphosphine, 1,2-diphenylethylphosphine and 1-phenylethylphosphine.

7. The process according to claim 1 or 2, carried out by first mixing phosphine (PH3) and aluminum chloride in a diluent to form a Lewis adduct and then adding the desired amount of the compound of formula (XIIIa) or (XIIIb) or cyclohexene or cyclopentene.

8. The method according to claim 7, wherein the diluent is selected from ●Aromatic hydrocarbons and halogenated aromatic hydrocarbons, ● Aliphatic hydrocarbons, and ●Halogenated aliphatic hydrocarbons or alkenes, and mixtures of the above diluents.

9. The method according to claim 1 or 2, carried out batchwise or continuously.

10. The method according to claim 1 or 2, wherein the reaction temperature is -30°C to 120°C.

11. The method according to claim 1 or 2, wherein the reaction pressure is 800 hPa to 10 MPa.

12. The method according to claim 1 or 2, carried out under an oxygen partial pressure of less than 10 hPa.

Images