Coupling of nucleophiles, vinyl compounds or CO with water,...

Details Coupling of nucleophiles, vinyl compounds or CO with water,... Coupling of nucleophiles, vinyl compounds or CO with water,...

2001-03-06

2003-04-15

Davis, Zinna Northington (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S136000

Reexamination Certificate

active

06548684

ABSTRACT:

The present invention relates to a process for the coupling of a) carbon monoxide together with water, ammonia, alcohols or primary or secondary amines or b) nucleophiles selected from the group of alcohols, thioles, amines, metallised hydrocarbons, CH-acidic compounds and metal cyanides, to organic compounds selected from the group of leaving-group-containing aromatics, hetero-aromatics with a C-bonded leaving group, aromatic or hetero-aromatic methyl compounds with a leaving group bonded to the methyl group, ethylenically unsaturated organic compounds with a C-bonded leaving group, or organic allyl compounds with a leaving group in allyl position, or c) vinyl compounds with leaving-group-containing aromatics, in the presence of Pd-phosphine complexes with ligands from the group of secondary aliphatic monophosphines as catalyst, and optionally in the presence of an inorganic base or organic nitrogen base; the use of Pd-phosphine complexes with secondary aliphatic monophosphines as catalysts for these coupling reactions; new Pd-phosphine complexes; and a composition comprising (a) a Pd(II) salt, a Pd(II) complex salt or a Pd(0) complex and (b) a secondary monophosphine.
It has been known for a long time that Pd-phosphine complexes catalyse the coupling of vinyl compounds, of carbon monoxide mixed with water, ammonia, alcohols or amines, or of nucleophiles, to aromatics, whilst cleaving a leaving group. An overview of this reaction is given in J. Tsuji, Palladium Reagents and Catalysts, John Wiley & Sons, 1996). The phosphine lidands used are primarily tertiary phosphines or ditertiary diphosphines, which are stable in the air and therefore easier to handle. The nucleophile-substituted aromatics are thereby obtainable in good yields and in reasonable reaction times, especially if tertiary phosphines with two to three sterically demanding alkyl groups are used as ligands (see for example A. F. Littke, G. C. Fu, Angew. Chem. Int. Ed. 1998, 37, 3387ff). The preparation of such tertiary phosphines is complex and expensive.
It has now surprisingly been found that for the coupling reaction the secondary monophosphines with sterically demanding aliphatic substituents, which are significantly simpler to produce and are partly available commercially, can be used as ligands for the Pd catalysts. Despite their lower basicity compared to tertiary monophosphines, the catalyst activity is only insignificantly affected and the desired nucleophile-substituted compounds are obtained in high yields.
A first object of the invention is a process for the coupling of
a) nucleophiles selected from the group of alcohols, thioles, amines, metallised hydrocarbons, CH-acidic compounds and metal cyanides, or of
b) carbon monoxide mixed with water, alcohols, ammonia, primary or secondary amines,
to organic compounds selected from the group of leaving-group-containing aromatics, hetero-aromatics with a C-bonded leaving group, aromatic or hetero-aromatic methyl compounds with a leaving group bonded to the methyl group, ethylenically unsaturated organic compounds with a C-bonded leaving group, or organic allyl compounds with a leaving group in allyl position, or
c) vinyl compounds with leaving-group-containing aromatics,
whilst cleaving the leaving group in the presence of Pd complexes with monophospholine ligands as the catalyst, whereby variants b) and c) are carried out in the presence of an inorganic base or organic nitrogen base, the process being characterised in that the Pd complex contains secondary monophosphines with aliphatic, branched or cyclic substituents as ligands.
The monophosphines used according to the invention may correspond, for example, to formula I,
HPR
1
R
2
  (I),
wherein R
1
and R
2
, independently of one another, signify &agr;-branched alkyl or cycloalkyl, or R
1
and R
2
, together with the P-atom, represent a P-heterocycloaliphatic radical with a total of 4 to 8 ring members. R
1
and R
2
may be substituted or unsubstituted.
R
1
and R
2
may be unsubstituted or substituted. Suitable substituents are, for example, —OH, —NH
2
, —NHC
1
-C
4
-Alkyl, —N(C
1
-C
4
-alkyl)
2
, —CN, —SO
3
H, —SO
3
M, —COOM, —COOH, —COOC
1
—C
4
-alkyl, C
5
-C
12
-cycloalkyl, C
5
-C
12
-heterocycloalkyl with 1 to 3 hetero atoms selected from the group O, S and N, C
1
-C
4
-alkoxy, C
6
-C
12
-aryl, C
4
-C
11
-heteroaryl with 1 to 3 hetero atoms selected from the group O, S and N, C
7
-C
12
-aralkyl, C
5
-C
12
-heteroaralkyl with 1 to 3 hetero atoms selected from the group O, S and N, C
7
-C
12
-aralkyl, C
5
-C
12
-heteroaralkyl with 1 to 3 hetero atoms selected from the group O, S and N, whereby M signifies Li, Na or K. Suitable substituents for the cyclic radicals are also C
1
-C
4
-alkyl. Cyclic substituents may be unsubstituted or substituted by halogen (preferably F, Cl or Br), C
1
-C
4
-alkyl C
1
-C
4
-alkoxy.
R
1
and R
2
as alkyl may contain for example 3 to 18, preferably 3 to 12, more preferably 3 to 8, and most preferably 3 to 6 carbon atoms. The cycloalkyl may contain for example 3 to 16, preferably 4 to 12, most preferably 5 to 10 ring carbon atoms. The P-heterocycloaliphatic radical preferably contains a total of 5 or 6 ring members.
The &agr;-branched alkyl in question may be alkyl groups whose &agr;-carbon atom is substituted by one to three alkyl radicals. The alkyl radicals preferably contain 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms and most preferably 1 or 2 carbon atoms. Examples of alkyl radicals are butyl, propyl and preferably ethyl or methyl. A few examples of branched alkyl are isopropyl, iso- and tert.-butyl, 2-methyl-but-2-yl, 2- or 3-pentyl, 2-methyl-hex-2-yl and 2-heptyl.
The cycloalkyl in question may be mono- or polycyclic ring systems. The polycyclic ring systems may consist of, for example, 2 to 4 condensed rings. Examples of cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, [2,2,2]-bicyclooctyl, [3,2,1]-bicyclooctyl, [3,2,2]-bicyclononyl, and adamantyl.
The P-heterocycloaliphatic radical in question is preferably radicals in which R
1
and R
2
in formula I together are tetra- or pentamethylene.
An especially preferred group of secondary monophosphines is the one in which R
1
and R
2
are selected from the group isopropyl, isobutyl, tert.-butyl, cyclopentyl, cyclohexyl, norbornyl and adamantyl.
Leaving groups are known and are described in literature. Examples of leaving groups are, in particular, halides such as chloride, bromide and iodide, as well as the group R—S(O
2
)—O—, wherein R is fluorine, alkyl, halogen-alkyl, phenyl, halogen-phenyl, mono-, di- or trimethylphenyl or mono-, di- or tri(halogenmethyl)phenyl. Examples are fluorosulfonyloxy, methylsulfonyloxy, trifluoromethylsulfonyloxy, nonaflate and tosylate. Other known leaving groups are phosphoric acid ester groups of the formula (RO)
2
P(O)O—. Preferred leaving groups are halides; chloride and bromide are especially preferred. The organic compound may contain one or more leaving groups, for example 1 to 4, preferably one or two leaving groups. At least 0.5 equivalents of nucleophiles are used per leaving group, for example 1 to 5 or 1 to 2 equivalents per leaving group.
The organic compounds with leaving groups that may be mentioned are first of all aromatics. They may also be hydrocarbon aromatics, which contain, for example, 6 to 18 carbon atoms, preferably 6 to 16 carbon atoms, most preferably 6 to 12 carbon atoms.
Examples of hydrocarbon aromatics are benzene, pentalene, indan, indene, indoline, naphthalene, acenaphthylene, anthracene, phenanthrene, fluorene, pyrene, chrysene, naphthacene, diphenyl, diphenylether, diphenylthioether, diphenylmethane and stilbene. Benzene, diphenyl and naphthalene are preferred.
The organic compounds with leaving groups that may be mentioned are also hetero-aromatics. The hetero-aromatics may contain, for example 3 to 16 carbon atoms, preferably 4 to 13 carbon atoms, most preferably 4 to 9 carbon atoms, and at least one hetero atom selected from the group O, S, N and

Affiliated with

Also associated with

Rating

Coupling of nucleophiles, vinyl compounds or CO with water,... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Coupling of nucleophiles, vinyl compounds or CO with water,..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Coupling of nucleophiles, vinyl compounds or CO with water,... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3048894