| Preparation of mono-n-sulphonylated diamines -> Monitor Keywords |
|
|
  Preparation of mono-n-sulphonylated diaminesUSPTO Application #: 20070259776Title: Preparation of mono-n-sulphonylated diamines Abstract: The present invention relates to a process for preparing mono-N-sulphonylated diamines by reacting diamines with sulphonyl halides in the presence of water, base and organic solvents. (end of abstract) Agent: Lanxess Corporation - Pittsburgh, PA, US Inventors: Boris Elmar Bosch, Frank Gerhartz USPTO Applicaton #: 20070259776 - Class: 502167000 (USPTO) Related Patent Categories: Catalyst, Solid Sorbent, Or Support Therefor: Product Or Process Of Making, Catalyst Or Precursor Therefor, Organic Compound Containing, Organic Phosphorus Or Nitrogen, Except The Ammonium Ion, Organic Nitrogen Containing The Patent Description & Claims data below is from USPTO Patent Application 20070259776. Brief Patent Description - Full Patent Description - Patent Application Claims
[0001] This application is a divisional of U.S. patent application Ser. No. 10/463,799 filed Jun. 17, 2003, entitled Preparation of Mono-N-Sulphonylated Diamines, the contents of which are hereby incorporated by reference in their entirety. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The present invention relates to a process for preparing mono-N-sulphonylated diamines by reacting diamines with sulphonyl halides in the presence of water, base and organic solvents. [0004] 2. Brief Description of the Prior Art [0005] Mono-N-sulphonylated diamines, especially in optically active forms, have gained high industrial significance, for example, as ligands in catalysis (see, for example, Noyori et al. J. Amer. Chem. Soc. 1995, 117, 7562). [0006] The preparation of mono-N-sulphonylated diamines is known in principle. For example, R. A. Sheldon et al., Eur. J. Org. Chem. 1999, 2315 describe their preparation from diamines using sulphonyl halides in the presence of triethylamine. [0007] However, a disadvantage of this process is that mixtures of unsulphonated, mono-N-sulphonated and di-N-sulphonated products are formed which have to be subjected to a complicated chromatographic separation (see also EP-A 1 174 426). In the existing processes, the selectivities range from 30 to 85%, based on the desired mono-N-substituted diamine, which is unsatisfactory for industrial implementation. [0008] There was therefore a need to provide a process which enabled the preparation of mono-N-sulphonated diamines in an efficient manner with good selectivities. SUMMARY OF THE INVENTION [0009] A process has now been found for preparing compounds of the formula (I), where [0010] R.sup.1 and R.sup.2 are each independently C.sub.1-C.sub.20-alkyl, C.sub.4-C.sub.15-aryl or C.sub.5-C.sub.16-arylalkyl, or R.sup.1 and R.sup.2 together are a straight-chain or branched C.sub.3-C.sub.12-alkylene radical and [0011] R.sup.3 is C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.20-fluoroalkyl or C.sub.4-C.sub.5-aryl, which is characterized in that diamines of the formula (II) where [0012] R.sup.1, R.sup.2 and R.sup.3 are as defined under formula (I) are reacted [0013] in the presence of water and [0014] in the presence of organic solvents and [0015] in the presence of a base [0016] with sulphonyl halides of the formula (III) R.sup.3SO.sub.2X (III) where [0017] X is fluorine, chlorine, bromine or iodine and [0018] R.sup.3 is as defined under formula (I). DETAILED DESCRIPTION OF THE INVENTION [0019] For the purposes of the invention, the radical definitions and illustrations listed in general or within areas of preference, i.e. the particular areas and areas of preference, may be combined as desired. [0020] The compounds of the formula (I) and optionally the compounds of the formulae (II) and/or (III) are chiral. The invention explicitly encompasses both the pure stereoisomers (enantiomers and diastereomers) and any desired mixtures, for example racemates. [0021] Preferably, R.sup.1 and R.sup.2 are identical and are each phenyl or are together straight-chain C.sub.3-C.sub.8-alkylene, for example 1,3-propylene or 1,4-butylene, and R.sup.1 and R.sup.2 are more preferably identical and are each phenyl. [0022] R.sup.3 is preferably C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-fluoroalkyl, phenyl or naphthyl, each of which may be further substituted by no, one, two, three, four or five radicals which are selected from the group of C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-fluoroalkyl, fluorine and chlorine. [0023] R.sup.3 is more preferably methyl, trifluoromethyl, pentafluoroethyl, nonafluorobutyl, phenyl, p-tolyl, p-ethylphenyl, p-anisyl, p-ethoxyphenyl, p-chlorophenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, p-fluorophenyl, pentafluorophenyl and naphthyl. [0024] R.sup.3 is even more preferably p-tolyl, phenyl and naphthyl, and greatest preference is given to p-tolyl. [0025] X is preferably fluorine or chlorine, more preferably chlorine. [0026] Preference is given to using chiral compounds of the formula (II) which have an optical purity of 80% ee or more, more preferably a 90% ee or more and even more preferably a 98.5% ee or more. [0027] The optical purity is defined as: ee [S]=(m[S]-m[R])/m(S+R) where [0028] ee (S) is the optical purity of the enantiomer S, m(S) is the amount of the enantiomer S and m(R) is the amount of the enantiomer R. The enantiomeric excess is typically quoted in percent (% ee=ee/100). [0029] The process according to the invention is especially suitable for the preparation of the following compounds of the formula (II): [0030] N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-p-tolylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-o-tolylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-m-tolylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2- diphenylethyl]-phenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-4-ethylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-3-ethylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-2-ethylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-2,4,6-trimethylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-2,4,6-triisopropylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-4-chlorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-3-chlorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-2-chlorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-4-fluorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-3-fluorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-2-fluorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-4-methoxyphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-3-methoxyphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-2-methoxyphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-1-naphthylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-2-naphthylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-pentafluorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-methanesulphonamide, N-[(1R,2R) and (1S,2S)-2-amino-1,2-diphenylethyl]-trifluoromethanesulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-p-tolylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-o-tolylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-m-tolylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-phenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-4-ethylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-3-ethylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-2-ethylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-2,4,6-trimethylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-2,4,6-triisopropylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-4-chlorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-3-chlorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-2-chlorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-4-fluorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-3-fluorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-2-fluorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-4-methoxyphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-3-methoxyphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-2-methoxyphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-1-naphthylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-2-naphthylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-pentafluorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-methanesulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclohexyl]-trifluoromethanesulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-p-tolylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-o-tolylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-m-tolylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-phenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-4-ethylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-3-ethylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-2-ethylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-2,4,6-trimethylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-2,4,6-triisopropylphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-4-chlorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-3-chlorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-2-chlorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-4-fluorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-3-fluorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-2-fluorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-4-methoxyphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-3-methoxyphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-2-methoxyphenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-1-naphthylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-2-naphthylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-pentafluorophenylsulphonamide, N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-methanesulphonamide and N-[(1R,2R) and (1S,2S)-2-aminocyclopentyl]-trifluoromethanesulphonamide or mixtures of the particular enantiomers, in particular the racemates. [0031] The process according to the invention is carried out in the presence of water, base and organic solvent. Examples of suitable organic solvents are: [0032] amides, e.g. dimethylformamide, N-methylpyrrolidinone, optionally halogenated aliphatic or aromatic solvents having up to 16 carbon atoms, e.g. toluene, o-, m-, p-xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobenzene, the isomeric dichlorobenzenes, fluorobenzene, nitriles, e.g. acetonitrile and benzonitrile, sulphoxides such as dimethyl sulphoxide or mixtures thereof. [0033] Advantageously, the organic solvents are selected in such a way that the reaction mixture forms two liquid phases. Particularly suitable solvents for this purpose are optionally halogenated aliphatic or aromatic solvents having up to 16 carbon atoms, and preference is given to carbon tetrachloride, chloroform, dichloromethane and chlorobenzene, even greater preference to dichloromethane. [0034] The volume ratio of water to organic solvents can be, for example, 20:1 to 1:20, preferably a ratio of 10:1 to 1:10 and more preferably a ratio of 5:1 to 1:5. Continue reading... Full patent description for Preparation of mono-n-sulphonylated diamines Brief Patent Description - Full Patent Description - Patent Application Claims Click on the above for other options relating to this Preparation of mono-n-sulphonylated diamines patent application. ###  How KEYWORD MONITOR works... a FREE service from FreshPatents1. Sign up (takes 30 seconds). 2. Fill in the keywords to be monitored. 3. Each week you receive an email with patent applications related to your keywords. Start now! - Receive info on patent apps like Preparation of mono-n-sulphonylated diamines or other areas of interest. ### Previous Patent Application: Synthesis of poly (ethylene amine) on an oxide support Next Patent Application: Method for preparing solid catalysts for ethylene polymerization and copolymerization Industry Class: Catalyst, solid sorbent, or support therefor: product or process of making ### FreshPatents.com Support Thank you for viewing the Preparation of mono-n-sulphonylated diamines patent info. IP-related news and info Results in 1.67308 seconds Other interesting Feshpatents.com categories: Medical: Surgery , Surgery(2) , Surgery(3) , Drug , Drug(2) , Prosthesis , Dentistry |
||
