WO1999001418A1 - Method for aminating mononuclear aromatic compounds and polynuclear compounds containing at least one aromatic ring in the presence of an palladium complex catalyst - Google Patents
Method for aminating mononuclear aromatic compounds and polynuclear compounds containing at least one aromatic ring in the presence of an palladium complex catalyst Download PDFInfo
- Publication number
- WO1999001418A1 WO1999001418A1 PCT/EP1998/003943 EP9803943W WO9901418A1 WO 1999001418 A1 WO1999001418 A1 WO 1999001418A1 EP 9803943 W EP9803943 W EP 9803943W WO 9901418 A1 WO9901418 A1 WO 9901418A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- different
- alkyl
- alkenyl
- compounds
- terminal
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
- B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
- B01J2531/96—Water
Definitions
- the present invention relates to a process for the amination of mononuclear, aromatic compounds and multinuclear, at least one aromatic ring-containing compounds in the presence of palladium-containing complex catalysts.
- Transition metal-catalyzed nucleophilic substitutions on aromatics are of some importance in synthetic organic chemistry 15.
- Nickel and palladium-catalyzed C-C coupling reactions on aromatics in a homogeneous organic phase are known.
- Amination of aryl halides with tin amides or amines in the organic phase can be carried out in the presence of palladium complex catalysts.
- ligands of the palladium complex catalysts are tris (o-tolyl) phosphine or bis (diphenylphos-
- the object of the present invention was to provide a new process for the amination of mononuclear, aromatic compounds and noble, containing at least one aromatic ring-containing compounds, in which subsequently both the separation of the reaction product and the recovery of the complex catalyst from the reaction mixture can be done in a simple manner.
- This object is achieved by a process for the amination of mononuclear aromatic compounds and multinuclear compounds containing at least one aromatic ring by reacting mononuclear aromatic compounds and multinuclear compounds containing at least one aromatic ring with primary or secondary amine compounds in the presence of a base and one Palladium complex catalyst, characterized in that it is carried out in the presence of water and the palladium complex catalyst contains organic, water-soluble phosphine ligands in a molar excess, based on palladium.
- the mononuclear, aromatic compounds which can be used in the process according to the invention include aryl compounds of the formula I
- R are the same or different and C - Cg-alkyl, C2 - Cß-alkenyl or an optionally substituted
- X is preferably chlorine, bromine or iodine.
- R 1 , R, R, R and R 5 are preferably
- R, R, R, R and R substituted and can by the
- R are identical or different and represent C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl, phenyl or benzyl.
- pyridine compounds of the general formula III
- -COH, -OCR 10 , -COR, -CR 10 , -CN (R 1 ⁇ ) 2 or -CN means, where R are the same or different and C] - Cß-alkyl, C2 - C ⁇ -alkenyl or one optionally substituted phenyl radical.
- X is preferably chlorine, bromine or iodine.
- R, R, R and R 16 are preferably hydrogen,
- the phenyl ring is optionally substituted in the radicals R, R R, R, R and R and can be described by the formula IV,
- R, 19 J , R, 21 R 22 and R 23 are the same or different and are C - C4-alkyl, C2-C4-alkenyl, phenyl or benzyl.
- the new process can also be used in the amination of multinuclear compounds containing at least one aromatic ring.
- C6H4-P-CH3 means R 24 R 25 26, 27, 28, 29 and
- X is preferably chlorine, bromine or iodine.
- C3-C6 ⁇ alkynyl radical with a non-terminal C ⁇ C triple bond can in each case be straight-chain or branched, cyclic or acyclic.
- R 24 , R 25 , R 26 , R, R 28 , R 29 and R 30 are preferably hydrogen, 0 0
- the phenyl ring is optionally substituted in the radicals R, R, R 26 , R 27 , R 28 , R 29 , R 30 , R 31 and R 32 and can be described by the formula VI,
- R 33 , R 34 , R 35 , R 36 and R 37 are the same or different and represent Ci - C4 ⁇ alkyl, C2 - C4 alkenyl, phenyl or benzyl.
- Amine compounds of the formula VII can be used in the process according to the invention.
- R can be straight-chain or branched, cyclic or acylic. C 1 -C 6 -alkyl radicals are preferred.
- the phenyl ring in R and / or R can be substituted. In this case, it is described by the formula II listed above, the radicals R -, 12 in the phenyl ring of the formula II being preferred here for
- Methyl, phenyl or benzyl are available.
- R 41 -C-C ⁇ n-alkyl, C3-C ⁇ n-alkenyl with a non-terminal C C double bond, C3-C ⁇ n-alkynyl with a non-terminal C ⁇ C triple bond, oxygen or
- Phenyl ring, C ⁇ -C ⁇ n-alkyl, C3-C ⁇ n-alkenyl with non-terminal C C double bond, C3-C ⁇ n-alkynyl with non-terminal C ⁇ C triple bond, B (OR) 2 > Sn (R) 3 or Si (R) 3 represent, where R is the same or different and is -C-C4-alkyl, phenyl or benzyl.
- Ci-Cg-alkyl radicals are preferred.
- the phenyl ring in R 43 , R 44 , R 45 and / or R can be substituted. In this case it is described by Formula II-,
- radicals R -R in the phenyl ring of the formula TI h are preferably methyl, phenyl or benzyl.
- Palladium compounds which can be used are Pd acetate, Pd (dba) 2, PdCl2, PdBr2 Pdl2 or Pd (acac) 2, where (dba) is bis (dibenzylidene) acetone and (acac) is acetyl acetonate.
- organic water-soluble phosphine ligands of the palladium complex compounds are, for example, sulfonated triarylphosphines of the formula IX,
- Ar ⁇ _, Ar2 and Ar3 are the same or different and stand for a phenyl or naphthyl group
- Y] _, Y and Y3 are the same or different and for a straight-chain or branched Ci - C4-alkyl radical, a Ci - C4- Alkoxy radical, halogen, -CN, -NO2, -OH, -Ozucker, where the Sugar is a mono- or disaccharide, or -NR ° R 49 radical, in which R 48 and R49 are identical or different and represent a straight-chain or branched - C4-alkyl radical, M is hydrogen, ammonium or a quaternary ammonium ion , a monovalent metal or that
- the equivalent of a polyvalent metal is, m, 2 and ⁇ t3 are identical or different integers from 0 to 5 and n 1 n 2 unc n3 are identical or different integers from
- n ⁇ , n or n3 are 0 to 3, at least one number n ⁇ , n or n3 being equal to or greater than 1.
- a phosphine of the formula IX is preferably used in which Ari, Ar2 and Ar3 are phenyl groups, Y] _, Y2 and Y3 are hydrogen, a methyl, ethyl, methoxy or ethoxy radical or a chlorine atom, M is a cation the group of cations of sodium, potassium, calcium, barium or ammonium, is a tetramethylammonium, tetraethylammonium, tetrapropylammonium or tetrabutylammonium ion and mi, 1112 and 1T13 are identical or different integers from 0 to 3.
- Ar2 and Ar3 particularly preferably represent a phenyl group, mi, ⁇ ri2 and 1113 are equal to 0 and nj, n and n3 have the value 0 or 1, the sum of n + n2 + n3 having a value of 1 to 3 assumes and the S ⁇ 3M groups are in the m position.
- Tri (sulfophenyl) phosphine are particularly suitable for carrying out the process.
- Sulfonated diphosphines of the general formula X are also suitable as ligands,
- Ar ' is meta-CgH4S03M
- M is hydrogen, ammonium, a monovalent metal or the equivalent of a polyvalent metal
- Ph is a phenyl radical
- p is the same or different and is 0, 1 or 2
- r is the same or different and is 0 or 1.
- sulfonated diphosphines of the formula X is sulfonated 2, 2 '-bis (diphenylphosphino ethyl) - 1,1-binaphthaline ( "BINAS”) or sulfonated 2,2' - bis (diphenylphosphino) -1, 1-binaphthaline (“BINAP”).
- M is preferably a
- Sulfonated diphenylphosphinoferrocene can also be used as a ligand.
- phosphine ligands of the formulas IX and X in the catalyst system as uniform bindings to use.
- different stages of sulfonation of the phosphines and / or sulfonate mixtures with different cations M can be used.
- the formation of the palladium catalyst system containing phosphine ligands can either take place in a step preceding the amination or in situ during the amination.
- the catalyst system formation upstream of the amination is preferably already carried out in the reaction vessel or reactor in which the amination also subsequently takes place, but it can also take place in a separate reaction vessel.
- one of the aforementioned palladium compounds is combined with one or more of the aforementioned phosphines as complex ligands.
- the phosphine component is usually used in an aqueous solution.
- An organic solvent is also preferably added, which can then also be used as a solvent for the amination.
- the use of methanol has proven particularly useful here.
- the water-soluble palladium complex compounds which contain the organic water-soluble phosphine ligands are formed. Together with excess free phosphine, these palladium complex compounds form the catalyst system.
- the solution of the catalyst system can then be transferred to the amination reactor and, with the other starting materials, ie the mononuclear, aromatic compound or the multinuclear, at least one aromatic ring. holding compound and the primary or secondary amine are added.
- the components described above i.e. the palladium compound and the organic, water-soluble phosphine ligands are introduced into the amination reactor simultaneously with the starting materials.
- the molar ratio of phosphine complex ligand to palladium is (2-200): 1, preferably (3-200): 1. Based on the mononuclear, aromatic compound or the multinuclear, containing at least one aromatic ring compound, 0.001-25 mol%, preferably 0.01-20 mol% and in particular 0.1-5 mol%, of palladium is used.
- the palladium complex compounds can also contain other ligands, e.g. Halogens, preferably chlorine, bromine or iodine, -OAc, bis (dibenzylidene) acetone, acetylacetonate,
- Halogens preferably chlorine, bromine or iodine
- -OAc bis (dibenzylidene) acetone, acetylacetonate
- the amination of the mononuclear, aromatic compounds or the multinuclear, at least one aromatic ring-containing compounds with an amine compound is carried out in the presence of a base which is either in the form of an aqueous solution or in the solid state system can be added at a reaction temperature of 20-160 ° C, preferably 50-120 ° C within a reaction time of 10 min to 170 h, preferably 12-96 h.
- Suitable bases for the amination are, for example, alkali metal and alkaline earth metal hydroxides, methanolates, ethanolates, t-butylates, acetates, hydrogen carbonates and carbonates.
- alkali metal and alkaline earth metal hydroxides for example, alkali metal and alkaline earth metal hydroxides, methanolates, ethanolates, t-butylates, acetates, hydrogen carbonates and carbonates.
- organic solvent may also be present.
- organic solvents are methanol, ethanol, n- and i-propanol, n-, i- and t-butanol, tetrahydrofuran, di-n-butyl ether, 2-butanol, 2-butanone, dimethylformamide, dioxane, toluene, xylene , Ethylene glycol, diethyl ether, ethyl acetate, pentane, hexane, heptane, octane or mixtures of two or more of these solvents.
- Preferred mixtures of two organic solvents are those of a) methanol or ethanol and b) toluene, xylene, ethylene glycol, di-n-butyl ether, dioxane, pentane, hexane, heptane or octane.
- the reaction mixture in case A is separated by simple phase separation.
- case B a two-phase system is first produced by adding toluene, diethyl ether, ethyl acetate, di-n-butyl ether or dioxane.
- the catalyst system can be easily separated from the reaction products and unreacted starting materials in this way.
- the palladium-containing complex catalyst can be recovered from the aqueous phase or, in the case of a continuous reaction, recirculated into the reaction vessel.
- the aminated mononuclear aromatic compound or the aminated compound containing at least one aromatic ring is isolated from the organic phase.
- the new process opens up an elegant synthetic route to anthraquinone dyes, which are characterized by strong luminosity and lightfastness. According to case A, preference is given to working in an aqueous / organic two-phase system and in particular with a water / 2-butanol mixture. With the new process, doubly substituted 1, 5-dianilinoanthraquinones can also be obtained. It is known that ⁇ -chlo - or ⁇ -bromoanthraquinone with aniline in the presence of copper and copper acetate
- the organic phase is separated on silica gel 60 with hexane, hexane / ethyl acetate in a ratio of 10: 1 and hexane / ethyl acetate 4: 1.
- 270 mg (1.2 mmol) of l- (4-methylanilinophenyl) -l-ethanone (3) are obtained (yield 60% based on 4-bromoacetophenone).
- unreacted N-methylaniline (2) (108 mg; 1.0 mmol) can be recovered.
- NaTPPTS stands for trisodium 3, 3 ', 3 "-phosphanetriyl-tris (benzenesulfonate).
- the reaction mixture is then heated to boiling for t hours. After the solution has cooled, 5.0 ml of diethyl ether and 1.0 ml of water are added and the ether phase is separated off. The remaining catalyst solution is extracted again with 5.0 l of ether. The combined ether phases are with water washed and dried over magnesium sulfate. The crude product is cleaned cyclochromatographically using a chromatotron. 1- (4-Methylanilinophenyl) -1- ethanone is obtained in a yield of A%.
- Table 2 shows which halogenated anthraquinone and which amine was used and in what amount.
- the reaction time and reaction temperature are also given in Table 2. It is also shown whether the respective examples were carried out in accordance with general working instructions 2 or 3 and the reaction mixture was worked up in accordance with workup variant C or D.
- the cooled reaction mixture was extracted 5 times with 2 ml of toluene and the organic phase, after being evaporated to dryness, was completely dried on a rotary evaporator in an oil pump vacuum. After column chromatography on silica gel 60 using toluene as the eluent and concentration to dryness, a deep red color was obtained for 7 hours.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98939548A EP0998449A1 (en) | 1997-07-04 | 1998-06-27 | Method for aminating mononuclear aromatic compounds and polynuclear compounds containing at least one aromatic ring in the presence of an palladium complex catalyst |
JP50629699A JP2002508777A (en) | 1997-07-04 | 1998-06-27 | Method for aminating mononuclear aromatic compounds and polynuclear compounds having at least one aromatic ring in the presence of a palladium complex salt catalyst |
CA002294733A CA2294733A1 (en) | 1997-07-04 | 1998-06-27 | Method for aminating mononuclear aromatic compounds and polynuclear compounds containing at least one aromatic ring in the presence of an palladium complex catalyst |
KR1020007000019A KR20010021497A (en) | 1997-07-04 | 1998-06-27 | Method for aminating mononuclear aromatic compounds and polynuclear compounds containing at least one aromatic ring in the presence of a palladium complex catalyst |
BR9810669-4A BR9810669A (en) | 1997-07-04 | 1998-06-27 | Process for the amination of aromatic, mononuclear and polynuclear compounds, containing at least one aromatic ring in the presence of a palladium complex catalyst |
AU88019/98A AU8801998A (en) | 1997-07-04 | 1998-06-27 | Method for aminating mononuclear aromatic compounds and polynuclear compounds containing at least one aromatic ring in the presence of an palladium complex catalyst |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19728760A DE19728760C1 (en) | 1997-07-04 | 1997-07-04 | Amination or aryl compounds |
DE19728760.3 | 1997-07-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999001418A1 true WO1999001418A1 (en) | 1999-01-14 |
Family
ID=7834748
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/003943 WO1999001418A1 (en) | 1997-07-04 | 1998-06-27 | Method for aminating mononuclear aromatic compounds and polynuclear compounds containing at least one aromatic ring in the presence of an palladium complex catalyst |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0998449A1 (en) |
JP (1) | JP2002508777A (en) |
KR (1) | KR20010021497A (en) |
AU (1) | AU8801998A (en) |
BR (1) | BR9810669A (en) |
CA (1) | CA2294733A1 (en) |
DE (1) | DE19728760C1 (en) |
ID (1) | ID20521A (en) |
TW (1) | TW381070B (en) |
WO (1) | WO1999001418A1 (en) |
ZA (1) | ZA985826B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6235937B1 (en) | 1999-09-06 | 2001-05-22 | Bayer Aktiengesellschaft | Process for the preparation of nitrodiphenylamines |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69904448T2 (en) * | 1998-02-26 | 2003-10-23 | Massachusetts Inst Technology | METAL-CATALYZED ARYLATIONS AND VINYLATIONS OF HYDRAZINES, HYDRAZONES, HYDROXYLAMINES AND OXIMES |
-
1997
- 1997-07-04 DE DE19728760A patent/DE19728760C1/en not_active Expired - Fee Related
-
1998
- 1998-06-25 ID IDP980916A patent/ID20521A/en unknown
- 1998-06-27 BR BR9810669-4A patent/BR9810669A/en not_active Application Discontinuation
- 1998-06-27 KR KR1020007000019A patent/KR20010021497A/en not_active Application Discontinuation
- 1998-06-27 AU AU88019/98A patent/AU8801998A/en not_active Abandoned
- 1998-06-27 JP JP50629699A patent/JP2002508777A/en active Pending
- 1998-06-27 EP EP98939548A patent/EP0998449A1/en not_active Withdrawn
- 1998-06-27 WO PCT/EP1998/003943 patent/WO1999001418A1/en not_active Application Discontinuation
- 1998-06-27 CA CA002294733A patent/CA2294733A1/en not_active Abandoned
- 1998-07-02 TW TW087110689A patent/TW381070B/en not_active IP Right Cessation
- 1998-07-02 ZA ZA985826A patent/ZA985826B/en unknown
Non-Patent Citations (3)
Title |
---|
CHRISTIAN AMATORE ET AL: "New Synthetic Applications of Water-Soluble Acetate Pd/TPPTS Catalyst Generated in Situ. Evidence for a True Pd(0) Species Intermediate", JOURNAL OF ORGANIC CHEMISTRY, vol. 60, no. 21, 20 October 1995 (1995-10-20), EASTON US, pages 6829 - 6839, XP002082635 * |
GENET J P ET AL: "PALLADIUM-CATALYZED CROSS-COUPLING REACTIONS IN A HOMOGENEOUS AQUEOUS MEDIUM", SYNLETT, no. 9, 1 September 1992 (1992-09-01), pages 715 - 717, XP000561946 * |
JOHN P. WOLFE ET AL.: "An Improved Catalyst System for Aromatic Carbon-Nitrogen Bond Formation: The Possible Involvement of Bis(Phosphine) Palladium Complexes as Key Intermediates", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY., vol. 118, no. 30, 31 July 1996 (1996-07-31), DC US, pages 7215 - 7216, XP002082634 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6235937B1 (en) | 1999-09-06 | 2001-05-22 | Bayer Aktiengesellschaft | Process for the preparation of nitrodiphenylamines |
Also Published As
Publication number | Publication date |
---|---|
BR9810669A (en) | 2000-09-26 |
TW381070B (en) | 2000-02-01 |
EP0998449A1 (en) | 2000-05-10 |
KR20010021497A (en) | 2001-03-15 |
ID20521A (en) | 1999-01-07 |
ZA985826B (en) | 1999-01-25 |
AU8801998A (en) | 1999-01-25 |
DE19728760C1 (en) | 1998-10-29 |
JP2002508777A (en) | 2002-03-19 |
CA2294733A1 (en) | 1999-01-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0158875B1 (en) | Chiral-rhodium-diphosphine complexes for asymetric hydrogenations | |
EP0496306B1 (en) | Process for the preparation of 3-amino-9,13b-dihydro-1H-dibenz-[c,f]imidazo[1,5-a]azepine hydrochloride | |
EP0582692A1 (en) | Diphosphine ligands | |
DE19503119A1 (en) | Process for the production of aromatic olefins under the catalysis of palladacycles | |
EP1127874A2 (en) | Process for the preparation of substituted indoles | |
EP1899289B1 (en) | Method for producing aryl amines, aryl ethers and aryl thioethers | |
DE102007022389A1 (en) | Ruthenium complexes with (P-P) -coordinated ferrocenyl-diphosphine ligands, processes for their preparation and their use in homogeneous catalysis | |
DE60102587T2 (en) | CHIRAL LIGANDS FOR ASYMMETRIC CATALYSTS | |
EP0998449A1 (en) | Method for aminating mononuclear aromatic compounds and polynuclear compounds containing at least one aromatic ring in the presence of an palladium complex catalyst | |
EP1186609B1 (en) | Diphosphines | |
DE69931186T2 (en) | Preparation of water-soluble sulfated organophosphorus compounds | |
DE2106768B2 (en) | Complex compounds of organosodium compounds and chelate-forming polyamines, processes for their preparation and their use as telomerization catalysts and for the purification of organosodium compounds | |
EP0114359B1 (en) | Process for preparing perfluoroalkyl-substituted carbocyclic or heterocyclic compounds | |
DE60105506T2 (en) | SYNTHESIS OF N4, N4'-DIPEHNYL-N4, N4'-DI-M-TOLYL-BIPHENYL-4,4'-DIAMINE LEADING FROM A UNSYMMETRIC AMINE | |
WO1998028315A1 (en) | Phosphanes, their method of production and use in metal complexes | |
EP0818436A1 (en) | Process for the preparation of 4-hydroxyanilines | |
EP1775276A1 (en) | Process for the coupling of benzylamines and halogenated aromates | |
DE2943192A1 (en) | METHOD FOR PRODUCING INDOLINE DERIVATIVES | |
EP1161437A1 (en) | Phosphabenzene compounds and their use as ligands for hydroformylation catalysts | |
WO1999010356A1 (en) | Method for producing ruthenium complexes | |
EP1558621A2 (en) | Method for the production of compounds containing palladium (0) | |
EP0923517B1 (en) | Process for telomerizing dienes | |
WO2023198596A1 (en) | Organometallic compounds, production and use thereof | |
DE69924702T2 (en) | DIFLUOROMETHOXYBENZOLE DERIVATIVES AND THEIR USE AS INTERMEDIATE PRODUCTS | |
DE4321512C2 (en) | Process for the preparation of sulfonated arylphosphines |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU BR CA CN JP KR MX PL RO US VN |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 88019/98 Country of ref document: AU |
|
ENP | Entry into the national phase |
Ref document number: 2294733 Country of ref document: CA Ref country code: CA Ref document number: 2294733 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020007000019 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2000/000232 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1998939548 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09462290 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 1998939548 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020007000019 Country of ref document: KR |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1998939548 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1020007000019 Country of ref document: KR |