WO1999065862A1 - Verfahren zur katalytischen, symmetrischen disubstitution von carbonsäureamiden mit grignard-reagenzien - Google Patents
Verfahren zur katalytischen, symmetrischen disubstitution von carbonsäureamiden mit grignard-reagenzien Download PDFInfo
- Publication number
- WO1999065862A1 WO1999065862A1 PCT/EP1999/004254 EP9904254W WO9965862A1 WO 1999065862 A1 WO1999065862 A1 WO 1999065862A1 EP 9904254 W EP9904254 W EP 9904254W WO 9965862 A1 WO9965862 A1 WO 9965862A1
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- WIPO (PCT)
- Prior art keywords
- atoms
- general formula
- group
- alcoholate
- radical
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/66—Preparation of compounds containing amino groups bound to a carbon skeleton from or via metallo-organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0214—Aryloxylates, e.g. phenolates
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the 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
- 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
Definitions
- the present invention relates to a method for disubstituting carboxamides with Grignard reagents in the presence of
- Organometallic compounds as a catalyst and another organometallic compound as a cocatalyst Organometallic compounds as a catalyst and another organometallic compound as a cocatalyst.
- the invention therefore relates to a process for the preparation of compounds of the general formula (I)
- H, A, Ar, -Si (R 6 ) 3 , -Sn (R 6 ) 3 , -SR 7 , -OR 7 , -NR 8 R 9 or R 1 and R 2 or R 1 and R 3 or R 8 and R 9 can be connected to one another and together form a cyclic ring with 3 to 8 carbon atoms, which may be in addition to nitrogen contains at least one further heteroatom selected from the group -S-, -O- and -NR 6 -,
- R 4 A Ar, -Si (R 6 ) 3 , -Sn (R 6 ) 3 , -SR 7 , -OR 7 , -NR 8 R 9 , wherein R 8 and
- R 9 have the given meanings or R 8 and R 9 are connected to one another and together form a cyclic ring with 3 to 8 C atoms, which optionally also has, in addition to a nitrogen atom, at least one hetero atom selected from the group -S-, -O- and -NR 6 - contains; or where two R 4 radicals are connected to one another and together form a cyclic ring with 3 to 8 C atoms, which optionally contains, in addition to a nitrogen atom, at least one hetero atom selected from the group -S-, -O- and -NR 6 -, with the proviso that R 4 has a maximum of one hydrogen atom in the ⁇ position.
- R 6 , R 7 , R 8 and R 9 independently of one another A or Ar
- A is a straight-chain or branched alkyl radical with 1 to 10 C-
- Atoms straight-chain or branched alkenyl radical with 2 to 10 C atoms, or straight-chain or branched alkynyl radical with 2-10 C atoms or substituted or unsubstituted cycloalkyl radical with 3 - 8 C atoms, mono- or polyunsaturated cycloalkyl radical with 3 - 8 C -Atoms and
- Ar is a substituted or unsubstituted aryl radical with 6-20 C
- Atoms mean, characterized in that a compound of general formula (II)
- R, R and R have the meanings given for formula (I), by reaction with a nucleophilic reagent of the general form (purple) or a nucleophilic reagent of the general formula (IIIb)
- R 4 has the meaning given for formula (I), and
- the process is carried out in the presence of catalytic amounts of a metal alcoholate of the general formula (IV):
- Metal alcoholates in which R is isopropyl are preferably used.
- Ti (OiPr) 4 is particularly preferably used as the metal alcoholate, iPr corresponding to an isopropyl radical.
- the invention also relates to a corresponding process which is carried out in the presence of a cocatalyst.
- the present invention therefore also includes a process in which metal isopropylates and alkylsilyl halides are used as cocatalysts; namely metal isopropylates of the general formula (V) and alkylsilyl halides of the general formula (VI)
- M 'AI Ca, Na, K, Si or Mg, preferably Mg or Na
- s is an integer from 1 to 4 and the oxidation state of the metal
- a metal alcoholate selected from the group titanium alcoholate, zirconium alcoholate and hafnium alcoholate
- a ') magnesium shavings a carboxamide of the general formula (II), 1-15 mol% of a metal alcoholate selected from the group consisting of titanium alcoholate,
- Zirconium alcoholate and hafnium alcoholate based on the carboxamide at room temperature under an inert gas atmosphere in a solvent selected from the group consisting of toluene, THF, n-hexane, benzene and diethyl ether,
- carboxamides of the general formula (II) can be reacted with good yields in the process described here, in which R 1 , R 2 and R 3 can independently assume the following meanings:
- Aralkenyl or aralkynyl where in each case the aryl, alkenyl and alkynyl group can assume the given meanings, such as in phenylethynyl.
- R 1 and R 2 or R 1 and R 3 together form a cyclic ring with 3-8 C atoms which, in addition to nitrogen, contains further heteroatoms, such as -S-, -O- or -NR 6 - contains.
- Particularly preferred here are compounds in which a simple cyclic ring is formed by R 1 and R 2 or R 1 and R 3 , which includes the nitrogen of the carboxamide or in which R 1 and R 2 or R 1 and R 3 form a cyclic ring form, which contains an oxygen atom as another heteroatom.
- Grignard or lithium organic compounds of the general formulas (purple) or (IIIb) can be used as the nucleophilic reagent, in which the rest,
- R 4 preferably represents an alkyl radical having 1 to 10 carbon atoms, such as methyl, ethyl, n- or i-propyl, n-, sec- or t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like suitable isomers, or cycloalkyl having 3-8 C atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or corresponding methyl- or ethyl-substituted cycloalkyl groups or mono- or polyunsaturated cycloalkyl groups, such as cyclopentenyl or cyclopentadienyl or branched or unbranched alkenyl with 2 to 10 C atoms, such as allyl, vinyl, isopropenyl, prop
- aryl radicals with 6 to 20 carbon atoms optionally unsubstituted or mono- or polysubstituted, such as phenyl, naphthyl, anthryl, phenanthryl, monosubstituted or polysubstituted by substituents selected from the group NO 2 , F, Cl, Br, NH 2 , NHA, NA 2 , OH and OA, where A can have the meanings given above, can be single, multiple or fully halogenated, preferably fluorinated, or
- aralkyl radicals with 7 to 20 carbon atoms such as benzyl, optionally substituted one or more times by substituents, selected from the
- Group NO 2 , F, Cl, Br, NH 2 , NHA, NA 2 OH and OA where A can have the meanings given above, can be single, multiple or fully halogenated, preferably fluorinated
- radical R 4 in the general formula (purple) for, -Si (R 6 ) 3 , - Sn (R 6 ) 3 , -SR 7 , -OR 7 , -NR 8 R 9 , where R 6 , R 7 , R 8 and R 9 can independently assume the meanings given above, or R 8 and R 9 are bonded to one another and together form a cyclic ring with 3 to 8 C atoms, which, if appropriate, in addition to one
- Nitrogen atom can also contain at least one heteroatom selected from the group -S-, -O- and -NR 6 -;
- R 4 radicals in the general formula (IIIb) can represent an alkyl having _ 2-7 C atoms, so that the reaction according to the invention produces a compound of the general formula (I) in which two R 4 radicals are cyclic Form a ring with 3 to 8 atoms.
- R 4 particularly preferably has the meaning of an alkyl radical, such as, for example, methyl, ethyl, n- or i-propyl, n-, sec- or t-butyl, pentyl, hexyl, a '5 or cycloalkyl radical, such as, for example, cyclopropyl, cyclobutyl or cyclopentyl , Cyclohexyl, or an aryl group such as phenyl, or an aralkyl group such as Benzyi.
- an alkyl radical such as, for example, methyl, ethyl, n- or i-propyl, n-, sec- or t-butyl, pentyl, hexyl, a '5 or cycloalkyl radical, such as, for example, cyclopropyl, cyclobutyl or cyclopentyl , Cyclohexyl, or an ary
- the radical Z in the general formulas (purple) or (IIIb) preferably represents 0 for a MgX radical with X for Cl or Br or the Z radical for lithium.
- Grignard compounds such as: methylmagnesium bromide, ethylmagnesium bromide, n- or i-propylmagnesium bromide, i-, sec- or tert-butylmagnesium bromide, n-hexyimagnesium bromide, cyclohexylmagnesium chloride, 5 allylmagnesiumbromidomomidomomidomomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomagnomidomomidomomium
- the present invention thus also relates to the compounds of the general composition prepared by the process according to the invention Formula (I) in which the radicals R 1 to R 4 have the meanings given above.
- Metal isopropylates and alkylsilyl halides are suitable as cocatalysts in this reaction.
- these metal isopropylates of the general formula (V) and alkylsilyl halides of the general formula (VI) are suitable as cocatalysts in this reaction.
- Metal isopropylates are preferably used, in which s is an integer from 1 to 4 and the oxidation state of the metal and M 'is AI, Ca, Na, K, Si or Mg. Mg or Na are particularly preferred.
- Alkylsilyl halides in which R is alkyl are preferably used
- R is alkyl with 1 to 3 C atoms and X is chlorine are particularly preferred.
- silicon compounds are suitable as cocatalysts:
- metal alcoholate selected from the group consisting of titanium alcoholate, zirconium alcoholate and hafnium alcoholate
- titanium alcoholate selected from the group consisting of titanium alcoholate, zirconium alcoholate and hafnium alcoholate
- titanium alcoholate zirconium alcoholate and hafnium alcoholate
- titanium tetraisopropylate is preferably used.
- the metal alcoholate preferably titanium tetraisopropylate, is used as a solution in a suitable, predried solvent.
- Suitable solvents are e.g. aliphatic or aromatic hydrocarbons or ethers.
- Solvents selected from the group consisting of toluene, THF, n-hexane, benzene and diethyl ether are preferably used, which are dried before the reaction by methods known to the person skilled in the art. Drying can be done using magnesium sulfate, calcium chloride, sodium, potassium hydroxide or other methods.
- a preferred embodiment of the process according to the invention is that the titanium tetraisopropoxide used as catalyst in an amount of 1 to 15, preferably 1, 5 to 14, in particular 2 to 10, and very particularly preferably 3 to 6 mol%, based on one mol of the amide used as starting material is presented in the form of a solution which is adjusted to a temperature of 10 to 30 ° C., preferably to 15-25 ° C., particularly preferably to a temperature of about 20 ° C.
- the starting material is slowly added dropwise either as such in liquid form or dissolved in a solvent selected from the group consisting of toluene, THF, n-hexane, benzene and diethyl ether with stirring. Then one of the amount of cocatalyst to be reacted, if necessary also in a solvent, is added dropwise.
- the reaction mixture obtained is for short Time, ie stirred for a few minutes at a constant temperature.
- nucleophilic reagent of the general formula (purple) or (IIIb), in particular a Grignard reagent is then slowly added in excess to the reaction mixture thus obtained that a substitution of the geminal carbonyl carbon atom by two of the same
- nucleophilic reagent i. H. the Grignard reagent or the lithium compound
- the nucleophilic reagent used preferably a Grignard reagent, is added in an amount of 2.1 to 3 moles per mole of reactant reactant.
- the Grignard reagent is preferably added in an amount of 2.2 to 2.6 mol based on 1 mol of starting material. If a nucleophilic reagent or Grignard reagent of the general formula (IIIb) is used, it is added to the reaction solution in equimolar amounts based on the starting material, corresponding to twice the number of reactive groups.
- the reaction mixture is stirred for a while at a constant temperature until the reaction is complete.
- the Grignard reagent is prepared in situ by reacting magnesium with a compound of the general formula (purple ') or (IIIb'), in which R 4 and X have the meanings given above.
- the amount of Grignard compounds is preferably in situ Magnesium 2 to 5 times the molar amount, preferably 2.8 to 3.2 times the molar amount, based on the compounds of the general formula (II) used as starting material and the amount of the compound of the general formula (purple ') or (IIIb ') 2 to 3.8 times the molar amount, preferably 2.2 to 2.6 times the molar amount, based on the compound of the general formals (II).
- the reaction temperature can be adjusted to about 80 ° C., preferably 60 to 70 ° C., in particular 65 ° C., after the addition of the nucleophilic reagent has been completed and thorough mixing has taken place.
- a catalyst system consisting of a metal alcoholate, selected from the group consisting of titanium alcoholate, zirconium alcoholate and hafnium alcoholate, as a catalyst and a compound of the general formulas (V), (VI) or (VII) with the meanings given above is also an object of the present invention .
- This catalyst system in the preparation of the symmetrically substituted compounds of the general formula (I).
- reaction mixture can be worked up in a manner known to the person skilled in the art.
- the products can be used as salts with the help of hydrochloric acid solutions such.
- hydrochloric acid solutions such.
- a suitable amount of saturated ammonium chloride solution and water can be added and stirring is continued intensively for several hours (1-3 hours).
- the resulting precipitate is separated off and washed with a little ether, preferably diethyl ether.
- the filtrate becomes basic by adding a suitable alkali such as a NaOH, KOH, sodium or potassium carbonate solution, preferably sodium hydroxide solution
- phase > 10
- the phases that form are then separated and the aqueous phase is extracted several times (e.g. three times with 30 ml each in the above special case) with diethyl ether.
- the combined organic phases are washed with (e.g. 15 ml) saturated sodium chloride solution and can be dried over potassium carbonate, magnesium sulfate or sodium sulfate and filtered.
- the products can be purified in various ways by methods known to those skilled in the art, e.g. in the following way:
- the Grignard reagents can also be replaced by the corresponding lithium compounds.
- the corresponding lithium compounds like the Grignard compounds, can be prepared according to methods generally known to those skilled in the art and can be reacted according to the invention in the same manner as described above.
- the compounds of general formula (I) prepared according to the invention can, for. B. as intermediates for the production of sulfur- or selenium-containing amines for the chiral catalysis of diethylzinc syntheses (literature: Werth, Thomas; Tetrahedron lett. 36; 1995, 7849 - 7852, Werth, Thomas et all. Heir. Chim. Acta 79, 1996, 1957-1966) can be used.
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99932702A EP1087933A1 (de) | 1998-06-18 | 1999-06-18 | Verfahren zur katalytischen, symmetrischen disubstitution von carbonsäureamiden mit grignard-reagenzien |
US09/719,815 US6515180B1 (en) | 1998-06-18 | 1999-06-18 | Method for the catalytic, symmetric disubstitution of carboxylic acid amides with grignard reagents |
KR1020007014292A KR20010052927A (ko) | 1998-06-18 | 1999-06-18 | 그리냐르 시약에 의한 카복실산 아미드의 촉매적 대칭이치환 방법 |
JP2000554689A JP2002518365A (ja) | 1998-06-18 | 1999-06-18 | グリニャール試薬を用いたカルボキサミドの触媒性対称二置換法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19827161.1 | 1998-06-18 | ||
DE19827161A DE19827161A1 (de) | 1998-06-18 | 1998-06-18 | Verfahren zur katalytischen, symmetrischen Disubstitution von Carbonsäureamiden mit Grignardreagenzien |
Publications (1)
Publication Number | Publication Date |
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WO1999065862A1 true WO1999065862A1 (de) | 1999-12-23 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/004254 WO1999065862A1 (de) | 1998-06-18 | 1999-06-18 | Verfahren zur katalytischen, symmetrischen disubstitution von carbonsäureamiden mit grignard-reagenzien |
Country Status (6)
Country | Link |
---|---|
US (1) | US6515180B1 (de) |
EP (1) | EP1087933A1 (de) |
JP (1) | JP2002518365A (de) |
KR (1) | KR20010052927A (de) |
DE (1) | DE19827161A1 (de) |
WO (1) | WO1999065862A1 (de) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US20070087977A1 (en) * | 2004-11-16 | 2007-04-19 | Wendye Robbins | Methods and compositions for treating pain |
US20060111308A1 (en) * | 2004-11-16 | 2006-05-25 | Wendye Robbins | Methods and compositions for therapeutic treatment |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB921943A (en) * | 1959-11-25 | 1963-03-27 | Lilly Co Eli | Anti-hypertensive compositions |
US4020059A (en) * | 1975-06-02 | 1977-04-26 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Process for preparing tertiary amines |
DE2725245A1 (de) * | 1976-06-03 | 1977-12-15 | Labaz | Methylaminderivate, verfahren zu deren herstellung und diese enthaltende pharmazeutische oder veterinaermedizinische zusammensetzungen |
DE2657476A1 (de) * | 1976-12-18 | 1978-06-22 | Basf Ag | Morpholinderivate |
-
1998
- 1998-06-18 DE DE19827161A patent/DE19827161A1/de not_active Withdrawn
-
1999
- 1999-06-18 US US09/719,815 patent/US6515180B1/en not_active Expired - Fee Related
- 1999-06-18 KR KR1020007014292A patent/KR20010052927A/ko not_active Application Discontinuation
- 1999-06-18 EP EP99932702A patent/EP1087933A1/de not_active Withdrawn
- 1999-06-18 WO PCT/EP1999/004254 patent/WO1999065862A1/de not_active Application Discontinuation
- 1999-06-18 JP JP2000554689A patent/JP2002518365A/ja active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB921943A (en) * | 1959-11-25 | 1963-03-27 | Lilly Co Eli | Anti-hypertensive compositions |
US4020059A (en) * | 1975-06-02 | 1977-04-26 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Process for preparing tertiary amines |
DE2725245A1 (de) * | 1976-06-03 | 1977-12-15 | Labaz | Methylaminderivate, verfahren zu deren herstellung und diese enthaltende pharmazeutische oder veterinaermedizinische zusammensetzungen |
DE2657476A1 (de) * | 1976-12-18 | 1978-06-22 | Basf Ag | Morpholinderivate |
Non-Patent Citations (10)
Title |
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"BEILSTEINS HANDBUCH DER ORGANISCHEN CHEMIE, vierte Auflage, drittes und viertes Ergänzungswerk, Bd 20, erster Teil, S. 316", 1977, SPRINGER-VERLAG, BERLIN . HEIDELBERG . NEW YORK, XP002117681 * |
"HOUBEN-WEYL, METHODEN DER ORGANISCHEN CHEMIE, vol. XI/1, S. 820-823", 1957, GEORG THIEME VERLAG, STUTTGART, DE, XP002117680 * |
JERRY MARCH: "Advanced organic chemistry", 1985, JOHN WILEY, NEW YORK . CHISCHESTER . BRISBANE . TORONTO . SINGAPORE, XP002117736 * |
KUFFNER F. ET AL.: "Über hochverzweigte aliphatische Verbindungen", MONATSHEFTE FÜR CHEMIE, vol. 93, 1962, pages 496 - 475, XP002117676 * |
MANFRED T. REETZ ET AL.: "Chemoselective addition of organotitanium reagents to carbonyl compounds", CHEMISCHE BERICHTE., vol. 118, no. 4, 1985, VERLAG CHEMIE GMBH. WEINHEIM., DE, pages 1421 - 1440, XP002117770, ISSN: 0009-2940 * |
MANFRED T. REETZ ET AL.: "Stereoselective addition of organotitanium reagents to carbonyl compounds", CHEMISCHE BERICHTE., vol. 118, no. 4, 1985, VERLAG CHEMIE GMBH. WEINHEIM., DE, pages 1441 - 1453, XP002117771, ISSN: 0009-2940 * |
N. MAXIM ET AL.: "Sur la méthode de Bouveault....", BULLETIN DE LA SOCIETE CHIMIQUE DE FRANCE., vol. 5, no. 3, 1936, PARIS FR, pages 1084 - 1093, XP002117677 * |
VLADIMIR CHAPLINSKI ET AL.: "A new versatile reagent for the synthesis of cyclopropylamines...", SYNLETT., 1997, THIEME VERLAG, STUTTGART., DE, pages 111 - 114, XP002117679, ISSN: 0936-5214 * |
VLADIMIR CHAPLINSKI ET AL.: "Eine nützliche Synthese von Cyclopropylaminen aus Carbonsäurediakylamiden", ANGEWANDTE CHEMIE., vol. 108, no. 4, 1996, VCH VERLAGSGESELLSCHAFT, WEINHEIM., DE, pages 491 - 492, XP002117735, ISSN: 0044-8249 * |
YUYING C. HWANG ET AL.: "A synthesis of &-substituted amines", JOURNAL OF ORGANIC CHEMISTRY., vol. 50, no. 20, 1985, EASTON US, pages 3885 - 3890, XP002117673 * |
Also Published As
Publication number | Publication date |
---|---|
EP1087933A1 (de) | 2001-04-04 |
KR20010052927A (ko) | 2001-06-25 |
JP2002518365A (ja) | 2002-06-25 |
DE19827161A1 (de) | 1999-12-23 |
US6515180B1 (en) | 2003-02-04 |
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