Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B41/00—Formation or introduction of functional groups containing oxygen
  • C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B53/00—Asymmetric syntheses
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
  • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
  • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
  • C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
  • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
  • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
  • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/32—Oxygen atoms
  • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
  • C07B2200/07—Optical isomers

Definitions

• the present invention relates to a process for the preparation of optically active hydroxyl, alkoxy, amino, alkyl, aryl or chlorine-substituted alcohols or hydroxycarboxylic acids having 3 to 25 carbon atoms or their acid derivatives or cyclization products by hydrogenation of the correspondingly substituted ones optically active mono- or dicarboxylic acids or their acid derivatives.
• WO 99/38824 describes a process for the production of optically active alcohols by reducing optically active carboxylic acids in the presence of hydrogen-reduced Ru-containing catalysts which contain at least one further metal with atomic numbers in the range from 23 to 82.
• n is an integer from 0 to 8
• the acid anhydrides can also be used as carboxylic acid derivatives.
• the radicals R 5 and R 6 ' independently of one another, can also each represent - (CH 2 ) m -, where m is an integer from 4 to 7, in particular 4 or 5.
• a CH 2 group can be replaced by O or NR 8 ' .
• 3-hydroxy- ⁇ -butyrolactone in optically active form is particularly preferred in the production process according to the invention.
• 1, 2- and 1, 3-amino alcohols such as: ⁇ -alaninol, and in each case in the ⁇ or ⁇ form: leucinol, isoserinol, valinol, isoleucinol, serinol, threoninol, lysinol, phenylalaninol, tyrosinol, prolinol and the alcohols obtainable from the amino acids ornithine, citrulin, asparagine, aspartic acid, glutamine and glutamic acid by reaction the corresponding optically active ⁇ - or ⁇ -amino acids or their acid derivatives,
• the unsupported catalysts can be produced, for example, by reducing a slurry and / or solution in the aqueous or organic medium of the precious metal and the further active components according to the invention in metallic form or in the form of compounds, such as, for example, oxides, oxide hydrates, carbonates, nitrates, carboxylates , Sulfates, phosphates, halides, Werner's complexes, organometallic complexes or chelate complexes or mixtures thereof.
• supports such as carbon, carbon black, graphite, high surface activated graphite (HSAG), SiO 2 , Al 2 O 3 , TiO 2 , ZrO 2 , SiC, clays, silicates, montmorillonites, zeolites or mixtures thereof are preferred , Coals, graphite, HSAG, TiO 2 and ZrO 2 are particularly preferred for use as carrier materials.
• the supported catalysts according to the invention usually contain about 0.01 to 30% by weight of a noble metal selected from the group of the metals Pt, Pd, Rh, Ir, Ag, Au in metallic form or in the form of compounds and 0.01 to 50% by weight. %, preferably about 0.1 to 30% by weight and particularly preferably about 0.5 to 15% by weight, of at least one further element selected from the group of the elements: Sn, Ge, Mo, W, Ti, Zr , V, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Pb, Bi, Cr Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu in the metallic form or in the form of a compound or mixtures thereof.
• the percentages by weight are in each case based on the total weight of the finished catalysts and calculated in metallic form.
• Compounds of Sn, Ge, Cr, Mo or W are preferred, particularly preferably Sn in the form of the oxides or halides such as SnCl 2 , SnCl, SnO 2 , GeCl 4 or GeO 2 .
• the active components can be applied in one or more steps by impregnation with an aqueous or alcoholic solution of the respective dissolved salts or oxides or of dissolved oxidic or metallic colloids, or by equilibrium adsorption in one or more steps of the salts dissolved in aqueous or alcoholic solution or oxides or of dissolved oxidic or metallic colloids. Between individual equilibrium adsorption or impregnation steps, a drying step for removing the solvent and optionally a calcining step or reduction step can be carried out.
• Calcination can optionally be carried out after each application or drying step at temperatures in the range from approximately 100 to 800 ° C., preferably at approximately 200 to approximately 600 ° C. and particularly preferably at approximately 300 to approximately 500 ° C.
• a first impregnation step an element selected from the group of the elements: Sn, Ge, Mo, W, Ti, Zr, V, Mn, Fe, Co, Ni, Cu , Zn, Ga, In, Pb, Bi, Cr, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu from the respective oxides, oxide hydrates, carbonates, nitrates , Carboxylates, sulfates, phospho- phaten, Werner complexes, chelate complexes or halides applied to the carrier, then a drying step and optionally a calcining step and optionally a reduction step.
• another impregnation is optionally carried out with one or more elements selected from the group of elements: Sn, Ge, Cr, Mo, W, Ti, Zr, V, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Pb, Bi, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu from the respective oxides, oxide hydrates, carbonates, nitrates, carboxylates, sulfates, phosphates, Werner's complexes , Chelate complexes or halides with subsequent drying and optional calcination.
• elements selected from the group of elements: Sn, Ge, Cr, Mo, W, Ti, Zr, V, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Pb, Bi, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu from the respective oxides
• the noble metal selected from the group of metals Pt, Pd, Rh, Ir, Ag, Au is then applied to the support in the form of nitrates, carboxylates or halides. Finally, there is a further drying and optionally a calcining step.
• a further possibility for producing the supported catalysts according to the invention consists in the electroless deposition of a noble metal selected from the group of the metals Pt, Pd, Rh, Ir, Ag, Au and at least one further metallic component selected from the group of the elements: Sn, Ge, Mo , W, Ti, Zr, V, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Pb, Bi, Cr, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho , Er, Tm, Yb, Lu from the respective oxides, oxide hydrates, carbonates, nitrates, carboxylates, sulfates, phosphates, Werner's complexes, chelate complexes or halides onto the carrier material.
• a noble metal selected from the group of the metals Pt, Pd, Rh, Ir, Ag, Au
• the electroless deposition is advantageously carried out in aqueous or alcoholic slurry of the carrier material and the respective metal compounds by adding reducing agents such as.
• reducing agents such as.
• Ethanol and NaH 2 PO 2 are particularly preferred.
• a drying step is advantageously carried out at temperatures in the range from approximately 25 to approximately 350 ° C., preferably from approximately 40 to approximately 280 ° C. and particularly preferably from approximately 50 to approximately 150 ° C.
• the catalysts which can be used according to the invention usually have a specific surface area of about 5 to 3000 m 2 / g, preferably of about 10 to about 1500 m 2 / g.
• the optically active starting materials described above are hydrogenated in the presence of an organic or inorganic acid.
• the addition of acid is 0.5 to 1.5 equivalents, particularly preferably 1 to 1.3 equivalents, based on 1 equivalent of the basic groups which may be present in the starting materials.
• suitable organic acids are acetic acid, propionic acid and adipic acid.
• inorganic acids in particular sulfuric acid, hydrochloric acid and phosphoric acid, is preferred.
• the acids can, for example, as such, in the form of aqueous solutions or in the form of their separately prepared salts with the starting materials to be hydrogenated, for. B. as sulfates, hydrogen sulfates, hydrochlorides, phosphates, mono- or dihydrogen phosphates.
• optically active carboxylic acid or dicarboxylic acid to be reacted can be used with great success in bulk or in the form of an aqueous or organic solution.
• the hydrogenation can be carried out in suspension or in a continuous procedure in the fixed bed reactor in the liquid or gas phase.
• Suitable solvents for the reaction are, for example, the hydrogenation products themselves, water, alcohols such as. B. methanol, ethanol, propanol, butanol, ether such as e.g. THF or ethylene glycol ether. Water or methanol or mixtures thereof are preferably used as solvents.
• the reaction is usually complete when hydrogen is no longer taken up.
• the reaction time is usually about 1 to about 72 hours.
• the isolation and, if necessary, separation of the reaction products obtained can in principle be carried out by all customary processes known to the person skilled in the art. Extractive and distillative processes and purification or isolation by crystallization are particularly suitable for this.
• the process according to the invention is characterized in that the racemization of stereogenic centers of the substituted mono- or dicarboxylic acids used as starting compounds in optically active form is largely suppressed during the hydrogenation. Accordingly, the enantiomeric excess of the products obtained usually corresponds largely to that of the starting materials used in the process according to the invention.
• the reaction conditions are preferably chosen so that the enantiomeric excess of the desired product corresponds at least 90%, particularly preferably at least 95%, very particularly preferably at least 98% to that of the starting compound used.
• An advantage of the process according to the invention is that the decarbonylation known as a troublesome side reaction in such reactions is largely suppressed with the release of carbon monoxide and its subsequent reduction to methane or other lower alkanes. This leads to considerable safety advantages.
• the selected carrier material 100 g are heated with 200 ml of the selected acid and 400 ml of water to 100 ° C. for 45 min with stirring. After filtering and washing with water, the activated carrier material is dried at 80 ° C in a convection oven.
• the activation can also be carried out in a rotary evaporator or in a fixed bed reactor through which the activation solution flows, in order to minimize the mechanical destruction of the carrier.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Furan Compounds (AREA)
• Catalysts (AREA)

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• 2004
  • 2004-02-13 DE DE102004007498A patent/DE102004007498A1/de not_active Withdrawn
• 2005
  • 2005-02-08 KR KR1020067018660A patent/KR20060117369A/ko not_active Application Discontinuation
  • 2005-02-08 JP JP2006552521A patent/JP4786551B2/ja not_active Expired - Fee Related
  • 2005-02-08 WO PCT/EP2005/001234 patent/WO2005077870A1/de active Application Filing
  • 2005-02-08 US US10/588,948 patent/US20070142648A1/en not_active Abandoned
  • 2005-02-08 CN CN2005800048885A patent/CN1918095B/zh not_active Expired - Fee Related
  • 2005-02-08 EP EP05701373A patent/EP1716090A1/de not_active Withdrawn
  • 2005-02-08 CA CA002553700A patent/CA2553700A1/en not_active Abandoned

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