Classifications

• • 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
  • C07C29/143—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 ketones
• • 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
  • C07C29/14—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 a —CHO group
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• the present invention provides a novel and useful method for the reduction of aldehydes or ketones to the corresponding acrylates by isopropyl alcohol in the presence of a catalyst. It is about the method.
• This reduction involves a direct hydrogen transfer from the alcohol to the carbonyl group of the aldehyde or ketone within the range of the aluminum.
• the muisoprovoxide will act as a catalyst.
• the reaction system is simple, the reagents are relatively safe and inexpensive, and the reaction proceeds under mild conditions. It can be used for the reduction of polyaldehydes or ketones.
• this catalyst was gradually hydrolyzed by the moisture in the air to form alcohol and aluminum hydroxide, so it was necessary to pay attention to its storage.
• the catalyst is hydrolyzed to isolate the product from the reaction system.
• This reduction method of the present invention converts an aldehyde to a ketone into the corresponding alcohol in a high yield with few by-products.
• the product can be isolated by filtering out zirconium oxide and removing the solvent in the liquid bath reaction to obtain a product of sufficient purity. can be done.
• both continuous reaction and batch reaction are possible, and in both cases the product can be easily separated by the same method as in the case of liquid phase reaction. Wear .
• Hydrous zirconium oxide does not need to be adjusted before the reaction, and it is not soluble in water or other organic solvents, so it can be reused after recovery. It is also advantageous in that it does not generate industrial waste.
• the zirconium hydroxide used in the present invention is derived from zirconium sand or paddeleyite ore, which are abundantly present on the earth as mineral resources. Zirconium oxychloride
• an aqueous solution of oxyzirconium chloride When an alkaline aqueous solution is added to the solution, the oxyzirconium chloride decomposes and precipitation of microgels of zirconium hydroxide begins. .
• This amorphous material is stable in water alcohol and various other solvents, and exhibits ion-exchange properties with respect to various metal ions and alcohol Shows adsorptivity to
• the hydrous zirconium oxide thus obtained can be used as a reaction catalyst after being dried by increasing to about 80°C under reduced pressure and then classified. .
• the reaction is known in the liquid phase. It can be thought that alkoxide is replaced with hydrous zirconium oxide. Faster response It can be applied as it is, such as making it dull. That is, 0.1 to 10 g, preferably 1 to 3 g, is preferably 0.5 to 10 m for 1 mmol of anoredehyde or ketone. Alternatively, it can be added to 1 to 3 m of isopropyl alcohol and heated. It is desirable to distill off the acetone produced as a by-product during the reaction to promote the reaction. The desired product is obtained by distilling the filtrate as is, or by removing the solvent and allowing it to crystallize. be able to .
• the used zirconium hydroxide can be reused if it is washed with ethanol and then washed with water to remove the powder and dried.
• hydrous zirconium oxide is a highly active, stable and hard amorphous material, it can also be used in gas phase reactions. That is, the reaction vessel filled with zirconium hydroxide is heated to 70 to 200, preferably 75 to 110, and continuously heated to a boiling point. A carrier such as air, nitrogen, helium, argon, etc. is added after heating and gasifying a vinyl alcohol and an aldehyde or a ketone. Just let it flow with the gas. The outlet of the reaction tube is cooled with water, ice, or other coolant to condense the product, unreacted isopropyl alcohol, acetone, and the like. Isolation of the product may be carried out according to the liquid phase reaction.
• a carrier such as air, nitrogen, helium, argon, etc.
• Table 1 shows the type of aldehyde or ketone, reaction time, reaction product and yield.

Landscapes

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

Priority Applications (5)

Applications Claiming Priority (1)

Publications (1)

Family

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Family Applications (1)

Country Status (5)

Families Citing this family (13)

• 1985
  • 1985-03-05 JP JP60041930A patent/JPS61204143A/ja active Granted
• 1986
  • 1986-09-10 US US07/126,106 patent/US4877909A/en not_active Expired - Fee Related
  • 1986-09-10 EP EP86905412A patent/EP0281627B1/en not_active Expired - Lifetime
  • 1986-09-10 WO PCT/JP1986/000460 patent/WO1988001995A1/ja not_active Ceased
  • 1986-09-10 DE DE8686905412T patent/DE3680546D1/de not_active Expired - Lifetime

Non-Patent Citations (3)

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