WO1985001731A1 - Preparation of 6-carboxy-3,4-dihydro-2h-pyran - Google Patents

Preparation of 6-carboxy-3,4-dihydro-2h-pyran Download PDF

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Publication number
WO1985001731A1
WO1985001731A1 PCT/US1983/001799 US8301799W WO8501731A1 WO 1985001731 A1 WO1985001731 A1 WO 1985001731A1 US 8301799 W US8301799 W US 8301799W WO 8501731 A1 WO8501731 A1 WO 8501731A1
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WIPO (PCT)
Prior art keywords
carboxy
dihydro
pyran
hydrogen
inorganic base
Prior art date
Application number
PCT/US1983/001799
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English (en)
French (fr)
Inventor
Joachim Wilhelm Wolfram
Original Assignee
Ethyl Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ethyl Corporation filed Critical Ethyl Corporation
Priority to JP84500166A priority Critical patent/JPS60501757A/ja
Publication of WO1985001731A1 publication Critical patent/WO1985001731A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-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
    • C07D309/28—Heterocyclic compounds containing six-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

Definitions

  • This invention relates to 6-carboxy-3,4-dihydro2H-pyran and novel ring-substituted derivatives thereof. Further, the invention relates to processes for preparing same.
  • R 1 , R 2 , R 3 , R 4 and R 5 are the same or different and are hydrogen or linear or branched alkyl, aralkyl or aryl radicals having up to at least 20 carbon atoms and where R 6 is hydrogen, can be prepared by carbonylating a 1,4-disubstituted butane having leaving groups at the one and four positions corresponding to the formula:
  • R 1 , R 2 , R 3 , R 4 and R 5 are as defined above and X and Y are the same or different and are leaving groups, inert to solvolysis under the reaction conditions, in a liquid solvent medium, with carbon monoxide at a pressure of from 300 to 3000 psig in the presence of a catalytic amount of a metal carbonyl compound and an alkali metal inorganic base or an alkaline earth metal inorganic base.
  • exemplary leaving groups, X and Y include halo (e.g., bromine, chlorine or iodine), sulfonate (e.g., tosylate) and quaternary amines.
  • 1,4-disubstituted butane reactants suitable for use in the present process are known in the art as are methods for their preparation and, as defined above, are of the general formula:
  • R 1 , R 2 , R 3 , R 4 , R 5 , X and Y are as defined above.
  • a few examplary materials of this type include: 1,4-dibromobutane, 1,4-dibromopentane, 1,4-dibromo-3-methylbutane, 1,4-dibromo-2-methylbutane, 1,4-dibromo-3,3-dimethylbutane, 1,4-dibromo-2,2-dimethylbutane, 1,4-dibromo-3-methylpentane, 1,4-dibromo-2,3-dimethylbutane, 1,4-dibromo-2,3-dimethylpentane, 1,4-dibromo-2-(4'-ethylphenyl)butane, 1,4-dibromo-2-(4'-isopropylphenyl)butane, 1,4-dibromo-3-phenyl-butane, 1,4-dibromo-2-phenyl-butane, and
  • 4-bromobutyl-1-p-toluene sulfonate is 4-bromobutyl-1-p-toluene sulfonate.
  • a particularly useful reactant is 1,4-dibromobutane.
  • Products which can be made by the process of the present invention include, by way of example: 6-carboxy-3,4-dihydro-2H-pyran,
  • 6-carboxy-2-methyl-3,4-dihydro-2H-pyran 6-carboxy-3-methyl-3,4-dihydro-2H-pyran, 6-carboxy-4-methyl-3,4-dihydro-2H-pyran, 6-carboxy-3,3-dimethyl-3,4-dihydro-2H-pyran, 6-carboxy-4,4-dimethyl-3,4-dihydro-2H-pyran,
  • reaction is carried out in the presence of a mixture of water and alcohol as a reaction medium.
  • the alcohols employed for the reaction may be straight-chain, branched or cyclic, and preferably contain up to 6 carbon atoms.
  • Metha- nol, ethanol, propanol, isopropanol, ri-butanol, isobutanol, tertbutanol, and tert-amyl alcohol may be mentioned as examples.
  • Cyclic ethers such as tetrahydrofuran, also may be used.
  • a particularly preferred solvent alcohol is tert-butanol.
  • Mixtures containing about 10% to 907. by weight of water and about 90% to 107o by weight of alcohol generally are used.
  • Preferred mixtures contain 30% to 80% by weight water and 70% to 20% by weight alcohol.
  • the reaction takes place in the presence of a basic substance, suitably an alkali metal hydroxide or an alkaline earth metal hydroxide, employing a metal carbonyl compound.
  • a basic substance suitably an alkali metal hydroxide or an alkaline earth metal hydroxide, employing a metal carbonyl compound.
  • the 1,4disubstituted butane reactant undergoes reaction with the carbon monoxide and basic substance whereby 6-carboxy-3,4-dihydro-2H-pyran or the desired derivatives thereof are formed.
  • suitable basic agents which can be used in the practice of the process include: LiOH, NaOH, KOH, RbOH, Ca(OH) 2 , Ba(OH) 2 and Mg(OH) 2 .
  • the LiOH and Ca(OH) 2 are particularly preferred.
  • the amount of basic agent used can vary within wide limits. In general, the molar ratio of the alkali metal base or alkaline earth metal base to 1,4disubstituted butane reactant is preferably 10:1 to 1:1. In the process described herein, it is preferred to use metal carbonyl compounds as carbonylation catalysts.
  • These catalysts include particularly metal carbonyls such as iron pentacarbonyl, dicobalt-octacarbonyl and nickel-tetracarbonyl, or their salts such as, for example, the calcium, potassium or sodium salts thereof. Dicobalt-octacarbonyl is very particularly suited.
  • These catalysts can be added to the medium in the solid state or in the form of solutions in the solvent used for the carbonylation reaction.
  • the molar percentage of the metal carbonyl compound to the 1,4-disubstituted butane reactant is preferably from 0.1 to 25%.
  • the concentration of the 1,4-disubstituted butane used in the reaction solvent is not critical and can vary within wide limits. Thus, it can be between 1 and 30% by weight, based on the weight of the solvent, however, it is possible to go outside of these limits without disadvantage.
  • the present process is advantageously carried out by bringing the mixture consisting of the 1,4disubstituted butane reactant, the metal carbonyl catalyst and the alkali metal base or alkaline earth metal base, suspended in the mixture of water and alcohol , into contact , under nitrogen , in a suitable pressure-resistant reactor equipped with a stirrer, with a large excess of carbon monoxide (amount greater than 2 moles of carbon monoxide per mole of the starting 1,4disubstituted butane reactant) introduced at the desired pressure and temperature, in accordance with techniques suitable for bringing about the reaction between a liquid phase and a gas phase.
  • the carbonylation reaction is carried out at a temperature in the range of from 30°C. to 150°C., preferably from 50°C. to 100°C, over a period of time of from 3 to 60 hours, typically 3 to 20 hours.
  • the reaction takes place at elevated carbon monoxide pressures which may range from 300 psig to 3000 psig. Preferably, the reaction takes place at a pressure in the range of 500 psig to 1000 psig.
  • the carbon monoxide may contain or be mixed with an inert gas, such as nitrogen.
  • the product mixture On completion of the reaction, the product mixture is filtered, resulting in the alkali metal basic reagent or the alkaline earth metal basic reagent being separated from the liquid reaction components as the main solid component.
  • the desired 6-carboxy-3,4dihydro-2H-pyran product is easily separated from the resultant reaction mixture by such means as distillation, extraction, crystallization or the like. Since the der ivatives of 6-carboxy-3 , 4-dihydro ⁇
  • R 1 , R 2 , R 3 , R 4 and R 5 are the same or different and are hydrogen or linear or branched alkyl, aralkyl or aryl radicals having up to at least 20 carbon atoms with the proviso that at least one of R 1 , R 2 , R 3 , R 4 or R 5 must be other than hydrogen and R 6 is hydrogen.
  • R 1 , R 2 , R 3 , R 4 and R 5 are the same or different and are hydrogen or linear or branched alkyl, aralkyl or aryl radicals having up to at least 20 carbon atoms with the proviso that at least one of R 1 , R 2 , R 3 , R 4 or R 5 must be other than hydrogen and R 6 is hydrogen.
  • Example 1 Into a 300 mL autoclave were charged 9.02 g (52.0 mmoles) of 1-chloro-4-bromobutane and 70 mL of t-BuOH. Next, 0.9 g (2.76 mmoles) of Co 2 (CO) 8 were added under CO, and then a mixture of 15.4 g (approximately 200 mmoles) of lime and 30 mL of H 2 O were added. After 850 psi CO was charged to the autoclave, the reaction mixture was heated to 90°C over a period of time of approximately 1.hour and held at that temperature for 15 hours. The CO uptake stopped after approximately 7 hours.
  • CO Co 2
  • the solid was rinsed once with a 20 mL portion of a 50:50 t-butanol/water solution and then acidified with 150 mLs of HC1 solution containing approximately 450 mmoles of HC1.
  • the free acid was extracted from the aqueous solution with diethyl ether (2 x 120 mLs) to give a 1.12 g (19% yield) of 6-carboxy-3,4-dihydro-2H-pyran based on proton NMR data with internal standard.
  • the filtrate was extracted with 50 mLs of diethyl ether and the extract discarded.
  • the residual aqueous solution was acidified with 10% HCl and extracted with diethyl ether (3 x 50 mLs).
  • Example 2 Into a 300 mL autoclave were charged 8.83 g (40.93 mmoles) of 1,4-dibromobutane and 70 mLs of t-BuOH. Next, 0.7 g (2.05 mmoles) of Co 2 (CO) 8 were added under CO, and then a mixture of 12.11 g (163.7 mmoles) of lime and 30 mLs of H 2 O were added. After 850 psi CO was charged to the autoclave, the reaction mixture was heated to 90°C over a period of time of approximately 1 hour and held at that temperature for 15 hours. The CO uptake stopped after approximately 11 hours.
  • CO Co 2
  • the solid was rinsed once with a 20 mL portion of a 50:50 t-butanol-water solution and then acidified with 150 mL of HCl solution containing approximately 350 mmoles of HCl.
  • the free acid was extracted from the aqueous solution with diethyl ether (2 x 120 mLs) to give 0.21 g (41% yield) of 6-carboxy-3,4-dihydro-2H-pyran based on proton NMR data with internal standard.
  • the filtrate was extracted with 50 mLs of diethyl ether and the extract discarded.
  • the residual aqueous solution was acidified with 10% HCl and extracted with diethyl ether (3 x 50 mLs).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyrane Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/US1983/001799 1983-10-21 1983-11-15 Preparation of 6-carboxy-3,4-dihydro-2h-pyran WO1985001731A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP84500166A JPS60501757A (ja) 1983-10-21 1983-11-15 ６−カルボキシ−３，４−ジハイドロ−２ｈ−ピランの製造

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US54439983A 1983-10-21 1983-10-21
US544,399 1983-10-21

Publications (1)

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WO1985001731A1 true WO1985001731A1 (en) 1985-04-25

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PCT/US1983/001799 WO1985001731A1 (en) 1983-10-21 1983-11-15 Preparation of 6-carboxy-3,4-dihydro-2h-pyran

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EP (1) EP0159993A4 (enrdf_load_stackoverflow)
JP (1) JPS60501757A (enrdf_load_stackoverflow)
CA (1) CA1243327A (enrdf_load_stackoverflow)
WO (1) WO1985001731A1 (enrdf_load_stackoverflow)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4147702A (en) * 1977-01-05 1979-04-03 Monsanto Company 1,4-Dioxane polycarboxylates

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4147702A (en) * 1977-01-05 1979-04-03 Monsanto Company 1,4-Dioxane polycarboxylates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0159993A4 *

Also Published As

Publication number Publication date
EP0159993A1 (en) 1985-11-06
JPS60501757A (ja) 1985-10-17
EP0159993A4 (en) 1987-01-20
CA1243327A (en) 1988-10-18
JPS6220188B2 (enrdf_load_stackoverflow) 1987-05-06

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