US3350463A - Process for the manufacture of esters of orthoformic acid with alkanols with 2 to 6 carbon atoms - Google Patents

Process for the manufacture of esters of orthoformic acid with alkanols with 2 to 6 carbon atoms Download PDF

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Publication number
US3350463A
US3350463A US426445A US42644565A US3350463A US 3350463 A US3350463 A US 3350463A US 426445 A US426445 A US 426445A US 42644565 A US42644565 A US 42644565A US 3350463 A US3350463 A US 3350463A
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US
United States
Prior art keywords
carbon atoms
esters
acid
orthoformic acid
alkanol
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
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US426445A
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English (en)
Inventor
Hass Karl
Lenz Arnold
Bleh Otto
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Dynamit Nobel AG
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Dynamit Nobel AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/60—Preparation of compounds having groups or groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/06—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of high energy impulses, e.g. magnetic energy
    • B23K20/08—Explosive welding

Definitions

  • orthoformic acid esters of lower alkanols can be re-esterfied to form orthoesters of higher alkanols.
  • the orthoformic acid esthers of the lower alkanol is boiled with the higher alkanol with reflux, so that the low alkanol that is released during the slow process of re-esterification is drawn oif at the head.
  • Re-esterification under the above conditions is so slow that the process is uneconomicalit takes days to perform.
  • the addition of sulfuric acid has been proposed for the purpose of accelerating this re-esterification reaction.
  • esters of orthoformic acid with alkanols having 2 to 6 carbon atoms from orthoformic acid trimethyl ester with with alkanols having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, in the presence of 001 to 1 weight-percent, and preferably 0.04 to 0.6 weightormic acid.
  • the percentage of formic acid added is based on the total amount of the reactants.
  • the re-esterification equilibrium is established within a short time. Then the released ing composition can be ad usted, whereupon the percentage of the triester of the higher alkanol increases in such a manner that separation of the starting ester and the intermediate esters by distillation is economical.
  • An elevated temperature can be used.
  • the reactants can be heated to any temperature up to the boiling point of the mixture. It is desirable, however, to employ room temperature for the reaction.
  • the reactants can be left at room temperature until the new equilibrium for the reactants is established. This will commonly require a period of hours, for example 1-3 hours.
  • the process of the invention can also be performed continuously, if desired.
  • the alkauols, the starting ester and the intermediate esters are removed at the top, while the desired triester remains in the sump of the column.
  • the head product can then be fed back into the process at an appropriate point.
  • Example 1 Equivalent amounts of orthoformic acid trimethyl ester (106 grams) and ethanol (138 grams) are combined with 0.12 gram of formic acid and thoroughly mixed together until homogeneous. After two hours the re-esterification equilibrium has established itself. The mixture then contams orthoformic acid triethyl ester, orthoformic acid the remaining has the highest amounts to more than to the orthoformic acid.
  • Orthoformic acid triisopropyl ester 636 grams of orthoformic acid trimethyl ester are thorremainder produces 800 to 880 grams (70 to 77% of the theory) of orthoformic acid triisopropyl ester.
  • Example 3 Orthoformic acid tributyl ester: 530 grams of orthoformic grams of Torr produces about 1060 of the theory) of orthoformic acid tributyl ester.
  • Example 4 Orthoformic acid tripropyl ester: Equivalent quantities of trimethyl orthoformate and nmixed with 0.06% formic acid.
  • the head product contains mainly n-propanol, the intermediate esters and tripropyl orthoformate, plus a little methanol.
  • Process for the manufacture of a triester of orthoformic acid and an alkanol having 2-6 carbon atoms by liquid phase reaction which comprises contacting orthoformic acid trimethyl ester with an alkanol having 2-6 carbon atoms in the presence of 0.01-1 wt. percent of formic acid based on the total amount of the reactants, at a temperature and for a time sufficient for formation in said liquid phase of said triester of orthoformic acid and. alkanol containing 2-6 carbon atoms, methyl alcohol, and esters of said formic acid, and separating methyl alcohol and said esters of formic acid from said liquid phase by distillation.
  • Process according to claim is ethanol, isopropanol, n-butanol,
  • Process according to claim is ethanol.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US426445A 1964-01-18 1965-01-18 Process for the manufacture of esters of orthoformic acid with alkanols with 2 to 6 carbon atoms Expired - Lifetime US3350463A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1964D0043383 DE1205076C2 (de) 1964-01-18 1964-01-18 Verfahren zur Herstellung von Estern der Orthoameisensaeure mit Alkanolen mit 2 bis 6 Kohlenstoffatomen

Publications (1)

Publication Number Publication Date
US3350463A true US3350463A (en) 1967-10-31

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Application Number Title Priority Date Filing Date
US426445A Expired - Lifetime US3350463A (en) 1964-01-18 1965-01-18 Process for the manufacture of esters of orthoformic acid with alkanols with 2 to 6 carbon atoms

Country Status (8)

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US (1) US3350463A (en])
BE (1) BE658411A (en])
CH (1) CH447137A (en])
DE (1) DE1205076C2 (en])
FR (1) FR1420966A (en])
GB (1) GB1029092A (en])
LU (1) LU47801A1 (en])
NL (2) NL143834B (en])

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
NL6500507A (en]) 1965-07-19
BE658411A (en])
DE1205076C2 (de) 1973-07-05
DE1205076B (de) 1965-11-18
NL6500506A (en]) 1965-07-19
LU47801A1 (en]) 1965-03-15
NL143834B (nl) 1974-11-15
CH447137A (de) 1967-11-30
GB1029092A (en) 1966-05-11
FR1420966A (fr) 1965-12-10

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