US3157703A - Manufacture of aldehydes and ketones - Google Patents

Manufacture of aldehydes and ketones Download PDF

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Publication number
US3157703A
US3157703A US183020A US18302062A US3157703A US 3157703 A US3157703 A US 3157703A US 183020 A US183020 A US 183020A US 18302062 A US18302062 A US 18302062A US 3157703 A US3157703 A US 3157703A
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mol
solution
chloroform
reaction
alkyl
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US183020A
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English (en)
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Franzen Volker
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Carlisle Chemical Works Inc
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Carlisle Chemical Works Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
    • C07B35/04—Dehydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/44—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by —CHO groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation

Definitions

  • the present invention relates to a process for the preparation of aldehydes and ketones.
  • aldehydes and ltetones from alkylating agents such as alkyl halides, alkyl chlorosulfonic acid esters, alkyl p-toluene sulfonic acid esters (tosylates), alkyl sulfuric acid esters and alkyl sulfites.
  • alkylating agents such as alkyl halides, alkyl chlorosulfonic acid esters, alkyl p-toluene sulfonic acid esters (tosylates), alkyl sulfuric acid esters and alkyl sulfites.
  • Another object is to develop a one step procedure for preparing aldehydes and ketones from alkylating agents.
  • a further object is to prepare aldehydes and ketones in improved yields.
  • Yet another object is to prepare aldehydes and ketones from readily available materials such as alkyl halides and other esters.
  • alkylating agents such as alkyl halides, alkyl esters of chlorosulfonic acid, alkyl esters of p-toluene sulfonic acid, alkyl esters of benzene sulfonic acid, alkyl esters of sulfuric acid, alkyl esters of sulfuorous acid and also the corresponding cycloalkyl, alkenyl and aromatic esters of these acids.
  • alkylating agents such as alkyl halides, alkyl esters of chlorosulfonic acid, alkyl esters of p-toluene sulfonic acid, alkyl esters of benzene sulfonic acid, alkyl esters of sulfuric acid, alkyl esters of sulfuorous acid and also the corresponding cycloalkyl, alkenyl and aromatic esters of these acids.
  • R is H, alkyl or aryl
  • R is alkyl, alkenyl
  • aryl, aralkenyl, nitroaryl or haloaryl or R and R are joined together with the C to form a cycloalkyl or cycloalkenyl group.
  • X is halogen, R SO O where R is aryl or alkyl, OSO Cl,
  • X is halogen preferably it has an atomic weight between 35 and 127.
  • suitable alkylating agents there can be used ethyl iodide, ethyl bromide, propyl chloride, propyl bromide, propyl iodide, isopropyl bromide, n-butyl bromide, isobutylbromide, sec butyl bro ⁇ mide, n-butyl chloride, n-butyl iodide, n-hexyl iodide, n-hexyl bromide, n-arnyl chloride, neopentyl bromide, n-octyl iodide, n-octyl chloride, n-octyl bromide, isoamyl bromide, n-dodecyl bromide, cetyl bromide, cetyl chlorosulfonate, cyclooctyl chlorosulionate, sec amyl but
  • the alkylating agent e.g. the alkyl halide or the chlorosulfonic or tosyl ester is reacted in equal molar amounts or with an excess of anhydrous trimethylarnine oxide.
  • the molar ratio of the alkylating agent to the trimethylamine oxide is preferably between 1:1 and 1:4. It is desirable to run the reaction in an organic solvent in which the trimethylamine oxide is soluble, e.g. in chloroform.
  • the reaction can also be carried out in other solvent such as methylene chloride, dioxane, tetrahydrofuran, benzene, toluene, carbon tetrachloride xylene and dimethylformamide.
  • the reaction time is generally not longer than 20-30 minutes. In some cases it is even shorter. In many cases the resulting heat of reaction is sufiicient; in other cases, particularly with long chain halides and tosylates, additional heating is necessary to complete the reaction.
  • reaction solution e.g. a chloroform solution
  • a strong acid e.g. a strong acid
  • the aqueous layer is separated and the chloroform solution is washed with aqueous sodium bicarbonate or potassium bicarbonate solution. Then after separating Patented Nov. 3?, 19%4 the aqueous layer and drying, the chloroform solution is distilled. Also, after first cooling the reaction solution, the ammonium salt formed in the reaction can be precipitated by the addition of ether. If the aldehyde or the lzetone is stable, it can be recovered as the residue simply by distilling off the solvent after the removal of the ammonium salt.
  • Anhydrous trimethylamine oxide can be prepared from its hydrate in any convenient fashion, see Fieser et a1.
  • Organic Chemistry pages 239-240 but is preferably prepared by dehydration with dimethyl formamide, e.g. according to the following procedure:
  • EXAMPLE 7 Preparation of Dodecanal-I 0.2 mol of n-dodecyl bromide was added dropwise with slight heating and agitation to a solution of 0.4 mol of trimethylamine oxide in ml. of chloroform. After the addition the solution was boiled under reflux for 20 minutes. The solution was cooled and treated with double its volume of ether. Thereby the ammonium salt formed precipitated and was separated. The etherchloroform solution was washed thoroughly with 2 N hydrochloric acid and then aqueous sodium bicarbonate solution and dried. After removal of the solvents, the residue was fractionated to obtain dodecanal-l.
  • Boiling Point B.P. 144-145. Yield 21 g.
  • EXAMPLE 8 Preparation of Palmiticaldehyde 0.2 mol of cetyl iodide was slowly added dropwise to a solution of 0.5 mol of trimethylamine oxide in 150 ml. of chloroform. During the dropwise addition, the chloroform solution washeated slightly. The solution was boiled under reflux for 30 minutes. After cooling, the chloroform solution was treated with 400 ml. ether, whereby all of the ammonium salt formed was precipitated. The precipitate was separated, the ether-chloroform solution Washed with 2 N hydrochloric acid and aqueous sodium bicarbonate solution and dried.
  • EXAMPLE 10 Preparation of Benzaldehyde 0.2 mol of anhydrous trimethylamine oxide was dissolved in 55 ml. of chloroform and charged into a threeneck flask equipped with an agitator, dropping funnel, and reflux condenser. With cooling, 0.1 mol of benzyl chloride was added dropwise. Then the mixture was heated slowly to boiling and boiled under reflux for 50 minutes. After cooling, the solution was treated with an equal volume of 2 N hydrochloric acid, the layers are separated, and the chloroform solution was washed with aqueous sodium bicarbonate solution. The chloroform solution was dried and distilled.
  • EXAMPLE 12 Preparation of p-Nitrobenzaldehyde 0.2 mol of anhydrous trimethylamine oxide was dissolved in 60 ml. of chloroform and charged into a threeneck flask equipped with agitator, reflux condenser, and dropping funnel. With cooling, 0.15 mol p-nitrobenzyl chloride dissolved in 50 ml. of chloroform was added dropwise. The reaction solution became warm. After the addition was completed, the mixture was allowed to stand another 10 minutes at room temperature, then shaken thoroughly with 2 N sulfuric acid, the aqueous layer separated, and the chloroform layer dried and evaporated under vacuum. The p-nitrobenzaldehyde remained behind, as a residue having a melting point of 107 C. The yield was 12.1 g.
  • chloroform solution was washed thoroughly with 2 N sulfuric acid and dried. After removing the solvents, the p-tolylaldehyde remained behind.
  • a process of preparing a carbonyl compound of the group consisting of aldehydes and ketones comprising reacting trimethylamine oxide with an alkylating agent having a formula selected from the group consisting of OSO Cl l -o s o R4 where R; is alkyl, and
  • reaction is carried out with heating at a temperature up to the boiling point of the solvent.
  • reaction solution is acidified with aqueous mineral acid, separated from the acid, Washed with alkaline bicarbonate solution and then the carbonyl compound is recovered by removing the solvent by distillation.
  • a process of preparing an aldehyde comprising reacting anhydrous trimethylamine oxide with a primary alkyl halide having at least two carbon atoms, the halogen of said halide having an atomic weight of between 35 and 127.
  • a process of preparing an aldehyde comprising reacting anhydrous trimethylamine oxide with a primary dialkyl sulfate, said alkyl groups having at least two carbon atoms.
  • a process of preparing an aldehyde comprising reacting anhydrous trimethylarnine oxide with an aralkenyl halide having a single aromatic ring, the halogen of said halide having an atomic weight between 35 and 127.
  • a process of preparing a cyclic ketone comprising reacting anhydrous trimethylar'nine oxide with a cycloalkyl halide, the halogen of said halide having an atomic weight between 35 and 127.
  • a process of preparing a dialkyl ketone comprising reacting anhydrous trimethyiamine oxide with a secondary alkyl halide having at least three carbon atoms, the halogen of said halide having an atomic weight between 35 and 127.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US183020A 1961-04-05 1962-03-28 Manufacture of aldehydes and ketones Expired - Lifetime US3157703A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DED35796A DE1152696B (de) 1961-04-05 1961-04-05 Verfahren zur Herstellung von Aldehyden oder Ketonen

Publications (1)

Publication Number Publication Date
US3157703A true US3157703A (en) 1964-11-17

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ID=7042800

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US183020A Expired - Lifetime US3157703A (en) 1961-04-05 1962-03-28 Manufacture of aldehydes and ketones

Country Status (6)

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US (1) US3157703A (en, 2012)
BE (1) BE615018A (en, 2012)
CH (1) CH424745A (en, 2012)
DE (1) DE1152696B (en, 2012)
FR (1) FR1317560A (en, 2012)
GB (1) GB998525A (en, 2012)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4335052A (en) * 1979-11-29 1982-06-15 Dynamit Nobel Aktiengesellschaft Method of preparing substituted benzaldehydes
US4745229A (en) * 1986-02-28 1988-05-17 Kuraray Company Ltd. Process for preparing α, β-unsaturated aldehydes

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2888488A (en) * 1957-09-03 1959-05-26 Du Pont Process for the preparation of aldehydes

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE825547C (de) * 1949-11-23 1951-12-20 Bayer Ag Verfahren zur Herstellung von cycloaliphatischen Oximen und Oxoverbindungen
DE948417C (de) * 1954-01-30 1956-08-30 Bayer Ag Verfahren zur Herstellung von Nitrosoverbindungen bzw. Oximen und Oxoverbindungen aus sekundaeren Aminen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2888488A (en) * 1957-09-03 1959-05-26 Du Pont Process for the preparation of aldehydes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4335052A (en) * 1979-11-29 1982-06-15 Dynamit Nobel Aktiengesellschaft Method of preparing substituted benzaldehydes
US4745229A (en) * 1986-02-28 1988-05-17 Kuraray Company Ltd. Process for preparing α, β-unsaturated aldehydes
EP0234496A3 (en) * 1986-02-28 1989-11-29 Kuraray Co., Ltd. Process for preparing alpha, beta-unsaturated aldehydes

Also Published As

Publication number Publication date
GB998525A (en) 1965-07-14
FR1317560A (en, 2012) 1963-05-08
BE615018A (fr) 1962-09-02
CH424745A (de) 1966-11-30
DE1152696B (de) 1963-08-14

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