US3358015A - Preparation of unsaturated acid esters from unsaturated aldehydes - Google Patents

Preparation of unsaturated acid esters from unsaturated aldehydes Download PDF

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Publication number
US3358015A
US3358015A US323099A US32309963A US3358015A US 3358015 A US3358015 A US 3358015A US 323099 A US323099 A US 323099A US 32309963 A US32309963 A US 32309963A US 3358015 A US3358015 A US 3358015A
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US
United States
Prior art keywords
aldehyde
hydroperoxide
ester
reaction mixture
unsaturated
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
Application number
US323099A
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English (en)
Inventor
Schlossman Irwin
Charles N Winnick
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atlantic Richfield Co
Original Assignee
Halcon International Inc
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 Halcon International Inc filed Critical Halcon International Inc
Priority to US323099A priority Critical patent/US3358015A/en
Priority to BE655088D priority patent/BE655088A/xx
Priority to GB44690/64A priority patent/GB1015877A/en
Priority to LU47283A priority patent/LU47283A1/xx
Priority to NL6412904A priority patent/NL6412904A/xx
Priority to FR994411A priority patent/FR1450428A/fr
Priority to ES0305951A priority patent/ES305951A1/es
Priority to DE19641468044 priority patent/DE1468044A1/de
Priority to CH1458764A priority patent/CH435271A/fr
Application granted granted Critical
Publication of US3358015A publication Critical patent/US3358015A/en
Assigned to HALCON RESEARCH AND DEVELOPMENT CORPORATION reassignment HALCON RESEARCH AND DEVELOPMENT CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HALCON INTERNATIONAL, INC.
Assigned to ATLANTIC RICHFIELD COMPANY reassignment ATLANTIC RICHFIELD COMPANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HALCON RESEARCH AND DEVELOPMENT CORPORATION, A CORP. OF DE
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester

Definitions

  • This invention relates to processes for the production of carboxylic esters from corresponding aldehydes and alcohols, and more particularly to the production of an unsaturated ester from a corresponding unsaturated aldehyde by reaction of the latter with an organic hydroperoxide in the presence of a redox material dispersed in alcohol. It relates especially to preparing methyl methacrylate from methacrolein, methanol, t-butyl hydroperoxide and ferrous chloride and/or ferric chloride.
  • the process for preparing an ester from an aldehyde which comprises reacting an organic hydroperoxide with an aldehyde in the presence of a non-tertiary alkanol and a redox material of an element from the group of elements having an atomic number of 22 to 28, 50, 58 and 82 inclusive to form the alkanol ester of the acid corresponding to the aldehyde, the ester being recovered as product;
  • aldehyde is an alpha, beta-ethylenic aldehyde and the alkanol is primary and contains one to twelve carbon atoms;
  • reaction mixture contains substantially stoichiometric amounts of the hydroperoxide and the aldehyde, and an excess of the alkanol;
  • the ester is recovered by fractional distillation and purified, in known manner.
  • the ester-methanol azeotrope is obtained, and then the ester is separated therefrom, e.g. by extraction and/or distillation.
  • EXAMPLE III a Following the procedure of Example I except that 7.9 g. (0.4 mol) of FeCl .4H O and 9.7 g. (0.6 mol) of FeCl is used, in place of 10.0 g. if FeCl 4H O, methacrolein conversion is 53% and the selectivity to methylmethacrylate is 77 mol percent.
  • the bromides give similar results.
  • organic hydroperoxides are employed as oxidizing agents.
  • T-butylhydroperoxide gives particularly outstanding results.
  • Secondary or tertiary hydroperoxides generally are desirable.
  • Illustrative hydroperoxides can be represented generally by the formula ROOH where R is an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aralkyl, hydroxyalkyl, hydroxycycloalkyl, hydroxyaralkyl, and the like group having about 2 to 20 carbon atoms.
  • organic hydroperoxides are cumene hydroperoxide, cyclohexyl hydroperoxide, l-hydroxy-cyclohexyl hydroperoxide, cyclohex-Z-enyl hydroperoxide, and the like. Mixtures thereof can be used.
  • the process of the invention is particularly suitable for reacting unsaturated aldehydes for producing the corresponding monomeric esters, especially aldehydes and esters such as acrylic esters and alpha substituted acrylic esters which have a strong tendency to undergo polymerization.
  • aldehydes having up to 20 or more carbon atoms in the molecule may be used.
  • the process may be applied to such compounds wherein the unsaturation is in any location in the molecule, but the alpha, beta-ethylenic aldehydes are especially important.
  • the aldehydes may be substituted by hydroxy, ether, carboxylic acil, carboxylic acid ester, keto, nitro, and the like groups, or halogen atoms.
  • the reaction is carried out by adding an organic hydroperoxide or mixture of such hydroperoxides and a redox agent to a solution of an aldehyde such as an alpha, betaethylenic aldehyde in the appropriate reactive primary or secondary alkanol, for example, methanol, ethanol, or other non-tertiary alcohol having up to about 12 carbon atoms in the molecule.
  • an aldehyde such as an alpha, betaethylenic aldehyde in the appropriate reactive primary or secondary alkanol, for example, methanol, ethanol, or other non-tertiary alcohol having up to about 12 carbon atoms in the molecule.
  • Ferrous or ferric ion is a preferred redox agent, and it can be introduced by adding ferrous or ferric chloride or other soluble iron salt or salts to the reaction mixture; chlorides and bromides are the preferred salts.
  • redox agents which can be used instead of or together with the ferrous or ferric ions in the new process include cobaltous, manganous, stannous, cerous, nickelous, plumbous, titanous, chromous, vanadous and the like ions in solution, or mixtures thereof. These metals have atomic numbers 22 to 28, 50, 5'8 and 82.
  • the redox agent or mixtures thereof can be employed in stoichiometric amounts relative to the hydroperoxide or in excess thereof, e.g. up to about double the amount. However, less than stoichiometric amounts are operable and generally preferable. In general at least 0.05 equivalent of redox agent or agents per equivalent of hydroperoxide is used; a desirable range is 0.1 to 0.5 equivalent of agent per equivalent of hydroperoxide.
  • the redox agents may be employed in any one of their valance states. For example, equally good results are obtained with either ferrous or ferric chloride. An acidic environment is sometimes desirable, and it is achieved by adding a small amount of sulfuric or hydrochloric or other strong acid to the reaction mixture.
  • a redox couple may be employed, for example, ferrous-ferric or 60- balt-ous-cobaltic, and the like, or a mixed couple such as cobaltous-ferric, man-ganous-stannic and the like.
  • the concentration of the aldehyde or aclolein in the reaction mixture may be in the range of 1 to 50% by weight, preferably in the range of to
  • the reaction temperature may be from 50 C. to +150 C., desirably 0 to 100 C., and preferably in the range of room temperature or somewhat below up to about 60 C.
  • the pressure may be atmospheric, or above or below,
  • reaction time may be in the range. of. 10. minutes.
  • the ratio of the hydroperoxide is in the range of 0.1 to 2 mols per mol of the acrolein, preferably 0.5 to 1.0.
  • the process may be carried out batchwise, or in an intermittent or continuous manner.
  • the reaction may be carried out in an elongated reaction zone such as a tube or a tower or a plurality of reactors connected in series, and the hydroperoxide may be introduced at space points along the path of flow of the solution or mixture.
  • a process for the production of an organic ester which comprises: forming a reaction mixture which contains (1) an organic peroxide, (2) an alpha-beta-ethylenic aldehyde, (3) a non-tertiary alkanol having up to 12 carbon atoms per molecule and (4) a red-ox agent consisting essentially of at least one soluble ion selected from the group consisting of ferric and ferrous; said reaction mixture containing from 1 to 50% by weight of said aldehyde, a ratio of 0.1 to 2 moles per mole of hydroperoxide per mole of aldehyde, and 0.05 to 2 equivalents of said redox agent per equivalent of hydroperoxide; said reaction mixture being substantially free of copper ions; reacting said mixture at a temperature of -50 to C. to form an alk-anol ester corresponding to said aldehyde; and recovering said ester as product.
  • a process for the production of methylmethacrylate which comprises: forming a reaction mixture which contains (1) t-butyl hydroperoxide, (2) 'methylacrolein, (.3) methanol and (4) a redox agent. consisting of soluble ferric and ferrous ions; said reaction mixture containing 1 to 50% by weight of saidmethacrolein, 0.1 to 2 moles per mole of t-butyl hydroperoxide per mole of methacrolein, and 0.05 to 2 equivalents of said redox agent per equivalent of. hydroperoxide; said reaction mixture being substantially free of copper ions; reacting said mixture to form methylmethacrylate and recovering said methylmethacrylate as a product.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US323099A 1963-11-12 1963-11-12 Preparation of unsaturated acid esters from unsaturated aldehydes Expired - Lifetime US3358015A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US323099A US3358015A (en) 1963-11-12 1963-11-12 Preparation of unsaturated acid esters from unsaturated aldehydes
BE655088D BE655088A (fr) 1963-11-12 1964-10-30
GB44690/64A GB1015877A (en) 1963-11-12 1964-11-03 Production of carboxylic acid esters
LU47283A LU47283A1 (fr) 1963-11-12 1964-11-05
NL6412904A NL6412904A (fr) 1963-11-12 1964-11-05
FR994411A FR1450428A (fr) 1963-11-12 1964-11-10 Procédé de production d'esters carboxyliques
ES0305951A ES305951A1 (es) 1963-11-12 1964-11-12 Procedimiento para la obtencion de esteres carboxilicos
DE19641468044 DE1468044A1 (de) 1963-11-12 1964-11-12 Verfahren zur Herstellung von Carbonsaeureestern
CH1458764A CH435271A (fr) 1963-11-12 1964-11-12 Procédé de préparation d'un ester

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US323099A US3358015A (en) 1963-11-12 1963-11-12 Preparation of unsaturated acid esters from unsaturated aldehydes

Publications (1)

Publication Number Publication Date
US3358015A true US3358015A (en) 1967-12-12

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
US323099A Expired - Lifetime US3358015A (en) 1963-11-12 1963-11-12 Preparation of unsaturated acid esters from unsaturated aldehydes

Country Status (9)

Country Link
US (1) US3358015A (fr)
BE (1) BE655088A (fr)
CH (1) CH435271A (fr)
DE (1) DE1468044A1 (fr)
ES (1) ES305951A1 (fr)
FR (1) FR1450428A (fr)
GB (1) GB1015877A (fr)
LU (1) LU47283A1 (fr)
NL (1) NL6412904A (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3075000A (en) * 1961-08-21 1963-01-22 Shell Oil Co Oxidation of aldehydes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3075000A (en) * 1961-08-21 1963-01-22 Shell Oil Co Oxidation of aldehydes

Also Published As

Publication number Publication date
BE655088A (fr) 1965-04-30
FR1450428A (fr) 1966-06-24
NL6412904A (fr) 1965-05-13
DE1468044A1 (de) 1969-01-30
CH435271A (fr) 1967-05-15
LU47283A1 (fr) 1966-05-05
ES305951A1 (es) 1965-03-01
GB1015877A (en) 1966-01-05

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Owner name: ATLANTIC RICHFIELD COMPANY, 1500 MARKET STREET, PH

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:HALCON RESEARCH AND DEVELOPMENT CORPORATION, A CORP. OF DE;REEL/FRAME:003845/0048

Effective date: 19810304