US3130233A - Aldehydes and method of preparation - Google Patents

Aldehydes and method of preparation Download PDF

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US3130233A
US3130233A US57886A US5788660A US3130233A US 3130233 A US3130233 A US 3130233A US 57886 A US57886 A US 57886A US 5788660 A US5788660 A US 5788660A US 3130233 A US3130233 A US 3130233A
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cobalt
parts
pressure
aldehydes
hydrogen
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Warren D Niederhauser
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Rohm and Haas Co
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Rohm and Haas Co
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Priority claimed from US800402A external-priority patent/US3054813A/en
Priority to DER27439A priority patent/DE1151497B/de
Priority to FR821423A priority patent/FR1262598A/fr
Priority to GB9307/60A priority patent/GB945770A/en
Application filed by Rohm and Haas Co filed Critical Rohm and Haas Co
Priority to US57886A priority patent/US3130233A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/26—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing hydroxy groups
    • C07C47/27—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing hydroxy groups containing six-membered aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/55—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of oligo- or polymeric oxo-compounds
    • 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
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/228—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing six-membered aromatic rings, e.g. phenylacetaldehyde
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/228—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing six-membered aromatic rings, e.g. phenylacetaldehyde
    • C07C47/232—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing six-membered aromatic rings, e.g. phenylacetaldehyde having unsaturation outside the aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/48—Ring-opening reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Definitions

  • This invention concerns a process for treating 1,2- epoxides to yield aldehydes.
  • This invention also deals with a group of novel and useful B-hydroxyaldehydes and a d-unsaturated aldehydes.
  • the process of this invention comprises treating 1,2- epoxides with carbon monoxide and hydrogen gases under pressure and elevated temperatures in the presence of a hydrofor-mylation catalyst. There results useful aldehydes.
  • the instant process is applicable to compounds containing one or a plurality of 1,2-epoxide groups.
  • polyepoxides such as alkyl esters of epoxidized water-insoluble fatty acids or epoxidized glyceryl esters, there may be obtained products which are mixtures of poly-fi-hydroxyaldehydes and of poly-a,/3-unsaturated aldehydes.
  • alkyl esters of epoxidized water-insoluble fatty acids or epoxidized glyceryl esters there may be obtained products which are mixtures of poly-fi-hydroxyaldehydes and of poly-a,/3-unsaturated aldehydes.
  • it is preferred to use somewhat simpler starting materials which may be classified Within the following three groups:
  • Group A which may be represented by Formula I RCHCHR Where R and R are hydrogen atoms or alkyl groups containing from one to preferably twelve carbon atoms, R and R being alike or difierent;
  • Group B which may be represented by Formula II Where A is an aryl group, preferably containing from six to eight carbon atoms, such as phenyl, tolyl, and xylyl, and
  • R is an alkyl group containing from one to six, preferably one, carbon atoms.
  • the process of this invention yields valuable compounds, a number of which are new.
  • the products resulting from said groups A, B, and C, respectively, may be represented by the following formulas, in which the alphabetical designation corresponds to that given to the starting epoxides and the even numbers designate the afiunsaturated aldehydes, Whereas the uneven numbers specify the S-hydroXyaIdehyde products,
  • the 11, unsaturated aldehyde products include the isomers in which the formyl group and the vicinal vinylene hydro gen atom are on either carbon of the vinylidene insaturation.
  • the isomers in which the hydroxyl and formyl groups are interchangeably bonded onto either of the vicinal carbon atoms onto which originally the epoxy oxygen was bonded are included.
  • the term isomer is intended to define the position interchangeability of the formyl, hydroxyl, and vinylene hydrogen on the carbon atom originally supporting the epoxide oxygen.
  • 1,2- epoxides of the groups A, B and C are subjected to hydrogen and carbon monoxide gases under pressure and elevated temperature in the presence of a hydroformylation catalyst.
  • the total carbon monoxide and hydrogen gas pressure under which the reaction is carried out should preferably range from 900 to 10,000 p.s.i.; advantageously, it is maintained in the range of 1500 to 3000 psi.
  • the reactive temperatures range from to 200 0, preferably from to C.
  • the carbon monoxide and hydrogen gases are employed in a of 1 mole of each gas per epoxide equivalent in the starting material; an excess such as to 1.5 moles per epoxide equivalent of either one or both gases may be employed if desired.
  • the hydrogen to carbon monoxide ratio is not critical, a one to one ratio being quite suitable. Ratios of hydrogen to carbon monoxide in the range of 3 to 1 and 1 to 3, respectively, may also be employed when desired.
  • the gases may be fed to the reaction environment singly or mixed. To promote the reaction, the reacting vessel may be agitated.
  • the progress and extent of the conversion of the epoxides to the aldehydes may be followed by the consumption of the carbon monoxide and hydrogen gases, the conversion being substantially complete when no more consumption of the gases is registered.
  • bromine determinations, analysis for oxirane oxygen and hydroxyl number may be used as an aid in determining the extent of formation of ,B-hydroxyaldehydes and il-unsaturated aldehydes.
  • the reaction is carried out in the presence of one or more inert organic volatile solvents.
  • inert organic volatile solvents Suitable for this purpose are hydrocarbons, such as benzene, ethylbenzene, diethylbenzene, toluene, xylene, cumene, nhexane, propane, cyclohexane, and the like.
  • Such an optional inert solvent generally facilitates handling of r a the starting materials and of the products, particularly of the lower molecular weight materials.
  • the conversion of 1,2-epoxides to aldehydes is carried out in the presence of a hydrofor-mylation catalyst which is a compound of the metals of group VIII of the periodic table having an atomic number from 26 to 28, inclusive, and preferably capable of forming a metal carbonyl under the conditions of the reaction.
  • a hydrofor-mylation catalyst which is a compound of the metals of group VIII of the periodic table having an atomic number from 26 to 28, inclusive, and preferably capable of forming a metal carbonyl under the conditions of the reaction.
  • metals include iron, cobalt, and nickel.
  • Cobalt compounds have been found to be especially suited for the present purpose, particularly oil soluble cobalt salts such as cobalt salts of fatty acids containing two to eighteen, and especially four to eight, carbon atoms. Typical are cobalt butyrate, cobalt octanoate, cobalt oleates, and the like.
  • cobalt compounds include cobalt formate, cobalt acetate, cobalt carbonyl, cobalt anhydride, cobalt carbonate, Raney cobait, cobalt naphthenate, and the like. Finely divided reduced metallic cobalt may also be suitable in special cases.
  • the catalysts may be employed as such or deposited on granular carriers or in intimate mixtures with metallic, mineral, or ceramic materials like kieselghur, clay, glass powder, and the like.
  • the hydroformylation catalyst is used in an amount in the range of 0.1 to and preferably 0.5 to 2 weight percent, calculated as nickel, cobalt or iron metal based on the starting material.
  • 1 mole of a suitable epoxide and cobalt, as cobalt carbonyl in benzene, in an amount of 1% of carbonyl on the weight of epoxide are charged to a stainless steel autoclave.
  • the autoclave is fed with a mixture of carbon monoxide and hydrogen in a 1 to 1 molar ratio till the pressure reaches 2000 p.s.i.; heating is applied to reach 130 to 140 C. while the autoclave is rocked.
  • the pressure stops decreasing the conversion to aldehydes is substantially completed. Pressures and temperatures are allowed to drop and the products are isolated. This may be effectuated by suitable procedures as by fractional distillation under reduced pressure.
  • the aldehyde products formed are generally mixtures of B-hydroxyaldehydes, a,,6-unsaturated hydroxyaldehydes and their respective isomers.
  • the separation of saturated aldehydes from the unsaturated ones may be effectively carried out.
  • the formation of cap-unsaturated aldehydes may be further promoted by continuing heating the product resulting for the conversion of the starting epoxides, at atmospheric pressure or higher, preferably in the presence of water and an acidic catalyst, such as formic acid, acetic acid, boric acid, or mineral acid, such as sulfuric acid.
  • the isolation step it is preferable in the isolation step, to remove residual catalyst from the products of the conversion of the epoxides. This may be elfectuated by converting the cobalt to a water-soluble salt by acid-wash thermal treatment or other suitable means.
  • Typical 0:,B-UI1S2lt1l12ltGd aldehydes prepared in accordance with this method include:
  • the new ,B-hydroxyaldehydes of this invention are useful in the preparation of the corresponding 0:,[3-111158111- rated aldehydes.
  • Conversion to nap-unsaturated aldehydes may be effected by heating the aldols at high temperatures, such as above 150 C., at atmospheric pressures or under superatmospheric pressures.
  • this convension may be carried out in the presence of a catalyst.
  • the fi-hydroxyaldehydes of this invention are valuable in preparing glycols by catalytic reduction such as with platinum, nickel, Raney type catalysts, at temperatures above C. and at superatmospheric pressures.
  • the oxidation of selected [3- hydroxyaldehydes of this invention yields valuable hydroxydicar-boxylic acids.
  • the oxidation may be accomplished with a mild oxidizing agent such as alkaline solutions containing silver or copper salts, or hydrogen peroxide.
  • a mild oxidizing agent such as alkaline solutions containing silver or copper salts, or hydrogen peroxide.
  • methyl 8-hydroXy-9-formylstearate yields the corresponding acid ester.
  • the new 0:,5- unsaturated aldehydes of this invention are valuable for preparing unsaturated dibasic acids by oxidation.
  • Oxidation such as with hydrogen peroxide, under mild conditions yields hydroxyacids.
  • saturated aldehydes is as adjuncts in odoriferous compositions.
  • the more pungent mil-unsaturated aldehydes may be useful in insect repellent preparations, the other aldehydes which have more pleasant fragrance may be used as bases or
  • the autoclave When pressure dropped to 960 p.s.i. and no further drop is recorded, the autoclave is cooled to C. The product is removed; it is distilled rapidly and the distillate is separated from the lower water layer. The product is redistilled through a packed column to give 5.5 parts of methacrolein and 9 parts of crotonaldehyde.
  • Example 2 A hydrogenation bomb is charged with a mixture of 22 parts of ethylene oxide, 40 parts of xylene, and 3.5 parts of a benzene solution of cobalt carbonyl containing 3% cobalt. Pressure is applied to 1500 p.s.i. while heating is maintained within a range of 150 to 180 C. with rocking. When no further drop in pressure is recorded, the bomb is cooled to C. The product is removed and filtered to remove catalyst. Distillation under reduced pressure yields acrolein.
  • Example 3 A stainless steel autoclave of 300 cc. capacity is charged with 60 parts of 1,2-epoxyoctane, parts of xylene, and 8 parts of cobalt carbonyl in xylene containing 5% cobalt.
  • the closed vessel is filled with a mixture of carbon monoxide and hydrogen gas to a pressure of 2700 p.s.i.
  • the vessel is heated, with rocking, to and at a temperature of 135 C. for one hour. As the pressure stops decreasing, heating is discontinued and the vessel is allowed to Example 4 To a hydrogenation bomb of 300 cc.
  • Example 5 The bomb is charged with 87 parts of ethyl 9,10-epoxystearate, parts of benzene and 8 parts of cobalt butyrate in benzene having a 3% cobalt content. The reaction proceeds in the manner described above. The products are ethyl 9,(10)-hydroxy-10,(9)-formylstearate and ethyl 9, l0) -formyloleate.
  • Example 6 The procedure of Example 4 is again followed and the resulting oily product which is formed is fractionally distilled in the presence of 1 gram of phosphoric acid under reduced pressure. The product obtained is an increased proportion of methyl 9,(10)-formyloleate. Separation is eifectuated by fractional distillation under reduced pressure.
  • Example 7 Following the procedure of Example 4, octyl-9,l0- epoxystearate is treated in the presence of cobalt carbonyl with a mixture of carbon monoxide and hydrogen under pressure to yield octyl-9,(10)-hydroxy-(9)-forn1ylstearate and octyl-9,(10)-formyloleate. The products are separated by fractional distillation under reduced pressure.
  • Methyl 13(14)-epoxybehenate is treated in a similar manner to yield methyl l3,( l4)-hydroxy-14,(13)-formyldocosanoate and methyl 15,(l6)-formylerucate.
  • the products are separated by fractional distillation under a reduced pressure of 1 mm. of mercury.
  • Example 8 A mixture of 71 parts of 1-phenyl-2,3-epoxybutane, 40 parts of benzene, and 5 parts of a solution of cobalt carbonyl in benzene containing 3% cobalt are placed in a rocking autoclave.
  • the autoclave is filled with hydrogen and carbon monoxide in a 1 to 1 volume ratio to a pressure of 3000 p.s.i. and heated for 1 /2 hours at to C. When the pressure stops decreasing, heating is discontinued and the bomb is allowed to cool to room temperature.
  • Catalyst is filtered ofi and the product is distilled over a vacuum steam bath to give 77 parts of a mixture of 2-methyl-3-hydroxyl-4-phenylbutanal, 2-meth yl-S-phenyl-Z-butenal, and their respective isomers.
  • the products are separated by fractional distillation at pressure reduced to 1 mm. of mercury.
  • An aldehyde selected from the group consisting of at least one hydroxy aldehyde of the formula in which A represents an aryl group containing from six to eight carbon atoms, and R represents an alkyl group containing from one to six carbon atoms.
  • R is an alkyl group having one carbon atom.
  • a process which comprises reacting a 1,2-epoxide of the formula A-C1-I2CHOH-R4 with a mixture of carbon monoxide and hydrogen gases in a minimum amount of 1 mole of each gas, under a superatmospheric pressure ranging from 900 to 10,000
  • a process for preparing 2-methyl-3-hydroxyl-4- phenylbutanal which comprises reacting 1-phenyl-2,3- epoxybutene with a mixture of at least one mole of carbon monoxide gas and at least one mole of hydrogen gas under superatmospheric pressure, within a temperature range from 100 to 200 C., and in the presence of cobalt carbonyl, and isolating 2-methyl-3-hydroxy-4- phenylbutanal.
  • a process for preparing 2-methy1-3-phenyl-2-butenal which comprises reacting 1-phenyl-2,3-epoxybutene with a mixture of at least one mole of carbon monoxide gas and at least one mole of hydrogen gas under superatmospheric pressure, within a temperature range from 100 to 200 C., and in the presence of cobalt carbonyl, and isolating 2-methyl-3-phenyl-2-butenal.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US57886A 1959-03-19 1960-09-23 Aldehydes and method of preparation Expired - Lifetime US3130233A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL249503D NL249503A (en)) 1959-03-19
DER27439A DE1151497B (de) 1959-03-19 1960-02-27 Verfahren zur UEberfuehrung von 1, 2-Epoxyden in Aldehyde
FR821423A FR1262598A (fr) 1959-03-19 1960-03-15 Procédé de préparation d'aldéhydes à partir de 1, 2-époxydes notamment du type bêta-hydroxyaldéhydes et aldéhydes alpha-bêta non saturés et produits obtenus
GB9307/60A GB945770A (en) 1959-03-19 1960-03-16 Aldehydes and method of preparation
US57886A US3130233A (en) 1959-03-19 1960-09-23 Aldehydes and method of preparation

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US800402A US3054813A (en) 1959-03-19 1959-03-19 Aldehydes and method of preparation
US57886A US3130233A (en) 1959-03-19 1960-09-23 Aldehydes and method of preparation

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FR (1) FR1262598A (en))
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3463819A (en) * 1965-10-21 1969-08-26 Shell Oil Co Glycol production
US4376866A (en) * 1981-01-31 1983-03-15 Dynamit Nobel Ag Process for the preparation of α-hydroxymethylene arylacetic acid

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK2007204T3 (en) 2006-03-03 2017-07-24 The Univ Court Of The Univ Of Aberdeen Pest control agent including geranyl acetone
FR3025923A1 (fr) 2014-09-12 2016-03-18 Orange Discrimination et attenuation de pre-echos dans un signal audionumerique

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2102965A (en) * 1936-04-20 1937-12-21 Du Pont Manufacture of unsaturated aldehydes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2102965A (en) * 1936-04-20 1937-12-21 Du Pont Manufacture of unsaturated aldehydes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3463819A (en) * 1965-10-21 1969-08-26 Shell Oil Co Glycol production
US4376866A (en) * 1981-01-31 1983-03-15 Dynamit Nobel Ag Process for the preparation of α-hydroxymethylene arylacetic acid

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FR1262598A (fr) 1961-06-05
DE1151497B (de) 1963-07-18
NL249503A (en))
GB945770A (en) 1964-01-08

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