US3054813A - Aldehydes and method of preparation - Google Patents

Aldehydes and method of preparation Download PDF

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Publication number
US3054813A
US3054813A US800402A US80040259A US3054813A US 3054813 A US3054813 A US 3054813A US 800402 A US800402 A US 800402A US 80040259 A US80040259 A US 80040259A US 3054813 A US3054813 A US 3054813A
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Prior art keywords
cobalt
methyl
aldehydes
parts
hydroxy
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Expired - Lifetime
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US800402A
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English (en)
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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 to NL249503D priority Critical patent/NL249503A/xx
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Priority to US800402A priority patent/US3054813A/en
Priority to DER27439A priority patent/DE1151497B/de
Priority to FR821423A priority patent/FR1262598A/fr
Priority to BE588645A priority patent/BE588645A/fr
Priority to GB9307/60A priority patent/GB945770A/en
Priority to US57886A priority patent/US3130233A/en
Application granted granted Critical
Publication of US3054813A publication Critical patent/US3054813A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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
    • C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • 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

  • the process of this invention comprises treating 1,2- epoxides with carbon monoxide and hydrogen gases un der pressure and elevated temperatures in the presence of 21 hydroformylatiou catalyst. There results useful aldeydes.
  • 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-B-hydroxyaldehydes and of poly-u,,8-unsaturated aldehydes.
  • it is preferred to use somewhat simpler starting material-s which maybe classified within the following three groups:
  • Group A which may be represented by Formula I where R and R are hydrogen atoms or alkyl groups containing from one to preferably twelve carbon atoms, R and R being alike or different;
  • Group B which may be represented by Formula II where R represents an alkyl group containing from one to eleven carbon atoms, R represents an alkyl group containing one to eighteen, preferably one to eight carbon atoms, and
  • n is an integer from eight to eleven, the total number of carbon atoms of compounds of group B preferably ranging from twenty to thirty, and
  • Group C which may be represented by Formula HI 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 9- unsaturated aldehydes, whereas the uneven numbers specify the ,B-hydroxyaldehyde products,
  • the s unsaturated aldehyde products include the isomers in which the formyl group and the vicinal vinylene hydrogen atom are on either carbon of the vinylene unsaturation.
  • 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.
  • 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.; advan tageously, it is maintained in the range of 1500 to 3000 psi.
  • the reactive temperatures range from 100 to 200 0., preferably. from 120 to 150 C.
  • the carbon monoxide and hydrogen gases are employed in a-minimum 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 of both gases may be employed if desired.
  • the hydrogento 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 l and 1 to 3, respectively, may also be employed when desired.
  • the gasses 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 lt-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 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 hydroformylation 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 hydroformylation 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.
  • 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 eflectuated by suitable procedures as by fractional distillation under reduced pressure.
  • the aldehyde products formed are generally mixtures of ,B-hydroxyaldehydes, a,[i-11nsaturated hydroxyaldehydes and their respective isomers.
  • the separation of saturated aldehydes from the unsaturated ones may be effectively carried out.
  • the formation of a,fi-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 catalystfrom the products of the conversion of the epoxides. This may be efliectuated by converting the cobalt to a water-soluble salt by acid-wash thermal treatment or other suitable means.
  • Typical a,fl-unsaturated aldehydes prepared in accordance with this method include:
  • the new B-hydroxyaldehydes of this invention are useful in the preparation of the corresponding a,fl-unsaturated aldehydes.
  • Conversion to mil-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 conversion 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 100 C. and at superatmospheric pressures.
  • the oxidation of selected fi-hydroxyaldehydes of this invention yields valuable hydroxydicarboxylic 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 nip-unsaturated aldehydes of this invention are valuable for preparing unsaturated dibasic acids by oxidation. Oxidation, such as with hydrogen peroxide, under mild conditions yields hydroxy-acids.
  • Another use for the a,;8-unsaturated aldehydes is as adjuncts in odoriferous compositions.
  • a typical insect repellent composition may be prepared from:
  • Example 7 To a stainless steel autoclave of 300 cc. capacity, there are charged 29 parts of propylene oxide, 40 parts of xylene, and 5 parts of a solution of cobalt carbonyl in benzene containing 3% cobalt.
  • Example 4 To a hydrogenation bomb of 300 cc. capacity, there are charged 87 parts of methyl 9,10-epoxystearate, 50 parts of benzene, and 8 parts of cobalt carbonyl in benzene having a 3% cobalt content. Carbon monoxide and hydrogen are fed into the bomb to a pressure of 2600 p.s.i. and heat is applied to and maintained at 120 to 150 C. for one hour, with rocking. Upon a drop of pressure to 1420 p.s.i., and when no further uptake of gas is recorded, the bomb is cooled to room temperature. Catalyst is separated and solvent is distilled from the product.
  • Example 5 The bomb is charged with 87 parts of ethyl 9,10-epoxystearate, 5'5 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 9,610) -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,(l)-formyloleate. Separation is effectuated 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 care bonyl with a mixture of carbon monoxide and hydrogen under pressure to yield octyl-9,(10)-hydroxy-(9)-formylstearate and octyl-9,(10)-fonnyloleate. The products are separated by fractional distillation under reduced pressure.
  • Methyl 13,(14)-epoxybehenate is treated in a similar manner to yield methyl 13,( l4)-hydroxy-14,(l3)-formyldocosanoate and methyl 15,(16)-formylerucate.
  • the products are separated by fractional distillation under a reduced pressure of 1 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 l 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 oil and the product is distilled over a vacuum steam bath to give 77 parts of a mixture of Z-methyl 3 hydroxyl 4 phenylbutenal, 2- methyl-3-phenyl-2-butena1, and their respective isomers.
  • the products are separated by fractional distillation at pressure reduced to 1 mm. of mercury.
  • R represents an alkyl group containing from one to eight carbon atoms
  • R represents an alkyl group containing from one to eight carbon atoms
  • n represents an integer from 8 to 11, the total number of carbon atoms of the compound ranging from twenty to thirty.
  • a process which comprises reacting a 1,2-epoxide of the formula 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 p.s.i., at a temperature ranging from 100 to 200 C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US800402A 1959-03-19 1959-03-19 Aldehydes and method of preparation Expired - Lifetime US3054813A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL249503D NL249503A (fr) 1959-03-19
US800402A US3054813A (en) 1959-03-19 1959-03-19 Aldehydes and method of preparation
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
BE588645A BE588645A (fr) 1959-03-19 1960-03-15 Procédé de préparation d'aldéhyde à partir de 1,2, époxydes.
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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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3456017A (en) * 1965-10-21 1969-07-15 Shell Oil Co Glycol production
US3687981A (en) * 1968-01-17 1972-08-29 Du Pont Process for making a dioxane
US4873379A (en) * 1988-05-25 1989-10-10 Hoechst Celanese Corporation Process for making 1,3-diols from epoxides
US4935554A (en) * 1986-08-20 1990-06-19 Hoechst Celanese Corporation Process for making 1,3-diols from epoxides
US5053562A (en) * 1990-07-31 1991-10-01 Hoechst Celanese Corporation Process for making 1,3-diols from epoxides

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL80786C (fr) *
US2187334A (en) * 1935-01-16 1940-01-16 Deutsche Hydrierwerke Ag Condensation products of higher fatty acid compounds with boric acid
US2425200A (en) * 1947-08-05 Modifying drying oils
US2752394A (en) * 1951-12-18 1956-06-26 Sorensen Nils Andreas Method of manufacturing vanillin
US2774791A (en) * 1953-10-19 1956-12-18 Monsanto Chemicals Water soluble substituted p-hydroxybenzaldehyde-alkali metal and alkaline earth metal carbonate and bicarbonate solid complexes
US2820059A (en) * 1956-04-18 1958-01-14 Eastman Kodak Co Improved hydroformylation catalysts and reaction media containing nitrogen bases

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL80786C (fr) *
US2425200A (en) * 1947-08-05 Modifying drying oils
US2187334A (en) * 1935-01-16 1940-01-16 Deutsche Hydrierwerke Ag Condensation products of higher fatty acid compounds with boric acid
US2752394A (en) * 1951-12-18 1956-06-26 Sorensen Nils Andreas Method of manufacturing vanillin
US2774791A (en) * 1953-10-19 1956-12-18 Monsanto Chemicals Water soluble substituted p-hydroxybenzaldehyde-alkali metal and alkaline earth metal carbonate and bicarbonate solid complexes
US2820059A (en) * 1956-04-18 1958-01-14 Eastman Kodak Co Improved hydroformylation catalysts and reaction media containing nitrogen bases

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3456017A (en) * 1965-10-21 1969-07-15 Shell Oil Co Glycol production
US3687981A (en) * 1968-01-17 1972-08-29 Du Pont Process for making a dioxane
US4935554A (en) * 1986-08-20 1990-06-19 Hoechst Celanese Corporation Process for making 1,3-diols from epoxides
US4873379A (en) * 1988-05-25 1989-10-10 Hoechst Celanese Corporation Process for making 1,3-diols from epoxides
US5053562A (en) * 1990-07-31 1991-10-01 Hoechst Celanese Corporation Process for making 1,3-diols from epoxides

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