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WO1988002361A1 - Procede de catalyse acide - Google Patents

Procede de catalyse acide Download PDF

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Publication number
WO1988002361A1
WO1988002361A1 PCT/US1987/002498 US8702498W WO8802361A1 WO 1988002361 A1 WO1988002361 A1 WO 1988002361A1 US 8702498 W US8702498 W US 8702498W WO 8802361 A1 WO8802361 A1 WO 8802361A1
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WO
WIPO (PCT)
Prior art keywords
reactant
reaction product
group
acid
catalyst
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.)
Ceased
Application number
PCT/US1987/002498
Other languages
English (en)
Inventor
Gevork Minaskanian
James V. Peck
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.)
Nelson Research and Development Co
Original Assignee
Nelson Research and Development Co
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 Nelson Research and Development Co filed Critical Nelson Research and Development Co
Publication of WO1988002361A1 publication Critical patent/WO1988002361A1/fr
Priority to KR1019880700612A priority Critical patent/KR880701701A/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C07C5/2791—Catalytic processes with metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides

Definitions

  • This invention relates to an improved process for the acid-catalyzed conversion of a reactant into a reaction product.
  • Reactants which may be converted into reaction products in the process of this invention include hydrocarbons and heteroatom-substituted hydrocarbons, wherein said heteroatoms may be selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and halogen atoms.
  • olefins may be reacted with tertiary alkanes to provide alkylated products; olefins may be reacted with carboxylic acids to obtain esters; alcohols may be dehydrated to obtain olefins or ethers or reacted with an aromatic compound or a carboxylic acid to obtain an alkylated product or an ester, respectively; anhydrides may be reacted with an aromatic or an olefinic compound to obtain acetylated derivatives thereof; epoxides may be reacted to the corresponding glycols; etc.
  • the acidic catalyst may be used in a homogeneous or heterogeneous mode, i.e. the catalyst can be dissolved in the reactant-containing solution or the catalyst may exist in a different phase than the reactant and/or the reaction products.
  • Homogeneous acid catalysts may have certain advantages over heterogeneous acid catalysts, such as increased activity or selectivity, provided separation of the reaction products from the catalyst is easily carried out. Since such separation may be difficult, many times a heterogeneous acid catalyst is preferred, even if when the activity or selectivity is less than a homogeneous catalyst in the same reaction.
  • One widely used class of heterogeneous acid catalysts is the solid polystyrene sulfonic acids.
  • the present invention provides a process for the conversion of a reactant into a reaction product in the presence of an acid catalyst which comprises contacting said reactant with an acid catalyst comprising a compound represented by the general formula
  • X is selected from the group consisting of oxygen, sulfur or represents 2 hydrogen atoms
  • Z is the anion of a strong acid, 'and preferably Z is selected from the group consisting of chloride, bromide, bisulfate, nitrate or dihydrogen phosphate
  • R is hydrogen or a lower alkyl radical having from one to four carbon atoms
  • R is hydrogen or a methyl radical
  • n is 0 or 1 and o is 0 or an integer of from 1 to 17, at reaction conditions, and recovering a reaction product.
  • X is oxygen
  • Z is bromide
  • R is methyl
  • R 1 is hydrogen
  • n is 0.
  • m is 4 and o is an integer of from 1 to 17, e.g. an integer of from 5 to 11.
  • o is 11.
  • the most preferred acid catalyst comprises n-dodecyl- azacycloheptan-2-one, e.g. as the HBr salt.
  • This invention provides an improved process for converting reactants, especially organic reactants, to reaction products in the presence of an acid catalyst.
  • the improvement in said process is found in the choice of the compounds which function as the acid catalyst and are defined below.
  • these compounds increase the rate, of reaction, as compared to other well known acid catalysts, e.g. polystyrene sulfonic acids, (which comprises sulfonic acid groups pendant from a polystyrene polymer backbone) and are more stable with time and temperature, as compared to said polystyrene sulfonic acid catalysts.
  • the reactants utilized in the process of this invention are hydrocarbons or hydrocarbons substituted with heteroato s such as nitrogen, oxygen, sulfur, phosphorus and halogen atoms; and especially oxygen atoms.
  • the olefin is contacted with the acid catalyst, described below, in the presence of another reactant to yield reaction products of said olefin and said other reactant.
  • said second reactant may include a hydroxyl group to yield an ether or an alcohol.
  • alkanols having from one to four carbon atoms may be reacted with olefins having from two to seven carbon atoms in the presence of the acid catalysts described below to yield ethers.
  • Particularly preferred is the reaction of methanol and isobutylene, isoa ylene or propylene to yield methyl- tertiary butyl ether, methyl-tertiary amyl ether or methyl isopropyl ether, respectively.
  • Such reactions may take place at a temperature of from 15 to 200°C. and a pressure of from 1 to 10 atmospheres.
  • Olefins may also be contacted with a carboxylic acid in the process of this invention to yield esters.
  • straight chain olefins having from two to ten carbon atoms, isobutylene or cyclohexene may be reacted in the presence of carboxylic acids having from one to eight carbon atoms at a temperature within the range of 0°C. to 100°C. to yield the corresponding esters as the reaction product.
  • U.S. Patent 3,037,052 to Bortnick gives the details on this general reaction and is hereby incorporated by reference to show specific reactants and reaction conditions.
  • Particularly preferred reactions include the reaction of monoolefins having from one to eight carbon atoms, more preferably from two to four carbon atoms, with methacrylic acid, acrylic acid, acetic acid or phthalic acid to obtain the corresponding esters.
  • esters of acrylic acid and methacrylic acid are useful monomers for the preparation of acrylic plastics and rubbers.
  • the acetate esters are useful as solvents.
  • the phthalic esters are useful as plasticizers.
  • Alcohols having from one to eight carbon atoms, more preferbly from one to four carbon atoms are reacted, in the presence of the acid catalyst described below, to yield either ethers or olefins (by dehydration).
  • ethers or olefins by dehydration.
  • methanol or ethanol may be reacted at a temperature of from 40° to 100°C and a pressure of from 1 to 5 atmospheres to yield dimethyl ether or diethyl ether, respectively.
  • Tertiary butanol may be dehydrated to isobutene at a temperature of from 40°to 100 Q C.
  • butanediol may be dehydrated to tetrahydrofuran.
  • alcohols may be reacted in the presence of a second reactant to provide reaction products of said alcohol and said second reactant.
  • said second reactant may comprise a carboxylic acid group or an aromatic group to yield an ester or an alkylated aromatic, respectively.
  • anhydride Another reactant that may be used in the process of the present invention is an anhydride.
  • anhydrides such as acetic anhydride
  • acetic anhydride may be reacted with a compound having an aromatic group or an olefinic group to yield acetylated aromatics or acetylated olefins, respectively.
  • acetic anhydride may be reacted with anisole to provide p-methoxyacetophenone or with diisobutylene to provide 2,2-methyl, 6-oxo-hept-4- ene.
  • These reactions can be carried out at a temperature of from 40° to 100°C and a pressure of from 1 to 5 atmospheres.
  • Aldehydes or ketones may be condensed to provide the respective condensed products by means of the process of the present invention.
  • 2-ethylhexenal may be prepared by condensing two molecules of n-butyraldehyde at a temperature of from 40° to 100°C and a pressure of from 1 to 5 atmospheres.
  • methylisobutyl ketone may be condensed to l-methyl-4-methyl-6-oxo-9-methylnon-4-ene.
  • aldehydes and ketones having from one to ten carbon atoms,may be condensed to provide dimers thereof in the process of the present invention.
  • aldehydes and ketones may be reacted in the presence of-an aromatic compound to obtain the resulting reaction products.
  • acetone may be reacted with phenol to yield bisphenol A and formaldehyde may be reacted with aniline to yield diaminodiphenylmethane.
  • the above aldehydes and ketones may be reacted in the presence of an aromatic compound to obtain the resulting reaction products.
  • acetone may be reacted with phenol to yield bisphenol A and formalehyde may be reacted with aniline to yield diaminodiphenylmethane.
  • Peroxides or hydroperoxides may be decomposed to the corresponding decomposition products by the process of this invention.
  • cumene hydroperoxide may be decomposed to acetone and phenol at low temperatures as compared to the non-acid catalyzed decomposition.
  • the acid catalysts of this invention are not heat sensitive.
  • Glycols may be prepared by utilizing an epoxide as the reactant in the process of the present invention.
  • ethylene oxide and propylene oxide may be converted to ethylene glycol and propylene glycol, respectively.
  • Esters may be converted, efficiently, to carboxylic acid and alcohol in the present inventive process. Similarl acetals may be hydrolyzed by this process. For example, sucrose may be hydrolyzed to fructose and glucose. It is important to note that all of the above examples of reactants, reaction products and reaction conditions are known in the art. The present invention resides in the improvement to such process examples by use of the compounds described below, in detail, as the acidic catalyst to obtain increased rates of reaction, on an equivalent acid basis, as compared to other known catalysts, such as polystyrene sulfonic acid.
  • Gaseous hydrogen bromide is bubbled through a solution of l-(n-dodecyl)-azacycloheptan-2-one in diethyl ether to provide an immediate white precipitate.
  • the resultant suspension is filtered and the solid washed with diethyl ether. This is then dried under vacuum to give the hydrogen bromide salt of l-(n-dodecyl)- azacycloheptan-2-one.
  • the above acid catalysts are also useful as acid sources. These salts are stable, non-hygroscopic solids which are useful replacements for solid acid sources known in the prior art. Since they are of known stoichiometric composition, the exact equivalent of any desired amount of acid may be conveniently weighed and safely handled. This offers significant advantage over acid solutions, which are hazardous and must be titrated to determine exact acid content.
  • examples of the above salts' utility are removal of oxide impurities from a vapor-deposited semi-conductor coating, cleaning metals ranging from solder fluxing agents to household cleaners for plumbing fixtures by the dissolution of inorganic deposit without significantly attacking the base metal, and dissolution of various oxides present in the mill scale formed in the hot rolling process (steel pickling).
  • these agents function as acid inhibitors.
  • Other processes include converting lignocellulose to hexose and pentose, preparing invert sugar by reaction with a sucrose solution, hydrolyzing starch to obtain sugar syrups, cleaning chemical process equipment including austenitic stainless steel parts in, for example, supercritical steam generators and nuclear power systems, removing from equipment coritaminan ⁇ s such as wax from crude oil, tars from coal distillation, oil and grease used for lubrication, special grease-type preservatives used as protective coatings, cleaning and lubricating drilling bits, etc.
  • the "parent" compounds of the above acid salts are useful as acid scavengers.
  • excess acid may be removed from acid-washed equipment, acid burns may be treated with these non-toxic agents, trace amounts of acid unacceptable to chemical processes may be precipi ⁇ tated from the reaction solution with these agents, etc.
  • reaction rate is monitored by measuring the flow of the olefin, i.e. isobutylene, which is a reaction product arising from the dehydration of tertiary-butanol according to the reaction:
  • An induction period is observed, after which the reaction rate increases to a maximum and, over a long period of time, the catalyst activity declines as the tertiary butanol becomes rich in reaction product water. The water accumulates at the acid site, thereby "levelling" the acidity.
  • Example 2 In this example, the reaction between isobutylene and acetic acid to give tertiary-butyl acetate is catalyzed by the. acid catalyst of Example 1. This is accomplished either batchwise or in a continuous flow reactor. At a 2.4 to 3.3 mole ratio of acetic acid to isobutylene, 85 percent conversion to t-butyl acetate, based on isobutylene, is achieved utilizing a fixed bed reactor and 9-10 minutes contact time. Polymerization is not significant as only from a trace to 1.6 percent of CgH 16 is detected. The reaction conditions for this reaction is described in U.S. Patent 3,678,099 to Kemp, which is hereby incorporated by reference. While particular embodiments of the invention have been described it will be understood of course that the invention is not limited thereto since many obvious modifications can be made and it is intended to include within this invention any such modifications as will fall within the scope fo the appended claims.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Procédé amélioré de conversion, catalysée en condition acide, d'un réactant en produit de réaction, dans lequel l'amélioration consiste à mettre en contact ledit réactant avec un catalyseur acide représenté par la formule générale (I), dans laquelle X est choisi dans le groupe que représentent l'oxygène et le soufre, ou représente 2 atomes d'hydrogène; Z est choisi dans le groupe des anions d'acides forts, par exemple un chlorure, un bromure, un sulfate acide, un nitrate ou phosphate dihydrogéné; R1 est l'hydrogène ou un alkyle inférieur de 1 à 4 atomes de carbone; R est l'hydrogène ou un radical méthyle; m est un nombre entier de 2 à 6; n est 0 ou 1; et o est 0 ou un entier de 1 à 17, dans des conditions de réaction, et à recueillir le produit de la réaction. Les réactants qui peuvent être convertis en produits de réaction selon ce procédé comprennent les carbures d'hydrogène et les carbures d'hydrogènes substitués par des hétéro-atomes, lesdits hétéro-atomes pouvant être choisis dans le groupe comprenant l'azote, l'oxygène, le soufre, le phosphore et les atomes d'halogènes. On peut, par exemple, faire réagir des oléfines avec des alcanes tertiaires pour obtenir des produits alkylés; on peut faire réagir des oléfines avec des acides carboxyliques pour obtenir des esters; on peut obtenir des oléfines ou des éthers par déshydratation d'alcools ou faire réagir des alcools avec un acide carboxylique pour obtenir un produit alkylé ou un ester; on peut faire réagir des anhydrides avec un composé oléfinique ou aromatique pour en obtenir des dérivés acétylés; on peut faire réagir des époxydes avec les glycols correspondants etc.
PCT/US1987/002498 1986-10-01 1987-09-28 Procede de catalyse acide Ceased WO1988002361A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019880700612A KR880701701A (ko) 1986-10-01 1988-05-31 산 촉매화법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US91399586A 1986-10-01 1986-10-01
US913,995 1986-10-01

Publications (1)

Publication Number Publication Date
WO1988002361A1 true WO1988002361A1 (fr) 1988-04-07

Family

ID=25433787

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1987/002498 Ceased WO1988002361A1 (fr) 1986-10-01 1987-09-28 Procede de catalyse acide

Country Status (5)

Country Link
EP (1) EP0324787A4 (fr)
JP (1) JPH02500363A (fr)
KR (1) KR880701701A (fr)
AU (1) AU8108387A (fr)
WO (1) WO1988002361A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011037681A1 (fr) * 2009-09-24 2011-03-31 Signa Chemistry, Inc. Déshydratation catalytique d'alcools au moyen de catalyseurs acides non volatiles
KR20190004279A (ko) * 2016-05-06 2019-01-11 주식회사 쿠라레 공액 디엔의 제조 방법

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1217770A (fr) * 1981-09-11 1987-02-10 Eric F.V. Scriven Catalyseurs a base de derives de substitution en 4 de la pyridine
US4663467A (en) * 1984-03-05 1987-05-05 The Dow Chemical Company Novel porphyrinate and amine composition useful as catalysts in the preparation of alkylene carbonates
GB8414767D0 (en) * 1984-06-09 1984-07-11 Bp Chem Int Ltd Catalysis by supported catalysts
GB2198725B (en) * 1986-11-05 1991-01-16 Alter Sa Use of a series of quaternary ammonium salts as phase-transfer catalysts

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Vol. 102, No. 10 issued 1984 (Columbus, Ohio, USA), SOLODOVNIK, P.I. et al, Catalysis of Isocyanate Reaction with Alcohols and Water the Abstract No. 85019k, Latv. PSR Zinat. Akad. Vestis Kim. Ser. (6) 687-96, 1984 see entire reference. *
CHEMICAL ABSTRACTS, Vol. 80, No. 2, No. 2, issued 1973 (Columbus, Ohio, USA), KAPUSCINSKE, MELAL "Alkaline Polymerization of G-Caprolactams I.L. Effect of the Activator/Iniviator Ratio of the Molecular Weight Distribution" the Abstract No. 3994c. Collect. Czech. Chem. Commun. 38(8)2281-7 1973 see entire reference. *
CHEMICAL ABSTRACTS, Vol. 81, No. 23, issued 1974 (Columbus, Ohio, USA), ISAGAWA, KELAL, "Catalysis by Certain Unreadable Text in an Aqueous Phase". the Abstract No. 151587v J.Org.Chem. 39(21), 3171-2 1974 see entire document. *
CHEMICAL ABSTRACTS, Vol. 86, No. 10 issued 1976, (Columbus, Ohio, USA), KARASAWAY et al, "Thermosetting Epoxy Resin Composition" the Abstract No. 56274K Japankokai 51/115599 1976. *
See also references of EP0324787A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011037681A1 (fr) * 2009-09-24 2011-03-31 Signa Chemistry, Inc. Déshydratation catalytique d'alcools au moyen de catalyseurs acides non volatiles
CN102741199A (zh) * 2009-09-24 2012-10-17 西格纳化学有限责任公司 使用非-挥发性酸催化剂的醇的催化脱水
US9040741B2 (en) 2009-09-24 2015-05-26 Signa Chemistry, Inc. Catalytic dehydration of alcohols using non-volatile acid catalysts
US20150307413A1 (en) * 2009-09-24 2015-10-29 Signa Chemstry, Inc. Catalytic dehydration of alcohols using non-volatile acid catalysts
US9409832B2 (en) 2009-09-24 2016-08-09 Signa Chemistry, Inc. Catalytic dehydration of alcohols using non-volatile acid catalysts
KR20190004279A (ko) * 2016-05-06 2019-01-11 주식회사 쿠라레 공액 디엔의 제조 방법
KR102338451B1 (ko) 2016-05-06 2021-12-10 주식회사 쿠라레 공액 디엔의 제조 방법

Also Published As

Publication number Publication date
EP0324787A1 (fr) 1989-07-26
AU8108387A (en) 1988-04-21
KR880701701A (ko) 1988-11-04
JPH02500363A (ja) 1990-02-08
EP0324787A4 (fr) 1989-08-30

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