GB1011835A - Improved base-solvent or alkali metal-solvent catalyst system - Google Patents

Improved base-solvent or alkali metal-solvent catalyst system

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Publication number
GB1011835A
GB1011835A GB17649/62A GB1764962A GB1011835A GB 1011835 A GB1011835 A GB 1011835A GB 17649/62 A GB17649/62 A GB 17649/62A GB 1764962 A GB1764962 A GB 1764962A GB 1011835 A GB1011835 A GB 1011835A
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United Kingdom
Prior art keywords
olefins
phosphoramide
alkali metal
dimethyl
radical
Prior art date
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GB17649/62A
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ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
Esso Research and Engineering Co
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Filing date
Publication date
Priority claimed from US111173A external-priority patent/US3270084A/en
Priority claimed from US111172A external-priority patent/US3213155A/en
Priority claimed from US115302A external-priority patent/US3217050A/en
Application filed by Exxon Research and Engineering Co, Esso Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of GB1011835A publication Critical patent/GB1011835A/en
Expired legal-status Critical Current

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    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
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    • 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
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0257—Phosphorus acids or phosphorus acid esters
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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    • B01J31/0264—Phosphorus acid amides
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/24—Catalytic processes with metals
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
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    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
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    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
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    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/38—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes
    • C07C2/40—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes of conjugated dienes
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    • C07C2/406—Catalytic processes with hydrides or organic compounds
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    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/72—Addition to a non-aromatic carbon atom of hydrocarbons containing a six-membered aromatic ring
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    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
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    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
    • C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
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    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
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    • 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
    • C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
    • C07C5/2266—Catalytic processes not covered by C07C5/23 - C07C5/31 with hydrides or organic compounds
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25—Migration of carbon-to-carbon double bonds
    • C07C5/2506—Catalytic processes
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    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25—Migration of carbon-to-carbon double bonds
    • C07C5/2506—Catalytic processes
    • C07C5/2562—Catalytic processes with hydrides or organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/12—Olefin polymerisation or copolymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
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    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
    • B01J2231/325—Cyclopropanations
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
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    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides

Abstract

Chemical reactions involving the formation of a carbanion intermediate and catalysed by an alkali metal or hydroxide, alkoxide, hydride, amide or alkyl thereof are effected in an aprotic (neither donating nor readily accepting a proton) organic liquid, free of hydroxyl groups, having a dielectric constant above 15 at 25 DEG C. containing a dipolar radical with the proviso that when an alkali metal is used the organic liquid is free of hydrogen atoms on the dipolar radical and adjacent atoms. Specified liquids containing PO, CO, SO, SO2 or CS radicals are dimethyl sulphoxide, diisopropylsulphoxide, tetramethyl sulphonamide, bis-dialkylamino sulphoxide, tetramethylene sulphone, tetramethyl urea, dimethy acetamide, N,N-dimethyl formamide, t-butyl, N,N-dimethyl formamide, trimethyl phosphoramide, hexamethyl phosphoramide, tri-(ethyleneimine) phosphoramide, trimethyl phosphate, tris-(methylmercapto) phosphine oxide, N,N1-dimethyl thiourea and tetramethyl thiourea. The reaction mixture may be homogeneous or heterogeneous. Conditions used vary according to the reaction but generally the alkali metal or compound thereof forms 10-40% by weight of the catalyst-diluent composition. The reaction preferably runs at a rate of at least 0.1 wt. of feed/hour/wt. of catalyst. The temperature is in the range 15-400 DEG C. Specified reactions are: (1) Polymerization of mono- and di-olefins and vinyl compounds. In examples: (14) butadiene is polymerized to a viscous product in the presence of butyl lithium and hexamethylphosphoramide; (15) ethylene is polymerized to a viscous liquid in the presence of benzyl potassium and hexamethyl phosphoramide; (20) ethylene is converted to butane in the presence of sodium and hexamethyl phosphoramide followed by the addition of water or methy alcohol; (21) butadiene is polymerized to a viscous product in the presence of lithium or sodium and hexamethyl phophoramide and optionally added pentane. (2) Alkylation of alkyl aromatic side chains with olefins. An Example (19) describes the conversion of ethylene and toluene to propyl benzene and amyl benzene. (3) Isomerization of olefins. Examples describe the converion of 2-methylpentene-1 to 2-methylpentene-2 (Examples 1, 2, 6,8, 17, 18 and 23) butene-1 to cis-butene-2 (3) and other olefins (4 and 7) including 3-phenylpropane to 1-phenylpropane. (4) Generation of the carbene radical from halides, ethers, sulphides, or ammonia salts and the addition of the carbene to olefins, diolefins and aromatics. Norcarane is produced from cyclohexene and methyl chloride, or (Examples 11 and 12). (5) Homogeneous hydrogenation of olefins, diolefins and aromatics. (6) Formation of benzyne from any known benzyne precursors and reactions thereof. (7) Production of metal alkyls from metal and organic halides or of Grignard reagents from magnesium and organic halides. In an Example (22), benzyl chloride is added to a solution of potassium in hexamethylphosphoramide; on addition of water, toluene is formed.ALSO:Chemical reactions involving the formation of a carbanion intermediate and catalysed by an alkali metal or hydroxide, alkoxide, hydride, amide or alkyl thereof are effected in an aprotic (neither donating nor readily accepting a proton) organic liquid, free of hydroxyl groups, having a dielectric constant above 15 to 25 DEG C. containing a dipolar radical with the proviso that when an alkali metal is used the organic liquid is free of hydrogen atoms on the dipolar radical and adjacent atoms. Specified liquids containing PO, CO, SO, SO2 or CS radicals are dimethyl sulphoxide, diisopropylsulphoxide, tetramethyl sulphonamide, bis-dialkylamino sulphoxide, tetramethylene sulphone, tetramethyl urea, dimethyl acetamide, N,N-dimethyl formamide, t-butyl, N,N-dimethyl formamide, trimethyl phosphoramide, hexamethyl phosphoramide, tri-(ethyleneimine) phosphoramide, trimethyl phosphate, tris-(methyl mercapto) phosphine oxide, N,N1-dimethyl thiourea and tetramethyl thiourea. The reaction mixture may be homogeneous or heterogeneous. Conditions used vary according to the reaction but generally the alkali metal or compound thereof forms 10-40% by weight of the catalyst-diluent composition. The reaction preferably runs at a rate of at least 0.1 wt. of feed/hour/wt. of catalyst. The temperature is in the range 15-400 DEG C. Specified reactions are: (1) Polymerization of mono- and di-olefins and vinyl compounds. In examples: (14) butadiene is polymerized to a viscous product in the presence of butyl lithium and hexamethyl-phosphoramide; (15) ethylene is polymerized to a viscous liquid in the presence of benzyl potassium and hexamethyl phosphoramide; (21) butadiene is polymerized to a viscous product in the presence of lithium or sodium and hexamethyl phosphoramide and optionally added pentane.ALSO:Chemical reactions involving the formation of a carbanion intermediate and catalysed by an alkali metal or hydroxide, alkoxide, hydride, amide or alkyl thereof are effected in an aprotic (neither donating nor readily accepting a proton) organic liquid, free of hydroxyl groups, having a dielectric constant above 15 at 25 DEG C. containing a dipolar radical with the proviso that when an alkali metal is used the organic liquid is free of hydrogen atoms on the dipolar radical and adjacent atoms. Specified liquids containing PO, CO, SO, SO2 or CS radicals are dimethyl sulphoxide, diisopropylsulphoxide, tetramethyl sulphonamide, bis-dialkylamino sulphoxide, tetramethylene sulphone, tetramethyl urea, dimethyl acetamide, N,N-dimethyl formamide, t.-butyl, N,N-dimethyl formamide, trimethyl phosphoramide, hexamethylphosphoramide, tri-(ethyleneimine) phosphoramide, trimethyl phosphate, tris-(methylmercapto) phosphine oxide, N,N1-dimethyl thiourea and tetramethyl thiourea. The reaction mixture may be homogeneous or hterogeneous. Conditions used vary according to the reaction but generally the alkali metal or compound thereof forms 10-40% by weight of the catalyst-diluent composition. The reaction preferably runs at a rate of at least 0.1 wt. of feed/hour/wt. of catalyst. The temperature is in the range 15-400 DEG C. Specified reactions are:-(1) alcohol and cannizzaro condensations, malonic ester condensations and Michael additions; (2) alkylation of ketones with organic halides and metal alkyls with olefins; (3) carboxylation of alkyl aromatics or olefins to carboxylic acids, e.g. toluene yields phenylacetic acid and propylene yields acrylic acid; (4) carbonylation of alkyl aromatics or olefins to yield aldehydes; (5) generation of the carbene radical from halides, ethers, sulphides, or ammonia salts and the addition of the carbene to olefins, diolefins and aromatics; (6) hydroboration of olefine and diolefins; (7) reacting alkynes and alcohols to form vinyl ethers; (8) oxidation of alkyl aromatics or heterocyclics or of olefins to carboxylic acids or, in the presence of ammonia to the corresponding ammonium salt, or the oxidation of these starting materials to alcohols; the oxidation of benzene to phenol; the oxidation of alkyl aromatics to ketones and the oxidation of mercaptans to disulphides or sulphonic acids. In Examples (5) a butyl mercaptan is oxidized to the disulphide, (6) toluene is oxidized to benzoic acid and xylene to phthalic acid and (13) n-butyl mercaptan is oxidized to n-butyl sulphonc acid; (9) production of metal alkyls from metal and organic halides or of Grignard reagents from magnesium and organic halides. In an Example (22), benzyl chloride is added to a solution of potassium in hexamethylphosphoramide; on addition of water, toluene is formed.
GB17649/62A 1961-05-19 1962-05-08 Improved base-solvent or alkali metal-solvent catalyst system Expired GB1011835A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US111173A US3270084A (en) 1961-05-19 1961-05-19 Method of isomerizing olefins
US111172A US3213155A (en) 1961-05-19 1961-05-19 Monoolefin isomerization process
US115302A US3217050A (en) 1961-06-07 1961-06-07 Alkali metal catalyzed conversion of organic compounds

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GB1011835A true GB1011835A (en) 1965-12-01

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CH (1) CH419061A (en)
DE (1) DE1262274B (en)
GB (1) GB1011835A (en)
NL (1) NL278556A (en)
SE (1) SE317674B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0008727A1 (en) * 1978-08-24 1980-03-19 Hoechst Aktiengesellschaft Process for the hydrogenation of organic compounds
US4556754A (en) * 1982-02-19 1985-12-03 Chemische Werke Huels Aktiengesellschaft Process for the isomerization of isolated double bonds to conjugated double bonds in low-molecular weight homo- and/or copolymers of 1,3-dienes

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105675557B (en) * 2016-01-07 2019-01-25 济南大学 New method based on benzyne fluorescent reagent detection thiocarbamide content

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GB785760A (en) * 1953-09-23 1957-11-06 Union Carbide Corp Process for the production of cyclopentadiene compounds of transition elements
NL99130C (en) * 1956-12-10
BE570299A (en) * 1957-08-12
AT219056B (en) * 1957-12-03 1962-01-10 Consortium Elektrochem Ind Process for the polymerization of unsaturated compounds
FR1225915A (en) * 1958-05-28 1960-07-06 Purdue Research Foundation Process for the isomerization of internal olefins to terminal olefins
GB870949A (en) * 1958-12-17 1961-06-21 Ici Ltd Process of manufacture of ferrocene derivatives

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0008727A1 (en) * 1978-08-24 1980-03-19 Hoechst Aktiengesellschaft Process for the hydrogenation of organic compounds
US4556754A (en) * 1982-02-19 1985-12-03 Chemische Werke Huels Aktiengesellschaft Process for the isomerization of isolated double bonds to conjugated double bonds in low-molecular weight homo- and/or copolymers of 1,3-dienes

Also Published As

Publication number Publication date
CH419061A (en) 1966-08-31
NL278556A (en)
SE317674B (en) 1969-11-24
DE1262274B (en) 1968-03-07

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