GB890542A - Production of benzene and its trisubstituted and hexasubstituted derivatives - Google Patents
Production of benzene and its trisubstituted and hexasubstituted derivativesInfo
- Publication number
- GB890542A GB890542A GB35634/60A GB3563460A GB890542A GB 890542 A GB890542 A GB 890542A GB 35634/60 A GB35634/60 A GB 35634/60A GB 3563460 A GB3563460 A GB 3563460A GB 890542 A GB890542 A GB 890542A
- Authority
- GB
- United Kingdom
- Prior art keywords
- halide
- titanium
- nickel
- iii
- acetylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
- C07C2/48—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion of only hydrocarbons containing a carbon-to-carbon triple bond
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- 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
- C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
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- C—CHEMISTRY; METALLURGY
- 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
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/128—Compounds comprising a halogen and an iron group metal or a platinum group metal
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/133—Compounds comprising a halogen and vanadium, niobium, tantalium, antimonium or bismuth
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/135—Compounds comprising a halogen and titanum, zirconium, hafnium, germanium, tin or lead
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/138—Compounds comprising a halogen and an alkaline earth metal, magnesium, beryllium, zinc, cadmium or mercury
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The trimerization of acetylenes to benzenes is effected in the presence as catalyst of:- (i) an iron (III) halide or a titanium or nickel compound (ii) a metal of Group Ia, IIa, IIb, IIIa or the lanthanide series and (iii) a halide of an element of Group IIb, IIIa, IVa or Va, aluminium or an aluminium halide being essentially present; the Periodic Table references are to one in which the transition elements are in sub-Groups B and Group VIII and the remaining elements in sub-Groups A. In the catalyst system the compound (i) may be a lower alkyl titanate, e.g. titanium tetra-methylate, -ethylate or -propylate, a titanium halide, e.g. the tri- or tetra-chloride or -bromide, a titanium ester halide, e.g. diethoxy titanium dichloride or dibutoxy titanium dibromide, organo-titanium halides, e.g. bis-cyclopentadienyl titanium dichloride or dimethyl titanium dibromide, ferric chloride or bromide, or nickel salts or chelate complexes, e.g. nickelous chloride, bromide, iodide, carbonate, formate, acetate, oxalate, benzoate, oleate, sulphate or nitrate nickel acetylacetonate, nickel acetoacetic acid ester, nickel benzoyl acetonate, nickel monoacetyl-acetonate ethylate, nickel dimethylglyoxime, nickelous oxide, hydroxide or sulphide or nickelic hydroxide. Nickel compounds are preferably anhydrous, those containing water of crystallization may be used with an excess of metal (ii). The metal (ii) may be lithium, sodium, potassium, berryllium, magnesium, calcium, strontium, barium, aluminium, gallium, indium, zinc or cerium and preferably has a large surface area. The halide (iii) may be a chloride or bromide of boron, aluminium, gallium, indium, thallium, silicon, tin, zinc, phosphorus, antimony or bismuth. Where compound (i) is a halide and metal (ii) is aluminium, aluminium halide as halide (iii) may be formed in situ. A compound forming a complex with the halide (iii) may be used, e.g. an ether, thioether, sulphoxide nitrone, tertiary base, or alkali or alkaline earth halide, hydroxide, hydride or cyanide, typical examples being anisol, phenetol, diethyl ether, diphenyl ether, diphenylene oxide, diphenyl sulphide, thiobutyric acid, quinoline, triethylamine, sodium chloride, magnesium chloride, calcium chloride, lithium hydride, calcium hydride, and potassium cyanide. The mol. ratio of (i) to redox equivalent of (ii) to mol. of (iii) may be from 1:300:100 to 1:10:10 or the titanium compound may be in excess and the mol. ratio of the sum of (i) and (iii) to complex forming compound may be 1:0,2-3. The total amount of catalyst may be as low as 0,3% by weight of the acetylene. Two or all of the components of the catalyst are preferably ground in a ball mill at up to 150 DEG C. for 1-10 hours in the solvent to be used which is present in an amount of 0,2 to 0,5 that of the acetylene and may be, e.g. benzene, toluene, xylene, pentane, ethylbenzene, cumene, chlorobenzene, heptane, cyclohexane, iso-octane or tetrahydrofurane. Specification 802,510 is referred to.ALSO:The production of benzene or tri- or hexasubstituted benzenes by the trimerisation of acetylene or a mono- or di-substituted acetylene is effected in the presence as catalyst of (i) an iron (III) halide or a titanium or nickel compound; (ii) a metal of group Ia, IIa, IIba or the lanthanide series; and (iii) a halide of an element of group IIb, IIIa, IVa or Va; aluminium or an aluminium halide being essentially present; the Periodic Table references are to one in which the transition elements are in sub-groups B and group VIII and the remaining elements in sub-groups A. The starting material may be acetylene propine, butine-1, pentine-1, hexine-1, octine-1, dodecine-1, octadecine-9, octadecine-1, vinyl acetylene, phenyl acetylene, cyclohexyl acetylene, benzyl acetylene, butine-2, hexine-3, methyl ethyl acetylene or tolane. In the catalyst system the compound (i) may be a lower alkyl titanate, e.g. titanium tetra-methylate, -ethylate or -propylate, a titanium halide, e.g. the tri- or tetra-chloride or -bromide, a titanium ester halide, e.g. diethoxy titanium dichloride or dibutoxy titanium dibromide, organo-titanium halides, e.g. bis-cyclopentadienyl titanium dichloride or dimethyl titanium dibromide, ferric chloride or bromide, or nickel salts or chelate complexes, e.g. nickelous chloride, bromide, iodide, carbonate, formate, acetate, oxalate, benzoate, oleate, sulphate or nitrate nickel acetylacetonate, nickel acetoacetic acid ester, nickel benzoyl acetonate nickel monoacetylacetonate ethylate, nickel dimethylglyoxime, nickelous oxide, hydroxide or sulphide or nickelic hydroxide. Nickel compounds are preferably anhydrous, those containing water of crystallisation may beused with an excess of metal (ii). The metal (ii) may be lithium sodium, potassium, beryllium, magnesium, calcium, strontium, barium, aluminium, gallium, indium, zinc or cerium and preferably has a large surface area. The halide (iii) may be a chloride or bromide of boron, aluminium, gallium, indium, thallium, silicon, tin, zinc, phosphorus, antimony or bismuth. Where compound (i) is a halide and metal (ii) is aluminium, aluminium halide as halide (iii) may be formed in situ. A compound forming a complex with the halide (iii) may be used, e.g. an ether, thioether, sulphoxide nitrone, tertiary base, or alkali or alkaline earth halide, hydroxide, hydride or cyanide, typical examples being anisol, phenetol, diethyl ether, diphenyl ether, diphenylene oxide, diphenyl sulphide, thiobutyric acid, quinoline, triethylamine, sodium chloride, magnesium chloride, calcium chloride, lithium hydride, calcium hydride, and potassium cyanide. The mol ratio of (i) to redox equivalent of (ii) to mol of (iii) may be from 1 : 300 : 100 to 1 : 10 : 10 or the titanium compound may be in excess and the mol ratio of the sum of (i) and (ii) to complex forming compound may be 1 : 0.2-3. The total amount of catalyst may be as low as 0.3% by weight of the acetylene. Two or all of the components of the catalyst are preferably ground in a ball mill at up to 150 DEG C. for 1-10 hours in the solvent to be used which is present in an amount of 0.2 to 0.5 that of the acetylene and may be, e.g. benzene, toluene, xylene, pentane, ethylbenzene, cumene, chlorobenzene, heptane, cyclohexane, iso-octane, or tetrahydrofurane. The reaction temperature may be -5 DEG C. to 150 DEG C. and the pressure preferably atmospheric or up to 10 atmospheres gauge if low-boiling reactants are used.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE890542X | 1959-10-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB890542A true GB890542A (en) | 1962-03-07 |
Family
ID=6838807
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB35634/60A Expired GB890542A (en) | 1959-10-21 | 1960-10-18 | Production of benzene and its trisubstituted and hexasubstituted derivatives |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB890542A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5669161A (en) * | 1990-02-26 | 1997-09-23 | Huang; Ing-Jing | Shock-absorbing cushion |
-
1960
- 1960-10-18 GB GB35634/60A patent/GB890542A/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5669161A (en) * | 1990-02-26 | 1997-09-23 | Huang; Ing-Jing | Shock-absorbing cushion |
US6161240A (en) * | 1990-02-26 | 2000-12-19 | Huang; Ing-Jing | Shock-absorbing cushion |
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