GB830942A - Dimerization process - Google Patents

Dimerization process

Info

Publication number
GB830942A
GB830942A GB36920/56A GB3692056A GB830942A GB 830942 A GB830942 A GB 830942A GB 36920/56 A GB36920/56 A GB 36920/56A GB 3692056 A GB3692056 A GB 3692056A GB 830942 A GB830942 A GB 830942A
Authority
GB
United Kingdom
Prior art keywords
butadiene
ketone
phenyl
alkali metal
ethyl
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
Application number
GB36920/56A
Inventor
David Ross Carley
Walter Edward Foster
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.)
Ethyl Corp
Original Assignee
Ethyl Corp
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
Priority to US473487A priority Critical patent/US2773092A/en
Application filed by Ethyl Corp filed Critical Ethyl Corp
Priority to GB36920/56A priority patent/GB830942A/en
Priority to FR1168950D priority patent/FR1168950A/en
Publication of GB830942A publication Critical patent/GB830942A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • 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 Table
    • 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
    • B01J16/00—Chemical processes in general for reacting liquids with non- particulate solids, e.g. sheet material; Apparatus specially adapted therefor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/13—Dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/36—Polymerisation in solid state

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A conjugated polyene having between 4 and 16 carbon atoms or a vinyl aromatic hydrocarbon is dimerized by reaction with a finely dispersed alkali metal having a particle size not greater than 50 microns dispersed in at least 300% of an aliphatic solvent consisting of an ether (as defined) acetal or tertiary amine in the presence of between 0.0001 to 10% of a diaryl ketone, both percentages being based upon the weight of the alkali metal, the reaction medium being maintained at a temperature below about 50 DEG C., said polyene or vinyl aromatic hydrocarbon being employed in an amount not exceeding 1 mol. per mol. of alkali metal. The product is a dialkali metal adduct. Specified conjugated polyenes are butadiene, pentadiene, hexadiene, octadiene, decadiene, pentadecadiene, isoprene, 2-ethyl butadiene, dimethyl butadiene, tertiary butyl butadiene, 2-methyl pentadiene, 3-methyl pentadiene, 2-hexyl pentadiene, 2-methyl-octadiene-1,3; 2-methyl - octadiene - 2,4; 2 - ethyl decadiene-1,3; 3 - ethyl - decadiene - 2,4; allo - ocimene, 1 - phenyl butadiene, 2 - phenyl - butadiene, 1,4-diphenyl butadiene and naphthyl butadiene. The alkali metal (preferably sodium) may be dispersed in an inert solvent such as iso-octane, heptane, decane kerosene or di-n-butyl ether; if desired, the ether, acetal or tertiary amine may be used. Specified diaryl ketones include benzophenone, phenyl naphthyl ketone, di-naphthyl ketone, phenyl biphenyl ketone, di-biphenyl ketone, phenyl terphenyl ketone, biphenyl naphthyl ketone, diterphenyl ketone and fluorenone. A detailed list of suitable ethers, acetals and amines is given. The reaction is conducted in an inert atmosphere, e.g. nitrogen in the absence of moisture. The alkali metal adduct may be carbonated by pouring on to dry ice to give dicarboxylic acids having two more carbon atoms in the molecule than the dimer, or reacted with compounds containing carbonyl, thionyl or nitrile groups to give other compounds; for example, SO2 gives di-sulphinic acids, formaldehyde or epoxides give diols and cyanogen chloride gives dinitriles. The adduct may also be reacted with alkylaryl, acetylenic, nitrile and cyclodienyl compounds to effect transmetalation. The following are prepared in the examples: (1) disodiooctadienes and sebacic acid, 2-ethyl suberic acid, 3-ethyl suberic acid and 2,5-diethyl adipic acid; (2) decadienediols; (4) benzyl sodium (by transmetalation with toluene) and phenyl acetic acid; (7) C12 dicarboxylic acids; and (8) C14 dicarboxylic acids.
GB36920/56A 1954-12-06 1956-12-03 Dimerization process Expired GB830942A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US473487A US2773092A (en) 1954-12-06 1954-12-06 Dimerization process
GB36920/56A GB830942A (en) 1954-12-06 1956-12-03 Dimerization process
FR1168950D FR1168950A (en) 1954-12-06 1956-12-03 Dimerization process

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US473487A US2773092A (en) 1954-12-06 1954-12-06 Dimerization process
GB36920/56A GB830942A (en) 1954-12-06 1956-12-03 Dimerization process
FR1168950T 1956-12-03

Publications (1)

Publication Number Publication Date
GB830942A true GB830942A (en) 1960-03-23

Family

ID=60329871

Family Applications (1)

Application Number Title Priority Date Filing Date
GB36920/56A Expired GB830942A (en) 1954-12-06 1956-12-03 Dimerization process

Country Status (3)

Country Link
US (1) US2773092A (en)
FR (1) FR1168950A (en)
GB (1) GB830942A (en)

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2816916A (en) * 1953-01-26 1957-12-17 Nat Distillers Chem Corp Dimerization process
US2816917A (en) * 1953-01-26 1957-12-17 Nat Distillers Chem Corp Selective process for dimerization of unsaturated hydrocarbons
US2861981A (en) * 1954-02-05 1958-11-25 Nat Distillers Chem Corp Polyesters and isocyanate reaction products thereof
US2850540A (en) * 1955-03-22 1958-09-02 Nat Distillers Chem Corp Manufacture of glycols from conjugated aliphatic diolefins
US2902462A (en) * 1955-07-22 1959-09-01 Nat Distillers Chem Corp Polyester of a mixture of isomeric c10 dicarboxylic acids and process of making
US2839571A (en) * 1955-08-12 1958-06-17 Nat Distillers Chem Corp Ester products
BE550402A (en) * 1955-08-17
US2902463A (en) * 1955-08-19 1959-09-01 Nat Distillers Chem Corp Polyesters of a mixture of dicarboxylic acids having ten carbon atoms and process of making same
BE553799A (en) * 1955-12-30
US2865969A (en) * 1956-05-09 1958-12-23 Nat Distillers Chem Corp Chemical process for preparation of dialkali metal dimers of diolefins
US2837566A (en) * 1956-10-19 1958-06-03 Nat Distillers Chem Corp Process for recovery of organic acids
US2862027A (en) * 1956-10-22 1958-11-25 Nat Distillers Chem Corp Process for recovery of acids
US2837565A (en) * 1956-10-29 1958-06-03 Nat Distillers Chem Corp Chemical process for recovery of acids
US2852559A (en) * 1956-10-30 1958-09-16 Ethyl Corp Manufacture of malonic acid and its esters and salts
US2914578A (en) * 1956-12-28 1959-11-24 Nat Distillers Chem Corp Process for preparing organo sodium compounds
US2966526A (en) * 1957-07-31 1960-12-27 Nat Distillers Chem Corp Metalation reactions
US2954410A (en) * 1957-07-31 1960-09-27 Nat Distillers Chem Corp Metalation process
US2953607A (en) * 1958-05-20 1960-09-20 Studiengesellschaft Kohle Mbh Process for the preparation of tertiary alkyl cyclopentadienes
US2956087A (en) * 1958-12-04 1960-10-11 Nat Distillers Chem Corp Dimerization of vinyl aromatic compounds
US3090819A (en) * 1959-02-24 1963-05-21 Ethyl Corp Transmetalation process
US3032489A (en) * 1959-06-15 1962-05-01 Sun Oil Co Electrolytic production of acyclic carboxylic acids from hydrocarbons
US3119795A (en) * 1959-12-14 1964-01-28 Nat Distillers Chem Corp Polysulfide polymers produced by reaction of dialkali metal hydrocarbons with sulfurhalides
US3072706A (en) * 1960-09-08 1963-01-08 Cyclopentenyl cyclopenteneacetic acid and derivatives
US3133956A (en) * 1960-12-28 1964-05-19 Nat Distillers Chem Corp Dimerization process for producing adiponitrile
US3198841A (en) * 1961-11-24 1965-08-03 Shell Oil Co Alcohols from unsaturated hydrocarbons and carbonyl compounds
US3284511A (en) * 1961-12-13 1966-11-08 Nat Distillers Chem Corp Halogenated, diolefin-styrene polymers with terminal hydroxy groups
US4034000A (en) * 1963-09-23 1977-07-05 The Goodyear Tire & Rubber Company Difunctional polymeric dienes

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1832450A (en) * 1929-01-25 1931-11-17 Ig Farbenindustrie Ag Production of polymerization products from diolefines
US2352461A (en) * 1942-02-25 1944-06-27 Du Pont High molecular weight unsaturated organic acids and process of preparing them
US2716662A (en) * 1952-01-24 1955-08-30 Exxon Research Engineering Co Polycyclic dibasic acids
BE534092A (en) * 1953-01-26

Also Published As

Publication number Publication date
FR1168950A (en) 1958-12-18
US2773092A (en) 1956-12-04

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