US2959607A - Higher aluminum alkyls and products therefrom - Google Patents

Higher aluminum alkyls and products therefrom Download PDF

Info

Publication number
US2959607A
US2959607A US823285A US82328559A US2959607A US 2959607 A US2959607 A US 2959607A US 823285 A US823285 A US 823285A US 82328559 A US82328559 A US 82328559A US 2959607 A US2959607 A US 2959607A
Authority
US
United States
Prior art keywords
reaction
aluminum
aluminum alkyls
octene
temperature
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 - Lifetime
Application number
US823285A
Other languages
English (en)
Inventor
Frank X Werber
Frank A Mirabile
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.)
WR Grace and Co
Original Assignee
WR Grace and 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 WR Grace and Co filed Critical WR Grace and Co
Priority to US823285A priority Critical patent/US2959607A/en
Priority to DEG29603A priority patent/DE1142608B/de
Priority to FR827823A priority patent/FR1260864A/fr
Application granted granted Critical
Publication of US2959607A publication Critical patent/US2959607A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C07C29/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only starting from compounds containing carbon-to-metal bonds and followed by conversion of the -O- metal to -OH groups
    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/062—Al linked exclusively to C

Definitions

  • This invention relates a novel method of forming aluminum alkyls containing at least one n-octyl group and products therefrom.
  • this invention is directed to the formation of aluminum alkyls containing at least one n-octyl group by a displacement reaction between octene-2 and aluminum triisobutyl in the presence of a cobalt chloride catalyst at substantially atmospheric pressure.
  • the thusformed n-octyl containing aluminum alkyls can be converted to octanol-l by oxidation and hydrolysis.
  • the displacement reaction is operable at temperatures ranging fromroom temperature to 150 C., preferably 70-410 C.
  • the displacement reaction is performed at substantially atmospheric pressure, preferably under a blanket of an inert gas selected from the group consisting of nitrogen and the noble gases.
  • an inert gas selected from the group consisting of nitrogen and the noble gases.
  • CoCl catalysts are not critical. Relatively small amounts are adequate to catalyze the reaction. In general, a coCl ztriisobutyl aluminum mole ratio of 1:10 to 200 respectively is operable, preferably 1:100 is used. Larger amounts of CoCl can be employed but are unnecessary.
  • the quantity of octene-2 should be at least the stoichiometric amount necessary to react with the triisobutyl aluminum.
  • the oxidation step is preferably performed after cooling the reaction products of the displacement reaction to room temperature. Since the addition of oxygen to the displacement reaction product causes an exothermic reaction, it is preferred to initially add the oxygen slowly and then increase the rate of addition as the reaction progresses. In the oxidation .sarily carried out under pressure.
  • the hydrolysis-step may be performed under the same conditions of temperature and pressure as the oxidation step but is.- preferably carried out at room temperature and atmospheric pressure.
  • HCl is used as the hydrolysis reagent in the examples, any hydrolysis reagent which is capable of hydrolyzing aluminum alcoholates can be employed.
  • the analysis of the fractions obtained in Examples 1 and 2 were identified by a combination of gas liquid phase chromatography and infra-red spectra.
  • the gas liquid phase chromatography analysis were made on a Perkin- Elmer Model 1548 Vapor Fractometer by comparing the retention time of the fractions with commercially available isobutyl alcohol, octene-2, octanol-l and octanol-2, which were employed as standards.
  • the infra-red spectra of the aforesaid standards were then compared to the fractions to confirm identification on a Perkin-Elmer Model 21 Infra-red Spectrophotometer.
  • the analysis of the fractions appear in the analysis column under the appropriate method of analysis in the examples.
  • Example I To a three neeked reaction flask was added 0.089 mole aluminum triisobutyl (17.6 grams), 0.26 mole octene-Z (30.7 grams) and 0.00089 mole of CoCl The reaction mixture was heated to C. at which temperature isobutylene was evolved andcollected in the cooled graduated receiver. The temperature range during the reaction was fro-m 70102 C. At the end of 5 hours the displacement reaction was discontinued. The displacement reaction went to 64% completion as measured by the isobutylene collected in the graduated receiver.
  • the resulting alcoholates were hydrolyzed by adding cc. 10% HCl to the reaction flask and stirring for 5 hours. The contents of the reaction flask was then transferred to a separatory funnel wherein the organic layer was separated from the aqueous layer. The organic layer containing the thus-hydrolyzed alcoholates was dissolved in 100 cc.
  • the percent overall conversion to octanol-l based on octcne-2 was 18.25%.
  • Example 11 Using the equipment and procedure of Example I, 0.089 mole aluminum triisobutyl and 0.26 mole octene-2 was added to the three-necked reaction flask and heated to 95 C. at which temperature isobutylene was evolved and collected in the cooled graduated received. The run was continued for 5 hours during which time the temperature ranged between 70 and 105 C. At the end of the 5 hour period the displacement reaction went to 40% completion as measured by the isobutylene collected in the cooled graduated receiver. The remaining mixture containing the reaction products of the displacement reaction, excepting isobutylene, was diluted with 250 cc. of cyclohexane and cooled in an ice-salt water bath to about 5 C.
  • the presence of the catalyst CoCl is necessary in order to obtain primary alcohol, i.e. octanol-l from an octene-2 reactant.
  • the aluminum alkyls containing at least one n-octyl group prepared by the process of this invention are useful as intermediates in making octanol-l.
  • the octanol-l can be esterified with a variety of readily available dibasic acids such as phthalic, isophthalic, adipic pimelic, azelaic, sebacic acids and the like to give dioctyl esters useful as plasticizers for vinyl resins and lubricants.
  • the process that comprises reacting octene-2 with at least a stoichiometric amount of aluminum triisobutyl in the presence of a CoCl catalyst at substantially atmospheric pressure thereby forming aluminum alkyls containing at least one n-octyl group, subjecting the n-octyl containing aluminum alkyls to a member of the group consisting of oxygen and air to form alcoholates, hydrolyzing the alcoholates and recovering octanol-l.

Landscapes

  • 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)
US823285A 1959-06-29 1959-06-29 Higher aluminum alkyls and products therefrom Expired - Lifetime US2959607A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US823285A US2959607A (en) 1959-06-29 1959-06-29 Higher aluminum alkyls and products therefrom
DEG29603A DE1142608B (de) 1959-06-29 1960-05-05 Verfahren zur Herstellung von Aluminiumtrialkyl mit mindestens einer n-Octylgruppe
FR827823A FR1260864A (fr) 1959-06-29 1960-05-20 Perfectionnements apportés aux procédés pour la production de trialcoyl-aluminiumcontenant des groupes n-octyle, et pour leur conversion en octanol-l

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US823285A US2959607A (en) 1959-06-29 1959-06-29 Higher aluminum alkyls and products therefrom

Publications (1)

Publication Number Publication Date
US2959607A true US2959607A (en) 1960-11-08

Family

ID=25238315

Family Applications (1)

Application Number Title Priority Date Filing Date
US823285A Expired - Lifetime US2959607A (en) 1959-06-29 1959-06-29 Higher aluminum alkyls and products therefrom

Country Status (2)

Country Link
US (1) US2959607A (de)
DE (1) DE1142608B (de)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3149136A (en) * 1960-03-30 1964-09-15 Du Pont Aluminum diene polymers
US3153076A (en) * 1962-12-05 1964-10-13 Exxon Research Engineering Co Two-stage process for aluminum alkyl oxidation
DE1207388B (de) * 1962-12-19 1965-12-23 Shell Int Research Verfahren zur Herstellung von Aluminiumalkylen
US3282974A (en) * 1960-01-16 1966-11-01 Henkel & Cie Gmbh Preparation of aluminum trialkyl compounds
US3391175A (en) * 1962-02-27 1968-07-02 Ethyl Corp Process for producing high alkyl trialkyl aluminum compounds and vinyl olefins
US3412127A (en) * 1965-10-22 1968-11-19 Continental Oil Co Alkylaluminum oxidation process
US3474122A (en) * 1965-09-01 1969-10-21 Sumitomo Chemical Co Process for producing higher alkylaluminums
US5124465A (en) * 1991-03-25 1992-06-23 Ethyl Corporation Aluminum alkyls and linear 1-olefins from internal olefins
US5144053A (en) * 1991-03-25 1992-09-01 Ethyl Corporation Aluminum alkyls and linear 1-olefins from internal olefins
US5191145A (en) * 1991-03-25 1993-03-02 Ethyl Corporation Continuous process for preparing aluminum alkyls and linear 1-olefins from internal olefins
US5233103A (en) * 1992-06-29 1993-08-03 Ethyl Corporation Preparation of organoaluminum compounds and linear alcohols derived therefrom
US5430165A (en) * 1992-06-29 1995-07-04 Albemarle Corporation Method of oxidizing aluminum alkyls
EP0712823A1 (de) 1994-11-21 1996-05-22 Albemarle Corporation Isomeringskatalysator und Isomerisierungsverfahren
US5824833A (en) * 1994-11-28 1998-10-20 Amoco Corporation Dimerization catalyst and process using alkyl aluminum alkoxide
US20040210072A1 (en) * 2001-12-12 2004-10-21 Citron Joel David Manufacture of trialkylaluminum compounds and alpha-alcohols
WO2010091047A1 (en) 2009-02-06 2010-08-12 Dow Global Technologies Inc. Process of making aluminum alkyls

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2695327A (en) * 1950-06-21 1954-11-23 Ziegler Karl Dimerization of unsaturated hydrocarbons
US2835689A (en) * 1954-08-04 1958-05-20 Ziegler Production of aluminum trialkyls and aluminum alkyl hydrides
US2863895A (en) * 1956-06-12 1958-12-09 Exxon Research Engineering Co Method of oxidizing aluminum alkyls

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1014088B (de) * 1954-08-07 1957-08-22 Dr Dr E H Karl Ziegler Verfahren zur Herstellung primaerer Alkohole

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2695327A (en) * 1950-06-21 1954-11-23 Ziegler Karl Dimerization of unsaturated hydrocarbons
US2835689A (en) * 1954-08-04 1958-05-20 Ziegler Production of aluminum trialkyls and aluminum alkyl hydrides
US2863895A (en) * 1956-06-12 1958-12-09 Exxon Research Engineering Co Method of oxidizing aluminum alkyls

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3282974A (en) * 1960-01-16 1966-11-01 Henkel & Cie Gmbh Preparation of aluminum trialkyl compounds
US3149136A (en) * 1960-03-30 1964-09-15 Du Pont Aluminum diene polymers
US3391175A (en) * 1962-02-27 1968-07-02 Ethyl Corp Process for producing high alkyl trialkyl aluminum compounds and vinyl olefins
US3153076A (en) * 1962-12-05 1964-10-13 Exxon Research Engineering Co Two-stage process for aluminum alkyl oxidation
DE1207388B (de) * 1962-12-19 1965-12-23 Shell Int Research Verfahren zur Herstellung von Aluminiumalkylen
US3474122A (en) * 1965-09-01 1969-10-21 Sumitomo Chemical Co Process for producing higher alkylaluminums
US3412127A (en) * 1965-10-22 1968-11-19 Continental Oil Co Alkylaluminum oxidation process
US5124465A (en) * 1991-03-25 1992-06-23 Ethyl Corporation Aluminum alkyls and linear 1-olefins from internal olefins
US5144053A (en) * 1991-03-25 1992-09-01 Ethyl Corporation Aluminum alkyls and linear 1-olefins from internal olefins
US5191145A (en) * 1991-03-25 1993-03-02 Ethyl Corporation Continuous process for preparing aluminum alkyls and linear 1-olefins from internal olefins
US5233103A (en) * 1992-06-29 1993-08-03 Ethyl Corporation Preparation of organoaluminum compounds and linear alcohols derived therefrom
US5278330A (en) * 1992-06-29 1994-01-11 Ethyl Corporation Preparation of organoaluminum compounds and linear alcohols derived therefrom
US5430165A (en) * 1992-06-29 1995-07-04 Albemarle Corporation Method of oxidizing aluminum alkyls
EP0712823A1 (de) 1994-11-21 1996-05-22 Albemarle Corporation Isomeringskatalysator und Isomerisierungsverfahren
US5824833A (en) * 1994-11-28 1998-10-20 Amoco Corporation Dimerization catalyst and process using alkyl aluminum alkoxide
US20040210072A1 (en) * 2001-12-12 2004-10-21 Citron Joel David Manufacture of trialkylaluminum compounds and alpha-alcohols
US6861545B2 (en) 2001-12-12 2005-03-01 E. I. Du Pont De Nemours And Company Manufacture of trialkylaluminum compounds and α-alcohols
WO2010091047A1 (en) 2009-02-06 2010-08-12 Dow Global Technologies Inc. Process of making aluminum alkyls
US20100204500A1 (en) * 2009-02-06 2010-08-12 Clark Thomas P Process of making aluminum alkyls
CN102307888A (zh) * 2009-02-06 2012-01-04 陶氏环球技术有限责任公司 制造烷基铝的方法
US8247553B2 (en) 2009-02-06 2012-08-21 Dow Global Technologies Llc Process of making aluminum alkyls
CN102307888B (zh) * 2009-02-06 2014-11-05 陶氏环球技术有限责任公司 制造烷基铝的方法

Also Published As

Publication number Publication date
DE1142608B (de) 1963-01-24

Similar Documents

Publication Publication Date Title
US2959607A (en) Higher aluminum alkyls and products therefrom
US2636046A (en) Preparation of polyfunctional compounds
US3159626A (en) Triethylene-diamine alane and a process for its preparation
US3017438A (en) Storage
JPS5929180B2 (ja) グリコ−ル酸の製造方法
US2175811A (en) Manufacture of ketenes
US3092640A (en) Processes for preparing bis
US2068415A (en) Purification of alcohols
US3709946A (en) Preparation of acetylenic alcohols
US2968674A (en) Process for hydrolyzing dibasic acid esters while inhibiting the formation of color materials
US3188330A (en) Process for preparing esters and ketones from alcohols
US2373583A (en) Conversion of methyl formate to formic acid
US2937201A (en) Process for the production of azelaic acid
US3419615A (en) Production of cyclododecanol and cyclododecanone
US3313843A (en) Preparation of cinnamate esters
US2451350A (en) Preparation of unsaturated ketones
US3479394A (en) Process for the oxidation of cycloalkanes
US2876255A (en) Preparation of bromo acids and esters
US2820820A (en) Method for oxidizing glutaraldehydes
US3511855A (en) Production of beta-lactones
US3081344A (en) Preparation of esters by aldehyde condensation
US3089894A (en) Cyclohexyl borate and its preparation
US2975215A (en) Process for the production of higher boron alkyls from boron alkyls of lower molecular weight
US3657365A (en) Process for the manufacture of methyl or ethyl chloride from methyl or ethyl acetate
US2273269A (en) Preparation of organic esters