US3870745A - Complex of 2,6-dimethylnaphthalene and 2-cyano-6-methylnaphthalene - Google Patents

Complex of 2,6-dimethylnaphthalene and 2-cyano-6-methylnaphthalene Download PDF

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Publication number
US3870745A
US3870745A US410650A US41065073A US3870745A US 3870745 A US3870745 A US 3870745A US 410650 A US410650 A US 410650A US 41065073 A US41065073 A US 41065073A US 3870745 A US3870745 A US 3870745A
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Prior art keywords
dmn
complex
cmn
dimethylnaphthalene
mixture
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US410650A
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English (en)
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Howard P Angstadt
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Sun Ventures Inc
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Sun Ventures Inc
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Priority to US410650A priority Critical patent/US3870745A/en
Priority to CA207,910A priority patent/CA1024994A/en
Priority to IT28242/74A priority patent/IT1022736B/it
Priority to DE19742449699 priority patent/DE2449699A1/de
Priority to GB4559674A priority patent/GB1475091A/en
Priority to FR7435662A priority patent/FR2249054B1/fr
Priority to JP49122634A priority patent/JPS5082046A/ja
Priority to NL7414048A priority patent/NL7414048A/xx
Application granted granted Critical
Publication of US3870745A publication Critical patent/US3870745A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/20—Polycyclic condensed hydrocarbons
    • C07C15/24—Polycyclic condensed hydrocarbons containing two rings

Definitions

  • ABSTRACT A complex of 2,6-dimethylnaphthalene (2,6-DMN) [52] US. Cl. 260/465 R, 260/674 N a d 2-yan0-fi-methylnaphthalene (2,6-CMN) i5 [51] Int. Cl.
  • 2,6-DMN is useful in the manufacture of synthetic polyester fibers. It is well known that for this purpose the 2,6-DMN must be very pure as other DMN isomers seriously detract from the quality of the resulting fiber.
  • the 2,6-DMN can be obtained from certain petroleum fractions where it occurs naturally or it can be made synthetically such as by the procedure described in copending application of Sheldon L. Thompson, Ser. No. 263,731, filed June 9, 1972.
  • Use of either source of 2,6-DMN involves the problem of separating the 2,6- DMN from other DMN isomers, i.e., from mixture of alkylnaphthalenes.
  • the aforesaid Thompson application discloses a process wherein o-xylene is reacted with butadiene to form o-tolylpentene-Z which is then dehydrocyclized to l,5-dimethyltetralin and the latter is dehydrogenated and then isomerized to 2,6-DMN.
  • 2,6-DMN is found to also contain some 2,7-DMN for two reasons.
  • any p-xylene contaminant in the oxylene feed follows the corresponding reactions as the o-xylene resulting in 2,7-DMN.
  • small amounts of 2,7-DMN are formed.
  • a source of high-purity 2,6-DMN is the complex formed between 2,6-DMN and 2,6-CMN.
  • 2,6-DMN When the complex is heated to the boiling point of 2,6-DMN the latter is distilled off as a pure product leaving solid 2,6- CMN behind. Since the complex can be formed from the 2,6-DMN in an impure mixture thereof, i.e., from a relative impure 2,6-DMN, the complex is a desirable source of relatively pure 2 ,6-DMN.
  • the 2,6-DMN component of the complex can of course be pure 2,6-DMN but is preferably a mixture of DMN isomers containing 2,6-DMN.
  • Such mixtures are found in petroleum fractions such as a heavy reformate bottoms or a catalytic gas oil having a boiling range of say 460-650F.
  • Such fractions will usually contain -30 percent 2,6-DMN and l-% each of most of the other DMN isomers. If the catalytic gas oil fraction is fractionated to separate a 460540F fraction the DMNs are retained but certain other unwanted material such as trimethylnaphthalenes are removed.
  • the DMN isomer mixture can be a stream containing substantially all 2,6-DMN with very minor amounts, e.g. less than 5 percent, of, say, one other isomer such as the 2,7-isomer.
  • a stream can be obtained in the aforesaid Thompson process.
  • the 2,6-CMN is obtained by heating 2,6methylnaphthalenecarboxylic acid at l50-30()C in the presence of ammonia and an alumina or zeolite dehydrating agent.
  • the 2,6-methylnaphthaleneca'rboxylic acid can be obtained according to the procedure described in U.S. Pat. No. 3,340,155, issued Sept. 5, l967 to .l. D. Douros, Jr. et al.
  • the complexing can be carried out by contacting the 2,6-CMN with the liquid DMN isomer mixture.
  • the petroleum fractions containing 2,6-DMN are of course liquid at ambient conditions. If a solid mixture of, say, 2,6- and 2,7-DMN is employed, as might be obtained from a synthetic 2,6-DMN process, the mixture should be dissolved in a solvent such as petroleum ether.
  • the 2,6-CMN is also soluble in petroleum ether but the complex is less soluble and therefore precipitates.
  • the exact solubility of the complex in ether is not known but etherzcomplex weight ratios of about 10:1 are generally satisfactory.
  • the complex contains equal molar amounts of 2,6- CMN and 2,6-DMN.
  • the amount of 2,6-CMN employed is preferably less than or equal to one mole per mole of 2,6-DMN in the DMN isomer mixture.
  • the 2,6-CMN is not very soluble at room temperature in a petroleum fraction DMN isomer mixture and such a mixture plus 2,6-CMN is preferably heated to above 30C, say 60-65C, to speed dissolution of the CMN which, once in solution, complexes with the 2,6- DMN isomer almost immediately. After the complex is formed the entire mass is cooled to effect precipitation of the complex. Cooling to or somewhat above room temperature is usually adequate and cooling too far below this is disadvantageous since material other than the 2,6-DMN:2,6-CMN complex will ultimately also precipitate. If petroleum ether or the like is the solvent for the DMNs heating and cooling is not necessary since the DMNs and 2,6-CMN are soluble in ether at room temperature whereas the complex is less soluble and therefore precipitates.
  • the complex is useful as a source of relatively pure 2,6-DMN.
  • heating the complex to the boiling point of 2,6-DMN (262C at 1 atm) causes the complex to decompose liberating 2,6- DMN (melting point 108C) and leaving liquid 2,6- CMN (melting point l28-l29C).
  • the recovered 2,6-DMN will usually be essentially pure, i.e., a purity above percent by weight. The exact purity will vary depending upon the efficiency of the filtration or other separation steps employed, but the final 2,6-DMN product can if desired be recrystallized from alcohol to effect a final purification. Purities lower than 95 percent will be obtained if, for example, the cooling step is carried out at too low a temperature so that an impure complex is separated.
  • a vapor phase chromatographic analysis of the complex shows two peaks of equal area and having retention times equal to those of pure 2,6-DMN and 2,6- CMN. This shows the molar ratios of components and that under the conditions of the determination the complex is split into its component parts. No other peaks were present.
  • EXAMPLE 11 One gram of a 460-650F catalytic gas oil was mixed with 2,6-CMN in the ratio of one mole of the latter per mole of 2,6-DMN in the gas oil. The mixture was heated to 60-75C and the 2,6-CMN dissolved. The solution was then cooled to room temperature and the resulting precipitate separated by filtration. The precipitate was analyzed by VPC, which effected a separation of the two components thereof, and shown to have an equal molar 2,6-DMN and 2,6-CMN composition.
  • the purity of the 2,6-DMN was 99-100 weight percent.
  • the analysis (in weight percent) of the original gas oil is as follows:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US410650A 1973-10-29 1973-10-29 Complex of 2,6-dimethylnaphthalene and 2-cyano-6-methylnaphthalene Expired - Lifetime US3870745A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US410650A US3870745A (en) 1973-10-29 1973-10-29 Complex of 2,6-dimethylnaphthalene and 2-cyano-6-methylnaphthalene
CA207,910A CA1024994A (en) 1973-10-29 1974-08-27 Complex of 2,6-dimethylnaphthalene and 2-cyano-6-methylnaphthalene
IT28242/74A IT1022736B (it) 1973-10-29 1974-10-09 Conplesso del 2 6 dimetilnaftalene e del 2 ciano 6 metilnaftalene
DE19742449699 DE2449699A1 (de) 1973-10-29 1974-10-18 Komplexverbindung aus 2,6-dimethylnaphthalin und 2-cyano-6-methylnaphthalin
GB4559674A GB1475091A (en) 1973-10-29 1974-10-22 Separation of 2,6-dimethylnaphthalene by complexation
FR7435662A FR2249054B1 (enrdf_load_stackoverflow) 1973-10-29 1974-10-24
JP49122634A JPS5082046A (enrdf_load_stackoverflow) 1973-10-29 1974-10-25
NL7414048A NL7414048A (nl) 1973-10-29 1974-10-28 Werkwijze voor de bereiding van een komplex van 2,6-dimethylnaftaleen en voor de bereiding van zuiver 2,6-dimethylnaftaleen.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US410650A US3870745A (en) 1973-10-29 1973-10-29 Complex of 2,6-dimethylnaphthalene and 2-cyano-6-methylnaphthalene

Publications (1)

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US3870745A true US3870745A (en) 1975-03-11

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US410650A Expired - Lifetime US3870745A (en) 1973-10-29 1973-10-29 Complex of 2,6-dimethylnaphthalene and 2-cyano-6-methylnaphthalene

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US (1) US3870745A (enrdf_load_stackoverflow)
JP (1) JPS5082046A (enrdf_load_stackoverflow)
CA (1) CA1024994A (enrdf_load_stackoverflow)
DE (1) DE2449699A1 (enrdf_load_stackoverflow)
IT (1) IT1022736B (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4940832A (en) * 1988-06-13 1990-07-10 Tsutomu Miyashi Process for separating 2,6-dimethylnaphthalene
US4962274A (en) * 1988-09-10 1990-10-09 Kureha Kagaku Kogyo K.K. Process for separating alkyl-substituted naphthalene derivatives using clathrate complexes
US4963248A (en) * 1987-09-24 1990-10-16 Nippon Mining Co., Ltd. Process for production of dimethylnaphthalenes
US5045178A (en) * 1989-03-20 1991-09-03 Nippon Mining Co., Ltd. Process for production of methylnaphthalenes
US5059742A (en) * 1988-06-13 1991-10-22 Mitsubishi Oil Co., Ltd. Process for separating 2,6-dimethylnaphthalene
US5186816A (en) * 1990-03-12 1993-02-16 Nippon Mining Co., Ltd. Method of producing high aromatic-content solvents
US5321182A (en) * 1990-07-27 1994-06-14 Nippon Steel Chemical Co., Ltd. Process for preparing 2-alkyl-6-ethylnaphthalene

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003077599A1 (en) 2002-03-12 2003-09-18 Matsushita Electric Industrial Co., Ltd. Induction heating device
ES2334916T3 (es) 2003-07-15 2010-03-17 Panasonic Corporation Aparato de calentamiento por induccion.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3665044A (en) * 1970-05-01 1972-05-23 Sun Oil Co Fractionation of c12 bicycle aromatic hydrocarbons by 2-chloro,4-nitrobenzoic acid complex formation
US3670039A (en) * 1970-05-01 1972-06-13 Sun Oil Co Fractionation of c{11 {11 {11 bicyclic aromatic hydrocarbons by tetrahalophthalic anhydride complex formation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3665044A (en) * 1970-05-01 1972-05-23 Sun Oil Co Fractionation of c12 bicycle aromatic hydrocarbons by 2-chloro,4-nitrobenzoic acid complex formation
US3670039A (en) * 1970-05-01 1972-06-13 Sun Oil Co Fractionation of c{11 {11 {11 bicyclic aromatic hydrocarbons by tetrahalophthalic anhydride complex formation

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4963248A (en) * 1987-09-24 1990-10-16 Nippon Mining Co., Ltd. Process for production of dimethylnaphthalenes
US4940832A (en) * 1988-06-13 1990-07-10 Tsutomu Miyashi Process for separating 2,6-dimethylnaphthalene
US5059742A (en) * 1988-06-13 1991-10-22 Mitsubishi Oil Co., Ltd. Process for separating 2,6-dimethylnaphthalene
US4962274A (en) * 1988-09-10 1990-10-09 Kureha Kagaku Kogyo K.K. Process for separating alkyl-substituted naphthalene derivatives using clathrate complexes
US5045178A (en) * 1989-03-20 1991-09-03 Nippon Mining Co., Ltd. Process for production of methylnaphthalenes
US5186816A (en) * 1990-03-12 1993-02-16 Nippon Mining Co., Ltd. Method of producing high aromatic-content solvents
US5321182A (en) * 1990-07-27 1994-06-14 Nippon Steel Chemical Co., Ltd. Process for preparing 2-alkyl-6-ethylnaphthalene

Also Published As

Publication number Publication date
DE2449699A1 (de) 1975-04-30
IT1022736B (it) 1978-04-20
JPS5082046A (enrdf_load_stackoverflow) 1975-07-03
CA1024994A (en) 1978-01-24

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