GB2080822A - Process for isomerising 1-methylnaphthalene - Google Patents
Process for isomerising 1-methylnaphthalene Download PDFInfo
- Publication number
- GB2080822A GB2080822A GB8114723A GB8114723A GB2080822A GB 2080822 A GB2080822 A GB 2080822A GB 8114723 A GB8114723 A GB 8114723A GB 8114723 A GB8114723 A GB 8114723A GB 2080822 A GB2080822 A GB 2080822A
- Authority
- GB
- United Kingdom
- Prior art keywords
- reaction
- methylnaphthalene
- boron trifluoride
- phosphoric acid
- methyinaphthalene
- 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.)
- Granted
Links
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 20
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 6
- LKWKIVHUCKVYOA-UHFFFAOYSA-N phosphoric acid;trifluoroborane Chemical compound FB(F)F.OP(O)(O)=O LKWKIVHUCKVYOA-UHFFFAOYSA-N 0.000 claims abstract 2
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 8
- 238000006317 isomerization reaction Methods 0.000 claims description 3
- 239000003444 phase transfer catalyst Substances 0.000 claims description 3
- YQIVQBMEBZGFBY-UHFFFAOYSA-M tetraheptylazanium;bromide Chemical group [Br-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC YQIVQBMEBZGFBY-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- -1 1-substituted naphthalene Chemical class 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 229940041603 vitamin k 3 Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/274—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C5/2748—Acids of halogen; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/2756—Catalytic processes with hydrides or organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
There is provided a process for isomerising 1-methyl-naphthalene is formed at 100-160 DEG C in a two- liquid phase reaction with phosphoric acid-boron trifluoride as catalyst, the water content of the phosphoric acid being below 20% and boron trifluoride being passed through the reaction mixture during the reaction.
Description
SPECIFICATION
Process for isomerising 1-methylnaphthal- ene
The invention relates to a process for the selective isomerization of 1-methyinaphthal- ene, including 1-methyinaphthalene when present as the main component of methylnaphthalene mixtures.
Most of the rearrangements of 1-substituted naphthalene derivatives to 2-substituted naphthalene derivatives described in the literature are gas phase reactions over fixed catalysts at elevated temperature. Catalysts include kieselguhr (420"C), aluminium silicates (270-450"C), bauxite (450"C) and magnesium-modified zeolites (310-350"C). The liquid phase rearrrangement with alumina (350on) in an autoclave (31 bars) is also described.
All these reactions have a low degree of selectivity since in addition to the desired product, 2-methylnaphthalene, considerable amounts of the disproportionation products naphthalene and dimethylnaphthalene are also formed.
Another possible rearrangement reaction is the liquid phase reaction with Friedel-Crafts catalysts. In addition to anhydrous HF/BF3 (G.Suld, A.P. Stuart, Journal of Organic
Chemistry, 29, 2339-46 (1964)), AICI3 is also used for this purpose. However, when using AICI3 the process can be carried out only at a high degree of dilution since other dimethylnaphthalenes, naphthalene and also tarry products are formed in large amounts. In order to establish equilibrium conditions the process in therefore carried out in dilute carbon disulphide solutions (0.2%).
When working with hydrofluoric acid and boron trifluoride, the process is carried out in 10% benzene solution or n-hexane solution, and the hydrofluoric acid is used in a 55-fold excess. The reaction mixture is added to water to be worked up. Apart from the toxicity and corrosion problems, such a process is extremely uneconomic.
The object of the invention is thus to provide an improved process for the selective isomerization of 1-methyinaphthalene to 2methylnaphthalene at not too high temperatures in the liquid phase without diluents, in which, in addition to pure 1-methyinaphthal- ene, fractions with high 1-methyinaphthalene concentrations can also be used.
This object is solved according to the invention by a process for isomerising 1-methyina- phthalene and methylnaphthalene mixtures containing 1-methyinaphthalene as the main component, which process is characterised in that 2-methylnaphthalene is specifically formed in a two-liquid phase reaction with phosphoric acid/boron trifluoride as catalyst, the reaction is carried out at 100 to 160on, preferably 1 20 to 140"C, the water concentration of the phosphoric acid is below 20%, preferably below 5%, and boron trifluoride is passed through the mixture during the reaction.
According to a preferred process of the invention 1-methyinaphthalene or a 1-methylnaphthalene fraction is intensively mixed with an equal volume of 80-100% phosphoric acid saturated with boron trifluoride. During reaction, which typically takes about 3 hours, boron trifluoride is led through the solution to compendate for boron trifluoride losses from the complex. The temperature should in general be between 100 and 160"C. At higher temperatures the yields falls on account of tar formation, while at low temperatures the reaction proceeds too slowly and incompletely.A temperature of about 120"C has proved advantageous, since in this case the conversion of 1-methyinapthalene to 2-methylnaphthal- ene is still between 65-72%, and in addition the phosphoric acid has not begun to react too strongly with the boron trifluoride. Under these conditions the phosphoric acid can be reused many times without loss of yield. At the end of the reaction the reaction mixture can be allowed to cool and the phases separated in a separating vessel. The monomethylnaphthalene mixture is preferably washed with water and worked up by distillation according to known separation methods.
2-methylnaphthalene serves as a starting compound for menadion, vat dyes or also 2hydroxynaphthalenecarboxyiic acid for the fibres sector. The mixtures obtained by the reaction of the invention are particularly suitable for further processing, since for instance little if any naphthalene or dimethylnaphthalene is formed in the reaction. When using methylnaphthalene fractions the mixture must of course be previously freed from N-heterocyclics which might deactivate the catalyst.
The amount of catalyst can be reduced by adding phase transfer catalysts. For example, if the amount of catalyst is reduced to one quarter, a 70% yield of 2-methyinaphthalene typically falls to about 17%; addition of 0.35% by weight of tetraheptylammonium bromide (referred to amount of 1-methyina- phthalene used) raises the yield back to about 60%.
Example 1
20 Parts by volume of phosphoric acid (96%) were saturated with boron trifluoride.
After formation of the 1:1 complex, 20 parts by volume of 1-methyinaphthalene (98%) were added. The two-phase system was vigorously stirred for 3 hours at 120"C. During this time boron trifluoride gas was passed through the reaction mixture. After cooling and decanting, the reaction product (19.5 parts) was washed with water. The product contained 71.5% of 2-methynaphthalene and 27.1% of 1-methylnaphthalene. The phosphoric acid was suitable for repeated reuse without any loss of yield.
Example 2
Methylnapthalene fractions free from N-heterocyclics were used in accordance with the procedure of Example 1.
a) 83% 1-methyinaphthalene 6.8% 2-methyinaphthalene b) 93% 1-methyinaphthalene 1.6% 2-methylnaphthalene The reaction products had the following composition: a) 24.7% 1-methyinaphthalene
66.5% 2-methylnaphthalene b) 26.4% 1-methyinaphthalene 68.8% 2-methyinaphthalene Example 3
20 parts by volume of T-methylnaphthalene were reacted according to the procedure of
Example 1, but using only 5 parts by volume of phosphoric acid and adding 0.35% by weight of tetraheptylammonium bromide (referred to the amount of 1-methylnaphthalene employed). The reaction product contained 59.2% of 2-methyinaphthalene and 40.0% of 1 -methylnaphthalene.
Claims (6)
1. A process for isomerising 1 -methylna- phthalene, wherein 2-methyinaphthalene is formed at 100-160"C in a two-liquid phase reaction with phosphoric acid-boron trifluoride as catalyst, the water content of the phorphoric acid being below 20% and boron trifluoride being passed through the reaction mixture during the reaction.
2. A process according to claim 1, wherein a phase transfer catalyst is added to the reaction mixture.
3. A process according to claim 2, wherein the phase transfer catalyst is tetraheptylammonium bromide.
4. A process according to claim 1, 2 or 3, wherein the reaction is carried out at from 120 to 14or.
5. A process according to any of claims 1 to 4, wherein the water content of the phosphoric acid is below 5%.
6. A process according to any preceding claim, when applied to the isomerization of 1methylnaphthalene as main component of a methylnaphthalene mixture.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803028199 DE3028199C2 (en) | 1980-07-25 | 1980-07-25 | Process for the isomerization of 1-methylnaphthalene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2080822A true GB2080822A (en) | 1982-02-10 |
| GB2080822B GB2080822B (en) | 1983-11-02 |
Family
ID=6108075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8114723A Expired GB2080822B (en) | 1980-07-25 | 1981-05-14 | Process for isomerising 1-methylnaphthalene |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS5753417A (en) |
| DE (1) | DE3028199C2 (en) |
| FR (1) | FR2487335A1 (en) |
| GB (1) | GB2080822B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0442777Y2 (en) * | 1986-09-03 | 1992-10-09 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1540716A (en) * | 1966-10-13 | 1968-09-27 | American Cyanamid Co | Improved process for the isomerization of alkylated aromatic hydrocarbons |
-
1980
- 1980-07-25 DE DE19803028199 patent/DE3028199C2/en not_active Expired
-
1981
- 1981-05-14 GB GB8114723A patent/GB2080822B/en not_active Expired
- 1981-07-03 FR FR8113179A patent/FR2487335A1/en active Granted
- 1981-07-24 JP JP56115450A patent/JPS5753417A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2487335A1 (en) | 1982-01-29 |
| DE3028199A1 (en) | 1982-02-11 |
| DE3028199C2 (en) | 1983-02-10 |
| JPH0113454B2 (en) | 1989-03-06 |
| GB2080822B (en) | 1983-11-02 |
| JPS5753417A (en) | 1982-03-30 |
| FR2487335B1 (en) | 1984-10-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |